Production of Methanol From Natural Gas

Production Of Methanol From Natural Gas
Methanol
Methanol is an Alcohol whose chemical formula can be written as CH 3OH. It is a clear,
colourless liquid with a mild odour, and dissolves readily in most common organic solvents.
Methanol is one of the largest volume chemicals produced, with a world wide annual
production of about 13 million tons.
Methanol was first obtained commercially some 150 years ago
by the destructive distillation of wood. Today it is produced
mainly from the steam reforming of natural gas via a synthesis
gas intermediate. Methanol can and is , however also being
produced from such alternative feed stocks as coal and residual
fuel oil.
Methanol has been traditionally used as a chemical intermediate
for the production of formaldehyde, solvents, methyl
derivatives(chemical groups containing CH3) and increasingly acetic acid. Recently methanol
has gained importance as a clean burning fuel and fuel additive in such diverse uses as a
boiler fuel for NOx control , as an octane booster for gasoline by direct blending or as a methyl
tertiary butyl ether derivative and for fuel cell application .
1.1 Physical Properties.Methanol (CH3OH) is an alcohol fuel. Methanol is the simplest alcohol, containing one carbon
atom. It is a colorless, tasteless liquid with a very faint odor and is commonly known as "wood
alcohol."As engine fuels, ethanol and methanol have similar chemical and physical
characteristics. Methanol is methane with one hydrogen molecule replaced by a hydroxyl
radical (OH).
Physical Properties
Molecular weight
32.04
Boiling point
64.7C
Vapor pressure
97 Torr at 20C
Formula
CH3OH
Freezing point
-97.68C
Refractive index
1.3284 at 20C
Density
0.7913 g/mL (6.603 lb/gal) at 20C

0.7866 g/mL (6.564 lb/gal) at 25C
Dielectric constant
32.70 at 25C
Dipole moment
2.87 D at 20C
Solvent group
Polarity index (P')
5.1
Eluotropic value on alumina
0.95
Eluotropic value on octadecylsilane
1.0
Viscosity
0.59 cP at 20C
Surface tension
22.55 dyn/cm at 20C
Solubility in water
Miscible in all proportions
Melting Point
-97.7 0C
Flash point
11 oC
Auto ignition temperature
455 oC
Explosive limits
7-36 %
Heat of Formation
-201.3 MJ/kmol
Gibbs Free Energy
-162.62 MJ/kmol
Critical temperature
512.6 K
Critical pressure
81 bar abs
Critical volume
0.118 m/kmol
Heat of Vaporization
35278 kJ/kmol
Regulatory and Safety Data

Acute effects
Poisonous by ingestion or inhalation, may

cause respiratory failure, kidney failure,
blindness.
Chronic effects
As acute. Skin contact can cause dermatitis.
1.2 Reactions Of Methanol

Methanol is the 1st in a series of aliphatic, monohydric alcohols and undergoes many of the
reactions typical of this class of chemical compound , Methanol is also a typical member of this
series since it contains only one carbon atom . Methanol, for example can not undergo
elimination of the hydroxyl group and hydrogen to form the analogous olefins as do many of
the higher alcohols.
The reactions of the aliphatic alcohols including methanol generally involve hydroxyl group,
either through breaking of the C-O bond or O-H bond and substitution or displacement of the
H or _OH group, . the O-H and C-O bonds in alcohols are relatively strong, albeit polar and
kinetically labile. Hemolytic bond dissociation energies are in the order of 90 100 Kcal/ mole.
Because of this bond strength in alcohols, some activation of these bonds is often necessary
to achieve acceptable reaction rates.
1.3 CHEMICAL PROPERTIES OF METHANOL: CH3OH

Combustion of Methanol:
Methanol burns with a pale-blue, non-luminous flame to form carbon dioxide and steam.
2CH3OH
302 ===>
2CO2 +
4H2O
Oxidation of Methanol:
Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified Sodium
Dichromate, Na2Cr2O7, or with acidified Potassium Permanganate, KMnO4, to form
formaldehyde.
CH3OH
===>
Methanol
2H2 + O2 ===>
HCHO
H2
Formaldehyde
2H2O
If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then
to carbon dioxide and water.
HCHO
===> HCOOH ===> CO2 + H2O
Formaldehyde
Formic
Acid
Catalytic Oxidation of Methanol:

The catalytic oxidation of methanol using platinum wire is of interest as it is used in model
aircraft engines to replace the sparking plug arrangement of the conventional petrol engine.
The heat of reaction is sufficient to spark the engine.
Dehydrogenation of Methanol:
Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated to 300 C. Two
atoms of hydrogen are eliminated from each molecule to form hydrogen gas and hence this process is
termed dehydrogenation.
Cu
300C
CH3OH ===>
HCHO
+
Methanol
Formaldehyde
H2
Dehydration of Methanol:
Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid the
ester, dimethyl sulphate is formed.
2 CH3OH
Methanol
Conc H2SO4
===>
(CH3)2SO4
Dimethyl
Sulphate
+
H2O
Water
Esterification of Methanol
Methanol reacts with organic acids to form esters.
CH3OH
Methanol
H(+)
+
HCOOH ===>
Formic
Acid
HCOOCH3
Methyl
Formate
+ H2O
Water
Substitution of Methanol with Sodium

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is similar
to the reaction of sodium with ethanol.
2 CH3OH +
Methanol
2 Na ===>
Sodium
2CH3ONa
Sodium
Methoxide
+ H2
Hydrogen
Substitution of Methanol with Phosphorus Pentachloride

Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen
chloride, methyl chloride, (i.e. chloroethane) and phosphoryl chloride.
CH3OH
Methanol
PCl5 ===>
HCl
Phosphorus Hydrogen
CH3Cl
Methyl
POCl3
Phosphoryl

Pentachloride Chloride
Chloride
6
Chloride
Substitution of Methanol with Hydrogen Chloride

Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and water.
A dehydrating agent (e.g. zinc chloride) is used.
CH3OH +
Methanol
HCl
ZnCl2
===>
CH3Cl
Methyl
Chloride
H2O
1.4 USES OF METHANOL:The major portion of the methanol produced is used for making formaldehyde and a number of
chemical derivatives. Other applications include its use as solvents extractant and air
automation antifreeze. .
Methanol As A Solvent:Methanol is miscible with most organic liquids and is a solvent for variety of substance like
dyes, nitro cellulose, polyvinyl, butyl ethyl cellulose, Shellac and modified resin. It is used in
the manufacturing of wood and metal polishes. Water proofing formulation, coated fabrics,
aniline, and other inks, and duplicator fluids. Its solution have lower viscosities than similar
solution, made from other alcohols, methanol is uses in combination with 5 to 10 % of
polyhydroxy alcohol as a solvent for water soluble aniline dyes in the manufacture of non=grain-raising wood-stain, it is also used as a solvent for aniline dyes for leather and is
especially useful where uniform colour development is essential. Other application of this
products include its addition to asphalts paints to decrease their drying time and its use in both
natural and synthetic rubber solutions to lower the viscosity during processing . Methanol does
not dissolve cellulose acetate and acetate butyrate, polystyrene, polyethene, methylcrylate
resin, polyvinyl chloride, and co-polymers.
Methanol As An Extractant:Methanol is employed in a large scale in many industrial chemical processes as an extractant.
In the refining of gasoline and heating oil. The unisol process use caustic methanol solutions to
remove undesirable mercaptan impurities. Methanol may also be used to extract the aromatic
potion of petroleum form other hydrocarbons and patent literature describe its use in extraction
organic nitrites. From non polar hydrocarbon in the secondary recovery of crude oil by th
miscible phase method using alcohol methanol is the least expensive and most easy
recovered. A process has been developed to use a solvent of methanol and hexane in the
extraction of tars from Texas Lignite deposits.
Methanol is also uses for removing acid impurities from vegetable oils, dewaxing dimmer gum,
flash washing water soluble crystals, extracting inorganic salt such as potassium iodide and
barium and strontium halides, purifying hormones and crystallizing steroid.
Methanol As A Ceansing Agent:Methanol is used in many cleansing operations such as in washing steel surfaces before
coatings are applied , rinsing the interiors of electronic tubes before they are evacuated ,
cleaning resin sheets before further processing , It is employed as a reducing agent in the
vapor phase cleaning of copper, the bright annealing of brass and in soldering fluxes. Its is
also used in special preparation for dry cleaning leather goods, in glass cleaners and in
flushing fluids for hydraulic brake system.
Methanol As An Anti Freezing Agent

Methanol offers the advantages of low molecular weights, low costs and high efficiency when
used as an automotive or industrial antifreeze. The pressure up cap on the radiator of the
modern engine cooling system prevent losses by evaporations. Methanol-antifreeze solutions
are considered less result of internal leakage then the high boiling type. Fuel system antifreeze
and windshield washer fluid based on methanol add to the dependability and convenience of
motor transport in methyl ester of 2-4 D is a selective weed killer, methyl salicylate is used in
medicines flavorings and perfumes., dimethylpthalate is as insect repellent and a plasticizer for
cellulose acetate methyl P=hydroxyl benzoate is a mold inhibitor for aqueous preparations,
containing starch guans and oil. Methylcrylate polymerizes readily to form clear plastics.
Formaldehyde:Worldwide, the largest amount of formaldehyde is consumed in the production of ureaformaldehyde resins, the primary end use of which is found in building products such as
plywood and particle board .The demand for these resins, and consequently methanol, is
greatly influenced by housing demand. In the United States, the greatest market share for
formaldehyde is again in the construction industry. However, a fast-growing market for
formaldehyde can be found in the production on acetylenic chemicals, which is driven by the
demand for 1, 4 butanediol and its subsequent downstream product, spandex fibers.
Methyl T-Butyl Ether:MTBE is used as an oxygen additive for gasoline. Production of MTBE in the United States ha
increased due to the requirements of the 1990 Clean Air Act amendments, and has surpassed
formaldehyde as the largest domestic consumer of methanol. Projection for this use of
methanol are difficult to estimate due to the varying political and environmental considerations
that promote the use of cleaner burning motor fuels.
ACIDS:Methanol carbonylation has become the process of choice for production of this staple of the
organic chemical industry, which is used in the manufacture of acetate fibers, acetic anhydride,
and terephthalic acid, and for fermentation,
Methanol As An Alternative Fuel

Utilization of methanol as alternative fuel can be done through two different ways
that is by using directly in an internal combustion engine or by implementing methanol fuel cell
powered vehicles.
Pure methanol (M100) has been used in heavy-duty trucks and transit buses equipped with
compression-ignition diesel engines. Since 1965, M100 has been the official fuel for
Indianapolis 500 race cars. (The last time gasoline was used in the Indianapolis 500 was in
1964, when the race suffered a pile-up of cars that resulted in a gasoline fire and deaths.)
Typically, a blend of 85 percent methanol and 15 percent gasoline (M85) is used in cars and
light trucks. Pure methanol can also be reformed in fuel cells into hydrogen, which is then used
to power electric vehicles. Methanol-powered vehicles have been found largely in the West,
primarily in California. They can also be seen in the fleets of the federal government and the
New York
STORAGE AND SAFETY

Because methanol is corrosive to some metals and damaging to rubber and some
plastics, fuel storage tanks and dispensing equipment must be corrosion and damage
resistant. California requires that underground storage tanks for methanol be double walled.
Because methanol is water soluble, it could be quickly diluted in large bodies of water to levels
that are safe for organisms. Environmental recovery rates for methanol spills are often faster
than for petroleum spills. As with gasoline, methanol can be fatal when ingested. Inhalation of
fumes and direct contact with skin can also be harmful. Because pure methanol flames are
nearly invisible in daylight, gasoline is added as a safety precaution to provide color to a flame.
Added gasoline also serves to add a smell to this otherwise odorless liquid. Because of its high
flash point, methanol is less volatile than gasoline. It burns more slowly and at a lower
temperature. Methanol is transported by barge, truck, or rail. In the event of an
EMISSIONS
The methanol molecule has a simple chemical structure, which leads to clean
combustion; reports from emissions studies, however, vary more widely for methanol than for
other fuels probably because of differences among fuel blends used across the country and
because vehicles may not be optimized for using methanol. Comparisons of M100 with
gasoline and diesel have shown these results:
Carbon monoxide: Emissions vary sometimes lower, but are usually equal or slightly
higher.
Ground-level-ozone-forming potential: 30 to 60 percent less. (In order to take advantage of
this characteristic, vehicles must be properly adjusted.)
Nonmethane evaporative hydrocarbons: Usually less.
Toxics: M100 contains none of the carcinogenic ingredients such as benzene, 1,3-butadiene,
and acetaldehyde. M85 (with 15 percent gasoline) has 50 percent fewer toxic air pollutants
than gasoline.
Formaldehyde levels: Much higher, although still low. The toxicity of formaldehyde is lower
than that of other toxics, and formaldehyde emissions can be reduced dramatically with new
technology, such as improved catalytic converters.
Nitrogen oxides: Usually comparable or less.
Greenhouse gases: Comparable to gasoline.
Particulate matter: Buses using M100 emit significantly less than diesel-fueled buses.
Internal Combustion Engines Using Methanol

Several factors effect the use and selection of any fuel. Among the important ones are
engine design, net energy per pound, net energy per gallon and the sulfur content of
alternative fuel properties.
a-Pure methane
b-Octane rating above 100 are correlated with given conc. Of tetra ethyl lead in 150 octane.
c-Natural sulfur content very low but measurable.
Measuring a fuels selective potential energy can easily be done by defining that fuels BTU
content. A Btu defined as the amount of heat necessary to raise one pound of water, onedegree Fahrenheit.
At ambient temperature and atmospheric pressure, liquid methanol is basically similar to
gasoline or diesel fuel. Therefore methanol is easy to be stored and transported compared to
CNG & LNG. These characteristics make the price of methanol vehicles and refueling station
lower than the price of CNG or LNG vehicles and refueling station. For a certain type,
methanol vehicle is offered at lower price than gasoline vehicles, for the purchase of certain
No. OF vehicles.
Present design internal combustion engines run on liquid fuels. Methanol required few of any
engine modification to extract the maximum power from this fuel. As compared to gasoline,
methanol lowers some tailpipe emissions, namely the sulfur based HC, CO, as well as NOx.
Methanol contains only half the energy per gallon of gasoline but has a very high octane rating.
Increased compression ratios could yield 5-20 %. More power.
When methanol is used as a gasoline additive antiknock compound and fuel extender, it
becomes economical with very positive results especially from the emissions stand point. It
contains zero sulfur thereby reducing tailpipe acid significantly. Of the six most popular
attractive fuels presently available methanol has the second lowest Btu/lb, net energy yield. As
a result, fuel tanks will need to be enlarged for vehicles that run on pure methanol.
1.5 A Historical Overview

In their embalming process, the ancient Egyptians used a mixture of substances, including
methanol, which they obtained from the pyrolysis of wood. Pure methanol, however, was first
isolated in 1661 by Robert Boyle, who called it spirit of box, because he produced it via the
distillation of boxwood. It later became known as pyroxylic spirit. In 1834, the French chemists Jean-
10
and Eugene Peligot determined its elemental composition. They also introduced the
word methylene to organic chemistry, forming it from the Greek words methu, meaning "wine,"
and hyle, meaning "wood". The term methyl was derived in about 1840 by back-formation from
methylene, and was then applied to describe methyl alcohol. This was shortened to methanol
in 1892 by the International Conference on Chemical Nomenclature.
Baptiste Dumas
In 1923, the German chemist Matthias Pier, working for BASF developed a means to convert synthesis
gas (a mixture of carbon monoxide and hydrogen derived from coke and used as the source of
hydrogen in synthetic ammonia production) into methanol. This process used a zinc chromate catalyst,
and required extremely vigorous conditionspressures ranging from 30100 MPa (300
1000 atm), and temperatures of about 400 C. Modern methanol production has been made
more efficient through the use of catalysts capable of operating at lower pressures.
.
The first large scale commercial synthetic methanol process was introduced by BASF in 1923.
The process was based on the reaction of synthesis gas (a mixture of hydrogen and carbon
oxides) over a zinc chromite catalyst at relative high temp (300 to 400 Co) and high pressure
(250-350 atm). The synthesis gas was derived from coal via the water gas reaction.
The first synthetic methanol unit in the USA was located at Belle, West Virginia, at the
ammonia plant of Lazote, Inc, a subsidiary of Dupont and began operation in 1927. The unit
was actually installed to remove the 1 to 2 % carbon monoxide impurity in the ammonia
synthesis gas by utilizing the methanol synthesis reaction as purification step.
Up till the end of World War II, methanol was mainly produced as a co product using synthesis
gas from coke via the water gas or blue gas reactions as well as using off-gases form
fermentation, coke ovens and steel furnaces. These methanol units were relatively small (less
than 200 thousand tons per year, most in the 30 to 90 thousand tons per year range).
One of the major technological changes often overlooked in the methanol industry was
conversion from water-gas to natural gas as a source of synthesis gas for feed to the methanol
converters. Natural gas derived synthesis gas was much higher quality , contained much less
impurities and catalyst poisons , and was readily available in nearly unlimited quantity. 71% of
the carbon monoxide uses for the synthesis of methanol was obtained form coke or coal ,
where as by 1948 about 77% was derived from natural gas.
In 1966 , Imperial Chemical Industries (ICI) in England announced the second major break
through in methanol technology , the ICI low pressure process for synthesis of methanol using
a propri9etary copper based catalyst. The high activity copper based catalyst allowed the
methanol synthesis reaction to proceed at commercially acceptable levels tat relatively low
temp. (22-280 oC) thus allowing operation at significantly reduced pressure (50 atm) from that
needed for the high pressure process (350 atm ).
A number of improvements have been made in these early methanol process, principally in the
area of improved energy efficiency. Subsequent low pressure process have revolutionized the
industry and have allowed for the construction of more energy efficient and cost effective plant.
Now a days, modern low pressure methanol units have a capacity of about 400-1000 thousand
tons per year, operates at 50 to 100 atm.
11
12
RAW MATERIALS
Long-term availability energy consumption and environmental aspects are all considered in
choosing a raw material, however financial consideration are of primary importance.
Keeping above described factors in view, a fuel containing sufficient amount of hydrogen and
carbon monoxide is a possible raw material commonly known as synthesis gas for methanol
production.
Major resources from which synthesis gas be produced are
1. Natural Gas
2. Coal
3. Naphtha
4. Heavy hydrogen feed stock.
Extraction of synthesis gas from these sources is further described here:
2.1 SYNTHESIS GAS FROM COAL:The production of gaseous fuel from coal has been practiced for 100 of years but most of the
process for gasification was gradually replaced in the 1950s and 1960s by processes based on
low cost petroleum hydrocarbons. The oil shortage of the 1970 renewed a worldwide interest in
coal as chemical feedstock. However, recent falling prices of oil in the world have moderated
that short lived interest. During gasification, falling ground coal reacts with oxygen and steam
at elevated temp. to form a synthesis gas comprised mainly of carbon monoxide and
hydrogen, with lesser amount of carbon-dioxide, methane, nitrogen, argon, hydrogen sulphide,
tar and phenols. The quantities of the lesser components depend on the amount of impurities
found in the coal and in the amount of oxygen fed to the gasifier.
The heart of the coal based partially oxidation process in the gasification step. To achieve
maximum efficiency, a gasifier should operate at an elevated pressure, have low oxygen and
steam demand, have high carbon conversions and have low heat losses. It is also desirable to
achieve high reliability, to minimize or eliminate by-product formation and to accept a wide
variety of coals. Low temperature gasifiers produce considerably more methane, oils, phenols
and tar than high temperature ones. A slagging gasifier operated at temperature above the
fusion point so that ash is removed in the molten form; that temperature is typically b/w 24002700 oC.
Selecting the best gasifier for a particular operation is usually a matter of compromise, since
the designer must weigh many variables including the type of coal available, capacity, byproduct rates, and capital investment efficiency and so on. Most gasifiers fall into one of three
general categories atmospheric or low pressure, high pressure and second generation.
2.2 The Koppers-Totzok (K-T):Gasifier is an atmospheric process with extensive commercial experience in Europe,
Asia and South Africa. It will handle all coals; make virtually no by-products operate with high
thermal efficiency and high conversion. However, there is an extra cost associated with this
13
process (Low Pressure Process), because it operates at atmospheric pressure; the product
synthesis gas must be compressed before introduction to methanol synthesis loop. THE
WINKLER GASIFIER is another low pressure process widely used in Europe, Japan and
India. However, as a low-pressure process, it has the same advantages and disadvantages as
the K-T process
A high pressure process, the LURGIDRY ASH GASIFIER is the most widely used commercial
process. It has even more disadvantages than K-T process, forms numerous by-products, has
a limited ability to handle caking coals, and produces as large amount of methane (which must
be purged from the converter loop, if the gas is used for the methanol synthesis).
2.3 The British Gas Council Lurgi (BGC-Lurgi):Gasifier is another high pressure process, more efficient than LURGI DRY ASH PROCESS.
Due to reduced steam usage and higher capacity, however, it produces great amount of byproducts and has only a limited ability to handle caking coals.
The Texaco and Shell-Koppers:Gasifiers are two of the most promising second-generation process. Both offer many of
the similar advantages as the atmospheric gasifiers, but both are high pressure operations,
that accept all coals and make virtually no by- products.
A large number of purification steps are necessarily required to produce methanol synthesis
gas from the crude product gas leaving the gasifier since the raw gases contain no large
number of undesirable by-products.
Some or all of the following process steps may be required. Cooling with steam generation,
water washing, compression, sulfur removal, shift conversion of carbon monoxide and after
that hydrogen and carbon dioxide removal.
Kopper
Totzek
Pressure(atm) 1.4
Temp.(oC)
1500
OxygenReqd. High
Steam Reqd.
Low
Capacity
850
(tons/day)
Raw Product ---gas analysis
Vol%
Carbon
58.1
monoxide
Hydrogen
29.3
Carbon
11.0
dioxide
Methane
0.1
Hydrocarbon ---Inerts (N2, Ar) 1.5
Winkler
Lurgi
BGC Lurgi
Taxaco
1.4 2.1
930
Medium
Medium
1000
20 -27
540-590
Low
High
500
20 - 27
480-540
Low
Low
1250
21 - 83
1290
High
None
2000
Shell
Kopper
31
1480
High
Low
1000
----
----
----
----
----
35.0
24.6
60.6
46.3
67.7
40.8
22.0
39.8
24.6
27.8
2.6
35
17
29.9
1.1
1.2
Trace
1.0
8.7
1.1
1.2
7.6
0.4
1.0
0.2
---1.5
0.2
---1.1
14
2.4 SYNTHESIS GAS FROM NAPHTHA

During the 1950s an oversupply situation in Europe made naphtha an economical feed stock
for steam reforming. A series of alkali promoted catalyst was developed specifically for
naphtha, and by the early 1960s many European procedures where preparing synthesis gas
from light distillate naphtha. At the present time the price of the naphtha feedstock and mixing
it with a hydrogen stream so that the combined stream contain approximately 5% hydrogen
stream so that the combined stream contain nickel molybdate catalyst to convert organic
sulfur compounds to hydrogen sulfide and also to saturate alkenes. Desulphurization is then
conducted as described above for hydrogenation.
The sulfur free gas is fed to a reformer which contains catalyst specially designed for naphtha
reforming. A stream to carbon ratio as lo as 2 is used, where pressure range from 1500-4000
Kpa (200 to 575 Lb/in2g). Small amount of carbon dioxide can be added optionally to yield
synthesis gas composition similar to those obtained via hydrocarbon reforming.
2.5 SYNTHESIS GAS FROM NATURAL GAS:The majority of methanol synthesis plants now use catalytic reforming of natural gas for the
production of synthesis gas. The process consists of two steps Desulphurization and the
steam reforming section.
a) Desulphurization:Natural gas contains both organic and inorganic sulfur compounds that
must be improved to protect the both reforming and down stream methanol synthesis
catalysts. They can position the catalyst even as low as 0.5 PPM. Hydrodesulphurization
across a cobalt or nickel molybdenum zinc oxide fixed bed sequence is the basis for an
effective purification system.
The temperature in the range of 340-370 0C may be necessary.
R-SH + H2
R.H + H2S
ZnO + H2S
ZnS + H2O
Zinc oxide is capable to reduce the H2S concentration down to 0.3 PPM.The disadvantages
are that it is non-regenaratable must eventually be replaced. To have the advance warning
before the ZnO bed is completely converted to ZnS at this point is provided at 755 of bed
depth. When the ZnO changes to ZnS at this point, it is the time to renew the bed.Chlorides
and mercury may also be found in natural gas, particularly from off shore reservoirs.Activated
alumina or carbon beds can remove these poisons.
15
b. STEAM REFORMING:Once the sulphur has been removed from the hydrocarbon feed stream, the gas is
mixed with steam and reform to produce methanol synthesis gas. The following reactions
occur in the reformer.
CnH2n+2 + nH2O
nCO + (2n+1) H2
CnH2n+2 + 2nH2O
-1
nCO2 + (2n+1) H2
CnH2n+2 (n-1/2) H2O
-2
(3n-1)/4 CH4 + (n-1)4 CO2
-3
All three of these reactions are endothermic, and in full scale commercial reformer, all three
proceed essentially to completion.
The primary reforming equilibrium reaction involves methane and steam:
CH4 + H2O
CO + 3H2
H298 = 206.08 KJ/g
-4
The equilibrium reaction of carbon monoxide with steam, often referred to as the water gas
shift reaction, is also a significant contributor in this process.
CO + H2O
CO2 + H2
H298 = - 41.17 KJ/g
-5
Note that the reforming reaction (4) is endothermic and the water gas shift reaction (5) is
exothermic. Undesirable reactions may occur in the reformer, resulting in deposition o carbon
on the reactor walls, on the catalyst surface, or in the pores of the catalyst. This reduces the
catalyst activity.
CnH2n+2
nC + (n 1) H2
-6
CH4
C + 2H2
-7
2CO
C + CO2
-8
CO + H2
C + CO2
-9
CO + 2H2
C + 2H2O
-10
A critical examination of the equations presented above allows one to make some preliminary
conclusions concerning reformer operation. Since reforming reaction (4) is endothermic and
the water gas shift reaction (5) is exothermic , it is obvious that less methane and more carbon
monoxide and hydrogen would be obtained at higher temperature. It is also suggested that
decreasing pressure would decrease the amount of methane in the reformer product stream.
16
In a similar manner , increasing the partial pressure of the steam would result in a decrease in
the amount of methane in the product. A set of equations , which is used to calculate the
composition of exit stream, is eq.(4),(5) and eq.(8).
Carbon composition via eq-8 can theoretically be prevented by ensuring that steam is present
in excess of some minimum amount calculated using the equilibrium equations. Any increase
in steam also has the effect of increasing methane conversion. Most Commertial reformers
operate safely with steam carbon ratio in the range of 3 to 4.5.
Reforming catalysts contain from 12 to 25 % nickel as nickel oxide supported on calcium
aluminate , alumina or calcium titanate .Alkali metal compounds added to prevent carbon
formation and increase catalyst durability. The feed stream to the reformer is distributed over
hundreds of parallel catalyst filled tubes, the tubes are subjected to a temperature range of 860
to 950 oC, wit process gas exit temperature in the range of 750 to 850 oC & pressure range
from 4 to 35 atm (450 to 3550 Kpa). Gas hourly space velocities are usually on the order of
5000 to 8000 based on wet feed.
The flue gases temperatures are in the range of 980 to 1040 oC. These hot flue gases are
transferred to a convection section where they are cooled and used to super heat steam for
provide motive power for compressors and large pumps, process steam for reforminf and
reboil duty for distillation.
2.6 SELECTION OF RAW MATERIAL

Natural gas is the only most convenient and economical raw material available in Pakistan.
This God gifted treasure is found in large reserves at Sui, Mari and some other areas. Natural
gas is easily available , cheap raw material , containing low impurities and there are no
transportation and storage costs involved. Hence natural gas is the most economically suitable
raw material for synthesis gas.
Coal is another source for the Sun. gas production in Pakistan. Coal available in Pakistan at
MAkerwal, Dhodak and Kalabagh but its quality is very poor. However , the largest reservoirs
of coal in world now found in Pakistan at Thar. No doubt, these reservoirs contain small
amounts of sulfur about 0.1-0.7% but there are some other factors involved in degrading the
coal selectivity for Syn. Gas production , such as high transportation cost , handling and
storage cost , further more additional equipment (gasifier etc) and process costs. Coal contains
much impurities and mineral materials (as compared to the natural gas) lead to the formation
of the various pollutants during combustion having adverse environmental impacts when
emitted into the atmosphere. The environmental aspects that are associated with the use of
coal are, the formation of pollutants such as fly ash , sulfur oxides, nitrogen oxides and other
mineral materials. Also coke formation occur and this is higher compared to the natural gas
and this reduces the activity of catalyst and may stick to the walls of steam reformer which
reduce the heat transfer rate.
Naphtha is not economically viable for Syn gas production in Pakistan, its reservoirs are limited
in Pakistan and do not meet sufficiently the other demands (motor fuels). Its costs are too
much as compared to the natural gas, hence it is not usable , same is the matter involved in
selection of heavy hydrocarbons.
17
18
Capacity Selection
As mentioned earlier that currently thee is no methanol producing plant in
Pakistan and all is being imported from other countries (see in table).Major exporters are Saudi
Arabia and Iran.
Methanol consumption in Pakistan is about 26800 tons / year (90 tons /day), report issued by
Federal Bureau of Statistics 2004-2005. Lets take a look to the international market ; methanol
production is going to increase and foreign methanol producers are extending their capacities
in order to meet the growing demand (as shown in the tables, where world methanol plants
capacities supply /demand by the year 1998- 2007 are given , which contains the previous ,
present and anticipated capacities and shows comprehensive increasing trend in demand).
19
Also rising image so methanol as an Alternative Fuel for motor vehicles is a matter of great
consideration for scientists.
As far as Pakistan is concerned , gasoline and diesel prices are high and
unstable. CNG and LPG are used as alternative fuels but methanol is easy to be stored and
transported compared to CNG and LPG (it is a liquid fuel. These characteristics make the
prices of methanol vehicles and refueling stations cheaper than the price of CNG and LPG
vehicles and refueling stations. These methanol based vehicles will be available by the year
2005 in foreign markets and some major motor manufacturing companies may also invest in
Pakistan,
Raw material foe methanol synthesis (N.G) is cheaper here in Pakistan, which is
a primary factor involved in reducing its price ,also methanol is environmental friendly. In
Pakistan , methanol is being employed in making urea formaldehyde , acetic acid and
methalated spirit for pharmaceutical and dyes etc. industries. Now a new formaldehyde plant
is being installed by Dyno chemicals at Hub Industrial And Trading Estate. Super Chemicals
(Karachi) , Wah Nobel Chemicals (Wah Cantt.) and Pakistan Resins (Azad Kashmir) are also
manufacturing urea formaldehyde.
As A result of this brief discussion , we may say that our capacity of 150 tons/
day is reasonable , where 90 tons / day is present consumption in Pakistan and remaining 60
tons/ day could be exported and If demand of Pakistani market increases , we may reduce or
stop its export to fulfill out demand.
3.1 Methanol Imports In Pakistan

Countries
Asian
Countries NS
Bangladesh
China
Dubai
Germany
Indonesia
Iran
Kuwait
Laos
Malaysia
Natherland
New Zealand
Saudi Arabia
Singapore
2002-2003
2003-2004
3
2004-2005
3
LTR
Rs * 10 LTR
Rs * 10 LTR
Rs * 103
18000
336
26800
610
210000
13040
373651
690180
254266
-
2140
200
3094
10042
213426
-
200000
132040
450000
9751
26080
101570
100000
13040
281600
13040
31965758
440000
2700
5217
5434
534
647
1662
2892
328
11671
249
394528
11410
2309723
58612
4099556
114338
101100
27093185
13040
23752
2478
41170
1934
4481
298683
273

South
Africa 14768
Rep
Spain
Turkey
25600
Thailand
U.S.A
424633
U.K
Total (LTR)
27196520
Tons
26800
20
148
104
40
386
2863
232635
3000
33762679
36559
145
438026
79200
200000
34068859
43800
1024
2033
375831
21
22
23
24
25
26
4.1 Methanol Manufacturing Process

The Methanol Industry in Trinidad began with the construction of a 1,200 MT state-owned
methanol plant in 1983 (Trinidad and Tobago Methanol Companys first plant). Since that time,
the industry has expanded to include four larger plants with an annual production capability
close to 3 million MT of methanol.
At the MHTL Point Lisas Methanol Complex, methanol is made using the ICI Low Pressure
Methanol Synthesis Process. The two main raw materials used are natural gas (96% methane)
received from the National Gas Company (NGC) to provide the carbon and hydrogen
components and water from the Water and Sewerage Authority (WASA) to provide the oxygen
component. These raw materials undergo a series of chemical reactions to produce crude
methanol which is then purified to yield refined methanol, having a purity exceeding 99.9%.
The plants operate continuously 24 hours a day in a production process that can be divided
into four main stages: Feed Purification, Reforming, Methanol Synthesis and Methanol
Purification as shown in the flow sheet below:
STEP1 FEED PURIFICATION

The two main feed stocks, natural gas and water, both require purification before use.
Natural Gas contains low levels of sulphur compounds and undergo a desulphurization
process to reduce, the sulphur to levels of less than one part per million. Impurities in the water
are reduced to undetectable or parts per billion levels before being converted to steam and
added to the process. If not removed, these impurities can result in reduced heat efficiency
and significant damage to major pieces of equipment.
27
STEP 2: REFORMING
Reforming is the process which transforms the methane (CH4) and the steam (H2O) to
intermediate reactants of hydrogen (H2), carbon dioxide (CO2), carbon monoxide (CO). Carbon
dioxide is also added to the feed gas stream at this stage to produce a mixture of components
in the ideal ratio to efficiently produce methanol. This process is carried out in a Reformer
furnace which is heated by burning natural gas as fuel.
STEP 3 : METHANOL SYNTHESIS

After removing excess heat from the reformed gas it is compressed before being sent
to the methanol production stage in the synthesis reactor. Here the reactants are converted to
methanol and separated out as as crude product with a composition of methanol (68%) and
water (31%). Traces of byproducts are also formed. Methanol conversion is at a rate of 5% per
pass hence there is a continual recycling of the unreacted gases in the synthesis loop.
This continual recycling of the synthesis gas however results in a build-up of inert gases in the
system and this is continuously purged and sent to the the reformer where it is burnt as fuel.
The crude methanol formed is condensed and sent to the methanol purification step which is
the final step in the process.
STEP 4 : METHANOL PURIFICATION

The 68% methanol solution is purified in two distinct steps in tall distillation columns called the
topping column and refining column to yield a refined product with a purity of 99% methanol
classified as Grade AA refined methanol.The methanol process is tested at various stages and
the finished product is stored in a large secured tankage area off the plant until such time that
it is ready to be delivered to customers. Since
4.2 Methanol Process Description

The Leading Concept Methanol process in use at the Coogee Methanol Plant has various
advantages compared to the conventional methanol processes. Some of those advantages are
that it is efficient and compact and substantially reduces waste through the internal recycling of
process effluents.
28
Natural gas feedstock is delivered to the plant via a pipeline from the main Sui to plant location
carrying Bass Strait gas. The gas is first compressed and then purified by removing sulphur
compounds. The purified natural gas is saturated with heated and recycled process waste
water. The mixed natural gas and water vapour then goes to the gas heated reformer to be
partially converted to synthesis gas, a mixture of carbon dioxide, carbon monoxide and
hydrogen. This partially converted gas is then completely converted to synthesis gas by
reaction with oxygen in the secondary reformer.
The synthesis gas is then converted to crude methanol in the catalytic synthesis converter.
The crude methanol is purified to standard quality specifications by removing water and
organic impurities through distillation. The water and organic impurities are recycled.
Process Description
The Coogee Energy plant is designed to produce 164 tones per day of methanol from about 5
TJ/day of Bass Strait natural gas.
The plant consists of four main process steps : feed gas preparation, synthesis gas generation,
methanol synthesis and distillation supported by utilities and offsite units.
Feedgas Preparation
Natural gas is compressed to about 45 bar and sulphur removed by hyrodesulphurisation in
the purifier. The desulphurising gas is cooled and flows to the saturator where it contacts with
hot water over a bed of packing. The saturated gas leaving the vessel contains about 92% of
the steam required for reforming. Saturator make up is 90% process condensate and the
balance refining column bottoms water. Prior to leaving the saturator the gas stream is
contacted with recycled fusel oil where waste products from methanol synthesis are stripped
off. A blow down stream is required to control dissolved solids. Additional steam generated in
the boiler is made up to the gas stream to achieve 3.0:1 steam to carbon ratio for reforming.
The total feed stream is then heated in the gas heated reformer preheated. Both the preheated
and boiler are fired with a mixture of synthesis loop purge gas and natural gas.
4.3 Synthesis Gas Generation

Reactions
There are three main chemical reactions which occur in this process step :
Steam reformingCH4 + H2O = CO + 3H2
Shift reaction -
CO + H2O = CO2 + H2
29
The net effect of these reactions is the production of a synthesis gas stream which is
composed of carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2).
Description
Preheated gas flows from the preheater to the tube side of the advanced gas heated reformer
(AGHR). The feedstock is heated from the feed temperature of 425 C as it passed down
through the catalyst and the reforming reactions start. The AGHR contains 19 reforming tubes
which contain the reforming catalyst.
Hot reformed gas exits the bottom of the reforming tubes and flows to the tube side exit of the
AGHR at about 700C. The heat required for the endothermic reforming reaction is derived
from cooling the secondary reformer effluent in the shell side of the AGHR. About one quarter
of the methane is reformed in the AGHR.
The partly formed gas flows from the AGHR to the combustor/secondary reformer where the
bulk of the reforming takes place. The heat required for the endothermic reforming in both the
AGHR and secondary reformer is provided by partially burning the AGHR effluent with pure
oxygen in the combustor located integrally at the top of the secondary reformer. Oxygen is
injected into the gas via a specially designed gun. About 0.50 tonne of oxygen per tonne of
methanol is required.
The oxygen is completely consumed and the resulting hot gas stream passes over the
secondary reforming catalyst. Reforming reactions continue and the gas leaves the secondary
reformer at up to 1000C with less than 0.5% methane slip. The secondary effluent passes to
the AGHR shell and thence through the heat recovery train to provide heat for the saturator
circuit and distillation reboilers. The process condensate which condenses out of the reformed
gas is recycled back to the saturator. After heat recovery the reformed gas is finally cooled and
then compressed to about 70 barg in the synthesis gas compressor to be fed as synthesis gas
to the synthesis loop.
Bass Strait natural gas contains about 93.6 mol% of methane, 3.5 mol% of ethane with the
balance being predominantly propane, nitrogen and carbon dioxide. On an offshore facility with
less sophisticated gas separation facilities there may be higher levels of higher hydrocarbons
such as components but the oxygen consumption would increase.
The synthesis gas joins the synthesis loop recycle gas from the circulator to pass through the
loop interchanger and be fed to the methanol converter at about 130 C. The converter is a
tubular cooled converter design where the gas is preheated to reaction temperatures inside the
tubes as it flows up through the hot catalyst bed. This type of converter maximizes catalyst
efficiency as it enables a temperature profile to be maintained inside the converter that is close
to the maximum reaction rate curve. The hot reacted gas leaves the converter and provides
heat to the saturator water circuit and the loop interchanger before finally being cooled. Crude
methanol is separated from the uncondensed gases in the loop catch pot and the gases
recirculated back to the converter via the circulator.
30
Distillation
Crude methanol from the loop catch pot is filtered to remove traces of wax, let down in
pressure and fed to the product purification section. This section consists of a topping column
and a refining column. Unlike most methanol distillation columns these columns are packed
with structured packing. Reboiler duty is provided by reformed gas. The product methanol
specification is for a water content of less that 0.10 wt %. The water bottoms from the refining
column has a specification of less than 100 ppm of methanol and is recycled back to the
saturator. Other synthesis byproducts such as higher alcohols are collected as fusel oil and
recycled back the saturator.
4.4 LCM -The Low Cost Methanol Technology

Introduction
The emphasis on reducing the cost of production of methanol is nothing new. Aside from a
short period after the invention and commercial introduction of the Low Pressure Methanol
Process by ICI in the mid-1960s, that pressure has always been present. ICI itself was no
stranger to this as many of its older businesses were in commodity products whose profitability
relied critically on minimizing the cost of production in order to maintain acceptable margins.
However, cost of production is not just a case of reducing capital cost, although undoubtedly
this is an important part of the total picture. Often the installed cost of the plant appears to be
given greater weighting than is justified from a simple economic assessment. It is
understandable, though, that at the time of selection of the technology vendor, everyone's
mind tends to be focused on the need to raise the money, and fixed and variable costs of
operation can recede into the distance.
Methanex and Synetix have been working together for some time to identify the optimum route
for syngas generation for the manufacture of methanol and other GTL products. Many options
were investigated, but it was determined that the Synetix Syngas Generation (SGG) process
offered the most economic route and the methanol process based on SGG, the LCM Process,
was the most attractive option at high capacities.
Historical Perspective
It was against a background of intense competitive pressure on its Fertilizer Business that ICI
mandated its Catalyst and Technology Licensing Department (now a part of Synetix) to
develop a compact reforming process to revolutionize the manufacture of ammonia. In many
31
ways, the process that was developed, LCA, was revolutionary and ahead of its time, but the
fundamental principles behind the project were similar to those operators need to adopt to
prosper in today's highly competitive methanol industry.The legacy of ICI's commitment in
building the LCA plants at its Severnside Works in the late
1980s is that the Synetix Gas Heated Reformer (GHR) can no longer be thought of as new
technology. It is well-proven now, with over 30 operating years experience spread over the 4
plants that have been built around the technology. These plants are:
Absolutely key to the successful operation of these units has been the adoption of the correct
metallurgy to withstand the conditions within the reformer. There can be no doubt whatsoever,
that metal dusting has been overcome as an issue within the range of operating conditions of
these plants. However, without detracting from the importance of the metallurgy, it is the
mechanical design of the reformer that turns concept into reality. With the introduction of the
Advanced Gas Heated Reformer (AGHR) into the Coogee Energy MRP in April 1998, Synetix
incorporated a number of novel features that significantly simplified the compact reformer in
terms of design,construction, maintenance and operation.
Key Success Factors

Clearly, many factors are important to an operator/investor in making a project successful. A
number of these factors is listed below.
Selling price
Financing costs
Gas price
Import tariffs
Delivery costs
Maintenance costs
Manpower costs
Plant installed cost
Plant efficiency
Plant reliability
Items 1-3 are commercial issues over which the operating company has varying degrees of
influence. Items 4 and 5 will be very location specific, with the latter being a key factor as
methanol is transported from more remote locations to the consuming markets. Items 6-10 are
influenced by location, but it is in these aspects that choice of technology and the standard of
engineering design can have a major impact. The focus of the rest of the paper will be mainly
on these areas.
Compact Reforming
The term "Compact Reforming" implies that the main aim of the new technology is to reduce
the size. This was indeed a consideration, and it may be the only benefit offered by certain
types of compact reforming device. However, when Synetix was developing the syngas
process for the new ammonia plants for ICI, there was a much broader goal, which included
the complete elimination of steam generation and the steam system. This required a complete
32
rethink and a major simplification of the whole heat recovery scheme. The intention was to use
the hot reformed gas from the Secondary Reformer to provide the heat directly for the methane
steam reaction in a heat exchanger reformer. It was not the first time such an idea had been
proposed, but the major stumbling block was always the fact that metal dusting conditions
were present on the hot side of the heat exchanger.
Many options had been considered by others, including approaches that would avoid metal
dusting by, for example, using ceramic tubes, but none had been successful. The
breakthrough by Synetix came in first identifying materials that were resistant to metal dusting
under the conditions envisaged and then in proving that they were resistant in a full-scale,
single-tube reformer operating under real process conditions. This trial unit was built and
operated on ICI's Bellingham, UK site and provided essential process design data, but more
importantly verified the selection of metallurgy.
The first successful implementation of compact, heat exchange reforming on the industrial
scale was in the GHRs installed on the LCA plants at Severnside, UK in 1988. The first
successful deployment of the AGHR was at Laverton, Australia in 1998.
Operability of the LCM Process

The absence of steam raising and a steam system offers many benefits, but it does mean that
there is no obvious source for the process steam required for the methane steam reforming
reaction. Fortunately, this is an easy issue to address since Synetix have used a saturator
circuit for many years as a way of recovering low grade heat and turning it into process steam
without raising steam directly. Water is pumped through a set of heat exchangers and warmed
up before being contacted in a packed tower with the natural gas feed from the Purification
section. The saturator typically provides J to of the process steam required in a conventional
plant, but this concept can easily be extended to provide all of the steam needed for the
methane steam reforming reaction in the AGHR. Of course, as this is the only source of steam,
the saturator circuit assumes a greater importance than before.
In the LCM Process, between 30 and 40% of the heat being supplied into the saturator circuit
comes from the methanol synthesis loop. So, if the synthesis loop were not running, there
would be a significant shortfall of heat that would need to be acquired from elsewhere or the
whole plant would have to shut down. Normally, whenever there is a trip on a plant, everything
is done to try to maintain flow through the reformer and firing on it in order to avoid a
temperature cycle. This is where another valuable feature of the LCM Process becomes
important, and that is the ease of start-up and shut-down, which means that a temperature
cycle on the reformer is of rather less concern. The AGHR can be thought of as simply a feed
effluent exchanger around the Secondary Reformer. Start-up then requires nothing more than
a mechanism to get the Secondary above the auto-ignition temperature of the feed gas and
the whole unit will come on stream very quickly. Following a plant trip, heat is trapped within
the Secondary by the feed effluent exchangers preventing it cooling too much. From a cold
restart, heating is achieved using a simple catalytic combustor as a start-up heater generating
hot syngas. On the LCM Process it may take up to 12 hours from introduction of feed gas
before the plant is making methanol, whereas on a warm restart (which could occur even after
several days off line) the time taken can be 6 hours or less.
33
34
METHANOL SYNTHESIS
The heart of any Methanol synthesis process is Methanol converter. The converter contains
the catalyst over which synthesis gas is converted to methanol. The main difference between
competing methanol process today lies in the converter and its method of temperature control
and heat recovery.
5.1 TYPES OF CONVERTER:The four basic types of converters are
Quench Converter
Multiple Adiabatic Converter
Tube-cooled Converter
Steam Raising Converter
1. QUENCH CONVERTER:The quench converter was the basis for the initial ICI low pressure methanol
process. Quench type converters used multiple catalyst beds, typically contain three to six
catalyst beds. Bed volumes are sized to help control the exothermic methanol synthesis
reaction. Additionally, cool feed gas is injected between beds to control or quench catalyst bed
inlet temperature. Reaction heat is recovered through added heat recovery exchangers located
downstream of the converter.
2. MULTIPLE ADIABATIC CONVERTER:The adiabatic converter system employs heat exchanger rather than quench gas for
introduce cooling. Because the beds are adiabatic, temperature profile exhibits still the same
saw tooth approach to maximum reaction rate, but catalyst productivity is somewhat improved
because all of the gas passes through the entire catalyst volume. Costs for vessels and
exchangers are generally higher than for quench converter system.
3. TUBE-COOLED CONVERTER:The tube cooled converter functions as interchanger, consisting of a tube filled vessel
containing catalyst on the shell side. The combined synthesis and recycle gas enters the
bottom of the reactor tubes, where it is heated by reaction taking place in the surrounding
catalyst bed. The gas turns at the top of the tubes and passes down through the catalyst bed.
The principle advantage of this reactor is in the reduced catalyst volume, since the reduction
path move closely follows the maximum rate line.
Converter performance can further be enhanced by extending the catalyst below the tube
cooled area to act as a further adiabatic reaction zone.
35
4. STEAM RAISING CONVERTER:There are varieties of tubular steam raising converters available, which feature radial
or axial flow, with the catalyst on either shell or tube side. The near isotherm reaction of this
rector type is the most thermodynamically efficient of the types used, requiring the least
catalyst volume, lower catalyst peak temperatures also results in reduced by-product formation
and longer catalyst life.
36
Low pressure drop, both in converter and heat exchanger equipment, to minimize
recycle compression energy.
High conversion per pass that reduces required cycle, minimizes synthesis loop capital
cost & maximizes reaction heat recovery.
Efficient recovery of exothermic reaction heat of methanol synthesis.
Corrosion resistance to formation of iron carbonyls that can poison the catalyst and
promote formation of undesirable hydrocarbon by-products.
A high yielding, commercially proven, long life synthesis catalyst to minimize costly
catalyst replacement.
Low capital cost.
Good economy of scale, high capacity single train converter.
5.2 METHANOL SYNTHESIS TECHNOLOGY TODAY

Different companies have been involved in practicing their technologies for methanol
synthesis. But the question is which company offers the most dependable and economically
viable process.
This is visualized by the percentages obtained by evaluating their practical applications as
shown below:
Company Name
Production Rate
Imperial Chemical Industry (ICI)
61%
LURGI CORP.
27%
Mitsubishi Gas Chemicals (MGS)
8%
KELLOGG
3%
5.3 ICI LOW PRESSURE METHANOL PROCESS

Most of the difficulties involved in developing the new Low Pressure methanol process were
successfully overcome by the ICI 50atm process.
Methanol was first synthesized commercially at low pressure when ICI commissioned its 300tons/dayplant at Birmingham in December, 1966. a copper based catalyst, more active and
selective was used. The greater activity of this catalyst permits the synthesis of methanol from
gaseous mixture of hydrogen and carbon dioxide at much lower pressure and temperature of
the order of 50 atm and 250 oC respectively. Several innovatory features were incorporated in
the design. They include a new simple type of quench bed converters, larger in diameter then
conventional converters and easy catalyst charging and discharging procedure. The use of
rotary machine of synthesis gas compression which was significant, because it demonstrated
the concept of single stream unit, well known in large scale ammonia plant, was now a
practical proposition for small methanol production units.
37
In 1972 ICI commissioned a 1100 tons/day plant based on their latest technology. It operates
at 100 atm and uses a modified version of original low-pressure methanol synthesis catalyst.
For capacity greater than 500 tons/day, the 100 atm process plants are adopted, whereas for
smaller plants of outputs from 150-500 tons/day, the 50 atm process is used.
5.4 LURGI LOW PRESSURE METHANOL PROCESS

At the end of fifties, Lurgi began development of a low pressure methanol process, using
highly active copper catalyst at 50 atm pressure. At that time, the space time yield and catalyst
life was not satisfactory (Sulfur Poisoning) which resulted in the suspension of further
development work.
38
In 1964 research work was resumed. At that time the purification of synthesis gas (Using Lurgi
Rectisol (50 atm process) was no longer a problem. Several years of development work
required in selecting from numerous catalysts available a suitable catalyst. Because of Lurgis
experience in Fisher Tropsch synthesis reactor, the methanol reactor was based on a design
worked out of Fisher Tropsch Synthesis.
This reactor is similar to a vertical
and tube heat exchanger and
was a promising solution, to both
reactor design and heat recovery
problem. The tubes closed at
their lower end by the hinged grid
with boiling water, maintaining a
substantially uniform catalyst
temperature over the reactor
cross section and over the full
length of the tubes.
Early 1970 Lurgi decided to build
its own methanol plant with a
small capacity to serve mainly for
demonstration purposes and also
to study the problems which
might come up in the large scale
plants. The first commercial plant
with a capacity of 4000 tones/yr
was built at wesseting (West
Germany) in April, 1971. This plant was built in two days, was designed on the basis of a
computer programme.
5.5 ADVANTAGES OF THE LOW PRESSURE METHANOL PROCESS

Reduced by-product formation resulting in lower feed stock consumption per ton of
methanol.
Reduced compression cost due to lower operating pressure.
The ability to use steam directory compressors on small plants.
Lower steam pressure through out the plant.
The avoidance of CO2 addition in natural gas based plant without incurring large
financial penalties.
Simplicity in design and low-pressure equipment, suitable for large and small plant.
Commissioning period.
Proved in wide practical services.
PROCESS SELECTION
In 1966, an Imperial Chemical Industry (ICI) is the first, which announced the low
pressure process for synthesis of methanol using proprietary copper based catalyst.
39
A number of other companies in the late 1960s and early 1970s announced their own low
pressure processes and proprietary copper-based catalyst; these companies included Lurgi,
Mitsubishi etc.
Today two processes are mostly used.
1) ICI low pressure
(61%)
2) Lurgi low pressure process (27%)
ICI process used Cu-Zn-Al catalyst while Lurgi process used CU-Zn-V or Cu-Mn-V catalyst.
Besides the catalyst, these processes differ in their method of temperature control and heat
recovery.
ICI use quench type adiabatic converter with multiple catalytic beds. Bed volumes are sized to
help control the exothermic methanol synthesis reaction. Additionally, cool feed gas is injected
between beds to control or quench catalyst bed inlet temperature. Reaction heat is typically
recovered through added heat recovery exchangers located downstream of the converter.
Whereas Lurgi used shell and tube (Isothermal type) converter with boiling water for
temperature controls. Overall results of quench type converter is best than other type of
converter.
The main drawback of water cooled tubular (Isothermal) converter is that internal tube sheets
have failed in some tubular isothermal methanol converter design. The long down times
associated with a catastrophic converter failure could financially devastate most procedures. In
addition converter internal baffles, expansion joints, gas distributors and internal exchangers
can fail and cause internal leaks. These components should be extremely rugged to withstand
the operating abuse imposed by actual commercial operation.
Cost is another major factor for the selection of process. ICI process has low cost as compare
to the other processes. Therefore the ICI process is also called ICI LCM (Low Cost Methanol)
process. Thats reason ICI LCM process is mainly used in the world. Considering these entire
factor we select the ICI LCM process.
40
41
6.1 DESULPHERIZER CATALYST

Hydrocarbon feeds for steam reforming must have a very low sulfur contents, since nickel
reforming catalysts are quite susceptible to poisonings even by levels as low as 0.5PPM. In
many cases, sulfur can be removed b y adsorption over a bed of activated carbon at 15-500C.
Frequent regeneration may be necessary; which can be accomplished by heating the bed and
for stripping it with steam or hot gases. The activated carbon bed adsorbs high boiling sulfur
compounds such as mercaptans, much more rapidly than low boiling compounds such as H 2S
.As a result, adsorption over a sacrificial guard bed of zinc oxide at temperature in the range of
340-370 0C. Hydrodesulphurization may be necessary for organic sulfur compounds that are
not removed by either zinc oxide or carbon bed. This is accomplished by mixing the sulfur
containing steam with hydrogen, so that the hydrogen contents are approximately 5%, the
resulting mixture is passed over a bed of cobalt or nickel molybdate catalyst at temperature of
290-370oC. Under these conditions, sulfur compounds are conditions, sulfur compounds are
converted to hydrogen sulfide, which can be removed in a zinc oxide bed. Now a days, codes
are used to represent the catalysts shown here: The KATALCO range of absorbents and
hydrogenation catalysts ensures an optimized system for meeting individual plant
requirements.
Sulfur Removal Catalysts
Hydrodesulphurization Catalyst.
KATALCO32-4
KATALCO 41-6
KATALCO 61-1
PURASPEC 2570
These catalysts are used by ICI.
6.2 STEAM REFORMING CATALYST

Reforming catalyst usually contain from 12-25% nickel oxide supported on calcium aluminate
titanate. Calcium aluminate has generally replaced calcium aluminum silicate, has support
material to avoid the problem of silica migration encountered in earlier catalyst formulation.
Alkali metal compounds added to prevent carbon formation and to increase catalyst durability
include potassium aluminum silicate, potassium carbonate and potassium poly aluminate,
sulfur chlorine and arsenic compounds. Poison the catalyst, sulfur poisoning is reversible, but
chlorine and arsenic poisonings are severe and generally irreversible.
Synetix has been associated with pre-reforming catalysts since the 1960s and together with
kvaerner process technology recently launched the new CRGLH series of catalysts. These
have been demonstrated to be the most active and robust commercially available product for
this application.
KATALCO
25-4
KATALCO
57-4
KATALCO
23-4
KATALCO
46-Serie
KATALCO
23-4Q
KATALCO
25-4Q
42
6.3 METHANOL SYNTHESIS CATALYST

High Pressure Catalyst
Zinc Chromite catalyst, reduced zinc oxide promoted with Chromia was the catalyst used in the
1st large scale commercial methanol process developed by BASF in Germany in 1920s.
The zinc Chromite catalyst with improvements over the years was only the catalyst of
consequence used for the high process methanol process, up until the high pressure process
was phased out in 1970s.
Although BASF is credited with a 1st commercial methanol process generally attributed to G.
TART in FRANCE in 1921. He defined his methanol catalyst has being all metal, oxides and
salt active in hydrogenation. Small unit was built near Paris to test catalyst for PARTARTS
process and began operation in 1923. The unit was designed to operate at 150-200 atm
pressure. 300-6000C, with hydrogen to carbon monoxide feed gas ratio of 2:1.
The BASF high pressure methanol process was operated at 250-3500 C, similar to the
conditions purposed by PARTART. Now low pressure, process commonly called ICI low
pressure process is used because of its practical feasibility.
6.4 LOW PRESSURE CATALYST

Early in the developing methanol industry, it was recognized that to significantly improve the
high pressure methanol process, a much more active catalyst than zinc chromite was needed.
A more active catalyst would permit operation at lower temperatures and pressures, yet still
allow acceptable production rates to be mentioned. Copper based catalysts known from the
1920s have been more active than zinc chromite. Copper based catalysts, however, were also
known to be much more susceptible to poisoning by sulfur, chlorine, etc. than zinc Chromite,
Zinc Chromite, for example, could tolerate sulfur levels of more than PPM in the feed gas,
whereas for copper based catalysts, sulfur must be kept below 1 PPM. Generally poor quality
of synthesis gas and the limited purification techniques available at that time resulted in an
unacceptably short operating life for the copper based, catalysts and precluded their
commercial use.
A second breakthrough in the methanol technology occurred in 1966 with the introduction of
ICIs low-pressure process for the production of methanol. This was made possible by a major
improvement in synthesis gas quality from the introduction of hydrocarbon steam reforming
and improved purification techniques for the hydrocarbon feed stock. The synthesis gas from
steam reforming contained only trace quantities of impurities and proved ideal for methanol
synthesis with a copper catalyst. The ICI process, using a much more active copper based
catalyst could operate efficiently at 50 atm pressure and at temp. of 220-280oC.
The copper based catalyst developed by ICI was also more selective than the high pressure
zinc chromite catalyst and operated at a much lower temp. Consequently, it produced a
significantly lower of impurities than zinc Chromite as shown in following table.
43
LEVEL OF IMPURITES PRODUCED BY MS CATALYSTS

Impurity
ZnO/Cr2O3 catalyst
Cu/ZnO catalyst
Dimethyl ether
5000-10000ppm
20-150ppm
Carbonyl compds
80-220ppm
10-35ppm
Higher alcohols
3000-5000ppm
100-2000ppm
Methane
Variable
None
6.5 SOME OTHER SALIENT FEATURES

Copper based catalyst produced no methane.
The possibility of a highly exothermic runaway methanation reaction leading to catalyst
sintering and possible converter damage was a continual threat in the high pressure process.
This improvement is selectivity for the copper based catalyst over zinc Chromite was estimated
to reduce feed stock requirements from 5-10% for the equivalent amount of methanol
produced.
Hence ICI methanol catalysts were both active and long lived and generally considered a
benchmark in industry and represented a significant achievement in heterogeneous catalysis.
Catalysts used by ICI in methanol synthesis in accordance with SYNETIX are:KATALCO 51-8 PPT for ARC-Reactors.
KATALCO 51-8 PPT for Tubular and quench type reactors.
6.6 RECENT CATALYST DEVELOPMENTS

Following ICIs breakthrough in methanol technology in 1966, other companies quickly
followed with their own alternative low-press. Methanol processes and catalysts.
Companies that currently have both a methanol process and catalysts, include ICI,
Lurgi, Haldor Topsoe, BASF, Ammonia Casale and Mitsubishi Gas Chemical.
A patent survey of representative copper based methanol catalysts is shows in
following table.
Company
Ammonia casale
BASF
DUPONT
HALDOR TOPSOPE
ICI
Catalyst
system
Cu-Zn-Al-Cr
Cu-Zn-Al
Cu-Zn-Al-CrMn
Cu-Zn-Al
Cu-Zn- Cr
Cu-Zn-Al
Cu-Zn-Al
Typaical
atomic
ratio
29:47:6:18
32:42:36
38:38:0.4:12:12
50:19:31
37:15:48
61:30:9
64:23:13

LURGI
Cu-Zn-V
Cu-Mn-V
MITSUBISHI
GAS Cu-Zn-MP
CHEMICAL
Cu-Zn- Cr
Cu-Zn-B
SHELL
Cu-Zn-Ag
Cu-Zn-Re
UNITED CATALYSTS
Cu-Zn-Al
44
61:30:9
48:30:22
55:43:2
55:43:2
61:38:1
61:24:15
71:24:5
62:21:17
6.7 CURRENT CATALYST COMPOSITION

All commercial low-pressure methanol catalyst contains copper and zinc oxides together with
one or more additional promoters, usually aluminum or chromium oxide. ICI, for example,
reports a standard industrial catalyst to contain copper oxide, zinc oxide and Alumina in a ratio
of 60:30:10, respectively.
45
46
Balance Around Distillation Column

A = 150 Tons/day
Light ends (L)
Distillation
Column
A4
Distillation
Column
CH3OH 99.85% 149.775

H2O
0.14%
0.216
HCHO 0.003%
0.0045
CH3COOH 0.003% 0.0045
(2)
(1)
CH3OH
H2O
CO2
HCHO
CH3OCH3
C2H5OH
C3H7OH
C5H11OH
CH3COOH
80% wt %
18%
0.20%
0.40%
0.40%
0.30%
0.20%
0.20%
0.30%
W
Waste Water
Basis:- One day Operation

Methanol Balance:0.8 A4 =
0.9985 A
A4
187.21
CH3OH in A4
149.775 tons
H2O in A4
33.69
CO2 in A4
0.3748 tons
HCHO in A4
0.748
tons
CH3OCH3 in A4
0.748
tons
tons
tons
Total light ends in A4
1.87
C2H5OH in A4
0.561 tons
C3H7OH in A4
0.374 tons
C5H11OH in A4
0.374 tons
CH3COOH in A4
0.561 tons
Total Heavy ends in A4 =
tons
1.872 tons
tons
tons
tons
tons
47
Calculation of W:Water in W
=
=
CH3COOH in W
= CH3COOH in A4 =
= 0.557 tons
C2H5OH in W
=
=
C2H5OH in A4
0.561 tons
C3H7OH in W
=
=
C3H7OH in A4
0.374 tons
C5H11OH in W
=
=
C5H11OH in A4
0.374 tons
35.35 tons
So,
Water in A4 - Water in A
33.48 tons
CH3COOH in M
Now,
% of H2O
94.71 %
% of CH3COOH
1.57
% of C2H5OH
1.58
% of C3H7OH
1.05
% of C5H11OH
1.05
HCHO in L
=
=
HCHO in A4 - HCHO in A
0.744 tons
CO2 in L
=
=
CO2 in A4
0.374 tons
Calculation of L:-
CH3OCH3 in L
=
=
CH3OCH3 in A4
0.748 tons
Total L
= 1.86 tons
% of HCHO
39.85 %
% of CO2
= 20.04 %
% of CH3OCH3
= 40.09 %
Now as
A4
A4
= 7800.78 Kg/hr
48
187.21 tons/day
&1 day = 24 hrs

1 ton = 1000 kg
So,
Now arranging the whole data in a tabular form,
Component
So,
Wt %
Wt
Mol.Wt k.Mole Mole %
CH3OH
H2O
CO2
HCHO
CH3OCH3
C2H5OH
C3H7OH
C5H11OH
CH3COOH
80%
18%
0.2%
0.4%
0.4%
0.2%
0.3%
0.3%
0.2%
6240.6
1404.1
15.60
31.20
31.20
23.40
15.60
15.60
23.40
32
18
44
30
46
46
60
88
60
A4
276.43 K.Mole/hr
195.0
78.0
0.35
1.04
0.67
0.50
0.26
0.17
0.39
276.4
70.54
28.21
0.128
0.376
0.245
0.184
0.094
0.064
0.141
Balance Around Converter:Basis:-
1 hr Operation
Recycle stream
H2
75%
Mol %
CO
13% Mol %
CO2
9% Mol %
N2
3% Mol %
A6
A2
A7
A3
Reactor
A1
Separator
M
H2 76.68%
CO 13.78%
CO2 9.41%
N2 0.13%
Mol %
Mol %
Mol %
Mol %
A4
276.43
K.Mol /hr
CH3OH
70.54
H2O
28.21
CO2
0.128
HCHO
0.376
CH3OCH3 0.245
C2H5OH
0.184
C3H7OH 0.0940
C5H11OH 0.0641
CH3COOH 0.1410
C Balance:23.19% A1
22% A7
+ 72.79611 * A4/100
23.19% A1
22% A7
+ 201.235
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
(1)
49
N2 Balance:0.13%
A1
A1
3% A7
2307.69% A7
(2)
Putting Eq (2) in (1),

535.15% A7
513.15% A7
= 201.23
A7
22%
A7
+ 201.235
39.21 K.Mol /hr
So,
H2 in A7
CO in A7
CO2 in A7
N2 in A7
=
=
=
=
29.41
5.09
3.52
1.17
K.Mol /hr
K.Mol /hr
K.Mol /hr
K.Mol /hr
So Eq(2) becomes,
A1
= 904.96
K.Mol /hr
Now,
H2 in A1
CO in A1
CO2 in A1
N2 in A1
=
=
=
=
693.93
124.70
85.15
1.176
K.Mol /hr
K.Mol /hr
K.Mol /hr
K.Mol /hr
Reactor:Now suppose,
50%
conversion of CO & CO2 per pass
50%
* {( 124.70 + 13% * A6 )
+ ( 85.15 + 9% * A6)} = 195.0
50%
* {( 209.86 + 22% * A6 )} = 195.0

209.86 + 22% * A6 = 390.03
22% * A6
A6
= 180.17
= 818.98 K.Mol /hr
So,
H2 in A6
CO in A6
CO2 in A6
N2 in A6
=
=
=
=
614.23 K.Mol /hr

106.46 K.Mol /hr
73.70
K.Mol /hr
24.56
K.Mol /hr
Balance at point M:A=
A1 + A 6

A2
1723.95 K.Mol /hr
A5
A6 + A 7
A5
858.20 K.Mol /hr
50
Balance at point B:-
Balance Around the Separator:A3
A4
A5
A3
1134.63 K.Mol /hr
Balance Around the Separator1:-
D2
H2 57.42%
CO 10.32%
CO2 7.04%
N2 0.10%
H2O 25.11%
Separator
A1 = 904.96 K.Mol /hr

H2
CO
CO2
N2
By vol
By vol
By vol
By vol
By vol
76.68%
13.78%
9.41%
0.13%
Mol %
Mol %
Mol %
Mol %
W1
H2O 100%
Overall Balance:D2
D2
=
=
W 1 + A1
W1 + 904.96
(3)
H2O Balance:25.11% * D2
W1
(4)
Putting (4) in (3),

D2
= 25.11% * D2 +
74.89% * D2 = 904.96
D2 = 1208.39 K.Mol /hr
So,
H2 in D2
CO in D2
CO2 in D2
N2 in D2
H2O in D2
=
=
=
=
=
693.86 K.Mol /hr

124.70 K.Mol /hr
85.07 K.Mol /hr
1.18 K.Mol /hr
303.4 K.Mol /hr
Now putting value of D2 in Eq(4) , we get,

W1
= 303.4 K.Mol /hr
904.96
51
Balance Around Heat Exchanger:-
D1
D2 = 1208.39 K.Mol /hr
Heat Exchanger
As No mass transfer take place in Heat Exchanger, So

D1
= D2
= 1208.39 K.Mol /hr
and D1 has the same composition as the D2.
Balance Around the Steam Reformer:Natural gas

Steam Reformer
CH4
C2H6
C3H8
CO2
N2
93.40% By vol
3.50% By vol
1.50% By vol
1% By vol
0.60% By vol
D1 = 1208.39 K.Mol /hr
H2
CO
CO2
N2
H2O
S
H2O 100 %
57.42%
10.32%
7.04%
0.10%
25.11%
By vol
By vol
By vol
By vol
By vol
Steam
C - Balance:105.9% * D
D
= 209.77
= 198.09 K.Mol /hr
H2 - Balance:402.7
+ S = 997.29
S
= 594.57 K.Mol /hr
Natural gas to steam ratio:S/D = 3.00

This ratio matches with the value given in literature , which proves it to be right.
So,
CH4 in D
C2H6 in D
C3H8 in D
CO2 in D
N2 in D
K.Mol /hr
Mol. Wt Kg / hr
=
=
=
=
=
16
30
44
44
28
185.0
6.93
2.97
1.98
1.18
2960.25
207.99
130.73
87.15
33.27
Total
52
= 3419.439 Kg / hr
So finally,
3419.4 Kg / hr
= 82.06 tons/day
&
S
= 594.57 K.Mol /hr

= 256.85 tons/day
1 k.mol H2O = 18 Kg
53
54
Energy Balance
Balance Around Steam Reformer:S
H2O = 1
450 oC
F
= 198.08 K.mol/hr
855 oC
S.R
Kmol/hr
CH4 =
C2H6 =
C3H8 =
CO2 =
N2
=
Mol Fractions
0.934
185.01
0.035
6.93
0.015
2.97
0.01
1.98
0.006
1.18
H2 =
CO =
CO2 =
N2 =
H2O =
F1 =1208.39 K.mol/hr
Kmol/hr Mol Fractions

0.574
693.85
0.103
124.70
0.070
85.07
0.00098 1.18
0.251
303.42
Heat In By F:Cp of CH4
= ( 34.31 + 5.47E-02 T +
0.934
32.045 + 5.11E-02 T + 3.42E-06 T2
0.035
Cp of CO2
Cp of N2
1.020
+ 2.26E-01 T * ( 68.032 +
0.01
* ( 36.11 +
0.361 +
= ( 29 +
0.006 *
4.23E-04
2.26E-01
3.17E-08 T )
T - 1.31E-04 T
+ 3.17E-08 T )
T2 + 4.76E-10 T3)
T - 2.89E-05
T2 + 7.46E-09 T3 )
4.23E-02 T -
2.89E-05 T
T -
2.20E-03 T +
( 29 +
1.31E-04 T +
+ 3.39E-03 T - 1.97E-06
=
CP Net
( 49.37 + 1.39E-01 T - 5.82E-05 T2 +7.28E-09 T3)
= ( 36.11 + 4.23E-02
- 1.03E-08 T3)
+ 4.87E-03 T - 2.04E-06 T2 + 2.55E-10 T3)
= ( 68.032
0.015
- 1.10E-08 T3)
1.39E-01 T - 5.82E-05 T2 + 7.28E-09 T3)

*
= 1.72
T3)
- 1.10E-08
( 34.31 + 5.47E-02 T + 3.66E-06 T2
Cp of C2H6 = ( 49.37 +
Cp of C3H8
3.66E-06 T2
2.89E-07 T
5.72E-06
+ 7.46E-09 T )
7.46E-11
T )
T2 - 2.87E-09 T3 )
2.20E-03 T + 5.72E-06 T
0.174 + 1.32E-05 T + 3.43E-08 T

2
2.87E-09 T )
3
- 1.72E-11 T )
= (35.32 + 5.98E-02 T -8.37E-07 T -9.49E-09 T3)
Heat In by F
= 198.08
=
=
=
m Cpnet dt
55
RANGE = 25 to 450 oC
*1000 / 3600 [ 35.32907 * 425 + 5.98E-02 * 100937.5

- 3.43E-08 * 30369791.67 - -9.49E-09 * 10251464844 ]
55.024
*
2.11E+04
1.16E+06
Watts
1.16E+03
KW
Heat In By S:Cp of Steam
Heat In By S
= 33.46
+ 6.88E-03
mCpsteam dt
+ 7.60E-06T2 - 3.59E-09 T3
RANGE =
25 to 450 oC
= 594.57 * 1000/3600 * [ 33.46 * 425

+ 6.88E-03 * 100937.5
+ 7.60E-06 * 30369791.67 - 3.59E-09 *10251464844
]
= 165.15
* 1.51E+04
= 2.50E+06
Watt
= 2.50E+03
KW
Total Heat of Reactant = HR = 3.66E+03 KW
Heat Out By F1 :Cp of H2 = 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3

= 0.574 * ( 28.84
+ 7.65E-05 T
+3.29E-06 T2 - .70E-10 T3 )
= 16.55 + 4.39E-05 T + 1.89E-06 T2 - 4.99E-10 T3

Cp of CO = 28.95
= 0.1032
+ 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3

+ 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3 )
* ( 28.95
+ 3.66E-07 T2 - 2.29E-10 T3
= 2.98 + 4.24E-04 T
Cp of CO2 = 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3

= 0.0704
* ( 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3 )
= 2.54 + 2.98E-03 T - 2.03E-06 T2 + 5.25E-10 T3

Cp of N2
= ( 29 + 2.20E-03 T
= 0.00098 * ( 29
+ 5.72E-06 T2 - 2.87E-09 T3)
+ 2.20E-03 T + 5.72E-06 T2
= 0.028 + 2.16E-06 T + 5.61E-09 T2

Cp of H2Og
33.46
= 0.2511
- 2.87E-09 T3)
- 2.81E-12 T3
+ 6.88E-03 T + 7.60E-06 T2 - 3.59E-09 T3

* (33.46
+ 6.88E-03 T +7.60E-06 T2 - 3.59E-09 T3
56
= 8.40 + 1.73E-03 T + 1.91E-06 T2 - 9.02E-10 T3

Cp Net
Heat Out By F1
= 30.51994 + 5.18E-03 T
mCpnet dt
= 1208.391 *
=
=
=
+ 2.14E-06 T2
- 1.09E-10 T3
RANGE = 25
to
855oC
1000/3600 [ 30.51 * 830 + 5.18E-03 * 365200

+ 2.14E-06 * 208336916.7 - 1.09E-10 * 1.33599E+11 ]
335.66 * 2.77E+04
9.28E+06 Watts
9.28E+03 KW
Heat of reaction:CH4
C2H6
H2O
2H2O
C3H8
CO
+
+
CO
2CO
3H2O
3H2
(1)
+ 5H2
(2)
3CO +
H2O
CO2
Heat of formation of CH4

Heat of formation of CO
Heat of formation of H2O
Heat of formation of CO2
Heat of formation of C2H6
Heat of formation of C3H8
=
=
=
=
=
=
-74.84
-110.52
-241.82
-393.51
-84.66
-119.84
7H2
H2
(4)
Kj/g.mol
Kj/g.mol
Kj/g.mol
Kj/g.mol
Kj/g.mol
Kj/g.mol
SO,
H1
H1
H2
H2
H3
H3
H4
H4
=
=
=
=
=
=
=
206.14
206146
347.27
347279
513.75
513758
-41.164
Kj/g.mol
Kj/K.mol
Kj/g.mol
Kj/K.mol
Kj/g.mol
Kj/K.mol
Kj/g.mol
-41164
Kj/K.mol
From eq 1 :-
X1 =
185.05
K.mol of CO per hr
From eq 2 :From eq 3 :From eq 4 :-
X2 =
X3 =
X4 =
13.8
8.91
83.1
K.mol of CO per hr
K.mol of CO per hr
K.mol of CO2 per hr
Total Heat of reaction =

=
=
44113745
12253.82
12253.82
Kj/hr
Kj/sec
KW
(3)
57
So,
Heat Required
Hin
- Hout
=
=
6.63E+03
2.39E+07
Hreaction
Kj/sec
Kj/hr
Natural Gas Required:Calorific value

So,
Natural Gas Required
=
=
975
Btu/ft3
36351607.5
Kj/m3
Heat Req / C.V

6.57E-01 m3/hr
Energy Balance Around Heat Exchanger:o
354 C
4.8 Mpa
F1
= 1208.391 K.mol/h
= 376 o C
F2
855 C
B.F.W (AT 80 C)
Heat In By F1
= 9.28E+03
Kj/sec
Heat Out By F2 :Cp Net = 30.51 + 5.18E-03 T + 2.14E-06 T2 - 1.09E-10 T3

Heat Out By F2 =
mCpnet dt
RANGE = 25
to
376 oC
= 1208.39 * 1000/3600 [ 30.519938 * 351 + 5.18E-03 * 70375.5
+ 2.14E-06
* 17713917 - 1.09E-10 * 4996695688 ]
= 335.6642 * 1.11E+04
= 3.73E+06 Watts
= 3.73E+03 KW
Heat Transfer
=
=
Heat in - Heatout
5.55E+03 KW
Water Required:
T1
T1
T2
T2
=
=
=
=
30 o C
303 K
361 oC
634 K
HL
125.7
Kj/kg
HV
3104.35
Kj/kg
58
So,
H =
H =
HV - HL
2978.65
Kj/kg
Now,
Q =
m * H
m = Q/H
Avg Mol. Wt = 9.93
m =
1.86E+00 Kg/sec
m = 6.71E+03 Kg/hr
= 8133.07 Kg/hr
Energy Balance Around point "A"

M6
M1
904.96 K.mol/hr
H2
CO2
CO
N2
=
=
=
=
=
8660.50 K.g/hr
16.03%
43.27%
40.32%
0.38%
=
=
819.041 K.mol/hr
8133.07 Kg/hr
H2 =
15.10%
CO2 =
39.89%
CO =
36.62%
N2
A
100 oC
8.45%
M2 = 1724.0 K.mol/hr
H2 = 15.57%
CO2 = 41.61%
CO = 38.53%
N2
= 4.29%
Heat In by M1:M1
=
Avg. Cp =
T
=
Q1
8660.505 K.g/hr
2.727
Kj/Kg.K
100 oC (373K)
t =
298 K
m Cp T
= 1771290
Kj/hr
Heat In by M6:M6
=
8133.07
Avg. Cp =
2.727
T
= 35 o C
= 308 K
=
Kg/hr
Kj/Kg.K
Q6
= mCp T
221789 KJ/hr
So,
Total Heat In:Qt =

=
1993079
Q 1 + Q6
1993079
Heat In
mCpT
KJ/hr
=
Heat Out

1993079
1993079
43.48
T
=
=
=
=
=
59
16809.05 * 2.727 * ( T - 298 )

45838.28 * ( T -298 )
( T -298 )
341.48
K
68.48 o C
Energy Balance Around Reactor :230 oC

M2 =
1724.005 K.mol/Hr
0.5
16809.05 K.g/hr
M3 =1134.69K.mol/hr
Reactor
0.5
75 C
Heat In By M2 Stream:Avg. Cp =
2.727
Kj/Kg.K
Qin
=
=
=
mCp dt
+
Kj/hr
KW
In M2
CO = 13.39%
Heat Of Reaction:CO
4698423.28
5844380.18
1623.43
1145956.8
CO2 = 9.10%
+ 2H2
CH3OH
H =
H =
-90.77
-90770
CO2
KJ/g.mol
KJ/K.mol
+ 3H2
H =
H =
-49.58
-49580
(1)
CH3OH
KJ/hr
KJ/K.mol
+ H2O
(2)
Conversion =
So,
X1
X2
X3
= 115.4 K.mol of CH3OH per hour

= 78.44 K.mol of CH3OH per hour
= 78.44 K.mol of H2O per hour
Total Heat Of Reaction
= -10476867 + -7778331
= -18255198 Kj/hr
= -5070.888 KW
Heat Out By M3 Stream:Cp of H2
= 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3

= 0.567 * [ 28.84 +7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3 ]
50%

= 16.36 +
Cp of CO
= 28.95
60
+ 1.87E-06 T2 - 4.93E-10 T3
4.34E-05 T
+ 3.55E-06 T2 - 2.22E-09 T3
+ 4.11E-03 T
= 0.098 * [ 28.95 + 4.11E-03 T
+ 3.55E-06 T2 - 2.22E-09 T3
= 2.84 + 4.04E-04 T + 3.49E-07 T2 - 2.18E-10 T3

+ 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3
Cp of CO2 = 36.11
0.068 *[ 36.11+ 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3
2.89E-03 T -1.97E-06 T2 + 5.10E-10 T3
= 2.46 +
Cp of N2
+ 5.72E-06 T2
= ( 29
+ 2.20E-03 T
= 0.022 * [ 29
+ 2.20E-03 T
+ 5.72E-06 T2
-
33.46 + 6.88E-03 T + 7.60E-06 T2 -
+ 7.60E-06 T
= 0.0687 * [ 33.46 + 6.88E-03 T

=
- 2.87E-09 T3)
+ 1.30E-07 T2
= 0.651 + 4.99E-05 T
Cp of H2Og
- 2.87E-09 T3)
2.300375
+ 4.73E-04 T
Cp of CH3OH = ( 42.93
= 0.17187 * [ 42.93
= 7.378379
3.59E-09 T3
- 3.59E-09 T3
+ 5.23E-07 T2 - 2.47E-10 T3
+ 8.30E-02 T
+
6.51E-11 T3
8.30E-02 T
+ 1.43E-02 T
- 1.87E-05 T2 - 8.03E-09 T3 )
- 1.87E-05 T2 - 8.03E-09 T3 )
- 3.21E-06 T2 - 1.38E-09 T3
Cp of HCHO = ( 34.28 + 4.27E-02 T + 0 - 8.69E-09 T3 )

= 9.16E-04 * [ 34.28 + 4.27E-02 T + 0 - 8.69E-09 T3 )
= 3.14E-02
+ 3.91E-05 T + 0.00E+00 - 7.96E-12 T3
Cp of C2H5OH = ( 61.34 + 1.57E-01 T -
8.75E-05 T
= 4.48E-04 * [ 61.3 + 1.57E-01 T -
Cp NET
Qout
8.75E-05 T
+ 1.98E-08 T )
2
+ 1.98E-08 T )
2
= 2.75E-02 + 7.04E-05
T - 3.92E-08 T
= 3.21E+01 + 1.82E-02
T - 2.36E-06 T - 9.06E-10
mCpnet dt
Range :-
+ 8.88E-12 T
25
to
315.19
2.89E+06
9.17E+03
Watts
290 oC
= 1134.69 * 1000/3600 [ 3.21E+01 * 2.65E+02 + 1.82E-02 *

3.61E+04 -2.36E-06 * 6555792 + -9.06E-10 * 5314019375 ]
=
=

=
2.89E+03
= Qin
=
61
KW
- Qout
-6.14E+03
Qreacion
KW
Heat Balance Around Separator:o
35 C
o
Separator
35 C
Heat transfer =
35 C
Energy Balance Around Distillation(Light Ends)
40 C
V
Qv
L =1.8695 tons/day
= 1869.5 Kg/day
Distillation
column
M4 = 187.22 tons/day
= 187220 Kg/day
35 oC
308 K
70 C
CH3OH =
80%
H2O =18%
CO2 =0.20%
HCHO =
0.40%
CH3OCH3 = 0.40%
C2H5OH =
0.30%
CH3COOH = 0.30%
C5H11OH = 0.20%
C3H7OH = 0.20%
Heat In By M4 Stream:
Cp of CH3OH = 80%* 2.95
= 2.36 KJ/Kg.K
Cp of H2O
18% * 4.18
W = 185.35 tons/day
Qb
= 185350 Kg/day

=
Cp of CO2
62
0.7524 KJ/Kg.K
= 0.20%
* 1.09
= 0.0021 KJ/Kg.K
Cp of HCHO = 0.40% * 1.192

= 0.0047 KJ/Kg.K
Cp of CH3OCH3
Cp of C2H5OH
= 0.40% * 1.75
= 0.007 KJ/Kg.K
= 0.30% * 2.5
= 0.0075 KJ/Kg.K
Cp of CH3COOH = 0.30% * 2.05

= 0.0061 KJ/Kg.K
Cp of C3H7OH
= 0.20% * 2.41
= 0.0048 KJ/Kg.K
= 0.20% * 2.26
= 0.00452 KJ/Kg.K
Cp of C5H11OH
Cp NET
= 3.149 KJ/Kg.K
= mCpT
= 245674.6 KJ/hr
QM4
Heat Renoved In Condenser:In this column , we saparate the dissolve gases from crude methanol mixture.The
gases pass through the condenser.Here the purpose of condenser is to condense the vapor of
methanol if it passes with gas stream.As such , there is no reflux.
we assume,
Temp of "V" stream = 40 oC
= 313 K
Temp of "L" stream =
=
Input
Qv
Qc
Ql
Qv
Cp of HCHO = 0.39877 * 1.256

= 0.500 KJ/KG.K
Cp of CO2
= 0.2 * 1.09
= 0.218 KJ/KG.K
Cp of CH3OCH3 = 0.401 * 1.88
25 oC
298 K
Output
+
-
Ql
Qc
(1)
63
= 0.75 KJ/KG.K
Cp NET
= 1.47
KJ/KG.K
Substituting the values in Eq (1),

Qc =
=
1721.19
1721.19
Kj/hr
*
KJ/Kg.K
*
KJ/Kg.K
*
KJ/Kg.K
*
KJ/Kg.K
*
KJ/Kg.K
KJ/Kg.K
2.85
0
= 0.478 KW
Heat Added By Reboile Qb:Cp of CH3OH
=
=
Cp of H2O
=
=
Cp of HCHO
=
=
Cp of C2H5OH
=
=
Cp of CH3COOH =
=
Cp NET
=
0.80807
2.30
0.181
0.75
2.40E-05
3.01E-05
0.00302
0.0047
0.00302
0.0061
3.07E+00
4.18
1.25
1.56
2.05
So,
Heat Out by stream.
Q
=
mCpT
= 1068261
Kj/hr
Balance
Qb + QM4
Qb
Input
=
Output
=
Qc +QP + QL
= QC + Qp + QL - QM4
=
824307.5 Kj/hr = 228.97 KW
Steam required:Qb is supplied by super heated steam.

P
= 4800
Kpa
=
1654
KJ/Kg
Q
=
m
m
=
Q/
=
498.37
Kg/hr
Water Required:Qc is removed by cooling water with a termperature risse of 15 oC.

Qc
m
=
=
=
m CpT
Qc / CpT
27.45 Kg/hr
64
Energy balance of distillation (Heavy ends) Column:65 oC

Hv
V
Qv
Distillation
column
P = 185.35 tons/day
=185350 Kg/day
53 oC
L
Hl
M =150 tons/day
HM = 150000 Kg/day
95 oC
Qb
Heat In By "P" stream:= 1068261 KJ/hr
W = 35.3475 ons/day
= 35347.5 kg/day
Heat Removed By Condenser Qc:R

L
V
=
=
=
=
=
=
L/M
158.01
158010
L+M
308.01
308010
1.0534
tons/day
Kg/day
tons/day
Kg/day
At steady State:Input
=
Output
VHv
= MHm + LHl + Qc
Qc = VHv -MHm - LHl
(2)
At
65 oC
or
338 K
Enthalpy of vapors = Hv = 1804.8 Kj/Kg
At
53 oC
or
326 K
Enthalpy of Condensate Hl = Hm = 670.5
Kj/Kg
Substituting the values in eq (2)..we get
Qc =
Qc =
=
V =
3.08E+05
Kg/day
L =
1.58E+05
Kg/day
5.56E+08 - 100575000 - 1.06E+08
3.49E+08 Kj/day
1.46E+07 Kj/hr
= 4055.56 KW
Heat Added By Reboiler Qb:Heat Out By "W" Stream:

Qw =
mCpT
=
10194219 Kj/day
=
424759.1 kKj/hr
Balance:Input
QB + Q p
=
=
Output
Qc + Qw + Qm
Qb = Qc + Qw + QM - Qp
= 1.50E+07 + 4190625 - 1068260.964
= 1.81E+07 Kj/hr = 5027.78KW
Steam Required:Qb is supplied by super heated steam .

P
= 4800 Mpa
= 1654 KJ/Kg
Q
=
m
m
=
Q/
= 1.09E+04 Kg/hr
Water required In condenser:

Qc is removed by cooling water with a termperature risse of 15 oC.
Qc
=
mCpT
m
= Qc/CpT
=
232174.2
Kg/hr
65
66
67
Production of Hydrogen
Hydrogen has been produced and used for
industrial purposes for over one hundred years. Of
the worlds total hydrogen production of
approximately 45 mill. tons, over 90% comes from
fossil raw materials. The largest producers of
hydrogen are the fertiliser and petroleum
industries.
Sale of hydrogen has increased by 6% annually in the
last five years. This is closely related to the increased use of hydrogen in oil refineries, which is
a result of the strict requirements on the quality of fuels. This development is expected to
increase. Hydrogen is used elsewhere in many other process industries and laboratories, and
compressed hydrogen gas can be bought from most gas retail stores.
Many renewable energy sources vary considerably on a daily and seasonal basis. An energy
system based on such sources must be able to store energy to balance out variations.
Correspondingly, the great distances usually seen between the energy sources and the
consumers necessitates transportation of the energy. For both these purposes it may be
practical to convert the energy to hydrogen.
It should be noted that as an energy carrier, hydrogen is neutral as to the actual source of
energy. One could, for instance, envision large scale electrolysis based on nuclear power. Due
to the environmental problems surrounding nuclear power, such a solution would, in our view,
defeat the purpose.
Production of hydrogen based on fossil raw materials

Strongly simplified, the majority of the processes described below are based on heating
up hydrocarbons, steam and in some instances air or oxygen, which are then combined
in a reactor.
Under this process, the water molecule and the raw material are split, and the result is H 2, CO
and CO2. In other words, the hydrogen gas comes from both the steam and the hydrocarbon
compound. Another method is to heat up hydrocarbons without air until they split into hydrogen
and carbon.
68
Gasification of coal
Gasification of coal is the oldest method of producing hydrogen. In
the old gas plants, the original gas piped in to cities was produced this way. This gas contained
up to 60% hydrogen, but also large amounts of CO. Typically, the coal is heated up to 900C
where it turns into a gaseous form and is then mixed with steam. It is then fed over a catalyst
usually nickel.
There are also other more complex methods of gasifying coal. The common factor is that they
turn coal, treated with steam and oxygen at high temperatures, into H 2, CO and CO2. In
addition, sulphur is released from the raw material and creates sulphur and nitrogen
compounds. As with CO and CO2, these compounds must be handled in an environmentally
friendly way.[Winter et al 1988] Today there are large coal gasification plants in Europe, South
Africa and the USA, and technologies for gasification of coal is the object of a great deal of R &
D within the coal industry.
Steam reforming of natural gas

Natural gas consists mainly of methane, mixed with some heavier hydrocarbons and CO 2. By
applying high temperature steam to the methane, hydrogen and carbon oxides are created.
Steam reforming is the most common method of producing hydrogen today. The formula for
the chemical reaction is:
CH4 + H2O -> CO + 3H2
And for the following shift reaction:
CO + H2O -> CO2 + H2

Which produces:
1 mol methane =-> 4 mol hydrogen
The percentage of hydrogen from water is 50%.
Steam reforming of natural gas is currently the cheapest way to produce hydrogen, and
accounts for about half of the worlds hydrogen production. Steam, at a temperature of 7001000 C, is fed methane gas in a reactor with a catalyst, at 3-25 bar pressure.
In addition to the natural gas being part of the reaction process, an extra 1/3 natural gas is
used as energy to power the reaction. New methods are constantly being developed to
increase the efficiency, and maximising the heat process makes it possible to increase the
utilisation to over 85% and still make a profit.
A large steam reformer which produces 100,000 tons of hydrogen a year can, roughly
speaking, supply one million fuel cell cars which have an annual average driving distance of
16,000 km. Steam reforming of natural gas produces 7.05 kg CO2 per kilogram of hydrogen.
69
There are two main types of steam reformers for small scale hydrogen production:
conventional, down-sized reformers, and specially constructed reformers for fuel cells. The
latter operates under lower pressure and temperature than conventional reformers, and are
more compact.
Work is under way to build a modified steam reformer with a built-in CO2 remover. This will
make it possible to produce hydrogen at a lower temperature than regular steam reformers.
These reformers will reduce the cost of hydrogen production by 25-30% compared to
conventional technology, mainly due to reduced capital and operating expenses.
The most common method of "on-purpose" hydrogen production is the steam reforming
process. The main process step involves the reaction of steam with a hydrocarbon over a
catalyst at around 750-8000C (1380-1470F) to form hydrogen and carbon oxides. However,
there are several other steps to remove impurities and maximize hydrogen production. The
main steps involved are as follows:
Feedstock purification - removal of poisons such as sulphur and chloride to maximize the life of
the downstream steam reforming and other catalysts
Feedstock Purification
The catalysts used in the steam reforming process are poisoned by trace components in the
hydrocarbon feed, particularly sulphur, chlorine and metal compounds. Sulphur is the
commonest problem, the nature and level of sulphur species being dependent on the source,
pre-treatment and molecular weight of the hydrocarbon. Chlorine compounds are less common
and metal compounds are typically found in some heavier LPG and naphtha feeds.
The best way to remove sulphur compounds is to convert the organic sulphur species to H2S
over a hydrodesulphurization catalyst. The HDS catalyst removes organic-sulphur compounds
by reaction with hydrogen to convert the sulphur to H2S.
The next step is sulphur removal with an absorbent. The same catalyst similarly converts any
organic-chloride species to give HCl and also acts as an absorbent for most problematic metal
70
species. A second absorbent is used for chloride removal.

CO + 3H2 = CH4 +H2O
CO2 + 4 H2 = 2CH4 + 2H2O
Most catalysts are formulated on a calcium aluminate base with the active nickel incorporated
in a NiO/MgO solid solution. This results in negligible nickel sintering during operation.
Deactivation mostly results from solvent carry over from the upstream CO 2 removal section.
Steam Reforming Catalysts

This is the heart of the hydrogen generation process. The main steam reforming reactions are:
CH4 + H2O = CO + 3 H2
CxHy + H2O = x CO + (x + 0.5y) H2
and
CO + H2O = CO2+H2
The reaction takes place across a nickel catalyst packed in tubes in a fired furnace. An excess
of steam is used to promote the reforming reaction and avoid carbon deposition on the
catalyst.
Some flowsheets may have pre or post-reforming in addition to the conventional steam
reformer. Newer plants tend to be PSA-based, with typically only a High Temperature Shift bed
rather than both High and Low Temperature Shift.
This selection considers the feedstock types and operating conditions. The selection is usually dictated
by the heaviest hydrocarbon feed and may involve two or three catalyst types in order to obtain optimum
performance.
The
main
categories
of
catalyst
are
as
follows.
Burner Combustion Efficiency

Conserving fuel in heating operations such as melting or heat treating is a complex operation.
It requires careful attention to the following:
Refractories and insulation
Scheduling and operating procedures
Preventative maintenance
Burners
Temperature controls
Combustion controls
71
Furnace Efficiency
Conventional refractory linings in heating furnaces can have poor insulating abilities and
high heat storage characteristics. Basic methods available for reducing heat storage effect and
radiation losses in melt and heat treat furnaces are:
1. Replace standard refractory linings with vacuum-formed refractory fiber insulation material.
2. Install fiber liner between standard refractory lining and shell wall.
3. Install ceramic fiber linings over present refractory liner.
The advantages?
R
efractory fiber materials offer exceptional low thermal conductivity and heat storage.
These two factors combine to offer very substantial energy savings in crucible,
reverberatory and heat treat furnaces.
With bulk densities of 12-22 lbs/cu ft, refractory fiber linings weigh 8% as much as
equivalent volumes of conventional brick or castables.
Refractory fibers are resistive to damage from drastic and rapid changes in
temperature.
Fiber materials are simple and fast to install.
The density of fiber
refractory is low, so
there is very little
mass in the lining,
therefore
much less heat is
supplied to the lining
to bring it to operating
temperature.
This
results
in
rapid
heating on the startup.
Conversely,
cooling is also rapid,
since there is less
heat stored in the
lining.
The steam reformer

with
cold
outlet
manifold system
The steam reformer is a
furnace
in
which
a
multiplicity of tubes filled
with catalyst are heated by
72
burning fuel. The process gas temperature required at the outlet of the catalyst-filled tubes is
about 740 - 880C at a pressure of up to 40 bar. lnevitably, the service life of components
such as the reformer tubes is limited. Material deterioration occurs by
the combined effect of creep, alternating thermal and mechanical stresses, external and
internal oxidation and carburisation. Inlet manifold Burners Reformer tubes Cold outlet
manifold system.
Advantages:
A uniform mixture of gas and oxygen along with sufficient reaction space to ensure equalised
gas temperatures prior to contact with the catalyst.
Safe burner design.
No metallic internals in the
combustion zone.
The Combustion Process

The combustion in fired heaters
takes place in the burner. The
types of burners and how they
function are not covered in detail in
this section. The amount of heat
released can be easily calculated
for a gas when we know the
composition of the fuel and the
heating values of the various
components. For liquid fuels, the
heating values are obtained by a
calorimeter
test.
From these values and using the
standard combustion equation, we
can determine the composition of
the flue gas. As an example, the
combustion of methane could be
stated :
CH4 + 2O2 --- > CO2 + 2H2O

Of course for fuel gases containing
many more components and
burning in air rather than pure
oxygen, the equation gets more
complicated. Therefore, a task that
in itself is quite simple, becomes a
burden to do by hand, but can be
easily accomplished by a simple
computer program. The heating
values normally used in fired
heater design are the LHV.
73
Burner Types & Selection

Burners for fired heaters can be generally divided into two categories, natural draft and forced
draft. The natural draft type burner requires less pressure differential to provide the required air
for combustion then the forced draft burner. Air pressure differential, or pressure drop, across
a natural draft burner would normally fall in the 0.1 to 1.0 in H 2O range, where the forced draft
burner would normally require 0.3 to 4.0 in H2O. Burner combustion air can also be induced by
the fuel gas flowing through a venturi section. Also burners have different air registers for
primary and secondary air intake. The air may be delivered to the registers by an air plenum.
In addition to burners being classified by the draft requirements, they are also described by the
fuel they burn such as oil or gas or combination. There are numerous fuels which may be
burned including:
Refinery Gas Propane or Heavier Gas
Natural Gas
High Hydrogen Gas
Waste Gas
No. 2 Fuel Oil
No. 6 Fuel Oil Other Liquids

Burners may be of the low NOx which may incorporate staged air or fuel designs. These burner
types have become almost standard in the developed world where environmental air standards
demand the best combustion technology available.
Burners may be designed for mounting in the heater floor, side walls, or end walls. The burner
tips can be designed for various shapes or flame patterns.
In conclusion, there is such a wide variety of types and configurations of burners available from
the many manufacturers, that selecting a particular burner for a design requires that the
designer work closely with the burner manufacturer to assure the correct selection
Burning with low excess air:

For many years, it was not uncommon to see furnaces operating with 50 to 100% excess air. It
was simply easier for the operator to just make sure there was plenty of air. Of course this
method of operation also resulted in reduced efficiency and more NO x generation. As fuel
costs and environmental concerns has risen, these practices have changed. With the excess
air at levels of 15 to 30%(lower for gas and higher for oil), the furnace could be operated with a
minimum of monitoring. In recent years, development of advanced instrumentation has allowed
continuous automatic furnace monitoring and control of excess air, and the percent excess air
can now be reduced below the 10-30% limit. EPA tests concluded that a 19% average
reduction of NOx can be achieved by reducing the percent excess air from an average of 20%
to an average of 14%. This method is somewhat limited since it can cause other problems
such as carbon monoxide and soot emissions..
74
Purpose Of Excess Air

Perfect combustion is achieved when all the fuel is burned using only the theoretical amount of
air. Perfect combustion cannot be achieved in a fired heater. Complete combustion is achieved
when all the fuel is burned using the minimal amount of air above the theoretical amount of air
needed to burn the fuel. With complete combustion, the fuel is burned at the highest
combustion efficiency. Incomplete combustion occurs when all the fuel is not burned, which
results in the formation of soot and smoke.
Oxygen for combustion is obtained from the atmosphere, which is about 21% oxygen by
volume or 23% by weight. About 2000 cubic feet of air is required to burn one gallon of fuel oil
at 80% efficiency at sea level. About 15 cubic feet of air is required to burn one cubic foot of
natural gas at 75% at sea level. Most of the 79% of air that is not oxygen is nitrogen, with
traces of other elements. Nitrogen is inert at ordinary flame temperature and forms few
compounds as the result of combustion. Nitrogen is an unwanted "parasite" that must be
accepted in order to obtain the oxygen. It contributes nothing to combustion, it increases the
volume of combustion products to be vented, it steals heat from the reaction and now creates
a growing environmental problem as well.
Air required in combustion is classified as:
Primary Air
Primary air controls the rate of combustion, which determines the amount of fuel that can be
burned.
Secondary Air
Secondary air controls combustion efficiency by controlling how completely the fuel is burned.
Excess Air
Excess air is air supplied to the burner that exceeds the theoretical amount needed to burn the
fuel. Combustion air requirements are based on the composition of the fuel used and the
design of the burner. Fuels commonly used contain nitrogen, ash, oxygen, sulfur, carbon and
hydrogen. When a fuel has a large volume of nitrogen that must be accepted along with the
desired oxygen, more excess air should be provided. That excess air has a chilling effect on
the flame. Some fuel particles fail to combine with oxygen and pass out of the stack unburned.
Natural gas contains more hydrogen and less carbon per unit of heat content than oil and
consequently its combustion produces a great deal more water vapor which withdraws a
greater amount of heat from the flame. Therefore gas efficiency is always slightly less than oil
efficiency.
Air requirements for combustion are generally expressed in cubic feet of air per gallon of oil or
per cubic foot of gas for convenience because fans, ducts and other air moving devices are
75
rated in cubic feet per minute or cubic feet per hour. The Fuel/Air Ratio for combustion is
actually a weight ratio based on the required weight of oxygen for a given weight of fuel.
Preheated Combustion Air

There are basically two ways to obtain preheated combustion air and reduce the amount of
fuel required. One process would use heat from an external source to preheat the combustion
air, such as waste steam or flue gases from other sources. The other method would be to
utilize the flue gas from the heater to preheat the combustion air.
In either case, the heat available in the preheated air is taken into account in the radiant heat
transfer as described in section 4, Heat Transfer Concepts. In the second case, the additional
heat removed from the flue gas in the air heater is taken into account when calculating the
overall efficiency of the heater. The amount of heat available in the flue gas can be calculated
using the enthalpy of the flue gas at the entering
and exiting temperatures.
Cylindrical Radiant Section

The radiant section in a vertical tube, cylindrical
fired heater contains tubes in a vertical position.
The tubes may be along the refractory wall, as in
a circular pattern, or they may be exposed to the
radiating flame from both sides, as in a cross or
octagonal pattern.
Shield Section
The shield section contains the tube rows that
"shield" the convection rows from the direct
radiant heat. Just below the shield tubes are two
important monitoring points. The first is the
"bridgewall"
temperature
which
is
the
temperature of the flue gas after the radiant heat is removed including the radiant heat to the
shield tubes above, but before the convective heat to the shield tubes. The other is the draft
measurement at this point, since for most heater designs, if it is negative at this point, it is
negative throughout the furnace.
Convection Section
The convection section is located in the cooler flue gas
stream. It often contains rows of extended surface tubes
to improve the efficiency of the furnace. The flue gases
can be cooled to a very low temperature, but caution
must be used to avoid going below the dew point of the
flue gas with the metal temperature of the tubes or
surface, since this could cause corrosion.
76
Flue Stack
The flue stack on the heater is very important for several reasons. In addition to just getting the
flue gasses up and out of the way where they won't endanger people, they also perform other
functions. In the example shown, draft or flow of the flue gas is controled by an induced draft
fan. In a natural draft furnace, the draft created in the stack is what "pulls' the flue gasses
through the furnace convection
Damper
The main damper in the stack is used to control draft in the furnace. It is normal adjusted to
achieve a negative 0.05 inches H2O pressure at the bridgewall. It is not used to control
combustion air which is controlled by air plenum dampers or air registers at the burner(s). In
the example used herein, it is used to redirect the flue gasses to the air preheat system.
DESIGNING OF STEAM REFORMER

Radiant Section:1)
Assumed average heat flux

= 10,000 Bto/hr /ft2
2)
ACP
=2
average flux
=2
10,000
= 20,000 Btu/hr/ft2
3)
Overall Exchange factor

f = 0.6 (assumed)
4)
5)
ACP f
= 33333.33 Btu/hr ft
Tube surface temperature:Ts = 700 F
6)
Evaluate Ta from fig 19.14 kern

Ta = 1571 F
Ta
7)
Q = 2.38
8)
QF = /
107 kj/nr
= 855s
2.38 10 7
=
0.85
77
kj/hr
= 28000000 kj/hr
28000000
Btu/hr
1.055
QF
QF
= 26540284.36 Btu/hr
Fuel consumption qF =
QF Btu / hr
lower heateing value at full Btu / hr
Methane is fuel and lower heating value of methane = 21500 Btu/lb
26540284.36
21500
qF
qF
= 1234.43 lb/hr
From Graph given in nelson .

lb air
lb fuel
as oxygen used in 20% Excess

II)
qA
= Amount of w.r used
= qF
lb air
lb fuel
= 1234.43
18
qA = 22219.77 lb/nr.
Entering temp of air = 357 C
= 674.6 F
= 1134.6 R
Enthalpy of entering air
HA
= 4711.49 Btu/lb uel

= 162.49 Btu/lb.
QA
HA
= 162.49
QA
qA
22219.77
= 3610490.43 Btu/hr
18

III)
78
QW = 2% at QF
QW =
2.0
100
3610490.43
QW = 72209.80 Btu/lb
IV)
Amount at fuel consumed
QF = 1234.43
16
= 77.2 moles
From equation
CH4 + 2O2
Oxygen Consumed = 77.2
= 154.3 Moles
As oxygen is supplied in 20% excess so
Oxygen supplied = 154.3
1.2
= 185.2 moles
Oxygen in flue gas = 185.2 154.3
= 30.9 moles
Nitrogen in flue gas = 185.2
0.79
0.21
= 696.7 moles
CO2 in flue gases = 77.2 moles
H2O in flue gases = 2
77.2
= 154.4 moles
Ta = 1610 F
= 2070 F
From Himmelblau
qN2 = 696.7
11570
= 8060819 Btu/hr
qO2 = 30.9
12100
= 373890 Btu/hr
qX120 = 13100
154.8
= 2027880 Btu/hr
CO2 + 2H2O
qCO2 = 17900
79
77.2
= 1381880 Btu/hr
Qa = q N2 + qO2 =
qHW - qCO2
8060819 + 373890 2027880 1381880
Qa = 5024949 Btu/hr.
Now Net heat load
Q = QF + QA QW Qa
Q = QNet Qa
Q = 26540284.36 + 3610490.43 72209.80 4392522.6
= 2.56
107 Btu/hr
(It is very closed to actual heat load i,e. 2.65

8)
Assume tube length =30ft

Dia of tubes = 5 = 5/12 ft.
Centre to centre distance = 10/12 ft
As our furnace is vertical tube single layer

Height at furnace
= length at tubes
= 30ft
9)
Surface area at tubes

= Dl
=
0.416
30
As = 39.28 ft2
Heat transferred part tube
Qtube = are flux
surface annex at tube
= 10,000
39.28
Qtube = 392814 Btu/hr

No at tubes =
Q ( Btu / hr )
Qtube
2.65 10 7
= 68 tubes
392814
107 Btu/hr)

Ntube = 68 tubes
10)
Diameter of furnace
2
C C distance
R = No of tubes
10
12
= 68
56.66
2
R=
R = 9.02 ft
D = 18.04 ft
11)
(effectiveness factor )
=
C dis tan ce
0 . D at tubes
10
=2
5
From Fig 19.11 Kern

= 0.87
12)
Ac
Ac p = (no at tubes) (length at each tube) (C C distance)
= 68
30
10/12
Ac p = 1700 ft2
13)
AT = Total area at furnace

=
18.04
30
AT = 1700.23 ft2
14)
AR = A T -
Acp
= 1700.23 (0.87
1700)
= 221 ft2
15)
AR
ACP
221
0.87 1700
AF
ACP
0.149
This factor is used to evaluate if
16)
Mean beam length.
0.149
80
81
Using table 19.1 kern at page # 691,

L = 2/3 ( 30 * 29.753 * 20.085)1/3 (For dimension ratio 1:1:1)
L = 17.4 ft
17)
Emissivity at Gas: EG
i)
From Graph given in Nelson (18 . 16)

For 20% Excess air
at H2O + CO2 = 0.178 atm
From reaction
CH4 + 2O2
CO2 + 2H2O
at CO2 = 1/3
= 1/3
0.178
= 0.0593
at H2O = 2/3
= 2/3
0.178
at H2O = 0.118 atm.

ii)
From Fig 19.12 Kern For CO2 using PP at CO2 = 0.0593 atm
TS = 806 F
Ta = 1571 F
qCO2 = 300 Btu/hr.ft2
qCO2 = 1780 Btu/hr ft2
qCO2
L = 300
qCO2
L = 1780
qCO2
L = 5220 Btu/hr.ft
qCO2
L = 30972 Btu/hr ft
17.4
17.4
From Fig 19.13 kern for H2O cap using pp at H2O cap = 0.118 atm.
At
iv)
TS = 806 F
Ta = 1571 F
qH2O = 280 Btu/hr.ft2
qH2O = 1600 Btu/hr ft2
qH2O
L = 280
qH2O
L = 1600
qH2O
L = 4872 Btu/hr.ft
qH2O
L = 27840 Btu/hr ft
AT
Ta
17.4
17.4
82
at CO2
CO2
H 2O
0.0593
0.178
= 0.333
PHO
L + PCO2
= (0.118
6.9) + (0.0593
6.9)
= 1.2213
From Fig 19.12 kern
% correction = 6 %
v)
qb = 0.173 Eb
T
100
6b = 1
qb at Ta = 0.173
1571 460
100
= 29436.47 Btu/hr ft2
qb at Ts = 4444.07 Btu/hr ft2
vi)
EG =
EG =
Ea = Emissivity at Gas
qCO 2
QH 2O Ta
qb Ta
30972 27840
29436.47
EG = 0.689
qCO 2
QH 2O TS
qb TS
5220 4872
4444.07
100
% cor
100
100 6
100
94
100
EG = 0.648
18)
From Fig 19.15 kern

At AF/ Acp = 0.149
EG = 0.648
f = 0.61
(Which is very close to true assumed value at f = 0.6)
(a):-
83
ACP f
25600000
0.87 1700 0.61
ACP f
= 28375.4
20)
Calculate actual Ta:

From Fig 19.14 kern
Using
ACP f
= 28375.4
And town made at Ts = 800 F
Ta = 1550 F
(Assumed made at Ta was 1571 F which is not far away from 1560 F.
Hence we can consider our calculation and assumptions correct.)

Moreover the convection section is also designed according to the exit temperature of the
gaseous stream from the radiant section.
Specification Sheet
Type
Process
Item Required
Item No.
Heat Required
Efficiency
Furnace Duty
Inlet Temperature
Outlet Temperature
Pressure
Standard length of each tube
No. of tubes
No. of rows
Volume of reformer
Material of Construction of tube
No of burners
Radiant Section of Steam Reformer

Continuous
1
S-1
2.257 * 107 Btu/hr
87%
2.594 * 107 Btu/ hr
842 oF
1571 oF
1.6 Mpa
30 ft
45
5
558.85 m3
HK-40,25% Cr , 20% Ni
22
84
Types of Heat Recovery Equipment

Choosing the type of heat recovery device for a particular application depends on a number
of factors. For example air-to-air equipment is the most practical choice if the point of recovery
and use are close+ coupled. Air-to-liquid equipment is the logical choice if longer distances are
involved.
Included in this section are five types of heat recovery systems.
Economizers
Heat pipes
Shell and tube heat exchangers
Regenerative units
Recuperators
Heat Exchanger As Waste Heat Boiler :

A heat exchanger is a device for transferring heat from one
fluids are separated by a solid wall so that they never mix
fluid
to another, where the
Definition of heat exchanger :

A heat exchanger is a heat transfer device that is used for transfer of internal thermal
energy between two or more fluids available at different temperatures.
In most of the exchangers the fluids are separated by a heat transfer surface and
ideally they dont mix. The word exchanger really applies to all type of equipment in which
heat is exchanged but is often used specifically to denote equipment in which heat is
exchanged between two process fluids. Such as:
Classification of Heat Exchanger
:
In general industrial heat exchangers are classified according to there Construction:
Transfer processes
Degrees of surface compactness
Flow arrangements
Pass arrangements
Phase of the process fluid
Heat transfer mechanism
Parallel flow heat exchanger:

In parallel-flow heat exhangers, the two fluids enter the exchanger at the same end,
and travel in parallel to one another to the other side. Parallel-flow Heat Exchanger
Figure shows a fluid flowing through a

pipe and exchanges heat with another
fluid through an annulus surrounding
the pipe. In a parallel-flow heat exchanger
fluids flow in the same direction. If the
specific heat capacity of fluids is
constant, it can be shown that:
where,
dQ/dt= Rate of heat transfer between
two fluids
U= Overall heat transfer coefficient
A= Area of the tube
T= Logarithmic mean temperature
difference defined by:
Heat Exchanger Selection Criteria :

When selecting a heat exchanger for a given duty the following points must be considered
Material of construction
Operating pressure and temperature
Flow rates
Flow arrangements
Performance parameters--thermal effectiveness and pressure drops
Fouling tendencies
Types and phases of fluids
Maintenance, inspection, cleaning, extension, and repair possibilities
Overall economy
Fabrication technique
Intended application
85
86
Failures of Heat Exchangers :

Damage to heat exchangers is frequently difficult to avoid. Some common causes of
failures in heat exchangers are listed below:
Pipe and tubing imperfections

Welding
Fabrication
Improper design
Improper materials
Improper operating conditions
Pitting
Stress-corrosion cracking (SCC)
Corrosion fatigue
General corrosion
Crevice corrosion
Shell And Tube Heat Exchanger:

The most commonly used heat exchanger is shell and tube type. It is the work horse of
industrial process heat transfer. These exchangers are being used in 90% of the process
industries now days.
Advantages of Shell and Tube Exchanger than other Exchangers :
It is used for high heat transfer duties.

It occupies less space.
Its compactness is more.
Its maintenance is easy.
It can be fabricated with any type of material depend up fluid properties.
Classification of Shell and tube heat exchanger:

Shell and tube (or tubular) heat exchangers are used in applications where high
temperature and pressure demands are significant. Shell and tube heat exchangers
consist of a bundle of parallel sanitary tubes with the ends expanded in tube sheets.
The bundle is contained in a cylindrical shell. Connections are such that the tubes can
contain either the product or the media, depending upon the application. The major
limitation is that they cannot be used to regenerate, but they can transfer lots of heat
due to the surface area. There are many different types or designs of shell and tube
87
heat exchangers to meet various process requirements. Shell and Tube heat
exchangers can provide steady heat transfer by utilizing multiple passes of one or both
fluids. Tubular heat exchangers are also employed when fluid contains particles that would
block the channels of a plate heat exchanger. There are several types of shell and tube heat
exchangers including U-tube, straight, spiral, and finned tube.
Figure:
shell and tube heat exchanger with countercurrent flow
Figure 1. Shell-and-tube-heat exchanger with one shell pass and one tube pass; crosscounterflow operation
Maintenance aspects:
Special consideration shall be given to determine if the heat exchanger shall be located
in a horizontal or vertical position due to maintenance and inspection requirements.
Space for tube bundle withdrawal, access for platform crane, inspection requirements
may also affect the choice of heat exchanger type.
Tubeside and shellside fluid allocation:
The criteria for fluid allocation shall be:

The most corrosive to be tubeside.
The higher pressure fluid to be tubeside.
Severe fouling fluids shall be allocated the side which is accessible.
Shellside boiling or condensation is usually preferred.
Specific pressure drop.
MAIN PARTS OF SHELL AND TUBE HEAT EXCHANGER:

The principal components of an STHE are:
shell;
shell cover;
tubes;
88
channel;
channel cover;
tube sheet;
baffles; nozzles.
DESIGNING OF WASTE HEAT BOILER

Designing of 12 counter flow shell & tube heat exchange in which 31095.68 lb/hr
(14134.4 kg/sec) of hot Synthesis Gases leaving the bottom of a Steam Reformer at 1571oF
(855 oC) and will be cooled to 725 oF (385 oC) by 13566.49 lb/hr (6166.58 kg/sec) of water
coming from Steam Drum at 80 oF(176 oC) and heated to 669.2 oF (354 oC) to convert into
superheated steam at 50psi.
T1 = 1571 oF(855 oC)
T2 = 725 oF (385 oC)
t1 = 176 oF(80 oC)
t2 = 280.4 oF(138 oC) (It is the Saturation temp at 50psi)
t3 = 669.2 oF(354 oC)

Steps involved in the designing are:
STEP 1:-(Heat Balance)

To complete the specification, the duty (heat transfer rate) needed to be calculated.
Now,
For hot Synthesis Gases,
The heat duty or heat transfer rate
= WCp
= 14134.4 x 0.707 x (1128 658)

= 5450.54 kW (18599012 Btu/hr)
Now as the a huge amount of energy is transferred to water which is converted into steam. So,
here we shall consider the heat transfer with phase change. And there occurs three zones
through which the water is converted into steam which are given below,
1. Pre heating zone
2. Vaporizing
3. Superheating
Cp of water at 109 oC = 1 Btu/lb. oF
Latent heat of vaporization = = 922.6 Btu/lb (2144kJ/Kg)
Cp of steam at 246 oC
= 1.59 Btu/lb.oF
(3.7 kJ/Kg.K)

Cp(t2-t1)
Cp(t3 - t2)
89
= 104.4 Btu/lb (242.31kJ/Kg)

= 343.9 Btu/lb. (798.42kJ/Kg)
Ti
T2
t2
t1
Now,
Qcold
= m * (cp(t2 - t1)+ +Cp * (t3 - t2))

m = 13566.49 lb/hr (6166.58 kg/hr)
Now,
For Pre heating zone q1 =
mCpT
= 1416342 Btu/hr
For Vaporizing zone q2 =
m*
= 12516868 Btu/hr
For Superheating zone = q3 =
mCpT
= 4665803 Btu/hr
Qcold
= 18599012 Btu/hr (5450.544 kW)
STEP :- (Weighted t)
t1
= LMTD1 = [(T1 - t2) - (T2 - t1)] / [ ln(T1-t2) / (T2-t1)]

= 867.61 oF (464.22 oC)
t2
= LMTD2 = [(T1 - t3) - (T2 - t2)] / [ln(T1 - t3) / (T2 - t2)]

= 646.78 oF (341.38 oC)
t3
= LMTD3 = [(T1 - t2) - (T2 - t2)] / [ln(T1 - t2) / (T2 - t2)]

= 793.85 oF (423.25 oC)
q1/t1 = 1632.47 Btu/hr. oF

q1/t2 = 19361.61 Btu/hr. oF
q1/t3 = 5877.41 Btu/hr. oF
q/t = 26871.54 Btu/hr. oF
So,
Weighted t = Q/ q/t
= 692.15 oF (366.75 oC)
STEP 3:- (Selection of Ud (Overall design coefficient)

From D.Q.Kern, Page -840 And Table #8
Or (fig 12.1 and Table 12.1 coulson 6)
Our Hot fluid is the combination of different gases i. e; gases (75%) and steam(25%)
For gases to water system Ud range is: 2 to 50 Btu/hr.ft2.F (6.31 to 157.64 W/m2.K)
Ud for gases = 37.5 Btu/hr.ft2.F (118.23 W/m2.K)
Now
For steam to water system Ud range is : 200 to 700 Btu/hr.ft2.F (630.56 to 2206.96W/m2.K)
So, max Ud for hot fluid = 212.5 Btu/hr.ft2.F (669.97W/m2.K)
And we select,
Ud = 70 (220.69 W/m2.K)
STEP 4:- ( Total Surface Area)

Q = ud A
A = Q / ud
Tw
Tw
A = 35.681 m2 (383.88 ft2)
Using a spilt ring floating heat exchanger for efficiency and ease of cleaning.
Assume From D.Q.Kern , Page -843 And Table #10
Tube outside dia (do) = l in = 0.0254m
16 BWG, Tube inside dia (di) = 0.022 m (0.870in)
From Coulson Vol. 6 & Peter & Timmerhaus 5th edition
The standard length of tubes in
shell & tube exchanger is 6,8,12,16,20&24ft.
We select length of tube = 14ft = 4.268m
STEP 5:- No. of tubes:

At = (area of one tube)
do L
= 3.14 x 0.0254 x 4.268

= 0.3406m2 (3.655ft2)
90

Nt
= no of tubes = Ao / At
= 35.68 / 0.3406
= 104.361
Nt
104 tubes
Tube Pitch
Pt
= 1.25 do
= 1.25 x 0.0254
= 0.3175 m
For 2 tubes passes, tube per pass = 52

Tube cross sectional area = At
/ 4 (di2)
= /4 x (0.022)2
= 0.000384 m2 (0.594 in2)
So area per pass
= 52 x 3.84 x 10-4
= 0.01994 m2 (0.214 ft2)
Mass Velocity = G = W c / At
= 85.89 kg/sec.m2 (63229.3 lb/hr.ft2)
ut = tube side velocity = G/3600* ro
= 1.769 m/sec
The velocity is satisfactory between 1 to 2 m/sec.
STEP 6:- (TUBE BUNDLE AND SHELL DIA)

From table 12.4 for 2 tube passes and square pitch (Coulson 6)
K1 = 0.156
n1 = 2.291
91
92
For square pitch Pt = 1.25 do

Db = do (Nt / K1)1/n1
= 0.0254 (104 / 0.156) 1/2.291
Tube bundle dia (Db ) = 0.434m (1.4237ft)
For a spilt ring floating head exchanger the typical shell clearance from (fig 12.10
coulson 6)
Shell clearance = 57 mm = 0.057m (2.204 in)
So,
Ds = Shell inside dia = 0.434 + 0.057
= 0.490 m
STEP 7:Re = G x di /
(water at 109 oC ) = 0.36cp (0.8712 lb/hr.ft)

(steam at 138 OC) = 0.0324 lb/hr.ft (13.42 kg/m.sec)
(steam at 246 OC) = 0.026 lb/hr.ft (11.1 kg/m.sec )
So,
NRe1 = 5261.852
NRe2 = 141466.2
NRe3 = 171033.9
PRANDTLE NUMBER:Pr = C x
/k
C (Btu/lb. oF)
K (Btu/hr.ft. oF)
Water
1.1
0.0187
Steam
1.41
0.0241
Superheated Steam
1.59
0.0282
93
Pr1 = 51.25
Pr2 = 1.89
Pr3 = 1.51
From Kern page # 834,fig # 25
L / di = 193.10
JH1 = 320
JH2 = 640
JH3 = 570
Heat transfer Coefficient :hi = JH Re Pr1/3 (K / do)

hi 1= 1493.94 w/m2.Co (263.25Btu/hr.ft2.F)
hi 2 = 1299.744 W/m2.C (229.03 Btu/hr.ft2.F)
hi 3 = 1256.58 W/m2.C (221.42 Btu/hr.ft2.F)
Now,
hio = hi*ID/OD
hio 1= 1299.73 W/m2.C
So,
hio 2 = 1130.78 W/m2.C

hio 3 = 1093.23 W/m2.C
SHELL SIDE HEAT TRANSFER COEFFICIENT

(Ds)
= inside dia of shell = 0.490 m
From Coulson Vol.6 Page # 650

The baffle spacing is used range from 0.2 to 1 times the shell dia.
Assume take a baffle spacing
= Ds * 0.8
= 0.490 * 0.8
= 0.392m
This baffle spacing give good heat transfer with out too much high-pressure drop.
No. of baffles
= length of tube / baffle spacing
94
= 4.268 / 0.392
= 10.86
As
Flow Area = As = ID*C*B / 144*Pt

Where, C = (Pt - OD ) = 0.0063m (0.25in)
= 0.0384 m2 (0.413ft2)
As
SHELL SIDE EQUIVALENT DIA :

de
= 1.27 / do (pt2 0.785 do2)
de
= 0.0251 (or From Fig 28 Kern)
Mass Velocity G
= W / As
= 102.16 Kg/m2.sec (75214.23 lb/hr.ft2)
REYNOLD NO :
Re
= Ds * G /
= 77700.65
( = 0.033cp = 0.0798 lb/ft.hr)
PRANDTL NO:Pr
=C* /K
C = 0.707 Btu/lb.F
K = 0.12 Btu/hr.ft.F
Pr
= 0.471
Use 25% Cut Segmental Baffles
From fig 28 Kern

JH
= 170
ho
= jH x Re x Pr1/3 (k/de)
ho
= 192.81 Btu/hr.ft2.F (1094.192 w/m2Co)
CLEAN OVERALL COEFFICIENT:Uc = (hio * ho) / (hio + ho)

Uc1 = 104.68 Btu/hr.ft2.F

Now,
A1 = q1 / (Uc1*dt1)
= 15.59 ft2
A2
= q2/(Uc2*dt2)
= 197.59 ft2
A3
= q3/(Uc3 * dt3)
= 60.99 ft2
At = 195.56 ft2
Weighted clean overall coefficient Uc:- q/At

= 98.007 Btu/hr.ft2.F
DESIGN OVERALL COEFFICIENT:-
Area of heat exchanger:

Surface area per linear feet = 0.2618 ft2/ft
As = Nt * L * as
= 381.18 ft2 (35.43 m2)
Q = Ud *A*tm
uo required
= Q / Ao
uo required
= 70.49 Btu/hr.ft2.F (222.25 w/m2.K )
Uo estimated
= 70
Btu/hr.ft2.F (220.69 W/m2.K)
Rd = (Uc - Ud) / (Uc * Ud)
= 0.006 Btu/hr.ft2.F
PRESSURE DROP:
TUBE SIDE PRESSURE DROP:-
95
96
Fanning
Specific
Pt (psi) =
friction
Gravity (s)
(f*G2*L*n)/(5.22*E10*D*s*t)
factor (f)
ft2/in2
Water (pre heating
0.0003
0.0179
0.495
0.00015
0.00186
0.0000377
0.00013
0.000023
0.00264
zone) at Nre1
Steam( Vaporizing
Zone) at NRe2
Superheated
Steam(superheating
zone) at NRe3
So,
Total Pressure Drop = 0.498 psi
PRESSURE DROP FOR SHELL SIDE:For
NRe = 77700.65
From kern Fig # 29,

f
= 0.0004 ft2 / in2
N + 1 = 12 * L / B
= 10.88
S
= 0.00529
Ps
= (f*Gs * 62 * Ds * (N+1)) / (5.22*E10*De * s *)

= 1.737 psi
SPECIFICATION SHEET
Identification Item:
Heat Exchanger (WHB)
No. Required =
97
Function: To produce super heated steam by using the high temperature of

Synthesis gas.
Operation: Continuous
Type: 1-2 Horizontal Shell and Tube Heat Exchanger
Tube side Boiling
Heat Duty = 18599012 Btu/hr
Material of construction= carbon steel
Tube Side:
Tubes OD: 1 in, 16 BWG
Fluid handled cold water
104 tubes each 14 ft long
Flow rate = 13566.49 lb/hr
2 passes
Pressure = 50 lbf/in2
Square pitch
Temperature = 80oF to 669.2oF
Pressure drop = 0.498psi
Shell Side:
Shell ID =19.29 in 1 passes
Fluid handled: Synthesis Gas
Baffles spacing = 19.29 in2.

Pressure = 7 atm
Temperature = 1571oF to 725 oC
Pressure drop = 1.737 psi

25% cutoff segmented baffle
Utilities: Cold water

Ud assumed = 70 Btu/hr.ft2.0F
Ud calculated = 70.49 Btu/hr.ft2.0F
Uc calculated = 98.01 Btu/hr.ft2.0F
Allowed dirt factor = Rd = 0.006
98
Air-Cooled Heat Exchangers

Purpose
The purpose of this paper is to provide some general information on air-cooled heat
exchangers and answer some of the commonly heard questions. This is a mixture of fact and
opinion. Wherever the opinion is obvious to me, I have attempted to show it by use of italics.
Why use an air-cooled heat exchanger?

Air-cooled heat exchangers are generally used where a process system generates heat which
must be removed, but for which there is no local use. A good example is the radiator in your
car. The engine components must be cooled to keep them from overheating due to friction and
the combustion process. The excess heat is carried away by the water/glycol coolant mixture.
A small amount of the excess heat may be used by the car's radiator to heat the interior. Most
of the heat must be dissipated somehow. One of the simplest ways is to use the ambient air.
Air-cooled heat exchangers (often simply called air-coolers) do not require any cooling water
from a cooling tower. They are usually used when the outlet temperature is more than about
20 deg. F above the maximum expected ambient air temperature. They can be used with
closer approach temperatures, but often become expensive compared to a combination of a
cooling tower and a water-cooled exchanger.
Types of coolers
Water-Coolers. These coolers use a tube and shell heat exchanger .
Air-Coolers. These coolers use a fined tubed heat exchanger and motor driven fans or
centrifugal blowers to move air through the cooler
SELECT A WATER-COOLER IF:
Adequate water supplies are available from tower, city or well sources.
Water supply is of good quality.
Heat recovery is not practical or unimportant.
Plant ambient temperatures consistently exceed 95F.
Ambient air is polluted with large dust and dirt particles
99
Water Cooler (ADVANTAGES & DISADVANTAGES)
Offer lower capital investment.

Operates more efficiently on hot summer days.
Easier to operate.
Does not offer summer ventilation.
But cost expensive
SELECT AN AIR COOLER IF:
Adequate water supply not available from tower or well sources.

Water supply is not of good quality.
Heat recovery is practical and important.
Plant ambient temperature will not consistently exceed 95F.
Ambient air is not polluted with large dust and dirt particles.
To make the process economic.
Air Cooler (ADVANTAGES & DISADVANTAGES)
Somewhat more costly to purchase and operate but cheaper than water cooler.
Gives less cooling on hot summer days.
Consumes more electricity.
Offers summer ventilation and winter supplement heating.
No problem arising for thermal and chemical pollution of cooling fluids.
Flexibility for any plant location and plot plan arrangement like installation over other
units
Reduction of maintenance costs such as cleaning limited, when needed, to the inside of
exchanger tubes.
No need of over sizing of the equipment due to tube fouling.
Easy installation by bolted assembly
What are headers?

Headers are the boxes at the ends of the tubes which distribute the fluid from the piping to the
tubes.
Why are some coolers forced draft and some induced draft? Which is
better?
It depends. The majority of air-cooled exchangers is of forced draft construction. Forced draft
units are easier to manufacture and to maintain. The tube bundle is mounted on top of the
plenum, so it can be easily removed and replaced. The fan shaft is short, since it does not
have to extent from the drive unit through the tube bundle and plenum to the fan, as in an
induced draft design. Forced draft units require slightly less horsepower since the fan are
moving a lower volume of air at the inlet than they would at the outlet. If the process fluid is
very hot, the cooling air is hot at the outlet. This could cause problems with some fans or fan
100
pitch actuators if the fan is

exposed to very hot exhaust
air. Since forced draft
coolers do not have the fans
exposed to hot exhaust air,
they are a better choice in
such cases.
However, induced draft units
have some advantages, too.
A common problem with
forced draft coolers is
accidental warm air
recirculation. This happens
when the hot exhaust air is
pulled back in to the fans.
Since a forced draft cooler
has a low air velocity at the
exhaust from the bundle and
a high velocity through the fan, a low pressure area is created around the fan, causing the hot
air to be pulled over the side or end of the bay. For this same reason, there should never be a
small space between the bays of a bank of forced-draft cooler. Induced draft cooler have a
high exhaust air velocity through the top-mounted fan, and a lower velocity into the face of the
tube bundle below. This tends to minimize the probability of accidental air recirculation. Also an
induced draft plenum does not have to support the tube bundle so some weight can often be
saved in this area.
Plenums, dispersion angle, and fan coverage:

The API specification includes a number of paragraphs about fan coverage and dispersion
angle. This is for a very good reason. The actual air coming from a fan does not distribute itself
evenly at first. The most air flow is seen around the fan tip area. If you measure the air flow
across the face of a tube bundle, it is often very different around the fan blade tip as opposed
to the center of the fan or the corner of the bundle. However, as the plenum becomes deeper,
this localized effect is diminished as the air becomes more evenly distributed. All of the heat
transfer programs assume that the air is distributed perfectly evenly.
The fan coverage is the ratio of the fan area to the bundle face area. The higher this ratio, the
better the fan coverage. The API minimum is 40% with a 45 degree maximum dispersion angle
from the fan ring to the middle of the tube bundle at the middle of the sides or the middle of the
ends of each fan chamber. More fan coverage or a lower dispersion angle can improve the air
distribution. (See Figure 6 on Page 14 of API 661for a sketch of this.)
What kinds of controls are used?

As one might expect the best kind of control scheme depends on the application. Does the
process require a very tight control on the process outlet temperature, or is it better to allow the
process temperature to go down with the ambient air temperature. Is there a possibility of
101
freezing the process? Is there a pour-point problem? Is the cost of operating the fan motors a
significant factor? The following is a list of some of the commonly used control devices for air
coolers, but in no particular order.
1. Manually operated louvers.
2. Electrically or pneumatically operated louvers.
3. Pneumatically actuated automatic variable-pitch fans.
4. Variable-frequency fan drives.
5. Warm-air recirculation systems for freezing/pour point control in cold climates.
6. Steam coils.
Design of Air Cooler

Hot fluid
= Synthesis gas
Cold fluid
=
Air
P
=
90
psi
Mass flow rate =
28655.24 lb/hr
At 90psi, dew point = 320.27 oF
Inlet temp = T1
= 320.27 oF
= 160.15 oC
Outlet temp. = T2 = 203.41 oF
o
95.23 C
Mean Temp.
= 261.84 oF
Total pressure
=
90 psi = 6.12 atm
Partial pressure of water = 19.03 psi
= 1.29 atm
Entering Molar Composition

Components
Mol %
H2
57.42
CO
10.32
CO2
7.041
N2
0.104
H2O
25.1
Weighted Temperature differnce

Overall Balances:
Water Vapor Pressure,pv = 19.03 psi =
1.29 atm

Inert Pressure , pg
102
= 70.96 psi =
4.82 atm
Exit :
Partial pressure of water at 203.4 oF = 11 psi
Vapor pressure
= 11 psi
Inert Pressure
= 79 psi
Lb mol steam inlet = 534.03
Remaining lb moles = 1990.6
Lb mol steam exit = 277.17
lb moles of steam condensed = 256.85
Heat Load ;
For interval 320 to 203 oF:
= 894.97 Btu/lb
o
cp at 261 F
= 0.46 Btu/lb. oF
Heat of condensation =
Latent heat
=
m*
= 4137894 Btu
sensible heat
= m cp T
= 248529.4 Btu
Heat from uncondensed steam = 268183.1 Btu
Heat from non condensibles
= 4806459
Btu
Qc = 4137894
Qs = 5323172
So, total heat load
= 9461065
Btu/hr
Heat Duty:
Q
= mcp(T1 - T2)
Mean Cp = 0.71ss
9461065
Btu/hr
Now,
For gases and air system , the overall heat transfer coefficient U =
17
53 Btu/hr.ft2.F
From Coulson & Richardson ,6th Vol.
Bundle Selection:First Assumption :

From Table # 2.17, page #82
Bundle
size.(ft)
4 * 24
Air Data:-
No of tubes
74
Face Area
(ft2),FA
70
Frank L Evans Vol-2 And 2nd Edition

Inside Effective Surface
area(ft2)
378
103
Inlet temp. of air = 25 oC

t1
= 77 oF
Density at 25C & 14.7psia = 0.0716 lb/ft3
Specific heat of air = Cp = 0.55
Air face velocity
= Fa = 675
Btu/lb. oF
ft/min
At page #82
Calculating Air Flow Rate:

w =
=
* Fa * FA * 60
202986
lb/hr
Average Temp. Difference of Air:

(t2 - t1)avg =
t2
t2
Q / wCp
= 84.74 F
= t1 +
84.74
o
= 161.74 F
LMTD:
t1 =
T 1 - t2
LMTD
= 158.5 oF
= (t1 - t2)/ln(t1/t2)
= 141.86 oF
t2 = T2 - t1 = 126.4 oF
LMTD Correction:R
P
Correction factor Ft
= (t2 - t1)/(T1 - T2)

= 0.72 oF
= (T1 - T2)/(T1 - t1)
= 0.48
=a/b
Where,
a = {(R2 + 1)0.5/ (R - 1)] * ln[(1 - P)/(1 - RP)]
b = ln [2/P - 1 - R + (R2 + 1)1/2] / {2/P - 1 - R - (R2 + 1)1/2]
(1 - P)/(1 - RP)
=
ln[(1 - P)/(1 - RP)] =
(R2 + 1)0.5/(R - 1) =
[2/P - 1 - R + (R2 + 1)1/2] =
{2/P - 1 - R - (R2 + 1)1/2] =
So,
Ft
0.797
-0.22
-4.49
3.67
1.20
= 0.91
LMTD corrected:
LMTD(cor.) =
LMTD * Ft
o
= 129.3 F
Overall Heat Transfer Coefficient:
104
Q = UaA LMTD
Ua = Q/A*LMTD
= 193.55 Btu/hr.ft2. oF
As it is above the range mentioned,So another set of bundle is considered.
2nd Assumption:
Bundle
size.(ft)
One 4 * 24
One 8 * 24
Total
No of tubes
74
166
148
Face Area
(ft2),FA
70
181
251
Inside Effective Surface

area(ft2)
378
849
1227
Now,
Calculating Air Flow Rate:
w =
=
* Fa * FA * 60
727849.8
lb/hr
Average Temp. Difference of Air:

(t2 - t1)avg = Q/wCp
= 23.63 oF
t2
= t1 +
23.63
t2
= 100.6 oF
LMTD:
t1 =
T1 - t2 = 219.6 oF
t2 = T2 - t1 = 126.4 oF
LMTD
=
(t1 - t2)/ln(t1/t2)
=
168.7 oF
LMTD Correction:R =
=
P =
=
(t2 - t1)/(T1 - T2)

0.202
(T1 - T2)/(T1 - t1)
0.48
Correction factor Ft =
(1 - P)/(1 - RP)
=
ln[(1 - P)/(1 - RP)]
=
(R2 + 1)0.5/(R - 1)
=
[2/P - 1 - R + (R2 + 1)1/2] =
{2/P - 1 - R - (R2 + 1)1/2] =
So,
LMTD corrected:
Ft = 0.983 oF
0.57
-0.55
-1.279
3.98
1.94
105
LMTD(cor.) = LMTD * Ft
= 165.9 oF
Overall Heat Transfer Coefficient:
Q = Ua A LMTD
Ua = Q / A*LMTD
= 46.46 Btu/hr.ft2.F
It is quite satisfactory and within the range , so our 2nd assumption is right.
Heat Transfer Coefficient Calculations:

Inside Film Coefficient(Tube Side)
Inside film coefficients based on the number of bundles calculated are determined
from,
hic =
his =
0.76 (k/di) *(di3 ro2 g2 * n * L/ m)1/3

0.0225 (k/di)*(di G/ )0.8 *(cp /k)0.4
hic =
his =
k =
di =
ro =
g =
n =
L =
Inside film coefficient for condensation Btu/hr.ft2.F

Inside film coefficient for subcooling Btu/hr.ft2.F
thermal conductivity Btu/hr.ft2.F
Inside tube diameter,ft
density ,lb/ft3
= 60.5
lb/ft3
Acceleration of gravity ,4.18E08,ft/hr2
No. of tubes in paralllel
Length of the heat transfer ,ft
where,
= = Viscosity ,lb/hr.ft2
m =
Flow rate lb/hr
G =
Mass velocity ,lb/hr.ft2
Cp =
Specific heat ,Btu/lb.F
The outside film coefficient based on the inside surface area for the described bundle is
180Btu/hr.ft2.F at a face velocity of 675 ft/min.
Using 316SS,1in. OD for 18 BWG tubes
OD =
=
ID =
=
1 in
0.083 ft
0.902 in
0.075 ft
Wall thickness = 0.049 in

= 0.004 ft
= m * 4/ * di2 * n
= 43653.80 lb/hr.ft2
Avg. Cp = 0.71
L = 12 ft

Avg.
Avg. K
= 0.122
= 0.06
rmi =
xdi / km dm
rmi =
x =
km =
dm =
=
km =
inside metal resistance to heat transfer

Tube wall thickness,in
Metal thermal conductivity ,Btu/hr.ft.oF
Mean tube diameter, in
0.951 in = 0.079 ft
9.4 Btu/hr.ft.F
rmi =
0.00041 hr.ft2.oF/Btu
his =
ha =
72.75 Btu/hr.ft2.F
180 Btu/hr.ft2.F
where,
So,
1/Us = 1/his + 1/ha + rmi + x/ k + f

1/Us = 1/his + 1/ha + rmi + x/k + f1 + fo
where,
ha =
Air film Coefficient for heat transfer (based on inside surface)
f =
Fouling factors
Inside fouling factor =
fi = 0.0001 hr.ft2.F/Btu
Outside fouling factor =
fo = 0.001 hr.ft2.F/Btu
2
f
= 0.0011 hr.ft .F/Btu
So,
1/Us =
Us =
0.0208
48.047 Btu/hr.ft2.F
This is closed to the above determined
Now calculating corrected area,
hic
= 0.76 k/di [di3 ro2*g2 * n * L / *W)0.333

=
493.66 Btu/hr.ft2.F
For condensing:
1/Uc = 1/hic + 1/ha + rmi + x/k + f

1/Uc = 1/hic + 1/ha + rmi + x/k + f1 + fo
1/Uc =
Uc =
0.009
109.97 Btu/hr.ft2.F
Area Requirment Determination:

Ac / As = (Qc/Qs) * (Us/Uc) * (LMTDs cor./LMTDc cor.)
Qc
= 4137894 Btu/hr
106
107
Qs
= 5323172 Btu/hr
Ac/As
= 0.33 * (LMTDs cor./LMTDc cor.)
First Assumption :
70% of total area is used for condensation
30% of total area is used for subcooling of fluid
Air Flow =
727849.8
lb/hr
Air Flowc =
509494.9
lb/hr
Air Flows =
218354.9
lb/hr
(t2 - t1) c avg =
=
Q/wCp
14.76 oF
(t2 - t1) s avg =

=
Q/wCp
44.32 oF
LMTDc
=
=
(t1 - t2)/ln(t1/t2)
172.45 oF
LMTDs
=
=
(t1 - t2)/ln(t1/t2)
159.94 oF
So,
Ac/As
=
0.339 * (LMTDs cor./LMTDc cor.)
Ac/As
=
0.314
42.85% not equal to 0.314
Area Requirment Determination:

Ac/As =
Qc
=
Qs
=
(Qc/Qs) * (Us/Uc) * (LMTDs cor./LMTDc cor.)

4137894
Btu/hr
5323172
Btu/hr
Ac/As =
0.339
* (LMTDs cor./LMTDc cor.)
2nd Assumption :
76%
24%
Air Flow =
Air Flowc =
Air Flows =
of total area is used for condensation

of total area is used for subcooling of fluid
Q = UaA LMTD
lb/hr
3144799
lb/hr
1277561
lb/hr
(t2 - t1) c avg =

=
Q/wCp
2.39 oF
(t2 - t1) s avg =
Q/wCp
t2 =
2.39 oF

=
7.57 oF
108
7.57 oF
t2 =
(t1 - t2)/ln(t1/t2)
207.63 oF
LMTDc
=
=
LMTDs
= (t1 - t2)/ln(t1/t2)
=
205.6 oF
So,
Ac/As
=
0.339
* (LMTDs cor./LMTDc cor.)
Ac/As
=
0.336
31.57% almost equal to 0.336425
So,
Ac = 356.24
As = 856.63
Total = 1212.87
ft2
The total area caculated is 15 ft2 less than the total area of the set of
bundle assumed.This is acceptable .Additional subcooling will be expected.
Tube side Pressure Drop Calculation

G
= 43653.80 lb/hr.ft2
Avg = 0.122
a
= Outside Surface area per lin ft = 0.2618

= Inside Dia = 0.902 in
= 0.075 ft
Re = D * G / Avg = 26893.6
f =
0.00017
From Kern Table 10
ft2 / in2
Density of air = PM/RT = 90*29/10.726*721.8

Desity of feed = PM/RT
= 90*11.35025 / 10.726*721.8
s = Specific Gravity = Desity of feed / Desity of air =

L = length of Tube
0.391279
24 ft
Pt = f * G2 * L n / 5.22*10110 *D*s*
Volumetric Flow Rate = nRT/P
= 6157.1 m3/hr =
P
= 90 psi
216262.5
Velocity = Volumetric flow rate / area * No.of tubes
ft3/hr

= 3441.9 ft/hr
109
= 0.956 ft/s
T = 721.8 oR
Pr =
=
4n/s*(V2/2g)(62.5/144)
0.062 psi
PT =
=
Pt + Pr
1.28E+00 psi
Spaecification Sheet
Item No
A-1
Type
Forced Draft
No. of item
Function
To condense water vapors

from gases
Operation
Continuous
Heat Duty
2772.6 KW
No. of tubes
240
Face Area
241 ft2
Face Velocity
675 ft/min
LMTD Corrected
74.4oC
Supposed Ud
0.074 to 0.32 KW/m2.oC
Calculated Ud
0.26 KW/m2.oC
Gases Mass Flow Rate
13025 Kg/hr
Air Flow Rate
330840 Kg/hr
Inside Effective Area
114.1m2
Calculated Area
112.7 m2
110
THEORY OF REACTOR
Reactor selection criteria
1- conversion
2- selectivity
3- productivity
4- safety
5- economics
6- availability
7- flexibility
8- compatibility with processing
9- energy utilization
10- feasibility
11- investment operating cost
12- heat exchange and mixing
Reacti
on
rate
Volume
of
reactor
Volume
flow
rate
Model
Outlet
concent
ration
Inlet
concentr
ation
Contacti
ng
pattern
Selected Reactor:
Catalytic Packed Bed Reactor
Heterogeneous catalytic reactors are the most important single class of reactors utilized
by chemical industry. Whether their importance is measured by the whole sale value of
goods produced, the processing capacity or the overall investment in the reactors and
associated peripheral equipment, there is no doubt as to prime economic role that
reactors of this type play in modern technology society.
Commercially significant types of Heterogeneous Catalytic Reactors.
The types of reactors used in industry for carrying out heterogeneous catalytic reactions may
be classified in terms of relatively small numbers of categories. One simple means of
classification is in terms of relative motion of the catalyst particles or lack there of we consider.
111
Reactors in which the solid catalyst particles remain in a fixed position relative to one
another (fixed bed, trickle bed and moving bed reactors).
Reactors in which the particles are suspended in a fluid and are constantly moving
about (fluidized bed and slurry reactors).
Fixed Bed Reactors.

In its most basic form a fixed bed reactor consists of a cylindrical tube filled with catalyst
pellets. Reactants How through the catalyst bed and are converted in to products. Fixed
bed reactors are often revered to as packed bed reactors. They may be regarded as the
work horse of the chemical industry with respect to number of reactors employed and the
economic value of materials produced. Ammonia synthesis, sulphuric acid production (by
oxidation of SO2 to SO3) and nitric acid production (by ammonia oxidation) are only a few of
the extremely high tonnage process that make extensive use of various forms of packed bed
reactors.
The
catalyst
constituting
the
fixed
bed
will
generally
be employed in one of the
following configurations
A single large bed
Multiple horizontal beds supported on trays arranged in a
Vertical stack
Multiple parallel packed tubes in a single shell
Multiple beds each in their own shell
The use of multiple catalyst sections usually arises because of the need to maintain adequate
temperature control with in the system. Other constraints leading to the use of multiple beds
include those of pressure drop or adequate fluid distribution. In addition to the shell and tube
configuration, some of possibilities for heat transfer to or from fixed bed reactors include the
use of internal heat exchangers, annular cooling spaces or cooling thimbles are circulation of a
portion of the reacting gases through an external heat exchanger.
The packing itself may consist of spherical, cylindrical or randomly shaped pellets, weir
screens or gauzes, crushed particles or a variety of other physical configurations. The particles
usually are 0.25 to 1.0 cm in diameter. The structure of the catalyst pellets is such that the
internal surface area far exceeds the superficial (external) surface area so that the contact
area is in principle, independent of pellet size. To make effective use of the internal surface
112
area, one must use a pellet size that minimizes diffusional resistance with in the catalyst pellet
but that also gives rise to an appropriate pressure drop across the catalyst bed. Some
considerations which are important in the handling and use of catalysts for fixed bed operation
in industrial situations are discussed in the catalyst hand books.
Advantages:
A fixed bed reactor has many unique and value able advantages relative to other reactor
types. One of its prime attributes is its simplicity, with the attendant consequence of low costs
for construction, operation and maintenance relative to moving bed or (fluidized bed operation.
It requires a minimum of auxiliary equipment and is particularly appropriate for use in small
commercial units when investments of large sums for control, catalyst handling and supporting
facilities would be economically prohibitive-. Another major advantage of this mode of
Advantages
Catalytic Fixed
Bed Reactor
Disadvantages
The fluid flow regimes

approach plug flow, so
high conversion can be
achieved.
The intra-particle
diffusion
resistance is very
high.
Pressure drop is low.
Comparatively low
Heat and mass
transfer rates
Owing to the high holdup there is better radial

mixing and channeling
is not encountered.
High catalyst load per
unit of reactor volume
Catalyst
replacement is
relatively hard and
requires shut
down.
operation is implicit in the- u.-e of the term "fixed bed reactor" (i.e.) there are no problems in
separating the catalyst from the reactor effluent stream. (In many fluidized bed systems
catalyst recovery can be quite troublesome and require substantial equipment costs). An other
important attribute of fixed bed reactors is the wide variation in space times at which they can
be operated. This flexibility is extremely important in situations where one is likely lo encounter
wide variations in the quantity or quality of the feed stock to be processed. For example high
temperatures or high pressure reactions employing solid catalyst, economic considerations
usually dictate that the process becomes commercially viable only when a fixed bed reactor is
employed.
113
HEAD AND CLOSURE OF REACTOR

The ends of cylindrical vessels are closed by heads of various types .The
principle types are as follows;
1.
Flat plates and flat heads
2.
Hemispherical heads
3.
Ellipsoidal heads
4.
Torispherical heads
Hemispherical, elilipsoidal and torispherical heads are collectively referred to as
domed heads. Torispherical heads are often referred to as dished ends.

Torispherical heads are most commonly used end closure for vessel up to
operating pressure 15 bars. Flat ends are not a structurally efficient form, and very thick plates
would be required for high pressure or large diameter. A hemispherical head having cost
higher than torispherical heads and are used for high pressure. Closure to 10 bar ellipsoidal
heads will prove to be most economical closure to use. Ellipsoidal head is selected because
pressure is 8 bars so it is more economical.
Type of Reactor
Characteristics
Tubular fixed bed

Reactor
Tubular reactor that is paced with solid catalyst particles
Kinds of
Phases
Present
Usage
Advantages
Disadvantages
1. Gas
phase/
solid
catalyzed
1. Used
primarily in
heterogeneous
has phase
reactions with
a catalyst
1. High
conversion
per unit
mass of
catalyst
1. Undesired
thermal
gradients may
exist
2. Gassolid rxns
2. Low
operating
cost
3.
Continuous
operation
2. Poor
temperature
control
3. Channeling
may occur
4. Unit may be
114
difficult to
service and
clean
Comparison Of Continuous & Batch Packed Bed Reactors

A continuous packed bed reactor has the following advantages over a batch packed
bed reactor:
1.
2.
3.
4.
Easy, automatic control and operation

Reduction of labor costs
Stabilization of operating conditions
Easy quality control of products
Chemical Kinetics
Chemical kinetics is the study and discussion of chemical reactions with
respect to reaction rates, effect of various variables, re-arrangement of atoms,
formation of intermediates etc. There are many topics to be discussed, and each
of these topics is a tool for the study of chemical reactions. By the way, the study
of motion is called kinetics, from Greek kinesis, meaning movement.
At the macroscopic level, we are interested in amounts reacted, formed, and the rates of their
formation. At the molecular or microscopic level, the following considerations must also be
made in the discusion of chemical reaction mechanism.
Molecules or atoms of reactants must collide with each other in chemical reactions.
The molecules must have sufficient energy (discussed in terms of activation energy) to
initiate the reaction.
In some cases, the orientation of the molecules during the collision must also be
considered.
Reaction Rates
Chemical reaction rates are the rates of change in concentrations or amounts of either
reactants or products. For changes in amounts, the units can be one of mol/s, g/s, lb/s, kg/day
etc. For changes in concentrations, the units can be one of mol/(L s), g/(L s), %/s etc.
With respect to reaction rates, we may deal with average rates, instantaneous rates, or initial
rates depending on the experimental conditions.
Thermodynamics and kinetics are two factors that affect reaction rates. The study of energy
gained or released in chemical reactions is called thermodynamics, and such energy data are
called thermodynamic data. However, thermodynamic data have no direct correlation with reaction
115
rates, for which the kinetic factor is perhaps more important. For example, at room
temperature (a wide range of temperatures), thermodynamic data indicates that diamond shall
convert to graphite, but in reality, the conversion rate is so slow that most people think that
diamond is forever.
Factors Influence Reaction Rates

Many factors influence rates of chemical reactions, and these are summarized below. Much
more extensive discussion will be given in other pages.
1. Nature of Reactants
Acid-base reactions, formation of salts, and exchange of ions are fast reactions.
Reactions in which large molecules are formed or break apart are usually slow.
Reactions breaking strong covalent bonds are also slow.
2. Temperature
Usually, the higher the temperature, the faster the reaction. The temperature effect is
discussed in terms of activation energy.
3. Concentration Effect
The dependences of reaction rates on concentrations are called rate laws. Rate laws are
expressions of rates in terms of concentrations of reactants. Keep in mind that rate laws
can be in differential forms or integrated forms. They are called differential rate laws and
integrated rate laws. The following is a brief summary of topics regarding rate laws.
o rate laws: differential and integrated rate laws.
o Integrated
rate
laws:
First
Order
Reactions
Second Order Reactions
Rate laws apply to homogeneous reactions in which all reactants and products are in
one phase (solution).
4. Heterogeneous reactions: reactants are present in more than one phase
For heterogeneous reactions, the rates are affected by surface areas.
5. Catalysts:
substances
used
to
facilitate
reactions
By the nature of the term, catalysts play important roles in chemical reactions.
116
Design Calculations For Packed Bed Reactor (Quench Type)
1
50 % of feed
i.e ;
862.005Kmol/hr
at 230C &
50 atm
H2 =
CO =
CO2 =
N2 =
76.68%
13.78%
9.41%
0.13%
50 % of feed
i.e ;
862.005 Kmol/hr
at 75C
H2 =
CO =
CO2 =
N2 =
F= 1724.01Kkol/hr
= 16809.05 Kg/hr
P = 1473.863 Kmol/hr
CO
CH3OH
H2O
CO2
HCHO
N2
C2H5OH
H2
C3H7OH
C5H11OH
CH3OCH3
CH3COOH
76.68%
13.78%
9.41%
0.13%
0.120661
0.065684
0.027296
0.082785
0.003053
0.00152
0.003814
0.693739
0.000342
0.00057
0.000457
7.87E-05
117
Heat in at Point 1:Cp of H2
= 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3

= 0.766 * [ 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3 ]
= 22.11 + 5.87E-05 T + 2.52E-06 T2 - 6.67E-10 T3
Cp of CO
= 28.95 + 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3

= 0.138 * [ 28.95 + 4.11E-03 T + 3.55E-06 T2 - 2.22E-09T3
= 3.98 + 5.66E-04 T + 4.89E-07 T2 - 3.06E-10 T3
Cp of CO2
= 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3

= 0.094 * [ 36.11 + 4.23E-02 T - 2.89E-05 T2 +7.46E-09 T3
= 3.397 + 3.98E-03 T - 2.72E-06 T2 + 7.02E-10 T3
Cp of N2
= ( 29 + 2.20E-03 T + 5.72E-06 T2 - 2.87E-09 T3)

= 0.0013 * [ 29 + 2.20E-03 T+ 5.72E-06 T2 - 2.87E-09 T3)
= 0.037 + 2.86E-06 T + 7.44E-09 T2 - 3.73E-12 T3
= 29.53 + 4.61E-03 T + 3.01E-07 T2 - 2.74E-10 T3
Total
(2
230 oC
503 K
Reference Temperature = 25 oC = 298 K
Temperatures =
Qin
m1Cp dt
= 1724.01 * 0.5 *1000/3600 [ 2.95E+01 * 2.05E+02 + 4.61E-03 *

2.61E+04 + 3.01E-07 * 4050458 - 2.74E-10 * 699504844 ]
= 239.44 * 6.18E+03
= 1.48E+06
Watts
= 1.48E+03
KW
Heat of Reaction;CO
2H2
H =
H =
CO2
CH3OH
-90.77
-90770
3H2
H =
H =
KJ/g.mol
KJ/K.mol
CH3OH
-49.58
-49580
KJ/hr
KJ/K.mol
So,
X1
X2
X3
= 34.62
= 23.53
= 23.53
K.mol of CH3OH per hour

K.mol of H2O per hour
=
(1)
-3143060 - 2333499
-5476560 Kj/hr
+ H2O
(2)
Conversion = 30%

=
118
-1521.27 KW
Heat out by stream 3:Cp of H2
= 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3

= 0.69 * [ 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3]
= 19.98 + 5.30E-05 T + 2.28E-06 T2 - 6.03E-10 T3
Cp of CO = 28.95 + 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3

= 0.112 * [ 28.95 + 4.11E-03 T +3.55E-06 T2 - 2.22E-09 T3
= 3.26 + 4.64E-04 T + 4.00E-07 T2 - 2.50E-10 T3
Cp of CO2 = 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3
= 0.076 * [ 36.11 + 4.23E-02T - 2.89E-05 T2 +7.46E-09 T3
= 2.747 + 3.22E-03 T -2.20E-06 T2 + 5.68E-10 T3
Cp of N2
= ( 29 + 2.20E-03 T + 5.72E-06 T2 - 2.87E-09 T3)

= 0.0015 * [ 29 + 2.20E-03 T + 5.72E-06 T2 - 2.87E-09 T3)
= 0.0435 + 3.30E-06 T + 8.58E-09 T2 - 4.31E-12 T3
Cp of H2Og = 33.46 + 6.88E-03 T + 7.60E-06 T2 -3.59E-09 T3

= 0.031 * [33.46 + 6.88E-03 T + 7.60E-06 T2 -3.59E-09 T3 ]
= 1.057 + 2.17E-04 T + 2.40E-07 T2 - 1.14E-10 T3
Cp of CH3OH = ( 42.93 + 8.30E-02 T - 1.87E-05 T2 - 8.03E-09 T3 )
= 0.077*[ 42.93 + 8.30E-02 T -1.87E-05 T2 - 8.03E-09 T3 ]
= 3.344 + 6.47E-03 T - 1.46E-06 T2 - 6.26E-10 T3
Cp of HCHO
= ( 34.28 + 4.27E-02 T + 0 - 8.69E-09 T3 )

= 3.20E-03 * [ 34.28 + 4.27E-02 T + 0 - 8.69E-09 T3 )
= 1.10E-01 + 1.37E-04 T + 0.00E+00 - 2.78E-11 T3
Cp of C2H5OH = ( 61.34 + 1.57E-01 T - 8.75E-05 T2 + 1.98E-08 T3 )

= 3.80E-03*[ 61.34 + 1.57E-01 T- 8.75E-05 T2 +1.98E-08 T3 ]
= 2.33E-01 + 5.97E-04 T -3.32E-07 T2 + 7.54E-11 T3
Cp NET
Qout
= 3.08E+01 + 1.12E-02 T - 1.06E-06 T2 + 2.24E-10 T3
mCpnet dt
Range :-
25
290oC
= 745.526* 1000/3600 * [ 3.08E+01 *2.65E+02 + 1.12E-02 * 3.61E+04

- 1.06E-06 * 6555792 + 2.24E-10 * 5314019375 ]
= 207.0905556 * 8.55E+03
= 1.77E+06 Watts
= 1.77E+03 KW
Total Heat out:H
= Q in
- Q out
= -1.23E+03 KW
Q reacion
119
Now, this is the amount of heat which should b e removed to bring the stream # 3
, again at the reaction temperature of 230C.And it is achieved by quenching with the help of
stream # 2.Now it is required to find out the temperature at which stream #2 should be added .
Cp of H2 = 28.84 + 7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3
= 0.766 * [ 28.84 +7.65E-05 T + 3.29E-06 T2 - 8.70E-10 T3 ]
= 22.114 + 5.87E-05 T + 2.52E-06 T2 - 6.67E-10 T3
Cp of CO = 28.95 + 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3
= 0.137 * [ 28.95 + 4.11E-03 T + 3.55E-06 T2 - 2.22E-09 T3
= 3.98 + 5.66E-04 T + 4.89E-07 T2 - 3.06E-10 T3
Cp of CO2 = 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3
= 0.094 * [ 36.11 + 4.23E-02 T - 2.89E-05 T2 + 7.46E-09 T3
= 3.397 + 3.98E-03 T - 2.72E-06 T2 + 7.02E-10 T3
= ( 29 + 2.20E-03 T + 5.72E-06 T2 - 2.87E-09 T3 )
= 0.0013 * [ 29 + 2.20E-03 T + 5.72E-06 T2 - 2.87E-09 T3]
= 0.037 + 2.86E-06 T + 7.44E-09 T2 - 3.73E-12 T3
Cp of N2
= 29.53 + 4.61E-03 T + 3.01E-07 T2 - 2.74E-10 T3
Total
Temperatures =
75
348
Qin
290
563
C
k
mCp dt
= 862.005 *1000/3600 [ 2.95E+01 * -1.55E+02 + 4.61E-03 *

-2.36E+04 + 3.01E-07 * -3915042 + -2.74E-10 * -691692344 ]
= 239.4458 * -4.69E+03
= -1.12E+06 Watts
= -1.12E+03 KW
So if the feed stream #2 is added at temperature of 75 oC , then the reaction temperature of 230C is
again achieved .
Energy Balance Around 2nd Bed :Outlet stream from 1st bed plus feed stream #2 will be total feed for the 2nd bed.So,
Total amount of heat in Bed # 2:

Qin
=
=
Heat Of Reaction:-
mCp dt
2126 KW
CO =
CO2 =
13.39%
9.10%

CO
+ 2H2
H =
H =
CO2
CH3OH
-90.77
-90770
(1)
KJ/g.mol
KJ/K.mol
+ 3H2
H =
H =
120
CH3OH
-49.58
-49580
KJ/hr
KJ/K.mol
+ H2O
(2)
Conversion =
20%
So,
X1
X2
X3
= 23.08
= 15.68
= 15.68

K.mol of H2O per hour
=
=
=
-2095373
-3651040
-1014.18
+
Kj/hr
KW
-1555666
Heat Out By Stream 4:-
Cp of H2
= 28.84 + 7.65E-05 T + 3.29E-06 T - 8.70E-10 T

2
3
= 0.692 * [ 28.84 +
7.65E-05 T + 3.29E-06 T - 8.70E-10 T ]
2
3
= 19.98 + 5.30E-05 T + 2.28E-06 T - 6.03E-10 T
Cp of CO
= 28.95 + 4.11E-03 T + 3.55E-06 T - 2.22E-09 T

2
3
= 0.112 * [ 28.95 + 4.11E-03 T + 3.55E-06 T - 2.22E-09 T
2
3
= 3.265 + 4.64E-04 T + 4.00E-07 T - 2.50E-10 T
Cp of CO2
= 36.11+ 4.23E-02 T - 2.89E-05 T + 7.46E-09 T

2
3
= 0.0761 * [ 36.11 + 4.23E-02 T - 2.89E-05 T + 7.46E-09 T
2
3
= 2.747971 + 3.22E-03 T - 2.20E-06 T + 5.68E-10 T
Cp of N2
= ( 29 + 2.20E-03 T + 5.72E-06 T - 2.87E-09 T )

2
3
= 0.0015 * [ 29 + 2.20E-03 T + 5.72E-06 T - 2.87E-09 T )
2
3
= 0.0435 + 3.30E-06 T + 8.58E-09 T - 4.31E-12 T
Cp of H2Og
= 33.46 + 6.88E-03 T + 7.60E-06 T - 3.59E-09 T

2
3
= 0.0316 * [ 33.46 + 6.88E-03 T + 7.60E-06 T - 3.59E-09 T
2
3
= 1.057 + 2.17E-04 T + 2.40E-07 T 1.14E-10 T
Cp of CH3OH = ( 42.93 + 8.30E-02 T - 1.87E-05 T - 8.03E-09 T )

2
3
= 0.077 * [ 42.93 + 8.30E-02 T - 1.87E-05 T - 8.03E-09 T )
2
3
= 3.344 + 6.47E-03 T 1.46E-06 T - 6.26E-10 T
Cp of HCHO
= ( 34.28 + 4.27E-02 T + 0 - 8.69E-09 T )

3
= 3.20E-03 * [ 34.28 + 4.27E-02 T + 0 - 8.69E-09 T )
3
= 1.10E-01 + 1.37E-04 T + 0.00E+00 - 2.78E-11 T
2
Cp of C2H5OH = ( 61.34 + 1.57E-01 T - 8.75E-05 T + 1.98E-08 T )

2
3
= 3.80E-03 * [ 61.34 + 1.57E-01 T - 8.75E-05 T +1.98E-08 T )
2
3
= 2.33E-01 + 5.97E-04 T - 3.32E-07 T + 7.54E-11 T
Cp NET
= 3.08E+01 + 1.12E-02 T - 1.06E-06 T
+ 2.24E-10 T
Qout
mCpnet dt
=
=
=
=
= Qin
- Qout
121
o
Range :-25
to
290 C
728.33 * 1000/3600 [ 3.08E+01 * 2.65E+02 +1.12E-02 *
3.61E+04 - 1 .06E-06 *6555792 + 2.24E-10 * 5.31E+09 ]
202.3139 * 8.55E+03
1.73E+06 Watts
1.73E+03 KW
Qreacion
= -1.37E+03 KW
So Total Heat Out At Point 4 :-1.37 + -1.12 = -2.53E+03 KW
Reactor Design With Space Velocity:Type:Catalyst:

Catalyst size :
Bed Void Fraction
Bulke density ;
Packed Bed Reactor

Cu-Zn-Al
3 mm
0.5
1120 Kg/m3
Operating Conditions:Temperature = To = 230 o C = 503 K

Pressure
= P = 50 atm
Mass flow rate in = 16800.64 Kg/hr = 1732.025 K.mol/hr
Average Mol.wt =
9.7
Density =
Density =
PM/RT
11.30216 Kg/m3
R =
0.08205 m3*atm/k-mol*K
Now,
The compositions of the components entering into the reactor are:
molar flow rate
conc.(K.mol/m3)
H2
CO
CO2
N2
=
=
=
=
76%
13.50%
9%
1.50%
1316.33
233.82
155.88
25.98
k.mol/hr
k.mol/hr
k.mol/hr
k.mol/hr
Space Velocity = 250 hr-1

= 0.069 sec-1
Residence time = 14.4 sec
Now
Volumetric Flow Rate = q = Mass flow rate/density
0.885
0.157
0.104
0.017
122
= 1429.65 m3/hr
= 50481.0 ft3/hr
Volume of bed
= Vol. flow rate * residence time

= 201.92 ft3
= 5.71 m3
And finally,
Toal reactor volume
= Vol.of bed * (1+ void fraction)

= 403.84 ft3
= 11.43 m3
Diameter and Length of reactor:We assume,

L/D = 5
L = 5 *D
Volume = Area * Length
Area
= 0.785 D2
403.84 = 0.785 D2 * 5 * D
403.84 = 3.925 D3
D3
= 102.89 ft3
D
= 4.67 ft
radius = r = 2.339 ft
r2 = 5.47 ft2
L
= 23.39 ft
And
= 7.13 m
Extra length added for ceramic balls to support the catalyst & gap between the beds = 20%
So,
Total Length = 28.07 ft = 8.56 m
Area
= 0.785 * 21.88
= 17.18 ft2
= 1.59 m2
Total Volume = 1.59 * 8.56
= 13.67 m3
Weight of Catalyst
= Vol. of bed * bulk density of catalyst
Taking no of beds
So,
Catalyst per bed
=
=
226155.2 lb
2
113077.57 lbs
Wall thickness for cylendrical shell:t =

Working pressure
Design pressure
=
=
Pi*Di /(2fJ - Pi) + c

50
1.1
atm
* 50
123
= 55 atm = 5.57 N/mm2

Inside Dia (without wall thickness) = 4.68 ft
= 142.60 cm
= 1426.05 mm
Effiiciency of joint
= j =
0.85
Corrosion Allowance =
0.3 mm
Allowable Working stress =
107
N/mm2
=
1056.00 atm
So,
t =
45.07
+
0.3
=
45.37
mm
= 4.53
cm
=
0.148
ft
Weight of reactor
Weight of shell
= pi * dia * length * thickness * desnity
Density of Stainless steel 316 = 498 lb/ft3
= 25476.32 lbs
Weight of heads
= 2*[2*pi * r2 *thickness * density]

= 2547.6 * 2
= 5095.26 lbs
so,
wt of catalyst
= 226155.16 lb
Total weight =
256726.7
lbs
= 116693.97 Kg
Now,
Extra weight due to nozzles, amnholes , saddles etc.
For vertical position = 20% increase
So,
Actual total weight = 308072.09 lbs
= 140.03
tons
Calculation of Pressure Drop:

From Erguns Equation
P
L
G
1
gc Dp
150 1
Dp
1.75G
Where
mass velocity of feed = G = Mass flow rate / Cross sectional area
= 10520.20 kg/hr.m2 = 0.597 lb/ft2.sec
Partical diameter
= DP = 3 mm =
0.0098 ft
=
0.003 m
gc = 1.30E+07
m.Kgm/hr2.Kgf
= 9.81 lbm*ft/lbf*sec2
Avg, viscosity =
1.12E-05 lb/ft.sec = 0.060 kg/m.sec

Avg . Density =
=
124
11.751 Kg/m3
0.732 lb/ft3
So, after putting all the values in the formula, we get

Pressure drop = P = 70.61 lb/ft2
= 0.033 atm
= 0.490 psi
Design With Kinetics:

Now if the kinetics from the literature is available and in the following form,
-r co = k pco pH2 2
Order of Reaction = 3
Then first convert it into the concentration form by using the ideal gas relation and for the
gases variable volume factor is used, and final relation for the above equation takes the
shape like this,
r co =
kR3T3 Cco3[(1 - Xa)/(1 + Xa)*(M- 2Xa)2/(1 + Xa)2 * (To/T)
Where To / T is added to count for the temperature variations. More the value of K is also
given with the kinetics in the literature as such,
k =
7.60E-06 mol (kg cat.)-1 min-1 atm-3 at 230C
Ao = CO
Bo = H2
M = Bo/Ao = CH2/Cco
Now , the design equation for the packed bed is ,
C Ao
W
FAo
(From Octave Levenspiel. Page # 46)
XA
dX A
rA
0
Now putting the all values in the above equation and getting the area under the curve for
solving the complex equation. And finally the value of the wight of the catalyst is obtained and
further procedure is same as above mentioned.
125
Specification Sheet
Equipment no.
R-1
No. of Units
Carbon steel
Type
Catalytic fixed bed
Process
Adiabatic
Operation
Continuous
Catalyst Size
3mm
Catalyst porosity
0.5
Catalyst Type
Shape
Cu ZnO Al(60%-30%10%)
Cylindrical
Residence Time
0.033 hr
Space Velocity
30.3 hr-1
Conversion
50%
Fluid handled
Synthesis Gas
Operating Pressure
50 atm
Operating Temp.
230oC
Length
15.92 m
Shell Diameter
2.65 m
Thickness
6.9 cm
Volume
88.04 m3
Head thickness
6.9 cm Torispherical
126
Basic principle and objective

The primary job of the gas liquid separators is to separate vapor and liquid, but they
may also serve as liquid surge drums.
The basic design principle of a vapor liquid separator is to provide a sufficiently low gas
velocity so that liquid and vapor will separate.
The separation of the mixture is actually done due to the actions of gravity and
impaction and also on density basis.
Types of the vapor liquid separators

Knockout drums.
Vertical gas liquid separator.
Horizontal gas liquid separator.
Selection criteria
Length to diameter ratio.
Separator liquid surge characteristics.
Gas to liquid ratio.
Space limitations.
Types OF Mist Eliminator

The mist eliminators are of two types
Knitted wire mesh
Vane type mist eliminator
Vane Type Mist Eliminators

Vane eliminators consists of closely spaced
plates mist strikes on adjacent vane there
they held by surface force.
Mesh Eliminators
Mesh eliminators are made up of plastic or
stainless steel wire with diameter of 0.006-0.011
inch
Application of mist eliminators

Proper application of mist eliminator is based on understanding how they work. Vane and
mesh devices both employ the same mechanismknown as inertial impaction
127
128
Selection of mist eliminator

The efficiency of vane mist eliminators is generally acceptable only for droplets larger
than 10 or 20 microns.
A vane unit is generally more expensive than a mesh pad in the same application.
Separator design
Diagram of separator
Design considerations
Pressure = 50atm
Temperature=308.15 K
Mass flow rate of liquid,ML=7817.45 Kg/hr
Mass flow rate of vapor,MV = 8545.48 Kg/hr
Liquid Density, = 811.09 kg/m3
L
Vapor Density, V = 19.34 kg/m3

Volumetric flow rate of vapors = Qv =.122 m3/sec
Volumetric flow rate of liquid = QL = 0.0027 m3/sec
Step 1:
Vapor liquid separation factor:
The term used for the separation
factor is
(ML/ MV). (V / L)0.5 =0.142
From fig find K
= 0.27 ft/sec
= 0.082m/sec
Step 2:
Calculate the maximum
velocity for the system:
Vmax
0.50
= K [(L - V) / V]
0.50
= 0.082 [(811.09 19.34)/19.34 ]
= 0.524 m/sec
Step 3:
Minimum vessel cross-sectional area
Amin = QV/ Vmax
= 0.122 / 0.524
= 0.235 m2
Step 4:
Diameter of the vessel is calculated as
129
130
0.5
= [4 Amin / ]
= 0.547 m
D = Dmin + 0.1524
= 0.547 + 0.1524
= 0.7 m
Dmin
Step 5:
Liquid level
Assume residence time = 4min
Vessel volume,
V = QL ( residence time)
= 0.0027 60 4
= 0.643 m3/sec
LL = V 4/( D2)
= 1.51 m
Step 6:
The height of separator can be calculated by following formula
L = LL+ 1.5D + 0. 46
= 3.07 m
Step 7:
Calculate L/D ratio
L/D = 3.07 / .70
= 4.38
Specification sheet
Unit name
Liquid-gas separator
No. required
Stainless steel
Type of Mist Eliminator
Mesh Pad
Diameter
0.7m
Length
3.07m
Pressure
50 atm
Temperature
308.15K
Fluid handled
Liquid gas mixture
Liquid level
1.51 m
Holding Time
4 min
131
DISTILLATION
A process in which liquid and vapor mixture of two or more substances is separated into its
component fractions of desired purity, by the application and removal of heat.
Distillation is based on the fact that the vapor of a boiling
mixture will be richer in the components that have lower boiling
points.
Therefore, when this vapor is cooled and condensed, the
condensate will contain more volatile components. At the same
time, the original mixture will contain more of the less volatile
material.
All distillation involve two processes: vaporization followed by
condensation. In a distillation a liquid mixture is heated until it is
boiled, then the vapor above the boiling liquid is removed,
condensed and collected as a liquid distillate.
The molecules in a liquid are in constant motion and have a tendency to escape from the
liquids surface and enter the gaseous phase. The pressure exerted by these gaseous
molecules is called the vapor pressure of the liquid. The temperature at which the liquids
vapor pressure is equal to external pressure over the liquid is called the boiling point of a
liquid.
Separation of components from a liquid mixture via distillation depends on the differences in
boiling points of the individual components. also, depending upon the concentrations of the
components present; the liquid mixture will have different boiling point characteristics.
Therefore, distillation depends upon the vapor pressure of liquid mixtures. Distillation columns
are designed to achieve this separation efficiently.
Although many people have a fair idea what distillation means, the important aspects that
seem to be missed from the manufacturing point of view are that:Distillation is the most
common separation technique.It can contribute to more than 50% of plant operating costs. It
consumes enormous amounts of energy, both in terms of cooling and heating requirements.
132
The best way to reduce operating costs of existing units is to improve their efficiency and
operation via process optimization and control. To achieve this improvement, a thorough
understanding of distillation principles and how distillation systems are designed is essential.
TYPES OF DISTILLATION
Extractive distillation:Extractive distillation is defined as distillation in the presence of a miscible,
high boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the
other components in the mixture. Used for mixtures having a low value of relative volatility,
nearing unity. Mixtures having a low relative volatility can not be separated by simple
distillation because the volatility of both the components in the mixture is nearly the same
causing them to evaporate at nearly the same temperature to a similar extent, whereby
reducing the chances of separating either by condensation.
Flash Distillation
In the flash evaporation process is when the liquid is preheated and is then subjected to a
pressure below its vapor pressure causing boiling or flashing to occur. Sea water is first heated
in tubes and is then put in a chamber with a vapor pressure lower than in the heating tubes
and the liquid evaporates. The vapors flash off the warm liquid and the salts exit with the
remaining water. The process seems inefficient because the evaporation of a small amount
causes the temperature to drop dramatically. For example, when only 7.1% of the liquid is
evaporated off, the temperature drops 40 degrees, from 100 to 60 degrees Celcius. However,
since the design is so simple, it has become a close competitor to multiple-effect evaporation
economically. This is true especially in larger plants.
Steam distillation:Steam distillation is a special type of distillation (a separation process) for

temperature sensitive materials like natural aromatic compounds.
Steam distillation is employed in the manufacture of etherial oils for, for instance, perfumes. In
this method steam is guided over the plant material containing the desired oils. It is also
employed in the synthetic procedures of complex organic compounds.
Vacuum distillation:Vacuum distillation is a method of distillation whereby the pressure

above the solution to be distilled is reduced to less than one Atmosphere (unit) causing
evaporation of the most volatile liquid(s) (those with the lowest boiling points.) Vacuum
distillation is used with or without heating the solution; some distillation processes use both
vacuum and thermal action.
Vacuum distillation works on the principle that boiling occurs when the vapor pressure of a
liquid exceeds the ambient pressure (atmospheric pressure above it or pressure in the
133
distillation apparatus.) In standard thermal distillation, the vapor pressure is increased. In

vacuum distillation, the ambient pressure is decreased.
Azeotropic distillation:Azeotropic distillation is any of a range of techniques used to

break an azeotrope in distillation. A common distillation with an azeotrope is the distillation of
ethanol and water. Using normal distillation techniques, ethanol can only be purified to
approximately 95% (hence the 95% (190 proof) strength of some commercially available grain
alcohols).
PLATE/TRAY TYPE COLUMNS :To optimize the mass transfer between vapor and liquid in thermal
separations, various types of plates are used. Usually, trays are
horizontal, flat, perforated to offer vapor passages, specially
prefabricated metal circular sheets, which are placed at a regular
in a vertical cylindrical column. On these elements, the reflux liquid
and encounters the vapor which must pass through it.
distance
circulates
Trays have two main parts:

1) The part where vapor (gas) and liquid are being contacted; the
contacting area. And
2) The part where vapor and liquid are separated, after having been contacted; the down
comer
area.
TRAY DEVICES:In the design of the distillation column, the most important step is estimation of number of
134
stages (plates) or trays.
CLASSIFICATION OF TRAYS:Classification of trays is based on:
Type of plate used in the contacting area

Type and number of down comers making up the down comer area
Direction and path of the liquid flowing across the contacting area of the tray
Vapor (gas) flow direction through the (orifices in) the plate
Presence of baffles, packing or other additions to the contacting area to improve the
separation performance of the tray.
Selection Criteria of any tray:The principal factors to consider when comparing performance of three types of plate i.e.,
sieve plate, valve tray, bubble-cap tray are as follows:-
Cost:Cost of plate depends upon material of construction used. For mild steel, the ratio of cost
between plates is
Sieve plate
3
valve plate
1.5
bubble-cap plate
:
1.0 .
Capacity:There is little difference in the capacity rating of the three types (the diameter
of the column required for a given flow rate).The ranking is
Sieve tray
>
valve tray
>
bubble-cap tray
Operating Range:Operating range means the range of vapor and liquid rates over which
the plate will operate satisfactorily. Bubble-cap plates have a positive seal for liquid and so
operate at very low vapor flow rates. Sieve trays rely on the vapor flow rate through holes to
hold the liquid on the plate. And cannot operate at very low vapor rates. But with good design,
it will give satisfactorily results.
Pressure drop:It is an important parameter for plate design, particularly for vacuum
process. It depends upon the plate design.On the basis of pressure drop the ranking is
Bubble-cap tray >
valve tray
>
135
sieve tray
. Type Of Plates Used In The Contacting Area:There are mainly three types of trays.
1. Sieve Trays.
2. Valve Trays.
3. Bubble Cap Trays.
Sieve Trays :-( Perforated Trays):Advantages:They are simple to design.

These trays are very cheap.
Sieve trays give lower pressure drop.
It gives high efficiency.
They give us efficient mass transfer.
Disadvantages:When misoperation occurs, mass transfer

ceases.
Due to misoperation, efficiency drops because of weeping.
Misoperations are foaming and forth formation depending upon the nature of liquid.
It is also sometimes unacceptable for low liquid loads when weeping has to be
minimized.
Valve Trays:Advantages:Although slightly more expensive than Sieve Trays.

They can operate over a wide range of pressure.
It gives low pressure drop.
Valve trays may be uses for a wide range of flow
rates.
Because of their flexibility and price, they are
replacing bubble cap trays.
It can operate at large capacities.
Their cost is less than bubble cap trays.
In this, entrainment and weeping are controllable.
136
Disadvantages:It pressure drop is greater than sieve tray.

Their cost is 20% higher than sieve plates.
Bubble Caps:Advantages:It is widely used due to its performance.

Entrainment is controlled here.
They are capable of dealing with very low liquid
rates.
Weeping is also controlled in bubble cap trays.
They are useful for operation at low reflux.
They are required to provide maximum tray
flexibility.
Disadvantages:Bubble Caps are a relatively high cost than both sieve and valve trays.
Capacity of bubble cap trays is also lower than both sieve and valve trays.
It gives high pressure drop.
They cause problems in large columns.
Their construction is very complicated.
BASIC DISTILLATION EQUIPMENT AND OPERATION

Main Components of Distillation Columns
Distillation columns are made up of several components, each of which is used either to
transfer heat energy or enhance material transfer. A typical distillation contains Column
internals such as trays/plates and/or packings which are used to enhance component
separations everal major components
a vertical shell where the separation of liquid components is carried out
a reboiler to provide the necessary vaporisation for the distillation process
a condenser to cool and condense the vapour leaving the top of the column
a reflux drum to hold the condensed vapour from the top of the column so that liquid
(reflux) can be recycled back to the column
137
The vertical shell houses the column

internals and together with the
condenser and reboiler, constitute a
distillation column. A schematic of a
typical distillation unit with a single
feed and two product streams is
shown below:
Basic Operation and Terminology
The
liquid
mixture that is to be processed is known as the feed and this is introduced usually somewhere
near the middle of the column to a tray known as the feed tray. The feed tray divides the
column into a top (enriching or rectification) section and a bottom (stripping) section. The feed
flows down the column where it is collected at the bottom in the reboiler. Thus, there are
internal flows of vapour and liquid within the column as well as external flows of feeds and
product streams, into and out of the column. The vapour moves up the column, and as it exits
the top of the unit, it is cooled by a condenser. The condensed liquid is stored in a holding
vessel known as the reflux drum. Some of this liquid is recycled back to the top of the column
and this is called the reflux. The condensed liquid that is removed from the system is known as
the distillate or top product.
Heat is supplied to the reboiler to generate vapour. The source of heat input can be any
suitable fluid, although in most chemical plants this is normally steam. In refineries, the heating
source may be the output streams of other columns. The vapour raised in the reboiler is reintroduced into the unit at the bottom of the column. The liquid removed from the reboiler is
known as the bottoms product or simply, bottoms..
Packings
Packings are passive devices that are designed to increase the interfacial area for vapourliquid contact. The following pictures show 3 different types of packings
138
These strangely shaped pieces are supposed to impart good vapour-liquid contact when a
particular type is placed together in numbers, without causing excessive pressure-drop across
a packed section. This is important because a high pressure drop would mean that more
energy is required to drive the vapour up the distillation column.
Packings versus Trays

A tray column that is facing throughput problems may be de-bottlenecked by replacing a
section of trays with packings. This is because:
packings provide extra inter-facial area for liquid-vapour contact
efficiency of separation is increased for the same column height
packed columns are shorter than trayed columns
Packed columns are called continuous-contact columns while trayed columns are called
staged-contact columns because of the manner in which vapour and liquid are
contacted.
DISTILLATION COLUMN DESIGN

Feed
Components wt%
CH3OH
H2O
7722.917 Kg/hr
Kg/hr
6240.6
1404.02
Mol. Wt.
32
18
274.36 K.mole/hr
K.mole
195.02
78
Mole%
71.08
28.60
About (71.08 + 28.43 = 99.51%) of the feed consists of methanol and water. Thus binary
distillation can be assumed.
Distillate = 6238 Kg/hr = 195.53 K.mole/hr
Component
wt%
CH3OH
H2O
Kg/hr
Mol. Wt.
K.mole
Mole%
6228.18
9
32
18
194.63
0.5
99.65
0.348
139
Waste = 1484.68 Kg/hr = 78.84 K.mole

Component
wt%
H2O
CH3COOH
Kg/hr
Mol. Wt
K.mole
Mole%
1395.166
23.1526
18
60
77.51
0.3858
98.31
0.49
We get
Xf = 0.71
Xd = 0.9974
Xw = 0.005
From Unit Operation by McCabe &Smith (page # 583)
Equilibrium Data for Methanol Water is given as follows:
X
Y
0.1
0.2
0.3
0.4
0.5
0.417 0.579 0.669 0.729 0.78
0.6
0.7
0.8
0.9
1.0
0.825 0.871 0.915 0.9591 1.0
Where
X = Mole fraction of M.V.C in Liquid phase
Y = Mole fraction of M.V.C in Vapor phase
Now after drawing equilibrium curve
Xd - Yf
Yf - Xf
Minimum Reflux Ratio = Rm =
= (0.9974 0.874)/(0.874 0.7)
= 0.75244
Reflux Ratio = R = 1.5* Rm
= 1.5 * 0.75244
=1.13
The Points Of Top Operating Line:(0 , Xd/(R+1))
(0 , 0.486)
; (Xd , Xd)
; (0.9974 , 0.9974)
The Bottom Operating Line Points :-
(Xw , Xw)
(0 , 0)
This point joins where the top operating line cut the feed line
140
From Graph
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
q. l i ne
T op Oper at i ong Li ne
x=y
B ot t om Oper at i ng Li ne
0.2
0.4
0.6
0.8
The ideal number of plates / stages = 11
Efficiency And Total Number Of Real Stages

From PETER and TIMMERHAUS (page # 665)
Eo = 17 61.1 Log f, avg
Where
Eo = Overall column efficiency percent.
Average temperature of column = 87.5 oC = 189.5 oF
Viscosity of Methanol
0.257 cp
Viscosity of Water
0.325 cp
=
=
(0.7108 * 0.257)
0.257 cp
Now
Eo
=
=
17 61.1 Log (0.257)

55.25 %
Actual number of trays in column = 11 / 0.5525

= 20
(0.2843 * 0.325)
141
Feed should be entered on plate # 7

Maximum vapor flow rate in rectifying section = Vn = 416.46 kg mole/hr
Maximum liquid flow rate in rectifying section = Ln = 220.7 kg mole/hr
Maximum vapor flow rate in stripping section = Vm = 416.47 kg mole/hr
Maximum liquid flow rate in stripping section = Lm = 495.31 kg mole/hr
Plate spacing initial estimate = 0.5m = 18in
Calculation of column diameter based on flooding velocity
Calculate FLV = liquid vapor flow factor
FW
LW
VW
V
L
LW = liquid mass flow rate kg/s

VW = vapor mass flow rate, kg/s
FWTop
220.7 1.15
416.46 750
= 0.022
FLV Bottom
495.31 .5
416.47 962
= 0.04
From figure 11.27 Coulson and Richardson vol.6

t1 = a constant obtained from fig 11.27
K1 Top = 0.08
K1 Bottom = 0.085
Flooding Velocity:
Uf = flooding velocity
0.2
Uf
K1
V
V
20
U f bottom
0.085
142
0.2
962 0.5 58
0.5
20
= 4.3 m/s
U f Top
750 1.15 19
0.08
1.15
20
0.2
= 2.17 m/s
Based on 85% flooding velocity
Superficial Vapor Velocity
Maximum volumetric Flow rate
U base
4.3 0.85 3.5 7 m/s
U v,top
2.17 0.85 1.9 m/s
V/
Top
3.21 m3/sec
Bottom
6.5 m3/sec
Net Area Required

Maximum volume metric flow rate / superficial velocity
Top
3.21/1.9
Bottom
6.5/3.57
1.6m2
= 1.8 m2
As first trial take down comer area as 12% of the total.

Column cross sectional area
Base
1.8/0.88
2.01 m2
Top
1.6/0.88
1.8 m2
Column Diameter
Diameter = (4 Area / )
Area =
d2
1.81 4
Top
2.01 4
,
Bottom

= 1.5 m
143
= 1.60 m
From fig.11.28 Coulson Volume no.6
Our required flow pattern is single pass

Provisional Plate Design
Column diameter (base)
Column Area Ac
1.6 m
Ac
d2
2.01 m2
0.12 2.01
Downcomer area Ad
Net area An
Active area Aa
Hole area Ah take 10% Aa
0.23 m2
Ac Ad
2.01 0.23
1.78 m2
Ac 2Ad
2.01 2(0.23)
1.55m2
0.1 1.55 = 0.155 m2
Weir length
Ad / Ac = 0.23 / 2.01 = 0.12
(From figure 11.31 vol.6)
lw / dc
lw
0.76
1.6
lw
0.76
1.22 m
Take weir height , hw
50 mm
Hole diameter, dh
5 mm
Plate thickness
5 mm
144
Check Weeping
Lm
Maximum liquid rate
Minimum liquid rate at 70% turn down
495.31 18 / 3600 = 2.48 kg/sec

0.7 2.48
= 1.74s kg/sec
how
= weir crust
Maximum how
2.48
750
962 1.22
2/3
= 12.45 mm liquid
Minimum how
750
1.74
962 1.22
2/3
= 9.8 mm liquid
At minimum hw + how = 50 + 9.8
= 59.8 mm liquid
From fig 11.30, Coulson and Richardson Vol.6
K2 = 30.4
U min
K2
U min
30.4 0.9 25.4 5

1/ 2
0.5
0.9 25.4 d h
v
1/ 2
= 14.2 m/s
Actual minimum vapour velocity
min. vapour rate

Ah
0.70 6.5
0.155
= 28.1 m/s
So minimum vapor rate will be well above the weep point.
145
Plate Pressure Drop

Dry Plate Drop
Max. Vapour velocity through holes
U h = Volumetric Flow Rate / Hole Area

6.5
0.155
U h
38m / s
Fom fig. 11.43

for plate thickness/hole dia = 5/5 = 1
and
Ah
Ap
Co
Ah
Aa
.155
1.55
0.1
= 0.84
From Eq.11.88 Coulson vol.6
U
51 h
Co
hd
hd
38
51
0.84
2
V
L
0.5
= 40.2 mm liquid
962
Residual Head
hr
12.5 10 3
962
12.9mm liquid mm liquid
Total Pressure Drop

ht = hd + (hw + how) + hr
Total pressure drop = 40.2+ (50 + 12.45) + 12.9
ht = 115.55 mm liquid
146
Down comer Liquid Backup

Take hap = hw 10 = 40 mm
Area under apron Aap 1.22 40 10
= 0.0488 m2
As this is less than Ad use Aap in eq. 11.92 coulson vol.6 i.e,
2
hdc
hdc
166
l wd
L Aap
2.48
166
962 0.0488
= 0.463 mm liq.
Backup in down comer

hb
= (hw + how) + ht + hdc
hb
=(50 + 12.45) + 155.55 + 0.463

= 218.46 mm liq. = 0.218 m liq.
hb < (Tray spacing + weir height)

0.218<1/2(0.5+0.05)
So tray spacing is acceptable
Check Residence Time

tr
tr
Ad
hbc L
Lwd
0.23 0.218 962

2.48
= 12.8 sec
> 3 sec. so, result is satisfactory
Check Entrainment
Uv
= Maximum Volumetric Flow Rate of vapors/Net Area
147
UV
6.5/ 1.78
3.42 m/s
Percent flooding
3.42/4.3
0.795 = 79.5 %
FLV(base) = 0.04
From fig. 11.29 coulson vol.6
Fractional Entrainment
= 0.076 well below 0.1 Satisfactory
Trial Lay Out

Use cartridge type construction. Allow 50 mm imperforated strip round plate edge; 50 mm wide
calming zone.
From fig. 11.32
Lw/Dc =
0.76
99o
Angle subtended at plate edge by imperforated strip = 180 99 = 81o

Mean length, imperforated edge strip:
tr
1.175 50 10
81
180
50 10
1.175 50 10
Area of imperforated edge strip Ap/

Mean length of calming zone
Area of calming zone Acal
1.59
2 0.83 50 10
1.59)
sin
99
2
0.0168m2
0.83m
0.080m2
Total area of perforations, Ap = Aa Ap/ - Acal = 0.859 0.016 0.080 =0.763 m2

Ah
Ap
0.0859
0.763
0.112
From fig. 11.33 Coulson vol.6

lp/dh = 2.7
Satisfactory within 2.5 - 4.0
No of Holes
Area of one hole
1.964 10
Number of Holes = Hole Area / Area of one hole
No. of holes
0.155
1.964 10
= 6620
Specification Sheet
Equipment
Distillation column
Operation
Continuous
Function
Final production of Methanol
No.of Trays
20
Efficiency
55.25%
1.13
Top Diameter
1.5 m
Bottom Dia.
1.6 m
Height
10.06 m
No. of Holes
6620
Superficial velocity =
80% of Flooding velocity
No weeping
Fractional entrainment =
0.076
Pressure Drop
115.55 mm liquid
Tray Thickness
5mm
Weir Height
50 mm
Weir Length
1.2 m
Tray Spacing
1.5ft
Area of one Hole =

Total Hole Area
0.0000196 m2
= 0.115 m2
Down Comer Area = 0.23 m2
148
149
150
Compressor Selection
A compressor selection study shall be made in the conceptual engineering phase i.e. by use of
computerised selection programs and data bases. The results from the preliminary selection
may include some or all of the following variables:
Number and types of compressor casings.
Number of impellers in each casing.
Rotational speeds.
Type of seals.
Frame size.
Performance data.
Rating and operating conditions.
Rotor stability.
Rotor dynamic and aerodynamic behaviour.
Sparing alternatives.
Re-wheeling strategy.
Advanced seals and bearings.
Type of base plate.
Weight & space requirements.
Normally we use centrifugal or reciprocating compressor in our refrigeration
process. For high pressure requirement we usually use reciprocating compressors and for low
pressure requirement we prefer centrifugal compressor. Over reciprocating compressor due to
its some advantages
We selected centrifugal compressor because here we need a low pressure for
saturation of our refrigerant. The Centrifugal Compressor forRefrigeration system was
designed and developed by Dr. Willis H.Carrier in 1922.this compressor increases the
pressure of low pressure vapor refrigerant to a high pressure by centrifugal force.
Hermetic sealed compressors:When the compressor and motor operate on the same shaft and are enclosed in
a common casing, they are known as HERMETIC SEALED COMPRESSORS.
The advantages of the hermetic sealed compressors are:
The leakage of refrigerant is completely prevented
It is less noisy
It requires small space because of compactness
The lubrication is simple as the motor and compressor operate in a sealed space with
lubricating oil.
Advantages of Centrifugal Compressor over Reciprocating Compressor
151
Since the centrifugal compressors have no valves, cylinders, connecting rod etc
therefore the working life of these compressors is more as compared to reciprocating
compressors.
These compressors operate with little or no vibrations as there are no unbalanced
masses.
The operation of centrifugal compressor is quiet and clean
The centrifugal compressor run at high speeds (3000 r.p.m), therefore these can be
directly connected to electric motors or steam turbines
Because of high speed, these compressors can handle large volumes of vapors
refrigerants, as compared to reciprocating compressors.
The centrifugal compressors are especially adapted for systems ranging from 50 to
5000 tones. They are also used for temperature range between -900 C and 100C
The efficiency of these compressors is considerably high.
Compresor Selection:Inlet pressure P1 =

=
=
=
=
=
1.6
Mpa
232.12 psi
15.79 atm
33425.9 lb/ft2
246.82 psia
35542.7 lb/ft2
Outlet Pressure = P2 = 5.065 Mpa

=
734.81 psi
=
49.98766 atm
=
105813.8 lb/ft2
=
749.51
psia
=
107930.6 lb/ft2
Compression ratio = P2 / P1
= 3.03
From Plant Design & Economics For Chemical Engineering
By Timmerhous K.D , page # 524, 4th edition,
If P2/P1 > 5 ,then there can be multistage compressor, but in our case it is 3.03
which < 5, so
Single stage compressor
Avg.Mol.wt of gases =
R
Inlet Temp. T
Density = PM/RT
9.7 gm/gmol
= 0.00008206 m3.atm/gmol.K
= 35o C
= 308 K
= 6.060 Kg/m3
152
Now,
Molar flow rate of gases
= 904.964 kmol/hr
= 8778.15 kg/hr
Volumetric flow rate
= 1448.47 m3/hr
= 851.88 ft3/min
So,
From Compressor selection Diagram , Coulson vol-6,page # 432,

Selected Compressor:
Centrifugal Compressor
Power Calculations:
From Timmerhous Page # 524,edition # 4th
Single Stage Compressor Eq.
hp =
3.03*E-5 K * P1 * qfm1 * [(P2/P1)(K-1)/K - 1]/(K - 1)
where,
hp
= Horse power requirement, ft-lbf/lnm
P1
= Intake pressure ,lbf/ft2
P2
= Final delivery pressure, lbf/ft2
qfm1 = Cubic feet of gas per minute at intake conditions
Ratio of specific heat at constant pressure to constant volume K
= Cp / Cv
(Average value since for gases the value of lies between 1.2-1.4)
So,
Hp
= 1.09 E+03
Efficiency = 70%
So,
Hp
=
=
=
1.56E+03
1.16E+06 watts
1.16E+03 Kw
Specification Sheet:
Type
Centrifugal Compressor
Feed flow rate
8778.15
Inlet Pressure
33425.90 lbf/ft2
Outlet Pressure
105813.8 lbf/ft2
Compression Ratio
3.036
Material
construction
Power
Kg/hr
of Carbon steel
1.56E+03 hp
153
Fan Selection
Flow rate of air
Density of air at 35C
=
=
qA = 22219.77 lb/nr
0.0716 lb/ft3
So,
Volumetric Flow rate of air = 310332 ft3/hr
=
5172.2 ft3/min
Discharge pressure
=
14.7 psig
=
29.4 psia
The head
=
29564.25 ft-lbf / lbm
Now,
Hp
=
1.57E-04 Q * p
From Perry 6-21 , 5th edition
Where,
Q =
Fan volumetric discharge, ft3/min
p =
Fan operating pressure,inches of water column
Convert the pressure units into inches of water column,
So,
p =
407.16 in.of water
Finally,
Hp =
3.31E+02
The operating efficiencies of fans range from 40-70%
Form Perry, 6-21
We select the efficiency i.e; 70%
Therefore,
hp =
4.72E+02
Specification Sheet:
Type
Fan Volume
Temperature of air
Fan Operating Pressure
Head
Power required
Centrifugal Axial Flow

5172.2 ft3/min
35 oC
407.16 in.of H2O
29564.25 ft-lbf/lbm
4.72E+02 hp
154
Introduction
A condenser is a two-phase flow heat exchanger in which heat is generated from the
conversion of vapor into liquid (condensation) and the heat generated is removed from the
system by a coolant. Condensers may be classified into two main types: those in which the
coolant and condensate stream are separated by a solid surface, usually a tube wall, and
those in which the coolant and condensing vapor are brought into direct contact.
The direct contact type of condenser may consist of a vapor which is bubbled into a pool of
liquid, a liquid which is sprayed into a vapor, or a packed-column in which the liquid flows
downwards as a film over a packing material against the upward flow of vapor. Condensers in
which the streams are separated may be subdivided into three main types: air-cooled, shelland-tube, and plate. In the air-cooled type, condensation occurs inside tubes with cooling
provided by air blown or sucked across the tubes. Fins with large surface areas are usually
provided on the airside to compensate for the low airside heat transfer coefficients. In shelland-tube condensers, the condensation may occur inside or outside the tubes. The orientation
of the unit may be vertical or horizontal. In the refrigeration and air-conditioning industry,
various types of two-phase flow heat exchangers are used. They are classified according to
whether they are coils or shell-and-tube heat exchangers. Evaporator and condenser coils are
used when the second fluid is air because of the low heat transfer coefficient on the air side.
In the following sections, the basic types of condensers are shown:
Types of Condensers
Tubular condensers
Plate-type Condensers
Air-Cooled Condensers
Direct Contact Condensers
Selection of condenser
One of the more important actions taken by the design engineer in arriving at a
satisfactory solution for a specific heat exchange is the careful selection of the
condenser type that should be used. In the chemical industry the preferred choice in
the past has been the tubular condensers for which there are well-established codes
and standards prepared by TEMA (Tubular Exchanger Manufacturers Association) and
ASME (American Society for Mechanical Engineers). However, to attain higher thermal
efficiencies while minimizing capital costs, the use of other types of condensers has
received considerable attention in both the chemical industry and other manufacturing
industries.
155
The selection process normally includes a number of factors, all of which are related to the
heat-transfer application. These factors include, but are not limited to, the following items:
1. Thermal and hydraulic requirements
2. Material compatibility
3. Operational maintenance
4. Environmental, health, and safety considerations and regulations
5. Availability
6. Cost
Condensers desired properties

Any condenser selected must be able to provide a specified heat transfer, often
between a fixed inlet and outlet temperature, while maintaining a pressure drop
across the exchanger that is within the allowable limits dictated by process
requirements or economics.
The exchanger should be able to withstand the stresses due to fluid pressure
and temperature differences.
The material or materials selected for the exchanger must be able to provide
protection against excessive corrosion.
The propensity for fouling in the exchanger must be evaluated to assess the
requirements for periodic cleaning.
The exchanger must meet all the safety codes.
Potential toxicity levels from all fluids must be assessed, and appropriate types of
condenser selected to eliminate or minimize the human and environmental
effects in the event, of an accidental leak or failure of the exchanger.
Finally, to meet construction time constraints and project cost controls, the
design engineer may have to select a heat exchanger based on a standard
design used by the fabricator to maintain timeliness and reduce costs.
Note that heat exchangers often do not operate at the conditions for which they
were designed. For example, if fouling allowances are included in the design, the heat
exchanger will be over-designed initially and under-designed prior to shutdown for
periodic cleaning. As a consequence, the outlet conditions from the exchanger will vary,
with possible downstream effects.
156
Four Condenser Configuration are Possible

1)
2)
3)
4)
Horizontal with condensation is shell side and cooling medium in the tubes.
Horizontal with condensation in tube side cooling medium in shell side.
Vertical with condensation in the shell.
Vertical with condensation in the tubes.
Horizontal shell side and vertical tube side are the most commonly used types of condensers.
In this process we have used the normal mechanism for heat transfer in commercial
condenser, which film wise condensation. Since vapor-liquid heat transfer changes usually
occur at constant or really constant pressure in industry, the vaporization or condensation of a
single compared normally occurs isothermally. If a mixture of vapors instead of a pure vapor is
condensed at constant pressure, the change does not take place isothermally in most
instances.
Fixed tube type condenser

Fixed tube type condenser is probably used more often than any other type. The construction
is simple and economical. The inside of the tubes can be cleaned mechanically or chemically,
while the outside of the tubes requires chemical cleaning. An expansion bellows is often used
to accommodate excessive stresses caused by thermal expansion
DESIGN CALCULATIONS OF CONDENSER

Mass flow rate of the process stream (Methanol) = m = 28268.17 lb/hr
Condensation takes place at
Temperature = 1490F
Pressure
= 1atm
Latent heat of vaporization = 488 Btu/lb
Heat Load
Qc = m
= 28268.17 488

= 13794866.96 Btu/hr
Water Flow rate

Use 25oF rise in temperature of water
Qc
C p t
13794866.96
1 25
= 551794.68 lb/hr
=
551794.68
= 1104.03gpm
8.33 60
1104.03
ft3/sec =
= 2.46 ft3/sec
7.48 (60)
g.p.m =
LMTD = 50 oF
Water Flow Area

Set minimum water tube velocity = 5.5 ft/sec
Then,
Total tube Cross-section flow area = 2.46/5.5 = 0.4473 ft2
No of Tubes
Use 1 -inch 16 BWG tube
Tube flow area = 0.985 / 144= 0.00684 ft2/tube
No of Tubes = 0.4473 / 0.00684 = 65 tubes per pass
Value of UD Assumed
UD =140 Btu/hr.ft2 oF
Heat Transfer Area

A
13794866.96
50 140
= 1970 ft2
Tube Length Required:Out side area / tube = 0.3271 ft2/ft

Total tube Footage = 1970 / 0.3271 = 6025 ft
Tube length =16 ft
157
6025
65 16
=5.8 use six pass
No. of tubes= 390
No. of passes =
Shall Diameter
Use 39-inch I.D shell with 6 tube pass with 390 tubes total,
16 ft long on 1 9/16 -inch triangular pitch.
Trial area = 390 0.3271 16
= 2041 ft2
Flow Area
Flow area per pass= 65 .00684 = 0.4446 ft2/pass
Baffle spacing = B = 39 in
Tube pitch = 1.5625 in
Clearance = 0.3125 in
Water Velocity
Water velocity in tubes = 2.46/0.4446 = 5.53 fps/pass
Shell Side Calculations

Flow Area
ID C B
144Pr
as
as
39 0.3125 39
144 1.5625
= 2.1125 ft2
Mass Velocity
Gs
Gs
m
as
28268.17
2.1125
= 13381.4 lb/hr ft2
Condensing Loading
158

m
LN1/3
t
28268.17
2/3
15.5 390
= 34.16 lb/hr
Physical Properties
Thermal conductivity kf = 0.11 Btu/hr-ft-oF
Specific gravity sf = 0.76 lb/hr-ft
Viscosity f = 0.33 cp
Value of film coefficient

From Figure (literature)
ho = 260 Btu/hr-ft2-oF
Tube Side Calculations for Film Coefficient

Mean water Temperature = 97.5 oF
Velocity in tubes = 5.53 fps
From graph (literature) value of hi = 1260 Btu/hr-ft2-oF
Correction factor for 1 -inch tube Fw = 0.87
Correction to outside of tube:
hio = hi
I.D
Fw
O.D
hio = 1260
1.12
0.87= 980 Btu/ hr-ft2-oF
1.25
Overall heat transfer coefficient

1
1
1
ro rio
U D ho
hio
Put values
1
1
1
0.001 0.001
U 260
980
UD = 145.68 Btu/ hr-ft2-oF
Area Required
Qc
T UD
13794866.96
= 1877.25 ft2
A
145.68 50.47
159
160
Overall Clean Coefficient
h ioh o
h io h o
UC
UC
260 980
260 980
= 205 Btu/hr-ft2 oF
Dirt Factor
Rd
Rd
UC U D
UCUD
205 145.45
= 0.002 hr-ft2-oF / Btu
145.45 205
Pressure Drop (Shell Side)

Reynolds No.
= 0.011 2.42
= 0.0266 lb/ft hr
De = 0.07584 ft
Res = DeGs/
= 0.07584 13381.4 /0.0266 = 3.8
For Res = 3.8 104
Friction factor for shell side f = 0.0016
No. of crosses, N + 1 = 5
Specific gravity = Sv = 0.001173
Shell I.D = 39/12 = 3.25 ft
Kern fig 15
vap
Pressure Drop
Ps
fG s2 D s N
2 5.22 1010 D e s
2
0.0016 13381.4
3.25 5
=
5.22 1010 0.07584 0.0011733 2
= 0.7 psi
Pressure Drop (Tube Side)

Tube flow area = 0.985 in2
aL =
390 0.985
144 6
= 0.4446 ft2
Kern fig 28
104
Kern fig 29

Gt = w/aL
= 551794.68/.4446
= 1241103.64 lb/hr ft2
= 0.72 2.42
=1.74 lb/hr ft2
Ret =
1.12 1241103.64
=6.66 104
12 1.74
From fig 26 (Kern)

f = 0.00013
Pt
fG 2t Ln
5.22 1010 D s
0.00013 (1241103.64)2 16 6
Pt
5.22 1010 0.0933 1 1
=3.95psi
End return loss from graph 27 (kern)

V2/2g =.21
Pr = (94n/s)(V2/2g)
Pr
= 5.04 psi
Total Pressure, Tube side
PT
Pt
Pr = 5.04+3.95 = 9 psi
SPECIFICATION SHEET
Identification Item: condenser
No. Required = 1
Function: Condense vapors of methanol by removing the latent heat of
vaporization
Operation: Continuous
Type: 1-6 Horizontal Condenser
Shell side condensation
Heat Duty = 13794866.96 Btu/hr
Material of construction= carbon steal
161

Tube Side:
Tubes OD: 1.25 in2, 16 BWG
Fluid handled cold water
390 tubes each 16 ft long
6 passes
Pressure = 14.7 lbf/in2
1 9/16 triangular pitch
Temperature = 85oF to 110oF
Pressure drop = 9.54psi
Shell Side:
Shell ID =39 in2 1 passes
Fluid handled: Methanol
Baffles spacing = 39 in2.
Flow rate = 28268.17 lb /hr

Pressure = 14.7 psi
Temperature = 149oF
Pressure drop = 0.7 psi

25% cutoff segmented baffle
Utilities: Cold water

Ud assumed = 140 Btu/hr.ft2.0F
Ud calculated = 145.68 Btu/hr.ft2.0F
Uc calculated = 205 Btu/hr.ft2.0F
Allowed dirt factor = Rd = 0.002
162
163
164
MECHANICAL DESIGN:
1
SHELL THICKNESS:
ts =
P*D
2 fJ P
Where,
ts = Shell thickness =?
P = Design Pressure = 1.76 N/mm2
Di = Inner diameter of shell = 0.70m = 695.12mm
Permissible strength for carbon steel = 95 N/mm2
J = Joint factor = 85%
ts = [1.76 x 695.12/ (2 x 95 x .85 1.76)]
= 1223.41/ 159.74
= 7.66 mm
So, minimum shell thickness is = 7.66 mm ( including corrosion allowance)
NOZZLE DIAMETER:
Material used = carbon steel
Feed nozzle for Gases,
Mass flow rate of shell side fluid = m = A v = 31095.68 lb/hr = 14134 kg/hr
Density of gases = 5.27 kg/m3
Velocity of gases = 27641.36 m/hr
A = m / v
= 14134 / 5.27 * 27641.36
= 0.097 m2
Diameter of the nozzle = [0.097 x 4 / pi]1/2
= 0.352 m
= 13.85 in. = 352 mm
Feed nozzle outlet also has the same diameter.
NOZZLE THICKNESS:
Corrosion allowance = C =2 mm
tn =
P * Dn
C
2* f * J P
= [1.76 x 352/ {(2 x 95 x 0.85) 55.445}] + 2

= 3.8 + 2
= 5.8 mm
165
HEAD THICKNESS:
Take a floating head, the thickness can be calculated as:
th = PRcW / 2fJ
where , th = thickness of head
P = 1.76 N/mm2
W = ( 3 + Rc / Rk)
Rc = Crown radius = outer radius of shell = 7.66 + 695.12 = 702.78 mm
Rk = Knuckle radius = 0.06 Rc = 42.16 mm
So,
W = 1.52
th = (1.76 x 702.78 x 1.52)/(2 x 95 x 0.85)

= 11.64 mm
Taking.002mm corrosion allowance we have,
th = 11.64 +.002
= 11.643 mm
The Rods & Spacers:

The rods and spacers shall be provided to retain all cross baffles and tube support
plates accurately in position from Ludwig (2nd edition , vol, 3 ,page # 26) table # 10.6
For shell diameter 864-1220 mm
Diameter of tie rod is 12.8 and number of rods = 8
Spacers diameter = 12 mm
Baffle Detail :
Baffle cut : 25% cut (the length of the baffle from the shell to the flat edge of the baffle is 75%
of the diameter of the shell)
Baffle diameter:
From Coulson & Richardson (vol 6, 3rd edition ,page # 651)

For shell diameter of 886 to 1067 mm , baffle diameter is given by the relation,
Db = Ds 4.8 mm
= 695.12 + 4.8
= 699.92 mm
Baffle spacing : According to TEMA standard should not less than 1/5(shell diameter) , So
B = 0.696 m = 696 mm
Number of baffles = N + 1 = Lt / B
Where ,
Lt = 10ft = 3.048 m
So no of baffles = 3.048 / 0.696 = 4.38 = 5
166
Let thickness of the baffles = 0.5 in = 12.7 mm

From Ernest Ludwig ,TEMA standard 1978, page # 11
Height of baffle = 0.75 * Ds
= 0.75 * 695.12 = 521.34 mm = 0.52 m
TUBE SIDE:
Material used = Stainless Steel 316
No. of tube passes = 2
Number of tubes = 100
Allowable stress = 0.0001 N/mm2
Outside diameter
= 1.5 in = 0.038 m
Inside diameter
= 1.37 in = 0.034 m
Wall thickness of tubes = 0.065 in. = 0.00165m

Length of tubes = Lt = 10ft = 3.048 m
For Square pitch ,Pt = 1.875 in = 0.048 m
Here the feed is
= water
Working Pressure
= 1.6Mpa = 15.8 atm = 232.12 psi = 1.6 N/mm2
Design Pressure
= 1.1 * 1.6 =1.76 N/ mm2
Inlet temp.
= 30 oC
Outlet temp.
= 354 oC
TUBE SHEET THICKNESS:

tts
0.25 * P
F *G *
f
0.5
= 1 x 0.40 (0.25 x 1.76 / 95)0.5

= 0.027 m
CHANNEL DESIGN:
a. Channel Length
= 1.3 x (cross sectional area of tube/pass)/Ds

= 1.3 x 0.5 * pi /4 x (0.038)2 / 0.696
=.0.0011 m
b. Channel thickness:
tc = Gc (kP/f)1/2
= 0.40 x (0.3 x 1.76 / 95)1/2
= 0.0298 m
NOZZLE DESIGN FOR TUBE SIDE:

Now nozzle design for water inlet:
Material used Is Stainless Steel 316
Mass flow rate of water = 14769.34 lb/hr = 6713.33 Kg/hr
Density of water = 1000 kg / m3
Velocity of tube side fluid = v = 0.0798 ft/sec = 87.585 m/hr
m = A v
A = m/v
= 6713.33/(1000 x 87.585)
= 0.076 m2
Diameter of the nozzle = d = (0.076 x 4/ )1/2
= 0.31 m = 12.2 in = 309.88 mm
Nozzle Thickness:tn =
Pd * Dn
2* f * J P
=(1.76 * 309.88)/(2* 95 *0.85 1.76)

= 3.41mm
Now, nozzle thickness with corrosion allowance = 5.41 mm
SUPPORT DESIGN:
For this shell and tube heat exchanger, we use a saddle type of support.
Material used : low carbon steel
Diameter of shell = Ds = 695.12 mm
Working Pressure = 15.8 atm
Shell thickness
= 7.66 mm
Head Thickness = 11.643 mm
Corrosion Allowance = 2mm
167

Permissible stress = 95 N/mm2
Rc = Crown radius = outer radius of shell = 7.66 + 695.12 = 702.78 mm
Rk = Knuckle radius = 0.06 Rc = 42.16 mm
R = Ds/2 = 695.12/2 = 347.6 mm = 0.347 m
Distance of saddle canter from shell end = A = 0.5 R =173.8 mm
Total depth of head (H) = (Ds Rc / s)1/2
= (695.12* 702.78/2)1/2
= 494.22 mm
SHELL WEIGHT:
Ws = * (r20-ri2)*L*of shell material
of shell material = 7700 Kg/m3

Ws = * (0.7022 0.6952) x 3.7 x 7700 / 4
= 218.7 kg
TUBE WEIGHT:
Wt = /4 x [Do2-Di2] * L *.nt *
Density of tube material = 7800 kg/m3

= /4 x [(0.038)2 (0.0348)2] x 3.7 x 100 x 7800
= 526.68 kg
Fluid load in the shell:

W1 = (shell volume tube volume) gases
= [Ds2 L/4 n do2 l/4] * 5.27 kg/m3
= [* 0.6952 * 3.7/4 -100 * 0.0382 * 3.04 /4] * 5.27
= 6.82 kg
Fluid load in the tube :

W2 = n * di2 l * liquid / 4
= 100 * 3.14 * 0.0342 * 3.04 *1000 /4

= 275.86 kg
Now,
Total Weight = Wt = Ws + Wt + W1 + W2
`
= 526.68 + 218.7 + 6.82 + 275.86
= 1028.06 kg
WEIGHT OF TIE ROD, END COVERS, BAFFLES:

WA
= 500 kg
Total weight = 500 + 1028.06
= 1528.06 kg
LONGITUDINAL BENDING MOMENT:

The bending moment at the support is:
168

M1 = Q*A[ 1 {(l A/L + (R2 H2)/2A L)/(1 + 4/3 H/L)}]
Q = W/2 [L + 4/3 H]
L = 3.7 m, H = 494.22 mm = 0.494 m
Q = 1528.06 / 2 [3.7 + 4/3 x 0.494]
= 1861.99 kg`
Let us take A = 0.25 m
M1 = 1861.99 x 0. 25 * [1 {1 0.25/3.7 + (0.3472 0.4942)/(2 x 0.25 x 3.7)}/{1
+ 4/3 x 0.494/3.7}]
= 1239.6 x 0.25 [1 (0.437 /1.1780)]
= 1239.6 x 0.25 * (0.6288)
= 194.88 kg m
The bending moment at the center of span is calculated by:s
M2 = QL/4 [ {1 + 2(R2 H2)/L2}/{1 + 4/3 H/L} 4A/L]
= 1861.99 x 3.7 /4 [{1+2(0.3472 0.4942)/3.72}/{1+4/3x 0.494/3.7} .025 x
4/3.7]
= 1861.99 x 3.7 /4 (0.83 - 0.27)
= 970.65 kg m
STRESSES IN SHELL AT THE SADDLE:

f1 = M1 / k1 R2t
k1 = 0.107 m
= 194.88 /(0.107 x 3.14 x 0.3472 * 0.01)
= 481720 kg/m = 48.17 kg / cm2
f2 = M1 / (k2 R2t)
k2 = 0.192 m
= 194.88/(0.192 x 3.14 x 0.3472 * 0.01)
= 268458.67 kg/m2 = 26.84 kg/cm2
And stress in the shell at mid point:
F3 = M2/ ( * R2 t)
F3 = 970.65/(3.14*0.3472 * 0.01)
= 256728.48 kg/m2 = 25.67 kg/ cm2
The stresses are well within the permissible limit. Hence design support is acceptable.
169
170
171
Instrumentation and Control

The main objective of specifying and using of instruments and controls systems are
To safe the plant operation by keeping the process variables within the operating limits
and detects the dangerous situations since developed.
To control the product rate and quality within the specified quality.
To operate the process at the lowest production cost.
11.1 Final Control Elements

Is the mechanism which alters the value of the
manipulated variable in response to the output signal from and automatic controller. In a
majority of systems the final control element is and automatic control valve which throttles the
flow of a manipulative variable.
Controller
The job of the controller is to compare te process signal from the transmitter with
the set point signal and to send out an appropriate signal to the control valve. There are three
basic types of controllers which are
Proportional action which moves the control valve indirect proportional to the magnitude
of the error.
Integral action (reset) which moves the control valve based on the time integral of the
error and the purpose of integral action is to drive the process back to its set point when
it has been disturbed.
Ideal derivative action and its purpose is to anticipate where the process is heading by
looking at the time a rate of change of the error.
11.2 Commercial Controllers

The three actions are used individually or combined in three basic controllers.
Proportional
Proportional integral (P.L)
Proportional Integral derivative (P.I.D)
11.3 Transmitters
Is the interface between the process and its control system and its job is to convert the sensor
signal into a control signal.
Sensors
The instruments on the process which measure the properties and important
variables such as temperature, pressure, flow rate and level.
11.4 Typical control Systems

Level Control
172
In any equipment where an interface exists between two phases (e.g. liquid- vapor), some
means of maintaining the interface at the required level must be provided. This may be
incorporated in the design of the equipment as is usually done for decanters or by automatic
control of the flow from the equipment. Figure shows a typical arrangement for the level control
at the base of a column. The control valve should be placed on the discharge line from the
pump.
Pressure Control
Pressure control will be necessary for most systems handling vapor or gas. The method of
control will depend on the nature of the process.
Flow Control
Flow control is usually associated with inventory control in a storage tank or other equipment.
There must be a reservoir to take up the changes in flow rate. To provide flow control in a
compressor or pump running at a fixed speed and supply a near constant volume output, a bypass control would be used.
Alarms, Safety Trips, And interlocks

Alarms are used to alert operators of serious, and potentially hazardous, deviations in process
conditions. Key instruments are fitted with switches and relays to operate audible and visual
alarms on the control panels and enunciator panels. Where delay, or lack of response, by the
operator is likely to lead to the rapid development of a hazardous situation, the instruments
would be fitted with a trip system to take action automatically to avert the hazard, such as
shutting down pumps, closing valves, operating emergency systems. The basic components of
an automatic trip system are
1. A sensor to monitor the control variable and provide and output signal when a preset
values exceeded (The instrument).
2. A link to transfer the signal to the actuator, usually consisting of a system of pneumatic
or electric relays.
3. Ana actuator to carry out the required action, close or open a valve, switch off motor.
Interlocks
Where it is necessary to follow a fixed sequence of operations for example, during a plant
start-up and shut down, or in batch operations interlocks are included to prevent operators
departing from the required sequence, they may be incorporate in the control system design.
Various proprietary special lock and key systems are available.
173
11.5 CONTROL SCHEMES OF DISTILLATION COLUMN

GENERAL CONSIDERATION
Objective
In distillation column control any of following may be the goals to achieve
Over head composition.

Bottom composition
Constant over head product rate.
Constant bottom product rate.
Manipulated Variables
Any one or any combination of following may be the manipulated variables
Steam flow rate to reboiler.

Reflux rate.
Overhead product withdrawn rate.
Bottom product withdrawn rate
Water flow rate to condenser.
LOADS OR DISTURBANCES
Flow rate of feed
Composition of feed.
Temperature of feed.
Pressure drop of steam across reboiler
Inlet temperature of water for condenser.
CONTROL SCHEME
Overhead product rate is fixed and any change in feed rate must be absorbed by
changing bottom product rate. The change in product rate is accomplished by direct level
control of the reboiler if the stream rate is fixed feed rate increases then vapor rate is
approximately constant & the internal reflux flows must increase.
ADVANTAGE
Since an increase in feed rate increase reflux rate with vapor rate being approximately
constant, then purity of top product increases.
DISADVANTAGE
The overhead reflux change depends on the dynamics of level control system that adjusts it.
174
175
176
177
178
HAZOP STUDY
12.1 INTRODUCTION
A HAZOP survey is one of the most common and widely accepted methods of systematic
qualitative hazard analysis. It is used for both new or existing facilities and can be applied to a
whole plant, a production unit, or a piece of equipment It uses as its database the usual sort of
plant and process information and relies on the judgment of engineering and safety experts in
the areas with which they are most familiar. The end result is, therefore
reliable in terms
of engineering and operational expectations, but it is not quantitative and may not consider the
consequences of complex sequences of human errors.
The objectives of a HAZOP study can be summarized as follows:
To identify (areas of the design that may possess a significant hazard potential.
To identify and study features of the design that influence the probability of a hazardous
incident occurring.
To familiarize the study team with the design information available.
To ensure that a systematic study is made of the areas of significant hazard potential.
To identify pertinent design information not currently available to the team.
To provide a mechanism for feedback to the client of the study team's detailed
comments.
A HAZOP study is conducted in the following steps:
1)
Specify the purpose, objective, and scope of the study. The purpose may he the
analysis of a yet to be built plant or a review of the risk of un existing unit. Given the
purpose and the circumstances of the study, the objectives listed above can he
made more specific. The scope of the study is the boundaries of the physical unit,
and also the range of events and variables considered. For example, at one time
HAZOP's were mainly focused on fire and explosion endpoints, while now the scope
usually includes toxic release, offensive odor, and environmental end-points. The
initial establishment of purpose, objectives, and scope is very important and should
be precisely set down so that it will be clear, now and in the future, what was and
was not included in the study. These decisions need to be made by an appropriate
level of responsible management.
2)
Select the HAZOP study team. The team leader should be skilled in HAZOP and in
interpersonal techniques to facilitate successful group interaction. As many other
experts should be included in the team to cover all aspects of design, operation,
process chemistry, and safety. The team leader should instruct the team in the
179
HAZOP procedure and should emphasize that the end objective of a HAZOP survey
is hazard identification; solutions to problems are a separate effort.
3)
Collect data. Theodore16 has listed the following materials that are usually needed:
Process description
Process flow sheets
Data on the chemical, physical and toxicological properties of all raw materials,,
intermediates, and products.
Piping and instrument diagrams (P&IDs)
Equipment, piping, and instrument specifications
Process control logic diagrams
Layout drawings
Operating procedures
Maintenance procedures
Emergency response procedures
Safety and training manuals
Table-: HAZOP Guide Words and Meanings

Guide Words
Meaning
No
Negation of design intent
Less
Quantitative decrease
More
Quantitative increase
Part of
Qualitative decrease
As well as
Qualitative Increase
Reverse
Logical opposite of the intent
Other than
Complete substitution
4)
Conduct the study. Using the information collected, the unit is divided into study
"nodes" and the sequence diagrammed in Figure , is followed for each node. Nodes
are points in the process where process parameters (pressure, temperature,
composition, etc.) have known and intended values. These values change between
nodes as a result of the operation of various pieces of equipment' such as distillation
columns, heat exchanges, or pumps. Various forms and work sheets have been
developed to help organize the node process parameters and control logic
information.
180
When the nodes are identified and the parameters are identified, each node is studied
by applying the specialized guide words to each parameter. These guide words and their
meanings are key elements of the HAZOP procedure. They are listed in Table.
Repeated cycling through this process, which considers how and why each parameter
might vary from the intended and the consequence, is the substance of the HAZOP study.
5)
Write the report. As much detail about events and their consequence as is
uncovered by the study should be recorded. Obviously, if the HAZOP identifies a not
improbable sequence of events that would result in a disaster, appropriate follow-up
action is needed. Thus, although risk reduction action is not a part of the HAZOP,
the HAZOP may trigger the need for such action.
The HAZOP studies are time consuming and expensive. Just getting the P & ID's up to
date on an older plant may be a major engineering effort. Still, for processes with significant
risk, they are cost effective when balanced against the potential loss of life, property, business,
and even the future of the enterprise that may result from a major release.
13.2 HAZOP Study of Storage Tank for Methyl Alcohol

A HAZOP study is to be conducted on IPA storage tank, as presented by the piping and
instrumentation diagram show in figure.
In this scheme, IPA is unloaded from tank trucks into a storage tank maintained under a
slight positive pressure until it is transferred to the process. Application of the guide words to
the storage tank is shown in Table along with a listing of consequences that results from
process deviation. Some of the consequences identified with these process deviations have
raised additional questions that need resolution to determine whether or not hazards exist.
Methyl Alcohol
Storage Tank
Figure- Piping and instrumentation diagram
181
Deviations
from
operating
conditions
Level:
Less
What event could

cause this deviation
182
Consequences of
this deviation on
Process
item of equipment
indications
under
consideration
Tank runs dry
Pump cavitates
Rupture of discharge
line
V-3 open or broken
V-1 open or broken
Tank rupture (busting
of vessel)
Reagent released
More
Unload too much
from column
Reverse flow from
Temperature: process
Less
Temperature of inlet
More
is colder than normal
Temperature of inlet
is hotter than normal
External fire
Reagent released
Reagent released
Reagent released
LIA-1
FICA-1
LIA-1,
FICA-1
LIA-1
LIA-1
LIA-1
Tank overfills
LIA-1
Tank overfills
LIA-1
Possible vacuum
Region released
Tank fails
183
184
13.1 CHEMICALS IN THE ENVIRONMENT: METHANOL

Chemicals can be released to the environment as a result of their manufacture,
processing, and use. EPA has developed information summaries on selected chemicals to
describe how you might be exposed to these chemicals, how exposure to them might affect
you and the environment, what happens to them in the environment, who regulates them,and
whom to contact for additional information. EPA is committed to reducing environmental
releases of chemicals through source reduction and other practices that reduce creation of
pollutants.
WHAT HAPPENS TO METHANOL IN THE ENVIRONMENT?

Methanol evaporates when exposed to air. It dissolves completely when mixed with
water. Most direct releases of methanol to the environment are to air. Methanol also
evaporates from water and soil exposed to air. Once in air, it breaks down to other chemicals.
Microorganisms that live in water and in soil can also break down methanol. Because it is a
liquid that does not bind well to soil, methanol that makes its way into the ground can move
through the ground and enter groundwater. Plants and animals are not likely to store
methanol.
HOW DOES METHANOL AFFECT HUMAN HEALTH AND THE ENVIRONMENT?
Effects of methanol on human health and the environment depend on how much
methanol is present and the length and frequency of exposure. Effects also depend on the
health of a person or the condition of the environment when exposure occurs. People have
died as a result of drinking large amounts of methanol. Drinking smaller, non lethal amounts of
methanol adversely affects the human nervous system. Effects range from headaches to
incoordination similar to that associated with drunkenness. Delayed effects such as severe
abdominal, leg, and back pain can follow the inebriation effects of methanol. Loss of vision
and even blindness can also occur after exposure to amounts of methanol causing inebriation.
These effects are not likely to occur at levels of methanol that are normally found in the
environment.
Human health effects associated with breathing or otherwise consuming smaller amounts of
methanol over long periods of time are not known. Workers repeatedly exposed to methanol
have experienced several adverse effects. Effects range from headaches to sleep disorders
and gastrointestinal problems to optic nerve damage. Laboratory studies show
that repeat exposure to large amounts of methanol in air or in drinking water cause similar
adverse effects in animals.
13.2 Different Hazards

TYPES OF
HAZARD /
EXPOSURE
FIRE
ACUTE HAZARDS /
SYMPTOMS
Highly flammable. See Notes.
PREVENTION
NO open flames, NO
sparks, and NO
FIRST AID /
FIRE FIGHTING
Powder, alcohol-resistant
foam, water in large amounts,
185
smoking. NO contact
with oxidants.
carbon dioxide.
In case of fire: keep drums,
etc., cool by spraying with
water.
EXPLOSION
Closed system,
ventilation, explosionproof electrical
equipment and
lighting. Do NOT use
compressed air for
filling, discharging, or
handling. Use nonsparking handtools.
EXPOSURE
AVOID EXPOSURE
OF ADOLESCENTS
AND CHILDREN!
Vapour/air mixtures are explosive.
Inhalation
Skin
Cough. Dizziness. Headache.

Nausea. Weakness. Visual
disturbance.
Ventilation. Local
exhaust or breathing
protection.
Fresh air, rest. Refer for

medical attention.
MAY BE ABSORBED! Dry skin.

Redness.
Protective gloves.
Protective clothing.
Remove contaminated clothes.

Rinse skin with plenty of water
or shower. Refer for medical
attention.
Redness. Pain.
Safety goggles or eye

protection in
combination with
breathing protection.
First rinse with plenty of water

for several minutes (remove
contact lenses if easily
possible), then take to a
doctor.
Abdominal pain. Shortness of breath.

Vomiting. Convulsions.
Unconsciousness. (Further see
Inhalation).
Do not eat, drink, or

smoke during work.
Wash hands before
eating.
Induce vomiting (ONLY IN

CONSCIOUS PERSONS!).
Refer for medical attention.
Eyes
Ingestion
SPILLAGE DISPOSAL
PACKAGING & LABELLING
Evacuate danger area! Ventilation. Collect leaking

liquid in sealable containers. Wash away remainder
with plenty of water. Remove vapour with fine water
spray. Chemical protection suit including selfcontained breathing apparatus.
F Symbol
T Symbol
R: 11-23/24/2539/23/24/25
S: (1/2-)7-16-36/37-45
UN Hazard Class: 3
UN Subsidiary Risks:
6.1
UN Pack Group: II
Do not transport with food and

feedstuffs.
IMPORTANT DATA
Physical State; Appearance
COLOURLESS LIQUID, WITH
CHARACTERISTIC ODOUR.
Routes of exposure
The substance can be absorbed into the body by inhalation and
through the skin, and by ingestion.
Physical dangers
The vapour mixes well with air, explosive
Inhalation risk
A harmful contamination of the air can be reached rather quickly
186
mixtures are easily formed.
on evaporation of this substance at 20C.
Chemical dangers
Reacts violently with oxidants causing fire
and explosion hazard.
Effects of short-term exposure

The substance irritates the eyes, the skin and the respiratory
tract. The substance may cause effects on the central nervous
system, resulting in loss of consciousness. Exposure may result
in blindness and death. The effects may be delayed. Medical
observation is indicated.
Occupational exposure limits

TLV: 200 ppm; as TWA (skin) (ACGIH 1999).
TLV (as STEL): 250 ppm; (skin) (ACGIH
1999).
Effects of long-term or repeated exposure

Repeated or prolonged contact with skin may cause dermatitis.
The substance may have effects on the central nervous system,
resulting in persistent or recurring headaches and impaired vision.
13.3 Health & Safety

Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria. As a
result, there is a small fraction of methanol vapor in the atmosphere. Over the course of
several days, atmospheric methanol is oxidized by oxygen by the help of sunlight to carbon
dioxide and water.
Methanol burns in air forming carbon dioxide and water:
2CH3OH + 3 O2 2CO2 + 4H2O
A methanol flame is almost colorless. Care should be exercised around burning methanol to
avoid burning oneself on the almost invisible fire.
Methanol is toxic, as its metabolites formic acid and formaldehyde cause blindness and death. It
enters the body by ingestion, inhalation, or absorption through the skin. Fetal tissue will not tolerate
methanol. Dangerous doses will build up if a person is regularly exposed to fumes or handles
liquid without skin protection. If methanol has been ingested, a doctor should be contacted
immediately. The usual fatal dose: 100125 mL (4 fl oz). Toxic effects take hours to start, and
effective antidotes can often prevent permanent damage. This is treated using ethanol or
fomepizole[1]. Either of these drugs acts to slow down the action of alcohol dehydrogenase on
methanol, so that it is excreted by the kidneys rather than being transformed into toxic
metabolites. Though it is miscible with water, methanol is very hard to wash off the skin; it is
best to treat methanol like gasoline.
Symptoms of methanol ingestion are similar to those of intoxication: headache, dizziness,
nausea, lack of coordination, confusion, drowsiness, followed by unconsciousness and
death.The ester derivatives of methanol do not share this toxicity.Ethanol is sometimes
denatured (adulterated), and thus made undrinkable, by the addition of methanol. The result is
known as methylated spirit or "meths" (UK use). (The latter should not be confused with meth, a
common abbreviation for methamphetamine.)
Pure methanol has been used in open wheel racing since the mid-1960's. Unlike petroleum
fires, methanol fires can be extinguished with plain water (while methanol is lighter than water,
187
they are miscible, and addition of water will cause the fire to use its heat boiling the water). The
decision was made shortly after the death of two drivers
13.4 Dangers of Methanol

Methanol is a clear, colorless liquid with a faint odor like alcohol. The smell is not very strong
and is considered a poor indicator of vapor concentration. You might also know methanol as
methyl alcohol, methyl hydrate, carbinol, wood alcohol or wood spirit.
Methanol is used as a solvent for lacquers, paints, varnishes, cements, inks, dyes, plastics and
various industrial coatings. It is also used in the production of pharmaceuticals, formaldehyde
and other chemical products. Methanol appears as an ingredient in many products, from
industrial solvents to windshield-washer fluid and nail-polish remover. It is also used as a fuel.
Inhalation of methanol vapor is the most common route of occupational exposure. Poisonings
have also resulted from absorption through the skin; although it is only a mild skin irritant, it
can be absorbed through the skin in toxic amounts. Accidental swallowing is also possible.
Methanol tastes and smells much like common alcohol (ethanol) and has been used as a
substitute in illegal alcoholic beverages. In March 1997, three people died in northern Ontario
as a result of methanol poisoning from a bad batch of moonshine.
13.5 Effects of Methanol Poisoning

As little as four milliliters can cause blindness and 80 to 150 milliliters can be fatal; about half a
milliliter per kilogram of weight is deadly. Drinking methanol causes effects similar to common
alcohol, such as an upset stomach and dizziness, with the addition of pronounced vision
problems. After these effects disappear, they reappear six to 30 hours later, only with much
greater severity. severe symptoms tend to appear 18 to 24 hours after consumption. the
relapse time makes it imperative to seek medical help as soon as possible.
The most seriously poisoned lose consciousness and die of respiratory or heart failure. those
who do not die may stay in a coma for as long as a week and may be left blinded.
Accidental swallowing of methanol is not likely in the workplace. Should it happen, get medical
help immediately. Never try to make the casualty throw up, but if that does happen hold the
person leaning forward to reduce the risk of methanol being drawn into the lungs. you can give
240 to 300 milliliters of water to dilute the methanol in the stomach.
Like common alcohol, methanol is broken down in the liver. Methanol breaks downs to
produce formaldehyde and formic acid, which are responsible for many of the toxic effects. the
body takes several days to eliminate the methanol.
Short term exposure to methanol vapor can irritate the eyes, nose and throat and cause
headache, nausea, throwing up, dizziness and trouble breathing. other common symptoms of
drunkenness, such as lightheadedness, giddiness, blurred vision and dilated pupils, might also
188
appear. the symptoms depend on the level and length of exposure and can vary from person
to person.
Industrial exposures to methanol vapors can cause death or blindness. many reported
incidents have involved working in confined spaces without proper ventilation or respiratory
protection. fortunately, increased awareness of the dangers of methanol, combined with safer
work practices, have reduced the number of serious poisonings in recent years.
Long term exposure to methanol has been linked to headaches, mood changes, eye and skin
irritation, trouble sleeping, stomach problems and visual impairment. Repeated short term
exposures can also lead to such symptoms.
Methanol is a flammable liquid and can pose a serious fire risk. It burns with a pale blue flame
not usually visible in normal light. Its flash point is 12 c. above this temperature enough vapor
is produced to create a flammable mixture with air. The vapor is heavier than air and can travel
along the ground to a distant source of ignition and flashback. Containers may explode in the
heat of a fire. Although methanol is normally stable, contact with strong oxidizing agents
increases the risk of a fire or explosion.
189
190
1. Product Identification
Synonyms: Wood alcohol; methanol; carbinol
CAS No.: 67-56-1
Molecular Weight: 32.04
Chemical Formula: CH3OH
2. Composition/Information on Ingredients
Ingredient
CAS No
Percent
Hazardous
--------------------------------------- ------------ ------------ --------Methyl Alcohol
67-56-1
100%
Yes
3. Hazards Identification
Emergency Overview
POISON! DANGER! VAPOR HARMFUL. MAY BE FATAL OR CAUSE BLINDNESS IF
SWALLOWED. HARMFUL IF INHALED OR ABSORBED THROUGH SKIN. CANNOT BE
MADE NONPOISONOUS. FLAMMABLE LIQUID AND VAPOR. CAUSES IRRITATION TO
SKIN, EYES AND RESPIRATORY TRACT. AFFECTS CENTRAL NERVOUS SYSTEM AND
LIVER.
Health Rating: 3 - Severe (Poison)
Flammability Rating: 3 - Severe (Flammable)
Reactivity Rating: 1 - Slight
Contact Rating: 3 - Severe (Life)
Lab Protective Equip: GOGGLES & SHIELD; LAB COAT & APRON; VENT HOOD; PROPER
GLOVES; CLASS B EXTINGUISHER
Storage Color Code: Red (Flammable)
Potential Health Effects

Inhalation:
A slight irritant to the mucous membranes. Toxic effects exerted upon nervous system,
particularly the optic nerve. Once absorbed into the body, it is very slowly eliminated.
Symptoms of overexposure may include headache, drowsiness, nausea, vomiting, blurred
vision, blindness, coma, and death. A person may get better but then worse again up to 30
hours later.
Ingestion:
Toxic. Symptoms parallel inhalation. Can intoxicate and cause blindness. Usual fatal dose:
100-125 milliliters.
Skin Contact:
Methyl alcohol is a defatting agent and may cause skin to become dry and cracked. Skin
absorption can occur; symptoms may parallel inhalation exposure.
191
Eye Contact:
Irritant. Continued exposure may cause eye lesions.
Chronic Exposure:
Marked impairment of vision has been reported. Repeated or prolonged exposure may cause
skin irritation.
Aggravation of Pre-existing Conditions:
Persons with pre-existing skin disorders or eye problems or impaired liver or kidney function
may be more susceptible to the effects of the substance.
4. First Aid Measures

Inhalation:
Remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give
oxygen. Get medical attention immediately.
Ingestion:
Induce vomiting immediately as directed by medical personnel. Never give anything by mouth
to
an
unconscious
person.
Get
medical
attention
immediately.
Skin Contact:
Immediately flush skin with plenty of water for at least 15 minutes while removing
contaminated clothing and shoes. Get medical attention. Wash clothing before reuse.
Thoroughly clean shoes before reuse.
Eye Contact:
Immediately flush eyes with plenty of water for at least 15 minutes, lifting lower and upper
eyelids occasionally. Get medical attention immediately.
5. Fire Fighting Measures

Fire:
Flash point: 12 oC (54 oF)
Autoignition temperature: 464 oC (867 oF)
Flammable limits in air % by volume:
Flammable Liquid and Vapor!
Explosion:
Above flash point, vapor-air mixtures are explosive within flammable limits noted above.
Moderate explosion hazard and dangerous fire hazard when exposed to heat, sparks or
flames. Sensitive to static discharge.
Fire Extinguishing Media:
Use alcohol foam, dry chemical or carbon dioxide. (Water may be ineffective.)
192
Special Information:
In the event of a fire, wear full protective clothing and NIOSH-approved self-contained
breathing apparatus with full facepiece operated in the pressure demand or other positive
pressure mode. Use water spray to blanket fire, cool fire exposed containers, and to flush nonignited spills or vapors away from fire. Vapors can flow along surfaces to distant ignition source
and flash back.
Extinguishing media which must not be used for safety reasons:
Do not use a solid water stream as it may scatter and spread fire.
Specific hazards :
Burns with colorless flame.
Special protective equipment for firefighters:
Wear self-contained breathing apparatus and protective suit.
Specific methods:
Standard procedure for chemical fires.
Hazchem Code:
2WE
6. Accidental Release Measures

Personal precautions:
Evacuate personnel to safe areas. Remove all sources of ignition. Wear self-contained
breathing apparatus and protective suit. Keep people away from and upwind of spill/leak.
Environmental precautions:
Contain or absorb leaking liquid with sand or earth. Consult an expert. Prevent liquid entering
sewers, basements and work pits; If substance has entered a water course or sewer or
contaminated soil or vegetation, advise police.
Methods for cleaning up:
Soak up with inert absorbent material (e.g. sand, silica gel, acid binder, universal binder,
sawdust). Transfer to covered steel drums. Dispose of promptly.
7. Handling and Storage

Handling: Use only in well-ventilated areas. Do not breathe vapors or spray mist. Avoid
contact with skin, eyes and clothing. Take necessary action to avoid static electricity discharge
(which might cause ignition of organic vapors.)
Storage: Keep tightly closed in a dry, cool and well-ventilated place. Keep away from heat and
sources of ignition. Store in original container. Electrical equipment should be protected to the
appropriate standard.
8. Exposure Controls/Personal Protection

Airborne Exposure Limits:
For Methyl Alcohol:
- OSHA Permissible Exposure Limit (PEL):
193
200 ppm (TWA)

- ACGIH Threshold Limit Value (TLV):
200 ppm (TWA), 250 ppm (STEL) skin
Ventilation System:
A system of local and/or general exhaust is recommended to keep employee exposures below
the Airborne Exposure Limits. Local exhaust ventilation is generally preferred because it can
control the emissions of the contaminant at its source, preventing dispersion of it into the
general work area. Please refer to the ACGIH document, Industrial Ventilation, A Manual of
Recommended Practices, most recent edition, for details. Use explosion-proof equipment.
Personal Respirators (NIOSH Approved):
If the exposure limit is exceeded and engineering controls are not feasible, wear a supplied air,
full-facepiece respirator, airlined hood, or full-facepiece self-contained breathing apparatus.
Breathing air quality must meet the requirements of the OSHA respiratory protection standard
(29CFR1910.134). This substance has poor warning properties.
Skin Protection:
Rubber or neoprene gloves and additional protection including impervious boots, apron, or
coveralls, as needed in areas of unusual exposure.
Eye Protection:
Use chemical safety goggles. Maintain eye wash fountain and quick-drench facilities in work
area.
9. Toxicological Information
Methyl Alcohol (Methanol) Oral rat LD50: 5628 mg/kg; inhalation rat LC50: 64000 ppm/4H;
skin rabbit LD50: 15800 mg/kg; Irritation data-standard Draize test: skin, rabbit: 20mg/24 hr.
Moderate; eye, rabbit: 100 mg/24 hr. Moderate. Investigated as a mutagen, reproductive
effector.
Acute toxicity: LD50/oral/rat = 6200 1300 mg/kg.
LD50/inhalation/4h/rat = 48 mg/l.
LD50/dermal/rabbit = 20000 mg/kg.
Sensitization: Toxic by inhalation. Irritant effect on eyes.
Long term toxicity: Repeated and prolonged exposure; May cause irreversible eye damage.
Chronic toxicity: Chronic exposure may cause permanent damage of health.
10. Ecological Information

Environmental Toxicity:
This material is expected to be slightly toxic to aquatic life.
Mobility: Completely miscible with water. Volatile / gaseous.

Persistence / degradability: Readily biodegradable, according to appropriate OECD test.
Biochemical oxygen demand (BOD) = 48-82% of theoretical oxygen demand (ThOD)
Bio accumulation: Bio accumulation not significant.
Estimated Bio concentration factor (BCF) = 0.2
Ecotoxicity: LC50/96h/bluegill sunfish = 15400 mg/l.
NOEL/48h/daphnia = 1000 mg/l.
Toxicity to algae = 8000 mg/l.
Toxicity to bacteria = 530 mg/l.
11. Disposal Considerations

Waste from residues / unused products:
Can be incinerated, when in compliance with local regulations.
Contact waste disposal services.
Contaminated packaging:
Empty containers can be land filled after cleaning, when in compliance with local regulation.
Continued on next page
12. Transport Information

Domestic (Land, D.O.T.)
----------------------Proper Shipping Name: METHANOL
Hazard Class: 3
UN/NA: UN1230
Packing Group: II
Information reported for product/size: 358LB
International (Water, I.M.O.)
----------------------------Proper Shipping Name: METHANOL
Hazard Class: 3, 6.1
UN/NA: UN1230
Packing Group: II
Information reported for product/size: 358LB
13. Regulatory Information

Classification according to European directive on classification of hazardous
preparations 90/492/EEC
Contains: METHYL ALCOHOL
Symbol(s): F Highly flammable,
194
195
R phrase(s): R11 Highly flammable.

R23/25 - Toxic by inhalation and if swallowed.
S phrase(s): S1/2 - Keep locked-up and out of reach of children.
S7 - Keep container tightly closed.
S16 - Keep away from sources of ignition No smoking.
S24 - Avoid contact with skin.
S45 - In case of accident or if you feel unwell, seek medical advice immediately
(show the label where possible.)
Recommended restrictions: Take notice of labels and material safety data sheets for the
working chemicals.
Take necessary action to avoid static electricity discharge (which might cause
ignition of organic vapors.)
Recommended use: General purpose solvent.
14. Other Information

NFPA Ratings: Health: 1 Flammability: 3 Reactivity: 0
Label Precautions:
Avoid breathing vapor.
Avoid contact with eyes, skin and clothing.
Wash thoroughly after handling.
Label First Aid:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult,
give oxygen. If swallowed, induce vomiting immediately as directed by medical personnel.
Never give anything by mouth to an unconscious person. In case of contact, immediately flush
eyes or skin with plenty of water for at least 15 minutes while removing contaminated clothing
and shoes. Wash clothing before reuse. In all cases get medical attention immediately.
15- Personal protection equipment:

Respiratory protection: Incase of insufficient ventilation wear suitable respiratory equipment.
Hand protection: Neoprene gloves / butylrubber gloves.
Eye protection: Goggles giving complete protection to eyes.
Skin and body protection: Rubber or plastic boots, Chemical resistant apron / complete suit
protecting against chemicals.
196
197
MATERIAL OF CONSTRUCTION
Many facto rs h a v e to be c o n s i d e re d when s e l e c t i n g e n g i n e e r i n g m a t e r i a l , b u t f o r
c h e m i c a l process p l a n t to o v e r r i d i n g c o n s i d e r a t i o n is u s u a l l y th e a b i l i t y to resist
corrosion. The process designer w i l l he responsible for re comm en ding m a t e r i a l s
t h a t w i l l be s u i t a b l e fo r t h e process c o n d i t i o n . He must also co nsi de r t h e
r e q u i r e m e n t s of t h e m e c h a n i c a l d es ig n engineer; t h e m a t e r i a l selected must
h a v e s u f f i c i e n t . s t r e n g t h a n d lie e a s i l y worked. The most economical m aterial t h a t
salislles both process and mechanical requirements should be selected; t h i s w i l l be
th e m a t e ri a l t h a t gives t h e lowest cost over the w o r k i n g l i f e of t h e p l a n t , a l l o w i n g
for m a i n t e n a n c e a nd replacement.
Other
factors
such
as
p ro d uct
c o n t a m i n a t i o n a n d process safety, must also be considered.
STAIN LESS STEELS

There are more t h a n 100 d i f f e r e n t types of s t a i n l e s s steels. These m a t e r i a l are h ig h
c h r o m i u m or hi g h n i c k e l c h r o m i u m alloys of c o n t a i n i n g small amounts of o t h e r
essential c o n s ti t u e n ts . They have e x c e l l e n t corrosion -resistance .and h e a l r e s i s t a n c e pr op er t i es . The most common s t a i n l e s s steels , s u c h as type 302 or t y p e
304, c o n t a i n a p p r o x i m a t e l y IS per c ent c h r o m i u m and 8 percent n i c k e l , and are
designated as 1 <S-is stainless steels.
TYPES
A wide range of st a inle ss steels is a va i l a b l e , w i t h co m p o sit io n t a i l o re d to give the
properties required for sp e cif ic applications. Type 304 (the so-called I S/S stainless
steels): the most generally used stainless steel. It contains the m i n i m u m (V
and Ni t ha t give a .stable austenitic structure. The carbon co n t en t is low enough
for heal treatment not to be normally needed w i t h t h i n section to p re ven t weld decay
Type 304L: Low ca rbo n ve rsion of t yp e 304 ( - 0.03 per ce n t ( ' ) used for t h icke r
welded section, where carbide p re c ip it a t io n wo u ld occur wi t h type 304.
Type 32 I L: A stabilized version of 304, stabili zes w i t h t i t a n i u m to prevent carbide
precipitation d u r in g welding. It has a s l i g h t l y higher strength than 304L,and more
su itab le lor h igh temperature use. Type 347: Stabilized with niobium
Type 316: In t h i s a llo y , molybdenum is added lo im p ro ve (he corrosion resistance in
reducing condition , such as in d i l u t e s u l p h u r i c acid, and, in practical, to solutions
containing chlorides.
Type 3 I6L: A low carbon version of type 3 16, wh ich sh o u ld be specified if welding or
heat treatment is lia ble lo cause carbide p re cip ita tion in type 3 16. Type 309/310: Alloy
with a high chromium content, to give greater resistance to o xi d a t io n at h i g h
temperatures above 500 'C. Sigma phase is an inlermetallic compound, FeCr.
198
MECHANICAL PROPERTIES
The austenitic stainless steels have greater st r en gt h t h a n t h e p l a i n carbon steels,
particularly at elevated temperatures
Resistance of Stainless Steel to Oxidation in Air

Maximum tempera Stainless steel type
ture,C
650
416
700 "
800
403,405,410,414
430,431
850
430F
900
302,303,304,316,317 3
, 21,347,348,1714CuMo
1000
30213,308,442
1100
309,310,314,329,446
199
SELECTION OF MATERIALS
The chemical engineer responsible for (he sel ection of materials construction must have a thorough
u n d e rs t an di n g of a l l t h e basic process information available. This knowledge of the process can
t h e n be used to select materials of const ructi on in a logical manner. A b r i e f p l a n for st ud yi ng
materials of construction is as follows .
1. Pr eli mi n ar y Selection
Experience, manufacturers data, special liter atur e, general literature,
Availability, safely aspects, pr eliminar y laboratory tests.
2. Laboratory Testing
Reevalualion of apparently suitable materials under process conditions
3. Interpretation of Laboratory Results and Other Data
Effect of possible impurities, excess temperature, agitation, and presence of
air in equipment.
Avoidance of electrolysis
Fabrication method.
4. Economic Comparison of Apparently S u i t a b l e Materials
Materials and maintenance cost, probable li f e, cost of product degradation,
liability to special hazards.
SELECTION OF MATERIAL OF CONSTRUCTION
200
Sr. No
Equipment
Material
Reformer tubes
HK 40
Waste Heat Boiler
SS-304-shall,SS304-Tube
Air Cooler
SS
Condenser
CS-Shell,SS-304
Tube
Compressor
CS
Reactor
SS-316
Separator
SS-304
Distillation Column
SS-304
201
202
PURCHASED EQUIPMENT COST

Cost in year A
= Cost in year B * (Cost index in year A/Cost index

in year B)
Marshall and Swift Equipment Cost Index

Cost in 2002
924
Cost index in 2003
1062
Cost index in 2004
1092
Cost index in 2005
1132.1
$1
Rs. 60
Rs. 90
REACTOR (FIXED BED)

Diameter
2.5 ft =
30 in
Length
Volume
= 57.56 ft3 =
Weight
Stainless Steel 316
Pressure
50 atm
12.5 ft
430.55 gallon
6491.16 lb
735 psi
From Peter and Timmerhaus ( Page No = 732 , 542 , Table No . 06)

Cost of reactor column in 1990 =
8(W)-0.34 * W * Material factor * pressure factor
Range of W
800
Material factor
2.75
Pressure factor
3.8
Substituting the values, we get
100000 lb
Cost of Column in 1990
203
= 80(6491.16)-0.34 * (6491.16) * 2.75 * 3.8

= $ 274372
=
274372 * (1132.1/924)
= $336165
Cost of column in 2005

Now
Catalyst used
Weight of catalyst
=
=
Reference
Cu-Zn-Al
2331.181 lb
internet
(http:// www.cere.energy.gov\hydrogenandfuel cell/pdfs/nn0123 aw.pdf)

Cost of catalyst
= $ 7/lb
Total cost of catalyst

=
$16318
2331.18 *7
Cost of reactor
=
=
336165 +16318
$ 352483
Cost of reactor in Rs.
= Rs 21148980
DISTILLATION COLUMN
Diameter
= 5.427 ft
Length
50 ft
Plate type
sieve
No. of plates
31
Pressure
Stainless l Steel 304
Cost of distillation column
Cost of vertical column + Cost of sieve plates.
From Coulson Vol. 6

Page No.
255
1.654 m
15.24 m
1.1 atm
Third Edition
Fig (b)
Cost from fig * material factor * pressure factor

Material factor
Pressure factor
(22*1000) * 2* 1
$ 44000
(cost from fig) * material factor
Cost of plates in 2002
Cost of total plates in 2002
Cost of dist. column in 2002
500 * 1.7
$ 850
850 * 31
$ 26350
44000 + 26350
= $ 70350
Cost of dist. column in 2005
70350 * (1132.1/1062)
= $ 74994
Cost in Rs.
Rs. 4499618
HEAT EXCHANGER (W.H.B)

Type
1-2 Exchanger
Area
307.2 ft2
Internal pressure
300 psi rating
SS-304 shell SS-304 tubes
Refrences: F.O.B Gulf Coast U.S.A.

http://www.matche.com/equip.cost / reactor . htm
purchased cost in 2002
$ 34200
34200 * 1132.1 / 1092 = $ 35456
CONDENSER
204
Type
1-2 Exchanger, Floating Head
Area
978.76 ft2
Internal pressure
150 psi rating
CS-shell-SS-304-tubes
Refrences : F.O.B. Gulf Coast U.S.A.

http://www.matche.com /equip.cos / reactor , htm
$59800
59800 * 1132.1 / 1092
= $ 61996
Purchased cost in Rs.
= Rs. 3719760
COMPRESSOR
COMPRESSOR TYPE
Compressor power
= 1722.83 hp
= Carbon Steel
Purchased cost in 2002
= $530600
Cost in 2005
530600 * 1132.1 / 1092
$ 550084
Cost in Rs.
Centrifugal 1000 psi
= Rs. 33005040
PHASE SEPARATOR
Diameter
Height
Pressure
=
0.824 m
= 6.11 m
= 50atm
= SS
205

From coulson Vol. 6
Page No.
Figure 6.5b
206
Third Edition
Cost from fig * material factor * pressure factor
Cost from figure
$ 9.4 * 1000
Material factor
Pressure factor
=
=
2
1.8

Cost in 2005
Cost in rupees
=
=
=
9.4*1000*2*1.8=$33840
33840*1132.1/1062 =
Rs.2164440
$36074
FAN
Type
=
centrifugal vein axial
Capacity
=
2125ft3/ min
From Petter and Timmerhaus page # 35
Purchase cost in 1990
=
$8010
Cost in 2005
=
800*1132.1/924 = 58800
AIR COOLER
Exchanger type
=
air cooled bare tube area
Area
=
514ft2
Internal pressure
=
300psi rating
=
S.S
Reference ; F.O.B GULF COAST USA
Hhtp://www.matche.com/equipcost/reacter/htm
Purchased cost in 2002`
=
$50000
Cost in 2005
=
50000*1132.1/1092 = $51836
Cost in Rs.
=
Rs3110160
STREAM REFORMER
Number of tubes
=
45
Length of one tube
=
30 ft
Surface area per unit length =
1.31ft2/ft
Total surface area
=
45*30*1.31
=
1768.5ft2
Reference: internet
http://www.cheme/cornell.edu/courses/ cheme462/syllabus/costing/factmethod/pdf
steam reformer (HK40)
=
$500/ft2
Firebox cost
=
$50000+$50/ft2
Cost of tubes
=
500*1768.5 =
$884250

Firebox coct
=
Cost of steam reformer
=
Cost of steam reformer in Rs. =
207
50000+50*17683.5
884250+138425
Rs.61360500.
=
=
$138425
$1022675
TOTAL PURCHASED EQUIPMENT COST E IN 2005

Equipment
Reactor
Distillation Column
Heat Exchanger
Condenser
Compressor
Phase Separator
Fan
Air Cooler
Steam Reformer
Cost of one
Equipment
352483
74994
35456
61996
550084
36074
980
51836
1022675
Number of
Equipment
1
2
12
2
2
5
2
2
1
Cost of equipments
352483
149988
425472
123992
1100168
180370
1960
103672
1022675
Total purchased equipment cost, E =$3460780
CAPITAL INVESTMENT ESTIMATION

(based on delivered equipment cost)
(Table # 17: Page # 183/P&T)
DIRECT COST
Item
Percent of Delivered
Equipment
purchased equipment delivered cost
100
Purchased equipment installation
47
Instrument and control
18
Piping
66
Electrical
11
Building
18
Yard improvements
10
Service facilities
70
Land
06
TOTAL DIRECT PLANT COST
Cost $
3460780
1626567
722940
2284115
380686
622940
346078
2422546
207647
11974299
INIDRECT COST
Engineering And Supervision
33
Construction expenses
41
TOTAL DIRECT AND INDERECT COST
Contractors Fee
21
Contingency
42
FIXED CPITAL INVESTMENT, F
1142057
1418920
14535276
726764
1453528
16715568
Working Capital
W.C
Total capital investment

T.C.I.
=
=
=
=
=
=
208
15%of total capital investment

86%of purchased equipment cost
0.86*3460780
$2976271
Fixed Capital Investment + Working Capital
$19691839
RAW MATERIAL COST

Natural gas required
=
5094m3/hr
Price of natural gas which is used for steam reformer in Pak-Arab fertilizer in june 2005
Natural gas price
=
62.57Rs./106 Btu
C.V.
=
935 Btu/ ft3
Natural gas price
=
10526 Rs./hr
Cost of natural gas per year =
Rs. 73843200
As, Raw Material cost
=
10-50%of total product cost
So,
Taking raw material cost
=
40%of total product cost
Total product cost
=
Rs. 184608000
T
=
$3076800
MANUFACTURING COST
Tbale # 27- Page 210/P&T
Component of cost
%age
Raw material, R
40%T
Operating labour, O
12%T
Direct supervisory and clerical labour
18%T
Utilities, U
10%T
Maintenance and repair, M
3%F
Operating supplies
0.75%F
Laboratory charges
10%F
Patents and royalties
3%T
DIRECT PRODUCTION COST
II. Fixed charges
Fixed charges
=
=
III. Plant overhead cost

Plant overhead cost =
=
Manufacturing cost =
Cost $
1230720
369216
553824
307680
501467
125367
36922
92304
3217500
015*T
$461520
0.1*T
$307680
direct production cost + fixed charges + plant
209
overhead cost.
$3986700.
GGENERAL EXPENSES
Components of cost
Administration cost
Distillation and selling cost
Research and development
Financing (Interest)
GENERAL EXPENSES
%age
40%T
10%T
5%T
2%T.C.I
Cost $
123072
307680
153840
393837
978429
TOTAL PRODUCT COST

Total Product Cost
Manufacturing Cost + General Expenses
3986700 + 978429
$ 496512
PRODUCT COST PER LITER

As capacity
150 tons/day
50271107 Lit/year
4949094/(5.271 * 107)
$ 0.0865
F.C.I Land
16715568 207647
Vs
10 years
(V Vs) / n
(16507921 0) /10
$ 1650792
Rs 99047520
Product cost per liter
Rs 5.2
DEPRECIATION
PROFIT
In june 2005
Methanol price / LTR in Asia =
Now
Rs 10

Profit / year
=
=
=
210
50271 * 107 (10 5.2 ) 99047520

Rs 17760480
$ 2926008
PAYOUT PERIOD
Payout Period
fixed capital investment/(profit/year + depreciation/year)
Payout Period
16715568/(2926008+1650792)
3.65 year
TURNOVER RATIO
Gross Annual Sales
5.721 * 107 * 10
TURNOVER RATIO
5.721 * 108 * Rs
$9535000
Gross Annual Sales/Fixed Capital Iinvestment
9535000/16715568
0.57
211
212
SITE SELECTION AND ECONOMIC ASPECTS

Methanol is the product mainly used for the manufacturing of formaldehyde, acetic acid and
MTBE. Currently there is no methanol plant in Pakistan and about 90 tons pe day is to be
imported to occupy its consumption. In Pakistan it is used as raw material for urea formaldehyde,
acetic acid, and also used as methalated spirit in pharmaceuticals, dyes etc. after comparing with
the Asia and international markets rates, we can easily say that our product can capture 100%
market of methanol in Pakistan.
Our plant production capacity is 150 tons per day. The remaining 60 tons per day could be
exported. We can compete Asia and international markets due to low product cost , also material
(N.G) for the production of methanol is easily available in Pakistan at low rates.
Keeping in mind the factors, we discuss now, what should be the plant site.
1) PLAND
As mentioned earlier that we cover 100% methanol market in Pakistan and
remaining is to be exported. Our main market is Karachi because two urea formaldehyde,
pharmaceutical, and dying etc. plants are there. So a site near the Karachi and the seaport is
preferred, where it could be exported from.
The industrial zones are,
KARACHI INDUSTRIAL ZONES:
a) Site Karachi
b) Site North Karachi
c) Korangi Industrial Area
d) Karachi Export processing Zone
e) Qasim Industrial Zones
HUB INDUSTRIAL AND TRADING ESTATE (BALOCHISTAN)
There are number of
projects in Karachi industrial zones so by now land has become costly and only (approximately)
30% of industrial area is available where in Hub and Industrial and Trading Estates (HITE) 95 %
industrial area is available. Also environmental constraints are becoming strict in Karachi
industrial zones. On the other hand HITE is nearest industrial area to port Qasim, it is newly
being developed, land as relatively less costly and environmental constraints would be not strict
as in Karachi zones.
So from land point of view HITE is more suitable.
1) RAW MATERIAL
The major raw material for manufacturing of methanol is Natural
Gas. Raw material is easily available in HITE but it is not available in Karachi industrial zones
except in Site North Karachi, the plots allotment has been frozen.
2) MANUFACTURING AREA
Karachi is the nearest city to HITE and having a
favorable market. On the other hand we can export easily using Port Qasim. The suitable markets
for export are Korea, Japan, Russia, India, Europe, etc.
3) TRANSPORTATION
Recently new plan for infrastructure is introduced by Govt.
and implemented, in which it is planned to connect Hub Industrial and Trading Estate (HITE)
with Punjab through national highway and with Karachi by coastal highway passes.
213
So there will be no problem for product transportation.
4) ENVIORNMENTAL IMPACT AND EFFLUENT DISPOSAL

At Karachi industrial zones there
are number of plants working, so environmental issues are arising day by day and in future
environmental constraints would become more strict. On the other hand HITE is newly being
developed so environmental constraints are less strict and sufficient land area is available for
disposal.
5) UTILITIES
In Hub and Trading Estate (HITE) water, Natural Gas, Electric Power,
Telephone is available and seawater is used for cooling purposes so cooling tower is not required
as used by HUBCO.
6) POLITICAL AND STRATEGIC CONSIDERATIONS

Balochistan is relatively backward area as
compare to the other provinces of Pakistan. So federal as well as provincial government is
planning and keenly interested in developing this region and HITE is a part of this. Therefore in
order to attract the investors and trades, government shall definitely be providing the incentives
such as tax concessions and other inducements (HITE is a Tax Free Area).
7) LABOUR AND MANPOWER

In HITE (Balochistan) cheaper labour is available for
plant construction work and for operation. There is one limitation associated that HITE
(Balochistan) as compare with Karachi Industrial Zones i.e., the availability from Karachi and
others. Therefore this limitation is not overwhelming.
INFORMATION ABOUT INDUSTRIAL ZONES

Hub Industrial and Trading Estate (HITE)
Location
Hub, District Lasbela
Year of Establishment
1982
Total Number of plots
1440 plots
Size of plots
Variables
Uptake/number of plots allotted
150 plots
Industrial plots availability
Available, Occupaney-5%
Infra structure
Road, water, gas power, telephone
Type of industry
Power generation plastic industries
Nearest city
Karachi
PORT QASIM INDUSTRIAL ZONES

Location
Port Qasim
1980
Total Area
2700 acres + 8300acres+1000 acres
Total Number of Plots
Not Fixed
Size of Plots
Variable
Uptake/Number of Plots Allotted
Large Tracts Available
Industrial Plots Availability
Available
Infra structure
Roads, Water, Power, Port
Type of Industry
Port Related Activities
Nearest City
Karachi
Karachi Export Processing Zones

Location
Landi, Industrial Area, off Mehran Highway
1989
Total Area
500 acres
Not Fixed
Size of Plots
Variable
Uptake/ No. of Plots allotted
103 Plots
Available
Infrastructure
Roads, Water, Power
Type of Industry
Garments, Electronics, precision Machining,

Light Chemical, Leather, food processing
214

Nearest City
Karachi
Site Karachi
Location
Mango Pir Road Karachi
1947
Tptal Area
4460 acres
1956
Size of Plots
0.5-1 acres
Uptake/No. of Plots allotted
100%; Occupancy full
Nil
Infrastructure
Roads, Sewerage, Electricity, Water Supply,

Telephone
Engineering, Textile, Consumer Goods,
Telephone
Karachi
Type of Industry
Nearest City
Site North Karachi

Location
Scheme No. 33 North Karachi
1983
Total Area
1029 acres
280
Size of Plots
0.5 acres and to industry requirements
Uptake/No. of Plots allotted
98 Plots; occupancy full
Plots are available but the allotment has been

frozen
Power, Water, Gas Telephone, Internet,
Roads.
Textile, Garments, hosiery, Light
Engineering, soap, poultry, electronics,
Cotton, Dyeing.
Infrastructure
Type of Industry
215

Nearest City
216
Karachi
Korangi Industrial Area

Location
South East of Karachi, about 20 km from the

city centre
1961-69
Total Area
3500 acres
2700Plots
Size of Plots
160 sq. yards-5000 sq. yards
Uptake /No. of Plots allotted
2571 operating units
Available; Occupancy 60%
Infrastructure
Roads, Electricity, Water Supply, Sewerage,

Telephone, Railway Siding available
Textile, Garments, hosiery, Leather, Jute
Thread, Pharmaceutical Products, Cosmetics,
Soap, Sanitary Items, Basic Chemicals, Paints
Karachi
Type of Industry
Nearest C ity
NOMENCLATURE
as = Area of shell
at = Flow area per tube
B = Baffle Spacing
C = Clearance b/w tubes
Cp = Specific Heat Capacity
D = Inside diameter of tubes
De = Equivalent diameter of shell
Ds = Inside diameter of shell
F = Friction Factor
Gt = Tube side mass velocity
Gs = Shell side mass velocity
hi , ho = Inside and Outside film coefficient
hio = Value of hi when referred to the tube ,OD,Btu/hr.ft2.oF
Hv = Heat of vaporization
ID = Internal Diameter
L = Tube Length,ft
LMTD = Log Mean Temperature Difference
M = Mass flow rate of vapors
mm,mw,mDME = Mass Flow rate of vapors of methanol,water,DME
n = Number of passes
OD = Outer Diameter
PT = Tube Pitch
P, Pt, Pr = Total,tube,return pressure drop
Ps = Pressure drop of shell
Q = Heat Flow
Rd = Combined dirt factor
Re = Reynolds number, dimensionless
s = Specific Gravity
w = Mass Flow Rate of water
= Viscosity
= Viscosity ratio, ( / w) 0.14
ML = Mass flow of liquid entering vessel (kg/h)
MV = Mass flow of vapor entering vessel (kg/h)
K = Separator sizing factor (m/s)
Vmax = Maximum allowable vapor velocity in separtor (m/s)
A = Vessel cross sectional area (m2)
r = Vessel radius (m)
D = Vessel diameter (m)
QL = Volumetric liquid flow entering vessel (m3/s)
QV = Volumetric vapor flow entering vessel (m3/s)
217
Refernces
Books
Shreves Chemical Process Industries(5th Edition) by George T.Austin
Elementary Principle of Chemical Process(3rd Edition) by Richard M.Felder
,Ronald W. Rousseau.
Synthetic fuels by Ronald F. Probstein, R. Edwin Hicks.
Petrochemicals by Dr. B.K. Bhaskararo.
From Hydrocarbons to Petrochemicals by Lewis F. Hatch ,Sami Matar
Hand book of Petrochemical & Downstream Projects.
Encyclopedia of Chemical Processing & Design , Vol-29 by John J. Maketta
Encyclopedia of Chemical Technology, Vol-16 (4th Edition)
Chemical Process Principles by Olaf A. Hougen , Kenneth M. Watson
Coulson and Richardsons Chemical Engineering Vol-1 (5th edition), Vol-2 (4th
edition), Vol-3 (3rd edition), Vol-6 (2nd & 3rd edition)
Unit Operation of Chemical Engineering (5th edition) by Warren L.McCabe ,
Julian C.Smith ,Peter Harriott.
Plant design and Economics for Chemical Engineers(4th edition) by Max. S.
Peter, Klaus D. Timmerhaus.
Applied Process Design for Chemical Engineering , by Branan.
Equipment Design Handbook For Refineries and Chemical Plant Vol-2 (2nd
Edition) by Frank L.evans.
Process Heat transfer by D.R Kern
Perrys Chemical Engineering Handbook by Robber H. Perry & Don Green
Chemical Process Equipment Selection & Design by Stanely M. Wales
Chemical and Catalytic Reaction Engineering by James J. Carberry.
218
219
An introduction to Chemical Engineering Kinetics & Reactor design by Charles G.

Hills . Jr.
Fundamentals of Heat Exchanger Design by Ramesh K. Shah
Methanol Synthesis Technology by Sunggyu Lee
Chemical Reactor Design by Peter Harriott
Chemical Process Engineering by Harry Silla
Basic Principles and Calculations in Chemical Engineering (6th Edition) by
Himmelblau David M.
Web Sites:
www.google.com
www.methanol.org/methnaol/
www.drycoolers.com
www.boilerdesign.com
www.science.uwaterloo.ca
www.ttmethanol.com

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