Professional Documents
Culture Documents
DESIGN OF FORMALDEHYDE
PRODUCTION PLANT
GROUP 4
14778
14988
14771
15049
16219
CERTIFICATION OF APPROVAL
DESIGN OF FORMALDEHYDE
PRODUCTION PLANT
GROUP 4
14778
14988
14771
16219
APPROVED BY:
_______________________
DR. BHAJAN LAL (Group Supervisor)
DATE:
CHEMICAL ENGINEERING DEPARTMENT
UNIVERSITI TEKNOLOGI PETRONAS
ACKNOWLEDGEMENT
Upon completion of Final Year Plant Design Project, project team would like to express
their heartfelt gratitude to individuals and organization that have helped the team through
the process. Without assistance and guidance, it would not be a smooth and successful
process. First of all, sincere thanks and highest appreciation goes to the most important
person who has played a very big role in this project, the project supervisor, Dr. Bhajan
Lal. Throughout the process, he had given proper guidance to the team and ensures the
team is on the right track of the process.
The project team would also like to express their gratitude to Chemical Engineering
Department of Universiti Teknologi PETRONAS (UTP) for providing Final Year Plant
Design Project course for the program as a platform for the students to apply the knowledge
from undergraduate studies in actual application on plant design.
The team would like to thank the Final Year Plant Design Projects committees,
especially Dr. Sekhar Bhatacharjee for giving his insights on the process design and
frequent updates on the materials and documents related in completing the project. Thanks
for their efforts in organizing seminars and briefing for all the project teams to let them
understand the procedure of the project and guide them in the process. The seminars and
briefings were indeed very helpful and insightful.
Sincere gratitude goes to Group 4 team members for their team spirits, hard work and
determination. Last but not least, project team would like to appreciate individuals that are
either directly or indirectly involved in making this project a grand success.
TABLE OF CONTENTS
Background ............................................................................................................ 10
1.2
1.3
Objective ................................................................................................................ 12
1.4
CHAPTER 2:
2.1
3.2
3.2.1 Explosion of drums in Kalyani, Nadia District, West Bengal, India .................... 43
3.2.2 Explosion in a resins production unit at Georgia-Pacific Resins, Inc. in Columbus,
Ohio................................................................................................................................ 45
3.3
LIST OF FIGURES
Figure 1: World demand for methanol in 2007...................................................................... 14
Figure 2: West Europe Methanol Supply & Demand ............................................................ 18
Figure 3: Middle East Methanol Supply & Demand ............................................................. 19
Figure 4: Southeast Asia Methanol Supply & Demand ......................................................... 19
Figure 5: Northeast Asia Methanol Supply & Demand ......................................................... 19
Figure 6: South America Methanol Supply & Demand ......................................................... 20
Figure 7: North America Methanol Supply & Demand ......................................................... 20
Figure 8: Global Formaldehyde Supply & Demand .............................................................. 21
Figure 9: Global Formaldehyde Demand by Region ............................................................. 21
Figure 10: World Methanol Demand by Region ................................................................... 22
Figure 11: West Europe Price Trend...................................................................................... 23
Figure 12: Northeast/Southeast Asia Price Trends ............................................................... 23
Figure 13: US Methanol Price Trend ..................................................................................... 24
Figure 14: Methanol Pricing Mechanism............................................................................... 24
Figure 15: Molybdenum Oxide Price Trend(MetalPrices.com, 2014)................................... 25
Figure 16: Ferromolybdenum Price Trend (MetalPrices.com, 2014) .................................... 25
Figure 17: Iron Oxide Pricing (StandardCeramic.com, 2014) ............................................... 26
Figure 18: Vanadium Pentoxide Pricing (StandardCeramic.com, 2014) ............................... 26
Figure 19: Silver Price Trend (SilverPrice.com, 2014).......................................................... 27
Figure 20: Schematic Diagram on selection of site criterion ................................................. 30
Figure 21: Kedah Map and location of Gurun ....................................................................... 38
Figure 22: Plant Layout ......................................................................................................... 40
Figure 23: Layers of Protection Concept ............................................................................... 51
Figure 24: Characteristics and features of methanol .............................................................. 58
Figure 25: Flowchart of formaldehyde production by the BASF process ............................. 61
Figure 26: Flowchart of formaldehyde production with recovery of methanol by distillation
............................................................................................................................................... 62
Figure 27: Flowchart of formaldehyde production by the Formox process ........................... 63
Figure 28: Batch operation..................................................................................................... 66
Figure 29: Continuous operations .......................................................................................... 67
Figure 30: Block diagram of incomplete conversion of methanol with distillative recovery of
methanol................................................................................................................................. 71
Figure 31: Block diagram of complete conversion of methanol (BASF) .............................. 72
Figure 32: Block diagram of Formox process ....................................................................... 73
Figure 33: Combined composite curve .................................................................................. 80
LIST OF TABLES
Table 1: Overview of methanol applications ......................................................................... 15
Table 2: Price range of catalysts ............................................................................................ 27
Table 3: Price range of various companies for formaldehyde ............................................... 28
Table 4: Price range for materials .......................................................................................... 29
Table 5: Comparisons of possible locations (Jasmir & Nadzri, 2010; McMorrow & Talip,
2001) ...................................................................................................................................... 33
Table 6: Weightage criteria .................................................................................................... 36
Table 7: Weighted evaluation on potential site ...................................................................... 37
Table 8: Job hazard analysis (JHA) for explosion of drums in Kalyani, Nadia District, West
Bengal, India (Bhattacharjee et al., 2014) .............................................................................. 44
Table 9: Summary of chemical hazards information ............................................................. 48
Table 10: Preventive measure to reduce risk at workplace .................................................... 50
Table 11: Basic strategies in inherent safety chemical process ............................................. 52
Table 12: Specifications of the methanol for production of formaldehyde ........................... 58
Table 13: Comparison of between batch and continuous process operation ......................... 68
Table 14: Economic comparison of three process routes....................................................... 75
Table 15: Stream Data ........................................................................................................... 76
Table 16: Shifted temperature ................................................................................................ 77
Table 17: Temperature Portioning Table ............................................................................... 78
Table 18: Heat cascade diagram ............................................................................................ 78
EXECUTIVE SUMMARY
Formaldehyde is a commonly used chemical compound that exists in various forms and at
room temperature, is a colorless, distinctive, strong and even pungent smelling, flammable
and gaseous substance. Formaldehyde has been used in a number of industries for various
purposes such as: for the manufacturing of building materials like pressed wood products
(mostly as an adhesive resin), fiber board, plywood, cigarette smoke, fuel burning appliances
and kerosene space heaters. Additional uses in household products include: additive for
permanent press, an ingredient in glues, and as a preservative in medical laboratories as
embalming fluid, and as a sterilizer. Since Formaldehyde is a by-product of combustion and
other inherent processes, it can be found in significant concentrations and in various
environments. The main objective of this project is to design an economically feasible
formaldehyde production plant with the plant capacity of 50, 000 ton per year. The
development of plant should consider all the relevant criteria required in order to make the
most optimize production plant. The location chosen for the plant is in Labuan because raw
material ethanol is easily transported from the port to plant area.
The first two chapters of the project emphasizes on the introduction and literature
review. The problem statement, objectives and scope of study of the project are being
discussed thoroughly in the first chapter. Chapter 2 gives details regarding existing
process description for formaldehyde manufacture, the process route chosen, physical
and
chemical
properties
of
materials
involved
in
formaldehyde production,
Chapter 3 mainly focuses on preliminary hazard analysis. The hazards for formaldehyde
are identified and the control measures are detected. Apart from that, the environmental
issues are taken into consideration to produce a green, sustainable and environmental
friendly process of the formaldehyde plant.
Chapter 4 focuses on highlighting the main section of the project design, which is the
conceptual design analysis. The hierarchical approaches are briefly discussed as it is
a systematic approach to determine the type of process implemented. The reactor
design and separation synthesis are also being reviewed to produce a feasible and
economical plant design. Plant would be operated in continuous mode. The preferred
reactor used for this project is plug flow reactor and this selection of reactors is
important to maximize the production of formaldehyde. Using different patents as basis,
three process flow sheets are developed. The most feasible process flow is chosen from
the highest yield of product and comparison between economic potential 1 and
economic potential 2 for all the three process flow sheets.
CHAPTER 1: INTRODUCTION
1.1
Background
The purpose of this project is to design a plant that produce formalin which is 37
weight % of formaldehyde in water as the main product of the overall process and to
execute the design and evaluation on safety aspects, site selection, conceptual design,
material and energy balance, heat integration and preliminary economic evaluation.
Formaldehyde is an organic compound with the formula CH2O or HCHO. It is the
simplest aldehyde and is also known by its systematic name methanal. The common name of
this substance comes from its similarity and relation to formic acid.
A gas at room temperature, formaldehyde is colorless and has a characteristic
pungent, irritating odor. It is an important precursor to many other materials and chemical
compounds. In 1996, the installed capacity for the production of formaldehyde was
estimated to be 8.7 million tonnes per year.(G.Reuss) Commercial solutions of formaldehyde
in water, commonly called formol, were formerly used as disinfectants and for preservation
of biological specimens. It is commonly used in nail hardeners and/or nail varnish.
Formaldehyde is more complex than other simple carbon compounds in that it adopts several
different forms. One vital derivative is the cyclic trimer metaformaldehyde or 1,3,5-trioxane
with the formula (CH2O)3. There is as well an infinite polymer called paraformaldehyde.
These compounds behave similarly as the molecule CH2O.
When dissolved in water, formaldehyde forms a hydrate, methanediol, with the
formula H2C(OH)2. This also exists in equilibrium with various oligomers (short polymers),
depending on the concentration and temperature. A saturated water solution, of about 40%
formaldehyde by volume or 37% by mass, is called "100% formalin". A small amount of
stabilizer, such as methanol, is usually added to suppress oxidation and polymerization. A
typical commercial grade formalin may contain 1012% methanol in addition to various
metallic impurities.
Formaldehyde can be produced by various reactions such as the catalytic oxidation,
dehydrogenation and also direct oxidation of methane. Catalytic oxidation remains as the
most viable and economical process to produce formaldehyde yet. And most commonly used
catalysts
for
this
process
are
silver metal
10
or
mixture
of
1.2
Problem Statement
From the Methanol Market Services Asia (MMSA) report (2013) on Formaldehyde
Supply and Demand Balance, we can see that the demand of formaldehyde has been
increasing gradually since the year of 2009. For the year 2013, there is an increase in
formaldehyde demand of 4.92%. In 5 years time since 2009, we can see an increase in
demand of staggering 36.38%. This shows that, the global consumption of formaldehyde is
increasing with a very good pace. Especially here in Asia as most of the countries are
growing economically.
In Malaysia, there are only a few significant plants that are producing formaldehyde
such as ChemstationAsia, Hexza Corporation, and NewQuest Trading under Kuok Groups.
Formaldehyde Industry is still growing and the demands for Formaldehyde are quite high
globally.
factors
and
relevant issues
are taken
into
consideration when
designing a new petrochemical plant. Factors that need to be emphasized are safety issues
related to process, health and environment; plant location, energy consumption
and proper process route to ensure the plant are operated through green, sustainable
and environmental friendly process.
11
1.3
Objective
The main objective of the plant design project is to produce the required amount of product
while ensuring that the plant operations is economically feasible without disregarding the
environmental and safety aspect. The team is required to propose the best design at the
end of this project. Apart from that, the objectives of this design project include the
following:
To study about the raw materials and product used in the process. The study
encompasses their properties, market survey, cost, application, supply and
demand of the global market.
To study on the alternatives routes of producing the products.
To identify and select the best process route to produce the desired products to
propose a proper plant location for the design project.
To determine the safety precaution actions for the plant.
To develop the complete material and energy balance calculations.
To generate material, energy balances and heat integration network for a
petrochemical plant using computer aided design engineering software (e.g.
ICON/HYSIS).
To evaluate the economic feasibility of the plant by determining the
economic potentials for all possible routes.
12
1.4
Scope of work
In order to ensure the work progress is in accordance with the timeline of proposed
activities, milestones and deadlines, details and proper scope of work need to be established
and well-planned. Below are the details of the scope of work in order to reach the
objectives in this course:
Conducting literature review from journals, books, and any other reliable studies
regarding the raw materials, chemical and physical properties of the intermediate
product, product and by-product, economic evaluations for the production of
product, usage of the desirable product, main and alternative routes
products
production,
safety
and
for
desired
related issues
Identifying and selecting the best process route for a particular design project,
developing the best possible process flow sheet for the selected chemical
process route.
Determining the plant location based on several factors such as costs,
transportation, accessibility, utilities tariff, raw materials supply and local
legal requirements.
Developing the complete material and energy balance calculations for all
processes as well as heat integration for the selected process.
Determining the economic potential and cost estimation for all processes.
Applying related computer-aided design and engineering software such
as HYSYS, Microsoft Office Visio, MATLAB and AutoCAD as tools
for designing task.
13
CHAPTER 2:
2.1
LITERATURE REVIEW
liquid with a mild alcoholic odor. It freezes at -97.6C, boils at 64.6C and has a density of
791 kg/m3 at 20C. Today, methanol is mainly a feedstock for the chemical process industry
used for the production of varied chemical products and materials. Worldwide, almost 65%
of the methanol production is used to obtain formaldehyde. Figure 1 below shows the world
demand for methanol in 2007 (Cheng, 1994).
Methanol is a high production volume chemical with many commercial uses and it is
a basic building block for hundreds of chemical products. Many of its derivatives are used in
the construction, housing or automotive industries. Consumer products that contain methanol
include varnishes, shellacs, paints, windshield washer fluid, antifreeze, adhesives, de-icers,
and Sterno heaters (Olah, Goeppert, & Prakash, 2009). In 2009, the Methanol Institute
estimated a global production capacity for methanol of about 35 million metric tons per year
14
(close to 12 billion gallons), a production capacity in the United States (U.S.) of nearly 3.7
million metric tons (1.3 billion gallons), and a total U.S. demand for methanol of over 8
million metric tons. Methanol is among the highest production volume chemicals reported in
the U.S. EPAs Toxic Release Inventory (TRI) (Cheng, 1994; Olah et al., 2009).
While production has switched to other regions of the world, demand for methanol is
growing steadily in almost all end uses. A large reason for the increase in demand is its use
in the production of biodiesel, a low-sulfur, high-lubricity fuel source.
2.1.2 Production of Methanol Indirect Route via Syngas
The conversion of natural gas to methanol via syngas is a widely used industrial
process. Methanol synthesis from syngas is an exothermic reaction and operates at high
temperature, around 200-300C (Cheng, 1994). Production of syngas is traditionally
performed in one step by steam reforming. Many of the modern processes adopt two-step
reforming, which is primary steam and auto-thermal reforming. According to Olah et al., the
primary reformer is simplified and reduced in size and can be operated at a reduced
temperature. Oxygen is blown to the auto-thermal reformer first to produce carbon monoxide
and water with heat generation. The secondary reforming operates at higher temperature to
ensure low leakage of methane. The combined process is integrated to produce
stoichiometric syngas for methanol synthesis. The process reduces energy consumption and
investment and is particularly suitable for larger capacities. The two step reforming process
has been used by Topsoe, Lurgi, Mitsubishi and others (Olah et al., 2009).
Oxygenate in gasoline
Oxygenate in gasoline
15
Chemicals
Formaldehyde
Urea-formaldehyde resins
Phenolic resins
Acetylenic chemicals
Polyacetal resins
Vinyl acetate
Acetic anhydride
Ethyl acetate
Acetic acid
Chloromethanes
Methyl chloride
Methylene chloride
Other uses
Solvent
Antifreeze
Inhibitor
Substrate
2.2
corrosive and flammable gas with a pungent, suffocating odor. Formaldehyde is available in
the environment from either natural or industrial sources. Formaldehyde is produced in large
quantities industrially. It is predominantly used commercially as a solution in water at
concentrations in the range of 25 56 % formaldehyde (Anonymous, 2000). A solution of
approximately 37% formaldehyde is commonly known as formalin and is used as a tissue
fixative for histology and pathology.
Formalin is a common constituent used in the manufacture of many complex
materials. It is used in the production of resin polymers for permanent adhesives such as
those used in fiber board, particle board, plywood and carpeting. It is also used in foam
insulation and as paper and textile finishing treatments. Formaldehyde at approximately 5%
in a solution with water is used as a disinfectant and fumigant in hospitals, ships, dwellings
and animal handling facilities, as it is effective in killing most bacteria, viruses and fungi
(Anonymous, 1994). Formaldehyde can be considered to occur naturally in the environment
because it is produced form the breakdown of methane by sunlight. Formaldehyde is also
formed from the combustion of organic materials such as wood fires and tobacco smoke.
2.2.2 Routes of Exposures to Formaldehyde
The possible routes of exposure to formaldehyde are ingestion, inhalation, dermal absorption
and rarely, blood exchange as in dialysis.
16
2.2.2.1 Air
Assuming a breathing volume of 20 m3 per day for an average adult, given the air
levels mentioned above and making assumptions of the time spent in various environments,
one can calculate inhalation exposure per day. Average time estimates lead to the conclusion
that people spend 6070% of their time in the home, 25% at work and 10% outdoors. If one
assumes that normal work exposures are similar to home exposures, and the data given on
the occurrence of formaldehyde in air are used, the daily exposure resulting from breathing is
about 1 mg/day, with a few exposures at > 2 mg/day and a maximum of about 8 mg/day
(Organization, 2001).
2.2.2.2 Food
Formaldehyde occurs naturally in foods, and foods may be contaminated as a result
of fumigation, cooking and release from formaldehyde-resin-based tableware. Formaldehyde
has been used as a bacteriostatic agent in some foods, such as cheese. Fruits and vegetables
typically contain 360 mg/kg, milk and milk products about 1 mg/kg, meat and fish 620
mg/kg and shellfish 1100 mg/kg. The daily intake is difficult to evaluate, but a rough
estimate from the available data is in the range of 1.514 mg/day for an average adult, most
of it in a bound and unavailable form (Organization, 2001).
2.2.3 Applications of Formaldehyde
Formaldehyde is used extensively in the woodworking and cabinet-making
industries. Urea-formaldehyde is used in the glues that bond particle board together. The
particle board is used underneath wood veneer and plastic laminate. Cabinets, bank counters,
and veneered and laminated woodwork all use particle board containing urea-formaldehyde
under the plastic laminate and wood veneer (Pinto, Gladstone, & Yung, 1980).
According to Pinto et al., formaldehyde is a common building block for the synthesis
of more complex compounds and materials. Products generated from formaldehyde include
urea formaldehyde resin, melamine resin, phenol formaldehyde resin, polyoxymethylene
plastics, 1, 4-butanediol, and methylene diphenyl diisocyanate. The textile industry uses
formaldehyde-based resins as finishers to make fabrics crease-resistant. Formaldehyde-based
materials are keys to the manufacture of automobiles, and used to make components for the
transmission, electrical system, engine block, door panels, axles and brake shoes.
17
2.3
18
19
Based from figures above, the methanol can be easily acquired from South America,
Southeast Asia and Middle East since their production outweighs their demand domestically.
As for formaldehyde, the supply and demand can be seen in Figure 7 & 8.
20
21
Both of these figures shows that a market window particularly for demand of formaldehyde
is steadily increasing in size and the three regions in focus are Northeast asia, North America
and Europe. Therefore, these regions are where the potential customers can be found.
22
23
Based on the three price trends, the price trend of Notheast/Southeast Asia is the most
reasonable ($300-350/ton) and considering it is the price setter, methanol would best be
bought from Northeast/southeast Asia region.
24
25
26
Price(USD)/kg
Molybdenum Oxide
20.00
Ferromolybdenum
24.00
Iron Oxide
7.60
Silver
Based on Table 2 above, the cheapest catalyst is iron oxide while the most expensive
is silver. For peak performance, ferromolybdenum and vanadium pentoxide can be
deployed with price below $100/kg which still less expensive compared to silver.
27
Price Range
$ 31890.00/ton
$350-500 / ton
Purity
Min. Order
Supply Ability
$387-419 / ton
5 Tons
Qingdao
Xinyongan $400-450/ ton
Chemicals Co., Ltd
5 Metric Tons
20 Tons
Xinxiang
Kolanky
Technical Co., Ltd.
Henan Xinxiang No. 7
Chemical Co., Ltd.
Zhejiang
Junhao
Chemical Co., Ltd
Guangzhou
Derou
Chemical Industry Co.,
Ltd.
Xinxiang
Kolanky
Technical Co., Ltd.
YongHua
Chemical
Technology
(Jiangsu)
Co., Ltd.
Toronto
Research
Chemicals
$1450-1850
/ ton
$1450-1850
/ ton
18 Tons
$95670/ton
1 Ton
1 Metric Ton
18 Tons
1500
Metric
Ton/Metric Tons
per Month
1000
Metric
Ton/Metric Tons
per Month
10000 Ton/Tons
per Month
1,000 Ton/Tons
per Month
2000
Metric
Ton/Metric Tons
per Month
880 Ton/Tons per
Month
880 Ton/Tons per
Month
1 Metric Ton
$1000-10000
/ton
1000
Kilograms
$1450-1850
/ ton
$260-520 / ton
18 Tons
$183981539679 / ton
1 Metric Ton
300
Metric
Ton/Metric Tons
per Month
880 Ton/Tons per
Month
10
Metric
Ton/Metric Tons
per Day
96%
$511051899448 /ton
98%
$44330/ton
$24530/tonl
96%
98%
Based on the supply ability, purity, pricing range and minimum order, the preferable
price for selling formaldehyde is in range of $20000-100000/ton.
28
By referring Table 3, based on the supply ability, purity, pricing range and minimum
order, the preferable price for selling formaldehyde is in range of $20000100000/ton.
After compiling the price range and trend of reactant, catalysts and product, the
following table is formed:
Table 4: Price range for materials
Material
Price range
Methanol
$300-350/ton
Iron Oxide
$7.60/kg
Formaldehyde
29
2.4
Raw Material
Availability
Political,
Economic and
Strategic
Consideration
Location With
Respect To
Marketing Area
Waste Disposal
Transportation
Land
Availability &
Cost
Utilities
Labour Supply
30
2.4.2.3 Transportation
Water, railroads, and highways are the common means of transportation used by
major industrial concerns. The kind and amount of products and raw materials determine
the most suitable type of transportation facilities. If possible, the plant site should have
access to all three types of transportation. Land transport such as road and rail
transport is being increasingly used. The road transport is more suitable for a local
distribution from a central warehouse meanwhile the rail transport is more suitable for
long distance transport of bulk chemicals as it cheaper. Seaport facilities will help in the
exportation and importation of the product and raw materials via tankers while the
availability of airport is convenient for the movement of personnel and essential equipment
supplies.
2.4.2.4 Utilities
Basic facilities such as water supply, power supply and supporting utilities must be
located near to the location site in order to run the chemical process more convenient and
effective. Power requirements are high in most industrial plants, and fuel is ordinarily
required to supply these utilities. Consequently, power and fuel can be combined as one
major factor in the choice of a plant site. Large quantities of water supply are needed for
cooling and general use in a chemical plant.
31
labor
will
mainly
involve
in
the
construction,
management,
operation and the maintenance of the plant. Skilled construction workers will usually
be brought in from outside local area but there should be an adequate pool of unskilled
workers available locally and workers suitable for training to operate the plant. Available,
inexpensive manpower from the surrounding area will contribute in reducing the cost
of operation. Besides that, the turnover rates, local pay rates and competing industries
must also be considered.
2.4.2.6 Suitable land Availability
The cost of the land depends on the location selected. Enough space area with
reasonable land prices should be identified and selected in order to reduce the
investment cost in designing a plant location. It is important to choose the lowest land price
when starting a new plant to gain the highest economic value. That said, the land must also
be suitable and should be spacious keeping in mind of a future expansion.
2.4.2.7 Waste Disposal
A good industrial site is when it is provided with a good waste disposal facility. It is
important to provide an efficient and correct waste disposal in order to prevent or reduce any
pollution which then can affect the human. If there are none, then the best way is to choose
the area which is the nearest to this facility. However, this factor is not a great concern as the
operations of this plant only produce water as the waste and the plant itself will be built with
a wastewater treatment plant.
32
Table 5: Comparisons of possible locations (Jasmir & Nadzri, 2010; McMorrow & Talip,
2001)
Selection
Criteria
Land
price
Area
available
Water
supplier
Electricity
supplier
Methanol
supplier
Gurun, Kedah
- PETRONAS CUF
Highway
North-South highway
KK-Sulaman highway
Railway
Gurun
Railway
Station
Sultan Abdul Halim
Airport
Penang Port (60km)
Pulau Bunting Port
(project
completion
2016) 19km
Large population
Airport
Port
facility
Labor
Supply
Waste
disposal
Political,
Economic
and
Strategic
Large population
- PETRONAS CUF
-Dewan Bandaraya Kota Kinabalu
- Majlis Perbandaran
Kedah
Companies
developing
infrastructure
of
industrial park:
33
Bulk
Large population
- PETRONAS CUF
Investment Incentives
Pioneer status
Investment
tax
Considera
tion
allowance
Income
tax
exemption of 100%
for
5
years
commencing from the
year company derives
statutory income, or
Investment
tax
allowance (ITA) of
100% on qualifying
capital expenditure for
5 years
Stamp
duty
exemption
on
instruments
of
acquisition or leasing
of property relating to
industrial park
Companies
undertaking promoted
activities
in
the
industrial park:
Customised
incentives based on
merit of each case, or
Income
tax
exemption of 100%
for
8
years
commencing from the
year company derives
statutory income, or
Investment
tax
allowance (ITA) of
100% on qualifying
capital expenditure for
5 years
- Import duty and
sales tax exemption
on raw materials,
components,
machinery,
34
35
5-4 Marks
3-2 Marks
Land price
Price of land below RM Price of land more than Price of land more than
20 psf
Natural
gas Able
RM 20 psf
to
obtain
RM30 psf
supplier
1-0 Marks
Water supplier
Able
to
obtain
state
Electricity
Able
obtain
supplier
state
Port facility
facility
Availability
Airport
facility
international airport
Political,
Economic
airport
Railway
facility
network
railway
and
Strategic
Consideration
36
of Unavailability of railway
No tax benefits
Selection Criteria
Gurun
Industrial Kota
Kinabalu
Lahad
Datu
Industrial
Park,
Area
Industrial Park
Water supplier
Electricity supplier
Port facility
Airport
Railway
Highway
Waste disposal
Tax Benefits
Total
48
29
40
Percentage
96%
58%
80%
Ranking
Land price
Raw
materials
supplier
37
Sabah
Based on matrix comparison in the above table, Gurun Industrial Estate has been
chosen as a proposed location to build formaldehyde plant. The following are the attractive
features of Gurun Industrial Estate:
After researching suitable plant locations, we have decided to suggest the location to be in
Gurun, Kedah, Malaysia as it is closest to one of the methanol suppliers in Malaysia.
Gurun Industrial area is a suitable place to set up a plant. The advantages are including cheap
industrial land prices. Furthermore it has become a platform mainly for petrochemical
industries (PETRONAS Fertilizer Kedah) and other technology industry. There are several
major factories in Gurun industrial zone, namely Perwaja Steel, Modenas and Naza. There
are also good roads and highways for ease of transportation. Gurun can be reached via the
federal highway within Kedah, the North-South Expressway and it even has its own train
station. The main junction in the town center connects the western part of Kedah to the town
of Jeniang and the district of Sik.
38
Below are details of PETRONAS Fertilizer Kedah (PFK), the methanol supplier of
interest.
Methanol Supplier
Company Name
Type
: Wholly Owned
Address
Principal Activity
Principle Activity
: Petrochemicals
Capacity
Uses (Methanol)
39
According to Figure 17, which is a simple plant layout, the process area and non-process
area are separated. The places where most workers are present, such as administration
building, laboratory, control room and cafeteria should be located near to each other to
minimize travelling time for the worker to go from one place to another. In addition, the
plant also has a storage tank to store methanol and warehouse to store the end products.
The warehouse is built with a loading and unloading bay for customers to collect the
finished product. The loading and unloading bay is monitored by the guards in the guard
room. Lastly, the plant also has garden for landscaping, parking lots and a security building.
Trees are also planted in plant site to induce a good and healthy environment. Moreover,
visitors lounge is equipped with an entertainment room for the guests and potential buyers.
40
The PHA starts in the concept phase of project. This analysis targeting to identify the safetycritical areas in the project, hazards and the safety design of the project. Besides that, it
also focus in evaluating the hazards and the operation requirement in the project. This PHA
will provide the important information regarding the causes and control of the hazards. It
is the first step or initial effort in the hazard analysis that starts during the initial design
phase of the project. The identification of the most ranked hazard and control measures will
provide the basic or foundation to analysis that will come later as the cycle of project
development in the progress.
ii.
PHA is the precedent of SSHA. This SSHA was design to work on the safety risk assessment
of the projects subsystem that is more detail and thorough than the information
provided by PHA. The SSHA will checks and verifies that the design of the projects
subsystem will follow the safety requirement and also explore the previously
undetected hazards. It also checks on the risks of the subsystems design, the human factor,
and the functionality of the components. HHSA also investigate the
functional
relationship of the tools used including the software, and also suggesting the
method of controlling the hazards. The SSHA effort should begin when the preliminary
design and concept definition are established, and it should continue through the detailed
design of components and software.
41
iii.
Integrated Hazard Analysis should identify hazard causes and controls that cross
system functional and physical boundaries and should identify the organizations
responsible for assuring mitigation for the hazard causes. An integrated hazard is an event
or condition that is caused by or controlled by multiple systems, elements, or subsystems.
Systems that cross one or more system or element are considered integrated systems
and they are addressed by an integrated hazard analysis.
iv.
The
purpose
of
the
O&SHA
is
to
perform
detailed
safety risk
assessment of a systems operational and support procedures. The O&SHA examines human
induced hazards to hardware, software, equipment, facilities, and the environment.
An O&SHA describes what a human can do to create hazards and how the hardware,
software, equipment, facilities, and environment can create hazards for humans. Generally,
the O&SHA examines those operations that are procedurally controlled activities. It
identifies and evaluates hazards resulting from the implementation of operations or
tasks performed by persons during maintenance.
42
3.2
India. On this day, ammonia was used as catalysts instead of the normal operation of using caustic soda.
Hence, there was no safety procedure on using ammonia as catalyst, unlike the usage of caustic soda
which the procedure was readily documented and well-known of. The operation was however started with
manual control with the supervision of an expert. The phenol, formaldehyde and liquid ammonia were
stored in separate storage tanks (Bhattacharjee, Neogi, & Das, 2014). Liquid ammonia was added
manually by an operator into the reactor and stirring arrangement was started slowly. During the addition,
the catalyst somehow spilled on the hand on the operator and he felt some burning effect out of the
incident. The temperature of the reaction mass was already raised by steam heating to nearly 100C and it
kept on shooting up drastically. The supervisor sensed the change of situation and instructed to drain the
reaction mass into drums available from the plant. These few drums which had been filled up were closed
with lids and transferred to open distance. There were still some reactants left in the reactor. According to
Bhattacharjee et al., after few minutes, those drums exploded one after another. The residual mass in the
reactor was drained to the other empty drums and those drums were not closed. These drums did not
explode.
Job hazard analysis (JHA) is a valuable technique used for hazard identification and risk
assessment in industrial processes. JHA identified the proper job procedure after carefully studying and
recording each step of the job and then identifying the existing or potential job hazards to determine the
best way to perform the job to reduce or completely eliminate the hazards potential. The JHA consists of
three main steps:
1. Identification chooses a specific job, break down the job into a sequence of stages and
identify the possible incident that might occur during the work.
2. Assessment evaluate the risk that might occur during the work.
3. Actionmeasure to reduce or eliminate the risk.
43
Table 8: Job hazard analysis (JHA) for explosion of drums in Kalyani, Nadia District, West Bengal, India
(Bhattacharjee et al., 2014)
Basic job steps
Potential hazards or
injuries
This process is based Wrong catalysts make
on ammonia catalyst
runaway
reaction
occur.
Cause
Adequate
cooling Inadequate cooling
arrangement
increases temperature
should be provided
As the temperature
increases
in
the
reactor, the reaction
rate also increases. As
the
reaction
rate
increases
the
generation of water
vapor also increases
which increases the
pressure in the
reactor
Adequate
vent
arrangement in the
extreme
condition
should be provided;
otherwise, there is
possibility
of
explosion due to over
pressure.
In store, material
should be kept in
proper order. Display
of MSDS in
working
areas
is
required to avoid
mixing the wrong
chemical
in
the
process
Wrong reactants or
catalysts or wrong
sequences in the input
to the reactor can also
make the
reaction runaway
Chemicals should be
labelled and the use of
PPEs for carrying the
chemicals
Proper reactants or
catalyst should be
identified and used for
the reaction and
also used in proper
sequence
44
45
3.3
methanol can cause headaches, sleepiness, nausea, confusion and even death. The odor threshold of
methanol is few times higher than the threshold limit value-time weighted average. Depending upon
severity of poisoning and the promptness of treatment, survivors might suffer permanent blindness or
nervous effects. Methanol however has minor effect to eye contact. It may cause eyes irritation and
burning. In case of contact, immediately flush eyes with plenty of water for continuous 15 minutes.
Methanol is a flammable liquid which can burn without a visible flame. The release can cause an
immediate risk of fire and explosion. All ignition sources should be eliminated, absorbent materials
should be used. Inherent safety design such as installation of dikes around methanol feed is favorable to
contain spill from spreading to nearby equipment. Cleanup of methanol feed should be managed by same
teams of trained workers only to make sure the consistency of operating procedures. While operating it,
personal protective wear such as fire-fighting should be worn and all ignition sources should be kept far
away.
3.3.1.2 Storage and handling of methanol
When transferring or storing methanol, dedicated systems are preferable. Non-dedicated systems
should be cleaned, flushed and sampled before being used, in order to ensure product integrity.
Equipment should be clearly labeled to indicate that it is for methanol service only. When not in use, the
equipment must be protected from contamination.
In handling methanol, all ignition sources such as smoking and open flame should be eliminated.
Passive protective measure such as explosion proof electrical equipment should be use. Furthermore,
accurate procedural steps of using proper electrical grounding should be in place to avoid accidents.
In terms of storage, methanol should be stored in enclosed area to avoid ignition and human contact for
safety purpose. Dikes must be installed around the storage tank to avoid spreading of spill in case leakage
occurs. Storage tanks of welded construction are normally satisfactory. They should be designed and built
in conformance with good engineering practice for the material being stored. While plastics can be used
for short term storage, they are generally not recommended for long-term storage due to deterioration
effects and the subsequent risk of contamination.
46
3.4
avoid irritation. If there is serious inhalation of formic acid, the victim should be evacuated to a safe area
as soon as possible. Tight clothing is loosening up such as a collar, tie, belt or waistband. If breathing is
difficult, oxygen is administered. If small spill of formic acid occurs, it is diluted with water and mop up,
or absorbed with an inert dry material to be placed in an appropriate waste disposal container.
3.4.2 Carbon monoxide, CO
3.4.2.1 Accidental release and first aid measures of CO
If CO is inhaled, remove to uncontaminated area. Artificial respiration must be provided if not
breathing. If breathing is difficult, oxygen should be administered by qualified personnel. If large amount
of CO is ingested, immediate medical attention is required. In terms of fire-fighting measures, CO has
severe fire hazard and explosion hazard. The vapor is heavier than air, and may ignite at distant ignition
sources and flash back. Vapor/air mixtures are explosive and containers may rupture or explode if
exposed to heat.
Under accidental release measure; heat, flames, sparks and other sources of ignition should be
avoided. Water spray can be used to reduce vapors. Unnecessary people should be kept away from the
area. This can be done by putting up safety labels or isolate the hazard area.
3.4.3 Carbon dioxide, CO2
3.4.3.1 Accidental release and first aid measures of CO2
In case of CO2 is contact to skin and frostbite or freezing occur, immediately flush with plenty of
lukewarm water (105-115 F; 41-46 C). Hot water is prohibited to be applied. If warm water is not
available, gently wrap affected parts in blankets. Get immediate medical attention.
3.5
put on to avoid skin and eye contact with the chemical. To clean up formaldehyde, absorbent paper is
used to pick up all liquid spill material. The absorbent paper is then sealed, as well as contaminated
clothing, in a vapor-tight plastic bag for eventual disposal. All contaminated surfaces are washed with a
soap and water solution. For fire-fighting measure, alcohol foam, CO2, or dry chemical can be used to
47
fight fire. If there is skin contact with formaldehyde, the affected area must be washed thoroughly under
flowing water with soap solution.
3.5.1.2 Storage and handling of formaldehyde
When the workers are handling formaldehyde, PPE must always be worn. Hands washing must be
performed after handling is done. Workers should have minimal direct contact of formaldehyde while
handling it. Furthermore, formaldehyde should be stored in such place that is well-ventilated, cool and
dry.
Summary of the chemical and physical properties of the main chemical component involved, and
potential hazards posed by the materials or chemicals used and produced by this plant are shown in Table
9.
Table 9: Summary of chemical hazards information
Chemical
Class
Risk
Methanol
Flammable
Irritant
Iron oxide
Formalin
Flash
point
Safety Measures
Handling/storage
Can
cause 11oC
erythema
or
dermatitis.
Toxicity
can
cause blindness.
First
Aid:
Rinse/wash affected
area with running
water, get fresh air.
Fire Fighting: Use
CO2 to extinguish,
suppress gases with
water jet
Keep in well-ventilated
area, away from sources
of ignition. Ensure all
equipment is electrically
grounded before transfer.
Irritant
First
Aid:
Rinse/wash affected
area with running
water, get fresh air.
Ensure
storage
can
support its weight and
doesnt strain in reaching
for materials.
Irritant
Corrosive
Carcinogenic
50oC
and can cause
inflammation
First
Aid:
Rinse/wash affected
area with running
water, get fresh air.
48
Formic
acid
Corrosive
Flammable
Can
cause 49.5oC
severe
skin
burns and eyes
damage
First
Aid:
Rinse/wash affected
area with running
water, get fresh air.
Take off clothing and
dont
induce
vomiting
if
swallowed
Fire Fighting: Use
water spray, alcoholresistant foam, dry
chemical or carbon
dioxide.
Methyl
formate
Irritant
Toxic
to 19oC
nervous system
and
organs.
Irritating to eyes
and skin.
First
Aid:
Rinse/wash affected
area with running
water, get fresh air.
Ensure
storage
can
support its weight and
doesnt strain in reaching
for materials.
Keep away from heat.
Keep away from sources
of ignition. Ground all
equipment
containing
material. Store in a
segregated, cool, wellventilated
area.
Refrigerated room is more
preferable.
Methane
Flammable
Asphyxiating
188oC
and may cause
frostbite.
49
3.6
hazards, or reduce their magnitude, severity or likelihood of occurrence, by careful attention to the
fundamental design and layout. Less reliance is placed on add-on engineered safety systems and
features, and procedural controls which can and do fail (Mansfield, Poulter, Kletz, & Britain, 1996).
Table 10: Preventive measure to reduce risk at workplace
Type
of Description
Example
measure
Minimize hazard using process or equipment
Passive
Containment
dike
around
design features which reduce frequency or
formaldehyde and methanol
consequence without the active functioning of
storage tanks.
any device.
Fire-resistant walls around
methanol feed methanol is
highly flammable.
Controls, safety interlocks, automatic
shut down systems
Multiple active elements
Sensor -detect hazardous
condition
Logic device - decide what to
do
Control element -implement
action
Prevent incidents, or mitigate the
consequences of incidents
Active
50
Confined
space
entry
procedures.
Cleanup procedure for absorber
Other than focusing on the Layer of Protection Concept, designing an inherently safer system or
facility is another good approach to prevent such a tragedy to take place in future. Inherently safer design
is a new and different approach to chemical process safety. Instead of working with existing hazards in a
chemical process and adding layers of protection, the engineer is challenged to reconsider the design and
eliminate or reduce the source of the hazard within the process (Allen and Shonnard, 2012). Approaches
to the design of inherently safer processes have been grouped into four categories of Minimize, Moderate,
Substitute and Simplify which will has the further breakdown in Table 3 below.
51
Description
Example
Minimize
Moderate
Simplify
Substitute
52
3.7
important aspect through the environment considerations as well to ensure safety compliances in the
plant. In Malaysia, several laws and legislation to should be referred and followed such as Electricity
Supply Act 1990, Occupational Safety and Health Act 1994 (OSHA), Environment Impact Assessment
(EIA) Procedures and Requirements in Malaysia, Environmental Quality Act 1974 (EQA) and Factory
and Machinery Act 1967 (FMA). The important of those legislations were to help us to designing a better
plant that giving minimum impact to the surrounding neighborhood and also the long terms of
environmental effect. PEAR refers as the effects of any single thing happened in the plant must be based
on personnel, environment, assets and reputations of the company. Hence, they should be better
mitigation measure for reduce any unwanted incident to occur.
Proper planning in designing the equipment is required in providing the safest process with an
economical value. The designing of the equipment should follow codes and standards that have been
provided through American Society of Mechanical Engineers (ASME), American Petroleum Institute
(API) or even PETRONAS Technical Standard (PTS) that is developed by PETRONAS. In compliance
with process safety management, hazards as well should be identified earlier through Hazard and
Operability Studies (HAZOP) which is the most common practice in any of petrochemical plants, Hazard
Identification Study (HAZID), Layer of Protection Analysis (LOPA) or What If Study. It is important
to maintain the asset integrity of the plant and ensure earlier prevention steps have been taken foreseeing
any hazard that could happen threatening the safety of the plant.
By following those rules, regulations and guidelines, the plant can proceed for its operation in
taking considerations on the safety issues, hazard and environment perspective for mitigate the possible
ways to generate sustainable development. Following are the industrial laws and acts that are to be
adhered before designing a plant.
3.7.1.1
Malaysian government has established the legal and institutional framework for
environmental protection. The purpose is to promote environmental friendly and sustainable
development. During early stage of planning, investors are encouraged to consider the
environmental factor. They should consider several factors including the pollution control, waste
management, waste prevention and effluent waste water/discharge.
The objective of this law is upon the prevention, abatement and control pollution and
enhancement of environment by restricting discharge of waste which applies to the whole
Malaysia.
Follows are the subsidiaries act related to process plant industry:
53
a)
b)
c)
d)
e)
f)
g)
h)
i)
Environmental
Quality
(Prescribed
Premises)
54
(Scheduled
Treatment
and
Disposal
3.7.1.2
Occupational safety and health is a cross-disciplinary area concerned with protecting the
safety, health and welfare of people engages in work or employment. The reasons for establishing
good occupational safety and health standards are frequently identified as:
Moral - An employee should not have to risk injury at work, nor should others
associated with the work environment.
Economic- many governments realize that poor occupational safety and health
performance results in cost to the state (for example through the social
payments to the incapacitated, costs for medical treatment).
The Occupational Safety and Health Act 1994 (Act 514) is a piece of Malaysian
legislation which has been gazette on 25th February 1994 by the Malaysian parliament. The purpose
of this act is to make further provision for securing that safety, health and welfare of persons at work,
for protecting others against risks to safety or health in connection with the activities of persons at
work.
The Act has been applied throughout Malaysia to the industries specified in the First
Schedule:
1.
Manufacturing
2.
3.
Construction
4.
5.
6.
7.
55
8.
9.
10.
Safety
and
Health
(Employers'
Safety
and
Health
General
Safety
and
Health
(Control
of
Industry
Major
Accident
Regulations 1996
3.
Occupational Safety and Health (Safety and Health Committee) Regulations 1996
4.
5.
Occupational Safety and Health (Safety and Health Officer) Regulations 1997
6.
7.
Occupational
Chemicals
Safety
and
Health
(Use
and
Standards
of
Exposure
of
Occupational
Safety
and
Health
(Notification
of
Accident,
Dangerous
56
In formaldehyde production plant, most uses methanol as their feedstock rather than using
natural gas key compound as their feedstock as the process for converting the latter substances
such as propane or butane are not major industrial significance for economic reasons. Methanol
conversion process does not compete with processes that use partial dehydrogenation of CO or
oxidation of methane because of the higher yields of the former process.
As the main feedstock is methanol the specifications of the methanol for production of
formaldehyde are listed in Table 10. Yet, crude aqueous methanol obtained by high-, mediumor low-pressure synthesis can also be used for those processes. The methanol contains low
concentration of inorganic impurities and limited amounts of other inorganic compounds.
Therefore the need for the methanol to be subjected to purification and preliminary distillation to
remove low-boiling point components arises.
57
Specifications
Methanol content
Relative density
0.7928 g/cm3
1C
Ethanol content
< 2 g/L
Sulfur content
Chlorine content
For the sake of simplicity the methanol feedstock is assumed to have 100% purity with
specification as follows for our references:
58
(1)
(2)
(3)
The extent, to which each of these reactions occurs, depends on process data. However
byproducts are also formed in the following secondary reactions.
CH2O CO + H2 H = +12.5 kJ/mol
(4)
(5)
(6)
where
cF
formaldehyde concentration
co
oxygen concetration
59
rate constant
time
A complete reaction mechanism for the conversion of methanol to formaldehyde over a silver
catalyst has not yet been proposed but there are some authors postulate that a change in
mechanism occurs at ca. 650C. However there are new findings that look into the reactions
mechanism from spectroscopic investigations which indicate the influence of different atomic
oxygen species on reaction pathway and selectivity. The production of formaldehyde over a
silver catalyst is carried out under strictly adiabatic conditions. Temperature measurements both
above and in the silver layer show that sites still containing methanol are separated from sites
already containing predominantly formaldehyde only by a few millimeters..
The oxygen in the process air is shared between the exothermic reactions, primarily reaction (2)
and, to a lesser extent depending on the process used, the secondary reactions (5) and (6). Thus,
the amount of processed air controls the desired reaction temperature and the extent to which
endothermic reactions (1) and (4) occur.
The addition of inert material to the reactants is also another important factor affecting the yield
of formaldehyde and methanol conversion besides, the catalyst temperature. Water is added to
spent methanol-water-evaporated feed mixtures and nitrogen is added to air and air-off-gas
mixtures, which are recycled to dilute the methanol-oxygen reaction mixture. The throughput per
unit of catalyst area provides another way of improving the yield and affecting the side reactions.
The theoretical yield of formaldehyde obtained from reactions (1) - (6) can be calculated from
actual composition of the plant off-gas by using the following equation:
1
(%2 ) + (%)
(%) = 100 [+ +
]
0.528(%2 ) + (%2 ) 3(2 ) 2(%)
Percentage signifies concentrations in vol% and r is the ratio of mole of unreacted methanol to
moles of formaldehyde produced. The equation takes into account the hydrogen and oxygen
balance and the formation of byproducts.
60
Super heater
61
Super heater
j)
Anion-exchange unit
62
4.1.3
Formox Process
Anion-exchange unit
In Formox, a metal oxide (iron, molybdenum, or vanadium oxide) is used as a catalyst for
methanol conversion to formaldehyde. Many of this process has been patented since 1921.
63
Usually the oxide mixture has an Mo:Fe atomic ratio of 1.5-2.0, small amounts of V2O5. CuO,
Cr2O3, CoO and P2O5 are also present. Special conditions are prescribed for both the process and
the activation of catalyst. The Formox process has been described as two-step oxidation reaction
in the gaseous state which involves an oxidized and a reduced catalyst.
CH3OH + Kox CH2O + H2O + Kred
Kred + O2 Kox
H= -159 kJ/mol
CH2O + O2 CO + H2O
H= -215 kJ/mol
H= -215 kJ/mol
The methanol oxidation is inhibited by water vapor. A kinetic describing the rate of reaction by a
power law kinetic rate of expression of the form.
=
3 2 2
Where x = 0.94 0.06; y = 0.10 0.05 and z = -0.45 0.07. The rate is independent of
formaldehyde partial pressure. The measured activation energy is 98 6 kJ/mol.
Methanol feed is passed to a steam-heated evaporator. Freshly blown-in air and recycled
off-gas from the absorption tower are mixed and, if necessary, pre-heated by means of the
product stream in a heat exchanger before being fed into the evaporator. Atypical reactor for this
process has a shell with a diameter of ca. 2.5 m that contains tubes only 1.0 1.5 m in length. A
high-boiling heat transfer oil circulates outside the tubes and remove the heat of reaction from
the catalyst in tubes. The process employs excess air and temperature is controlled isothermally
to a value of ca. 340C; steam is simultaneously regenerated in a boiler. The air-methanol feed
must be a flammable mixture, but if the oxygen content is reduced to 10 mole% by partially
replacing air with tail gas from absorption tower, the methanol content in the feed can be
increased without forming an explosive mixture. After leaving the reactor, the gasses are cooled
to 110C in a heat exchange unit and are passed to the bottom of an absorber column. The
formaldehyde concentration is regulated by controlling the amount of process water added at the
top of the column. The product is removed from the water-cooled circulation system at the
bottom of absorption column and is fed through an anion-exchange unit to reduce the formic
acid content. The final product contains up to 55wt% formaldehyde and 0.5 1.5% wt %
64
methanol. The resultant methanol conversion ranges from 95 99 mol % and depends on the
selectivity, activity, and spot temperature by the catalyst, the latter being influenced by the heat
transfer rate and the throughput rate. The overall plant yield is 88 91 mol %.
Well-known processes using the Formox method have been developed by
Perstorp/Reichhil (Sweden, Great Britain, and United States), Lummus (United States),
Montecatini (Italy), and Hiag/Lurgi (Austria).
The tail gas does not burn by itself as it consists essentially of N2, O2, and CO2, with a
few percent of combustible components such as dimethyl ether, carbon monoxide, methanol, and
formaldehyde. Combustion of Formox tail gas for the purpose of generating is not economically
justifiable. Two methods of reducing atmospheric emission have been developed. The off gas
can be burned either with additional fuel at a temperature of 700 - 900C or in a catalytic
incinerator at 450 550C. However the latter system employs a heat exchanger and is only
thermal-efficient if supplementary fuel for start-up is provided and if abnormal ratio of oxygen:
combustible components are used.
4.2
Process Operating Mode
Chemical reactors are vessels designed to contain chemical reactions. It is the site of conversion
of raw materials into products and is also called the heart of a chemical process. The design of a
chemical reactor where bulk drugs would be synthesized on a commercial scale would depend
on multiple aspects of chemical engineering. Since it is a very vital step in the overall design of a
process, designers ensure that the reaction proceeds with the highest efficiency towards the
desired output, producing the highest yield of product in the most cost effective way. Reactors
are designed based on features like mode of operation or types of phases present or the geometry
of reactors. They are thus called:
Tubular Reactor
65
Discontinuous production
Flexibility
Many reactors particularly in the fine chemical industry are operated in a pure batch manner.
During the reaction period there is a change in substrate and product concentration with
time. The other periods, example are emptying, cleaning, filling, are time lost.
4.2.1.1 Benefits of Batch Operation
Batch reactors are very versatile and are used for a variety for different unit operations
(batch distillation, storage, crystallization, liquid-liquid extraction etc). Batch operation is
most flexible. Reactors can be used for multiple purposes. This is particularly important or
the fine chemical industry where multiple products are produced in one plant. Batch reactors
are excellent at handling difficult materials like slurries or products with a tendency to foul.
Batch reactors represent an effective and economic solution for many types of slow
reactions.
66
Continuous production
The steady state will develop only after a start-up period usually 4 times the residence time (t=
V/F). Continuous reactors are mainly used for large-scale production. Frequent use is made of
continuous reactors in the laboratory for studying kinetics.
67
Batch Process
Continuous Process
of Can be used with all types of Easier for use with flowing materials
materials (with non-flow materials, (today, almost any material can be
it is easier to use the batch process). produced with the continuous
process; investment cost is the
decisive factor).
Installation
size
Reactor
Volume
produces
Better
for
production.
Feeding raw Raw materials are fed before the Constant feeding of raw materials
start of the reaction.
during the entire reaction process.
materials
It is easier to
Control of the Simple control.
set of actions control reaction conditions (pH,
Manual
in the system pressure, temperature).
control can also be done.
68
Product(s)
Trouble
shooting
Quantities
produced
Variety
products
the plant
Product
development
stage
central
and
69
Parameters
Flow
Batch Operation
Disconnected, with
dominant flows
Moderate
Moderate
High
Moderate
and Moderate
Flexibility
Capital Investment
Maintenance Cost
Labour Skill
Volume of Feed
Product
Product Quality
Power Consumption
Residence Time of Feed
Not constant
High
Long
some
Continuous Operation
Continuous
Very low
Very high
Moderate
Very high
Very high
Constant
Low
Short
70
4.3
10
8
1
Figure 30: Block diagram of incomplete conversion of methanol with distillative recovery of methanol
Streams
Molar Flow (kmol/hr)
MetOH
H2O
N2
O2
CH2O
Total
Mass Flow (kg/hr)
MetOH
H2O
N2
O2
CH2O
Total
10
100
0
3761.905
1000
0
4861.905
112.6
1.9682
3761.905
1000
0
4876.473
14.1876
100.3806
3761.905
950.7938
87.4
4914.667
14.1876
319.24
0
0
87.4
420.8276
0
100.5634
0
0
0
100.5634
0
0
3761.905
950.7938
0
4712.699
0.70938
220.6842
0
87.4
308.7936
13.47822
2.007612
0
0
0
15.48583
0.87822
0
0
0
0
0.87822
12.6
2.007612
0
0
0
14.60761
3200
0
105333.3
32000
0
140533.3
3603.2
35.4276
105333.3
32000
0
140972
454.0032
1806.851
105333.3
30425.4
2622
140641.6
454.0032
5746.32
0
0
2622
8822.323
0
1810.142
0
0
0
1810.142
0
0
105333.3
30425.4
0
135758.7
22.70016
3972.315
0
0
2622
6617.016
431.303
36.13702
0
0
0
467.4401
28.10304
0
0
0
0
28.10304
403.2
36.13702
0
0
0
439.337
71
6
1
100
0
3761.905
1000
0
4861.905
100
3.254
3761.905
1000
0
4865.159
3
100.254
3761.905
951.5
97
4913.659
3
244.9241
0
0
97
344.9241
0
146.6752
0
0
0
146.6752
0
2.00508
3761.905
951.5
0
4715.41
0
0
3761.905
951.5
4713.405
0
2.00508
0
0
0
2.00508
3200
0
105333.3
32000
0
140533.3
3200
58.572
105333.3
32000
0
140591.9
96
1804.572
105333.3
30448
2910
140591.9
96
4408.634
0
0
2910
7414.634
0
2640.153
0
0
0
2640.153
0
36.09144
105333.3
30448
0
135817.4
0
0
105333.3
30448
0
135781.3
0
36.09144
0
0
0
36.09144
72
6
1
100
0
3761.905
1000
0
4861.905
100
3.254
3761.905
1000
0
4865.159
1
102.254
3761.905
950.5
99
4914.659
1
249.9741
0
0
99
349.9741
0
149.7652
0
0
0
149.7652
0
2.04508
3761.905
950.5
0
4714.45
0
0
3761.905
950.5
4712.405
0
2.04508
0
0
0
2.04508
3200
0
105333.3
32000
0
140533.3
3200
58.572
105333.3
32000
0
140591.9
32
1840.572
105333.3
30416
2970
140591.9
32
4499.534
0
0
2970
7501.534
0
2695.773
0
0
0
2695.773
0
36.81144
105333.3
30416
0
135786.1
0
0
105333.3
30416
0
135749.3
0
36.81144
0
0
0
36.81144
73
4.4
6617.016 kg/hr (RM 490.00 per kg) 100 kg/hr (RM 1.91688 per kg)
RM 3242, 146.52
74114.63 kg/hr (RM 490.00 per kg) 100 kg/hr (RM 1.91688 per kg)
RM 36315, 977.01
74114.63 kg/hr (RM 490.00 per kg) 100 kg/hr (RM 1.91688 per kg)
RM36315, 977.01
74
4.5
Justification of Process Route Selection
Considering the economics aspects of the three formaldehyde process in practice, it is certainly
obvious that the size of the plant and the cost of methanol will be vital. The Formox process is proven
to be advantageous. Regarding the attainable yield of formaldehyde; still, in comparison with the
silver process, Formox requires larger plant and higher investment cost. For the purpose of cost
comparison, a study has been carried out on basis of $ 200 /t and a plant production capacity of 20
000 t/a of 37 wt% formaldehyde. The results are tabulated as follows:
Table 14: Economic comparison of three process routes
Complete
Methanol
Conversion
Formox
Process
6.6
Incomplete
Conversion
and
Methanol
Recovery
8.6
1.24
1.22
1.15
255
Methanol
250
Catalyst
and 5
Chemical
Byproduct credit n.a..
(stream)
12
Utilities
LP Steam
3.4
Power purchased
3.4
Cooling water
2.9
Process water
2.4
267
Variable cost, $/t
27
Direct fixed cost, $/t
18
Total allocated fixed
cost, $/t
312
Total cash cost, $/t
33
Depreciation, $/t
345
Production cost, $/t
33
Return of Capital
investment (ROI), $/t
378
Cost of production
and ROI, $/t
252
247
5
227
232
7
n.a.
12
20
9.5
4.3
2.8
3.3
272
29
20
13
321
43
364
43
291
48
339
48
407
387
Total
capital
investment, $/t
Methanol
Consumption, t/t
Raw Materials, $/t
75
9.6
8.0
4
1.0
240
30
21
5.1
Pinch Analysis
Before proceeding to design the heat exchanger network in the formalin plant proposed, pinch
analysis has been carried out. Through the analysis, the system maximization of heat recovery,
heating and cooling utility consumption minimization and optimization for the selection of utility
sources and the trade-off between energy costs and capital costs can be achieved. Listed below is the
information required prior pinch analysis:
i.
ii.
iii.
iv.
Temperature
Supply (C)
Temperature
Target (C)
Duty (kW)
Cp
(kW/C)
Cold Stream 1
Cold Stream 2
126.3
25.07
150
150
371.6
1052
23.7
124.93
15.6793
8.42072
Hot Stream 1
343
110
4070
-233
17.4678
76
The data above are retrieved from aspen HYSYS simulation. The simulation does not include external
utilities and thus may only be incorporated after this analysis. The values of Cp are calculated using
the following equation.
= ||
Which
Q
Cp
= +
Shifted
Supply (C)
Cold Stream 1
Cold Stream 2
121.3
20.07
145
145
15.67932
8.420716
Hot Stream 1
348
115
17.46781
The tabulated data below is then used to carry out temperature interval heat balance. The enthalpy
values (H) are calculated by multiplying T with Cp. The positive value of enthalpy (H) indicates
the domination of cold streams, where there is a net deficit of heat in that particular temperature
interval. All is surplus and the heat integration is below the pinch.
77
Interval Streams
Cp (kW/C)
H (kW)
(C)
348
Surplus/
Deficit
H1
193
-17.46781
-3371.29
Surplus
23.7
-24.726414
-586.02
Surplus
6.3
-1.78849
-11.27
Surplus
94.93
15.67932
1488.44
Deficit
145
121.3
C1
115
20.07
C1
After getting the temperature interval heat balance done, the values of H for each temperature
intervals are used to carry out problem table cascade in order to determine the minimum hot/cold
utility and the pinch temperature for hot and cold streams.
78
required in the process. The pinch temperature of the process is 348.0 C while the pinch temperature
of hot stream and cold stream are shown as below.
, = +
, =
, = 348.0 +
, = 348.0 + 5
, = 353
, = 348.0
, = 348.0 5
, = 343
All of the data above are used to construct composite curve and grand composite curve which are
useful to determine the heat recovery and optimizing the energy.
5.1.3 Composite Curve
Grand composite curve is constructed using the heat cascade as the total of surplus and deficit heat
energy are added and by using this value a shifted temperature versus total heat accumulated is then
plotted. From the grand composite curve, the heat generated and heat sink can be determined.
Furthermore, the value of heat utilities and cold utilities requirement from the graph can be tallied
with the heat cascade. Besides that, the heat recovery can too be determined to further optimize the
energy so that the starting cost of the plant will reduce. An online tools/software (http://www.uicche.org/) has been used to plot the grand composite curve and composite curve. Below is the result for
combined composite curve and grand composite curve.
79
The temperature difference, T between a pair of hot stream and cold stream must always
be greater than Tmin (10 C).
ii.
CP rule (i.e. Cp,hot Cp,cold for above pinch) must not be violated unless the pair is
away from pinch.
80
Besides, there are three rules of thumb that must be taken into consideration during designing heat
exchanger network:
The Heat Exchanger Network design is shown as in the figure below. The amount of cold utilities
requirement is 2480.18 kW while no hot utilities is required.
Looking at the diagram above, the pairing is done between hot stream 1 and cold stream 1. The
pairing is according to the rule that mentioned previously; both T is more than Tmin; the streams
are only at the below pinch region and thus Cp cold must be lower than Cp hot.
The diagram above also indicates that a cooling utility is needed. As for this part, it is suggested to use
cold water as a medium to cool the stream right after the integration is done. For this part, it is further
explained in chapter 6.
81
As the summary of PFD after integration requires proper design of heat exchanger unit that will be
done next semester, the following will be the summary report on the PFD before integration. The
following diagram is a first process flow diagram that describes all the major properties of the stream
and equipment involved in it.
82
83
Methanol is chosen as the main raw material for the production of formalin by catalytic
oxidation process. Formox process is chosen as the best process route because it yielded highest
amount of formalin production which is 74114.63 kg/hr. Based on economic potential
evaluation, it has higher profit compared to the other processes.
From the feasibility research that was carried out, Gurun, Kedah is identified to be the best
location for formalin production plant due some important factors such as the availability of sea
port for the easy access for import of raw material and export of product. Besides that, the
utilities required by the proposed plant are available in sufficient amount.
As for recommendations, the project team discovered that there is a necessity to obtain more in
depth information on the environmental effects of the process. Next, the detailed information
regarding to the process such as reaction and equipment selection could be taken into
consideration as it would affect the production of formalin. This information could add more
value to the project.
84
REFERENCES
Anonymous. (1994). Formaldehyde (Vol. 16, pp. 10). New York: Schnell Publishing Company.
Anonymous. (2000). Formaldehyde (Vol. 162, pp. 44-44). NEW YORK: CHEMICAL WEEK
ASSOC.
Babu, J Ramesh. (2007). Layer of Protection AnalysisAn effective tool in PHA: Report.
Bhattacharjee, Gargi, Neogi, Susmita, & Das, Sudip Kumar. (2014). Phenolformaldehyde
runaway reaction: a case study. International Journal of Industrial Chemistry, 5(2). doi:
10.1007/s40090-014-0013-9
Cheng, Wh-Hsun. (1994). Methanol production and use: CRC Press.
Jasmir, Shah Nadzri Bin, & Nadzri, Shah. (2010). Reliability Centered Maintenance
Implementation at CUF Kertih.
Mansfield, D, Poulter, L, Kletz, T, & Britain, Great. (1996). Improving inherent safety.
OFFSHORE TECHNOLOGY REPORT-HEALTH AND SAFETY EXECUTIVE OTH.
McMorrow, Julia, & Talip, Mustapa Abdul. (2001). Decline of forest area in Sabah, Malaysia:
relationship to state policies, land code and land capability. Global Environmental
Change, 11(3), 217-230.
Olah, George A, Goeppert, Alain, & Prakash, GK Surya. (2009). Beyond oil and gas: the
methanol economy: John Wiley & Sons.
Organization, World Health. (2001). Chapter 5.8 Formaldehyde. Air Quality Guidelines, 2.
Pinto, Joseph P, Gladstone, G Randall, & Yung, Yuk Ling. (1980). Photochemical production of
formaldehyde in Earth's primitive atmosphere. Science, 210(4466), 183-184.
85