PROGRESS OF BUTADIENE PRODUCTION /71w .E. C& War Production
Bwrd, Washington, D. C.
AT FREQUENT interval^, chemical tmm~become worda or p h r m wed by the publio. Such teams as “VitalniLW”, “sulfodrugs”, “ethyl gas”, and “ p W d are typical. Thie &E contribution of the chemist is the word “butadiene”, for it has no doubt be811 heard more times over the radio, in the hslls of Congreed, and on the street, and neen mom frequently in the newspapera, megasines, and on the scmn than any other chemical tma The we of eucb term and phrases nsusllg implim that the substance is new and bas suddenly caught the public eye. Butadiene is important, but it is not new, for it wea reportedin the technical literature about eighty years sgo. Many of ita chemical and physioal properties have been lmown to the chemi~tafor yeam. Dwing the past year I have read betweem fiveandtentbow aand printed pagea on the production and properk of butadiene. Such reading has been primarily in the 6dd of applioations for patenta and patenta and scienti6c articles, although there mu& be included the pagea of testimony before congmadond committees, newqmper articles, opiniom of n e w ~ ~ ~ analpta per and d o comment9tors, magsdne articles, etc. Butadiene comtitutea but one part of the s y n W c rubber program, and the literatureon rubber from plants, aub stitutea for rubber such as wood, wire, and *ring wheels, q w dBerent types of rubber, and rubberlike producta is e voluminous. The battleoeck of the oresent mthetic rubber orimam. at least for the moment, d the pm;lucfon of but&&. ’he purpose of thin paper is to p-t emne of the bintory and technical facta pertaining to the production of butdiem en that this problem may be viewed in the proper pmpectiva For yesrs the American people have beeneducated to relish and cheriah the advantages of tranepOrtation, and rubber is an esential factor for the transportation of laborem to work, farmers to market, vacationers, and j u t plain joy r i b . qeOember 7 brought UB to a full realization of our dependence upon rubber and f o c d the attention of the people of America u p n those responsible for developing a synthetic rubber program. The meal ulwged with the lwpmibiity of the syn rubber pmgram decided tbat the h d a of thin oountry be met best by allmsting the largeat portion of the p b e r pmgram to the production of Buns 8 diemandstyroma lntheligh6of terials available at that time this ap choice. Something had to be started--availebe badto he &,a call for w l u n k had to be then the program had to be built around th qualised to produce.
There wea su6icient intar& in butadiene thirty yeam ago en that patenta w m hued by the United Statea Patent Of6w on this subjd. Sice then many patenta have hued on the production and separation of butadiene. Of thesn, approximately 50 per cent have issued to c i k m of Germany. The ~olvceaof butadiene ean be divided into two large groupe-namely, compounds containing carbon and hydro-
gen, and compounds containing carbon, hydrogen, and oxy. gen. It may be n-ry to convert theae compounds into interndates and thewe into butadiene, but theee group constitute a basic chilicatiou. The carbon-hydrogen compounds come hom the raw materials oil and d, and the carbon-h-xygen comgounds come primarily from plant products. No attempt will be made to list all of the methods for the production of butadiene. The following meare among those which inventom considered of arfficient importam to patent. CARBON-HYDROGEN COMPOUNDS Among the &y methods for the production of butadiene WBB the conversion of carbon-hydrogen cornpounds into ndiddorobutane. Thin hsa been d e c o m p d into butadiene and bydmgen chloride under a variety of couditiona Hydm gen cbloride and stenm have bean used 88 diluenta, and the reaction haa been conducted in caat iron t u b , ceramic tubea, and Scjdpmf metah at temperaturea fmm 350’ to 700° C. Silica gel, active carbon, and many metal hnlidea and oxides have been umd BE catslyats. Butylene dibromide passed over soda Lime at e00” C. yields butadiem; bubbling it through molten aluminum chloride at 550’ C. ala0 rmulta in the p m ductioq of butadiene. Butane, butylene, and chlorine psased throughquartrtubesst400’to650’C.~tintheformstion of butsdiene, ethylene, and hydrogen chloride. Halogenammonium halogenidea beated with ausli pmdooe butadiene. Compounds of either of the following t y p have been wed, where X is a halogen:
,
X
h
I N D U S T B I A L A N D EMQIIt&&iRa
, 1942
Yearn sgo t e h m e t b y l wa9 ~ treated witb methyl iodide and potsssium hydroxide to form tdmnwthylane haxamdbyldiamine iodide which in turn wa9 mted with silvex bydmxide to form the quatarwry arnmonhtm "s*; then upon heating, butadiew, aster, and nerefonned:
y5-"a
YJ% N -C (H J)
65
b5 ..
+"J+4KOH+k
CBIYISTRT
1261
in tubes lined with tin, silicon, lead,eta. Ethylene and hydro. carbon pmduots have been heated to EO@-120Oo F. and at LODO pounda preaaue with the pmduction of butadiene and mhny other bypmducta. Propylene can be converted into etesfsne and thewsinto butylene, wbicb is dehydrcgenated to pmdw butsdiapa p d over or through Typical is the reaction of vinyl bromide and sin:
.
+-+a
+
ac"Br Lhr+
&Brt
+ Cas
Aoetylene can be converted into butadiene by four stsgaa which involve converting acetylene into acetaldehyde, condensing this into aldol, hydmgmating aldol to 1,3-butylw (CHa)dN(CEL)dIs W H - - - t 2 A g I (CgS,[N(CH&OHh glycol, snd d e h y d d q the butylene glycol to butadiene. NaphtheMs, tmpanes, byclotrexeme, cyolobexane, and teh(CE)~IN(C&)IOHIS 2N(Cgh 2JW CJI, bydrobanzane ham bum hmtd under vsryinet wnditions to pmduoe b u t s d i hydrogm, metbane, e b , etc. In *MetbyI allyl trimethyl ammoniumhydroxide can dso be gener&, the resotionr have been carried out at temperaiuree converted into butadiene. m or less in the pres of 550°to 700' C. at sbonphmio p Diacetylene can be obtained by paaaing amtyime over Of SUOh OakdYMt9M @ & W dbh,caldUm dtdIlBb, active charoo$ at 500" c. E (- E). If&oxideq pbosphatea, and ohmmatason nilioa gel,platinum and creetylene in peaed through an aqueous solution of chromic quart.,lwrdntmntiumluanste. adfate and the solution nubided to oathodic reduction, Butediene wa9 obtained 29 yearn ago from oils, free of cydio butadiene and vinylacetylene am produd. Butediene may or mmatic compounds boiling above 150°C. and containing be obtained by passing diaoetylslre and hydrogen gasat rloo 10 to 20 csrbon atom per moleoule, by heating them to to 80" C. over 6nely divided nickel and other metals. Ving700' C. Fluid hvdrocarbonn have bean craoked eevarelv to form very reective'moleoular fragments which H E bavebeenreaatedwith the products of more cu--c=c* Synthetic Rubber Being Agitated to Achieve the Necamoderate oraoking e of Coagulation of the Latexlike Liquid o f t h e remainder ich as Resulted horn the Polymerization of Butadiene of t h e b y d r o o a r and Other Chemicals has been hydrogenated bonn to pmduca but+ under a vsriety of wnCoVan, Standwd Oil C-am d k w J v n diene. ditionn to pmduca butsMany inventigationa diene. In some bave been made of the vinylacetylene and hypmdudion of butadiene dmgenhavebeenpassed from butane and butylover platinum and niokel ene. Butaaecanbede catalynta at 15 to 100 hydrogenated at atmospounds pressure at pberio pressure and 1oO'C. Bubblingvinyl1 1 0 0 O F. by passing it acetylene thniugb d u over ohmmio oxide on tim, such M amalgems activsteddumins. An and water, sin0 dust and much 88 42 p a cent alkali, and other s o w conversion per p m hss Of hYdmgen, been olaimed. The hybutadiene, owing to the drwenissepareted,thus preferential byleaving butylene for tion, in this inntanca, of furtherdebydmgenation the triple bond. to butadiene. *ButylThe direct c o n d o n ene has been dehydroof ethylene into but+ genated at 600-700' c. diene has been p r o p o d and 0.25 atmwpbm in by passing t h e gas writact with sin0 oxide, throughaquart.vee8el duminum oxide, etc., M and utilidog resonsnce psrriers mted aith radiation of the vaporchmmium, vanadium, ized metal. More BUOmolybdenum, ursnium, oessfulclaimshavebeen tun@- titaniw ah,.. . made forthedirect union conium, oerium, of ethylene and ace$ylbsbnium, and thsehnn sneat3oto6oatms oxides. S t e a m bas pberes pressure and been used as a at 4000 to Mw)' c. diIurmttodsoreeaeerrin tubes containing bondepoeitsoathe rlL.Limetd&or
+
+
5
-
+
+
"wx DiT
,************
.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol.
..................... cydohol,
E@ has been heated to
I
600-800° C. in
34. Na 11
with a conversion first to the monoacetate and then to butadiene; approximately €0per mt conversion by we of two cyclea has been reportd. 8. V. Lebedex (British P a t e n t 331,482) claims the conversion of alcohob, conteining less than four carbon atom, into butadiene by the we of dehydration and dehydrogenation catalyste at suitable temperaturea and low pressure. The producta are cooled a3 quickly ea poseible to increase the yield. He hae claimed an 18 per cent conversion of
porcelain tubealilled with imn filings I with the production of butadiene. Moaohalogenated monohydric almhols passed over alumina at 350' C. yield butadiene, hydroohloria acid, a n d w a t e r . nButyraldehyde has been passed over aluminurnsilicateat 500-600" C. and Sampling the Latexlike Fluid to Make Sure the Pol meriration of 80 mm. pressure of 95 per m butadiene pert ethyl paas Butadiene Has Been Effected on Schedule in the &e Reactor to produce butaalcohol through a C o r n , SImdard 011 Comanv d New Jemv diene and water. quarts tube at The older aldol 400' C. and 0.25 process, involving atmosphere pressure, containing aluminum oxide ea a dehydration catalystand conversion of aldol (2-hydroxybutyraldehyde,C W E O H C H A H O ) to 1,3-butylene glycol has been modified by zinc oxide ea a dehydrogenation catalyst. This yield has paeaing a mixture of aldol, ethyl alcohol, and water over bean greatly improved. The theoretical yield of butadiene from alcohol is 58.1 per cent: aluminum oxide at 300" C. with a3 high &B 25 per cent conversion to butadiene. acr"--i) 2 a O H, C A 4-Methyl-l,3dioxane or butylene glycol formal has been prepared by reacting together sinc chloride, parafbnnaldeAmong the substanoes obtained during the pyrolysis of alcohol are butadiene, hydrogen,ethylene, acetaldehyde,%butene, byde, methylene chloride, and propylene. When butylene butyl alcohol, diethyl ether, methyl ethyl ketone, aldol, croglycol formal is hented at 270' C. in the presence of Bteam and tonaldehyde, h, and hexadiene. pbosphoric acid c a t d ~butadiene , is prudud. Alcohol has been converted into acetaldehyde, and a mixTetrahydmfurane has been pBesed over granulated pumice ture of alcohol and mtddehyde passed over suitable catdy&a mated with mercurow phosphate, calcium phphate, blue to produce butadiene: t,un&ic oxide, d u r n phcephate, nickel, silver, lead, and cobalt compounds at 250" to 450"C. to produce butadipma c&c" c.&oH--i) 2 W +e& Butyl alcohol has been dehydrated to butylene and then dehydmgenated to produce butadiene. The nltm4ons stndiea made of this o v d reaction indicate &poww which rmdt in a variety of prodThe number of invmtigations of the dehydration of 1,s that in-te U&. butylene glycol with the produdion of butndiene is indicstive of the tuntdihg possibilities of this p.It has been RECOVERY OF BUTADIENE heated in the presence of aulfuric wid at %XIo C. under pre+ DX5dtiea in the e8paratiw of butadiene from suhstaacar ("B with a3 high a3 80 p r cent convermion clsimed for the process Butyleneglplhasbeenpsssedovermanycatslysts sasocisted with it are indicated by the close boiling wink of such ea triethyl phosphate,. ph-horua oxychloride, phob mme other fouFcarbon compounds: pborua trichloride! phosphonc md depositad on pumiw, md milh- Point. c phosphorus, durmnum phosphste, m o d u m phosphate, -11.7 and thorium atrate and oxidea at temperaturea fmm '276' -6.7 -6.a tw35OoC. in the ure~831ceand a b c e of nddad water vwor -44 -0,s ea a diluent and at pressurea up to a~ abmphm, with ihs +1.0 production of butadiene. 1,3-Butyhe glycol has been die +8.7 tilled in the preeance of Bulfaniliaaoidandmde naphthalene Each method used for the pmduction of butadiene d t a nulfonic acid at temperatwen of 16O"to 2 4 0 O t o produce but& diene. Another Drocesa involvina the UBB of 2 , a - b u t ~ h in the pre6fmm of oertain impurities which must be removed. A b many methods give yield^ 80 low that considerable conglycol has bean iG eateaificstion &h acetic acid in theire+ ceaimtion of the butadiene is ne%sary. No economical ence of benzene and sdfurio d to form butylene diacetete. This compound is then separated by distillation methcd bss b m developed by which mme compound can be fed into one end of a tube and be converted into butadiene and passed thmugh tubea psoEaa with quartz. chip at 650' C.
+ +
+
-
uncontaminated with substencm which inpolve no Sepsration di5dties. The cheonist hss at his dieposal many mathods for the separation of tbeae constituents. The p F b h reverb to selecting those metbodagiving the best and moat economical separstion. Among the substances which have been proposed are maleic acid, maleic anhydride, dimethyl phthalate, ethylene chiomhydrin, dichlomtbyl ether, glycol aoetates, glycol monoethyl ether, lactic soid nitrile, diethyl tertrste, aniline, toluidine, pbenyl hydrasine, furfural, water, and Soetona. Isobutylene may be separated from butadiene by UBB of 65per cant sulfuric acid. Sulfur dioxide forma both crptdine (soluble) compounds and amorpbous (ioluble) compoundswith dienes. Addition of hydrochloric acid, acetyl chloride, nuUuryl chloride, tbionyl chloride, and sulfonic chlorides pmmote the formation of the desirable crystalline sulfoxides which can be separated and which, upon behg heated, easily decompose. Properties of mondone,
haw been studied in detail. Butadiene forma a f l o w solid compound with a solution of cuprous chloridd&ochloric acid, wheress butylene remain~in solution. Heating the solid compound to 30.100°C. r e l the ~ butadiene. Many aubstanoee have been prop a d aa addition agenta to the cuprous cbloride Bolntion to inita e0iciency; among theea agenta am ammonium chloride, ammonia, stannous chloride, sodium chloride, and ethylene glycol. MODERN PROCESSES
Those charged with the responsibility for butadiene production had no way of knowing how long this war will Lsst or how much synthetic rubbar will be needed each year. Two 888umption. had to be made: It DlBy be 8 long WBT, and the dermsnd for synthetic rubber will inbeyond e v ~ nthe preaent estimates. The pmgrsm for the production of butadiene had to hinge amund these 888umptioas. EIUC~ractusl =terisl 118 wBB 8vailsb1e ws ~k -bled. Among the @c pinta investigated Were:
1. Whst wan Lnown mmrdima
the d u c t i o n of
Dmcesaes wbich wera P r o d ?
4. 5.
Are hm W ldateiiae8 d b h UOW? WU these IUW mat&& wntinue to be avaikble if
the war lasts for wed vearsr
aooordingtotheprop@p~sl 7. Are the materiels avdable for the oonstmction ofPE%?'w continue, ar will the.manpwa needed for the duction of the raw mstenals and the o w tion of plaot.be avshble? to these questions &odd determine theThe policy ' the production of butadiene.
tL
T
Testing a Tank to Determine b G m and Oxygen Content before Allowing Butediene to Enter Babdlme ann01 b. dond In h n b sonhlnlng ox -.nr eo.~.qu.ntly, bdon buiadime plml i s Ih. atinqden mud be pmgd of air
-ad
Ca*.v.S~.ndUd CiIConp.nrdN~rJvnr
It ww SoQnapparent that two group of techniarl mennamely, the rublm and petroMum ch&t.v-wera the ones who had UM best baekgmm&f&the pmdnction of butediene. They had Svitd int.er&in rhlk-the formar beasus3 their oompsnieaof rubber products, and the l a t h because k-sdd g a d h e and petroleum p d u c t a dnd without tires Lhe sele 02 gssoline would dmp to a low level. Ttlemfelq118 a reutter of inauranm,these two groupl had mme background in the pmduction of butsdiene. Industrial companies earpressed their wibgmea to pool tbdr ddata on the production of butadiene. &me of this infko$tion in in the form of application for pstents Ned in the patent 0 5 c a It in obvious that such a pooling of teahnidal data would ee b l e the drsigning of plants wing tb6 beat steps. The adjustsatmt of royalties baaed on the& &pplicationa for patante which will later isme 118 petpmta must wsit until the wsr in over. There is a more importsnt
The mw materid most cloedy relsted to butsdisae is butylene. A pmoess wae a-uiilable for w n m bt@kte to A butadiene by the removal of two atolas of G t e d amount of butylene wan adlable, snd a potentisl adequate amount of butene could be produced by utiliration of mitable pro-. The s6ep frombutene to butykme is d y . Momevery&orthssbeanmadetorewverallthe butylene available without the construotion of new plants. Alcohol and ethylene therefrom were also avsilable but the demands for thesa made it impossible to consider them for the major portion of the butadiene program. This 8ppliea e q l d y well to c y c l o ~ . * The American people have been 80 tbomughly c o n f d regarding the rubber &orb?@ that a true picture in diffirmlt to present. If we deal with this in the orderly fashion with which we approach a d problem, much of the confusion should dieappear. Thus among the factual data obtainable are the following:
-.
lasl
INDUSTRIAL A N D ENGINEERING CHEMISTRY
sr sr sr sr sr sr sr
Vd. 34. No. 11
he m o t do, for suoh clsims might mult in addw confusion to the general program and thus dowing down the war &Ort. The momentary confusion in the production of but& diene is the natural result of the CMtive genius of scientiuta. If we had but one method for the production of butadiene then we would have to u88 that method. It in exaqmatiitohearpeoplestate that wewouldbebetter off were that the case. To adopt mch a philosophy or to wiab for such a state of affsirs could only mult in the defeat and downfall of this powerful nation. An long nu we preserve our democratic way of life we can expect rapid technological advance. It is probable that other methods and improvements in the production of butadiene will be discovered before the war L over, and some of them may be adapted to planta now nnder comtrnction. The following methods for the prodnction of butadiene have reached Bdiicient maturity that plants have been built, are in the pmcees of construction, or are in &e pilot plant etsge in the united staka today:
c
’I
sr sr sr
1. T h e r m a l d n n ~ l a n t . 9 2. Catalytic crack& plants to m ~ v e r tbutane into butylene and thenoe into butadiene 3. Ethyl alcohol lanta 4. Butvlena dvco?nlanm 5.
1. The stock pile of natural rubber in the United States. The stock pile of used rubber now available for reclaim
2.
=’e
.
amount of synthetic rubber in actual production at the
p m t time.
Estimaka can be made regarding: 1. The amount of natural rubber which may be imported in the near future. 2. The amount of pdak rubber which can be obtained by
fnrther sal 3. me%-%Fyou may expect fmm the tim on your own am. 4. The data of m m &on and the estimated capacity of the new synthetic rubber p ta. 5. The estimated requkpent.9 for rubber.
&’
Many propomla have been made to alleviate the rubber I have read hnndreda of them. T h m dealing with wooden w h d , spring contmp tiom, old eaaiogs sewed together, old Caeineg lilled with Bum, old casings blanketed with canvas and 0 t h ntmtagic mi+ terials are useless. I have discussed pmasees of nlaking 80 WZEWthetio rubber with individual8 whose Proabout it. fhme tive that the inventor would not tell anof these are stock promotion schemes and wi8hfulthinldng; others are device which would compete with Rube Gddfiespmt C i v d b t i O n is 80 eOaUSt0med to 8 c h t i f i O luirn~ku that credence is given to practicaUy any propod which myone ia williner to -un=. In msny hyp-5thefiosl 8dV811WS in science pses mouth to mouth* p a w to paper, anM over the air wave8 until they the h h Of truth. Pnnctwing such bubbIes d t a in the de5tion of the originator and leaven a mur taete in the mouth of anyone gullible enough to bite on the story. In time of war 110 one should want to be guilty of claiming to be able to do something nhortsge until new tires are available.
-
But51 d C X O 1 pht.9
CRACKING PLANTS
THEW ~ C K I N O . The term “quick butadiene” has been wmnwwly applied to the production of butadiene by thermal crscldng. Some have implied that it was the qui& solution to the production of butadiene and have estimated that thousands of tom of butadiene could be made availablein a few months. Othera have conceived that “quick butadiene’’ meant a method which the oil companies originated on the spur of the moment. The term “quick butadiene” haa no technical signi6cmca and should not be used. Many inveatigationa on the production of butadiene by thermal cracking have been reported in the literature. The wnditiom necemuv for hiah vields have k e n reinvesthted during rewnt mon& beca&ihe proMvls offered a w&ility of adding to the over-aU production of butadiene in the United Statea. If naphtha and light oil feed stock are thermally cracked at 13C+1400° F., some butadiene is produced. The actual vield obtsined deoenda uwn the accnracv of temperature cokrol, the methoh of a t k i n g the tem-berature, the dduents. the char& stock. and the soeed with which the spray quen& or oth& cooling &owas is attained. he time interval at the ODtimum tennoerature should not be more a fmtion of seoond. M h y methods have been used to attgin the bpmturefor theshort be of c o n ~ t . b o n g the methods pro& are:
a
1. Charging stock is mix$ with superheated steam. Steam-bydrowbon muturea are duect-cracked in regenof air ia added to tFe ing stock, thereby raising the temperatureof the ramamuq ntocg 4. Hot flue gaa at tem turps M high M m0 F. m used to raise the tempratwe oEcharging stock by direat mixing. 2.
er~~$g~mount
It is obvious that theee general methods can be modified in many ways. In some cfaea idle petroleum apparatus hss been
0 0
M
76 7
16 0
a
Sinolrir
citie8 &rrics PhiUp P"f""""
sum ilC0 Koppn Unitd KOUoitad Koppn united KOUnlted Cuhidc & chrlxm C.rbii* & C u b o m Cubicle & Cubon Cubide & Cubon cvbids &cub. Cubh&C u h Cubid. & C k h
a
1 0
6
0
10
10 10 10 0 0 0 26
aa
18 10
put into w. High-praaure equipment in operated at low prsanve in pmducing the great& Jrields of butadiene by this p-. Some equipment considered d e for operation at higb p m m m CM fit into the pmqram for making butadiene at low prrsaurss. At p-t four thermd cracking projecte ara in the pmgmm, and the wtimated production of butadiene from the49 units is 107,800 tons a year. The only cyclohexane at present contemplated 88 a charging stock ia that obtained coincidental with the naphtha and light oils used. The demand for beauem is meb that ita by-tion and pyrolyeis to butadiene cannot be developed at the present time. PETROLEUM CATALYllC CRACKJNG
By ita very nature of construction,petroleum equipment is capable of many modihtions. Cbangw in chrging stock, temperahue and P atslsats, wch condensing equipment, eta., reudt in dii7erent pmduots. Thpse factu are estrem& imwrtant and are not almm fully a~~recisted In thi pduction of butadiene from pe&le&, the ided char& stock would be butylene. The seoond choice would be a-&un, of butylene and butane, and the third choice would be butane. If butane in available and ia converted into
OTHER SOURCES OF BUTAMWE
ALCOHOL. The well-estabbhed Carbide & h b o u ChemiCSlsCorporstionpro~forbutadienefromalcoholwillbeused to pmduoe 220,000 tons of butadiene a year. Esch of these eleven unite pmduedng 2Q,ooO tons yearly will require approximstely S0,OOO gallom of alcohol per day. This mema approximately sO,ooO,ooObushels of corn for the production of 220,OOO tons of butadiene. Butadienehas been made ona commercialacale in European countries wing ethyl alcohol BLI the feed stock. The Publicker Commercial Alcohol Company haa tested the pof Waclsw S d e w i c s and reports a convmionof greater than3.8 per cent of lsO-proof alcohol into butadiene by 8 %ingle paas over a catslyst at an elevated temperature. The unconvertad alcohol and the water are separated from the hydrogen, ethylene, butylene, and butadiene. The butadiene content of the butylenebutdene mixture is reported BLI about 80 pm cant. By-product ethylem, .¶MU quantitieu of strstegio msterisls for plant construation, and availability of oatelpst are the favored clsima oh this prooesk BI~TLBNE GLTWL The p d u r e for the fermmt8tion of grain with the production of 2,3-butyIene glypol hss been Btudied at Iowa State Colleg~,the Northern Ragional Ra 6 Sons, and 0 t h
een operated in a large pilot the separetion of 2,3-butylene method utilircs butyl alcohol by sepsration of the butylene fmmthe butyl alcohol. Ewry mlve the problem of separation
mn claimed that 2,3-butyle~4glycol can be pyagreemmt on this point. It is a fact
pmducta into butadiene. Those of any consequence are in the Rubber Reserve Pool and the technical are bmg exohanged between aU p r u h conc?xned. It s b l e i t mme of the recent developments can be adapted to p under conaideration.
production qf hiph.Jields of butadiene. B r wing only one pyrolysis dumber, fobwed by awsration fmm thsmOlIoa5ekteandrecyoieof~ ,an Dvpwu c o n d o n of 88 p q aent has baen plant equipmen*. Ewt to ten of ths re
INDUSTRIAL A N D ENGlNEEBING CliEM1STBt
laga
VaL 34 k 11
..
butadiene. Brrrn ALCOHOL. C!onsiderable~wpwimentd .rrork bsk been done on the production of b u t u h e from b u t a d but thelowovmallyisldofbutadiene(pMhablylerstllsa2fiundn per bushel of grain), the equipment requimd, and otber war uaesforbutan~mskethisproeessnatthemoment. Raw Ma--. Feed stack for the production of butadiene falls into five groups: idcobol, mixed bydrocarbom, butylenebutane m i x t m , butylene, and butane. Catalysts, solvents, and otber miacellaneoun chemicals constitute the other chemical requirements of the butadiene program. By exchange of tecbnical data and proper seleotion and distribution of cstalysta, i t i s anticipated that the manufacture of tbesa raw materials will be on schedule with the completion of the plants. Likewise, determination of the solvents used in the separation and’conmtration of butadiene h made poesible early commitmentaand docstion of these chemicals. COSTS AND PRODUCTION RATES
The cost of plants is not a matter of history and therefore cannot be recorded. The eetimaka vary greatly, ea shown in the testimony before the Gillette Commit&. The fsctom which determine the merit of the process are not n d y the cost of the plant but the quantities of strategic materiala needed for its construction, the time required to construct the plant, the asBured wdability of the feed stock, and the manpower and materials to produce the feed stock.
1 1 1 1 1
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
At first it may appear that prcgresa in the production of butadiene is very slow. This is not the c m . We must not ask the technical men to do the impossible. Remennbea th& the construction of butadiene plants starts at the drawing boa&. Deeign and drafting are slow jobs, but once complete, the orders for the materialn are placed, and the sasermbly of the parta ~ o e on s more rapidly. Comidahg the state of the deaign work when this enteaprise wan launched,it h been a heavy responsibility for those aanying the buden. Only a strong and vigornus nation endowed with a wealth of raw mataridswould have the courage to undertake an output of synthetic rubber from 2600 tom in 1939,MMO in 1840, 12,000 in 1941,80,000 in 1942,826,000in 1943, and nearly l,ooO,aoO tons in 1944. The Japs have u n d h t e d ow technical ability if they thought that by taking natural rubber away from us we were licked. We willbouncelight back with synthetic rubber. Those who look upon the creation of the billiondollar synthetic rubber industq an a war baby, wbicb will dieappear with ow victorion8 conclusion of the war, may be mistaken. Those needles8 debstes on butadiene frompetroleum w. butadiene iium grain, which are based on the theory that synthetio rubber is a war baby and hence will be easier to strangle if butadiene is produced from petmleum than if thowands of fanuem are put out of work, abould end for the duration of the war. Technical men r e a h that, if improvements in the future developmenta of synthetic rubber wntinne an they have in the past, natural rubber at any price may not be able to compete with synthetic rubber. we may have only scrstched the Burfsce with these dedopments. It is ~ h b l that e plant equipment will be p t l y simplified, low-molermlsFweight butadiene polymers may be formed and used, less pure butadiene may be required, separationssimpli6ed, handling costs rn duced, and the h a l synthetic rubber greatly improved The technical men may develop short cuts and the use of low-grade butadiene and thereby make rapid advances in the output of synthetic rubber. With the equitable allocation of tmnqmrtation, careful comervation of d new and usable tiree, development of bhpmvemhts in reclaimiog rubber, adequate facilities for m a p matariale for tires, we of rubber substitutm where poanile, development witbiu the United State of natural rubber and importation of it, and the combotion of synthetic rubber plants with all w i l e speed, we bope to meet this problem. The Ammu -car, S o m m is pmud of the part ite me.mbem am shsring in this stupemdons h k . have worked to the utmoat of their ability and ask no o h dthan to have apart in ow ultimate v i m .
Synthetic Rubber Bein Taken from a Movin &It and Piled Ready for kipment
