Propylene Oxide Derivatives, June 1991

PROCESS
ECONOMICS
PROGRAM
SRI INTERNATIONAL

Menlo Park, California

94025
Abstract
Process Economics Program Report No. 198
PROPYLENE OXIDE DERIVATIVES

(June 1991)

This report presents the preliminary process designs and economics for the manufacture
of four propylene oxide derivatives: propylene carbonate, ally1 alcohol, isopropanolamines,
and propylene glycol methyl ethers. The report also includes a review of the patent literature
related to these four chemicals. The basic chemistry of these manufacturing processes and
the status of the industry are also provided.

PEP’88 MKG
 Propylene Oxide Derivatives, June 1991

Report No. 198

PROPYLENE OXIDE
DERIVATIVES

by MARTHA K. GUERRA

June 1991

A private report by the

PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025

 Propylene Oxide Derivatives, June 1991

For detailed marketing data and information, the reader is referred to one of the SRI
programs specializing in marketing research. The CHEMICAL ECONOMCS HANDBOOK
Program covers most major chemicals and chemical products produced in the United
States and the WORLD PETROCHfMCALS Program covers major hydrocarbons and their
on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL
derivatives
PRODUCERS services provide detailed lists of chemical producers by company, product,
and plant for the United States, Western Europe, Canada, and East Asia.
 Propylene Oxide Derivatives, June 1991

CONTENTS

1 INTRODUCTION .................................................... l-l

2 SUMMARY ......................................................... 2-l

PROPYLENE CARBONATE ............................................. 2-l

ALLYL ALCOHOL .................................................... 2-1

ISOPROPANOLAMINES ............................................... 2-3

PROPYLENE GLYCOL METHYL ETHERS .................................. 2-3

3 INDUSTRY STATUS ................................................. 3-l

PROPYLENE OXIDE PRODUCTION AND LIST PRICE ........................ 3-l

PROPYLENE OXIDE CONSUMPTION ..................................... 3-l

United States ................................................... 3-5
Western Europe ................................................. 3-6
Japan.. ........................................................ 3-7

PROPYLENE OXIDE DERIVATIVES AND THEIR USES ....................... 3-8

Urethane Polyether Polyols ........................................ 3-8
Propylene Glycol ................................................. 3-9
Dipropylene Glycol ............................................... 3-9
Glycol Ethers .................................................... 3-l 0
Nonurethane Polyether Polyols ..................................... 3-l 3
lsopropanolamines ............................................... 3-13
Polyoxypropyleneamines .......................................... 3-15
Allyl Alcohol .................................................... 3-15
Propylene Carbonate ............................................. 3-16
Other Derivatives ................................................ 3-l 7

4 CHEMISTRY ....................................................... 4-l

PROPYLENE CARBONATE ............................................. 4-l

ALLYL ALCOHOL .................................................... 4-2

ISOPROPANOLAMINES ............................................... 4-2

PROPYLENE GLYCOL ETHERS ......................................... 4-3

...
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 Propylene Oxide Derivatives, June 1991

CONTENTS (Continued)

I PROPYLENE CARBONATE FROM PROPYLENE OXIDE AND CARBON DIOXIDE 5-l

PROCESS REVIEW ................................................... 5-l

PROCESS DESCRIPTION .............................................. 5-2

PROCESS DISCUSSION ............................................... 5-9

Reaction Conditions .............................................. 5-9

Conversion, Selectivity, and Yield .................................. 5-9

Product Recovery ................................................ 5-9

Materials of Construction .......................................... 5-10

Storage Tanks ................................................... 5-10

Waste Disposal .................................................. 5-10

Plant Flexibility .................................................. 5-10

COST ESTIMATES ................................................... 5-10

8 ALLYL ALCOHOL FROM PROPYLENE OXIDE ............................ 6-l

PROCESS REVIEW ................................................... 6-l

PROCESS DESCRIPTION .............................................. 6-2

PROCESS DISCUSSION ............................................... 8-9

lsomerization Reactor ............................................ 6-9

Catalyst ........................................................ 6-9

n-Propanol Formation ............................................ 6-9

Selectivity and Yield .............................................. 6-9

Catalyst Regeneration ............................................ 6-10

Tankage ........................................................ 6-10

Waste Treatment ................................................ 6-10

Materials of Construction .......................................... 6-10

COST ESTIMATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-10

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 Propylene Oxide Derivatives, June 1991

CONTENTS (Continued)

7 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA ......... 7-l

PROCESS REVIEW ................................................... 7-l

PROCESS DESCRIPTION .............................................. 7-3

PROCESS DISCUSSION ............................................... 7-13

Reactors ....................................................... 7-13

Separation of Ammonia and Water from Products ..................... 7-13

Product Separation ............................................... 7-13
Materials of Construction .......................................... 7-14

Storage Tanks ................................................... 7-14

COST ESTIMATES ................................................... 7-14

8 PROPYLENE GLYCOL METHYL ETHERS ................................ 6-l

PROCESS REVIEW ................................................... 6-l

PROCESS DESCRIPTION .............................................. 6-3

PROCESS DISCUSSION ............................................... 8-11

ReactorsR-lOlA&B .............................................. 6-11

Feed Ratio of Methanol to PO ...................................... 8-11
Catalyst ........................................................ 6-11

Separation of Isomers ............................................ 8-12

Reactor R-102 .................................................. 8-l 2

Materials of Construction .......................................... 6-12

Storage Tanks ................................................... 6-13

COST ESTIMATES ................................................... 6-13

APPENDIX A: PATENT SUMMARY TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-l

APPENDIX 8: DESIGN AND COST BASES .................................. B-l

DESIGN CONDITIONS ................................................ B-3

COST BASES ....................................................... B-3

CAPITAL INVESTMENT ............................................... B-3

PRODUCTION COSTS ................................................ B-4

EFFECT OF OPERATING LEVEL ON PRODUCTION COSTS ................... B-5

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 Propylene Oxide Derivatives, June 1991

CONTENTS (Concluded)

APPENDIX c: PHYSICAL PROPERTIES ..................................... C-l

APPENDIX D: CITED REFERENCES ........................................ D-l

APPENDIX E: PATENT REFERENCES BY COMPANY ......................... E-l

APPENDIX F: PROCESS FLOW DIAGRAMS ................................. F-l

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 Propylene Oxide Derivatives, June 1991

ILLUSTRATIONS

5.1 PROPYLENE CARBONATE FROM PROPYLENE OXlDE

AND CARBON DIOXIDE
PROCESS FLOW DIAGRAM . . . . . . . . . . . . ..*..................... F-3

5.2 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
PROPYLENE CARBONATE PRODUCT VALUE
AS A FUNCTION OF TOTAL FIXED CAPITAL INVESTMENT . . . . . . . . . . . . 5-15

6.1 ALLYL ALCOHOL FROM PROPYLENE OXIDE

PROCESS FLOW DIAGRAM . . .,..,..,....,....,..,.....,........ F-5

7.1 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

MOLAR DISTRIBUTION OF MEA, DEA, AND TEA
AS A FUNCTION OF AMMONIA/E0 MOLAR FEED RATIO . . . . . . . . . . . . . 7-2

7.2 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

PROCESS FLOW DIAGRAM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . F-9

7.3 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

PROPYLENE OXIDE COST VERSUS PRODUCT VALUE
FOR ISOPROPANOLAMINES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-25

7.4 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

EFFECT OF OPERATING LEVEL ON PRODUCT VALUE . . . . . . . . . . . . . . . 7-26

6.1 PROPYLENE GLYCOL METHYL ETHERS

PROCESS FLOW DIAGRAM . . . . . . . . . . . . . . ..*.................... F-13

8.2 PROPYLENE GLYCOL METHYL ETHERS

MOL RATIO OF MONO- AND DIETHYLENE GLYCOL METHYL ETHERS
OBTAINED AT VARIOUS METHANOL TO EO MOLAR FEED RATIOS . . . . . 8-17

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 Propylene Oxide Derivatives, June 1991

l
TABLES

2.1 PROPYLENE CARBONATE, ALLYL ALCOHOL, ISOPROOPANOLAMINES,

l AND PROPYLENE GLYCOL METHYL ETHERS

ESTIMATED PRODUCTION COSTS ..........,.................... 2-2

3.1 WORLD PRODUCERS OF PROPYLENE OXIDE ....................,. 3-2

3.2 REGIONAL CONSUMPTION OF PROPYLENE OXIDE BY END USE ....... 3-5

3.3 U.S. CONSUMPTION OF PROPYLENE OXIDE BY YEAR ............... 3-6

3.4 WESTERN EUROPEAN CONSUMPTION OF

PROPYLENE OXIDE BY YEAR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-7

3.5 JAPANESE CONSUMPTION OF PROPYLENE OXIDE . . . . . . . . . . . . . . . . . . 3-8

3.6 WORLD PRODUCERS OF GLYCOL ETHERS . . . . . . . . . . . . . . . . . . . . . . . . 3-l 1

3.7 WORLD PRODUCERS OF ISOPROPANOLAMINES .................... 3-14

3.8 WORLD PRODUCERS OF ALLYL ALCOHOL ........,............... 3-l 6

3.9 WORLD PRODUCERS OF PROPYLENE CARBONATE ................. 3-17

5.1 PROPYLENE CARBONATE

PATENT SUMMARY . . . . . . . . . ..*............................... A-3

5.2 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
DESIGN BASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..*...... 5-4

5.3 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
MAJOR EQUIPMENT . . . . . . . . . . . . . . ..*.......................... 5-5

5.4 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
UTILITIES SUMMARY . . .,................,.,................... 5-7

5.5 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
STREAM FLOWS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-B

5.6 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
TOTAL CAPITAL INVESTMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-l 2

5.7 PROPYLENE CARBONATE FROM PROPYLENE OXIDE

AND CARBON DIOXIDE
PRODUCTION COSTS ..,..................,.................... 5-13

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 Propylene Oxide Derivatives, June 1991

TABLES (Continued)

6.1 ALLYL ALCOHOL

PATENT SUMMARY ........................................... A-5

6.2 ALLYL ALCOHOL FROM PROWLENE OXIDE

DESIGN BASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-4

8.3 ALLYL ALCOHOL FROM PROPYLENE OXIDE

MAJOR EQUIPMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-5

6.4 ALLYL ALCOHOL FROM PROPYLENE OXIDE

UTlLlTlES SUMMARY . . .*.........,,.............,............. 6-7

6.5 AUYL ALCOHOL FROM PROPYLENE OXIDE

STREAM FLOWS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..*........ 6-8

6.6 ALLYL ALCOHOL FROM PROPYLENE OXIDE

TOTAL CAPITAL INVESTMENT ,.,....,.............,......a...... 6-l 2

6.7 ALLYL ALCOHOL FROM PROPYLENE OXIDE

CAPlTAL INVESTMENT BY SECTION .,...,........................ 6-13

0
6.8 ALLYL ALCOHOL FROM PROPYLENE OXIDE
PRODUCTION COSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-14

7.1 ISOPROPANOLAMINES
PATENT SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-6

7.2 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

DESIGN BASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-5

7.3 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH@0 = 5:l
MAJOR EQUIPMENT ,.......,................................*. 7-6

7.4 ISO~ANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH$PO = 2O:l
MAJOR EQUIPMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-8

7.5 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH$PO = 5:l
UTlLlTlES SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-10

7.6 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH@0 = 2O:l
UTlLlTlES SUMMARY . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . ..a...... 7-10

7.7 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH#O = 5:l
STREAM FLOWS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-l 1
0
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 Propylene Oxide Derivatives, June 1991

TABLES (Continued)

l
7.8 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA
NH3:PO = 20:1
STREAM FLOWS . . ..*.............................a........... 7-12

7.9 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH3:PO = 5:l
TOTAL CAPlTAL INVESTMENT ..,.........................*...... 7-l 7

7.10 ISOPROPANOLAMINES FROM PROF’YLENE OXIDE AND AMMONIA

NH3:PO = 2O:l
TOTAL CAPITAL INVESTMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-18

7.11 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH3:PO = 5:l
CAPITAL INVESTMENT BY SECTION . . . . . . . . . . . . . . ..#............. 7-19

7.12 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH3:PO = 2O:l
CAPITAL INVESTMENT BY SECTION .,...,.,.......,,.,........... 7-20

7.13 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH3:PO = 5:l
PRODUCTION COSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-21

7.14 ISOPROPANOLAMINES FROM PROPYLENE OXIDE AND AMMONIA

NH3:PO = 2O:l
PRODUCTION COSTS ..,.,...,................................. 7-23

8.1 PROPYLENE GLYCOL METHYL ETHERS

PATENT SUMMARY ..,............,...*.a..................... A-7

8.2 PROPYLENE GLYCOL METHYL ETHERS

DESIGN BASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..#....... 8-5

8.3 PROPYLENE GLYCOL MONOMETHYL ETHERS

MAJOR EQUIPMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-6

8.4 PROPYLENE GLYCOL MONOMETHYL ETHERS

UTILITIES SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-8

8.5 PROPYLENE GLYCOL METHYL ETHERS

STREAM FLOWS . . . . . . . . . . . . . . . . ..a........ ................... 8-9

8.6 PROPYLENE GLYCOL MONOMETHYL ETHERS

TOTAL CAPITAL INVESTMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-14

8.7 PROPYLENE GLYCOL MONOMETHYL ETHERS

PRODUCTION COSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..*..........s 8-15

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 Propylene Oxide Derivatives, June 1991

TABLES (Concluded)

c.1 PHYSICAL PROPERTIES OF PROPYLENE CARBONATE ............... C-3

C.2 PHYSICAL PROPERTIES OF ALLYL ALCOHOL ...................... C-3

(2.3 PHYSICAL PROPERTIES OF ISOPROPANOLAMINES .................. C-4

C.4 PHYSICAL PROPERTIES OF PROPYLENE GLYCOL METHYL ETHERS .... C-4

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