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CCB 4013 PLANT DESIGN PROJECT I

SEMESTER SEPTEMBER 2014

DESIGN OF FORMALDEHYDE
PRODUCTION PLANT

GROUP 4

ANWAR FARID BIN SHAHUDIN

14778

BASEM MOHAMMED ALI ALI

14988

CHUA YIN CHING

14771

DANESKUMAR A/L MANOGARAN

15049

EFI ISKANDAR BIN ZAINUDDIN

16219

CHEMICAL ENGINEERING DEPARTMENT


UNIVERSITI TEKNOLOGI PETRONAS
SEPTEMBER 2014

CERTIFICATION OF APPROVAL

CCB 4013 PLANT DESIGN PROJECT I


SEMESTER SEPTEMBER 2014

DESIGN OF FORMALDEHYDE
PRODUCTION PLANT

GROUP 4

ANWAR FARID BIN SHAHUDIN

14778

BASEM MOHAMMED ALI ALI

14988

CHUA YIN CHING

14771

DANESKUMAR A/L MANOGARAN 15049


EFI ISKANDAR BIN ZAINUDDIN

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

EXECUTIVE SUMMARY .................................................................................................... 8


CHAPTER 1: INTRODUCTION ....................................................................................... 10
1.1

Background ............................................................................................................ 10

1.2

Problem Statement ................................................................................................. 11

1.3

Objective ................................................................................................................ 12

1.4

Scope of work ........................................................................................................ 13

CHAPTER 2:
2.1

LITERATURE REVIEW ............................................................. 14

Introduction to Feed Properties .............................................................................. 14

2.1.1 Background of Methanol ...................................................................................... 14


2.1.2 Production of Methanol Indirect Route via Syngas ........................................... 15
2.1.3 Applications of Methanol...................................................................................... 15
2.2

Introduction to Product Properties ......................................................................... 16

2.2.1 Background of Formaldehyde ............................................................................... 16


2.2.2 Routes of Exposures to Formaldehyde ................................................................. 16
2.2.3 Applications of Formaldehyde .............................................................................. 17
2.3

Market Survey and Analysis .................................................................................. 18

2.3.1 Global supply and demand .................................................................................... 18


2.3.2 Price Trends for Raw Materials & Products ......................................................... 22
2.4

Site Location Feasibility Study .............................................................................. 30

2.4.1 Site Considerations................................................................................................ 30


2.4.2 Selection Criteria................................................................................................... 30
2.4.3 Potential Plant Locations....................................................................................... 33
2.4.4 Weighted Evaluation ............................................................................................. 36
2.4.5 Plant Layout .......................................................................................................... 40
CHAPTER 3: PRELIMINARY HAZARD ANALYSIS .................................................. 41
3.1

Introduction to Hazard Analysis ............................................................................ 41

3.2

Previous Accidents on Similar Type of Plant ........................................................ 43

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

Material and Chemical Hazards in Feed ................................................................ 46

3.3.1 Methanol ............................................................................................................... 46


3.4

Material and Chemical Hazards of By-products .................................................... 47

3.4.1 Formic acid ........................................................................................................... 47

3.4.2 Carbon monoxide, CO .......................................................................................... 47


3.4.3 Carbon dioxide, CO2 ............................................................................................. 47
3.5

Material and Chemical Hazards of Product ........................................................... 47

3.5.1 Formaldehyde ....................................................................................................... 47


3.6

Possibility of Reducing Potential Consequences of an Accident ........................... 50

3.6.1 Implementing Inherent Safety Aspects ................................................................. 50


3.6.2 The Layers of Protection Analysis (LOPA) .......................................................... 51
3.7

Safety and Environmental Regulations .................................................................. 53

3.7.1 Requirements by Local Safety Regulations and Design Guidelines ..................... 53


CHAPTER 4: CONCEPTUAL DESIGN ANALYSIS ..................................................... 57
4.1

Preliminary Reactor Design ................................................................................... 57

4.1.1 General Process for Formalin Production ............................................................. 57


4.1.2 Silver Catalyst Processes ...................................................................................... 59
4.1.3
4.2

Formox Process .............................................................................................. 63

Process Operating Mode ........................................................................................ 65

4.2.1 Batch Operation .................................................................................................... 66


4.2.2 Continuous Operation ........................................................................................... 67
4.3

Preliminary Reactor Optimization ......................................................................... 71

4.3.1 Incomplete conversion of methanol with distillative recovery of methanol ......... 71


4.3.2 Complete Conversion of methanol (BASF) .......................................................... 72
4.3.3 Formox Process ..................................................................................................... 73
4.4

Economic Potential Analysis ................................................................................. 74

4.4.1 Incomplete conversion of methanol with distillative recovery of methanol ......... 74


4.4.2 Complete Conversion of methanol (BASF) .......................................................... 74
4.4.3 Formox Process ..................................................................................................... 74
4.5

Justification of Process Route Selection ................................................................ 75

CHAPTER 5: HEAT INTEGRATION ............................................................................. 76


5.1

Pinch Analysis ....................................................................................................... 76

5.1.1 Stream Data Extraction ......................................................................................... 76


5.1.2 Problem Table Algorithm ..................................................................................... 77
5.1.3 Composite Curve................................................................................................... 79
5.1.4 Heat Exchanger Network (HEN) Design .............................................................. 80
CHAPTER 6: PROCESS FLOWSHEETING .................................................................. 82
CONCLUSION AND RECOMMENDATION ................................................................. 84
REFERENCES..................................................................................................................... 85

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

Figure 34: Grand composite curve ......................................................................................... 80


Figure 35: Heat Exchanger Network (HEN) grid .................................................................. 81
Figure 36: PFD before integration ......................................................................................... 82
Figure 37: PFD after integration ............................................................................................ 82

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,

economic outlook and site feasibility study.

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 5 explains the process of implementing heat integration on the integrated


plant. The heat integration study is done by applying the pinch analysis method. Design
grid diagram, grand composite curve and heat exchanger network (HEN) are developed
with the aid of SPRINT software. Heat integration is necessary in order to
optimize the energy usage in the plant. The process flow sheeting before and after
implementing heat exchanger network are attached in this section.

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

an iron and molybdenum or vanadium oxides.

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.

The project team is responsible to design an integrated formaldehyde production


plant with formaldehyde production capacity of 50,000 metric ton per year (MTPY) to
meet customers demand in Malaysia as well as targeted countries in the Southeast Asia
region that has a high demand on formaldehyde.
Various

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.

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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.

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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

environmental considerations and any other

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.

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CHAPTER 2:
2.1

LITERATURE REVIEW

Introduction to Feed Properties


2.1.1 Background of Methanol
Methanol, also called as methyl alcohol or wood alcohol, is colorless, water soluble

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).

Figure 1: World demand for methanol in 2007

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).

2.1.3 Applications of Methanol


Applications of methanol in the energy industry may be via four approaches:
methanol to gasoline conversion, methanol to methyl tert-butyl ether (MTBE) for
reformulated gasoline, neat methanol or methanol blends as automobile and fuels, and
dissociation or reforming of methanol to syngas for a variety of fuel usage (Cheng, 1994).
Table 1 below shows the overview of methanol applications.
Table 1: Overview of methanol applications
Direct derivatives or uses

Secondary derivatives or uses

Fuel or fuel additives


Neat methanol fuel
Methanol blended with gasoline
MTBE
TAME
Methanol to gasoline

Oxygenate in gasoline
Oxygenate in gasoline

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Chemicals
Formaldehyde

Urea-formaldehyde resins
Phenolic resins
Acetylenic chemicals
Polyacetal resins
Vinyl acetate
Acetic anhydride
Ethyl acetate

Acetic acid

Chloromethanes
Methyl chloride
Methylene chloride

Organic paint-removal solvent


Solvent and cleaning applications

Other uses
Solvent
Antifreeze
Inhibitor
Substrate

2.2

Introduction to Product Properties


2.2.1 Background of Formaldehyde
Formaldehyde, the largest chemical product derived from methanol, is a colorless,

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.

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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.

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2.3

Market Survey and Analysis

2.3.1 Global supply and demand


The players for methanol supplies are in West Europe, Middle East, Southeast Asia,
Northeast Asia, South America and North America region. According to market review by
Johnson (2012), all regions roughly have steady or increasing production and demands.
Production and demands from aforementioned region can be seen in Figure 1-6.

Figure 2: West Europe Methanol Supply & Demand

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Figure 3: Middle East Methanol Supply & Demand

Figure 4: Southeast Asia Methanol Supply & Demand

Figure 5: Northeast Asia Methanol Supply & Demand

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Figure 6: South America Methanol Supply & Demand

Figure 7: North America Methanol Supply & Demand

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.

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Figure 8: Global Formaldehyde Supply & Demand

Figure 9: Global Formaldehyde Demand by Region

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.

Figure 10: World Methanol Demand by Region

2.3.2 Price Trends for Raw Materials & Products


The production of formaldehyde is made possible thanks to the raw material: methanol.
Thus, in order to select the most reasonably priced raw material, the price trends from
different regions should be considered. Costs from transportation will be considered too for
raw materials. Besides that, the product price should be considered as well as to justify
whether the plant will be profitable or not.

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2.3.2.1 Raw material prices - Methanol

Figure 11: West Europe Price Trend

Figure 12: Northeast/Southeast Asia Price Trends

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Figure 13: US Methanol Price Trend

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.

Figure 14: Methanol Pricing Mechanism

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2.3.2.2 Catalyst prices


There are various types and combinations of catalyst involved in oxidation of
methanol to form formaldehyde. There are molybdenum oxide, ferromolybdenum,
iron oxide, vanadium pentoxide and silver,

Figure 15: Molybdenum Oxide Price Trend(MetalPrices.com, 2014)

Figure 16: Ferromolybdenum Price Trend (MetalPrices.com, 2014)

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Figure 17: Iron Oxide Pricing (StandardCeramic.com, 2014)

Figure 18: Vanadium Pentoxide Pricing (StandardCeramic.com, 2014)

26

Figure 19: Silver Price Trend (SilverPrice.com, 2014)

Table 2: Price range of catalysts


Catalysts

Price(USD)/kg

Molybdenum Oxide

20.00

Ferromolybdenum

24.00

Iron Oxide

7.60

Vanadium Pentoxide 60.00


518.27

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.

2.3.2.3 Product prices - Formaldehyde


The most important aspect of planning and designing of a plant is to ensure the products
produce is highly marketable and at a competitive prices in order to generate profits.

The statistics on formaldehyde pricing is classified as the pricing corresponds to feedstock of


companies. However, by comparing the price range provided by selected companies, the
pricing for formaldehyde in production can be estimated.

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Table 3: Price range of various companies for formaldehyde


Manufacturer
MasterTech
Shijiazhuang
Xinlongwei Chemical
Co., Ltd.
Henan CXH Purity
Industrial And Trading
Co., Ltd.
Henan Luckybee New
Technology Co., Ltd.

Price Range
$ 31890.00/ton
$350-500 / ton

Purity

Min. Order

Supply Ability

1 Twenty-Foot 5000 Ton/Tons


Container
per Month
1 Twenty-Foot 4000 Ton/Tons
Container
per Month

$387-419 / ton

5 Tons

Qingdao
Xinyongan $400-450/ ton
Chemicals Co., Ltd

5 Metric Tons

Quzhou Juhui Chemical $100-300/piece


Materials Co., Ltd.
Zouping
Changshan $1000-3000
Town Zefeng Fertilizer /ton
Factory
Zhejiang
Junhao
Chemical Co., Ltd.

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

Beijing Hwrk Chem


Co.,ltd.
Guangzhou
Puen
Scientific
Instrument
Co., Ltd.
Fishersci
Beijing
Ouhe
Technology Co. Ltd

$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

Ferromolybdenum + Vanadium pentoxide $84.00/kg


$20000-100000/ton

Formaldehyde

29

2.4

Site Location Feasibility Study

2.4.1 Site Considerations


The selection of site for our formaldehyde production plant is very vital, so that it has all
the support required to make maximum profit with minimum operating cost. There are
many important factors that must be considered when selecting a suitable site.

2.4.2 Selection Criteria

Raw Material
Availability
Political,
Economic and
Strategic
Consideration

Location With
Respect To
Marketing Area

Waste Disposal

Transportation

Land
Availability &
Cost

Utilities

Labour Supply

Figure 20: Schematic Diagram on selection of site criterion

30

2.4.2.1 Raw Material Availability


In order to select the best location to build a chemical plant, a major factor to be considered
is the source of raw materials. In this project, the plant needs to have a capacity to produce
formaldehyde at the rate of 50,000 tons/year. In order to produce these large amounts of
product, a large volume of raw material is needed. Therefore, the plant should be located
near to the source of its raw material (e.g. methanol) or have an easy access to the raw
material. The considerations of this factor are important to lower the cost of operation.
Furthermore, other factors such as raw materials storage, transportation expenses, supply
availability and reliability were also taken into account.

2.4.2.2 Location with Respect to the Marketing Area


The cost of production versus the cost of transportation determines the selection of location
with respect to the above criteria. Most chemical process plant has significantly higher
production cost compared to the cost for bulk transportation. Therefore, most of the time the
location selected is near to the transportation hub particularly sea port. This will enable the
delivery of the finished products to customer as quickly and as cheaply possible.

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

2.4.2.5 Labor Supply


An adequate labor supply is still needed from various disciplines despite of the increasing
usage of the automation. Plant should be located where sufficient labor supply is
available. The

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.

2.4.2.8 Political, Economic and Strategic Consideration


Stable country and political situation where there is not much possible public disturbance.
Financial incentives provided by the government and the tax policy. Financial facilities
provided by the local businesses. Local regulations on zoning, building codes, nuisance
aspects, and transportation facilities can have a major influence on the final choice of a
plant site.
Based on the factors listed above, possible locations are evaluated and location of the plant
will determined based on the evaluation.

32

2.4.3 Potential Plant Locations


Listed are the choices of location
1. Gurun Industrial Estate, Pahang
2. Kota Kinabalu Industrial Park, Sepangar
4. Lahad Datu Industrial Park, Sabah

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

Kota Kinabalu Industrial Park

RM7.00 psf ( Gurun RM 28-RM 30 psf (KKIP)


Industrial zone)
1528.5 hectares
N/A

Lahad Datu Industrial Park


RM 30 psf
1618.7 hectares

- PETRONAS CUF

Diversified Water Resources Sdn. - PETRONAS CUF


Bhd.
- LahadDatu Water Supply
SdnBhd
- PETRONAS CUF
KKIP Power Sdn. Bhd.
- PETRONAS CUF
- TenagaNasionalBerhad
PETRONAS Petronas Labuan Methanol plant
Petronas Labuan Methanol
Fertilizer
Kedah
plant
Gurun

Highway

North-South highway

KK-Sulaman highway

Malaysia Federal Route 13

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

Kota Kinabalu International Airport Lahad Datu Airport


(KKIA)
5 km from Sepangar Container Port
- Liquid & Dry
Terminal

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

equipment, spare parts


and consumables that
are not produced
locally
and
used
directly in the activity.

35

2.4.4 Weighted Evaluation


The two proposed sites are evaluated in a table as per below. The ranking was done from 1
(poor), 2 (fair), 3 (good), 4 (very good) to 5 (excellent).
Table 6: Weightage criteria
Factors

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

large Able to obtain natural Unable to obtain natural

natural gas supply locally

supplier

1-0 Marks

gas supply from near gas supply locally or


neighboring countries

from near neighboring


countries

Water supplier

Able

to

obtain

large Able to obtain water Unable to obtain enough

water supply from the supply from neighboring water supply


same state
to

state

Electricity

Able

obtain

large Able to obtain electricity Unable to obtain enough

supplier

electricity supply from supply from neighboring electricity supply


the same state

state

<10 km proximity to port <30 km proximity to port >30 km proximity to port

Port facility

facility
Availability

Airport

facility

of Availability of domestic Unavailability of airport

international airport

Political,
Economic

airport

Complete network and Complete

Railway

facility

network

well maintained railway

railway

Excellent tax benefits

Good tax benefits

and

Strategic
Consideration

36

of Unavailability of railway

No tax benefits

Table 7: Weighted evaluation on potential site

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:

Figure 21: Kedah Map and location of Gurun

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

: PETRONAS Fertilizer (Kedah) Sdn Bhd

Type

: Wholly Owned

Address

: KM3 Jalan Jeniang, PO Box 22, 08300 Gurun, Kedah,


Malaysia

Principal Activity

: Production of ammonia, granular urea, methanol, and


formaldehyde.

Principle Activity

: Petrochemicals

Capacity

: 375,000 MT/Year Ammonia, 600,000 MT/year Urea,


66000 MT/year Methanol

Uses (Methanol)

: Methanol is used as raw materials for glycerine; paper and


textile; pharmaceuticals industries, formaldehyde and fuel

39

2.4.5 Plant Layout

Figure 22: Plant Layout

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

CHAPTER 3: PRELIMINARY HAZARD ANALYSIS


3.1
Introduction to Hazard Analysis
System hazard analysis is the most crucial elements in the System Safety. The hazard
analysis is the examination of a system to identify and classify each potential hazard
according to its severity and like hood of occurrence and to develop the mitigation
measures to those hazards to protect the public (Hardy, 2010). There are four main types of
hazard analysis that regularly being used in the industries.
i.

Preliminary Hazard Analysis (PHA).

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.

Subsystem Hazard Analysis (SSHA).

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.

System/ Integrated Hazard Analysis (SHA/IHA).

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

Operating and Support Hazard Analysis (O&SHA).


general

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

Previous Accidents on Similar Type of Plant


3.2.1 Explosion of drums in Kalyani, Nadia District, West Bengal, India
The incident occurred on 26 Aug. 2001 around 2:45 p.m.in Kalyani, Nadia District, West Bengal,

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

Any kind of operating Accident, blast, or


negligence
explosion occurs

Required safe job


procedures
Wrong
catalyst Proper catalyst should
concentration
nitric be added
acid used

Reaction is highly Implement


various
exothermic, so any protective measures
negligence can make such as trainings
the situation accident
prone

44

3.2.2 Explosion in a resins production unit at Georgia-Pacific Resins, Inc. in Columbus,


Ohio.
At approximately 10:42 a.m. on Wednesday, Sept. 10, 1997, an explosion occurred in a resins
production unit at Georgia-Pacific Resins, Inc. in Columbus, Ohio. The blast was reported to be felt at
least 2 miles and possibly as far as 7 miles away according to various news accounts and other reports. As
a result of the explosion, one worker was killed and four others injured. The explosion extensively
damaged the plant. The explosion also resulted in the release of a large quantity of liquid resin and
smaller quantities of other chemicals within the facility. Three fire fighters were injured during the
response, treated for first-degree chemical burns, and released.
Georgia-Pacific was manufacturing a phenolic resin in an 8,000-gallon batch reactor when the
incident occurred. An operator charged raw materials and catalyst to the reactor and turned on steam to
heat the contents. A high temperature alarm sounded and the operator turned off the steam. Shortly after,
there was a large, highly energetic explosion that separated the top of the reactor from the shell. The top
landed 400 feet away. The shell of the reactor split and unrolled, and impacted against other vessels. A
nearby holding tank was destroyed and another reactor was partially damaged. The explosion killed the
operator and left four other workers injured.
Accident investigation had been performed and analyzed. Some of inherent safer design strategies
such as moderate, minimize and substitute can be implemented here to prevent such incidents from
happening in the future. Under substitution, the process of phenol-formaldehyde reactions can be
substituted or amended with other alternative process routes. Typically, phenol-formaldehyde reactions
are highly exothermic and sensitive to a variety of physical and chemical conditions. Once a reaction is
initiated, heat generated by the reaction increases the reaction rate generating more heat. For
minimization, we can look into minimizing the potential for human error occurrence. Possible human
errors should be anticipated and carefully evaluated because a simple error could have catastrophic
results. Managers should implement various protective measures, such as temperature control,
instrumentation, and interlocks to eliminate opportunities for human error, especially in critical manual
operations. To eliminate or rather reduce human error, standard operating procedures (SOPs) should
always be updated and safe to be abided by the operators. Touching in the SOPs, it should be evaluated
and modified when necessary to minimize the likelihood of an undetected human error. Supervisors
should audit SOPs regularly, including the direct observation of employees and conducting employee
interviews to ensure the SOPs are fully understood. Adequate numbers of trainings must be provided to
the operator who is responsible to perform the specific job. New workers should be under close
monitoring of supervisors when performing new procedures. They are also encouraged to work along-side
with the experienced supervisors to pick-up new skills to handle the job better in the future, thus reducing
human error occurrence indirectly.

45

3.3

Material and Chemical Hazards in Feed


3.3.1 Methanol
3.3.1.1 Accidental release and first aid measures of methanol
Inhalation of methanol is a major health concern. Inhalation of high airborne concentrations of

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

Material and Chemical Hazards of By-products


3.4.1 Formic acid
3.4.1.1 Accidental release and first aid measures of formic acid
In case of eye or skin contact, flush the affected part with tap water for continuous 15 minutes to

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

Material and Chemical Hazards of Product


3.5.1 Formaldehyde
3.5.1.1 Accidental release and first aid measures of formaldehyde
In case of accidental release of formaldehyde, rubber gloves and chemical splash goggles must be

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

Can cause lung -damage,


irritating to eye
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.

Irritant
Corrosive

Carcinogenic
50oC
and can cause
inflammation

First
Aid:
Rinse/wash affected
area with running
water, get fresh air.

Keep away from heat.


Keep away from sources
of ignition. Ground all
equipment
containing
material. Store in a
segregated, cool, wellventilated area. Keep
container tightly closed
and sealed until ready for
use.

Fire Fighting: Use


dry
chemical
powder,
alcohol
foam, water spray or
fog.

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.

Ground all equipment and


lines. Ensure absence of
ignition source. Protect
from physical damage.
Store in upright position
and in cool, dry, wellventilated area.

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.

Fire Fighting: Use


dry
chemical
powder,
alcohol
foam, water spray or
fog.

Methane

Flammable

Asphyxiating
188oC
and may cause
frostbite.

First Aid: Flush


affected area with
cool/lukewarm
water, get fresh air.
Take off clothing and
get fresh air. If
necessary,
give
artificial
resuscitation
Fire Fighting: Use
dry chemical or CO2.
Water spray or fog.
Do not extinguish a
leaking gas
fire
unless leak can be
stopped.

49

Ground all equipment and


lines. Ensure absence of
ignition source. Protect
from physical damage.
Store in upright position
and in cool, dry, wellventilated area.

3.6

Possibility of Reducing Potential Consequences of an Accident


3.6.1 Implementing Inherent Safety Aspects
An inherently safer approach to hazard management is one that tries to avoid or eliminate

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

Procedural Standard operating procedures, safety rules


and standard procedures, emergency response
procedures, training

Active

50

High level alarm in a tank shuts


automatic feed valve
A sprinkler system which
extinguishes a fire
Emergency shutdown system

Confined
space
entry
procedures.
Cleanup procedure for absorber

3.6.2 The Layers of Protection Analysis (LOPA)


The various measures for prevention and mitigation of major accidents may be thought of as
lines of defence (LODs) or layers of protection (LOPs). These lines or layers serve to either prevent an
initiating event (such as loss of cooling or overcharging of a material to a reactor, for example) from
developing into an incident (typically a release of a dangerous substance), or to mitigate the consequences
of an incident once it occurs (Babu, 2007). This is illustrated in Figure 18 below.

Figure 23: Layers of Protection Concept

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

Table 11: Basic strategies in inherent safety chemical process


Strategy

Description

Example

Minimize

Practice of using small quantities of


hazardous substances or energy that
involved in a certain process.
By doing so, consequences of
unwanted accidents such as fire and
explosion can be eventually reduced.
At the same time, it improves the
effectiveness and feasibility of other
protective system as well.

Size of methanol and formaldehyde


storage tanks should be as practical as
possible.

Moderate

Use less hazardous conditions or


facilities

Usage of a suitable and compatible


catalyst type to lower the activation
energy of the reaction.
Concentration of methanol in feed
should be minimized to nearest
possible without affecting the process
production.
Dilution is applied in our process
route to inject methanol into produced
formaldehyde.

Simplify

Designing the facility to make it easier


to operate

Substitute

Changing process to use less


hazardous materials to produce less
hazardous reaction chemistry.
In addition, we can also replace a
hazardous material with a less
hazardous one.

52

Reactors and absorbers should be


designed to withstand the operation
pressures to reduce the maintenance
costs of equipment.
Simplest process route with highest
production should be used.
Process route with less equipment
create lesser hazards.
Process route is substituted with the
one gives lower operating cost.

3.7

Safety and Environmental Regulations


3.7.1 Requirements by Local Safety Regulations and Design Guidelines
Through the designing the plant for the production of formaldehyde, we should taking care on

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

Environmental Quality Act (EQA) 1974

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)

Environmental Quality (Prescribed Premises) (Scheduled Wastes Treatment and


Disposal Facilities) Regulations 1989

b)

Environmental Quality (Clean Air) Regulations 1978

c)

Environmental Quality (Prescribed Activities) (Environmental Impact Assessment)


Order 1987

d)

Environmental Quality (Prescribed Activities) (EIA) Order 1987

e)

Environmental Quality (Licensing) Regulations, 1977

f)

Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979.

g)

Environmental Quality (Refrigerant Management) Regulations 1999.

h)

Environmental Quality (Scheduled Wastes) Regulations 2005

i)

Environmental

Quality

(Prescribed

Premises)

Facilities) Order 1989

54

(Scheduled

Treatment

and

Disposal

3.7.1.2

Occupational Safety and Health Act (OSHA) 1994

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).

Legal - Occupational safety and health requirements may be reinforced in civil


law and/or criminal law; it is accepted that without the extra "encouragement" of
potential regulatory action or litigation, many organizations would not act upon
their implied moral obligations.

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.

Mining and Quarrying

3.

Construction

4.

Agriculture, Forestry and Fishing

5.

Utilities (electricity, gas, water and sanitary services)

6.

Transport, storage and communication

7.

Wholesale and retail trades

55

8.

Hotel and restaurants

9.

Finance, insurance, real estate and business services

10.

Public services and statutory authorities.

Follows are the list of regulations under this Act:


1.
Occupational
Policy

Safety

and

Health

(Employers'

Safety

and

Health

General

Statements) (Exception) Regulations 1995


2.
Occupational
Hazards)

Safety

and

Health

(Control

of

Industry

Major

Accident

Regulations 1996
3.

Occupational Safety and Health (Safety and Health Committee) Regulations 1996

4.

Occupational Safety and Health (Classification, Packaging and Labelling of


Hazardous Chemicals) Regulations 1997

5.

Occupational Safety and Health (Safety and Health Officer) Regulations 1997

6.

Occupational Safety and Health (Prohibition of Use of Substance) Order 1999

7.
Occupational
Chemicals

Safety

and

Health

(Use

and

Standards

of

Exposure

of

Hazardous to Health) Regulations 2000


8.

Occupational

Safety

and

Health

(Notification

of

Accident,

Dangerous

Occurrence, Occupational Poisoning and Occupational Disease) Regulation 2004

56

CHAPTER 4: CONCEPTUAL DESIGN ANALYSIS


4.1

Preliminary Reactor Design

4.1.1 General Process for Formalin Production


Formaldehyde reacts with many compounds to produce methylol derivatives. It can react with
phenol, urea, melamine and even organometallic compounds to give metallic substituted
methylol compounds. Formaldehyde is produced industrially from methanol. There are three
processes that are mainly used in the industry to produce formaldehyde. The processes are as
follow:
A. Partial oxidation and dehydrogenation with air in the presence of silver catalyst crystals,
steam, and excess methanol at 680-720C with 97 - 98% conversion of methanol.
B. Partial oxidation and dehydrogenation with air in the presence of crystalline silver or
silver gauze, steam, and excess methanol at 600-650C with 77-78% of methanol
conversion. The conversion is completed by distilling the product and recycling the
unconverted methanol.
C. Oxidation only with excess air in the presence of a modified iron -molybdenum vanadium oxide at 250 - 400C with 98 -99% methanol conversion.

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

Table 12: Specifications of the methanol for production of formaldehyde


Parameter

Specifications

Methanol content

> 99.85 wt%

Relative density

0.7928 g/cm3

Maximum boiling point range

1C

Acetone and acetaldehyde content

< 0.003 wt%

Ethanol content

< 0.001 wt%

Volatile iron content

< 2 g/L

Sulfur content

< 0.0001 wt%

Chlorine content

< 0.15 wt%

For the sake of simplicity the methanol feedstock is assumed to have 100% purity with
specification as follows for our references:

Figure 24: Characteristics and features of methanol

58

4.1.2 Silver Catalyst Processes


The silver catalyst processes to formaldehyde are usually taking place at an atmospheric pressure
and at 600 - 720C. The reaction temperature depends on the excess of methanol in the
methanol-air mixture. The composition of the mixture must lie outside the explosive limits. The
amount of air that is used is too, determined by the catalytic quality of the silver surface. The
following main reactions occur during conversion of methanol to formaldehyde:
CH3OH CH2O + H2 H = +84kJ/mol

(1)

H2 + 1/2 O2 H2O H = -243 kJ/mol

(2)

CH3OH + 1/2 O2 CH2O + H2O H = -159 kJ/mol

(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)

CH3OH + 3/2 O2 CO2 + 2 H2O H = -674 kJ/mol

(5)

CH2O + O2 CO2 + H2O H = -519 kJ/mol

(6)

Other byproducts include methyl formate, methane and formic acid.


The endothermic dehydrogenation reaction (1) is highly temperature-dependent, conversion
increasing from 50 % at 400C to 90 % at 500C and to 99% at 700C. The temperature
dependence of the equilibrium constant for reaction Kp is given by:
log Kp = (4600/T)-6.470
Kinetic studies with silver on carrier show that reaction (1) is a first order reaction. Thus, the rate
of formaldehyde formation is a function of the available oxygen concentration and the oxygen
residence time on the catalyst surface:

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

4.1.2.1 Complete conversion of methanol (BASF)

Figure 25: Flowchart of formaldehyde production by the BASF process


From Figure 20 above, the labelling of the equipment are as per follow:
a) Evaporator
b) Blower
c) Reactor
d) Boiler
e) Heat exchanger
f) Absorption column
g) Steam generator
h) Cooler
i)

Super heater

61

4.1.2.2 Incomplete conversion and distillative recovery of methanol

Figure 26: Flowchart of formaldehyde production with recovery of methanol by distillation


From Figure 21 above, the labelling of the equipment are as per follow:
a) Evaporator
b) Blower
c) Reactor
d) Boiler
e) Distillation column
f) Absorption column
g) Steam generator
h) Cooler
i)

Super heater

j)

Anion-exchange unit

62

4.1.3

Formox Process

Figure 27: Flowchart of formaldehyde production by the Formox process


From Figure 22 above, the labelling of the equipment are as per follow:
a) Evaporator
b) Blower
c) Reactor
d) Boiler
e) Heat exchanger
f) Formaldehyde absorption column
g) Circulation system for heat-transfer oil
h) Cooler
i)

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

In the temperature range 270 400C, conversion at atmospheric pressure is virtually


complete. However, conversion is temperature dependent because at > 470C the following side
reaction increases considerably:
CH2O + O2 CO + H2O

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:

Batch or Continuous depending on the mode of operation.

Homogeneous or Heterogeneous depending upon the phases present.

They may also be classified as:

Stirred Tank Reactor

Tubular Reactor

Packed Bed Reactor

Fluidized Bed Reactor

65

4.2.1 Batch Operation

Figure 28: Batch operation


Meanwhile, batch reactor is the generic term for a type of vessel widely used in the process
industries. Its name is something of a contradiction since vessels of this type are used for a
variety of process operations such as solids dissolution, product mixing, chemical reactions,
batch distillation, crystallization, liquid/liquid extraction and polymerization. In some cases,
they are not referred to as reactors but have a name which reflects the role they perform
(such as crystallizer, or bio reactor). Batch operation has the following characteristics

Time variant conditions

Discontinuous production

Downtime for cleaning and filling

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

4.2.2 Continuous Operation

Figure 29: Continuous operations


Continuous reactors (alternatively referred to as flow reactors) carry material as a flowing
stream. Reactants are continuously fed into the reactor and emerge as continuous stream of
product. Continuous reactors are used for a wide variety of chemical and biological processes
within the food, chemical and pharmaceutical industries. A survey of the continuous reactor
market will throw up a daunting variety of shapes and types of machine. Beneath this variation
however lies a relatively small number of key design features which determine the capabilities of
the reactor. When classifying continuous reactors, it can be more helpful to look at these design
features rather than the whole system. Continuous operation has the following characteristics:

Continuous production

Steady state after start-up period (usually)

No variation of concentrations with time

Constant reaction rate

Ease of balancing to determine kinetics

No down-time for cleaning, filling, etc.

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

4.2.2.1 Benefits of Continuous operation


The rate of many chemical reactions is dependent on reactant concentration. Continuous reactors
are generally able to cope with much higher reactant concentrations due to their superior heat
transfer capacities. Plug flow reactors have the additional advantage of greater separation
between reactants and products giving a better concentration profile. The small size of
continuous reactors makes higher mixing rates possible. The output from a continuous reactor
can be altered by varying the run time. This increases operating flexibility for manufacturers.
Table below summaries the comparison of between batch and continuous process:

Table 13: Comparison of between batch and continuous process operation


Description
Types
materials

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

Relatively large installations. Very Relatively


small
installations.
big investment in land and Significant savings in land and
installations.
installations.

Reactor

Changes occur in the concentrations At all locations, conditions are


of materials over time.
constant
over
time
(durable
conditions).

Volume
produces

Better
for
production.

small-volume Better for large scale production and


long run process.

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

Complex control. Automatic control


must be used. Control of reactor
conditions is more difficult. Control
must be exercised over the rate of
flow of the materials.

Product(s)

Extraction of materials only after all Continuous extraction of products at


the actions is finished with the all times during the reaction.
conclusion of the reaction.

Trouble
shooting

A fault or dealing with a batch


requiring repair does not cause
problems in the other stages.
Appropriate tests are conducted after
each stage.

Quantities
produced

Preferable when production of small Preferable for large scale production.


quantities of a specific material is
planned.

Variety
products
the plant

The installations are interconnected,


so a fault in one causes a stoppage in
all the others. Material that has been
damaged cannot be repaired under
the same working conditions. It
must be isolated and the process
restarted.

of Preferable when the plant produces a Preferable for a


in wide variety of materials and when permanent product.
the product is likely to be changed
now and again, while using the same
reactor.

Product
development
stage

central

and

Preferable when the process is Preferable after the conclusion of all


relatively new and still unfamiliar. the stages of grossing-up and
In this case the initial investment is economic feasibility tests.
in a smaller batch reactor, and thus
the economic risk is smaller.

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

Preliminary Reactor Optimization


4.3.1 Incomplete conversion of methanol with distillative recovery of methanol
9

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

4.3.2 Complete Conversion of methanol (BASF)


8

6
1

Figure 31: Block diagram of complete conversion of methanol (BASF)


Streams
Molar Flow (kmol/hr)
MetOH
H2O
N2
O2
CH2O
Total
Mass Flow (kg/hr)
MetOH
H2O
N2
O2
CH2O
Total

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

4.3.3 Formox Process


8

6
1

Figure 32: Block diagram of Formox process


Streams
Molar Flow (kmol/hr)
MetOH
H2O
N2
O2
CH2O
Total
Mass Flow (kg/hr)
MetOH
H2O
N2
O2
CH2O
Total

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

Economic Potential Analysis

4.4.1 Incomplete conversion of methanol with distillative recovery of methanol


EP1
=
Revenue Cost of Raw Material
=

6617.016 kg/hr (RM 490.00 per kg) 100 kg/hr (RM 1.91688 per kg)

RM 3242, 146.52

4.4.2 Complete Conversion of methanol (BASF)


EP1
=
Revenue Cost of Raw Material
=

74114.63 kg/hr (RM 490.00 per kg) 100 kg/hr (RM 1.91688 per kg)

RM 36315, 977.01

4.4.3 Formox Process


EP1
=
Revenue Cost of Raw Material
=

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

CHAPTER 5: HEAT INTEGRATION


The objective of performing heat integration is to recover as much heat as possible in the overall
process. It is one of the methods to minimize and eliminate unnecessary costs by optimizing the
energy as efficient as possible. By introducing heat exchangers while maintaining the operating
conditions where cold streams require heating and hot streams require cooling the maximum
efficiency could be achieved. Pinch Temperature Method analysis is used for this particular matter.

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.

Data extraction from streams

ii.

Problem Table Algorithm (PTA)

iii.

Construction of Composite Curve (CC) and Grand Composite Curve (GCC)

iv.

Heat Exchanger Network (HEN) design

5.1.1 Stream Data Extraction


The first step of heat integration is the extraction and tabulation of hot streams and cold streams of the
process. The detail is as follows:

Table 15: Stream Data


Stream Name

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

duty of heater and cooler (kW)

Cp

Heat Capacity (kW/C)

Change in temperature (C)

5.1.2 Problem Table Algorithm


Before calculating the minimum utility requirements, problem table algorithm is first executed by
shifting of temperatures for both hot streams and cold streams. The minimum temperature difference,
Tmin is set to be 20 C. The shifted temperature for each stream is calculated by using the equation as
below:
=

= +

Table 16: Shifted temperature


Stream Name

Shifted
Supply (C)

Temperature Shifted Temperature Target Cp


(C)
(kW/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

Table 17: Temperature Portioning Table


T

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.

Table 18: Heat cascade diagram


Based in the table above, the minimum hot utilities is QH,min = 0 kW and the minimum cold utilities
is QC,min= 2480.18 kW. This indicates that it is a threshold problem where only cold utility is

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

Figure 33: Combined composite curve

Figure 34: Grand composite curve

5.1.4 Heat Exchanger Network (HEN) Design


During pairing of the streams, two rules must be obeyed to ensure the network is feasible:
i.

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:

Do not transfer heat across the pinch

Do not use cold utilities above the pinch

Do not use hot utilities below the pinch

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.

Figure 35: Heat Exchanger Network (HEN) grid

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

CHAPTER 6: PROCESS FLOWSHEETING


A process flow diagram is developed before heat integration. It is as below.

Figure 36: PFD before integration

Figure 37: PFD after integration

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

CONCLUSION AND RECOMMENDATION


It has been proven conceptually that the setting up of a formalin plant in Malaysia is feasible and
crucial in order to meet the global high demand especially in the Northeast Asia, North America
and Europe region. Construction of formalin production plant in Malaysia is technically feasible,
economically attractive, has high market potential, has feasible economic potential and
environmentally friendly. The plant is designed in such a way that it is safe to operate with
optimum production.

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

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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

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