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Ammonia

97/98-6 August 1998

TABLE OF CONTENTS

Page I SUMMARY A. B. INTRODUCTION COMMERCIALLY AVAILABLE AMMONIA PROCESS TECHNOLOGY 1. Brown & Root Braun Purifier Process 2. Haldor Topsoe Low Energy Ammonia Process 3. ICI Katalco (a) ICI-AMV Process (b) ICI-LCA Process 4. Linde Ammonia Concept (LACTM) 5. M.W. Kellogg Kres-KAAP Process 6. UHDE Low Energy Technology COST OF PRODUCTION GLOBAL MARKET OVERVIEW 1. Demand 2. Supply 3. Trade 1 1 2 2 5 5 5 5 6 6 7 8 8 8 11 13 16 16 16 17 19 20 21 21 21 22 22 25 27

C. D.

II

CHEMISTRY AND TECHNOLOGY A. B. AMMONIA PROPERTIES OVERALL PROCESS DESCRIPTION 1. Feedstocks for Ammonia Synthesis 2. Hydrogen Production 3. Synthesis Gas Purification 4. Ammonia Synthesis GENERIC PROCESS REVIEW 1. Natural Gas Purification 2. Syngas Production (a) Steam Reforming (b) Partial Oxidation (c) Byproduct Hydrogen Rich Streams

C.

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TABLE OF CONTENTS (Continued)

Page Syngas Purification (a) Shift Conversion (b) Removal of Carbon Dioxide (1) Methyldiethanolamine (MDEA) (2) Potassium Carbonate (c) Removal of Residual Carbon Oxides by Methanation (d) Dehydration (e) Cryogenic Separation 4. Ammonia Synthesis and Separation (a) Catalyst and Reaction Heat (b) Kinetics and Equilibrium Considerations (c) Operating Pressure (d) Synthesis Converters and Loop (e) Purge Gas THERMAL EFFICIENCY AND ENERGY BALANCE 1. Thermal Efficiency of Ammonia Plants 2. Energy Consumption and Recovery in Ammonia Plants 3. 27 28 29 31 31 32 33 33 33 33 34 35 37 38 38 38 41 44 44 44 44 44 45 45 45 45 47 47 47

D.

III

COMMERCIAL AVAILABLE PROCESS TECHNOLOGY A. BROWN & ROOT BRAUN PURIFIER PROCESS 1. Technology Features (a) Mild Primary Reforming (b) Secondary Reforming with Excess Air (c) Cryogenic Purification Unit 2. Process Description (a) Feed Desulfurization (b) Primary Reforming (c) Secondary Reforming (d) Shift Conversion (e) Carbon Dioxide Removal and Methanation

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TABLE OF CONTENTS (Continued)

Page (f) Drying and Cryogenic Purification (g) Ammonia Synthesis and Recovery HALDOR TOPSOE LOW ENERGY AMMONIA PROCESS 1. Technology Features 2. Process Description (a) Reforming (b) Shift Conversion (c) Gas Purification (d) Synthesis (e) Ammonia Plant Optimization ICI KATALCO 1. ICI-AMV Process (a) Technology Features (b) Process Description (1) Excess Air to the Secondary Reformer (2) Lower Synthesis Loop Pressure (3) Purge Gas Hydrogen Recovery 2. ICI-LCA Process (a) Technology Features (b) Process Description LINDE AMMONIA CONCEPT (LACTM) 1. Technology Features 2. Process Description (a) Desulfurization (b) Primary Reformer (c) Isothermal Shift (d) Pressure Swing Adsorption (PSA) (e) Nitrogen Production (f) Ammonia Synthesis 48 48 49 49 49 49 50 50 50 51 51 51 51 52 52 52 53 53 53 53 54 54 55 55 55 57 57 57 57

B.

C.

D.

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TABLE OF CONTENTS (Continued)

Page E. M.W. KELLOGG KRES-KAAP PROCESS 1. Technology Process (a) KRES Front End (b) KAAP Ammonia Synthesis 2. Process Description (a) Raw Synthesis Gas Preparation and KRES Front End (b) Synthesis Gas Purification (c) Ammonia Synthesis and KAAP Catalyst (d) Ammonia Refrigeration System UHDE LOW ENERGY TECHNOLOGY 1. Technology Features 2. Process Description (a) Steam Reforming and Carbon Monoxide Shift (b) Carbon Dioxide Removal and Methanation (c) Ammonia Synthesis and Hydrogen Recovery RECENT LICENSOR EXPERIENCE 58 58 58 59 59 59 63 63 64 64 64 65 65 67 68 71 74 74 74 74 75 75 75 75 76 76 77 77 82

F.

G. IV

PROCESS ECONOMICS A. COST OF PRODUCTION METHODOLOGY 1. Battery Limits 2. Production Costs (a) Variable Costs (b) Direct Fixed Costs (c) Allocated Fixed Costs (d) Financing AMMONIA COST OF PRODUCTION 1. Capital Cost Data 2. Cost of Production 3. Sensitivity Analysis HISTORICAL AMMONIA PRICING

B.

C.

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Page V NEW DEVELOPMENTS AND PLANT MODERNIZATION A. NEW DEVELOPMENTS AND INDUSTRY TRENDS 1. Heat Exchange Reforming 2. Pre-reforming 3. Shift Catalysts for Low Steam to Carbon Ratios 4. Low Temperature Ammonia Synthesis Catalyst 5. Carbon Dioxide Removal 6. Advanced Process Control 7. Trends in Ammonia Plant Size and Costs REVAMP AND PLANT MODERNIZATION 1. Higher Efficiency Converters 2. Reformer Design (a) Reformer Tubes (b) Steam to Carbon Ratio 3. Modification of Shift Unit 4. Molecular Sieve Dryer 5. Combustion Air Preheat 6. Process Feed Saturator 7. Improved Carbon Dioxide Removal 8. Purge Gas Recovery 9. Methanolation 84 84 84 85 86 86 87 87 88 89 91 92 92 92 93 93 94 94 94 95 95 97 97 97 98 99 101 101 103 105

B.

VI

COMMERCIAL ANALYSIS A. INDUSTRIAL APPLICATIONS 1. Fertilizer Uses and Industrial Applications 2. Nitrogen Fixation - The Nitrogen Cycle 3. Handling, Transportation, and Storage GLOBAL MARKET OVERVIEW 1. Demand 2. Supply 3. Trade

B.

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Page C. NORTH AMERICA 1. United States (a) Demand (b) Supply (c) Trade 2. Canada (a) Demand (b) Supply (c) Trade WESTERN EUROPE 1. Demand 2. Supply 3. Trade EASTERN EUROPE AND THE FORMER SOVIET UNION (FSU) 1. Demand 2. Supply 3 Trade SOUTH AND EAST ASIA 1. China (a) Demand (b) Supply (c) Trade 2. India (a) Demand (b) Supply (c) Trade 3. Indonesia (a) Demand (b) Supply (c) Trade 108 108 108 109 109 109 109 110 110 110 110 111 111 111 111 112 112 113 113 113 115 115 115 115 116 117 117 117 118 118

D.

E.

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Page 4. Japan 5. Other LATIN AMERICA 1. Demand 2. Supply 3. Trade PRODUCING COMPANIES 118 118 119 119 119 120 120 128 129 132

G.

H.

ACKNOWLEDGMENTS REFERENCES PERP TITLE INDEX

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TABLES

Page Table I.A.1 Table I.D.1 Table I.D.2 Table I.D.3 Table II.A.1 Table II.C.1 Table II.C.2 Table II.C.3 Table II.D.1 Table II.D.2 Table II.D.3 Table III.C.1 Table III.G.1 Table IV.B.1 Table V.B.2 Table VI.B.1 Table VI.B.2 Table VI.B.3 Table VI.C.1 Table VI.F.1 Table VI.F.2 Table VI.H.1 Typical Properties of Ammonia Ammonia Demand Summary, 1997-2010 Ammonia Capacity Summary, 1997-2010 Ammonia Net Trade, 1997-2010 Typical Properties of Ammonia Typical Compositions of Byproduction Hydrogen Rich Streams Major Carbon Dioxide Removal Processes Relative Energy Requirements for Bulk Carbon Dioxide Removal Definition of Thermal Input and Credits for Ammonia Plants Cost and Thermal Efficiencies of Ammonia Plants Developments of Ammonia Plant Energy Consumption Typical Reforming Conditions for the ICI AMV Process Ammonia Licensor Experience Data (By Country) Cost Estimate of Ammonia Production Approximate Energy Savings in Revamping Options Ammonia Demand Summary, 1997-2010 Ammonia Capacity Summary, 1997-2010 Ammonia Net Trade, 1997-2010 U.S. Ammonia End Use Breakdown, 1997 Fertilizer Application Rates - China India's and China's Fertilizer Contribution to Food Production Ammonia Capacity Producing Companies, 1998 1 10 12 15 16 27 30 32 39 40 41 52 72 78 91 102 104 107 108 114 116 121-127

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FIGURES

Page Figure I.A.1 Figure I.A.2 Figure I.D.1 Figure I.D.2 Figure I.D.3 Figure I.D.4 Figure II.B.1 Figure II.B.2 Figure II.C.1 Figure III.A.1 Figure III.D.1 Figure III.E.1 Figure III.E.2 Figure III.F.1 Figure III.F.2 Figure III.F.3 Schematic Diagram of Ammonia Plant Based on Natural Gas Feedstock Global Capacity by Feedstock, 1998 World Ammonia Balance, 1995-2010 Global Ammonia Demand, 1995-2010 Global Ammonia Capacity, 1997 Estimated Global Ammonia Net Trade, 1997 Schematic Diagram of Ammonia Plant Based on Natural Gas Feedstock Global Ammonia Capacity by Feedstock, 1998 Equilibrium Concentration on NH3 in Synthesis Brown & Root Braun Purifier - Process Flow Diagram Process Flow Diagram of Linde's Ammonia Concept (LAC) M.W. Kellogg Integrated KAAP/KRES Process Flow Diagram Open Tube Reforming Exchanger UHDE's Low Energy Technology Steam Reformer and Co Shift UHDE's Low Energy Technology CO2 Removal and Methanantion UHDE's Low Energy Technology Ammonia Synthesis and Hydrogen Recovery Net Cost of Ammonia Production Ammonia Prices Compared to Base Case Ammonia Price History, 1987-1997 Development of Ammonia Plant Energy Consumption, 1960s-1990s World Ammonia Balance, 1995-2010 Global Ammonia Demand, 1995-2010 Global Ammonia Capacity, 1997 Estimated Global Ammonia Net Trade, 1997

3 4 9 11 13 14

18 19 36 46 56 60 62 66 69 70 80 81 82

Figure IV.B.1 Figure IV.B.2 Figure IV.C.1 Figure V.B.1

90 101 103 105 106

Figure VI.B.1 Figure VI.B.2 Figure VI.B.3 Figure VI.B.4

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