How To Make Formic Acid

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1 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Abstract Process Economics Program Report No. 156 FORMIC ACID (August 1983) Worldwide production of formic acid is about 200,000 metric tons/yr at present, It is used in the United States in applications partly dependent on its strong acidity (textile dyeing, tanning, and leather treating) and partly on its other chemical properties (chemical synthesis and pharmaceuticals). In Europe, use as a silage preservative is also important. Formic acid is produced in conjunction with other chemical operations--in the United States as a by-product of acetic acid manufacture by butane oxidation, and in Europe as a coproduct in the manufacture of formamide. A primary formic acid process is considered likely to become the main formic source in the future. Interest at present appears centered on a two-step procedure: reaction of methanol and carbon monoxide to form methyl formate, followed by hydrolysis to give formic acid and methanol, the latter being recycled. Three versions of this process are described and evaluated in this report, the versions being based on patents of the Leonard Process Company, BASF, and the Halcon/Scientific Design/Bethlehem Steel group. In our evaluations, the three processes all use an identical methanol carbonylation operation, but differ in the hydrolysis and' product recovery step. As might be expected, the three technologies give product values within a couple of cents per lb of each other. The methanol carbonylation economics appear potentially superior to those of the butane oxidation process. PEP'81 RH/HWS

(textile dyeing, tanning, and leather treating) and partly on its other chemical properties (chemical synthesis and pharmaceuticals). In Europe, use as a silage preservative is also important.

2 Report No. 156 FORMIC ACID by ROBERT HOCH HAROLD W. SCHEELINE I I a cl m A private report by the August 1903 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. most major chemicals The CHEMICAL ECONOMICS HANDBOOK Program covers and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hidrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe. ii

PETROCHEMICALS Program covers major hidrocarbons and their derivatives on a worldwide basis.

4 CONTENTS 1 INTRODUCTION SUMMARY...,... 3 PROCESS CHEMISTRY... Historical Background... ;... Methanol Carbonylation.... Hydrolysis.... Reaction Rate... Back-Esterification... Hydrolysis Conversion... Formic Acid Dehydration... Other Processes... 4 INDUSTRY STATUS AND TRENDS.... Properties and Uses... Acid Strength... Unique Chemistry.... Other Uses... Demand... Existing Uses... Proposed Uses... Relative Demand for Glacial and Azeotropic Formic Acid... Supply... Effect of New Technology on Supply Pattern DESIGN BASIS Feed and Product Specifications... Methanol Carbonylation Discussion of Hydrolysis Design Basis Leonard Hydrolysis BASF Hydrolysis Halcon/SD Hydrolysis Materials of Construction PROCESS DESCRIPTION... Carbonylation Step.... Leonard Process... BASF Process.... Halcon/SD Process iii

.. Existing Uses... Proposed Uses... Relative Demand for Glacial and Azeotropic Formic Acid... Supply... Effect of New Technology on Supply Pattern.... 5 DESIGN BASIS.......... Feed and Product Specifications.

5 CONTENTS 7 COMPARISONS OF PROCESS ECONOMICS Comparison of Carbonylation/Hydrolysis Economics Economic Comparison with Existing Butane Oxidation APPENDIX A APPENDIX B APPENDIX C APPENDIX D APPENDIX E APPENDIX F APPENDIX G EFFECT OF PRESSURE ON FORMIC ACID-WATER AZEOTROPE COMPOSITION EQUIVALENCE OF FORMIC ACID TO MINERAL ACIDS... ph OF FORMIC ACID SOLUTIONS..., POTENTIAL MARKET FOR FORMIC ACID AS NATURAL RUBBER LATEX CQAGULANT "OPTIMIZATION" OF HYDROLYSIS WITHOUT VAPOR REUSE... "OPTIMIZATION" OF HYDROLYSIS WITH VAPOR REUSE... ECONOMICS OF ACETIC ACID BY LOW PRESSURE CARBONYLATION OF METHANOL CITED REFERENCES... PATENT REFERENCES

............. EQUIVALENCE OF FORMIC ACID TO MINERAL ACIDS... ph OF FORMIC ACID SOLUTIONS...,....... POTENTIAL MARKET FOR FORMIC ACID AS NATURAL RUBBER LATEX CQAGULANT.

6 ILLUSTRATIONS 6.1 Formic Acid by Leonard Process Flow sheet Formic Acid by BASF Process Flow sheet Formic Acid by Halcon/SD/Bethlehem Process Flow sheet Effect of CO Cost on Product Value of Formic Acid Acetic Acid by Butane Oxidation Effect of Formic Acid Credit on Product Value of Acetic Acid , , V

3 Formic Acid by Halcon/SD/Bethlehem Process Flow sheet... 131 7.

7 TABLES A Summary of Formic Acid Economics... Carbonylation of Methanol to Methyl Formate Summary of Selected Patents.... Hydrolysis Patents Summary of Selected Patents.... Formic Acid Extraction and Concentration Summary of Selected Patents.... Methanol Dehydrogenation Summary of Selected Patents.... U.S. Consumption Pattern for Formic Acid in U.S. Producers of Formic Acid.... Formic Acid Producers in Western Europe.... Distribution of Formic Capacity by Process... Design Conditions for Carbonylation.... Comparison of Hydrolysis Processes... Design Conditions for Hydrolysis--Leonard.... Design Conditions for Hydrolysis--BASF... Design Conditions for Hydrolysis--Halcon/SD.... Formic Acid by Leonard Process Stream Flows... Formic Acid by Leonard Process Major Equipment... Formic Acid by Leonard Process Total Capital Investment... Formic Acid by Leonard Process Production Costs... Formic Acid by BASF Process Stream Flows... Formic Acid by BASF Process Major Equipment and Utilities Summary.... Formic Acid by BASF Process--75 Percent Case Total Capital Investment... Formic Acid by BASF Process--85 Percent Case Total Capital Investment... Vii

... Methanol Dehydrogenation Summary of Selected Patents.... U.S. Consumption Pattern for Formic Acid in 1979... U.S. Producers of Formic Acid.... Formic Acid Producers in Western Europe.

8 TABLES A Formic Acid by BASF Process--75 Percent Case Production Costs.., Formic Acid by BASF Process--85 Percent Case Production Costs Formic Acid by Halcon/SD/Bethlehem Process Stream Flows Formic Acid by Halcon/SD Process Major Equipment Formic Acid by Halcon/SD Process Total Capital Investment Formic Acid by Halcon/SD Process Production Costs Comparison of Formic Acid Economics Effect of Scale on Product Value of Formic Acid Acetic Acid by Butane Oxidation Variable Costs viii

.. 88 Formic Acid by Halcon/SD Process Major Equipment... 89 Formic Acid by Halcon/SD Process Total Capital Investment.

FURNACEPHOSPHORUS AND PHOSPHORICACID PROCESS ECONOMICS PROGRAM. Report No. 52. July 1969. A private report by. the

Report No. 52 FURNACEPHOSPHORUS AND PHOSPHORICACID by GEORGE E. HADDELAND July 1969 A private report by. the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA CONTENTS 1 INTRODUCTION........................