A

Project Report On
MANUFACTURING ASPECTS METHANOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR
THE DEGREE OF
BACHELOR OF ENGINEERING
IN
CHEMICAL ENGINEERING
Submitted By : Internal Guide :
Joshi Ashwin 140280105022 Prof. Rajul P Bhatt
Makhija Ashish 140280105023 Assistant Professor
Mangukiya Rushil 140280105024 L.D.C.E.
Mendaparya Nikunj 140280105026

OCT-2017
DEPARTMENT OF CHEMICAL ENGINEERING
L.D.COLLEGE OF ENGINEERING, AHMEDABAD
 INDEX
Chapter Title Page
No. No.
Certificates
Acknowledgements
Abstract
1 History :
Problem Summery & Possible Solutions
Aims & Objective of the Project
Market of Methanol
New end Uses
World Methanol Demand by Uses
2 Physical and Chemical Properties
3 Uses
4 Manufacturing Process of Methanol
5 Selection of Process and Details with Design
6 Block Diagram
7 Conclusion
8 References
 CERTIFICATE

Chemical Engineering Department, L. D. College of Engineering,

Navrangpura, Ahmedabad
This is to certify that the report entitled MANUFACTURING
ASPECTS OF METHANOL has been carried out under my guidance
in fulfillment of the Degree of Bachelor of Engineering in Chemical
Engineering (Final Year) of Gujarat Technological University,
Ahmedabad during the academic year 2017-18.
Enrollment No. Name of Students
140280105022 Joshi Ashwin
140280105023 Makhija Ashish
140280105024 Mangukiya Rushil
140280105026 Mendaparya Nikunj

Prof. Rekha Kanzariya Dr. S. P. Parikh

Assistant Professor Head Of Department
Chemical Engineering Chemical Engineering
L.D. College Of Engineering L.D. College Of Engineering
Ahmedabad-380015 Ahmedabad-380015
 ACKNOWLEDGEMENT
We take this opportunity to express our profound gratitude and deep
regards to Dr. G. P. VADODARIA Principal of L. D. College of
Engineering and also a deep thank you to Dr. S. P. Parikh, Head of
Chemical Engineering Department of L. D. College Of Engineering. As
well as thanks to our project guide Prof Rajul P.Bhatt for their guidance
monitoring and constant encouragement throughout the course of this
project. The blessing, help and guidance given by them from time to
time shall carry us a long way in the journey of life on which we are
about to embark.
We would like to convey our thanks to all the faculty members for their
cooperation in our project work. We would like to thank LIBRARY IN-
CHARGE and SUPPORTING STAFF of Chemical Engineering
Department for their direct or indirect help in our project.
We would like to thank our family members, our friends for direct and
indirect support during our project work.
 Abstract[1]
Methanol CH30H, is a colorless liquid at ambient temperatures with a
mild, characterstic alcohol odor. Originally called wood alcohol since it
was obtained from the destructive distillation of wood, today
commercial methanol is sometimes referred to as synthetic methanol
because it is produced from synthesis gas, a mixture of hydrogen and
carbon oxides, generated by a variety of sources.
Methanol has traditionally been used as a solvent and as a feedstock for
bulk organic chemicals (primarily formaldehyde), with modest growth
potential. However, after 1990, demand for methanol as a feedstock for
methyl tert-butyi ether (MTBE) accelerated when the latter became a
significant oxygenated component in motor fuels. As a result, methanol
has evolved into a globally produced and traded commodity with
expected future growth in the alternate and oxygenated fuel sectors,
driven by both strategic and environmental considerations.
 History[2][3]
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.
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. 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
(3001000 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.
 Problem Summery & Possible Solutions[4]

1. CATALYST DEACTIVATION is one of the Major problem.

For this, Temperature Condition & Gas Load must strictly
controlled.
THERMAL DAMAGE to the Catalyst can occur after use of
Non-Optimum Recycle Gas
Incorrect Temperature Control
Incorrect Catalyst in the Start-Up phase

2. DEPOSITION of Carbon on Catalyst of Reformer as follows:-

2CO <--> CO2 + C H300K = -172.6 KJ/mole.

Possible Solutios :
The Possible Solutions would be usage of Proper Temperature
Measuring/Controlling Device and Proper Flow
Measuring/Controlling Device(for preventing Gas-Load),thus to
avoid above Problems.
The DEPOSITION of Carbon can largely be prevented by using
Excess Steam and avoiding long residence time in the critical
temperature range about 700 C.

Aims & Objective of the Project

Modifications & Cost Effective

Modifications like Using of PLATE HEAT EXCHANGER rather
than Shell & Tube Heat Exchanger.
 Market of Methanol[5]
The global methanol industry has undergone dramatic changes in the
past 15 years.
These changes have included a shift in regional demand dominance, the
development of new end uses, and the emergence of new production
centers. These factors have resulted in new tradeflows, pricing and
economic dynamics which have previously not existed in the industry
with closer links to other chemical product areas, adding further
complexity in determining market direction.
The shift in the demand center China has emerged as the dominant
country with respect to both methanol capacity and demand owing to its
rapid economic growth.
China represented just 12% of global methanol demand in 2000 while
North America and West Europe represented 33% and 22%,
respectively. By 2015, Chinese methanol consumption had grown to
54% of global demand while North American had fallen to 11% and
West Europe to 10%
Chinese demand has grown significantly in traditional methanol
derivatives, such as formaldehyde and acetic acid, but there has also
been large, step like growth into new end uses, such as light olefins
production, as well as expanded demand into energy applications, such
as DME and direct gasoline blending.
 New End Uses[5]
Fuel applications for methanol have been relatively minor historically
with very limited direct use as a motor fuel.
Chinese direct blending use of methanol into the countrys gasoline pool
has seen an average annual growth rate of 25% from 2000 to 2015,
resulting in gasoline blending becoming the third largest demand
segment for methanol by 2015. Produced from methanol, DME is
primarily used as an aerosol propellant in the West, making for a rather
small overall market.
However DME can also be used as a fuel, either when used instead of
diesel in road vehicles or blended into liquefied petroleum gas (LPG).
The latter has been widely seen at the consumer level for home cooking
and heating in China.
This market segment is large enough that methanol consumption into
DME has grown from virtually nothing in 2000 to represent the fourth
largest methanol derivative. A newer and very rapidly growing demand
segment for methanol is in the production of light olefins (methanol-to-
olefins, MTO).
In an MTO unit, merchant methanol is used as a feedstock; it is not a
unit which is back integrated to the feedstock for methanol.Such
integrated coal-toolefins (CTO) or gas-to-olefins (GTO) units do not
have an impact on the methanol markets as they neither buy nor sell
methanol as it is simply an intermediate phase in the overall process.
For these reasons, the subsequent comments related to MTO refer to
only those units that consume methanol produced by non-associated
methanol units.
As of 2016, MTO units exist exclusively in China with production
beginning in late 2011 at very modest levels of methanol consumption.
World Methanol Demand by region[5]
 Physical and Chemical Properties[2][3][1][4]
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 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 C Flash point 11 C
Auto ignition temperature 455 C
Explosive limits 7-36 %
Heat of Formation -201.3 MJ/kmol
Gibbs Free Energy -162.62 MJ/kmol
 CHEMICAL PROPERTIES
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.

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. Combustion of Methanol:
Methanol burns with a pale-blue, nonluminous flame to form carbon
dioxide and steam.
2CH3OH + 302 ===> 2CO2 + 4H2O

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.
CH3OH ===> HCHO + H2
 Methanol Formaldehyde Dehydration of Methanol
Methanol does not undergo dehydration reactions. Instead, in reaction
with sulphuric acid the ester, dimethyl sulphate is formed.
Conc H2SO4 + 2 CH3OH ===> (CH3)2SO4 + H2O
Sulphate Esterification of Methanol Methanol reacts with organic acids
to form esters.
H + CH3OH + HCOOH ===> HCOOCH3 + H2O
 Uses
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 Cleansing 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.

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
fastgrowing 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
pileup 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.
Methanolpowered 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.
MANUFACTURING PROCESSES OF METHANOL[4][1][6]

1. BASF i.e (Baden Aniline and Soda Factory)

Founded 100 years ago.
Catalyst:-Zinc-Chromium
But this Catalyst requires 25-35 MPa Pressure to work effectively.
Also,the SELECTIVITY of Catalyst was not good.
MANDATED to use RECIPROCATING COMPRESSOR and
limited single trail plant capacity 450 TONS/DAY.

2. ICI i.e (Imperial Chemical Industries Business Companies &

Firms)
Founded around 60 years ago in United Kingdom.
They Developed a more ACTIVE Catalyst
COPPER-ZINC-ALUMINA.
It could operate at 5-10 MPa.
It has HIGHER SELECTIVITY.

3. LURGI PROCESS
LURGI Developed a similar a similar Catalyst,and made his own
process,and had used TUBULAR-STEAM-RAISING REACTOR.
This Low-pressure Revolutionzed the Industry,Train Capacity increased
upto 2200 TONS/DAY. (4-5 times Capacity had been increased) and It
had used CENTRIFUGAL COMPRESSORS.
 SELECTION OF PROCESS[4][6]

The main advantages oflhe low pressure process are lower investment
and production costs, im proved operational reliability, and greater
flexibility in the choice of plant size.
Industrial methanol production can be sub divided into three main steps:
1) Production of synthesis gas
2) Synthesis of methanol
3) Processing of crude methanol
PRODUCTION OF SYNTHESIS GAS :[6][1]
Carbonaceous materials such as coal, coke, natural gas, petroleum,
and fractions obtained from petroleum (asphalt, gasoline, gaseous
compounds) can be used as starting materials for synthesis gas
production. Economy is of primary importance with regard to
choice of raw materials. Long-term availability, energy
consumption, and environmental aspects must also be considered.
Natural gas is generally used in the largescale production of
synthesis gas for methanol synthesis. in a few processes (e.g.,
acetylene pro duction), residual gases are formed which have
roughly the composition of the synthesis gas required for methanol
synthesis.
Synthesis gases are characterized by the stoichiometry number S:S
where the concentrations of relevant components are expressed in
volume percent. The stoichiometry number should be at least 2.0
for the synthesis gas mixture. Values above 2.0 indicate an excess
of hydrogen. whereas values below 2.0 mean a hydrogen
deficiency relative to the stoichiometry of the methanol formation
reaction. Natural Gas. Most methanol produced worldwide is
derived from natural gas. Natural gas can be cracked by steam
reforming and by partial oxidation. In steam reforming the
feedstock is catalytically cracked in the absence of oxygen with the
addition of water and possibly carbon dioxide. The reaction heat
required is supplied externally. In parrafin oxidation, cracking
takes place without a catalyst. Reaction heat is generated by direct
oxidation of part of the feedstock with oxygen. in a combination of
the two processes, only part of the natural gas stream is subjected
to steam reforming. The remainder passes with the reformed gas to
an auto thermal reformer where the natural gas is partially oxidized
by oxygen. Only the production of synthesis gas by steam
reforming is discussed here in some detail.
The catalysts used in steam reforming are extremely sulfur
sensitive; sulfur concentrations < 0.5 ppm quickly, poison the
catalyst. A gas purification stage therefore pro codes the reformer
stage. if sulfur occurs primarily in the form of higher boiling
compounds (e.g., mercaptans).
SYNTHESIS OF METHANOL[1][4]
Important reactions for the formation of methanol from synthesis
gas are discussed below:-
CO + 2H2 <--> CH3OH H300K = -90.77 KJ/mole.
CO2 + 3H2 <--> CH3OH + H2O H300K = -49.16 KJ/mole
CO2 + H2 <--> CO + H2O H300K = 41.21 KJ/mole.
In one pass only about 50% of the synthesis gas is converted
because thermodynamic equilibrium is reached. Therefore, after
methanol and water are condensed out and removed, the remaining
synthesis gas must be recycled to the reactor. A simplified flow
diagram For methanol synthesis is shown in Figure. The make up
synthesis gas is brought to the desired pressure (5-10 MPa) in a
multistage compressor (D).The unreacted recycle is added before
the recycle stage. A heat exchanger (b) transfers energy from the
hot gas leaving the reactor to the gas entering the reactor. The
exothermic Formation of methanol takes place in the reactor (at) at
200-300 C. The heat of reaction can be dissipated in one or more
stages. The mixture is cooled further (c) after passing through the
heat exchanger (b); the heat of condensation of methanol and water
can be utilized at another point in the process. Crude methanol is
separated from the gas phase in a separator (d) and flashed before
being distilled. Gas from the separator is recycled to the suction
side of the recycle compressor (e). The quantity of purge gas from
the loop is governed by the concentration and absolute amount of
inert substances and the stoichiometry number. lf hydrogen is used
to adjust the composition of the fresh gas to give the required
Stoichiometry number it can be recovered from the purge gas by
various methods (e.g., pressure swing absorption). The purge gas is
normally used for reformer heating.
Reactor Design[4][7][8][9][10]
Current industrial processes for producing methanol differ
primarily in reactor design. Many different reactors are available
[109]; they may be either adiabatic (c.g., lCl) or quasi isothermal
(e.g., Lurgi). The [CI process (Fig. 4) accounts for 60 %, and the
Lurgi process (Fig. 5) for 30% of worldwide methanol production.

Adiabatic Reactors
The lCl process (Fig. 4) uses an adiabatic reactor with a single
catalyst bed [110). The reaction is quenched by adding cold gas at
several points. Thus. the temperature profile along the axis of the
reactor has a sawtooth shape. ln the Kellogg process, synthesis gas
flows through several reactor beds that are arranged axially in
series [ill]. ln contrast to the lCl quench reactor, the heat of
reaction is removed by intermediate coolers. The Haldor Topsoe re
actor operates on a similar principle, but synthesis gas llows
radially through the catalyst beds [2]. Ammonia -Casale S. A. has
developed a reactor that employs a combination of axial and radial
flow (mixed flow). This type of reactor initially developed for
ammonia plants is offered by Davy McKee in lCl license.
DISTILLATION OF CRUDE METHANOL[4][7][1][9][12]
The methanol contains low-boiling and highboiling components
(light and heavy ends). The light ends include dissolved gases,
dimethyl ether. methyl formate, and acetone. The heavy ends
include higher alcohols, long chain hydrocarbons, higher ketones,
and esters of lower alcohols with formic, acetic. and propionic
acids. Higher waxy hydrocarbons consisting of a mixture of mostly
straight-chain > C8-C14 compounds are also formed in small
amounts. They have low volatility and thus remain in the
distillation bottoms, from which they can easily be removed
because of their low solubility in water and low density.
The impurities in crude methanol are generally separated in two
stages. First, all components boiling at a lower temperature than
methanol are removed in a light ends column. Pure methanol is
then distilled overhead in one or more distillation columns.
BLOCK DAIGRAM[4][6][11]
 CONCLUSION
It was Originally believed that the main process Tha produce
methanol was equation(1), Previously CO2 was being Scrubbed
from the Reactant Mixture (CO,H2 & CO2).Then the presence of
CO2 in the mixture proved Increment of the Methanol
Production.Now, Mainly CO2 converted into Methanol, while CO
act as a Reducing agent for Oxygen at the Surface of the Catalyst.
This,to reach the necessary Stoichiometry of Synthesis gas for
Methanol synthesis,Carbon Dioxide is mixed if CO2 is not
available.
In FUTURE we will be working on the following:
Material Balance
Energy Balance
Equipment Design
Plant Layout
 Refrences
1. Reference is Ullmans's Encyclopedia for Industrial
Chemistry

2. Elementary Principle of Chemical Process(3rd

Edition) by Richard M.Felder ,Ronald W. Rousseau

3. Synthetic fuels by Ronald F. Probstein, R. Edwin

4. Hicks

5. Kirk and Othmer encyclopedia of chemical technology

6. Market Report by IHS Chemical Bulletin

7. Manufacturing of Methanol by MITSUBISHI HEAVY

INDUSTRIES LIMITED (United State Patent)

8. Process Equipment and Design by B.I Bhatt & Suchen

B. Thakore

9. Chemical and Catalytic Reaction Engineering by

James J. Carberry.

10. Coulson and Richardsons Chemical Engineering

Vol-1 (5th edition), Vol-2 (4th edition), Vol-3 (3rd
edition), Vol-6 (2nd & 3rd edition)
11. Chemical Reaction Engineering by Octave Levenspiel

12. Unit Operation of Chemical Engineering (5th

edition) by Warren L.McCabe , Julian C.Smith ,Peter
Harriott.

13. Shreves Chemical Process Industries(5th Edition) by

George T.Austin

14. Process Calculation by B.I Bhatt & Suchen B.Thakore

15. Perrys Chemical Engineering Handbook by Robber

H. Perry & Don Green