PROCESS ECONOMICS PROGRAM

Transcription

1 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Mmlo Park, California Abstract Process Economics Program Report No. 1lE METRACRYLIC ACID AND METHACRYLIC ESTERS (July 1980) Continued growth in markets for methacrylate polymers for acrylic sheets and acrylic coatings has led to increased demand for the monomers, chiefly methyl methacrylate, but also including smaller amounts of specialty methacrylate esters made from methacryllc acid. New processes have been proposed to replace the established route for making methyl methacrylate from acetone, hydrogen cyanide, and methanol. The acetone cyanohydrln route suffers from production of acidic wastes; the newer processes avoid these wastes and may also offer lower capital investment, lower production costs, and direct production of me&acrylic acid. This report presents technical and economic evaluations of several new methyl methacrylate processes. Detailed process descriptions and cost estimates are given for processes that begin with lsobutylene, t-butanol, or mixed butylenes, and produce methacrylic acid via methacrolein. Recesses that begin with lsobutyric acid or ally1 acetate are also included. A sixth process is based on production of methyl methacrylate from ethylene, carbon monoxide, methanol, and formaldehyde, via methyl propionate. In their present stage of development, the last three processes appear to have about the same production costs as the acetone cyanohydrin route. The three processes that produce a methacrolein lntermediate are msrkedly superior economically to the acetone cyanohydrin route, on the basis of new plant construction and current raw msterials costs. PEP 79 RHS

2 Report No. 11 B METHACRYLIC ACID AND METHACRYLIC ESTERS SUPPLEMENT B by ROBERT H. SCHWAAR and MADHAV M. KOORSE a Cl 1 I m A private report by the July 1980 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii

4 CONTENTS 1 INTRODUCTION SUMMARY... 3 General Aspects... 3 Economic Aspects... 4 Technical Aspects... 9 Isobutylene Oxidation... 9 t-butanol Oxidation Mixed Butylenes Oxidation Propylene Carbonylation Dehydrogenation of Isobutyric Acid Hydroformylation of Ally1 Acetate Methyl Propionate Route Acetone Cyanohydrin Route INDUSTRY STATUS Consumption of MMA Other Countries ROUTES TO METHACRYLATE ACID AND METHYL METHACRYLATE Isobutylene Routes Propylene Routes Ethylene Routes METHYL METHACRYLATE FROM ISOBUTYLENE VIA METHACROLEIN Feedstock Supply Review of Processes Oxidation of Isobutylene to Methacroleln Catalyst Reaction Conditions Feed Compositions Results Separation of Methacrolein from Reactor Product Oxidation of Methacrolein to Methacrylic Acid Catalyst Reaction Conditions Feed Composition Liquid-Phase Processes Separation of Methacrylic Acid from Reactor Product Esterification of Methacrylic Acid with Methanol iii

5 CONTENTS Separation and Purification of Methyl Methacrylate. Production of Methyl Methacrylate from Methacrolein, not via Methacrylic Acid... Combination Processes... Oxidation of Isobutylene to Methacrylic Acid inonestep... Oxidation/Esterification of Methacrolein to Methyl Methacrylate... Methyl Methacrylate from Isobutylene in One Step. Process Description... Oxidation of Isobutylene to Methacrolein... Oxidation of Methacrolein to Methacrylic Acid... Esterification of Methacrylic Acid with Methanol.. Process Discussion... Oxidation of Isobutylene to Methacrolein... Oxidation of Methacrolein to Methacrylic Acid... Reactor Design.... Recovery of Methacrylic Acid... Recovery of Unreacted Methacroleln... Distillation Steps... Methacrylic Acid Storage... Esterificatlon of Methacryllc Acid with Methanol.. WasteStreams... Materials of Construction... Cost Estimates... Capital Costs... Production Costs of Methyl Methacrylate... Production Costs of Methacrylic Acid METHYL METHACRYLATE FROM t-butanol Feedstock Supply... Review of Patents... Process Description... Oxidation of t-butanol to Methacrolein... Oxidation of Methacroleln to Methacrylic Acid and Esterificatlon of Methacrylic Acid with Methanol Process Discussion... Oxidation of t-butanol to Methacrolein... Reactor Design... Waste Streams... Materials of Construction ; \ iv

6 CONTENTS CO8t E8tilWte Capital CO8t Production CO8t METHYLMETHACRYLATE FROMMIXED BUTYLENES Review of Processes Procees Description Oxidation of Mixed Butylenes to Methacrolein and Butadiene Separation of Butadiene-Rich Stream Methacrolein Oxidation to Methacrylic Acid and Esteriflcation of Methacrylic Acid with Methanol PrOCe88 Di8Cu88iOn Reactor Design Waste Stream Material8 of Construction CO8t E8tilWte capital CO8t Production CO8t METRYL METBACRYLATE FROM ETHYLENE VIA PROPIOXIC ACID OR METHYLPROPIONATE Review of Patent Production of Proplonic Acid Methacrylic Acid from Propionic Acid Methyl Propionate from Ethylene, Carbon Monoxide, andmethanol Methyl Methacrylate from Methyl Propionate Methylal Production PrOCe88 De8criptiOn Revised Economic Evaluation Capital co8t Production CO8t METHYL METHACRYLATE FROM PROPYLENE VIA ISOBUTYRIC ACID OR METRYLISOBUTYRATF, Review of Patent Manufacture of Ieobutyric Acid Route8 from Propylene to 18Obutyric Acid Other ROUte8 to Isobutyric Acid Dehydrogeuation of Isobutyric Acid to Methacrylic Acid Manufacture of Methyl Isobutyrate V

7 CONTENTS Methyl Isobutyrate Dehydrogenation to Methyl Methacrylate Combined Carbonylation and Dehydrogenation Production of Methacrylic Acid via alpha-hydroxy- Isobutyric Acid; Production of Methyl Methacrylate via Methyl alpha-hydroxy-isobutyrate Dehydration of alpha-hydroxy-isobutyric Acid to Methacrylic Acid Dehydration of Methyl alpha-hydroxy-isobutyrate to Methyl Methacrylate Formation of alpha-hydroxy-isobutyrlc Acid Formation of Methyl alpha-hydroxy-isobutyrate Production of Methacrylic Acid via beta-hydroxy- Isobutyric Acid boce88 Description Dehydrogenation of Isobutyric Acid to Methacrylic Acid Esterification of Methacrylic Acid with Methanol PrOCe88 Di8CU88iOIl Dehydrogenation of 18obutyric Acid to Methacrylic Acid Reactor Design PolymerFormation Methacrylic Acid Storage Waste Stream Material8 of Construction CO8t E8tilllde Capital CO8t Production Costs of Methyl Methacrylate Production Costs of Isobutyric Acid METHYL METHACRYLATE FROM PROPYLENE BY OTHER ROUTES Acetone Cyanohydrin Route Process Review Process Description Preparation of Acetone Cyanohydrin HydrOly8i8 of Acetone Cyanohydrin Esterification of Methacrylamide Sulfate Recovery and Purification of Methyl Methacrylate PrOCe88 Di8cU88iOn Preparation of Acetone Cyanohydrin HydrOly8i8 of Acetone Cyanohydrin Esterification of Methacrylamide Sulfate Recovery and Purification of Methyl Methacrylate vi

8 CONTENTS co8t Estimates... Route8 via Isobutyraldehyde... Methacrolein from Isobutyraldehyde (1)... Isobutyrlc Acid from Isobutyraldehyde (2)... Methyl Isobutyrate from Isobutyraldehyde (3)... Methacrylic Acid from Isobutyraldehyde (4)... Methacrylic Acid from Ally1 Acetate... Hydroformylation of Ally1 Acetate... Oxidation of Mixed Aldehydes... Vapor-Phase Deacetoxylation... Economic Evaluation... Methyl Methacrylate from Methylacetylene METHYL METHACRYLATE FROM ISOBUTYLENE BY OTHER ROUTES... Methyl Methacrylate from Methacrylonltrile... Methacrylonitrile from Isobutylene... Methacrylamide Sulfate from Methacrylonltrile (1)... Methacrylamide Sulfate from a Methacrylonitrile-Acetone Cyanohydrin Mixture... Methyl Methacrylate from Methacrylamide Sulfate (2)... Methacrylonitrile Hydrolysie to Methacrylic Acid (3).. Methacrylonitrlle HydrOly818 to Methyl Methacrylate (4). Methacrylamide from Methacrylonitrile (5)... Methyl Methacrylate from Methacrylamide (6)... Methacrylic Acid from Methacrylamide (7)... Miscellaneous Route8 from Isobutylene to Methyl Methacrylate... Methyl Methacrylate from Methyl t-butyl Ether... Methyl Methacrylate via Methyl Pivalate... Methyl Methacrylate via Methallyl Acetate and Diacetoxyisobutylene... Methacrylic Acid via Isobutylene Glycol and alpha-hydroxy- Isobutyric Acid... Isobutyric Acid from Isobutylene METHYL METHACRYLATE FROMMATERIALS OTHER THAN ETHYLENE, PROPYLENE, OR ISOBUTYLENE... APPENDIXA DESIGN AND COST BASES... APPENDIX B CONVERSION, SELECTIVITY, AND YIELD vii

9 CONTENTS APPENDIX C AZEOTROPES CITED REFERENCES PATENT REFERENCES BY COMPANY Viii

10 ILLUSTRATIONS 2.1 Manufacture of Methyl Methacrylate Effect of Plant Capacity on Total Fixed Capital Route8 to Methacrolein From C4 Fraction Route8 to Methyl Methacrylate and Methacrylic Acid from Propylene Route8 to Methyl Methacrylate and Methacrylic Acid from Ethylene METHYL METEACRYlATE FROM ISOBUTYLENE VIA METHACROLEIN 5.1 Process Flow Diagram Effect of Raw Material Price8 on Production Cost Effect of Operating Level and Plant Capacity on Production Cost METRYL METRACRYWl!E FROM t-butanol 6.1 Procees Flow Diagram Effect of Raw Material Price8 on Production Cost Effect of Operating Level and Plant Capacity on Production Cost METHYL METHACRYLATE FROMMIXED BUTYLENES 7.1 Process Flow Diagram Effect of Raw Material Price8 and Butadiene Credit on Production Cost Effect of Operating Level and Plant Capacity on Production Coet METHYL METBACRYLATE FRCM ETHYLENE VIA METRYL PROPIONATE 8.1 Effect of Raw Material Price8 on Production Cost Effect of Operating Level and Plant Capacity on Production Cost ix

11 ILLUSTRATIONS METHYL METBACRYLATE FROM ISOBUTYRIC ACID 9.1 Process Flow Diagram Effect of Raw Material Price8 on Production Cost Effect of Operating Level and Plant Capacity on Production Cost METHYL METHACRYLATE FROM ACETONE VIA ACETONE CYANOHYDRIN 10.1 Process Flow Diagram Effect of Raw Material Price8 and Ammonium Bisulfate Credit on Production Cost Effect of Operating Level and Plant Capacity on Production Cost X

12 TABLES 2.1 Summary of Cost Estimate8 for Methyl Methacrylate Manufacture METRYL METHACRYLATE PRODUCERS 3.1 United State Weetern Europe Japan Other Countries Vapor-Phase Oxidation of Ieobutylene to Methacrolein Summary of Selected Patent8 on Catalysts Methacrolein Recovery Patent Summary Vapor-Phaee Oxidation of Methacrolein to Methacryllc Acid Summary of Selected Patent8 on Catalysts Methacrylic Acid Recovery Patent Summary E8terifiCatiOn of Methacrylic Acid with Methanol PatentSummary Oxidation of Isobutylene to Methacrylic Acid in One Step PatentSummary Oxidation/Esterification of Methacrolein to Methyl Methacrylate PatentSummary METBYL METHACRYLATE FROM ISOBUTYLENE VIA METBACROLEIN 5.8 Bases and A88UmptiOn Major Equipment Utilities Summary StreamFlows Xi

13 TABLES METBYL METBACRYLATF, FROM ISOBUTYLENE VIA METRACROLEIN 5.12 WasteStreams Capital Investment Major Capital Equipment Costs Production Cost Production Costs of Methacrylic Acid Vapor-Phase Oxidation of t-butanol to Methacrolein PatentSummary METRYL METRACRYlXTE FROM t-butanol VIA METBACROLEIN AND METRACRTLIC ACID Bases and A88UmptiOn Major Equipment Utilities Summaries StreamFlOW Waste Stream8 from Section Capital Investment Major Capital Equipment Costs Production CO8t Oxidation of Mixed Butylenes to Methacrolein and Butadiene PatentSummary METRYL METBACRTLATE FROM MIXED BUTYLENES 7.2 Base8 and Assumption Major Equipment Utilities summary StreamFlows Waste Stream8 from Section Capital Investment xii

14 TABLES 7.8 Major Capital Equipment Costs Production Cost Methyl Propionate from Ethylene, Carbon Monoxide, and Methanol Patent Summary Methyl Methacrylate from Methyl Propionate Patent Summary METRYL METHACRYLATE FRCR4 ETRYLENE VIA METRYL PROPIONATF, 8.3 Base8 and h38wlption Capital Investment Major Capital Equipment Cost Production Costs Dehydrogenation of Isobutyric Acid to Methacrylic Acid PatentSummary i Methyl Ieobutyrate Production by Propylene Carboxylation PatentSummary Dehydrogenation of Methyl Isobutyrate to Methyl Methacrylate Patentsummary METRYL METBACRYLATE FROM ISOBUTYRIC ACID k8e8 and A88mption8... Major Equipment... Utilities Summary... StreamFlows... Waete Streams... Capital Investment... Major Capital Equipment Cost8... Production CO8t Xiii

15 TABLES ISOBUTYRIC ACID FROM PROPYLENE 9.12 h8e8 alld h8ulllptioll Production CO8t ME- METBACRYLATE FROM ACETONE VIA ACETONE CYANOHYDRIN 10.1 Summary of Recent Patent b8e8 audhsulllptioll Production CO8t Methacrolein from Isobutyraldehyde Patent&mazy Isobutyric Acid from Ieobutyraldehyde PatentSummary Mawfacture of Methacrylonitrile Patent Sufmuary Miscellaneous Processes Patentsummrary xiv