p. 1 

# OAR Box 1877 Prepped by Keeia Richards



# Document

Number: 

# 8 ) ll-B- 5 Docket Number: 

# A-90-1 9

Printed 12/2/200810:36:46

AM Sheet 8of 46

### P. 2 

# A-90-1 9 ll-B-5 MEMORANDU M TO : FROM : DATE : Proces s Vent s Docke t A-90-1 9

Wand a Floy

d October , 199 0 

# IMJLU I

SUBJECT : HO

NNESHAP : Industr

yCharacteristics/Aceti c Anhydrid e Attache d i s a product-proces s summar y(PPS ) fo r th

e productio n o f Aceti c Anhydrid e vi a Cardonylatio n o f Methy l Acetate , vi a ai r oxidatio n o f Acetaldehyde , an

d vi a Dehydratio n o f Aceti c Aci d category . Thi s PP S wa s develope d a s par t o f th e Industria l Profil e projec t i n suppor t o f th e Hazardou s Organi c NESHAP (HON ) regulator yeffort . Informatio n i n thi s PP S i s use d a s a basi s fo r emission s an d cos t impac t estimate s fo r th e HO Nprogram . Liste d belo w ar e th e ke yreference s use d i n developing th e attache d PPS . 198 9 Director

yo f Chemica l Producer s USA . SR I International , California , pp . 428-429 . Lowenheim , Fredric k A . et . al . Faith . Keye s an d Clark' s Industria l Chemicals . 4t h edition . John Wile y& Sons , Ne w York , 1975 . pp . 16-20 . Weissermel , Klau s an d Arpe , Hans-Jurgen . Industria l Organi c Chemistry . Verla g Chemie , Ne w York , 1978 . pp . 160-163 . Kent , Jame s A . Riegel' s Handboo k o f Industria l Chemistry . 7th edition . Va n Nostran d Reinhol d Company , Ne w York , 1974 . p . 791 . Meyers , Rober t A . Handboo k o f Chemical s Productio n Processes . McGraw-Hil l Boo k Company , Ne w York , 1986 . pp . 1.1- 3 t o 1.1-8 . Wiseman , Peter . A

n Introductio n t o Industria l Organi c Chemistry . 2n d edition . Applie d Scienc e Publisher s LTD , London , 1979 . pp . 103-104 . Kirk-Othmer . Concis e Encyclopedi a o f Chemica l Technology . 3r d edition . John Wile y& Sons , Ne w York , 1985 . pp . 10-11 . Austin , Georg e T . Shreve' s Chemica l Proces s Industries . 5t h edition . McGraw-Hil l Boo k Company , Ne w York , 1984 . p . 768 . Shreve , R . Norri s an d Brink , Jr. , Joseph . Chemica l Proces s Industries . 4t h edition . McGraw-Hil l Company , Ne w York , 1977 . p . 709 . 

# In e Correspondin g Oaaiit

yAssurance A-90-1 9 Documen t i s Docke t Ite m nB 

# " 25 2P. 3 

# a

. //fe-/c/. ' /Ja.loJi.' 

## Preparer : Oate : s-n-io Reviewer : P>oduct~fcroce$ $ Cfct e ADMINISTRATIV E NOTE S 

# /O^lH-1 Pr Hour s spen t o n thi s PP S %-0 L'J P- P Nam e ACETI

C ANHYDRID E V'Oa -=?, V OX/Jof/oy- » /

qcefa/d^n/e 

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# < W / •7 Pat e Cleared , Initial s

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# acetyl ^h^t l$olo

Plan t wit hCit v

bu t n o Count v

(plan t name , city , state ) 

# ri Q ^ °P. 4



## /l^/iclO /VycXbaJ-/ 

## Preparer : Date : g - 1-7-40 

## Reviewer : Chemica l Nant

a PRODUCT-PROCES S SUMMAR Y (PPS ) 

## o. ctf: c ^ *

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# Alternativ e Cfttoticif'Ift

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## 1. 8 Comment s

## Us e Patter n P. 5



## 2. 0 Chemica

l End-Us e Re

f # Jh__ , P

g # ' ^ - Re f Yea r "7 5 _Uje _ 

# Percen t

Cellulos e esters (includin g cellulos e acetate , acetate butyrate , and acetate propionate ) Aspirin Miscellaneou s Percent 9 5

10 0

• i 3

## 3. 0 U.S . Producers 

## Re f #_ 9 , P

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Proces s Ai ri s bubble d throug

h liqui d acetaldehyd e i n a reacto ri n th e presenc e o

f 2 % (base d on th e weighto f acetaldehyde ) catalyst , such a s a mixture of

coppe ran d cobal tacetate s o rmanganes e acetate , which prevents th e formatio n o f explosiv e amounts o

f peraceti c acid . Ap proximatel y 1.4 parts of aceti c aci d pe r1 par to f acetaldehyd e i s presenta s a diluen tt

o promot e aceti c anhydrid e formation . Methy l or ethy l acetate , triacetin , orbenzen e ma y als o b e use d a s a diluent , an d th e las ti s generall y utilize d i n conjunctio n wit h aceti c aci d a s a withdrawin g agen

ti n subsequen tvacuu m distillatio n to allo w separa tio n of th e reactio n mixtur e fro

m wate ra tlowe rtemperatures . | Th e reacto ri s maintaine d ata temperature o f 5 0 to 70 ° C , an d th e pressur e i s approximatel y 6 0 ps i (41 0 kPa) . Th e overheatfro m th e crud e vacuum colum n i s fractionate d i n a n aldehyd e column , yieldin g acetaldehyd e fo

rrecycl e a s th e overhead and wate ran d diluen ta s bottoms . Th e diluen ti s returned t o th e reacto rafte rth e wate ri s separated . Th e dehydrate d mixture o f aceti c anhydrid e and aceti c aci d fro m th e bottom o f th e crud e vacuum colum n i s separate d b y distillation . Aceti c aci d i s removed a s overhead , an d th e aceti c anhydrid e i s withdrawn fro m a bottom plate . Th e catalys ti s take n fro m th e botto m to b e reused . Th e aceti c anhydrid e ma y b e furtherpurifie d b y vacuum dis tillation . Variation s o

f thi s proces s involv e typ e an d amounto f diluent , and severa l stage s i n th e reacto r(wit h oxygen injectio n into each stage ) undermilde rreactio n conditions . Presen ttrend s ar

e awa y fro m ai ran d towar

d oxygen . In on e continuou s proces s usin g ethy l acetat e a s th e diluen tan d a catalys t concentratio n o

f 1% (cobal tacetate an d coppe racetate i n a weightrati o of 2:1) , th e reactio n i s carrie d outat50° C and 4 5 ps i (31 0 kPa) . Oxyge n i s injecte d atvariou s points alon g th e pat h of liqui d travel , wit

h th e overall oxygen suppl y limite d t o 1 t o 2 % excess . Unde rthes e condi tipjns^95% ^ conversion s o f acetaldehyd e ar

e obtained . Bot

h acetufanhy drid e an d aceti c aci d are produce d i n a 50:5 0 weigh tratio . Th e sam e proces s when carrie d outi n th e absenc e o f th e diluen tgive s a highe roxidatio n rat

e butyield s a loweraceti c anhydride / aceti c aci d ratio (ca . 2:3) .P.1 0



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Materia l Requirement s

Basis— 1 metri c ton aceti c anhydrid e Acetaldehyd e Catalys t Diluen t(les s recovery ) 

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### ^ ' ' "«)><>J> Date : s-»7~9 o Reviewer : ADMINISTRATIV E NOTE S 

# Product-Proc ^ cod i loZr'+ l Hour s spen t o n thi s PP

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# y / 

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## Ai r Oxidatio nReactio n Oxidatio nReactio n Alkylatio nReactio n Carbonylatio nReactio n Halogenatio nReactio n Condensatio nReactio n Dehydrogenatio nReactio n Dehydrohalogenatio nReactio n Esterificatio nReactio n Hydrogenatio nReactio n Hydrohalogenatio nReactio n Hydroformylatio nReactio n Hydrolysi s Reactio n Nitratio nReactio n Oxyacetylatio nReactio n Oxyhalogenatio nReactio n Sulfonatio nReactio n Catalyti c Reformatio n Hydrodlmerlzatlo nReactio n Re f 

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# 4. 5 Writte nDescriptio n Inth e lef t margin , indicat e reference s an dpag e number s throughou t writte n description .

Proces s Vapors o f glacia l aceti c aci dcontainin g 0. 2 t o 0.3 % triethylphosphate (TEP ) are passedint

o atubular

(chrome-iro n alloy ) reactor heate dt o 70 0 t o 800° C under

reduce dpressure (20

0 torr) . A s reactio n gase s leave th e converter , ammoni aga s ( 1 kg/4. 2 k g TEP ) i s injectedint

o th e strea mt o preven t reversion o

f th e ketene i

n th e product . Th e reactor

exit vapor s containin g aceti c anhydride , aceti c acid , ketene , an dwate

r ar e le dt o aserie s o

f condenser s wher

e wea k aceti c aci d(30% ) i s condensedbefor e i t ca n reac t wit h th e ketene . Th e un

condensedketene i s absorbe di n aceti c aci dt

o giv e aceti c anhydrid e (90% purity) , whic

h i s the n fractionate dt

o yiel daspecification product . Keten e ma

y als o b e prepare dfro

macetone according t

o th e equatio n CH.COCH , - CH,=C= 0 + CH , Aceton e vapor s ar e passe dthrough avoi dchrome-iro n tube . Th e temperature o

f th e tub e i s 65 0 t

o 670 ° C , an dth e contac t

tim e i s about 0.2 5 to 5 sec . Th e unchangedacetone i s condensedan drecycled . Th e gaseou s keten e i s absorbe di n glacia l aceti c aci dt

o giv e aceti c anhy dride . Yield s base do

n acetone ar e about

8 0 t o 95% . Conversio

n pe r pas s varie s fro

m1 5 t o 25% .P.2 8



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Basis
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# ID ' 

# •969 c. ^ ^ 

# 198 9 DIRECTOR

Y O F CHEMICAL PRODUCER

S UNITE D STATE S O F AMERIC A

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 Producer s Program .



# RADIA N LIBRAR Y VP.5 8



### 198 9 DIRECTORY O F CHEMICA L PRODUCER S

UNITE D STATE S PRODUCT S Actti c Mi d (Cont'd ) Hoechs t Celanes e Corp . Hoechs t Celanes e Chemica l Group , Inc . Quantu m Chemica l Corp . US I Divisio n Sterlin g Chemicals , Inc . Unio n Carbid e Corporatio n Chemical s an d Plastic s Busines s Grou p Solvent s an d Coating s Material s Divisio n Clea rLake , Texa s Pampa , Texa s Dee rPark , Texa s Texa s City , Texa s

Brownsville . Texa s Taft , Louisian a TOTA L Annua l Capacit y (Million s o f Pounds ) 

### no o 55 0 62 0 59 0

70 0 4 0 4,45 0 Proces s an d Remarks Methano l n-Butan e LP O Methano l carbonylatio n (lo w pressure ) Methano l carbonylatio n (lo w pressure )
n-Butan e LPO ; plan t i s mothballed . Peraceti c aci d co-produc t Notes : n-Butan e LP O » n-Butan e liqui d phas e oxidatio n Th e followin g companie s recove rby-produc t aceti c acid : Ai rProduas , Hoechs t Celanese , Dow , d u Pont , Eastman , Monsanto , an d Rhone-Poulenc . Source : SR I internationa l estimate s a s o f Januar y 1 , 1989 . Aceti c aci d amid e (See : Acetamide ) Aceti c acid , benzy l este r (See : Benzy l acetat e unde rFlavo r an d Fragranc

e Chemicals) Aceti c acid , 2-butoxyethy l este r (See : 2-Butoxyethy l acetate ) Aceti c acid , 4-tert-butylcyclohexy l este r (See : p-tert Butylcyclohexy l acetat e unde rFlavo ran d Fragranc e Chemicals) Aceti c acid , buty l este r (See : n-Buty l acetate ) Aceti c acid , sec-buty l este r (See : sec-Buty l acetate ) Aceti c acid , tert-buty l este r (See : ten-Buty l acetate ) Aceti c acid , dimethylamid e (See : N,N-0imethylacetamide ) Aceti c acid , 1-ethenyM,5-dimethyl-4-hexeny l este r (See : Linaly l acetat e unde rFlavo ran d Fragranc e Chemicals) Aceti c acid , 2-ethoxyethy l este r (See : 2-Ethoxyethy l acetate ) Aceti c acid , ethy l este r (See : Ethy l acetate ) Aceti c acid , 2-ethylhexy l este r (See : 2-Ethyl- l -hexy l acetate ) Aceti c acid , hepty l este r (See : n-Hepty l acetat e unde rFlavo r an d Fragranc

e Chemicals

) Aceti c acid , isobuty l este r (See : isobuty l acetate ) Aceti c acid , isopropy l este r (See : isopropy l acetate ) Aceti c acid , methy l este r (See : Methy l acetate ) Aceti c acid , 2-phenethy l este r (See : Phenethy l acetate unde r Flavo ran d Fragranc

e Chemicals) Aceti c acid , 2-phenethy l este r (See : Phenethy l acetat e unde r Flavo ran d Fragranc

e Chemicals) Aceti c acid , pheny l este r (See : Pheny l acetate ) Aceti c acid , propy l este r (See : n-Propy l acetate ) Aceti c aci d m-toly l este r (See : m-Cresy i acetate unde r Medicina l (Pharmaceutical ) Chemicals) Aceti c acid , p-toly l este r (See : p-Toly l acetate unde rFlavo r an d Fragranc

e Chemicals) Aceti c aldehyd e (See : Acetaldehyde ) Aceti c anhydrid e (Acety l oxide ) Eastma n Koda k

Compan y Eastma n Chemica l Products , In e Tennesse e Eastma n Compan y
Hoechs t Celanes e Corp . Hoechs t Celanes e Chemica l Group , Inc . Textil e Fiber s Grou p Kingsport , Tennesse e

Pampa , Texa s Narrows , Virgini a Roc k Hill , Sout h Carolin a Annua l Capacit y (Million s o f Pounds ) 70 0 50 0 30 0 25 0 25 0 Proces s an d Remarks

Ketene/aceti c acid ; aceti c aci d fro m acetaldehyd e an d recycle d fro m cellulos e acetate . Methy l acetate ; carbo n monoxid e fro m coal-base d synthesi s ga s Ketene/acen c aod ; aceti c aci d fro m butan e oxidation . Ketene/aceti c acid ; aceti c ao d recycle d fro m cellulos e acetat e Ketene/aceti c acid ; aceti c aci d recycle d fro m cellulos e acetate .



### 42 8 SR I Internationa l (Continued )P.5 9



### PRODUCT

S 98 9 DIRECTORY O F CHEMICA L PRODUCER S UNITE D STATE S Aceti c anhydrid e (Cont'd ) Union Carbid e Corporatio n Chemicals an d Plastic

s Busines s Grou p Solvent s an d Coating s Material s Divisio n Brownsville , Texa s Source : SR I Internationa l estimate s a s o f Januar y 1 , 1989 . TOTA L Annua l Capacit y (Million s o

f Pounds ) 

### 25 0 2,25 0 Proces s en d Remark

s
Aceti c aci d fro m butan e oxidatio n

Aceti c ethe r (See : Ethy l acetate ) Acetidi n (See : Ethy l acetate ) Acetin , tr i (See : Triacetin ) AcetiSOeugeno l (See : Isoeugeny l acetat e unde rFlavo ran d Fragranc e Chemicals ) Acetoacetanilid e (a-Acetylacetanilide ) (/3-Ketobutyranilide ) Eastma n Koda k Company Eastma n Chemica l Produas , inc . Tennesse e Eastman Compan

y Kingsport , Tennessee Hoechs t Celanes e Corp . Specialt y Produa s Grou p Coventry , Rhod e Islan d Lonz a Inc . Organi c Intermediate s Divisio n Bayport , Texa s Acetoacet-o-anisidid e (Acetoacetyi-o-anisidine ) (Methoxyacetoacetanilide ) Eastma n Kodak Compan y Eastma n Chemica l Produas , Inc . Tennesse e Eastman Compan

y Kingsport , Tennessee Hoechs t Celanes e Corp . Specialt y Produa s Grou p Coventry , Rhod e Islan d Lonz a Inc . Organi c Intermediate s Divisio n Bayport , Texa s Acetoacet-o-chloranilid e (o-Acetoacetochloroanilide ) (2 - Chloroacetoacetanilide ) Hoechs t Celanes e Corp . Specialt y Produa s Grou p Coventry , Rhod e Islan d Acetoacet-diethylamid e (N,N-Diethy l acetoacetamide ) Lonz a Inc . Organi c Intermediate s Divisio n Bayport , Texa s Acetoacet-2,5-dimethoxy-4-chloroanilid e 3-amino-4 - methy l benzamid e Hoechs t Celanes e Corp . Specialt y Produa s Grou p Coventry , Rhod e Islan d AcetoacetHJimethylamid e (N,N-Dimethylacetoacetamide ) Eastma n Kodak Compan y Eastma n Chemica l Produas , Inc . Tennesse e Eastman Compan

y Kingsport , Tennessee Unz a Inc . Organi c Intermediate s Divisio n Bayport , Texa s Acetoaceti c acid , ethy l este r (See : Ethy l acetoacetate ) Acetoaceti c acid , methy l este r (See : Methy l acetoacetate ) Acetoaceti c este r (See : Ethy l acetoacetate ) Acetoacet-monomethylamid e Unz a Inc . Organi c Intermediate s Divisio n Bayport . Texa s o-Acetoacetochloroanilid e (See : Acetoacet-o-chloranilide ) 2',4'-Acetoacetoxylidid e (See : Acetoacet-m-xyiidide ) Acetoacet-sulfanili c aci d Hoechs t Celanese Corp . . Specialt y Produa s Grou p Acetoacet-o-toluidid e Eastman Kodak

Compan y Eastman Chemica l Produas , Inc . Tennesse e Eastman Compan y Hoechs t Celanese Corp . Specialt y Produa s Grou p Lonz a Inc . Organi c Intermediate s Divisio n Acetoacet-m-xylidid e (2',4-Acetoacetoxyiidide ) Eastman Koda k

Compan y Eastman Chemica l Produas , Inc . Tennessee Eastman Compan y Kingsport , Tennessee Hoechs t Celanese Corp .

id r Coventry , Rhod e Islan d Kingsport , Tennessee Coventry , Rhod e Islan d Bayport . Texa

s
Specialt y Produa s Grou p Lonz a Inc . Organi c Intermediate s Divisio n Coventry , Rhod e Islan d Bayport , Texa

s Acetoacetyl-o-anisidin e (See : Acetoacet-o-amsidide ) Acetocinnamon e (See : 4-Phenyl-3-buten-2-on e unde rFlavo r an d Fragranc e Chemicals ) 4-Acetc-3,5-dimethyl-2,6-dinitHMert-butylben*en e (See : 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitro-acetophenon e unde rFlavo ran d Fragranc e Chemicals ) Acetoguanamin e (2,4-Diamino-6-methyl-s-triazine ) (6 - Methyl-1,3,5-triazine-2,4-diamine ) Dixi e Chemica l Company Baypon , Texa s Acetoguanamine-formaldehyd e resin s (See : Triazon e resin s unde rPlastic s an d Resins ) Acetohexamid e (See : Medicina l (Pharmaceutical ) Chemicals ) Acetoi n (See : 3-Hydroxy-2-butanon e unde rFlavo ran d Fragranc e Chemicals ) 2'-Acetonaphthon e (See : Flavo ran d Fragranc e Chemicals ) /3-Acetonaphthylen e (See : 2'-Acetonaphthon e unde rFlavo r an d Fragranc e Chemicals )

Aceton e (Dimethy l ketone ) (0-Ketopropane ) (2-Propanone ) Allied-Signa l Inc . Engineered Material s Secto rPhiladelphia , Pennsylvani a Annua l Capacit y (Million s o

f Pounds ) 41 5 Proces s an d Remark

s Cumen e peroxidatio n (Continued ) SR I Internationa l 42 9

# FAITH , KEYES , AN D CLARK' S



# INDUSTRIA L CHEMICAL S

Fourth Edition

FREDERIC K

A . LOWENHEI M Plainfield, New Jersey Consultant 

# MARGUERIT E K . MORA N Mgr. Technical

Information Center, M & T Chemicals Inc. Rahway, New Jersey

A WILEY-INTERSCIENC E PUBLICATIO N 

### JOH N WILE Y & SON S NewYor k

Chicheste rBrisban e Toront o

# ACETI C ANHYDRID E (CH,CO), 0

Fro m Acetaldehyd e Wati r

Ac»llld«hyd « Catalytt Qiluen t 

# T i—L- i Ai r 

# M Nitroge n

Ructo r

Wate r Acetaldehyd e

T o aldehyd e colum n Diluen t an d wate r (—••» «



# J - K c E 3 C J U 

# T *C«ti C

i d -Aceti c anhydrit e Catalyt t '•tur n 

### Reactio n CH 3 

### CH O + O a

### - » CH 3 

### COOO H

CH 3 

### COOO H + CH 3 

### CH O - (CH 3 

### CO) 2 

### 0 + H a 

### O

70-757 c yiel d Materia l Requirement s

Basis— 1 metri c to

n acetic anhydride Acetaldehyd

e Catalys t Diluent (les s recovery) Ai r 120 0 k g lk g 165 0 k g Variable Proces s Ai r i s bubble dthroug h liqui dacetaldehyd e i n areacto r i n th e presenc e o

f 2 % (base do n th e weigh t o f acetaldehyde ) catalyst , suc h a s a mixtur e o

f coppe r an dcobal t

acetate s o r

manganes e acetate , whic h prevent s th e formatio n o f explosiv e amount s o

f peraceti c acid . Ap proximatel y 1.4 part s o f aceti c aci dpe r

1 par t o f acetaldehyd e i s presen t a s adiluen t

t o promot e aceti c anhydrid e formation . Methy l o r ethy l acetate , triacetin , o r benzen e ma y als o b e use da s adiluent , an d 1 6P.6 2



### ACETI C ANHYDRID E 1 7 

# HD E

o 3 

# r Aceti c

aci d 

### •-Aceti c anhydrid e 

# T Catalys t retur n 

### COOO H 3 

### CO) 2 

### 0 + H 2 

### 0 th e las t i s generall y utilize din conjunctio n wit h aceti c aci da s a withdrawin g agen t

in subsequen t

vacuu mdistillatio n t o allo w separa tio n ofth e reactio n mixtur e fro mwate r a t lowe r temperatures . Th e reacto r

i s maintaine da t

atemperatur e o

f 5 0 t o 70°C , an dth e pressur e i s approximatel y 6 0 ps i (41 0 kPa) . Th e overhea t fromth e crud e vacuu mcolum n i s fractionate di n a n aldehyd e column , yieldin g acetaldehyd e fo

r recycl e a s th e overhea dan dwate r an ddiluen t

a s bot toms . Th e diluen t

i s returne dto th e reacto r afte r th e wate r

i s separated . Th e dehydrate dmixtur e o f aceti c anhydrid e an daceti c aci dfromth e botto mo f th e crud e vacuu mcolum n i s separate db y distillation . Aceti c aci di s remove da s overhead , an dth e aceti c anhydrid e i s withdraw n fromabotto mplate . Th e catalys t i s take n fro

mth e botto mt o b e reused . Th e aceti c anhydrid e may b e furthe r purifie db y vacuu mdis tillation . Variation s o

f thi s proces s involv e typ e an damoun t o f diluent , an d severa l stage s i n th e reacto r (with oxygen injectio n int o eac h stage ) unde r milde r reactio n conditions . Presen t trend s ar e awa

y fromai r

an dtowar doxygen . I n on e continuou s proces s usin g ethy l acetat e a s th e diluen t an dacatalys t concentratio n o

f 1 % (cobal t

acetat e an dcoppe r

acetat e in aweigh

t rati o o f 2:1) , th e reactio n i s carrie dou t a t 50° C an d4 5 ps i (31 0 kPa) . Oxygen i s injecte da t

variou s point s alon g th e pat h o f liqui dtravel , wit

h th e overal l oxygen suppl y limite dt o 1 t o 2 % excess . Unde r thes e condi tions . 95 % conversion s o f acetaldehyd e ar e obtained . Bot h aceti c anhy drid e an daceti c aci dar e produce di n a50:5 0 weight ratio . Th e sam e proces s whe n carrie dou t i n th e absenc e o

f th e diluen t

give s ahighe r oxidatio n rat e bu t

yield s alower

aceti c anhydrid e aceti c aci d rati o (ca . 2:3) . ihvdride 120

0 k g 1 k g 165 0 k g Variable tyd e i n areacto r

i n th e dehyde ) catalyst , suc h a s a manganes e acetate , whic h int s o f peraceti c acid . Ap 1 par t o f acetaldehyd e i s drid e formation . Methy l o r • o b e use da s adiluent , an d Fro mAceti c Aci d(Ketene ) iMbato t 

## % * V Catalyst Vapoiw^l-te«c«ir|.^fconden« r !-»., £



# F Weatacct K ao d OOf ) 

# T J T Ta n totfc


### Reactio n CH3COO H -* • CH 2 

### =C= 0 + H 2 

### 0

CH3COO H + CH 2 

### =€=0- > 

### (CH 3 

### CO) 2 

### 0

85-897 o yiel d

### 1 8 INDUSTRIA L CHEMICAL S Materia l Requirement s

Basis— 1 metric to

n acetic anhydride Aceti c acid135 0 k g Catalys t Smal l Proces s Vapor s o f glacial aceti c aci dcontainin g 0. 2 to 0.3 % triethylphosphat e (TEP ) ar e passe dint o atubula r (chrome-iro n alloy ) reacto r heate dt o 70 0 to 800° C unde r

reduce dpressur e (20 0 torr) . As reactio n gase s leav e th e converter , ammoni aga s ( 1 kg/4. 2 k g TEP ) i s injecte dinto th e strea mt o preven t

reversio n ofth e keten e in th e product . Th e reacto r

exi t vapor s containin g aceti c anhydride , aceti c acid , ketene , an dwate r

ar e le dto aserie s o

f condenser s where wea

k aceti c aci d(30% ) i s condense dbefore i t can reac t

wit h th e ketene . Th e uncondense dketen e i s absorbe di n aceti c aci dto give aceti c anhydrid e (90 % purity) , whic h i s the n fractionate dto yiel daspecificatio n product . Keten e ma y als o b e prepare dfromaceton e accordin g to th e equatio n

CH,COCH , - CH a 

### =C= 0 + CH4 

### Aceton e vapor s ar e passe dthroug h avoi dchrome-iro n tube . Th e temperatur e o

f th e tub e i s 65 0 t o 670°C , an dth e contac t tim e i s abou t 0.2 5 t o 5 sec . Th e unchange daceton e i s condense dan drecycled . Th e gaseou s keten e i s absorbe di n glacia l aceti c aci dt o giv e aceti c anhy dride . Yield s base don aceton e ar e abou t 8 0 t o 95% . Conversio n per pas s varie s from1 5 t

o 25% . Us e Patter n Cellulos e ester s (including cellulos e acetate , acetat

e butyrate , and acetate propionate ) Aspiri n Miscellaneou s Percen t 95

10 0

### -AL S ACETI C ANHYDRID E 1 9 Production-Aceti c Anhydride ihydrid e 

### 135 0 k

g Smal l

2 t o 0.3 % triethylphosphat e ro n alloy ) reacto r

heate dt o >rr) . A s reactio n gase s leav e TEP ) i s injecte dint o th e th e product . ti c anhydride , aceti c acid , ndenser s wher e wea k

aceti c ; t wit h th e ketene . Th e un i dt o giv e aceti c anhydrid e dt o yiel daspecificatio n i e accordin g t o th e equatio n
= 0 + CH , oi dchrome-iro n tube . Th e n dth e contac t

tim e i s abou t ondense dan drecycled . Th e ti c aci dt o giv e aceti c anhy 8 0 t o 95% . Conversio n pe r

Percen t 9 5

10 0 2 0 6 —

0 6 1954 195 6 195 8 1960 196 2 1964 196 6 196 8 197 0 197 2 19r i P'ice-Aceti c Anhydrid e

1 2 .«- 195 4 195 6 195 8 i96 0 196 2 196 4 196 6 196 8 197 0 197 2 197 1 

### Miscellaneou s Properties. Colorless , highl y refractiv e liqui dwit h astron g aceti c odor . Mol . w

t Spg r Weight

per gallo n 9.0 1 l b (29°C ) Solubl e i n al l proportion s i n ethano l an dethe r a t roo mtemperature . I n col dwate r

i t i s solubl e t o th e exten t o f 13. 6 g/10 0 ml , bu t

decompose s i n ho t water . 102.0 9

1.08 3 20°C/2 0 m p b p -T3.1° C

139.9° C

Flas h poin t

(ope n cup ) Ignitio n temperatur e Vapo r densit y (ai r

— 1 ) Explosiv e limit s (

% b y volum e i n air ) Threshol dlimi t

valu e (ppm ) Grades. Technica l (9 8 an d99%) , cp . 64° C 390 ° C 3.5 2 Lowe r 2. 9 Uppe r 10. 3 5P.6 5 

# f 2 0 

### INDUSTRIA L CHEMICAL S Containers and

Regulations. Aluminu mdrum s an dtan k cars , tan k trucks , carboys , an dglas s bottles . A whit e DO T shippin g labe l i s required . Economi c Aspect s Aceti c anhydrid e i s mad e i n greates t quantit y b y it s chie f

users , cellu los e acetat e manufacturers , o r b y well-integrate dorganic-chemical manufacturer s who mak e awid e variety o f relate dcompounds . Th e two manufacturin g processe s describe dappea r t o b e competitive . I

f amanu facture r als o produce s acetaldehyd e fo r othe r uses , th e acetaldehyd e oxidatio n proces s will probabl y b e preferred . Fo r year s som e aceti c anhydrid e wa s mad e fromacetylen e vi a ethyliden e diacetate , bu t th e on e plan t

usin g th e proces s ha s bee n shu t down . Mos t plant s ar e comparativel y large . Th e smalles t ha s acapacit y o

f 27 millio n kg/year , wherea s th e other s vary fro m100-million-kg t

o 385 - million-kg capacity . I t i s reasonabl e to believ e tha t th e futur e o

f aceti c anhydrid e manu factur e will b e closel y relate dt o th e futur e o f cellulos e acetate , henc e will b e governe db y gain s or losse s o f th e latte r

i n th e textil e an dplas tic s fields . Manufacturer s an d Plan tSite s Celanes e Corp. , Pampa , Texas ; Cumberland , Md. ; Narrows , Va. ; Roc k Hill , S . C . FM C Corp. , Meadsville , Pa . Tennesse e Eastma n Co. , Kingsport , Tenn . Unio n Carbid e Corp. , Brownsville . Texas ; Texa s City , Texa s

# Klau s Weisserme l Hans-Jiirge

n Arp e 

# Industria l Organic Chemistr

y Importan

t Ra w Material s and Intermediate s Translate db

y Alexander Mulle n



# Verla g Chemi e • Weinhei

m• Ne w Yor k 197 8P.6 7



### 16 0 7. Oxidation Products of Ethylene 3 a s chloroaceti c acid s fo

r organi c synthese s mos t importan t

chloroaceti c acid : CICH ; COO H via liquid-phas e chlorinatio n o f CHjCOO H wit

h favore dapplicatio n i

n carhox>meth\lcellulos e H H N !_••' ' •-' 0 H . M_ / CHiO H ' V ' t ' CH,OCH,COO H

-l . precurso r

fo r anhydrides : keten e an daceti c anhydrid e 5 solven t fo r liquid-phas e oxidation s
6 . substrat e fo

r fermentatio n to L-lysin e o r L-glutami c aci d 

### Chloroaceti c acid s ar e als o important

aceti c ad The mos t significan t o f thes e is monochloroacet



### j denVa,iv 

### « 5



### - worldproductio n i s estimate dto be approx . 18 0 00 n ^ ^ er n Europe' s share being approx . 120.00 0 t/ aT h ''^"i - ture o f monochloraceti c acidresult s fro mth e ch l * m3nn{ 

### *- aceti c aci di

n th e liqui dphas e a

t approx . 85 T ' na,| 

### ° n o f catalys t but ofte n i n the presenc e o

f initiator s such ' anhvdrid e o r

acetv l chloride . Monochloroaceri r ^J ^ac<:,l c 

### , . ' ' gaeid 

### .as*p n being a n importan t

startin g materia

l fo r th e manu f carboxymethylcellulose . is als o a n intermediat

e fo r " ^ ° ' dye s andpharmaceutical preparations . ' Pesticides . Industriall y significan

t secondar y product s o

f aceti c aci d are als o intermediate s (such a s aceti c anhydrid e an dk wil l b e deal t wit h i n th e followin

g sections . ne | 

### Aceti c acidis als o usedas solven t fo r liquid-phas e oxidati

o fo r exampl e i

n th e oxidatio n o

f p-xylen e t

o terephthalic aa

d dimethy l terephthalat e (cf. Sectio n 14.3.2) . Anothe r applicatio n o

f aceti c acidi s its fermentation t o L-Ks , o r L-glutami c acid . I

n th e Ajinomoto process , aceti c aci dserv e (alon g wit h othe r conventional nutrients ) a

s th e mai n sourc e m carbon . I f aceti c acidi s introduce das ammoniu macetat e the n nitroge n an dcarbo n are fe dto th e fermentatio n b

y mean s o f single carrier . I

n contras t to th e manufactur

e o f D.L-Ksin e v tu 

### syntheti c processe s (cf. Section s 10.3.1. 4 an d11.3.31 . fermen

tatio n method s lea

ddirectl y to L-lysine . Other nutrien t source s use dfo r L-lysine manufacture are carbohydrate s suc h a s maiz e product s o r

molasses .

aceti c aci dform s tw o anhydrides : 1 . intermolecular : aceti c anhydride (Ac ; 0 ) o f greate rim portance , an

d 2. intramolecular : keten e (diketene ) Ac. O productio n (i n 10001) :

197 4 197 5 US A 74 1 66 1 Japa n U S 10 2 W . German y 7 4 5 4 n.a . = no tavailabl e 197 6 n.a . Il l 6 6 Ac. O manufactur

e vi a tw o routes . 1. oxidativ e dehydratio n o f CHjCH O 

### 7.4.2 . Aceti c Anhydrid e an d Ketene Aceti c anhydride , th e intermolecular , an dketene . th

e intramolecular , anhydrid e o

f aceti c aci dar

e ver y closel y relate dt o aceti c aci da s fa

r a s manufacture , applicatio n an dimportanc

e are concerned . Th e availabl e productio n figure s fo r anhydride i

n th e mos t importan t industrial countrie s are summarize di n th e adjacen t table . Keten e an dits dimer

(diketene ) are quantitatively o f mino r importance . I

n 197 3 th e capacitie s i

n W . German

y amountedt

o approx . 20-30.00 0 t/a . Ther e are tw o differen

t industrial route s fo

r manufactunn

g aceti c anhydride . On e proces s typ e i s amodifie dacetaldehyd

ei 6 8 M M



### 7.4. Secondary Products of Acetaldehyde 16 1 ceti c aci dder,v atlve s 

### hloroaceti c aci dTK »x . 180.000 , a 

### . w " C 00t h a ^manuf a ; 

### • J 'J e chl 0 r 

### , nat 

### , 0 n o f 

### * - Cusu 

### a " y without tlat0r 

### * suc

h a s ace, l c 

### •aceticacid . asu e 

### ll a s r 

### th e manufacture „ f 

### 'ediat e fo r pesticides . s o f aceti c aci dwhic

h 'hydrid e andketene ) s . l-phas e oxidations , as ^terephthali c aci do

r nentatio n to L-lysine ess . aceti c aci dserve s as th e main sourc e o

f ioniu macetate , the n itationbymeansof a ur e o f D.L-lysin e via Jnd11.3.3) . fermen the r nutrien t source s drate s suc h a s maiz e .nidation , wherea s the othe r involve s keten e as a

n inter mediate . Ih e modifie dacetaldehyd e oxidatio n was develope db y Hoechst-Knapsack

andavariant

b y Shawinigan . Insteado

f M n ,cetat e amixtur e o f C u andC o acetat e was use da s catalyst . Th e primar y acety l radical , resultin g fro macetaldehyd e b

y abstractio n o

f hydroge n (cf. Aceti c Aci db y Oxidatio n o

f Acetaldehyde . Sectio n 7.4.1.1) . i s oxidize dt o th e acety l catio n usin g Cu : 

### ® . whic

h the n react s wit

h aceti c aci dforming aceti c anhydride : CHjCH O CH,C .



### o -o> » CH.C ® I t 

### o (45 ) CH»C ® + CHjCOO H I I O CH 3 C * O + H a CH, C 

### I n aparalle l reaction , peraceti c aci di s forme db y additio n o

f 0 : 

### t o th e acety l radica

l wit h subsequen t

abstractio n o

f hydroge n fro macetaldehvde . Th e aci dserve s t o reoxidiz e Cu ® t o Cu 2 

### ® : C H 3 C-0-0- H + Cu ® - • Cu 1 ® + CHjC O + OH Q M 

### o (46) 2 . dehydratio n o f AcO H via keten e m I: proces s principl e homogeneousl y catalyze dliquid-phas e oxi datio n o f CHjCH O *it h C

u C o acetat e while formin g AcO H a

s co-produc t proces s characteristic s azeotropi c H. O removal hinder s Ac. O hv drolysi s examp ^ o

f process : Hoechst-Knapsac k Shawiniga n



### n dketene . th e in - •r y closely relate dto on an dimportanc e •drid e i n th e mos t ze di n th e adjacent ntitativel y o

f mino r rmany amounte dto fo r manufacturin g difiedacetaldehvd e Aceti c aci dresultin g fro m th e acetox y radica l i s thu s a n essen tia l co-product. Th e wate rforme d ca n no w initiat e th e secondar

y reaction o

f aceti c anhydrid

e t o aceti c aci

d i f i tis no tquickl y removed fro

m the equilibriu

m b y distillatio n wit

h a n entraining agent, e.g. ethy l acetate , a

s i n the industria

l process . Wit

h 9 5 % conversion o f acetaldehyde a

n optima l ratio (56:44 ) o

f anhydrid e t o aci d is attained . I n th e acetic anhydrid

e manufacturin

g proces s involving th

e dehydratio

n o f acetic aci d via keten e (Wacke

rprocess) , acetic aci d i s initiall y thermall y dissociated int

o ketene an

d H 2 

### 0 . The reactio n take s plac e i n the presenc

e o f triethy l phosphat

e a t 700-750° C an

d reduced pressure : to 2: principle s o f two-ste p process : 1 . catalyticall y regulate dketen e equilib rium , retro-reactio n hindere dby :P.6 9



### 16 2 7 . Oxidation Products of Ethylene I . I neutralizatio n o

f catalys t 1.2 . quenchin g (lowerin g o f temperature ) o

f cracke dgase s 

### CHjCOO H ^ * H, C = C = 0 -f

- H, 0 (\H

- + J? ^ **lmJi. (47 *

2 . Ac- O manufactur e wanon-catalyze dex othermi c AcO H additio n t o keten e 

### Finally , th e resultin g H 3 

### PO. , i s neutralize di n the ga s phase wit h NH 3 

### o r pyridin e an

dthe cracke dgas is coole di n orde r t o freez e the equilibrium . Th e higher

boilin g accompanyin g substance s (aceti c anhvdrid e aceti c acid , an

dwater) are separate dfro mthe gaseou s keten

e b y mean s o f asystemo

f graduate dcoolers . Afte

r removin g th e 

### water , they are recycle dt o the crackin g stage . Th e keten e selectivit y reache s almos t

90 % (base do

n CH 3 

### COOH) . Th

e keten e purifie di

n thi s wa y i s directl y fe

dt o th e acetic aci

d(e.g i n th e Wacker

process ) wit

h aliqui drin

g pum p an dthe n converte da t 45-5 5 ° C into aceti c anhydride : H, C = C = 0 + CHjCOO H - (CHjCOk O 

## «f

c advantage s o

f process : 1 . isolabl e keten e intermediat e 2 . chea p AcO H utilizabl e e.g. fromothe r processe s 3 recovere daceti c aci dfromacetylatio n wit h Ac. O applicabl e alternativ e keten e manufactur e accordin g t o principle: homogeneousl y catalvze ddemethanaiio n of (CH.,),C O 

### I n thi s stage , selectivit

y approache s 100% . Thi s aceti c mhydrid e proces s ha s th e advantag e tha t keten e ca n b e obtaine do n deman da s intermediar

y product . Furthermore , a n aceti c aci d feedstoc k fro mth e mos t

economi c proces s ca

n b e employe do r aceti c aci dresultin g fro

macetylatio n reaction s wit h aceti c anhydrid e ca

n b e reused . Beside s bein g synthesize dfro maceti c acid , ketene ca

n als o b e obtaine dfro

maceton e via thermolysi s a t 600-700 J 

### C i

n th e presenc e o

f asmall amoun t

o f CS : 

### : CH»COCH

, H I 

### H»C-O 0 + CH «

application s o

f Ac ; 0 an d ketene : 1 . foracetylation . e.g. Ac z O foracety l cel lulose , keten e fo

r Ac. O 

### A keten e selectivit y o f 70-80 % i s attainabl e wit h a n aceton e conversio n o

f 2 5 % . Aceton e crackin g i s onl y o f mino r industna l importance . A plan t

i s operate db

y Hofman n L aRoch e i n th e USA . Th e main applicatio n o

f aceti c anhydrid e i s as a

n acetylatin g agent , abov e all i

n th e manufacture o

f acety l cellulose , a

s wel l a s i n th e manufacture o

f pharmaceutical s (e.g. acetylsalicylicacid , acetanilid e etc.) an do

f intermediat e products . Keten e i s als o employe da s a

n acetylatin g agent . Th e specia l cas e concernin

g th e acetylatio n o

f aceti c aci dt o aceti c anhydride i s th e mos t importan t example .P.7 0

7. 4 . Secondary Products of A cetaldehyde 1 6 3

(47 ) ize di n th e ga s phas e wit

h coole di n orde r t o freez e anceslaceticanhydride . ro mth e gaseou s keten e lers . Afte r

removin g th e kin g stage . Th e keten e do n CHjCOOH) . Th e dt o th e aceti c aci d(e.g. n g pum p an dthe n con ie : ))j O (48 ) 10% . Thi s aceti c anhv ten e ca n b e obtaine do n hermore . a n aceti c aci d es s ca n b e employe do r reaction s wit h aceti c cid . keten e ca n als o b e a t 600-70 0 ° C i

n th e Keten e i s als o use din additio n reaction s (includin g th e dimeri zatio n t o diketene) . Diketen e i s obtaine db y keten e dimerizatio n i n trickl e towers . int o whic h aliqui dstrea mo f th e diketen e i s introduce di n counte r curren t t o keten e a

t 35-40°C : 2 . fo r diketen e formatio n

Hj C 

### H 2 

### COO*= * V l (^--.g^/mol ) (50 ) Th e reactio n virtuall y goe s t o completion . Mino r amount s o

f keten e ar e washe dou t

o f th e off-ga s usin g dilut e aceti c acid . Th e diketen e mus t

b e redistille dwit h particula r car e sinc e i

t i s polymerize db y acidi c o r basi c compounds . Diketen e i s a n importan t startin g materia l fo r

th e manufactur e o f acetoaceti c aci dderivative s resultin g fro mth e aci do r bas e catalyze dadditio n o

f alcohols , ammonia , amines , hydrazines , etc. Acetoaceti c aci danilides , wit h substitutio n o n th e pheny l ring , fin dwid e applicatio n a s dy e an dpharmaceutica l intermediate s jus t a s th e pyrazolon e derivative s obtaine dfro mdiketen e an d substitute dpheny l hydrazines . Vtonomeri c keten e form s (3-lactone s wit h aldehydes , e.g. pro piolacton e i s obtaine dfro mformaldehyd e in th e presenc e o f A1C1, : HCH O + H,C-C O lAW. l 

# a. (51 ) diketen e als o usedfo r manufactur e o

f acetoaceti c acidderivative s limportan t intermediates )

3 . fo r additio n reactions , e.g. wit h HCH O to propiolacton e wit h CH,C H = CHCH O to sorbi c jc: d

(49 ) labl e with a n aceton e nl y o f mino r industria l nan n L aRoch e in th e i e i s a s a n acetylatin g t\ l cellulose , a s wel l a s .g. acetylsalicyli c acid , iducts . Keten e i s als o fecial cas e concernin g mhydrid e i s th e mos t Wit h crotonaldehyde , keten e i s converte dint o alabil e P-lac ton e whic h ca n stabiliz e itsel f b y polyeste r

formatio n (cf. Sorbi c Acid , Sectio n 7.4.3) . 7.4.3 . Aldo l Condensatio n o f Acetaldehyd e an d Secondar y Product s Acetaldehyde , a n aldehyd e wit h activ e a- H atoms , ca n rea ai n acharacteristi c wa y t o for madime r (acetaldol) : }CH,CH O •=*-> CH,CH(OHKH,CH O 

### (St t



# {"--8SH acetaldehyd e homo-aldolization ' t o 0-hydroxybutyraldehyd e (acetaldol ) als o co-aldolization ' e.g. wit h HCH O t o pentaerythritol (cf. Sectio n 8 3 1 )

# KE-15+ 

# Riegel' s 

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

Edite d by 

# Jame s A . Ken t Colleg e o f Engineerin g Michiga n Technologica l Universit y Houghton , Michiga n



# VA N NOSTRAN D REINHOL D COMPAN Y MIWYOR KCINCINNAT I ATLANT A DALLA S SA N FRANCISC O

LONDO N TORONT O MIL80URM I 

# RADIA N LIBRARr " DURHAM , N.C .P.7 2

SYNTHETI C ORGANI C CHEMICAL S 79 1 

### y fo r th e produc dride . fl-Butanol, thrito l combine d 0 pe r cen t o f th e c e th e fat

e o f by it s us e as a

n intermediate , fu

il l have astron g i s made today •, althoug h pro thy l alcoho l an d

. carrie dou t

in ycled , an donl y uct . Som e aceti c io n of rc-butane i announce dfo

r lano l an dcarbo n

, acetaldehyd e i s ssedthroug h th e 0 7 5 psi . Manga

nt , i s use din th e o n o f th e explo d . Acetaldehyd e • i wit h wate r an d h e liqui dreacto r :nt glacia l aceti c ant s us e cobal t 1 a s th e catalyst , m t per pas s are : r pressure s an d Aceti c aci di s use dchiefly t o produc e aceti c anhydrid e fo

r cellulos e acetat e manufacture . I n addition , sizeabl e quantitie s are consume d i n th e productio n o f

viny l acetate , acetat e es ter s andsalts , an dchloroaceti c acid . Produc tio n o f aceti c aci dwa s reporte da s 1.77 billio n pound s i n 1969 . Acetic Anhydride. Aceti c anhydrid e i s pro duce dmainl y b

y processe s using acetaldehyd e an daceti c aci dwith coppe r an dcobal t

ace tate s wit h som e manganes e acetate . Concen tration s o f

catalyst s ar

e generall y 1 t o 2 pe

r cent . Abou t

1. 4 part s o f aceti c aci dpe

r par t o f acetaldehyd e ar

e fe dt o th e reacto r

system . The reacto r

i s ru n at 50-7 0 pe r cen t an dabou t 6 0 psi . Finishin g i s don e i n avacuu mdistilla tio n train . I n som e newer processe s oxyge n replace s ai r a s th e oxidizin g agent . Th e reactio n i s carrie d ou t a t lower temperature s an dpressures . Highe r (9 5 per cent ) conversion s of

acetalde hyd e ar e obtained , an daceti c anhydrid e an d aceti c aci dare produce din a50:5 0 weight ratio . Runnin g th e sam

e proces s i

n th e absenc e of diluen t give s ahigher

oxidatio n rate bu t

a lower (2:3 ) anhydride-aci dratio . O f th e 1.6 8 billio n pound s of aceti c anhy drid e reporte dproduce di n 1969 , som

e 8 5 pe r cen t probabl y wa s use dt o mak e cellulos e ace tates , abou t

1 0 pe r cen t fo r vinyl acetate , an

d 5 pe r cen t fo r aspiri n an dothe r

esterificatio n reactions . Vinyl Acetate. Of

som e 72 9 millio n pound s produce di

n 1969 , les s than 100 millio n wer e produce db y th e ne

w oxyacetylatio n proces s (usin g ethylene , aceti c acid , andoxygen) . Th e ne w proces s yield s acetaldehyd e as aby-prod uc t i n adequat e quantit y t o be converte dt o th e aceti c aci dneeded . Thi s mean s tha t th e onl y ne t feedt o th e comple x i s ethylene . A t present , som

e 60 0 millio n pound s of viny l acetat e capacit

y exist . I t i s apparen t

that thi s i s anothe r

cas e where acetylen e i s rapidl y bein g replaced . A flo

w diagra mfo r th e oxy acetylatio n proces s i s show n i n Fig . 25.14 . Ethylen e Oligomer s 

### Linea r primar y alcohol s an dct-olefin s i n th e C 6 

### t o C 1 0 

### rang e an dth e C 1 2 

### t o C 1 8 

### rang e hav e become importan t

industrial chemical s i

n re cen t years . Th e linea

r alcohol s i

n the C 6 

### t o C 1 0 

### rang e ar

e usedt o mak

e plasticizer s fo

r

Processing. 50 , No. Fig . 25.1 4 Viny l acetate b y oxyacetylatio n process . [Hydrocarbon Processing, 50 , No. 11, 219 (1971);copyright 1971 by Gulf Publishing

Co. IP.7 3

IES T PHYSIC S HANDBOO K KFO RMECHANICA L RIN G CALCULATION S \NDBOO K > RESIN S AL ENCINEER S )BOO K ;ULATION S Y
vTIO N METHOD S ESSE S DBOO K RFUNDAMENTAL S RAPPLICATION S • GINEERIN G < FO RCHEMICA L 

# HANDBOO K O F CHEMICAL S PRODUCTIO N PROCESSE S ROBERT A . MEYER

S EDITOR IN

CHIEF CHEMICAL

PROCESS

TECHNOLOGY

HANDBOOK

SERIES

OG Y 

### McGRAW-HIL L BOO KCOMPAN

Y Ne w York St . Loui s Sa n Francisc o Aucklan d Bogot a Hambur g Johannesbur g Londo n Madri d Mexic o Montrea l Ne w Delh i Panam a Pari s Sl o Paul o Singapor e Sydne y Toky o Toront oP.7 4



# L l Halco n S D Grou p Aceti c Anhydrid e Proces s B . Jura n Halcon SD Group, New York, New York

Introductio n Perspectiv e Proces s Descriptio n andChemistr y Yield s Produc t Specification s Waste s an dEmission s Economic s Reference s 1- 4 1- 4 1- 4 1- 6 1- 6 1- 7 1- 7 1- 9

1.131.1-4 ORGANI C CHEMICAL S 

### INTRODUCTIO N A ne w proces s t o manufactur e aceti c anhydrid e wa s commercialize ddurin g IQB. . Thi s rout e start s wit

h methano l an dcarbo n monoxide , an ddoe s no t p r0 c throug h aceti c aci do r

acetaldehyd e a s d o olde r technologies . It

thu s represe n significan t

advanc e fo r

C , chemistry , define da s th e synthesi s o f higher-numbe r

' bo n molecule s fro msingle-carbo n feedstocks . Aceti c anhvdrid e i s produce dfro mC , material s b y Tennesse e Eastman Co panv , adivisio n o f

Eastma n Kodak , usin g technolog y jointl v develope db v East m an dth e Halco n S D Group . Capacit y o f th e plant , locate da

t Kingsport , Tennes s i s 50 0 millio n lb/y r

(227,00 0 Mg/yr) , makin g i t th e world' s larges t

aceti c anhvdrir

i facility . Eastma n produce s synthesi s ga s fo r methano l manufactur e an dC O fort h carbonylatio n reactio n by gasifyin g coal . 

### PERSPECTIV

E Aceti c anhydrid e i s amatur e intermediat e chemical , whos e domesti c 198 4 produ c tio n wa s abou t

1 billio n l b (454,00 0 Mg) . Al l curren t U.S . productio n is base do n aceti c aci dcrackin g t o ketene , whic h i s furthe r reacte dwith additiona l aci dto vie M th e anhydride . Som e companie s i n Europ e stil l oxidiz e acetaldehvd e t o anhvdride althoug h th e economic s o f thi s proces s ar e les s favorabl e tha n th e keten e route Th e majo r

en dproduct s o f

aceti c anhydrid e ar e cellulos e acetat e fibers an dplaj . tics . Mos t

o f th e fiber

materia l i s use dfo r

cigarett e filters , whil e alesse r amount n use dt o produc e fabric s fo r th e appare l industr y an dth e home . A smal l quantity.. r aceti c anhydrid e i s use di n th e manufactur e o f pharmaceutical s an dplasticizer s an dt o mak e th e explosive , cyclonite . With relativel y matur e processe s an daslowl y growin g market , i t might see m ther e woul db e littl e incentiv e t o develo p ne w technolog y fo r th e productio n ,,\ aceti c anhydride . However , th e rapi dsurg e i n energ y an dfeedstoc k cost s dunn

j th e 1970 s provide da n impetu s t o searc h fo r route s t o intermediate s tha t consume d les s energ y pe r

uni t o f produc t an dtha t

relie do n mor e secure , an dmor e witiel v available , feedstock s tha n thos e base do n oil . I n 1980 , Halco n S D an dTennesse e Eastma n announce djus t suc h aproces s fo

r aceti c anhydride . I t

i s base do n methano l an dCO , material s tha t ca n b e mad e fro

m awid e variet y o f

feedstock s rangin g fro mnatura l ga s t o naphtha , residua l oil . coal, lignite , an doi l shale—i.e. , an y hydrocarbo n materia l tha t ca n b e gasified . More

over , utilit y cost s pe r

uni t o f produc t ar e far les s fo r thi s ne w C,-base dtechnology . Eastman' s decisio n t o utiliz e th e carbonylatio n rout e t o aceti c anhvdrid e represente daswitc h t o lower-production-cos t technolog y an damor e secur e an dabundan t feedstock , coal . 

### PROCES S DESCRIPTIO N AND CHEMISTR Y Th e carbonylatio n proces s fo r aceti c anhydrid e involve s tw o steps , an dth e flowshee t will loo k

slightl y differen t

dependin g o n whethe r recycl e aceti c aci dis avail -P.7 6

A1. S

o wa s commercialize ddurin g 1983 . monoxide , an ddoe s no t procee d r technologies . I

t thu s represent s a th e synthesi s o f

higher-numbe r

car crial s b % Tennesse e Eastma n Com ulog y jointl y develope db v Eastma n it . locate da t

Kingsport . Tennessee , di e world' s larges t

aceti c anhvdrid e hano l manufactur e an d(!(' ) fo r th e

lical , whos e domesti c 198 4 produc arren t L'.S . productio n i s base do n -eacte dwit

h additiona l aci dt o viel d oxidiz e acetaldehvd e t o anhvdride , favorabl e tha n th e keten e route , ar c cellulos e acetat e fibers an dplas ett e filters, whil e alesse r amoun t i s

. an dth e home . A smal l quantit y o f f pharmaceutical s an dplasticizers . \l v growin g market , i

t migh t see m technolog y fo r

th e productio n o f energ y an dfeedstoc k

cost s durin g .te s t o intermediate s tha t consume d o n mor e secure , an dmor e widel v : announce djus t

suc h aproces s fo r O . material s tha t

ca n b e mad e fro m a l ga s t o naphtha , residua l oil . coal , ateria l tha t

ca n b e gasified . More -

- fo r thi s ne w C,-base dtechnology , rout e t o aceti c anhvdrid e repre - !og v an damor e secur e an dabun - 

### >TR Y

. • invoke s tw o steps , an dth e How Aliethe r recycl e aceti c aci di s avail HALCO N SD CROU P ACETI C ANHVDRID E PROCES S 1.1-5 hie . (Recycl e aci di s derive dfro mth e productio n o f cellulos e acetat e whe n aceti c nhvdrid e i s reacte dwith cellulose , o r fro mothe r

commercia l acetvlatio n processes. ) Whe n recvel e aceti c aci di s no t readil y available , aceti c anhvdrid e i s mad e fro m uethano l an dC O onlv . a s show n i n Fig . 1.1-1 . Tw o mo l o f methv l acetat e ar e car herniate dwit

h 2 mo l o f

C O t o giv e 2 mo l o f

anhvdride . Hal f

th e anhvdrid e i s remove da s product , whil e th e othe r hal f i s recycle dan dreacte dwit h methano l t o (riv e 2 mo l o f

methv l acetat e an d1 mo l o f water . Thu s th e overal l reactio n i s meth ano l plu s C O t o viel daceti c anhydrid e an dwater , th e wate r alway s bein g removed . Ih e methanol , o f

course , i s mad e fro mC O an dhvdrogen . s o aceti c anhsdrid e derive dentirel y fro msynthesi s ga s i s th e result . Whe n recvel e aceti c aci dis available , however , a s i s th e cas e fo r Eastman' s oper ations , th e proces s follow s th e chemica l rout e show n in Fig . 1.1-2 . Methano l i s esterifie dwit

h th e aceti c aci dt o viel dmethv l acetat e an dwater . I n th e sam e manne r as previously , th e wate r

i s remove dan dth e methv l acetat e i s carbonvlate dt o form aceti c anhydride . Th e bloc k

proces s flowshee t

fo r producin g aceti c anhydrid e fro mmethano l an d QO. withou t

a n externa l suppl y o f

aceti c acid , i s show n i n Fig . 1.1-3 . Methv l acetat e I s forme db y mean s o f

anove l an defficien t

system . Th e este r

i s mad e a

t nearl y quantitativ e yields , whil e considerabl y les s capita l an denergy - ar e require dcom pare dwith classica l esterificatio n technologies . Sulfuri c aci da t lo w concentration s is use da s acatalvst . Th e reactio n i s carrie dou t i n atowe r

reacto r a t essentiall y li> 0 percen t conversio n an dselectivity , an dpurifie dmethv l acetat e i s recovere da s a distillat e product . I n th e carbonylatio n section , methv l acetat e an dcarbo n monoxid e combin e t o formaceti c anhvdride . A multicomponent . homogeneou s cataUti c svste mpermit s th e reactio n t o procee dunde r moderat e condition s o f temperatur e an dpressure .

2MeOA c Acj O 2C 0

2MeO H 2Acj O ZMeOA c Nj O 2MeO H 2C 0 Acj O M a 0 (Ne t I FIG. 1.1- 1 Chemistr

y of aceti c anhvdrid e productio n whe n n o recycl e aceti c aci dis available . MeOA c • methylacetate ; Ac 2 0 = . aceti c anhvdride ; MeOH - methanol .
MeO H MeOA c HOA

c C O MeOA c ACz O Mj

O
MeO H HOA

c C

O Ac 2 0 H 2 0 (Net ) FIG . 1.1- 2 Chemistr

y o f aceti c anhydrid e productio n wit h th e us e o f availabl e aceti c acid . HOAc • aceti c acid .

### 1.1-6 CarDo n monond e ORGANI C CHEMICALS 

### • Metnano i Esterificatio n Methy l aceiot e o 1 ia t io n |

• I Wate r Recycl e aceti c anhydrid e P-jr.ficatio n •ice ' i-"' it FIG . 1.1- 3 Schemati c (lowshee t o f aceti c anhvdrid e production . 

### Reacto r effluen t i s reduce di

n pressur e an dfe

dto th e purificatio n sectio n Aceti c anhydrid e is separate dfro mligh t an dheav y impuritie s b

v conventiona

l distillation ; th e produc t

meet s th e mos t

rigi dindustr

y specifications . YIELD S __ _ Reacto r an ddistillatio n yield s throughou t th e proces s ar e ver

y high . The estenti . catio n o f methano l t o methyl acetat e proceed s nearly quantitatively , an dth e \i<i a fo r thi s sectio n i s over

99. 9 percent . Selectivit

y o f carbonvlatin g methv

l acetat e t, , aceti c anhydrid e i

s wel l abov e 9 5 percent , as i

s th e overal l viel

dfro mmethanol :. , produc t anhydride . High-purity carbo n monoxid e is no t require dfo

r th e carbonylatio n reaction, an dacheape r

C O feedwit

h severa l percen t hydroge n o r

othe r inert s i n i t i s accentabl e an deven preferre di n term s of

cost . Th e vieldo n C O depend s pnmar. K s n 

### th e inert s leve

l i n th e feedgas , bu t

typicall y wil l b e abou t 9 0 percent . v



### PRODUC T SPECIFICATION S High-purit

y aceti c anhydrid

e i s produced b

y th e distillatio n of

th e reacto r

effluent . Typica l sales specifications ar

e a s follows : Aceti c anhydrid

e Specific gravit

y Colo r(Pt.-Co . scale) Reducing substances 99. 0 w t % (min. ) 1.08 0 t o 1.08 5 5 max. Pin k colo rshal

l be retained fo

r a t leas t 5 mi n whe n 0. 1 m L of 0.L V KMnO, i

s adde d to 2-m L sampl e Acetic aci d make s u p essentially al

l the remainin

g 1 percentof

th e product .P.7 8

IEMICAL S

j | 

### ' nd e

ndrid c produ c 

### <

/lotio n | 

### ' catio n

ion . Aceti c OrOOuC I HALCO N SD CROUP ACETI

C ANHYDRID

E PROCES S 1.1-7

ir e an dfe dt o th e purificatio n section , m dheavy impuritie s bv conventiona l dis I industr y specifications .

t th e proces s ar e ver

y high . Th e esterifi - ;eed s nearl y quantitatively , an dth e viel d .tivit v o f carbonviatin g methv l acetat e t o

. a s i s th e overal l yiel dfro mmethano l t o equire dfo r

th e carbonvlatio n reaction , i t hvdroge n o r

othe r inert s i n i

t i s accept Th e yiel do n C O depend s primaril y o n il y will b e abou t

9 0 percent .

b v th e distillatio n o f

th e reacto r

effluent . nin. ) 8 5 hal l b e retaine dfo r

a t leas t 5 mi n whe n •AN KMnO , i s adde dt o 2-m L sampl e mainin g 1 percen t

o f th e product . ^CTE S AN D EMISSION S The carbonvlatio n proces s fo r aceti c anhydrid e fro mmethano l an dC O result s i n h e f or matio n o f

thre e wast e streams : vente dgases , wate r o f esterification , an d l,eavv organics . Iner t gase s enterin g wit h th e carbo n monoxid e fee dmus t b e purged . Thi s ven t strea mcontain s C O a s well , an di s thoroughl y treate di n aserie s o f scrubber s t o recove r essentiall y al l organi c material s befor e discharge . I t i s sen t t o aboile r

o r oC es s furnac e fo r

combustio n o f

th e C O (an dan y hydroge n tha t ma v b e present) . Esterificatio n o f

methano l yield s 1 mo l o f wate r pe r mol e o f methv l acetat e tbrnied . Thi s aqueou s wast e strea mi s sufficientl y strippe do f organic s in th e ester h e atio n sectio n tha t

it s disposa l doe s no t

pos e an y problem . Tvpicallv . i t coul db e •onibine dwith othe r

plan t aqueou s waste s fo r

eithe r biotreatmen t

o r direc t dis nosal . dependin g o n loca l conditions . Th e smal l quantitie s o f

hea w organi c compound s forme din th e reactio n sectio n an din th e distillatio n equipmen t ar e dispose do f

b v incineration . ECONOMIC S Th e estimate dbatter y limit s capita l cos t fo r aplan t t o produc e 50 0 millio n l b v r (•J2T.00 0 Mg/yr ) o f

aceti c anhydrid e by th e Halcon / Eastma n carbonvlatio n proces s I s $6 3 million , a s show n i n Tabl e l.l-l . Assume di n makin g thi s estimat e ar e L'.S . Gul f Coas t construction , afirst-quarte r 198 3 cos t

basis , an dn o impor t

o f recycl e aci dint o th e plan t (i.e. , al l acetyl s generate dwithi n th e proces s us e onl y methano l an dC O feedstocks) . Operatin g requirement s ar e als o give n i n Tabl e l.l-l . Abou t 0.6 6 weigh t

o f methano l an d0.6 2 weigh t o f C O ar e require dpe r

weigh t o f aceti c anhvdrid e pro duced . Stea mi s use da t th e rat e o f

1. 6 lb/l b anhydride . A se t o f uni t price s ha s bee n assume ds o tha t aceti c anhvdrid e productio n cost s can b e calculated . Thes e uni t price s fo r

feedstock s an dutilitie s ar e give n in Tabl e TABL E 1.1- 1 Operatin g Requirement s fo r Manufactunn g 50 0 Millio n l b (227,00 0 Mg/yr ) o f

Aceti c Anhydrid e b y th e Carbonvlatio n Proces s Batter y limit s capita

l cost * Annua l operatin g requirement s Methano l Carbo n monoxid e Catalvst s an dchemical s (cost ) Stea m Electri c power Coolin g water

circulation t Fue l credi t $6 3 million 3.2 8 X 10

f i l b (1.4 8 X 10* kg

) 3.0 9 X 10° l

b (1.4 0 X 10 " kg

) $1. 0 millio n 7.9 5 X IO

6 l b (3.6 0 X 10

6 kg ) 1. 4 X 10'kWh(5 X 10 : MJ ) 1.2 X 10 1 0 ga

l (4. 5 X 10 1 0 L

) 1. 6 X 10 " Bt

u (1. 7 X 10 " kj ) •Basis : U.S . Gul

f Coast , first-quarter

1983 . t7' C rise.P.7 9

1.1-8 ORGANI C CHEMICAL S 1.1-2 , an dar e indicativ e o f earl y 198 3 costs . C O a t$0.0 4 pe rpoun d($0,08 8 pe r kilogram ) i s base do n synthesi s ga s generatio n o n a larg e scale

— large rtha n th e quantit y neede dsolel y fo r aceti c anhydrid e production . Thi s coul db e done , for example , bv includin g methano l manufactur e a s wel l i n a coal-to-chemical s com plex . Alternatively , methano l an dC O coul db e purchase dfro mlarge-scal e produc ers , wh o currentl y us e natura l ga s bu t will b e usin g a variet v o f carbo n source s i

n th e future . L'sin g th e operatin g requirement s an duni t cost s show n in Table s 1.1- 1 an d1.1 - 2 . th e productio n cos t

fo r aceti c anhvdrid e ca n b e calculated . Thi s informatio n i s summarize di n Tabl e 1.1-3 , whic h present s simplifie deconomic s usin g a1 0 percen t depreciatio n rat e an da2 0 percen t retur n o n investment . Th e productio n cos t of . SO . 1 8 pe r

poun do f

anhvdrid e (SO.4 0 pe r

kilogTam ) i s considerabl y belo w th e lat e 198 2 sellin g pric e o f

abou t $0.3 0 pe r

poun d($0.6 6 pe r

kilogram) , an dth e proces s thu s offer s asignifican t

advantag e ove r

ane w plan t

tha t woul dproduc e aceti c aci d first, the n anhvdrid e vi aketene .

TABL E 1.1- 2 Ini t Cost s Methano l Carbo n monoxid e Stea m(mediu mpressure ) Electri c powe

r Coolin g wate

r $0.60/ga l ($0.2 0 kg ) $0.04/lbi$0.088'kg ) $6/thousan dl

b iSO.0132 . kg

) $0.04/kVV h (SO.0 1 ll.MJ ) $0.10,'thousan dga

l ($0.026 5 m' )

TABL E 1.1- 3 Economic s o

f Producin g 50 0 Millio

n lb/y r (227.00 0 Mg

, vn o f Aceti . Anhvdrid e Capita l cost s Battery limits capita l cos t Offsite s Tota l fixe d capita l Productio n cost s Ra w material s Utilitie s Fixe d cost s Depreciation , @ 10%/y r Return , @ 20%/y r Cenera l an d administrative , sales , researc h Produc tvalu e $6 3 millio n $2 5 millio n $8 8 millio n M b Anhydrid e t, kg Anhvdrid e 8. 6 1.2 1. 8 1. 8 3. 6 1. 3 18. 3 18. 9 2. T 4. 0 4. 0 7. 9 2. 9 40. 3

# A n Introductio n t o



# INDUSTRIA L ORGANI C CHEMISTR Y Second Edition

PETE RWISEMA N Department

of Chemistry University of

Manchester

Institute of

Science and

Technology

APPLIE D SCIENC E PUBLISHER S LT D

LONDO NP.8 1

• V T O INDUSTRIAL ORGANI C CHEMISTR Y 

### leroxide . peraceti c acid : CH,C - 4 - X H 0 

### I I CHjCOO 0 

### I I CH,C - 

## + 0

• I CH,COOH peracetic acid 

### les , peraceti c aci dcleave s readil y acros s t o give fragment s that

ca n participat e i

n OXIDATION 10 3 

### Th e oxidatio n i s normall y carrie dou t wit h air , a t temperature s i n th e rang e 6 0 t o 8 0 °C . manganes e o r cobal t acetat e bein g use d a s th e catalyst . Yield s o

f abou t 95 % ar e obtained , th e main los s bein g throug h beta -scissio n o f acetoxy radicals : O 

### I I CHjCO CO , CH , CO , + H, 0 + othe rproduct s 

### I f th e oxidatio n i s carrie dou t i n th e presenc e o

f amixture o

f cobal t an dcoppe r

acetates , amixture o

f aceti c aci dandaceti c anhydrid e i s obtained : CH,C - 4

- Cu 2 ' CH, C 4 - Cu + CH,CO - + HO O O CH,C - 4

- CH,CO H 

### ot to b e th e mai n rout e b

y which aceti c th e peraceti c aci dreact s wit h acetalde thy l peracetate . which the n decompose s i free radicals , t o aceti c acid : 

## > c 

## x —CH 

## > c 

## ; H H O H O

- H O H O 

## II I 1 ^CHjC
—OOCCH , •CH.COOCCH , 

## I I 3

## ' I' H H H

* - hydroxyethyl peracetate -CH , :CH,CO, H CH, C 4 - CHjCOH

CH,COO H 4

- Cu * 

### // CH, C 

### \ , 0 + H ' / CH, C O CH,CO - 4

- Cu : * 4 - O H 

### Thi s i s th e basi s fo

r on e o f th e commercial processe s fo r th e manufactur e o

f aceti c anhydride . I

t i s als o mad e fro

maceti c aci d show n below : 700-80 0 ° C

CH,CO, H , • . , , • ,— ' CH,=C= 0 •» • H, 0 ^"' ^ 2 methyl phosphat e (catalyst ) <«'<"

« CHj=0= 0 + CHjCOO

H CHj C O

CH, C / 

# V104 INTRODUCTION T O INDUSTRIA L ORGANI C CHEMISTR Y 

### Th e mai n use s o

f aceti c aci dan daceti c anhydrid e ar e i n th e manufactur e o

f acetates , o

f which cellulos e acetat e (Sectio n 8.11 ) an dviny l acetat e (Section s 5.1 2 an d5.16 ) ar e th e mos t impor tant . A s we wil l se e late r i n thi s chapter , acetaldehyde-base droute s t o aceti c aci dan daceti c anhydrid e ar e comin g under increasin g competitio n fromothe r

routes . 5.4 Oxidation of

Cyclohexane Th e hydrogen s o

f cyclohexan e ar e muc h more difficul t t o remov e tha n th e aldehydi c hydroge n o f acetaldehyde . o r

th e tertiary hydroge n o

f cumene , an dmor e sever e condition s ar e require dfo r it s oxidatio n tha n in th e case s o f thes e compounds . Partly as a consequenc e o

f thi s an dth e fac t

tha t th e product s ar e mor

e readil y oxidise dthan th e cyclohexan e itself , th e chemistr

y in volve di s muc h mor e comple x tha n in th e tw o previou s cases . Th e oxidatio n o

f cyclohexan e ca

n give rise to alarg e number o f products . I t

i s carrie dou t

commerciall y o n aver

y larg e scal e fo

r th e manufactur e o

f cyclohexanol/cyclohexanon e mixture s ('mixe d oils') , whic h ar e intermediate s i n nylo n manufacture . Th e reac tio n follow s th e typica

l step s u p t o th e formatio n o

f th e hydro peroxide . (Note : for

th e sake o

f simplicity , only thos e hydroge n atom s whic h ar e involve din th e reactio n are shown i n th e followin g reactio n schemes. )

+ X
4-0 , - X H H\.00 -

+ C 4 H 1 2P.8 3 

# IO>W-# 0

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 WILEY-INTERSCIENC E PUBLICATIO N Joh n Wile y & Son s NEWYOR K•CHICHESTE R •BRISBAN E •TORONT O •SINGAPOR EP.8 4

1 0 ACETI C ACI D AN D DERIVATIVE S Healt h an d Safet

y Factor s An y solutio n containin g mor e tha n hal f aceti c aci di n wate r

o r organi c solvent s i s considere dcorrosive . Thes e solution s caus e damag e t o skin , eyes , nose , an dmouth . Ther e i s n o burnin g sensatio n upo n applicatio n t o unbroke n skin , althoug h symptom s appea r a s blister s withi n 3 0 mi n t o 4 h . Ther e i s littl e o r

n o pai n experienced , unles s sensor y nerv e receptor s ar e attacked . Medica l car e shoul db e sough t immediately . Particula r car e i s neede dwhe n handlin g aceti c aci dt o avoi dspillin g i t o n th e ski n o r clothin g an dt o avoi dbreathin g th e vapors . Whe n exposed , was h aceti c aci dawa y wit h larg e amount s o f wate r o r dilut e sodiu mbicarbonat e solution . Washin g blister s tha t hav e alread y appeare dwil l no t alleviat e th e pain . Leav e area s wher e th e odo r o f aceti c aci dvapor s i s noticeable . Glacia l aceti c aci dcause s sever e gastri c difficultie s i f swallowed , bu t th e precis e toxi c dos e fo r human s i s no t

known . OSH A standar dfo r ai r i n wor k place s i s atime-weighte daverag e of 1 0 ppm . FRAN K S . WAGNER , JR . Celanes e Chemica l Compan y A.I . Popo v i

n J.J . Lagowski , ed. , The Chemistry of Nonaqueous Solvents, Vol . 3 , Academi c Press , Inc. . Ne w York , 1966-1976 , Chapt . 5 . ACETAMID E Acetamide , CH 3 CONH 2 , mo l w t 59.07 , i s acolorless , deliquescen t substanc e compose dof rhombohedra l crystals . Als o know n a s aceti c aci d amide , ethanamide , an dmethane-carboxamide , i t i s odorles s whe n pure ; otherwise , i t

ha s adistinctiv e odo r

du e t o a n unknow n impurity . I t i s a n excellen t dipola r solven t fo r organi c an dinorgani c compounds ; i t i s compatibl e wit h hydrocarbons , ketones , esters , organi c acids , alcohols , water , ammoniu msalts , an dammoni aan dit s derivatives . It s hig h dielectri c constan t

( f = 59 ) make s i t

asuitabl e solven t

fo r inorgani c compounds . Physica l an d Chemica l Propertie s Acetamid e ha s m p 81.0°C , b p 221.2°C , n : D 8J 1.4274 , d| £1.15 9 g/cm 3 , an dvapo r

pressur e (a t

105°C l 1.3 3 kP a(1 0 m mHg) . I t i s chemicall y neutra l i n th e classica l sens e bu t basi c enoug h t o accep t aproto n fro ma stron g acid . I t

react s wit h alkal i metal s t o giv e th e correspondin g meta l derivatives , eg , CH 3 CONHNa . I t i s usefu l i n th e brominatio n of acid sensitiv e compound s sinc e i t form s astabl e comple x wit h hydroge n bromid e (CH 3 CONH 2 )•_,. HB r whic h i s insolubl e i n commo n brominatio n solvents . Acetamid e i s dehydrate dt o acetonitril e whe n heate deithe r wit h phosphoru s pentoxid e o r aceti c anhydride . I t

i s saponifie db y ho t alkal i an dhydrolyze db y ho t acid . I t ca n b e converte dt o aceti c aci dbyheatin g wit h minera l acid s an db y reactio n wit h nitrou s acid . Preparatio n On e o f th e mos t

widel y use dmethod s of manufactur e i s classica l svnthesi s fro maceti c aci dan dammoniu mcarbonate : CH,C(0)O H (NH,),CO , CH,C(0)ONH 4 - •CHXONH. , - HO H cloth , films, an dcoatings ; a s ahumectan t fo r paper ; a s astabilize r i n peroxides ; a s ara w materia l i n organi c synthesis ; an di n th e preparatio n o f hypnotics , insecticides , an davariet y of plastics . THERES A A . MORETT I American Hoechs t

Corporatio n J . Zabicky , The Chemistry ol Amides, Interscienc e Publishers , adivisio n o f Joh n Wile y & Sons . Inc. , Ne w York , 1970 . ACETI C ANHYDRID E Aceti c anhydride , (CH 3 CO) 5 0 (ofte n abbreviate dAc 2 0) , i s amobile , colorles s liqui dwit h apenetrating , chokin g odor , closel y relate dt o aceti c acid . I t i s th e larges t

commerciall y produce daci danhydride ; curren t U.S . productio n range s fro m50 0 t o 75 0 thousan dmetri c ton s annually . I t i s use di n industr y fo r acetylatio n reaction s an da s asolven t i n laborator y applications . Th e greates t singl e applicatio n i s i n th e manu factur e of

cellulos e esters , chiefl y cellulos e acetat e (se e Cellulos e acetat e an dtriacetat e fibers; Cellulos e derivatives , esters) . I t i s als o use di n starc h acetylatio n t o mak e textil e sizin g agents , i n salicyli c aci dacetyla tio n t o aspiri n (se e Salicyli c aci dan drelate dcompounds) , an di n electro lyti c polishin g of

metals , especiall y aluminum , an dsemiconducto r processing . A n undetermine dquantit y goe s int o th e manufactur e o f chloroaceti c aci d(se e Aceti c acid , halogenate dderivatives ) an dacety l chlorid e (qv) . I t

i s peculiarl y usefu l fo r oxidatio n reactions , no t onl y o f metal s bu t

als o fo r organi c compounds . Physica l an d Chemica l Propertie s Th e physica l propertie s o f aceti c anhydrid e ar e give n i n Tabl e 1 . Th e chie f

impurit y i n aceti c anhydrid e i s aceti c acid , whic h i s trouble som e t o remov e completely . Purit y o f th e produc t

i s bes t gauge db y th e refractiv e inde x o r

th e specific conductivity . Trace s o f aceti c aci dar e detecte db y near-i r

spectroscopy . Aceti c aci dca n b e estimate db y differ enc e whe n th e anhydrid e i s assaye dwit h aniline . Therma l decompositio n o f aceti c anhydrid e yield s ketene . i n auni molecula r

dissociatio n proces s betwee n 28 0 an d650°C , makin g thi s a convenien t

wa y t o prepar e keten e i n th e laborator y (se e Ketene s an d relate dsubstances) . Photolysi s of aceti c anhydrid e generate s ethan e an d carbo n monoxid e i n approximatel y equa l amounts , an dcarbo n dioxid e i n smalle r quantities . Aceti c anhydrid e appear s t o ioniz e t o acetyliu man d acetat e ion s althoug h i t i s practicall y a n electrica l insulato r whe n sal t free . Th e acetyliu mion , CH 3 CO* . occur s i n strongl y aci dsolutions . Potassiu macetate , rubidiu macetate , an dcesiu macetat e ar e ver y solubl e i n aceti c anhydride , bu t sodiu macetat e i s onl y slightl y soluble . Bariu m acetat e i s th e onl y solubl e alkaline-eart h acetate . Heavy-meta l acetate s ar e poorl y soluble . Tabl e 1 . Physica l Propertie s of Aceti c Anhydrid e
Widel y use dlaborator y method s ar e

CH 3 COC l - 2 NH. , - CH 3 CONH 2 - NH 4 C I (CH 3 CO) 2 0 - 2 NH : ) - CH 3 CONH 2 + CH 3 COONH 4 CH 3 COOC 2 H 5 - NH 3 - CH 3 CONH 2 + C 2 H, 5 O H Th e mos t

efficien t metho di s distillatio n of ammoniu macetate . Acetamid e i s produce di n technica l an dreagen t grades , th e latte r obtaine db y furthe r

recrystallization . Acetamid e i s shippe di n fiber carton s an di n 500- g packages , an dshoul db e store di n acool , dr y area . I t i s analyze db y hydrolysi s t o th e acid , o r b y esterification . Acetamid e i s use da s genera l solven t an di n th e textil e industry ; i t als o ha s application s a s a n accelerato r i n th e estimatio n o f

bilirubin ; a s a n antidot e agains t

monofluoroacetamid e poisoning ; a s a n antaci di n th e lacquer , explosives , an dcosmeti c industries ; a s aplasticize r i n leather , Propert y

meltin g point . ° C boilin g point , ° C a t

101. 3 kP a( 1 atm ) vapo r pressur e equation . kP a( A - 6.2">14 ) (m mH g ( A - 7.1265 ) therma l conductivity , liquid . m W . i mKi . a t tO' C specifi c heat , J/kg" . a t 20° C hea t o f vaporizatio n a t

bp . •].'%" density , df. g/cm ' refractiv e index , nj 1 surfac e tension . m N / m( - dv n -cm) , a t 20 C C viscosity . mP as ( - cP) , a t 20° C dielectri c constant , f 2 " dipol e moment , C m 6 V a -7-4.1. 1 138.6. 1 lo g p = A 13 6 181 7 4(»i. « 1.082 0 1..W9 2 :IJ.6. r > 0.90 1 22. 1 9.: l » 1 0 lu e
1-127. 8

{IH*- t)

"T o conver t

J t o cal , divid e b y 4.184 . "T o conver t

C mt o debve , divid e b y 3.33 6 x 1 0 ''*>.ACETI C ACI D AN D DERIVATIVE S 1 1

Acetaldehyd e add s t o aceti c anhydrid e t o furnis h ethyliden e diacetate , CH 3 CH(0 2 CCH 3 ) 2 . Th e higher carboxyli c aci danhydride s ma y b e pre pare dconvenientl y by adoubl e decompositio n reactio n wit h aceti c anhydrid e an dth e higher acid . Sinc e aceti c aci dboil s lowe r tha n th e othe r fatt y acids , i t

ca n b e distille dan dth e higher aci danhydrid e recovered . Manufactur e Ther e ar e thre e mai n route s t o aceti c anhydrid e tha t ar e thoroughl y understoo dfro

man engineerin g standpoint ; th e processe s depen dfunda mentall y upo n thei r

distinctiv e ra

w materials , ie , aceti c acid , acetone , an dacetaldehyde , fo

r anhydrid e manufacture . Th e aceti c aci dproces s involve s th e endothermi c decompositio n o f aceti c aci dt o keten e an dth e additio n o f keten e t o aceti c aci din th e liqui dphas e t o produc e aceti c anhydride . CH.,C(0)O H + CH 2 =C=0 - (CH 3 CO) 2 0 +62. 8 kJ/mo l (1 5 kcal/mol ) Th e aceton e proces s involve s asimila r therma l decompositio n o f aceton e t o keten e i

n areactio n tha t

i s les s endothermic . Pyrolysi s gase s ar e quenche di n aliqui drecycl e mixtur e compose do f aceti c aci dan d anhydride ; th e quenche dgase s consis t o f ketene , aceti c acid , aceti c anhydride , unconverte dacetone , an dth e permanen t gases . Durin g con densation , practicall y al l th e keten e react s wit h aceti c aci dt o for

maceti c anhydride . Thre e distillation s recove r th e acetone , amixtur e o f aceti c aci dan danhydrid e (whic h i s use dfo r quenching) , an dpur e aceti c anhydride . Liquid-phas e acetaldehyd e oxidatio n yield s aceti c aci d(a s aby-prod uct ) an dacetaldehyd e monoperacetate , which decompose s int o aceti c anhydrid e an dwater . Th e produc t ma y b e remove da s aliqui dor a vapor ; a s avapor , th e concentratio n o f aceti c anhydrid e i s highe r tha n tha t o f aceti c acid ; ai r

i s usedt o entrai n th e aceti c anhydrid e an dwate r a s fas t a s the y ar e made . Purificatio n o f th e liqui dproduct s i s compara tivel y easy ; low boilin g substance s ar e remove dwith ethy l acetat e or aceti c aci dbefor

e th e anhydrid e i s distilled . A numbe r

o f othe r route s t o aceti c anhydrid e manufactur e investi gate dinclud e methy l acetate , aby-produc t o f methano l carbonylatio n (se e Aceti c acid) , pyrolyze dt o keten e i n asyste msimila

r t o tha t use dfo r aceton e o r

carbonylate dt o aceti c anhydrid e i n th e presenc e o f meta l catalyst ; an dsodiu macetat e an dcarbo n dioxid e reaction s for msodiu m bicarbonat e an daceti c anhydrid e i n aqueou s solutions . Health an dSafet

y Factor s Aceti c anhydrid e ha s apowerful effec t o n th e human body . Th e odo r threshol di s 0.4 9 mg/m 3
. an dth e eye s ar e affecte dby a s littl e a s 0.3 6 mg/m 1
. Concentration s > 0.0 3 mg/m 3 throughou t aregula r workday ar e inadvisable . Aceti c anhydrid e penetrate s th e ski n quickl y an dcan for mpainfu l burn s an dblister s tha t ar e slow t o heal , l t

i s particularl y dangerou s t o th e tissue s o f th e eyes , nose , an dmouth ; rubbe r gloves , masks , an dgoggle s ar e recommended . FRANKS . WAGNER , JR . Celanes e Chemica

l Compan y GV . Jeffreys . The Manufacture of Acetic Anhydride. 2n

ded. . th e Institutio n o f Chemica l Engineers . London, 1964 . ACETY L CHLORID E Acety l chlorid e (ethanoy l chloride) , CH 3 C0C1 , i s acolorless , mobil e liqui dwit h apungen t

odor . I t fume s i n mois t air , an dit s vapor s ar e extremel y irritatin g t o th e eyes , nose , an dthroat . Acety l chlorid e i s useda s acatalys t i n th e chlorinatio n o

f aceti c acid ; fo r thi s us e i t

i s mad e in situ fro

maceti c anhydrid e an dby-produc t hydroge n chloride . I t

i s use da s apowerful acetylatin g agen t in organi c synthesis , particularl y wit h aLewi s aci dcatalyst ; i t will acetylat e many compounds , eg , benzene , tha t canno t b e acetylate dwit

h aceti c aci do r aceti c anhydride . Acety l chlorid e i s usedt o synthesiz e pharmaceutical s an ddyes ; i

n th e preparatio n o

f acetanilide , acetophenone , an dothe r acety l derivatives ; an di

n th e laboratory t o determin e hydroxy l groups ; in qualitativ e organi c analyse s fo r distinguishin g tertiar y fro mprimary an dsecondary amines . I t i s als o use dt o for

mphenoli c compoun d derivatives ; a s achlorinatin g agent fo r inorgani c compounds ; a s a catalys t in esterificatio n an dhalogenatio n o f aliphati c acids : an din th e nitratio n o

f thiophene s an dothe r

compounds . Acetylaceton e ha s bee n prepare di n 80

% yiel dfro

macety l chlorid e by athree-stag e proces s involvin g an additio n compoun do f acety l chlorid e an daluminu mchlo ride. Specialty application s includ e it s us e a s acatalys t i n th e esterifica tio n o f cellulos e b y aceti c anhydride ; t o accelerat e th e reactio n an d improv e th e wetfastnes s o f th e resultan t

yams ; i n th e manufactur e o

f a pour-poin t

depressan t

fo r lubricatin g grease ; a s astabilize r agains t polymerizatio n o

f organi c isocyanate s o r

diisocyanates ; an da s arubber ' antiscorc h agent . Physic* ! an dChemical Propertie s Acety l chlorid e ha s m

p -112.86°C , b p 51.8°C , flash p t 4.5°C . d' f 1.105 1 g/cm 3 , nj, 0 1.38708 , surfac e tensio n 26. 7 - 1. 0 mN/ m( = dyn/cm i a t 14.8° C an d21. 9 mN/ ma t 46.2°C , laten t

hea t o f fusio n A ( W , ) (Uquid ) 275. 3 kJ/mo l (65. 8 kcal/mol) , an dbonddissociatio n energ y o f carbon-chlorin e bon d320. 9 kJ (76. 7 kcal) . I t i s solubl e in acetone , glacia l aceti c acid , ethy l ether , benzene , toluene , chloroform , an dcarbo n disulfide , an di s use da s asolvent . Acety l chlorid e decompose s vigorously i n wate r t o for maceti c aci dand hydrochlori c acid . I t

react s wit

h alcohol s an damines . Acetamide i s forme db y treatin g acety l chlorid e with anhydrou s ammoni aor wit h concentrate daqueou s ammoniaca l solutions . Potassiu msulfid e an d potassiu mhydroge n sulfide reac t with acety l chlorid e t o for macety l sulfid e an dthioaceti c acid . Acety l chlorid e react s wit h acetylen e a

t lo c C in th e presenc e o

f aluminu mchlorid e t o give methy l viny l ketone . Aceti c anhydrid e i s forme di n th e reactio n o f acety l chlorid e wit

h sodiu m acetate . I t

decompose s a t

400° C ove

r anickel catalys t

int o carbo n monoxid e (62%) , hydroge n (32%) , hydroge n chloride , ethylene , an dcarbo n dioxide . I t

react s wit

h zinc , aluminum , an dothe r metal s t o for

mth e chlorid e o f th e meta l an davariety o f organi c compounds . Preparatio n Larg e scal e in situ industrial productio n o f acety l chlorid e use s th e actio n o f hydroge n chlorid e a t

85-90 c C on aceti c anhydride , t o produc e apracticall y quantitativ e yield . Commercially , i t i s prepare db

y treatin g sulfu r dioxid e an dchlorin e with sodiu macetat e followedby distillation . Laborator y manufactur e involve s th e reactio n o f phosphoru s trichlorid e wit h aceti c acid . Industria l equipmen t fo r acety l chlorid e i s usuall y mad e o f glass , glass-line dsteel , Teflon , Teflon-line dsteel , o r heavy-wal l poly ethylene . Acety l chlorid e i s shippe di n 220- L (58-gal ) polyethylene-line ddrum s an di n 100- g an d500- g packages . I t carrie s th e U.S . DO T Whit e Label designatio n fo

r acorrosiv e substance . I t i s produce di

n bot h apractica l an dareagen t

grade . Healt h an d Safet

y Factor s Acety l chlorid e violentl y decompose s wit h wate r an dalcoho l an di s easil y hydrolyze dint o aceti c aci dan dhydrochlori c acidb y bod y mois ture . I t ha s atoxi c effec

t o f it s ow n becaus e i t

react s wit

h th e S H group o f protei n molecules . It

i s highly toxi c an dcorrosiv e an dastron g irritant . I t

mus t b e usedwit

h adequat e ventilation , an dproper protec tiv e clothin g shoul db e worn . It s vapo r form s explosiv e mixture s with air . Spill s or leakag e o

f acety l chlorid e shoul db e treate dwit h sodium bicarbonate . THERES A A . MORETT I America n Hoechst Corporatio n G.A . Olah , Friedel-Cra/ts and Related Reactions, Interscienc e Publishers , a division o f Joh n Wile

y & Sons , Inc. . Ne

w York , 1963 .

# AL-W ) 

# Shrcvc' s Chemica l Proces s Industrie s GEORG E T . AUSTIN 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 d Bogot a Hambur g Johannesburg Londo n Madrid Mexic o Montrea l Ne w Delh i Panama Paris Sa o Paul o Singapor e Sydne y Toky o Toront o 

# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK * N CP.8 7

76 8 Chap. 34

Palroehmmleala abouta 2 5 percen tconversio n t o acetaldehyde . wit

h recirculatio n makin

g a 9 0 t o 9 5 yiel d possible . (4 ) Lowe rmolecula rweigh tparaffi n hydrocarbons ar

e onidize d no n ******* call y t o produc e mixe d compounds , amon g the m acetaldehvd e an d aceti c aci

d S » C yn * suc h mixture s i

s difficult. 3e P*'«io n o f Since nearly 5 0 percen to f th e acetaldehyd e produce d i s use d t o mak e aceti c aci

d m f marke ti s questionable . Aceti c aci d produce d directl y b y th e carbonylation o

f methanol * k " already cutdeepl y int

o th e market. **** .Acetic acid

i s widel y used , an

d muc h i s converte d t

o aceti c anhvdride. 1 1 Eastman 1 2 i

s currentl y buildin g a ver y large plan

tt o produc e thes e an

d othe rch e fro m coal . Th e reactio n betwee n keten e an d aceti c aci d produces the anhvdrid e bu^'h * amoun to f energ y require d t

o produc e th e keten e iaceton e i s cracked t

o give ketene ' ' methane ) i

s ver y large . inc l 

### 3| l l v ,CH,),C O - CH 2 =-C- 0 + CH , CHj-C= 0 + CH3COOH - (CH,COii O Keten e i s used immediatel y afte rmanufactur e becaus e i tdoe s no tstor e well . Th

e maw r< o f aceti c anhydrid e i

s i n makin g vinyl acetate and othe racetylations . Ethylene glycol,** used i n antifreeze , 4 0 percent , and i n fibers an

d films. 5 0 percen ti s majo rpetrochemical and ha s bee n fo rman y years . Th e deman d i

n 198 1 wa

s 2 X IQ

9 ' Lik e mos to f th e othe ralcohols , i

twa s originall y mad e by reactin g chlorine an d wate rHOCl' . wit h ethylen e to for

m th e chlorohydrin , which wa s the n hydrolyze d t

o yiel d glyco

l Thi s procedur e and severa

l others (formaldehyd e + CO t , fermentation , oxidatio n o f propan e 1 i s now technicall y and environmentall y obsolete . Th e currentl y favored process start s wit h ethylen e and react

s i twit h oxyge n o

rairi n a tubularreacto rove ra silveroxid e catalvstt o l<> r m ethv l en e oxide . Becaus e th e volatility o f glyco l i s low , i ti s preferabl e t

o purif y the ethylen

e oxide , the n conver ti

tt o glyco l by hydration . Durin g th e hydration , however , polygly, 0 t s particularl y di - and tri-ethyleneglycol s are formed . Th e reaction s are :

H,C=CH , • 1/2 O j Mi O CH,—CH , * (CO , »n d H 2 0 b y combustio n 1 \ / 0 CH,—CH , * H, 0 CH,—CH 2 * polyiiyco

U O H O H Ethylen e dichlorid e (unde r1 ppm ) i s adde d t o a mi

x o f ethylen e and ai

ri n the rati o o f 1 1 0 t o reduc e oxidatio n to COt , and th e mixtur e i s passed ove ra supporte d silve roxide catalys t a tatmospheri c pressure an d 280° C wit h a 1- s contac ttime . Thi s cause s a 6 0 t o 70 percen

t "Rot h e tal. . Low Pressur e Proces s fo rAceti c Aci d via Carbonylatio n o f Methanol . CHEhATECH 1(10 ) 60 0 (1971) . "Jeffreys , The Manufacture of Acetic Anydride, 2d ed. , Th e Institutio n o f Chemica l Engineers , London . 1964 . U A Gian tStep : Aceti c Anhydrid e from Coal . Chem. Week 127 (3 ) 4 0 (1980 ) ^Hydrocarbon Process. 8 0 (11 ) 161-16 3 (1981) .

# r P.8 8 

# SH-3? 7 fourth edition 

# CHEMICA

L PROCES S INDUSTRIES

R . NORRI S SHREV E Late ProfeuorEmeritus of Chemical

Engineering Purdue University 

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

Engineer Profet$orand

Chairman of

Chemical

Engineering Washington State Univenitv

McGRAW.HILL BOO KCOMPAN Y New York St. Louis San Francuco Auckland Bogotd DOutldorf

Johannetburg London Madrid Mexico Montreal .Vm rDelhi Panama Paris SOo Paulo Singapore Sydney Tokyo Toronto 

# RADIA N LIBRAR Y

DURHAM , N.C .Librar y o f Congres s Catalogin g i a Publicatio n Dat a Shreve , Randolp

h Norris , 1885-1975 . Chemica l proces s industries . Include s bibliographie s andindex . 1 . Chemistry , Technical . I . Brink , Joseph A. , date , joint author . II . Tide . TP145.S 5 197 7 660. 2 77-423 6 ISB N 0-07-057145- 7

Copyrigh t © 1977 , 1967 , 195 6 b

y McGraw-Hill , Inc . Al

l right s reserved . Copyrigh t 194 5 b y McGraw-Hill , Inc . Al

l rights reserved . Printe di n the UnitedState s o

f America . N

o par t o f thi s publicatio n ma

y b e reproduced , store di

n aretrieva

l system , or transmitted , i

n an y for mor b y an y means , electronic , mechanical , photocopying , recording , or otherwise , withou

t the prio r written permissio n o

f the publisher . 3456789 0 FGRFG R786543210 9

The editors for

this book

mere Jertmy Robinson and Esther Gelatt, and the production supervisor was Teresa F. Leaden. It was set in Bodoni Book. Printed and bound by Fairfield

Graphics.i s consume di

n th e chemica l indus t r . largel y becaus e o

f enhance dyield s pmen t size , an dreduce dhea t i os s ^ m dvapo r

phases , usin g avariet y °e aerature s (abou t

-I00°C ) ar e e m n i „ ° , teat remova l i s alarg e one . Oxiriati r ie C O to methanol , henc e th e \ w " ipa . Tex. , oxidiz e propan e an db U i an , . in g chemicals . Ai r

ha s bee n use dh te dfromemployin g oxygen . Som e ,,(- ••rmaltlehvde . acetaldehvde . ar^i , •it oxidation i s employe dt o rais e ____[ i l ga s to mak e acetylen e (Chap . 7 1 I t i s reporte dtha t

Celanese' s new o f titaniu mve

t reported . i s obtaine dwit

h oxvge n fo

r an v o\\,* •" - . c - t i ehyde . formaldehyde , methanol , an d iffi n chai n lengt h an dth e highe r th e -elective : acobal t

catalys t wit h liquid , lerea s amanganes e catalys t furnishe r .elanes e a t Pampa. 4 7 Tex. , fo

r butan e nillio n l b i n 1976 1 bv fou r

methods sulfate s i n sulfuri c aci dunde r

apres i t o f reaction) . Idehvd e b v passin g throug h acopper Halogenation and Hydrohalogenation 70 9 Th e acetaldehvd e i s vaporize dfro mth e solutio n an dabsorbe di n water , separat e fro mresidua l gases . Th e acetaldehyd e i s distilled . Th e conversio n an dviel 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 dwith ai r noncatalvticall v t o produce , amon g man y othe r compounds , acetaldehvd e an daceti c acid . Th e selectivit y o f th e proces s i s reasonable , onl y 1 5 t o 20 % of th e paraffi n bein g oxidize dt o C O an dC0 2 . an dth e remainde r yieldin g condensabl e organi c product s suc h a s acetaldehvd e an daceti c acid . Recover y o f th e prod uct s a s pur e component s require s specia l distillations . Acetic acid

51 and anhydride usin g oxvge n ar e produce db v th e oxidatio n of acetaldehvde . Man v 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 methv l acetat e diluen t an dwit h manganes e acetat e catalys t presen t t o preven t

th e formatio n of

explosiv e amount s of

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 anhvdrid e an daceti c acid . ar e separate dan dpurifie di n aserie s of bubble-ca p columns , th e crud e stil l an dth e anhvdrid e stil l operatin g unde r

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

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

i s als o emplove di n variou s othe r acetylations . A development 0 2 ha s bee n th e productio n o f acetaldehyde-monoperacetat e (AMP ) 2CH 3 CH O + 0 2 O —H O H

ultraviole tligh l r u r ^ ^ .' 0° C 

### \ 0 - / \

- 0 CH 3 b v th e controlle dlow-temperatur e oxidatio n o f acetaldehvde . Th e AMP ca n b e use dt o produc e epoxide s o r

2 mo l of

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

one-fift h of al l ethylen e oxid e i s stil l bein g mad e b v th e ol dproces s throug h chloro hvdrin . bu t

a n increasin g amoun t eac h year

i s manufacture db v ai r o r oxvge n actin g o n pur e ethylene : C,H 4 + iO , 123-30 0 psi.

.-atalvs t CH. , 

### | \ " I CH , 

### 0\g) At

f = -3 5 kca

l

= -4 3 kca

l rectifyin g to giv e 99 % acetaldehvde . loechst 4 9 fo r

th e direc t

oxidatio n o

f aqueou s solutio n o f

coppe r chlorid e t h ai r o r oxyge n i s passed : Yiel d 55-65% , conversio

n pe rpas s 25-50% , Productio n in 197 4 was 4.2 6 billio n lb . Aromatic oxidation 5 * products are include d in variou s chapter s o f thi s book . A s Tabl e 37. 6 indicates , ther e i s a fundamenta l chang e in the sourc e of aromatic s fro

m coa l an dcoa l ta r

t o petroleum . Se e als o Fig . 38. 4 an d Tabl e 38.6 . OXO - O RHYDROFORMYLAT10N 5 5 Th e ox o proces s i s a metho d of convertin g a-olefin s t

o aldehyde s and/o ralcohol s containin g on e additiona l carbo n atom . Th e olefi n i n liqui dstat e i s reacte d

I \'6 K'il l il.-^ . njitiun- . rf-lVri-ni'*"- . Ilm,,-harl- . !10 . '.x Profit , pp . J32-23 4 lriow.:hart fo rovidalio n "Hoechs tReveal s Wacke rProcess , Chem. Eng. iVetra . Apr . 17 . 1961 . p . 52 : Petrochemica l Handbook : Pel. Refiner. 42(11) , 1963 ; Cuccioni . Acetaldehyd e vi a Ethylen e Oxidation . Chem. Eng. (V.K) . 70(25) . 15 0 (1963) . "Goldstein , op. eit.. p . 373 : Sittig , Aceti c Aci d an d Anhydride . Noves . 1965 : Austin . Industriall y Significan tOrgani c Chemicals . Chem. Eng. (S.Y.). 81(2) . 12 8 (1974) . "Phillip s e tai. U.S . Pat . 2.804.47 3 (1957) . "Goldstein , op. eit.. pp . 156-159 : Hydrocarbon Process.. 52(11) , 12 9 (1973) . 54 Phthali c anhydrid e flowchart. Fig . 34.12 ; Hydrocarbon Process.. 52(11) , 15 9 (1973) . 55 Groggins . op. eit.. pp . 651-69 3 an d particularl y p . 68 3 (kinetic s an d flow diagram) ; Goldstein , op. eit.. pp . 204ff. : How Ox o Stay s i

n th e Race . Chem. Week. Jun e 6 . 1964 : Hahn , op. eit.. pp . 104-116 .