Dut the first edition . . . + Provides detailed, comprehensive, practical information regarding all aspects ofthis ustry. It offers coverage of the latest equipment, technology and construction eral —Chemical Engineering World .« useful to those interested in the manufacturing, the use and the environmental acts of phosphatic fertilizers.” Bulletin ofthe International Society of Soil Science ¢ book is of major significance in its field... . Professionals inthe industry ... will itinvaluable.”| —Chemisiry in Australia wut the second edition . . . -~--hly updated and enlarged to reflect significant changes that have occurred in the ‘acid indusiry and its markets since the previous edition was published, the dition contains new and expanded material on crystal growth -juiai® processes... material balance calculation methods. .. filtration. ... entration systems ... rock grinding, ... fluorine recovery and environmental effects nvestment costs, and, especially, commercial ore. iding an in-depth look at phosphoric acid production in today's economy. this single- ¢ reference also reveals, rough ilustrations and case studies, solutions to the most mon engineering and production problems . . . shows how commercial phosphate entrates can be applied to present technology and gives detailed tables of phosphate 3. and demonswates methods of calculating such important factors as « sance and agitation. ut the author... 2 Bass isa consulting enginer inthe chemical industry and main shareholder of. 8 consulting fim specializing in phosphoric acid. Previously he was development manager at Compagnie Fragaise de!’ Azote, France. Mi: Becket 2 of Several papers on phosphoric acid production, and be has worked ina wide y of phosphoric acid programs in 34 countries over a 35-year period. He studied ical enginering atthe Ecole Nationale Supticure de Chimie de Srasbourg, France. d inthe United Stater of America ISBN: 0-8247-—7976—2 Marcel dekker, Inc new york base! -hong kong ang technology & = 3 a o ploy ovoydsoud pue seyeydsoud g a Edition, Revised and Expanded Becker LI/10.6/001 EX.2/2 (1989) fertilizer science and technology series—volume 6 Phosphates and Phosphoric Acid Raw Materials, Technology, and Economics of the Wet Process Second Edition, Revised and Expanded HPO, Pierre BeckerPhosphates | | | | | and Phosphoric AcidFERTILIZER SCIENCE AND TECHNOLOGY SERIES EDITORS TRAVIS P. HIGNETT. DEREK A. PALGRAVE onsitant A.W. Chater Lx Inernaton!Feriizer Doncaster, England Deveiooment Center Muscle Shea Alsbare Vol. 1. Phosphoric Acid (in two parts), edited by A. V. Slack (Part If, cut of print) Vol. 2. Ammonia (in four parts), edited by A. V; Slack and G. Russell James Vol. 3. Phosphates and Phosphoric Acid: Raw Materials, Technology, and Economics of the Wet Process, Pierre Becker Vol 4. Nitric Acid and Fertilizer Nitrates, edited by Comeltus Keleri Vol. 5. Manual of Ferilizer Processing, edited by Francis T: Nielsson Vol. 6. Phosphates and Phosphoric Acid: Raw Materials, Technology, and Economics of the Wet Process. Second Edition, Revised and Expanded, terre Becker Additional Volumes in Preparation Phosphates and Phosphoric Acid RAW MATERIALS, TECHNOLOGY, AND ECONOMICS OF THE WET PROCESS. Second Edition, Revised and Expanded Pierre Becker NSCS ‘Strasbourg, France With contributions by MICHEL DUTHOIT KLAUS FRANKENFELD MICHEL GAURON TOBY NOGUERIA WILLIAM E. RUSHTON PAUL ANTHONY SMITH lected ilustrations by Nathalie Becker Mancet Drxeer, Inc. New York - BasetLibrary of Congress Cataloging-in-Publication Data sett Tol amt phones vd «re nn, wasp, et cc's kms re ee, hy a itor es nm Sepang oT pled ee tame Includes bibliographies and index. iat : id 1. Phosphoric acid. 2. Phosphates. I. Title. 11. Series. TP2IT.PSB4 1989 668". 625--de19 88-23626 cP Copyright © 1989 by MARCEL DEKKER, INC. All Rights Reserved Neither this book nor any part may be reproduced or transmitted in any form or by any means, életronic or mechanical, including photo- copying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. MARCEL DEKKER, INC. 210 Madison Avenue, New York, New York 10016 Current printing (last digit): 09876 5 PRINTED IN THE UNITED STATES OF AMERICA Foreword I am indeed flattered to be given the privilege of writing the Fore- word for this second edition of Plerre Becker's most successful vol- ‘ume on phosphoric acid. Since it appeared in 1983, the book has become the standard text for phosphoric acid, due not only to the expertise of Pierre, but also to the talented staff of helpers who, together, have amassed an amazing amount of useful data, such that the work becomes a virtusl design manual. ‘The Foreword for the first edition was written by Philippe Morailion, who referred to the progress mde over the preceding 35 years. 1 like to think of myself as a bridge to a technology even further back than that, through my 25 years of association with Wittiam C. Weber and E. J. Roberts of the Dorr Company, later Dorr-Otiver. Bill Weber and “Doc” Roberts were the principals in the success~ ful development of the prototype for the "strong acid” dinydrate process, which still predominates today. The phosphate fertilizer industry in the late 1920s wes just emerging from being based ex- clusively on normal super phosphate. The use of phosphoric acid to bind the new, cheaper synthetic ammonia was suggested in a 1930 article by Weber. In 1931 the Dorr Company, which hsd supplied, worldwide, over the previous decade, fifteen or more phosphoric acid plants using ‘the week-acid, countereurrent decantation process, brought into operation a new phosphoric acid plant at Cominco's metallurgical facility at Trail, British Columbia, Canada. The design started out as a single-stage hemihydrate process. The filtration of the hemt slurry on internal drum filters, without the availability of synthetic fiber filtercioths, was unsatisfactory.Foreword Berging from the unsuccessful hemi : _Baerging proces, the dihydrate teoh- igue of using substantial slurry recirculation and proves cate ono! ints resulted in varlyisproved eryutale an acid sents 380 705, tntead of th to 2 HO oe fine Plant produced a total 120 tons per day of P05 in es. “This ao enormous by the standards o that ere autan lee ony ghospore ald‘ wae on ite my to the huge pro tive plants of today, the technology of Whigh fe 20 wel ewtoed by Pierre Becker in tis updated edison, David W. Leyshon Jacobs Engineering Group, Inc. Preface to the Second Edition Five years have passed sinco the first edition of Phosphates and Phosphoric Acid was published, and in that time decisive trends for the phosphoric acid industry and its markets have taken place: New leader countries have set up modern and efficient state-owned phosphoric acid production industries. To date, the largest plant is no longer in the United States, but in Morocco. ‘The volume of phosphoric acid trade has skyrocketed, reaching ‘almost 4 million tons of POs as acid by the end of 1987. This 43s equivalent to an average increase of 6t per year. Large phosphoric acid-demanding areas, such as India with an #t yeerly increase, have promoted a worldwide acid trade. China is showing a similar trend, slthough it may be delayed for some time. However, the worldwide movement toward higher capacities and ad- ditional production units has resulted in a situation of general over- ‘eapacity with a consequential world market price depression. ‘Smaller end older production units, and those that offered no particular economic advantages, have known hard times, and many ‘of them have not survived the challenge of the large state-owned industries. Furthermore, some were forced to shut down because they could no longer afford environmental improvements that are now required by more sensitive municipalities. ‘The economic assets that are generally mentioned with regard to leader positions in the phosphoric acid industry consist essentially of obtaining integrated phosphate or sulfur raw materiel sources. Both ingredients represent an average of 60804 of the current production costs for phosphoric acid. With regard to these dazzlingvt Preface to the Second Edition numbers, technology is often somewhat underestimated or even for~ gotten. In fect, the actual manufacturing costs account for only U.8.$30-50 per ton of Py0g as acid, out of the current U.S.$360- 380 delivered price (by early 1988). But what about capital charges? They often yield up to U.S.$100 Per ton of P05, as @ result of the invested technology. If said technology is well chosen and thoroughly engineered, a large part of the hundred-dollar bill can be saved. Furthermore, the chosen technology and engineering studies not only can save on investment costs; they also can save on energy, Taw materials, and maintenance costs, and enhance productivity and uality—all this, of course, with the least-polluting effects. The objective of this book is to improve technology by increasing the understanding of phosphates end communicating the progress made in fertilizer technology. For the second edition, the number of coauthors was enlarged, and the following sections were particularly improved: crystal growth, nondihydrate systems, material balance calculation, filtration, concentration, environmental concerns, and, especially, commercial ore data section. In alphabetical order, my coauthors are listed with their contribu- tions: Michel Duthoit, Head of Reseerch and Development Laboratory, COFAZ, Le Havre, France [Chapter 10, in collaboration with Pierre Becker and Michel Gauron) Klaus Frankenjeld, Head Research and Development Department, Chemische Fabrik Budenheim, Budenheim, Federal Republic of Germany {Section 8.5.1) Michel Gauron, Chemical Engineer, ENSCS, Strasbourg, France, and Head of Research and Development Department, COFAZ, Le Havre, France [Chapter 10, in collaboration with Pierre Becker and Michel Duthoit} Toby Nogueira, Engineering Consultant, Broken Arrow, Oklahoma {Sections 4.1 to 4.9) Wiliam E. Rushion, Division Manager, Swenson [Chapter 7, in col- kaboration with Pierre Becker] Paul Anthony Smith, Head of Engineering Division, Prayon Develop- ment §.4. [Section 2.1.2] To all of them I want to express my thenks for their cooperation. J also want to thank my wife, Marie-Louise, and my daughter, Nathalie, for their support. 4 Avenue de Brimont 78400 Chatow France Pierre Becker Preface to the First Edition Almost fifteen years have passed since Marcel Dekker published A. V. Slack’s volume about phosphoric acid. Phosphoric acid technology during these years has not been stagnating: some sys- tems became old-fashioned, others improved: some of the more elab orate processes succeeded while others experienced setbacks. Energy and raw material prices have increased considerably and ore qualities heve changed. New phosphoric acid production centers have been crested. Countries such as Morocco and Tunisia, which formerly only mined phosphate ores, became large phosphoric acid Producers; Jordan, Senegal, Togo, and Brazil are to follow a similar he PetNew construction meterials and equipment end better Knowledge of technology resulted in improved and larger-sized production units. Environmental problems such as calcium sulfete disposal and fuo- ride emission became of primary importance in industrialized countries, often outweighing the decision to implement a now project. The technology of phosphoric acid nevertheless still remains very empirical. The authors of this book, having all participated in this evolution, felt it was time to make their experience available to others. We have had several primary goal ‘To give an updated picture of phosphoric acid production technology in today's economic situation ‘To suggest methods for solving engineering and production problems ‘that regulerly occur in phosphoric acfd technology and to illustrate them with many examples ‘To offer our engineering and plant experience viti Preface To show how the various iunds of commercial .nds of commercial phosphate concentrates apply to present tecia:civgy, by presenting detailed tables of phos- Phate rock anelysis ineluding specific industrial characteristic fac Ors auch as grinding capability, specific sulfuric acid consumption igures, filtration capacities, sludge formation from the concen- {rated acid, chemical and physical properties of produced acids, and soon ‘To maintain a link between technology and economics The render wil find throughout the book » considereble data trom production and pilot plant experience with phasphetes of Aitferent origins. Project engineers te nell as production engineers should find this volume tobe a sin aousce of helpful inforwaions 1 would ike to express my sppredation to Michel Geuson and Miche! Duthot, who assisted in the preparation of Chapter 10, Pierre Becker Contents Foreword David W. Leyshon Preface to the Second Edi Preface to the First Edition 1. Introduction to the Chemistry and Economics of Phosphates and Phosphoric Acid Production 4.1 Phosphates: Their Share in Earth's Crust, Life, and World Economy Geology and Occurrence of Phosphate Deposits Phosphoric Acid Production: Particularities of ‘the Wet Process Technology 1.4 History of Phosphoric Acid Chemistry and Production Using the Wet Process 1,8 Raw Materials for Wet Process Phosphoric Acid Produetion 1.8 Current Developments References 1.2 1.3 2, Industrial Process Chemistry 2.1 Wet Process Review 2.2 Reaction and Crystallization 2.3 Empirical end Mathematical Approach to Crystal Growm end Size Distribution Laws; Effect on Filtration Rates; Size Distribution as Reactor Efficiency Indicator References 2 32 4B 43 aa 1683 a 6 Contents Process Systems and Calculations 79 3.1 Material Balance 180 3.2 Reoyele Acid System 192 3.2 Heat Balance 201 34 210 3.5 220 232 Phosphate Rock Grinding 233 4.1 Grinding Requirements 234 4.2 Mechanism of Breakage; Particle Size Distribution 238 4.3. Short History of Grinding aa 4.4 Energy Required to Grind Phosphate Rock 22 4.5 Dry Grinding 259 4.6 Wet Grinding 264 4.7 Closed-Loop Grinding 28 4.8 Boll Mile 230 4.9 Rod Mills 299 4.10 Pendulum or Ring Roller Mills 303 4.11 Roller Mis 320 References 325 ‘The Reaction System 3a 5.1 Raw Materials Feeding and Metering 331 5.2 Slurry Resetor 337 5.3. Agitation 380 5.4 Mechanical Foam Breaking 372 5.5 Heat Removal 385 5.6 Pumping and Cirovlating 308 5.7 Fluorine Emission Control 401 References aa The Filtration System as 6.1 Fundamentals 425 6.2 Factors That Influence Performance 492 8.3 Filtration and Cake Wash Diagrams; P205 Balance ‘Throughout the Filtration System 435 6.4 The Know-How and Daily Problems of the Operator 45 6.5 Choosing a Filter 354 References 462 Contents h Acid Concentration Systems T.1 Process Design Considerations 1.2 Equipment Design Considerations 1.3. Superphosphoric Acid References Product Acid impurities and Sludge &.1 Impurities in the Production Acid 8.2 Wet Process Phosphoric Acid Sludge 8.3. Sludge Removal Practices 8.4 Clarification Equipment 8.5 Selective Removal of Impurities from Wet Process Phosphoric Acid References ‘9. Phophogypsum: Expensive Waste or Profitable By-Product? 9.1 Present Status: Megnitude of the Problen 9.2 Gypsum Disposal: Dispersion into a Moving Body of Water 9.8 Gypsum Disposal: Impounding on Land 9.4 Gypsum Disposal: Dry Stacking with Land Reclaiming 9.5 Salable Products References 10. Corrosion 10,1. Corrosion with Phosphorie Acid Production 10.2 Contributing Factors 10.3 Instant Corrosion Monitoring 10.4 Recommended Alloys for Use with Phosphoric ‘Acid Production References 11, Investment and Manufacturing Costs 11.1 Investment Costs 11.2 Manufecturing Costs 11.3 Maintenance Costs 1.4 Economie Comparison of Different Rocks Reference Appendix A: Phosphate Rock Data Sheets Appendix B: Useful Tables and Diagrams Index st 463 474 489 491 493 493 502 Bu 518 528 532 337 537 538 543 589 560 586 s71 st 573 583 54 585 387 37 592 598 608 618 619 ns 733and Phosphoric Acid Phosphates1 Introduction to the Chemistry and Economics of Phosphates and Phosphoric Acid Production 1.1 PHOSPHATES: THEIR SHARE IN EARTH'S CRUST, LIFE, AND WORLD ECONOMY Phosphates occur most commonly in the earth's crust as the calcium ‘component of orthophosphoric acid, the latter, H3PO4, being derived from pentavalent phosphorus oxide. Phosphorus averages 1180 ppm in the eerth’s crust, and thus ranks as the eleventh most frequent element. By contrast, sulfur and nitrogen have values of 520 and 46 ppm, respectively. Nature has taken advantage of the manifold aspects of the chem- ical Dehavior of phosphorus, which has thus become indispensable for life. The organie phosphatic compound DNA (deoxyribonucleic acid) is the backbone of the genetic code in living cells, and ATP (adenosine triphosphate) monitors energy conversions in these cells. ‘The bones of mammals heve a Pz05 content of 27%, whereas vegeta tion averages 18 P20s in dry material.* Living creatures supply their phosphate needs by food, and Phosphates in food arise from hiologies! phosphorus uptake from available soll components. Since phosphates are unevenly distributed ‘and not available to plants at the current levels of farming, it is the goal of the phosphate industry to supply phosphate fertilizers of the necessary quality and quantity to farmland areas throughout the world. Phosphate fertilizers constitute 908 of the world's phosphat industry (see Table 1.1). With some 149 million tons of commercial "POs: phosphorus pentoxide equivalent content in phosphate rocks and phosphetic fertilizers.2 Chapter 1 TABLE 1.1 World Phosphate Consumption anu avy a, 1980 PDs (thousends of tons) Percentage Fertilizer 32,000 0 Detergents 1,590 4.5. Animal feed Liao 3.3 Food and beverages 280 0.7 Surface treatment 230 0.6 Water treatment 80 0.25 Dentistry, toothpastes 80 0.22 Fire extinguisher 40 oat Others 10 0.8 Total 35,600 100 Source: Ref. 1. phosphate ore, phosphates contribute some U.S. $3.5 billion to the world's raw material trade, and phosphate products account for over U.S. §16 billion. 1.2 GEOLOGY AND OCCURRENCE OF PHOSPHATE DEPOSITS ‘To produce such large tonnages, it is evident that phosphate ores, ‘the raw materiil for phosphoric acid production, will be mined in many parts of she world. Phosphate ores are of two major geological origins: 1, Sedimentary 2. Igneous and metamorphic The most easily mined phosphate deposits are found in the great sedimentary basins. Studies of the formation of these phosphate deposits that occurred about 70 million years ago have led to many theories [2]; for example, climate, ocean currents, and geographical factors affect the deposition of the phosphates. Generally, these sedimentary deposits are associsted with matter derived from living creature; thus they contain organic compounds. These phosphate ‘ore bodics, widely varying in thickness, are intercalated with sediment 1y stratus of other waste materials or similar ores inter- penetrated by gangue minerals [3]. Introductic 3 From the aforementioned it appears that the sedimontary phos: Lh. 08 are subject to many varistions and to differing compost- tions within the seme source. Phosphate ores with igneous and tnetemorphic origin also are subject to wide changes. They have almost infinite varieties of geologicel structures and complex mineral suites and ere subject to a great munber of substitution processes within thelr ehemical somposition (4]. These ores account for ap- proximately 198 of total production. Most phosphate ores, whatever thetr origin, have to be concen- trated or beneficiated before they can be consumed or sold on the international phosphate market. Commercial phosphate ores or "phosphate rocks” have one property in common: their phosphetic content is a phosphate-fluorine-calcium combination of apatitic struc- ture. The phosphate rock producers express the content of thefr products as BPL* grade, More recent literature uses the term TPL (total phosphate of line). Because of the increase in demand, the original sources of high- grade ore (essentially Morocco, the United States, and the USSR) are no longer sufficient and new deposits are being mined in approx- imately 32 countries with considerable varistion in quality and eompo- sition (see Table 1.2). The general rise in rew material prices in 1074 meant thet certain phosphate deposits and qualities previously considered uneconomical or too low in quality are now being exploited. Consequently, lower-priced, lower-quality phosphates began to find # growing market. At the beneficiation stage, different techniques may be used to treat the same ore for removal of the gangue end assoclated in- purities. This gives rise to further varieties in the finished ore concentrate product. It is cleer. therefore, that phosphoric acid technology, heving to rely on raw materials of grest variety and of permanently fluctuating composition, has to readapt itself constantly. Phosphoric acid cen be produced from these raw materials via two major process routes: the wet process, using sulfuric acid attack, and the electric furnace process, using electrical energy to Produce elemental phosphorus 2s a first stage. Because of current energy prices, the electric furnace process, although it can cope with Jower~grade phosphate rocks, has been largely abandoned ex- cept in cases where elemental phosphorus is needed. The wet process, which is the subject of this book, accounts for over 908 of the cur- rent phosphoric acid production. “BPL is an abbreviation for "bone phosphate of lime" for Cag(PO4)2. To convert BPL grades into P20; equivalent grade, divide by 2.183.7 Chapter 1 Introduction : TABLE 1.2 Chemical Composition of Some Phosphate Rosk Concentrates® BPL FeQly gO Ne Source Country Rock name grade POs F C02 | ese ene ert eee eee See tee 41S 08 LS 1 Australia Duchess, eo ss 320 LS Saaneteetiera cecnate ecient acetce sete iaa 2 Brasil Sacupirenage ete ee aea® f O6 40 06 28 OL On 4 Aracha ae ee 0.0 0.8 52.9 02 08 OL 09 4 a Yunan Saas 2300 21 40 LO 2 Finland Silinarvi 80 26 43 ie 20 862 (04) O88. 06 2 Treg Akeshat ae Hee. a 64 504 03 0.2 09 O85 4 Jordan Russeifa 66-68 a5 66 ie 23 518 O04 02 05 0.9 4 Morocco Khouribga ne 88 O50 5.7 510 etn 4 Buecraa = ae 0.0 Oo 52.1 04 02 v4 2 Neuru ee 250 25 467 8.7 08 BLT 4 Pera Sechure = eal On 1.0 620 02 0.7 20 0.3. 4 South Africa Palabora ae a) O90 5.0 80.0 11 09 00 08 4 Senegal a ar 8 03 45 808 10 Looe 4 Togo - a8 a a3 2.8 504 04 OF 07 4 Tunisia Mouleres lavé 65 6.8 28.3 20 oT 1 aaa Ghilieaiok. 7 A 53 0.0 20 80.5 069 O85 D1 O86 4 Kola 35 29 20 ne wo us a2 1 Kersten a re) 283 te oot 1 Kingisepp a a0 88 a 47 11 1508 Os 4 Us. Florida 68 3.7 8 1 ia m2 11 ow 05 05 4 Florida i at 5 : 8 a2 ir it 03 os 4 Florida 8 ns ca i 22 52808 O68 10 4 N. Carolina 12 40 2 i calcined 1S 41.6 1.8 z on 1 Tennessee pe es oo 0600 one? 2 ‘Vietnam Kamdheng 18-79, 36.1 22 48 1 ES “For a more detailed analysis, see Appendix A. Sources: 1, British Sulphur; 2, World Bank; 3, Internstional ' Superphosphate Manufacturers Association; 4, author's files, |6 Chapter 1 1.3. PHOSPHORIC ACID PRODUCTION: PARTICULARITIES OF THE WET PROCESS TECHNOLOGY By its nature, wet process technology conserves most of the impur- ities found in the original phosphate ore, which are then induded in the phosphoric acid produced. Consequently, the variety of the Phosphate ores influences not only the process used but also the ‘composition and characteristics of the phosphoric acid produced. Wet process phosphoric acid technology, which will be described in the next sections, essentially comprises sulfuric acid attack and separation of the phosphoric acid produced from the calcium sulfate erystals resulting from the reaction. Both the attack end the separa- tion, whieh is effected by filtration, are considerably affected by the neture of the ore and its impurities. Besides calcium phosphate, the phosphate ores contain 10-15 major impurities and another 18 or so trace elements.* Organic matter, also present in many ores, is not included in this estimation. Esch clement contained in the ore has its individual transfer coef- ficient into product acid and waste solids. Without enumerating all the effects on processes and economics due to the impurities, some of the more common are: 1. Effect on erystaltization: ‘The ealeium sulfate qualities, due to the presence of the various impurities, affect filtration rates |'y a factor of 4 from one phosphate ore to another. 2, saling: Vessels and pipework are subject to deposits of vari- a Kinds. Heat transfer coefficients, pressure drop in pipe- ‘k, are subject to heavy alterations. 3. ..udge formation: Some impurities are subject to delayed pre- wpitetion in the stored product acid or the final concentrated ‘cid, These are sludges—a difficult problem for the phosphoric producer. 4. Corrosion: Despite the use of exotie alloys, pump impellers and agitator turbines can be subject to rapid deterioration by corrosion. 3. Environmental aspects: Acidic fluoride compounds evolve from reaction vessels and concentration plants. They have to be Fecove. + and combined to produce salable or at least harmless compu... ‘3. Trace elements such es cadmium have aroused great . crn, and in the case of specific phosphete rock sources, have affe sied their sales pstterns considerably. “Mainly heav. : tals end rere earth elements. Introduction 7 Many impurities, despite tedious procedures, cannot be enalyzed uantitatively with accuracy, either from the phosphate rock or from the phosphoric acid produced. For example, it is possible for a 15 to 25% absolute deviation in iron and aluminum contents, respectively, to be found within the seme ore sample as measured by different laboratories. If the problems listed sbove characterizing phosphoric acid wet process technology are not discouraging enough, consider, too, the ‘complications from dust, foam, and so forth. From the foregoing it is obvious that the science of phosphates and the technology of phosphoric actd is somewhat esoteric. Words such as "technology" or "calculation," in this ease, have to be em- ployed very carefully. Sometimes traditional calculation methods can ‘be used and sometimes one has to rely on experience and.accept @ Simple estimation based on similar cases. ‘An understanding of what and how to calculate in phosphoric acid technology is the objective of this book. We hope the reader will derive some adventage from the many years the various authors have spent in the dust and effluent gases of phosphorie acid plants, watching filter cakes end plugging pipes! Like human beings, phosphates are fascinating; they never be- have consistently. They like to be trested differently every time. Once you are married, even if only to phosphates, you need to use a fresh approach day by day. 1.4 HISTORY OF PHOSPHORIC ACID CHEMISTRY AND PRODUCTION USING THE WET PROCESS The production of phosphoric acid by means of the wet process began to be developed intensively following World War Il. As a simple transformation of calcium from a phosphate to a sulfate, the reaction is PO) ,Ca, + 31,80, + 6H,0 » 350,Ca - 24,0 + POR, «Ay ‘The reality is, in fect, not as simple because of the technology that must be used. The phosphate attack and the formation of the calcium Sulfete take place on their own, so to spesk, but the eslcium sulfate corystels (gypsum or henthydrate) then have to be separated from the phosphoric acid thet is produced. ‘This separation must be thoroughly completed since, at the price of phosphoric acid, even a small loss at the filter will show up qulekly in the economies of the operation. A properly functioning Plent wil, under normal running conditions, lose 0.58 of the acid during filtration. This percentage is increased by startups. and8 Chapter 1 the measured average should not exceed 1% (measured average of the acid losses in the liquid effluents that accompany the rejected Sypsum, which does not include the losses of combined Pg0s contained in the gypsum). Good separation at the filter is achieved when crystallization at the reactor is "good." This type of crystallization has not, however, Proven easy to perfect; several decades of work have been required, ‘The science of "good crystallization" in a phosphoric medium has been perfected only by means of experimentation, which explains ite long. ‘slow evolution, In mixing phosphate with eulfurie acid, early pro- ducers were forced to conclude that great caution was necessary in this operation on an industrial scale, for a number of reasons. ‘The phosphate, being very porous, reacts extremely quickly without allowing the sulfete crystals to grow ini a regular manner. ‘The reaction is very exothermic, and the celories must be evacuated sinee, if the medium is too hot, no more SO4Ca-2H;0 is created; but instead, semi- or hemihydrate or anhydrous material forms, which ean recrystellize on the filter. Also, if the reaction becomes too hot, the phosphate is blocked in sulféte shells (coating) and the attacking yield is bad Garge-seale losses of unattacked P03). ‘Similarly, one has to work in a relatively diluted medium (27-308 with dihydrate processes, 40-453 for most cases with henihydrate processes). With growing P20s concentration, viscosity increases Gramatically and prohibits econonical filtration. Mass transfer and crystallization quality can be affected considerably. The first wet process phosphoric acid plants built between the World Wars I and II generally produced between 25 and §0 tons of P05 per day. The problems of mixing and agitation were poorly understood, so thet the reactive media were not really hemogencous and were highly supersaturated. The poor orystals were therefore Separated by decanting, an operstion necessitating huge volumes of equipment. 1 was able to see one of these installations before it was de- molished. The reagents were mixed in premixers fitted with grest Wooden stirrers turning slowly and the reactions were completed in gnormons reaction tanks. The gypsum was separated by decanting. The total size of the operation meant that 700 m? was needed to Produce 20 tons of P20s per day in the form of 25% acid by using the high-grade phosphates available st that time. To reduce the problem of supersaturation in the premixers, slurry was recycled after the reactions has been completed in a long series of reaction tanks. The problem of calefum sulfate crystallization within media with @ greater concentration of P205 hes fascinated many researchers ‘and es far back as 1930, Nordengreen took out patents for the manu- facture of more concentrated (40% Pz0s) phosphoric acid by means Introduetion 9 of the formation of hemhydrate or anhydrite (Ce80, 0.5130, CeS09). Nevertheless, this process, like others, often ran into trouble on an industrial seale, and it was not until the 1970s that plants worked well with good yields from erystellizations other than calcium sulfate dinydrate, Jt was the Japanese who after much research in this erea menaged to construct the first full-scale industrial units with an acceptable field by Siltering gypsum recrystallized from hemihydrate precipitated in the first stage. “The idea of having purer gypsum for subsequent use was one of the main reasons for the development of this tech- nique, Natural calcium sulfate, @ rare mineral in Japan, is used in the production of cement. In the 1960s there was a proliferation of hemihydrate-dihydrate Processes (or vice versa), most of them involving double separation Of the ealeium sulfate. The economics of these processes have some- times been dubious since a 28 recovery gain (U.S.$6 per ton of P05) and a few percentage points more concentration from plants which often produce a by-product steam that can be used for the Phosphorice acid concentration process do not necessarily justify ‘dditionel investment. and increases in maintenance costs. But difficult goals seem to create human incentives, and in spite of the great number of technical problems and a certain number of industrial failures with a consequent reconversion back to the di- hydrate route, about 75 phosphoric seid plants among the total of about $20 plants in the world now work with nondihydrate routes. ‘This is 238 of the total number of plants, but less than 208 of the capacity because most of them are medium-sized or small units. Most Of these nondihydrate units, about one in two, use the Japanese Nissan process, a hemihydrate into dihydrate recrystallizing process with one Sitration operetion, A significant event should be mentioned here: Dutch phosphoric acid producing company had tivo plents operating simultaneously, one a dihydrate and the other a heal. hydrate single-stage process. In 1982 they decided, after consider ing their specific energy economics, to convert their dihydrate plant into a second hemathydrate operation. In the field of dihydrate processing, the importance of mixing and agitation gradually improved and, toward the end of the 1960s, ¢ French company developed a plant with a single reaction tank. demon- strating that repid attack and good crystallization could take place together at the same time, provided that dispersion and the reactive Yolume were sufficient. The statistical age distribution of the crystals arriving at the filter did not seem to be as important es in the past. ‘The idea of a single reaction tank was very attractive to engi- Beers, and even those who had believed in multitank operations brought these together in the form of compartments within single shell while carrying on circulation by means of pumps. The new10 Chapter 1 single-tank reactors allowed thelr disciples plenty of scope to use thelr imagination, and extraordinary shapes were patented, ranging from egg-shaped to cigdr-shaped. Of these, only the flat cylinder, ‘the rectangular parallélepiped, and the ogg have survived in any numbers. ‘The others have more or less disappeared, being too Iarge to find any room in a museum. The evotution of stirring techniques can be gauged from the amounts of energy consumed per cubic meter in reaction as well es from the total volume in reaction compared to daily production. As late as the end of the 1960s, certain engineering firms were still Proposing seven cubic meters of rection volume per ton of POs per day. Today it is common to recommend 1.8-1.8 m9 for the dihyarete process, but some licensors operate with lower reaction cepecities, estimating investment costs for reaction volume higher than tho for increased filtration capacity. Although modern filtration equip- ment has been improved considerably during the current decade, the ‘most economical investment ratio-reaction volume/fitration capacity Temains a case-by-case assessment, Moro or less comparable dihydrate techniques have been developed {in paralici in five geographical areas: Florida, Belgium, France, England, and Tunisia. Belgium and Florida developed the same pro- ess, th Prayon process, whic accounts for the largest in size and the gre.:sst number of dihydrate plants throughout the world (almost half of :.al phosphoric acid production). The Rhdne-Poulene proves (Fig. 111 from France comes next with some 50 plants, followed by Jacobs-Lzr (formerly Dorr-Oliver) with 27 plants. Next is SIAPE with its special design for low grade, foaming rock from Tunisia, follow: by Fisons, England. A new process, the Gulf-Swenson iso- therms: process, appeared some years ago and is utilized by six plants Di.ring the late 1960s and the 1970s plant sizes increased and a 1000-» civic ton P205 plant gradually became the standard size. But the ir : vasing size of the production units brought with it problems assoc’ ed with the relative decrease in surface area. Cooling, which was viously carried out by bubbling with sir boxes (a crude sys- tem tit should not be allowed outside the laboratory, if at all), ie @ fu: sion of the surface area of the slurry. The system demands @ lot 0, nergy Garge volumes of eit have to be forced through the slur and the resultant thermal exchange is poor. Consequently, it ww. secessary to discharge large volumes of polluted air (70,000 m3/h ior every 100 tons of P205 per dey. 1 the same time, still using alr circulation, ways were developed to ¢ 1 td of the calories by spraying the slurry through the air, whi) 5 more economical of energy, Nevertheless, cooling still needs 2. sm amount of air and, in the resctor, the necessary surface ar - volume ratio tends fo bring large plants close to the geo- me norms of Csisembert cheese, Introduction FIG. 1.1 World's largest phosphoric acl plant (8 x 600 tons/day POs), Rhéne-Poulenc process at Djorf Lasfar, Morocco. (Courtesy of Office Cherifien des Phosphates, Morocco.) Vacuum cooling, in which the slurry is pumped into a vacuum chamber, where evaporation (whence the cooling) is instanteneous and not related to the surface area of the reactor, allows systems to be enlarged more easily. However, it is more expensive, and lange quantities of polluted cooling water are extracted instead of sir. Filtration has improved greatly thenks to improvements in filters, which can be sized to suit production capecities of 1200-1800 tons of P05 per day and even more with new projected filter sizes. Counter- flow washings with hot vater being recycled one or two limes produce very good filtration recoveries. The appearance of plastic materials in the 1960s meant that one could replece stainless steel tubing and separators, thereby reducing cepital end maintenance costs. Filter speeds are now higher end, since the specific rate of filtra- tion increases with the speed of revolution of the filter, it has been Possible to increase substantially the number of tons filtered per square meter of effective filtration area, A filter revolving et one revolution every 4 min will filter 1.4 times more per square meter than a filter turning once every 8 min.2 Chapter 1 This fect, combined with inprovements in filter cloth, means that it 1s now easy to produce 7 tons of P20s per square meter (at @ speed of one filter revolution every 4 min) with a Florida phosphate, and with a filtration recovery greater then 98%, whereas 20 years ago this figure would have seemed a daydream in spite of the quality of phosphates, which was then quite superior. Current developments deviate slightly from the direction that phosphoric acid techniques had long been following. This is due to the appeerance of poorer quality raw materiels. As a result of price increases, numerous deposits which were known but not previously exploited for reasons of quality or profitebility are now supplying inoreasing tonnages, mostly in national markets. As result, new plants have to be simple, robust (often the new minerals are more corrosive), and easy to operate (the local fermer should be able to operate them after suitable retraining). ‘These now developments have given added impetus to the di- hydrate process which 15 years ago was thought to be doomed to slow extinction because of more elaborate processes. Today even with exotic newcomers appearing in the phosphate rock world market, it is still a reliable process capable of guaranteeing economical production ‘of phosphoric acid. 1.5. RAW MATERIALS FOR WET PROCESS PHOSPHORIC ACID PRODUCTION 1.5.1 Commercial Phosphate Rocks Technology and Economics World Phosphate Rock Production and Resources In 1986 the world's phosphate rock production was estimated to be 142 million tons of commercial ere. There are some 200 minerals con- taining more than 18 P205, but the most important for the phosphoric ecid industry is the apatite group [5]: (Ca, Ney, MED g(FODDg (COQ),F Cs OWE, If mined st 1975 prices, the world reserves of commercial-grade phos- phste rock would be 117,000 million metric tons.1 Consequently, the current growth rate for phosphate rock production should not be Limited by considerations for searce ore deposits. ‘As mentioned previously, there ore two main types of apatite de- posits: sedimentary and igneous. Sedimentary deposits are the most important for phosphate rock production; about 95% [6] of the ‘sith y = (0.99% to 0.5x). {Based on data from the U.S. Bureau of Mines. Introduction 13 present world production is of thet origin. Both sedimentary and igneous phosphate ores are associated with 2 large number of impurities. Sedimentary rocks exhibit a wide range of chemical composition becouse of the various types of associated gangues. As compared with igneous ore, sedimentary rocks contsin more carbonates and fluorides and usually more iron and aluminum. They present as a Porous materiel and offer a large surfece for chemical reaction. Most of the time they contain organics, which are responsible for the ‘consequent coloring and foaming that occurs in the acid and finished products. The largest sedimentary rock mining areas are in Florida and Morocco, both areas producing together about 60 million tons of com- mercial rock. Igneous rocks are produced in the USSR (Kola), South ‘Africa, Brazil, and Finland. : Mining and Beneficiation ‘To bring a phosphate rock onto the international market, the ore has to be mined, concentrated, and transported to the nearest port, from where it is shipped to a phosphoric acid plant or sone other type of Phosphate-consuming industry. Minability of @ deposit from an economic point of view is possible when the sum of the costs of these operations fits the current economics of the phosphate industry and when the phosphate rock meets a certain number of quality standards. Mining is done by either open cast mining ot underground mining. Open cast mining (Figs. 1.2 and 1.3) consists of removing the over- burden covering the phosphate bed and recovering the ore by me- chanical shovels or by hydraulic methods. The economics of open cast mining depend essentially on the thickness of the overburden leyer end the ore bed as well es the yield of recovery of the Py05 contained in the mined ore bed. Economic conditions can allow up to 2.5-2 m® of material to be removed per ton of reclaimed ore. When the overburden is too large, underground mining has to be chosen, which has been done, for ex- anple, in Tunisia, (Figs. 3.4 and 1.5), Jordan, and Egypt, and for the igneous Kola rock in the USSR. Beneficiation or upgrading of the phosphate ore has called for a number of different techniques. In favorable cases, to reach con- mercial grades of some 208 of POs, only sereening and drying is necessitated (e.g., in Morocco, Nauru, and Christmes Island). How- ever, in most cases the ore quality needs removal of some by-product impurities. For sedimentary rock, suitable techniques for ecor fore concentration are: crushing and screening or grinding, fe" * by pneumetic particle size selection and washing and deslining hydrocyciones or classifiers. These techniques are based on pr “ide size selection. The phosphete ore particles usually occur within article size ranges between 60-80 um and 1000-1400 um.4 Chapter 1 FIG, 1,2 Removal of overburden in Togo. (Courtesy of Compagnie To. riaise des Phosphates.) +lotation, another ore concentration technique, also is applied ss phosphate ores. It can be used when silica has to be removed ina the ore, Most igneous rocks are beneficiated by flotation. « ucite (COxCa), a very frequent by-product of phosphate ores, is wodoult to separate by flotation, ‘4 Jess ‘vequent technique is calcination, It is sometimes selected tu destroy suite, but even though CO2 is released, CaO remains with the o:: and is not easy to leach out by washing. Rut calcination also destr ;< organics and prevents foaming in the later chemical Tock trea: yt; therefore, it is still used in several plants (e.¢., in Israel * - North Carolina). Formerly operated within rotary kilns, calsinatio: srrently uses fluid-bed technology, providing better temperatt. 1 and residence-time control, for improved homogeneous quality s\| ‘ards. Cadmium removal is also obtained by ealeination, but high. peratures than those needed to destroy organics are required Pho’ i. rock calcination usually reduces the original qualities of the 0, . terms of phosphoric acid production (depleted filtration Introduction 45 FIG. 1.3 Open cast mining in Morocco. (Courtesy of Office Cherifien des Phosphates, Morocco.) rates). The changes, however, seem to affect the ore as a function of the amount of CO removed from the ore by the calcination. Con- sequently, high-COg-containing rocks are more affected. Preliminary Chemical Valuation ‘The ideal phosphate, without impurities and giving high filtration rates and low sulfuric acid consumption factors, does not exist. Each fone has its own character. "Phosphate is a living ore,” said 4. Frochen, a French expert, and this is what makes phosphate tech- nology 20 diverse and variable according to the phosphate ere origin, Each rock has its own behavior when ground, attacked, erystallized, and filtered, The resulting phosphoric acid will have its own color, viscosity, and impurities. The impurities contained in the phosphate rocks are the mein responsible factors for the individual behavior of each ore, Usually, when considering a phosphate rock as a potential raw material, the first approach is to analyze its chemical composition, f.e., the P205 content and its impurities. This permite « preliminary16 FIG. 1.4 Old-time underground mining in Tunisia. Compagnie des Phosphates de Gafsa, Tun: Chapter 1 (Courtesy of Introduction av FIG. 1.5 Modern underground mining in Tunisia. (Courtesy of Compagnie des Phosphates de Gafsa, Tunisia.) assessment. The folowing criteria concern the most common impur- ities. Detailed evaluation of the effects of the impurities will be in Sections 2.2.5, "Effect of Impurities,” 3.1.6, 3.5, 5.7, 6.22, 8.18.5, 10.2, and Appendix A. The preliminary criteria for appre- ciating the quality of a rock depends on the final product we want to manufacture. To produce phosphoric acid, the main criteria for Phosphate ore are: P205 content or TPL (BPL) grade: when above 33¢ P05 (12 TPL), up to 388 P05 (83 TPL), or evon 398 (85 TPL) the rock is considered as. high grade. The current grade is 30-398 P05 (85-12 TPL). From 26 to 308 (57-65 TPL) is considered lon grade, There is very few commercial grade below 26¢ 20s (56 TPL). Ca0 content: affects the sulfuric acid consumption. Ech percent of CeO needs an equivalent of 17.5 kg H2S04 per ton of rock.18 Chapter 1 High CaO has an economic effect only. Relatively pure acid can be produced from ore containing very large amounts of calcite. Fluorine: usuelly occurs in sedimentary rock as 10% of the P25 weight. Fluorine can be a corrosive component if not enough reactive silica is also present. With a high sodium content (18 or more) most of it will precipitate during the phosphoric acid reaction. About half the remaining part in the product acid escapes when concentration by evaporation is operated. ‘S03 (sulfates): only a dead weight. However, the existing S03 in phosphate rock will save the corresponding amount of sulfuric acid curing the acidulation. Chiorine: an undesirable impurity, because of corrosion danger Usually becomes dangerous beyond 0.18, its corrosive action is enhanced by interactions with other impurities (FH, SO 4H2). Sidz: as quartz, only a dead weight. Reactive silica (from clays, for example) is needed to combine with fluorides to prevent corrosion. However, highly reactive silica will depress filtration rates (use floculants). 1203 and FeO: not a problem during phosphoric acid menufac- ture but afterward when using the phosphoric acid. Sludge formation with the concentrated acid; builds water-insoluble components in the phosphate fertilizer. Usual merchant-grade limit to be considered: A1,0, + Fe,0, 0.02 < < 0.08 ‘Too low an sluminum content is not welcomed either, because of increased corrosion and lower physical properties with fertilizer products downstream. fg0: stays with the acid phase. Increases viscosity strongly. MgNH4PO4 formation when the acid is ammoniated. Difficult manufacture of superphosphoric acid beyond a certain threshold (0.68 in rock). Naz: precipitates as NagSiP¢ from the acid. Organics: foaming ducing redction, dark cloudy solids suspended in product acid. Trace elements: cen affect crystallization and recrystellization by ‘adsorption on erystal surfaces (can be dramatic in case of non- dihydrate processes with reerystalization). They may have toxic effects in specific final products (animal feed or fertilizer). Productios. | osts, Sales Prices, and CIF Prices for Phosy’. » Rocks Produ. Costs. The production cost analysis for commercial phosphate . can be assessed by considering the following items: sduetion 19 Mining: removing of overburden or underground operations, exeavation of the phosphate ore 2, Transportation: from the mine to the beneficiation plant by truck, transportation belt, or liquid pumping 8. Beneficiation: crushing, screening, washing, flotation, end calcination, 4. Waste disposal: slimes, tails, to be piled or settled 5. Utilities: “water, energy supply, and so forth 6. Transportation to Inading port and storage: truck, railwey, conveying belt, and so on 7. Administrative taxes and miscellaneous costs 8. Financial charges: depreciation and interest Whereas it is easy to obtain comprehensive cost sheets from mining operations in Florida, it is rather difficult to obtsin these figures from other countries, especially when the mining operation is government-owned. Consequently, not much information is aveil- able from the literature. Besides, it is very difficult to give a general view of phosphate rock mining costs. ‘There are wide varia- tions because of the geological nature of the deposits and the type of mining used. The overburden to be removed can be very little or as high as 25-30 m. The thickness of the ore bed, the compo- sition of the ore, the transportation distance between the mine and the beneficiation plant, and the yield of recovery during beneficia- tion bring a lot of additional cost variations. Even within a given mine, the costs cen vary widely from one deposit to another becaust of these factors. Table 1.3 shows some mining characteristics of six major phosphate deposits. In some countries taxes on mining have been raised, such as the severance tax in the United States, which eccounted for as much as U.S.$2.46/ton of concentrate in 1986. In 1987 it was reduced to U.S.$1.97/ton, and is expected to be U.8-$1.49/ton in 1988, The total investment cost for a rock mine edds enother variable cost factor. Whereas a figure of U-S.$50/ton of phosphate rock con- centrate produced annually can be considered economical for a new mining site, some new projects account for as much as U.S.$180—200/ ton (see Table 1.4). Having described the difficulties in getting 2 general cost estimate for mining and beneficistion, 1 do not want to leave this section with- out attempting to give & picture of the production costs. Table 1,5 shows, for each of the ‘sted items, low, mean, and high expenses That could be made available from operating mines and implemented Projects. Nevertheless, the numbers from Table 1.5 have to be used cerefully. It is evident that there are very few mines operating ex- clusively under favorable conditions—low expenses—and there will evidently be no mine with all unfavorable conditions—high expenses. Among those with unfavorable economic conditions are the undergroundP205 60-70 recovery efficiency (4) Concentration ratio 2.22.3 P.O, grade (4) Ore Product 10-15 a3 (in) Ore bed Average thickness of oversurden (m) 46 Deposit TABLE 1.3 Mining Characteristics of Some Major Phosphate Deposits Florida Pebble chapter 1 Introduction a | TABLE 1.4 investment Costs for Phosphate Rock Mines in Florida (U.S, Dollars per geese | __ fst Fon of commercial Rook) vol ia-1960 5 i Mia-1970 15-38 = Early 1980 65-90 a {8 e 3 18 | Seuree: International Ferticer Assocation sa -1€ Annual Conference, Monte Carlo, 1960. : | 2f Se asssl82é 2223/88 TABLE 1.5 Phosphate Rock Production Costs Items (U.S. Dollars) 3 Favorable Unfavorable as i conditions ‘Mean ‘conditions esse Mining 25 68 10-15 Cy Open cast, Togo, Morocco: Underground Bs Sorden, Fiore CTuneia) elig Transportation 0.5-0.8 one 1? Sieg - ser gee Benefictation 12 25 5-10 gi Togo Florida Senegal, Tunisie é2 Waste disposal 02 0.1 2 ae Utilities 0.5 1 2 aad ‘Transportation to 280/88 \ loading port a Le enn s 434) 8 i Tunisia, Jorden a5 | Port loading costs 0.5 Me g2 | paministeative taxes fs ‘nd alscelaneous £ uP costs 1 be 2 & |s3 Capital costs per 40-50 50-80 0-200 e 2 : annual ton of Florida, Morocco N. Carolina, Brazil tslig | Fock prodused Tunista BEI gE Capital charge per $2162 ton of rock +s 88 222 Chapter 1 mining operations in Tunisia, which also have high beneficistion costs and long-distance transportation to the loading port and the Brazilian Valep mine, operating in a very remote place with a low ore grade and, consequently, heavy beneficiation and transportation costs. It is evident that depreciation and capital charges are subject to subsequent variations. Furthermore, they are difficult to estimate for old sites or extensions of old sites with existing infrastructure: In these cases, the capital costs ean be substantially reduced. Consequently, the numbers trom Table 1.5 are not simply additional costs. Actually, the effective production costs of the major pro- Gucers, including depreciation and finsnclal charges, range epprox- imately between U.S.525 to U.S.$40/ton of commercial ore concentrate. Sales Prices. Until 1972, phosphate rock was sold at very low prices. The general price increases for raw materials and energy have induced a considerable phosphate rock price escalation, ending at its peak in 1975 with a consequential 30% drop in phosphate fer~ tilizer consumption in developed countries (see Fig. 1.6 and Table 1 of Appendix B). This was foliowed by a subsequent price leveling. Between 1977 and 1980, consumption had recovered and the initial growth rate of 5% seemed to be reconfirmed. But another attempt in 1980/81 to re-increaso to higher prices by an additional U.8.$11-18 on FOB® basis, initiated by the U.S. phosphate rock producers be- cause of skyrocketing mine investment costs (see Table 1.4), failed and turned into another setback in phosphate fertilizer consumption. This time, the compulsory effect of the major economic factors ~high interest, high U.S. dollar currency rate, and sluggish fertilizer markete—have led to @ very severe fall in consumption and prices for both finished products and raw materials. ‘The 1982 FOB price level for 10-72 Florida rock, for example, hhas fallen to about U.S.$33 and the same grade of Morocco rock to U-S.$38 (both prices to meet a common CIF European port price). ‘Since 1984 no major price changes have been registered, Until 1981, phosphate rock producers published listed prices on eslendar- year basis. However, contracted prices, also generally negotiated on a calendar-yeer basis, did not necessarily meet the listed price. Recently, phosphate rock price policies have become more confidential. In general, prices are still negotiated on a calendar-year basis with individual buyers. Some practiced prices are published now and then by fertilizer intelligence such as Green Market! or Phosphorus and Potassium, + but it is rather difficult to get a comprehensive view of ‘Free on board: in export harbor. Yoreen Market: Fertilizer Market Intelligence Weekly, McGraw-Hill Publication. price for phosphste rock loaded on board vessel ‘4 Phosphorus and Potassium, a British Sulphur Corporation publication, uss$/metric ton In tion 23 j| & ae = — be —— so Fe oe ? rs 20 es Year FIG, 1.6 Phosphate reck, FOB price varistions. 72 BPL; 2, Florida rock, 72 BPL. 1, Moroeeo rock,eT Chapter 1 the market situation. For some cases, special detls are practiced: netback phosphate rock prices tied to finished product market prices or barter deals with countries having foreign exchenge problems. Special deals offer the advantage of selling at undefined price levels without disturbing a company's current market prices. Price Variations Related to the P205 Grade and Composition of Commercial Rock. It is evident that phosphate rock prices are sub- ject to variations according to their P203 grade. For 1981 and 1987, for exemple, Florida rock prices and grades were offered as shown in Table 1.6. Physical qualities, phosphate rock composition, end impurities also effect the prices, but these variations are to be Regotiated case by case because they are related mainly to the Purchaser's specific plant economics. The factors subject to pries reduction can be items such as dust formation (size analysis when plant is close to residential area), grindability (plant with bottleneck at grinding section), Ca0/P30s Tatio (sulfuric acid consumption), organics (foaming, color of acid), iron and aluminum content (sludge formation), heavy metals content (animal feed), and others. In these cases, a discount on the phos Phate rock price must compensate for the additional expenses of the purchaser for the incriminating characteristic or impurity. In Sec~ tion 11.4, some case studies with calculated price variations illustrate this economic aspect. Table 1.7 shows the world deliveries of phos- phate rock by grade. Special attention must be paid to U.S. domestic prices, which ‘appeer to be substantially lower than U.S. export prices. Also, TABLE 1.6 Florida Rock Prices and Grades Price (FOB) (U-S.$/metrio ton) Grede (BPL) 1981 1982 13-15 49-31 29-92 0-72 46 28-30 68-70 44-48 25-21 66-68 aoa 64-66 40 Introduction 25 TABLE 1.7 World Deliveries by Grade (Thousands of Tons) BPE. 1981 1985 65 or below 32,876 24,007 66-68 36,091 83,738 60-72 26,336 28,566 ne 8, 085, 2,091 18 end over 21,856 12,562 World total 129,884 150, 964 Soureé: International Fertilizer Association. these price differences versus TPL grades are not consistent. The reasons for these inconsistencies originate from several facts: ‘The U.S. domestic market is mainly a captive market: the producing mine and the consumers plant belong to the same company. ‘The export market is based on negotisted sales contracts between the phosphate rock producers and independent buyers. Some of the domestic phosphate rock delivery contracts are based con tolling (ore price contracted on effective mining costs). Higher-grade phosphate rocks are usually reserved for export. If the export market is weak these grades will be consumed locally. ‘The local market nevertheless will not pay the same price incre- ment for high grades as does the overseas market (freight charges). For lower grades the argument works in reverse. Table 1.8 shows phosphate rock list prices for Florida and Morocco rock for 1978-1979, 1980, and 1987 by grades, and Table 1.9 shows the U.S. export and domestic prices practiced in 1879, 1980, 1985, 1986, and 1987 for the various Florida rock grades. GIF Costs. CIF (cost-insurance frelght) costs include phosphate rock plus transportation costs between the rock producer's loading port and unloading port. Usually, if the plant is not integrated into a min- ing area, this is achieved by sea transportation. The comme: ize for phosphate rock transportation vessels is between 10,000 and £1,00027 Int oduetion = ~ - e9°¥e oper woe 99-09 ou ose ose cous coer sour ote sou see ous 1908 Inte sores eon ae vee ste ovo cette tse ov-9% ona wa-an oe atae ove wis or se-or 60-2 i e009 yaodxg = odxg = wodxg=—wodxg = opsouoq = oda onsewoq “Tau adVUD 2861 9861 s86t oer sist (SxsTOG “S"A WaUIND) oY VPHOLA 40} seoIZg STS oHSewOR PUL IOIXT 6° TIUVI - ove seat ov0E 69-29 8-62 ores oe - Sh-be ‘synossno se-sz oes o-oF ze site | ons ove ove oL-se ~ 0s covey ow dion v8qunoun 60-2 oo-re 00s soe 89 - o0-9¢ 00°82 ss-or ae e-08 000 00-08 sovee ae s°60-s-te 00K 008s ssvve su epHoLt 2861 oat 6x6 aust pep uyBHEO 26 Crm £4 oxotiog “S*n wuesing) yoo mwudeoud 40} SO0KLa pousGnd oT GIGVE28 Chapter 1 metric tons, according to the depth of the loading and unloading ports, ‘the yearly phosphate rock consumption, and the size of the consumer's storage facilities. Freight charges-can account for as high as 25-50% of the CIF costs in unfavorable cases (¢.g., transportation from the United States or central Africa to India). Because of the number of factors affecting freight charges, they are extremely variable. Some of these factors are: Geographical location of the producer's mine and the purchaser's plant, Possibility of getting return freight for the unloaded vessel Unloading port characteristics (draft limits, size of vessels) Size of vessels used Generel freight market trends (availability of vessels) Table 1.10 indicates some freight charges from major loading ports. The freight market is a very important cost factor for phosphate rocks. Traditionally, and also because of the price hikes of the last few years, the phosphate rock market is a buyers’ market. It will probably be that way in the future. Consequently, the CIF price ‘at mejor unloading ports sets the phosphate rock price pattern. Florida and Morocco, for example, have to cope with a common CIF Rotterdam price with subsequent differing FOB prices. Maritime phosphoric acid trensportation was started in 1969, initiated by a private company, F.F.M. of Mexico, and experienced rapid growth. In 1970, only 400,000 metric tons/yr P205 were registered worldwide, but acid shipments reached nearby 4 million tons of P05 in 1987 (merchant-grade acid plus superphosphorie acid). Modern phosphoric acid cerviers are made of stainless steel and range in capacity from 1000 to $0,090 tons with loading-unloading rates of 1000 tons/hr. More than 200 vessels are operating at Present. Most of the vessels can also sovep! other liquid chemicals, Which permits flexibility by return freight and other cost advantages im. Chemical Composition of Commercial Phosphate Rocks ‘Table 1.11 shows some of the major commercial phosphate rock grades found in the world market or consumed by integrated phosphoric acid production plants. Detailed data sheets of the more important commercial phosphate rocks are found in Appendix A. These data sheets are suitable for a preliminary investigation when choosing a rock for a given production plant, or vice versa. Introduetion 29 TABLE 1.10 Representative Freight Retes for Phosphate Rock, Sulfur, and Phosphoric Acid (U.S. Dollars per Metric Ton of Material) According to Loading Port Destination and Cargo Size Freight rate Loading port Cargo size range, and material Destination (metric tons) 1986-1987 Aqaba Phosphate West coast of India 15,000 8-13 Soviet Black Sea - Te Arab Gulf Sulfur Morocco 25,000 13 Dakar Phosphate West coast of India 15,000 18-21 Morocco Phosphate Antwerp 25,000 a1 India 20, 000 19-23 Phosphoric acid India 10,000 32-37 Bast Mediterranean Sea 6,000 18 Rotterdam 10, 000 19-12 Tunisia Phosphoric acid indonesia 15,000 40-42 South Africa Phosphoric acid Northwest Europe 15,000 32-33 Turkey 12,000 80 U.S. Gulf Phosphate Antwerp 50,000 6.0-7.0 Phosphoric acid India 15,000 42-43 Rotterdam 32,000 18 ‘Turkey 22,000 a Vancouver Sulfur Rotterdam 50,000 12.5 Morocco 35,000 18-182 Chapter 1 TABLE 1.11 World Prous ion of Commercial Ph «don of Commercial Phosphate Ore Concentrate by Countries (Thousands of Metric Tex Country 1980 1984 1986 Algeria 1,025.4 1,000.2 1,208.3, Australia - 14.5 24,3 Bras 2,921.3 3,854.9 4,508.8 China 10, 728.0 14,210.0 9,500.0 Christmas Islands 1713.3 1,256.6 825.0 Colombia 5.3 28.1 21.2 Egypt 658.3 1,083.4 12m. Finland 124.8 arts 527.0 India 427.2 159.2 750.0 Trag - 1,500.0 2,000.0 Israel 2,610.5 3,912.3 3,673.2 Jordan 4,242.7 6,263.1 8,249.2 Korea, Dem. Rep. 500.0 500.0 500.0 Mexico 330.0 374.9 600.0 Morocco 18, 824.2 21,244.9 2117.9 Nauru Island 2,086.7 1,358.5 1,498.6 Pakistan - - 50.0 Peru 13.9 127 5.2 Senegal 1,458.0 1,878.5 1,880.5, South Africa 3,262.0 2,564.1 2,922.5 Sti Lanka - 16.0 15.0 Sweden ~ at6 wis Syria 1319.4 1,514.0 1,608.0 ‘Tanzenia - 14.5 10,0 Togo 2,992.8 2,695.6 2,318.9 Tunisia 4,581.9 5,345.9 5,950.6 Turkey 21.3 95.6 27 USSR 24, 668.3 32,000.0 33, 200.0 uw 1 on + 411 (continued) Country 1880 1984 1986 us. 53,262.8 47,145.3 38,883.7 Venezuela - - 172.5 Vietnam, Dem. Rep. 400.0 200.0 300.0 Zimbabwe - 125.0 134.3 Other 213.3 I - 151,829.9 141, 949.3 World total 138, 450.4 eer 1.5.2 Sulfur Beside phosphate rock, sulfur by means of sulfuric acid is the Second raw material needed for phosphoric acid production. Wet Process phosphoric acid is the major world sulfur consumer, with nearly 50% of the total production. Sulfur is produced from brim- stone (37 million tons per year as $), pyrites (11.4 million tons as 8), and other forms (9.1 million tons of 8). ‘The world sulfur production and prices have been subject to strong variations well before the price cycles of phosphate rock and fertilizers (see Table 1 in Appendix B). The prices of the world "sulfur-in-all-forms" production are, consequently, strongly affecting phosphoric acid econonies. Roughly 0.8-1 ton of sulfur is consumed to produce 1 equivalent ton of P05 by the wet process. Offer and domand have been estimated to balance closely; even so, the phos~ Phate fertilizer growth rate is expected to be rather minimal for the next § years. However, it is not to be expected that higher sulfur prices will last for # longer period beoause phoophate fertilizer Production economies would then avoid expensive sulfur consumption in one or more of several ways: Use pyrites or waste smelter sulfuric acid, Use partial acidulation or ground rock fertilizers. Use nitric acid instead of sulfuric acid. Recycle calcium sulfate to manufacture 12804. ‘Table 1.12 indicates world sulfur production by geographical ereas.32 Chapter 1 TABLE 1.12 World Sulfur in All Forms of Production (Millions of Tons) Se eee cee eee eee 1980 1984 1986 Western Europe 7.84 7.88 1a Africn 0.88 0.92 1.01 Asia 4.36 4.84 6.08 Oceania 0.18 0.27 0.24 North America 19.83 18.18 18.61 Letin America 21 2.87 2.91 Total Western world 35.82 34.62 36.87 Communist worta 13.40 19.67 20.38 World total 55.20 54.29 56.95 SE ee eee 1.6 CURRENT DEVELOPMENTS 1.6.1 Preliminaries For the first time in the history of phosphates, world consumption has suffered a setback (see curve 2, Fig. 1.1). Following the high Growth rates registered during the 1960s and 1970s, both phosphate Tock mining and phosphoric acid production capacities were built up accordingly (curves 1 and 3, Fig. 1.7). However, only 708 of mining and acid production capacities are currently operating. Why Reduced Growth Rates? ‘The lergest share of phosphate fertilizer consumption is still by the developed countries. “However, the effects of overanticipated food production and associated lowering of prices, together with increased prices for raw materials and fertilizer (fourfold rise betwoen 1970 and 1980), led farmers to apply fertilizer at reduced rates. Phos- phatic fertilizers consumed by French farmers, for example, have ropped from 2.1 x 108 metric tons POs in 1876 to 1-4» 108 metric tons POs in 1986. The consumption drop in the developed world could not be offset by the third world's growth rate, although some countries, such as India, have greatly increesed ferittizer applica tion rates. Because of the inverted growth rate in developed areas, the supply and demand gap hes become uneven around the world Private U.S. and European fertilizer industries have been hit most Introduction 33 P205 IN 1000+mt year FIG. 1.7 World P05 capacity and consumption, 1955-1985, 1, World Pg0s as rock capacity; 2, world P20 as rock consumption; 3, total PgOs as acid capacity; 4, total P05 wet-process capacity; 5, World Py0s as acid consumption; 8, world P20 wet-process acid consumption.M Chapter 1 ‘severely, whereas the state-backva Moroccan and Jordanian mine- integrated phosphoric acid industry, for example, can expect an improved supplier position following the present era of over capacity (because a large number of plants in Burope and the United States have been shut down) 1.8.2 The Era of the Great Overturns Looking et the world's regional phosphorie acid production and con- ‘Sumption throughout the past decede, we can see dramatic changes. Whereas the U.S. phosphate industry dealined nearly 208, countries lke Morocco, Tunisia, and Jordan have expanded their capacities considerably. The phosphoric acid plant in Djorf Lasfar, Noroceo (ig. 1.1), is, to date, the largest phosphoric acid plant in the world. Former importing countries. such as Brazil and the Philip- Pines, now produce their own phosphate fertilizers. Industrial phosphates, also produced predominantly in developed countries, cannot register better results. Their progress is stalled primarily by environmental problems. Detergent manufacturers, the larger users of industrial phosphates, are said to be responsible for river and lake eutrophication. The total consumption of industrial Phosphates is expected to show a noarly zero growth rate (see Tables 1.13 and 1.18) TABLE 1.13 Industrial Phosphate Consumption Trends in the United States (Metric Tons per Year) eee 1989 1984 (expected) Detergent builders and 167, 400 163, 300 water treatment Food end beverages 28,100 32,100 ‘Toothpaste 2,700 2,700 Metal finishing 22,700 12,700 Others 115, 500 118, 500 Exports 24,000 24,000 ‘Tota 351,400 353,300 Source: Chemical Week, Mar. 19, 1986, tion 35 4 1.14 Industrial Phosphate Market by Region and End Use, = (Thousands of Tons of P205) Soaps, detergents, Water cleaners | Food treatment Others Total Western Burope 47 36 22 60 555 Eastern Europe 238, 13 13 18 2r7 North America 342 n 6 as 563 Africa 6 5 2 ‘ ar Latin America 207 3 10 10 240 Asia and Oceania 215 u u 13 313 Total 1510 153122 1902036 Source: World Bank 1.6.3 World's P,0, Demand Expectations: Key Factors ‘The forecasts made daring the past decade have all proved over- estimates. The present careful projections, 2.3-2.5% P70s demand growth per year [8 9], may be heavily influenced by the disep- pointing results of previous forecasts. ‘There are too many key factors working in opposite directions to make completely dependable forecasts. The key factors are as follows: Factors in Favor of Improving the Market Situation Phosphate rock mining overcapacity Large developing countries with high population densities at the Threshold of high agricultural and industrial growth rates, for example, India and China Increasing availability of sulfuric smelter acid as a rew material for phosphoric acid U.S. currency rate Plant shutdowns. Market-Depressing Factors Low food prices High farming yields36 Chapter 1 Ei gilass Environmental concerns SgeE/s aa Calcium sulfate disposal concerns Bas High sulfur prices & Comments to Key Factors Phosphate Rock Overcapasity. This was discussed before co et (Section 1.6.1 and Fig. 1.7). ata Growth rete (QNPR/yr) Developing Countries. India and Chine both have enormous consumption needs, as can be seen from Table 1.15. India hes registered an 8% average growth rate for P05 consumption during the past 10 years. Its scarce reserves of domestic raw material will aes Keep the country a large POs importer. The 1985-1966 consumption Bee|2 2 Tate of 2.06 million tons of P;0s is expected to expand to 3.4 million eee)" 1g tons in 1991-1992 [20]. China's need for phosphete fertilizers is 52 even larger. Chinese experts estimate that 9 million tons of POs & will be used in 2000 [11]. However, there are transportation and infrastructure problems; changes in management, knowledge, end habits; and finencial needs to be considered. Consequentiy, it een «2 be assumed that the medium-term growth rate of fertilizer use in § elie. China will probably not be es high as in India, Table 1.16 shows i g2ol2ig some key figures for China, Whereas the main nitrogen fertilizer j gis|a" 8 still used in China is ammoniun bicarbonate, fused phosphates and By single superphosphates are the main phosphatic fertilizers. To date, & very little phosphoric acid has been produced in China, and it gs represents only few percent of the total consumption, , g383a It is very likely tet Chine wil have to topert phoephorle sci ieaeSl ee. and phosphatic fertilizers in large amounts before domestic mining gagge |e es tnd Industry wil take over the large demand. Current needs 2 fb4as estimated et 2 million tons of P05 in excess of actual consumption. bes However, imports will have to be met by the availability of foreign currencies or commodities. Smelter Acid Availabitity. Increasing supplies of smelter acid will be available in the neer future. In 1986, 7.3 million tons were available, but Chile, Mexico, Australia, Canada, the Dominican Re Public, and others will come on line with large additional tonnages, 50 that in 1993 the tonnage should exceed 12 millions. The use of 760 1080 235 Population 1966 nitions) ‘ABLE 1.18 Key Figures and P05 Consumption for Various Countrics cheap smelter acid instead of expensive sulfur will be essentially a 2t3 problem of logistics [7,13] ag i g2¢ U.S. Currency Rate. Internationa) pres for phosphates and ul phosphatic fertilizer are rated in U.S. dollars, Large buyers such ~ as India wil have thein purchasing power improved by @ low US, dollar exchange a: ga 1.80 1.86 2.2 28 0.9 11,540 2,170 11,000 53.3 1.6 o 8 130 30 0 ance vustralia vaail98 ter1 TABLE 1.18 China Key Figures EEE 1975 1980 1984 ee eee eeamee Population (billions) 0.820 0.983, 1.036 Employed by phosphate 180 182 192 fertilizer industry (thousands) Sulfuric acid 4.85 7.64 8.7 production Gaillions of metric tons) Nitric acid produetion 0.30 0.23 0.26 (millions of metric tons) POs fertilizer production 1.53 2.31 2.36 POs fertilizer importation 0.027 oat 0.30 Farmlend ar 366 360 (nitions of hectares) Average industrial 238 15.58 9.128 growth rate Billion kWH produced 198 301 318 TO Source: Ref. 12. Plant Shutdowns. It is very difficult to forecast the number of shutdowns that are to be expected; there may be more then has been forecasted. Low Food Prices. Unfortunately, farmers and the fertilizer industry will have to cope with low food prices for a number of years, In countries with high population densities and low per eapita income (and there are many of these), governments will back @ policy of iow food prices. Poor farmers ere easier to control than are hungry yobs in overpopulated urban areas, 30 there is little hope for change. High Farming Yields. Continued worldwide improvements in Production technology combined with a decreased rate of world con- sumption has resulted in enormous corn, rice, and grain stocks, severely affecting world's erop prices. Environmental Concerns. Environmental concerns will affect both P05 demand and production capacities and have already severely ‘sifected industrial phosphate consumption in a number of developed Introduction 99 countries. Involved primarily is sodium tripolyphosphate (STPP), 8 principal component in washing powders. A number of European countries have, by decree, limited STPP levels in detergent formula- tions (e.g., Norway, Sweden, West Germany, Finland, Italy, Austria). Some jurisdictions have even banned STPP {e.g., Switzerland and a number of western states in the United States (where regulations are carried out at the stste rather than the federal level)]. STPP is Said to be responsitle for the cutrophicstion of rivers and lakes to which it ie carried in wastewaters. Some developed countries, having traditionally used high fertilizer application rates, have raised soil protection laws and have set phosphate soil concentration limits and special use taxes (e.g., Netherlands, Denmark). Another environnental concern is cadmium, contained in most Phosphate ores. Cadmium is difficult and expensive to remove from phosphoric acid (see Section 9.5.1). Because of cadmium, the Dutch phosphoric acid industry is currently fighting for its life against environmentally concerned government authorities. Calcium Sulfate Disposal. The problem of large calcium sulfate waste disposal connected to phosphoric wet process acid production has foreed a number of plants located in highly populated areas to reduee their capacities. This problem is of more concern in developed countries than in others. Morocco, for example, does not seem to ‘suffer from environmentalistic pressures despite sending some 30,000 tons of gypsum per day into the ocean. High Sulfur Prices. Sulfur costs often outweigh phosphete raw material costs. Depending on the phosphate rock composition, 0.8-1 ton of suifur is consumed per ton of P03 produced. ‘The sulfur Producers seem to maintain a world sulfur shortage, letting the situa- tion improve from tine to time to discourage the development of alternative sources. Price peaks occurred during the 1960s and 1960s, snd prices ‘skyrocked in 1980, efter which they have stayed at & high level (see Appendix B, Teble B.1). (Peaks of U.S.$170/ton were regis- tered in 1985-1986.) Severe shortages were announced in 1986. Currenuy, prices are declining. 1.6.4 Conclusions ‘The unexpected current world market situation in the phosphate industry has not discouraged forecasting activities; in fact, there never was so much. Most forecasters predict low growth rates, typically 2.3-2.58 per year. The most pessimistic [14] predicts a 2.08 rate. Whatever the gronth rate, strong competition between mine-integrated, government-backed industries in developing countries and environmentally burdened (often private) producers in developed40 Chapter 1 () () FIG. 1.8 Modern superphosphoric ecid plant of capacity 1200 mt/day P05 at La Skirra, Tunisia, completed in 1988. (a) Two acld units, () pipeline to harbor, Introduction a ‘countries has initiated a nonreversible trend to move the phosphate industry toward rock sources locsted in areas with fower economical and environments! constraints. Ironically, the developed countries! production units have the advantage of more modern, better per- forming equipment (Fig. 1.8). Furthermore, most rock producers, now phosphoric acid producers, will try to maintain a high rock price policy to enhance the trend. Such competition will hardly permit the survival of companies without assets. For those who do not have any raw material at their disposal, only high technology and associated alternate produets can strengthen their position. Sulfuric acid should be used twice (with Phosphoric acid as an end use), and waste products should be Processed into marketable products. Energy should be saved through- out the piant. This may not always be easy or even feasible, but if there is no other alternative, we have to try. Some producers have already done it nicely. REFERENCES 1 Dipl. Chem. Dieter Rohe, Der Phosphatmarkt zeigt sich elastisch, Chem. Ind. 34 (May 1982). M. G. de Belinko, Some Thoughts on the Genesis of Sedimentary Marine Phosphate Beds, Phosphorus Potassium, No. 106, March-April 1980. 8. 3. R. Lehr and C. MoClollan, Phosphate Rocks: Important Factors in Their Economic and Technical Evaluation, CENTO, Symposium of the Mining and Beneficiation of Fertilizer Minerels, November 19-24, 1973, pp. 194-142. 4. 5. R. Lehr, Phosphate Rax Material—A Look Ahead. TVA short course in modern fertilizer technology, Tennessee Valley Authority, Muse Shoals, Ale., June-July 1977. 8. J. R. Lehr, C. McClellan, J. P. Smith, A. W. Frazier, Société Chimique de France, Collogue International pour les phosphates mineraux. ‘Toulouse, France, Merch 16-20, 1967, pp. 29-44. 6. W. F. Sheldrick and H. Stier, World Phosphate Survey, Background Papers. 1. B. Jahns, The World Trade of Phosphorie Acid, Oct. 1987, Enlarged Meeting of the Raw Materials Committee of IFA, Seville, Spain, October 1997, International Fertilizer Association, Paris. 8. K. F. Isherwood, 1987 Survey of Phosphate Fertilizers and Phosphoric Acid for Fertilizer Use, International Fertilizer Association, September 1987. 9. W. F. Sheldrick, The Methodology and Calculation of Regional and World Supply, Demand and Balances, 1995/86- 1991/92, World Bank. 10. Fertilizer Statistics 1985/86, The Fertilizer Association of India, New Deihi.42 a. 2. 13. ua. Chapter 1 D. Leitch and K. ¥ —, Modern Lesson irom an Ancient Land Progress, Septembx tober 1987. it China Chemical Indus.., 1985/86, Sclentific and Technical Information, Research Institute of the Ministry of Chemical Industry of China, Beijing, China. K_ G. Aitken, C.1-L. Inc. paper presented at Rew Meterile ‘ommittee, Orlando, Fla,, May 1987, Internetionel Fereiia Association, Paris. a T. J. Wright, Outlook for Phosphetes, Fertilizer Industry Roun: Table, New Orleans, La., November 1867. nde 2 Industrial Process Chemistry 2.1. WET PROCESS REVIEW 2.1.1 Dihydrate Systems In the early development stage, dihydrate systems showed very dis- similar design features. However, intense investigation of dihydrate process chemistry has thoroughly established the basic principles governing the process. Ample literature is available [1,2]. Still, Several drawbacks of dihydrate processes remain, some of them in- herent in the system itself: relatively weak product acid (27-308 POs) and consequently, high downstream energy consumption, and ‘68 P05 losses, most of them as oocrystallized P05 within the pattern of the calcium sulfate dihydrate orystals that ere disposed of. ‘The advantages of dihydrate systems are, however, also well established: 1. There is no phosphate rock quality Limitation. 2. On-line time is high, 3. Operating temperatures are low. 4. Startup and shutdown are easy. 5. Large units ean be built. 6. Wet rock can be used (saving drying costs for phosphate rock). To date, whatever its origin, a dihydrate process can be considered to be made up of the following sections: 1. A phospate grinding section (for most cases) 2. Metering of the raw materials and recycled wash acid from the iter 4a4“ Chapter 2 3. A phosphoric acid reaction section, where gypsum is formed 4. A filtration section, where the 28-30% P20s product acid is separated from the gypsun erystals Three flow diagrams, including material and energy balances for units of 1000 metric tons per day of product acid, will serve as an introduction to the principle of dihydrate process (Figs. 2.1, 2.2, and 2.3). Figure 2.1 refers to a dry low-grade rock (28.8 P05): Fig. 2.2, a dry high-grade rock (36.7% POs); and Fig. 2.3, a low- grade wet rock (28.88 P05, dry basis, with 36% water). Note the sig- nificant differences between high- and low-grade rock in: Sulfuric acid consumption Slurry flow and gypsum formation Heat relesse P05 losses Phosphate Grinding Section Some grades of commercial rock, including Kola, Togo, Talba (Senegal), Bukraa (Morocco), and North Carolina, do not need grinding, their particle size distribution being acceptable for a dihydrate reaction section. Most other phosphate rock needs particle size reduction, generally by bali or rod milis, with roller mills used for smaller units. Ball and rod mills can operate with wet or dry rock. Wet rock is used for mine-integrated unit operations, where rock benefication is achieved by washing or flotation and drying costs can be saved by feeding wet rock into the system. The use of wet rock reduces the amount of filter wash water and thus depresses filter cake washing, which causes P205 acidic losses to increase slightly (see Figs. 2.1 and 2.3), However, the loss is acceptable and not as important as it is with hemihydrate systems, where filter water becomes scarce with wet rock feed. The particle size distribution currently required for dihydrate reaction system is 60-70% below 150 um. Grinding and grinding equipment are described in Chapter 4. Metering of Raw Materials Phosphate rock feed, sulfuric acid flow, and return acid from the filtration section must be continuously fed and controlled precisely by the weight belts of flowmeters. This equipment is described in Section 5.1. Phosphoric Acid Reaction Section The reactor, whether single- or multitank, contains an agitated reaction volume in circulation. Often a buffer tank, out of the tase un ten ee U Retura acié 29 9? Density 48 Ps Gsm Ls + Gate water 120.0» P29 pregnacion 0.5 rots Z08 FIG. 2.1 tons per hour for dihydrate phosphoric acid unit, operating at @ Material and energy balance flowsheet, expressed in metric rate of 1000 tons of P05 produced as acid per day. Rat 220s, 18.8%; S03, 3.88; CoO, 49.7%; 8i09, 3.38; COp, * A125, 0.68; Fey0s, 0.58; MgO, 0.5%; NazO, 1,08, terial: SP, 8.685 4530, Taree 66.5 ¢] ake 130.9 ¢ fice 1348 ¢ a Return sci 291.9 04 oensity as P29 woe Gypsin 25st Cake water 130.0 ¢ P20 Hroregnetion , Tout wt 53.3 Product acid 159.2 ¢ Density 1377 Pe aoe i (308) ‘preanation FIG. 2.8 Materiel and energy balance flowsheet expressed in metric tons per hour for dinydrate phosphoric acid unit, operating at a rate FIG. 2.2 ateriat and energy balarce flowshaet expressed in metric tons per | > for dihydrate phosphorie acid unit, operating st rato of 1000 tons of P205 produced as acid per day. ‘Raw material: same of 1000. PgOg produced as acid per day. ‘Raw materid: P25, + rock as Fig. 2.1, a5 wet rock with 36% water content. Note the 36.78; Su 4.3%; CaO, 51.2%; SiOg, 4.5%; COg, 1,68; F, 3.8%; 3 lower heat evacuated, because heated process water is replaced by Als, 1.6.; Feg03, 1.08; MgO, 0.18; NagO, 0.28, . cold sluice water with the rock feed, 46 a8 Chapter 2 circulation and installed before the filter, is supposed to give an additional margin of error to the total retention time of the phos- phate particles. Generally speaking, reaction volumes correspond to ratios of 41.5-2.5 mi/ton of P05 produced per day. However, by "pushing" production, plants can sometimes be found working et a ratio of less than 1 m9/ton of P205 produced per day. ‘Since erystaltization is often spread unevenly among the various tanks or reaction sections, precipitation rates per cubic meter are sometimes very high. In older premixer tanks figures of more than 1 ton of S04Ca-2H20 per cubic meter were common, whereas modern single-tank units work at about 0.09-0.180 ton of gypsum per cubic meter per hour. ‘The cooling necessary to maintain a temperature of 70-80°C in the reactor and 70-75°C at the filter is provided either by a cooling airflow or by a vacuum cooling system of pumped slurry cycle. Air ‘cooling Is based on various ratios according to the technology in- volved: 30,000-70,000 m3/nr per 100 tons of P20s per day (30,000 m3 is low, while 70,000 m3 is far too high). Vacutim coolers work at various slurry flow rates, which calls for a different temperature difference in each case. In practice At fs between 2 and 10°C. Cooling system scaling problems are obvi- ously greater with 10°C than with 2°C, Filtration Section Filtration, too, is subject to a large variety of flow ratios according to the nature of the process. but above all it is a function of phos- phate quality. The use of additives (floceulants) can sometimes im- prove these values. Poor phosphates operate at around 2 tons of Pus per day per square meter of filtration area; the most common, commercial phosphates, 4-5 tons; good ones, 7 tons, and the best, about 9 or even 10 tons of PyOs per day per square meter of effes- tive filtration section area All these values are expressed on a base for filters working, at a filtration cycle time of 4 min with @ washing yield of P05 recovery over 998 with 28-308 acid. Faster filters improve on these figures, and slower ones lower them. Three {ter types are currently used for wet process phosphoric acid production: belt Miters, pan filters, and table filters. The largest single Milter can to date achieve produetion rates up to 1800 metric tons of P205 per day (see Chapter 6) ‘The recycled acid flow varies as @ function of the P205/Ca0 ratio in the phosphate. ‘The lower this ratio, the more POs has to be re- ‘cycled to keep the slurry compecition within the necessary atendards. In Fig. 2.1, with low-grade rock, recycled P2Os/produced P25 Industrial Process Chemistry 49 ratio is 1.64, whereas it is only 0.98 with high-grade rock (Fig. 2.2) (see also Section 3.2). This is one of the most important factors to con- sider when assessing a new rock versus the adapted process technclogy. High recycle P20s rates endanger some technologies, such as wet grinding or high-strength acid processes. Whereas the yield following recovery with wet grinding of the high-grade rock (Fig. 2.2) would still be over 95%, the low-grade rock (Fig. 2.3) would drop from 95.49 recovery to 94%, because of reduced cake wash flow. Product acid resulting from dihydrate operations currently yields 21-308 Py0s. However, it can be lower when very low grade rock is consumed. Calcium sulfate resulting from the reaction is calcium sulfate dinydrate, which is for most cases wasted to piles or sent into bodies of moving water. Environmentally safe recycling into useful products is under investigation. 2.1.2. Nondihydrate Processes (Hemihydrate Processes) State of the Art, 1987 Traditionally, phosphoric acid has been produced under reaction conditions of 28-32% P205 snd temperatures of 70-80°C, the calcium sulfate being essentially precipitated as dihydrate. Local require ments in Japan caused the need for modification of this technique, and some low-strength hemhydrate recrystallization processes were developed that produced a high-quality calelum sulfate for gypsum board manufacture. These processes were still limited to approx- imately 30-35% P205 in the product acid. More recently, in a number of cases of differing local require- ments, the incentive to produce an acid of high strength (40-50% P05) without the use of steam has caused a number of companies to accept the challenge of high-strength hemihydrate technology. If the cost of oil and power were again to increase, the economic ad- vantages of production of higher-strength acid without the use of steam would once more be of greater interest. Sinoe the publication of the first edition of this book there has. been a general tendency to reduce acid strength in the high-strength Processes from 80% to 42-45% P05 (this is probably due to higher values for the P20s/energy ratio), but this intermediate strength can easily be obtained without the use of steam by hot water loop con- centration (by evaporation) of the dihydrate product acid. (The hot water is obtained from sulfurie acid intermediate absorption heat recovery via heat exchanger systems [3-18] (see also Section 7.1.1). In fact, when considering revamps, the conversion from dihydrate to hemidihydrate requires a large investment and considerable space. In many cases the lower’ investment, low space requirement, and’ w50 Chapter 2 risk of hot water evaporation of dihydrate acid may well be much more interesting than the novel high-strength phosphoric acid technologies. The industrial experience gained from the increasing number of operating plants should ensble prospective purchasers of this type of technology to have a chance to evaluate the real savings of each process, thus enabling them to evaluate the overall performance of this type of process, whereas previously they could obtain only the claims made by the process licensors. The growth of high-strength processes has been somewhat slow during the last five years, but this can easily be justified, as the overall growth rate in the industry has been very small; also, the price of oil has decreased very markedly and has up to now shown very few signs of increasing, at least in the medium term. Hemihydrate processes do require a high level of technical and operational expertise in order {o avoid unwanted transformation of ‘the semistable hemihydrate into dihydrate. Nevertheless, in certain ‘cases the operation of a single stage hemihydrate process cen some- times be simpler than the respective dihydrate plant, due mainly to the possible absence of grinding, evaporation, and storage sections. Conversely, two-stage hemihydrate/dihydrate processes with recrystal- Nization and double filtration can be more difficult to operate than the equivalent dihydrate process. Utilization of the reaction/fitration system of a single-stage plant fs normally about 85-958 of available opersting time. This excludes one 2-week or two i-week shutdowns. Thus the operating time is from 298 to 333 days/year. There is a large variation due to stan- dards of maintenance, proximity of suppliers, end the scaling/corro- sion tendencies of each phosphate. It is well known that whatever the process or produet, the longer the process trein (number of items of equipment without intermediate buffer storage), the lower the utilization fector. Thus any processes with two {tration stages can expect utilization of only about 80-908, or 289-316 days/year. ‘Thus the plant size of any two-stage process wil need to be about 5% greater in instantaneous capecity to give the same annual produe- tion rate as a single-stage plant. How significant capital cost is compared with other costs, such as raw materials, utilities, maintenance, and lobor, has to be fully evaluated in each case, but in many eases the raw material costs ere heavily weighted in the overall production cost. Hemihydrate Processes Availeble Process Routes [19-29]. In order to compare the many hemi- hydrate processes and dihydrate processes, it has been necessary to classify them into five "process routes." This generalization, although aiding evaluation, does not account for the specifie ad- vantages or disadvantages of each process as to plant performance, Industrial Process Chemistry 5 Process, or engineering considerations. This treatment 1s intended only es @ preliminary guide; the advantages or disadvantages quoted should be confirmed by discussions with each process licensor. Each process route is defined by the process philosophy, in- cluding attack conditions and number of filtration stages. It is not intended to imply that all processes within each process route per- form in the same manner. However, the physical chemistry is esseh- tially the same, and differences in product and by-product quality and raw material consumption should in general be small for a given phosphate. The five basic process routes are designated as follow: 1. Dil (dihydrate): conventionel dihydrate process, elther single- or multitank, normally producing acid 28-308 P205 (e.g., Prayon, Norsk Hydro DH, Siape, Rhéne-Poulenc, Gulf-Swenson, Jacobs- Dorr, and others) 2. HRC (hemtdihyarcte recrystaltization): single filtration stage; reaction in hemihydrate regime followed by reerystellization to Ginydrate and fitration to produce 30-328 P205 acid (e.g. Nissan H, NKK [50-39}) 3. DH/HH (diheminydrate): reaction as dihydrate at @ slightly higher strength (52-398 P25); separation of product acid with- out cake washing; conversion to hemihydrete and countercurrent washing of hemihydrate cake (e.g., Central-Prayon {40~45)) HH (hemihydrate): single-stage hemihydrate process producing 40-488 P05 acid directly from the filter (e.g., Norsk Hydro HH, Oxy-Hemihydrate, and Prayon PHIL (46-6i)) 3. HDH (hemiainydrate):" reaction in hemihydrate regine, filtra- ion to produce 40-528 P05 acid; washing and repulping of hemihydrate cake in recrystallization tenk; conversion to di- hydrate with the liberation of the lattice loss and the filtration of the dihydrate cake (e.g., Norsk Hydro HDH, Nissen C, Prayon PH2, Oxy-Recrystéllization, Jacobs HYS'[62~86]) ‘Typical block flowsheets outlining process steps are shown in Fig. 2.4. A comparison of the technologies available tabulated by process route is preseated in Table 2.1, The advantages and dis advantages of each process route are listed in Table 2.2. Case Studies. Every production unit for phosphoric acid has its own requirements regarding raw materials, utilities, product quality, and by-product quality. The five process routes can be classified into four specific cases in terms of these characteristics. 1. Weak acid: impure gypsum; process route: dinydrate. Under these restraints the proven dihydrate processes are normally still superior, even with increasing power costs, provided that steam is available for evaporetion. Process modifications have enabledAquo Spmys 101g — ‘ss0001d 5 0} poyzoauos y gzeI Chapter 2 TABLE 2.2 Advantages and Disedvantages of the «.. ..us Process Routes freee OEE eee Process route Advantages Disadvantages See EEE DH Simple design Acid has high levels of Al Flexible on rock source "4 F peSESPuSran Produces acid at 28-308 Ps Ease of operation/ shutdown Requires a lower grade of stainless steel Wet rock grinding possible Normally, requires steam for ‘evaporation Efficiency of the order of 95% May require rock grinding Requires 308 acid storage ‘and evaporator Postprecipitation before and after evaporation Requires clarification for merchant-grade acia Production HRC Single-stage filtration Requires a fine rock grind Proven process on Requires sulfuric acid sedimentary rocks dilution Produces a pure Recrystallization difficult with eypoun igneous rocks Higher efficiency (978). Large recrystallizetion volume Slightly higher acid ed strength (30-32% May solubilize higher levels P,0,) of partially soluble Lower sulfuric acid ee consumption Requires 3% acid storage and evaporation Postprecipitation before and efter evaporation Requires clarification for merchant-grade acid Tow filter area strial Process Chemistry 55 ABLE 2.2. (Continued) Process, route Advantages Disedvantages Rock slurry feed unaccept- able, can accept moist rock Requires sophisticated materials of construction DH/HH Flexible as to rock ‘Two-stage acid separation, source lower utilization Proven prosess High capital cost Produces a pure Requires steam for conversion aor Required 35% acid storage and Higher effisiency (988) evaporation concentration Higher aci¢ strength Requires clarification for 62-368 7,0) merchant-grade acid Loner sulfurie acid ae ‘eonsumption Rock slurry feed unacceptable Self-drying hemihydrate Requires final rehydration of cake hemihydrate to gypsum Gypsum can be used Normally, requires rock directly for gringing pret Solubilizes more impurities Care required in design and shutdown Requires sophisticated ‘materials of construction HH Single-stage filtration So far, limited number of Produces strong acid rocks processed industrialy directly, 40-488 Large filter area required for P.O, 488 PO, ecia High lattice loss, low efficiency (90-948) Produces impure hemihyérate Tight water balance, cannot produce high-strength acid Produces purer acid ower $04, Al, and ®) No intermediate storage if acid is produced at user's strength58 Chapter 2 TABLE 2.2 (Continued) Process route Advantages Disadvantages Limited postprecipite- from wet phosphete or weak tion/simple sulfuric acid ere Requires higher-grade alloys erent Care required in design and Ease of operation shutdown High mechanical losses from filter ‘A flooded filter causes high losses Sulfuric acid consumption sensitive to overall efficiency HDH Produces strong acid Two-stage filtration, lower directly, 40-52% P,Os Produces purer acid (low 804, Al, E) Limited postprecipita- tion/simple Glarifieation Uses coarse rock Low sulfuric acid consumption High efficiency (98.5+4) Uses more wash than HH and DH/HH utilization HH filter cloths washed with filtrate from DH filters Reerystalization difficult for ‘igneous rocks So far, limited number of rocks process industrially Requires higher-grade alloys Care required in design and shutdown High recrystallization volume Cannot use rock slurry and produce 508 P05 acie Recycling of organics between ters Produces a purer evpsum Recrystallization tank acts as catch tank for stertup/shutdown nd mechanical losses from HH filter Industrial Process Chemistry 37 coarser grinds of rock to be used, wet rock grinding can be om- ployed, and agitation power end circulation power are being used more effectively. The flexibility of phosphate source is also ad- ‘vantageous to producers who buy phosphate on the open market. Although the dihydrate process cannot be claimed to be trouble-free, the problem areas are well known and can be allowed for. The maintenance costs and on-line time can be defined fairly accurately for any phosphate source and level of maintenance expertise. This process route suffers most when high-purity gypsum is required. Under specialized local conditions the other four process routes may be competitive, but careful evaluation should be made before the DH Process is discarded. 2. Weak acid: pure calcium sulfate: process routes: hemi- hydrate-recrystallization and dihemihydrate. The: routes can be joined in commercial comparisons. noted for the high-quality calcium sulfate they produce, the higher overall recovery, and the slightly higher acid strength produced. The disadvantage is a complex process train. However, as the pri- mary aim is to produce pure calcium sulfate, it saves equipment that would be required for gypsum cleanup. ‘These processes have many of the disadvantages of hemihydrate Processes and still produce relatively weak acid (30-358 P05). As ‘such, their competitiveness will tend to decline as experience with the high-strength two-stage HDH processes gradually increases; how- ever, the Central-Prayon process does enable a great reduction in gypsum drying costs, as it can produce a pure hemihydrate for direct use after drying or a pure "dry" gypsum after allowing the hemihydrate cake to reconvert and absorb most of the free water. Processes available 21 URC: Nissan H (Fig. 2.5), NKK, and Mitsubishi DH/HH: Central-Prayon (Fig. 2.6) 3. Strong acid: reduced efficiency; clean acid: low investment; Procese route: homthydrate. The hemihydrate processes have o¢- verely limited applications, especially os the two-stage HDH hemi- hydrate processes are developed commercially. The hemihydrate process suffers from @ high lettice loss and limited wash water. ‘The higher the acid strength produced, the greater the problem. The sulfuric acid consumption is about 1.7% less than thet of « typical

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