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Chemical Engineering Third assignment 09.11.

09 Introduction

Design and Professional Skills A MANUFACT URE OF ST YRENE

Styrene is a trivial name given to phenyl ethene (C6H5CH=CH2), which is also known as phenyl ethylene, vinyl benzene, cinnamene and styrol. It is one of the most important unsaturated aromatic polymers produced on a commercial scale. Crude styrene was first isolated in the 19 th century by distilling storax (a natural balsam obtained from a flowering plant, Styrax officinalis). Although it was known to polymerize, it was not at first produced on a commercial scale because the polymers produced were brittle and cracked easily. The breakthrough came when a high purity monomer was produced by the Dow Chemical Company and BASF AG in 1937. Subsequent advances in technology led to successful polymer production and its use during World War II for the manufacture of synthetic rubber. Current world production of styrene and its products is about 25 106 tonnes per year (worth 25 billion) about 30% of this is produced in the USA alone. The major manufacturer of styrene monomer in the UK was, until recently, BP Chemicals at Baglan Bay (near Swansea). BP Chemicals, Shell Chemicals and many others are active elsewhere in Europe and in Singapore, among many parts of the world. Manufacture of plastics consumes about 95% of the total styrene produced. 50 - 60% is used in addition polymerization to produce polystyrene for packaging whilst the remainder is co-polymerized with compounds such as acrylonitrile and butadiene to produce styrene-acrylonitrile, styrene-butadiene (synthetic rubber) and other similar addition compounds. Methods for the manufacture of styrene

1. 2.

Pyrolysis of petroleum and also recovery from various petroleum processes. Side-chain chlorination of ethylbenzene (EB) followed by hydrolysis to produce alcohols with subsequent dehydration to produce styrene. Although used in the past, these methods are no longer economic. Styrene is now produced entirely from EB, either by oxidative conversion (~ 10%) or by dehydrogenation reactions (~ 90%).


Oxidative conversion of EB Air is sparged through liquid EB at around 135C and 800 - 1500 kPa pressures to produce the hydroperoxide by: C6H5CH2CH3 + O2 C6H5CH(OOH)CH3 The hydroperoxide formed is then catalytically reacted with propylene at 100 130C to produce phenyl ethanol, C6H5CH(OOH)CH3 + CH3CH=CH2 C6H5CH(OH)CH3 + CH3CHOCH2 (-phenyl ethanol) (propylene oxide) In the final stage, -phenyl ethanol is separated from propylene oxide and dehydrated to produce styrene as follows, C6H5CH(OH)CH3 C6H5CH=CH2 + H2O The process is known as the SMPO process because propylene oxide is the co-product.

4. Dehydrogenation of EB EB is catalytically dehydrogenated in the presence of superheated steam. The main reaction is,
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C6H5CH2CH3 C6H5CH=CH2 + H2 The reaction is endothermic. Therefore, the EB feed is mixed with superheated steam before it is passed through the catalytic reactor. The Steam does not react with EB but it supplies some of the necessary heat of reaction. The catalyst most commonly used for this reaction is based on iron oxide (Fe2O3) which will lose its efficiency on prolonged use due to the formation of lower oxides. Chromia (Cr2O3) is added to stabilize the catalyst. In addition, small quantities of K2CO3 are also added to prevent the formation of coke around the catalyst particles. The conversion of EB to styrene (i.e. moles of EB that actually react to produce styrene per unit mole of EB in the feed) depends on temperature. Temperatures in excess of 650C decrease the yield of styrene due to thermal cracking of EB and styrene and so the temperature is maintained at 600 - 650C to minimize these undesirable reactions. The conversion of EB to styrene is also affected by the operating pressure. The reaction given above shows that 2 moles of products (1 mole of styrene + 1 mole of hydrogen) are formed from 1 mole of the reactant. Hence, if the partial pressure of styrene in the reactor is reduced, the forward reaction, to produce more styrene, will be favoured (Le Chateliers Principle). This can be achieved easily by reducing the total operating pressure and/or adding more steam to the feed mixture to reduce the partial pressures. In most licensed processes since the 1970s, reduced pressure is used and about 8 to 10 moles of steam are usually added to each mole of EB in the feed. Useful references 1. Short HC and Bolton L, Chemical Engineering, 92, (Aug) 30, 1985 2. Styrene, Chen S-S, in Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition, 22, 956, John Wiley & Sons, 1997. 3. Petrochemical Handbook, Hydrocarbon Processing, 80, (March) 132-3, 2001

Brief details of the process You are required to manufacture 30000 kg h-1 styrene, using catalytic dehydrogenation of EB: Pure EB is mixed with 10% of the steam and then the mixture passed through the Heat Exchanger 1 (HE1) (at 3 barg pressure and 150C) in which the EB is vapourised. The vapour mixture of steam/EB leaving the HE1 passed through the Heat Exchanger 2 (HE2) to be heated to approximately 530C. The remaining 90% of the steam is superheated first to 350C in the Heat Exchanger 3 (HE3) then to 800C in a gas fired superheater. This superheated steam is then mixed with the steam/EB mixture from
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HE2 immediately before it enters the reactor and at this point the steam/EB ratio is about 1.4-1.7/1 by mass. All the Heat Exchangers 1, 2 and 3 are heated using the products stream from the reactor. Why is this feed heating strategy used? The combined flow of EB and steam enters the reactor at 660C. The catalyst is 5 5 mm cylindrical pellets of 87 % Fe2O3, 11 % KOH and 2 % Cr2O3. The steam does not react with the EB, but it helps to provide the necessary heat of reaction (by cooling itself). It also reduces the partial pressure of styrene and improves the conversion of EB to styrene. A pressure of 40kPa (~6psia) is maintained in the reactor. The Relative Molecular Masses (in g/mol) for the compounds are: Benzene = 78 Methane = 16 Ethane = 30 Methylbenzene (Toluene) = 92 Ethylbenzene = 106 Styrene = 104 Hydrogen = 2 Steam or Water = 18 1. The reactor Complete conversion of EB to styrene is not achieved under normal operating conditions. For the purpose of this exercise, assume that 65 mole % of the EB entering the reactor is converted to products and by-products. 96.4% of the EB that is converted goes through the styrene synthesis reaction (1) C6H5CH2CH3 C6H5CH=CH2 + H2 (EB) (Styrene) (1)

Some of the hydrogen formed in reaction (1) reacts with EB to produce unwanted by-products and also some of the unconverted EB can polymerize to form tars, which have very high Relative Molecular Masses (RMM). The most important side reactions (which will generate the by-products) can be summarized as follows: a) 1% of the EB converted reacts with hydrogen from reaction (1) to produce benzene and ethane as shown in (2) below: C6H5CH2CH3 + H2 C6H6 + C2H6 (EB) (Benzene) (Ethane) (2)

b) 2 % of the EB converted reacts with some of the hydrogen produced in reaction (1) to form toluene and methane as shown in (3) below: C6H5CH2CH3 + H2 C6H5CH3 + CH4 (EB) (Toluene) (Methane) c) 0.6 mole % of the EB entering the reactor is polymerized to form tars. C6H5CH2CH3 Tar (4) (EB) NOTE: The RMM of tar is not known - make the assumption that 1.0 kg of tar is formed from 1.0 kg of EB that is polymerized. The product mixture leaving the reactor therefore contains styrene, methylbenzene (toluene), benzene, ethane, methane, hydrogen, steam, tar and the un-reacted EB. This mixture leaves the reactor at 560C, and much of its heat is recovered as it passes through the heat exchangers used to preheat the reactor feed as explained before. The temperature of this product stream at the end of the preheating section is about 180C. Remember, though, that the reactor contents were maintained at reduced pressure. At some stage the pressure must be raised up to atmospheric again. 2. The Condenser and the Organics Separator How will you now separate the condensed steam from the organic liquids (which include the tar)?
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It may be useful to know that the solubility of the organics in water is negligible (less than 0.01 % by mass). However, some organic vapours are lost from the liquid phase are considerable at the temperature and pressure of separation, and it can be assumed that 14.6 mass% of the benzene and 5.1 mass% of the methylbenzene escape in the gas phase which, therefore, will contain all the ethane, methane and hydrogen, and also some organic vapours (benzene and methylbenzene). Also small amounts (2% each) of the ethylbenzene and styrene will escape in the gas phase. Can you see any use for this gas stream? 3. The distillation train The organic liquids are separated into individual components using a series of distillation columns (called a train) each operating at different temperature and pressure. Unfortunately, during the distillation some of the styrene is polymerized to form polymers. These will also have very high molecular weight compounds of unknown RMM. However, these and the tars formed in the reactor may be considered to be non-volatile so that they always remain in the bottom product of each column. Assume that 0.22 mole% of the styrene that enters any column is converted to polymers. NOTE: Assume that 1 kg of styrene that polymerizes will produce 1 kg of polymer. Think what must be achieved in this distillation train. You must remove, as far as it is possible, all the components that are more volatile than the product styrene and also all the components that are less volatile, including the tars and polymers. The styrene monomer product should be free of tars and polymers but may contain very low concentrations of minor contaminants such as unconverted ethylbenzene and volatile by-products. It is desirable that you recover as much of the unconverted ethylbenzene as possible since you should then be able to consider whether it may be worthwhile putting this back into the process. Where would you feed such a recycle stream back into the process? You will not achieve this in one single distillation column, so you must think about the minimum number of columns in the train that would enable you to achieve your objectives. Think where the components will go (i.e. to top or to bottom product streams in each column), not forgetting to consider all the contaminating by-products and unconverted raw material as well as the desired styrene product. As a rule of thumb at this stage you just need to assume that the purity of the product streams (top or bottom) will increase as the height (and therefore number of stages) of the column increases. Next term you will calculate this more exactly. Think also what temperature and pressure you might need to operate at in each column. Hint: Some or all of the columns may operate at pressures below atmospheric. Why? Basic physical data (boiling points, etc.) for many of the components of the streams in this process can be found in: Perry R H and Green D W, Perrys Chemical Engineers Handbook Seventh Edition, McGraw-Hill, New York, 1997. For websites, try the IChemE Resources page ( and the really excellent NIST websites (especially

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What you have to do? - Start now! The brief (the assignment) is:
Your team is brought up as external consultants to investigate the possibility of investing in building a plant that would produce approximately 30000 kg/hr of styrene. The project is still in the preliminary phase and the engineers of the organization have suggested a process that it is attached. This assignment is a group assignment and you will have to divide the tasks but each group member need to learn how to do the mass balance calculations for the process. Describe the flowsheet, and explain the reasoning behind it: identify the processes and main plant elements and their function (for example reactors, distillation columns, heat exchangers, separators, filters, absorption towers, centrifuges any, some or none of these) specify the conditions (P,T, solvent, etc.) and the phases present in each part of the process estimate (very approximately) the conversions and yields that might be obtained estimate (very approximately) the sizes of the main plant equipment. estimate the costs involved with building a plant You are to develop the flowsheet/process flow diagram not based on rigorous and detailed calculation. The emphasis will be on approximation and estimation. The objective is to get you to have a realistic feel for the quantities and sizes involved without resource to detailed calculations (these will be the subject of an exercise in the second semester). Also, you will learn to make the assumptions needed to get started. The questions set out in the introduction should help you to get on. Each group will submit a single report. The group will receive a single mark (50% of the module mark) but the award of marks to individuals in the group is guided by the peer assessment exercise (see item 4). Also each member of the group will include in the group report: 1. A process flow diagram labeling the streams, equipments and process conditions (T, P) and 2. Auto CAD drawing of a piece of equipment used in the plant (see item 5) below.


You are at the first stages of a Design. You are assessing the feasibility of a proposed process and reporting the results of your work to a prospective client. So, you must set out a process that you believe can achieve the production objective.


In setting out your process you must show the bases for your proposal and support it by reasoned argument. What assumptions have you had to make to get to where you are? Give references for your conclusions, especially numerical data.


In the next stages of design (in the second semester) you will need more information on your process and the materials you are handling, particularly in relation to any hazard that they may pose. If you come across such information during your research now, note down the source and keep it as a useful reference. Remember that hazard is defined not just in terms of safety, environmental and property impacts, etc., but also in terms of hazard to the successful completion of the project.


We will ask you to assess each other in a process of peer assessment. Your group will have to agree on a percentage figure for each member, which represents how you all agree on the contribution made by that individual to the team report. The absolute value of that figure does not matter; it is the value relative to other members of the group that is important and that will be used to inform the final mark awarded to each member of the group. A template for the Group Peer Assessment Report is attached. Records should be kept at each meeting!


Each Group must submit the following: A group/team report, typed on A4 paper (max 10 pages) A Labeled Flow Diagram of the process carried out by each individual member of the group Each person will have also to include in the group report an Auto CAD drawing of a piece of equipment that will be used in the plant. A Group Peer Assessment Report

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All the above together with the Coursework Receipt completed have to be submitted by 10:30am on Monday 7th December in ART-LT6 where the first round of oral presentations will take place. This year there are 21 groups, so 10 groups will present their work on Monday 7 th December in ART-LT6 from 11-1pm and the other 11 groups will present on Thursday 10 th December in ARTLT7. The groups will only be told on the Monday 7 th December after submitting their team report which groups will be presenting on the first round of presentations. So every group must be prepared to present. The groups not selected will be asked to leave and they will present their work on Thursday 10th December. The selected groups will then upload their presentations in the computer. You will present as a group for 10 minutes and 2 minutes questions to your peers. Working in a group may be a new skill for you, but it is vitally important. Decide what can be delegated to individuals, and what must be done as a group. Try to be clear about what is agreed: who will do what, and by when? Make clear notes (in meetings, and in your individual tasks), and share these with the rest of the team. Agree when and where your next meeting will be, and make sure that absent teammembers are told. Keep a record of the people present in the meetings. Leave yourself time at the end to assemble the final report! Design Meeting Record Team: Date of meeting: Time: Venue: Those in Attendance: Apologies Received: Item: Description: Action Required By:

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