Free Motion for Summary Judgment - District Court of Federal Claims - federal

Case 1:05-cv-01075-TCW

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Exhibit 2, continued

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Attachment 6

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A C.I.P. Catalogue record for this book is available.from the Library

ISBN.0-7923-5032-4(HB) I SBN 0-7923 -501 I- 1 (PB) "

Published by Kluwer Academic Publi.~hets, P.O. Box 17, 3300 AA Dotdrech~, The Netherlands,
Hardbound Edition: Sold and dis~butcd i~ ~he U.S.A. and Canada by Kluwer Academic Publishers, IOl Philip D~ve, No~ell, MA 02061, U.S.A. In all other coun~es, sold and distribute~ by Kluwer Academic Publishers, P,O, Box 322, 3300 AH Dordrecht, Tho N~h~rlands, , SoRbound Edition: Sold and distributed by IFDC, P,O. Box 2040, Muscle Shoals. AL 35661, U.S,A.

Printed on acid-free paper
This manual has been prepared by the U~ted Nat~o~ IndtmrtaI Development Orgxnizatton and International Fertilizer Development Center (I~ within UNIDO proJ~=t XP/GLO/93/094, The views expre~ed In ~his pubH~tlon are ~o~ o~e aulhors and do not nee~y~fleet the ~ews of the $ecre~at of ~0 or of Mention of firm names and cemmcrelal products do~s not imply the endorsement or' UN[DO or IFDC. Copyright 0 1~98 (year d flr~ publlc~tion), by United Nations I.udmtrial Development.Organization (UNIDO) and International $'ertflLzer Development Center O/~D~, All Rights Reserved,

No par1 of the material protected by this copyright notice may be reproduced or utilized in any form or by an)' means, electronic or mechanical, including photocopying, recording or by an), information storage and retrieval system, wit, hour written permission from the copyright owner. Printed in the Netherlands

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Table of Contents
Page Chapter 1. Generd Concepts, Classification, TerminolofW' an~ D~ons ........................ 1 2 1.1 ]n~u~on .................................................................................................................................... 2 1.2 Plant N~ ................................................................................................................................ l.g Fe~er G~de ......................: ........................................................................................................ 2 1.4 Nu~ent A~il~bil~ ......................................................................................................................... I.$ Fe~ Re~on~ ....................................................................................................................... 1.6 Fe~e¢ S~dfi~fions .................................................................................................................... 1,7 Ta~oI~ ~ Dd~flons ............................................................................................................ 1,8 Fa~l]~-Re[a~d ]~o~on ~c~ ................................................ ; ............................................ 13 Chapter 2, ~e ~o]e of F~ers ~ A~c~re 2,1 D~mand for A~I~ Pr~u¢~ ~d Plant Nu~en~ ...................................................................... 2,2 22 2.3 ~ncep~ of So~ F~ll~ ................................................................................................................ ~ 2.4 F~dam~l~ o~ ~, P, and K ...................................................................................................... ,, 28 .2.5 39 2,6 Pro~table E~r U~ .................................................................................................................. 2.7 Soll Pr~uc~ ~d ~t~bili~ ......................................................... 2.8 ~efe~c~ ...................................................................................................................................

3.3 3.4 3.5 3.6 3,7 3.8

S~sB~al ~ of F~li~er Colophon, 1~B0-95 .................................................................. 55 T~ds ~ Fe~r T~ ............................................................................................................ Tz~ds ~ F~er ~ ............................................................................................................... £me~ing ~nte~ of F~r Pr~ucB~ .......................................................................................65 66 [nd~ ~~ ~ Older ~u~n~ Ar~ 6 ~d~ ........................................~ .......................................................................................... 9

4,1 Inh'oduction .................. : ............................................................. . ........................................... ~ ...... 71 o,.2 R~c~nt Economic and Po{itica[ De~elopmanl~ and 4.3 Fulu~ Outlook for 4.4 Fuha~ Outlook for Fertilizer Supply ................................................................................................ 75 4.5 Fertilizer Supp|~-De, mand Baiance~ .................................................................................~. ..............78 4.6 Summa~t ..................................................................................................................................... 80 ~.7 Prlc~ Outlook ..................................................................... ' .......................................................... 81 ~.8 References ................................................................................................................................... Chapt~r $. Fertilizer Paw Materials 5.,~ AvailabiIlty and Sowces of Paw Materials ............... , ........................................................................ 85 S.2 Nitrogen Fe~:~t~r~ ....................................................................... . .............................................. 85 5.3 Phospl~ta Rock ................................................................. 90 5.4 Sulfur ......................................................................... 126 5.5 Potash ......................................................................... 131 5.6 Rdemn, ces .............................................. ~ .................. ". .............................. ~ ................................ 152

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158 Chapter 6. F'roductlon of Ammonia ................ ; ............................................................ 159 6,1 Ammonia ~ly Process Development ........................................................................................... 160 6.2 Ph~i~l Prope~ of ~mon~ ..................................................... L .......... 160 , .................. 6.3 Feeds~ for ~o~ ~on ................................................................. 6.4 ~u~on Te~o[~ o£ ~on~ ............................................................................................. 164 182 6-5 P~ ~da~on ~e~ of Heaw H~o~n~ ..................................... L ............................... 184 : ..... ~ ........................................... 6.6 ~onia From ~. ....................................... . ........... 187 6.7 ~mo~ ~rom ~ecWol~ H~r~ ................................................................ ~ ......................... IB8 6,8 E~noml~ of Ammo~a ~on ....................................................... 6.9 Fu~ ~lopment of ~nia T~ol~ ............................................................................... 191 192 6,10 Referen~ .................................................................. 195 ~a~er 7. Tr~s~Ration and Storage of A~o~a ..................................................... 196 7.1 Intr~u~on 7.2 ~monia Storage ........ ' ....................................................... : ....................................................... 197 199 7.3 Tr~o~on of Ammonia ................................ ~.: ..................................................................... 7.4 Re{erenc~ ................................................................................................... : .............. ; .............. 206 Cha~er 8. ~ff~c A~d, ~itra~, and ~on~um Sa~ ....... , .......................................... ~ 8.1 ~odu~on ................................................................................................................................ 209 209 8.2 H~ Add .................................................................................................................................. 8.3 ~~ Hi,ate ..................................................................................................................... 220 8.~ PolYgon Con~ol ......................................................................................................................... 2~ 8.5 Pr~u~on of Caldum ~monium Hi,ate .................................................................................... 236 8.6 O~er Hik~en ~mpo~ Us~ as F~ers ............................................................................. '. 238 8.7 References ................................................................................................................................. ~ Chapter 9. Urea ......................................................................................................... 256 ~ ..................................................... 257 9.1 In~ucfi~ .......................................................................... 9.2 Prope~ of U~ ...................................................................................................................... 258 9.3 Pmc=s Operat~g Variables ......................................................................................................... 258 9.4 Urea Proc=~s ............ ~ .............................................................................................................. 259 9.5 Urea ~lshing Proc~s~ ................ : ............................................................................................ 266 268 9.6 ~onomi~ .................................................................................................................................. 9.7 Refemnc~ ............... '...; .............................................................................................................. 268 Chapter IO. Uqu~ Fe~il~e~ ~d N~o~ Solutions ........ ~ .......................................... 2~ ~ 10.1 ~u~on .................................... ~ ........................................................................................... 272 10.2 Hidden ..................................................................................................................................... .274 , ................................. ~ ............. 279 10,3 R~d Pho~hates ......................................................................... ~ .............................. 283 [0.4 Su~emion Fe~ze~ ................................................................................... 10.5 S~ciaI~ ~d F~ers .............................................................................................................. 289 10.6 ~v=~ent Co~ ......................................................................................................................... 292 10.7 5~ ................................................................................................................................... 293 ~0.8 References ................................................................................................................................. 293 ~=pt= 11, Sul~ri{ ~d Phosphoric A~ .................................................................. =95 II.i Sulfuric Acid .............................................................................................................................. -296 " 11,2 Wet-Process Phosphoric Acid 311 11.3 Superphosphoric Acid ....................................................... 332 11.4 Sh|pment of Phosphoric Acid ................................................ 333 11.5 Use of Byproduct Gypsum .......................................................................................................... 36 3 11,6 U'd]izat~on of FluorL~e ................................................................................................................. 39 3 II.7 Uranium Extra.on ................................................................................................................... 40 3 11,8 PUrification of Phosphoric Acid ......................: ............................................................................341 11.9 Production of Phosphorlc Acid Using Acids Other Than Sulfuric .................................................... ;345 11.10 Phosphoric Acid Production by the Electric Furnace Process 348 ................. 11,11 Phosphoric Acid Production by the Blast-Furnace Process .................... 350 11.12 Wet-Process Licensers ...................................................... ~ .................................... 351 11.13 References ................................................................. 351

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354 Chapt++ 12, Fe~ilizePs Derived Prom Phosphoric Acid .................................................. 355 In~uc~on .............................................................................................................................. 1:2.1 355 . ......................... 12.2 THpIe Supe~hosphate ................. ., ......................................................... " 361 12.3 ~mo~ Phosph~ 370 1~.~ Non~ranul~ ~ ..................................................................................................................... ~on~um Po~hosp~ ........................................................................................................ 12.5 1~.6 Compara~Ve ~onom~ of TSP and D~ ................................................................................... 376 12,7 O~ Fefl~l~ers Made From ~ho~c Acid ............................................................................... ~ ......................................................................................381 1~,8 P~ss ~nsors ~d Con~a~o~ ....... 1~.9 Refe~nc~ ..............................................................; ................................................................. 381 Chapter !5. N~ophospha~ ~e~e~ 385 13,1 ln~u~on F~dam~s o[ Nibop~o~tes ...............................................................................................385 13.2 13.3 N~bopho~hate Pro~s~ .......................................................................................................... 13.~ Odd~ ~oc~ W~ ~!~ P~c~pi~Oon ....................................................................................387 13-5 ~ ~-~d Pr~s ................................................................... 395 13.60~er ~ess~ ........................................................................................................................ 397 13~7 Ad~ta~ ~d D~g~ of ~e N~bopho~hate Route ......................................................... 1~.~ O~opment ~ ~Oti~ ~d ~rket Share .............................................................................. 398 13.9 R~erenc~ ................................................................................................................................ Ch~er 14. ~er Pho~h~e ~e~ ......................................................................4~0 14~1 Single S~e~ho~hat~ (~P) ......................... 1~.2 Pho~ha~ Rock ~ a F~l~er ....................................................................................................~05 1~.3 Basi 5~B ........ ~ ........................................................................................................................ ~ 14,4 P~t~ Pho~hat~ .......................................................................................................... ..... ~09 ~ne M~ ............................................................................................... ................................ ~10 ~ 1~.5 1~.6 F~d ~ Ma~ium Phosp~o~ ......................................................................................... : 1~.8 C~ Me~ph~phate.., ................................................ ......................................................... ~11 ~11 Dt~ci~ Ph~phate ................................................................................................................. 1~.9 1~,10 ~agn~um Phosp~tes..., ...........................................................................................................~1~ ~1~ 1~.11 Ur~ Sup~hosphote ~SP) ....................................................................................................... 1~.1~ References ...................................... Chaptez 1S. Potash ~e~e~ ...................... 15.1 In~ucO~ ...................................................., ...................................................................... ~17 15.2 Potash ~ Agd~ ................................ 15.~ Pr~u~ ~W ..............................................~ ......................: ....................................~ .............. ~0 15.50~er Po~m Fe~ii~zers ......................................................................................................... 15.6 Che~cal~mde Po~sh~ .......................................~ .....................................................................~30 15.7 Re{e~n~ ................................................................................................................................ Chapter 16. Compoun~ ~e~e~ ............................................................. 16,1 Inb~ucOon .............................................................................................................................. 16.2 Tren~ ~n SuppI~ ~nd Demand for Compound,Feri~izers ............................................................... 433 ' 433 16.3 Role of Compound Fertilizers 16,4 Compound Ferlilizm P~oducaon Technolo~ ................................................................................434 16.5 Physical and Chemical Parameters for Produdng Agglomerated ~ ...........................................435 16.6 Processes for Manu~actm~g Compound Fer~l~zers ....................................................................... 16.7 Un|~e Requireraents For Hanufactudn~l Urea-Based Granular Compound Fertilizers ....................... 44? 451 16.8 Investment and OI:~ating Costs ................................................................................................. 16,9 References ........................................................~ .......................................................................454

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Chapter 17. Secondary Nutrients and Micronutrients ............................ ; .......... ; ........... 456 17,1 Secondary Nut~ents ....................................................... .' ..................................................... .. .... 457 17,2 Micronutrlents .............................................. : ............................................... ~ .... 460 4 17.3 Preparation of Fertl]h~rs Containing M]cronutrients ..................................................................... 62 17.4 Other Useful Elements ................................................................................................................ 467 17.5 Acknowledgment ................................................;..:. ..................................................................468 17.6 R~ferences ................................................................................................................................46.8 Chapter 18, Physical Properties of Fertilizers ............. ~ ...........................................; ..... 410 : 18.1 Intro~udton ...............................: .............................................................................................471 18.2 Physical Properties of Solid Fe.~tilizers ..........................................................................................471. 18.3 Physical Properties of Ruld Ferl~z'~rs .......................................................................................... 94 4 18.4 References ................................................................................................................................499 Chapter 19. Environmental Protection and Pollution Prevention ................................... 06 5 19.1 ]n~rodu~o. .............................................................................................................................. 50? 19.2 Environmental b~ues Related to the Use of Fertilizers ................................................................... 508 19.8 F.qv~ronmental Impact of the Fe~lizer Industry ........~ ..................................................................... 512 19.4 Phosphogypsum .................................................... ; ................................................................... 535 19.5 Environmental Impact Assessment ..............................................................................................537 19.6 The Role of International Organizations ................................................................................~ .....540 . : 19.7 BestAva~lable Technology (BAT) ................................................. ......................................." ....... 540 19.8 ISO 14000 ............................................................................................................................... 542 19.9 References ................................................................................................................................ 43 5 Chapter 20, Planning for the D~velopment of a Ferti.~.er Industry ................................ 545 20.1 ~ntroduction ............................................................. 20.2 Strategies and Policies of Fertiliz~ Industry Development ..............................................................547 20.3 Estimates of Demand an~ Requirements ............................................................................... ....... 549 20.4 Establishment and Development of the Fertilizer Industry ..............................................................558 20.5 P~ving the Way to Plant Operation ............................................................................................. 64 5 ¯ 20.6 References. ............................................................................................................................... .567 Chapter 21. Economie~ of Fertilizer Manufacture .........................................................568 21.1 ]ntrodu~on ............................................................................................................................... 569 21.2 The Stn~cture oflnvestment Costs ..............................................................................................570 21.3 The Structure of Production Costs ...............................................................................................575 21.4 Rnancial AnaJysls ............................................................................................ ......................... 577 ; 21.5 Economic 21.6 Use of Computers for Fmand~l Economic Analysis ...: ..................................................................586 21.7 Guidelines for Achiev~n~ WelFEstabl]sh~d Projects ........................................................................586 21.8 Refen~ces ................................~ ...............................................................................................600 Chapter 22, Challenges Facln~ the Fertlllzer Industry .... ..............................................601 , .,,.. .............................................. 22.1 Introduction ........................................ 602 22.2 Resolution ol Macroeconomlc Contradici~ons ................................. 602 22.3 Fe~.er P~odu~on C~pacity and Demand ..................................................................................603 22.4 T~andormatton From PubJtc to Private ........................................................................................604 22,5 Establishment of Hew Fadl~ties ................................................................................................... 05 6 22.6 Potential for Reducing Fertilizer Costs .........................................................................................607 22.7 G, zneral Conclusion~ ..................................................................................................................608 22,8 References ................................................................................................................................ 09 6

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Table 11.29. Typical Uranium Contents of Phosphate Rocks and Phosphoric Adds (30% PrOs)
Inurn

acid, mtial pure ~phoIpro-

Rock Source Algeria Brazil Israel Jordan Morocco Tunisia Rodda N. Carolina

UsOs ppmw in Rock 110-140 80 50-150 120-150 90-140 50-100 180-150 80

UaOs ppmw in Add . 130 80 165 165 140 80 190 80

~d o! oride ,rfor
~zs to

Because the phosphoric add from the stripping section is more concentrated in uranium than the oriflinal acid, it passes to th~ second cycle where extracfioD wRh an organic solvent is again performed to separate the uranium, which is finally recovered as UaOs, According to the process, the solwnt used in the second cycle is the same as that used in the first cycle and is either a synergistic combination of DF_~A and TOPO in kerosane o~a mixture of mona- and dioctylphenyl phosphoric acid (OPPA), also in kerosene [37]. The different commercial processes c~n!~ generally divided into three categories:
1. Those using only OPPA as solvent indud~ the IHC and U,$, Phosphoric Products processes, but recently only Gardinier, Inc., has used this ~xbacta~t,.

~ro;trade ;id is lan~. able. ¯ sting :rude stalls

and other countries, the steep and continuing increase in the cost of conventional hydrocarbon fuels since 1973, and a significant increase in the capacity of indlvldual phosphoric acid plants. The price of uranium peaked at about US $95/kg in mid-1978, Mter having remained static at US $15.5/kg for several years untl11975.

Those using a DEPA/TOPO mixture include the Prayon, Freeport Uran|urn Recover~ Co., Wyoming Mineral Corp., and COGEMA-APC processes. Those in which a DF.PA/TOPO mixture is used in one cycle and OPPA in another, such as the UNC Recovery Corp. and the Earth Sciences, Inc., processes. Several other companies have also considered processes of this type. UNC Recovery Corp. developed a single-stage process that uses an alkpl pyrophosphoric acid ext~actant; this process was intended for commercial use by Prodeco Inc., a whol[y-ow~ed subsldi~-y. I 1.8 Purification of Phosphoric Acid
For most fertilizer production processes, purification of wet-proces~ phosphoric acid isnot necessary, However, there are tWO common fertilizer uses that may call for partial purification: "Memhant-grade" acid that is shipped by rail, barge, or ocean vessels and is often stored at shtppln~ and receivin~ terminals shard be purified sufficiently so that formation of insoluble precipitates (sludge) during shipping and storage is minimized,

con-

sedlthan ound

In the early 1980s eight commercial plants in the United States and one In Canada were recovering uranium from wet.process phosphoric acid. At about the same time, a commercial uranium facility was constructed at the Chimie Rupe[ subsidiary of Societe de Prayon in Belgium, and others were planned in France by RhonePoulenc ~d APC, using their own technoloyles, and in Japan by a consortium headed by the Power Reactor and Nuclear Development Corporation, using its own
process,

con-

mck
asses

~ount dthe ~yed, ~hate
n are

The technology for the commercial pl~ts is based on solvent extraction although other methods have been developed. Much of the development work on solvent extraction was done by the U.$. Governmenbown~ Oak Ridge National Laboratory (ORNL) ir~ Tennessee [34,35]. Most of th~ processes use either octyl pyrephosphoric acid solvent (OPPA), as in the earlies~ processes in the United States, or various combinations of solvents, developed later by ORNL, di(2~thylhdcsyI) phosphoric acid (DEPA), trioctyl phosphine oxide (TOPO), and octylphenylphosphorlc acid (OPAP).

uilt In on in horic
'.W inwere

The ORNL research program resuhed in the development of two basic processes, ~ese processes ~re dmi. tar as fro" as equlpmant iS co~cern~, and they diIfer only in the solvent used [36], Uranium extraction is Althouflh ammonium polyphosphate sequesters most achieved in a process that comprises two cyc!es (P3gure of the common impurities, excessive amounts of some l ~.28). In the first cycle, uranium is extracted from phos- impurities (especially maynesium and organic matter) phoric acid wRh an organic solvent in five stages and cause precipitate ~ormation. Superphos-phoric acids usuthen stdppod from this solvent with fresh phosphoric ally do not form sludge, but magnesium and titanium have been k~own to cause sludge-forming precipitates. acid.

Phosphoric acid to be us~ in the production of liquid fertilizers, such as ammonium polyphosphate solution, sometimes requires partial purification to prevent.formation of precipitates upon ammoniatton or during storage of the ammontated solution,

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Fe metal - ~ gallmln (DEPA-TOPO process) 32% P=0~ uranium product solution -~ 8aal/min ' O.09 Ib UsOs/gal ] uranium-free URANIUM STRIPPING (3 STAGES) 54% P~Os ~" NaClOs

(OPAP

SCRUBBING , II

STRIPPING ~Ammonium_~arbonate

W::,o, ...........
FILTRATION CALCINATION
I

basis: 1,000 short tons/d of PzOs yield -i,000 Ib/d of UsOs

(NH~)~UO~(COa)~~l U~Os

- Solvent: 0.3 M DEPA + 0.075 M TOPO in refined kerosene ** - 32% P=Os, 400 gal/min (0.0017 Ib U~Oe/gal

Figure t !.28. Plow Diagram o£ the Oak Ridge Uranium Extraction Process.

A major fraction of sludge in most merchar~z-sludge acids is the compound (Fe0PJ)sKHt4(PO4)a ¯ 4H~O. It preclpJ~t~ slo~y over ~ ped~ ~f ~er~ ~e~; ~e~ fore, long storage perils are re.red to ensure r~sonable comple~on of ~e precipi~on reason. In ~e pr~uction o~ s~i~ ~po[yphospha~ and o~er conde~ed pho~hat~ for u~ as b~lde~ ~ detergent, the w~ten~s of ~e pr~uct and ~ me~ ions (~thout ~f~ and potassi~) are ~e p~dp~ con-

corn. For use in human food proces~ng and ard~al feed supplement production, the content 0[ toxic |mpurit~es must be dL,~nbhed to tnsign|~cant levels. These include ~uodn~, arsenic arid any heavy meta|s that are present in t~e phosphate rock.and sulfuric ~cid. When purified add is required only for the prod~on of phosphates, bnpu~ty removal is ,~adlitated by neutralization; since many impuHtles are rapidly precipitated as tns0|ub~e phosphates. When it b no~ permissible to neutralize the

342

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add, It I$ necessary to rely on physical treatment such as solvent extraction or ion exchan~]e, with or without chemical treatment. Phosphoric acid manuhcturers purl[ytng phosphoric acid for sale have inclined towards this type of treatment, usually based on solvent extraction. [n most cases when chemicals are used (e.g., in the case of removing arsenic), they react with the impurity alone and do not chemically alter the phosphoric acid,
11,8.1 Removal of Oeganl© Materials in the oxidlzlng.and dehydrating envkonment of the attack section, organic imp~ties tend to be decompo~d to carbon; if the rock has a re[sUrely high organic content, the resultant add will be bla&: Two methods of removing th~s discoloration include calclning the rock, whle.h destroys a good proportion of the organic matter, and h'eatlng the acid w~th active carbon, with or without a flocculating agent. Conducting the ]after treatment at a moderate temperature (60~-80~C) increases the efficiency of organics remove[ to the extent filet it may be possible to avoid calcining some hlgh-organic rocks. Other techniques that have been proposed rely on using a special floccuL=tin~ agent or hydrogen peroxide in the presence of a mixed, metal oxides ¢atllyst,

Other mlwnts that could be used include acetone, methyl ethyl ketone, other lower alcohols, and dioxane. Various processes of this route have b~en r~ported; these processes include Ch~mlsche Fabrik Budenhelm, TVA (methanol/ammonia), Gouldlng (methanol/ pomatum dihydr~jen phosphate), and Rupel (methanol/ potassium chloride). The inco~venience of this type of process is that the phosphoric acid must be separated from a large volume of solvent, usually by stripping, which is expeaslve.
E~traalon - The alternative method of purifying phosphoric acid by means of organlc solvents is liquid/ liquid extractlon; crude phosphoric acid is brought into countercurrent contact with a par'dally or su~,-tantiM]y water-immiscible solvent in a series of mixer-settlers. In general, the partition coefficient of phosphoric acid between the aqueous solution and the solvene is very urffawrable; thus the crude acid is usually concentrated before processing and only a rdatlvely small propo~on of ~e acid is extracted, The remaining partially depleted ra~r~ie, Containing most of the Impurities, is usually disposed of in fertilizer manufacture.

i

had illes lude

Depand~ on the degree of purification required, the extract may be washed with purified phosphoric acid Even if wet-process phosphoric acid is concentrated and is then usually contacted wlth water, into which the to the superphosphorlc acid stage, it still contains too ma)orRy of the add passes, "l-ha ¢nd product is a somemuch fluorine for production of feed phosphates al- what weaker but much purer acid ~an ~e ofiglnal crude though the other impurity levels may be acceptable for acid and a depleted solvent phase, which is recycled. animal feed. For animal feed preparation, it is desirable In the Prayon process (Figure 11.29), acid purificathat the phosphorus: fluorine ratio should be at least 100. P .. IF, but normal wet-process phosphoric, acid tion is carried out using a mixed organic solvent, has a P : F ratlo of between 15 : I and 54. I, depend- isopropyi ether (DIP~) and t~-n-butyl phosphate ~BP) ing on i~s concenb'ation, the composition of the rock after pretreatment of the add to remove these impurities that affect th~ coefficien~ of distribution between from which it is made, and its production condRion~. the organic and aqueous phase (F, SO~ and As). Acid Several procedure~ have been proposed to remove purification involves four operations= solvent extraction; fluorine from phosphoric acid based on volatilization or re-~xtractionl s~paration M solverlt from purifie8 acid; chemical precipitation, in the latter case with or without and color clarification, Concentration follows purificaother impurities. A commercial technique developed by tion, Four volumes of solvent (50~95% DlPi~/5%-50% Ocddental Cherrdcal Co. involves feeding slllca and TBP by volume) are contacted countercurrently with one steam into hot 54% P~O~ phosphoric acid and remov- volume of acid at 5°-25~. This yields two phases; one ing the volati[ized fluorine compounds by scrubbing with is an aqueous raffinate, contafnin~ most o~ the impurifluosiliclc acid. ties, which is stripped in an evaporator to release, for recycle, any ether it contains and to provide a rafftnate return acid stream that is sent to fertilizer-grade acid 11,8,~ So~ve~t Pror-~ss~ storage. The second phase is Organic and contains the l~,.edpitatlon- in ~ ~ of pr~, a l~ge of water-m~cible organic solwnt is added to th~ pho~- solvent and acid. The purity el acid in the organic phase is phoflc add, w~ch causes se~ng of many of ~e dis- further increased by washing] this phase with water. solved impurities out of solution and enables the Re-extraction of the acid is Mvored by a slight tern. a~d.olvent m~re to be separated, perature increase and involves countercurrent washing

Inca uble

Particularly, if methanol is used, alkali metal or am- with water to produce a purified acid. The final steps in monium ions must be present in sufficient quantities to the process are stripping tO remove residual traces o| convert the sludge impurities into less-soluble double mrs. solvent, addition of a sold chemical absorbent, filtration
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ACII~ PRETR~ATMENT Le~e.d~ Re~urn acid Cake T-5 So~ven~ bu~eP ves~e~ ANb {VAP~RAT I~N ~ (Pr~y~hes)

Figure 11,29. Pravon's Process for Phosphoric AcM PuriBeation,

to remove a~y organ]c matter (which gNes a yellow dis. coloration), and concenh'ation (which is affected in a vacuum concentrator). The resultant technlca~ acid, Prapphos P, attar defluor|nation ~ves a foed~ra~e add, Prayphos P5; A pharmaceu~cal grade is also possible.

In the Albdght and Wi~on process the impure add is concentrated to the level d 74%.80% o~ total a~d{tV (% H~PO~ + % Hz$O~, ~4% - 5~% P~Os) and then fled. N~t, It Is contact~ ~ 1.2-1.6 p~ by weight of me~yl isobu~l ketone ~ in a r~ctar to glve The/Irm, ~dbright and Wilson, is an early pioneer of orga~e ~act o~ pho~hodc acid while lea~ng most so]vent-extractlon technoIogp in the United Kingdom. of ~e impulses ~d a propo~on of ~e P=O~ ~ Its first designed plant (40,000 tpy P~Os) ~gan opera- aqueous ph~e or raff~at~ (R~ure 11,30),
tlon in 1976. The company's second plant (90,000 tpy P~O~), intended mainly ~or sodium tripol9phosphate ($TPP) manu/acture, began operation In 1979. The third p]ant~ which came into operation in 1987, produces food-~Irade phosphoric acid. All three plants are Whltehaven, where a wet-process phosphoric acid plant is located. The first U.S. plant based on the solventextraction process began produ~on in 1990 at Aurora, N.C. Owned.by Purified Acid Partners, this unit is a ioint venture of Texasguff Inc., Albdght and Wilson Ltd., and OlIn Corporation. The constr~ctIon costs for the unit, which has a capacity of I09,000 tpy P~Os ol purified acid, amounted to US $40 million The ~ndtmtrlal phosphoric acid ~ in Aurora requires no purification for organics or sul|ale removal, but flUOrine must b~ remou~d by har~er evaporation L~ the pr~ence Of active silica.

Mul~tage countercuaent extraction is carded o~t in a vertlcal cylindrical column eq,,~pped with rotating-disc agltators and sbtor rings. Acid enters near the top of the column and solvent near the bottom~ the add-laden solvent leaves the top of the column and a dens~ aqueous phase ~s discharged at the bottom, The organic extract, which contains 50%-60% (by.welght) of P~Os, is scrubbed with a r~Jativeiy pure aqueous solution of phoric add in a multistage countercurrenI scrubbing tern, using 0.3-0,5 units of P=Os tot each unit o~ In the extract. The used scrub liquor pa~s~ back to the first stage, the extTacfion column, where it enters near the top and emerges in the aqueous Impurity-containing raifinate. The mfflnate is then stripped to recover the MIBK, and the Impure phosphoric acid ~s used In the phosphatic

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ceases are used to produce compound NP or NPK fertOlzers, it Is tex, hrdca]hj feasible to produce phosphoric acid that is substantially free of calcium or nitrates by separation methods involving solvent ~xtractio~1, One such process using tertiary amy[ ~l¢ohol as the solvent was developed in Finland and described by Lounamaa D0h however, no commercial use has been reported, Several processes usin9 hydrochloric acid have been developed or patented, but only that developed by the Israel MinL~9" lndu~u3, (IMI) has been used ommer~=lly [411. The IMI process has been described in a UNIDO publication [42], A brief description of the main stages of the process follows,
magnum u~d

1. Dissolution of phosphate rock by hydrochloric add, which results in an aqueous solution of calcium chloride and phosphoric acld; 2, L|quidqiquid contacting in a number of solvent extraction steps to obtain a solution of substanOaJly pure phosphoric acid; and 3. Acid concentration to @otaln 95% H~PO4 (69% P~.Os). The raw materials and reagents used are as follows;

Figure 11.30. PuriFication of Wet-Process Ex~raction.

I~diRht the,

.~ of

aos-

an~

1. Phosphate rock (any commercial grade). The P~Os fertilizers, About 0,4 tonne of P~Os is found in the recovery is more than 98%. raffinate for each tonne of P~.Os ~n the impure feed acid, The solub~ty of MIBK in phosphoric acid is low, less 2, Hydrochloric acid for acidulation can be used as a solution of 20% H¢l or higher or in gaseous form by than 2%, so that little steam is required for s~pptng. combining absorption with reaction. For economic The scrubbed organic extract Is re-extracted with water reasons, concentrated acid ks preferred because most in a two-stage sy~em to glve the reqUtred purified phosof the water accompanying the acid must be evapo¯ phorle acid product, which also needs stripping for solrated ¯ in a later stage of the process. HC] consumpvent removal. In addition, evaporation Is necessary to tion is dependent on the composition of the rock. concentrate the pure add for sale. The MIBK solvent, after PL~)s recovery, IS recycled to the extraction stage. .Acid consumption foe Rorida rock of 34% P~Os is about 2 tomes H¢I (calculated as ~00%) per tonne However, the soIv~r~ ~rad~aIIy accumu]ates impurities, of and occasional]l/a quantity is removed from circulation for distillation; which consists of evaporation and conSolvent. $~veral solvents can be used for extraction. densafion without reflux. Those preferred are technical isoamyl alcohol (L~A), n-b~0rlo[, or a mixture Of both. Solvent makeup Is 4 When there are no possibilJtles to use raffinate in ferk~/tonne P~Os. tilizer production, it must be strongly a¢idffled with sulfuric acid before additional extraction; most of the PsOS Process v,~ater. is driven into the solvent phese~ impurities remain in the acidified aqueous phase, which ts netRra]Jzed with Auxiliary remjents. D~pendlng on thz type of rock lime before disposal as waste. and the method of se~paration of insolubl~ residue from dissolution liquor, minor quantities of filter aids or flocculating agents may be required. 11,9 Production of Phosphoric Add Using Adds Other Thzm Sulfuric 11,9,1 DissoluOon and Mechanic, el Separation of Insoluble Residue Phosphate rock can be dissolved by several organic The dissolution of .phosphate rock is essentially arid ~orgsnic acids to produce phosphoric acid. The use of nitric add for I~is purpose is described in Chap- composition of fluorapatRe by HC! according to the fob ter 13, Commercial nitrophosphate processes produce lowing equation; phosphoric acid that contains nitrates; hence, these pro- Cal0FdPO~)~ + 20 HCI-~ 2 HF + 6 H~PO4 ÷ 10 CaCl~