p. 1


# OAR Box 1877 Prepped by Keeia Richards



# Document

Number: 

# 7) II-B- 4 Docket Number: 

# A-90-1 9

Printed 12/2/200810:36:46

AM Sheet 7 of 46

## P. 2



# MEMORANDU M TO : 

## Proces s Vent s Docke t A-90-1 9 

# A-9 0 

# 1 9 ll-B- 4

FROM : Wand aFloyd DATE : Octobe r

1990 SUBJECT : HO N NESHAP : Industr y Characteristics /

Acetaldehyd e Attache di s aproduct-proces s summar y (PPS ) fo

r th e productio n o

f Acetaldehyd e vi aai r oxidatio n ethylen e category . Thi s PP S was develope da s part o f th e Industria l Profil e projec t i n support

o f th e Hazardou s Organi c NESHA P (HON ) regulator y effort . Informatio n i n thi s PP S i s use da s abasi s fo r emission s an dcos t

impac t estimate s fo

r th e HO N program . Liste dbelo w ar e th e ke

y reference s use di n developin g th e attache dPPS . "Chemica l Profile " In : Chemical Marketin g Reporter . Schnel l Publishin g Company , Inc. , Ne w York . Ma

y 12 , 1986 . "Chemica l Product s Synopsis " In : Mannsvill e Chemical Products . Ne w York , February 1985 . Weissermel , Klau s an dArpe , Hans-Jurgen . Industrial Organi c Chemistry . Verla g Chemie , Ne w York , 1978 . pp . 145-150 . Shreve , R . et . al . Chemical Proces s Industries , 4t h edition . McGraw-Hil l Boo k Company , Ne w York , 1987 . p . 692 , pp . 708-710 . White , Howard . Introductio n t o Industria l Chemistry . Joh n Wile y & Sons , Ne

w York , 1986 . pp . 66-69 . Austin , Georg e T . Shreve' s Chemical Proces s Industries . 5t hedition . McGraw-Hil l Book Company , New York , 1974 . pp . 767-768 . Kent , Jame s A . Riegel' s Handboo k o f Industrial Chemistry . 8t

hedition . Va

n Nostran d Reinhol dCompany , Ne

w York , 1974 . pp . 936-937 . 1989 Directory o

f Chemical Producer s USA . SR I International, California , 1989 . p . 427 .P. 3



# EPA-450/3-80-028d . Organic Chemica l Manufacturin

g Vol . 9 : SelectedProcesses . Decembe r 1980 . p . III-l . Kirk-Othmer . Concis e Encyclopedi ao f Chemica l Technology . 3r

dedition . John Wile

y & Sons , Ne w York, 1985 . pp . 7-8 . "Acetaldehyde. " In : Chemica l Hazardou s Information Svste m(CHRIS) . U.S . Departmen t o f Transportation , 1985 . EPA-450/3-87-026 . "Appendi x D. " In : Hazardou s Wast

e Treatment . Storag e an

dDisposa l Facilitie s (TSDF) . Jul

y 1990 . Sitting , Marshall . Handboo

k o f Toxi c an dHazardou s Chemical s an

dCarcinogens . 2n

d edition . Noyes Publications , Ne w Jersey , 1985 . pp . 21-22 .

*in . 

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# CHEMICA L PROFIL E ; 

# Fro m th e Bookshel f ?> £ 

# Acetaldehyd e ,*: , SUPPL Y "-' PMOUCS R CAPACITY * 

### CiUnin.BayCTy.Tt i 22 S
, Langview , T m 47 » Total . 70 0 i o f pound * pa r year . Cslanaaa' s <8 0 iWo n poun d pa r ya r pfe M a l Clea r Lata . Ta»_ , ha a baa n W a sine * 1M1 . Prafl a laa t publalte d 5/30/13 ; tt* ravMon,S.12/M . 

### DEMAN D 1988:65 0 millio n pounds ; 1988:65 0 minio n pounds ; 1990:65 0 millio n pounds . 

### GROWT H

Historica l (1978-1988) : minu s 3. 9 percent pe r yea . future : fla t throug h 1990 . 

### PRIC E

USE S Historica l (1982-1988) : High , 37%c . pe r pound , tanktrucks ,

dh/d. ; low , 6c . pe r pound , sam e basis . Curren t 35Vic . to 37V_c . pe r pound , sam e beale .
Aceti c add , 5 0 percent ; exports , 1 4 percen t mlscelaneous , includin g lacti c ad d an d crotonaldehyde , 1 3 percent ; pyridin e an d pyriudln e basse . 8 percent ; pentaerythrttol , 7 percent ; peraceti c 

### STRENGT H

Exports remai n strong , particularly t o Mexico , totallin g ove r 8 0 frtHo n pound s las

t year , u p fro m abou t 6 5 mMio n pound s i n 1983 . 

### WEAKNES S

q^acitti ii-jizatto n i s expecte d t o b e abou t 5 0 percen t thi s yea r because o

f therepBEbmen t o

f acetaldehyd e oxidatio n b y methano l carbonylatio n ove r th e las t severa l years . 

### OUTLOO K

Aceti c aci d deman d ma

y declin e throug h 199 0 shoul d Eastma n decid e t o expen d its coa l gasificatio n ptvt t Th e expension , i f de cided upon , woul d b e i n plac e prio r t o 199 1 an d woul d subetantial y _-4____a__a____________

> _i^^Ha*_____Hu* d Jtf^ v ____*_____!__

__•_______ ! !___

. »_•__________. ^^^^k^^^^^ A
____________ _y^^A^*^ oecreese oeman a rar aceoc ac n n aceoc arwiyonue praoucoon . A s slight growt h i s expecte d fo r en d use e suc h pentaerythrtto l an d pyridinee , minima , growt h i n acetaldehyd e deman d ca n b e expecte d I

f Eastma n opts no

t t o expen d its coa l gasificatio n plan t 

# Corrosio n Contro l Covering tb e fundamenta

l coocepti , technique s an

d technology o

f corrobn, thi s book * i s presented a s a n aid (o ral l practical engineers in the process * whetherthei rbackgroun

d i s in chemical , civi l o rmechanical engineering . I tdeal s wit

h corrosio n phenomen

aan d thei rmechanisms , attributes o f material s an

d thei rcorrosio n characteristic s an d tb e corrosiv e natur

e o f environments . Th

e informatio n presented i s intended to hel p the rngintt i ant*** ! correc tcorrosio n problem s bu tto preventthem a tth e startb y selecting the***'* ! material an

d using moder

n corrosio n technology i

n design an

d application . *^** H A recen testimat e o

f th e total cos to

f corrosio n i n th e U

S put s th e figur e a tas_ _ W O billio n peryear . O

f thi s amount, perhap s f

55 billio n i s irreducible . Th e autbw* ou tthatth e breakdow

n o f material s becaus e o

f corrosio n cannotalway s b e avoided* i s italway s economical o rdesirabl e to do so . I ti aassumed well-engineera

d rr__ _ already representtb e optimum combinatio n o f construction material s an

d apptwil z 1 corrosio n control measures . Thus , barring technology breakthroughs ther e is DOWS? " ity forfurthereconomies . Fo rexample , th e corrosio n o f som e equipmen

t(toSe i lifetim e o f a n aceti c ad d planti s regarded a s simpl y one o f th e cost s o

f doin g b^W * •CORROSIO

N CONTRO

L I N TH E CHEMICA

L PROCES

S INDUSTRIES

. ^ ^ B y C . P . Dillon . Cloth . 10 9 pages. U Q laches. McGraw-Hil l Boo kCompany

, Ne wYork . N. Y m 

# Federa l Biotechnolog yActivitie s This book* presents a

n overvie w a

_.>.•

_-fit h specifi c information o

n tb e | Federal policies , issue s an

d research in i-i*

. chnotogy tha

tpertain particularl

y t o • agriculture . Ti n U

S governmentha s cv"» ' Tabl e Involvementan d fundin g i n bj___^ . ' oology research , an

d i s continuing to an..*tona e th e need forthi s researc h intht-yn^ j alread y involve d i n agricultural research alon g wit h th e agencie s thathav

e "plrilf a' relate d programs . Th e boo kurge s thatUS governmentpolicie s aa d issue s b e resolve d in suc

h awa y ia_ rj government, universitie s an d industr y can wor ktogethe ri n orderto achiev e viabl e a g ' productive results . Additionally , i ti s fel tthere mustcontinue to b e Federa l rem-**- ^ . suppor ti n thi s Hel

d alon g wit

h private research in ordert o enhance potentia l
_ * commercialization . Hopefully , thi s wil l hel p th e US to fin d solution s t

o worldrfe-- ij ^ problems , increas e agricultural trad e aa d enabl e th e nation t

o continu e t o tar n . leadershi p in th e new an

d exdtin g biotechnology industry . •PLAN T AGRICULTURE

, FEDERA L BIOTECHNOLOG

Y ACTIVITIES: B

y Caroly n Block . Cad * J 21 0 pagaa. « X »Vt Indus . Nora

s Publications, Mil

l Roa d a tGran d Avenue , Par tRidge , NJ . tri** " 119 . 

# Jh e Chemistr

yo f Glas s This book * presents dat

ao o arelativel y youn

g branc h o f chemistry , compri_i_gft*

) boundar y are abetwee n chemistry , physics , mineralogy , biology and, recently. i a awel L The fiel d represents aspecia l branc h of-high-temperature chemistr y i ai chemica l processe s o

f transformatio n o

f matte rtak e plac e an

d ha s le d t o som e r ove rth e pas ttwent

y yea n thatwould hardl

y hav e bee

n believe d possible befor

a1 thermore , i ti s likel y glas s an d silicat e chemistry wil l assum e eve n mor e impartanea

l mankin d a tth e tu n o

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y u classica l source s o

f ra w material s —oi l i ga s an d ore s —begi n t o b e deplete d a s abasi s fo rmaterial developmentan d f Th e volum e ha s been conceive d a s atex tforuniversity-leve l student s o f (__ • a an d industry . It s conten ti s largel y th e cor e o f acours e atth e Friedrich-Schilkr l slty i n Jena , Wes

tGermany , offere d sinc e IN I an d update d annually . I

n sonee r boo kgoe s beyon

d educational need

aand thu s mightb e useful to thos e alread y I th e Held . •(^EM__rniYOPGI-__&ByW.VotilTrisrtaUdbyN.Krtk_tCV)t__J_Sp-g«»«Xlt i America n Cerami c Society, Int . Coimhaa, Otrto . IM . 

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PttdvU S^Af 4 *—c£ffiSSS £ FEBRUAR Y 198 5 Cortland , Ne wYor k 13045-023 0 Previou s Report — Januar y198 3 ACETALDEHYD E FOCUS....Acetaldehyd e i s a n organi c intermediat e o r buildin g bloc k chemica l whic h ha s los t positio n i n th e U S an d mos t othe r part s o f th e worl d fo r th e synthesi s o f a variet yo f majo r chemicals . Acetaldehyd e wa s onc e use d commerciall ya s a rawmateria l fo r aceti c acid , butyraldehyde , glyoxal , glycerin , an d viny l ace tat e monomer . Althoug h Eastma n ca n stil l produc e significan t quantitie s o f coproduc t aceti c aci d fromac etaldehyde , al l o f thes e majo r chemica l commoditie s ar e currentl ysynthesize d directl yi n th e U S fro m othe r rawmaterial s and processe s whic h ar e generall ymor e economic . Aceti c acid , produce d b yth e liquid-phas e oxidatio n o f acetaldehyde , wa s previousl yth e dominan t de
rivativ e o f acetaldehyde . Methano l carbonylatio n i s currentl yth e mos t widel yuse d technolog yfo r aceti c aci d synthesis . Som e aceti c anhydride , a derivativ e o f aceti c acid , i s no wproduce d b yEastma n b

ycarbon
ylatin g methy l acetat e wit h carbo n monoxide . Wit h th e ne wprocesses , Celanes e and Eastma n place d unit s producin g aceti c aci d b yth e oxidatio n o f acetaldehyd e o n standby . Aceti c aci d mad e fromacetaldehyd e i s no t competitiv e wit h materia l mad e fromlo wcos t methanol , .excep t wher e th e acetaldehyd e ma yb e derive d fromsubsidize d fermentatio n ethano l i n countrie s suc h a s Brazil . Unde r certai n marke t conditions , East man' s coproduc t aceti c aci d mad e fro macetaldehyd e use d a s a co-oxidan t i n terephthali c aci d manufactur e ca n b e competitive . I n th e Eastma n process , paraxylen e i s oxidize d t o terephthali c aci d and acetaldehyd e i s oxidize d t o aceti c acid . Th e aceti c aci d i s recovere d rathe r tha n decomposin g t o carbo n dioxid e an d water . I n th e US , solven t ester s ar e th e secon d larges t derivativ e o f acetaldehyde . Texa s Eastma n produce s ethy l acetat e fromacetaldehyd e b ydimerization . Thi s ethy l acetat e synthesi s i s nove l i n th e U S bu t i s mor e widel yuse d elsewher e i n th e world. I n a relate d synthesis , Eastma n als o produce s isobuty l acetat e vi a acetaldehyde . Pentaerythritol, pyridines , an d peraceti c aci d ar e majo r derivative s o f acetaldehyd e whic h hav e ha d stati c o r declinin g growt h pattern s i n th e U S i n recen t years . Lowe r volum e derivative s suc h a s 1, 3 butyl
en e glycol , lacti c acid , crotonaldehyde , and chlora l ar e als o matur e commodities . I n additio n t o th e end o f o n purpos e aceti c aci d productio n i n th e US , glyoxal , viny l acetate , glycer
in , and butyraldehyd e ar e n o longe r produce d fro macetaldehyde . Th e attritio n i n derivativ e manufactur e and deman d stagnatio n i n majo r en d use s ha s probabl yreduce d U S deman d fo r acetaldehyd e t o th e rang e o f \ billio n pounds . Deman d fo r derivative s othe r tha n coproduc t aceti c aci d ha s probabl ydroppe d belo w25 0 millio n pound s pe r year . OUTLOOK....Futur e U S acetaldehyd e consumptio n wil l remai n relativel ystati c a t abou t 45 0 millio n pound s pe r yea r unles s aceti c aci d market s requir e increase d production . U S export s o f acetaldehyd e t o Canad a ar e expecte d t o continu e a t a rat e o f abou t 1 0 millio n pound s pe r year . Export s t o Mexic o wil l depen d o n fu
tur e Peme x output . U S export s t o Mexic o supplemen t productio n b yPemex . Th e pyridin e requiremen t coul d declin e furthe r eithe r becaus e o f foreig n competitio n o r replacemen t ra wmaterials . Acetaldehyd e i s th e bes t rawmateria l fo r pyridin e and th e picolines , bu t technicall ymany othe r chemical s wil l produc e pyridin e i f reacte d wit h ammonia . Acetaldehyd e i s thu s always*vulnerabl e t o replacemen t b

ysom e othe r chemica l i n thi s application . PRICING....Th e U S merchan t marke t fo r acetaldehyd e i s concentrate d i n a smal l numbe r o f buyer s o f larg e quantitie s use d t o produc e pentaerythritol, pyridines , peraceti c acid , and othe r derivatives . Excep t fo r mino r quantities , merchan t marke t sale s ar e a t negotiate d price s whic h ar e considerabl ybelo wth e publish

e d lis t price . Becaus e o f th e limite d numbe r o f producer s and majo r customers , actua l pricin g i s propri

etar yand confidential . y AVERAG E PRIC E RANG E - ACETALDEHYDE Cent s Pe r Poun d - Freigh t Allowe d - Tank s - Easter n 196 0 Trad e Lis t 1 0 PPL Y AND DEMAM). . .

196 0 Capacit yn a Productio n 100 0 Export s Deman d 100 0 196 5

1 0 •Million s 196 5 160 0 120 0 120 0 197 0

9 197 5 1 6 o f Pounds... . 197 0 20d 0 160 0 2 0 158 0 197 5 150 0 100 0 6 0 94 0 198 0 2 8 Estimated . 198 0 

## Tvio o 90 0 12 0 78 0 198 2 33 1 198 3 

## 35 ? ...Domesti c U S 198 2 80 0 65 0 3 5 61 5 198 3 80 0 70 0 6 0 64 0 198 4 ""37 ?
198 4 75 0 65 0 9 5 55 5 198 5 3 7
198 5 75 0 63 0 12 0 51 0 198 6 "3 7
198 6
45 0 198 8 3 9
198 8
48 0 199 0 4 1
199 0
48 0 Al l dat a i s estimated . U S Governmen t source s d o no t separatel yrepor t productio n o r export s o f acetaldehyde . Export s ar e principall yt o Mexico . Imports , les s tha n \ millio n pound s i n 1984 , ar e separatel yreporte d b yth e Burea u o f Census . AVAILABILITY.... Curren t U S effectiv e operatin g capacit yfo r acetaldehyd e i s betwee n 700-80 0 millio n pounds . I n addition , a n estimate d 60 0 millio n pound s o f capacit ya t th e Celanes e plan t a t Clea r Lake , T X ha s reportedl ybee n o n standbysinc e 1982 . Becaus e o f hig h acetaldehyd e expor t deman d and th e somewha t unexpecte d nee d fo r producin g aceti c aci d fromacetaldehyd e a s a coproduc t o f terephthali c acid , effectiv e capacit yha s operate d a t a rat e ove r 80S 5 fo r th e pas t fe wyears . I t i s anticipate d tha t th e U S acetaldehyd e operatin g rat e wil l dro p wel l belo w70 S fo r th e balanc e o f th e 1980' s unles s supplementa l aceti c aci d i s agai n unexpectedl yrequired . Ethylen e and derivativ e acetaldehyd e hav e bee n readil yavailabl e i n Europ e a t competitiv e prices . Thi s ha s ha d th e effec t o f reducin g U S acetaldehyd e deman d sinc e som e derivativ e manufacture , suc h a s pyridine , ha s reportedl ybee n transferre d t o facilitie s i n Europe . I n Brazil , Coperb a increase d acetaldehyd e capacit yt o 60,00 0 metri c tons/yea r b yearl y1984 . Thi s ma teria l wil l b e use d locall yfo r derivative s manufactur e o r ma yb e exported .P.2 4

PRODUCER S AM ) CAPACITIE S - ACETALDEHYD E - MILLION S O F POUND S PRODUCE R LOCATIO N198 5 CAPACIT Y Celanes e Chemica l Ba yCity , TX 25 0 Texa s Eastma n Longview , TX 50 0 TOTA L 75 0 Base d o n trad e estimates . Celanes e als o ha s 60 0 millio n pound s o f idle d capacit ya t Clea r Lake , TX . Peme x ha s 20 0 millio n pound s o f capacit ya t L a Cangrejera , Mexico . EN D USES....Acetaldehyde , als o know n a s aceti c aldehyde , ethy l aldehyde , and ethanal , i s a clea r col
orless , highl yvolatil e liqui d wit h a pungen t odor . I t i s flammabl e an d highl yreactive . Acetaldehyd e i s readil yoxidize d t o aceti c aci d o r reduce d t o ethanol . Aldo l condensatio n form s crotonaldehyd e and highe r aldehyde s suc h a s 2-ethylbutyraldehyd e an d relate d compounds . Th e aldo l reactio n o f acetaldehyd e an d formaldehyd e yield s pentaerythritol . I t condense s wit h pheno l o r ure a t o for mthermosettin g resin s fo r varnishe s and ename l oils . Wit h aromati c an d aliphati c amines , i t form s dyestuff s and rubbe r chemicals . Unti l replace d bymor e economica l carbonylatio n processes , aceti c aci d wa s th e majo r derivative . I n th e mi d 1970's , aceti c aci d productio n accounte d fo r abou t 2/ 3 o f U S acetaldehyd e consumption . Eastma n stil l produce s aceti c aci d a s a coproduc t o f terephthali c aci d usin g acetaldehyd e a s th e co-oxidant . Th e proces s i s flexibl e an d Eastma n ca n maximiz e aceti c aci d outpu t t o mee t interna l an d marke t demand . Dependin g o n Eastman' s rat e o f operation , aceti c aci d vi a terephthali c aci d ma yaccoun t fo r betwee n 3 0 t o 605 5 o f tota l domesti c deman d fo r acetaldehyde. Este r production , particularl yethy l acetat e an d isobuty l acetate , i s currentl yth e secon d larges t outlet . Eastma n produce s ester s a t Longview , T X fromacetaldehyde . th e Tischenk o proces s involve s th e liquid-phas e dimerizatio n o f acetaldehyd e i n th e presenc e o f catalyti c amount s o f a n aluminu malkoxide , activate d b

yanhydrou s aluminumchloride . Pentaerythrito l manufactur e accounte d fo r abou t 10S . o f U S acetaldehyd e consumptio n i n 1984 . Penta erythrito l i s a soli d polyo l use d principall yt o mak e alkyd resin s fo r protectiv e coatings . Rosi n ester s an d acrylat e ester s base d o n pentaerythrito l ar e als o use d fo r coating s an d inks . Othe r pentaerythrito l ester s hav e applicatio n i n syntheti c lubricant s an d specialize d fluids . I t i s als o a ra wmateria l fo r th e explosiv e PET N(pentaerythrito l tetranitrate ) use d chiefl ya s a booste r fo r TNT . Pyridin e chemistr yals o make s up abou t 10 % o f demand . Acetaldehyd e i s reacte d wit h formaldehyd e an d ammoni a t o produc e pyridine , methy l ethy l pyridine s and picolines . Thes e chemical s hav e man yuses , includ

in g surfactants , pharmaceuticals , and plastics . Acetaldehyd e i s converte d t o peraceti c aci d whic h give s u p it s peroxyge n ato mt o doubl e bonds , produc
in g epoxides , wit h aceti c aci d a s a coproduct . Th e larges t us e fo r peraceti c aci d i s a s a ra wmateria l fo r epoxidize d oils , use d a s plasticizers . Epoxidize d soybean , linsee d and tal l oil s ar e als o produce d usin g hydroge n peroxide . Unio n Carbid e continue s t o us e a peraceti c aci d rout e fo r plasticizer s an d resins . Othe r significan t derivative s o f acetaldehyd e includ e 1, 3 butylen e glycol , crotonaldehyde , lacti c aci d an d chloral . Celanes e produce s 1, 3 butylen e glycol . Eastma n aldol s acetaldehyd e an d dehydrate s th e acetal
do l t o mak e crotonaldehyde . Monsant o react s acetaldehyd e wit h hydroge n cyanid e t o mak e acetaldehyd e cyano hydri n (lactonitrile ) whic h i s subsequentl yhydrolyze d t o lacti c acid . Abou t 5 millio n pound s o f acetalde
hyd e ar e converte d t o chlora l fo r us e a s a rawmateria l fo r DD T fo r approve d applications . EN D US E PATTER N- 198 4 ESTIMAT E DERIVATIV E PERCEN T Aceti c Aci d (vi a terephthali c acid ) Ester s (include s ethy l acetate ) Pentaerythrito l Pyridine s Peraceti c Aci d Othe r 

### 5 5 1 0 1 0 1 0 

### 5 1 0 MANUFACTURING....I n th e U S an d Mexico , al l acetaldehyd e i s no wproduce d b ydirec t oxidatio n o f ethylene . Unti l th e introductio n o f ethylen e oxidatio n processes , mos t acetaldehyd e i n th e U S wa s mad e fro methanol . Smal l amount s o f acetaldehyd e wer e als o previousl yproduce d i n th e U S and elsewher e b yth e vapo r phas e oxidatio n o f propane . Overseas , i n Europ e particularly, acetylen e ha s bee n use d a s th e ra wmaterial . Becaus e o f th e bette r economic s o f direc t ethylen e oxidation , acetaldehyd e productio n fro methy l alco
ho l decline d rapidl yi n th e lat e 1960's/earl y1970' s i n th e US . Durin g th e period , U S ethano l wa s derive d fro methylene . I n recen t years , fermentatio n derive d ethano l ha s becom e a n importan t ra wmateria l fo r acetaldehyd e i n Brazil . Lo wcos t o r subsidize d fermentatio n ethy l alcoho l ma ybecom e a lon g ter mrawmate ria l sourc e fo r acetaldehyd e i n othe r countrie s b yvapo r phas e catalyti c oxidativ e dehydrogenation . I n th e direc t oxidatio n o f ethylene , proces s variation s ca n us e oxyge n o r air . Th e choic e depend s o n loca l condition s suc h a s oxyge n cost , utilit yprice s and ethylen e purity . Th e Hoechst-Uhd e proces s employ s a catalys t solutio n o f coppe r chlorid e containin g smal l quanti

tie s o f palladiu mchloride . I n th e reaction , ethylen e i s oxidize d b ypalladiu mion . Palladiumchlorid e i s reduce d t o elementa l palladiu mand HC l an d i s re-oxidize d b ycupri c chloride . Durin g catalys t regenera tion , th e cuprou 8 chlorid e i s re-oxidize d t o cupri c ion . Titanium-line d equipmen t i s use d becaus e reaction s occu r i n th e presenc e o f chlorid e ion . Th e acetaldehyd e produce d i s condense d an d scrubbe d wit h wate r fro munreacte d ga s whic h i s recycled . Crud e acetaldehyd e i s separate d fro mbyproduct s an d wate r b ya two-stag e distillation . ENVIRONMENTAL ASPECTS....Liqui d acetaldehyd e i s a ski n an d ey e irritant . Vapor s irritat e mucou s membranes . Exposur e t o hig h concentration s o f vapo r ca n induc e narcosia . Th e 1984/198 5 recommende d ACGI H threshol d limi t valu e i a 10 0 pp m fo r a tim e weighte d average . Acetaldehyd e i s o n th e EP Alis t o f suspecte d hazardou s ai r pollutants .

T o th e bes t o f ou r knowledge , th e informatio n containe d herei n i s accurate . However , w e d o no t assum e anyliabilit ywhatsoeve r fo r th e completenes s o r accurac yo f thi s report .P.2 5



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Chemical

Products

Bo x23 2 • Cortland , Ne w Yor k 1304 5 • (607)753-870 0

# Klau s Weisserme l Hans-Jiirgen Arp e 

# Industria l Organi cChemistr y Importan t Ra w Material s an d Intermediate s Translate db

y Alexander Mulle n



# Verla g Chemi e • Weinhei

m• Ne w Yor k 197 8a 

### mmoni ur n

a 

### " citabl e Jnd70-| 0 

### „ ''ymersan d i( 

### ed . fo r ex - -fibers . The c 

### syntheses , vit h NH , 0 r 

### • ^ n als o be ther e wa s still amanufacturin g capacit y (world-wide ) o

f

- > 64,00 0 t' aacetaldehyde . mainl y locate di n Eastern blo c coun tries , base don acetylene . I

n W. Germany , approx . 350,000 1 o f acetaldehyde wer

e manufacture di

n 197 6 using primarily the ethylene-base dWacker-Hoechs t process . Veb ai s th e onl y compan y possessing aplant

(80,00 0 t/a ) fo

r th e dehydrogena

tio n o f ethanol . Th e availabl e productio n figure s fo r acetaldehyd e i

n th e most importan t industria l countrie s are summarize di n th e adjacent table . From197 4 onwardth e U S figure s are no longe r avail

able ; howeve

r i n 197 5 th e productio n capacit y amounte dto approx . 730,00 0 t/a . 

# \JO|P ^ 7.3. Acetaldehyde 14 5

acetaldehyd e productio n (in millio n t) :

197 3 US A 0.6 4 W . German y 0.3 7 Japa n 0.6 1 W . Europe' ) 0.5 2 n.a . = no tavailable 197 4

n.a . 0.4 3 0.5 8 0.6 0 197 5 n.a . 0.2 7 0.5 2 0.4 0 197 6 n.a . 0.3 5 0.6 2 0.5 0

' ) estimated 

### dehyd e ha s ongl y influ

edstoc k an d rol e i n th e lydratio n o

f ermany and -a l policy . igtheoxida

ddegree . I n io n resulte d i g o f natura l lopment o f ioechs t o n l y replace d 7.3.1 . Acetaldehyde via Oxidation o f Ethylene 7.3.1.1 . Chemica

l Basi s Th e principl e r»

f th e ***-rn_*

e s s currentl y i n genera l us e - tfre 

### partial oxidatio n o

f ethylen e t o acetaldehyd e - i s base do n th e observatio n made b

y F.C . Phillip s back

i n 1894 , showing that platinu mmeta

l salt s stoichiometrically oxidiz e ethylen e selec

tivel y to acetaldehyd e while themselve s bein g reduce dt o th e metal . However , industrial applicatio n was first possibl e afte

r th e decisiv e discover

y b y Wacke r o f acatalyti c proces s using a redo x systeman dth e development o f suitabl e technologica

l operatio n b

y Wacke r an dHoechst . Th e total process , develope dby Wacker an dHoechs t

betwee n 195 7 an d1959 , ca

n b e summarize da s a

n exothermi c catalyti c direc t oxidation : manufactur e o f acetaldehyd e fro

m ethylene : vi apartia l oxidatio n o

n noble meta

l catalyst s combined wit

h aredox syste

m



### ISA , Great 'ta l acetal

t amounte d 600,00 0 t/ a cetaldehyd e ivde , whic

h "ee n discon

i e wer e shu t l y manufac

ver , i n 197 6 H 2 

### C = CH2 

### + 0.5O,' M 

### ' c 

### "'"'''CH i 

### CH O _W

_> 58kca l "24 3 y 

### /mo A (30 )
Th e catalys t

i s atwo-component

systemconsistin g o

f PdCl 2 

### an d CuCl 2 

### . PdCl 2 

### function s a s th e actual catalys t operatin g via ethylen e complex formatio n an dligandexchange . Th e essential partial step s i

n th e mechanis mar e regarde da s bein g th e forma

tion o f ar t charge-transfer

complex , rearrangemen t t o ao complex an dit s decompositio n int o th e fina l products : .principle o f Wacker-Hoechstdirec

toxida tion process* . homogeneously catalyzed , via -x-o-Pd ; ® complexes , ver

y selectiv e oxidatio n o f H 2 C=CH 2 t o CHjCH O14 6 

### 7. Oxidation Products of Ethylene

characteristic s o

f oxidatio n mechanism : intramolecula

r transfer o f O H ligando

f P d to ethyleni c C . i.e. total aldehyd e oxygen derive dfro

maqueou s medium Cl . ,O H P d 

# cr\ H2C * -i O CH
_ C l -i ©

Pd-C 2 H 4 O H C l (31 )

CH3CH O + Pd ° + 2 Cl ® + H ®
CuC U reoxidizes Pd

° t o PdCI : an

d i s itsel f simultaneously regenerated t o th e divalen t oxidatio n stat

e 

### CuC U reoxidize s the zerovalent palladiumto the divalen

t state . Althoug h numerou s othe r

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n als o conver

t Pd ° into Pd2 

### ® , copper

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t state t o th e divalent state with.0 2 

### . Th e previou s net

equatio n summarize s th e variou s reaction s takin g place . The

y ca n b e formall

y dividedinto the rapi dolefi n oxidation : H 2 

### C = CH, + PdCl 2 

### + H 2 

### 0 - . CHjCHO + P d+ 2 HC l

andth e rate determinin g regeneration : (32 )



### P d+ 2CuCl2 

### r*PdCl 2 

### + 2CuC l (33) 

### 2CuCl + 0.5O 2 

### + 2 HC

l - . 2CuCl 2 

### + H 2 

### 0 (34 ) 

### Th e rate o f bot h partial reaction s ca

n b e regulate dwit

h respec t to eachothe r

b y adjusting th e HCl content , the regeneratio n being accelerate db

y ahighe r HCl concentration . Thus , the require dquantit y o f palladiumsal

t fo r th e selective oxidatio n o

f ethylen e ca

n b e limite dto catalyti c amount s b y a larg e exces s o

f CuCl 2 

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mEthylene , Sectio

n 9.2.1.2) .

industria l operation o

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### 7.3.1.2 . Operatio n o f Process The industrial manufactur e o f acetaldehyd e ensue s i

n atwo phase , i.e. gas/liquid , system . Th e gaseou s reactio n components , ethylene , air

o r 0 2 

### , reac t wit hth e aqueou s catalys t

solutio n i n a titaniu mor

line dbubbl e colum

n reacto r afte r acidification wit

h hydrochlori c acid .

### 7.3. Acetaldehyde 14 7

(3 1



### -nt state , we n Pd " ecaus e i t e t o th e reaction s •i dolefin
HC l (32 )

(33 ) (34) 

### h respec t neratio n selectiv e mts b y a

. Sectio n Two proces s variant s hav e bee n develope da t th e sam e time : 1 . Single-step proces s - i

n whic h th e reactio n andregeneratio n ca n be conducte dsimultaneously i n th e sam e reactor . 0 : 

### i s employe da s oxidizing agent . 2 . Two-step proces s - i

n whic hthe reactio n andregeneratio n take plac e separatel y in tw o reactors . I n thi s case , air

ca n b e usedfo r th e oxidation . I n th e single-step process , ethylen e an d0 : 

### ar e fe dinto th e catalys t solutio n a

t 3 ba r an d120-130°C . 35-45*7 . o f th e ethylen e is converted . Th e resultin g hea t o f reactio n i s utilize d to distill of

f acetaldehyd e a s wel

l a s water fro mth e catalys t solution , whic

hmus t b e recycle dt o th e reactor . B y thi s mean s approx . 2.5-3. 0 m3 

### H : 

### 0/ t acetaldehyd e are recycled . I t i s necessar y t o us e apure 0 2 

### an dethylen e (99. 9 vol.-% ) feedin order t o avoi dethylen e losse s whic h wouldotherwis e occu

r o n dischargin g th e accumulate diner t gas . I n th e two-step process , ethylen e i s almos t completely con verte dusing th e catalys t

solutio n at

105-110° C and1 0 bar . Afte r reducin g th e pressure an ddistillin g of f a n acetaldehyde/ H 2 

### 0 mixture , th e catalys t solutio n i s regenerate dusing air a t 10 0 ° C an d1 0 ba

r in th e oxidatio n reacto r

andthe n recycle dt o th e reactor . Sinc e th e 0 2 

### in th e air i s thereb y largely removed , a residua l ga s wit hahig hN 2 

### conten t

i s obtaine dwhic

hca n b e useda s a n iner t gas . Th e advantage s o

f th e total ethylen e conversio n an dth e applicatio n o f ai r contras t wit hth e disad

vantage s (greate r

investment

arisin g fro

mth e doubl e reacto r systema t highe r pressure an dth e catalys t

circulation) . I n bot hprocesse s th e aqueou s crud e aldehyde i s concentrate d an dpurifie dfro

mby-product s sucha s aceti c acid , croton aldehyde an dchlorin e containin g compound s b y atwo-step distillation . Th e selectivitie s are almos t equal (94% ) i

n bot h cases . I n 1978 , th e world-wide capacitie s o f th e plant s operatin g ac cordin g t o th e Wacker-Hoechs t proces s were approx . 2. 6 mil

lion t acetaldehyde . tw o variant s ar e possible : I single-ste p process , reactio n an dregener atio n i n same reactor , i.e. O , an dC : H 4 kee p catalys t

i n astationary , activ e stat e 2 . two-ste p process , reactio n an dregenera tio n i n separat e reactor s wit

h exchang e o

f catalys t charg e (activ e an dinactiv e form) characteristic s o

f single-ste p process : incomplete C,H 4 conversio n require s re cycling o f C,H 4 , i.e . C ; H 4 an d0 , mus t b e largely fre e o f inert s

characteristics o

f two-ste p process : tota l C 2 H tconversion allows highe rshar e o f iner tcomponents , regeneration wit h ai r saves ai rfractionation plant, bu

tcatalystcirculation consumes mor

e energ y tha n gas recycling method higherinvestmentcosts becaus e o f doubl e reacto rset-u p

isolatio n o

f acetaldehyd e via two-ste p purification : 1. separation o

f low boiling substances (CHjCl , C2

H 5 C1 , C0 2 , C 2 H 4 ) 2 . separation o

f hig h boiling substances (CHjCOOH , CH 3 CH=CHCHO , ClCH2 CHO ) expansion o

f Wacker-Hoechstprocess : world-wide capacit

y - approx. 2. 6 million t/ a(1978 ) 

### i n atwo inonents , :utionin a itio n wit h 7.3.13 . DevelopmentTrend s The majo r amount o f acetaldehyd e (dependin g o n countr y approx . 50-70% ) i s processe dt o aceti c acidan daceti c anhy

dride . Therefore eac h variatio n in th e aceti c acidmarke t mus t affec t the acetaldehyd e situation . I f anothe r mor e economica

l CHjCH O i s economically ver y closely boun d to AcO H a

s it s mai n secondar

y produc t

### 14 8 7 . Oxidation Products of Ethylene

c > CH 3 CH O converte dt o AcOH : Western Europ e 197 0 US A 197 4 Japa n 197 4 6 9 5 0 5 8 othe r AcO H manufacturin g processe s ca n therefor e affec

t th e CHjCH O productio n e.g. high an dlow pressur e carbonylatio n of CHjO H a s oil independent AcO H pro cesse s
o r othe r acetaldehyd e processe s with : I . cheape r feedstocks , e.g. ethan e (Lummu s process )

. simpler operatio n o

f process , e.g. b

y heterogeneousl y catalyze dC,H 4 gas phas e oxidatio n (UC C process )

acetaldehyd e manufacture fro methano l ac cordin g t o dehydrogenatio n principl e wit h tw o proces s variants : 

### manufacturin g proces s fo r aceti c acidshoul dgain i

n importanc e i n the future , thi s wouldhav e a n unavoidabl e effec

t on acetaldehyd e manufacturin g capacity .



## fPr. a b 

### Suc heconomi c pressure couldb e exerte db y th e carbonylatio n o f methanol , sinc e synthesi s ga s represent s th e net ra w materia l bas e (cf. Sectio n 7.4.1.3) . Processe s employing ethan e directly , insteado f th e mor e valu

abl e ethylene , t o manufactur e acetaldehyd e - e.g. i n CuO-CuCl 2 

### melt s (Lummus ) - coul dals o b e o f interest , i f thes e processe s ca

n b e industrially operate dunder economi c condi

tions . Alternativ e processe s suc ha s th e gas-phas e oxidatio n o f l ethylen e o n heterogeneou s catalys t systems , e.g. base do

n I Pd-V 2 

### 0 5 

### (UCC) , hav e no t foun dan y industria l applicatio n u

p I until now . 7.3.2 . Acetaldehyde fro

m Ethano l Analogou s t o th e manufactur e o f formaldehyde fro

m methanol , acetaldehyd e ca n b e obtaine db

y catalyti c dehy

drogenatio n o

f ethanol : C 2 

### H5 

### O H -££!••

> CHjCH O + H2 

### (\H

. 20kcal , ,\ + 84k J /mo 1 Ift : o f hyc l da t

(35 ) I n t

int : mi x cat * atu i tio n 

### in g vers pro C O

1 . endothermi c dehydrogenatio n favore d wit h C u metal unde r

H 2 formatio n 2 . exothermi c oxidativ e dehydrogenatio n wit hA g metal unde r

H 2 0 formatio n
to I: ethano l dehydrogenatio n wit h proces s characteristic : limitatio n of

conversio n via temperatur e regulatio n 

### I n contras t t o th e methano l manufacture , a n oxidatio n i s no

t useda s a n alternative . Instead , tw o modification s o f th e dehy

drogenatio n ar e customary : 1 . Dehydrogenatio n o n silver , o r preferably copper

catalysts , as wel l as : 2 . oxidativ e dehydrogenatio n wit hsilve r catalyst s i

n th e pre senc e o f oxygen . Tol: I n th e USA , fo

r example , th e dehydrogenatio n o f ethano l is mainl y conducte do n Cu-catalyst s activate dwit h Zn , C o o r

Cr . A frequently applie dproces s originate s fro mth e Carbid e & Carbo n Corp . Th e temperatur e i s regulate dt o 270-30 0 ° C s o that th e ethano l conversio n i s limite dt o 30-50% . B y thi s mean s an acetal

Acc* th e pro p pha s cata i at 4 1 oxi d 7.4. 1 15- : mai r

### 7.3. Acetaldehyde 149

rtanc e 1 

### acet dehyde selectivit y o f approx . 90 % ca

n be attained . The by

product s formedare ethy l acetate , highe r alcohols , and ethylene . The simultaneously resultin g hydrogen ca n b e direct

l y employe dfo

r hydrogenation s on accoun t o f its purity . latio n aterial

- valu

- •ga i n 

### fthes e condi

tion o f e don io n u p

dehy

- (35 ) is not dehv



# tf £ *•* . -** " .

- * < To 2:



### I f the dehydrogenatio n o

f ethano l is conducte di

n th e presenc e o f air o r oxygen , th e concomitant

combustio n o

f th e resultin g hydrogen supplie s th e necessar y heat o f dehydrogenatio n (oxi

dativ e dehydrogenatio n or autothermi c dehydrogenation) :



# I C 2 

### H 5 

### OH + 0.5O 2 

### - • CHjCHO + H 2 

### 0 (36 ) At f 43 kcal , 18 0 k j /mo l 

### I n the industrial process , silve r catalyst s are preferentially used i n th e for mo f wir e gauze s or

crystalline charges . Ethano l vapor s mixedwit hair at 3 ba r an da t 450-550° C are ledover

th e catalyst . I n accordanc e wit hth e amount

o f air acertai n temper ature ensue s a

t whic h th e heat o f oxidatio n an dhea

t consump tio n o f th e dehydrogenatio n compensate on e another . Depend

in g o n th e reactio n temperatur e ther e i s 30-50 % ethano l con versio n pe r

pass , th e selectivit

y bein g 85-95% . Th e by

product s are aceti c acid , formic acid , ethy l acetate , CO , an d C0 2 

### . I n bot hproces s modifications , th e acetaldehyd e i s separate d fro mth e non-reacte dalcoho l an dby-product s via variou s washe s anddistillation s andthereb y purified . Th e ethano l reco vere dfro mth e abov e i s recycle dt o th e reaction . to 2: oxidative dehydrogenation wit h proces s characteristics : , dehydrogenation a

s primar y step , oxidatio n a s secondar

y step

mos teconomi c operation : thermoneutral , i.e. measure d amoun to f ai r bring s hea tevolutio n an

d consumption int

o equilibriu m

bot h proces s routes characterized b y incom plete ethanol conversio n (30-50% ) an d thus b y involved distillatio n an

d recycle op eration s •its , a s 

### pre ano l i s orCr . •id e & thano l acetal

7.3.3 . Acetaldehyde via Cj/C 4 

### Alkane Oxidatio n Accordin g t o aproces s develope db y Celanes e andoperate din th e US A sinc e 194 3 (capacit y in 1969 , approx . 160,00 0 t ) propan e or

propane/butan e mixture s ca n b e oxidize din th e ga s phas e t o produc e mixture s containin g acetaldehyde . Th e non catalyti c reactio n take s plac e according t o aradica l mechanis m a t 425-460° C an d7-2 0 bar . A variant o f th e Celanes e butan e oxidatio n proces s conducte din th e liqui dphas e (cf. Sectio n 7.4.1.2. ) employ s oxyge

n o r air a s oxidizing agent . Approx . 15-20 % o f th e hydrocarbo n i s completely oxidized . The re maining complex reactio n mixtur e contains , beside s acet les s importan tacetaldehyd e manufactur e fro m Cj/C 4 alkanes wit

h proces s charac teristics : radical , unselective oxidative degradation lead s t o numerous oxidatio n product s

### 15 0 7 . Oxidation Products of Ethylene

involve dproduc t

.eparatio n require s con siderabl e investment

an doperatin g costs , essentiall y determinin g the economi c outcom e

application s o

f acetaldehyde : almos t n o direc t use , bu t importan t

secon dar y product s such a s CHjCOOH . (CHjCO).O . H 2 C=C=O.CH,COOC,H, . CH 3 CH=CHCH O n-C 4 H,0 H C 4 H 0 CH(C,H«|CH,0H . etc. tendencie s i

n acetaldehyd e application : increase i n AcOH/Ac 2 0 shar

e decreas e i n /i-butanol/2-ethylhexano l shar e



# <J

acetaldehyd e applicatio n dependento n country : Japan : ethyl acetat e peracetic aci

d co-oxidatio n o

f p-xylen e W . Germany : ethy

l acetat e 

### aldehyde , mainl y formaldehyde , methanol , aceti c aci d M-propanol , methyl ethy l ketone , acetone , andnumerou s othe r oxidatio n products . The separatio n o

f th e oxidizedproduct s take s plac e afte r de

composing th e peroxide i

n a n involved , an

dtherefore costly , combinatio n o

f extraction s an ddistillations .
7.4 . Secondar y Product s o f Acetaldehyd e Acetaldehyd e i s a

n importan t

precurso r fo r th e manufactur

e o f numerou s organi c heav

y chemicals , e.g. aceti c acid , acetic anhydride , ketene-diketene , ethy l acetate , crotonaldehyde , w-butanol , 2-ethylhexanol , pentaerythritol , chloral , pyridines , an dman y others . Th e followin

g tabl e (Tabl e 7-5 ) relatin g t o th e consumption breakdow n fo

r acetaldehyd e show s clearly tha t th e manufac

ture o f aceti c aci dan dit s anhydrid e account s fo r th e greatest , as wel l a s a n increasing , share o

f th e acetaldehyd e production . Furthermore , i

t ca n als o b e seen tha

t th e manufactur

e o f n-butano l an d2-ethylhexanol , base do n acetaldehyde , ha s be

com e mor e andmor

e displace di

n favo r o f th e propen e hy

droformylatio n (cf. Sectio n 6.1) . Tabl e 7-5 . Breakdow

n o f Acetaldehyd

e Consumptio

n (i n wt.-%) .

Aceti c aci d an d anhydrid e •t-Butano l 2-Ethylhexano l Variou s (e.g. ethy l acetate , pyridine , alkylpyridine s etc). 197 0 45 1 9 1 7 1 9 US A 197 4 5 0 1 4 1 1 2 5 Japan 197 0 197 4 4 8 5 8 1 8 1 7 1 5 1 9 2 5 BR

D 1975 70



### -

- 30 

### Acetaldehyde' s share o

f th e product s liste dunde r "various " differs fro mcountr y t o country . For

example , i

n Japan approx . 14 % o f th e acetaldehyd e productio n was usedfo r ethy l acetat

e (1974 ) wherea s th e correspondin g W . German figur e (1975 ) was a s muc

h a s 20% . Thi s acetaldehyd e applicatio n doe s no t exis t i n th e US A (cf. Sectio n 7.4.4) . In Japan afurthe r 7 % wa s employe di

n 197 4 fo r th e manufactur

e o f peraceti c acid(cf. Sectio n 7.4.1.1 ) andi

n th e co-oxidatio n o

f /••-xylen e to terephthali c

area s poss e Germanv . 7.4.1 . Acet Aceti c acid quantitative US A i n l l 

### countr y (T acidprodu ' Japan th e recession , wit h almo s Tabl e 7-6 .
US A W . Germa i Japa n The prod t I n som e c b y th e f e vinegar ) t is obtain e approx . 1 duce din syntheti c For man \ fro mace : processe : Wacker ; Aceti c a c facturing stock fr c Moreov * drocarb i ligh t pa : BP.Cel . o f th e CP.3 3 

# SH-3* 7

fourth edition 

# CHEMICA

L PROCES S INDUSTRIE S

R . NORM S SHREV E late ProfettorEmeritus of Chemical

Engineering Purdue L'nivenity 

### JOSEP H A . BRINK , JR . Consulting Chemical

Engineer Profettorand

Chairman of

Chemical

Engineering Washington State University

McGRAW-HIL L BOO KCOMPAN Y .V w York St. Louil

San Franciico Auckland BogoU DOlseldorf

Johannesburg London Madrid Mexico Montreal .Vtt rDelhi Panama Pari. Sao Paulo Singapore Sydney Tokyo Toronto 

# RADIA N LIBRAR Y

DURHAM , N.C .P.3 4

69 2 [Chap. 38]Petrochemicals TABL E 38. 4 Petrochemicals from Ethylene in 1974

Refinery crocke d gas e Produced annually, millions Basic derivatives Ethvlen e oxid e Vi adirec t oxidatio n Vi achlorohvdrin Ethv l alcoho l (industrial ) Fro methylene . 9 6 B y fermentation . 4
Polvethvlen

e Stvrene Fro methvlene andbe

n Ethv l chlorid e Ethylene plu s hvdroge

n Qilorinatio n o

f ethan e Ethvlen e dichlorid

e B v direct chlorination 1 By-produc t o f ethylene Ethylen e dibromid

e and

sources 

### %

ien e (o r reformate }

chlorid e major ) chlorohydrin production of pounds 4.26 0

2.00 0

8.-15 0 6.40 0

65 9
9.30 0
32 5 Uses, %

Clvcols , 5 Glvco l ethers . 7 Ethanolamines , 6 No n ioni c detergents . 1 1 Other . 1 1 Aldehvdes . 1 4 Othe r chemicals . 2 6 Solvent . 1 2 Flavors , cosmetics , detergents . 3 0 Other . 1 8 Film, sheet , molding , an

dextrusion . 9 0 Polvstvrene , 5 1 SBRan dlatex . 12. 5 Miscellaneou s resins . 29. 5 Other . 7 TEL . -8 0 Mino r amount s fo

r othe r et h vi ation s (suc h a s ethyl cellulose) Vinv l chloride . 7 8 Scavenge r i n antiknock

fluid, 3 Other , 1 9 Scavenge r i n antiknock

fluid. 5 0 Source: Chem. Mark. Rep. (1974 . 1975) . (cotolyst ) Polyethylen e Ethonolomine s Ammoni a Oxyge n (catalys t Ethylen e

Chlorohydri n AlKcl i Ethylen e oxid e Wate r Hydroge n cyanide ,
Chlorin e Ethylen e

dichlorid e ETHYLEN E 

# a Hydroge n chlorid e Dehydro genatio n Acrylonitril e

Bromin e Ethylen e dibromid e Viny l chlorid e

Crackin g o f ethone , propan e " A \ \

Hydroge n \ \ \ chlorid e \ \ Wate r \ (catalyst ) Sulfuri c aci d Benzen e Ethy l chlorid e

Sulfuri c ester

s Ethylbenzen e Wate r f Ethy l alcoho l
Styren e •**•* " Polyglycol s
Ethylen e gi >cg l

Oi-an d triethyi n glycol s

Alcohol s o r alky l phenol s

Glyco l ether s O M ' polyglyco l ethers

Fig. 3S. 2 Petrochemical s fro methylene . [McGraw-Hill Encyclopedia, vol. 10. p. .6 . 1966 (newe r plant s fo r acrylonitii k ste mfro mpropylene) : se

e als o Chem. Eng. Dcskbook. 80(23) . 3 4 (1973). | (catalyst )

Fig. 38.3

Petrochemical s fro m propylen e a n fo r acrylonitril e 3te m fro m propylene—se e text . sume r o f butadiene ; isobutvlen e (rubber) . Che' Important a s thes e chemica

l co i i n th e genera

l chapter s o

f thi s book . • in g text . Chemica

l engineer s dire* chemica l econom y have calle

dupo n t o improve their

manufacturing i

n ai l Indeed , awell-develope

dchemica l pr a"system." 1 1 "Svstems, " accordi r 1961 . "White (Atlanti

c Refinin g Co.) , ChetmcaP.3 5

70 8 [Chap. 38]

Petrochemicals 

### k0*dw<,i-r.->y •?• * .3 . •>Wrf, i/( i



# PU.S . oxyge n capacit y production , o r 17.00 0 tons/da y i n 1976 . i s consume di n th e chemica l industry Sitti g point s ou t

tha t oxyge n i s ofte n mor e economica l tha n air . largel y becaus e o f enhance dyield reduce drecycl e intervals , highe r reactio n rates , reduce dequipmen t size , an dreduce dhea t los s nitrogen . Th e reaction s ar e carrie dou t i n both th e liqui dan dvapo r phases , usin g avariet

y f catalysts . V 2 0, . for

example . In th e latte r

case , fairl y hig h temperature s (abou t 400°C ) ar e employ d and . sinc e th e reaction s ar e highl v exothermic , th e proble mo f hea t remova l i s alarg e one . Oxidat i give s synthesi s ga s (Chap . 71 . bu t hydrogenatio n convert s th e C O t o methanol , henc e th e lat t chemica l i s presente dunde r Hvdrogenatio n (q.v.) . Th e Celanes e Corp. . a

t it s larg e plant s a

t Bisho p an dPampa . Tex. , oxidiz e propan e an dbuta n a s suc h o r

a s LP G an dobtai n alarg e numbe r of oxvgen-containin g chemicals . Ai r ha s bee n use dbu

t i n recen t enlarge doperations , increas e i n productio n ha s resulte dfro memplovin g oxvgen . Som e o f th e product s ar e methanol , aceti c acid , aceti c anhvdride . formaldehvde . acetaldehvde . aceton e butvraidehvde . ethvl acetate , butanol . an dvinv l acetate . Partial oxidation i s employe dto rais e the temperatur e an dt o oxidiz e partiall y ahydrocarbon , e.g. . natura l ga s to mak e acetvlen e (Chap . 7 ) o r unde r othe r condition s to furnis h channe l blac k (Chap . 8) . I

t i s reporte dtha t

Celanese' s ne

w acetaldehvd e plan t

a t Ba v Citv . Tex. , involve s th e larges t us e of titaniu mye t

reported . LPGoxidation take s plac e wit h air . Create r

productio n i s obtaine dwit h oxvge n fo

r an v give n plan t size . Product s prepare dwithou t acatalvs t

ar e acetaldehvde . formaldehyde , methanol , an d man v oxvgenate dpetrochemicals . Th e longe r th e normal-paraffi n chai n lengt h an dth e highe r the pressure , th e easie r

th e oxidation . Catalyst s ar e importan t an dselective : acobal t

catalys t wit h liquid

phas e butan e vield s 76 % aceti c acid , an d6 % formi c acid , wherea s amanganes e catalys t furnishe s 62 % aceti c an d23 % formi c acid , this bein g th e experienc e of Celanes e a t

Pampa. 4 7 Tex. , fo

r butan e liquid-phas e oxidatio n a t 80 0 psi g an d175°C . Acetaldehyde^i s produce dcommerciall y (abou t 1,60 0 millio n lb i n 1976 ) b y four methods : 1 . Bv th e hydratio n o

f acetvlene : C,H 2 + H 2 0 • CH3 CH O Yiel d95% , conversion 55 % Acetvlen e i s passe dint o asuspensio n o f ferri c an dmercurou s sulfate s i n sulfuri c aci dunde r apres sur e of 1 5 ps i betwee n 7 0 an d100° C (maintaine db y th e hea t of reaction) . 2 J Frgfl}

- eHij!_alcohol . vapor-phase dan doxidize dt o acetaldehvd e b y passin g throug h acoppero r silver-gauz e catalvst : C.H.OH^ ) -KW 2 (£ ) -*^ » CH 3 CHO(£) + H 2 0(# ) L\H = -4 3 kca

l Yiel d85-95% , conversion 20-35 % Th e produc t

i s recovere db y scrubbin g with ethy l alcoho l an drectifyin g t o giv e 99 % acetaldehyde . ."• j Frnif l ethvlen e b v th e Wacke r proces s develope db y Hoechst 4 9 for th e direc t

oxidatio n o

f ethvlene , usin g eithe r

ai r o r 99 % oxygen . Th e catalys t i s a n aqueou s solutio n o f coppe r chlorid e (promoter ) an dpalladiu mchloride , throug h whic h ethylen e with ai r o r oxyge n i s passed : CH 2 :CH 2 + PdO , + H 2 0 — P d+ 2H Q + J0 2 > Pdd 2 • CH 3 CH O + P d+ 2H Q

riptions
. rrOr.nrP.
. flowcharts. ''Sittig . Combinin g Oxyge n an d Hydrocarbon s forProfit , chap . 7 . pp . 101- I Itl . F u and tabulate d variation s wit h change s in temperatur e an d pressur e on oxyge n ratio . 48 Goldstein . op. cit.. p . 332 ; Sittig . Combinin g Oxyge n an d Hydrocarbon s fu rProfit, pp . 232-23 4 (flowchartfo roxidation fro m alcohol) . *•" Hydrocarbo n Process. S2(ll) . 9 1 (1973) . Th e acetaldehyd e i s vaporize df n Th e acetaldehyd e i s distilled . T depicte di

n Fig . 38.11 . 4 . Fro mlower

paraffins , produce , amon g man y othe r co m i s reasonable , onl y 1 5 to 20 % i vieldin g condensabl e organi c pr o uct s a s pur e component s requir t Acetic acid

51 and anhvdn Man y alternativ e route s ar e avai Th e acetaldehyd e i s oxidiz f catalys t presen t t o preven t

th e I abou t 6 0 psi , an dth e temperat u ar e separate dan dpurifie di n a_ operatin g unde r

vacuum . I

n 19 ' l b of aceti c anhydride . Th e m o acetate . It

i s als o employe di

n v _ o f acetaldehyde-monoperacetat e
2CH 1 CH O - 0. , ultrauol. i Irzh i
b y th e controlle dlow-temperatu epoxide s o r

2 mo l of

aceti c aci d Ethylene oxide 03 i s a n im p ethylen e oxid e produce dbein g wear out , abou t

one-fift ho f al l e t hydrin , bu t

a n increasin g amo c ethylene : CH. ,

ten-fair? • \ " _..-imp.. . • .t_l , . CH. , Yiel d55-65% , conversion pe

r Productio n i

n 197 4 wa s 4.2 6 bi . Aromatic oxidation 5 *prodt. indicates , ther e i s afundament ; petroleum . Se e als o Fig . 38. 4 a i OXO - O RHYDROFORMYLA . aldehyde s and/o r

alcohol s contai n "Hoechs tReveal s Wacke rProcess . 42(11) . 1963 ; Cuccioni . Acetaldehvd e via 51 Goldstein . op. cit.. p . 373 ; Sittig . Chemicals . Chem. Eng. (.V.K.I . 81(2) . 12 . "Phillip s e tat.. U.S . Pat. 2.804.47 3 ^Goldstein , op. cil.. pp . 156-159 : h ••••Phthali c anhvdrid e flowchart. Fig . ." • ****Groggins

. op. cit.. pp . 651-69 3 an < Ox o Slav s i n th e Race . Chem. tfeek. Jun e976 . i s consume di n th e chemica l industry , a n air . largel y becaus e of enhance dyields , equipmen t

size , an dreduce dhea t los s t o ui dan dvapo r

phases , usin g avariet v o f temperature s (abou t

400° Q ar e employe d n o f heat remova l i s alarg e one . Oxidatio n i s th e C O t o methanol , henc e th e latte r Pampa . Tex. , oxidiz e propan e an dbutan e itainin g chemicals . Ai r

ha s bee n used , bu t •esulte dfro memployin g oxvgen . Som e of le . formaldehyde , acetaldehvde . acetone. , 'artial oxidation i s emplove dt o rais e th e atura l ga s t o mak e acetylen e (Chap . 7 ) o r 8) . I t i s reporte dtha t

Celanese" s ne w us e of titaniu mvet

reported . io n i s obtaine dwit

h oxvge n for

an v give n taldehvde . formaldehyde , methanol , an d •paraffin chai n length an dth e highe r th e in dselective : acobal t

catalys t wit h liquid

-

. wherea s amanganes e catalvs t furnishe s o l Celanes e a t

Pampa. 4 7 Tex. , fo r

butan e H O millio n lb i

n 1976 ) bv four

methods :

•us sulfate s i

n sulfuri c aci dunde r

apres heat of reaction) , ''taldehvd e b v passin g throug hacopper - \H * -4 3 kca

l

n drectifyin g t o giv e 99 % acetaldehyde

- •> y Hoechst 4 9 for

th e direc t

oxidatio n of a n aqueou s solutio n o f

coppe r chlorid e wit h ai r o r oxvge n i s passed : Halogenation and Hydrohalogenation 70 9 Th e acetaldehyd e i s vaporize dfro mth e solutio n an dabsorbe di n water , separat e fromresidua l gases . Th e acetaldehvd e i s distilled . Th e conversio n an dyiel dar e approximatel y 95% . A flowchart 30 i s depicte di n Fig . 38.11 . 4 . Fro mlowe r

paraffins . Propan e an dbutan e ca n b e oxidize dwit h ai r noncatalvticall v t o produce , amon g man v othe r compounds , acetaldehvd e an daceti c acid . Th e selectivit y o f th e proces s i s reasonable , onl v 1 5 t o 20 % o f th e paraffi n bein g oxidize dt o C O an dCO. . an dth e remainde r yieldin g condensabl e organi c product s suc h a s acetaldehvd e an daceti c acid . Recover v of th e prod

uct s a s pur e component s require s specia l distillations . Acetic acid

51 and anhydride usin g oxyge n ar e produce db y th e oxidatio n of acetaldehvde . Man y alternativ e route s ar e availabl e (e.g. , fermentation . Chap . 31) . Th e acetaldehyd e i s oxidize db y ai r with methy l acetat e diluen t an dwit h manganes e acetat e catalys t presen t t o preven t

th e formatio n o f

explosiv e amount s o f

peraceti c acid . Th e pressur e i s abou t 6 0 psi , an dth e temperatur e a t 5 0 t o 70°C . Th e products , aceti c anhydrid e an daceti c acid . ar e separate dan dpurifie di n aserie s o f bubble-ca p columns , th e crud e stil l an dth e anhydrid e stil l operatin g unde r

vacuum . I n 1974 , 2,27 7 millio n l b o f aceti c aci dwer e produce dand . 57 0 millio n l b o f aceti c anhydride . Th e mos t importan t

us e o f aceti c anhydrid e i s i n th e makin g o f cellulos e acetate . I t

i s als o employe di n variou s othe r acetylations . A development 5 2 ha s bee n th e productio n o f acetaldehyde-monoperacetat e (AMP ) 0---H 0 H 2CH 3 CH O + 0 2 u "3t' lif> " . CH 3 3 ^ 0 0 CH , o° c b y th e controlle dlow-temperatur e oxidatio n o f acetaldehyde . Th e AM P ca n b e use dt o produc e epoxide s o r

2 mo l o f

aceti c acid . Ethylene oxide 53 i s a n importan t chemica l intermediate , yieldin g ethylen e glyco l (hal f o f th e ethylen e oxid e produce dbein g s o consumed) , ethanolamines , an dacrvlonitrile . Unti l th e plant s wea r out . abou t

one-fift h of al l ethvlen e oxid e i s stil l bein g mad e b v th e ol dproces s throug h chloro

hydrin , bu t

a n increasin g amoun t eac h yea r

i s manufacture db y ai r o r oxvge n actin g o n pur e ethylene : C 2 H 4 + |0 2 

### J__________

_ 125-30 0 ps.. ' calaKs t CH. , I \ I / CH , ;0</r l _./ / = -3 5 kca

l
Yiel d55-65% , conversion pe

r pas s 25-50% , Productio n i n 197 4 wa s 4.2 6 billio n lb . Aromatic oxidation 54 products ar e include di n variou s chapter s o f thi s book . A s Tabl e 37. 6 indicates , ther e i s afundamenta l chang e i n th e sourc e of aromatic s fromcoa l an dcoa l ta r t o petroleum . Se e als o Fig . 38. 4 an dTabl e 38.6 . OXO

- O RHYDROFORMYLATION 5 5 Th e ox o proces s i s ametho dof convertin g o-olefin s t o aldehyde s and/o r

alcohol s containin g on e additiona l carbo n atom . Th e olefi n i n liqui dstat e i s reacte d

' I II - lul l ,l.-., T ,i..n-
. r.*>r.n.-.**
. fl"«**h*'"- ratin
. ' - I' T Hn.ni
. pp , 232-23 4 |llu»<*har i fo roxidatio n •"Hoechs tReveal s Wacke r Process . Chem. Eng. \etis. Apr . 17 . 1961 . p , 52 : Petrochemica l Handbook : Pet. Rrnner. 42(11) . 1963 ; Guccioni . Acetaldehyd e vi aEthylene Oxidation . Chem. Ung. (V . >".) . 70(251 . 15 0 (1963i . •^Goldstein , op. cit.. p . 373 : Sittig . Acetic Aci dan dAnhvdride . \oves . 1965 : Austin . Industriall y Significan

t Organic Chemicals . Chem. Eng. (V . )*.) . 81(2) . 12 8 (1974) . "Phillip s et

ai. U.S . Pat . 2.804.47 3 (1957) . "Goldstein , op. cit.. pp . 156-159 : Hydrocarbon Process.. 52(11) . 12 9 (1973) . "Phthali c anhydride flowchart. Fig . 34.12 : Hydrocarbon Prore.tt.. 52(11) . 15 9 (1973) . ****Groggins

. op. cit.. pp . 651-69 3 an

dparticularl

y p . 68 3 (kinetic s an

dflow diagram) : Goldstein , op. cil.. pp . 204ff. : Ho w Ox o Stay s i n th e Race . Chem. Week. Jun e 6 . 1964 : Hahn . op. cit.. pp . 104-116 .P.3 7

71 0 [Chap. 38] in a single stage, using oxygen

Ethylen e 1

Oxyge n Petrochemical Recycl e ga s s

Gaseou s reactio nREACTIONANDREGENERATION mixtur e ; d strea m

a _ U J S o h - !/* > i •* —water

Acetaldehyd e solutio nDISTILLATIONDEGASSING

Wate r • Wast e ga s

or in two stages, using air Reactio n mixtur e wit h catalyst .

Offga s

Ethylen e Wast e ai r



## 1

S.. 2 2 = Ai r Crud e acetaldehyd e
U J a
Uju . QU J Spen t catalys t acetaldehyd e

•Wast e ga

s

solutio n Fig. 38.11 Oxidatio n of ethvlen e t o acetaldehvd e b v th e Wacke r process . Acetaldehyd e

wit h amixtur e of

hydroge n and carbo n monoxid e i n th e presenc e o f asolubl e cobal tcatalys tt o produc e th e aldehyd e (and som e alcohol) ; al l orpar to f th e aldehyd e i s the n hydrogenate d ove ra nicke l catalys tto for

m alcohol . Th e reactio n i s exothermic , abou t3 5 kca l bein g liberate d pergrammol e of olefi n reacted . Th e usual ra w material s are synthesi s ga s (Chap . 7 ) an d a-olefins . Th e principal olefin s use d are propylen e and th e C 7 to C 1 2 copolymer s o f

propylen e and isobutylene . Propylen e reacts wit

h synthesi s ga s to yiel d th e followin g products : CH 3 CH:CH

2 + C O + H

2 * Propylen e 17S*'C . 25 0 it m CH 3CH 2 CH,CH O + CH3CHCH

O + CH

3CH 2CH,CH

2 O H + CH

3CH 2CH,O H CH , CH , Thes e are , respectively , a-butyraldehyde , isobutyraldehyde , n-butanol , and isobuty l alcohol . Industriall y mos tuse d i s th e C 7 olefi n copolymer , which yield s th e mixture of corresponding C galcohols . Additio n o f th e C O grou p to di e doubl e bon d i s about60 % terminal an d 40 % secondary . A typical C 7 H 1 4 olefi n yield s th e followin g isocty l alcoho l derivatives : 3,4-dimethyl-l-he___no l 3,5-dimethyl-l-hexano l 4,5-dimet h vl- 1 -hexano l 3-methyl-l-heptano l 5-methyl-l-heptano l Others POLYMERIZATION * o f pe t Industries , Chap . 35 , Syntheti c mos timportantindustrie s are b . a s presente d i

n Chap . 37 . MISCELLANEOU S A fe w chemica l conversions . Two im t forme ris fully covere d i n Cha p Carbon disulfide is no

w m a and sulfur 3 7 is describe d i n CP ! CH 4 <*) + «(,)-*! & - <_-,o , 'OO'C
. 20-3 0 p » Yiel d90 % (o n methane ) pe r p Th e H 2 S ca n b e converte d an dcellophane . Productio n i s a SELECTE D REFEREIVCE S Augustine , R . l~ : Catalyti c Hydrogenation . Barry . W . R. : Structura l Analysi s of Petr o Brownstein . A . M : L.S . Petrochemicals . F Edmister . W . C : Applie dHydrocarbo n T h Gould . R. F . (ed.) : Literatur e of Chemica l Guthrie . V. : Petroleu mProduct s Handboo i Hatch , L F. : Isopropy l Alcoho l McGraw- l : Highe r Ox o Alcohols , Wiley , 19 5 Hatton . R. E. : Introductio n t o Hydrauli c E Hoiberg , A . J . (ed.) : Asphalts , Tar s an dPi Kobe , K . A. , an d1.1. McKetta , Jr . (eds.) : MeUan , I.. * Industria l Solvent s Handbook . . ' : Polyhydri c Alcohols , Sparta n Boo . Sittig , M. : Aromatics . .Moves . 196 6 (paten t : Chemical s fro mEthylene . Moves . : Chemical s fro mPropylene . Moves . : Pollutio n Contro l i n th e Organi c * Smith . C W . (ed.) : Acrolein . Wiley . 1962 . Topchiev , A . V. , et

al.: Syntheti c Material s Vervalix u C

- H. : Fir e Protectio n Manua l fo r Waddams . A . L : Chemical s fro mPetroltu n

"Groggina , op. cit.. pp . 856 , 943 ; Gol < '"Sittig , Combinin g Oxyge n an dHydr o methan e process) : Haines . Carbo n Disulfide . 38 Go__ttein , op. cit., p . 93 . reactio n co t

### •Sim 
# Introductio n t o

Industria l Chemistr

y
HOWAR D L . WHIT E CIBA-GEIG Y Corporatio n (Ret )

A Wiley-lnterscienc e Publicatio n 

## JOH N WILEY & SON S Ne wYor k •Chicheste r •Brisban e •Toront o •Singapor

e6 6 ORGANI C CHEMICA L PROCESSE S

wit h variou s catalysts
. I f thi s i s successful , th e proces s coul d the n b e conducte d a t th e sam e throughpu t temperatur e a s th e oxychlorination
. 

### 4.2. 3 Acetaldehyd e A recen t review o f acetaldehyd e (WittcofT , 1983 ) discusse s th e lates t synthese s an d use s o f thi s product
. W e no wexamin e th e Wacke rreaction , a cycli c proces s fo rmanufacturin g acetaldehyde
. Thi s proces s use s a n equimola ramoun t o f copper(II ) chlorid e an d a smal l quantit yo f palladiu m chlorid e a s catalyst
.

PdCI 2 + CH 2 =CH 2 + H 2 0 - CH 3 CH O + Pd ° + 2HC I (1 )

Pd ° + 2CuCI 2 - PdCI 2 + 2CuC I (2 ) 2CuC I + 2HC I + 0.5O 2 - 2CuCI 2 + H 2 0 (3 ) Onl ya catalyti c quantit yo f P d i s neede d i n thi s proces s becaus e th e CuCI 2 reoxidize s th e Pd ° a s soo n a s i t i s forme d lEq
. (2)|
. Th e CuC l forme d i n th e oxidatio n o f th e P d i s reoxidized t o CuCl 2 b y0 2 an d HC l |Eq
. (3)|
. 

### A. Mechanism

of the Wacker Reaction C l C f 

# .0/ 

# X.

' c i c r 

# i r * - H 2 C + C 2 H < U C l 

## H 2 

## CS V H 2 C C l 

## + c r

C l + H,0^ = P d + C l



# H 2 

# C y \ H 2 C O H ,

Hj C 

### II " Hj C 

# 3 

# /* P d 

# H 2 

# C y \ H, C O H + H *

Th e rate-determinin g ste p i s th e transformatio n o f th e hydrox yethylen e palladiu m com ple xint o th e 0-hydroxy-ethy l palladiu m comple x 4. 2 INDUSTRIA L PROCESSE S USIN G ETHYLEN E CHEMISTR Y [(C 2 H 4 )PdCI 2 (OH)J - + H 2 0 - I(HO-CH 2 -CH 2 )PdCI 2 ( H 2 0)] - 6 7

C H 

### I C H 2 

### I O H 

## c i c r 

# X

I O H 

### C l c f \ / H 3 

### C Pd H C ^ S I O H



### ' C l P I H 

### 3 C \ f 

# H./ V -CH,CH O + H * + Pd ° + 2 C l S=H 2 0 FIGUR E 4. 3 Mechanis m o f th e Wacke rreaction
. (Reproduce d wit h permissio n fro m R
. Prins , Chemistry

and Chemical

Engineering

of Catalytic

Processes, R
. Prin s an d G
. Schuit , Eds. , Copyrigh t 198 0 Martinu s Nijhoff/Dr
. W
. Junk , Dordrecht , Th e Nether lands , p . 423 , 425. ) Figur e 4. 3 show s th e mechanis m o f th e Wacke rreaction
. I t wil l b e discusse d furthe ri n Sectio n 11.2
. Thi s mechanis m ha s bee n discusse d b yPrin s (1980 , pp . 423-425)
. 

### B. Manufacturing

Conditions

for Acetaldehyde

(Wacker

Method) Th e proces s condition s fo rmanufacturin g acetaldehyd e hav e bee n take n fro m th e wor k

o f Jir a e t al
. (1976 , p . 97)
. Se e Figur e 4.4
. 1
. Stream s o f ethylen e an d oxyge n ar e separatel ypipe d int o th e botto m o f a towe r(A ) containin g copper(II ) chlorid e solutio n mixe d wit h a smal l amoun t o f palladiu m chloride
. Th e reacto ri s hel d a t 130° C an d 3 at m pressure .ORGANI C CHEMICA L PROCESSE S

6 8 Separato r Ligh t an d distillatio n Coole rcolum n Scrubbe rFina l distillatio n Off-ga s Low boilin g

materia l H 2 O J kondense r^ 1 Steam ,

fl*-^ i Produc t

_, , 'it?

I I uuuciw..,
—coole r C 2 H 4 ' 7-± I (10% ) I j , (99.8% ) *>k£ tT Gas-cycl e pum p Crud e aldehyd e Off-wate r Produc t FIGUR E 4. 4 Acetaldehyd e manufacturin g (lo w sheet . (Reprinte dwit hpermissio n fro m Hydrocarbon Processing, Vol . 55 , no . 3 . March , 1976. ) 2 . Fro mth e reacto r

(A ) i s evolve dacetaldehyde , wate r vapor , an dun reacte dethylen e an doxygen . Thes e gase s ar e sen t t o th e demister-sep

arato r (B) . An y catalys t

solutio n carrie da s amis t i s returne dt o (A) . 3 . Th e strea mfro m(B ) i s coole di n (C ) an dsen t t o ascrubbe r

(D) . Her e awate r spra y dissolve s th e acetaldehyd e formin g asolutio n whic hi s carrie dt o vesse l (F.) . Th e remaining gase s ar e recycleda s show n t o (A) , afte r an y consume dethylen e ha s bee n replaced. Smal l amount s o f

reactio n ga s ar c remove dt o preven t buildu p o f

con taminants . Som e o f th e catalys t

solutio n i s sen t

t o th e regenerato r

(H) , alon g wit h sufficien t oxyge n t o conver t

coppcr(l ) t o copperdl ) chlorid e an ddecom

pos e by-products . Th e temperatur e i n (H ) i s 170°C . 6 . Th e erod e aqueou s acetaldehyd e i s separate dfro mlo w boilin g materia l i n adistillatio n colum n (F) . whic h i s operate da s a n extractiv e distillatio n wit h water . (Se c Sectio n 9.1.1. ) 7 . Acetaldehyd e i s separate dfro mwate r i n afractionatin g distillatio n col

um n (G) . Hig hboilin g materia l i s remove da s ahighe r boilin g fractio n o r a s distillatio n residue . 

### 4.2. 4 Reaction s o f Acetaldehyd e W e no w revie w procedure s fo r th e manufactur e o f

variou s product s tha t ar e •o^ri^r t n mo n a n industria l scal e usin g acetaldehyd e a s ara w material . 4 . 

### 5 . 4. 2 INDUSTRIA L PROCESSE S USIN G ETHYLEN E CHEMISTR Y 6 9 

### A. Butanol Butano l ha s bee n prepare db y thre e processes . Th e procedure s wer e develope d becaus e o f

th e nee dfo r

cos t reduction. Onl y reactio n 2 use s acetaldehyde . 1 . Butano l wa s first

prepare db y fermentatio n (se e Sectio n 3.1.5) , aproces s tha t ma y becom e significan t again , dependin g o n petroleu mcosts . 2 . Whe n petroleu mproduct s becam e inexpensive , th e proces s base do n ac etaldehyd e becam e popula r an dwa s use dfo r

man y years . Thi s i s give n i n th e followin g equation : 2CH 3 CH O •*

- CH 3 CHOHCH 2 CH O - CH 3 C H = CHCH O



# V ' CH3CH2GH2GH2O H 3 . Th e lates t

process , calle dhydroformylatton , i s discusse di n Sectio n 4.3.4 . T o prepar e butanol , propylen e i s th e ra w materia l (Wittcoff , 1980) .

C H 3 CH=CH 2 + H 2 + C O - CH 3 CH 2 CH 2 CH O

- » CH 3 CH 2 CH 2 CH 2 O H + isome r Propionaldehyd e i s th e onl y produc t o f hydroformylatto n o f

ethylene . Thi s i s a majo r ra w materia l fo r

propioni c acid . C H 2 =CH. , + H j + C O - CH 3 CH 2 CH O - CH 3 CH 2 COO H 

### B. Acetic

Acid and Peracetic

Acid Thi s proces s ha s bee n reviewedb y Weisserme l an dArp e (1978 , pp . 152-153) . Oxidatio n o f

acetaldehyd e ca n b e mad e t o yiel deithe r aceti c aci do r

peraceti c acid , dependin g o n th e conditions .

CH 3 CH O - CH 3 C O ^CH 3 COO O - CH 3 COOO H ° 7 peraceti c aci d CH 3 CH O + CH 3 COOO H - CH 3 CHOHOOCOCH 3 - 2CH 3 COO H (1 ) (2 ) 

### Withmil dcondition s (15-40°C ) at 2 5 ba r an d.,r . on e get s peracet c ac.a s th e mai n product . T o mak e aceti c acid , th e procedur e , s t o acceleratth e ox , datio n b y radical formatio n a s wel l a s decompos e o f peraceU c ac £Th e catalyst s use dar e Mn o r C o acetates . Th e catalys t enter s mt o th e react.on a s shown :

# AUL-W 1 

# Shrevc' s Chemica l Proces s Industrie s GEORG E T . AUSTI N ProfessorEmeritus of

Chemical

Engineering Washington State University


# Fift h Editio n

McGraw-Hil l Boo k Compan y Ne w Yor k St . Loui s Sa

n Francisc o Aucklan dBogotaHambur g Johannesbur g Londo n Madri dMexic o Montrea l Ne w Delh i Panam a

Pari s Sao Paul o Singapor e Sydne y Toky o Toront o 

# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK . N CP.4 2

Manufacture of

Petrochemical* 

### 76 7
e chloride , 7 0 percent , an dt o alcoho l an dammonia . Methyl , nparativel y smal l market s an d s ammoni ain th e vapo r

phase . ethod . Th e proble mi

s t o sto p Usually i t i s desire dt o break mos t readil y availabl e oxidan t to carry away muc h hea t an d afe w rar e cases , ozon e i s th e mair . an dth e stee l industr y i s era l thousan dmetri c ton s pe r _l v becaus e o

f increase dyields , pmen t size , an dreduce dheat isedindustrially . Al

l oxidatio n lajo r problem . Th e commonest impa , Tex. , whic h oxidiz e pro variety o f oxygen-containin g wgen . replacin g air . Product s ivde , formaldehyde , acetone , ost o f separatin g suc h mixture s lectio n fo r LP Goxidatio n give s 1-phase oxidatio n o

f butan e a

t .•eti c aci dan d6 percen t

formi c eti c an d2 3 percen t

formic . ; oxidation . Th e major

process . > e db v decompositio n t o pheno l n l is als o mad e by th e oxidatio n sitio n o f hydrocarbons . Example s ar e th e manufactur e o f carbo n blac k

(Chap . 8 ) an dacety len e (Chap . 7) . In Europe , formic acid

i s mad e b y th e oxidatio n o f formamide . "Al l formi c aci dproduce d in th e Unite dState s i s produce da s aby-produc t o f th e liqui dphas e oxidatio n o f n-butan e t o aceti c acid." 2 7 Th e by-produc t sourc e i s expecte dt o dr y u p i n th e future , an dth e mos t prom isin g rout e to replac e it

i s throug h carbonylatio n o f methanol . Caprolactam, adipic acid, and hexamethylene diamine 1 *ar e al l mad e fro mcyclohexane . Almos t al l high-purit y cyclohexan e i s obtaine db y hydrogenatin g benzene , althoug h som e fo r solven t us e i s obtaine db y carefu l distillatio n o f selecte dpetroleu mfractions . Several oxidativ e route s ar e availabl e t o chang e cyclohexan e t o cyclohexanone , cyclohex

anol , an dultimatel y t o adipi c aci do r caprolactam . I

f pheno l i s hydrogenated , cyclohexanon e can b e obtaine ddirectly ; thi s wil l reac t with hydroxylamin e t o giv e cyclohexanon e oxim e whic h convert s t o caprolacta mo n aci drearrangemen t (Chap . 35) . Cyclohexan e can als o b e converte dt o adipi c acid , the n adiponitrile , whic hca n b e converte dt o hexamethylenedi

amine . Adipi c aci dan dhexamethylenediamin e ar e use dt o for mnylo n 6,6 . Thi s rout e t o HMD A i s competitiv e with alternativ e route s throug hbutene . Acetaldehyde ha s abris k sal e a s aprecurso r

o f aceti c acid , 1,3-butylen e glycol , glyoxal , pentaerythritol , peraceti c acid , an dpyridines . Th e deman di n 198 1 wa s 40 9 X IO 6 kg . Ther e ar e severa l competin g processes . (1 ) Th e olde r proces s b y th e hydratio n o f acetylen e i s n o longe r significant . (2 ) Th e Wacke r proces s develope db y Hoechst 2 9 start s wit hethylen e an d oxidize s it directl y with ai r

o r 99 % oxyge n (Fig . 38.9) . Th e catalys t i s palladiu mchlorid e wit h acoppe r chlorid e promoter . Th e ethylen e ga s i s bubbled , a t atmospheri c pressure , throug h th e solutio n a t

it s boilin g point . Th e heat o f reactio n i s remove db y boilin g o f th e water . Unreacte dga s i s recycle dfollowin g condensatio n o f th e aldehyd e an dwater , whic h ar e the n separate db y distillation. (3 ) Passin g ethy l alcoho l over acoppe r o r silver gauz e catalys t

give s 27 Aquil o an dHorlenko , Formi c Acid , Hydrocarbon Process. 5 9 (11 ) 120 (1980) . M Lowenhei man dMoran , op . cit. , p . 201 . "Acetaldehyde , Hydrocarbon Process. 6 0 (11 ) 12 1 (1981) .
ear . Mos t v5 4 percent ) goe s int o -. • plasticizers . benzoy l chloride , liquid-phas e toluen e oxidatio n •nt . A n olde r process 2 5 involvin g •sition int o benzoi c aci di s still i f th e oxidatio n o

f xylene s an d all v by th e partia l oxidatio n o f tion . an dseveral modification s c startin g materials , hu s brin g abou t

th e decompo

- .1981 ) -,-s. Hydrocarbon Proeeas. 3 9 *6 ) Product s an d stea m

Reacto r contain s catalys t i n solutio n
Wate r Ethylene | Ai r 

# X

Preliminar y oxidize r Wast e gase s
Condense r 

# -l

Aldehyd e stil l Steo m Wast e gase s
1 ' Condense r 1 s Co t ndense r Acetaldenyd e Purificatio n stil l Crotonaldehyd e 

# Ok CJ ) Reboile r Spen t catalys t solutio n Hig h boiler

Fig . 38.9 . Flowchar

t fo r acetaldehyd

e b y ai r oxidatio n o f ethylene .76 8 Chap, a * Petrochemicals abou t a2 5 percen t

conversio n t o acetaldehyde , with recirculatio n makin g a9 0 to 9 5 yiel dpossible . (4 ) Lowe r molecular

weigh t paraffi n hydrocarbon s ar e oxidize dno PCr ?* n * call y t o produc e mixe dcompounds , amon g the macetaldehyd e an daceti c aci dSe ' suc h mixture s i s difficult . ' parat,0 »o f Sinc e nearl y 5 0 percen t

o f th e acetaldehyd e produce di s use dto make aceti c aci dit s f marke t i s questionable . Aceti c aci dproduce ddirectl y b y th e carbonylatio n o f methanol * h " alread y cu t

deepl y int o th e market . *• * Acetic acid

i s widel y used , an dmuc hi s converte dto aceti c anhydride. 3 1 Eastman 3 2 i s currentl y buildin g aver y larg e plan t

to produc e thes e an dother che m fro mcoal . Th e reactio n betwee n keten e an daceti c aci dproduce s th e anhydrid e b t' k amoun t o f energ y require dt o produc e th e keten e (aceton e i s cracke dto eiv e 3.. . !

... . , & ^ciene an d methane ) i s very large .

i i- l (CH 3 ) 2 C O - CH 2 = C = 0 + CH < C H 2 =C= 0 + CH 3 COO H —(CH 3 CO) 2 0 Keten e i s use dimmediatel y afte r manufactur e becaus e i

t doe s no t stor e well . Th e majo

r •__ . o f aceti c anhydrid e i s i n makin g viny l acetat e an dothe r acetylations . Ethylene glycol, 33 use di n antifreeze , 4 0 percent , an di n fibers an dfilms , 5 0 percen t i s a major petrochemica l an dha s bee n fo r man y years . Th e deman din 198 1 wa s 2 X 10

9 k e Lik e mos t o f th e othe r alcohols , it

wa s originall y mad e b y reactin g chlorin e an dwate r (HOCI ) with ethylen e t o for

mth e chlorohydrin , whic hwa s the n hydrolyze dt o yiel dglycol . This procedur e an dseveral other s (formaldehyd e + C0 2 , fermentation , oxidatio n o f propane) i

s no w technicall y an denvironmentall y obsolete . Th e currentl y favore dproces s start s wit h eth

ylen e an dreact s it

wit h oxyge n o r

ai r i n atubula r

reacto r over asilver oxide catalys t

t o t-*r m ethylen e oxide . Becaus e th e volatility o f glyco l i s low , i

t i s preferabl e to purif

y th e ethvlen

e oxide , the n conver t

it t o glyco l b y hydration . Durin g th e hydration , however , polyglyiols , particularl y di

- an dtri-ethyleneglycol s ar e formed . Th e reaction s are :

HrtC'^'^CHo 1/

2 0 , A«, 0 CH,—CH , + (CO , an dH, 0 b y combustion ) 0 CH,—CH , •*

• H, 0 • \/ CH 2 —CH 2 + polyglycol s O H O H Ethylen e dichlorid e (unde r 1 ppm ) i s adde dt o ami x o f ethylen e an dai r

in th e rati o o

f 1:1 0 t o reduc e oxidatio n t o COj , an dth e mixtur e i s passe dover asupporte dsilver

oxide catalyst a t atmospheri c pressur e an d280° C with a1- s contac t time . Thi s cause s a6 0 t o 7 0 percen t '"Rot h e t al. , Lo w Pressur e Proces s fo r Aceti c Aci dvi aCarbonylatio n o f Methanol , CHEMTECH 1(10 ) 60 0 (1971) . 3 1 Jeffreys , The Manufacture of Acetic Anydride, 2 ded. , Th e Institutio n o f Chemical Engi

neers , London , 1964 . 3 2 A Gian t Step : Aceti c Anhydrid e fro mCoal , Chem. Week 127 (3 ) 4 0 (1980) . ^Hydrocarbon Process. 6 0 (11 ) 161-16 3 (1981) .

•41 3 ••!• •

# Riegel' s 

# Handboo k o f Industria l Chemistr y EIGHT H EDITIO N

Edite d by 

# Jame s A . Ken t

Detroit , Michiga n

TORONT O LONDONMELBOURN E

# H*.\^cV * 1 •V K
93 8 RIEGEL' S HANDBOO KO F INDUSTRIA L CHEMISTR Y

Fig . 25.1 1 Vapor-phas e direc t hydratio n o f ethylen e t o ethanol
. {Hydrocarbon Processing, 50 , no. 11, ISI (1971); copyright

1971 by

Gulf Publishing

Co.) Ethylbenzen e 

### Ethylbenzene ha

s bu tone majo

rend-use an

d tha tis the manufactur

e o f styrene . I

n 1978 , ethylbenzen e wa

s the fifth larges

tconsumero f ethylene , accounting forabou t2.2 6 billio n pounds. * Thi

s represent

s abou ta7 percen

t averag e annua l growt h i n th e lastte n years . I n addition t o bein

g produced b y the alkylatio n o f benzene wit

h ethylene , ethylbenzen e i s als o isolate d fro

m mixed xylen e stream

s o r a s aby-produc

to f cumen e manufacture . These lattersource

s accountforles s tha

n 1 0 percen

t o f the ethylbenzen e used today . Ethylbenzene synthesi s b y reaction o f ethy lene wit h benzene i s carrie

d ou teitherin the liqui d phas

e usin g aluminu

m chloride a

s the catalyst , o

ri n the vapo

rphase wit

h aphos phoric acid oralumina-silic acatalyst . Yields abou t9 5 percen

tar e obtained in eithercase . Figur e 25.1 2 shows aflo w diagra m o f a n ethyl benzene process . Th e principa

l use s fo rstyrene , mad

e b y catalyti c crackin

g o f ethylbenzene , ar

e i n polystyrene , styrene-butadien e latex an

d plas tics , SB Rrubber

, an d i n the cross-linkin

g o f unsaturate

d polyeste rresins , see Chapte

r10 . Fo

rmor e details , Acetaldehyde , Aceti c Acid , Viny l Acetate 

### Acetaldehyde. Acetaldehyde production peake d i n 196 9 a

t1.65 billio n pounds . O f this , 685 millio n o r4 2 percen

twa s mad e b y direc t oxidatio n o f

ethylene . I

n 1978 , productio

n wa s one billio n pounds . Ove r9 7 percen

to f thi s wa s b y ethylen e oxidatiofiri Th e direc t oxidatio n process use

s cupri c chlorid e an d a smal l amoun to f palladiu m chloride i n aqueou

s jsMottgna s the catalyst . Th e reactio n is exo- - thermi c an d i s controlled by evaporation . Th e gaseou s reaction mixtur

e i s scrubbe

d t o remov e acetaldehyde an

d overhea d gase s ar e recycled . Th e liquid fro

m the reaction mixtur

e is regenerate d wit h oxygen t o retur

n the coppe

rt o th e cupri c stat e an d palladiu m meta l bac k t o palladiu m chloride . Se

e Figur e 25.13 . Th e alternat e processes consis to f

oxidatio n o f ethy l alcohol an

d glycerin by-product

. About7 0 percen

to f acetaldehyde consume

d i s use d forthe production o f

acetic aci

d an dSYNTHETI C ORGANI C CHEMICAL S 93 7

>0 , no. 11. 151



### mor e details ,

Acetate 

### uction peaked O f this , 68 5 l e by direc

t , production 7 percen to f Th e direc t lorid e an d a l e i n aqueous action i s exo - -oration . The be d to remov

e ar e recycled . nixture i s re

th e coppert o neta l bac kt o .13 . o f oxidatio n roduct . /d e consumed :eti c acid an

d 

# <= ?

Monoalkylate d Produc t

Recycl e Benzen e Recycl e Pal yalky l Benzene s Fig . 25.1 2 Alka r ethylbenzen e procett . {Hydrocarbon Proceuing, SO, no. 11, 125 {1971): copyright

1971 by Gulf Publishing

Co. ) 

### anhydride . Pentaerythritol , peracetic acid , pyridine , glyoxal , 1,3-butylene glycol , an d chlora l al l combined consume the remainin g 3 0 percen

to f acetaldehyde . Sinc

e the fat e o f acetaldehyde i s determined b y its use a s a n aceti c acid-acetic anhydrid e intermediat

e an d futur e aceti c aci

d technology appear

s to be firml

y base d o n methanol , acetaldehyde con sumption will dro

p ove rthe nextfe

w years . Hig h unit-valu

e product

s ar e derive d fro m pyridin e compounds ; thus , althoug h mas s con sumption o f

acetaldehyde will no tloo k ex citing , growt

h i n valu e o f product s will be attractive . Separato r Reactio n Gase * Reacto r Acetaldehyd e Fractionator Wate r

Ai rStea m Wate r

Acetaldehyd e Catalys t Regeneratio n Sectio n Strippe r

-Stea m 

# e_3 - Recycl e Compresso r Wate ran d Heav y Impuritie s

Fig . 26.1 3 Acetaldehyd e b y tingle-ttag e Wacke r procan . {Hahn, A. V., "Tha Petrochemical

Industry,"p. 243, McGraw-Hill, 1970.)P.4 7



# S T 

# ~ ^ o 

# r ^ 198 9 DIRECTOR

Y O F CHEMICA L PRODUCER S UNITE D STATE S O F AMERICA

Informatio n i n thi s Director y is fo r th e sol e an d privat e us

e o f sponsor

s o f th e Director y o f Chemica l Producers Program .



# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK , N CP.4 8



### PRODUCT S 198 9 DIRECTOR Y O F CHEMICA L PRODUCER S UNITE D STATE S Abboticin e (See : Erythromyci n stearate unde rMedicina l (Pharmaceutical ) Chemicals ) Abomasa l enzym e (See : Renni n unde rEnzymes ) AB S resin s (See, : Acrylonitrile-butadiene-styren e resin s unde r Plastic s an d Resins

) 6-AC A (See : 6-Aminocephalosporani c aci d unde rMedicina l (Pharmaceutical ) Chemicals ) Accelerator s (See : Rubbe rProcessin g Chemicals ) Acclaim ®

1EC (See : Fenoxaprop-ethy l unde rPesticides) Acephat e (See : Pesticides ) Aceta l (See : Flavo ran d Fragranc e Chemicals ) Acetaldehyd e (Aceti c aldehyde) (Ethanal ) (Ethy l aldehyde) Eastma n Koda k Compan y Eastma n Chemica l Products , Inc
. Texa s Eastma n Compan y Hoechs t Celanes e Corp
. Hoechs t Celanes e Chemica l Group , Inc
. Longview , Texa s Ba yCity , Texa

s Annua l Capacit y (Million s o

f Pounds ) 50 0 25 0 Ra w Materia l Ethylen e Ethylen e TOTA L 76 0 Note : Hoechs

t Ceianese's 45 0 millio n pound-per-yea rplan t a t Clea rLake , Texas , ha

s bee n idl e sinc

e 1981 , an d probabl ywil l no t be restarted
. Source : SRI Internationa l estimates a s o f Januar y1 , 1989
. Acetaldehyde , diethy l aceta l (See : Aceta l unde rFlavo ran d Fragranc e Chemicals

) Acetaldehyd e 1,1-dimethylhydrazon e Dixi e Chemica l Compan

yBayport , Texa s Acetaldehyde , diphenethy l aceta i (See : Phenethy l aceta l unde rFlavo ran d Fragranc e Chemicals ) Acetaldehyde , dipropy l aceta l (See : 1,1-Dipropoxyethan e unde rFlavo ran d Fragranc e Chemicals ) Acetaldehyd e ethy l ci s 3-hexeny l aceta l (See : Lea f aceta l unde rFlavo ran d Fragranc e Chemicals ) Aceta l resin s (See : Polyaceta l resin s unde rPlastic s an d Resins ) Acetamid e (Aceti caci d amide ) Henle yManufacturin g Inc
. Genera l Chemica l Corporatio n Whittake rCorporatio n Chemical s Grou p Heic o Divisio n Acetamidoadamanthan e E
. I
. d u Pon

t de Nemour

s & Company , Claymont , Delawar e Delawar e Wate rGap , Pennsylvani a

Linden , Ne

wJerse y Agnchemical s Departmen t 1-Acetamido—4-aminobenzen e (See : 4'-Aminoacetanilide ) p-Acetamidoanilin e (See : 4'-Aminoacetanilide ) 2-Acetamidoethano l (See*
. N-[2-Hydroxyethyl ] acetamide) 4-Acetamido-2-ethoxybenzoi c acid , methy l este r (See : Ethopabat e unde rMedicina l (Pharmaceutical ) Chemicals ) 4-Acetamidopheno l (See : Acetaminophe n unde rMedicina l (Pharmaceutical ) Chemicals ) Acetamidothymo l Hercules Incorporate d Resins , divisio n Reichhol d Chemicals , Inc
. Coatin g Polymer

s & Resin s Divisio n Jefferson , Pennsylvani a

Gulfport , Mississipp i 5-Acetamido-2,4,6-triiodo-N-methylisophthalami c aci d (See : lothalami c aci d unde rMedicina l (Pharmaceutical ) Chemicals ) Acetaminophe n (See : Medicina l (Pharmaceutical ) Chemicals ) Acetanilid e (Acetylaminobenzene) (Acetylaniline ) (N Phenylacetamide) Merck & Co. , Inc
. Merck Chemica l Manufacturin g Divisio n Albany , Georgi a Acetanisol e (See : 4'-Methoxyacetophenon e unde rFlavo ran d Fragranc e Chemicals ) Acetat e C- 9 (See : Nony l acetat e unde rFlavo ran d Fragranc e Chemicals ) Aceteugeno l (See : Eugeny l acetat e unde rFlavo ran d Fragranc e Chemicals )

Aceti c aci d (Ethanoi cacid ) (Methanecarboxyli c acid ) (Se e also : Peraceti c acid ) Borde n Chemical s an d Plastic s Partnershi p Geismar, Louisian a
Eastma n Koda k Compan y Eastma n Chemica l Products , Inc
. Tennesse e Eastma n Compan y Kingsport , Tennesse e Annua l Capacit y (Million s o

f Pounds ) 140

16 0 35 0 Proces s an d Remark

s Methano l carbonylation ; plan t restarte d wit h approximatel y4 0 millio n pound s o f capacit

yi n Januar y1988 ; remainin g capacit yi s o n standby
. Coal qa s coproduc

t Acetaldehyd e oxidatio n

SR I Internationa l (Continued ) 

### 42 7P.4 9 

# K£-M-MO

KIRK-OTHME R 

# CONCIS E ENCYCLOPEDI A O F CHEMICA L TECHNOLOG Y

PLEAS E D O NO T REMOV E FRO M LIBRAR Y

RADIA N LIBRAR Y RESEARC H TRIANGL E PARK , N C A WIIEY-INTERSCIENCEPUBLICATIO N Joh n Wile y & Son s NEW YOR K•CHICHESTE R - BRISBAN E - TORONT O •SINGAPOR EP.5 0 

### '•\-rtrnt. (<iVfc . -QtPii/r. ± r 

### b/xcucOo 

# m$ ACETALDEHYD E plate s ca n b e compute d analyticall y usin g aspecial for m o f th e Kremse r equations . CR . WILK E UR S VO N STOCKA R Universit y o f California , Berkele

y T.K . Sherwood , R.L . Pigford , an d CR . Wilke , Mass Transfer, McGraw-Hil l Boo k Co. , Inc. , Ne w York, 1975 . R.E . Treybal , Mass TransferOperations. McGraw-Hil l Book Co. , Inc. , New York , 1955 . CR . Wilke an

d U.V . Stockar , Ind. Eng. Chem. Fundam. 18<2) , 88 (1977) . R.H . Perr y and CH . Chilton , eds. . Chemical Engineer's Handbook, 6t h ed. , McGraw-Hill , Inc. , New York, 1983 . ACACIA . Se e Diuretics ; Gum s an d mucilages . ACAROID , ACCROIDES . Se e Resins , natural . A€tTAtDtKYD E Acetaldehyde , CH 3 CHO , i s acolorless , mobil e liqui d wit h apungen t odortha ti s somewha tfruity an d pleasan ti n dilut e concentrations . I ti s a n importan tintermediat e i n th e productio n of aceti c acid , aceti c anhytjride . ethv l acetate , peraceti c acid , pentaerythritol . chloral , glyoxal . alkvlamines . an d pyridines , an d wa s use d extensivel y durin g Worl d War I a s a n intermediat e formakin g aceton e from aceti c acid . Acetaldehyd e occur s i n trace s i n al l rip e fruit s tha thav e atar ttast e before ripening; i ti s a n intermediat e produc to f alcoholi c fermentatio n buti s reduce d almos timmediatel y t o ethano l (se e Fermentation) . A n intermediat e produc ti n th e decompositio n of sugar s i n th e body , i t occur s i n trace s i n th e blood . Acetaldehyd e i s aproduc tof mos thydro carbon oxidations . Physica l Propertie s Acetaldehyd e i s miscibl e i n al l proportion s wit h water , an d mos t organi c solvent s suc h a s acetone , benzene , ethy l alcohol , ethy l ether , gasoline , paraldehyde , toluene , xylenes , turpentine , an d aceti c acid . Tabl e 1 give s som e o

f th e physica l propertie s o f acetaldehyde . Chemica l Reaction s ( a-cs^-^lrlaJ^-rle . —^ - . ) Acetaldehyd e i s ahighl y reactiv e compoun d exhibitin g th e reaction s o

f aldehyde s (qv) . Acetaldehyd e decompose s a ttempe j above 400° C t o form methan e an d carbo n monoxide. I n aqueou s solu Tablel . Physica l Propertie s of Acetaldehyd e Propertie s Values meltin g poin t boilin g pointat101.3 kP

a( 1 atm) , " C density , g/cm* 1 refractive index , nTM vapordensity (air- 1) specifi c heatat0°C , J/(g - K) a a t25° C laten theato

f vaporization , kJ/mol " heato f solutio n in waterat0°C , kJ/mol " a t25° C flash point , closed cup , ° C ignitio n temperature i

n air, ° C explosiv e limit s o

f mixture s with air, vo l % acetaldehyd e "T o convertJ t o cal , divid e by 4.184 . -123. 5 20.1 6 0.8045 1.3311 3 1.5 2 2.1 8 1.4 1 25.7 1 -8.2 0 -6.8 2 -3 8 16 5 4.5-60. 5 tions , i texist s i n equilibriu m wit h th e hydrate , CH 3 CH(OH) 2 . Th e eno l

form , viny l alcoho l (CH 2 =CH0H) , exist s i n equilibriu m wit h acetalde hyd e t o th e exten to f

approximatel y on e molecul e pe r30,000 . Acetalde hyd e eno l ha s bee n acetylate d wit h keten e t o for m viny l acetate . Dependin g o n th e reactio n conditions , i ti s readil y oxidize d wit h oxyge n o rai rt o for

m aceti c acid , aceti c anhydride , an d peraceti c aci d (se e Aceti c aci d an d derivatives) . Peraceti c aci d i s forme d commercially , eithe rthroug h lo w temperatur e oxidatio n of acetaldehyd e i n th e pres enc e o f meta l salts , ultraviole tirradiation , o rozone ; o rdirectl y b y liquid-phas e oxidatio n wit h acobal tsal tcatalys t(se e Peroxide s an d perox y compounds) . Th e nitric aci d oxidatio n o f acetaldehyd e yield s glyoxal . Acetaldehyd e i s readil y reduce d t o ethano l (qv) , usin g catalyst s suc h a s nicke l an d coppe roxid e t o suppor tth e vapor-phas e hydrogenation . Whe n aminera l acid , suc h a s sulfuric , phosphoric , o rhydrochlori c acid , i s adde d t o it , paraldehyde , 2,4,6-trioxane , acycli c trimer , i s formed . Metaldehyde , acycli c tetramer , i s forme d a ttemperature s belo w 0° C i n th e presenc e o f

dry hydroge n chlorid e o rpyridine-hydroge n bromide . Polyacetaldehyde , a n unstable , rubbery polyme rwit h a n aceta l struc ture , form s i n afew day s from acetaldehyde ; polyacetaldehyd e ha s n o practica l significanc e (se e Aceta l resins) . Th e base-catalyze d condensatio n o f acetaldehyd e lead s t o th e dime r acetaldol , whic h ca n b e hydrogenate d t o form 1,3-butandiol , o rdehy drate d t o for m crotonaldehyde , whic h ma y als o b e made directl y b y th e vapor-phas e condensatio n o f acetaldehyd e ove racatalyst . Th e base catalyze d reactio n o f

acetaldehyd e wit h exces s formaldehyd e i s th e commercia l rout e t o pentaerythrito l (se e Alcohols , polyhydric) . Th e vapor-phas e reactio n o f acetaldehyd e an d formaldehyd e a t475° C ove ra catalys tgive s acrolein . Ethy l acetat e i s commerciall y produce d b y th e Tischenk o condensatio n o f acetaldehyd e wit h a

n aluminu m ethoxid e catalyst ; wit h isobutyraldehyde , thi s yield s amixtur e of ethy l acetate , isobuty l acetate , an d isobuty l isobutyrate . Butadien e (qv ) ca n b e made b y th e reactio n o

f acetaldehyd e an d ethy l alcohol . Th e Strecke ramin o aci d synthesi s give s alanin e (se e Amin o acids) . Grignar d reagent s giv e secondar y alcohols . Manufactur

e ( ***«H0*~*t» *****k*^^ : fr**& vlTM*.(>*Kr>t& Acetaldehyd e i s produce d commerciall y b y th e oxidatio n o rdehydro genatio n o f

ethanol , th e additio n o f wate rt o acetylene , partial oxidatio n of hydrocarbons , an d th e direc toxidatio n of ethylene . Th ° AireStIJT"'* - phas e oxidatio n of

ethvlen e (th e Wack^-l-fnprhs tnrn^pj-s ) j s th p nrr***.**.

. of choige : i n 1976 , 2 9 companie s wit h > 82% o f th e world' s 2. 3 x IO6 tpe ryea rplan tcapacit y use d thi s process . A catalyti c solutio n of lalladiu m chlorid e i s use d t o form acetaldehyde : C H 2 =CH 2 + PdCl 2 + H 2 0 - CH 3 CH O + P d + 2 HCl Th e metalli c palladiu m i s reoxidize d t o PdCl 2 wit h CuCl 2 , an d th e cuprou s chlorid e forme d i s reoxidize d wit h oxyge n orair . Th e ne tresul t i s aproces s i n whic h ethylen e i s oxidize d continuousl y throug h aserie s o f oxidation-reductio n reactions . Ther e ar e tw o variation s fo rth e productio n o f acetaldehyd e b y th e oxidatio n o

f ethylene : th e two-stag e proces s develope d b y Wacker-Chemi e an d th e one-stag e proces s develope d b y Farbwerk e Hoechst . I n th e two-stae e process , ethylen e an d oxyge n (air ) reac ti n th e liqui d phas e i n tw o stages . In th e first, th e ethvlen e i s almos tcompletel y converte d t o acetaldehyd e i n on e pas s i n atubula rplug-flo w reacto rmade of titanium . Acetaldehyd e produce d i n th e firstreacto ri s remove d b v adiabati c flashing i n atower . Th e catalys tsolutio n i s recycle d fro m th e flash-tower bas e t o th e secon d stage , o roxidation , reactor , wher e th e cuprou s sal ti s oxidize d t o th e cupri c stat e wit h air . Intjw^fljkgtaggjjrocess , ethylene , oxygen , an d recycle d ga s are directe d t o avertica l reacto rforcontac t wit h th e catalvs tsolution . Acetaldehyd e i s produce d commerciall y b y th e catalyti c oxidatio n o f ethy l alcohol , carrie d ou tby passin g alcoho l vapor s an d preheate d ai r ove rasilve rcatalys ta t480°C . Olde rcommercia l processe s produce d acetaldehyd e b y th e hydratio n o f acetylen e unde rpressur e i n avertica l reacto rcontainin g amercury catalys tdissolve d i n sulfuri c acid . Acetaldehyd e ma y als o b e made from methy l viny l ethe ran d ethyliden e diacetate , bot h o f

whic h can b e mad e fro m acetylene . I ti s als o forme d a s 

### \ACETA L RESIN S P.5 1

acoproduc t

i n th e vapor-phas e oxidatio n o f saturate dhydrocarbons , eg , butan e or mixture s containin g butane , wit h air , or , i n higher

yield , oxyge n (se e Hydrocarbo n oxidation) . Unlik e th e acetylen e route , thi s metho dha s almos t

n o chanc e t o b e useda s amain process . 4££tAldfi_tt__ e i s produce din arhodium-catalvzed-orgrey * <**«p«hl g o f wiwcrtin f

ayfl-'-T*'

- si s ga s (^ U + H 2 ) directl y int o acetaldehvd e in asineie_step . IJ\ the ypflr s l^w.* . _n[ | hevonri

j interna . I

n t^ c ••-_ » o f synthesi s gas fro

mcoa l jT_c^,-„_i_,r

, pt ; ara w material fo

r acetaldehyd e productio n wil l increas e (see Fuels , synthetic) . ^—•—•**• » Healt h an d SafetyFactor s Althoug hi n normal industrial operatio n ther e i s n o healt h hazardi

n handlin g acetaldehyd e i

f norma l precaution s ar e taken , i t ma y be harm

fu l in th e following ways : i t paralyze s th e respiratory muscles , cause s panic , ha s agenera

l narcoti c actio n which prevent s coughing , cause s irritatio n o

f th e eye s an dmucu s membranes , accelerate s heart action , an dcause s headach e an dsore throa t whe n breathe di

n high concentra tions . Carbo n dioxid e solution s in acetaldehyd e hav e aweakenedodor an dar e particularl y pernicious . Prolongedexposur e cause s adecreas e i

n re dan dwhit e bloo dcell s an dasustaine drise in bloodpressure . Th e maximumallowabl e concentratio n o f acetaldehyd e in air

i s 20 0 ppm . Mixture s o

f acetaldehyd e vapor

wit h ai r ar e flammable andexplosive i f th e concentration s o

f aldehyd e an doxyge

n ris e abov e 4 an d9%, respec tively . Economi c Aspect s an d Uses Futur e growt

h wil l depen don th e development o f alowe r cos t proces s base do n synthesi s gas , an da

n increase ddeman dfo

r processe s base do

n acetaldehyd e activatio n technique s an dperaceti c acid . Sinc e 1940 , th e productio n patter n ha s change dfro mhydratio n o

f acetylen e an doxida

tio n o f ethy l alcoho l t o liquid-phas e oxidatio n o f ethylen e usin g th e Wacker-Hoechs t

processes . Acetaldehyd e productio n i s linkedwit h th e deman dfo

r aceti c acid , aceti c anhydride , cellulos e acetate , vinyl acetat e resins , acetat e esters , pentaerythritol , syntheti c pyridin e derivatives , terephthali c acid , an dperaceti c acid . No ne w acetaldehyde-base dplant s ar e expecte ddu e t o th e risin g cost s o f ethylen e a

afeedstoc k cost s increase . Methano l carbonylatio n i s th e preferre drout e t o aceti c aci d an dwill continu e fo

r th e next 10-1 5 year s (se e Aceti c acid) .

H.J . HAOEMAYER Texas Eastma

n Compan y R . Jir aan dW. Freiesleben , "Olefi

n Oxidatio n andRelatedReaction s wit h Grou p VIII . Noble Meta

l Salts, " i

n E . Becke

r an dM . TsutsUi , eds. , Organometallic Reactions, Vol . 3 , Interscience Publishers , adivisio n o f Joh n Wile y & Sons , Inc. , Ne

w York , 1972. J . Smid t andco-workers , Angew. Chem. 71 , 17 6 (1959) . U.S . Pat . 3,240,80

3 (Mar . 15 , 1966) , B . Thompso n an dS.D . Neele

y (t o Eastma n Koda k Co.) . U.S . Pat . 3,714,23 6 (Jan . 30 , 1973) , H_N . Wrigh t an dHJ . Hagemayer

, Jr . (t o Eastma n Koda k Co.) . ACETA L RESIN S Acetal resins , als o know n a s polyoxymethylenes , polyacetals , an d aldehyd e resins , ar e engineerin g thermoplastic s tha t hav e broadus e a s replacement s fo

r metal s in awide variety o f application s (se e Engineer

in g plastics) . The y ar e high molecula r weigh t polymer s wit

habasi c molecula r structur e o

f repeatin g carbon-oxyge n links . ^CH, . .CH.. . CH . XH, CH, . m . 

### '

### ^ o o o 

### N> ^ ^ Thi s alternatin g oxymethylen e structure , OCH 2 , give s th e resin s a chemistry similar

t o th e simpl e acetals . Homopolymer s consis t solely o f thi s carbon-oxygen backbone , wherea s copolymer s hav e th e oxymethy

len e structur e occasionally interrupte db y acomonome r uni t sucha s a n ethylen e linkag e fro

methylen e oxide . Propertie s vary dependin g o n th e number-averag e molecula r weight , th e typ e o

f additive s o r

reinforcing agents , an dwhethe r th e resin i s a copolymer

o r ahomopolymer . For

example , additives , eg , glas s fibers i n th e copolymer , ca

n improv e tensil e strength andstiffnes s (see Com

posites ; Laminate dandreinforcedplastics) . Th e resin s posses s hig h stiffness , excellent

dimensiona

l stability , high tensil e an dimpac t strength , goodabrasio n resistance , an dalo w coefficien

t o f friction . The y resis t attac k by man y organi c compounds , but are unsuitabl e in contac t wit h stron g acids . Th e copolyme r offer s superio r resistanc e t o stron g bases . Acetal resin s ar e coveredby Federa l Specification s L-P-392aan db y AST M Specificatio n D 213 3 which identif y th e resin by specific gravity , meltin g point , an dmelt

flow rate . Acetal resin s ar e frequently usedt o reduc e cos t an dimprov e perfor

manc e in application s wher e one acetal par t

replace s severa

l metal parts , (se e Engineerin g plastics) . Trad e name s an dproducer s o f commercia

l product s include Delri

n (DuPont) , Celcon (Celanese) , Hostafor m(Celanese—Hoechst) , Duraon (Celanese—Diacel) , an dUltrafor m(BASF-Degussa) . Manufactur e Homopolymer . Commercia l homopolyme

r productio n i s basedo

n th e polymerizatio n o

f formaldehyde throug h monome r purification , poly

- , merization , end-cappin g wit h alky l or

acyl groups , andfinishing. Th e concentratio n o

f chain-transfer

agent s mus t

be reduced , althoug h hig h molecula r weight polymer s hav e bee

n produce dwit

h a s much a s 0.9* . wate r present . Th e monome

r i s purifiedthroug h scrubbin g wit h an iner t liquid , partia l polymerizatio n t o remove chain-transfer impurities , conversio n o f formaldehyd e t o ahemiforma l andsubsequent

decomposition t o purifie dformaldehyde , an dtreatmen t wit h P 2 0 5 . Ther e ar e tw o mai n polymerizatio n reactions : th e first i s additio n t o th e doubl e bon do

f th e monomer . Th e secondi s growt h o f acompletely crystallin e polymer

i n aqueou s or

alcoho l mediu

mby stepwis e equi

libriu mwithsolvate dmonome r usin g crystallizatio n a s th e drivin g force . Anioni c initiator s includ e amines , phosphines , ammoniumandsulfoniu m salts , amides , amidines , etc .

-CH 2 0 " + CH 2 = 0 - ~CH 2 OCH 2 0 " (anionic ) -OCHJ + 0=CH 2 - -OCHjOCHj * (cationic ) Cationi c initiator s includ e sulfuri c o r phosphori c acid , Lewi s acids , an d stabl e cations . Ionizin g radiatio n i s als o effective . Th e polyme r i s end

cappe dfo r stabilizatio n b y reactio n wit h aceti c anhydride . I t

i s finished withth e additio n o

f antioxidants , typicall y o

f th e amide or

amin e type . Copolymer . Commercia

l copolymer s ar e mad e by th e trimerizatio n o f formaldehyd e t o trioxane , purificatio n o f trioxane , copolymerization , stabilizatio n b y alkalin e hydrolysis , an dfinishing. Th e copolymerizatio n o f trioxane , lik

e formaldehyde polymerization , i s b y cationi c initiatio n using , i n thi s case , boron fluoride etherat e o r othe r boron fluoride coordinatio n complexe s wit horgani c compounds . Cationi c polymeriza

tio n i s relativel y complicate dandma y involv e th e oxoniu

mion a s wel

l a s th e carbocation . Tranaacetalizatio n can . occu r a s aside reaction . Th e polymerizatio n i s carrie dout i n th e presenc e o

f 0.1-1 5 mol

% o f th e comonomer , yieldin g apolyme r havin g 85-99.9 $ oxymethylen e unit s (—OCH 2—) ; thus , th e polyme r i s stil l predominantl y apolyoxymethy

lene , allowin g it s classificatio n a s a n acetal resin . Healt h an d Safet

y Factor s Durin g th e processin g o

f acetal resin s i n moldin g o r extrusio n equip

ment , some decompositio n ca n occu r wit h evolutio n o

f formaldehyde . Formaldehyde , a s an ai r

contaminant , i s regulate dunder OSHA . Th e Nationa l Sanitatio n Foundatio n ha s liste danumber o f acetal composi

tion s fo r us e i n contac t

wit h potabl e water . Th e FDA regulation s 2 1 CF R177.247 0 an d2 1 CF R177.245 0 cove

r acetal s repeatedl y usedin contac t with food . K J . PERSA K L.M . BLAI R E.I . d u Pon t d e Nemour s & Co. , Inc .P.5 2

commo n Synonym e Aceti c aldehyd a Ethint l Ethy t aldehyd e Floats tn d mix*, mtf i water . Bo*n g point n 69'F . Sharp , fruit y odo r
Flammable , irritatin g vapo r i s produce d

Avoi d contac t wit n iiqui a an d vapo rKee o peopl e away . Wea rgoggle s an d seit-containe d breamin g apoaralus
. Shu t of t ignitio n source s an o cal l 'ir e department , Slayupwin d an o us e wate rsprayt o knoc k down " vapor . Sto p discharg e i f possible
. 'scal e an o remov e aiscnarge d materia l Notif yloca l neait n an d pollutio n contro l agencie s

Fir e

Exposur e

Wate r Pollutio n FLAMMABLE . Flashbac k

alon g vapo r trai l ma

y occur . Vapo r ma

y explod e rf ignited i n a n enclose d area . wea r goggie

s an d seil-containe d Dreathtn g apparatus . Combat tire s iro m saf e distanc e o rprotecte d locatio n Extinguis h wit h dr

ychemical , alcoho l foam , o rcartoo n dioxid e Wate r ma

y t » ineffectiv

e o n tire . Coo i expose d container s wit h wate r

CAL L FO R MEDICA L AI D VAPO R irritatin g to eyes , nose an d throa t I f inhaled , wil l caus a nausea , vomiting , headache , difficul t breathing , o rlos s o f consciousness . Mov e t o fres n air
. 1 1 breathin g ha s stooped , giv e artificia l respiration , i f breathin g i s difficult , giv e oxygen . LIQUI D W W bu m ski n an d eyas . Harmfu l i f swallowed . Remov e contaminate d clothin g an d shoes
. Flus h affecte d area s wit h plentyo f water . I F > N EYES , hot d eyelid s ope n an d flus h wit h plent yo f water . I F SWALLOWE D an d victi m i s CONSCIOUS , hav e victi m dnn h wate r o rmilk
.

HARMFU L T O AQUATI C UF E I N VER Y LO W CONCENTRATIONS . Ma y b a dangerou s i t i

t enters wate r intakes . Notifyloca l healt h an d wildlif e officials
. Notifyoperator s o

f nearoywate rintakes
. 1 . RESPONS E TO DISCHARG E {80 0 Roepono o Method s HamWwofc ) Isau o warning-hig h flanvnabiMy Disperse an d (lus h

3 . CHEMICA L DESIGNATION S 3. 1 C O Compa_b4_t

y Ctaaa s Aldehyd e 3. 2 Formula : CHiCH O 3 J IMO/U N Designation : 11/108 9 1. 4 DO T I D No - 100 9 3. 9 CA S Reglatr y No. * 7S-07- 0 2. 1 U I LABE L 0-_a: 3

4 . OBSERVABL E CHARACTERISTICS 4. 1 Physica l Stat e (a a shipped * Liqui d 4 J Colo r Colorles s 4 J Odo r Pono-abng , maty , inar p pungen t

S. HEALTH HAZARD

S 9. 1 Paraona l Proloc-v o Equipmen t Rubbe r gloves , ay * goggles , an d otna r equipmen t 1 0 pravan t an y contac

t wit h body . &gani c canista r o r a r pac k a a required . Jm\ Symptom o . oBoartn g Expooura : Breathin g vapor a wi l bo irritatin g an d ma y caua a nauiaa . vomiting , headache , an d unoonodouanaaa . Contac t wit h ayo a ma

y caua a bums . Ski n contac t Iro m clothin g wa i wKt i mechanica l rauaa i bum a o r aavar o rrttation . 5. 3 Troatman t of Expooura : INHALATION : ramov a victi m t o Iroa h
_ r i l breelhin g Ita a stopped , giv o artilicua l reapraoon * i l biaatliin g ia difficult , giv a oxygon ; ca l a phyaicia n at onco . SKIN : was h wit h aoa p an d watar . EYES : fluah wa n watar . 9. 4 Thraano M umt t latum 10 0 pp m 9. 9 Shor t Ta m limalam m Umtta : 5 0 pp m M r t o na n 5. 4 Toxicit y b y Ingestion . Grad o 2 ; LO. o •0. 9 to Sg/kg (rs « 5. 7 Lat a Toxicity : Dat a no t availabl e 9 J Vapo r ((tea ) Irritan t Charactartatlca : vapo r i a modaratal y matin g auc h tha t paraonna l w * no l uauall y tolarat a modaral a o r hig h concentrations . 9. 9 Uqui d o r Sd W IntUttt Characteristics : Minimu m hazard . H spile d o n clothin g an d allowed 1 0 remain , ma

y caua a smartin g an d reddenin g o l th a akin . 9.1 0 Odo r Threehok t 0.2 1 pp m 9.1 1 IOL H Value : 1000 0 pp m t FIR E HAZARDS •. 1 Ftee h PO M -38- F C.C : -58- F O C 8 J FlammaWa Umtt a I n Ai r 4H.-80 * 8 J F_ » EmngUaHn g Agents : Or y chenscol . aJcohol loam , carto n diond a 9. 4 Flr a Cr_ngi_ar_n g Agant a No t t o b a Used : Wata r ma

y b a nadoctiv a 9. 9 Spada l Haiard a o f ConmusBo n Preducta : Produco

a mtann g vapo r wha n haata d 9. 9 Behavio r I n Flra : vapor a a m haavia r tha n m an d ma y trava l a conaidarabl o diatancato a source o

f ignrtio n an d (las h back . 9 7 ignmo n Temperature : MS' F 9 4 Electrica l Hoard : Clas s 1 . Grou p C 9. 9 Burnin g Rata : 3. 3 mm/min . 8.1 0 Adtobotl c Flam e Temperature : Oal a no t avadabl e fCentftutdl 7. CHEMICA L REACTIVIT Y 7. 1 Ra-cBvtt y wit h Wata r N o raactio n 7. 2 RaoctMl y wit h Commo n MatarlalB : N o reectio n 7. 1 StaMtt y Durin g Tranapor t Stabl e 7. 4 Noutraa__i g Agant a fo r Add a an d Couadc c No

t portman t 7 J PorymortiaBon : May occu . Avoi d hen . dual , stron g oxidizn g o r reducin g substances , atron g add a an d baaa a 7M biMbito s o f Pofymeftiedon : Non a 7. 7 Mola r Rati o (Baactan t t o Product) : Oata no

t tvaHabta 7 J naacttvtt y Onup: 1 9

I WATE R POLUmO M 9. 1 Aquati c Toxicity : 5 3 ppm/98 hr/sun«ah/T_./_ea h wata r 70 ppm/2 4 hr/pi n parch/TL^/aa R wata r (_ * Watartow l Toxicity : Oa u no t avaaac M S J Btotoglce l Oxygo n Oomen d (BOO * 93-127% . S day

s a. 4 Foo d Chai n Concentratio n Potential ;

9 . SHIPPIN G INFORMATIO N 9. 1 Ondooo f Purity : >gg % 9. 2 Storag a Tampaialm a Ambian t 9 J Inor l Atmoopfiora : Inarta d 9. 4 VanUng : Salaty rata )

« . FIREHAZ A 8.1 1 Stolel-omauk . Ai r t o Fua l Ratio : 7 80 0 (Es t 9.1 2 Flam a Temperature : Oata no t availabi a 18 . HAZAR D ASSESSMENT COOE (Ba a Haaar d Meeaamen f Handbook) A-B-C-K-L-M-N- Z

11. 1 t u

11 J

12 . 12. 1 I 2 J i l l 12. 4 12 J 12 J 12. 7 12 J 12 J 12.1 0 12.1 1 12.1 2
12.1 1 12.1 4 12.1 8 12.1 8 12J S 12J 8 12J 7 11 . HAZAR D ClASSirKATION S Cod e o f Federa l Aegutattone : Flanwnabl a kquM

) NA S Hazar d Ratin g to r Bu t Wata r Tranaportatlon : Cataffory Platin g Rr a 4 Healt h Vapo r imtan t 3 Poison s 2 Wata r PoMw n Huma n Toncrt

y 3 Aquati c Toxicit

y 2 Aestheti c Effec

t 3 Reactivit y Othe r Chemcat s 2 Wata r 2 Self Reactor . 0 NFP A Hazar d OaaaMcatton :

Catagor y Ctaaalfl c atlo n Haalt h Hazard IBha) 2 FlammabiMy (Rad ) 4 Raactwt , (Yat-w l 2

PHYSICA L AN O CHEMICA L UtOKATI- S Phyaica l Stat a a l 1i* C an d 1 8tn : Ugu d Molacula r Walgft t 44.0 9 BoMn g Poin t a t 1 atn . 88.7- F - 20.4- C - 283.8' K Freezin g Pon e -189- F
_-123- C . 150- K Critica l Tamparatura : 370' F - 188* C - 481' K Critica l Praaaura : 92 0 pai a . 5 8 at m . 9. 7 MN/m > SpacM M Gravity : 0.78 0 at _0* C (liquid ) Liqui d Surfac e Tanaton c No t paninan t Uqu M wata r tntarfada l Tanalon : No l partinan t Vapo r (Oaa ) Dpacin e Oravlty : 1 5 Rati o o f Spadfl c Hoat a o f Vapo r (Oaa) : 1.19 2 Latan f Haa t of tam^mmt.mumm. 24 5 8tu/l b - 13 8 cal/ g - 5 6 9 X 10 * J/k g Haa t o f Combuatlor e -10.80 0 Btu/ D

. -580 0 eal/ g - -248. 4 X to 1 J/k g Haa t of DaconipoaHlon : Not pamnon t Haa t of SolutlOff No

t parbnan t Haa t of Potytnarlmtaf E No t portvian t Haa l o f Fuatarc Oata no t avaNabl a Umftln g Value : Oata no t availabl e Ra w Vapo r Praaaura : 25. 8 pai a

R0 S (Continued ) )

JUN E 198 5P.5 3

12.1 7 SATURATE D UOUI D DENSIT Y Temperatur e (degree s F ) - 2 0 —1 0 0 1 0 2 0 3 0 4 0 5 0 6 0 Pound s pe rcubi c

foo t 52.49 0 52.06 0 51.63 0 51.20 0 50.77 0 50.34 0 49.91 0 49.48 0 49.05 0 12.1 8

UOUI D HEA T CAPACIT Y Temperatur e (degree s F ) —10 0 —8 0 - 6 0 —4 0 —2 0 0 2 0 4 0 6 0 Britis h therma l uni t

pe rpound- F .29 7 .30 0 .30 4 .30 8 .31 1 .31 5 .31 9 .32 2 .32 6 12.1 9

UOUI D THERMA L CONDUCTIVIT Y Temperatur e (degree s F ) 2 8 3 0 3 2 3 4 3 6 3 8 4 0 4 2 4 4 4 6 4 8 5 0 5 2 5 4 5 6 5 8 6 0 6 2 6 4 6 6 6 8 Britis h therma l

unit-inc h pe rhour squar e foot- F 1.31 7 1.31 4 1.31 1 1.30 7 1.30 4 1.30 1 1.29 7 1.29 4 1.29 1 1.28 7 1.284 1.28 1 1.27 7 1.274 1.27 1 1.26 7 1.26 4 1.26 1 1.25 8 1.25 4 1.25 1 12.2 0 * UQUI D VISCOSITY Temperatur e (degree s F) Centipois e N O T P E R T 1 N E N T

12_2 1 SOLUBILIT Y I N WATE R 12.2 2 SATURATE D VAPO R PRESSUR E 12_2 3 SATURATE D VAPO R DENSITY 12.2 4 IDEA L GA S HEAT CAPACITY Temperatur

e (degree s F

) Pound s pe r10 0 pound s o f wate r Temperatur e (degree s F ) Pound s pe rsquar e inc h Temperatur e

(degree s F ) Pound s pe rcubi c foo t Temperatur e

(degree s F ) Britis h therma l uni t

pe rpound- F M I S C I B L E 0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 7 5 8 0 8 5 9 0 9 5 10 0 10 5 11 0 11 5 120 12 5 2.70 4

3.11 1 3.56 7 4.08 0 4.65 2 5.29 1 6.00 2 6.79 0 7.664 8.62 9 9.69 3 10.86 0 12.15 0 13.56 0 15.10 0 16.78 0 18.61 0 20.61 0 22.77 0 25.12 0 27.66 0 30.40 0 33.36 0 36.56 0 39.99 0 43.68 0 0 5 1 0 1 5 2 0 2 5 3 0 3 5 40 4 5 5 0 55 6 0 6 5 70 7 5 8 0 8 5 9 0 9 5 10 0 10 5 11 0 11 5 12 0 12 5 .0241 4

.0274 7 .0311 7 .0352 7 .0398 0 .0446 0 .0502 9 .0563 3 .0629 4 .0701 6 .0780 4 .0866 1 .0959 3 .1060 0 .1170 0 .1288 0 .1415 0 .1552 0 .1700 0 .1858 0 .2028 0 .2209 0 .2403 0 .2610 0 .2831 0 .3066 0 0 2 0 4 0 6 0 8 0 10 0 12 0 14 0 16 0 18 0 20 0 22 0 24 0 26 0 28 0 30 0 32 0 34 0 36 0 38 0 40 0 42 0 44 0 .26 9

.27 6 .26 3 .29 0 .29 8 .30 5 .31 2 .31 9 .32 6 .33 3 .33 9 .34 6 .35 3 .36 0 .36 6 .37 3 .37 9 .38 6 .39 2 .39 8 .40 5 .41 1 .41 7

# sr-ftt-33 * c.a 

# HANDBOO KO F TOXI C AN D HAZARDOU S CHEMICAL S AN D CARCINOGEN S Secon d Editio n

iagin g rocess jn t d e .orpo - * . Uni 

### b y 

# Marshal l Sitti g Princeto n Universit y 

# '3*55 "



# n p NOYE S PUBLICATION S

Park Ridge , Ma

wJersey , USA. 

# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK , N C•^r-Kjj*-. ; IJW H **' B, 1«B5 * 

### -^ssf^'r*- ' ^^f- w Acetaldehyd e 2 1 Reference s (1 ) U.S . Environmenta l Protectio n Agency , Acenaphthene: Ambient

Water Criteria, Repor t P B 296-782 , Washington , OC (1980) . (2 ) Sax , N.I. , Ed. , Dangerous Properties

of Industrial

Materials

Report, 4, No . 1 , 38-41 , New York , Va n Nostran d Reinhol d Co
. (1984) .



### ACENAPHTHYLEN E Se e "Polynuclea rAromati c Hydrocarbons. "



### ACETALDEHYD E cM 3 

### CMO o Hazardou s substanc e (EPA ) o Hazardou s wast e (EPA ) Description : CH 3 CHO , acetaldehyde , i s a flammable , volatil e colorles s liqui d wit h a characteristi cpenetrating , frui t odor
. I t boil s a t 20 ° t o 21°C
. Cod e Numbers : CA S 76-07- 0 RTEC S A B 192500 0 U N 108 9 DO T Designation : Flammabl e liquid
. Synonyms : Aceti c aldehyde , aldehyde , ethanal , ethy l aldehyde
. Potentia l Exposure : Acetaldehyd e ca n be reduce d o roxidize d t o for m aceti c acid , aceti c anhydride , acrolein , aldol , butanol , chloral , paraldehyde , an d penta erythritol
. I t i s als o used i n th e manufactur e o f disinfectants , drug s (A-41) , dyes , explosives , flavorings , lacquers , mirror s (silvering) , perfume , photographi c chemicals , phenoli c an d ure a resins , rubbe raccelerators an d antioxidants , varnishes , vinegar , an d yeast . I t i s als o a pesticid e intermediat e (A-32)
. NIOS H estimate s tha t 2,43 0 worker s ar e expose d t o acetaldehyde
. Acetalde hyd e i s th e produc t o f mos t hydrocarbo n oxidations ; i t i s a norma l intermediat e produc t i n th e respiratio n o f highe rplants ; i t occur s i n trace s i n al l rip e fruit s an d ma y for m i n win e an d othe ralcoholi cbeverages afte rexposur e t o air
. Acetaldehyd e i s a n intermediat e produc t i n th e metabolis m o f sugar s i n th e bod y an d hence occurs i n trace s i n blood
. I t ha s bee n reporte d i n fres h lea f tobacc o a s wel l a s i n tobacc o smoke an d i n automobil e an d diese l exhaus t (A-5)
. I t ha s bee n foun d i n 5 o f 1 0 wate rsupplie s surveye d b y EP Awit h th e highes t concentra tion s i n Philadelphi a an d Seattl e a t 0. 1 mli (A-2)
. Incompatibilities : Stron g oxidizers , acids , bases , alcohol , ammonia , amines , phenols , ketones , HCN , HfeS
. Permissibl e Exposur

e Limit s i n Air : Th e Federa l standar d (TWA ) i s 20 0 pp m (36 0 mg/m 3 ) ; however , th e ACGI H 1983/8 4 recommende d TL V i s 10 0 pp m (18 0 mg/m 3 )
. Th e tentativ e S.TE L i s 15 0 pp m (27 0 mg/m 3 ) an d th e IDL H leve l i s 10,00 0 ppm . Determinatio n i n Air : Acetaldehyd e mayb e collecte d b y impinge ro rfritte d bubble ran d the n determine d colorimetricall y(A-8)
. Permissibl e Concentratio n i n Watar : Huma n exposur e t o acetaldehyd e prob abl yantedate s recorde d history , inasmuc h a s acetaldehyd e i s th e majo rmetabo -2 2 Handboo k o f Toxi can d Hazardou s Chemical s an d Carcinogen s lit e o f ethy l alcohol
. A n additiona l sourc e o f widesprea d huma n exposur e i s tobacc o smoke
. Th e pharmacolog yan d toxicolog yo f acetaldehyd e hav e bee n studie d mos t extensivel yi n it s relationshi p t o alcoho l toxicit yan d huma n me tabolism
. Because o f thi s backgroun d o f huma n an d laborator yexperience , ther e appear s t o b e n o nee d t o establis h limit s fo racetaldehyd e i n drinkin g wate r (A-2)
. However , EPA(A-37 ) ha s se t a n ambien t environmenta l goa l o f 2,48 0 /j.g/ 2 fo racetaldehyd e o n a healt h basis
. Route s o f Entry : Inhalatio n o f vapor , ingestion
. Harmfu l Effects an d Symptoms : Local - Th e liqui d an d th e fairl ylo wlevel s o f th e vapo rare irritatin g t o th e eyes , skin , uppe rrespiratorypassages , an d bron chi
. Repeate d exposur e ma yresul t i n dermatitis , rarely , an d ski n sensitization
. Systemic - Acut e involuntar yexposur e t o hig h level s o f acetaldehyd e vapors ma yresul t i n pulmonar yedema , precede d b yexcitement , followe d b ynarcosis
. I t ha s bee n postulate d tha t thes e symptom s ma yhav e bee n simila rt o thos e o f alcohol , whic h i s converte d t o acetaldehyd e an d aceti c acid
. Chroni c effect s hav e no t bee n documented , an d see m unlikely , since voluntar yinhalatio n o f toxicologicall ysignifican t level s o f acetaldehyd e ar e preclude d b yit s irritan t propertie s a t level s a

s lo wa s 20 0 pp m (36 0 mg/m 3 o f air)
. Point s of Attack : Respirator ysystem , lungs , skin , kidneys
. Medica l Surveillance : Consideratio n shoul d b e give n t o skin , eyes , an d respiratorytrac t i n an ypreplacemen t o rperiodi c examinations
. First Aid : I f thi s chemica l get s int o th e eyes , irrigat e immediately
. I f thi s chemica l contact s th e skin , flus h wit h wate rpromptly
. I f a perso n breathe s i n larg e amount s o f thi s chemical , move th e expose d perso n t o fres h ai ra t onc e an d perfor m artificia l respiration
. Whe n thi s chemica l ha s bee n swallowed , get medica l attention
. Giv e larg e quantitie s o f wate ran d induc e vomiting
. D o no t make a n unconsciou s perso n vomit
. Persona l Protectiv

e Methods : Wea rappropriat e clothin g t o preven t repeate d o rprolonge d ski n contact . Wea reye protectio n t o preven t an ypossibilit yo f eye contact . Employee s shoul d was h promptl ywhe n ski n i s wet . Remov e clothin g immediatel yi f we t o rcontaminate d t o avoi d flammabilit yhazard
. Provid e eye wash
. Respirato r Selectio n (A-4) : 1,000ppm : CCROV F 5,00 0 ppm : GMOV c 10,000ppm : GMOVfb/SAF/SCBA F Escape : GMOV/SCB A Disposa l Metho d Suggested : Incineratio n (A-31)
. Reference

s (1 ) U.S . Environmenta l Protectio n Agency , Chemical Hazard Information

ProfHe:

Acetaldehyde, (Preliminary) , Washington , D C (1979) . (2 ) U.S . Environmenta l Protectio n Agency , Acetaldehyde, Healt h an d Environmenta l Effects Profil e No . 1 , Washington , DC , Offic e of Soli d Wast e (Apri l 30,1980) . (3 ) Sax , N.I. , Ed. , Dangerous Properties

of Industrial

Materials

Report, 1, No . 1 , 25-6 , Ne wYork , Va n Nostran d Reinhol d Co . (1980) . (4 ) Se e Referenc

e (A-61) . (5 ) Se e Referenc

e (A-60) . (6 ) U.S . Environmenta l Protectio n Agency , Chemical Hazard Information

Profile Draft Report: Acetaldehyde, Washington , D C (Apri l 29,1983) ._. P.5 7 

## tmaammmmmmmi^^tmmmmt^a^mmi^tmm^^

INDUSTRIA L ORGANI C CHEMICAL S PROCES S NO . 8 4 Acetaldehy4fiL_-.(Wacker process ) C 2 

### H 4 

### + 1/ 2 0 2 

### >-\CH 3 

### CHO U hea t (24 4 kJ/mole ) Functio n - Th e Wacke r proces s employ s a n aqueou s catalvs t solutio n
o f palladiu mchloride , promote d b ycoppe r chloride . Th e catalys t act s a s th e oxyge n carrie r and cause s selectiv e conversio n o f ethylen e t o acetaldehyde . Th e reactio n step s essentiall y are : PdCl , Reaction : C,H . + 2CuCl „ + H o 

### 0 =-+ • CH,CH O + 2HC 1 + 2CuC l 2 4 2 2 3 Regeneration : 2CuC l + 2HC 1 + l/20 2 

### • 2CuCl 2 

### + H 2 

### 0 Ther e ar e tw o basi c proces s variations , dependin g upo n suc h factor s
a s oxyge n cost , utilitie s prices , an d availabl e ethylen e purity . I n th e single-stag e process , pur e oxyge n i s employe d a s th e oxidant . Th e reacto r effluen t i s condense d and water-scrubbed . Unreacte d ga s i s recycle d int o th e reactor . By-product s an d wate r ar e separate d fro mth e acetaldehyd e produc t b ydistillation . Bot h th e reactio n an d regeneratio n ar e effecte d a t th e sam e time . I n th e two-stag e process , th e oxidan t i s air . Th e reactio n i s
^[ carrie d ou t wit hcatalys t solutio n an d ethylen e i n on e reactor , an d X * th e regeneratio n i s carrie d ou t wit h ai r i n a separat e reactor . Lowe r 

# ki purit yethylen e ca n b e use d wit h thi s versio n o f th e process . However ,

/ thi s proces s form s mor e by-product s an d require s hig h operatin g pres sures . Th e productio n o f acetaldehyd e b yvapo r phas e oxidatio n o f propane " ric h LP G i s considere d obsolete . 2 . Inpu t Material s (pe r metri c tonn e acetaldehyde )

6-23 6

### Ethylen e 99. 8 vol . % , k g 3 Oxygen , N

m Catalyst : PdCl 2 

### , g CuCl 2 

### + 2H 2 

### 0 , g HC l (100% ) use d a s 30 % aqueou s solvent , k

g 3 . Operating Parameter s Temperature , °C(°F ) Pressure , kP a (atm ) 4 . Utilitie s 3 Coolin g wate r (25°C) , m 3 Cooling wate r (12°C) , m

3 Proces s water , m 3 Deionize

d water , m Steam , metri c ton Electri c power , M

J (kWh ) Credi t fo

r nitroge

n (protectio

n gas) , Nm-

3 

### (63 7 kPa )

t o flar e (air) . Single-stag e 

## 67 0 27 5 0. 9 15 0 

## 4

130(266 ) 29 4 (2.90 )



## 30 0

- 

## 6 3 1. 6 75 4 (210 )

Ethane : 2. 2 kg/M g acetaldehyd e Ethylene : 27. 4 kg/M g acetaldehyd e Acetaldehyde : trace Methane : trac e Methy l chloride : trac e Two-stag e * 

### 67 0

- 

## 0. 9 15 0 1 5

- 

### 784-88 3 (7.74-8.71 ) 

## 20 0 1 2

-

- 

## 1. 2 * * 

### 30 0 

## 90 0

Ethylen e o f lower purit

y result s i

n slightly

higher consumptio

n * * 

### Includin

g ai r compressio

n
6-23 7P.5 9



### Purificatio n sectio n- acetaldehyd e strippe r ven t t o flar e (air ) Methy l chloride : 8.6 5 kg/Mg acetaldehyd e Acetaldehyde : trac e 3 A typica l Wacke r proces s discharge s abou t 4. 4 m (1,20 0 gallons )
o f wast e pe r to n o f product . The chlorinate d aldehyde s ar e th e principa l contaminant s i nthe waste stream s whic hhav e a CO D o f 3 approximatel y

1 0 cg/ m

(10,00 0 mg/1) . Th e two-stag e proces s yield s relativel y smal l amount s o f a rathe r concentrate d wast e wate r whic hmus t b e pretreate d befor e norma l biodegradation . Th e single-stag e yield s considerabl y mor e o f a mor e dilut e waste wate r suitabl e fo r biodegradation . 6 . EP A

sourc e classificatio ncod e - Non e 7 . Reference s Morse , P . L. , "Acetaldehyde, " Repor t No . 24 , Stanfor d Researc h Institute , Menl o Park , California , Apri l 1967 . Gloyna , E . F. , an d Ford , D . L. , "Th e Characteristic s an d Pollutiona l Problem s Associate d wit hPetrochemica l Wastes, " fo r FWPCA , Contrac t No . 14-12-461 , Februar y 1970 . Austin , G . T., "Th e Industriall y Significan t Organi c Chemical s - Par t 1, " "Chemica l Engineering, " January 21 , 1974 , p . 127 . "197 5 Petrochemica l Handbook, " "Hydrocarbo nProcessing, " 54^ , Novembe r 1975 , p . 100 . Jira , R. , e t al. , "Hydrocarbo nProcessing, " 55_ , Marc h1976 , p . 99 .

6-23 8

### INDUSTRIAL ORGANI C CHEMICAL S PROCES S NO . 12 4 Acetaldehyd e (fro

m ethanol ) CH 3 

### CH 2 

### O H + 1/ 2 0 2 A£ 

### - * CH.CH O + H 2 

### 0 1 . Functio n - A s o f 1974 , onl y 15 % o f the Unite d State s acetaldehyd e capacit y

wa s base d o nethanol . Ther e ar e tw o processe s fo r conversio n o f ethano l t o acetaldehyde , i.e. , oxidativ e dehydrogenatio nan d catalyti c dehydrogenation . Oxidativ e dehydrogenatio n Th e vapo r phas e reactio ni s carrie d ou t ove r soli d silve r gauz e catalys t a t 538° C (1000°F) . Aqueou s ethanol , steam , an d ai r ar e fe d t o th e oxidize r (reactor) . Th e reacto r effluen t i s condense d ^^_____________----_^M___^^_ » 

### an d i s passe d t o a phas e separato r whic hals o serve s a s a scrubbe r (refrigerate d water) . Th e of f gase s ar e vente d fro m the syste

m an d th e was hi s combine d wit hthe liqui d stream . Th e combine d liqui d strea m i s sen t t o a flas hcolum nwher e i t i s separate d int o acetal dehyd e product , alcoho l fo r recycle , an d waste water . Th e acetaldehyd e produc t fro

m th e flas hcolum

ni s sen t t o anethano l recover y stil l wher e acetaldehyd e produc t i s take nfro m the top an

d the bottom s (primaril y

ethanol ) ar e recycle d t o th e reactor . Catalyti c dehydrogenatio n Th e primar y

reactio nis : CH 3 

### CH 2 

### O H -*=-• • CH 3 

### CH O + H 2 

### Th e vapo r phas e reactio ni s carrie d ou t ove r a soli d coppe r catalys t promote d b y cobal t or chromiu m ona nasbesto s suppor t a t 260° C (500°F) . Th e recover y an d isolatio nsystem s ar e almos t identica l t o thos e i n oxidativ e dehydrogenation . Th e yield s i nbot hprocesse s rang e fro

m 8 5 t o 95% . 6-32 4

# h P.6 1



# L 2 . Inpu t Material s Oxidativ e dehydrogenation : ai r ethano l stea m wate r Catalyti c dehydrogenation : ethano l - 115 0 kg/metri c ton (2,53 5 lbs/ton ) acetaldehyd e 3 . Operating Parameter s

Oxidativ e dehydrogenation : temperatur e - 538° C (1000°F ) pressur e - 41 0 kP a (4.0 5 atm ) flo w rat e - no t give n equipmen t - multitubula r reactor ,

phas e separator , flas h column , stil l catalys t - soli d silve r gauz e Catalyti c dehydrogenation : temperatur e - 260° C (500°F ) pressur e - no t give n flow rat e - no t give n equipmen t - se e oxidativ e

dehydrogenatio n catalys t - soli d coppe r catalys t

promote d b

ycobal t o r chromiu mo n a n asbesto s suppor t 4 . Utilitie s - Th e wate r usage s o f tw o plant s are : Proces s wate r Coolin g wate r Plan t 1 5. 9 kg/kg produc t 47. 2 kg/kg produc t Plan t 2 0.4 5 kg/kg produc t 45. 4 kg/k g produc t 6-32 5P.6 2 

## •Hi

Wast e Stream s Ai r - Of f gase s fro mthe phas e separator ; i t ha s bee n estimate d that 12. 2 Mg (2 7 MM lb ) o f C O i s emitte d annuall yfro mthi s industry . Wate r - Th e onl ywastewate r strea mgenerate d i s eithe r fro mth e acetaldehyd e flas h colum n o r ethano l recover ystill . I t contain s liqui d product s suc h a s acetaldehyde , ethanol . an d ethy l acetate . Dat a o n two plant s (on e using eac h o f th e tw o processes ) wa s a s follows : Plan t 1 Flo w



## CO D

BO D 6. 0 m J 

### /

45 4 k g produc t 0.18 6 kg/m 3 

### (18 6 mg/1 ) 1. 1 kg/45 4 kg 0.08 4 kg/m 3 

### (8 4 mg / 1 ) 0.5 0 kg/45 4 kg Plan t 2 52 9 dm 3 

### / 45 4 k g produc t



## TO C 14. 4 kg/m J 

### (14,40 0 mg/1 ) 7. 6 kg/45 4 k g 6 . EP ASourc e Classificatio n Cod e - Non e 7 . Reference s

Austin , G . T. , "Industriall ySignifican t Organi c Chemical s - Part 1, " "Chemica l Engineering, " January21 , 1974 , p . 128 .

6-32 6P.6 3


# £EFt t Unite d State s

Environmenta l Protectio n Agency Offic e o f Ai r Quality Plannin g an d Standard s Resesrc h Triangl e Par k N C 2771 1 

# TtZ

EPA-450/3-80-028 d Decembe r198 0 

### Ai r 

# Organi c Chemica l Manufacturin g Volum e 9 : Selecte d Processes

miwwi" T

### III- l

III . PROCES S DESCRIPTIO N
INTRODUCTION In th e Unite d State s 94.9 % o f th e acetaldehyd e capacit y i s base d o nth

e Hoechst Wacke r process , whic hconsist s o f two-ste p ai r oxidatio no f ethylene . Approxi matel y 4.7 % i s base d o n oxidatio no f ethanol , an d the remainin g 0.4 % i s recovere d a s by-produc t fro

m othe r processes . Hydratio no f acetylen e an d oxidatio n o f saturate d hydrocarbon s (butan e an d propane) , onc e processe s o f majo r importanc e i nthe Unite d States , hav e give nwa y t o th e mor e economi c ethylene-base d process . A rhodiu m catalyze d proces s capabl e o f convertin g synthesi s ga s directl y int o 2 acetaldehyd e i n a singl e ste p wa s reporte d i n1974 . Thi s proces s ma y become importan t i n the futur e a s coa l gasificatio nmethod s ar e perfected .

B 

### . ACETALDEHYD E FRO M ETHYLEN E Th e direc t liquid-phas e oxidatio no f ethylen e t o acetaldehyd e by mean s o f a palladiu

m chloride-cupri c chlorid e catalys t wa s discovere d i n1956 . Th e com mercia l proces s wa s develope d and license d by the consortiu

m o f Hoechs t and Wacke r i n Germany i n th e lat e 1950 s and earl y 1960s . Sinc e 196 0 al l reporte d 4 ne w plant s hav e use d th e Hoechst-Wacke r technology . Direc t oxidatio n o f ethylen e t o for m acetaldehyd e i s accomplishe d throug ha serie s o f oxidation-reductio n reactions . Th e catalys t i s a naqueou s solutio n o f palladiu

m chlorid e an

d cupri c chloride . Th e reactio no f ethylen e wit han aqueou s palladiu

m chlorid e solutio nt o for m acetaldehyd e i s represente d b y Eq . (1 )

C 2 

### H 4 

### + PdCl 2 

### + (ethylene ) (palladiu m chloride ) 

## H 2 

## 0

(wat e C H CH O 

## P d + 2HC 1 (1 ) (acetaldehyde ) (metalli c (hydrochlori c

palladium ) , acid )
Th e palladiu

m i s reoxidize d t o palladiu m chlorid e b y

cupri c chlorid e a s show n b y Eq . (2) .
P d + 2CuCl . -> • PdCl „ + 2CuC l

2 

## (2 ) (palladium ) (cupri c chloride ) (palladiu m (cuprou s chloride ) chloride )P.6 5 

# Revie wDraf t
EPA-450/3-87-02 6 

# I I I Hazardou s Wast

e Treatmen t Storag e an d Disposa l Facilitie s (TSDF ) —Ai r Emissio n Model s

Emissio n Standard s Divisio n

U.S . ENVIRONMENTA L PROTECTIO N AGENC Y Offic e o f Ai r an d Radiatio n Offic e o f Ai r Quality Plannin g an d Standard s Researc h Triangl e Par k N C 2771 1 Jul y 1990

### cn-rat o NM E CA S | M.W

. D84SIT

Y VAP.PRES

S SOUBILn Y H LA

WCONST.DIFF.HUB * (Q/NC ) (fmha)

(«B/I ) (ataMra/Mol ) (cnfi/Mc ) BOILING DDT.AI RPOINT (a£/Nc)(<hg.C ) VAPO R PRESSUR

E COEFFICBENT

S
S-VU__N0kETMtL-3-ISOXAZ0La

_2769-86- 4 114. 1 6-OfjORO-l,3-CYCLOP_HrAD_B C 24 6 100.0 0 6-HYDR0KY-l,3-C.CLOPB*ITAOIB C 72 8 61.0 0 6-ME1HYl_FURRfiA

L 620-02- 0 110.1 1 6-iEnm.-i,3-cYa_aPENrADiB c 26619-91- 6 80.1 4 Kamam*. 86-32- 9 1M.2 1 1.0 7 ACBWHTWAB C 208-86- 8 168.2 1 ACETAUDBIYDE 7S-07- 0 44. 0 0.7 9 ACETAMID E 60-36- 6 68.0 7 ACETI C ACI D 64-19- 7 60.0 6 1.0 6 ACETI C ANHYDRID E 108-24- 7 102.0 9 1.0 4 ACEIO E 67-64- 1 68.0 8 0.7 9 AOEID E 76-06- 8 68. 0 0.7 9 ACETONITRIL E 76-06- 8 41.0 8 0.7 8 ACETOPHB-OC 96-86- 2 120.1 6 1.0 8 ACETY L OUORID E 7»-36- 6 78.6 0 1.1 1 ACETY L DIETHVU-ALOrttT E 26 6 194.0 0 ACETYUEN E 74-86- 2 26.0 4 ACROLEI N 107-02- 6 66. 1 0.8 4 ACRYLAMID E 79-06- 1 71.0 9 O.O O ACRYLI C ACI D 79-10- 7 72.1 0 0.0 0 ACRYLONITRIL E 107-18- 1 68. 1 0.8 1 AOWIUNTANE DICARBOXYLI C ACI D 828-61- 8 180.2 6 AQAMWfTAN

E DICHLORID E 17 1 207.1 0 ADIPI C ACI D 124-04- 9 146.1 4 1.8 7 AUHCAR 8 116-06- 3 190.2 9 ALDRI N 609-00- 2 864.9 8 ALLY L ALCOHO

L 107-18- 6 68. 1 0.8 6 ALLYL CHLORID E 107-O6- 1 78.6 8 0.9 4 ALPH A METHY

L STYRB C 98-88- 9 118.0 0 O.O O AlPH A IETHV L STYRB E DDJER S 8 8 236.0 0 •lph»-CHL0RO-b«U-ICTHYt_NAPHlH86-62- 2 178.6 6 ALPHA-HYDRQXYACETALDB1YD E 6 0 ALPHA-HYDRQXYM)IPIMID E 42 9 162.0 0 •Ipha-METHYLSTYRB E (-4 ) 98-93- 9 118.1 9 •iphfr-PICOLIh E 1333-41- 1 93.1 4 0. 1

O.00 6 78 0 1 16.4 1 6.28 6 26 6 26 6 9 0 1 287. 8 20 0

0. 2 2 6000 0 0. 2 2 2 68000 0

IOO O 108 6 4 0 244. 2 0.01 2 6. 2 6.17E-0 7 11 4 4 2

0. 2 O.000022 6

28. 8 0.07 6 600 0

0.0 1 10 0 2 2 2 IOO O 2 2000 0 7.61E-C 6

E.OOE-O S 4.06E-0 6 2.20E-O 7 4.01E-0 B 7.71E-0 8 1.14E-0 4 9.GOE-0 6 1.20E-O 7 6.27E-0 B 6.91E-0 6 2.60E-0 6 2.60E-O 6 6.80E-0 6 1.41E-0 6 O.OOE-tO

O 1.94E-0 5 1.26E-0 8 6.66E-0 6 6.20E-1 O l.OOE-0 7 6.80E-0 6 1.O4E-0 3 6.08E- U 8.17E-0 6 8.66E-0 2 1.80E-0 6 3.71E-0 1 6.91E-0 8 1.18E-0 2 8.83E-0 8 9.G0E-0 6 1.62E-0 6 6.91E-0 3 4.66E-0I 7 O.OOE«0 0 O.OOEO O 278. 0 7.72 8 2634.23 4 246.67 6

1.41E-0 5 1.24E-0 1 20. 8 8.00 6 1600.01 7 291.80 9 1.20E-0 6 9.33E-0 6 1.14E-0 6 1.14E-0 6 1.66E-0 6 O.00E«O O 1.16E-0 6 l.lSE-O

l 2.86E-0 1 1.24E-0 1 1.24E-C1 1.28E-0 1 O.00E«O 0 9.90E-O2

1.22E-0 6 1.06E-O

1 1.06E-0 6 9.70E-O2 1.06E-0 6 9.60E-O2 1.34E-0 6 1.22E-0 1
0.84E-O 6 6.69E-0 2
1.14E-0 6 1.14E-0 1 O.OOE«0 0 O.00E«O 0 1.14E-0 6 2.64E-0 1 118. 0 7.38 7 1638.81 8 222.30 9 139. 6 7.14 9 1444.71 8 199.81 7 66. 2 7.11 7 1210.69 6 229.66 4 G6. 2 7.11 7 1210.69 6 229.66 4 81. 6 7.11 9 1314. 4 28 0 202. 3 9.13 6 2878. 8 27 3 E2. 0 6.94 8 1116.96 4 223.66 4
63. 0 2.38783 3 87. 0 O O O 141. 6 6.66 2 648.62 9 164.68 3 77. 4 7.03 8 1232.6 3 222.4 7
266. 0
97. 0 1.36740 6 46. 0 O -38. 8 6.92 3 1486 . O O 202.4 0

### *•# ]



## • Estimat e th e biodegradatio nrat e constant s usin g th e followin g methodology : Approximat e K^axfro * availabl e dat a fo r K^ * fo r compound s o f simila r structur e and/o r functiona l groups ; an d Approximat e K i eithe r b y usin g th e followin g correlation : KjU/h/g ) - 0.13 5 K Q W



## 0.3 8 wher e K-

octanol-wate r partitionin g coefficien t o r b y usin g th e defaul t (average ) valu e fo r K\, whic hi s K\ * 1 L/h/g , an

dthe ncalculat e K s 

## as : K s 

## * Kmax-^l Th e followin g propertie s ar e give nfo r eac hchemica l (liste db y name an dChemica l Abstrac t Sourc e [CAS ] number) : Molecula r weigh t Densit y Vapo r pressur e a t 2 5 * C Solubilit y Henry' s la

w constan t Diffusio ncoefficien t i nwate r Diffusio ncoefficien t i nai r Boilin g poin t Coefficient s fo r th e Antoin e equatio nfo r estimatin g vapo r pressur e a t temperature s othe r tha n2 5 °C . T o estimat e vapo r pressure s a t temperature s othe r tha n2 5 *C , th e Antoin e equatio ncoefficient s ar e use dwit hth e followin g equation :

log/jQ V Vapo r Pressur e (m

m Hg ) » A 

# J

_ wher e A , B , an

dC • th e Antoin e equatio ncoefficien t T » temperatur e i n*C . Two approache s ma y

b e use dt o introduc e a new compoun dan

dit s propertie s int o CHEMDAT7 . First , th e dat a fo r on e compoundin CHEMDAT 7 ma y

b e replace dwit hdat a fo r th e compoundo f interes t inth e D- 7

# w P.6 8



## column s specifie dabove . Wit hthi s approach , th e lis t o f compound s in CHEM0AT 7 remain s constan t a t 62 . Th e secondapproac hinvolve s append in g th e ne w

compoun dan 1 It s propertie s t o th e existin g lis t o f chemi cal s inCHEMOAT7 . Al l th e equations/calculation s mus t the nb e copie d fro m on e o f th e existin g row s vi a Lotu s 1,2, 3 int o th e appropriat e cell s inth e ne w

ro w o f th e spreadsheet . A s mentione dabove , th e inclusio ni nCHEM0AT 7 o f al l o r a larg e par t o f th e chemical s liste d inthi s appendi xcoul dresul t inincreasin g th e tim e require dt o exer cis e CHEMDAT 7 an

dcoul dpreven t it s us e onsome microcomputers . Th e propertie s o f interes t liste dabove , wit hth e exceptio no f th e CA S number , mimi c thos e incolumn s B , D-M , andQ o f th e CHEM0AT 7 spreadsheet .

D- 8