Abstract Process Economics Program Report 37C ACETIC ACID (December 2001)

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1 Abstract Process Economics Program Report 37C ACETIC ACID (December 2001) This report appraises the current commercially dominant methanol carbonylation technologies for acetic acid production based on the recent developments in catalyst technology. In addition, two alternate but comparatively newer technologies employing the oxidation of hydrocarbons (ethylene and ethane) are evaluated. The following technologies are dealt with: BP Cativa TM technology. Celanese Acid Optimization (AO) technology. Showa Denko Single-step Ethylene Oxidation technology. SABIC (Saudi Basic Industries Corporation) Ethane Oxydehydrogenation technology. BP s Cativa TM, a methyl carbonylation technology, is an improved version of the original Monsanto s rhodium catalyzed acetic acid technology which BP inherited from Monsanto in Instead of rhodium, Cativa TM employs BP s proprietary iridium (and iodides) based promoted catalyst. The new catalyst offers a higher reactivity, increased catalyst stability, reduced byproducts and lower energy consumption in product purification as compared to original rhodium catalysts. Celanese also originally licensed the acetic acid technology from Monsanto in the late 1970s. But now it is the sole owner. The AO technology is a result of a number of improvements and optimizations in the original Monsanto technology. AO technology is founded on proprietary rhodium (and iodide) based catalyst materials, which impart a high stability to the catalyst system permitting carbonylation at lower water concentrations. Some catalyst formulations use iridium in combination with rhodium. By-product formation is much reduced and optimized purification methodologies result in increased product purity. From the capital investment viewpoint, Celanese, as our estimates indicate, has a slightly higher capital intensity than that of BP. SD s (Showa Denko s) ethylene route to acetic acid makes acetic acid production independent of methanol and carbon monoxide (CO). This process, which offers capability for a singlestep ethylene conversion to acetic acid, is a more cost effective variance of the conventional twostep ethylene oxidation process (via acetaldehyde). The (palladium catalyzed) process is useful at small capacities to meet local requirement of acid. However, its economics are not comparable with those of methyl carbonylation technology. SABIC s (molybdenum, vanadium and niobium/palladium/lanthanum catalyzed) ethane based route to acetic acid is another alternative technology for acetic acid which is being tested for commercialization. Like SD, this technology may offer cost effective means for acid production for regionalized demand. The technology has not been yet demonstrated even on a semi commercial scale and bears of all kinds uncertainties typical to a new process. Ethylene and CO 2 are PEP 01 SNN

2 the major by-products. CO 2 may be an environmental concern if it does not find an end user. Ethylene and acetic acid production need to be balanced according to their demand. PEP 01 SNN

3 R eport No. 37C A C E T IC A C ID by S Y E D N. NA QV I Dec ember 2001 A private report by the P R OC E S S E C ONOMIC S P R OG R A M S R I Menlo P ark, C alifornia Subsidiary of SRI International

4 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by SRIC pursuant to this agreement For detailed marketing data and information, the reader is referred to one of the SRI Consulting 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 SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

5 CONTENTS 1 INTRODUCTION SUMMARY OVERVIEW Industry Status Technology Status TECHNOLOGIES BP CATIVA TM TECHNOLOGY FOR ACETIC ACID CELANESE TECHNOLOGY FOR ACETIC ACID SHOWA DENKO ONE-STEP ETHYLENE OXIDATION PROCESS FOR ACEDIC ACID SABIC ETHANE OXIDATION PROCESS FOR ACETIC ACID PROCESS ECONOMICS Methanol carbonylation (BP's Cativa TM versus Celanese Acid Optimization) C 2 Hydrocarbons Oxidation (SD's Ethylene-versus SABIC's Ethane-based Oxidation) INDUSTRY STATUS WORLD CAPACITIES GLOBAL PRODUCTION / CONSUMPTION BP CATIVA TM TECHNOLOGY FOR ACETIC ACID TECHNOLOGY REVIEW Carbonylation Rate Catalyst System Reaction & Reaction Conditions By-products/Impurities Products Separation PROCESS DESCRIPTION iii

6 CONTENTS (Continued) Section Methanol Carbonylation Section Product Purification PROCESS DISCUSSION Design Conditions Catalyst Reactor By-Product Steam Gas Scrubbing Product Purification Materials of Construction Process Waste Effluents COST ESTIMATES Fixed - Capital Costs Production Costs CELANESE TECHNOLOGY FOR ACETIC ACID TECHNOLOGY REVIEW Catalyst System Carbonylation Rate Carbonylation Conditions Main Reactions By-products Products Purification PROCESS DESCRIPTION Section Methanol Carbonylation Section Product Purification PROCESS DISCUSSION Design Conditions iv

7 CONTENTS (Continued) Catalyst Reactor By-Product Steam Gas Scrubbing Product Purification Materials of Construction Process Waste Effluents COST ESTIMATES Fixed - Capital Costs Production Costs SHOWA-DENKO ONE-STEP ETHYLENE OXIDATION PROCESS FOR ACETIC ACID TECHNOLOGY REVIEW Catalyst System Reaction Mechanism Oxidation Conditions By-products Product Purification PROCESS DESCRIPTION Section Ethylene Oxidation Section Acid Purification PROCESS DISCUSSION Design Conditions Catalyst Reactor By-product Steam Product Purification v

8 CONTENTS (Continued) Materials of Construction Process Waste Effluents COST ESTIMATES Fixed - Capital Costs Production Costs SABIC ETHANE OXIDATION PROCESS FOR ACETIC ACID TECHNOLOGY REVIEW Catalyst System Major Reactions Oxidation Conditions By-products Product Purification PROCESS DESCRIPTION Section Ethane Oxidation Section Acid Purification PROCESS DISCUSSION Selection of Process Design Feed Catalyst Reactor By-product Steam Product Purification Materials of Construction Process Waste Effluents COST ESTIMATES Fixed - Capital Costs Production Costs vi

9 CONTENTS (Concluded) APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAM... E-1 vii

10 ILLUSTRATIONS 4.1 BP Cativa TM Technology for Acetic Acid Process Flow Diagram... E-3 4.2A BP Cativa TM Technology for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Methanol Price (Co Price Unchanged) for Base Capacity Plant B BP Cativa TM Technology for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Co Price (Methanol Price Unchanged ) for Base Capacity Plant BP Cativa TM Technology for Acetic Acid Effect of Operating Level and Plant Capacity on Product Value of Acetic Acid Celanese Technology for Acetic Acid Process Flow Diagram... E-5 5.2A Celanese Technology for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Methanol Price (at Constant Co Price) for Base Capacity Plant B Celanese Technology for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Carbon Monoxide Price (at Constant Methanol Price) for Base Capacity Plant Celanese Technology for Acetic Acid Effect of Operating Level and Plant Capacity on Product Value of Acetic Acid Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Process Flow Diagram... E Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Ethylene Price for Base Capacity Plant Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Effect of operating Level and Plant Capacity on Product Value of Acetic Acid Sabic Ethane Oxidation Process for Acetic Acid Process Flow Diagram... E Sabic Ethane Oxidation Process for Acetic Acid Production Costs and Product Value of Acetic Acid as a Function of Ethylene Price for Base Capacity Plant Sabic Ethane Oxidation Process for Acetic Acid Effect of Operating Level and Plant Capacity on Product Value of Acetic Acid viii

11 TABLES 2.1 Methanol Carbonylation Technologies Total Capital Investment Methanol Carbonylation Technologies Production Costs C 2 Hydrocarbons Oxidation Technologies Total Capital Investment C 2 Hydrocarbons Oxidation Technologies Production Costs Cativa TM, Acid Optimization & Ethane-Oxidation Technologies Total Fixed Costs Cativa TM, Acid Optimization & Ethane-Oxidation Technologies Production Costs Virgin Acetic Acid Producers Supply/Demand Summary for Acetic Acid by Acetic Acid-Producing Region a Consumption of Acetic Acid by Product Projected Demand of Acetic Acid by Major Product BP Cativa TM Technology for Acetic Acid Patent Summary... A BP Cativa TM Technology for Acetic Acid Design Bases and Assumptions BP Cativa TM Technology for Acetic Acid Stream Flows BP Cativa TM Technology for Acetic Acid Major Equipment BP Cativa TM Technology for Acetic Acid Utilities Summary BP Cativa TM Technology for Acetic Acid Total Capital Investment BP Cativa TM Technology for Acetic Acid Capital Investment by Section BP Cativa TM Technology for Acetic Acid Production Costs ix

12 TABLES (Continued) 5.1 Celanese Technology for Acetic Acid Patent Summary... A Celanese Technology for Acetic Acid Design Bases and Assumptions Celanese Technology for Acetic Acid Stream Flows Celanese Technology for Acetic Acid Major Equipment Celanese Technology for Acetic Acid Utilities Summary Celanese Technology for Acetic Acid Total Capital Investment Celanese Technology for Acetic Acid Capital Investment by Section Celanese Technology for Acetic Acid Production Costs Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Patent Summary... A Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Design Bases and Assumptions Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Stream Flows Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Major Equipment Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Utilities Summary Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Total Capital Investment Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Capital Investment by Section Showa Denko One-Step Ethylene Oxidation Process for Acetic Acid Production Costs Sabic Ethane Oxidation Process for Acetic Acid Patent summary... A-18 x

13 TABLES (Continued) 7.2 Sabic Ethane Oxidation Process for Acetic Acid Design Bases and Assumptions Sabic Ethane Oxidation Process for Acetic Acid Stream Flows Sabic Ethane Oxidation Process for Acetic Acid Major Equipment Sabic Ethane Oxidation Process for Acetic Acid Utilities Summary Sabic Ethane Oxidation Process for Acetic Acid Total Capital Investment Sabic Ethane Oxidation Process for Acetic Acid Capital Investment by Section Sabic Ethane Oxidation Process for Acetic Acid Production Costs xi

Abstract Process Economics Program Report 36E LINEAR LOW DENSITY POLYETHYLENE (August 2008)

Abstract Process Economics Program Report 36E LINEAR LOW DENSITY POLYETHYLENE (August 2008) Abstract Economics Program Report 36E LINEAR LOW DENSITY POLYETHYLENE (August 2008) LLDPE has established itself as the third major member of the global polyethylene business along with LDPE and HDPE.