TI: QU TRNH TY MU NG BNG CT TRAO I ION

GVHD : SV : MSSV :

Th.S H XUN HNG L V HNG 10326741

TP. H Ch Minh thng 5 nm 2012

MC LC
MC LC.........................................................................................................................2 LI M U....................................................................................................................2

LI M U Vi nhng iu kin t nhin thun li nc ta, ngnh Ma ng l mt trong nhng ngnh c thun li pht trin v u tin u t hng u. u t vo Ma ng, th nht p ng trc mt nhu cu tiu th ng trong nc ang dn c nng cao theo iu kin mc sng ca ngi dn ngy cng c nng ln.Th hai l phc v cho xut khu ng ra th gii thu ht thm li nhun cho Quc gia. Cng vi s pht trin khng ngng ca khoa hc k thut th i sng ca con ngi cng ngy cng c ci thin v nng cao, ko theo s tng ln v nhu cu s dng ng ma, cc sn phm t ng ma. Tuy nhin phn ng ngi tiu dng hin nay thng rt t cc thng tin v cch sn xut ng, cng nh nhng hng dn v cch lm sao c th chn mt sn phm ng tt, an ton. Trong cng nghip sn xut ng, thng thng th khi cy ma c a vo sn xut khng h qua cng on ra s b no nn nc ma hn hp thu c sau khi p lun c mt cc cht khng ng. Cc cht ny nh hng ln n qu trnh sn xut cng nh cht lng ca sn phm, phn ln lng cht ny khng c li cho khu ch bin ng, n lm tng ho tan ca saccaroza, tng mt cui, tng tn tht ng trong qu trnh ch bin. Ngoi ra, nu c acide th s gy chuyn ho ng saccharoza. V vy, trong cng ngh sn xut ng th qu trnh lm sch v ty mu nc ma hn hp sau khi p l cng on ht sc quan trng khng th b qua. Nc ma hn hp c nhiu thnh phn ho hc phc tp, c th coi nc ma l mt h keo phc tp. Do , qu trnh lm sch v ty mu nc ma da vo l thuyt ho hc ca cc cht keo ch yu da vo cc yu t nh: pH, nhit , cht in ly, cht trao i ion. Trong , cc cht trao i ion l mt trong nhng yu t quan trng tc ng n qu trnh lm sch. V vy, trong bi tiu lun ny chng em s ch trng tm hiu v vai tr ca cc cht trao i ion trong qu trnh lm sch v ty mu nc ma. Ngoi ra, k thut ny cn ng dng

cho vic thay th cc ion to mt ln bng cc ion to mt t hn, tng hiu sut thu hi ng. Do thi gian v kin thc cn hn hp nn chc chn s c nhng sai st trong qu trnh lm bi, rt mong c v cc bn b qua v ng gp kin bi lm ca chng em c hon thin hn.

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GVHD: Th. S H XUN HNG

CHNG I: TNH HNH SN XUT NG VIT NAM V TRN TH GII 1.1 Tnh hnh sn xut Ma ng trn th gii Hin nay, trn th gii sn xut ng t khong 160 triu tn/nm. Cc nc sn xut ng ln trn th gii l Brazil, n , Thi Lan, Trung Quc chim 50% sn lng v 56% xut khu ca th gii. Theo bo co mi nht t Hip hi ma ng th gii ISO, sau 2 nm nhu cu tiu th vt tng cung th gii ln n 15 triu tn, lng ng tn kho ang mc rt thp v phi cn t nht 2 nm phc hi li mc tn kho trc y. Trong v ma mi 2011-2012 bt u t thng 10 sp ti, lng ng thng d c d bo ch t khong 779,000 tn ng, st gim mnh so vi d bo s thng d khong 3 triu tn ng, nguyn nhn xut pht t s st gim sn lng bt ng ti Brazil Ngun cung ng trn th trng th gii d bo tip tc gim trong nm 2011 do thi tit xu lm gim sn lng ma v c ci ng. Cng ty t vn Kingmsan SA d bo th trng ng th gii nin v 2010/11 s thiu ht 370.000 tn khi sn lng ch 165,14 triu tn cn tiu th 165,51 triu tn. n , nc sn xut ng ln th hai v tiu th ln nht th gii, c d bo tng sn lng ln 24,5 triu trong nm nay v s c ln u tin trong vng 3 nm ngun cung vt cu. n cng l nc sn xut ng ln duy nht c d bo sn lng tng. 1.2 Tnh hnh sn xut ng Vit Nam Ngnh sn xut ng ti Vit Nam c t lu i, t khi ngi dn chng ta bit lm nn mt ma t cy ma, nhng ngnh cng nghip ma ng ti Vit Nam ch mi bt u pht trin vo u nhng nm 1990, vn cn rt non tr v kh lc hu. Cho n giai on hin nay ngnh ma ng ti Vit Nam vn cha pht trin mnh c th tr thnh ngnh cng nghip ch lc ca nn kinh t. Nc ta sn xut 3 loi ng chnh: - ng tinh luyn RE hay cn gi l ng ct trng - ng vng RS - ng xay (hay ng th) c trng ca ngnh ma ng Vit Nam l c tnh thi v, thng ch yu thu hoch,vn chuyn v sn xut trong thi gian khong 5 thng (thng 11 n thng 4 nm sau),sau tn kho thnh phm bn cho cc thng cn li trong nm. V vy nn chi ph tn tr hng ha ny rt cao v gi thnh sn phm kh cao. Hin ti, sn xut ng trong nc mi ch p ng c khong 70% nhu cu tiu th, phn cn li ch yu nhp khu t Trung Quc v Thi Lan. Th phn tiu th hin nay ngoi SBT, LSS, BHS v NHS, trn th trng ng cn c Cng ty ng Qung Ngi v Cng ty ng Cn Th l cc cng ty ln c sc cnh tranh cao. Phn cn li ca th trng l cc cng ty ng nh chim di 2% th phn v cc doanh nghip nhp khu ng kinh doanh chim di 2% th phn. Nhn chung qua cc nm, tnh trng cnh tranh khng din ra d di do ngun cung yu hn cu. Tuy nhin trong nm 2011, sn lng ng trong nc p ng c nhu cu tiu th, B Cng Thng li cho nhp 250.000 tn ng gy tnh trng d tha. Sn lng sn xut trong nc cc nm gn y ch dao ng quanh mc 900.000 tn 1,1 triu tn/nm; trong khi nhu cu khong 1,4 1,5 triu tn. Loi tr cc khon nhp khu lu qua bin gii, mi nm Vit Nam cn nhp khu trong hn ngch khong 300.000 tn ng. Quota nhp khu ng: k t nm 2010, khi thu nhp khu chnh ngch gim v 5% v p dng chnh sch quota nhp khu linh hot, thay i theo hng lng ln ty thuc vo nhu

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GVHD: Th. S H XUN HNG

cu ni a. Vit Nam phi nhp khu ng gn 30% sn lng tiu th hng nm, trong khi s cnh tranh ca cc doanh nghip ni a cn thp, do vy gi ng trong nc b tc ng ln bi gi ng th gii.

Hnh 1. Hnh cy ma ng 1.3. Phn tch swot ngnh ma ng Vit Nam im mnh im yu - Ngnh ma ng ng vai tr rt - Gi thnh ng cao do my mc cng quan trng cung cp nguyn liu cho ngh lc hu, cng sut thp, hiu sut thu ngnh thc phm v nhu cu tiu th ca hi ng ca cc nh my thp, ng thi ngi dn. iu ny cho thy u ra ca Vit Nam l nc mi tham gia vo th ngnh ma ng rt n nh. trng ny. - Vit Nam c iu kin t nhin - Gi ng trong nc chu nh hng thun li cho pht trin ca cy ma do ln bi gi nguyn vt liu v gi ng c th m rng vng nguyn liu. th gii. - Chi ph nhn cng r, th trng tiu - Din tch trng ma nh l, nng sut th ln. Nhu cu tiu th ni a ca ma thp. Cc doanh nghip sn xut ng Vit Nam ngy cng tng cao ( nm 2011 cha pht trin vng nguyn liu tp trung khong 1,4 triu tn) dn n cnh tranh nguyn liu u vo - c s u i v thu v cc chnh gay gt. sch ca chnh ph nn hot ng ca - Vn u t cho cng ngh sn xut ln, ngnh t chu ri ro do bin c ca th do cc doanh nghip kh m rng sn trng. xut v nng cao cht lng. C hi - Tc tng trng GDP cao, nn kinh t nhn c s quan tm ca nh u t nc ngoi. iu ny c chng minh t th t l dng vn FDI v Vit Nam ngy cng cao, y chnh l yu t thu ht u t mi vo ngnh ma ng. - Ngnh ma ng th gii ang trn phc hi ng thi nhu cu v ethanol tng cao. Trong thi gian ti gi ng th gii c kh nng tng nh. - Mc tiu th ng bnh qun u ngi ca Vit Nam tng trng kh cao. Thch thc - Chu nh hng ln bi gi ng th gii v quan h cung cu. - Cc doanh nghip trong nc cn non tr nn s kh ch ng trong hot ng sn xut kinh doanh dn n cha c hng pht trin vng nguyn liu n nh - Vi chnh sch bo h ca nh nc mt mt thc y cc doanh nghip m rng pht trin sn xut ng thi cng s nh hng n tnh hot ng lin tc ca ngnh khi thu nhp khu ng cao. - Chu ri ro ln bi thay i kh hu v c tnh thi v cao.

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Trong khi sn xut ng trong nc ch p ng 70% nhu cu do tim nng t ni a cn rt ln.

GVHD: Th. S H XUN HNG

- Cc nh my ng trong nc c quy m va v nh, thit b v cng ngh lc hu, hiu qu v cht lng sn phm thp.

1.4. Cc phng php ty mu ng hin nay 1.4.1. Kh nng s dng H2O2 x l dung dch ma ng Cc s liu thu c trong phng th nghim cho thy dng H2O2 c kt qu tt hn so vi phng php sulfit ha v mt kh mu, kh polyphenol, axit amin v tinh bt cho dung dch ma ng nh hng i vi cc tnh cht khc nh: tinh khit, hm lng tro khi x l bng H 2O2 cng ang c th nghim. Nc ma p l dung dch cha nhiu thnh phn gm ng saccharozo, ng kh, cc axit hu c v cc cht mu. Trong qu trnh ch bin, cc sn phm nh melanoidin, melanin v caramen c hnh thnh lm dung dch ma p bin mu. Kh cc cht mu trong nc ma p l vn kh m ngnh sn xut ng phi gii quyt. Ti n , ngi ta thng s dng SO 2 lm trong v ty nc ma p sn xut ng trng. Mt hn ch ca qu trnh sulfit ha l a thm thnh phn SO2 vo ng. V H2O2 c mt vi u im hn SO2 nh chi ph thp, sn c, khng c hi v l cht ty sch nn n c ngi ta th dng lm cht ty mu cho nc ma mi p. H2O2 khng nhng kh c mu ca nc ma p m cn tip tc kh cc cht cn li c kh nng to mu trong sut qu trnh sn xut. Cc thc nghim c tin hnh trong phng th nghim mt nh my ng a phng n . Ngi ta ly 5kg nc ma c c t quy trnh sn xut thng thng em x l nhit 50oC vi H2O2 50% v nng H2O2 trong nc ma c c l 10-50 phn triu (ppm). Nhng hn ch trong qu trnh s dng SO2 lm trong nc ma p v ty mu nc ma c c cng c khc phc khi ngi ta b sung thm. H2O2 c s dng th nghim trong qu trnh ty mu nc ma p, nc ma c c, ng tinh luyn nng chy v ru mu. H2O2 oxy ha cc cht mu thnh loi khng cn kh nng to ra mu v chng s d b loi b nh cc cht hp ph. Trong cc th nghim nc ng ma c c c sulfit ha, x l thm bng H2O vi liu lng 20-50 ppm ngi ta thy mu ca nc ng ma c c cn gim tip 3 -5% na. X l nc ng ma c c bng H2O2 khng ch lm cht mu b kh, m cn lm cho cht lng ni chung ca ng tt hn v gim c c cc polyphenol, axit amin v tinh bt, Hm lng polyphenol c th gim 8-9%. H2O2 c th phn hy axit amin thnh amoniac v hp cht cacbonyl, t t l kh 4%. Tinh bt l thnh phn c vai tr chnh lm tng nht v lm chm qu trnh kt tinh ng. T l kh tinh bt t 20% khi x l bng H2O2, H2O2 l cht thn mi trng, khng c, c tc dng ty, ng c ngnh ma ng quan tm. 1.4.2.Phng php sunfat ha K thut sunfit ho l phng php bo qun rau qu hoc loi b mu trong cng ngh sn xut ng bng SO2 hoc H2SO3. C hai phng php sunfit ho l kh v t. - i vi phng php t: ngi ta dng dung dch SO2 c chun b sn trong nc lnh vi nng thch hp ho dn vo sn phm - i vi phng php kh: th c th np trc tip kh SO2 t cc bnh cha vo trong phng, hoc n gin hn l t lu hunh trong phng cng sinh ra kh SO2. Dng SO2 v H2SO3 c hi n sc kho, v th vic sunfit ho ch c dng cho nhng quy trnh cng ngh nhm x l bn

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GVHD: Th. S H XUN HNG

thnh phm ch bin c un si (v khi un si kh SO 2 s bay ln) .Trong cng ngh sn xut ng l mt v d in hnh kh kh SO2 ra khi thnh phm, ngi ta c th dng nhit ca hi nc x l trc tip bng cch cho bn thnh phm vo ni, y ni c h thng ng phun hi nc. Phng php ny kh rt nhanh v sch nhng c nhc im l do hi nc phun trc tip cho nn hm lng nc tng ln v khi c c th tn thi gian cng nh nng lng v c khi lm cho phm cht thnh phm b gim v hiu sut thu hi. Cn gi l phng php SO2, v ta s dng lu hunh di dnh kh SO2 lm sch nc ma. C th chia lm 3 loi: 1.4.2.1. Phng php sunfit ho axit (thng SO2 vo nc ma n pH axit) Dng ph bin trong sn sut ng knh trng

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Hn hp nc ma Sa vi H3PO4 Gia vi (pH = 6,46,6) Gia nhit 1 (t = 60 65oC) SO2 Xng SO2 (ln 1) (pH = 3,4 3,8)

GVHD: Th. S H XUN HNG

Sa vi

Trung ho (pH = 7,0 7,3) Gia nhit 2 (t = 102 105oC) Thng lng Nc bn

Nc lng trong

L c
Nc lc trong Bn

Gia nhit 3 (t = 110 115oC) C c Xng SO2 (ln 2) (pH = 6,2 6,4)

SO2

Mt ch

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GVHD: Th. S H XUN HNG

1.4.2.2. Phng php sunfit ho kim nh (Ch xng SO2 vo nc ma, khng thng SO2 vo mt ch v sn phm ng th) Dng sn xut ng th, nu so vi phng php vi th hiu qu loi cht khng ng tt hn, tuy nhin thit b phc tp v tiu hao nhiu ho cht nn hin nay t ph bin. Hn hp nc ma Gia vi kim nh Ca(OH)2 (pH = 8,0 9,0) Gia nhit 1 (t = 60 65oC)

SO2

Trung ho (pH = 7,0 7,2) Gia nhit 2 (t = 100 105oC)

Thng lng

Nc bn

Nc lng trong

Lc

C c

Nc lc trong

Bn

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GVHD: Th. S H XUN HNG

1.4.2.3. Phng php sunfit ho kim mnh c im ca phng php ny l dng 2 im pH (pH trung tnh v pH kim mnh), do c th loi c P2O5, SiO2, Al2O3, FeO3, MgO... Nhng iu kin cng ngh ca phng php ny cn cha n nh.

1.4.3 Phng php than hot tnh Than hot tnh c dng trong cng nghip ng ch yu kh mu cho ng c mu tt hn v ci tin ng k nhng c tnh ca qu trnh sn xut. X l bng than hot tnh gip cho vic tch nhng tc nhn trn b mt v cht keo (cht c trong phn t ln) lm tng sc cng ca b mt v gim nht. iu ny lm tng t l kt tinh ca ng v tng s phn tch si r v cht kt tinh bng phng php ly tm

. 1.4.4 Phng php trao i ion Phn loi nha trao i Tnh cht trao i ca nha T ion c quyt nh bi cc nhm c tr ng trong sn (khung) cao phn t ca nha v cc ion linh ng. Cc nhm ny mang in tch m hoc dng to cho nha c tnh kim hoc acid. Cc nhm c trng trong ionit ni vi

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GVHD: Th. S H XUN HNG

cc ion linh ng c du ngc li bng lin kt ion . Cc ion linh ng ny c kh nng trao i vi cc ion khc trong dung dch.

Nha trao i cation (cationit) L nhng cht c c trng acid. Trong cu to mng li
ca nha c mang in tch m (nhm c trng mang in tch m) km theo nhm c trng c mt cation linh ng c kh nng trao i vi cc cation khc trong dung dch.Cc ion linh ng ca cationit thng l H, thng c gi l nha T cation dng H. Nu thay H bng Na, nha c gi l Na-cationit. Cc nhm c trng ca cationit : -SO3H, -COOH, -OH (ca phenol), H 2PO3- Cc nhm c trng cng nhiu, kh nng trao i cng tng, ng thi, ho tan trong n c ca nha cng tng. Nu tng ni ngang trong cu trc ca nha aionit th kh nng trao i, ho tan gim nhng trng s t ng. - C hai loi cationit: Cationit acid m nh: nhm c trng l -SO3H, -PO3H.C kh nng phn ly thnh ion linh ng, t linh ng trong tt c cc mi trng trung tnh, kim, acid. Do kh nng trao i ca chng khng b nh hng bi pH ca dung dch. Cationit acid yu: Nhm c tr ng -COOH, -OH.Phn ly yu trong mi trng acid, kh nng trao i ph thuc vo pH ca mi trng. Trong mi trng ki m, kh nng phn ly mnh nn kh nng trao i ln. Trong mi trng acid, kh nng phn ly thp, dn n kh nng trao i thp Nha trao i anion (anioit): Cc nhm hot ng mang in tch dng, to cho anionit c tnh kim, cc anion linh ng c th trao i vi cc anion khc trong dung dch. Nhm c trng: kim amin bc 1, 2, 3, 4. Cc anion linh ng thng l OH, Cl. . . Anionit kim mnh: Nhm c trng l kim amin bc 4. Nhm OH nh vo nh lc tnh in. Anionit kim mnh c mc phn ly ion tt trong tt c cc mi trng nn kh nng trao i ca chng khng ph thuc pH ca mi trng. Anionit kim yu: Nhm c trng l kim amin bc 1NH 2 , bc 2 =NH v bc N . Anionit kim yu ch phn ly trong mi trng kim yu

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GVHD: Th. S H XUN HNG

Hnh 2. Quy trnh sn xut ng tinh luyn c s dng phng php tymu bng trao i ion CHNG II: PHNG PHP TY MU NG BNG CT TRAO I ION 2.1. C s ca phng php Phng php ny c thc hin bng nha trao i ion.Nha trao i ion c quyt nh bi cc nhm c trng trong sn (khung) cao phn t ca nha v cc ion linh ng. Cc nhm ny mang in tch m hoc dng to cho nha c tnh kim hoc acid. Cc nhm c trng trong ionit ni vi cc ion linh ng c du ngc li bng lin kt ion. Cc ion linh ng ny c kh nng trao i vi cc ion khc trong dung dch. 2.2.Mt vi thut ng s dng trong k thut trao i ion Khi lng ring ca ht nha (density of resin) bn c hc (mechanical resistance) Kch thc ht nha (grain size) Dung lng tng (total capacity): l lng ion c trao i trong mt n v trng lng ca nha Kh nng tch mui (salt splitting): lng ion Na b hp th bi nha dng H (hay lng H i ra khi nha) trong mt n v khi lng hay mt n v th tch xp (porosity) Dung lng trao i (exchange capacity): khi lng ion gi c trn mt n v th tch vt liu trao i Ion leakage: nng ca ion khng mong mun b tch ra trong dung dch x l. ng cong Breakthrough

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GVHD: Th. S H XUN HNG

2.3. Khi qut v cht trao i ion L hp cht cao phn t, khng tan trong nc, lm trong sng nc khi qua cht trao i ion, c kh nng gii phng ion v trao i ion ca mnh vi ion khc c trong dung dch. Cht trao i ion cng cn c gi l nha trao i ion. Nha trao i ion cn gi l ionit, cc ionit c kh nng hp thu cc ion dng gi l cationit, ngc li cc ionit c kh nng hp thu cc ion m gi l anionit. Cn cc ionit va c kh nng hp thu cation, va c kh nng hp thu anion th c gi l ionit lng tnh Cht trao i ion c hai dng: cht trao i ion dng (cationit) v cht trao i ion m(anionit). Mi dng ca cht trao i ion u c nhng tnh cht ring bit. 2.4.Cc loi vt liu trao i ion Cc loi vt liu trao i ion c phn thnh nhiu loi ph thuc vo cc ng dng khc nhau Cc loi vt liu v c c s dng khi yu cu v tinh khit khng cao lm. ci thin bn vt l ca ht nha, phng php gn cc loi vt liu trao i ion vo mt loi vt liu khc (c th v c hoc hu c) c nghin cu v pht trin mnh.Vt liu trao i cn: bn ho, ho tan thp, chi ph thp. 2.4.1.Vt liu t nhin 2.4.1.1. Loi v c Nhiu khong v c trong thin nhin c s dng: st (bentonite, kaolinite,illite), mica v zeolite (nh analcite, chabazite, sodalite v clinoptilolite) c tnh cht trao i ion. Trong zeolite t nhin l loi vt liu c s dng u tin trong cng ngh trao i ion. St thng s dng lm cht n, cht chn lp cht thi phng x . t st thng s dng trong cc thit b gin on, t khi s dng cho hot ng dng ct v c th hn ch dng chy qua ct.Cc loi aluminosilicate t nhin cng thng c s dng trong x l nc thi. N hot ng nh l: vt liu trao i ion v cht lc c bit.St v zeolite thin nhin tuy c thay th dn bi cc loi vt liu tng hp song n vn c dng trong mt s ng dng no y do r v sn c trong thin nhin. Mt s nhc im ca loi vt liu ny: - Dung lng trao i thp-Bn c thp - Kch thc l xp khng khng ch c - Cc ht st c khuynh hng to thnh cc ht keo - Kh gia cng ng kch thc theo yu cu - C th b phn hu trong mi trng acid hoc kim 2.4.1.2. Loi hu c Mt lng ln cc cht hu c c tnh cht trao i ion nh : polysaccharides(cellulose, algic acid, rm, than bn), proteins (nh casein, keratin v collagen) v cc loi than (nh than bn, than nu). Mc d dung lng hot ng ca cc loi vt liu ny thp nhng vn c s dng rng ri do gi thnh thp. Cc nhc i m chnh ca loi vt liu ny: - Dung lng trao i thp so vi cc loi vt liu khc - Trng n ln v d b pettize ho-Vt liu cenllulose v protein rt khng bn vi phng x - Cu trc vt l km-Tnh cht vt l khng ng nht - chn lc km - Khng bn khi pH nm ngoi dy pH trung tnh.

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GVHD: Th. S H XUN HNG

2.4.1.3. Vt liu bin tnh ci thin dung lng trao i, chn lc mt s vt liu hu c c bin tnh. V d vt liu trao i ion trn c s cellulose c bin tnh bng cch a thm vo nhm phosphate, carbonic hoc nhm chc acid khc. 2.4.2.Vt liu tng hp 2.4.2.1. Vt liu v c tng hp *Zeolites: l lo i v t liu v c u tin c s dng trn mt quy m ln tch cht nhim phng x. Zeolite l loi vt liu trn c s l aluminosilicate, c th tng hp di dng bt, ht hoc vin. u im: u im ca loi ny l c th thay i tnh cht ho hc trong mt khong rng, kch thc l xp c khng ch , bn nhit. Nhc im: Chi ph cao hn so vi loi c sn trong thin nhin Bn ho hc, bn trong cc mi trng pH khc nghit km D nt, bn c hc km. chn lc v dung lng ca zeolite c th ph hp vi cc cng ngh c mui thp. Nu trong dng thi c mt cc ion khc, cc tm hot ng ca zeolite b cc ion ny chim gi do s gim dung lng hot ng. V d khi c K, kh nng trao i ca zeolite vi Ce b gim i. Trong dung dch c nng mui cao, dung lng hot ng ca zeolite l rt nh . Cc hp cht ca Ti, Si-Ti: Trong nhiu nm qua, oxide v hydro oxide ca Ti c bit n kh nng tch loi ion trong dung dch. Nm 1955 UK v sau l c v Nht s dng hydroustitanium oxide (HTiO) tch uranium trong nc bin vi quy m ln 2.4.2.2.Vt liu hu c tng hp Ngy nay, nhm ln nht trong loi vt liu ny l nha trao i ion dng bt (5-150m) hay dng ht (0,5-2mm). Mch hydrocarbon phn b ngu nhin to nn mt mng li rt linh ng. Trn mch ny c mang cc in tch c nh trn cc v tr khc nhau. Nha khng tan do c cc lin kt ni ngang. Lng ni ngang s nh hng n kch th c ht nha qua sng, kh nng trng, chuyn ng ca cc ion linh ng, cng v bn c hc. Lng ni ngang ln, s lm tng cng ca nha, tng bn c , t l xp v t trng trong dung mi. Khi vt liu ny ngm trong dung mi hoc trong nc, n s trng ln. Mc trng ph thuc vo c tnh ca c dung mi v chnh vt liu, n b nh hng bi cc yu t sau: phn cc ca dung mi, lin kt ngang, dung lng trao i, solvat ho mnh hay yu ca nhm c nh, kch thc solvat ca cc ion trao i, nng dung dch. u im ni bt ca loi vt liu ny dung lng trao i ln, p dng rng ri, a lnh vc, chi ph kh r so vi mt vi loi v c tng hp khc Cc loi nha chnh trong nhm ny l: Polystyrene divinylbenzene (DVB): L sn phm copolymer ca styrene v DVB. ni ngang c quy t nh bi lng DVB. Nng DVB thp s lm cho nha m m, kh nng trng rt mnh trong cc dung mi. Cc nhm chc c nh (nhm c trng) c gn vo trong mng li mch polymer to nn kh nng trao i ion.

QU TRNH TY MU NG BNG CT TRAO I ION

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GVHD: Th. S H XUN HNG

V d nh nhm SO3H, thng t 8 n 10 nhm cho 10 vng benzene. H+ s l ion linh ng (hay ion i counterion) s tham gia trao i vi cc cation trong dung dch. Khi gn cc nhm NH3+ hay N2+ vo trong mch polymer, nha trao i anion c to ra. Cc ion i s l OH - , Cl - . Phenolic: L sn phm trng ngng ca phenol v formaldehyde vi nhm OH- l nhm c trng, c nh trong mch polymer, l loi nha trao i cation acide yu. tng cng acid cho nha, nhm -SO3H c gn vo nha. Nh vy nha s c hai chc nng cha c nhm acid mnh SO3H v nhm acid yu OH. Sn phm a trng ngng (polycondensation) ca resorcinol, formaldehyde c s dng rng ri n tc Cs. Cng c th gn thm nhm phosphoric acid vo mch polymer tng kh nng lm vic ca nha. Acrylic : L nha trao i ion acid yu, c nhm -COOH trong mch. L sn phm copolymer ca acrylic hay methacrylic acid vi DVB. Nhm COOH c kh nng tch mui thp nhng trong mi trng kim n c i lc mnh vi Ca 2+ v cc ion tng t khc. Cc nhm acid khc c th gn vo nha nh PO 32- ,PO 33- ,HPO 22.4.2.3.Vt liu composite L loi vt liu kt hp mt hay nhiu vt liu trao i ion vi cc loi vt liu khc.To ra cc composite ny s lm tng bn c th s dng trong ct. Zeolite to ra dng ht trn cht mang l aluminium oxide. Mt loi khc c bit n l ph cupric ferric haxacyanoferrate trn si polyacrylic. Vt liu ny s dng tch nc thi phng x trong nh my nguyn t .Mt loi composite khc l s kt hp vt liu trao i v c vi magnetic Fe3O4 .Do vy s d dng tch loi ra khi bo ho nh t trng. Loi vt liu ny tr thnh thng phm. 2.5. Cu to v phn loi cht trao i ion 2.5.1. Cu to Trong cu to ca cht trao i ion, c th phn ra hai phn. Mt phn gi l gc ca cht trao i ion, mt phn khc gi l nhm ion c th trao i (nhm hot tnh). Chng ho hp trn ct cao phn t. Dng phng php tng hp ho hc, ngi ta ch to c cht trao i ion hu c gi l nha trao i ion (resin). Resin c to ra bi s trng ngng t styren v divinylbenzen (DVB). Phn t styren to nn cu trc c bn ca Resin. DVB l nhng cu ni gia cc polime c tnh khng ho tan v giai bn. Cu ni trong Resin l cu ni 3 chiu. Trong Resin c cu trc rng. Cht trao i ion dng c tnh acid mnh hoc yu v trao i ion m c tnh kim mnh v yu. 2.5.2 . Phn loi: c 4 loi Resin + Resin Cation acid mnh + Resin Cation acid yu + Resin Anion baz mnh + esin Anion baz yu

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Phn loi Acid mnh Acid yu Acid yu Nhm hot ng Acid sunfuric SO3N Acid cacboxylic Acid photphoric PO(OH)2 P* 1 4-5 2-3

GVHD: Th. S H XUN HNG

Cu hnh tiu biu

CH2-CH-CH2COOH

Kim mnh Amin bc bn CH2N + (Cl3)ClKim yu CH2NH Amin bc hai R

1 6-9

P* l logarit hng s phn ly cu acid v kim. 2.6. Tnh cht ca cht trao i ion Tnh cht vt l: - Mu sc: vng, nu, en, thm. Trong qu trnh s dng nha, mu sc ca nha mt hiu lc thng thm hn mt cht. - Hnh thi: nha trao i ion thng dng trn - n: khi em nha dng keo ngm vo trong nc, th tch ca n bin i ln. - m: l % khi lng nc trn khi lng nha dng kh ( m kh) hoc dng t ( m t). - Tnh chu nhit: cc loi nha b nh hng bi nhit u c gii hn nht nh, vt qu gii hn ny nha b nhit phn gii khng s dng c. Nhit hot ng tt t 20-50 oC. - Tnh dn in: cht trao i ion m dn in tt, tnh dn in ca n ph thuc vo dng ion. - Kch thc ht: Resin c dng hnh cu d = 0,04 - 1,00 mm. - Tnh chu mi mn: trong vn hnh cc cht trao i ion c st ln nhau v n ngt, c kh nng d v vn. y l mt ch tiu nh hng n tnh nng thc dng ca n. - Tnh chu oxy ho: cht oxy ho mnh c th lm cho nha b lo ho (tr) Tnh cht ha hc - Dung lng trao i: l biu th mc nhiu t ca lng ion c th trao i trong mt loi cht trao i ion. C 2 phung php biu th dung lng trao i: theo th tch lg/m3 v theo khi lng mgl/g. - Tng dung lng trao i: ch tiu ny biu th lng gc hot tnh c trong cht trao i. - Dung lng trao i cn bng: biu th dung lng trao i ln nht ca cht trao i ion trong mt loi dung dch no nh, nn khng phi l hng s. - Dung lng trao i lm vic: Dung lng trao i c xc nh di iu kin vn hnh thc t.

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GVHD: Th. S H XUN HNG

Tnh nng thun nghch ca phn ng trao i ion - Phn ng trao i ion l phn ng thun nghch. Da trn tnh cht ny ngi ta dng dung dch cht hon nguyn, thng qua cht trao i ion mt hiu lc khi phc li nng lc trao i ca n . - CaR2+ 2H+ nhaTh d : 2HR + Ca2+ trao i 2HR+,Ca2+(hon nguyn)CaR2+ 2H+ Tnh acid, kim: tnh nng ca cht Cationit RH v cht Anionit ROH, ging cht in gii acid, kim. Tnh trung ho v thu phn: Tnh nng trung ho v thu phn ca cht trao i ion ging cht in gii thng thng. Tnh chn la ca cht trao i ion: hm lng ion thp trong dung dch, nhit bnh thng, kh nng trao i tng khi ho tr ca ion trao i tng. 2.7.C ch hot ng Cht trao i ion dng c tnh axit mnh Cha nhm SO3H c th trao i d dng H+ ca mnh vi tt c tr s pH. Cha nhm COOH ch trao i trong mi trng trung tnh v mi trng biu th tnh kim. Cht trao i ion dng vi nhm hot ng OH c tnh acid yu ch cho ion + H trong dung dch kim. Cht trao i ion m cha nhm hot ng c tnh kim, c kh nng phn ly trong dung dch. Nhng nhm hot ng tiu biu ca cht trao i ion m l: -NH2 , =NH , N Nhng cht trao i ion m kim mnh c kh nng cho ion pH bt k. C ch phn ng ca cht trao i ion m cn cha bit r nh cht trao i ion dng. C th coi HCl nh l cht b hp ph hoc hai phn ng sau c th xy ra: RNH2 + HCl RNH3Cl (1) RNH3 + OH- + ClRNH3Cl + H2O (2) Phn ng (1) l phn ng hp ph. Cn phn ng (2) l phn ng trao i. - Khi s dng cht cao phn t l cht trao i ion trong dung dch khi tip xc vi nc. Cht trao i ion khi tip xc vi nc b trng ln, nc thm nhp vo bn trong, dn n s phn ly cht hot ng : RSO3H R-SO3- + H+ - Nhm SO3 gn cht vo lp li c th chuyn ng nhng khng ri v tr ca mnh, ngc li ion H+ c th chuyn ng t do bn trong ht trao i v xoay quanh n, v c gn cht bng lc ht tnh in. Khi tip xc vi dung dch, cht in ly c th xm nhp vo mng li ca ht trao i. Nu ion dng ca cht in ly c i lc ln hn ion dng ca cht trao i th xy ra s trao i ion . Ion H+ ca cht trao i ion, trao i vi ion dng ca cht in ly v ion H+ khuch tn vo dung dch. o C th biu din s trao i ion H+ vi ion dng ca dung dch 2RdH + Ca(HCO3)2 = Rd2Ca + 2H2O + 2CO2 y RdH cht trao i ion lm vic vi chu k hydro. Cht trao i ion dng c th lm vic vi chu k khc. V d: 2RdNa + CaCl2 = Rd2Ca + 2NaCl RdNa Cht trao i ion lm vic vi chu k Na

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GVHD: Th. S H XUN HNG

Qa trnh trao i trn c biu din bng phng trnh: 2(Rd2COO-Na+) + CaCl2 2(RdCOO)-Ca2+ + 2NaCl C rt nhiu gi thuyt gii thch c ch qu trnh trao i ion hin nay cn cha thng nht. Trong cng ngh x l nc gi thuyt thch hp nht coi cht trao i ion l vt cht c cu to dng keo. Trn quan im , ngui ta cho rng trn b mt cao phn t ca cht trao i ion c rt nhiu lp in tch kp ging b mt keo. Ion trong lp in tch kp theo mc hot ng ln nh c th phn ra: lp hp ph v lp khuch tn. Lp ion c tnh hot ng tng i km b hp ph bm cht vo b mt cao phn t gi l lp hp ph hay lp c nh, n bao gm lp ion bn trong v mt b phn ion ngc du Cnh ngoi lp hp ph, cc ion c tnh hot ng tng i ln, c kh nng khuch tn vo trong dung dch nn gi l lp khuch tn. Khi nha trao i ion gp dung dch nc c cht in gii, cc tc dng sau y s din ra: Tc dng trao i : Cc ion ngc du trong lp khuch tn v ion ngoc du khc trong dung dch trao i v tr ln nhau. Nhng do qu trnh trao i ion khng gii hn lp khuch tn, do quan h cn bng ng trong dung dch cng c mt s ion ngc du trc tin trao i n lp khuch tn, sau s trao i vi cc ion ngc du trong lp hp ph. Tc dng nn p: Khi nng mui trong cc dung dch tng ln, c th lm cho lp khuch tn b nn p li. T mt s ion ngc du trong lp khuch tn bin thnh ion ngc du trong lp khuch tn bin thnh ion ngc du trong lp hp phPham vi hot ng ca lp khuch tn nh li lm bt li cho qu trnh trao i ion. Do cn ch nu nng dung dch hon nguyn qu ln, khng nhng khng th nng cao m cn gim thp hiu qu hon nguyn. 2.8. Vai tr ca phng php trao i ion trong ty mu ng Hin nay, vic ng dng cht trao i ion trong ngnh ng kh ph bin v phong ph, c bit trong sn xut ng tinh luyn v glucoza tinh th. Phng php trao i ion: L qu trnh trao i ion da trn s tng tc ho hc gia ion trong pha lng v ion trong pha rn (ct nha). Trao i ion l mt qu trnh gm cc phn ng ho hc i ch (phn ng th) gia cc ion trong pha lng v cc ion trong pha rn (l nha trao i). S u tin hp thu ca nha trao i dnh cho cc ion trong pha lng nh cc ion trong pha lng d dng th ch cc ion c trn khung mang ca nha trao i. Qu trnh ny ph thuc vo tng loi nha trao i v cc loi ion khc nhau. 2.9. Trao i vi cht mu trong nc ma Cht trao i ion khi tip xc vi nc b trng ln, nc thm nhp vo bn trong dn n s phn ly cht hot ng. Khi tip xc vi dung dch, cht in ly c th xm nhp vo mng li ca ht trao i ion. Nu ion ca cht in ly c i lc ln hn ion ca cht trao i th xy ra s trao i ion. Cht trao i ion dng: H+Rd- + K+AK+Rd- +H+A- (mui bt k) Cht trao i ion m: Ra+OH- + H+ClRa+Cl- = Ra+Cl- + H2O Qa trnh trao i ion trong nc ma xy ra nh sau. Trc ht, nc ma i qua ct trao i ion dng loi nhng cht ion dng ca cht khng ng trong nc ma.

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GVHD: Th. S H XUN HNG

Trc khi cho nc ma vo ct ion dng cn lm lnh khong 20OC ngn nga s chuyn ho ng. Sau nc ma i qua ct ion m loi acid t do. Cht trao i ion qua nhiu ln s dng kh nng trao i km dn , cn ti sinh li. C th dung acid mnh, v d H2SO4 (4-8%) ti sinh cht trao i ion dng. Nu lp trao i c nhiu ion Ca2+ trc khi ti sinh cn cho NaCl qua lp trao i loi ion Ca2+. Nu khng cho mui NaCl th khi cho H2SO4, CaSO4 kt ta s to thnh v ng li trn b mt cht trao i. Phn ng ti sinh cht trao i dng : 2(K+Rd-) + 2H+SO422(H+Rd-) + 2K+SO42Ti sinh cht trao i ion m thng dung kim mnh nh NaOH (2-4 %) . C th dung NH4OH thay th cho NaOH s to thnh NaCl c v mn nh hng n v mn ca nc ma. Dng NH4OH lng ti sinh tn tht nhiu hn. Phn ng ti sinh: Ra+Cl- + OHRa+OH- + Na+ClCht trao i ion sau khi qua x l acid v kim, ra nc v a dung li. Lng nc dung ra gp 7 ln trng lng cht trao i ion.

Hnh 3: h thng ct trao i ion trong qu trnh ty mu ng gim lng tn tht ng do chuyn ha c th dung c ch trao i ion hn hp v nghch o v dung cht trao i ion m c tnh kim mnh c th loi ion m c mi trng trung tnh v kim yu Nc ng c a qua cc ct nha c kh nng trao i ion Anionit s tch cc ion mang mu lm gim mu ca nc ng.Sau nc ng c bm qua bn lc ceramic (lc s) thnh nc ng tinh lc (fine liquor). u, nhc im ca phng php
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GVHD: Th. S H XUN HNG

mu ng th phng php ny c kh nng kh mu n 90% Nhc im: ca phng php ny l chi ph u t v vn hnh kh cao nn t c s dng cho cc cng trnh ln v thng s dng cho cc trng hp i hi cht lng x l cao. 2.10.Qu trnh ra ngc: (qu trnh ti ch ) y l bc u tin cn thit chu n b cho qu trnh ti sinh ht nha ( s dng ht hoc bo ho) Dng ra i t di ln.Tc ng vt l ca ra ngc: Tng vt liu c ti xp hn, gin ra, sp xp li lm cho dng cht lng i t trn xung s c phn b ng u hn khi hot ng tr li. Cn bn c ra sch khi thit b Cc ion c phn b ng u hn trong ton b tng nha. Khi lng ring ca ht nha, kch thc ht, nht ca dung dch nh hng n kh nng lm sch ht nha bng qu trnh ra ngc, a cc tp cht l lng thi ra ngoi. Thng thng, nc c dng ra ngc v s dng mt lng ln, r ti n.Trong mt iu kin no , hot ng nh mt my lc cc cht rn l lng. Khi lm mm nc x l bng vi, lp kt ta c th hnh thnh trn tng nha trao i. Qu trnh ra l cn thit. C th dng kh nn ph v lp kt ta ny trc khi ra ngc. i khi ngi ta s dng cc ho cht khng ch s hnh thnh cc khi kt ta ny. 2.10.1.Ti sinh Sau ra ngc Tc nhn ti sinh (TNTS) s dng ph thuc vo loi nha v loi ion s trao i. Nha anion c ti sinh bi dung dch NaOH hoc Na2CO3 . Nhiu yu t nh hng n qu trnh ti sinh: Loi nha v lng ni ngang. Loi tc nhn ti sinh. Thnh phn ca tng nha sau khi hot ng. Tc chy Nhit tinh khit ca tc nhn ti sinhTNTS Nng ca tc nhn ti sinh TNTS Thi gian tip xc 2.10.2.Lng tc nhn ti sinh TNTS s dng Nu tc nhn ti sinh l n ho tr , th nng ca n t nh hng n qu trnh gii hp ca cc ion n ho tr . Nu th tch ca tc nhn ti sinh khng tip xc tt, quy lut ny s b ph v .Khi t ng nng tc nhn ti sinh c th ci thin c kh nng gii hp cc ion ho tr 2. Nng tc nhn ti sinh thng thng 2-30%, hay dng nht l 5-10%. Trong mt vi trng hp, kt ta c th lm tt nghn tng ht nha. V d : gii hp Ca t nha trao i cation bng H2SO4 . Kt ta CaSO4 c th c tho i khi hot ng gin on. Dng nng tc nhn ti sinh long ban u, sau tng dn n cui qu trnh gii hp.Cc ion khc nhau, m c gn vo nha cng khc nhau do kh nng gii hp cng khc nhau. Cui qu trnh, cc ion kh gii hp s b gi li trong tng nha,cc ion d gii hp s b ra sch nc ra ngc. tinh khit ca tc nhn ti sinh cng c ch . V d : Cl c i lc mnh vi nh a anion kim mnh loi 1. Dng NaOH (ti sinh) c cha mt lng Cl ng k s khng tt v s gii hp khng hon ton Cl s lm gim kh nng lm

u im: ca phng php l rt trit v x l c chn la i tng. Trong cng ngh ty

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GVHD: Th. S H XUN HNG

vic ca ht nh a.Tc chy ca tc nhn ti sinh l mt nhn t rt quan trong. Thi gian tip xc phi m bo ti sinh t cc i. Thi gian ph thuc vo tng loi nha, loi ion cn tch. V d : nha cation polystyrene sulfonat ho, c 8% ni ngang, ti sinh 30 pht bng dung dch tng ng. Cng loi nha ny, lng ni ngang l 12% th phi cn n 60 pht.Cc anion Cl - , SO4- , CO3- d dng b gii hp ra khi nh a kim mnh. SiO2 tch kh hn, thi gian tip xc l 90 pht ti sinh mt lng tng ng. Trong lc ch cn 30 pht i vi cc ion khc. Trong tr ng hp c bit cn lu khi ti sinh nha cation bng H2SO4. Khi dng chy rt nh, hoc nng tc nhn ti sinh qu ln,CaSO4 s to ra, bt kn tng nha. Khc phc bng cch tng dng chy hoc gim nng H2SO4 .Mc gii hp s quyt nh hiu sut ti sinh v cng nh kh nng lm vic ca ht nha. Nu tc nhn ti sinh s dng ng, y , cc ion c th trao i s b gii hp t nha v nha T khi phc li kh nng lm vic. Vic ny chi ph cao, t s dng CHNG III: THIT B CT TRAO I ION 3.1. Thit b trao i ion

Hnh 4.Hnh thit b kh mu ng Trao i ion l mt phng php lm mm, kh khong vn ang c s dng rng ri. Nguyn l hot ng ca cc loi vt liu hu nh ging nhau. S khc bit ch th hin r cu to v quy trnh cng ngh sn xut vt liu trao i ion Ion l mt nguyn t mang in tch, nguyn t mang in tch m gi l Anion. Nguyn t mang in tch dng gi l Cation

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GVHD: Th. S H XUN HNG

Hnh 5.Hnh m t v trao i ion trong qu trnh ty mu Chu trnh vn hnh ca b trao i ion: Khi gp iu kin thun li, cc ion tri du c th kt hp vi nhau to thnh cn, vng. Mt s c hi cho sc khe, mt s gy mt m quan. x l hin tng ny, ngi ta dng Ht nha trao i ion. Theo nguyn l, nhng ht mang in tch tri du s ht nhau, ngi ta dng loi ht nha tch Cation ht cc ion m v ngc li. Khi cc ht nha bo ha (khng th ht thm c na) ngi ta phi sc li. Qu trnh ny c th din ra lin tc hay theo chu k, t ng hay th cng ty vo quy m v sn phm c th. 3.2. Ht nha trao i ion Tu theo ng dng hoc yu cu x l c th, c th s dng loi vt liu trao i ion khc nhau. Tuy nhin, c th dng cc vt liu in hnh nh sau: Lm mm nc: s dng ht nha chuyn lm mm nc hoc ht nha trao i cation mnh; Kh khong: s dng ht nha trao i cation v anion trong nhiu thit b khc nhau Kh ion hn hp: s dng ht nha hn hp trong cng mt thit b; Kh ion ton b: s dng ht nha trao i cation mnh, yu v anion mnh, yu trong cc thit b khc nhau. Kh mu ng: Ht nha ion kh mu c ng dng rng ri trong cc nh my ng tinh luyn. Ty theo mu u vo cao hay thp m ta s dng cc loi nha no t c hiu qu v kinh t nht. c im ht nha khi dng trong ty mu ng : Ngun gc xut x r rng Kch thc ng u cho php h thng vn hnh vi nng sut cao v chi ph vn hnh thp hn cc loi ht thng, ng thi tui th vn hnh cho php cng cao hn. 3.2.1. Mt s loi ht nha trao i ion hin nay s dng trong ty mu ng FFIP Nha trao i anion gc baz mnh: - FFIP l loi nha trao i anion gc baz mnh dng 1 (tnh kim mnh nht), dng ht, c sn xut t polystyrene copolymer vi nhm chc trimethyl benzyl ammonium (-N+R3).
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GVHD: Th. S H XUN HNG

- Indion FFIP l loi nha c dung lng trao i, thm thu v bn c hc cao, c kh nng ti sinh nhanh. Vi cu trc l ng nht, Indion FFIP t b nhim bn bi cc cht hu c v d dng ra sch khi ti sinh. Indion FFIP thng c s dng trong cc thit b sn xut nc siu tinh khit v c kh nng kh cac axt yu nh silic v cabonic. C th dng trong b lc anion hoc b lc cation anion hn hp. - Khi trao i bo ha c th ti sinh bng dung dch NaOH theo cng chiu hoc ngc chiu dng nc. bn s dng: t nht 3 nm nu thc hin theo ng quy trnh ca nh sn xut. - Indion FFIP l sn phm ca Tp on Ion Exchange, sn xut ti n t nm1964 v c xut sang cc nc M, Anh, Nht, Nga, Thi Lan, Philippin, M Lai, Ch lm vic ti u: - Nhit lm vic ti a: 60oc. Khong pH lm vic: 0 14. dy ti thiu ca lp vt liu: 750 mm. Tc lc ti a: 60 m/gi. Tc ra ngc: 3 m/gi - Thi gian ra ngc: 5 pht. Tc ti sinh: 3 18 m/gi. Thi gian ht ha cht ti sinh: 30 45 pht. Nng dung dch ti sinh: NaOH 2 5%. Tng lu lng nc ra: 3 6 ln th tch ht nha

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Tiu lun CNSX NG-BNH-KO

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1. 2. 3. 4. 5. A. 6.

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TI LIU THAM KHO K ngh sn xut ng ma,Nguyn Ng- L Bch tuyt Phan Vn Hip-Phm Vnh Vin- Mnh Hng, Nh xut bn khoa hc k thut 1984, Trang 114 Gio trnh cng ngh sn xut ng - Trng HCN TP H Ch Minh. Gio trnh cng ngh sn xut ng NXB Nng Nghip H Ni 2000, Ch bin Trn Mnh Hng Robert H. Perry, Don W. Green, James O. Maloney, Perrys Chemical engineers Handbook , Chapter 16 Adsorption and ion exchange, 1999 Ronald W. Rousseau, Handbook of separation process technology , 1987,chapter 13. Tager, Physical Chemistry of Polymer , 1972 F.C Nachod, J. Schubert, Ion Exchange resin , 1956, Academic press inc. Andrei A. Zagorodni, Ion Exchange Materials Properties and Applications ,2007 http://yeumoitruong.com/forum/showthread.php?2748-PHU%C6%A0NG PH%C3%81P-TRAO-%C4%90%E1%BB%94I-ION http://giaoan.violet.vn/present/show?entry_id=4119955 http://www.google.com.vn/imgres?q=cot+trao+doi+ion http://www.oxychemicals.com.vn/attachments/183_Nhua%20trao%20doi%20ion.pdf http://tanatech.com.vn

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