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

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 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

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 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.

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 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: LITERATURE REVIEW ............................................................. 14
2.1 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

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 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 Formox Process .............................................................................................. 63
4.2 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

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 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

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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

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 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

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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.

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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 or a mixture of
an iron and molybdenum or vanadium oxides.

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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 for desired
products production, safety and 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: LITERATURE REVIEW

2.1 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 Oxygenate in gasoline
MTBE Oxygenate in gasoline
TAME
Methanol to gasoline

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

Chloromethanes
Methyl chloride Organic paint-removal solvent
Methylene chloride 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

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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)

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 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
Silver 518.27

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 Price Range Purity Min. Order Supply Ability

MasterTech $ 31890.00/ton
Shijiazhuang $350-500 / ton 1 Twenty-Foot 5000 Ton/Tons
Xinlongwei Chemical Container per Month
Co., Ltd.
Henan CXH Purity 1 Twenty-Foot 4000 Ton/Tons
Industrial And Trading Container per Month
Co., Ltd.
Henan Luckybee New $387-419 / ton 5 Tons 1500 Metric
Technology Co., Ltd. Ton/Metric Tons
per Month
Qingdao Xinyongan $400-450/ ton 5 Metric Tons 1000 Metric
Chemicals Co., Ltd Ton/Metric Tons
per Month
Quzhou Juhui Chemical $100-300/piece 20 Tons 10000 Ton/Tons
Materials Co., Ltd. per Month
Zouping Changshan $1000-3000 1 Ton 1,000 Ton/Tons
Town Zefeng Fertilizer /ton per Month
Factory
Zhejiang Junhao 1 Metric Ton 2000 Metric
Chemical Co., Ltd. Ton/Metric Tons
per Month
Xinxiang Kolanky $1450-1850 18 Tons 880 Ton/Tons per
Technical Co., Ltd. / ton Month
Henan Xinxiang No. 7 $1450-1850 18 Tons 880 Ton/Tons per
Chemical Co., Ltd. / ton Month
Zhejiang Junhao 1 Metric Ton
Chemical Co., Ltd
Guangzhou Derou $1000-10000 1000 300 Metric
Chemical Industry Co., /ton Kilograms Ton/Metric Tons
Ltd. per Month
Xinxiang Kolanky $1450-1850 18 Tons 880 Ton/Tons per
Technical Co., Ltd. / ton Month
YongHua Chemical $260-520 / ton 1 Metric Ton 10 Metric
Technology (Jiangsu) Ton/Metric Tons
Co., Ltd. per Day
Toronto Research $183981- 96%
Chemicals 539679 / ton

Beijing Hwrk Chem $95670/ton

Co.,ltd.
Guangzhou Puen $511051- 98%
Scientific Instrument 899448 /ton
Co., Ltd.
Fishersci $44330/ton 96%
Beijing Ouhe $24530/tonl 98%
Technology Co. Ltd

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 $20000-
100000/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
Formaldehyde $20000-100000/ton

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,
Location With
Economic and
Respect To
Strategic
Marketing Area
Consideration

Waste Disposal Transportation

Land
Availability & Utilities
Cost

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 Gurun, Kedah Kota Kinabalu Industrial Park Lahad Datu Industrial Park
Criteria
Land RM7.00 psf ( Gurun RM 28-RM 30 psf (KKIP) RM 30 psf
price Industrial zone)
Area 1528.5 hectares N/A 1618.7 hectares
available
Water - PETRONAS CUF Diversified Water Resources Sdn. - PETRONAS CUF
supplier Bhd. - LahadDatu Water Supply
SdnBhd
Electricity - PETRONAS CUF KKIP Power Sdn. Bhd. - PETRONAS CUF
supplier - TenagaNasionalBerhad
Methanol - PETRONAS Petronas Labuan Methanol plant Petronas Labuan Methanol
supplier Fertilizer Kedah plant
Gurun

Highway North-South highway KK-Sulaman highway Malaysia Federal Route 13

Railway Gurun Railway - -
Station
Airport Sultan Abdul Halim Kota Kinabalu International Airport Lahad Datu Airport
Airport (KKIA)
Port Penang Port (60km) 5 km from Sepangar Container Port - Liquid & Dry Bulk
facility Pulau Bunting Port Terminal
(project completion
2016) 19km
Labor Large population Large population Large population
Supply
Waste - PETRONAS CUF -Dewan Bandaraya Kota Kinabalu - PETRONAS CUF
disposal - Majlis Perbandaran
Kedah
Companies - Investment Incentives
Political, developing
Economic infrastructure of Pioneer status
and industrial park: Investment tax
Strategic

33
Considera allowance
tion - 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 1-0 Marks

Land price Price of land below RM Price of land more than Price of land more than
20 psf RM 20 psf RM30 psf
Natural gas Able to obtain large Able to obtain natural Unable to obtain natural
supplier natural gas supply locally 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 state
Electricity Able to obtain large Able to obtain electricity Unable to obtain enough
supplier electricity supply from supply from neighboring electricity supply
the same state state
Port facility <10 km proximity to port <30 km proximity to port >30 km proximity to port
facility facility facility
Airport Availability of Availability of domestic Unavailability of airport
international airport airport
Railway Complete network and Complete network of Unavailability of railway
well maintained railway railway
Political, Excellent tax benefits Good tax benefits No tax benefits
Economic and
Strategic
Consideration

36
Table 7: Weighted evaluation on potential site

Lahad Datu
Gurun Industrial Kota Kinabalu
Selection Criteria Industrial Park,
Area Industrial Park
Sabah
Land price 5 2 2
Raw materials
5 3 3
supplier
Water supplier 5 3 5
Electricity supplier 5 4 5
Port facility 3 5 5
Airport 5 5 5
Railway 5 0 0
Highway 5 3 5
Waste disposal 5 3 5
Tax Benefits 5 - 4
Total 48 29 40
Percentage 96% 58% 80%
Ranking 1 3 2

37
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 safety-
critical 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. Operating and Support Hazard Analysis (O&SHA).

The general purpose of the O&SHA is to perform a 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 Cause Required safe job

injuries procedures
This process is based Wrong catalysts make Wrong catalyst Proper catalyst should
on ammonia catalyst runaway reaction concentration nitric be added
occur. acid used

Adequate cooling Inadequate cooling As the temperature Adequate vent

arrangement increases temperature increases in the arrangement in the
should be provided reactor, the reaction extreme condition
rate also increases. As should be provided;
the reaction rate otherwise, there is
increases the possibility of
generation of water explosion due to over
vapor also increases pressure.
which increases the
pressure in the
reactor

In store, material Proper reactants or Wrong reactants or Chemicals should be

should be kept in catalyst should be catalysts or wrong labelled and the use of
proper order. Display identified and used for sequences in the input PPEs for carrying the
of MSDS in the reaction and to the reactor can also chemicals
working areas is also used in proper make the
required to avoid sequence reaction runaway
mixing the wrong
chemical in the
process

Any kind of operating Accident, blast, or Reaction is highly Implement various

negligence explosion occurs 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 Flash Safety Measures Handling/storage

point

Methanol Flammable Can cause 11oC First Aid: Keep in well-ventilated

Irritant erythema or Rinse/wash affected area, away from sources
dermatitis. area with running of ignition. Ensure all
Toxicity can water, get fresh air. equipment is electrically
cause blindness. Fire Fighting: Use grounded before transfer.
CO2 to extinguish,
suppress gases with
water jet

Iron oxide Irritant Can cause lung -- First Aid: Ensure storage can
damage, Rinse/wash affected support its weight and
irritating to eye area with running doesnt strain in reaching
and skin. water, get fresh air. for materials.

Formalin Irritant Carcinogenic 50oC First Aid: Keep away from heat.
Corrosive and can cause Rinse/wash affected Keep away from sources
inflammation area with running of ignition. Ground all
water, get fresh air. equipment containing
material. Store in a
Fire Fighting: Use segregated, cool, well-
dry chemical ventilated area. Keep
powder, alcohol container tightly closed
foam, water spray or and sealed until ready for
fog. use.

48
Formic Corrosive Can cause 49.5oC First Aid: Ground all equipment and
acid Flammable severe skin Rinse/wash affected lines. Ensure absence of
burns and eyes area with running ignition source. Protect
damage water, get fresh air. from physical damage.
Take off clothing and Store in upright position
dont induce and in cool, dry, well-
vomiting if ventilated area.
swallowed
Fire Fighting: Use
water spray, alcohol-
resistant foam, dry
chemical or carbon
dioxide.

Methyl Irritant Toxic to 19oC First Aid: Ensure storage can

formate nervous system Rinse/wash affected support its weight and
and organs. area with running doesnt strain in reaching
Irritating to eyes water, get fresh air. for materials.
and skin. Keep away from heat.
Fire Fighting: Use Keep away from sources
dry chemical of ignition. Ground all
powder, alcohol equipment containing
foam, water spray or material. Store in a
fog. segregated, cool, well-
ventilated area.
Refrigerated room is more
preferable.

Methane Flammable Asphyxiating 188oC First Aid: Flush Ground all equipment and
and may cause affected area with lines. Ensure absence of
frostbite. cool/lukewarm ignition source. Protect
water, get fresh air. from physical damage.
Take off clothing and Store in upright position
get fresh air. If and in cool, dry, well-
necessary, give ventilated area.
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
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
Passive Minimize hazard using process or equipment 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.

Active Controls, safety interlocks, automatic High level alarm in a tank shuts
shut down systems automatic feed valve
Multiple active elements A sprinkler system which
Sensor -detect hazardous extinguishes a fire
condition Emergency shutdown system
Logic device - decide what to
do
Control element -implement
action
Prevent incidents, or mitigate the
consequences of incidents

Procedural Standard operating procedures, safety rules Confined space entry

and standard procedures, emergency response procedures.
procedures, training Cleanup procedure for absorber

50
 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 Size of methanol and formaldehyde

hazardous substances or energy that storage tanks should be as practical as
involved in a certain process. possible.
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.

Moderate Use less hazardous conditions or Usage of a suitable and compatible

facilities 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 Reactors and absorbers should be
to operate 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.

Substitute Changing process to use less Process route is substituted with the
hazardous materials to produce less one gives lower operating cost.
hazardous reaction chemistry.
In addition, we can also replace a
hazardous material with a less
hazardous one.

52
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) (Scheduled Treatment and Disposal

Facilities) Order 1989

54
 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 Safety and Health (Employers' Safety and Health General

Policy
Statements) (Exception) Regulations 1995

2. Occupational Safety and Health (Control of Industry Major Accident

Hazards)
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 Safety and Health (Use and Standards of Exposure of

Chemicals
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-, medium-
or 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
k = rate constant

t = 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 Batch Process Continuous Process

Types of Can be used with all types of Easier for use with flowing materials
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 Relatively large installations. Very Relatively small installations.

size 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 Better for a small-volume Better for large scale production and
produces production. long run process.

Feeding raw Raw materials are fed before the Constant feeding of raw materials
materials start of the reaction. during the entire reaction process.

Control of the Simple control. It is easier to Complex control. Automatic control

set of actions control reaction conditions (pH, must be used. Control of reactor
in the system pressure, temperature). Manual conditions is more difficult. Control
control can also be done. must be exercised over the rate of
flow of the materials.

68
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 A fault or dealing with a batch The installations are interconnected,

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

Quantities Preferable when production of small Preferable for large scale production.
produced quantities of a specific material is
planned.

Variety of Preferable when the plant produces a Preferable for a central and
products in wide variety of materials and when permanent product.
the plant the product is likely to be changed
now and again, while using the same
reactor.

Product Preferable when the process is Preferable after the conclusion of all
development relatively new and still unfamiliar. the stages of grossing-up and
stage In this case the initial investment is economic feasibility tests.
in a smaller batch reactor, and thus
the economic risk is smaller.

69
Parameters Batch Operation Continuous Operation
Flow Disconnected, with some Continuous
dominant flows
Flexibility Moderate Very low
Capital Investment Moderate Very high
Maintenance Cost High Moderate
Labour Skill Moderate Very high
Volume of Feed and Moderate Very high
Product
Product Quality Not constant Constant
Power Consumption High Low
Residence Time of Feed Long Short

70
4.3 Preliminary Reactor Optimization

4.3.1 Incomplete conversion of methanol with distillative recovery of methanol

10 9

1 2 5 6

3 4 7

Figure 30: Block diagram of incomplete conversion of methanol with distillative recovery of methanol

Streams 1 2 3 4 5 6 7 8 9 10
Molar Flow (kmol/hr)
MetOH 100 112.6 14.1876 14.1876 0 0 0.70938 13.47822 0.87822 12.6
H2O 0 1.9682 100.3806 319.24 100.5634 0 220.6842 2.007612 0 2.007612
N2 3761.905 3761.905 3761.905 0 0 3761.905 0 0 0 0
O2 1000 1000 950.7938 0 0 950.7938 0 0 0
CH2O 0 0 87.4 87.4 0 0 87.4 0 0 0
Total 4861.905 4876.473 4914.667 420.8276 100.5634 4712.699 308.7936 15.48583 0.87822 14.60761
Mass Flow (kg/hr)
MetOH 3200 3603.2 454.0032 454.0032 0 0 22.70016 431.303 28.10304 403.2
H2O 0 35.4276 1806.851 5746.32 1810.142 0 3972.315 36.13702 0 36.13702
N2 105333.3 105333.3 105333.3 0 0 105333.3 0 0 0 0
O2 32000 32000 30425.4 0 0 30425.4 0 0 0 0
CH2O 0 0 2622 2622 0 0 2622 0 0 0
Total 140533.3 140972 140641.6 8822.323 1810.142 135758.7 6617.016 467.4401 28.10304 439.337

71
 4.3.2 Complete Conversion of methanol (BASF)
8 7

6
1 2 5

3 4

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

Streams 1 2 3 4 5 6 7 8
Molar Flow (kmol/hr)
MetOH 100 100 3 3 0 0 0 0
H2O 0 3.254 100.254 244.9241 146.6752 2.00508 0 2.00508
N2 3761.905 3761.905 3761.905 0 0 3761.905 3761.905 0
O2 1000 1000 951.5 0 0 951.5 951.5 0
CH2O 0 0 97 97 0 0 0
Total 4861.905 4865.159 4913.659 344.9241 146.6752 4715.41 4713.405 2.00508
Mass Flow (kg/hr)
MetOH 3200 3200 96 96 0 0 0 0
H2O 0 58.572 1804.572 4408.634 2640.153 36.09144 0 36.09144
N2 105333.3 105333.3 105333.3 0 0 105333.3 105333.3 0
O2 32000 32000 30448 0 0 30448 30448 0
CH2O 0 0 2910 2910 0 0 0 0
Total 140533.3 140591.9 140591.9 7414.634 2640.153 135817.4 135781.3 36.09144

72
 4.3.3 Formox Process
8 7

6
1 2 5

3 4

Figure 32: Block diagram of Formox process

Streams 1 2 3 4 5 6 7 8
Molar Flow (kmol/hr)
MetOH 100 100 1 1 0 0 0 0
H2O 0 3.254 102.254 249.9741 149.7652 2.04508 0 2.04508
N2 3761.905 3761.905 3761.905 0 0 3761.905 3761.905 0
O2 1000 1000 950.5 0 0 950.5 950.5 0
CH2O 0 0 99 99 0 0 0
Total 4861.905 4865.159 4914.659 349.9741 149.7652 4714.45 4712.405 2.04508
Mass Flow (kg/hr)
MetOH 3200 3200 32 32 0 0 0 0
H2O 0 58.572 1840.572 4499.534 2695.773 36.81144 0 36.81144
N2 105333.3 105333.3 105333.3 0 0 105333.3 105333.3 0
O2 32000 32000 30416 0 0 30416 30416 0
CH2O 0 0 2970 2970 0 0 0 0
Total 140533.3 140591.9 140591.9 7501.534 2695.773 135786.1 135749.3 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

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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 Incomplete Formox

Methanol Conversion Process
Conversion and
Methanol
Recovery
Total capital 6.6 8.6 9.6
investment, $/t
Methanol 1.24 1.22 1.15
Consumption, t/t
Raw Materials, $/t 255 252 227
Methanol 250 247 232
Catalyst and 5 5 7
Chemical
Byproduct credit n.a.. n.a. 12
(stream)
Utilities 12 20 13
LP Steam 3.4 9.5
Power purchased 3.4 4.3 8.0
Cooling water 2.9 2.8 4
Process water 2.4 3.3 1.0
Variable cost, $/t 267 272 240
Direct fixed cost, $/t 27 29 30
Total allocated fixed 18 20 21
cost, $/t
Total cash cost, $/t 312 321 291
Depreciation, $/t 33 43 48
Production cost, $/t 345 364 339
Return of Capital 33 43 48
investment (ROI), $/t
Cost of production 378 407 387
and ROI, $/t

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 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 Temperature Duty (kW) T Cp

Supply (C) Target (C) (kW/C)
Cold Stream 1 126.3 150 371.6 23.7 15.6793
Cold Stream 2 25.07 150 1052 124.93 8.42072

Hot Stream 1 343 110 4070 -233 17.4678

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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)

T = 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:

=
2

= +
2

Table 16: Shifted temperature

Stream Name Shifted Temperature Shifted Temperature Target Cp

Supply (C) (C) (kW/C)
Cold Stream 1 121.3 145 15.67932
Cold Stream 2 20.07 145 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 T Cp (kW/C) H (kW) Surplus/

(C) Deficit

348 H1
193 -17.46781 -3371.29 Surplus
145
23.7 -24.726414 -586.02 Surplus
121.3

C1 6.3 -1.78849 -11.27 Surplus

115
94.93 15.67932 1488.44 Deficit
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.

, = +
2

, =
2

, = 348.0 +
2

, = 348.0 + 5

, = 353

, = 348.0
2

, = 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.uic-
che.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. (2000). Formaldehyde (Vol. 162, pp. 44-44). NEW YORK: CHEMICAL WEEK
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Babu, J Ramesh. (2007). Layer of Protection AnalysisAn effective tool in PHA: Report.
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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
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Olah, George A, Goeppert, Alain, & Prakash, GK Surya. (2009). Beyond oil and gas: the
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