Tinh ch axit photphoric trch ly v sn xut cc sn phm cha ln 1.

M U

Nc ta c ngun qung apatit tng i phong ph, cng nghip phn ln cng c xy dng v ang pht trin. Tuy nhin nhiu sn phm cha photpho nh cc mui photphat dng trong chn nui n cc sn phm tinh khit vn cn phi nhp ngoi. Trc y sn xut nhng sn phm ny, ngi ta dng n axit photphoric iu ch t photpho nguyn t. T nhng nm 60 ca th k trc c nhiu cng trnh nghin cu tinh ch axit photphoric trch ly v n nhng nm 80 c p dng vo sn xut qui m cng nghip. Bn bo co chuyn ny cp n nhng phng php tinh ch photphoric trch ly, gii thiu mt cng nghip tin tin c p dng vo sn xut, so snh mt s ch tiu v chi ph sn xut ca hai phng php, nhng bin php nng cao cht lng v h gi thnh sn phm ng thi trnh by mt s kin v pht trin cng ngh sn xut axit photphoric sch nc ta. Do ngun thng tin truy cp c cng c hn, chng ti s trnh by nhng s liu hin c vi mc cao nht v nhng suy ngh ring v vn ny.

2. PHN GII THIU 2.1. Tnh hnh sn xut v s dng axit photphoric sch v cc sn phm lin quan Axit photphoric sch c s dng trong nhiu ngnh cng nghip nh x l kim loi, sn xut natri tripolyphotphat, thc n khong b sung cho gia sc, gia cm v thy sn, cng nhip thc phm, cng nghip dc...

Nhng nm gn y nhu cu x l kim loi gim mi nm khong 3 - 5% do vt liu kim loi ngy cng c thay th bng cht do, nht l trong cng nghip sn xut t. Ngoi ra, lng axit dng sn xut natri tripolyphotphat cng gim v vn nhim nc thi. Trong khi nhu cu axit photphoric cho x l nc v nht l cng nghip thc phm li tng ng k. Mt trong nhng lnh vc cng s dng nhiu axit photphoric sch l sn xut thc n khong cho chn nui. Bng 1. T l s dng axit photphoric sch ti mt s quc gia v khu vc Sn phm EU Nht M

Bn X l kim loi 25 X l nc 20 Sn xut Natri Tripolyphotphat 40 32 Cng nghip thc phm 15 Sn xut thc n khong cho gia sc 22 13 Cc ngnh khc 38 55 40 Cng ty Potash Corp hin ang vn hnh 5 nh my sn xut photpho dng cho chn nui M v mt nh my Braxin vi sn lng 1,3 triu tn/ nm: Bng 2. Tnh hnh sn xut sn phm photphat ca Cng ty Potash Corp n v: 1000 tn/nm

Tn v a im Maseilles, Illinois White spring, Florich Monocanxi photphat

Cng sut, ngn t/n Sn xut 248 192 218 154

Photphat kh flo Weeping Water, Nebraska Kingston,North Carolina Fosfats do Braxin Tng cng * S liu nm 2001

100 209 141 70 1296

89 170 63 53 724

Postash Corp l mt cng ty sn xut a dng nht cc mt hng v mui photphat axit photphoric tinh ch dng cho sn xut thc phm v ung, x l kim loi, cht ty ra tng hp v in t. Do c chin lc a dng ha v u t hp l m Potash Corp sn xut axit photphoric tinh ch v thc n khong chn nui vi gi r nht th gii. Axit photphoric tinh ch ca Cng ty c sn xut ng vi 2 loi, l loi "thc phm" dng trong cng nghip dc phm, thc ung, thc phm v men v loi "k thut" dng cho cng ngh m in, chng r kim loi, sn xut cht kt dnh v cht chng chy. Nm 2001, ring phn sn xut axit photphoric tinh ch ca Postash Corp l 168000T P205. Axit photphoric tinh ch c tp trung sn xut Aurona, ni gn ngun qung photphat c cht lng tt. Cc sn phm photphat dng cho chn nui c sn xut di nhiu dng khc nhau, trong ch yu l monocanxiphotphat (52%), photphat kh flo (15%), natri photphat (3%) v mt lng nh MAP/DAP (1%). Mt phn ng k (29%) sn phm photphat c sn xut di dng dung dch. Sn lng photphat dng cho chn nui t 2,07 t USD (2001), chim 11% doanh s ca Postash Corp. Li nhun thu c khong 48 triu USD, chim 12% tng s li nhun. Braxin cng c chin lc m rng nhanh, th trng thc n chn nui. Khu vc thng mi nng nghip chim khong 40% GDP ca Braxin, tng ng gn 320 t USD/nm. Lnh vc chn nui c ngha quan trng vi khong 8,5

triu km2 c s dng cho chn nui. Tng s n gia sc khong 170 triu con, gm 30 triu con nui ly sa v 140 triu con ly tht, gp i tng n gia sc ca M. Nm 2000, Braxin xut khu 615 ngn tn tht b, ch yu sang chu u (62%) v Trung ng (21%). Chn nui gia cm Braxin cng pht trin mnh. Nm 2001 nc ny xut khu 250 ngn tn, tng gp i nm 2000. Hin ti Braxin hng ti mc tiu s t ti 7 triu tn sn phm gia cm/nm. Do nhu cu tng mnh nn th trng thc n chn nui Braxin xy ra cnh tranh si ni. Cc cng ty ca Braxin nh Sernana (b phn ca Bunge) cnh tranh vi Cargill v Ajimoto; cng ty Fosfatos do Braxin cng phi cnh tranh pht trin v ang l mt i th mnh, chim c 8-10% th phn. Cng ty ny bn c 750-800 ngn tn dicanxi photphat (DCP) v thu c khong 150 triu USD/nm. Tng t cc nh u t So Vieente s m rng cng sut ln 80b ngn tn/nm DCP ng ht thay cho sn phm bt hin c, nh ang c s dng rng ri M. Trung Quc, lin quan n sn xut axit photphoric phi k n hn 400 nh my sn xut MAP, DAP, TSP quy m nh t 30 ngn n 60 ngn tn/nm v khong 10 nh my DAP cng sut t 150 ngn n 450 ngn tn/nm trn c s nhp khu cng ngh ca cc cng ty nc ngoi. Tnh hnh sn xut axit photphoric v phn cha ln trn c s axit photphoric nh sau: Bng 3. Tnh hnh sn xut cc sn phm cha ln Trung Quc n v: 1000 tn P2O5/nm Tn sn phm 2001 2002 2003 2004 2005 2006 2007

Axit

4.101

4.080

4.610

4.793 2.671 1.338 115 1.758 Industial

5.093 2.921 1.338 115 1.758 Corp sn

5.374

5.374

photphoric DAD 2.287 2.287 2.487 MAD 1.062 1.062 1.338 TSP 115 115 115 NPK 1.735 1.758 1.758 Trong c cng ty Nanjing chemical

3.142 3.142 1.338 1.338 115 115 1.958 1.958 xut canxi photphat

vi thng hiu tam gic . Cng ty Yunnan Phosphate Fertilizer lin doanh vi Cargill Fertilizer sn xut 130.000 tn axit photophoric/nm (tnh theo P2O5) v ang xy dng mt nh my 180.000 tn/nm gn Cn Minh. Cn cng ty Sino Arab chemical Fertilizer Co l lin doanh vi PIC (C - oet) v GCT (Tuynidi) tnh H Bc sn xut 480.000 tn DAP trn c s axit photphoric trch ly nhp t Tuynidi. Hin ti Trung Quc vn phi nhp cng ngh nng cng sut sn xut axit photphoric. Cn cc nc khc trong khu vc nh Thi Lan, Indonexia, Philippin, Bangladesh, xtrylia, Nht Bn, Hn Quc, n ngi ta cng sn xut v bun bn axt photphoric nhng khng c s liu c th. Danh sch cc Cng ty kinh doanh trong lnh vc ny c ghi phn ph lc. Hin ti axit photphoric sch c sn xut theo 2 phng php l phng php i t photpho vng nhit in (H3PO4 nhit) v axit c tinh ch t axit photphoric trch ly (H3PO4 tinh ch). Hin nay, theo nh gi, sn lng axit sch ca cc nc trn th gii khong hn 2,2 triu tn/nm, trong lng axit tinh ch t H3PO4 trch ly khong 1,7 triu tn/nm. T l gia 2 loi axit ny c s dng cc chu lc (khng k sn xut thc n khong) theo t l c trnh by bng 4. Bng 4. T l s dng 2 loi axit photphoric sch ti mt s khu vc

n v: % Cc vng H3PO4 nhit H3PO4 tinh ch Bc M 86 14 Ty u 31 69 Chu 49 51 Chu Phi 24 76 M La Tinh 52 48 xtrylia v Chu i Dng 26 74 Nguyn liu sn xut axit photphoric nhit l photpho nguyn t vi chi ph cho nguyn liu chim ti 95,5% tng chi ph sn xut axit nhit. Ngi ta thy cng ngy cng gim phn axit photphoric nhit l do gi nhin liu v gi in tng, ng thi vn u t c bn cho sn xut axit nhit cng tng. Do vy, ngi ta nghin cu v pht trin cng ngh tinh ch axit photphoric trch ly v sn phm tinh ch t axit photphoric trch ly ngy cng p ng y c v lng v cht i vi cc nhu cu s dng. 2.2. Mt s phng php tinh ch axit photphoric trch ly 2.2.1. Cc tp cht thng c trong axit photphoric trch ly Axit photphoric trch ly thng cha nhng ion ca tp cht ha tan c trong qung photphat v trong axit sunfuric (tc nhn phn ng phn hy qung photphat) cng vi nhng tp cht do n mn thit b khi sn xut. Nga c 3 tiu chun v axit photphoric tinh ch, cn theo tiu chun ca Hng Fison c tiu chun ha v p dng vo tiu chun cng nghip v axit photphoric nh sau (bng 5, 6): Bng 5. Tiu chun v axit tinh ch ca Nga n v: % Thnh phn P2O5 SO4 Mac T2 39,5 0,12 Mac T3 53,5 0,14 Loi nng cp 54,0 0,185

Fe F Pb As TBP SS T2: T3:

0,016 0,08 -

0,022 0,024 -

0 0 TY 2142 - 001 - 00209450 - 95 TY 2142 - 001 - 00209450 - 95

0,022 0,004 5,6 ppm 1,75 ppm 4 ppm 0

Loi nng cp: TY 2142 - 002 - 00209450 - 96

Bng 6. Tiu chun axit photphoric tinh ch ca Fison, hng S.L.R n v: % Thnh phn H3PO4 Canxi (Ca) ng (Cu) St (Fe) Ch (Pb) Magi (Mg) Khi nghin cu T l Thnh phn T l 85% min Niken (Ni) <0,002 <0,02% Kali (K) <0,01% <0,002% Km (Zn) <0,002 <0,005 Tng lu hunh <0,01 <0,002 Tng silic <0,005 <0,005 Tng clorua <0,005 iu ch axit photphoric trch ly t qung apatit nguyn khai

Lo Cai (HITACHI ZOSEN, Test report on Lao-Kay apatite for photphoric acid production, PAT Fertilizer Project July - 1975) ngi ta thu c axit c thnh phn ha hc nh sau (bng 7): Bng 7. Thnh phn axit photphoric trch ly t qung apatit Lo Cai n v: % Tn thnh phn Trong apatit Trong axit H3PO4

trch ly P2O5 32,46 28,96 SO3 0,03 3,52 CaO 43,68 0,02 MgO 1,73 1,56 Fe2O3 1,54 1,14 Al2O3 1,54 1,17 SiO2 9,98 0,46 F 2,93 1,27 MnO 1,05 0,03 Na2O 0,07 0,03 K2O 0,66 0,10 Cl 0,02 0,02 Pb 24 ppm 0,4 ppm V 40 ppm 57 ppm As 16 ppm 6 ppm Hg 1 ppm 0,1 ppm Cd 0,00 0,0 T bng 7 c th thy a axit photphoric trch ly v dng axit sch cn tch loi cc tp cht v c c axit. 2.2.2. Mt s phng php tinh ch axit photphoric Hin c 4 phng php tch tp cht c trong axit photphoric trch ly l phng php trao i ion, phng php kt tinh, phng php trung ho v kt ta, phng php chit bng dung mi hu c hoc polyme hu c. Sau y l 3 phng php ph bin hn c: 2.2.2.1. Phng php trao i ion v hp ph Theo phng php ny, ngi ta dng nha trao i anionit loi tp cht anion SiF62- v SO42- dng cationit loi cc tp cht cation. Tch loi tp cht anion trong axit photphoric trch ly Ngi ta nghin cu chi tit qu trnh hp ph anion cha flo v ion SO42- t axit photphoric c c hoc axit iu ch theo phng php dihydrat, hemihydrat.

Khi tn ti ng thi ca nhiu anion tp cht trong axit photphoric th kh nng hp th ca cc anion s gim theo dy NO3->SiF62-> SO42-> PO43-. Sau khi hp th, gii hp c th dng dung dch amoniac, amoni cacbonat, diamoni phophat. Trng hp dng diamoni phophat, flo tch ra dng (NH4)2SiF6 ho tan tt, cn khi dng hai cht u th dung dch (NH4)2SiF6 b thu phn thnh amoni florua v SiO2. giai on u, flo trong axit photphoric c loi bng cch kt ta dng Na2SiF6. Hm lng flo trong axit gim 0,2 - 0,4%. Sau tip tc tinh ch bng anionit. Hm lng flo sau khi tinh ch khng qu 0,006%. Axit tch flo bng phng php trao i ion thch hp sn xut thc n khong b sung cho gia sc. Nhng do phc tp v ti sinh anionit v thu hi flo nn tt nht l kt hp loi s b flo bng cch kt ta, sau lm sch bng anionit. Mt phng php n gin cng dng loi flo l cho kt hp c c axit photphoric trch ly v hp ph bng than hot tnh, sau loi anion sunfat bng stronti cacbonat. Bng phng php ny c th thu c cc loi sn phm axit sch vi hm lng tp cht nh bng 8: Bng 8. Mt s loi sn phm axit photphoric sch c iu ch theo phng php hp ph kt hp kt ta. Hm lng tp cht, % P2O5 F SO4 SiO2 Al2O3 0,017 0,0075 Fe2O3 0,02 0,007 Loi axit Axit K thut 39 0,052 0,12 1,35 Axit tinh ch 54 0,008 0,01 0,017 Tch cc tp cht cation trong axit photphoric trch ly

Cc tp cht canxi, magi c trong axit photphoric trch ly nu khng c loi b th qu trnh c c axit s gp kh khn do nht v im si tng cao.

loi b magi, ngi ta dng cationit, th d nh loi b cationit KY - 2. Khi , canxi b loi hon ton cn magi gim xung ti 0,14% v c th c c axit ti 60 - 65% P2O5. Trng hp khng kh canxi, magi trong axit, khi c c n nng 55% P2O5 mc kh flo s khng vt qu 42%. Vic tch canxi, magi cho php nng mc kh flo n 80 - 85%. 2.2.2.2. Phng php trung ho v kt ta tp cht. Ngi ta dng silic oxit hot tnh phn ng vi ion flo trong axit thnh SiF4 chuyn vo pha kh. Khi c c axit, dng natri sunfit kh cc cation kim loi nng v bari cacbonnat kt ta ion sunfat. Tuy nhin phng php ny khng loi trit c cc tp cht v ch c dng loi s b hoc kt hp vi cc phng php khc hay p dng cho trng hp iu ch axit photphoric mc sch khng cn qu cao nh sn xut natri tripolyphotphat dng cht ty ra tng hp. 2.2.2.3. Phng php chit bng dung mi hu c Gii thiu chung Phng php tinh ch axit photphoric trch ly bng cht cch chit vi hu c c nhiu u im l tnh chn lc cao, c th tin hnh qu trnh lin tc, t ng ho cao. Nhng nhc im c bn ca phng php ny l kh nng d gy chy n bi tc nhn chit hu c. V nguyn tc, c th chia ra hai phng php chit bng dung mi hu c. Theo phng php th nht (chit thun), H3PO4 chuyn vo pha hu c, cn tp cht li pha nc. u im ca phng php ny l gi thnh tng i thp v tc nhn chit d c p ng. Nhng nhc im ca phng php l tiu hao nhiu dung mi v gy tn tht H3PO4 , v mt lng ng k H3PO4 cn li

trong pha nc. Ngoi ra vic ti sinh dung mi hu c kh kh khn do kh tch trit chng khi H3PO4 . Theo phng php th hai (chit ngc), flo v cc tp cht khc c tch khi H3PO4 bng dung mi hu c. Phng php ny kinh t hn v gim chi ph v gim tn tht dung mi, nhng li i hi nhng dung mi c tnh chn lc cao vi cc tp cht. Tch H3PO4 bng dung mi hu c (chit thun) Qu trnh chit xy ra theo c ch solvat - hydrat vi s to phc HC.H3PO4.H2O (HC - l dung mi hu c). Ngi ta nghin cu hn 40 dung mi thuc loi ru mch thng, mch vng, keton, aldehyd, este n v phc, cc amin v v hydrocacbon. Cc dung mi c nghin cu theo s bin i h s phn b axit H 3PO4 xp theo dy: ru, keton, este, aldehyd, hydrocacbon. Kh nng chuyn vo dung mi ca cc axit v c vo iu kin cn bng bn gim theo dy: HNO3, HCl, H2SO4, H3PO4. S c mt cc axit khc trong dung dch s thc y s chuyn H3PO4 vo pha dung mi. Nhng hp cht ca nhm, magi v st c trong axit photphoric trch ly cng c tc dng lm gim tan ca H3PO4 theo dy: Al, Fe, Mg. Kh nng ha tan ca cc ru mch thng i vi H3PO4 s tng vi s tng in mi. Tc nhn tch hiu qu hn c l ru propylic v izopropylic. Ru propylic gi thnh s cao, nn hp l hn l dng ru izopropylic (RIP). Tinh ch H3PO4 bng RIP: Khi b sung ru vo axit photphoric trch ly cc tp cht v c s tch ra dng kt ta nhy (gel), kh tch loi bng phng php c hc. d tch kt ta gel ngi ta iu chnh mi trng chit bng kim (NaOH, NH3, soa).

Vi mc ch tng kh nng lm sch axit photphoric trch ly, ngi ta nghin cu nh hng ca cc mui nh sunfat nhm v magi n qu trnh tinh ch do to thnh hp cht florua ca nhm v magi khng tan. Hin nay ngi ta quan tm nht l dung mi hu c photpho hu c. H3PO4 khan hon ton trn ln vi tributylphotphat (TBP). Khi , to thnh phc 3 TBP. H3PO4.6H2O. Mc d TBP t hn ru RIP nhng ti sinh kh n gin. Ngi ta dng nhng dung dch alkyl, aryl hoc alkylarylphophat trong cht pha long hu c. Tc nhn chit tt hn c l dung dch TBP trong kerosin (du ha) v hexan. Vic ti chit c thc hin bng nc. u im c bn ca vic dng dung mi photpho hu c l ho tan ca tc nhn chit trong pha nc thp v d ti sinh. Nhc im lm sch khng cao v cn phi x l s b axit H3PO4 ngn nga to thnh gel H2SiO3. Qu trnh tinh ch axit photphoric trch ly bng ru c giai on chng ct tiu hao nhiu nng lng, v vy trong nhng trng hp cn iu ch photphat natri hoc amni vi tinh khit dng cho cng nghip thc phm ngi ta thay giai on chng ct bng cch trn tc nhn chit hu c vi cha RIP, H3PO4 v nc vi NaOH hoc NH3. Th d, khi trn tc nhn hu c vi dung dch NaOH 50% s thu c 2 pha lng d tch ring. Pha trn cha RIP c quay v cng on chit, pha di l dung dch mononatri photphat c em i sy. Sn phm thu c cha 52,9 % P2O5; 0,02 % F; Vt cc ion SO42-, Al3+, Fe3+, Mg2+ v Ca2+. Theo hng ny, hin nay ngi ta dng polyme hu c, th d polyetylenglycol gi r v d ti sinh, t tn tht hn. S cng ngh mt chu trnh sn xut natri hydrophotphat t axit photphoric trch ly gm 4 giai on (hnh 4) l: trung ha mt phn H3PO4 bng sa, chit dung dch NaHPO4 bng polyetylenglycol v tch ring pha mi, c c pha hu

c v kt tinh NaHPO4 (c th ti kt tinh), cui cng l ti sinh dung dch polyetylenglycol. Hm lng cc nguyn t tp cht trong natri hydrophophat thu c khi dng polyetylenglycol c khi lng phn t 1500 v 2000, c ghi trong bng 9: Bng 9. Thnh phn tp cht trong cc mu NaHPO4 Natri Nguyn t hydrophotphat GOST 4174-76% Sn phm (khi dng PEG 1500), % khi Sn phm (khi dng PEG 2000),

lng % khi lng K.lg V 5.10-4 1.1.10-3 1.1.10-3 C < mu CN < mu CN -4 -5 Cr 5.10 1.0.10 5.4.10-6 Mn 5.10-4 5.4.10-3 3.4.10-3 Fe 5.10-4 2.4.10-3 1.2.10-3 Co 5.10-4 3.4.10-5 1.9.10-5 Ni 5.10-4 1.3.10-4 8.5.10-5 Cu 5.10-4 2.3.10-4 1.3.10-4 Zn 5.10-4 4.1.10-4 1.5.10-4 As 5.10-4 7.4.10-5 7.4.10-5 Cd 5.10-4 < mu CN < mu CN Sr 5.10-4 1.6.10-4 9.6.10-5 Zr 5.10-4 6.9.10-5 5.3.10-5 Pb 5.10-4 9.8.10-6 4.4.10-4 Th 5.10-4 7.4.10-6 5.1.10-6 U 5.10-4 5.9.10-5 6.8.10-5 Tch tp cht t H3PO4 trch ly bng tc nhn chit hu c (chit ngc) tch tp cht ra khi axit photphoric trch ly bng phng php chit, ngi ta thng dng amin c khi lng phn t ln v cc hp cht amin bc bn. V nguyn l c ch ca qu trnh tch tp cht bng tc nhn chit hu c cng tng t nh chit H3PO4, ngha l cng to thnh solvat-hydrat. Hiu sut chit cng

ph thuc vo h s phn b ca cc tp cht trong h, tc dng qua li ca cc ion v mt s yu t khc. Th d, khi chit flo bng dung dch 30% trialkylamin (TAA) trong kerosin (du ha) s to thnh mui hydrat c thnh phn (TAAH) 2.SiF6.2H2O. Trong trng hp ny, qu trnh dim tch cng ng vai tr ln: ion phophat y flo khi pha nc, cn nhng ion sunfat, clo, natri li y flo khi pha hu c. Axit photphoric trch ly l mt h phc tp v thnh phn nn ngoi cc anion, cc cation cng nh hng ng k n mc tch flo, trc tin l nhm, st, magi. Cng ty Monsanto Co. nghin cu tch flo v ion sunfat bng dung dch amin v mui ca chng hoc bng dung dch amoni bc 4 trong dung mi hu c. Nhng dung mi c dng phi khng ho tan trong nc v cha t nht 2 nhm th k nc, ng thi thnh phn ca mi nhm phi c t 7 n 15 nguyn t cacbon. Amin - 1 khng thch hp tinh ch axit photphoric trch ly v thin v kt ta dng mui. Cc amin mch thng - 2, - 3 cha t hn 7 nguyn t cacbon trong 2 nhm th li ha tan trong nc; cc amin mch thng -2, -3 cha nhiu hn 15 nguyn t cacbon trong 2 nhm th li khng ho tan trong pha hu c; cn cc amin nhm (-1, -2, -3) l nhng tc nhn chit km. Tc nhn pha long c th dng l kerosin (du ha), benzon, toluen, nitrobenzen, mt s ru, clorofooc, tricloetylen, v.v... phn lp cc pha tt hn, ngi ta khuyn ngh b sung vo dung dch amin (trong tc nhn pha long hu c) mt lng 5-10% ru mch thng (hexanol-1 v hexanol-2, 4methyl-2-pentanol-2, 2-etyl bectanol, octanol-1, dodecanol hoc tetradecanol). ti sinh tc nhn chit ngi ta dng nc hoc dung dch kim (trng hp dng amin t do) v dung dch axit (trng hp dng mui amin).

Vi quan im tch chn lc flo th tc nhn chit tt c dng l trialkylamin do dung mi ny khng t v sn phm chp nhn c. Gn y ph bin l dng photphinoxit v trin vng hn c l photphinoxit vi cc gc th khc nhau. i vi axit photphoric trch ly c c, h s phn b flo v sunfat tng ng bng 17 v 4, nn phng php chit rt thch hp tinh ch cc axit c c, trong khi cc phng php khc li kh gii quyt. T l ti u ca O/W ca pha cht hu c v pha nc khi chit bng dung dch 30% trialkylamin trong bezen l 1:3; Khi mc tch flo t cc i. Tng nng trialkylamin trong bezen h s phn chia flo v sunfat tng, nhng khi nht ca tc nhn chit tng, lm s phn lp ca h kh khn hn. tch tc nhn chit ra khi H3PO4, ngi ta ra bng nc vi t l th tch 1:1. ng thi vi chuyn H3PO4 vo pha nc cng km theo khong 15% flo v gn 9% ion sunfat. Mun tch hon ton 2 tp cht ny, ngi ta x l cht chit bng dung dch NH3 (thi gian tip xc pha 4-7 pht). Pha nc nhn c cha hp cht flo, ion sunfat v kt ta SiO2. to iu kin kt ta SiO2 tt ngi ta dng dung dch amoniac nng 5-15%. Khi nng ny cao hn, pha hu c s b ln SiO2. S nguyn l tinh ch axit photphoric trch ly bng cch chit vi trialkylamin c gii thiu trn hnh 5. Khi tinh ch axit photphoric trch ly c c, tn tht trialkylamin l 25g/T H3PO4 hoc 0,005% lng ban u, hm lng amin trong axit sau khi tinh ch khng vt qu 0,0025%. Qu trnh tinh ch H3PO4 trch ly bng phng php chit vi dung mi hu c c ph bin Ty u, Israel, M. Nhng hng dn du v tinh ch axit H 3PO4 trch ly l Prayon (B), Albright and Wilson (Anh), Chemische Fabric Budenheim v Hoechst (c), Rbrone Poulence (Php), Haifa Chemical v Bateman (Israel).

 Nga hin mi ch c mt s dy chuyn pilot cng sut 15.000T axit photphoric/nm. 2.3. Cng ngh sn xut H3PO4 tinh ch ca Cng ty Prayon Nh my Fosbrasil l c s sn xut axit photphoric tinh ch ln nht Nam M. Nh my ny bt u sn xut t nm 1987 gm 3 thnh vin l Qimbrasil (c m photpho v nh my axit photphoric trch ly), Monsanto (c th trng v nh my sn xut photphat cng nghip) v Prayon (c cng ngh tinh ch axit photphoric bng dung mi). Cng sut thit k ban u l ca Nh my 25.000 T/nm tnh theo P2O5, trong 20.000 T/nm l sn phm k thut; 5.000 T/nm l axit x l s b. Th trng ch yu l Baxin, khch hng chnh l Monsanto Do Braxin v mt s c s sn xut ung nh. Thi gian qua, cng sut nh my c nng ln 50.000 T/n, trong 40.000 T/n l axit tinh ch, 10.000 T/n l axit x l s b. Th trng chnh vn l Braxin nhng cn xut khu sang Achentina, Chile, Paragoay, v.v... Sp ti, cng xut s c m rng n 90.000 T/n axit tinh ch phc v cho th trng trong nc v xut khu sang Bc M, chu u v Chu Phi. V cng ngh, ngi ta c b sung v ci tin nhiu so vi thit k ban u. B phn x l s b gm cc giai on loi b sunfat, flo v asen, c c n nng khong 60% P2O5, lc v lng. Sau , axit c lm lnh v c a vo b phn chit bng dung mi hu c. Tc nhn chit l hn hp dung mi gm Izopropyl ete (l thnh phn chnh) v photphat este (l thnh phn ph). Qu trnh chit gm 3 bc. Trc tin l chit trn thit b chit c ng xon lm lnh bn trong. Dung mi bo ho P2O5 i ra t thit b chit ra bng nc loi b tp cht kim loi; nc ra li c quay vng, cn axit photphoric c ti (gii) chit v i vo b phn ngng 500 C; ete ln trong axit s c lm bay hi kit v axit c c c n nng 85% H3PO4. Cui cng d lng

ca dung mi trong axit s c loi trong thp cha than hot tnh. Axt photphoric dng cho mt s nhu cu c bit c ngi ta x l thm (loi b) flo bng phng php gin on a hm lng flo xung di 10 ppm. i vi axit loi Codex cn giai on oxi ho cc cht hu c (d lng ca cc cht thuc tuyn ni qung photphat chuyn vo axit H3PO4 trong qu trnh sn xut), hm lng cht hu c cn di 10 ppm. loi ion sunfat ngi ta dng phng php kt ta bng bari cacbonat. d phng chy n, ngi ta np kh nit vo nhng khong trng trong cc thit b v h thng. 2.4. V chi ph u t v chi ph sn xut 2.4.1. Chi ph u t Hin cha c y cc s liu v chi ph u t cho mt nh my sn xut H3PO4 tinh ch. Chng ti ch dn ra c mt s thng tin nh sau: Theo Paol Smith, nguyn Gim c k thut ca Prayon B, nay l c vn c lp ti Braxin, th chi ph u t cho h thng chit bng dung mi ca Fosbrasil ch chim non na chi ph ca ton b cng trnh, cn phn x l s b v phn x l axit cui dng mi phc tp. Theo s liu ca Potash Corp., Aurora Carolina (M), m rng cng sut thm 80.000 T/nm axit photphoric tinh ch (tnh theo P2O5) t sn lng 327.000 T/nm, h phi u t thm 73 triu USD (ch tnh cho phn tinh ch). Cng trnh ny s hon thnh vo qu 1 nm 2006. Nh vy c th suy ra sut u t cho 1 tn P2O5 vo khong 890 USD. Thng sut u t cho 1 tn P2O5 ca axit photphoric trch ly vo khong 300 USD. Cng sut m rng ny s p ng cho nhu cu ang tng c Bc v Nam M v y l nh sn xut ln nht th gii vi gi thp nht, do c s dng qung Bc Carolina, l qung c cht lng tt, t tp cht.

2.4.2. Chi ph sn xut Di y l chi ph sn xut cho 1 tn P 2O5 ca axit photphoric nhit v photphoric tinh ch bng phng php chit vi dung mi trong cng iu kin ti Florida (M) c cng sut 73.000 T/nm Bng 10. So snh chi ph sn xut c photphoric nhit v tinh ch Hng mc Qung photphorit (T) Lu hunh (T) Than cc (T) in nng (KWh) Hi (T) Nhin liu (KJ) axit nhit 3,7 0,6 6.700 5.442 axit tinh ch 3,8 - 4,1 1,0 300 5 - 10 -

Chi ph sn xut cho 1 tn P2O5 ca axit photphoric tinh ch bng dung mi theo phng php ca IMI Israll, dng axit HCl phn gii qung photphorit cng xut 45.000T/nm P2O5 trong iu kin min Trung pha Ty nc M nh sau (bng 11): Bng 11. Chi ph sn xut axit photphoric tinh ch theo phng php IMI (Irsael) Hng mc Nguyn liu v vt liu chnh Qung photphorit t (34% P2O5) HCl l (100%) Dung mi Nng lng in nng Hi Nc n v T T Kg KWh T m3 S lng 3,1 2,0 4,0 330 5,0 188

Trong khi , cng vi nh my sn xut H3PO4 tinh ch c cng xut 45.000 T/n P2O5 theo phng php trung ho v kt ta, chi ph sn xut theo 1 tn P2O5 nh sau: Bng 12. Ch ph sn xut axit photphoric tinh ch theo phng php trung ha v kt ta SiO2 hot tnh (Kg) Bari Cacbonat (Kg) Natri Sunfit (Kg) in (KWh) Nc (m3) 2.4.3. Chi ph ngoi sn xut 111 76 1.2 17 3,75

Trong sn xut axit photphoric nhit cng nh axit tinh ch c pht thi mt lng ln bi, hp cht flo v nc thi cn x l. Di y l s liu tnh ton ca hng Asthur D.Little Inc. v chi ph lm sch ngun thi i vi nh my cng sut 45.000T P2O5/nm trong iu kin nc M, cho sn xut axit photphoric nhit v tinh ch: Bng 13. Mt s chi ph ngoi sn xut i vi axit photphoric tinh ch n v: (USD/T P2O5)

Hng mc Chi ph lao ng cho cng nhn SX Chi ph cho cng nhn sa cha Ha cht in nng Chi ph thi x, bn Khu hao (9% u t) Thu v bo him (2% u t) Li nhun trn vn u t

axit nhit 0,94 0,83 3,27 0,04 1,88 1,86 0,41 4,14

Tinh ch theo pp trung ho v kt ta 1,08 0,26 1,95 0,03 3,58 0,58 0,13 1,30

Tinh ch bng dung mi 2,45 0,56 1,95 1,80 2,20 1,27 0,28 2,83

(20%) Tng cng 13,37 9,18 13,16 2.5. Vn nng cao cht lng v h gi thnh sn phm H3PO4 tinh ch sn xut theo phng php chit c iu kin nng cao cht lng v h gi thnh sn phm, ngi ta p dng cc gii php nh sau: 2.5.1. Nng cp v m rng chng loi sn phm Fosbrasil l nh sn xut axit photphoric tinh ch duy nht Nam M vi nhiu chng loi axit: Loi L-70 dng cho cng nghip nh x l nc ma ng; x l b mt kim loi ngi ta dng loi axit x l trc (tinh ch s b); Loi Codex (A-85) c dng cho cng nghip dc v thc phm; Loi k thut I-80 dng cho sn xut natri tripolyphotphat, nh bng nhm; Loi D-85 dng sn xut photpht thc n cho gia sc v trong mt s k thut c bit nh photpht ho b mt thp v x l du n.

2.5.2.Tng thm s thp chit Fosbrasil theo thit k ca Monsanto lc u ch c 3 thp chit, nhng do phi thch ng vi nhiu loi nguyn liu nhp ngoi nn ngi ta phi lp thm thp th 4 ng thi chuyn qu trnh t hng "chit thp" sang hng "chit cao". Mt khc gim c khi lng cn chit (ch dng sn xut phn bn), nh vy cng lm tng thm li nhun. tng hiu sut tch H3PO4, Nga ngi ta a ra s chit 10 cp , ng thi b xung H2SO4 vo cp th 4 ho tan cc mui photphat, m bo tch hon ton H3PO4, thm 4 cp ra bng dung dch diamoni photphat vi nng cao (~2,5 mol/l); Cn ti chit c tin hnh 6 cp bng nc. Phn TBP tun hon c dn ra ti sinh bng kim trong mt cp. H thng nh vy s t c hiu qu cao v loi b anion sunfat v cc cation khc (nh st, canxi, magi, asen). 2.5.3. tng hiu qu chit, ngi ta dng tributylphotphat (TBP) 100% thay cho dung dch tributylphotphat trong kerosin. 2.5.4.Tng cng qu trnh loi tp cht flo v sunfat. Vic loi trit flo v ion sunfat l vn phc tp v hp cht ca chng (trong iu kin chit) c h s phn b gn ging h s phn b ca axit photphoric. gim chi ph cho qu trnh loi flo, ngi ta dng phng php tch flo lin tc thay cho phng php gin on (Fosbrasil, 2002), dng bari cacbonat loi anion sunfat (Frobrasil) hoc dng stronti cacbonat ( Nga) sau ti ch stronti cacbonat t stronti sunfat bng soa. 2.5.5. X l cht hu c Cc cht hu c lm bn tributylphophat (TBP) trong qu trnh s dng trong chu trnh chit kn, tun hon. Cc hp cht ny lm cho TBP c mu nu thm, cn tr vic phn chia pha hu c v pha nc dn n gim phn lp v cui

cng l gim nng sut thit b, gy tng trong tn tht TBP theo dng nc. Cc cht hu c tch lu trong tc nhn chit ch yu l d lng thuc tuyn hp ph trn b mt ht khong apatit, sau chuyn vo axit photphoric trch ly. gim lng tp cht hu c trong tc nhn chit tun hon, ngi ta ti sinh tc nhn chit bng dung dch soa (Na2CO3). Ra tc nhn chit cng bng dung dch soa 10-15% 500 C vi t l Vh.c: Vnc = 3 : 1 trong hai cp v cui cng bng nc. 2.6. Ci tin thit b chit 2.6.1. C s khoa hc ci tin thit b Qu trnh chit c th xem nh qu trnh chuyn khi xa?y ra do s chnh lch th ca nhng cht chuyn dch trong cc pha. Khi chit axit v c s xy ra s tng tc ho hc gia nhng cu t b chit vi tc nhn chit. C ch qu trnh chit l to thnh phc hydrat-solvat vi cc tr s hydrat v solvat khc nhau. V mt ng hc ca qu trnh chit, thi gian cn thit xc lp cn bng khng nhng ph thuc vo tc khuych tn ca pha ny vo pha khc m cn ph thuc vo tc xy ra phn ng ho hc. Khi nng ca cc cht phn ng gim, dn ti gim tc khuych tn v tc phn ng ho hc. V mt thu ng hc cn phi quan tm n tnh cht l ho ca cc cht trong h nh nht, khi lng ring, sc cng b mt gia cc pha... V vy khi tnh ton thit b chit phi xc nh thi gian chuyn khi cn thit t c cn bng, thi gian tip xc pha trong khoang trn phi bng hoc ln hn thi gian cn qu trnh chuyn khi xy ra hon ton. Thit b chuyn khi cng hiu qu th th tch lm vic ca 1 cp cng nh khi cng nng sut. 2.6.2. Ci tin thit b chit Ngi ta nghin cu thit k mt s kiu thit b chit nh thp chit kiu xung v thit b chit ly tm (c ch to v vn hnh th nghim nhiu nm vi

nng sut 15.000T P2O5/nm ti Nga). Thit b chit ly tm l thit b chit hin i, t hiu qu cao khi tinh ch axit photphoric trch ly. Thi gian tip xc pha trong thit b ch tnh bng giy. Thit b chit ly tm gm 2 phn chnh l roto 1 vi ng c 2 v v 9. Phn di roto c trang b b phn vn chuyn kiu mi cho 3, cui c cch khuy 4. Trong roto b tr khong giao nhau 5 vi a phn tch 6, ng dn pha nh 7 v ca ra ca pha nng 8. Thit b lm vic nh sau: Dung dch ban u vo khoang trn 10; sau , huyn ph to thnh i vo khoang phn chia. Vi tc quay ca roto l 2740 vng/pht, pha phn chia theo lng t roto vo ngn thu gn vi v (ngn s 11 dng cho pha nng, ngn 12 l pha nh). Cc pha theo ng 14 v 15 chy ra ngoi. Tt c cc chi tit ca thit b tip xc vi dung dch c ch to t floroplast (teflon). 3. MT S KIN V PHT TRIN CNG NGH TINH CH AXIT PHOTPHORIC TRCH LY NC TA 3.1. D bo nhu cu v axit photphoric sch nc ta Theo nh gi, t l trung bnh ca cc sn phm sn xut t axit photphoric nc ta trong thi gian ti nh sau: Tn sn phm T l % Nitri tripolyphotphat 60 Cc mui photphat dng trong chn nui v thc phm 15 Cc mui photphat k thut 15 Cc sn phm khc 10 Nh vy, nhng h tiu th sn phm chnh i t axit photphoric sch l: Sn xut natri tripolyphotphat Sn xut thc n chn nui (gia sc, gia cm, thu sn) X l nc (nc ni hi nhit in v cng nghip)

Ty g, photphat ho st thp Cc nhu cu khc: Thc phm, tinh ch, ng, dc phm, cc loi

mui photphat k thut. Hin nay tt c nhu cu v axit photphoric sch u i t photpho vng hoc nhp ngoi. Theo d bo v pht trin nc ta (chin lc Dn s Vit nam 2001 - 2010), n nm 2010 dn s nc ta s vo khong 89 triu ngi, n nhng nm 2015 2020 s trn 100 triu ngi. Nhu cu v cht ty ra tng hp (tnh trung bnh cho mi ngi dn c thnh th v nng thn l 12kg/ngi/nm) tnh cho 100 triu dn s l: 100.000.000 ngi x 0,0,12 T/ng = 1.200.000T Lng natri tripolyphotphat (tnh vi mc 25% trong cht ty ra, hin nay ch khong 20%, cc nc tin tin trn 35%) dng sn xut cht ty ra tng hp s l: 1.200.000 T x 0,25 = 300.000 T Tnh theo P2O5 s l 170.000 tn P2O5 hay 75.000 tn photpho. Nu theo c cu nh trn (lng natri tripolyphotphat chim 60% tng lng mun photphat) th lng axit photphoric sch s cn: 170.000T : 0,6 280.000 T (tnh theo P2O5) Tnh theo photpho s l 122.000 tn/nm, cha k khong 15.000 tn photpho nguyn t dng sn xut cc sn phm khc. y l con s vt qu tm sn xut photpho vng trong nc v cn gii quyt sn xut axit photphoric sch bng con ng tinh ch axit photphoric trch ly. 3.2. Vn u t c bn sn xut axit photphoric tinh ch Nh trn nu, sn xut c lng axit photphoric sch ni trn (280.000 tn P2O5) nu theo phng php nhit in s gp kh khn, nht l v vic cung

cp in. Theo phng php tinh ch t axit photphoric trch ly vi hiu sut thu hi 93% cn u t sn xut c lng: 280.000 T : 0,93 300.000 T/nm (P2O5) Nh vy s cn khong 20.000 T/nm (P2O5) l phn cn thi dng sn xut phn bn (MAP hay DAP). Do c s sn xut axit photphoric tinh ch cn gn vi nh my sn xut phn bn. Vi sn lng axit photphoric nh trn, theo chng ti chia ra lm hai hoc ba giai on u t. Nu chia lm hai giai on th giai on u s u t c s sn xut axit photphoric trch ly vi sn lng 150.000T/nm (P2O5) v mt dy chuyn tinh ch kt hp theo hai phng php: - Phng php trung ho - kt ta: 100.000T/nm - Phng php chit bng dung mi hu c: 50.000T/nm Sn phm axit tinh ch theo phng php trung ho - kt ta ch yu sn xut natri tripolyphotphat v thc n khong dng cho chn nui. Cht lng sn phm natri tripolyphotpho t 55 - 56,8% P2O5; 3 - 4% SO4; 0,005% Fe; 0,003% As; v dicanxi photphat t 44% P2O5; 0,2%F; 0,008% kim loi nng (quy ra Pb); 0,002% As. Cn loi axit tinh ch theo phng php chit bng dung mi hu c dng cho cc sn phm tinh khit hn hoc xut khu. Tng hp cc s liu nh sau (bng 14): Bng 14. Tng hp nhu cu v axit photphoric sch H3PO4 trch ly H3PO4 tinh Nhu cu u t giai on 1 300.000 150.000 ch 280.000 Phng php Chit bng trung ha 90.000 dung mi 47.000

u t

150.000 giai on 2 t hiu qu kinh t cao khu cng nghip sn xut axit photphoric v cc mui photphat phn bn cn c lin hp vi nhau theo s (hnh 9): Theo d tnh ca chng ti, chi ph u t cho giai on 1 (cha k cho sn xut natri tripolyphotphat v thc n khong cho chn nui) s l (triu USD): Xng sn xut axit Sunfuric: Xng sn xut axit photphoric trch ly: Xng tinh ch axit photphoric Theo phng php trung ha kt ta: Theo phng php chit bng dung mi: Cng: 3 9 77 triu USD. 25 40

Nu tnh c xng sn xut natri tripolyphotphat v thc n khong dng cho chn nui s cn thm khong 3 - 4 triu USD. Tuy nhin, xut pht t thc t hin nay nc ta, nhu cu v natri tripolyphophat v thc n khong dng cho chn nui c tnh trn 100.000 tn/nm v cc cng ty lin doanh sn xut cht ty ra tng hp u nhp khu mt hng ny. V vy c th nghin cu mt phng n u t tng giai on, tin ti giai on sau xy dng ng b: giai on u nhp khu axit photphoric trch ly, tinh ch sn xut natri tripolyphotphat v mt s sn phm khc (hin ti Trung Quc ang nhp H3PO4 ca Tuynidi, Braxin nhp ca Marc), sau mi t sn xut axit photphoric trch ly v tinh ch su hn. Theo phng n ny, giai on u ch cn u t khong 7 - 10 triu USD. Gi axit photphoric tham kho: trong 5 nm qua gi u ng nc 250 USD/T P2O5 (gi FOB vnh galf - M, (xem phn ph lc).

4. KT LUN

Trn y l phn tng quan v tinh ch axit photphoric trch ly v d bo v nhu cu nc ta, ng thi xut mt s kin v pht trin cng ngh tinh ch axit photphoric trch ly v sn xut mt s sn phm mui photphat. Nhu cu sn phm axit photphoric sch l c, cn xem xt v kho st su hn v vn ny trc khi a ra quyt nh u t. TI LIU THAM KHO

- Tp ch Cng ngh Ho hc (Ting Nga) s 2, s 3, s 7, s 9 nm 2003; s 8, s 9 nm 2004; s 1, s 6 nm 2005. - Tp ch Cng nghip Ho cht (Nga) s 10 nm 2003 - Fertilizer International s 389, 390 nm 2002; s 345 nm 2003, s 401 nm 2004. - Phosphate. Published by Global Industry Analysts. Jan. 1,2004 http:// www.marketresearch.com/map/prod/912079.html - Announcement of Potashcorp September 24th, 2004 http:// www.potashcorp.com/investor relations/news - The Wet Phosphoric Acid Frocesces.www.geocities.com/waterose. Test/phosphor.html. 28/8/2005 Ph lc 1 "CY SN PHM" C NGUN GC T PHOTPHO Nhiu sn phm cha photpho khng phi u c sn xut t axit photphoric m t photpho nguyn t (s )

Nhng sn phm ny chim khong 10 - 15% tng lng sn phm cha photpho; s cn li mi c sn xut t axit photphoric sch. Do vic thay th axit photphoric nhit bng axit photphoric tinh ch ch t ra vi nhng sn phm loi ny. Ph lc 2 DANH MC CC CNG TY SN XUT V BUN BN AXIT PHOTPHORIC TRONG KHU VC CHU

1. Trung Quc - Yunnan Phosphate Fertilizer Industrial Co - SinoChem China National Chemicals Import & Export Corp. 2. Thi Lan - National Fertilizer Company Ltd 3. Indonexia - PT Petrokimia Gresik 4. Philipin - Philipinpine Phosphate Fertilizer Corporation (Philphos) 5. Bangladesh - TSP Complex Ltd 6. n - Southern Petrochemical Industries Corporation Ltd - Indian Farmers Fertilizer Cooperative Ltd - Gujarat State Fertilizer & Chemicalo Ltd - Grasim Industries Ltd - Fertilizer and Chemicals Travancore Ltd

- EID Parry Ltd - Albright & Wilson Chemicals India Ltd 7. xtrylia - Wes Farmers CSBP Limited - WMC Fertilizer Ltd 8. Nht Bn - Co - op Chemical Company Ltd 9. Hn Quc - Dongbu Hannong Chemical Company Ltd - Nam hae Chemical Corp. South Korea.