p. 1 

# RCRA Box 1883 Prepped by Ollie Stewart



## Document

Number: 

# 12 ) ll-B-17 3 Docket Number: 

# A-90-1 9

Printed 12/3/200810:42:10AM

Sheet 12 of 171P. 2 

# A-90-1 9 "-B-17 3
MEMORANDU M TO : Proces s Vent s A-90-1 9 FROM : WandaFloy

d DATE : Decembe

r 199 1 

# 1 finny f $& V/992 EP A AI R DOCKE T 

## SUBJECT : HO N NESHAP : Industr y Characteristics /

Ethylene Glycol Monobuty l Ether Acetate Attache di s aproduct-proces s summar y (PPS ) fo r the productio n o

f Ethylene Glyco

l Monobuty l Ether Acetate vi aesterification o f ethylene glyco

l monobutyl ether

wit h . aceti c acid . Thi s PPS wa

s developedas par

t o f th e Industria

l Profile Project

in suppor t o f th e Hazardou s Orgam

c NESHA P (HON ) regulator

y effort . Informatio n i

n thi s PPS i s useda s abasi s fo

r emission s an

dcost impact estimate s fo

r th e HON program . Listedbelow are th e ke

y reference s usedi

n developin

g th e attache dPPS . 198 9 Director y o f Chemica l Producer s USA . SR

I International , California , 1989 . p . 496 . Kent , Jame s A . Riegel' s Handbook o f Industria l Chemistry . 7t

h edition . Va

n Nostrand Reinhol dCompany , Ne

w York, 1974 . pp . 782-783 . Weissermel , Klau s an

dArpe , Hans-Jurgen . Industria l Organi c Chemistry . Verla g Chemie , Ne w York, 1978 . pp . 140-143 . 

# Th e torepfiig EaaR

j Paran a x Document i s Docke t ite m A-90-1 9

ll-B-25 2P. 3


## Preparer : /&&. JJOM/JL, 

## Oate : Reviewer : 

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## #

# KE-15+ 

# Riegel' s 

# H a ill l 

# ko f Industria l Chemistry 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 NI W VOU * CINCINNAT I ATLANTA DALLA S SA N FRANCISC O

LONDO N TONONT O MBLSOUftN S 

# RADIA N LIBRARr " DURHAM , N.C .Van Nostran d Reinhol d Compan y Regiona l Offices : Ne w York Cincinnati Chicag o Millbrae Dalla s Van Nostran d Reinhol d Compan y Internationa l Offices : Londo n Toront o Melbourn e Copyrigh tC 197 4 b y Litto n Educationa l Publishing , Inc . Librar y o f Congres s Catalo g Car

d Number : 73-1479 8 ISBN : 0442-24347- 2 Al l rights reserved . Certai n portion s o f thi s work copyrigh t© 196 2 b y Litto n Educationa l Publishing , Inc . N o parto f thi s wor k covere d b y th e copyright s hereo n ma y b e reproduce d o ruse d i n an y for m o rb y an y means-graphic , electronic , o rmechanical , includin g photocopying , recording , taping , o rinfonnatio n storag e an d retrieval systems-withou twritte n permissio n o f th e publisher . Manufacture d i n th e Unite d State s o f Americ a Publishe d b y Van Nostran d Reinhol d Compan y 13 5 Wes t50th Street, Ne w York , N.Y . 1002 0 Publishe d simultaneousl y i n Canad ab y Va n Nostran d Reinhol d Ltd . 1 5 1 4 1 3 1 2 1 1 1 0 9 8 7 6 5

Library o f

Congres s Cataloging i n Publicatio n Dat a Riegel , Emi l Raymond , 1882-196 3 Riegel' s handboo k o f

industria l chemistry . First-5t h ed . publishe d unde rtitle : Industrial chemistry ; 6t h ed . i n 196 2 unde rtitle : Riegel' s industria l chemistry . Include s bibliographica l references . 1 . Chemistry , Technical . I . Kent , Jame s A. , 1922 - ed . II . Title . III . Title : Handboo k o f industria l chemistry . TP145.R5 4 197 4 66 0 73-1479 8 ISBN 0442-24347- 21'R T l r •-TT v ?T"rrST'J"" " 

# T 78 2 RIEGEL' S HANDBOO K O F INDUSTRIA L CHEMISTR Y

i fou

r classe s accoun t

fo r mor e tha n 8 0 per

cen t o f th e production . Thes e are (1 ) th e alkyl
- phenol-ethylen e oxid e derivatives , (2 ) fatt y acid-alkanolamin e condensates , (3 ) tal l oil
- ethylen e oxid e adducts , an d(4 ) th e fatty acid
- ethylen e oxid e adducts . Th e alkanolamin e condensate s are foa

mstabilizer s i

n variou s detergen t formulations . Tal l oi l adduct s find us e i n househol ddetergents , chiefly automati c washe r products , becaus e o f

thei r low-sudsin g properties . Th e fatty alcoho l adduct s are use d mainl y a s light-duty detergents , thoug h som e tridecy l adduct s ar

e utilize da s foa

mstabilizers . Th e tren dha s bee n awa

y fromth e benzenoi d ether s becaus e o f

thei r biodegradability limi
- tations . Ethanolamines. Ethanolamine s ar e manu - facture db y reactin g ethylen e oxid e an dam- monia . Th e relativ e amount s of th e thre e amine s will depen dprimaril y o n th e ammoni a t o oxid e feedratio . NH 3 ^ £(HOC 2 H 4 )NH 2 ^ £ (HOC 2 H 4 ) 2 N H £^ £(HOC 2 H 4 ) 3 N Th e product s fromth e reactio n are separate d b y distillation . Durin g th e las t fe w years , eac h o f th e amine s ha s i n tur n bee n in th e greates t demand , s o processin g flexibilit y mus t b e maintained . Monoethanolamin e i s use dprimarily in de
- tergent s an da s a

n absorben t

for acid-ga s (H 2 S , C0 2 ) removal . I t

i s t o alesse

r extent , achemica

l intermediat e fo

r compound s suc h a s ethylen e imine . Diethanolamine' s major en d us e i s i n detergetns , bu t

it i s als o utilize di

n textile s an da s agas-purificatio n agent . Mos t o f th e triethanolamin e goe s int o th e produc
- tio n o f cosmetic s an dtextil e specialities . Isopropanolamines , derive dfrompropylen e oxid e an dammonia , are competitiv e with th e ethanolamines , an dbot h are uniqu e i n tha t the y are organi c compound s an dyet strongl y alkaline . Glycol Ethers. In th e sam

e wa y tha t wate r react s with on e or

more molecule s o f

ethylen e oxide , alcohol s reac t

t o giv e monoether s o f ethylen e glycol , producin g monoether s o f di
- ethylen e glycol , triethylen e glycol , etc. , a s by
- products . 0

/ \ RO H + CH 2 -CH 2 —ROC 2 H 4 O H

0 / \ + CH 2 —CH 2 —ROC 2 H 4 OC 2 H 4 OH . 0 / \ + CH 2 -CH 2 — •

ROC 2 rUOCjrUOCjH, , O H Sinc e thei r

commercial introductio n i n 1926 , glyco l ether s hav e becom e valuabl e a s indus
- trial solvent s an dchemical intermediates . Be
caus e glyco l monoether s contai n a —OCH 2 CH 2 O H group , the y resembl e acombi
- natio n o f ethe r an dethy l alcoho l in solven t properties . Th e mos t

commo n alcohol s used ar e methanol , ethanol , an dbutanol . Principa l use s for th e glyco l ether s are a s solvent s fo r paint s an dlacquers , a s intermediate s in th e productio n of

plasticizers , an da s ingredient s in brake flui dformulations . Th e mos t com- mo n trad e name s ar

e Dowanol® , Cellosolve® , an dPolysolve® . Condensatio n o f th e mono - ether s produce s glyco l diether s whic h ar e als o useful a s solvents . 2ROCH 2 CH 2 O H ^22s ,

ROC 2 H 4 OC 2 H 4 O R+ H 2 0 Alcohol-ethylen e oxid e product s hav e als o bee n develope di n whic h th e numbe r o f oxide unit s i s considerabl y "highe r i n orde r t o im
prov e wate r

solubility . Long-chai n fatty alco
hol s ar e condense dwith 10-4 0 molecule s of ethylen e oxid e t o produc e detergent s fo r th e textil e industry . Als o importan t ar e th e water - solubl e alky l pheny l ether s o f th e higher

poly
- ethylen e glycols . Phenol s reac t in th e sam

e wa y a s alcohol s t o giv

e polyglyco l ethers . The reactio n i s rapid , an dessentiall y quantitative . Thes e product s are detergent s o f th e sam e genera l clas s a s th e long-chai n alcohol-ethylen e oxid e condensates . Of recen t origi n i s th e interes t

i n th e ex - tremel y high molecula

r weight homopolymer s of ethylen e oxide . Thes e resins , trade-marke d

# T l

H 6 , is - •ea Di
- n t e d >a l o r h e >t s m - ® 10 - Is o

2 0 Is o id e mco - o f h e er - ly
- n e h e .ve . ,en- en e ex - ler s ke d Polyox® , have goo dwate r an dorgani c solvent solubilit y an dthu s are use dfo r thickenin g agent s an dwater-solubl e films. Chlorinate d Hydrocarbon s Th e manufactur e o f

chlorinate dhydrocarbon s form s a n importan t

par t of industrial chemis
- try today . Th e product s ar e useful a s solvents , chemica l intermediates , pesticides , monomers , an din many othe r

ways . Tabl e 25. 3 show s som e of th e large-volum

e materials . Chlorinate dderivative s o f aliphati c hydro
- carbon s are usuall y prepare db y on e o f thre e genera l methods : (1 ) additio n o f hydroge n chlorid e t o unsaturate dhydrocarbons , (2 ) ad
- ditio n of chlorin e t o unsaturate dhydrocar
- bons , o r (3 ) substitutio n o f

chlorin e fo

r hydro
- ge n i n eithe r

saturate dor

unsaturate dhydro
- carbons . In th e las t

case , hydroge n chlorid e i s a by-product . Example s o f

th e first metho dar

e th e additio n o f

HC l t o ethylen e t o for

methy l chlorid e an dth e additio n o f HC l t o acetylen e t o for mviny l chloride . Typical of th e secon d metho di s th e additio n o f chlorin e t o ethylen e t o for mdichloroethane . Th e thir dmethod , th e direc t substitutio n of

chlorin e fo

r hydrogen , usuall y involve s afree-radica l mechanism . Th e formatio n o f

chlorin e fre

e radical s occur s SYNTHETI C ORGANI C CHEMICAL S 783 spontaneousl y at

temperature s abov e 250° C an dincrease s with temperature . Th e formatio n ma y als o b e brough t

abou t b y th e actio n o f actini c light

a t lower temperatures . Thes e light
- activated , o r

photochemical , chlorination s may b e carrie dou t

in eithe r gas or liqui dphase . Th e principal use s fo

r chlorinate dhydrocar
- bon s ar e as solvents , chemica

l intermediates , an dinsecticides . Thei r

valu e as solvent s derive s fromacombinatio n o f

goo dsolven

t power , lo w flammability , an dhigh vapor density . Th e latte r propert y i s particularl y importan t in vapor degreasin g o f

metal part s ( amajo

r us e fo r trichloroethylene , perchloroethylene , and methy l chloroform) . Certai n o f th e com- pound s ar e o f value as chemical intermediates . Thus , ethy l chlorid e i s use dt o mak e tetraethy l lead ; an dethylen e dichlorid e i s use dt o mak e vinyl chloride , whic h in tur n i s polymerize dt o polyviny l chloride . Ethylene Dichloride (EDC). Whil e som e ethylen e dichlorid e (1,2-dichloroethane ) oc - cur s a s aby-produc t

o f chlorohydri n an dethy l chlorid e processes , th e bulk come s fro

mth e chlorinatio n o f

ethylene . Almos t

9 0 per cen t o f th e EDC produce din 196 9 wen t int o th e manufactur e o f

viny l chlorid e monomer . Fig
- TABL E 25. 3 Productio n an dSale s o f Some Halogenate d Aliphati c Hydrocarbons 3 Ethylen e dichlorid e Viny l chlorid e Carbo n tetrachlorid e Ethy l chlorid e Perchloroethylen e Trichloroethylen e Methy l chlorid e Dichlorodifluoromethan e Methylen e chlorid e Methy l chlorofor m Ethylen e dibromid e Trichlorofluoromethan e Chlorofor m Chlorinate dparaffin s Al l other s TOTA L halogenate d hydrocarbon s Production (1000lbs) 6,037,42 8 3,735,94 2 882,73 5 678,80 8 635,25 1 596,82 1 402,80 9 367,65 8 366,00 5 324,31 1 309,94 3 238,51 8 216,16 8 61,93 5 1,331,98 1 16,186,31 3 Sales

(1000lbs) 1,226,84 5 2,358,74 1 785,88 4 267,50 3 611,62 5 561,53 6 166,14 6 335,40 9 338,10 7 298,87 3
— 203,65 2 172,17 7 59,12 4 436,09 1 7,899,65 1 Sates Value

($1000) 36,34 5 103,10 0 42,69 8 16,59 9 42,52 9 39,62 6 8,72 9 85,20 3 25,89 1 33,28 8
— 37,47 6 10,80 7 7,58 4 144,20 2 677,39 6 U.S . Tarif f Commissio

n Report, 1969 .

# Klau s Weisserme l Hans-Jiirge n Arp e 

# Industria l Organic Chemistr

y Importan t Ra w Material s an d Intermediate s Translate db

y Alexander Mulle n



# Verlag Chemi e • Weinheim• Ne w Yor k 197 8P.2 6

Prof . Dr . Klau s Weissermel Dr . Hans-Jurge n Arp e Hoechs t A G Postfac h S00 3 2 0 D-623 0 Frankfur

t S O Wes t Germanv

Copy Editing : Dr . Han s F . Ebe l Thi s book contain s -1 3 Table s CIP-Kurzcitefaafnahme der Deu:>c.TL' n SiWtothek Weissermel , Klau s Industrial organi c chemistry : important ra w material s an

dintermediate s /

Klau s Weissermel : Hans-Jiirge n Arpe . - 1 . Aufl . - Weinheim . Ne w York : VerlagChemie . 1978 . Dt . Ause . u.d.T. : Weissermel . Klaus : Industrielleorganisch e Chemie . ISB N 3-527-25706- 3 (Weinheim) ISB N 0-S9573-0U5- 7 (Ne w York l NE : Arpe . Hans-Jiirgen : S \'erla g Chemi e GmbH . D-694 0 Weinheim , 197 8 Al l right s reserve dyincluding thos e o f translatio n int o foreign languages) . N o par t o f thi s book ma y b e reproduce di

n .m v for m- fry photoprint , rajcrofiim. or an y othe r mean s - no

r transmitte dor

translate dinto amachine languag e withou t written permissio n fro

m:h e publisiiers . Registere dnames , trademarks , etc . use di n Thistioofc . eier

c withou t specifi c indicatio n thereof , are no t to b e considere d unprotecte db

y law . Printer : Passavi aDruckere i GmbH Passa u Printe di n Wes t German y 

# Prefac e

Industria l organi c c l a s wel l as.-t o a n ,;K : presen t statu s o f k n Ther e 'Au s thu s asj n an dintermediate s i an dt o presen t

i t i n ; development , whic h fro mthei r

industria l in g discussion s with Thi s boo k

address e fro mi t th e chemist i manufacturin g pro c giear , informatio n a .int i r etii.vrock s .ilo

r discipline s i

n :h-.
- - . economist s - wil

l tecononii o interreiu ; Thi s boo k

i s arran g thei r tightes t possi t unavoidable . Th

e n A s arule , ih e man u me man dsignific a •appiica\ion s o

f th e ; product s ar e fret;'
- existin g technologi L more , economi c o r Th e author s ende; r informatio n ar e a t 1 . Th e mai n text . 2 . Th e synopsi s o

f i 3 . Flo w diagram s i

l Thes e thre e types o o r makin g brie f

n o note s whic h briefl y t o b e rapidl y info n14 0 7 . Oxidation Products of Ethylene
4 . a s startin g materia l i n organic synthese s (heterocycles ) ethanolamine production (in 1,0001) :

197 4 197 5 197 6 US A 13 9 11 7 13 0 W . German y 6 6 5 0 6 1 Japa n n.a 3 2 n.a. n.a. = no tavailable andcream s i n cosmeti c manufactur

e becaus e o

f thei r mil d alkalin e reaction . They are als o use di n th e manufactur

e o f heterocycle s i

n organi c synthesis . Th e availabl e productio n fi
gure s fo r th e most

important

industrial countrie s are summarize di n th e adjacent

table . Accord i reactin g approx . ClCH 2 i

secondar y product s o f ethanolamines : 1 . morpholine via aci

d catalyzed dehydra tion o f HN(C 2 H„OH) 2

2 . ethylenimin e = aziridine vi a indirec ttwo step cheinica

l dehydration wit

h semi-es tero f sulfuric aci

d a s intermediat

e Morpholine , whic h i s asolvent

an dintermediar

y product , i s obtaine dfro

mdiethanolamin e b

y dehydratio n wit

h 70 % H 2 S0 4 wit

h simultaneou s ring closure :
H N / \) H[H,S0. 1 .O H -H, 0 H N O

\/ (18) Ethylenimine , anothe r

intermediat e o

f commercia

l use , ca n be manufacture dfro

mmonoethanolamine . Th e industrial proces se s operate dtoda

y are usually two-step . Ethanolamin e i s ini
tially esterifie dwit

h 9 5 % H 2 S0 4 , t o P-aminoethy l sulfuric acid : Alon g • ca n oe i acidi c s coun t i i Ethylei ccssing media l
Anotlv wit h a l H2 NCH2CH2 O H + H 2 SG y - H 2NCH 2 CH 2 OS0 3 H + H 2 0 (19 ) RO H On heatin g wit

h stoichiometrical amount s o f NaO H a

t 220-250° C an d50-8 0 ba r i n th e secon dstep , th e acidi s cleave dfro

mth e semi-ester

forming th e imine via ring closure : H2NCH2CH2OSO3 H + 2 NAO H — • H 2 C—CH 2 T " H tNajS0 4 + 2 H a O (20 )

I f th e imine formatio n i s conducte di n aflo w tube , suitabl e residenc e time s o

f 4-1 0 s ca n b e arrange di

n orde r t o supres s secondar y reaction s such a s th e polymerizatio n o f ethylenimine . Th e imine selectivit y the n increase s t o 80-85 % (base do n ethanolamine) . Analogou s processe s were develope d b y BAS Fan dHoechs t

fo r th e manufacture o

f ethylenimine .7.2. Secondary Products of Ethylene Oxide 14 1 i r mil d tur e of 'tio n fi
e sum Accordin g t o aDo w process , ethylenimin e i s synthesize db y reactin g 1,2-dichloroethan e with NH 3 i n th e presenc e d f Ca O a t approx . 100°C : C1CH 2 CH 2 C 1 + NH 3 + Ca O alternativ e ethylenimin e proces s (Dow ) via cyclizatio n o

f dichloroethan e wit

h NH , an d HCI-accepto r

Ca O

duct , i s • 1 7 0 <7 r
(18 )

ca n b e >roces i s ini
jacid : H , 0 (19 ) ) H a t ici di s isure :
(20 )

iitabl e •pres s n of '-85 % lope d ine . H 2 C—CH 2 + CaCl 2 + H 2 0 N I H (21 )

Alon g with th e read y polymerizabilit y o f ethylenimine , whic h can occu r

spontaneousl y i n th e presenc e o f smal l amount s of acidi c substances , it s hig h toxicit y mus t als o b e take n int o ac coun t i n it s manufacture , storage , an dprocessing . Ethylenimin e i s mainly , converte dint o polyethylenimine , apro cessin g ai di n th e pape r industry . I t

als o serve s a s a n inter
mediat e in syntheses , e.g. urea s ar e forme dwith isocyanates . 7.2.4 . Glyco l Ether s Anothe r importan t

applicatio n of

ethylen e oxid e i s it s reactio n wit h alcohol s formin g glyco l monoalky l ethers : (cat. ) RO H + H 2 C-CH 2 • ROCH 2 CH 2 O H

O + RO-fCH 2 CH 2 -0^, H (22 )
Th e mos t frequentl y employe dalcohol s ar e methanol , ethanol , an dn-butanol . Th e industria l proces s i s simila r t o th e hydratio n o f ethylen e oxide , th e differenc e bein g tha t alkalin e catalyst s (suc h a s alkal i hydroxid e o r th e correspondin g alkal i alcoho
late ) o r Al 2 0 3 ar e usuall y employed . Th e secondar y product s - di- , tri
- an dhighe r

ethylen e glyco l monoalky l ether s - ar e i n genera l als o forme ddespit e agreate r exces s of

alcohol . Ethylen e glyco l monoethy l ethe r i s manufacture dfo r

exampl e a t 170-190° C an dapprox . 10-1 5 bar . Th e monoalky l ether s o f ethylen e glyco l ar e commerciall y know n a s Cellosolve® , Carbitol ® an dDowanol® . Thes e sub
stance s fin dapplicatio n i n numerou s areas ; the y are , fo r exam ple , solvent s in th e pain t an dlacque r

sector , component s fo r adjustin g viscosity i n brak e fluids , emulsifier s fo r minera l an d vegetabl e oils , a s wel l a s fo r manufacturin g paste s fo r bal l poin t pen s an dprintin g inks . Th e availabl e productio n figure s fo r application s o f ethylenimine : 1 . polymerizatio n t o - ( CH.CH : NH-) „ - auxiliar y i n pape r processin g 2 . intermediat e produc t

fo r synthese s principl e o

f monoalky l ethe r

formatio n o

f glycols : ethoxylatio n o

f alcohol s = alcoholysi s o f ethylen e oxid e

characteristic s o

f industrial process : for desire dmonoethoxylation . larg e exces s o f alcohol , catalyze dhomogeneousl y o r heterogeneousl y wit

h Al 2 O j favore dalkyl s i

n monoethers : R= -CHj . -C 2 H5 , -/1-C4H 9
application s o

f th e monoethers : 1 . o f monoethylen e glycol : favore dpaint

solvent , startin g material fo r diether s an dethe r

ester s 2 . o f highe r ethylen e glycols : component s fo

r brak e flutds . solvent

an d compoundin g agent , startin g material fo r diether s142 7 . Oxidation Products of Ethylene glycol ethe r

productio n (in 1,0001) : 197 4 197 5 197 6 W.German y 9 1 7 3 8 3 Japa n n.a . 2 8 3 8 n.a . = no t

availabl e

two-ste p manufactur e o

f dialky l ether s o

f glycol s 1 . conversio n int o Naalcoholat e glyco l ether s i n W . Germany andJapan are summarize di n the adjacent table . Th e U S figure s have not been published . Othe r industrially important

iner t aproti c solvent s are obtaine d b y etherificatio n or

esterificatio n o

f th e remainin g O H group i n th e glyco l monoalky l ethers . Dimethy l glycol s suc h as dimethyl glycol (Glyme® ) an ddimethy l diglycol (Diglyme® ) are th e mos t important member s o

f thi s group . Ethylen e glyco

l dialkyl ethers , exemplifiedb y dimethy l ether , are generally manufacture dwaatwo-step process . Initially , the monomethy l ethe r

i s converte db

y mean s o

f NaO H into the alcoholate ; th e water

o f reactio n bein g remove db

y distillation : CHj-fOCHjCHj-^O H + NaO H (23 )

- CH 3 -40CH,CH 2 ^ON a+ H 2 0 2 . alkylatio n wit

h alky l chlorid e o r

sulfate , preferabl y methylatio n wit h CH 3 C 1 o r (CH 3 0),S0 2 I n th e secondstep , th e sodiumalcoholate i s etherifie dwit h a n alkyl chlorid e (usually methyl chloride ) or dimethy l sulfate : CH 3 -fOCH 2 CH 2 ^-ON a+ CH 3C 1 (24 )

- . CH 3 -fOCH 2 CH 2 ^-OCH 3 + NaC l

new dimethy l ethe r

manufactur e (Hoechst : Ger-O S 2434057 , 1974 ) two-step : 1 . reactio n o

f monoglyco l ethe r

wit h HCH O t o formal , catalyze dwit

h H© 2 . hydrogenolysi s o

f forma l wit h Ni/AI,0 , • SiO , A s thi s metho di s burdene db y th e stoichiometri c consumptio n o f chlorin e an

dalkali , ane

w improve droute t o ethylen e glyco l dimethy l ethe r

was developed . Th e monomethy l ether s ar e reacted , using proton s a s catalysts , wit h formaldehyde leading t o th e formatio n o

f formal s whic

h are the n hydrogenolyze d (using aspecia

l N i catalyst) t o equimola

r amount s o

f mono methy l anddimethy l ether s o f th e correspondin g mono- , di- , tri
- or higher ethylen e glycols :

|H e l CH 3 OC 2 H 4 O y 2 CH 3 OC 2 H 4 O H + HCH O -*CH 2 + H 2 0 CH 3 OC 2 H 4 o ' (25 )
CH 3 OC 2 H 4 O x . -

• * CH o + Ho CH 3 OC 2 H 4 0 (cat. ) CH 3 OC 2 H 4 O H + (26 ) CH 3 OC 2 H 4 OCH 3 The monomethy l ethe r

i s recycle dt o th e forma

l manufacturing stag e resultin g i

n th e followin

g ne t equation :7.2. Secondary Products of Ethylene Oxide 14 3 rize di n th e shed . r e obtaine d ) H grou p i n as dimethy l r e th e mos t •thy l ether , nitially , th e H int o th e stillation : (23 )

- H 2 0
: dwit h a n sulfate : CH 3 OC 2 H 4 O H + HCH O + H 2 (27) ICM- l • CH 3 OC 2 H 4 OCH 3 + H 2 0 Ethylen e glycol dialky l ethers , bein g relativel y inert , ar e emp loye da s aproti c solvent s fo r organometalli c reactions , e.g. Grig
nar dreaction s o r

i n boro n chemistry , a s wel l a s i n th e manufac
tur e o f polyurethan e paints . Mixture s of bolyethylen e glyco l dimethy l ethers , CH 3 (OCH 2 CH 2 ) n OCH 3 with approx . 4 t o 7 ethylen e oxid e units , fin dapplicatio n a s absorptio n agent s in Allied' s "Selexo l process" . I n th e latte r cas e natura l ga s an d synthesi s ga s ar e free db y pressurize dwashin g fro macidi c com ponent s suc h a s H 2 S , C0 2 o r S0 2 . Th e acidi c gase s ar e the n successivel y release db y reducin g th e pressur e i n astepwis e manner . I n orde r t o esterif

y th e fre e O H groups , th e ethylen e glyco l monoalky l ether s ar e reacte dwith carboxyli c acids , especiall y aceti c acid , usin g proton s a s catalysts : application s of glyco l dialky l ethers : 1 . aproti c solvent s 2 . tetra - t o heptaglyco l dimethy l ethe r mix
ture s a s Selexol ® for

purificatio n o

f natur a l an dsynthesi s ga s accordin g t o principl e o f pressur e dependen t

reversibl e absorp
tio n o f acidi c gase s

(24 ) + NaC l CjH 3 OC 2 H«O H + CH 3 COO H (28 ) i*C 2 H 5 OC 2 H 4 OCCH 3 + H 2 0



## 6 sumptio n :n e glyco l ther s ar e e leadin g :enolyze d o f mono mo- , di- .

, + H 2 0 (25 ) Ethy l glyco l acetat e i s a n excellen t solven t fo r nitrocellulos e an d cellulos e ethe r

use di n pain t

manufactur e an dfinishing . I n 1972 , 5,00 0 t

ethy l glycol acetat e wer e consume di n W . Germany . 7.2.5.1,2-GIyco l Carbonat e 1,2-Glyco I carbonate , als o know n a s ethylen e carbonate , wa s originall y onl y obtainabl e fro mglyco l an dphosgen e via doubl e eliminatio n of

HCl . I n 1943 , I G Farbe n discovere dane w rout e usin g ethylen e oxid e an dC0 2 : glyco l ethe r ester , e.g. CH 3 OC : H 4 OA c an dC 2 H 3 OC ; H 4 OA c ar e favore dsolvent s for

cellulos e derivative s

manufactur e of

glyco l carbonate : traditionall y via glyco l reactio n wit h phos
gene , today via catalyti c additio n o f CO , t o E O
(26 ) H 2 C—CH 2 + C0 2 [c« . I . 

# r~ \ o. \/ O (A/ / 2 3 kcal

"9 6 k J /mol (29 )

actunn g Hiil s develope dthi s proces s t o industria l maturit y an dstarte d u p asmalle r

productio n uni t

i n W . Germany . Ther e ar e tw o plant s operatin g i n Rumani ausin g th e sam e process , thei r tota l Hiil s proces s operate di n plant s i n W . Ger
man y an dRumani aP.3 1 

# S T - ^ F - 00?39/-_bie I959 C.^ 

# 198 9 DIRECTOR

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

a i _ £=2 Informatio n i n thi s Oiractor y i s fo r th a sol a an d privat a us

a o f sponsor

s o f th a Oiractor y o f Chamica ! Produca n Program .

I'.ll W ••4 .....'• •I ' * •P.3 2



# £lil > 33 3 RAVENSWOO D AVENU E MENL O PARK , CALIFORNI A 9402 5 (415)859-362 7 FAX : (415)326-551 2 

### TWX : 910-373-204 6 TELEX : 33448 6

Copyrigh t O 198 9 SR I rmemationaJ . prohibited . Printe

d i n US A Unauthorized us e or reproductio n o

f al l o r an y par t o f thi s documen t i s

## B 136 9 DIRECTORY O F CHEMICA L PRODUCER S UNITE D STATE S PRODUCTS 2-(2-Birtoxyethoxy ) ethano l (Butoxydiettiylene'glycol ) ' (Butoxydiglycol ) (Diethylen e glyco l monobuty l ether ) (Diglyco l monobuty l ether

) Do w Chemica l U.S A Eastma n Koda k

Compan y Eastma n Chemica l Products , In c Texa s Eastma n Compan y Occidenta l Petroleu m Corporatio n Cai n Chemica l Inc. , subsidiary Petrochemica l Divisio n Shel l Oi l Compan y Shel l Chemica l Company , divisio n Unio n Carbid e Corporatio n Chemical s an d Plastic s Busines s Grou p Solvent s an d Coating s Material s Oivisio n Midland , Michiga n Longview , Texa s Bayport , Texa s Geismar , Louisian a
Seadrift , Texa s 2-{2-Butoxyethoxy ] ethano l acetat e (See : 2-(2 - Butoxyethoxy

) ethy l acetate ) 2-[2-[2-Butoxyethoxy ] ethoxy ] ethano l (See : Butoxylnglycol ) a-[2-[2-Butoxyethoxy ] ethoxy]-4,5-methylenedioxy-2 - propyltoluen e (See : Piperony l butoxide , technica l unde r Pesticides) 2-<2-Butoxyethoxy ) ethy l acetat e (2-{2-Butoxyethoxy ] ethano l acetate ) (Diethylen e glyco l monobuty l ethe racetate ) (Diglyco l monobuty l ethe racetate ) Eastma n Koda k

Compan y Eastma n Chemica l Products , Inc . Tennesse e Eastma n Compan yKingsport , Tennesse e 1-Butoxyethoxy-2-propano l Unio n Carbid e Corporatio n Chemical s an d Plastic s Busines s Grou p Specialt yChemical s Oivisio n Institute , Wes t Virgini a 2-6utoxyethy l acetat e (Aceti c acid , 2-butoxyethy l ester ) (2 - Butoxyethano l acetate ) (Ethylen e glyco l monobuty l ethe racetate ) (Glyco l monobuty l ethe racetate ) Eastma n Koda k

Compan y Eastma n Chemica l Products , Inc . Tennesse e Eastma n Compan yKingsport , Tennesse e 2-Butoxyethy l octadecanoat e (See : 2-Butoxyethy l stearate unde rPlasticizers) 2-Butoxyethy l oleat e (See : Plasticizers) 2-Butoxyethy l oleate , sulfated , sodiu m sal t (See : Anioni c unde rSurface-Active Agents) 2-Butoxyethy l stearat e (See : Plasticizers) N-[Butoxymethy]-2-chloro-2',6'-diethylacetanilid e (See : Butachlo runde rPesticides) p-Butoxypheno l Fran k Enterprises , Inc . Columbus , Ohi o n-Butoxypropano l Unio n Carbid e Corporatio n Chemical s an d Plastic s Busines s Grou p Specialt yChemical s Oivisio n Sout h Charleston , Wes t Virgini a Butoxytriethylen e glyco l (See : Butoxytriglycol ) Butoxytriglyco l (2-[2-{2-Butoxyethoxy ] ethoxy] ethanol ) (Butoxytriethylen e glycol ) (Triethylen e glyco l n-buty l ether ) (Triglyco l monobuty l ether ) Do w Chemica l U.S A Midland , Michiga n 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 Seadrift , Texa s n-Buty l acetat e (Aceti c acid , buty l ester ) (Buty l ethanoate ) BAS F Corporatio n Chemical s Oivisio n Basi c Organi c Chemical s Grou p Freeport , Texa s Eastma n Koda k

Compan y Eastma n Chemica l Products , Inc . Tennesse e Eastma n Compan yKingsport , Tennesse e Hoechs t Celanes e Corp . Engineerin g Plastic s Grou p 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 Bishop , Texa s

Seadrift , Texa s Texa s City , Texa s
TOTA L Note : Al l capacitie s ar e extremel yflexibl e an d ca n accommodat e othe ralcoho l ester s as well . Source : SR I Internationa l estimate s a s o f January1 , 1989 . Annua l Capacit y (Million s o f Pounds ) 2 5 4 5 5 0

8 0 Remarks

Tota l esterificatio n capacit yi s a n estimate d 120-15 0 millio n pounds/yaar . Tota l esterificatio n capacit yi s a n estimate d 12 0 millio n pounds/year .
Seadrif t plan t produce s primaril y glyco l ethe resters , bu t ca n produc e alky l acetates . Tota l capacit yfo ralky l acetate s (n-propyl , isopropyl , isobutyl , n butyl , an d amyl ) a t th e tw o Texa s location s i s 13 0 millio n pounds/year . 20 0

49 6 SR I Internationa l __^_a__^__ t

__t_)__S__i