Heuristics for Process Synthesis Friday, 7 July 2020 8:05 p Ref: Seider etal Used here for educational purposes only. Do not distribute.Chapter 6 Heuristics for Process Synthesis 60 onjecrives: This chapter returns to the steps of preliminary process synthesis in Section 2.3 in which a strategy is recommended that involves assembling the process operations to create a buse-case process flowshee in a specitic order, a follows: ‘Chemical reations (o eliminate dtferences in molecular type), ‘Mixing and recycle (io distribute the chemicals) Separation (to eliminate differences in composition). “Temperature, pressure, and phase change. “Task integration (o combine operations into unit processes. In Section 2.3, asthe operations are inserted into alternative owsheets to manufacture vinyl chloride, rules of thumb ot heuristics are utilized. For example, when positioning the direct chlorination operation, itis assumed that because the reaction is nearly complete at 90°C, ethylene and chlorine can be fed in stoichiometric proportions. Furthermore, when pesitioning the pyrolysis, ‘operation, the temperature and pressure are set at $00*C and 26 alm to give a 60% conversion, These assumptions and specifications ate based upon many factors, notte least of which is experience inthe manufacture of vinyl chloride and similar chemical. In this, ase, a patent by the B. F. Goodrich Co. [British Patent 938,824 (October 9, 1963) indicates the high conversion of ethylene and chlorine over aferic chloride catalyst at 90°C and recommends the temperature and pressure levels of the pyrolysis section, The decision not to use ethylene in excess, to be sure of consuming all ofthe toxic chlorine, is based upon the favorable experimental conversions reported by chemists. Inthe distillation operations, the choice ofthe key components, the quality of te Feed stcaans and the distillation products, and the pressure levels ofthe lowers are also based upon rules of thumb, In fact, heurisis like these and many others can be organized into an expert system, which can he wilized to synthesize sections of this and similar chemical processes, "Normally, design eums use heuristics when generating the alternatives that make up the syaesis re, such a that shown in Figure 27. For the most part, heuristics are easy to apply; that is, they involve the siting of temperatures, pressures, excess amounts of chemicals, and so on, Often they require litle analysis in that simple material halances ean be completed without iterations before proceeding tothe next synthesis step. Consequently, several promising flowsheets, or base-case designs, ate generated rapidly with ‘relatively ile effort. For these Nowshees, the assumptions are check, «process Mow diagram is assembled (eg, Figure 2.17), and complete material balance i carried out often using the process simulators discussed in Chapter 7. ‘Clearly, the heuristics used by a design team to generate the symthesis wee are eruial inthe design process. Section 2.3, provides just a brief introduction to these heuristics, and ence, iis the objective ofthis chapter to deseibe the principal heuristics lwsed in process design more thoroughly. A total of $3 heuristics are presented in Sections 6.2 tough 6.9. Ia many cases, the heuristics are accompanied by examples. For quick reference, the heuristics ae collected together in Table 6.2 a the end of this chapter. Additional guidance inthe selection of equipment is given in Chapters 16 and 17 when determining equipment purchase and ‘operating costs, Chapter 8 when designing chemical reactors, Chapter 12 when designing heat exchangers, Chapter 13 when sizing Aistllation towers, and Chapter 14 when sing pumps, compressors, and gas expanders, ‘Afler studying this chapter and the heuristics in Table 6.2, the reader should: |. Understand the mporance of selecting reason paths that donot involve Loic orhazirdowschemicalsand when wnavoid- ble, to reduce their presence by shortening residence times in the process units and avoiding their storage in Taree ‘quanuies. 2, (BEADLE TO SHABUIEUNECHEMIEAIE] when generating a process lowshect, to account forthe presence of inert species that ‘would otherwise build up to unacceptable concentrations, 0 abhieve a high selectivity wo the desired products, and co accomplish, when feasible, reactions and separations inthe same vessels (eg eactve disillations) 3. Be able oan hersicy nO Oo separate us, prs, pri mires an cer ‘operations involving the processing of solid paricles, including the presence of liquid andlor vapor phases 1324. Be able wo distribute the chemi 62° Row Materials Chemical Reastons 133 ls, By using excess reactants, inert diluents, and cold (or hot) shots, to remove the exothermic (supply the endothermic) heas of reaction, These distributions can have a major impact on the cesuling process integration 5. Understand the advantages, wheo applicable, of pun igi rar than compressing Vapor) ‘Through several examples, including the symthesis of a process to hydrodealkylate toluene to benzene. and the exercises atthe end ofthe chapter, the eader shouldbe able to apply the heuristics in Table 6.2 when generating a synthesis ree and creating base-case designs 6.1 INTRODUCTION {As intrxduced in Chapter 2. the fist step in process desig ivol- ves process synthesis, thai, the creation of alternative process flowsheeis to produce a specific chemical product. For this Purpose, heuristics rules of thumb) are commonly used, at leas, initially. In this chapter, many more heuristics are discussed, far beyond those used in the synthesis of the vinyl-chloride and tissue plasminogen activator (WPA) processes in Chapter 2 Through usage ofthese heuristics, i is normally possible to ere- ale a promising “hase-caseflowsheet(s).” which is subsequently analyzed more carefully in Chapier 7, When used he relied and optimized ubrough careful material and energy halance analysis, equipment sizing, and cost estimation using process simulators, For each of the five synthesis steps, this chapter systema cally presents a more complete set of heuristics, beginning with the first step: Select Raw Materials and Chemical Reactions in Section 6.2. Then, after sets of heuristics are presented, with examples to ilustrate their use, some of the heuristics are applied forthe synthesis of a hase-case desig, one involving the hydrodealkylation of toluene to produce benzene, which begins in Example 6.1. This chapter is intended to show how such a hase-case design can be created rapidly prio othe ative usage of process simulators. Note, however, thal even when using heuris- lis, process simulators are often used for supporting calculations (eg. to estimate physical properties) as illustrated occasionally in the examples that follow. The formal usage of process simu lators for design specifications, ecyele calculations, equipment sizing, cost estimation, andthe lke, is introduced in Chapter 7 6.2. RAW MATERIALS AND CHEMICAL REACTIONS. {As discussed in Section 2.3, the selection of raw materials and chemical reaction is often suggested by chemists, biologist, biochemist, or other persons knowledgeable about the chemical conversions involved. In revent years, with the tremendous increase in awareness of the need 10 avoid hundling hazardous and toxic chemicals, in connection with environmental and safety regulations (as discussed in Sections 3.4 and 3.6), raw materials and chemical rections are often selected to protect the environment and avoid the safety problems that are evident in Material Safety Data Sheets (MSDS). For example, recall that ‘when the viny-chlorde process was synthesize in Section 2:3, the reaction of acetylene with IIC1 was rejected because ofthe high costo acetylene. Today. in addition the reaction path would be rejected onthe basis of the ‘In connection with the handling of hazardous chemicals, the 1984 accident in Bhopal India, in which water was accidentally ‘mixed with the active inlermediate methyl isocyanate, focused ‘worldwide attention on the nee o reduce the handling of highly reactive intermadiates, As discussed in Section 36, within an hour of the accident, « huge vapor cloud swept across Bhopal leading to the death of over 3.800 victims inthe vicinity ofthe Vion Carbide plant. This accident, together with the discovery of polluted groundwaters adjacent 10 chemical plants, especially those tha process nuclear fuels, have led safety and enviroment experts o call fora sharp reduction inthe handling of hazardous, chemicals, For these reasons, societal neds are increasingly being for- ‘mulated that call for new processes to avoid or shaply reduce the handling of hazardous chemicals. As an example, consider the manufacture of ethylene glycol, the principal ingredient of antireeze. Ehylene glyeol is produced commonly hy 1 reac BS. cmiri0, hte, ep on on AR cB +140 + big da te boy The first reaction involves the partial oxidation of eylene over an Ag-gauze catalyst Because both reactions are highly exother- ‘ic, they need 10 be controlled carefully. More important from safety point of view, a water spill into an ethylene oxide stor tage tank could lead o an accident similar tothe Bhopal incident Yet itis common in processes with two reaction steps to store the imermediates so as to permit the produets to he generated con- tinuously, even when maintenance problems shut down the first, reaction operation. Given the societal need to eliminate the storage of large qua tikes of reactive intermediates such as ethylene oxide, four ater- native processing concepts ae possible 1. Eliminate te storage tank()-causing intermiteninterup- tions in the production of ethylene glycol when the oxida- tion reaction shuts doen.134 Chapter Heuristis for Process Symbss 2. Use coslly chlorine and caustic (compared to oxygen from ir) im single reaction step: On OH ACH, + Ch, + 2N8OH(ag) = CH H+ 2NaCl «R3) This alternative requires more expensive raw materials, but completely avoids the intermediate 3. Asethylene oxie is formed, react it with carbon dioxide to form ethylene carbonate, a much ess active intermediate This reaction ° i fen, v0o,-f Yp usc, (Ry ‘occurs smoothly over a tetraethylammonium bromide catalyst. Ethylene carbonate ean be stored safely and hydrolyze to form the ethylene glycol product as needed. 4. Carry out reactions (RI) and (R4) consecutively over an ‘Agegauze catalyst by reacting ethylene in a stream con- taining oxygen and carbon monoxide. To consider this as an alternative processing concep, laboratory of pilot plant data on the rates of reaction ae necessary. In summary, here is an increasing emphasis on retroliting processes to eliminate active intermediates and in the design of ew processes avoid these chemicals entirely. Furbermore, the designers of new provesses are being asked with increasing fre ‘quency to select raw materials and reactions accordingly. Thes Ihave bocome important considerations in the early stages of peo= cess design, EXAMPLE 6.1 Toluene ‘Synthesis of a Process to Hydrodealkylate This example involves the syness of « process o hydodealkylate toluene, which was actively used following World War when it ‘came favorable to convert Large quates of toluene, which Was “ eran om —l Cally ott Cnty ee asain cena 2th Cay Al tno hoger needed to make th explosive TNT, o benasne for ws in the manufictre of eelohetane, a precursor of mon. In this case, 4 pruct design allemative involves the conversion of toluene to Tenzsne and, for this purpose. the principal reaction path is well tine. I involves Ct HH + Cth + CH, ep ‘which is aecommpaio bythe side reaction «w Laboratory dat indicate thatthe reactions proceed imesershy without a catalyst at temperatures in the range of 1,200-1270"F ‘with approximately 75 mol of the lune converted o benzene and approximately 2 mo of the benzene produced inthe bydodcalk- Taton reaction converted wo hipensL Because the reactions exeix in series ina single processing unit usa singe reaction operation ‘is pononed in the fowsbes, as shown in Figare 6.1, The plant opacity x bas onthe conversion of 274.2 Thm of tle, ot approximately 200 MMIb/se, assuming operation 330 days pe yar Here, the overall mass Blanc i cared ut assuming that al of ‘the unread toluene i espe and consume inthe process be syesized. Furtbemore, 2 nl ofthe enite pradction of benzene ‘converted to hipensL Before inserting the reaction operation nto a lows. itisimpor tantto check the feasibility ofthe economic potent, EP (Le. the sles ‘minus the cost of rw materials, ot including the costo lites and ‘operating cons). Using prices fo, and CH, rom [CS Chemical [Big nate 2013 a 2014 estates fo Hy td CH, Cost cent) H 059 cH, o2t c, ost CH 047 Cally unable the economic potent per pound of benzene (assuming negligible conversion 19 Cys) only 14 cent C,H, Note, however, that afer Workd War with large exces of tone available its unit cost ‘was much lowet—and the economic potential was much higher Even ‘without the costo quent ants operation the EP was sufcieatly Tage to proceed with the next step in proven synthe, Dissiation of Chemical Figure 61. Reaction operation forthe Iydrodcaltylation of ene.63 DISTRIBUTION OF CHEMICALS Inthis subsection, several heuristics are presented beginning with the need for excess chemicals in carrying out reaction operation, Excess Chemicals [After the reaction operations are positioned in a process flow~ sheet, the sources of chemicals (ie, the feed streams and reactor effluents) are distributed among the sinks for chemicals (ue the feed streams to the eaction operations and the proiuts fom the process) In this distribution, decisions are made conceraing (1) the use of one chemical reactant in excess in a reaction ‘operation, (2) the handling of inert species that enter in the Feed streams, and (3) the handling of undesired byproducts generated in side reactions. For example, as we have seen in Figure 2.3. one Land E/E < 1, the conversion to ally, chloride is highest at intermediate temperatures. Inthe early stages of process synthesis, when distributing the chemicals, these considerations. are helpful in seting the temperature, pressure, and the ratio of propyl a—@—e © ac. ® re ° c= crc, 0, c= crca+Ha le (ahead) cucutice.c. a (seropropa) a ques artcr.c sna {iblropropens) ® Figure 6.7 Competing rations: (a) series reactions (b) pale! reactions) serie parallel eactons (exothermic aly Vacuum ‘When process pressures Jess than the ambient pressure are required, special devices and considerations are necessary. Vac~ ‘uum operation ig most common in crystallization, distillation, ‘drying, evaporation, and pervaporation operations. A vacuum Inside the equipment causes inleakage of ambien-pressure ait ‘A vacuum system is used to remove this air together with aay associated vapor inthe process stream that passes through the ‘equipment. For contimous processes, vacuums are predomi- nantly inthe range of 1-760 torr (0.13-101.3 KPa) In this range, it is common t0 use a vacuum pump, which compresses the 8 from vacuum (suction pressure) 19 ambient pressure, or a jet-jector system, which uses flow of pressurized water or steum to mix with and remeve the gas to create the vacuum, “To design the vacium system, it is necessary to estimate the inleakage of ar, determine the total amount of gas (inleakage