FERTILIZER MANUAL

Developments in Plant and Soil Sciences Volume 15

1. J. Monteith and C. Webb, eds., Soil Water and Nitrogen in Mediterranean-type Environments. 1981. ISBN 90-247-2406-6

2. J.C. Brogan, ed., Nitrogen Losses and Surface Run-off from Landspreading of Manures. 1981. ISBN 90-247-2471-6

3. J.D. Bewley, ed., Nitrogen and Carbon Metabolism. 1981. ISBN 90-247-2472-4

4. R. Brouwer, I. Gasparikova, J. Kolek and B.C. Loughman, eds., Structure and Function of Plant Roots. 1981. ISBN 90-247-2510-0

5. Y.R. Dommergues and H.G. Diem, eds., Microbiology of Tropical Soils and Plant Productivity. 1982. ISBN 90-247-2624-7

6. G.P. Robertson, R. Herrera and T. Rosswall, eds., Nitrogen Cycling in Ecosystems of Latin America and the Caribbean. 1982. ISBN 90-247-2719-7

7. D. Atkinson et al., eds., Tree Root Systems and their Mycorrhizas. 1983. ISBN 90-247-2821-5

8. M.R. Saric and B.C. Loughman, eds., Genetic Aspects of Plant Nutrition. 1983. ISBN 90-247-2822-3

9. J.R. Freney and J.R. Simpson, eds., Gaseous Loss of Nitrogen from Plant-Soil Systems. 1983. ISBN 90-247-2820-7

10. United Nations Economic Commission for Europe. Efficient Use of Fertilizers in Agriculture. 1983. ISBN 90-247-2866-5

11. J. Tinsley and J.F. Darbyshire, eds., Biological Processes and Soil Fertility. 1984. ISBN 90-247-2902-5

12. A.D.L. Akkermans, D. Baker, D. Huss-Danell and J.D. Tjepkema, eds., Frankia Symbioses. 1984. ISBN 90-247-2967-X

13. W.S. Silver and E.C. Schroder, eds., Practical Application of Azolla for Rice Production. 1984. ISBN 90-247-3068-6

14. P.G.L. Vlek, ed., Micronutrients in Tropical Food Crop Production. 1985. ISBN 90-247-3085-6

15. T.P. Hignett, ed., Fertilizer Manual. 1985. ISBN 90-247-3122-4

Fertilizer Manual

Edited by

TRAVIS P. HIGNETT International Fertilizer Development Center (IFDC) Muscle Shoals, Alabama USA

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V. 1985

Library of Congress Catalog Card Number: 84-27810

ISBN 978-90-481-8290-9 ISBN 978-94-017-1538-6 (eBook) DOI 10.1007/978-94-017-1538-6

Copyright

© 1985 by Springer Science+Business Media Dordrecht Originally published by Martinus Nijhoff/Dr W. Junk Publishers, Dordrecht in 1985 Softcover reprint of the hardcover 1 st edition 1985

Ali rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publishers, Springer-Science+Business Media, B.V.

PREFACE

This Fertilizer Manual was prepared by the International Fertilizer Development Center (IFDC) as a joint project with the United Nations Industrial Development Organi­zation (UNIDO). It is designed to replace the UN Fertilizer Manual published in 1967 and intended to be a reference source on fertilizer production technology and economics and fertilizer industry planning for developing countries. The aim of the new manual is to describe in clear, simple language all major fertilizer processes, their requirements, advan­tages and disadvantages and to show illustrative examples of economic evaluations.

The manual is organized in five parts. Part I deals with the history of fertilizers, world outlook, the role of fertilizers in agriculture, and raw materials and includes a glossary of fertilizer-related terms.

Part II covers the production and transportation of ammonia and all important nitrogen fertilizers-liquids and solids.

Part III deals with the characteristics of phosphate rock, production of sulfuric and phosphoric acid, and all important phosphate fertilizers, including nitrophosphates and ammonium phosphates.

Part IV deals with potash fertilizers-ore mining and refining and chemical manufac­ture; compound fertilizers; secondary and micronutrients; controlled-release fertilizers; and physical properties of fertilizers.

Part V includes chapters on planning a fertilizer industry, pollution control, the economics of production of major fertilizer products anJ intermediates, and problems facing the world fertilizer industry.

In planning the new manual it was decided to concentrate on the chemistry, technology, and economics of fertilizer production and to include only enough information on market­ing, Jistribution, and use to serve as background material. The reasons for this decision were: (I) it was necessary to confine the scope of the project to a manageable level; (2) as this project is a joint one with UNIDO, the subject matter should mainly be limited to that agency's interest, and (3) other publications were planned or available on planning, policies, marketing, distribution, and agricultural use of fertilizers. For example, the Food and Agriculture Organization of the United Nations (F AO) has several publications on these subjects, and IFDC has published a bulletin titled Suggested Fertilizer-Related Policies for Governments and International Agencies which deals with planning of a fertilizer industry at the government level.

The new manual uses internationally accepted terminology, and all data are in metric units but not necessarily Sl units. English units are given in some cases when the original data are in those units, but metric equivalents are also shown.

Special emphasis is given to the economics of fertilizer production. Basic cost data are for manufacturing operations in industrial areas of developed countries-United States or Europe-since conditions in developing countries vary widely. However, there are examples and discussions of how the economics of various processes is likely to be affected by conditions in some developing countries. Estimated costs are given in suffi­cient detail to assist those who may wish to adapt the estimates to their own situation.

In comparison with the previous manual, the treatment of phosphate fertilizers and compound fertilizers has been greatly expanded. New chapters have been added on controlled-release fertilizers and the physical properties of fertilizers. The scope of treat­ment of nitrogen fertilizers is about the same as in the previous manual, but extensive updating has been necessary. Two new chapters were added on transport and storage of ammonia and on factors affecting the choice of a nitrogen fertilizer. Overall, no more than 20% of the new manual can properly be termed a revision of the old one; 80% is entirely new.

v

The project was under the direction of Travis P. Hignett, IFDC Special Consultant, who either wrote or reviewed and edited all chapters. Dr. H. R. Tejeda of IFDC prepared chapter III; F. P. Achorn of the Tennessee Valley Authority (TVA) prepared chapter X; R. C. Smith of AMAX, Inc., prepared chapter XVIII; George Hoffmeister, Jr., of TVA prepared chapter XXII; C. Keleti of UNIDO prepared chapter XXIII; and M. C. Verghese of UNIDO prepared chapter XXVI except for the section on modules, platforms, and barges which was supplied by C. J. Pratt of The World Bank. A major part of chapter V was taken from a chapter of UNIDO's World-Wide Study of the Fertilizer Industry: 1975-2000 prepared by R. L. Cook. T. P. Hignett wrote all other chapters; however, numerous people assisted by supplying information and reviewing drafts. IFDC gratefully acknowledges the cooperation of many individuals in various industrial organizations in Europe, North America, and elsewhere and those in TVA, FAO, UNIDO, The World Bank, ISMA, the Fertilizer Institute, and the Sulphur Institute.

All chapters were reviewed by UNIDO, and many helpful comments were received. In addition, all chapters were reviewed by at least one other person (usually two or three others). The reviewers were selected from the fertilizer industry, the above-mentioned organizations, or IFDC staff. Special mention is due Ernest Frederick, recently retired from TV A, who ably served as technical editor, also to Mrs. Marie Thompson, IFDC, for general editing, and to Mrs. Barbara Holder for layout, as wel1 as to the IFDC Word Processing Center for many hours of typing and revisions.

It is unavoidable in a work of this magnitude that some of the information will be obsolete when it is printed. Readers should keep in mind that when authors refer to "current" or "present" situations they usua11y mean 1978 unless otherwise specified.

vi

ACRONYMS OF ORGANIZATIONS

ADIFAL ..... *Latin American Association for Development of the Fertilizer Industry AID ............................... Agency for International Development ANDA .......................... Associa~ao Nacional para Difusao de Adubos AOAC .......................... Association of Official Agricultural Chemists APEA ........................ Association des Producteurs Europeens d 'Azote ASEAN ............................... Alliance of Southeast Asian Nations ASTM .............................. American Society for Testing Materials BASF .................................. Badische Anilin-und Soda-Fabrik CAST ....................... Council for Agricultural Science and Technology DSM ............................................ Dutch State Mines EEC ................................... European Economic Community ESCAP ................ Economic and Social Commission for Asia and the Pacific F AI ..................................... Fertiliser Association of India FAO .................. Food and Agriculture Organization of the United Nations FCI. .................................... Fertilizer Corporation of India FCIA ............................... Foreign Credit Insurance Association FIAC ............................. Fertilizer Industry Advisory Committee GUANOMEX . . . . . . . . . . . . . . . . . . . . . . . Guanos y Fertilizantes de Mexico ICI ...................................... Imperial Chemical Industries !CIS . . . . . . . . . .................. International Centre for Industrial Studies IDA .............................. International Development Association IDCAS ....................... Industrial Development Centre for Arab States IFDC . . . . . . . . . . . . . . . . . International Fertilizer Development Center ILO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . International Labor Organization IMI . ......................................... Israel Mining Industries IRRI. ............................... International Rice Research Institute !SMA ......... Originally "International Superphosphate Manufacturers Association" NFDC. . National Fertilizer Development Center (TV A) OECD. . .Organization for Economic Cooperation and Development OMVS ........................... *Senegal River Development Organization OPEC ........................ Organization of Petroleum Exporting Countries PEC ................................ Societe Potasse et Engrais Chimiques SAl. . . . . . . . . . . . . . ................... Scottish Agricultural Industries SBA. . . . . . . . . ..... Societe Beige d'Azote SELA. TVA ...... UKF. UN ... UNCTAD .. . UNIDO .... .

*Translation.

FRG. GDR. PRC. U.K .......... . U.S ........... . U.S.S.R ...

.......... *Latin American Economic System . ............. Tennessee Valley Authority

. ... Unie van Kunstmestfabrieken br . .............................. United Nations

. ..... United Nations Conference on Trade and Development . .... United Nations Industrial Development Organization

ABBREVIATIONS FOR COUNTRIES

...... Federal Republic of Germany . ... German Democratic Republic . ..... People's Republic of China

. United Kingdom of Great Britain and Northern Ireland . . . . . . . . . ..... United States of America

. . Union of Soviet Socialist Republics

VII

CLASSIFICATION OF COUNTRIES

For statistical purposes the UN standard classification is used for developed and developing countries:

Developed Countries Includes North America (Canada and United States), Western Europe, Eastern

Europe (including U.S.S.R.), Japan, Israel, South Africa, Australia, and New Zealand.

Developing Countries Includes Latin America (all American countries not included in "North America"),

Asia (except Japan and Israel), Africa (except South Africa), and Oceania (except Australia and New Zealand). Turkey is included in Asia although it is partly in Europe.

Note: Use of country names in connection with specific locations does not imply a judgment by IFDC as to the boundaries of any country when those boundaries are disputed.

Regional Grouping of Countries: Where a regional grouping of countries is given (e.g., "Middle East"), such groupings

are taken from a referenced source of information. Use of such groupings does not imply any judgment by IFDC as to its validity nor does it necessarily imply approval of the group name.

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MATHEMATICAL SYMBOLS, ABBREVIATIONS, AND CONVERSION FACTORS USED IN THIS MANUAL a

Monetary Value

$ ................................ U.S. dollar (unless otherwise indicated) ¢ .................................................. cent= $0.01 mill ..................................................... $0.001 Rs ...................................................... rupee

Linear Measurement

m ............................... meter= 3.28 feet (ft) = 39.37 inches (in) em ............................. centimeter= 0.01 meter= 0.3937 inch (in) mm ......................................... millimeter= 0.001 meter 11m ......................................... micrometer or "micron" km ........................................ kilometer = 0.62 mile (mi)

Area Measure

m2 ................................ square meter= 10.76 square feet (ft2) cm2 ........................... square centimeter= 0.155 square inch (in2) km2 ............................ square kilometer= 0.386 square mile (mi2) ha ...................... hectare= 10,000 square meters (m2) = 2.471 acres (A)

Weight

g .................. gram= 0.032 troy ounce (oz) = 0.035 avoirdupois ounce (oz) mg ........................................ milligram= 0.001 gram (g) )lg . .................................... microgram = 0.000001 gram (g) kg ........................... kilogram= 1,000 grams (g)= 2.205 pounds (lb) t. .................... ton (metric)= I ,000 kg= 2,205 lb = I. I 02 short tons (st)

(All "tons" in this manual are metric tons unless otherwise stated.) g-mole ........ gram mole= the molecular weight of a compound multiplied by I gram

Volume

m3 ...................... cubic meter= 35.34 cubic feet (ft3) = I ,000 liters (I) cm3 ............................. cubic centimeter= 0.061 cubic inch (in3) I. .......................... liter= 0.264 U.S. gallons (gal)= 1.057 quart (qt) bbl ...................... barrel (of petroleum)= 42 gallons (gal)= 159liters (I) ml ....................... milliliter= I cubic centimeter (cm3) approximately Nm3 ................... cubic meter (of gas) measured at "normal" temperature

and pressure (0°C and 1 atm) Tcm ........................................... trillion cubic meters

Yields or Application Rates

kg/ha .................... kilograms per hectare= 0.892 pounds per acre (lb/A) t/ha ........... tons per hectare= 14.87 bushels per acre (bu/A)(wheat) 15.93 bu/A

of maize (The bushel is a unit of volume (35.24 liters) but is usually determined by weighing grain and dividing by a standard

weight per bushel which is characteristic of the specific grain.)

a. Factors for converting metric units to English or SI units (Systeme International d'UniHis) or vice versa.

IX

Weight per Unit of Volume (Density)

sp gr ....... specific gravity =the ratio of the weight of a substance to the weight of an equal volume of water at 4°C; no dimensions; numerically equal to density in g/cm3

g/cm3 ........... grams per cubic centimeter= 62.43 pounds per cubic foot (ib/ft3) kgfm3 ............................ kilograms per cubic meter= 0.0624 lb/ft3 t/m3 ..................................... tons per cubic meter= g/cm3

Note: For definitions of true, apparent, and bulk densities or specific gravities, see chapter XXII.

Concentrations

g/1 ................................................ grams per liter mgfm3 ..................................... milligrams per cubic meter p.gfm3 ..................................... micrograms per cubic meter

Work-Energy-Heat

cal ......................................... calorie = 4.184 joules (J) kcal .................. kilocalorie= I ,000 cal= 3.968 British thermal units (Btu) kJ ............................................. kilojoule = 0.239 cal GJ ................ gigajoule = !09 joules= 0.948 million Btu= 0.239 million kcal

Power

W ...................................... watt= I joule per second (J/s) kW ....................... kilowatt = I ,000 watts (W) = 1.34 horsepower (hp) kWh ....................................... kilowatt-hour= 3,413 Btu

Heating Value per Unit of Volume or Weight (Also Heat of Formation)

cal/g .... calories per gram= kilocalories per kilogram (kcal/kg) = 1.8 Btu/lb = 4.187 1/g kcal/m3 ........................ kilocalories per cubic meter = 0.1123 Btu/ft3

(Used to denote heating value of fuel gas; the temperature and pressure should be stated; usually 0°C and 1 atm in scientific work. The natural gas industry

uses "standard conditions" of 60°F and 14.7lb/in2.)

Pressure

kg/cm2 ....... kilograms per square centimeter= 14.7 pounds per square inch (ib/in2) atm ..................... atmosphere= 14.7 lb/in2 = I kg/cm2 (approximately) atm ....... I 01.325 kilonewtons per square meter (kN/m2) = I 01.325 kilo pascals (kPa) mm Hg ...................... millimeters of mercury= 133.3 Pa = 0.0013 atm psia .................................... pounds per square inch absolute psig ...................................... pounds per square inch gauge

Temperature

°C ......................... degrees Celsius or centigrade; °C x 1.8 + 32 = °F °F ................................ degrees Fahrenheit (°F- 32) 5/9 = °C

X

Plant Capacity or Production Rate

tpd . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . tons per day tph ................................................. tons per hour tpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . tons per year

Note: All tons are metric unless otherwise specified.

Other Abbreviations

f.o.b .................. free on board =cost at plant or port including loading on a ship or other conveyance

pH ................ logarithm of the reciprocal of the hydrogen ion concentration in grams per liter (pH= log 1/W g/1). A solution of pH 7 is neutral; lower pH's are acidic and higher pH's are alkaline.

dia .................................................... diameter CRH ........................................ critical relative humidity LPG ......................................... liquefied petroleum gas LNG ........................................... liquefied natural gas SNG ................................. substitute (or synthetic) natural gas HTS ................................... high temperature shift (catalyst) LTS ................................... low temperature shift (catalyst) LHV ......................................... low heating value (gas) CEC ........................................ cation exchange capacity

Abbreviations of Common Fertilizer Materials

For abbreviations of the names of common fertilizer materials and definitions of fertilizer-related terms, see chapter IV.

Particle Size - Screen Size

For comparison of screen sizes in different systems, see chapter XXII, table 2.

XI

CONTENTS

Chapter Page

Part One-Introduction and Background

I. HISTORY OF CHEMICAL FERTILIZERS A. Introduction . ......................................... 3 B. Chemical Fertilizers .................................... .4

1. Phosphate Fertilizers ................................ .4 2. Nitrogen Fertilizers ................................. .4 3. Potash Fertilizers .................................... 5 4. Other Nutrients ..................................... 5 5. Compound Fertilizers ................................. 5 6. More Intensive Agriculture ............................. 6 7. Statistical Review of Growth in Fertilizer Production and

Consumption: 1950-76 .............................. 6 II. OUTLOOK FOR THE FERTILIZER INDUSTRY (1978-2000)

A. Introduction . ........................................ 11 B. Fertilizer Use ........................................ 11 C. Fertilizer Production ................................... 13

1. Value of Production ................................. 14 2. Raw Materials ..................................... 14 3. Organic Fertilizer Materials ............................ 14 4. Location of Fertilizer Plants ........................... 14 5. Marketing ....................................... 15 6. Financing ........................................ IS 7. Manpower ......................... , ............. 16 8. Pollution Control .................................. 16

D. Policies of Governments and International Agencies . .............. 16 III. ROLE OF FERTILIZER IN AGRICULTURE

A. Introduction . ........................................ 18 1. The Contribution of Fertilizer to Agricultural Output .......... 18 2. The Effect of Fertilizers in Crop Production ................. 19 3. The Soil. ........................................ 20 4. Fertilizer Nutrients ................................. 24 5. Effect of Crop Variety and Cultural Practices ........ '. ....... 25 6. Moisture Supply and Fertilizer Response ................... 26

B. Economics of Fertilizer Use . .............................. 27 1. Production Economics Aspect .......................... 27 2. Some Further Topics ................................ 29 3. Fertilizer Policy Aspects .............................. 29

REFERENCES .......................................... 30 IV. GENERAL CONCEPTS AND DEFINITIONS

A. Fertilizers: General Definition . ............................ 32 1. Fertilizer Availability ................................ 3 2 2. Fertilizer Regulations ................................ 33 '3. Expression of Plant Nutrients-Oxide vs. Elemental Form ........ 33 4. Definition of Some Fertilizer Terms ...................... 33

V. FERTILIZER RAW MATERIALS AND RESERVES A. Estimate of Raw Material Requirements ...................... 36 B. Availability and Sources of Raw Materials ..................... 37

1. Ammonia Feedstocks ................................ 37 2. Phosphate Rock ................................... 39

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Chapter Page 3. Sulfur ......................................... .40 4. Potash .......................................... 42 5. Other Raw Materials ............................... .42 6. Water .......................................... 42

REFERENCES .......................................... 43

Part Two-Nitrogen Fertilizers

VI. PRODUCTION OF AMMONIA A. History of Ammonia Synthesis . ............................ 49 B. Steam-Reforming Processes ............................... 51

1. Thermochemical Data ............................... 51 2. Feedstocks for Steam-Reforming Processes .................. 51 3. Technology of Steam-Reforming Process ................... 54

C. Partial-Oxidation Processes Using Hydrocarbon Feedstock .......... 60 D. Processes for Production of Ammonia from Coal . ................ 61 E. Ammonia from Electrolytic Hydrogen . ....................... 63 F. Economics of Ammonia Production ......................... 63

1. Capital Requirements ................................ 63 2. Production Cost and Gate Sale Price Estimates ............... 65 3. Economics of Small-Scale Ammonia Plants .................. 70

REFERENCES .......................................... 71 VII. TRANSPORTATION AND STORAGE OF AMMONIA

A. Introduction . ........................................ 73 B. Ammonia Storage ..................................... 73 C. Transportation of Ammonia .............................. 75

1. Ocean Transportation of Ammonia ....................... 75 2. Shipment of Ammonia by Barge ......................... 76 3. Transportation of Ammonia by Pipeline ................... 77 4. Transportation of Ammonia by Rail ...................... 79 5. Transportation of Anhydrous Ammonia by Truck ............. 80 6. Comparison of Various Methods of Ammonia Transportation ..... 81

REFERENCES .......................................... 82 VIII. AMMONIUM SALTS, NITRIC ACID, AND NITRATES

A. Introduction . ........................................ 83 B. Ammonium Sulfate . ................................... 83

1. Properties of Ammonium Sulfate ........................ 83 2. Production Methods ................................. 83 3. Crystallization Technology ............................ 84 4. Chemical and Physical Specifications ...................... 84 5. Production Details .................................. 84 6. Storage and Handling ................................ 88

C. Ammonium Chloride ................................... 88 1. General Information ................................ 88 2. Properties of Ammonium Chloride ....................... 89 3. Production Methods ................................. 89

D. Nitric Acid ......................................... . 91 1. Historical Development .............................. 91 2. Properties of Nitric Acid .............................. 91 3. Oxides of Nitrogen ................................. 92 4. Chemical and Theoretical Considerations in Production of

Nitric Acid from Ammonia ........................... 92 5. Production Considerations ............................ 94 6. Technical and Economic Comparisons ..................... 99 7. Materials of Construction ............................ 100

xiv

Chapter Page E. Ammonium Nitrate ................................... I 00

1. Properties of Ammonium Nitrate ....................... 100 2. Hazards of Ammonium Nitrate ........................ 101 3. Production Methods ................................ 102 4. Finishing Processes ................................ I 03 5. Pollution Control ................................. 104

F. Sodium Nitrate . ..................................... 105 1. General Information ............................... I 05 2. Principal Uses .................................... I 05 3. Properties of Sodium Nitrate .......................... 105 4. Production Methods ................................ I 05 5. Storage ........................................ 106

G. Potassium Nitrate .................................... 106 H. Calcium Nitrate . ..................................... 106

I. General In formation ............................... 106 2. Properties of Calcium Nitrate .......................... 106 3. Production Methods ................................ 106 4. Storage ........... : . ........................... 107

REFERENCES ......................................... 107 IX. UREA

A. Introduction . ....................................... 109 1. Properties of Urea ................................. 109

B. Production Processes .................................. 110 1. Operating Variables ................................ Ill 2. Once-Through and Partial-Recycle Processes ................ 111 3. Total-Recycle Processes ............................. 112

C. Urea Finishing Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 I . Prilling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 2. TV A Pan Granulation ............................... 117 3. Norsk Hydro Pan Granulation ......................... 117 4. C&l Girdler Spherodizer Granulation .................... 118 5. Fisons Granular Urea Process .......................... 119 6. Spouted-Bed Granulation ............................ 119 7. Conversion from Prilling to Granulation ................... 119 8. Dust and Fume Recovery ............................ 119 9. Effect of Finishing Process on Biuret Content ............... 119

10. Comparative Cost of Granulation and Prilling ............... 120 11. Conditioning .................................... 120

D. Process Requirements . ................................. 120 REFERENCES ......................................... 121

X. PRODUCTION. PROPERTIES. AND USE OF NITROGEN SOLUTIONS AND USE OF ANHYDROUS AMMONIA FOR DIRECT APPLICATION

A. Introduction . ....................................... 122 B. Use of Anhydrous Ammonia . ............................ 123

1. Retail Operations ................................. 124 2. Application of Anhydrous Ammonia ..................... 125 3. Safety in Handling Ammonia .......................... 127

C. Nonpressure Nitrogen Solutions . .......................... 128 1. Production of Urea-Ammonium Nitrate (UAN) Solutions ....... !30 2. Application and Use ................................ 131

D. Aqua Ammonia . ..................................... 132 E. Pressure-Type Solutions ................................ 133

1. Use of Pressure-Type Nitrogen Solutions .................. 134 F. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134 REFERENCES ......................................... 135

XV

Chapter Page XI. SOME FACTORS INFLUENCING CHOICE OF NITROGEN FERTILIZERS

A. Introduction . ....................................... 136 B. Agronomic Considerations .............................. !36 C. Physical Properties and Safety . ........................... 137 D. Manufacturing Considerations ............................ 137 E. Economic Considerations ............................... 137 F. Estimated Cost and Gate Sale Price of Urea, Ammonium Nitrate,

and Ammonium Sulfate ............................... 138 I. Estimated Cost of Urea Production ...................... !38 2. Estimated Cost of Ammonium Nitrate Production ............ I41 3. Estimated Cost of Ammonium Sulfate Production ............ !43

Part Three-Phosphate Fertilizers

XII. PHOSPHATE ROCK AND SULFURIC ACID A. Introduction . ....................................... 149 B. Phosphate Rock ..................................... I 49

I. Apatitic Phosphates ................................ !50 2. Aluminous Phosphates .............................. !50 3. Accessory Minerals ................................ !50 4. Physical Properties ................................. !50 5. Factors that Influence Economic Potential ................. ISO 6. Direct Application of Phosphate Rock .................... !51 7. Methods for Measuring the Reactivity of Phosphate Rock ....... !52 8. Calcined Aluminum Phosphate ......................... !54

C. Sulfuric Acid ....................................... !54 I. Sulfuric Acid from Elemental Sulfur ..................... 155 2. Production of Sulfuric Acid from Pyrites or from

Smelter Operations ............................... !57 3. Production of Sulfuric Acid from Calcium Sulfate ............ 160

REFERENCES ......................................... 162 XIII. PHOSPHORIC ACID

A. Introduction . ....................................... 163 B. Production of Phosphoric Acid by Wet Processes Using Sulfuric Acid .. 163

I. Chemistry of Process ............................... 163 2. Heat Released in Reaction ............................ !63 3. Types of Processes ................................. !64 4. Description of Process .............................. 165 5. Economics of Phosphoric Acid. Production ................. 173 6. Shipment of Phosphoric Acid ......................... 175 7. Utilization of Byproduct Gypsum ....................... 176 8. Utilization of Fluorine .............................. 179 9. Puriflcation of Phosphoric Acid .................. ' ...... 179

C. Production of Phosphoric Acid Using Acids Other than Sulfuric . ..... 179 1. Dissolution and Mechanical Separation of Insoluble Residue ..... 180 2. Liquid-Liquid Contacting ............................ 180 3. Acid Concentration ................................ 181 4. Solvent Recovery from Spent Calcium Chloride Brine ......... 181 5. Construction Materials .............................. 181 6. Quality of HCI-Route Phosphoric Acid ................... I 81 7. Capital Investment. ................................ I 8 I 8. Process Requirements ............................... I82

D. Phosphoric Acid Production by the Electric Furnace Process . ....... 182 E. Phosphoric Acid Production by the Blast-Furnace Process . ......... 184 REFERENCES I85

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Chapter Page

XIV. FERTILIZERS DERIVED FROM PHOSPHORIC ACID A. Triple Superphosphate (TSP) . ............................ 187

I. Production of Nongranular Triple Superphosphate ............ 188 2. Direct Granulation of Triple Superphosphate ............... 188

B. Ammonium Phosphates ................................ 191 I. Ammonium Polyphosphate ........................... 194

C. Other Fertilizers Made from Phosphoric Acid .................. 196 I. Ammonium Phosphate-Sulfates ........................ 196 2. Ammonium Phosphate-Chloride ........................ 196 3. Ammonium Phosphate-Nitrate (APN) .................... 196 4. Urea-Ammonium Phosphates (UAP) ..................... 197

D. Use of Phosphoric Acid in Granulation Processes . ............... 198 E. Miscellaneous Fertilizer Uses for Phosphoric Acid ............... 198 F. Comparative Economics of TSP, DAP, and MAP . ............... 199 REFERENCES ......................................... 20 I

XV. NITROPHOSPHATES A. Chemistry of Nitrophosphate Processes ...................... 203 B. Calcium Nitrate Removal ............................... 203

I. Removal of Calcium by Ion Exchange .................... 204 2. Removal of Calcium by Sulfate Addition .................. 205

C. Addition of Phosphon·c Acid or Soluble Phosphates . ............. 205 D. Technology of Nitrophosphate Processes ..................... 206

I. Selection of Phosphate Rock .......................... 206 2. Extraction ...................................... 206 3. Calcium Nitrate Removal ............................ 206 4. Ammoniation .................................... 207 5. Finishing Processes ................................ 207 6. Some Other Nitrophosphate Processes .................... 207

E. Economic Evaluation of Nitrophosphate Processes . .............. 207 REFERENCES ......................................... 209

XVI. OTHER PHOSPHATE FERTILIZERS A. Single Superphosphate ................................. 211

I. Suitability of Phosphate Rocks ........................ 211 2. Chemistry of SSP ................................. 211 3. Production Methods ................................ 212

B. Enriched Superphosphate . .............................. 214 C. Basic Slag . ......................................... 214 D. Potassium Phosphates . ................................. 215 E. Bone Meal ......................................... 215 F. Fused Calcium Magnesium Phosphate ....................... 215 G. Dejluorinated Phosphate Rock . ........................... 216 H. Rhenania Phosphate . .................................. 216 I. Calcium Metaphosphate ................................ 217 1. Dicalcium Phosphate .................................. 217 K. Magnesium Phosphates . ................................ 217 REFERENCES ......................................... 217

XVII. SOME FACTORS INFLUENCING CHOICE OF PHOSPHATE FERTILIZERS I. Example of Economic Study .......................... 219

Part Four-Potash and Other Fertilizers

XVIII. POTASH FERTILIZERS A. Introduction . ....................................... 225 B. Agronomic and Industrial Significance of Potash . ............... 225

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Chapter C. D.

Page Mineralogy of Potash Ores . .............................. 225 World Potash Reserves ................................. 226

1. Canada ........................................ 226 2. United States .................................... 227 3. Central America .................................. 228 4. South America ................................... 228 5. Africa ......................................... 229 6. Middle East ..................................... 229 7. Europe ........................................ 229 8. U.S.S.R. ....................................... 230 9. Asia .......................................... 230

E. Mining . ........................................... 230 1. Shaft Mining ..................................... 230 2. Solution Mining .................................. 230 3. Brine Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

F. Beneficiating- Refining ................................ 231 1. Beneficiation of Sylvinite Ores ......................... 231 2. Beneficiation of Carnallite Ores and Brines ................. 233 3. Beneficiation and Utilization of Sulfate Ores ............... 234 4. Production of Potassium Sulfate by Thermal Processes ......... 236 5. Mannheim Process ................................. 236 6. Hargreaves Process ................................. 236 7. HCl Utilization ................................... 236 8. Uses of Potassium Sulfate ............................ 236

G. Production of Potassium Nitrate . .......................... 236 1. Southwest Potash Process ............................ 236 2. IMI Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 7 3. Other Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 8

H. Waste Disposal ...................................... 238 I. Chemical Grade Potash . ................................ 238 J. Potash Particle Size ................................... 239

1. Price Differential for Grades .......................... 239 2. Granulation of Potash Salts ........................... 240

K. World Potash Production Capacities ........................ 241 L. Prices and Production Costs . ............................. 242 M. World Potash Commerce .. .............................. 244 N. World Potash Consumption . ............................. 245 REFERENCES ......................................... 246

XIX. COMPOUND FERTILIZERS A. Choice of Grades . .................................... 248 B. Processes for Manufacture of Compound Fertilizers .............. 248

1. Dry Mixing of Fertilizers ............................. 249 2. Granulation of Mixtures of Dry Materials .................. 250 3. Granulation of Dry Materials With the Addition of Materials

That React Chemically ............................. 252 4. Slurry Granulation ................................. 254 5. Melt Granulation Processes ........................... 256 6. Prilling Compound Fertilizers ......................... 258 7. Bulk Blending .................................. _ . 260 8. Production of Fluid Compound Fertilizers ................. 263 9. Clear Liquid Fertilizers .............................. 263

C. Economics of Production of Compound Fertilizers .............. 266 REFERENCES ......................................... 268

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Chapter Page XX. SECONDARY AND MICRO NUTRIENTS

A. Secondary Nutrients .................................. 270 1. Calcium and Magnesium ............................. 270 2. Sulfur ......................................... 272 3. Incorporation of Secondary Nutrients in Granular Fertilizers ..... 272 4. Secondary-Nutrient Addition to Liquid Fertilizers ............ 273 5. Secondary-Nutrient Addition to Suspension Fertilizers ......... 273

B. Micronutrients ...................................... 273 1. Micronutrient Addition to Granular Fertilizers .............. 274 2. Micronutrient Addition to Liquid Fertilizers ................ 275

C. Other Useful Elements ................................. 276 REFERENCES ......................................... 276

XXI. CONTROLLED-RELEASE FERTILIZERS A. Controlled-Release Phosphate Fertilizers ..................... 278 B. Controlled-Release Nitrogen Fertilizers ...................... 278

I. Slightly Soluble Materials ............................ 279 2. Guanyl Urea Sulfate (GUS) and Guanyl Urea Phosphate (GUP) ... 279 3. Coated Soluble Materials ............................. 279 4. Nitrification Inhibitors ..................... _ ........ 282

C. Controlled-Release Potash Fertilizers . ....................... 282 D. Conclusions About Controlled-Release Fertilizers ............... 283 REFERENCES ......................................... 283

XXII. PHYSICAL AND CHEMICAL PROPERTIES OF FERTILIZERS AND METHODS FOR THEIR DETERMINATION

A. Introduction . ....................................... 284 B. Particle Size ........................................ 284

1. Effects on Agronomic Response ........................ 284 2. Effects on Storage and Handling Properties ................ 285 3. Effects on Blending Properties ......................... 285 4. Screen-Analysis Procedures ........................... 286

C. Segregation Properties ................................. 287 I. Segregation Due to Vibration. . . . . . . . . . . . . . . . . ....... 289

'"" Segregation Due to Flow (Coning) ...................... 289 3. Segregation Due to Ballistic Action ...................... 290 4. Antisegregation Measures for Blended Fertilizers ............. 290

D. Granule Hardness . . . . . . . . . . . . . . . . . . . . . . . ............ 290 I. Crushing Strength ................................. 290 2. Abrasion Resistance ................................ 291 3. Impact Resistance ....................... _ ......... 292

E. Bulk Density ....................................... 292 F. Angle of Repose ..................................... 292 G. Apparent Specific Gravity . .............................. 293 H. Critical Relative Humidity . ............. _ ................ 294

1. Direct Method . . . . . . . . . . . . . .................. 294 2. Isoteniscope Method ............................... 296 3. Electric Hygrometer Method .......................... 296 4. Vacuum Line Technique ............................. 296 5. Gas Chromatograph ................................ 296 6. Effects of Temperature .............................. 296

I. Rate and Effects of Moisture Absorption . .................... 296 1. Laboratory Absorption-Penetration Test .................. 297 2. Small-Pile Tests .............................. _ .... 298 3. Protection in Bulk Storage ........................... 298 4. Drillability Tests .................................. 298 5. Laboratory Flowability Tests .......................... 299

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Chapter Page J. Caking of Fertilizers . .................................. 299

1. Effects of Moisture Content .......................... 300 2. Effects of Particle Size and Hardness ..................... 301 3. Effects of "Conditioners" ............................ 301 4. Effects of Storage Temperature ........................ 302 5. Effects of Storage Pressure ........................... 302 6. Effects of Curing .................................. 302 7. Large-Bag Storage Tests ............................. 302 8. Small-Bag Storage Tests ............................. 304 9. Accelerated Caking Tests ............................ 304

K. Chemical Compatibility in Blends . ......................... 305 L. Dustiness and Conditioner Adherence ....................... 306

1. Design of Conditioning Drums ......................... 306 2. Measurement of Dustiness or Conditioner Adherence .......... 306 3. Use of Dust-Control Agents ........................... 308

M. Melting Point ....................................... 308 N. Physiological Acidity and Basicity of Fertilizers ................ 308

I. Methods for Determining Acidity and Basicity .............. 309 2. Some Limitations of Acidity-Basicity Ratings ............... 310

0. Salt Index ........................ : ................ 311 1. Method of Determination ............................ 311 2. Significance of Results .............................. 312 3. Usefulness of the Salt Index .......................... 312

REFERENCES ......................................... 312

Part Five-Planning and Economics

XXIII. POLLUTION CONTROL AND OTHER ENVIRONMENTAL FACTORS A. Introduction . ....................................... 319 B. Gaseous Effluents .................................... 319

1. Ammonia ....................................... 319 2. Nitrogen Oxides .................................. 320 3. Sulfur Oxides and Sulfuric Acid Mist. .................... 320 4. Gaseous Fluorides ................................. 3 21 5. Mist, Fumes, and Dust .............................. 321 6. Ammonium Nitrate ................................ 322 7. Urea .......................................... 322

C. Liquid Effluents ..................................... 322 1. Nitrogen Fertilizers and Intermediates .................... 3 22 2. Phosphate Fertilizers ............................... 323 3. Boiler and Cooling-Tower Effluents ..................... 324 4. Potash ......................................... 324

D. Solid Wastes . ....................................... 324 1. Gypsum ........................................ 324 2. Calcium Nitrate and Calcium Carbonate ................... 325 3. Arsenic Trioxide .................................. 325 4. Spent Vanadium Catalyst ............................ 325

E. Trends in Pollution Control and Legislation ................... 325 1. Developed Countries ............................... 325 2. Developing Countries ............................... 325 3. UNIDO's Role ................................... 325

F. Establishing a "Grassroots" Plantin a Developing Country ......... 325 1. Guide to Engineering Contractors' Plant Specifications ......... 326 2. Environmental Surveys .............................. 326

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Chapter Page G. Economic Aspects of Pollution-Control Costs . ................. 327 REFERENCES ......................................... 327

XXIV. PLANNING FOR THE DEVELOPMENT OF A FERTILIZER INDUSTRY A. Introduction . ....................................... 329 B. Estimates of Demand and Requirements ..................... 329 C. Marketing ......................................... 329 D. Natural Resources .................................... 330 E. Types of Fertilizer Production Facilities ..................... 330

1. Development of the Marketing and Distribution System ........ 331 F. Government Policies .................................. 331 G. Government Legislation and Regulations ..................... 331 H. Plant Location ...................................... 331 REFERENCES ......................................... 332

XXV. ECONOMICS OF FERTILIZER MANUFACTURE A. Assumptions for Plant Cost Estimates ....................... 333 B. Assumptions for Production Cost Estimates ................... 334

I. Capital- Related Costs ............................... 334 2. Capacity Utilization. . . . . . . . . . . . . . . . ........ 334 3. Labor-Related Costs ................................ 334 4. Raw Material Costs ................................ 33 5 5. Utilities ........................................ 335 6. Other Costs ..................................... 335 7. Cost of Bags ..................................... 335

C. Process Requirements . ................................. 335 D. Nitrogen Fertilizers ................................... 335

I. Ammonia ....................................... 335 2. Urea-Ammonia Complexes ........................... 338 3. Nitric Acid and Ammonium Nitrate ..................... 340

E. Phosphate Fertilizers .................................. 341 1. Sulfuric Acid .................................... 341 2. Phosphoric Acid .................................. 342 3. TSP, DAP, and MAP ............................... 343 4. Phosphate Complexes ............................... 343

F. Other Fertilizer Products ............................... 345 XXVI. PROBLEMS FACING THE WORLD FERTILIZER INDUSTRY

A. Need for More Fertilizer . ...................... ~ ........ 346 B. Infrastructure Difficulties ............................... 346 C. Delays in Constructing Fertilizer Projects and Bringing Them

Into Production . .................................... 347 D. Full Utilization of Existing Capacities ....................... 34 7 E. Contracting Procedures . ................................ 348 F. Rising Capital and Raw Material Costs . ...................... 348 G. Financing . ......................................... 349 H. Cyclic Nature of World Fertilizer Prices ...................... 349 I. Technology and Know-How Transfer ....................... 349 J .. Regional and Subregional Cooperation ...................... 349

I. Regional Cooperation ............................... 349 K. Future Developments That May Reduce the Cost of Fertilizer Plants

or Reduce the Quantity of Fertilizer Required ................ 350 1. New Methods for Gasification or Liquefaction of Coal ......... 350 2. Other Fossil Fuels ................................. 350 3. Nuclear Energy ................................... 3 50 4. Energy from Ocean Currents .......................... 350 5. Better Use of Organic Wastes .......................... 350 6. Biological Fixation of Nitrogen ........................ 350

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Chapter Page 7. Enzymatic or Catalytic Fixation of Nitrogen ............... 350 8. More Effective Use of Nitrogen Fertilizer .................. 350 9. Prefabrication of Fertilizer Plants or Modules ............... 350

L. Conclusion . ........................................ 3 53 REFERENCES ......................................... 353

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