Ammonia

92-5 May 1994

CONTENTS Page

I II

SUMMARY COMMERCIAL TECHNOLOGY A. INTRODUCTION B. AMMONIA FROM NATURAL GAS: CHEMISTRY AND TECHNOLOGY C. LICENSOR REVIEW 1. UHDE (a) Steam Reforming and Carbon Monoxide Shift (b) Carbon Dioxide Removal and Methanation (c) Ammonia Synthesis and Hydrogen Recovery (d) Steam System (e) Special Features (1) Reformer (2) The Secondary Reformer (3) Methanol Converter 2. M.W. Kellogg (a) Raw Synthesis Gas Preparation (b) Synthesis Gas Purification (c) Purified Synthesis Gas Compression and Ammonia Synthesis (d) Hydrogen Recovery Unit (e) Special Features (1) Combustion Air Preheat (2) Reforming and Heat Recovery (3) Shift Conversion (4) Molecular Sieves (5) Horizontal Ammonia Converter (6) Unitized Exchanger (7) Four-Level Refrigeration System (8) Steam System/Energy Cycle

1 8 8 8 9 12 12 16 20 23 25 25 28 29 30 30 33 35 37 38 38 39 40 40 41 41 42 42

3.

4.

5. 6. D.

(9) Construction Materials Haldor Topse (a) Gas Preparation (b) Shift Conversion and Gas Purification (c) Synthesis (d) Ammonia Plant Optimization Brown & Root Braun Purifier Process (a) Feed Desulfurization (b) Primary Reforming (c) Secondary Reforming (d) Shift Conversion (e) Carbon Dioxide Removal (f) Methanation (g) Drying (h) Cryogenic Purification (i) Compression (j) Ammonia Synthesis (k) Converter Effluent Cooling (l) Inert Gases (m) Ammonia Absorber and Stripper (n) Refrigeration and Product Separation (o) Process Condensate Stripper (p) Steam System (q) Special Features (1) Mild Reforming (2) Cryogenic Purifier (3) Adiabatic Converters (4) Hydrogen Recovery (5) Gas Turbine Carbon Dioxide Removal Licensors Economics

43 45 45 46 48 48 50 50 50 51 52 52 52 53 53 54 54 55 55 55 55 56 56 57 57 57 58 58 58 59 60 63 63 64 64

NONFIRED PRIMARY REFORMER 1. Process Choice 2. Process Description 3. Economics

III

NEW DEVELOPMENTS A. BACKGROUND B. ADVANCED PROCESS CONTROL C. KELLOGG REFORMING EXCHANGER SYSTEM D. BROWN & ROOT BRAUN TANDEM REFORMER E. UHDE COMBINED AUTOTHERMIC REFORMER F. KELLOGG ADVANCED AMMONIA PROCESS G. ADIABATIC PRECONVERSION (PREREFORMING) PLANT MODERNIZATION A. INTRODUCTION B. HIGHER EFFICIENCY CONVERTERS 1. Ammonia Casale 2. Haldor Topse 3. M.W. Kellogg C. REFORMER DESIGN D. STEAM TO CARBON RATIO E. MODIFICATION OF SHIFT UNIT F. REFORMER TUBES G. MOLECULAR SIEVE DRYER H. COMBUSTION AIR PRODUCT I. NATURAL GAS FEEDSTOCK SATURATOR J. CARBON DIOXIDE REMOVAL K. PURGE GAS TREATMENT L. METHANOLATION COMMERCIAL STATUS A. GLOBAL OVERVIEW 1. Nitrogen Fertilizers (a) Urea (b) Ammonium Nitrate (c) Ammonium Phosphates B. UNITED STATES 1. Demand (a) Urea (b) Ammonium Nitrate (c) Ammonium Phosphates C. WESTERN EUROPE

66 66 66 68 74 75 75 83 85 85 86 87 89 89 91 91 92 92 95 95 95 96 100 100 102 102 105 108 111 115 116 116 120 123 124 124

IV

D.

Demand (a) Urea (b) Ammonium Nitrate (c) Ammonium Phosphates SUPPLY

1.

124 125 126 127 128 144

REFERENCES

TABLES Page
Table I.1 Table I.2 Table I.3 Table I.4 Table I.5 Table I.6 Table II.A.1 Table II.C.1 Table II.C.2 Table II.C.3 Table II.C.4 Table II.C.5 Table II.C.6 Table II.C.7 Table II.D.1 World Ammonia Capacity by Feedstock, 1990 Global Ammonia Net Trade Global Ammonia Demand Global Ammonia Capacity Global Fertilizer Urea Demand Global Fertilizer Ammonium Nitrate Demand Global Ammonia Capacity by Feedstock, 1990 Development of Ammonia Plant Energy Consumption Number and Capacity of Ammonia Plants UHDE Low-Energy Technology Process: Analysis of Synthesis Gas after Methanation Topse Experience as Technology Supplier of Ammonia Plants Options in Shift Conversion Design Various Major Carbon Dioxide Removal Processes Cost Estimate of Ammonia (Anhydrous Liquid) Production: UHDE Low-Energy Technology Cost Estimate of Ammonia (Anhydrous Liquid) Production: ICI LCA Process Feed and Energy Uses in Conventional and KAAP Process Plants Capital Costs of Various Ammonia-Producing Plants Approximate Energy Savings in Revamping Options Designs Available for Converter Retrofitting Creep-to-Rupture Strength Ammonia Plant Improvement Ideas Global Ammonia Supply/Demand Balance Global Ammonia Net Trade Global Ammonia Demand Global Ammonia Capacity 1 5 5 6 6 7 8 10 11 19 45 47 61 62 65

Table III.F.1 Table III.F.2 Table IV.A.1 Table IV.B.1 Table IV.F.1 Table IV.J.1 Table V.A.1 Table V.A.2 Table V.A.3 Table V.A.4

82 83 86 88 95 99 103 104 104 105

Table V.A.5 Table V.A.6 Table V.A.7 Table V.A.8 Table V.A.9 Table V.A.10 Table V.A.11 Table V.A.12 Table V.A.13 Table V.A.14 Table V.A.15 Table V.A.16 Table V.A.17 Table V.A.18 Table V.B.1 Table V.B.2 Table V.B.3 Table V.B.4 Table V.B.5 Table V.B.6 Table V.C.1 Table V.C.2 Table V.C.3 Table V.D.1 Table V.D.2 Table V.D.3 Table V.D.4 Table V.D.5 Table V.D.6 Table V.D.7 Table V.D.8

Global Nitrogen Fertilizer Demand Global Nitrogen Fertilizer Capacity Global Nitrogen Fertilizer Supply/Demand Balance Global Nitrogen Fertilizer Net Trade Global Fertilizer Urea Demand Global Fertilizer Urea Capacity Global Urea Supply/Demand Balance Global Urea Net Trade Global Fertilizer Ammonium Nitrate Demand Global Fertilizer Ammonium Nitrate Capacity Global Ammonium Nitrate Supply/Demand Balance Global Fertilizer Ammonium Nitrate Net Trade Global Ammonium Phosphate Net Trade Global Ammonium Phosphate Capacity U.S. Ammonia End-Use Breakdown U.S. Ammonia and Nitrogen Fertilizer Supply/Demand Balance U.S. Urea End-Use Breakdown U.S. Urea Demand U.S. Ammonium Nitrate End-Use Breakdown U.S. Ammonium Nitrate Demand West European Urea Supply/Demand Balance West European Ammonium Supply/Demand Balance West European Ammonium Phosphate Supply/Demand Balance U.S. Ammonia Capacity, 1993 Canadian Ammonia Capacity, 1993 West European Ammonia Capacity, 1993 Latin American Ammonia Capacity, 1993 East European Ammonia Capacity, 1993 Asian/Pacific Ammonia Capacity, 1993 African Ammonia Capacity, 1993 Middle Eastern Ammonia Capacity, 1993

106 107 107 108 110 110 111 111 113 113 114 114 115 116 116 119 120 122 123 124 125 126 128 129-130 131 132-133 134 135-137 138-141 142 143

FIGURES Page
Figure II.C.1 Figure II.C.2 Figure II.C.3 Figure II.C.4 Figure II.C.5 Figure II.C.6 Figure II.C.7 Figure II.C.8 Figure II.C.9 Figure II.C.10 Figure II.C.11 Figure III.B.1 Figure III.C.1 Figure III.C.2 Figure III.C.3 Figure III.F.1 Figure III.F.2 Figure III.F.3 Figure IV.B.1 Figure V.B.1 Figure V.B.2 UHDE Ammonia Plant's Low-Energy Technology Steam Reformer and Carbon Monoxide Shift of UHDE's Low-Energy Technology Carbon Dioxide Removal and Methanation of UHDE's Low-Energy Technology Ammonia Synthesis and Hydrogen Recovery of UHDE's Low-Energy Technology UHDE's Ammonia Synthesis Main Features of Steam System of UHDE's Low-Energy Technology UHDE's Reformer Radiant Section Typical Radiant Section of Kellogg's Box-Type Steam Reforming Furnace Kellogg's Horizontal Intercooled Ammonia Converter Kellogg's Simplified Ammonia Plant Steam Balance Topse's S-300 Converter Advanced Process Control Strategies Reforming Exchanger Schematic Diagram Kellogg's Open Tube Reforming Exchanger Autothermal Reformer Ocelot/KAAP Retrofit Ocelot/KAAP Reactor Design KAAP Grass-Roots Synthesis Loop Mechanical Lay-out of In Situ S-200 Converter U.S. Nitrogen Demand U.S. Urea Supply and Demand 13 14 18 21 22 24 26 32 36 44 49 67 69 71 73 77 79 81 90 118 121