Synthetic Nitrogen Products

Synthetic Nitrogen ProductsA Practical Guide to the Productsand Processes

Gary R. MaxwellDuPont Chemical Solutions EnterpriseMemphis, Tennessee

KLUWER ACADEMIC PUBLISHERSNEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW

eBook ISBN: 0-306-48639-3Print ISBN: 0-306-48225-8

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PREFACE

Industrial products that are made from, or contain, nitrogen are described inparts of some encyclopedias and standard reference works. However it is notalways simple to determine from these varied sources the present status of thetechnology and markets for various nitrogen products.

We therefore perceived a need for a text that provides a comprehensivedescription of: 1) products that are made from or that contain nitrogen; 2) theprocesses that produce these products; and 3) the markets that consume theseproducts. I have attempted to present the material in a standardized format thatshould make this book easy to use and helpful to the readers. The standardformat for each product is: Introduction, Process, Production, and Uses, withsome variations in different chapters.

This book provides information that could be used by a wide range ofreaders:

Fertilizer companies—to evaluate different production processes and reviewgeneral trends in the market.Basic chemical companies—to evaluate different production processes andreview general trends in the market.Specialty chemical companies—to investigate new chemical productionand/or sales opportunities and the processes that could make those sales apossibility.Chemical distributors—to obtain a feel for the general market size for somechemicals and the basic handling and distribution procedures for variouschemicals.Engineering Companies—to evaluate different production processes andreview general trends in the market.Engineering and Chemistry Students—to learn more about practicalapplications of the principals that they have experienced in their classroomsand laboratories.

v

vi SYNTHETIC NITROGEN PRODUCTS

Business Students—to obtain information so they can evaluate industriesrelated to the nitrogen or nitrogen products.University professors—to obtain practical examples of how differentprocesses and products are used.Government Employees—to obtain information for elected officials tosupport their legislative proposals, to help develop market-based programswithin agencies and to provide guidelines in the preparation of regulationsthat affect nitrogen products.Investment Analyst and Venture Capital Companies—to gain anunderstanding of the technology that is used to produce various chemicalsand to review past trends in various markets.This information could be useful to companies in most regions of the world:North American companies, South American companies, Asian PacificCompanies, Middle East companies, European companies, CentralAmerican and Caribbean companies, and South African companies.However, developing or third-world countries will probably benefit themost from the comprehensive information in this book.

The volume is arranged into chapters for each of the nitrogen products thatare discussed. The first four chapters provide basic information about nitrogenand nitrogen products and processes. Chapters 5 through 22 provide detaileddescriptions of various nitrogen or nitrogen-containing products.

I have provided numerous tables, figures, and graphs to provide a visualsummary and description of much of the information that is discussed. Inaddition, I have used an extensive number of references that allow the reader toobtain additional information about the subject of interest to them. I have alsoattempted to provide as many Internet references as possible. The Internetprovides a vast amount of resources and references that are readily available andallow individuals to quickly obtain information that they need so they can bemore productive in their endeavors.

The index, containing numerous key words, enables the reader to rapidlyfind the required information.

I would like to express my thanks to Jim Kent for his encouragement andfor suggesting to the publisher that this book should be written. Many colleaguesinside the DuPont Company supported the development of this book by readingparts of the manuscript and providing me with reference material through ourlibrary and information services. I would also like to thank my uncle, Charles D.Scott, PhD for taking the time to review some of the key chapters in this book.Several companies and organizations graciously gave us permission to use theircopyrighted information in this book and made suggestions on how to improvethe description of their technologies. Without their cooperation, this book wouldnot have been very informative.

I would like to thank Kluwer for their confidence in me in the developmentof this book as well as Ken Howell, Senior Editor, Brian Halm, Production

PREFACE vii

Editor, and Catherine Wilson, Editorial Assistant, for their assistance andencouragement in preparing this book.

Gary R. Maxwell

DuPont Company

CONTENTS

INTRODUCTION TO NITROGENNITROGEN CHARACTERISTICSNITROGEN SEPARATION AND PURIFICATIONPRODUCTS UTILIZING NITROGEN

NITROGEN FIXATIONNITROGEN OXIDESNITRIDESAMMONIA

NITROGEN PRODUCTS: PRODUCTION AND CONSUMPTIONNITROGEN INDUSTRY: CAPACITY AND PRODUCTIONNITROGEN PRODUCT CONSUMPTIONAMMONIA PRODUCTION, CONSUMPTION, ANDFORECASTSINDUSTRIAL NITROGENWORLD TRADE IN NITROGEN PRODUCTS

Ammonia TradeTrade in Major Nitrogen Products

ENVIRONMENTAL ISSUES

HYDROGEN PRODUCTIONHYDROGEN PRODUCTION AND USESMANUFACTURING PROCESSES

ReformingPartial OxidationCoal and Coke Gasification

1.1.1.1.2.1.3.

2.2.1.2.2.2.3.

3.3.1.3.2.3.3.

3.4.3.5.

3.5.1.3.5.2.

4.

5.5.1.5.2.

5.2.1.5.2.2.5.2.3.

1136

77

1011

151618

2530333336

43

4750535790

106

ix

x CONTENTS

By-Product HydrogenElectrolysisOther ProcessesNew DevelopmentsInitial Purification of Synthesis GasCarbon Monoxide ShiftRemoval of Sulfur Compounds and Carbon DioxideFinal Purification of Synthesis GasCompression

AMMONIA SYNTHESISREACTION RATECATALYSTSENERGY EFFICIENCYAMMONIA PLANT DESIGN

Kellogg Brown & Root Advanced AmmoniaProcess–Plus (KAAP)Haldor TopsøeLinde Ammonia Concept (LAC)Leading Concept Ammonia (LCA)Ammonia CasaleUhdeConverter Comparison

AMMONIA SEPARATIONLARGE CAPACITY AMMONIA PLANTS

KBR DesignHaldor TopsøeUhdeLurgi and Ammonia Casale

AMMONIA PRODUCTION COSTSMATERIALS OF CONSTRUCTION

USES OF AMMONIACHEMICAL PRODUCTION AND OTHER USES

AcrylonitrileCaprolactamMiscellaneous Amines and NitrilesMetallurgyRefrigerationPulp and PaperPhosphate Ore FlotationHousehold CleanersAir Pollution Control

5.2.4.5.2.5.5.2.6.5.2.7.5.2.8.5.2.9.5.2.10.5.2.11.5.2.12.

6.6.1.6.2.6.3.6.4.

6.4.1.

6.4.2.6.4.3.6.4.4.6.4.5.6.4.6.6.4.7.

6.5.6.6.

6.6.1.6.6.2.6.6.3.6.6.4.

6.7.6.8.

7.7.1.

7.1.1.7.1.2.7.1.3.7.1.4.7.1.5.7.1.6.7.1.7.7.1.8.7.1.9.

116117120120128135138155162

163165169175175

178179180181183184187187189189189190192195197

199199199200200200201201201201201

SYNTHETIC NITROGEN PRODUCTS xi

Uranium Concentrate ProductionWater PurificationWaste TreatmentDuplicating ProcessesFabric TreatmentSemiconductor IndustryMiscellaneous

GENERAL AMMONIA INFORMATIONAMMONIA PROPERTIESAMMONIA TOXICITYAMMONIA QUALITYDISTRIBUTION AND STORAGEMATERIALS OF CONSTRUCTIONAMMONIA PRICE

NITRIC ACIDPHYSICAL PROPERTIESPROCESSES

ChemistryCatalystsOperating PressureConcentration of Nitric AcidWater Balance in Dual Pressure Azeotropic PlantsDirect Strong Acid Processes

STABILIZERSPOLLUTION ABATEMENT

Absorption AbatementAdsorption AbatementSelective Catalytic ReductionNon-Selective Catalytic ReductionAbsorption Plus Selective Catalytic ReductionNitrous Oxide Removal

MATERIALS OF CONSTRUCTIONMaterials for Weak Acid ProcessesMaterials for Strong Acid Processes

PRODUCTIONSTORAGE AND DISTRIBUTIONUSES OF NITRIC ACID

AMMONIUM NITRATEPROCESSES

7.1.10.7.1.11.7.1.12.7.1.13.7.1.14.7.1.15.7.1.16.

8.8.1.8.2.8.3.8.4.8.5.8.6.

9.9.1.9.2.

9.2.1.9.2.2.9.2.3.9.2.4.9.2.5.9.2.6.

9.3.9.4.

9.4.1.9.4.2.9.4.3.9.4.4.9.4.5.9.4.6.

9.5.9.5.1.9.5.2.

9.6.9.7.9.8.

10.10.1.

202202202202202202203

205205207208209210211

213213215217219223228230232233234234236236237237238245245246246248249

251251

xii CONTENTS

NeutralizationSteam PurificationEvaporationPrillingGranulationAir Abatement Equipment

PRODUCTIONSTORAGE AND DISTRIBUTIONUSES

UREAPROCESSES

PrillingGranulationMaterials of Construction

PRODUCTIONSTORAGE AND DISTRIBUTIONUSES

AMMONIUM PHOSPHATES AND AMMONIUM SULFATEAMMONIUM PHOSPHATES

MAP Powder ProcessesDAP Powder ProcessesGranular DAP and MAP ProcessesProduction of Ammonium PhosphatesUses of Ammonium Phosphates

AMMONIUM SULFATEProduction of Ammonium SulfateUses of Ammonium Sulfate

10.1.1.10.1.2.10.1.3.10.1.4.10.1.5.10.1.6.

10.2.10.3.10.4.

11.11.1.

11.1.1.11.1.2.11.1.3.

11.2.11.3.11.4.

12.12.1.

12.1.1.12.1.2.12.1.3.12.1.4.12.1.5.

12.2.12.2.1.12.2.2.

MELAMINEPROCESSESPRODUCTIONUSES

ALIPHATIC AMINESALIPHATIC AMINES

MethylaminesOther Alkyl AminesProductionUses

13.13.1.13.2.13.3.

14.14.1.

14.1.1.14.1.2.14.1.3.14.1.4.

253258258260261262262263265

267269277279280281283284

285285286288289291292293296297

299300305305

307307307313313315

SYNTHETIC NITROGEN PRODUCTS xiii

ETHANOLAMINES AND SECONDARY PRODUCTSETHANOLAMINE PROCESSPRODUCTIONUSESSECONDARY PRODUCTS OF ETHANOLAMINE

MorpholineEthylenimine

ETHYLENEDIAMINE AND CHELATING AGENTSETHYLENEDIAMINE

Ethylenediamine ProductionEthylenediamine Uses

CHELATING AGENTSManufacturing Processes for Chelating AgentsProduction and Uses of Chelating Agents

HEXAMETHYLENETETRAMINE (HEXAMINE)HEXAMINE PROCESSESPRODUCTIONUSES

HYDRAZINEPROCESSES

Raschig ProcessRaschig/Olin ProcessHoffmann (Urea) ProcessPeroxide ProcessBayer Ketazine ProcessMaterials of Construction

PRODUCTIONUSES

HYROGEN CYANIDESAFETYMANUFACTURE

Andrussow ProcessBMA ProcessFluohmic ProcessFormamide ProcessMethanol ProcessAcrylonitrile Process

15.15.1.15.2.15.3.15.4.

15.4.1.15.4.2.

16.16.1.

16.1.1.16.1.2.

16.2.16.2.1.16.2.2.

17.17.1.17.2.17.3.

18.18.1.

18.1.1.18.1.2.18.1.3.18.1.4.18.1.5.18.1.6.

18.2.18.3.

19.19.1.19.2.

19.2.1.19.2.2.19.2.3.19.2.4.19.2.5.19.2.6.

317317321322322322324

325325326327327327329

333334334335

337338338339342342344344346346

347348349350351354355357357

xiv CONTENTS

Other HCN ProcessesMaterials of Construction

PRODUCTIONUSES

ANILINE AND NITROBENZENEANILINE

Aniline ProcessesAniline ProductionAniline Uses

NITROBENZENENitrobenzene ProcessesNitrobenzene ProductionNitrobenzene Uses

CAPROLACTAMPROCESSES

Conventional ProcessDSM/HPO (Stamicarbon) ProcessBASF ProcessInventa-NO Reduction ProcessPNC or Toray ProcessSNIA Viscosa ProcessRecovery from Nylon 6 Waste

CAPROLACTAM PRODUCTIONCAPROLACTAM USES

OTHER NITROGEN COMPOUNDSADIPONITRILE AND HEXAMETHYLENEDIAMINEACRYLONITRILE

Process TechnologyProductionUses

METHYLMETHACRYLATEProcess TechnologyProductionUses

ACRYLAMIDEProcess TechnologyProductionUses

DIMETHYLFORMAMIDE

19.2.7.19.2.8.

19.3.19.4.

20.20.1.

20.1.1.20.1.2.20.1.3.

20.2.20.2.1.20.2.2.20.2.3.

21.21.1.

21.1.1.21.1.2.21.1.3.21.1.4.21.1.5.21.1.6.21.1.7.

21.2.21.3.

22.22.1.22.2.

22.2.1.22.2.2.22.2.3.

22.3.22.3.1.22.3.2.22.3.3.

22.4.22.4.1.22.4.2.22.4.3.

22.5.

358358358359

361361362365367367368370371

373374375378380382382384387388389

391391392392392394394394395395395395396396397

SYNTHETIC NITROGEN PRODUCTS xv

Process TechnologyProductionUses

CALCIUM CYANAMIDEOTHER COMPOOUNDS

ReferencesIndex

22.5.1.22.5.2.22.5.3.

22.6.22.7.

397397398398399

401411