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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
Print ©2004 Kluwer Academic/Plenum Publishers
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Created in the United States of America
New York
©2005 Springer Science + Business Media, Inc.
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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