New Generation Oxo Alcohols - IHS Home Page · PDF file3URFHVV(FRQRPLFV 3URJUDP $SULYDWHUHSRUWE\WKH Report No. 21F NEW GENERATION OXO ALCOHOLS by Dipti Dave October 2012 Santa Clara,

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© 2012 IHS PEP Report 21F

Abstract

Process Economics Program Report 21F

NEW GENERATION OXO ALCOHOLS

(October 2012)

This report follows a series of Process Economics Program reports on the topic of oxo

alcohols. The last report on the subject was PEP 21E, Oxo Alcohols, published in September

2010.

This report covers the BASF design concept for hydroformylation of raffinate II C4 olefin

feedstock for the production of n-valeraldehyde. The intermediate n-valeraldehyde is used for the

production of 2-propylheptanol by BASF aldol condensation and hydrogenation (based on patents

of Mitsubishi and Hoechst). The intermediate n-valeraldehyde is also used for the by-product

production of amyl alcohol.

The main focus of this report is evaluating the technoeconomics of the following three

process routes: (1) the production of n-valeraldehyde at a base case capacity of 260 million lb/yr;

(2) the production of 2-propylheptanol, at a base case capacity of 188 million lb/yr; (3) the by-

product production of amyl alcohol via direct hydrogenation of n-valeraldehyde, at a base case

capacity of 59 million lb/yr. We determine the total capital investment and product value for a

plant constructed in the US Gulf Coast region.

Process Economics Program

A private report by the

Report No. 21F

NEW GENERATION OXO ALCOHOLS

by Dipti Dave

October 2012

Santa Clara, California 95054

IHS Chemical agrees to assign professionally qualified personnel to the preparation of

the Process Economics Program’s reports and will perform the work in conformance with

generally accepted professional standards. No other warranties expressed or implied are made.

Because the reports are of an advisory nature, neither IHS Chemical nor its employees will

assume any liability for the special or consequential damages arising from the Client’s use of the

results contained in the reports. The Client agrees to indemnify, defend, and hold IHS Chemical,

its officers, and employees harmless from any liability to any third party resulting directly or

indirectly from the Client’s use of the reports or other deliverables produced by IHS Chemical

pursuant to this agreement.

For detailed marketing data and information, the reader is referred to one of the IHS

Chemical programs specializing in marketing research. THE IHS CHEMICAL ECONOMICS

HANDBOOK Program covers most major chemicals and chemical products produced throughout

the world. In addition the IHS Chemical DIRECTORY OF CHEMICAL PRODUCERS services

provide detailed lists of chemical producers by company, product, and plant for the United States,

Europe, Asia, South and Central America, the Middle East, Canada and Mexico.

CONTENTS

© 2012 IHS iii PEP Report 21F

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

BACKGROUND .......................................................................................................... 1-1

PROCESS .................................................................................................................. 1-1

PRODUCT PROPERTIES .......................................................................................... 1-1

MARKET GROWTH ................................................................................................... 1-3

REPORT OVERVIEW ................................................................................................ 1-4

2 SUMMARY ................................................................................................................. 2-1

WORLD CAPACITY ................................................................................................... 2-1

WORLD PLASTICIZER ALCOHOL PRODUCERS ................................................... 2-4

EXISTING COMMERICAL PRODUCTION ................................................................ 2-5

Supply—United States ............................................................................................... 2-5

Supply—Western European ....................................................................................... 2-5

Recently Planned Capacity Additions ................................................................... 2-6

Supply—China ............................................................................................................ 2-7

TECHNOLOGY AND LICENSORS ............................................................................ 2-8

Manufacturing Processes ........................................................................................... 2-8

n-Valeraldehydes ........................................................................................................ 2-9

2-Propylheptanol ........................................................................................................ 2-9

Amyl Alcohol ............................................................................................................... 2-9

N-VALERALDEHYDE PRODUCTION BASF CONCEPT .......................................... 2-9

Catalyst System .......................................................................................................... 2-9

Reaction Conditions ................................................................................................... 2-11

By-Products/Impurities ............................................................................................... 2-11

RECENT DEVELOPMENT ON CATALYZED HYDROFORMYLATION ................... 2-11

PROCESS ECONOMICS ........................................................................................... 2-12

Fixed-Capital Costs—n-Valeraldehyde ...................................................................... 2-12

Production Costs—n-Valeraldehyde .......................................................................... 2-12

Conclusion—n-Valeraldehyde .................................................................................... 2-13

Fixed-Capital Costs—2-Propylheptanol ..................................................................... 2-21

Production Costs—2-Propylheptanol ......................................................................... 2-21

Fixed-Capital Costs—Amyl Alcohol ............................................................................ 2-26

Production Costs—Amyl Alcohol ................................................................................ 2-26

CONTENTS (Continued)

© 2012 IHS iv PEP Report 21F

3 INDUSTRY STATUS .................................................................................................. 3-1

PRODUCTS ............................................................................................................... 3-1

MARKET GROWTH ................................................................................................... 3-1

WORLD CAPACITY ................................................................................................... 3-1

WORLD PLASTICIZER ALCOHOL PRODUCERS ................................................... 3-4

Supply—United States ............................................................................................... 3-5

Supply—Western European ....................................................................................... 3-5

Recently Planned Capacity Additions ................................................................... 3-6

Supply—China ............................................................................................................ 3-7

TECHNOLOGY AND LICENSORS ............................................................................ 3-8

Manufacturing Processes ........................................................................................... 3-8

n-Valeraldehydes ........................................................................................................ 3-8

2-Propylheptanol ........................................................................................................ 3-9

Amyl Alcohol ............................................................................................................... 3-9

4 TECHNOLOGY REVIEW ........................................................................................... 4-1

BACKGROUND HYDROFORMYLATION .................................................................. 4-1

Homogeneous Catalysis ............................................................................................. 4-2

HYDROFORMYLATION AND CATALYSIS ............................................................... 4-4

Catalytic Cycle ............................................................................................................ 4-6

Catalyst and Ligand Degradation ............................................................................... 4-7

N-VALERALDEHYDE ................................................................................................. 4-8

Catalyst System .......................................................................................................... 4-8

Reaction Conditions ................................................................................................... 4-9

By-Products/Impurities ............................................................................................... 4-10

RECENT DEVELOPMENT ON CATALYZED HYDROFORMYLATION ................... 4-10

Finland Study .............................................................................................................. 4-10

Japan Study ................................................................................................................ 4-11

China Study ................................................................................................................ 4-14

BASF .......................................................................................................................... 4-17

DOW ........................................................................................................................... 4-19

ALDOL CONDENSATION .......................................................................................... 4-21

Aldol Condensation Reactions ................................................................................... 4-21


© 2012 IHS v PEP Report 21F

BASF Aldol Condensation .......................................................................................... 4-21

Davy Aldolization-Dehydration Process ..................................................................... 4-22

5 N-VALERALDEHYDE FROM C4 OLEFINS BY BASF HYDROFORMYLATION ..... 5-1

PROCESS DESCRIPTION ........................................................................................ 5-1

Chemistry.................................................................................................................... 5-1

MAIN REACTIONS ..................................................................................................... 5-2

Process Chemistry ..................................................................................................... 5-2

Hydroformylation ........................................................................................................ 5-3

BASIS FOR DESIGN AND EVALUATION ................................................................. 5-4

Design References ..................................................................................................... 5-4


Section 100—Feed Distillation with Equilibrium Reaction and Isomerization plus

Hydrogenation ............................................................................................................ 5-7

Section 200—Hydroformylation with Pressure Separation and Recovery

Distillation ................................................................................................................... 5-7

Stream Flows .............................................................................................................. 5-8

PROCESS DISCUSSION ........................................................................................... 5-11

Section 100—Feed Distillation with Equilibrium Reaction and Isomerization plus

Hydrogenation ............................................................................................................ 5-11

Section 200—Hydroformylation with Pressure Separation and Recovery

Distillation ................................................................................................................... 5-12

Offsite Storage ............................................................................................................ 5-13

Environmental ............................................................................................................. 5-13

COST ESTIMATES .................................................................................................... 5-14

Fixed-Capital Costs .................................................................................................... 5-14

Production Costs ........................................................................................................ 5-14

CONCLUSION ............................................................................................................ 5-15

6 PRODUCTION OF 2-PROPYLHEPTANOL FROM N-VALERALDEHYDE .............. 6-1

ALDOL CONDENSATION .......................................................................................... 6-1

Chemistry for Aldol Condensation .............................................................................. 6-1

Hydrogenation ............................................................................................................ 6-2

Chemistry for Hydrogenation ................................................................................. 6-2



© 2012 IHS vi PEP Report 21F

Section 100—2-Propyl-2-Heptenal Production .......................................................... 6-3

Section 200—2-Propylheptanol Production ............................................................... 6-4


Raw Material Source .................................................................................................. 6-13

Catalysts ..................................................................................................................... 6-13

Reactors ..................................................................................................................... 6-13

Heat-Exchanger Sizing ............................................................................................... 6-14

Product Recovery ....................................................................................................... 6-14

Materials of Construction ............................................................................................ 6-14

Equipment Listing and Utilities Consumption ............................................................. 6-14

COST ESTIMATES .................................................................................................... 6-14



7 PRODUCTION OF AMYL ALCOHOL FROM N-VALERALDEHYDE ....................... 7-1

HYDROGENATION .................................................................................................... 7-1

Chemistry for Hydrogenation ...................................................................................... 7-1


Section 100—Amyl Alcohol Production ...................................................................... 7-2


Raw Material Source .................................................................................................. 7-8

Catalysts ..................................................................................................................... 7-8

Reactors ..................................................................................................................... 7-8

Heat-Exchanger Sizing ............................................................................................... 7-9

Product Recovery ....................................................................................................... 7-9

Materials of Construction ............................................................................................ 7-9

Equipment Listing and Utilities Consumption ............................................................. 7-9

COST ESTIMATES .................................................................................................... 7-9



APPENDIX A PATENT SUMMARY TABLES ................................................................ A-1

APPENDIX B DESIGN AND COST BASES................................................................... B-1

APPENDIX C CITED REFERENCES ............................................................................. C-1

CONTENTS (Concluded)

© 2012 IHS vii PEP Report 21F

APPENDIX D PATENT REFERENCES BY COMPANY ................................................ D-1

APPENDIX E PROCESS FLOW DIAGRAMS ................................................................ E-1

FIGURES

© 2012 IHS viii PEP Report 21F

2.1 World Consumption of Oxo Chemicals ................................................................. 2-4

2.2 Ligand Structure .................................................................................................... 2-10

3.1 World Consumption of Oxo Chemicals ................................................................. 3-4

4.1 Chemicals from Heterogeneous Catalytic (and Noncatalytic) Processing of

Crude Oil ................................................................................................................ 4-3

4.2 Chemicals and Classes of Chemicals That Are Manufactured by

Homogeneous Catalytic Processes ...................................................................... 4-4

4.3 Basic Catalytic Cycle for the Hydroformylation of Propylene with Rh/PPh3-

Based Catalyst ...................................................................................................... 4-7

4.4 Basic Catalytic Cycle for the Degradation of PPh3 Ligand and Catalyst ............... 4-8


4.6 Asymmetric Hydroformylation ................................................................................ 4-12

4.7 BASF Process Scheme for n-Valeraldehyde ........................................................ 4-18

4.8 Conversion of C4 Raffinate as a Function of Time ................................................ 4-20

4.9 Calixarene Bisphosphite Ligand ............................................................................ 4-20

4.10 Aldol Condensation and Hydrogenation Process Flow Diagram .......................... 4-22

4.11 Aldolization-Dehydration Process ......................................................................... 4-23

5.1 Production of n-Valeraldehyde from Raffinate II C4 Olefins

Process Flow Diagram .......................................................................................... E-3


5.3 n-Valeraldehyde Trimer ......................................................................................... 5-4

6.1 Production of 2-Propylheptanol from n-Valeraldehyde


7.1 Production of Amyl Alcohol from n-Valeraldehyde


TABLES

© 2012 IHS ix PEP Report 21F

1.1 Physical Properties of n-Valeraldehyde ................................................................ 1-2

1.2 Physical Properties of 2-Propylheptanol ............................................................... 1-2

1.3 Physical Properties of Amyl Alcohol ...................................................................... 1-3

2.1 World Capacity for Plasticizer Alcohols—2012 ..................................................... 2-2

2.2 World Consumption of Plasticizer Alcohols ........................................................... 2-3

2.3 Major World Producers of Plasticizer Alcohols ...................................................... 2-4

2.4 US Producers of n-Valeraldehyde ......................................................................... 2-5

2.5 Western European Producers of n-Valeraldehyde ................................................ 2-6

2.6 Announced Western European Capacity Additions for n-Valeraldehyde .............. 2-7

2.7 Chinese Producer of Plasticizer Alcohol ............................................................... 2-7

2.8 Relation between Base Capacity and Product Value ............................................ 2-13

2.9 n-Valeraldehyde from C4 Olefins by BASF Hydroformylation

Total Capital Investment ........................................................................................ 2-14


Capital Investment by Section ............................................................................... 2-15


Production Costs ................................................................................................... 2-16


Utilities Summary ................................................................................................... 2-18


Major Equipment ................................................................................................... 2-19











3.1 World Capacity for Plasticizer Alcohols—2012 ..................................................... 3-2

3.2 World Consumption of Plasticizer Alcohols ........................................................... 3-3

3.3 Major World Producers of Plasticizer Alcohols ...................................................... 3-4

3.4 US Producers of n-Valeraldehyde ......................................................................... 3-5

TABLES (Continued)

© 2012 IHS x PEP Report 21F

3.5 Western European Producers of n-Valeraldehyde ................................................ 3-6

3.6 Announced Western European Capacity Additions for n-Valeraldehyde .............. 3-7

3.7 Chinese Producer of Plasticizer Alcohol ............................................................... 3-7

4.1 Process Parameters for Several Hydroformylation Processes ............................. 4-6

4.2 Sequential Conversion of an Olefin Library to an Aldehyde Library ...................... 4-13

4.3 Effect of BISBIS/Rh Molar Ratio ............................................................................ 4-15

4.4 Effect of Reaction Temperature ............................................................................. 4-15

4.5 Effect of Pressure .................................................................................................. 4-16

4.6 Effect of Catalyst Concentration ............................................................................ 4-16

4.7 Effect of [1-Butene]/[Rh] Molar Ratio ..................................................................... 4-17

4.8 Effect of Recycling of Rhodium Catalyst ............................................................... 4-17

4.9 Raffinate II Stream Composition............................................................................ 4-18

4.10 C4 Raffinate Stream Composition .......................................................................... 4-19

5.1 Reaction Equipment Items with Name and Section Number ................................ 5-2

5.2 Butane and Butene Forming Reactions ................................................................ 5-2

5.3 Hydroformylation Reactions .................................................................................. 5-3

5.4 Process Sections ................................................................................................... 5-4


Design Basis and Assumptions ............................................................................. 5-5


Stream Flows ......................................................................................................... 5-9

5.7 Process Waste Streams ........................................................................................ 5-13

5.8 Relation between Base Capacity and Product Value ............................................ 5-15










Major Equipment ................................................................................................... 5-21


Design Bases......................................................................................................... 6-5

TABLES (Concluded)

© 2012 IHS xi PEP Report 21F


Stream Flows ......................................................................................................... 6-7


Major Equipment ................................................................................................... 6-10










Design Bases......................................................................................................... 7-4


Stream Flows ......................................................................................................... 7-5


Major Equipment ................................................................................................... 7-6









Documents

New Generation Oxo Alcohols - IHS Home Page · PDF file3URFHVV(FRQRPLFV 3URJUDP $SULYDWHUHSRUWE\WKH Report No. 21F NEW GENERATION OXO ALCOHOLS by Dipti Dave October 2012 Santa Clara,