Formaldehyde Production From Methanol

McMaster University 6 December, 2010 1280 Main Street West Hamilton, ON L8S 4L9

To: Mr. Matthew Hazaras From: Group 4 (G. Leota, J. Ma, H. Park, S. Park, G. Voloshenko) Subject: SDL Project

Dear Mr. Matthew Hazaras, As requested in the Engineering Economics and Problem Solving class, please find attached the final version of the formaldehyde plant report. The report studies the production of formaldehyde from methanol using a silver catalyst, and includes an overview of typical plant setup and operation, as well as sections on safety and troubleshooting. The economic aspects of running such a plant are also considered. The production of formaldehyde is a straightforward process. Methanol and air are combusted within a reactor in the presence of a silver catalyst. The product is a mixture of formaldehyde and methanol in water, which is then run through an absorber to remove inert gases and a distillation column to recycle residual methanol. The final product contains approximately thirty-seven weight percent formaldehyde in water with four weight percent methanol added as a stabilizer. The formalin solution may then be stored or used immediately in another application. Due to the health risks posed by working with formaldehyde and methanol, our proposed improvements to the process are the addition of a rupture disk to the methanol vaporizer and implementation of hermetically sealed canned pumps along points in the process handling formaldehyde. This will reduce the likelihood of leaks along the process, and therefore reduce exposure to these hazardous chemicals and lower their emissions from the plant. Sincerely, G. Leota J. Ma H. Park S. Park G.Voloshenko

CHEM ENG 4N04 Group 4

Final Report

G. Leota

J. Ma

H.Park

S. Park

G. Voloshenko

Dr. P. Mhaskar

December 6, 2010

Formaldehyde Production from Methanol

CONTENTS

1. Introduction .................................................................................................................................. 1

2. Process Overview ........................................................................................................................ 1

2.1. Formaldehyde ....................................................................................................................... 1

2.1.1. Physical and Chemical Properties ................................................................................. 2

2.1.2. Applications and Benefits of Formaldehyde ................................................................... 2

2.1.3. Formaldehyde Production in Canada ............................................................................. 2

2.2. P&ID Description ................................................................................................................... 3

3. Process Principles ....................................................................................................................... 4

3.1. The Feed Stream .................................................................................................................. 4

3.2. The Reactor Configuration .................................................................................................... 4

3.3. Separation Process ............................................................................................................... 5

3.3.1. The Absorber .................................................................................................................. 5

3.3.2. The Distillation Column .................................................................................................. 5

3.4. Storage .................................................................................................................................. 6

4. Operability .................................................................................................................................... 6

4.1. Operating Window ................................................................................................................ 6

4.2. Flexibility ............................................................................................................................... 8

4.3. Reliability ............................................................................................................................... 9

4.4. Efficiency ............................................................................................................................. 10

4.4.1. Equipment Capacity ..................................................................................................... 10

4.4.2. Equipment Technology................................................................................................. 11

4.4.3. Equipment Utilization.................................................................................................... 11

4.4.4. Process Structure ......................................................................................................... 11

4.4.5. Operating Conditions.................................................................................................... 12

4.4.6. Calculation of Efficiency ............................................................................................... 12

4.5. Transition ............................................................................................................................ 12

4.5.1. Start Up ........................................................................................................................ 12

4.5.2. Shut Down .................................................................................................................... 13

5. Troubleshooting ......................................................................................................................... 13

6. Health and Safety Aspect .......................................................................................................... 13

6.1. Material Safety .................................................................................................................... 14

6.2. Process Safety .................................................................................................................... 14

7. Economics ................................................................................................................................. 15

7.1. Relevant Issues .................................................................................................................. 15

McMaster University Final Report

7.1.1. Methanol Price ............................................................................................................. 15

7.1.2. Ontario’s new Smart Meter policy ................................................................................ 16

7.1.3. Housing Market Crisis in 2007 ..................................................................................... 16

7.2. Capital Cost Estimation ....................................................................................................... 17

7.3. Operating Cost Estimation .................................................................................................. 18

7.3.1. Using Ontario’s Smart Rate ......................................................................................... 19

8. Process Recommendations ....................................................................................................... 19

9. Conclusions ............................................................................................................................... 20

References .................................................................................................................................... 22

Appendix ........................................................................................................................................ 24

Appendix A- Sample Efficiency Calculations ............................................................................. 24

Appendix B- Troubleshooting Fishbone Diagram and Table ..................................................... 25

Appendix C - HAZOP ................................................................................................................. 26

Appendix D - MSDS of Formaldehyde and Methanol ................................................................ 29

Appendix E –Capital & Operating Cost Calculation ................................................................... 34

Tables

Table 1 List of alarm sign under possible system failure .............................................................. 14

Table 2 Hydro cost calculated via original rate, summer and winter Smart rate ........................... 19

Table B 1 High temperature of reactor causes and solutions ....................................................... 25

Table D 1 MSDS of Formaldehyde ................................................................................................ 29

Table D 2 MSDS of Methanol ........................................................................................................ 31

Table E 1 Capital Cost Table ......................................................................................................... 34

Table E 2 Operating Cost Table .................................................................................................... 35

Table E 3 Net present value calculations ...................................................................................... 36

Figures Figure 1. Formaldehyde production from methanol P&ID ............................................................... 3

Figure 2. Process flow diagram of the reactor ................................................................................. 4

Figure 3 Operating window of reactor with air flow rate vs. methanol flow rate (kmol/h) ................ 7

Figure 4 Historic methanol price from 2006 to 2010 [13] .............................................................. 16

Figure 5 Ontario's Smart Electricity Cost ....................................................................................... 16

Figure 6 Standard & Poor's Case-Shiffer home price index [15] .................................................. 17

Figure 7 Operating cost distribution............................................................................................... 19

McMaster University Chemical Engineering 4N04 Final Report

1. INTRODUCTION

Chemical manufacturers around the globe do careful analyses from many

perspectives prior to launching a new project. Starting from the basic background

research, to the market analysis, and finally to plant safety, multi-faceted and in-

depth research must be performed. Engineers perform crucial roles in this

process. They make sure the company maximizes profit from the operation while

keeping safety paramount.

Formaldehyde is a key chemical component in many manufacturing

processes. It is relatively simple to produce, although careful handling,

transportation and storage are required. In this report, analyses on the chemical

itself, reactions, safety, plant design, troubleshooting and economics were

performed. Finally, some conclusions and suggestions were presented.

2. PROCESS OVERVIEW

2.1. FORMALDEHYDE

Formaldehyde (CH2O) is known as the first series of aliphatic aldehydes.

The occurrence of formaldehyde is abundant in air and is also a byproduct of

several biological processes. The average person produces 1.5 ounces of

formaldehyde per day as part of normal human metabolism [1]. Plants and

animals produce formaldehyde as their byproducts. For example, Brussels

sprouts and cabbage emit formaldehyde when they are cooked [2].

Formaldehyde can be produced by oxidation of methanol with air in the

presence of catalyst. Formaldehyde may be produced at a relatively low cost,

high purity, and from a variety of chemical reactions, making formaldehyde one

of the most produced industrial chemicals in the world. Formaldehyde industries

have been grown since 1972, from a yearly global production volume of 7 million

metric tons up to 24 million metric tons in recent years [3]. In addition,

commercial uses of formaldehyde have widespread industrial applications, which

showcase how important the chemical is in our everyday lives.


2.1.1. PHYSICAL AND CHEMICAL PROPERTIES

Formaldehyde has a colorless and distinctive pungent smell even can be

detected in low concentrations. It is a highly flammable gas, with a flashpoint of

50°C. The heat of combustion is 134.l kcal/mol or 4.47kcal/g [4]. Formaldehyde is

soluble in a variety of solvents and miscible in water [4]. Formaldehyde usually

sold as 37 weight percent solution in water known as formalin.

2.1.2. APPLICATIONS AND BENEFITS OF FORMALDEHYDE

Because of its unique properties, formaldehyde has been used in all

kinds of products such as vaccines, medicines, fertilizers, carpets, plastics,

clothing, glues, x-rays, and plywood [2]. Most formaldehyde products find uses

as adhesives and wood coatings to provide weather-resistance [1].

Formaldehyde is an important ingredient in production of formaldehyde-

based material. The formaldehyde-based resins are used in production of glues

for household furnishing. The largest use of formaldehyde is in the manufacturing

of amino and phenolic resins. The phenolic molding resins are used in

appliances, electrical control, telephone and wiring devices [2]. In the automotive

and building industries, formaldehyde-based acetal resins are used in the

electrical system, transmission, engine block, door panels, and brake shoes [3].

2.1.3. FORMALDEHYDE PRODUCTION IN CANADA

Today, there are six companies in Canada that make formaldehyde at 11

different locations in five provinces. For the maximum cost effectiveness,

formaldehyde is made near the point of consumption. By capacity, Borden

Chemical is the largest producer in Canada, followed by Dynea Canada Ltd,

Celanese Canada, and ARC Resin Corp. Borden Chemical is also the largest

U.S. formaldehyde producer [1].


2.2. P&ID DESCRIPTION

As it shown in the Figure 1, the process of formaldehyde production

began with methanol and air mixture is to the reactor. Mixture is converted into

formaldehyde in the presence of a silver catalyst.

Figure 1. Formaldehyde production from methanol P&ID

Following the reactor contains a heat exchanger which contains water to

remove heat evolved from the reaction. The steam formed within the heat

exchanger is used as a heat source for the methanol vaporizer and the distillation

column. The formalin concentration is adjusted by regulating the water flow rate

into the absorber. The bottoms product from the absorber contains formaldehyde

and residual methanol, which is then sent to the distillation column. In the

distillation column, the formaldehyde is purified to a desired formaldehyde

concentration, after which it is sent to storage.


3. PROCESS PRINCIPLES

3.1. THE FEED STREAM

The feed to the reactor contains a compressed and vaporized mixture of

methanol in air. Both the air and methanol must be free of trace impurities such

as sulphur compounds and transition-based metals, which will poison the catalyst

and decrease its lifetime [5]. As the methanol enters the process as a liquid,

compression is achieved using a pump, while the air is compressed as well.

Both streams are independently heated using pressurized steam prior to being

mixed. To reach the upper explosive limit of methanol, a composition above 37

mole percent methanol in air is used to ensure optimal combustion [6].

3.2. THE REACTOR CONFIGURATION

Figure 2. Process flow diagram of the reactor

As it shown in Figure 2, the feed enters and is immediately combusted,

resulting in reactor temperatures between 630 and 700oC. Aided by the silver


catalyst, the oxidation-dehydration reaction proceeds along the following two

pathways:

CH3OH + ½O2 → HCHO + H2O ΔHRXN = -156 kJ/mole (1)

CH3OH → HCHO + H2 ΔHRXN = 85.0 kJ/mole (2)

The reaction converts 71 percent of the methanol into formaldehyde. The

reactor is configured to take advantage of the heat released from the reaction:

the catalyst, in the form of wire gauze, is suspended directly above a heat

exchanger tube bank [6]. The heat exchanger runs water, which is converted

into medium pressure steam and then run through the methanol vaporizer. The

heat exchanger cools the formaldehyde product to 100oC, preventing the

formaldehyde from decomposing into carbon monoxide and hydrogen. The

product stream contains inert gases, and a water, methanol and formaldehyde

vapour [6].

3.3. SEPARATION PROCESS

3.3.1. THE ABSORBER

The absorber functions to absorb any formaldehyde vapour from the reactor

product stream and removing any inert or unreacted gases. The column

contains 10 trays, each of which is 30 percent efficient [6]. Due to the high

water solubility of formaldehyde and methanol, 33 mole percent formaldehyde

and a 4 mole percent methanol solution is produced. Nitrogen and trace

amounts of formaldehyde and methanol are purged in the off-gas stream. The

product is sent to the distillation column for further removal of methanol to meet

product specifications [6].

3.3.2. THE DISTILLATION COLUMN

The distillation column removes the remaining 29% of the methanol that

was not combusted in the reactor, as well as reducing the concentration of

methanol in the formalin to meet application specifications. The column

contains 30 trays as well as a reboiler and partial condenser. The tops product

contains 99 percent methanol, which is recycled and mixed with the methanol


feed prior to pumping. The bottoms products contain formalin, which exits

containing 1 weight percent methanol, and is subsequently sent to storage [6].

3.4. STORAGE

Formalin storage is made difficult as the formation of formaldehyde

dimers and trimers, known as paraformaldehyde, occurs at temperatures below

25oC, while the formation of formic acid is favoured at temperatures above 25oC

[7]. Both materials are impurities and reduce the quality of the final formalin

product. In dilute quantities, methanol may be used to inhibit the degree of

polymerization of formalin, with 1 weight percent methanol typically used.

Storage at temperatures between 35 and 45oC further inhibits the formation of

formaldehyde polymers [4].

Formic acid is readily formed when formaldehyde vapours are oxidized by

atmospheric oxygen. The extent of acid formation may be reduced by storing

the formalin under an inert gas blanket.

4. OPERABILITY

4.1. OPERATING WINDOW

The operating window for the feed mixture to formaldehyde reactor is

shown below in Figure 3, which contains variables of methanol flow rate and air

flow rate in kmol/h. The flammability limit for methanol in air is between 6 and 36

mole percent. The feed ratio to the reactor is based on the product composition

requirement, though this is typically above the upper flammability limit to ensure

maximum methanol combustion.


Figure 3 Operating window of reactor with air flow rate vs. methanol flow rate (kmol/h)

The red solid boundary and orange boundary represent hard constraints that

cannot exist in the process. The red solid boundary corresponds to the lowest

ratio requirement, 36 mol percent methanol in air; where the red dash line (37

mol percent methanol in air) is the upper combustion limit. The orange line

represents the maximum flow rate of methanol; it is a hard constraint obtained

when the valve is fully open. Green and blue lines represent soft constraints: if

the process violates these two constraints, the operation profit will decrease. The

green boundary is the minimum opening for the methanol feed valve. The blue

boundary is the maximum acceptable methanol to air mole ratio which is 41%. If

the ratio goes over 41%, then more un-reacted methanol from reactor will go into

the downstream equipment, which increases absorber and distillation column

duties. The black dot at feasible region indicates sufficient flow rates at the

optimal ratio, which is 39:61for methanol to air flow rates respectively.

Regarding to the importance of the methanol and air mole ratio for the

whole operation, a ratio controller is recommended to regulate both flow rates.

Controlled flows of methanol are mixed in proper proportions with air through the

ratio controller arrangement before the reactants stream enters the reactor tubes.

Ratio control is a special type of feed forward control where two disturbances

0

50

100

150

200

250

40 50 60 70 80 90 100 110 120

Air F

low

rate

(km

ol/

h)

Methanol Flowrate (kmol/h)


(loads) are measured and held in a constant ratio to each other. It is mostly used

to control the ratio of flow rates of two streams. Both flow rates are measured but

only one can be controlled. In this process, methanol stream is the one to be

controlled. When the ratio has been measured, it is compared to the desired ratio

(set point) and the deviation (error) between the measured and desired ratios

constitutes the actuating signal for the ratio controller. Therefore, based on the

operating window’s constraints to set ratio controller, it can easily adjust the ratio

to get the maximum yield.

4.2. FLEXIBILITY

The operation of the formaldehyde plant relies on the digital controllers at

control room; thus, operators must carefully observe and maintain all dials in the

operating room at the corresponding set points within the operating window. For

example, when the production rate must be increased, the operator can adjust

the air flow rate and formaldehyde outlet flow rate settings to be higher, and then

the computer will make adjustments to the methanol flow rate increase based on

the set point on the ratio controller as mentioned at the operating window.

Meanwhile, the BFW flow rate would automatically increase to cool down the

reactor, since more heat will be released from the reaction. The formaldehyde

plant was mostly automated apart from two actions, which are the two manually

controlled actions involved with emergency shut off and the valves used for by-

passing purposes. Both of these manual actions are with regard to safety issues.

Existing “steering wheels” were adequate in terms of safety and

efficiency. Alarms for low flow rate, low methanol to air ratio, high reactor

temperature to ensure the reactor unit works properly and safely, and actual

product outcome did not deviate far from the set point within the operating

window. Moreover, employment of the recycle streams is considered as

increased the flexibility. Methanol separated from the distillation column should

be recycled to the feed stream in order to mix with the new methanol to the


reactor. This not only decreases the material cost for the plant, as methanol is

expensive, but also decreases environmental pollution.

Additional parallel equipment may also improve flexibility and reliability for

the formaldehyde plant, such as parallel valves, pumps, and so on. For example,

if the set point for production rate was set at maximum, both flow rates for

methanol and air would to increase respectively. However, one feed pump could

not afford the entire load; if there is a parallel pump present to share the load, it

would be enough methanol feed to mix with air to achieve set point methanol to

air ratio and set point production rate.

4.3. RELIABILITY

The formaldehyde plant achieved higher reliability based on strict regular

maintenance as opposed to equipment redundancy. Methanol and

formaldehyde are hazards to the environment and risky to health. Thus, failure of

plant was not acceptable primarily because of the effect on safety, not the affect

on production.

As mentioned at the flexibility section (4.2), additional parallel pumps and

valves could enhance the operating reliability. Other than sharing the heavy work

load for feed pump, employing a parallel pump can also increase the plant’s

availability. If one of the pumps does not work properly, the other pump can still

pump the feed to ensure the plant continues to operate. At the same time, a

technician can be sent to repair the malfunctioning pump. Another setup to

increase the reliability was employment of storage tanks before the recycle feed

pump to distillation column. This setup ensures that when there is not enough

recycled formaldehyde produced from the condenser, it would not affect the feed

to the pump, since the inventory of the storage tank could provide enough feed to

prevent cavitations. In general, the plant can operate 51 weeks in a year, and 24

hours per day [8]. The off-line week can be used for catalyst replacement and

simultaneous plant maintenance. All of these gives the plant had high plant

operability.


The ability to repair, diagnose and replace parts or the process system is

not limited to the formaldehyde plant operators and technicians. For the most

part, trouble shooting was done by operations from the control room or at the

problem site. Operators are equipped to perform small replacements and

repairs. However, when the complexity or size of the maintenance is too large,

outside contractors were hired to perform the task. In order to limit the need for

large scale repairs, the operators follow a strict Preventative Maintenance (PM)

Schedule. The following are some of the Preventative Maintenance

procedures followed rigorously by operators [8]:

Daily Basis

Methanol, Air, and BFW cutoff check

Weekly Basis

Reactor alarms testing

Semi-Annually Basis

Regular equipment check

Safety check

Three Years Basis

Safety valves removed and sent out for certification

Though PMs may not always require a shut down, they are generally time

consuming and costly. However, most of may be scheduled at the same time

when catalyst replacement takes place. Nevertheless, the costs of PMs outweigh

that of large scale equipment damage and possible equipment failure.

4.4. EFFICIENCY

4.4.1. EQUIPMENT CAPACITY

Ideally, the reactor will function at around 71% efficiency. The reactor

operation is maintained by the air to methanol ratio. Therefore, the both flow

rates are controlled with a ratio control. The air input stream acts as the wild

stream, which is not under control. The methanol stream will be controlled to

meet the maximum feasibility. The optimal ratio of reactants is 39 weight percent


methanols in air. This ratio must be adjusted before the feed enters the reactors

for the optimum productivity.

4.4.2. EQUIPMENT TECHNOLOGY

The equipment that is used in this plant is assumed to be all new. Most of

the equipment has a lifespan 8-10 years. Digital displays and digital controllers

are installed to allow the readings on the feed ratio. The digital control is there to

ensure safety and efficiency of the reactor. For the relieve valves, the

equipments will be check regularly and will be changed if it is ruptured. The

catalyst also will be replaced every 6 months to ensure maximum performance

[9].

4.4.3. EQUIPMENT UTILIZATION

In the production of formaldehyde, the usage of equipment depends on

the demands. However, since formaldehyde is a commodity with very high

demand every year, the production of the formaldehyde will continue normally. If

the price of methanol increased, the production rate will be adjusted. This is to

save the amount of electricity utilized and by producing more formaldehyde, the

extra cost will cover the lost from the increased in price of methanol.

In general, the production of formaldehyde will be mostly operated at

night. The electricity charge is much cheaper at night compare to in daylight.

Therefore, to increase energy efficiency, the plant will be operated mostly at night

to produce the same amount of formaldehyde.

4.4.4. PROCESS STRUCTURE

Due to the reaction is highly exothermic. The boiler feed water and the

reactor jacket is designed to produce steam from the reaction. The steam will

then be recycled to be use to heat up other solution. In this way, less power is

needed.

The heat exchanger inside the reactor is designed to cool down the

process. Instead of just dumping the catalyst into the reactor, the catalyst is

placed outside the heat exchanger. The silver wired gauze covering the outside


of heat exchanger will increase the surface area and hence give a better chance

for the catalyst to react with the methanol.

4.4.5. OPERATING CONDITIONS

The air and methanol mixture enters the reactor at temperature of 172oC

and pressure of 255 kPa [6]. The temperature of the mixture is to be brought as

close as possible to the reaction temperature to save more energy. The higher

temperature will give a better condition for the catalyst to convert the methanol

into formaldehyde. In order to operate efficiently, the temperature of the reactor is

best maintained at 630-700oC [10].

4.4.6. CALCULATION OF EFFICIENCY

The efficiency of the reactor is measured using equation (3).

𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒 ℎ𝑦𝑑𝑒 𝐷𝑒𝑡𝑒𝑐𝑡𝑒𝑑

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐸𝑛𝑡𝑒𝑟𝑒𝑑 (3)

The amount of formaldehyde detected and the amount of methanol entered the

reactor are measured from the outlet and inlet stream of the reactor in kmol/h.

The amount of methanol entered the reactor is 94.12 kmol/h and the amount of

formaldehyde coming out of the reactor is 66.82 kmol/h total. This gives the total

efficiency of around 71%, which means that most of formaldehyde is converted in

the reactor. The calculation of the reactor efficiency is shown in Appendix A.

4.5. TRANSITION

4.5.1. START UP

Startup of the process takes between one and two hours, and is

completed when the reactor reaches a steady state temperature between 630

and 700oC [10]. Both the air and methanol feeds begin supplying the reactor

and combustion of the methanol is allowed to occur. However, mostly carbon

dioxide and water vapour are formed from the combustion, and the products are

vented from the reactor instead of proceeding through to the absorber. The

waste gas will contain traces of methanol and formaldehyde if no scrubbing is


implemented to remove them. Once the reactor reaches its operating

temperature, the vent is closed and any products from the reaction are fed into

the absorber [11].

4.5.2. SHUT DOWN

Shutdown occurs by shutting off the methanol and air feeds to the

reactor. Any products formed at the time of shutoff are vented from the reactor

[8]. The vented gas will contain traces of methanol and formaldehyde unless it

is ignited at the vent outlet. Once flows have stopped and the reactor cooled

down, with traces of formaldehyde and methanol vented, it is possible to perform

maintenance on the process [8].

5. TROUBLESHOOTING

Due to the reaction is highly exothermic, the main trouble spot is on the

reactor. In the chemical reactor, if flow did not distributed, it would lead to “hot

spots” which can damage catalyst or vessel. In order to prevent those damages,

many temperature sensors are located at different locations in the bed provides

monitoring for poor distribution. Despite its high reliability, and low likelihood of

failure it can never been assumed the process is 100% trouble free. The fishbone

diagram and root cause table in Appendix B demonstrate some possible root

causes for high temperature in the reactor.

6. HEALTH AND SAFETY ASPECT

In 2008, Kolon chemical company in Korea exploded. From the explosion,

two workers died on site, and 14 people got severe injured. The causes of the

explosion were the out of control on temperature control in the reactor and

corrosion of the outlet pipe. In order to prevent this tragic accident, all employees

need to strictly train with MSDS and finish HAZOP analysis before runs the

process. HAZOP identification for the formalin plants is placed in Appendix C.


6.1. MATERIAL SAFETY

According to MSDS in Appendix D both methanol and formaldehyde are

highly toxic and inflammable. Direct exposure of the formaldehyde and methanol

to the skin or eyes can cause severe irritation and burns [4], [12]. Any incidents

of exposure to skin must be immediately washed with copious amount of water.

Not only from the direct contact, but it also can cause severe organ damages by

inhalation or ingestion [4], [12]. Therefore, the safety regulation strictly followed in

order to prevent the exposure to chemicals and danger of fire. Furthermore

details on handling, storage, first aid, fire measure, toxicology and so on are

explained in MSDS.

6.2. PROCESS SAFETY

As mentioned before, the process safety is regulated automatically by

placing multiple sensors and controllers in cascade and feed forward system.

Automatic alarm system catches any errors when process variables have

exceeded set point and it also indicates sensor failures. Table 1 shown below

lists the alarm messages that annunciate to operator. Lights illuminate and

buzzer goes off when errors are detected.

When the alarm goes off and lights are on, it will annunciate the operator

about the exact problem. Then the operator can press a button to immediately

stop the buzzer and either begins to fix the problem or restart.

Table 1 List of alarm sign under possible system failure

Parameters Alarm

Air flow Out of 6~ 36% of air and meOH ratio range

High/low air feed flow

Methanol flow Out of 6~ 36% of air and meOH ratio range

High/ low methanol feed flow

Exceed 720C High temperature reactor

Rupture disc burst of condenser Reactor failed

Level of distillation tray low Level of distillation tray condition


When part of the plant shut down to fix the problem, the equipment can be

damaged from the unexpected shut down. In order to prevent the damage,

multiple sensors and pumps installed in parallel, so it can function alternately to

continue the process. Therefore, it will not affect the main process.

Pressure relief valves builds on the reactor since the pressure of the steam

in the reactor would become too high to respond to controller also it can cause

high temperature. The spring release valves will allow the excess steam to

escape through pipes which lead to the roof of the building. And rupture disc will

build up next to valve as a back-up for larger relief.

Since the process dealing with highly toxic and flammable chemicals, when

it leaks or spilled, it should strictly follow containment system. For the spillage,

the area should evacuate and ventilate, and all possible source of ignition should

be eliminated. The spilled material should not empty into drain since it may

create fire or explosion.

A large red button for reactor is set up to enable a quick and immediate shut

down of the system and it should perform when the previous five safety

measures are not able to handle. Then, reactor will have to be restarted as

following the start up procedures. In this kind of a dangerous emergency,

evacuation of the building is necessary and the emergency unit will be respond.

7. ECONOMICS

7.1. RELEVANT ISSUES

7.1.1. METHANOL PRICE

Methanol is the primary feed in this plant. Methanol is directly converted

into formaldehyde and therefore it serves as essential part of the production. By

examining the methanol price in the past few years, it was observed that it

fluctuated in very high magnitude month by month. For example in January 2008,

the price went up to $832/ton whereas a year later in 2009, the price was marked

at $233/ton. Figure 4 summarizes the methanol price in past five years.


Figure 4 Historic methanol price from 2006 to 2010 [13]

7.1.2. ONTARIO’S NEW SMART METER POLICY

Ontario’s Ministry of Energy launched new Smart Meter policy. During the

off-peak period, the price is 5.1 ¢/kWh and during the on-peak, it increases to 9.9

¢/kWh [14]. This rate would affect the utility cost significantly for the plants in

Ontario. It is important to well-understand the new rate policy in order to take

advantage of it.

Figure 5 Ontario's Smart Electricity Cost

7.1.3. HOUSING MARKET CRISIS IN 2007

The Subprime Mortgage Crisis in 2007 hit the entire global economy. As

it was directly related to the incident, the housing market in North America

suffered and resulted many bankruptcies [15]. As it was mentioned earlier,

$442

0

200

400

600

800

1000P

rice

(U

SD

/ton)

Off-peak Mid-peak On-peak

0.051

$/kWh

0.081

$/kWh

0.099

$/kWh


formaldehyde manufacturing business heavily relies on the production of the

additive in wood products. Therefore the housing and construction market affect

the formaldehyde market. Because the housing market severely declined since

2007, the formaldehyde manufacturing business suffered as well. Figure 6 shows

the Standard & Poor’s Case-Shiller Index which is one of the housing price

indices. As it is shown in the figure, the housing market started decline during

2007.

Figure 6 Standard & Poor's Case-Shiffer home price index [15]

7.2. CAPITAL COST ESTIMATION

The capital cost of the plant was calculated using the cost estimation

calculations in Cost Estimation for the Process Industries by Dr. D. Woods [16].

There were seven heat exchangers (including one from the reactor), one reactor,

one compressor, two pumps and two separation equipments were considered. It

was concluded that the $5M ± 40% of capital cost required. The conclusion is

based on the bare module method of cost estimation. The Marshall & Swift

inflation factor between 1970 and 2009 was used to determine the present

purchase and installation costs for all components.

There were some unit-specific assumptions made during the calculations.

For example, the distillation column (T-02) was assumed to be a single pass type

100

150

200

Cas

e-S

hil

ler

Index


since it would give a sufficient separation of methanol and formalin. The

efficiency of the equipments were also considered in the calculations.

The major expenditures came from purchasing and installing the reactor

($410,000) and the two separation equipments ($1.5M and $1.7M). The

spreadsheet Table E1 found in Appendix E shows more specific calculations and

the costs for each equipment.

7.3. OPERATING COST ESTIMATION

Many aspects of plant operations were considered in this section to

estimate the annual operating cost of the plant. Current price of methanol, water,

hydro and man-power costs were considered. Table E2 in appendix E shows

more details of the calculations for the operating cost.

As it is drawn in Figure 7, the major expenditure comes from purchasing

the feed methanol. Then the utility cost follows. By manufacturing about 35,000

ton of 37% formalin every year will yield $6.3M annual operation profit.

However, this plant has an expected age of 10 years. The Net Present

Value (NPV) calculation was necessary to find out the value of this project until it

reaches the shut-down or major maintenance. 35% of tax was used as it is

widely used as corporate rate. Considering the last 10 years of inflations, 3% of

inflation rate was assumed. The equipments purchased and installed in the

beginning of the project were depreciable. After 10 years of the project, the NPV

was found to be about $27.5M, which is quite profitable. The NPV calculation

table is found in Table E3 from appendix E.

It is important to notice that this calculation is based on very bold

assumption; the price of formaldehyde and the price of methanol do not change

during the operation. This, definitely, is not true. As it was mentioned above, the

prices fluctuate in a very rigorous manner. In order to perform a better estimation,

an in depth market analysis is necessary.


Figure 7 Operating cost distribution

7.3.1. USING ONTARIO’S SMART RATE

The new policy on the electricity price would help to cut down the utility

cost. The plant is quite flexible in terms of production rate. It can increase and

decrease the formaldehyde production up to 20%. By increasing the production

rate during off-peak time and by decreasing during the on-peak time, it is still

possible to meet the annual production rate of 35,000 ton per year. An

investigation was done on how much the operating cost would be cut if this new

production rate was implemented. It was found that about $1M of utility cost

could be saved. The Table 2 shows the comparisons of the original and the new

method.

Table 2 Hydro cost calculated via original rate, summer and winter Smart rate

Energy uses (kW)

Original Rate

Smart Rate (Summer)

Smart Rate

(Winter)

15224.30556 $9,869,004 $8,922,113 $8,922,113

8. PROCESS RECOMMENDATIONS

The health risks of formaldehyde and methanol exposures are well

known. Chronic exposure to formaldehyde results in drying and cracking of the

skin, formation of lesions along the respiratory tract, and an increased risk of

contracting lung and nasal cancers. Exposure to methanol results in depression

Methanol

50%Energy

40%

Man-Power

4%

Others

6%


of the central nervous system, abdominal pain, and liver damage, as methanol is

converted into formaldehyde in the liver. It is possible to implement measures to

avoid leaks, exposures and reduce overall emission levels at the plant level.

For instance, the methanol vaporizer unit experiences a doubling in

pressure between the inlet and outlet. An uncontrolled increase of pressure in the

vaporizer may result in a leakage of methanol should the equipment begin to fail.

The implementation of a rupture disk within the methanol vaporizer unit will

effectively prevent methanol leakage while relieving any built-up pressure in the

vaporizer.

To reduce the likelihood of formaldehyde leaks, hermetically-sealed

canned motor pumps should be used. A canned pump contains the motor and

pump within an enclosure that does not contain any seals that can fail.

Implementing such a pump will greatly reduce the likelihood of formaldehyde

leaks in the plant.

9. CONCLUSIONS

In conclusion, the formaldehyde production is a reliable process since the

chemical plant has high availability and flexibility with dependable safety

structures and troubleshooting systems. With a reliable process, the efficiency of

the conversion reactor from methanol to formaldehyde is 71%, which is relatively

efficient operation compared to other reactors using different catalysts or with

different setup.

With highly automated controls, the whole process would be operated at

the desired set points in the operating window. However, if the process violates

the constraints limited by the operating window, alarms would go off to notify the

system and the operators. Then, corresponding troubleshooting or safety

process would be taken.

Finally, installation of hermetically-sealed canned motor pumps is

recommended to prevent formaldehyde leaks in the plant. Besides preventing

formaldehyde leaking, a rupture disk should be installed in the methanol


vaporizer unit to prevent any methanol leak as well. With all the additional

setups, the formaldehyde plant would achieve a safer and more efficient

manufacturing environment.


REFERENCES

[1] Formaldehyde: Brief history and its contribution to society and the U.S. and

Canadian economies. Arlington: The Formaldehyde Council, Inc. Feb 2005

[2] Betsy Natz, FORMALDEHYDE: FACTS AND BACKGROUND INFORMATION.

Arlington: The Formaldehyde Council, Inc. 2007

[3] Bizzari, Sebastian N. "Formaldehyde." Chemical Industries Newletter [Menlo Park,

CA] Mar. 2007

[4] Formaldehyde, Material Safety Data Sheet version 1.10, Sigma Aldrich Inc.,

Missouri, USA, February 2007

[5] Smith, R. Chemical Process Design and Integration. Chichester, West Sussex,

England: Wiley, 2005

[6] Large-scale design project; Formalin plants, West Virginia University, 2006

[7] Dynea Ireland Limited. Dynea Ireland Limited Standard Operating Procedure.

Dublin: Dynea Ireland Limited. Apr. 2006

[8] Safety Report. Rep. Dynea, 2006. Emergency Response.

[9] Solomon, S.J, and T. Custer. Atmospheric Methanol Measurement Using Selective

Catalytic. Tech. Bremen: Atmospheric Chemistry and Physics, 2005.

[10] Cybulski, Andrzej, and Jacob A. Moulijn. Structured Catalysts and Reactors. Boca

Raton: Taylor & Francis, 2006

[11] Safriet, Dallas. Locating and Estimating Air Emissions from Sources of

Formaldehyde. EPA, 1991.

[12] Methanol, Material Safety Data Sheet version 1.10, Sigma Aldrich Inc., Missouri,

USA, February 2007

[13] Methanex Monthly Average Regional Posted Contract Price History.

[14] "How Will TOU Pricing Work?" Ontario. 2010. Web. 25 Nov. 2010.

<http://www.ontario.ca/YOURMINISTRY/en/index.php>

[15] The First Quarter of 2010 Indicates Some Weakening in Home Prices According to

the S&P/Case-Shiller Home Price Indices, S&P INDICES, May 2010


[16] Woods, Donald R., Cost Estimation in the Process Industries, McMaster University,

1993


APPENDIX

APPENDIX A- SAMPLE EFFICIENCY CALCULATIONS

Methanol Entered: 94.12 kmol/h

Formaldehyde Detected: 66.82 kmol/h

danolEntereAmountMeth

DetectedrmaldehydeAmountofFoEfficiency

12.94

82.66Efficiency

Therefore, efficiency = 71%


APPENDIX B- TROUBLESHOOTING FISHBONE DIAGRAM AND TABLE

Table B 1 High temperature of reactor causes and solutions

Root Cause Symptoms Solutions

Sensor Failure Unfeasible data output

Zero output read

Regular maintenance check

Preventative maintenance

Scaling/Fouling Low Flow rate

Regular maintenance check

By-pass piping

Low contaminant of water and air

Insufficient

BFW

Poor cooling

BFW level low Check source of leaks

Relief valve

open failure

Pressure valve damaged

Low pressure reading Regular maintenance check


APPENDIX C - HAZOP

Unit: R-801 Formaldehyde Reactor

Node: BFW inlet (after the feed valve, before entering the reactor)

Parameter: Flow

Guide Word Deviation Cause Consequence Action

1. feed valve closed 1. temperature increase in

reactor

1. install back-up

control valves, or

manual bypass valve

2. level controller

fails and closes

valve

2. damage to the reactor,

possible heat exchanger

tubes failure

2. install back-up

controller

3. Air pressure to

drive valve fails.

Cosing valve

3. install control valve

that fails open

4. pipe blockage 4. a) test flow before

startup b) place filter

in pipe

5. boiler feedwater

service failure

5. install back-up BFW

source

6. install high

temperature alarm to

alert operator

7. Install high

temperature

emergency shutdown

8. install BFW flow

meter and low flow

alarm

more more BFW flow 1. feed valve fails

and open

1. reactor cools, however,

water builds-up

1. instruct operators

on procedure

2. controller fails and

opens valve

less less BFW flow 1. partially plugged

feed line

1. covered under "NO" 1. cover under "NO"

2. partial water

source failure

3. control valve fails

to repond

reverse reverse BFW

flow

1. failure of water

source resulting in

back ward flow

1. improper cooling,

possible runaway

1. install check valve

in BFW line

2. back flow due to

reactor pressure

2. install high pressure

alarm to alert operator

other than another material

besides BFW

1. water source

contaminated

1. possible loss of cooling

with possible runaway

1. isolation of BFW

source

2. possible damage the

reactor

2. install high

temperature alarm

no no BFW flow


Node: methanol inlet flow (Stream-6, after the preheater, before mix with air)

Parameter: Flow


no no methanol inlet

flow

1. pump failure 1. deficient quality product 1. install a low level

alarm on the adiabatic

reactor section

2. feed valves closed 2. backward flow, damage

the pump

2. install kick-back on

pumps

3. pipe blockage 3. high pollution 3. install a controllor

for valve's opened

4. methonal service

failure

4. regular inspection

and patrolling of

methanol transfer

lines and seals

5. install back-up

methanol resource

more more methanol

inlet flow

1. feed valve fails

and open

1. a) lower reaction rate b)

increase unused methanol

1. install flowmeter

after the pump

2. heat exchanger

tube leaks

2.deficient quality product 2. install controller for

valve's open

adjustment which

depends on the

flowrate of air

3. acidic product corroding

the adiabatic reactor shells

3. install ratio sensor

after the air stream

and methanol stream

mix

4. install ratio sensor

at the reactor product

stream

less less methanol

inlet flow

1. valve fails to open 1. cover under "NO" 1. cover under "NO"

2. partially plugged

feed line

other than another material

besides

methanol

1. methanol cource

contaminated

1. corrosion at the

adiabatic reactor

1. isolation of

methanol source

2. deficient quality product


Node: reactor tank

Parameter: Pressure


high high pressure 1. relief valve fails 1. pressure builds-up,

reactor tank explosion,

possible pipe falure

1. a) install pressure

sensor b) install back-

up relief valve

2. steam outlet line

blocked

2. vapour containts

statureated inside the

tank, temperuature

increase

2. test the steam flow

before startup

3. cooling water

temperature is high

3. vapour builds-up,

inefficient to remove heat

3. install temperature

meter

4. reaction rate over

the range

4. install high pressure

alarm to alert operator

5. reactants and

products outlet

blocked

5. install a pump at the

outlet

6. install flowmeter at

the reatant inlet

low low pressure 1. reactor tank

opens to

atmosphere

1. steam runaway, waste

energy, possible pollution

1. a) install ratio

sensor b) instruce

operators on

procedure

2. no cooling BFW

flow

2. reactor over heat,

temperature increase,

possible tank and pipe

failure

2. install high

temperaure alarm to

alert operator

3. reactant pipe line

blocked

3. no reaction take plance,

waste cooling feed and

energy

3. a) install flowmeter

at reactant pipe line

b) test the flow before

startup

4. relief valve fails to

close


APPENDIX D - MSDS OF FORMALDEHYDE AND METHANOL

Table D 1 MSDS of Formaldehyde

Name CAS # % TLV

1. Formaldehyde 50-00-0 30-40 Exposure limits: 0.3 ppm (0.37 mg/m3)

2. Methanol 67-56-1 15-May Exposure limits: 200 ppm (262 mg/m3)

3. Water 7732-18-5 Balance N/A

Physical state

pH

Odour threshold

Percent volatile

Freezing point

Boiling point

Specific gravity

Vapour pressure

Vapour density

Evaporation rate

Solubility

Flash point

Flammability

Fire extinguishing

procedures

Stability

Incompatibility

Routes of entry

Effects of acute

exposure

Effects of chronic

exposure

1.08 to 1.0975 (water = 1)

~40 mm of Hg (@39 ˚C)

0.62 to 1.04 (Air = 1)

Section 1: Hazardous Ingredients

Section 2: Physical Data

Section 3: Fire and Explosion Data

Section 5: Toxicology Properties

May react violently with: acids, alkalis, anhydrides, isocyanates, urea, phenol,

oxidizing agents, oxides, organic oxides, reducing agents, ammonia, aniline,

magnesium carbonate, performic acid, alkali metals, amines, hydrogen

peroxide, nitromethane, nitrogen dioxide, perchloric acid, perchloric acid-aniline

mixtures, bases, monomers, water reactive materials, magnesium carbonate

hydroxide.

Inhalation, ingestion, absorption through skin and eyes.

Death if inhaled or absorbed; severe eye irritation and burns; allergic dermatitis,

skin burns; bronchitis, pulmonary oedema; headache, dizziness, nausea,

vomiting; abdominal pain; blindness.

Nasal cancer, respiratory tract irritation; reproductive disorders, asthma,

dermatitis; multiple organ damage.

2.1 (n-Butyl acetate = 1) (Methanol).

Section 4: Reactivity Data

Miscible in water

50 - 78 degrees Celsius

Lower: 7%; Upper: 73%

Use DRY chemical, carbon dioxide, alcohol-resistant foam or water spray. Cool

containing vessels with flooding quantities of water until well after fire is out.

Stable. Conditions to avoid: heat, sparks and flame, temperatures below 20°C.

Clear, colourless liquid with strong formaldehyde odour.

2.8 - 4.0 (25 degree Celsius) (37% solution)

0.8 - 1 ppm

100% (V/V)

Insoluble polymer gradually forms.

90 - 100


Protective clothing

and PPE

Handling procedures

Spill Containment

Eye contact

Sking contact

Inhalation

Ingestion

Immediate first aid is needed to prevent eye damage. IMMEDIATELY flush eyes

with copious quantities of water for at least 20 minutes holding lids apart to

ensure flushing of the entire surface. Seek immediate medical attention.

DO NOT use an eye ointment.

Immediate first aid is needed to prevent skin damage. Immediately flush skin

with plenty of water for at least 20 minutes while removing contaminated

clothing and shoes. Seek immediate medical attention. Wash contaminated

clothing before reusing.

Remove patient to fresh air. Administer approved oxygen supply if breathing is

difficult. Administer artificial respiration or CPR if breathing has ceased. Seek

immediate medical attention.

If conscious, wash out mouth with water. DO NOT induce vomiting. Seek

immediate medical attention.

Section 6: Preventative Measures

Wear self-contained breathing apparatus, rubber boots and heavy rubber

gloves, and an acid suit.

Store in a cool place away from heated areas, sparks, and flame. Store in a well

ventilated area. Store away from incompatible materials. Do not add any other

material to the container. Do not wash down the drain. Do not breathe

gas/fumes/vapor/spray. In case of insufficient ventilation, wear suitable

respiratory equipment. Keep container tightly closed. Manipulate under an

adequate fume hood. Take precautionary measures against electrostatic

discharges. Ground the container while dispensing. Ground all equipment

containing material. Use only explosion proof equipment. Use non-sparking

tools. Watch for accumulation in low confined areas. Do not use pressure to

dispense. Storage temperature depends on methanol content and should be

controlled to avoid precipitation or vaporization. Handle and open container with

care. Take off immediately all contaminated clothing. This product must be

manipulated by qualified personnel. Do not get in eyes, on

skin, or on clothing. Wash well after use. In accordance with good storage and

handling practices. Do not allow smoking and food consumption while handling.

Section 7: First Aid Measures

Evacuate and ventilate the area. Stay upwind: Keep out of low areas. Eliminate

all sources of ignition. Dyke the area with sand or a natural barrier. Absorb on

sand or vermiculite and place in a closed container for disposal. Use nonsparking

tools. Transport outdoors. Wash spill site after material pick up is

complete. DO NOT empty into drains. DO NOT touch damaged container or

spilled material. Runoff to sewer may create fire or explosion hazard.


Table D 2 MSDS of Methanol

Name % (w/w) Exposure Limits LD60 LC60

Methanol

(CAS 67-56-1)

99-100 ACGIH TLV-TWA: 200 ppm, skin

STEL: 250 ppm, skin notation

OSHA PEL: 200 ppm

TLV Basis, critical effects:

neuropathy, vision, central

nervous system

5628 mg/kg

(oral/rat)

20mL/kg

(dermal/

rabbit)

64000 ppm

(inhalation/

rat)

Physical state

pH

Odour threshold

Freezing point

Boiling point

Vapour pressure

Vapour density

Solubility

Flash point

Autoignition temperature:

Lower Explosive Limit:

Upper Explosion Limit:

Sensitivity to impact:

Sensitivity to Static Discharge:

Hazardous Combustion Products:

Extinguishing Media:

Toxic gases and vapours; oxides of carbon and formaldehyde

Small fires: Dry chemical, CO2, water spray

Large fires: Water spray, AFFF(R) (Aqueous Film Forming Foam

(alcohol resistant) type with either a 3% or 6% foam proportioning

system.

Fire Fighting Instructions: Methanol burns with a clean clear flame that is almost invisible in daylight.

Stay upwind! Isolate and restrict area access. Concentrations of greater that 25% methanol in water can

be ignited. Use fine water spray or fog to control fire spread and cool adjacent structures or containers.

Contain fire control water for later disposal. Fire fighters must wear full face, positive pressure, self-

contained breathing apparatus or airline and appropriate protective clothing. Protective fire fighting

structural clothing is not effective protection from methanol. Do not walk through spilled product.

: - 97.8˚C

64.7 ˚C @ 101.3 kPa

12.8 kPa @ 20 ˚C

1.105 @ 15 ˚C

11 ˚C (TCC)

Section 3: Fire and Explosion Data

Miscible in water

6% (NFPA, 1978)

36% (NFPA, 1978), 36.5% (Ullmann, 1975)

Low

Low

385 ˚C (NFPA 1978), 470 ˚C (Kirk-Othmer 1981; Ullmann 1975)

detection: 4.2 - 5960 ppm

(geometric mean) 160 ppm

recognition: 53 - 8940 ppm

(geometric mean) 690 ppm

Not applicable

Liquid, clear, colourless

Section 2: Physical Data

Section 1: Hazardous Ingredients


Routes of entry

Effects of acute

exposure

Effects of chronic

exposure

Protective clothing

and PPE

Handling procedures

Spill Containment

Inhalation, ingestion, absorption through skin and eyes.

Section 5: Preventative Measures

Engineering Controls: In confined areas, local and general ventilation

should be provided to maintain airborne concentrations beloew

permissable exposure limits. Ventilation systems must be designed

according to approved engineering standards.

Respiratory Protection: NIOSH approved supplied air respirator when

airborne concentrations exceed exposure limits.

Skin protection: Butyl and nitrile rubbers are recommended for

gloves. Check with manufacturer. Wear chemical resistant pants and

jackets, preferably of butyl or nitrile rubber. Check with manufacturer.

Eye and Face Protection: Face shield and chemical splash goggles

when transferring is taking place.

Footwear: Chemical resistant, and as specified by the workplace.

Other: Eyewash and showers should be located near work areas.

NOTE: PPE must not be considered a long-term solution to exposure

control. PPE usage must be accompanied by employer programs to

properly select, maintain, clean, fit and use. Consult a competent

industrial hygiene resource to determine hazard potential and/or the

PPE manufacturers to ensure adequate protection.

Handling Procedures: No smoking or open flame in storage, use or

handling areas. Use explosion proof electrical equipment. Ensure

proper electrical grouding procedures are in place.

Storage: Store in totally enclosed equipment, designed to avoid

ignition and human contact. Tanks must be grounded, vented, and

should have vapour emission controls. Anhydrous methanol is non-

corrosive to most metals at ambient temperatures except for lead,

nickel, monel, cast iron and high silicon iron.

Soak up spill with non-combustible absorbent material. Recover

methanol and dilute with water to reduce fire hazard. Prevent spilled

methanol from entering sewers, confined spaces, drains, or

waterways. Restict access to unprotected personnel. Full. Put material

in suitable, covered, labeled containers. Flush area with water.

irriate mucous membranes, headaches, sleepiness, nausea, confusion,

digestive and visual disturbances, irritation of eyes or skin

brain disorder, blindness, emphysema, bronchitis

dermatitis; multiple organ damage.

Section 4: Toxicology Properties


Eye contact

Sking contact

Inhalation

Ingestion

Remove contact lenses if worn. In case of contact, immediately flush

eyes with plenty of clean running water for at least 15 minutes, lifting

the upper and lower eyelids occasionally. Obtain medical attention.

In case of contact, remove contaminated clothing. In a shower, wash

affected areas with soap and water for at least 15 minutes. Seek

medical attention if irritation occurs or persists. Wash clothing before

reuse.

Remove to fresh air, restore or assist breathing if necessary. Obtain

medical attention.

Ingestion: Swallowing methanol is potentially life threatening. Onset

of symptoms may be delayed for 18 to 24 hours after digestion. If

conscious and medical aid is not immediately

Section 6: First Aid Measures


APPENDIX E –CAPITAL & OPERATING COST CALCULATION

Table E 1 Capital Cost Table

Heat Exchangers

Area in m2 FOB Type Material Co 2009

Cost for

installationFp Fm

Additional

Factor

Additional

FOB Costs

Additional

Pipe CostsTotal BM

E-01 400 $21,407Floating

Headcarbon steel $104,445 $223,513 0.9 1 1 -$2,783 -$896 $324,280

E-02 5 $954Floating

Headcarbon steel $4,653 $9,957 0.9 1 1 -$124 -$40 $14,445

E-03 30 $3,403Floating


E-04 40 $4,174Kettle

Reboilercarbon steel $20,365 $43,582 0.9 1 1.35 $728 $235 $64,910

E-05 300 $17,452Floating


E-06 50 $4,891Floating


Compressors

Capacity

(kW)FOB Type Material Co 2009

Cost for

installationFp Fm

Additional

Factor

Additional

FOB Costs

Additional

Pipe CostsTotal BM

C-01 200 $39,937 Centrifugal carbon steel $194,856 $420,888 $615,744

Pumps

Capacity

(kW)FOB Type Material Co 2009

Cost for

installationFp Fm

Addition

FOB Costs

Additional

Pipe CostsTotal BM

P-01 0.5 $344 Centrifugal Cast Iron $1,679 $3,862 1 1 $0 $0 $5,542



Separation Towers

Size FOB Type Material Co 2009Cost for

installationFp Fm

Additional

Factor

Addition

FOB Costs

Additional

Pipe CostsTotal BM

T-01 25.22 $72,510 Absorber Carbon Steel $353,781 $1,117,948 1 1 $0 $0 $1,471,729

T-02 2.5 $82,733 Single Pass Carbon Steel $403,659 $1,275,564 1 1 1.2 $16,547 $5,328 $1,701,098

Reactor

Size FOB Type Material Co 2009Cost for

installationFp Fm

Additional

Factor

Addition

FOB Costs

Additional

Pipe CostsTotal BM

R-01 30 $12,200 Carbon Steel $59,524 $188,097 1.3 1 1.3 $8,418 $2,711 $258,750

Heat Exchanger (within reactor)

Area in m2 FOB Type Material Co 2009

Cost for

installationFp Fm

Additional

Factor

Additional

FOB Costs

Additional

Pipe CostsTotal BM

150 $10,669Floating


Capital Cost

Total

$5,019,199

± 40%


Table E 2 Operating Cost Table

Operating Cost Feed

Per year Price/unit Total

Water 21900 1.4726 $/m3 $32,250

Methanol 27375 442 $/metric tonne $12,099,750

Energy

Equipment

Energy uses

(MJ/h)

Energy uses

(kW) Hourly Cost Annual Cost

E-01 4000 1111.11 $82 $720,267

E-02 100 27.78 $2 $18,007

E-04 40000 11111.11 $822 $7,202,667

R-01 10000 2777.78 $206 $1,800,667

C-01 700 194.44 $14 $126,047

P-01 2.5 0.69 $0 $450

P-02 2.5 0.69 $0 $450

P-03 2.5 0.69 $0 $450

Total 54807.5 15224.31 $1,127 $9,869,004

Man Power

Classification

Number of

Persons $/year Subtotal

Plant Manager 1 $100,000

$100,000

Engineer 3 $60,000

$180,000

Production

Operator 9 $40,000

$360,000

General Workers 12 $35,000

$420,000

Total 25

$1,060,000

Total Operating

Cost $23,028,754

Revenue Product

Per year Price/unit Total

Formalin 35040 837.76 $/metric tonne $29,355,110


Table E 3 Net present value calculations

0 1 2 3 4 5

Capital Cost -$5,019,199

Water -$32,250 -$32,250 -$32,250 -$32,250 -$32,250

Methanol -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750

Energy -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004

Man-Power Cost -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000

Revenue $29,355,110 $29,355,110 $29,355,110 $29,355,110 $29,355,110

NCFBT -$5,019,199 $6,294,106 $6,294,106 $6,294,106 $6,294,106 $6,294,106

Account Balance -$5,019,199 $1,274,907 $7,569,013 $13,863,119 $20,157,225 $26,451,331

Depreciation $1,505,760 $1,054,032 $737,822 $516,476 $361,533

Book Value $5,019,199 $3,513,439 $2,459,408 $1,721,585 $1,205,110 $843,577

Gain Loss

Taxable Income $0 $7,799,866 $7,348,138 $7,031,928 $6,810,582 $6,655,639

Tax Payment $0 $2,729,953 $2,571,848 $2,461,175 $2,383,704 $2,329,474

NCFAT -$5,019,199 $3,564,153 $3,722,258 $3,832,931 $3,910,402 $3,964,632

Present Value -$5,019,199 $3,460,343 $3,508,585 $3,507,675 $3,474,342 $3,419,927

6 7 8 9 10

Capital Cost

Water -$32,250 -$32,250 -$32,250 -$32,250 -$32,250

Methanol -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750

Energy -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004

Man-Power Cost -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000

Revenue $29,355,110 $29,355,110 $29,355,110 $29,355,110 $29,355,110

NCFBT $6,294,106 $6,294,106 $6,294,106 $6,294,106 $6,294,106

Account Balance $32,745,437 $39,039,543 $45,333,649 $51,627,755 $57,921,861

Depreciation $253,073 $177,151 $124,006 $86,804 $60,763

Book Value $590,504 $413,353 $289,347 $202,543 $141,780

Gain Loss -$4,517,279

Taxable Income $6,547,179 $6,471,257 $6,418,112 $6,380,910 $6,354,869

Tax Payment $2,291,513 $2,264,940 $2,246,339 $2,233,319 $2,224,204

NCFAT $4,002,593 $3,615,813 $3,758,420 $3,858,245 $3,928,122

Present Value $3,352,109 $2,939,987 $2,966,931 $2,957,023 $2,922,892

NPV $27,490,615

Year

*35% Tax Rate and 3% Inflation Rate Used

Documents

Formaldehyde Production From Methanol