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

Formaldehyde Production from Methanol

CHEM ENG 4N04 Group 4 Final Report

G. Leota J. Ma H.Park S. Park G. Voloshenko

Dr. P. Mhaskar December 6, 2010

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

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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

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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 indepth 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.

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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 formaldehydebased 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].

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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.

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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 700 oC. Aided by the silver

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catalyst, the oxidation-dehydration reaction proceeds along the following two pathways: CH3OH + ½O2 → HCHO + H2O CH3OH → HCHO + H2

ΔHRXN = -156 kJ/mole

(1)

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. contains 10 trays, each of which is 30 percent efficient [6].

The column

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

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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 25 oC [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 45 oC 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.

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Air Flowrate (kmol/h)

250 200 150 100 50 0 40

50

60

70 80 90 100 Methanol Flowrate (kmol/h)

110

120

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

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(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 bypassing 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

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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.

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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

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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

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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 172 oC 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 𝑀𝑒𝑡 ℎ𝑎𝑛𝑜𝑙 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

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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.

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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 Air flow Out of 6~ 36% of air and meOH ratio range Methanol flow Out of 6~ 36% of air and meOH ratio range Exceed 720C Rupture disc burst of condenser Level of distillation tray low

Alarm High/low air feed flow High/ low methanol feed flow High temperature reactor Reactor failed Level of distillation tray condition

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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.

Price (USD/ton)

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1000 800 600 400 200 0

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$442

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.

0.081 $/kWh

0.099 $/kWh

0.051 $/kWh

Off-peak

Mid-peak

On-peak

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,

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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

Case-Shiller Index

2007. 200

150

100

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

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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.

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Man-Power 4%

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Others 6%

Energy 40%

Methanol 50%

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

15224.30556 $9,869,004

Smart Rate (Summer) $8,922,113

Smart Rate (Winter) $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

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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

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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.

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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. [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

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[16] Woods, Donald R., Cost Estimation in the Process Industries, McMaster University, 1993

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APPENDIX APPENDIX A- SAMPLE EFFICIENCY CALCULATIONS Methanol Entered: 94.12 kmol/h

Formaldehyde Detected: 66.82 kmol/h

Efficiency 

AmountofFo rmaldehydeDetected AmountMeth anolEntere d

Efficiency 

66.82 94.12

Therefore, efficiency = 71%

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APPENDIX B- TROUBLESHOOTING FISHBONE DIAGRAM AND TABLE

Table B 1 High temperature of reactor causes and solutions

Root Cause Sensor Failure

Symptoms

Solutions

 Unfeasible data output

 Regular maintenance check

 Zero output read

 Preventative maintenance  Regular maintenance check

Scaling/Fouling

 Low Flow rate

 By-pass piping  Low contaminant of water and air

Insufficient BFW

 Poor cooling  BFW level low

Relief valve

 Pressure valve damaged

open failure

 Low pressure reading

 Check source of leaks  Regular maintenance check

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APPENDIX C - HAZOP Unit: Node: Parameter:

R-801 Formaldehyde Reactor BFW inlet (after the feed valve, before entering the reactor) Flow

Guide Word Deviation no no BFW flow

Cause Consequence Action 1. feed valve closed 1. temperature increase in 1. install back-up reactor control valves, or manual bypass valve 2. level controller 2. damage to the reactor, 2. install back-up fails and closes possible heat exchanger controller valve tubes failure 3. Air pressure to 3. install control valve drive valve fails. that fails open Cosing valve 4. pipe blockage 4. a) test flow before startup b) place filter in pipe 5. boiler feedwater 5. install back-up BFW service failure 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 1. reactor cools, however, 1. instruct operators and open water builds-up on procedure 2. controller fails and opens valve

less

less BFW flow

1. partially plugged 1. covered under "NO" feed line 2. partial water source failure 3. control valve fails to repond

1. cover under "NO"

reverse

reverse BFW flow

1. failure of water source resulting in back ward flow 2. back flow due to reactor pressure

1. install check valve in BFW line

other than

another material 1. water source besides BFW contaminated

1. improper cooling, possible runaway

2. install high pressure alarm to alert operator

1. possible loss of cooling with possible runaway 2. possible damage the reactor

1. isolation of BFW source 2. install high temperature alarm

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

Guide Word Deviation Cause no no methanol inlet 1. pump failure flow

Consequence Action 1. deficient quality product 1. install a low level alarm on the adiabatic reactor section

2. feed valves closed 2. backward flow, damage 2. install kick-back on the pump pumps 3. pipe blockage 3. high pollution 3. install a controllor for valve's opened 4. methonal service 4. regular inspection failure and patrolling of methanol transfer lines and seals 5. install back-up methanol resource more

less

more methanol inlet flow

less methanol inlet flow

1. feed valve fails and open

1. a) lower reaction rate b) 1. install flowmeter increase unused methanol 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 3. install ratio sensor the adiabatic reactor shells after the air stream and methanol stream mix 4. install ratio sensor at the reactor product stream

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

1. cover under "NO"

2. partially plugged feed line other than

another material 1. methanol cource besides contaminated methanol

1. corrosion at the adiabatic reactor 2. deficient quality product

1. isolation of methanol source

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Node: Parameter:


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reactor tank Pressure

Guide Word Deviation high high pressure

Cause 1. relief valve fails

2. steam outlet line blocked

3. cooling water temperature is high 4. reaction rate over the range

Consequence 1. pressure builds-up, reactor tank explosion, possible pipe falure 2. vapour containts statureated inside the tank, temperuature increase 3. vapour builds-up, inefficient to remove heat

5. reactants and products outlet blocked

Action 1. a) install pressure sensor b) install backup relief valve 2. test the steam flow before startup

3. install temperature meter 4. install high pressure alarm to alert operator 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

2. no cooling BFW flow

2. reactor over heat, temperature increase, possible tank and pipe failure 3. no reaction take plance, 3. a) install flowmeter waste cooling feed and at reactant pipe line energy b) test the flow before startup

3. reactant pipe line blocked

4. relief valve fails to close

1. a) install ratio sensor b) instruce operators on procedure 2. install high temperaure alarm to alert operator

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APPENDIX D - MSDS OF FORMALDEHYDE AND METHANOL Table D 1 MSDS of Formaldehyde Section 1: Hazardous Ingredients Name

CAS #

%

1. Formaldehyde

50-00-0

30-40

TLV

2. Methanol

67-56-1

3. Water

7732-18-5 Balance

Exposure limits: 0.3 ppm (0.37 mg/m3)

15-May Exposure limits: 200 ppm (262 mg/m3) N/A

Section 2: Physical Data Physical state

Clear, colourless liquid with strong formaldehyde odour.

pH

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

Odour threshold

0.8 - 1 ppm

Percent volatile

100% (V/V)

Freezing point

Insoluble polymer gradually forms.

Boiling point

90 - 100

Specific gravity

1.08 to 1.0975 (water = 1)

Vapour pressure

~40 mm of Hg (@39 ˚C)

Vapour density

0.62 to 1.04 (Air = 1)

Evaporation rate

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

Solubility

Miscible in water

Section 3: Fire and Explosion Data Flash point

50 - 78 degrees Celsius

Flammability

Lower: 7%; Upper: 73%

Fire extinguishing

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

procedures

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

Section 4: Reactivity Data Stability

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

Incompatibility

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.

Section 5: Toxicology Properties Routes of entry

Inhalation, ingestion, absorption through skin and eyes.

Effects of acute

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

exposure

skin burns; bronchitis, pulmonary oedema; headache, dizziness, nausea, vomiting; abdominal pain; blindness.

Effects of chronic

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

exposure

dermatitis; multiple organ damage.

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Section 6: Preventative Measures Protective clothing

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

and PPE

gloves, and an acid suit.

Handling procedures 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. Spill Containment

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.

Section 7: First Aid Measures

Eye contact

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.

Sking contact

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.

Inhalation

Remove patient to fresh air. Administer approved oxygen supply if breathing is difficult. Administer artificial respiration or CPR if breathing has ceased. Seek

Ingestion

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

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Table D 2 MSDS of Methanol

Section 1: Hazardous Ingredients Name

% (w/w)

Exposure Limits

Methanol

99-100

ACGIH TLV-TWA: 200 ppm, skin 5628 mg/kg 64000 ppm

(CAS 67-56-1)

STEL: 250 ppm, skin notation

LD60 (oral/rat)

OSHA PEL: 200 ppm

LC60 (inhalation/ rat)

TLV Basis, critical effects:

20mL/kg

neuropathy, vision, central

(dermal/

nervous system

rabbit)

Section 2: Physical Data Physical state

Liquid, clear, colourless

pH

Not applicable

Odour threshold

detection: 4.2 - 5960 ppm (geometric mean) 160 ppm recognition: 53 - 8940 ppm (geometric mean) 690 ppm

Freezing point

: - 97.8˚C

Boiling point

64.7 ˚C @ 101.3 kPa

Vapour pressure

12.8 kPa @ 20 ˚C

Vapour density

1.105 @ 15 ˚C

Solubility

Miscible in water

Section 3: Fire and Explosion Data Flash point

11 ˚C (TCC)

Autoignition temperature:

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

Lower Explosive Limit:

6% (NFPA, 1978)

Upper Explosion Limit:

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

Sensitivity to impact:

Low

Sensitivity to Static Discharge:

Low

Hazardous Combustion Products: Toxic gases and vapours; oxides of carbon and formaldehyde Extinguishing Media:

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, selfcontained 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.

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Section 4: Toxicology Properties Routes of entry

Inhalation, ingestion, absorption through skin and eyes.

Effects of acute

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

exposure

digestive and visual disturbances, irritation of eyes or skin

Effects of chronic

brain disorder, blindness, emphysema, bronchitis

exposure

dermatitis; multiple organ damage.

Section 5: Preventative Measures Protective clothing

Engineering Controls: In confined areas, local and general ventilation

and PPE

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

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 noncorrosive to most metals at ambient temperatures except for lead, nickel, monel, cast iron and high silicon iron.

Spill Containment

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.

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Section 6: First Aid Measures Eye contact

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.

Sking contact

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

Inhalation

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

Ingestion

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

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APPENDIX E –CAPITAL & OPERATING COST CALCULATION Table E 1 Capital Cost Table Heat Exchangers Area in m2

E-01

FOB

400 $21,407

E-02

5

$954

E-03

30 $3,403

E-04

40 $4,174

E-05

300 $17,452

E-06

50 $4,891

Cost for installation

Fm

Additional Pipe Costs

Material

Co 2009

Floating Head

carbon steel

$104,445

$223,513

0.9

1

1

-$2,783

-$896

$324,280

carbon steel

$4,653

$9,957

0.9

1

1

-$124

-$40

$14,445

carbon steel

$16,603

$35,530

0.9

1

1

-$442

-$142

$51,548

carbon steel

$20,365

$43,582

0.9

1

1.35

$728

$235

$64,910

carbon steel

$85,150

$182,220

0.9

1

1

-$2,269

-$731

$264,371

carbon steel

$23,861

$51,063

0.9

1

1

-$636

-$205

$74,084

Floating Head Floating Head Kettle Reboiler Floating Head Floating Head

Fp

Additional Additional Factor FOB Costs

Type

Total BM

Compressors Capacity (kW)

C-01

FOB

200 $39,937

Type

Material

Co 2009

Centrifugal

carbon steel

$194,856

Type

Material

Co 2009


Fp

Fm



$420,888

Total BM

$615,744

Pumps Capacity (kW)

P-01 P-02 P-03

FOB

0.5 0.5 0.5

$344 Centrifugal $344 Centrifugal $344 Centrifugal

Cast Iron Cast Iron Cast Iron

$1,679 $1,679 $1,679


Fp

$3,862 $3,862 $3,862

Addition FOB Costs

Fm

1 1 1

1 1 1

$0 $0 $0


$0 $0 $0

Total BM

$5,542 $5,542 $5,542

Separation Towers Size

T-01 T-02

FOB

Type

25.22 $72,510 Absorber 2.5 $82,733 Single Pass

Material Carbon Steel Carbon Steel

Co 2009


Fp

$353,781 $1,117,948 $403,659 $1,275,564

Fm

1 1

1 1

Additional Addition Factor FOB Costs

1.2

$0 $16,547


Total BM

$0 $1,471,729 $5,328 $1,701,098

Reactor Size

FOB

Type

R-01 30 $12,200 Heat Exchanger (within reactor) Area in m2

FOB

150 $10,669

Material Carbon Steel

Type

Material

Floating Head

carbon steel

Co 2009

$59,524 Co 2009

$52,054


$188,097 Cost for installation

$111,395

Fp

1.3 Fp

0.9

Fm

1 Fm

1

Additional Addition Factor FOB Costs

1.3

$8,418


1

-$1,387


$2,711 Additional Pipe Costs

-$447

Total BM

$258,750 Total BM

$161,615

Capital Cost Total

$5,019,199 ± 40%

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Table E 2 Operating Cost Table

Operating Cost Feed Water Methanol

Per year 21900 27375

Price/unit 1.4726 $/m3 442 $/metric tonne

Total $32,250 $12,099,750

Energy

E-01

Energy uses (MJ/h) 4000

Energy uses (kW) 1111.11

E-02 E-04 R-01

100 40000 10000

C-01 P-01 P-02 P-03 Total

700 2.5 2.5 2.5 54807.5

Equipment

Hourly Cost

Annual Cost

$82

$720,267

27.78 11111.11 2777.78

$2 $822 $206

$18,007 $7,202,667 $1,800,667

194.44 0.69 0.69 0.69 15224.31

$14 $0 $0 $0 $1,127

$126,047 $450 $450 $450 $9,869,004

Man Power Classification

Number of Persons

$/year

Subtotal

Plant Manager

1

$100,000

$100,000

Engineer Production Operator General Workers Total

3

$60,000

$180,000

9 12 25

$40,000 $35,000

$360,000 $420,000 $1,060,000 Total Operating Cost

$23,028,754

Revenue Product Formalin

Per year 35040

Price/unit 837.76 $/metric tonne

Total $29,355,110

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Table E 3 Net present value calculations

Year Capital Cost Water Methanol Energy Man-Power Cost Revenue NCFBT Account Balance Depreciation Book Value Gain Loss Taxable Income Tax Payment NCFAT Present Value

0 -$5,019,199

2

3

4

5

-$32,250 -$32,250 -$32,250 -$32,250 -$32,250 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 $29,355,110 $29,355,110 $29,355,110 $29,355,110 $29,355,110 -$5,019,199 $6,294,106 $6,294,106 $6,294,106 $6,294,106 $6,294,106 -$5,019,199 $1,274,907 $7,569,013 $13,863,119 $20,157,225 $26,451,331 $1,505,760 $1,054,032 $737,822 $516,476 $361,533 $5,019,199 $3,513,439 $2,459,408 $1,721,585 $1,205,110 $843,577 $0 $0 -$5,019,199 -$5,019,199 6

Capital Cost Water Methanol Energy Man-Power Cost Revenue NCFBT Account Balance Depreciation Book Value Gain Loss Taxable Income Tax Payment NCFAT Present Value

1

$7,799,866 $2,729,953 $3,564,153 $3,460,343 7

$7,348,138 $2,571,848 $3,722,258 $3,508,585 8

$7,031,928 $2,461,175 $3,832,931 $3,507,675 9

$6,810,582 $2,383,704 $3,910,402 $3,474,342 10

-$32,250 -$32,250 -$32,250 -$32,250 -$32,250 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$12,099,750 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$9,869,004 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 -$1,060,000 $29,355,110 $29,355,110 $29,355,110 $29,355,110 $29,355,110 $6,294,106 $6,294,106 $6,294,106 $6,294,106 $6,294,106 $32,745,437 $39,039,543 $45,333,649 $51,627,755 $57,921,861 $253,073 $177,151 $124,006 $86,804 $60,763 $590,504 $413,353 $289,347 $202,543 $141,780 -$4,517,279 $6,547,179 $6,471,257 $6,418,112 $6,380,910 $6,354,869 $2,291,513 $2,264,940 $2,246,339 $2,233,319 $2,224,204 $4,002,593 $3,615,813 $3,758,420 $3,858,245 $3,928,122 $3,352,109 $2,939,987 $2,966,931 $2,957,023 $2,922,892

NPV

*35% Tax Rate and 3% Inflation Rate Used

$27,490,615

$6,655,639 $2,329,474 $3,964,632 $3,419,927

Formaldehyde Production From Methanol

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