Abstract Process Economics Program Report 21D OXO (December 1999)

“Oxo” products are the generic term for chemicals manufactured from oxo-chemistry; that is, the of olefins by using syngas (H2/CO).

RCH=CH2 + CO + H2 ® RCH2CH2CHO Common catalysts for the hydroformylation of olefins are Rh and Co. Rh is almost exclu- sively used with P-containing ligands (phosphines or phosphites). Co is used most commonly as the carbonyl (CO ligands).

This report deals with a subset of oxo-products—the C4-C10 alcohols derived from the alde- hydes produced by hydroformylation. These alcohols can be produced either by direct or by hydrogenating the dimers formed from of lower alde- hydes. Dominant technologies in the butyraldehyde-derived alcohols field are the Rh-catalyzed technologies of Union Carbide Corporation (UCC)/Kvaerner and Celanese. Exxon’s cocatalyzed technology dominates iso-nonyl and iso-decyl manufacture. SRIC’s analysis suggests that the Union Carbide/Kvaerner technology has only a slight pro- duction cost advantage over the Celanese water-soluble Rh/phosphine process. However, the UCC/Kvaerner technology does appear to have lower capital costs, primarily because of lower pressures and liquid flows in the hydroformylation process than those in the Celanese process. Exxon’s Co-catalyzed process for iso-nonyl alcohol, which competes with 2-EH in PVC plas- ticizer manufacture, appears to have an appreciable cost advantage over processes for 2-EH manufacture.

PEP’97 21D TM & VC CONTENTS

GLOSSARY...... xi 1 INTRODUCTION ...... 1-1 CONCISE SUMMARY OF FINDINGS...... 1-1 REPORT CONTENTS...... 1-1 2 SUMMARY...... 2-1 INTRODUCTION ...... 2-1 REPORT STRUCTURE...... 2-1 REFERENCES TO PREVIOUS PEP REPORTS ...... 2-2 SUMMARY OF INDUSTRY STATUS...... 2-2 SUMMARY OF PROCESSES REVIEWED...... 2-2 NBAL by the Hydroformylation of Propylene...... 2-2

Phosphite Process with C3 Recovery by Absorption ...... 2-3 Oil-Soluble Phosphine Process with Dual Reactors ...... 2-3 Water-Soluble Phosphine Process with a Secondary Reactor...... 2-3 NBA from NBAL by Hydrogenation...... 2-4 2-EH from NBAL by Condensation and Hydrogenation...... 2-4 INA from C8 Olefins by the Exxon Cocatalyzed Process ...... 2-4 CONCLUSIONS...... 2-5 3 INDUSTRY STATUS ...... 3-1 INTRODUCTION ...... 3-1 GLOBAL PRODUCTION AND CAPACITY...... 3-1 Current Production Capacity...... 3-2 INDUSTRY INTEGRATION...... 3-11 4 PROCESSES FOR THE PRODUCTION OF N-BUTYRALDEHYDE...... 4-1 INTRODUCTION ...... 4-1 CHEMISTRY...... 4-1 CATALYST SYSTEMS ...... 4-1 PROCESS REVIEW ...... 4-3

i CONTENTS (Continued)

5 N-BUTANOL FROM N-BUTYRALDEHYDE ...... 5-1 INTRODUCTION ...... 5-1 CHEMISTRY...... 5-1 PROCESS REVIEW ...... 5-1 Hydrogenation...... 5-1 PROCESS DESCRIPTION...... 5-1 PROCESS DISCUSSION...... 5-9 Materials of Construction ...... 5-9 Waste Streams ...... 5-9 Uncertainties...... 5-9 CAPITAL AND OPERATING COSTS...... 5-10 6 2-ETHYLHEXANOL FROM N-BUTYRALDEHYDE...... 6-1 INTRODUCTION ...... 6-1 CHEMISTRY...... 6-1 PROCESS REVIEW ...... 6-1 Condensation...... 6-1 Hydrogenation...... 6-2 PROCESS DESCRIPTION...... 6-3 Condensation...... 6-3 Hydrogenation...... 6-4 PROCESS DISCUSSION...... 6-13 Condensation...... 6-13 Hydrogenation...... 6-13 Materials of Construction ...... 6-13 Waste Streams ...... 6-13 Condensation Section...... 6-13 Hydrogenation Section ...... 6-13 Uncertainties...... 6-14 CAPITAL AND OPERATING COSTS...... 6-14

iii CONTENTS (Concluded)

7 EXXON PROCESS FOR ISONONYL ALCOHOL USING COBALT CATALYST...... 7-1 INTRODUCTION ...... 7-1 PROCESS REVIEW ...... 7-1 Cobalt Catalyst Recovery...... 7-2 Stripping...... 7-3 Demetalling...... 7-4 Preforming ...... 7-4 PROCESS DESCRIPTION...... 7-5 Section 100—Hydroformylation ...... 7-5 Section 200—Co Catalyst Recovery and Product Demetalling ...... 7-5 Demetalling...... 7-5 Preforming ...... 7-6 Section 300—Hydrogenation and Product Refining ...... 7-6 PROCESS DISCUSSION...... 7-17 Cracking of Heavy by-products...... 7-17 CAPITAL AND OPERATING COSTS...... 7-17 Feedstock Price Estimation ...... 7-18

iv FIGURES

4.1 NBAL Production by the Rh/Phosphine Catalyst Hydroformylation Mechanism...... 4-2 4.2 NBAL Production from Propylene...... 4-4

4.3 NBAL Production by the Phosphite Process with C3 Absorption...... 4-10

4.4 NBAL by the Propylene Phosphite Process with C3 Absorption...... E-3 4.5 NBAL Production by the Oil-Soluble Phosphine Process with Dual Reactors...... 4-24 4.6 NBAL by the Propylene Phosphite Process with Dual Reactors...... E-5 4.7 NBAL Production by the Water-Soluble Phosphine Process with a Secondary Reactor...... 4-37 4.8 NBAL from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor...... E-7 5.1 NBA from NBAL by the Hydrogenation of ...... 5-2 5.2 NBA from NBAL by Two-Stage Hydrogenation ...... E-9 6.1 2-EH from NBAL by Aldol Condensation ...... 6-2 6.2 2-EH from NBAL by the Hydrogenation of Condensed Aldehyde...... 6-3 6.3 2-EH from NBAL by Aldol Condensation and Hydrogenation...... E-11 7.1 Exxon Process for INA for the Process Described under Pep Report 21c...... 7-1 7.2 Exxon Process for INA Based on Pep’s Current Understanding of Exxon’s Process ...... 7-2 7.3 Exxon Process for INA: Catalyst Recovery...... 7-3 7.4 Exxon INA Process Using Co Catalyst ...... E-15

v TABLES

2.1 NBA from Propylene Process Economics for Combined Processes...... 2-7 2.2 2-EH from Propylene Process Economics for Combined Processes...... 2-8 2.3 Exxon Process for INA Process Economics Summary for Low and High Estimates of Feedstock Price...... 2-9 3.1 Global Oxo Alcohol Capacity, 1996 ...... 3-1 3.2 Global Oxo Alcohol Consumption, 1996...... 3-2 3.3 U.S., Western European, and Japanese Consumption by Alcohol Type, 1996 ...... 3-2 3.4 Global NBA Capacity by Company, 1996 ...... 3-3

3.5 Global Plasticizer Alcohol (C4-C13) Capacity by Company, 1996 ...... 3-3

3.6 U.S. Producers of Oxo Plasticizer Alcohols (C4-C13)...... 3-5

3.7 Western European Producers of Oxo Plasticizer Alcohols (C4-C13) ...... 3-6

3.8 Japanese, Korean, and Taiwanese Producers of Oxo Plasticizer Alcohols (C4-C13)...... 3-7 3.9 Chinese Producers of Oxo Plasticizer Alcohols (C4-C13)...... 3-8

3.10 Producers of Oxo Plasticizer Alcohols (C4-C13) under Other World Regions ...... 3-9 4.1 Process for NBAL Production ...... Patent Summary ...... A-3 4.2 ?HNP for Various P-Containing Ligands ...... 4-6

4.3 Butyraldehyde from Propylene by Phosphite Process with C3 Absorption Design Bases and Assumptions ...... 4-13

4.4 Butyraldehyde from Propylene Phosphite Process with C3 Absorption Stream Flows...... 4-15

4.5 Butyraldehyde from Propylene Phosphite Process with C3 Absorption Major Equipment...... 4-17

4.6 Butyraldehyde from Propylene Phosphite Process with C3 Absorption Utilities Summary...... 4-19

4.7 Butyraldehyde from Propylene Phosphite Process with C3 Absorption Total Capital Investment ...... 4-21

4.8 Butyraldehyde from Propylene Phosphite Process with C3 Absorption Production Costs...... 4-22 4.9 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Design Bases and Assumptions ...... 4-26

vi 4.10 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Stream Flows...... 4-27

TABLES (Continued)

4.11 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Major Equipment...... 4-29 4.12 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Utilities Summary...... 4-31 4.13 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Total Capital Investment ...... 4-34 4.14 Butyraldehyde from Propylene by the Oil-Soluble Phosphine Process with Dual Reactors Production Costs...... 4-35 4.15 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Design Bases and Assumptions ...... 4-39 4.16 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Stream Flows...... 4-41 4.17 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Major Equipment...... 4-45 4.18 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Utilities Summary...... 4-47 4.19 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Total Capital Investment ...... 4-50 4.20 Butyraldehyde from Propylene by the Water-Soluble Phosphine Process with a Secondary Reactor Production Costs...... 4-51 5.1 NBA from NBAL Patent Summary ...... A-17 5.2 NBA from NBAL by Two-Stage Hydrogenation Design Bases and Assumptions ...... 5-3 5.3 NBA from NBAL by Two-Stage Hydrogenation Stream Flows...... 5-5 5.4 NBA from NBAL by Two-Stage Hydrogenation Major Equipment...... 5-7

vii 5.5 NBA from NBAL by Two-Stage Hydrogenation Utilities Summary...... 5-8 5.6 NBA from NBAL by Two-Stage Hydrogenation Total Capital Investment ...... 5-11

TABLES (Continued)

5.7 NBA from NBAL by Two-Stage Hydrogenation Production Costs...... 5-12 6.1 2-EH from NBAL by Aldol Condensation and Hydrogenation Patent Summary ...... A-19 6.2 2-EH from NBAL by Aldol Condensation and Hydrogenation Design Bases and Assumptions ...... 6-5 6.3 2-EPA from NBAL Condensation Stream Flows...... 6-7 6.4 2-EH from 2-EPA—Two-Stage Hydrogenation Stream Flows...... 6-8 6.5 2-EH from NBAL Major Equipment...... 6-10 6.6 2-EH from NBAL Utilities Summary...... 6-12 6.7 2-EH from NBAL ...... 6-16 Capital Investment 6.8 2-EH from NBAL Production Costs...... 6-17 7.1 Exxon INA Process Using Co Catalyst Patent Summary ...... A-21 7.2 Exxon INA Process Using Co Catalyst Design Bases and Assumptions ...... 7-7 7.3 Exxon INA Process Using Co Catalyst Stream Flows...... 7-10 7.4 Exxon INA Process Using Co Catalyst Major Equipment...... 7-14 7.5 Exxon INA Process Using Co Catalyst Utilities Summary...... 7-16 7.6 Exxon INA Process Using Co Catalyst Total Capital Investment ...... 7-19 7.7 Exxon INA Process Using Co Catalyst Production Costs...... 7-20

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