p.1 

RCRA Box 1883 

Prepped by Ollie Stewart 

Document Number: 

12) ll-B-173 

Docket Number: 

A-90-19 

Printed 12/3/2008 10:42:10 AM Sheet 12 of 171 
P.2 

A-90-19 

"-B-173 

MEMORANDU M 

TO: Process Vents A-90-19 

FROM: Wanda Floyd 

DATE: December 1991 

1 finnyf 

$& V/992 

EPA AIR DOCKET 

SUBJECT: HON NESHAP: Industry Characteristics/ Ethylene Glycol Monobutyl 

Ether Acetate 

Attached is a product-process summary (PPS) for the production of Ethylene Glycol 

Monobutyl Ether Acetate via esterification of ethylene glycol monobutyl ether with . 

acetic acid. This PPS was developed as part of the Industrial Profile Project in support 

of the Hazardous Orgamc NESHAP (HON) regulatory effort. Information in this PPS is 

used as a basis for emissions and cost impact estimates for the HON program. 

Listed below are the key references used in developing the attached PPS. 

1989 Directory of Chemical Producers USA. SRI International, California, 1989. p. 496. 

Kent, James A. Riegel's Handbook of Industrial Chemistry. 7th edition. Van Nostrand 

Reinhold Company, New York, 1974. pp. 782-783. 

Weissermel, Klaus and Arpe, Hans-Jurgen. Industrial Organic Chemistry. Verlag Chemie, 

New York, 1978. pp. 140-143. 

The torepfiig EaaRj Parana 

x Document is Docket item 

A-90-19 

ll-B-252 
P.3 

Preparer: /&&. JJOM/JL, 

Oate: 

Reviewer: 

7/l\f}rt 

ADMINISTRATIVE NOTES 

Product-Proem Code iiZoi^A, 

Hours spent on this PPS 0-15 

P-P Name Q-JUAAVP^U^. QJLdi?sKj?. WlAt oAutc^l twswl*uh\l cHw AJCAhak. L/T>- e^eft'&'csdz'y^ 

Incomplete Items (parts of 

form you cannot complete) 

(line # and description) Date Cleared 

) 

Initials 

l.I-t.l (Pr»do^..j c^^. ^ price*-

+•5 - Cpftoce^ 4t**.ripfrn *JSsu*+jd ) 

S.O - [Vrsze^t £(rur Jtsu* . ) 

•b •fW^Y * isopr^ l A^wk , ^Kd M -W^cf* S****, *f"<f> UsOCU ^ cc* ^ ^ » 

Chemicals missing CA$ nqmfrers -rYv»v '^pnft ^ txehj^ dts<^[p^rK . 

( 

*UfK^ ) 

Plant with Citv but no County (plant name, city, state) 

£W»VA^ - ItoclaM.) KC^jispffirt' Te^^fS&t, 
P.4 

Preparer: faJlahJU. 

Date: 7/M/M 

Reviewer: 

PRODUCT-PROCESS SUMMARY (PPS ) 

Chemical mm eduJ/^ Vy ^ ^^n^tLth^. eJUr teMk. 

Alternative CHtjrieil^pMN) £- LJ-^^4uJ acgrW-e 

CASf II* Oil 

CHEMICAL SPECIFIC INFORMATION 

1.0 U.S. Production Ref # Pg # ., Ref Year 

(indicate the same reference information for any answers below from a 

different reference) 

l.I IBftlf^CP^wfiicMoft (Circle OfteV[mjTiions~oTkgj^ millions of gallons 

KO J*4A. 

-CCA^) 

tr\fj d.4i4XP-' 

gjft* ? S/Kq or SYqallon. 

1.8 Comments 
P.5 

> 

2.0 Cheaical End-Use Ref I ., P9 # ., Ref Year 

jlse. Percent 

K<? dajh^ h* dccfa* 

J 
3.0 U.S. Producers Ref # °l . Pg # ., Ref Year J±H 

1 Billions Of Kg or millions of gallons ^ <**&-

3.2 Naae, Location, and Capacity 

Process Used 

(use P-P f) 

EA&J-***+^ KrtfaJc. Kt^aSf><?rt~/

 77+vtussez, 

Total Capacity /r^y 'JarZK, 

• \ 
P.7 

PRODUCE-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) Ref # 10 Pg I tfl 

Commercially % Nat'l 

.. 0 Njmfi Viable (Y/n) Capacity 

P-P 1 w^iiuk y eM«rcLC£jr*U \n*. voUrl-CiCAhs*. oC Y__ Hro (**s<^d. 

DO; 

P-P 2 

P-P 3 

P-P 4 

P-P 5 

P-P 6 

4.1 Documentation of P-Ps Excluded 

P-P not 

Commercially Viable Reasons 

*.2T Process descrlM A , , !wW. 

trtw 

hoHyL 
P.8 

Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenat1 on Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenatlon Reaction 

sterification Reaction 

Hydrogenation Reaction 

Hydrohalogenatlon Reaction 

Hydroformylatlon Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenatlon Reaction 

Sulfonation Reaction 

Catalytic Reformation 

Hydrodimerizatlon Reaction 

Ref I 10 Pqf KS 

Generic Reaction 

4.4 Explain how you selected the reaction type in line 4.3. 
P.9 

, , mxm 0..cnpt1.n fef*_i£4£- , V -!^^ ) 

In the left aargin, Indicate references and page numbers throughout written 

description. 

f Tins t>ri&f descripfiiov i* * H Ouauidb * . .) 

r\f&vr*ud cfe$«w i'pfi?>*.— 

^^c^n^^+Un^ ** £^/>d&. All 
P.10 

^tj^rr frrd^*- <s I^K W *4 A- vnxfif^ t*AvL -f-cM •{& 

5.0 Process Flow Diagram (attach at end of package) H*ft*-

5.1 Flow Diagram Reference: Ref # , Pg # 

5.2 Comments on Flow Diagram 

5.3 ' Proce« Cwotielfci 

Component Types 

Distillation Columns 

Absorbers C^o re-^u^i A * forttxjJ) 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

Ref # IQ';3 . Pg # <4^lnfkJ 

iffpf'Tlir wrWnone 

J2_ 

J-

•b-Huur *«w eskrrf'. 

( 
P.11 

t^iJ^ti* 

6.0 Cheaical Data 

6.1 Balanced Chemical Reactions Ref # JQ , pg # J43_ 

c

* ti* £ CA± .1 UfL 

6.2 Chemical Tree Ref JS^J. 

feu*/* / , 7^ A , , 

1

 (tffwrtfiwaWJ J eM**jlu^fyc#\ 

o^ceMo O*CAC\ 
P.12 

6.4 Stoichlometry Ref # ' Pg # 

Show calculations and assumptions and then sumaarize in table on next 

page. 

tcma 0 

160.^4 y^u. 

"j±r^L '• /* * ~*J 4 . * ,^ £6 _ ^ 

^6 , 

n-<y 

O.il "7 
P.13 

6.4 Stolchloaetry Conversion Factors 

d ) Cbnye^ton Factor for ^-Product #3 

e) mmttt&^mmfzmt c&mmttsn 

f) Conversion Factor Comments 
P.14 

product) 

6.4.1 Product 

6.4.2 Raw Mater 1 aHsl 

#1 *M"JI&1A&~ Otl<AC+K. (jtysJTKi) 

#2 a-g^prVb tuud 

#3 

#4 

#5 

§,4,3 Co-Products 

#i 

#2 _ _ 

#3 

#4 _ 

#5 

6.4.4 Bv-Products 

#i Ux.o 

#2 

#3 ' 

#4 

#5 . 

6.4.5 Intermediates 

#1 

#2 

I&01A. 

III16Z 

64/^7 

0,14 

6.31 

o.il 
P.15 

7.0 Process Vent Emission Sources 

r:t m K "m%mw&r**um * •*< <>V.V*JW wA- , ««•"-> A— (Y/N) 

(Y/N) 

Ref I ., Pg # 

7.3 Comments Ref I ., Pg # 

7.4 Reactor vent emissions? 

7.5 Comments 

y. 

(Y/N) Ref # 10} S . Pg | !£*$** W5

) 

Ref # ., Pg # 
P.16 

(Y/N) 

/Jfrfde^^ • 

Ref #Ss . Pg # f^nts) 

7.9 Comments Ref # 

., Pg # 
P.17 

8.0 Transfer Emission Sources 

8\* iff 

Refi tQ 

/ (VN) 

., Pg # ii i 

Name I'.wKW.'X'KvSwJ'WvK 

8.2.1 Product 

8.2.2 Co-Products 

bu+c 

efW-gtcakkIIXOlX 

8.3 Comments Ref I ., Pg # 
P.18 

9.0 Storage Emission Sources Ref # fO Pg # ^ 3 

r.r Are alllr^Ts stored? V (Y/N) 

9.2 Hhat materials are stored? 

Storage Service 

Nans |||i | Type 

'>*•!»*«* kuU 1*012. 

e&AtHL eiuctfl ^wTuri'^tuiir dbar cuthxk, H0416 -fWskd ^cAu^T 

9.2.2 Co-Products 

9.2.4 Intermediates 

9.4 Comments 
P.19 

10.0. Wastewater Ealsslon Sources 

10.2 Describe wastewater 

i (Y/N) 

Ref I /^ 5 Pg #• H3j(Hyt**A 

Stream Equipment Component 

Number Producing Wastewater 

#1 

#2 

#3 

Comments on flow 

ffeai'Mr F*>t*** d^sc.'pf*, Kdks,, rt*^* U of Hz0 a * 

distilltdriifa. Cc[. fcLSSuArtJ) 

X*4 ali*-.4to of Uf^ y r*A*j U- \*MM*-4%\ f» 

10.3 Stream Composition 

(provide only if readily available) 

Stream #1 

Ref # 

Steam #2 

.. Pg # 

Organics Organics 

HAPs HAPs 

TTT 

Water (O^*]) 

Other 

(^Uk) Water 

Other 
Stream #3 

Organics 

HAPs 

Water 

Other 

P.20 

10.4 Comments Ref # , pg # 
KE-15+ 

Riegel's 

Ha ill l kof 

Industrial Chemistry 

SEVENTH EDITION 

Edited by 

James A. Kent 

College of Engineering 

Michigan Technological University 

Houghton, Michigan 

VAN NOSTRAND REINHOLD COMPANY 

NIW VOU* CINCINNATI ATLANTA DALLAS SAN FRANCISCO 

LONDON TONONTO MBLSOUftNS 

RADIAN LIBRARr" 

DURHAM, N.C. 
Van Nostrand Reinhold Company Regional Offices: 

New York Cincinnati Chicago Millbrae Dallas 

Van Nostrand Reinhold Company International Offices: 

London Toronto Melbourne 

Copyright C 1974 by Litton Educational Publishing, Inc. 

Library of Congress Catalog Card Number: 73-14798 

ISBN: 0442-24347-2 

All rights reserved. Certain portions of this work copyright © 1962 

by Litton Educational Publishing, Inc. No part of this work 

covered by the copyrights hereon may be reproduced or used in any 

form or by any means-graphic, electronic, or mechanical, including 

photocopying, recording, taping, or infonnation storage and retrieval 

systems-without written permission of the publisher. 

Manufactured in the United States of America 

Published by Van Nostrand Reinhold Company 

135 West 50th Street, New York, N.Y. 10020 

Published simultaneously in Canada by Van Nostrand Reinhold Ltd. 

15 14 13 12 11 10 9 8 7 6 5 

Library of Congress Cataloging in Publication Data 

Riegel, Emil Raymond, 1882-1963 

Riegel's handbook of industrial chemistry. 

First-5th ed. published under title: Industrial 

chemistry; 6th ed. in 1962 under title: Riegel's 

industrial chemistry. 

Includes bibliographical references. 

1. Chemistry, Technical. I. Kent, James A., 1922-

ed. II. Title. III. Title: Handbook of industrial 

chemistry. 

TP145.R54 1974 660 73-14798 

ISBN 0442-24347-2 
1'R

T

 l

r •-TT

v

?T"rrST'J""" T 

782 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY 

i 

four classes account for more than 80 per cent 

of the production. These are (1) the alkyl-

phenol-ethylene oxide derivatives, (2) fatty 

acid-alkanolamine condensates, (3) tall oil-

ethylene oxide adducts, and (4) the fatty acid-

ethylene oxide adducts. The alkanolamine 

condensates are foam stabilizers in various 

detergent formulations. Tall oil adducts find 

use in household detergents, chiefly automatic 

washer products, because of their low-sudsing 

properties. The fatty alcohol adducts are used 

mainly as light-duty detergents, though some 

tridecyl adducts are utilized as foam stabilizers. 

The trend has been away from the benzenoid 

ethers because of their biodegradability limi-

tations. 

Ethanolamines. Ethanolamines are manu-

factured by reacting ethylene oxide and am-

monia. The relative amounts of the three 

amines will depend primarily on the ammonia 

to oxide feed ratio. 

NH

3 ^

£ (HOC

2

H

4)NH2 ^ £ 

(HOC

2

H

4

)

2

NH £^£ (HOC

2

H

4

)

3N 

The products from the reaction are separated 

by distillation. During the last few years, each 

of the amines has in turn been in the greatest 

demand, so processing flexibility must be 

maintained. 

Monoethanolamine is used primarily in de-

tergents and as an absorbent for acid-gas 

(H

2

S, C0

2

) removal. It is to a lesser extent, 

a chemical intermediate for compounds such 

as ethylene imine. Diethanolamine's major end 

use is in detergetns, but it is also utilized in 

textiles and as a gas-purification agent. Most 

of the triethanolamine goes into the produc-

tion of cosmetics and textile specialities. 

Isopropanolamines, derived from propylene 

oxide and ammonia, are competitive with the 

ethanolamines, and both are unique in that 

they are organic compounds and yet strongly 

alkaline. 

Glycol Ethers. In the same way that water 

reacts with one or more molecules of ethylene 

oxide, alcohols react to give monoethers of 

ethylene glycol, producing monoethers of di-

ethylene glycol, triethylene glycol, etc., as by-

products. 

0 

/ \ 

ROH + CH

2 -CH2 — ROC2

H

4

OH 

0 

/ \ 

+ CH

2—CH2 — ROC2

H

4OC2

H

4OH. 

0 

/ \ 

+ CH

2 -CH2

—• 

ROC

2 rUOCjrUOCjH,

, OH 

Since their commercial introduction in 1926, 

glycol ethers have become valuable as indus-

trial solvents and chemical intermediates. Because glycol monoethers contain a 

—OCH

2CH2

OH group, they resemble a combi-

nation of ether and ethyl alcohol in solvent 

properties. The most common alcohols used 

are methanol, ethanol, and butanol. Principal 

uses for the glycol ethers are as solvents for 

paints and lacquers, as intermediates in the 

production of plasticizers, and as ingredients 

in brake fluid formulations. The most com-

mon trade names are Dowanol®, Cellosolve®, 

and Polysolve®. Condensation of the mono-

ethers produces glycol diethers which are also 

useful as solvents. 

2ROCH

2CH2

OH ^22s, 

ROC

2

H

4OC2

H

4

OR + H

20 

Alcohol-ethylene oxide products have also 

been developed in which the number of oxide 

units is considerably "higher in order to improve water solubility. Long-chain fatty alcohols are condensed with 10-40 molecules of 

ethylene oxide to produce detergents for the 

textile industry. Also important are the water-

soluble alkyl phenyl ethers of the higher poly-

ethylene glycols. Phenols react in the same 

way as alcohols to give polyglycol ethers. The 

reaction is rapid, and essentially quantitative. 

These products are detergents of the same general class as the long-chain alcohol-ethylene 

oxide condensates. 

Of recent origin is the interest in the ex-

tremely high molecular weight homopolymers 

of ethylene oxide. These resins, trade-marked 
Tl 

H 6, 

is-

•ea 

Di- nt ed 

>al or he 

>ts m-

® 

10-

Iso 20 

Iso 

ide mco- of he 

er-

ly-

ne he 

.ve. 

,en-

ene 

ex-

lers 

ked 

Polyox®, have good water and organic solvent 

solubility and thus are used for thickening 

agents and water-soluble films. 

Chlorinated Hydrocarbons 

The manufacture of chlorinated hydrocarbons 

forms an important part of industrial chemis-

try today. The products are useful as solvents, 

chemical intermediates, pesticides, monomers, 

and in many other ways. Table 25.3 shows 

some of the large-volume materials. 

Chlorinated derivatives of aliphatic hydro-

carbons are usually prepared by one of three 

general methods: (1) addition of hydrogen 

chloride to unsaturated hydrocarbons, (2) ad-

dition of chlorine to unsaturated hydrocar-

bons, or (3) substitution of chlorine for hydro-

gen in either saturated or unsaturated hydro-

carbons. In the last case, hydrogen chloride is a 

by-product. Examples of the first method are 

the addition of HCl to ethylene to form ethyl 

chloride and the addition of HCl to acetylene 

to form vinyl chloride. Typical of the second 

method is the addition of chlorine to ethylene 

to form dichloroethane. The third method, the 

direct substitution of chlorine for hydrogen, 

usually involves a free-radical mechanism. The 

formation of chlorine free radicals occurs 

SYNTHETIC ORGANIC CHEMICALS 783 

spontaneously at temperatures above 250°C 

and increases with temperature. The formation 

may also be brought about by the action of 

actinic light at lower temperatures. These light-

activated, or photochemical, chlorinations may 

be carried out in either gas or liquid phase. 

The principal uses for chlorinated hydrocar-

bons are as solvents, chemical intermediates, 

and insecticides. Their value as solvents derives 

from a combination of good solvent power, 

low flammability, and high vapor density. The 

latter property is particularly important in 

vapor degreasing of metal parts (a major use 

for trichloroethylene, perchloroethylene, and 

methyl chloroform). Certain of the com-

pounds are of value as chemical intermediates. 

Thus, ethyl chloride is used to make tetraethyl 

lead; and ethylene dichloride is used to make 

vinyl chloride, which in turn is polymerized to 

polyvinyl chloride. 

Ethylene Dichloride (EDC). While some 

ethylene dichloride (1,2-dichloroethane) oc-

curs as a by-product of chlorohydrin and ethyl 

chloride processes, the bulk comes from the 

chlorination of ethylene. Almost 90 per cent 

of the EDC produced in 1969 went into the 

manufacture of vinyl chloride monomer. Fig-

TABLE 25.3 Production and Sales of Some Halogenated 

Aliphatic Hydrocarbons3 

Ethylene dichloride 

Vinyl chloride 

Carbon tetrachloride 

Ethyl chloride 

Perchloroethylene 

Trichloroethylene 

Methyl chloride 

Dichlorodifluoromethane 

Methylene chloride 

Methyl chloroform 

Ethylene dibromide 

Trichlorofluoromethane 

Chloroform 

Chlorinated paraffins 

All others 

TOTAL halogenated 

hydrocarbons 

Production 

(1000 lbs) 

6,037,428 

3,735,942 

882,735 

678,808 

635,251 

596,821 

402,809 

367,658 

366,005 

324,311 

309,943 

238,518 

216,168 

61,935 

1,331,981 

16,186,313 

Sales 

(1000 lbs) 

1,226,845 

2,358,741 

785,884 

267,503 

611,625 

561,536 

166,146 

335,409 

338,107 

298,873 

— 

203,652 

172,177 

59,124 

436,091 

7,899,651 

Sates Value 

($1000) 

36,345 

103,100 

42,698 

16,599 

42,529 

39,626 

8,729 

85,203 

25,891 

33,288 

— 

37,476 

10,807 

7,584 

144,202 

677,396 

U.S. Tariff Commission Report, 1969. 
Klaus Weissermel 

Hans-Jiirgen Arpe 

Industrial 

Organic Chemistry 

Important 

Raw Materials and 

Intermediates 

Translated by 

Alexander Mullen 

Verlag Chemie • Weinheim • New York 

1978 
P.26 

Prof. Dr. Klaus Weissermel 

Dr. Hans-Jurgen Arpe 

Hoechst AG 

Postfach S003 20 

D-6230 Frankfurt SO 

West Germanv 

Copy Editing: Dr. Hans F. Ebel 

This book contains -13 Tables 

CIP-Kurzcitefaafnahme der Deu:>c.TL'n SiWtothek 

Weissermel, Klaus 

Industrial organic chemistry: important raw 

materials and intermediates / Klaus Weissermel: 

Hans-Jiirgen Arpe. - 1. Aufl. - Weinheim. New York: VerlagChemie. 1978. 

Dt. Ause. u.d.T.: Weissermel. Klaus: Industrielleorganische Chemie. 

ISBN 3-527-25706-3 (Weinheim) 

ISBN 0-S9573-0U5-7 (New Yorkl 

NE: Arpe. Hans-Jiirgen: 

S \'erlag Chemie GmbH. D-6940 Weinheim, 1978 

All rights reserved yincluding those of translation into foreign languages). No part of this book may be reproduced in 

.mv form - fry photoprint, rajcrofiim. or any other means - nor transmitted or translated into a machine language 

without written permission from :he publisiiers. 

Registered names, trademarks, etc. used in Thistioofc. eierc without specific indication thereof, are not to be considered 

unprotected by law. 

Printer: Passavia Druckerei GmbH Passau 

Printed in West Germany 

Preface 

Industrial organic cl 

as well as.-to an ,;K: 

present status of kn 

There 'Aus thus a sjn 

and intermediates i 

and to present it in ; 

development, which 

from their industrial 

ing discussions with 

This book addresse 

from it the chemisti 

manufacturing proc 

giear, information a 

.inti

 retii.vrocks .ilor 

disciplines in :h-.- -. 

economists - will tecononiio interreiu; 

This book is arrang 

their tightest possit 

unavoidable. The n 

As a rule, ihe manu 

mem and significa 

•appiica\ions of the ; 

products are fret;'-

existing technologiL 

more, economic or 

The authors ende;r 

information are at 

1. The main text. 

2. The synopsis of i 

3. Flow diagrams il 

These three typeso 

or making brief no 

notes which briefly 

to be rapidly infon 
140 7. Oxidation Products of Ethylene 

4. as starting material in organic syntheses 

(heterocycles) 

ethanolamine production (in 1,0001): 

1974 1975 1976 

USA 139 117 130 

W. Germany 66 50 61 

Japan n.a 32 n.a. 

n.a. = not available 

and creams in cosmetic manufacture because of their mild 

alkaline reaction. They are also used in the manufacture of 

heterocycles in organic synthesis. The available production figures for the most important industrial countries are summarized in the adjacent table. 

Accordi 

reacting 

approx. 

ClCH2i 

secondary products of ethanolamines: 

1. morpholine via acid catalyzed dehydration of HN(C2H„OH)2 

2. ethylenimine = aziridine via indirect twostep cheinical dehydration with semi-ester of sulfuric acid as intermediate 

Morpholine, which is a solvent and intermediary product, is 

obtained from diethanolamine by dehydration with 70% 

H2S04 with simultaneous ring closure: 

HN 

/ \) H [H,S0.1 

.OH -H,0 

HN O 

\ / 

(18) 

Ethylenimine, another intermediate of commercial use, can be 

manufactured from monoethanolamine. The industrial processes operated today are usually two-step. Ethanolamine is initially esterified with 95 % H2S04, to P-aminoethyl sulfuric acid: 

Along • 

can oei 

acidic s 

count ii 

Ethylei 

ccssing 

medial 

Anotlv 

with al 

H2NCH2CH2OH + H2SGy - H2NCH2CH2OS03H + H20 

(19) ROH 

On heating with stoichiometrical amounts of NaOH at 

220-250°C and 50-80 bar in the second step, the acid is 

cleaved from the semi-ester forming the imine via ring closure: 

H2NCH2CH2OSO3H + 2 NAOH — • H 2C—CH 2 

T" 

H 

t NajS04 + 2 HaO 

(20) 

If the imine formation is conducted in a flow tube, suitable 

residence times of 4-10 s can be arranged in order to supress 

secondary reactions such as the polymerization of 

ethylenimine. The imine selectivity then increases to 80-85% 

(based on ethanolamine). Analogous processes were developed 

by BASF and Hoechst for the manufacture of ethylenimine. 
7.2. Secondary Products of Ethylene Oxide 141 

ir mild 

ture of 

'tion fie sumAccording to a Dow process, ethylenimine is synthesized by 

reacting 1,2-dichloroethane with NH3 in the presence df CaO at 

approx. 100°C: 

C1CH2CH2C1 + NH3 + CaO 

alternative ethylenimine process (Dow) via 

cyclization of dichloroethane with NH, and 

HCI-acceptor CaO 

duct, is 

•1 70 <7r 

(18) 

can be 

>rocesis inijacid: 

H , 0 

(19) 

)H at 

icid is 

isure: 

(20) 

iitable 

•press 

n of 

'-85 % 

loped 

ine. 

H 2C—CH 2 + CaCl 2 + H2 0 

N 

I H 

(21) 

Along with the ready polymerizability of ethylenimine, which 

can occur spontaneously in the presence of small amounts of 

acidic substances, its high toxicity must also be taken into account in its manufacture, storage, and processing. 

Ethylenimine is mainly, converted into polyethylenimine, a processing aid in the paper industry. It also serves as an intermediate in syntheses, e.g. ureas are formed with isocyanates. 

7.2.4. Glycol Ethers 

Another important application of ethylene oxide is its reaction 

with alcohols forming glycol monoalkyl ethers: 

(cat.) 

ROH + H2C-CH2 • ROCH2CH2OH 

O 

+ RO-fCH2CH2 -0^,H 

(22) 

The most frequently employed alcohols are methanol, ethanol, 

and n-butanol. The industrial process is similar to the hydration 

of ethylene oxide, the difference being that alkaline catalysts 

(such as alkali hydroxide or the corresponding alkali alcoholate) or Al 2 03 are usually employed. The secondary products -

di-, tri- and higher ethylene glycol monoalkyl ethers - are in 

general also formed despite a greater excess of alcohol. 

Ethylene glycol monoethyl ether is manufactured for example 

at 170-190°C and approx. 10-15 bar. 

The monoalkyl ethers of ethylene glycol are commercially 

known as Cellosolve®, Carbitol® and Dowanol®. These substances find application in numerous areas; they are, for example, solvents in the paint and lacquer sector, components for 

adjusting viscosity in brake fluids, emulsifiers for mineral and 

vegetable oils, as well as for manufacturing pastes for ball point 

pens and printing inks. The available production figures for 

applications of ethylenimine: 

1. polymerization to -( CH.CH:NH-)„ -

auxiliary in paper processing 

2. intermediate product for syntheses 

principle of monoalkyl ether formation of 

glycols: 

ethoxylation of alcohols = alcoholysis of 

ethylene oxide 

characteristics of industrial process: 

for desired monoethoxylation. large excess 

of alcohol, catalyzed homogeneously or 

heterogeneously with Al2Oj 

favored alkyls in monoethers: 

R

 = -CHj. -C2H5, -/1-C4H9 

applications of the monoethers: 

1. of monoethylene glycol: 

favored paint solvent, starting material 

for diethers and ether esters 

2. of higher ethylene glycols: 

components for brake flutds. solvent and 

compounding agent, starting material for 

diethers 
142 7. Oxidation Products of Ethylene 

glycol ether production (in 1,0001): 

1974 1975 1976 

W.Germany 91 73 83 

Japan n.a. 28 38 

n.a. = not available 

two-step manufacture of dialkyl ethers of 

glycols 

1. conversion into Na alcoholate 

glycol ethers in W. Germany and Japan are summarized in the 

adjacent table. The US figures have not been published. 

Other industrially important inert aprotic solvents are obtained 

by etherification or esterification of the remaining OH group in 

the glycol monoalkyl ethers. Dimethyl glycols such as dimethyl 

glycol (Glyme®) and dimethyl diglycol (Diglyme®) are the most 

important members of this group. 

Ethylene glycol dialkyl ethers, exemplified by dimethyl ether, 

are generally manufactured waa two-step process. Initially, the 

monomethyl ether is converted by means of NaOH into the 

alcoholate; the water of reaction being removed by distillation: 

CHj-fOCHjCHj-^OH + NaOH (23) 

- CH3-40CH,CH2^ONa + H20 

2. alkylation with alkyl chloride or sulfate, 

preferably methylation with CH3C1 or 

(CH30),S02 

In the second step, the sodium alcoholate is etherified with an 

alkyl chloride (usually methyl chloride) or dimethyl sulfate: 

CH3-fOCH2CH2^-ONa + CH3C1 (24) 

-. CH3-fOCH2CH2^-OCH3 + NaCl 

new dimethyl ether manufacture 

(Hoechst: Ger-OS 2434057, 1974) 

two-step: 

1. reaction of monoglycol ether with HCHO 

to formal, catalyzed with H© 

2. hydrogenolysis of formal with 

Ni/AI,0, • SiO, 

As this method is burdened by the stoichiometric consumption 

of chlorine and alkali, a new improved route to ethylene glycol 

dimethyl ether was developed. The monomethyl ethers are 

reacted, using protons as catalysts, with formaldehyde leading 

to the formation of formals which are then hydrogenolyzed 

(using a special Ni catalyst) to equimolar amounts of monomethyl and dimethyl ethers of the corresponding mono-, di-, 

tri- or higher ethylene glycols: 

|Hel CH3OC2H4Oy 

2 CH3OC2H4OH + HCHO -* CH2 + H2 0 

CH3OC2H4 o' (25) 

CH3OC2H4Ox .-

•* CHo + Ho 

CH3OC2H4 0 

(cat.) CH3OC2H4OH 

+ (26) 

CH3OC2H4OCH3 

The monomethyl ether is recycled to the formal manufacturing 

stage resulting in the following net equation: 
7.2. Secondary Products of Ethylene Oxide 143 

rized in the 

shed. 

re obtained 

)H group in 

as dimethyl 

re the most 

•thyl ether, 

nitially, the 

H into the 

stillation: 

(23) 

- H2 0 

:d with an 

sulfate: 

CH3OC2H4OH + HCHO + H2 (27) 

ICM-l 

• CH3OC2H4OCH3 + H2 0 

Ethylene glycol dialkyl ethers, being relatively inert, are employed as aprotic solvents for organometallic reactions, e.g. Grignard reactions or in boron chemistry, as well as in the manufacture of polyurethane paints. Mixtures of bolyethylene glycol 

dimethyl ethers, CH3(OCH2CH2)nOCH3 with approx. 4 to 7 

ethylene oxide units, find application as absorption agents in 

Allied's "Selexol process". In the latter case natural gas and 

synthesis gas are freed by pressurized washing from acidic components such as H2S, C0 2 or S02 . The acidic gases are then 

successively released by reducing the pressure in a stepwise 

manner. 

In order to esterify the free OH groups, the ethylene glycol 

monoalkyl ethers are reacted with carboxylic acids, especially 

acetic acid, using protons as catalysts: 

applications of glycol dialkyl ethers: 

1. aprotic solvents 

2. tetra- to heptaglycol dimethyl ether mixtures as Selexol® for purification of natural and synthesis gas according to principle 

of pressure dependent reversible absorption of acidic gases 

(24) 

+ NaCl 

CjH3OC2H«OH + CH3COOH (28) 

i*C2H5OC2H4OCCH3 + H2 0 

6 

sumption 

:ne glycol 

thers are 

e leading 

:enolyzed 

of monomo-, di-. 

, + H 2 0 

(25) 

Ethyl glycol acetate is an excellent solvent for nitrocellulose and 

cellulose ether used in paint manufacture and finishing. In 

1972, 5,000 t ethyl glycol acetate were consumed in W. 

Germany. 

7.2.5.1,2-GIycol Carbonate 

1,2-GlycoI carbonate, also known as ethylene carbonate, was 

originally only obtainable from glycol and phosgene via double 

elimination of HCl. In 1943, IG Farben discovered a new route 

using ethylene oxide and C02 : 

glycol ether ester, e.g. 

CH3OC:H4OAc and C2H3OC;H4OAc 

are favored solvents for cellulose derivatives 

manufacture of glycol carbonate: 

traditionally via glycol reaction with phosgene, today via catalytic addition of CO, to 

EO 

(26) 

H2C—CH2 + C0 2 

[c«. I . r~\ o. 

\ / 

O (A// 

23 kcal 

"96 kJ /mol (29) 

actunng 

Hiils developed this process to industrial maturity and started 

up a smaller production unit in W. Germany. There are two 

plants operating in Rumania using the same process, their total 

Hiils process operated in plants in W. Germany and Rumania 
P.31 

S T - ^ F - 00?39/-_bie 

I959 C.^ 

198 9 DIRECTORY OF 

CHEMICAL PRODUCERS 

UNITED STATES OF AMERICA 

ai _ 

£=2 Information in this Oiractory is for tha sola 

and privata usa of sponsors of tha 

Oiractory of Chamica! Producan Program. 

I'.ll W • • 4 .....'• • I ' * • 
P.32 

£lil> 

333 RAVENSWOOD AVENUE 

MENLO PARK, CALIFORNIA 94025 

(415)859-3627 

FAX: (415)326-5512 

TWX: 910-373-2046 

TELEX: 334486 

Copyright O 1989 SRI rmemationaJ. 

prohibited. Printed in USA 

Unauthorized use or reproduction of all or any part of this document is 
B 

1369 DIRECTORY OF CHEMICAL PRODUCERS 

UNITED STATES PRODUCTS 

2-(2-Birtoxyethoxy) ethanol (Butoxydiettiylene'glycol) ' 

(Butoxydiglycol) (Diethylene glycol monobutyl ether) (Diglycol 

monobutyl ether) 

Dow Chemical U.SA 

Eastman Kodak Company 

Eastman Chemical Products, Inc 

Texas Eastman Company 

Occidental Petroleum Corporation 

Cain Chemical Inc., subsidiary 

Petrochemical Division 

Shell Oil Company 

Shell Chemical Company, division 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Solvents and Coatings Materials 

Oivision 

Midland, Michigan 

Longview, Texas 

Bayport, Texas 

Geismar, Louisiana 

Seadrift, Texas 

2-{2-Butoxyethoxy] ethanol acetate (See: 2-(2-

Butoxyethoxy) ethyl acetate) 

2-[2-[2-Butoxyethoxy] ethoxy] ethanol (See: 

Butoxylnglycol) 

a-[2-[2-Butoxyethoxy] ethoxy]-4,5-methylenedioxy-2-

propyltoluene (See: Piperonyl butoxide, technical under 

Pesticides) 

2-<2-Butoxyethoxy) ethyl acetate (2-{2-Butoxyethoxy] 

ethanol acetate) (Diethylene glycol monobutyl ether acetate) 

(Diglycol monobutyl ether acetate) 

Eastman Kodak Company 

Eastman Chemical Products, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

1-Butoxyethoxy-2-propanol 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Specialty Chemicals Oivision Institute, West Virginia 

2-6utoxyethy l acetat e (Acetic acid, 2-butoxyethyl ester) (2 -

Butoxyethanol acetate) (Ethylene glycol monobutyl ether acetate) 

(Glycol monobutyl ether acetate) 

Eastman Kodak Company 

Eastman Chemical Products, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

2-Butoxyethyl octadecanoate (See: 2-Butoxyethyl stearate 

under Plasticizers) 

2-Butoxyethyl oleate (See: Plasticizers) 

2-Butoxyethyl oleate, sulfated, sodium salt (See: Anionic 

under Surface-Active Agents) 

2-Butoxyethyl stearate (See: Plasticizers) 

N-[Butoxymethy]-2-chloro-2',6'-diethylacetanilide (See: 

Butachlor under Pesticides) 

p-Butoxyphenol 

Frank Enterprises, Inc. Columbus, Ohio 

n-Butoxypropanol 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Specialty Chemicals Oivision South Charleston, West 

Virginia 

Butoxytriethylene glycol (See: Butoxytriglycol) 

Butoxytriglycol (2-[2-{2-Butoxyethoxy] ethoxy] ethanol) 

(Butoxytriethylene glycol) (Triethylene glycol n-butyl ether) 

(Triglycol monobutyl ether) 

Dow Chemical U.SA Midland, Michigan 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Solvents and Coatings Materials 

Division Seadrift, Texas 

n-Butyl acetate (Acetic acid, butyl ester) (Butyl ethanoate) 

BASF Corporation 

Chemicals Oivision 

Basic Organic Chemicals Group Freeport, Texas 

Eastman Kodak Company 

Eastman Chemical Products, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Hoechst Celanese Corp. 

Engineering Plastics Group 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Solvents and Coatings Materials 

Division 

Bishop, Texas 

Seadrift, Texas 

Texas City, Texas 

TOTAL 

Note: All capacities are extremely flexible and can accommodate other alcohol esters as well. 

Source: SRI International estimates as of January 1, 1989. 

Annual Capacity 

(Millions of Pounds) 

25 

45 

50 

80 

Remarks 

Total esterification capacity is an 

estimated 120-150 million 

pounds/yaar. 

Total esterification capacity is an 

estimated 120 million 

pounds/year. 

Seadrift plant produces primarily 

glycol ether esters, but can 

produce alkyl acetates. 

Total capacity for alkyl acetates 

(n-propyl, isopropyl, isobutyl, nbutyl, and amyl) at the two Texas 

locations is 130 million 

pounds/year. 

200 

496 SRI International 

__^_a__^__t__t_)__S__i