Abstract Process Economics Program Report 44B ADVANCES IN AMMONIA TECHNOLOGY

(November 2009)

Although fundamental ammonia-manufacturing technologies have not radically changed in the last ten to fifteen years, numerous technological changes and improvements have taken place in processing technologies, aiming for increased energy efficiencies and, of late, for higher capital productivity and improved competitive profit margins from lower operating costs. Most of the above advantages are being achieved through development and implementation of better process conditions and more efficient equipment design.

In the last decade, several improved and more efficient ammonia technologies have already been commercialized worldwide by major licensors including Haldor Topsoe, KBR, Uhde and Ammonia Casale.

This PEP report provides an overview of ammonia technology developments in catalyst, process and hardware technologies since PEP Report 44A, Ammonia, issued in 1980. The report then develops process economics for production from the most common type of ammonia feed-stock, natural gas. The report will also highlight the major hallmarks of the technologies, along with the current commercial picture for the ammonia industry

Detailed technology descriptions and cost analyses of two current-day ammonia technolo-gies, the Uhde Dual Pressure process and the KBR PURIFIERplus process, are presented.

SRIC agrees to assign professionally qualified personnel to the preparation of theProcess Economics Program’s reports and will perform the work in conformance with generallyaccepted professional standards. No other warranties expressed or implied are made. Becausethe reports are of an advisory nature, neither SRIC nor its employees will assume any liability forthe special or consequential damages arising from the Client’s use of the results contained in thereports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employeesharmless from any liability to any third party resulting directly or indirectly from the Client’s use ofthe 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 SRIConsulting programs specializing in marketing research. THE CHEMICAL ECONOMICSHANDBOOK Program covers most major chemicals and chemical products produced in theUnited States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons andtheir derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICALPRODUCERS services provide detailed lists of chemical producers by company, product, andplant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

© SRI Consulting iii PEP Report 44B

CONTENTS

1 INTRODUCTION ........................................................................................................ 1-1

2 SUMMARY ................................................................................................................. 2-1

GENERAL ASPECTS................................................................................................. 2-1

TECHNICAL ASPECTS ............................................................................................. 2-3

Commercial Ammonia Technologies.......................................................................... 2-3

Advances in Ammonia Technologies ......................................................................... 2-4

Feedstock and Fuel .............................................................................................. 2-4

Steam Reforming.................................................................................................. 2-4

CO2 Removal........................................................................................................ 2-5

Synthesis Catalysts and Synthesis Loop ............................................................. 2-5

Capacity................................................................................................................ 2-6

Retrofits ................................................................................................................ 2-6

Coal-based Ammonia Production in China .......................................................... 2-7

CO2 Capture from Combustion Flue Gases for Urea Production........................ 2-7

The Uhde Dual Pressure Technology .................................................................. 2-7

The KBR PURIFIERplus Technology................................................................... 2-7

PROCESS ECONOMICS........................................................................................... 2-8

Uhde Dual Pressure Technology ............................................................................... 2-8

KBR PURIFIERplus Technology ................................................................................ 2-9

CONCLUSIONS ......................................................................................................... 2-11

3 INDUSTRY STATUS.................................................................................................. 3-1

GLOBAL SUPPLY AND DEMAND FOR AMMONIA.................................................. 3-1

Capacity...................................................................................................................... 3-3

Production................................................................................................................... 3-4

Consumption............................................................................................................... 3-6

Ammonia Prices ......................................................................................................... 3-7

Trade .......................................................................................................................... 3-9

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CONTENTS (Continued)

Transportation, Storage, Environmental and Safety Concerns.................................. 3-11

GLOBAL MARKET FOR AMMONIA DERIVATIVES ................................................. 3-12

Nitrogen Fertilizer ....................................................................................................... 3-12

Industrial Uses............................................................................................................ 3-13

UNITED STATES ....................................................................................................... 3-14

Consumption............................................................................................................... 3-16

Direct Application as Fertilizer.............................................................................. 3-18

Chemical Uses ..................................................................................................... 3-19

Other..................................................................................................................... 3-19

Distribution.................................................................................................................. 3-21

Trade .......................................................................................................................... 3-22

CHINA......................................................................................................................... 3-23

Consumption............................................................................................................... 3-25

Urea ...................................................................................................................... 3-25

Ammonium Bicarbonate ....................................................................................... 3-25

Ammonium Chloride ............................................................................................. 3-25

Ammonium Phosphates ....................................................................................... 3-26

Nitric Acid.............................................................................................................. 3-26

Ammonium Nitrate................................................................................................ 3-26

Ammonium Sulfate ............................................................................................... 3-26

Direct Application as Fertilizer.............................................................................. 3-27

Chemical Uses ..................................................................................................... 3-27

Trade .......................................................................................................................... 3-27

MIDDLE EAST............................................................................................................ 3-28

NATURAL GAS FEEDSTOCK ................................................................................... 3-29

United States .............................................................................................................. 3-30

China .......................................................................................................................... 3-31

4 TECHNOLOGY REVIEW OF AMMONIA PRODUCTION......................................... 4-1

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CONTENTS (Continued)

CHEMISTRY AND GENERIC PROCESS STEPS..................................................... 4-1

Desulfurization............................................................................................................ 4-2

Steam Methane Reforming (SMR) ............................................................................. 4-2

Partial oxidation (PO) ................................................................................................. 4-4

Autothermal Reforming (ATR).................................................................................... 4-4

Water-Gas Shift .......................................................................................................... 4-5

Removal of Carbon Dioxide........................................................................................ 4-5

Methanation ................................................................................................................ 4-7

Compression .............................................................................................................. 4-7

Ammonia Synthesis Loop........................................................................................... 4-7

FEEDSTOCKS ........................................................................................................... 4-10

AMMONIA TECHNOLOGY ........................................................................................ 4-12

Current Commercial Ammonia Processes ................................................................. 4-12

Uhde ..................................................................................................................... 4-12

KBR ...................................................................................................................... 4-16

Haldor Topsoe ...................................................................................................... 4-24

Ammonia Casale .................................................................................................. 4-28

Johnson Matthey Leading Concept Ammonia (LCA) Process............................. 4-32

Linde Ammonia Concept (LAC) Process ............................................................. 4-35

CATALYST ................................................................................................................. 4-36

Catalyst Poisons......................................................................................................... 4-36

Ammonia Synthesis Catalysts .................................................................................... 4-39

Alternative Ammonia Synthesis Catalysts.................................................................. 4-42

ADVANCED PROCESS CONTROL AND OPTIMIZATION....................................... 4-45

ENERGY EFFICIENCY .............................................................................................. 4-46

COAL-BASED AMMONIA PRODUCTION IN CHINA................................................ 4-48

Gasification ................................................................................................................. 4-49

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CONTENTS (Continued)

Sulfur Removal ........................................................................................................... 4-50

CO Shift ...................................................................................................................... 4-50

CO2 Removal.............................................................................................................. 4-50

Trace Element Removal ............................................................................................. 4-50

Ammonia Synthesis Loop........................................................................................... 4-51

CO2 CAPTURE FROM COMBUSTION FLUE GASES.............................................. 4-51

5 AMMONIA BY THE UHDE DUAL PRESSURE PROCESS...................................... 5-1

PROCESS REVIEW................................................................................................... 5-1

Historical Background................................................................................................. 5-1

Scale Up Considerations ............................................................................................ 5-2

Uhde Dual Pressure Process Technical Features ..................................................... 5-3

PROCESS DESCRIPTION ........................................................................................ 5-5

Feed Gas Preheating and Desulfurization ................................................................. 5-6

Primary Reforming...................................................................................................... 5-6

Process Air Preparation.............................................................................................. 5-6

Secondary Reforming................................................................................................. 5-7

Shift Conversion ......................................................................................................... 5-7

Carbon Dioxide Removal............................................................................................ 5-7

Methanation ................................................................................................................ 5-8

Compression and Ammonia Synthesis ...................................................................... 5-8

Ammonia Refrigeration, Steam and Cooling Water Systems .................................... 5-10

PROCESS DISCUSSION........................................................................................... 5-10

COST ESTIMATES .................................................................................................... 5-17

Capital Costs .............................................................................................................. 5-17

Production Costs ........................................................................................................ 5-21

6 AMMONIA BY THE KBR PURIFIERPLUS PROCESS............................................. 6-1

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CONTENTS (Continued)

HISTORICAL BACKGROUND ................................................................................... 6-1

KBR Purifier Ammonia Process ................................................................................. 6-2

KBR Reforming Exchanger System (KRES) .............................................................. 6-4

Tube Size.............................................................................................................. 6-5

Catalyst Shapes, Size and Testing ...................................................................... 6-5

Improved KRES Design........................................................................................ 6-6

KRES in Large-Scale Ammonia Plants ................................................................ 6-7

PROCESS DESCRIPTION ........................................................................................ 6-7

Free Gas Preheating and Desulfurization .................................................................. 6-8

Process Air Preparation.............................................................................................. 6-8

Reforming (Pre-reforming and KRES)........................................................................ 6-8

Shift Conversion ......................................................................................................... 6-9

Carbon Dioxide Removal............................................................................................ 6-10

Methanation ................................................................................................................ 6-10

Drying ......................................................................................................................... 6-11

Cryogenic Purification................................................................................................. 6-11

Compression .............................................................................................................. 6-11

Ammonia Synthesis Recovery.................................................................................... 6-12

Refrigeration and Ammonia Product Separation........................................................ 6-13

Steam and Cooling Water Systems ........................................................................... 6-13

PROCESS DISCUSSION........................................................................................... 6-13

COST ESTIMATES .................................................................................................... 6-24

Capital Costs .............................................................................................................. 6-24

Production Costs ........................................................................................................ 6-26

APPENDIX A: PATENT SUMMARY TABLES.................................................................. A-1

APPENDIX B: DESIGN AND COST BASES .................................................................... B-1

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CONTENTS (Concluded)

APPENDIX C: CITED REFERENCES............................................................................... C-1

APPENDIX D: PATENT REFERENCES BY COMPANY.................................................. D-1

APPENDIX E: PROCESS FLOW DIAGRAM.................................................................... E-1

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ILLUSTRATIONS

4.1 Principal Stages of Conventional Natural Gas-Based Ammonia Process ............ 4-2

4.2 KBR Conventional Ammonia Synthesis Loop ....................................................... 4-10

4.3 Horizontal Intercooled Ammonia Converter .......................................................... 4-10

4.4 Ammonia by Partial Oxidation of Heavy Hydrocarbons ........................................ 4-11

4.5 Coffeyville Petroleum Coke Gasification-Based Ammonia Production................. 4-12

4.6 Uhde Low Energy Ammonia Process Flow Scheme............................................. 4-13

4.7 Uhde Dual Pressure Ammonia Synthesis Flow Scheme ...................................... 4-14

4.8 Uhde 3-Bed Ammonia Converter .......................................................................... 4-15

4.9 KBR Unitized Chiller Flow Schemes ..................................................................... 4-18

4.10 KBR Purifier Flow Scheme.................................................................................... 4-18

4.11 KRES Process Flow Schemes .............................................................................. 4-21

4.12 KBR Open-Tube Reforming Exchanger................................................................ 4-22

4.13 KRES Exchanger Bundle Arrangement ................................................................ 4-22

4.14 KAAP Synthesis Loop ........................................................................................... 4-24

4.15 Topsoe Low Energy Ammonia Process Flow Scheme ......................................... 4-25

4.16 Topsoe Pre-Reforming Process Flow Scheme..................................................... 4-26

4.17 Haldor Topsoe Exchange Reformer Process Flow Scheme................................. 4-27

4.18 Topsoe S-350 Synthesis Loop .............................................................................. 4-28

4.19 Megammonia Process Flow Scheme.................................................................... 4-31

4.20 ICI LCA & AMV Process Block Diagrams ............................................................. 4-34

4.21 Flow Diagram of the Linde Ammonia Concept (LAC) Process ............................. 4-35

4.22 Jilin Chemical Residual Oil Gasification-Based Ammonia Production.................. 4-36

4.23 Basic Catalyst Materials in a Conventional 1,000 MTPD Ammonia Plant ............ 4-38

4.24 KAAP Radial Reactor ............................................................................................ 4-44

4.25 Historic Energy Efficiency of Ammonia Production ............................................... 4-48

4.26 Process Flow Scheme of CO2 Recovery from Flue Gases .................................. 4-52

5.1 Dual Pressure Ammonia Synthesis....................................................................... 5-4

© SRI Consulting x PEP Report 44B

ILLUSTRATIONS (Concluded)

5.2 Ammonia from Natural Gas by the Uhde Dual Pressure Process Process Flow Diagram .......................................................................................... E-3

5.3 Steam System ....................................................................................................... 5-13

6.1 KBR PURIFIERplus Process................................................................................. 6-1

6.2 KBR Purifier Process............................................................................................. 6-3

6.3 KBR Reforming Exchanger System (KRES)......................................................... 6-5

6.4 Enriched-Air KRES Ammonia Process.................................................................. 6-6

6.5 Ammonia from Natural Gas by the KBR Purifier Process..................................... E-7

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TABLES

2.1 Global Ammonia Supply and Demand .................................................................. 2-2

2.2 Global Ammonia Regional Demand Shift.............................................................. 2-3

2.3 Ammonia from Natural Gas Production Costs ................................................................................................... 2-10

3.1 Global Ammonia Supply and Demand .................................................................. 3-2

3.2 Global Ammonia Capacity ..................................................................................... 3-3

3.3 New Additions to Global Merchant Ammonia Production Capacity ...................... 3-4

3.4 Global Ammonia Production.................................................................................. 3-5

3.5 Operating Rates of Global Ammonia Industry....................................................... 3-6

3.6 Global Apparent Consumption of Ammonia.......................................................... 3-7

3.7 International Prices for Anhydrous Ammonia........................................................ 3-8

3.8 Global Imports of Ammonia................................................................................... 3-10

3.9 Global Exports of Ammonia................................................................................... 3-11

3.10 Global Consumption of Nitrogen Fertilizer ............................................................ 3-13

3.11 Estimated Global Market for Industrial Ammonia Applications ............................. 3-14

3.12 U.S. Ammonia Capacity by Producer, 2007.......................................................... 3-15

3.13 U.S. Ammonia Supply and Demand...................................................................... 3-16

3.14 U.S. Ammonia Consumption of Anhydrous Ammonia .......................................... 3-17

3.15 U.S. Ammonia Trade ............................................................................................. 3-22

3.16 U.S. Ammonia Imports .......................................................................................... 3-23

3.17 China Ammonia Supply and Demand ................................................................... 3-24

3.18 China Domestic Ammonia Prices.......................................................................... 3-28

3.19 Middle Eastern Ammonia Supply and Demand .................................................... 3-29

4.1 Facts and Figures of SMR and ATR ..................................................................... 4-5

4.2 Specifications of Razi Ammonia Plant and Purge Gases ..................................... 4-8

4.3 Uhde Ammonia Technology Milestones................................................................ 4-16

4.4 Recent KBR Ammonia Plant Awards and Experiences ........................................ 4-17

4.5 Haldor Topsoe Ammonia/Syngas Technology Milestones ................................... 4-28

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TABLES (Concluded)

4.6 Summary of Ammonia Synthesis Catalyst Poisons .............................................. 4-37

4.7 Topsoe Ammonia Synthesis Catalyst Facts and Figures ..................................... 4-41

4.8 Johnson Matthey Commercial Synthesis Catalyst Compositions ......................... 4-42

4.9 Reported Energy Intensity of the Most Efficient Ammonia Plants......................... 4-48

5.1 Uhde Dual Pressure Ammonia Process Design Bases ........................................................................................................ 5-11

5.2 Uhde Dual Pressure Ammonia Process Steam Flows.......................................................................................................... 5-14

5.3 Uhde Dual Pressure Ammonia Process Major Equipment ................................................................................................... 5-18

5.4 Uhde Dual Pressure Ammonia Process Total Capital Investment........................................................................................ 5-20

5.5 Uhde Dual Pressure Ammonia Process Production Costs ................................................................................................... 5-22

6.1 Recent KBR Purifier Process Awards and Experiences ....................................... 6-2

6.2 History of KBR Purifier Ammonia Process ............................................................ 6-4

6.3 KBR KRES Awards and Experiences ................................................................... 6-7

6.4 KBR PURIFIERplus Ammonia Process Design Bases ........................................................................................................ 6-15

6.5 KBR PURIFIERplus Ammonia Process Steam Flows.......................................................................................................... 6-18

6.6 KBR PURIFIERplus Ammonia Process Major Equipment ................................................................................................... 6-22

6.7 KBR PURIFIERplus Ammonia Process Total Capital Investment........................................................................................ 6-25

6.8 KBR PURIFIERplus Ammonia Process Production Costs ................................................................................................... 6-27