DEPARTMENT OF CHEMICAL ENGINEERING

DESIGN IV PROJECT 1 REVIEW OF PHTHALIC ANHYDRIDE PRODUCTION PROCESS

NAME: STUDENT NO: LECTURER:

MARISA A. RAJAN 20923855 MS S. VALLABH

DATE OF SUBMISSION:

17/02/2012

CONTENTS PAGE
PAGE: Introduction 3

Part 1: Process Description

Part 2: Hazards in PA Plants

Part 3: Environmental and Health and Safety Issues References

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INTRODUCTION

Background of Overall Project The project was given on 3 February 2012 by ABC Chemicals who amongst other products produce phthalic anhydride otherwise known as PA via partial oxidation process of o-xylene in a fixed catalytic bed reactor. I was asked to prepare a study to investigate the feasibility of a new production facility keeping in mind that the future for PA based products is strong and investment in future PA production is warranted.

Aims of This Report The aim of this report is to provide a process description along with a PFD as well as to discuss the hazards in the PA production process. Advantages and disadvantages of vent gas recycling(VGR) are also to be discussed and compared to conventional single-pass high loading system. Various treatment options for vent gases are also to be discussed along with the excess steam generation and usage in the process. The final aim is to discuss and present the health and safety factors of PA as well as o-xylene in an understandable format.

PROCESS DESCRIPTION Process Flow Diagram of Phthalic Anhydride Process

Air
C1

1
H1 R1

Salt Cooler and Steam Generator

Hot Oil 2
V1

Cold Oil

O-Xylene

1 4 5
SW1 SW2

CL1

6 Light Organics Maleic Anhydride

Crude PA ST1

PA 10
ST2 D1

PA 9
STR1

8
PT1

Lights impurities removed

Heavy Organics

LEGEND
Displayed Text
C1 H1 V1 R1 CL1 SW1-SW2 ST1-ST2 PT1 STR1

Description
Compressed Air Turbine Air Heater Vaporizer Reactor Cooler Switch Condensers Storage Tanks Pre-Treatment Vessel Stripping Column

Process Flow Diagram

Title
Drawing number: Drawn By: Student Number:

Phthalic Anhydride Production D001 M.A Rajan 20923855

Description of the PA Process In the production process of Phthalic Anhydride compressed air is heated and combined in a stream with heated o-xylene in a vapour-air mixture that is sent to a fixed bed catalytic reactor. In the reactor salts are circulated through the tubes filled with catalyst and act as a heat carrier. Reactor is also equipped with a steam generator that is used to drive the turbine. The reaction gas then leaves the reactor and is cooled down before being sent to the switch condensers. In the switch condensers, two condensers work alternately the product is cooled on the fin tube using cool oil and thereafter hot oil is sent to the condenser to melt the PA formed on the finned tubes, this happens in both condensers and hot and cool oil is switched to the alternately after a certain period of time this means that while one condenser is in condensing cycle the other is in the melting cycle. After the switch condensers the crude product is sent to storage and then to a treatment vessel, in the treatment vessel where chemicals are added to convert the phthalic acid formed to phthalic anhydride. The rest of the crude PA is sent to a stripping column, were maleic anhydride and other light organics are removed. The product stream from the stripping column is then sent to a refining column were the heavy organics such as Benzoic acids are removed. A molten product of Pthalic anhydride is then formed and can be stored until further usage.

Why is O-Xylene preferred over Naphthalene as feedstock? O-xylene is preferred over Naphthalene as feedstock mainly due to availability. Naphthalene is a byproduct produced from coal tar and dependant on the manufacturing of coke which is not of high quantities as compared to o-xylene which is readily available from the cracking of xylene mixtures in plants and refineries. Due to the fact that the coke manufacturing process did not produce sufficient amounts of naphthalene to keep up with demands, o-xylene then became a better alternative feedstock.

How do Hot Spots affect feed rate and how can they be reduced? A temperature maximum called hot spots develops due to thermal gradients along the catalyst tube. This causes a limit to be placed on the feed rate because of either damages to catalyst or in order to decrease the yield. Hot spots can be reduced by:

Using two or more catalyst and placing them in series, this would mean higher rubidium or potassium concentrations in the first bed and higher phosphorus concentrations in the second bed, by doing this the reaction will be limited initially.

It can also be reduced by varying temperatures. This would mean that the first zone would have a cooler temperature as compared to the other zones. Phosphorous levels may also be varied, by using different concentrations of inert packing along the length of the tube.

Why is it important for water condensation to be avoided in switch condensers? During the process of the Phthalic Anhydride production, switch condensers are used in a cyclic manner. While one of the condensers is in the melting stage the other would be cooled down using either water or oil, after a while the condensers would switch and the condenser initially running the melt down stage would now be in the cooling stage and vice versa. It is essential that the condensers run at temperatures above dew point of water to avoid condensation of water, if this occurs the water would then react with the phthatlic anhydride and produce phthalic acid which is corrosive and cause major implications forming compounds and affect flow of system.

What are the improvements noticed in downflow operation of switch condensers? The difference between the upflow type condenser and the improved downflow condenser is that instead of gas entering from the bottom and passing through the top of the internal tube bundles, gas now enters at the top and leaves through the bottom of the condenser. This means that phthalic anhydride which would usually form on the lower bundle is now formed on the upper bundle and the lower tube bundles are able to be washed during the melting stages with molten phthalic anhydride removing by-products such as maleic acid and phthalic acid which are highly corrosive and their iron salts are pyrophoric and can cause fires.

Advantages and disadvantages of the LAR process. The following are advantages of the low air ratio(LAR) process: The LAR process has an increase in catalyst productivity of 40% There is an increase in o-xylene concentration in the air and therefore a reductyion of the weight air/o-xylene ratio from a high of 20:1 to a considerably low 9.5:1. A reduction in the transfer price of production contributed by reduction in capital investment and energy consumption. 6

Decrease quantity of air required per unit production therefore decrease in size. Plant energy balance is improved by the reduction in the amount of sensible heat transferred downstream and corresponding increase in amount of heat removed by salt circulation inside the reactor.

Crude PA recovery is higher via the LAR process than the current technology. The risk of phthalic acid forming is considerably lower due to the fact that the MA/PA ratio is higher in the LAR process.

List of Chemicals that Phthalic anhydride is used to manufacture and there uses. Phthalic anhydride is used to manufacture many chemicals below are a list of chemicals and their uses: Plasticizers Plasticizers are used to produce upholstery fabric from normally rigid polymers and flexible sheets such as wall paper by combining with poly(vinyl chloride. This requires approximately 54% of the phthalic anhydride demand.

Unsaturated Polyesters Resins These are used to provide structural strength in boat hulls, tubs and spas, construction and synthetic marble surfaces. This contributes to approximately 21% of the phthalic anhydride demand.

Alkyd resins This is used to provide a binder for coatings used for either protection or decorative purposes by combining phthalic anhydride with polyhydric alcohols and fatty oils and acids. This requires approximately 17% of the phthalic anhydride demand.

Anthraquinone This is considered one of phthalic anhydrides derivatives and consumers a mere 10% of the demand. It is used as a building block for many dyes and in bleaching pulp for paper making.

Three specifications used to measure purity of phthalic anhydride. Below is a list of specifications used to measure the purity of Phthalic anhydride and their indications: Solidification Point This key specification is used as a sensitive indicator of the absolute purity. Molten Colour Stability This test shows the presence of impurities by a change in colour at high temperature intervals. Phathalic Acid Level Using gas chromatography the level maybe be found and shows how well moisture has been excluded during shipping and storage.

Hazards in Phthalic Anhydride Plants

There are many hazards in a Phthalic Anhydride plant, that can not only cause severe damage to equipment and affect process as well as the environment but more importantly may affect the working environment and safety of workers in that environment. There have been many accidents and explosions that have occurred in phthalic anhydride plants therefore special precautions need to be taken at certain points during the process. Below is some of the Hazards that can occur during the process and ways that have been found to counter act these problems: a) Hazard: The o-xylene/air ratio flammability limit should not exceed 1% o-xylene vapour by volume as this could result in explosions occurring. Consequence of Hazard: If the gases are not kept within the inflammable range, that is the o-xylene/air ratio is well above flammability limit pressures in the system will become very great and this would increase the risk of explosion by a substantial amount Remedy for Hazard: Equipment maybe designed to withstand the highest possible pressure by installing pressure relief devices so pressure surges are relieved safely.

b) Hazard: Heat transfer salt being an oxidiser causes a hazard if in contact with solid or liquid organic material that is the same temperature of the salt. Consequence of Hazard: Heat transfer salt in the molten form an oxidizer and if contact occurs with any organic material in the solid or liquid form at the same temperature a fire or explosion will surely result. Remedy for Hazard:

Organics usually are by-products that are of high molecular weight therefore they will condense out in the reactor discharge plenum and should be at the top of the reactor to avoid contact with heat transfer salt.

c) Hazard: Reactor tube leakage from the tubes into the salt causing gas pockets to interfere with heat transfer. Consequence of Hazard: A leakage from the tubes into the salt would cause an interference with the heat transfer from the portions of the tubes within the gas pockets, this would result in over heating of tubes by combustion of sub-surface of carburetted gas. The combustion combined with the contact of salt in the overheated tubes at these gas pockets cause a local overheating of salt giving oxidising gases the intensity to increase sub-surface combustion. Remedy for Hazard: An ideal remedy would be to design a reactor so that the flow of salt and baffle design would assist in the escape of gas discharged sub-surface to salt rather than obstructing the flow.

d) Hazard: Formation of Stagnant vapour in condensers and air supplying air to condensers while in melting cycle causing unwanted compounds to be formed and a risk of fire hazards.

Consequence of Hazard: Stagnant vapour in condensers causes the reaction to condense out and phthalic acid to react with the water and form phthalic acid which is a highly corrosive substance that plugs up the system and pyrophoric compounds may also be formed. If air is run through the condensers while they are in melting cycle causes an addition of oxygen which is a contribution to combustion and can present a great fire hazard due to the fact that in the melting cycle combustible hot oil is also present.

Remedy for Hazard: Condensers need to be operated at temperatures above dew point and converters should operate within flammable range to have a deficiency of oxygen/air in the condensers.

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Environmental and Health and Safety Issues

Advantages and Disadvantages of the VGR Process as Compared to the Single-Pass High Loading Process The vent gas recycle (VGR) process helps get the reaction mixture out of the inflammable range, which in a single-pass high loading process is inside the inflammable range at the front end of the reactor. The VGR process does this by reducing the oxygen concentration of the reaction gases by using a recycle stream and mixing fresh air with the vent gas and o-xylene. A number of advantages result from the VGR process compared to the single-pass high loading process and are as follows: Higher yield of PA and productivity The Phthalic Anhydride production increases from 114 wt% in the single-pass process to 116 wt% using the VGR process, this is obtained at a ratio of o-xylene/carrier gas of 85 g/Nm3 and can be as high as 100 g/Nm3 depending if the reactor is designed to remove more heat.

In flammability Hazard As discussed above the main aspect of the VGR process is to keep the reaction mixture out of the inflammable range that the mixture is in with the single-pass high loading process, by using a recycle stream.

Phthalic Anhydride condenser operations The single-pass high loading process uses nitrogen or other inert gases to avoid explosions, by blowing the gas into the condenser before melting the PA out, where as in the VGR process no inert gas is used as the oxygen concentration in the reacted gas is usually between 2.5 to 3 vol% and can be melted without any risk of explosion.

Energy Saving A high o-xylene concentration in the reaction gas of the VGR process makes the energy required for the gas compression considerably lower and the recovery of the high pressure steam is higher. This is a great advantage as the turbine is then generated by steam and can also generate electricity that can be used in the process.

Capital Investment Decreased In the VGR process all equipment becomes smaller due to the high o-xylene concentration in the reaction gas. This means that equipments such as reactor, compressor, heat exchanger, 11

condenser, etc. Are all smaller than that used in the single-pass high loading process and therefore capital investment is much lower in the VGR process.

Treatment Options for Vent Gases from Switch Condensers In the VGR process of producing phthalic anhydride the main reaction is carried out in the switch condensers were 99.5% of PA is condensed as solid and approximately 20% in liquid form. Vent gases are released from the switch condensers as well and some treatment options of these vent gases can include: Vessel Treatment The crude PA is in molten form from the switch condensers can be purified first by adding a treatment in a vessel before distillation and other refining procedures are followed to remove phthalide from the crude PA.

Recycled The vent gas can be recycled back into the reactor and thereafter be treated without any additional fuel in a catalytic incinerator sent as off-gas from the plant which is pollution free and its enthalpy can be recovered as high pressure steam.

Wet-Scrubber The vent gas can be sent to a water scrubber in order to remove the by-product maleic anhydride and again recycled gas is not dehumidified and stands at 10 Vol% steam concentration.

Steam Generation and Usage in PA Plant In the VGR process steam is produced in various aspects of the process the first being in the reaction gas were approximately 10vol% is the steam concentration, thereafter further steam concentration is developed after vent gas is, is treated in a catalytic incinerator and the enthalpy of this gas is recovered as high pressure steam. A further 10 vol% of steam concentration is produced after maleic anhydride is recovered via a wet scrubber. The catalyst used in the VGR process presumably increases the steam concentration while increasing the yield of PA. All of the steam accumulated at the various parts in the process can be used to provide energy to the turbine used for the compressor as well as provide electrical energy to the rest of the equipment for 12

the total process keeping in mind that the steam generated is relatively high while the equipment sizes have decreased considerably.

Health and Safety Factors When working with chemicals especially over a long period of time there are many health implications that may occur. It is very important to know these implications so that precautions may be taken. Below is the potential health effects and precautions that should be take when handling phthalic anhydride and o-xylene. Potential Health Effects: Phthalic Anhydride Contact over a long period of time with PA can cause burns to skin tissue, asthma and diseases that affect respiratory system as well as digestive system. PA is a severe irritant to the eyes, respiratory tract, skin and any other moist tissues that may be affected, therefore should contact occur with eyes or skin immediate washing with large quantities of water should be done.

O-Xylene O-xylene becomes a hazardous substance when ppm is above 100ppm, and can cause depression of central nervous system, irritation of nose and throat as well as redness and a burning sensation when contact with skin occurs. Contact with o-xylene over a large time period can cause liver and kidney damage. Extremely high concentrations of o-xylene above 1000ppm can cause in-coordination, loss of consciousness, respiratory failure and in severe cases even death.

Personal Protection: The following should be worn by individuals handling phthalic anhydride or o-xylene depending on extent of contact: o o o o o Safety Goggles Face shields Mask respirators Heavy leather gauntlets Impervious gloves and Aprons

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Explosion Hazards: Phthalic Anhydride in both dust and vapour forms acts as a reactant and can cause explosions. Water, Co2, dry chemicals or foam should be available to extinguish flames of burning anhydride should an explosion occur. It should also be a safeguard to prevent exposure of phthalic anhydride to copper oxide, sodium nitrite, nitric acid or sulphuric acid at temperatures above 80C as this would cause violent reactions to occur and explode. Places were production of PA occurs should be well ventilated and escape routes marked clearly in case of explosions.

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REFERENCES

1. (n.d.). Retrieved February 9, 2012, from http:www.ccohs.ca/oshanswers/chemicals/chem_profiles/xylene/health_xyl.html 2. L Verde and A Neri. (1984). Make Phathalic Anhydride with Low Air Ratio Process. Hydrocarbon Processing , 63, 83-85. 3. McKee, D. (1986). Low-Energy Phthalic Anhydride process. In R. Meyers, Handbook of chemicals Production Processes (pp. 1.14-2 to 1.14-7). New York: McGraw-Hill Book Company. 4. Othmer, K. (1996). Phathalic Acids. In Wiley, & M. Howe-Grant (Ed.), Encyclopedia of Chemical Technology (4 ed., Vol. 18, pp. 996-1005). New York: John Wiley & Sons.(1984). 5. Phthalic Acid and Derivatives. In Ullmann's Encyclopedia of Industrial chemistry (6 ed., Vol. 26, pp. 500-509). Germany: Wiley. 6. RF Schwab and WH Doyle. (1970). Hazards in Phathalic Anhydride Plants. Chemical Engineering Progress , 66, 49-53. 7. T. Sato, Y. Nakanishi and Y. Haruna. (1983). Recycling Vent Gas Improves Phathalic Anhydride Process. Hydrocarbon Processing , 62, 107-110.

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