PROCESS ECONOMICS PROGRAM

Transcription

1 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Process Economics Report No. 45A POLYOLS FOR POLYURETHANES (May 1982) ABSTRACT Polyols evaluated in this report are: a trifunctional polyester polyol; three polyols of high functionality made from sucrose, sucroseamine, and an aromatic compound containing nitrogen; a polyester polyol made from formaldehyde via formose; two polymer polyols grafted with acrylonitrile and with acrylonitrile/styrene, respectively; a polyol containing dispersed polyurea; a polytetramethylene ether glycol and a copolyester polyol made from tetrahydrofuran and ethylene; a polyester polyol made from adipic acid, diethylene glycol, and trimethylolpropane; a polyol made from residue in dimethyl terephthalate manufacture; and polybutadiene polyol. A semicontinuous process and a continuous process are evaluated and compared for the production of a trifunctlonal polyether polyol with a no1 wt of 3,000. The continuous process is competitive with the prevalently used semicontinuous process only If the reaction rate is accelerated by adding a chemical to promote the contact of the potaeslum hydroxide catalyst with the reactants. i Phosphorus- and halogen-containing polyols are reviewed. PEP'81 YCY

2 Report No. 45A POLYOLS FOR MAKING POLYURETHANES SUPPLEMENT A by YEN-CHEN YEN contdbutions by TUNG-SHENG TSAO a cl A private report by the May PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 For detailed marketing data and inform tion, the reader is referred to one of the SRI program specializing in marketing research. The CHEMICAL HANDBOOK Program covers most major chemicala and chemical products produced in the United States and the WORLD PElUOCHgt4ICALS Progrm covers major hidrocarbons and their derivative8 on a worldwide baris. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS rervices provide detailed lists of chemical producers by company, prod- uc t, and plant ior the United btates and Western Europe.

4 CONTENTS 1 INTRODUCTION. 1 2 SUMMARY... 3 General Aspects... 3 Technical Aspects of SRI's Design Cases... 9 A Polyol from Glycerol, Propylene Oxide, and Ethylene Oxide by a Semicontinuous Process... 9 A Polyol from Glycerol, Propylene Oxide, and Ethylene Oxide by a Continuous Process A Polyol from Sucrose A Sucrose-Amine Polyol An Aromatic N-Containing Polyol A Polyol from Formaldehyde A Polyol Grafted with Acrylonitrile A Polyol Grafted with Acrylonitrile and Styrene... 11,A Polyurea Polyol ;....' Polytetramethylene Ether Glycol (PTMEG) A Copolyether Glycol from TID? and Ethylene Oxide A Polyester Polyol from Adipic Acid and Diethylene Glycol A Polyester Polyol.from a Residue in DMT Manufacture Polybutadiene Polyol INDUSTRY STATUS GENERAL DISCUSSION ON POLYETRER POLYOLS Catalyst Purification Polyglycols and Difunctional Polyols TRIFUNCTIONAL POLYOLS A Semicontinuous Process for Making Polyols fromglycerol Process Description... ' Process Discussion CostEstimates A Continuous Process for Making Polyol from Glycerol Process Description Process Discussion Cost Estimates ill

5 CONTENTS POLYETHER POLYOLS WITH HIGH FUNCTIONALITY... Polyols from Nonreducing Sugar and a Polyhydric Alcohol with More than 4 C's... Polyols from Reducing Sugars and Other Carbohydrates. Nitrogen-containing Polyols... Polyols Containing Aromatic or Heterocyclic Rings... A Process for Making a Polyol from Sucrose... Process Description... Process Discussion... Cost Estimates... A Process for Making a Sucrose-Amine Polyol... 'Process Description... Process Discussion... Cost Estimates... A Process for Producing an Aromatic N-Containing Polyol Process Description Cost Estimates... Operation of the Units as a Part of a Large Plant POLYOL FROM FORMALDEHYDE VIA PORMOSE... :... Chemistry.... Review of Processes... Process, Descript,ion... Process Discussion... CostEstimates POLYMER POLYOLS.. Chemistry.... Review of Processes... A Process for Making a Polymer Polyol Grafted with Acrylonitrile... Process Description... Cost Estimates A Process for Maki~g'a'P~l~~r'P~l;oi 6rif;eci with AcrylonitrilelStyrene... Process Description... Gost Estimates....' POLYOLS MADE FROM OTHER POLYOLS..'. Modified Polyols.. A Process for Making a Polyol Containing a Dispersed Polyurea.. ' ' iv

6 CONTENTS 9 POLYOLS,%fADE FROM OTHER POLYOLS (continued) Process Description CostEstimates POLYTETRAMETBYLENE ETHER GLYCOL Chemistry... ; Review of Processes A Process for.making Polytetramethylene Ether Glycol Process Description Process Discussion CostEstimates A Process for Making Copolyether Glycol from TBF and EO Process Description... w Process Discussion CostEstimates POLYESTER POLYOLS Chemistry Review of Processes A Process for Making a Polyester Polyol from Adipic Acid and Diethylene Glycol Process Description Process Discussion... : Cost Estimates A Process for Makir;g'a'P~l;e;ter'P~l~oi ;r&m'a' Residue in DMT Manufacture Process Description Process Discussion Cost Estimates POLYBUTADIENE POLYOLS Chemistry Anionic Polymerization Free Radical Polymerization Degradation of High Mol Wt Polymers Review of Processes Applications of Polybutadiene Polyols Polyurethane Formation Polyesters Formation V

7 12 POLYBUTADIENE POLYOLS (continued) Hydrogenation of Polybutadiene Polyols; Halogenation of Polybutadiene Polyols A Process for Making Polybutadiene Polyol Process Description Process Discussion... ; Cost Estimates PHOSPHORUS- OR HALOGEN-CONTAINING POLYOLS Phosphorus-Containing Polyols Halogen-Containing Polyols APPENDIX A DESIGN AND COST BASIS 259 APPENDIX B EFFECT OF THE CIUQiICAL STRUCTURE OF POLYOLS. 261 APPENDIX C SOME PHYSICAL DATA USED IN THE DESIGN APPENDIX D SPECIFICATIONS,OF FINISHED PRODUCTS CITED REFERENCES... : PATENTREFERENCES BY COWANY Vi

8 ILLUSTRATIONS Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Semicontinuous Process Flowsheet.. a.. '.. :. : 301 Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Semicontinuous Process Effect of Operating Level and Plant Capacity on Production Cost and Product Value.. 54 Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Continuous Process Flowsheet Polyol from Sucrose Flowsheet... ;. 305 Sucrose-Amine Polyol Flowsheet Aromatic N-Containing Polyol Flowsheet., Polyol from Formaldehyde Via Formose Flowsheet,? 311 Polymer Polyol, Acrylonitrile Grafted Flowsheet Polymer.Polyol, Acrylonitrile-Styrene Grafted Flowsheet Polyol Containing Polyurea in Dispersion Flowsheet Polytetramethylene Ether Glycol Flowsheet Polytetramethylene Ether Glycol Effect of Operating Level and Plant Capacity on Production Cost and Product Value Copolyether Glycol from THF and EO Flowsheet. ;,. 321 Copolyether Glycol Effect of Operating.Level and Plant Capacity on Production Cost and Product Value Vii

9 ILLUSTRATIONS 11.1 Polyester Polyol from Adipic Acid and Diethylene Glycol Polyester Polyol from Residue in DMT Manufacture Flowsheet Polybutadiene Polyol Flowsheet Viii

10 TABLES Trifunctional Polyether Polyol, Wet Mol Wt 3,000 Cost Features 5 Polyols for Rigid Foams CostFeatures.'... 7 Polyols Useful in Elastomersand High Resilience Foams Cost Features 8 Polyols Produced in the United States for Polyurethane Application. 16 U.S. Producers of Polyether Polyols for Polyurethane Applications.,., 19 Polyether Polyols for Polyurethane Uses in the United States in Polyols Producers in,western Europe, 22 Polyether Polyols Producers in Japan 24 Polyether Polyols Producers.in Other Countries. 25 Catalysts.for Oxyalkylation 'PatentSummary.. 31 Continuous Tubular Reactors PatentSummary..? Purification of Polyols Patent Summary.. 33 Stabilizers for Polyols Patents-ry.. 36 Polyglycols and Difunctional Polyols PatentSuurnary.. 38 Several Grades of Polyols from Glycerol by Semicontinuous Process Production Capacity of Polyols 42 Several Grades of Polyols from Glycerol by Semicontinuous Process Major Equipment.,. 46 Several Grades of Polyols from Glycerol by Semieontinuous Process Utilities Summary. 47 ix

11 TABLES 5.4 Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Semicontinuous Process Design Bases and Assumptions Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Semicontinuous Process StreamFlows Several Grades of Polyols from Glycerol by Semicontinuous Process Capital Investment, Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Semicontinuous Process Production Costs Production Costs and Product Value of Various Grades of Polyols Comparison of Cost Features of Production of a Polyol (Mol Wt 3,000, PO/EO) in a Single-Product Plant and in a Multiple-Product Plant Polyol (Mel Wt 3,000) from Glycerol and PO/E0 by Continuous Process Design Bases and Assumptions Polyol (Mol Wt 3-,000) from Glycerol and PO/E0 by Continuous Process StreamFlows * Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Continuous.Process MajorEquipment Polyol (Mel Wt 3,000) from Glycerol and PO/E0 by Continuous Process Utilities Summary Polyol (Mel Wt 3,000) from Glycerol and PO/E0 by Continuous Process Capital Investment Polyol (Mol Wt 3,000) from Glycerol and PO/E0 by Continuous Process Production Costs. 63 X

12 TABLES 6.1 Polyols from Sucrose PatentSummary Polyols from Beducing Sugars, Starch, and Complex Carbohydrates Patent Summary < Nitrogen-Containing Polyether Polyols from Alkylene Oxides for Polyurethane Uses Patent Summary *. 72 Aromatic Polyols Patent Summary; Polyol from Sucrose Design Bases and Assumptions. 79 Polyol from Sucrose StreamFlows ; Polyol from Sucrose Major Equipment. *... i '.. 80 Polyol from Sucrose Utilities Summary,. 81 Polyol from Sucrose Capital Investment. '. '. 82 Polyol from Sucrose Production Costs..'..' 83 Sucrose-Amine Polyol Design Bases and &ssump&ms. 87 Sucrose-Amine Polyol StreamFlows 87 Sucrose-Amine Polyol Major Equipment. Sucrose-Amine Polyol Utilities Summary. 89 Sucrose-Amine Polyol Based on Texaco Patent Capital Investment.. i. 90 Sucrose-Amine Polyol Production Costa.. m Xi.

13 TABLES Aromatic N-Containing Polyol Design Bases and Assumptions. Aromatic N-Containing Polyol StreamFlows... Aromatic N-Containing Polyol Major Equipment.. Aromatic N-Containing Polyol Utilities Summary Aromatic N-Containing Polyol Capital Investment Aromatic N-Containing Polyol Production Costs Formose, Formit and Polyols from Formaldehyde % Summary of Bayer Patents Polyol from Formaldehyde via Formose Design Bases and Assumptions.. i. Polyol from Formaldehyde via Formose StreamFlows... Polyol from Formaldehyde via Formose MajorEquipment. Polyol from Formaldehyde via Formose Utilities Summary.,. Polyol from Formaldehyde via Formose Capital Investment Polyol from Formaldehyde via Formose Production Costs. Polymer Polyols PatentSunanary. Polymer Polyol, Acrylonitrile Grafted Design Bases and Assumptions..,. Polymer Polyol, Acrylonitrile Grafted.StreamFlows.. Polymer Polyol, Acrylonitrile Grafted Major Equipment Xii

14 TABLES 8.5 Polymer Polyol, Acrylonitrile Grafted Utilities Summary Polymer Polyol, Acrylonitrile Grafted Capital Investment Polymer Polyol, Acrylonitrile Grafted Production Costs Polymer Polyol, AcrylonitrilelStyrene Grafted Design Bases and-assumptions Pdlymer Polyol, Acrylonitrile/Styrene Grafted Stream Flows Polymer PolyoZ, Acryl&itrile/Styrene Grafted Major Equipment. ; Polymer Polyol, Acrylonitrile/Styrene Grafted Utilities Summary Polymer Polyol, Acrylonitrile/Styrene Grafted Capital. Investment Polymer Polyol, Acrylonitrile/Styrene Grafted Production Costs Modified Polyols Patent Summary Dispersion-Containing Polyols PatentSummary Polyol Containing Dispersed Polyurea Design Bases and Assumptions Polyol Containing Dispersed Polyurea StreamFlows Polyol Containing Dispersed Polyurea Major Equipment Polymer Containing. Dispersed Polyurea Utilities Summary Polyol Containing Dispersed Polyurea Capital Investment Polyol Containing Dispersed Polyurea Production Costs? Xiii

15 TABLES 10.1 Polytetramethylene Ether Glycol (PTMEG) from Tetrahydrofuran (TBF) PatentSummary Copolyether Polyols from TBF and Alkylene Oxides Patentsummary Polytetramethylene Ether Glycol Design Bases and Assumptions Polytetramethylene Ether Glycol StreamFlows ' Polytetramethylene Ether Glycol Major Equipment, Polytetramethylene Ether Glycol Utilities Summary Polytetramethylene Ether Glycol Capital Investment Polytetramethylene Ether Glycol Production Costs Copolyether Glycol from TBF and EO Design.Bases,and.Assumptions,., Copolyether Glycol from TBF and EO Stream Flows Copolyether Glycol from TBF and EO Major Equipment ;' Copolyether Glycol &cm TBF and EO Utilities Summary Copolyether Glycol from TBF and EO Capital Investment.., Copolyether Glycol from TBF and EO Productidn Costs Polyester Polyols,for.Polyurethane Uses PatentSummary..,.., Polyols from Lactones PatentSummary XIV

16 TABLES 11.3 Polyester Polyol from Adipic Acid and Diethylene Glycol Design Bases and Assumptions Polyester Polyol from Adipic Acid and Diethylene Glycol Stream Flows Polyester Polyol &om Adipic Acid and Diethylene Glycol lfajor Equipment Polyester Polyol from Adipic Acid and Diethylene Glycol Utilities Summary Polyester Polyoi from Adipic Acid and Diethylene Glycol Capital Investment.. : Polyester Polyol from Adipic Acid and Diethylene Glycol Production Costs Polyester Pqlyol from Residue in'dmt Manufacture Design Bases and Assumptions Polyester Polyol from Residue in DMT Manufacture StreamFlows.. : Polyester Polyol from-residue in DMT Manufacture Major Equipment.,.' ; Polyester Polyol from Residue in DHT Manufacture Utilities Summary V Polyester Polyol from Residue in DMT Manufacture Capital Investment Polyester Polyol from Residue in DMT Manufacture Production Costs Polybutadiene Polyols Preparation' Patent Summary..., Polybutadiene Polyol Design Bases and Assumptions Polybutadiene Polyol Stream Flows.. : Polybutadiene Polyol Major Equipment Polybutadiene Polyol Utilities Summary 239 xv

17 TABLES 12.6 Polybutadiene Polyol Capital Investment.,,.,,.,., Polybutadiene Polyol Production Costs Phosphorus-Containing Polyols as Reactive Flame Retardants in Polyurethane Patent Summary Halogenated Polyols.Useful in Polyurethanes Patentsummary B.l Effect of the Chemical Structure of Polyols XVI