7 Production of Olefins “The three most important olefins wed for dhe production of pesrochentcals ate ethylene, propylene and butadiene, tnd ther production is ineeparable, All tre are produced fn various ratios bythe cracking of feedstocks us differen as ‘thane and crude ol (Table 7). hylene the dontnaat olefin with « production of 28 billion pounds in 1978. The past and predicied sources of ‘tiylee in the United States are shown in Fg. 7-1? len Evrope aboot 06 is obtained by eracking naphiha, Fig. 7 22 It has sen bees predicted that in 1990 the sources of stylene in Europe willbe: naplnha (67%), gas el (20%), LPG 5), and ethane (1%). Tn both the United States and Burope, heavier feedstocks are playing a greater role in sabylene production at supplies ‘of uadilonal feedsiocks (ethane, LPG, and naphtha fil to keep pace wth ethylene ema As feedstocks progres from ethane through heavier frac- ons with lower Aydrogen content the yield of ethylene ‘creases and feed per pourd of eylene increases mark ‘edly. Heavy go ll requires over three ines the amount of feed per pound of ethylene as for ethane cracking. The cot TABLE 7-1—Typleal Yields from Various Feodstocks (Including Ethane Recycle) n acai by ih NO overage ty weit Fig. 7.2—The Wester Europe sources of nnfene—past ani?72 From Hydrocarbons to Petrochemicals amount of propylene, butadiene and BYX also increases tit increase in molecolar weight of the feedstock, “The feedstock of choice is determined by the olefin and [WTX eistibution desired. Of special interests the decrease in the etiylene to propylene weight ratio as the feedstock becomes Reaver, With ethane the ratio is Tto 0017, with propane the ratios 1100.35, with botane 1 00-39, wih ull. Fange naphtha 110 OA and wih heavy gs il he rato is 1 {o 050, Operation at a lower seventy wil increase the [propylene ethylene ratio, The yield of propylene as wells {hat ofethplene can be an important consideration in fee Stock selection. A in depth rendy by Janakievski on alter that feedstocks for olefin production indicates that the Fedaocks tobe utilized in he Middle East, especially Saudi Arabia, should be ight hydrocarbons from associated gas.® Una 196, ethylene production from heavy iguids was less than 25 of the total. The major impetus for this change in eedsock wae the anticipated decrease in natural gas pro- ‘docton. This change in feedstock increases the avila of propylene for petrochemical conversions. Its expected that the rao of propylene to ethylene wil rise from the ‘current 25:100 ro around 50100 by 1000. Te fas been predicted, however, thatthe consumption of. cehane ae a foe wil remain relatively stable in the United States forthe nent few year; there is even possibly that ‘thane wil show a stall increase in usage by 1985. The use (of propane i expected t rze gradually from 1979 through 18S, Butane wage probably will remain constant at less ‘ntl the LP gar from Middle East asocnted gas bits the market A relnively large source of ethylene comes from Tefinery gee An informal survey of thir souree has been reported by Bil K. Minton* ‘Unlzation of feedstocks in exiting operations has become a fine scence wrought by erder-of-magnitude changes in ‘ont, Wilkinson's review of ethylene price trends and the pomible ethylene supplyidemand balance reveals 2 high ‘Segree of uncertsnty ae to feedwock trends The United States name plate ethylene capacity as of “January 1, 1979, was 82.49 billion pounds. Thisinereased to bout 38 billion pounder by January 1, 1980, will i ‘crease to 40.5 billion poundsvear by January 1, 1981, and 42.6 billion poundsiycar by January 1, 1982.) Work-wide ‘ethylene capacity on January 1, 1980, was about 52 milion tonuyear. The worldwide geographical production of ety. lene in 1976 and the predicied. production ia 1990 are shown in Fig. 7-8!" Figure 74 shows the distribution of the 1979 noncommunis 43.2 milion metric ton ethylene capac Propylene isthe second most important olefin. Is growth rate is the fastest of any petrochemical raw material appre ‘ably higher than the growth rate of ethylene. The demand for petrochemical propylene now almost equal its Fuel tues and twill so0m Be the Larger of the two. In 1980 the petrochemical uiization is predicted to represent 54% and fuel products 46%. The fuel products are alylate, polymer ‘gtoline, refinery {uel and a component in LP-qas. ‘In 1980, 37% of petrockemical propylene will ome from refinery gases, and 63% ax a coproduet from ethylene production. Copreduct propylene capacity as of June 80, 1979, was about 5,00 millon metic tons per year. On the cocher hand, by 1985 the percentages are predicted to be equal, Other experts fee! that more propylene wil be drawn fom the refinery poo, whale sl others say that the supply ‘of propylene from refineries for chemical use is only moder- ely expandable. Obviously, predictions made in respect to propylene sources will be, at best, educated guess. This i Frequendy the situation when dhe compound is both an ‘important copreduc of a dominate main produc and also a byproduct of a large and importane refinery process. In sxidtion, propylene hi no. production of is own. The hanging eiylene feedstock picture compounds the probe lem ar does the phasing out of lead i gasoline. The constant increawe in the need tor alkylate and polymer gasoline to ‘alntain octane number wil divert refinery propylene from chemical t0 fuel uses. ‘Butadiene runs a poor third in the production and de mand rae wit ethylene and propylene. As with propylene, ‘butadiene isa coproducr with ediylene. It is produced at 2 rather constant 45% when the feedstock is butane or higher. The overall ratio of ethylene 1 butadiene is 110 vee sno te eee * = Asia Pace Kv [Px cena = Vs — con age _ eae = cr Po v0 sett wont gy If grete t on see oe“Ryo Gece fon ro Ox asm Ac. (P.7-4-Dattton of i 1679 noncomeit .185 lon mete {on aon cape 0.08. Coproduct butadiene capacity a6 of June 3, 1978, wa shout 0.98 lion metric wns per year. The 1978 United Sates prctuction of butadiene was 8.52 bilion pounds, the ‘nord-vide production exchading the USS. and China ‘rat 985 billion pounds, and the 1979 work-wide produc- ‘Son was about 994 blion pounds. ® ‘Butadiene n addition ro being an ethylene coproduct, i produced by butane and butene dehyarogenaton and isaso Shained from refinery off gas. Coprosict production a¢- ‘cuted for 38% of the 1978 production and this percentage 1s predicted to increase to 67% in 1985, This increase is ‘ellection of the expected ethylene shift to heavier feed- ‘lock. Ethylene crackers wil be te leading souree of buta- ene in the foture. Dehydrogenation of butane and the batencs is curcently being phased out as a butadiene voure However, Welch, Croce, and Christman have made an i depastudy of an oxidative dehydrogenation process for botene to butadiene snd find that conversion thd overall nergy cone show this process to he best for butadiene production Tisalse predicted that by 1981 butadiene demand should be about 4 billion pounds and at least 8.6 billion wil be eoproduct butadiene. Mott of the retaining 17 Bilion ‘pounds wl be imported ‘OLEFIN FEEDSTOCKS ‘The choice of feedtack for olefin production is progres: sively growing more complicated. The US. natural gas Droducion hat peaked out and the price ofall feedstocks hs increased dramatically along with constriction cont. Because ofthe changing feedstock picture, plant now must ‘be capable of handling a wide variety of aw materials 0 insure a supply positon. However, Lager of the Philips Chemical Dion of Philips Petroleum sated, "Unforty- Production of Olefins 73 rately, you cannot afford to design a plant to run on ‘everything from ethane vo gat ofl The snewer co dhe fed Socks the key to the whole projec. It involves looking at the fanure aalailty of each feedstock, the pricing of cack feedstock, and future eoproduet valves of propylene, buts iene, beneene and fuel ci Heavier feedstocks such a8 ‘apts, gas ol, and resis are becoming important precs- sor for pevorhemicals"® Currently only #-10% of the Unive Senter etlene plats can handle natural gas ils, NGL, and heavier feeds” “The plants uiling heavier feeds are more costly chan those signed foredhane but the beaver feds also produce Sppresiably more propylene, butadiene and BTX as copro dues. Thee separation i+ the major factor in the added production cost of the edhylene. This cost to some extent ompensied for by the coproduct exes. In this article we villbe concerned primany with aetaalproduetion process Taher than inthe economics ofthe process. For the verll picture one rust heep in mind that regardies ofthe feedstock, olefin production isa gigantic destroyer of energy, an enormous heatsink. Olefin prod tion every energy intensve© ‘With ll feedstocks, the main effort i 10 obtain high selecivi-~maxinum predation of olefins and aromatics And 2 minimum of methane and G,*. The main factors influencing the selevity are the ‘ypes of compounds present, the reaction temperature andi residence time, Fim eff, paral presure™ and sorface reactions Tn. general, the higher the molecular weight of the foodsck, the eater it cracks. For example, the typical fumace outlet temperatire for the cracking of ethane ie ca 800°C while the temperature for the cracking of ‘naphtha gas oil i ca 678-700° C. Paraffin hydrocarbons, alkanes, are the eaist to crack, Seraight chain parafing, n-alkanes, give high ethylene Yields while branched chain paraffins soparaffins, sch 4: Hobutane and isopentane, give high yields of propyl- ne. Napithenes, eycloparafing, are more resistant. to Cracking beenuse che ring must be opened fst. At low temperatures they tend to dehydrogenste to aromatic compounds Higher temperatures produce olefins and ‘Giolefina Aromatic. rings, benzene rings, tend. to. past through the cracking» fumace “unchanged. Aromatic compounds with side chaine such a toluene and the aylener, lose these side chains by hydodealkylation and become benzene cH, Cem Qs on This accounts for the relatively high benaene concontra- tion in pyrolysis gasoline Tn respect t0 residence time, conversion in the duid (bull conversion) has wo be distinguished from conver~ sion in the lamina layer near the tube wall ‘This is the foaled fl effect. The film effet ia function of uid ‘locity, tubewal femperature, and cil diameter. Oleins fre formed by primary Teactions and, therefore, require 4 Tow residence tine.