Abstract Process Economics Program Report 21D OXO ALCOHOLS (December 1999) “Oxo” products are the generic term for chemicals manufactured from oxo-chemistry; that is, the hydroformylation 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 hydrogenation or by hydrogenating the dimers formed from aldol condensation 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 alcohol 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