Abstract Process Economics Program Report 227 1,3-PROPANEDIOL AND POLYTRIMETHYLENE TEREPHTHLATE (December 1999)

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1 Abstract Process Economics Program Report 227 1,3-PROPANEDIOL AND POLYTRIMETHYLENE TEREPHTHLATE (December 1999) As an engineering thermoplastic, polytrimethylene terephthalate (PTT) combines the rigidity, strength, and heat resistance of the polyethylene terephthalate (PET) resins with the good processability of the polybutylene terephthalate resins. Currently, nylon carpet fiber is known for its resiliency, but it does not accept a wide variety of dyes (limiting the colors that can be provided) and tends to generate static charges. PET carpet fibers can be easily dyed but have neither the extreme wearability nor the resiliency of nylon. PTT fibers, on the other hand, have the dyeability of PET and also are static-resistant. In addition, PTT fibers appear to have resilience and wearability equivalent to that of nylon. The recent commercial availability of polymerization-grade 1,3-propanediol (PDO) allows commercialization of polypropylene terephthalate (commonly called polytrimethylene terephthalate, or PTT). PTT has recently been introduced in developmental quantities, and full-scale commercial facilities are now on stream with substantial expansions expected in the next few years by both Shell and DuPont. In addition to applications as an engineering molding and extrusion resin, PTT has remarkable properties as a fiber. This report examines the technology and economics of producing both PDO and PTT. We find that on a cost-per-pound basis PTT can compete favorably with nylon even in nylon s current severely price-depressed state. On a volume basis, however, the higher density of PTT will put it at a small economic disadvantage to nylon. Competition with PET will be based on superior properties at a significant cost premium for the PTT. Currently, DuPont (using Degussa technology) is producing PDO by hydration of acrolein and Shell is producing PDO by hydroformylation of ethylene oxide (EO). In addition, DuPont, in cooperation with Genencor, has a process under development to produce PDO from glucose (cornbased) using biosynthesis (fermentation). We have examined the technology and economics of these three PDO routes and found that the two chemical routes differ widely, with the acrolein process having a lower capital cost but a much higher raw material cost. Although both processes are currently commercial, the EO route will have the best long-term economics of the two. To remain competitive, the acrolein route must rely on integration back to propylene and the elimination of some crude acrolein purification steps. The third route, biosynthesis, is currently not commercial. The economics of the anaerobic route analyzed in this report are superior to those for the acrolein route but inferior to those for the EO route. If the newer aerobic route being developed by DuPont/Genencor meets the performance targets outlined in this report, it will be competitive with the EO route and could have a cost advantage when fully developed. The process is expected to be commercial by 2003 to PEP ERM & RGB

2 CONTENTS GLOSSARY...xv 1 INTRODUCTION SUMMARY OVERVIEW BACKGROUND PTT AND PDO CAPACITY TECHNICAL ASPECTS PDO from Acrolein PDO from EO PDO by Fermentation from Glucose PTT Production from PDO and TPA ECONOMIC ASPECTS PDO Economics PTT Economics INDUSTRY STATUS OVERVIEW PRODUCTION CAPACITIES CONSUMPTION United States Western Europe Asia ,3-PROPANEDIOL PRODUCTION CHEMISTRY ACROLEIN CHEMISTRY iii

3 CONTENTS (Continued) 4 1,3-PROPANEDIOL PRODUCTION CHEMISTRY (Concluded) EO CHEMISTRY OTHER EO ROUTES Glycerol ,3-Dichloropropene CHEMISTRY OF PDO PRODUCTION BY FERMENTATION Glucose to Glycerol Glycerol to PDO Regeneration of Co-Factor (NADH) POLYMERIZATION OF PDO TO PTT ,3-PROPANEDIOL FROM ACROLEIN PROCESS REVIEW Hydration Hydrogenation Background Two-Temperature Zone Hydrogenation PROCESS DESCRIPTION Hydration of Acrolein to HPA Hydrogenation of HPA to PDO Purification PDO Purification Ether Reclamation PROCESS DISCUSSION Section 100 Hydration of Acrolein Section 200 Hydrogenation of HPA to PDO iv

4 CONTENTS (Continued) 5 1,3-PROPANEDIOL FROM ACROLEIN (Concluded) Section 300 Purification Dewatering Column PDO Purification Column Ether Purification Column Ether Hydrolysis to PDO Materials of Construction Waste Generation COST ESTIMATES Variable Costs Capital Costs Production Costs Direct Costs Operating Level ,3-PROPANEDIOL FROM ETHYLENE OXIDE INTRODUCTION PAST PEP WORK OVERALL CHEMISTRY REVIEW OF EO TO PDO PROCESSES Hydroformylation Shell Chemical Company Union Carbide/Plastics Technology Corporation Hoechst Celanese Corporation Extraction Hydrogenation PROCESS DESCRIPTION v

5 CONTENTS (Continued) 6 1,3-PROPANEDIOL FROM ETHYLENE OXIDE (Concluded) Section 100 Hydroformylation of EO to HPA Extraction Treatment of Aqueous PDO Stream Treatment of the Extracted MTBE Stream Section 200 Hydrogenation of HPA to PDO Section 300 Purification PROCESS DISCUSSION Hydroformylation of EO to HPA Reaction Extraction MTBE Purification Aqueous Stream Stripping Hydrogenation of HPA to PDO Purification of PDO Materials of Construction Waste Generation COST ESTIMATES Variable Costs Capital Costs Production Costs Direct Costs Operating Level ,3-PROPANEDIOL BY FERMENTATION INTRODUCTION PDO AS A PRODUCT OF FERMENTATION PDO FROM FERMENTATION OF GLYCEROL vi

6 CONTENTS (Continued) 7 1,3-PROPANEDIOL BY FERMENTATION (Continued) PDO FROM CO-FERMENTATION OF GLYCEROL AND GLUCOSE PDO FROM FERMENTATION OF GLUCOSE Linked Fermentation Process Mixed-Culture Fermentation Process PROCESS DESCRIPTION Section 100 Media Preparation and Fermentation Batch Preparation of Biocatalyst Continuous PDO Synthesis Section 200 Concentration and By-Product Recovery Section 300 Water Removal and Product Purification PROCESS DISCUSSION Fermentor Selection Suspended-Cell Fermentor Immobilized Cells in a Packed-Column Fermentor Immobilized Cells in a Fluidized-Bed Fermentor Immobilization of Cells Multiple-Stage Continuous Fermentors Nitrogen Purging Biocatalyst Selection Operating Conditions for Fermentation Fermentor ph Fermentor Temperature Substrate Concentration Product Concentration Anaerobic versus Aerobic Conditions Anaerobic Fermentation Aerobic Fermentation vii

7 CONTENTS (Continued) 7 1,3-PROPANEDIOL BY FERMENTATION (Concluded) Alternative Recovery Methods Utility Use Waste Generation Aqueous Waste Organic Waste Gaseous Waste Materials of Construction COST ESTIMATES Capital Costs Production Costs Discussion of Capital Costs Effect of Operating Level on Product Value POLYTRIMETHYLENE TEREPHTHALATE PRODUCTION INTRODUCTION Overall Chemistry Side Reactions Naming of Polymer Molecular Weight Polymer Stability and Color REVIEW OF PTT PROCESSES Esterification Transesterification Polycondensation Solid-State Polymerization Fiber-Spinning viii

8 CONTENTS (Continued) 8 POLYTRIMETHYLENE TEREPHTHALATE PRODUCTION (Concluded) PROCESS DESCRIPTION Section 100 Esterification of PDO and TPA Section 200 Polycondensation and Shipping PROCESS DISCUSSION Heat Effect of Esterification Feed Solids Handling Feed Slurry (TPA in PDO) Handling Esterification Reactor Design Distillation Start-Up of Esterification Section Polymeric Additives Materials of Construction Waste Generation COST ESTIMATES Variable Costs Capital Costs Production Costs Direct Costs Operating Level ix

9 CONTENTS (Concluded) APPENDIXES A: PATENT SUMMARY TABLES B: AUXILIARY PRODUCTION COSTS C: DESIGN AND COST BASES D: CITED REFERENCES E: PATENT REFERENCES BY COMPANY F: PROCESS FLOW DIAGRAMS x

10 FIGURES 2.1 PDO Process Economics Major Chemical Reactions for Producing PDO from Acrolein Major Chemical Reactions for Producing PDO from EO Major Chemical Reactions for Producing PDO from Glycerol Major Chemical Reactions for Producing PDO from 1,3-DCP Enzymatic Glucose Route to PDO A Embeden-Meyerhof-Parnas Pathway to Pyruvate B Enzymatic Glucose Route to PDO Structure of Co-Enzyme A ADP/ATP Structure and Conversion Structure of Nicotinamide Adenine Dinucleotide Major Chemical Reactions Involved in Preparing PTT Side Reactions Involved in Preparing PTT Ether By-Product Reaction During Preparation of PTT PDO from Acrolein... F PDO from Acrolein: PDO Product Value versus Cost of Acrolein PDO from EO... F Conversion of EO to PDO PDOfrom Glucose... F Glycerol to PDO PDO from Glucose by Anaerobic Fermentation: Product Value versus Capacity Utilization PTT from TPA and PDO... F Overall Chemistry for Producing PTT from PDO and TPA xi

11 TABLES 2.1 Production Costs for Three Methods of Making PDO Production Costs for Making PTT PET Capacity by Raw Material Used U.S. Producers of PDO and PTT by Capacity Physical Properties of 1,3-PDO ,3-Propanediol from Acrolein: Patent Summary... A PDO from Acrolein: Design Bases PDO from Acrolein: Stream Flows PDO from Acrolein: Major Equipment PDO from Acrolein: Utilities Summary PDO from Acrolein: Total Capital Investment PDO from Acrolein: Capital Investment by Section PDO from Acrolein: Production Costs PDO from Acrolein: Direct Costs by Section ,3-Propanediol from Ethylene Oxide: Patent Summary... A PDO from EO: Design Bases PDO from EO: Stream Flows PDO from EO: Major Equipment PDO from EO: Utilities Summary xii

12 TABLES (Continued) 6.6 PDO from EO: Total Capital Investment PDO from EO: Capital Investment by Section PDO from EO: Production Costs PDO from EO: Direct Costs By Section ,3-Propanediol by Fermentation: Patent Summary... A PDO from Glucose by Anaerobic Fermentation: Design Bases PDO from Glucose by Anaerobic Fermentation: Stream Flows PDO from Glucose by Anaerobic Fermentation: Major Equipment PDO from Glucose by Anaerobic Fermentation: Utilities Summary PDO from Glucose by Anaerobic Fermentation: Total Capital Investment PDO from Glucose by Anaerobic Fermentation: Capital Investment by Section PDO from Glucose by Anaerobic Fermentation: Production Costs (No By-Product Credit) PDO from Glucose by Anaerobic Fermentation: Production Costs (With By-Product Credit) PDO from Glucose by Aerobic Fermentation: Production Costs PDO from Glucose by Aerobic Fermentation: Major Equipment PDO from Glucose by Aerobic Fermentation: Utilities Summary PDO from Glucose by Aerobic Fermentation: Total Capital Investment xiii

13 TABLES (Concluded) 7.14 PDO from Glucose by Aerobic Fermentation: Capital Investment by Section Polytrimethylene Terephthalate Production: Patent Summary... A PTT from PDO and TPA: Design Bases PTT from PDO and TPA: Stream Flows PTT from PDO and TPA: Major Equipment PTT from PDO and TPA: Utilities Summary PTT from PDO and TPA: Total Capital Investment PTT from PDO and TPA: Capital Investment by Section PTT from PDO and TPA: Production Costs PTT from PDO and TPA: Direct Costs by Section xiv