2

Chng 1 TNG QUAN 1. 1. Gii thiu v khong bentonite 1.1.1. S to thnh khong st trong thin nhin t st l mt loi t t nhin cha ch yu cc loi khong st, cn li l cc khong vt khc nh: goethite Fe(OH)3, gibbsite Al(OH)3, thch anh, trng thch c tn chung l khong phi st; Ngoi ra cn c mt s cht hu c nh cellulose, lignin, t st ni chung c to ra do s phong ha ha hc ca cc loi cha silicate di tc ng ca nc v kh carbonic, mt s loi t st li c hnh thnh do cc hot ng thy nhit (phong ha vt l) hoc do r cy lan dn trn mt t (phong ha sinh hc) [2]. Montmorillonite (MMT) thnh phn chnh ca khong st bentonite c trong cc loi t v cc trm tch cha st, phn ln c to thnh do tro bi ni la b phong ha [4]. 1.1.2. Thnh phn ha hc v cu trc Bentonite l loi st t nhin c thnh phn chnh l khong MMT v thm mt s khong khc nh Saponite, Nontronite, Beidellite. Ngoi ra ngi ta cn pht hin thy trong bentonite c mt s khong st nh kaolinite, clorite, mica v cc khong phi st nh: calcite, pyrite, magnetite, biolitcc mui kim v cc cht hu c. Bentonite cn gi theo tn khong chnh ca n l Montmorillonite. MMT c cng thc chung [(Al.M)2Si4O10](OH)2.nH2O, vi M l nguyn t kim loi Ca, Mg, Fe, Na, K, Phn tch thnh phn ha hc ca bentonite, ngoi nguyn t chnh nh silic, nhm, ngi ta cn pht hin thy s c mt ca cc nguyn t nh Fe, Ca, Mg, Na, K v hn 30 nguyn t ha hc khc dng vi lng nh Ni, Ti, Mo, Zn, Co, , cc c t nh As, Hg, Pb t pht hin thy [3]. MMT c cu trc lp 2:1, mi lp cu trc trong tinh th ca MMT c cu to t 2 tm t din (SiO4) lin kt vi mt tm bt din (Al(OH)6) gia qua cu ni O; Hai tm t din cng quay nh chung vo pha tm bt din (Hnh 1.1a). Cc nh chung ca t din v bt din kh nhiu do phn ln nhm OH b thay th bng O v quay u vo bn trong tm cu trc. Do cu trc nh vy nn

lc lin kt hydrogen gia cc lp khng cn na hoc c gi tr rt nh. Gia cc lp cu trc l cc cation trao i v nc hp ph. Chiu dy mt lp cu trc v lp cation trao i cng vi nc hp ph c xc nh l khong cch c bn d001 ca mng MMT [1]. (a) (b)

Hnh 1.1. S cu trc MMT (a)[20], nh AFM ca Na-MMT (b)[30] Mi lp cu trc c pht trin lin tc trong khng gian theo hng trc x v y. Cc lp cu trc c xp chng song song vi nhau v t ngt qung theo hng trc z, cc lp cation v nc hp ph to nn mt mng li khng gian ba chiu ca tinh th MMT (Hnh 1.1b). Trong mng li cu trc ca MMT thng xy ra s thay th ng hnh gia cc cation. S thay th ny dn ti s xut hin in tch m trong mng li; in tch c b tr bi cc cation nm trong khong khng gian gia hai lp; l cc cation Na+, K+, Ca2+, Mg2+, Fe2+, Li+, , chng b hydrat ha bi cc phn t nc khong khng gian gia hai lp cu trc. Ngi ta nhn thy rng in tch m trong mng li ca MMT xut hin ch yu mng bt din do s thay th ng hnh ca ion Al3+ bng ion Mg2+ ng vi t l Mg:Al ~ 1:(4-5). in tch m mng t din do s thay th ca ion Si4+ bi ion Al3+ ng vi t l Al:Si ~ 1:(15-30). V vy, in tch m ca mng phn b su trong lp cu trc m khng nm b mt ngoi ca lp cu trc nn nng lng lin kt ca cc cation trao i nm gia cc lp vi lp cu trc ca mng thp.

Cc cation c th chuyn ng t do gia cc mt phng in tch m v c th trao i vi cc cation khc, to ra kh nng bin tnh MMT bng cch trao i ion. S c mt ca cc cation kim hay kim th cng gy nhng bin i v cu trc mng ko theo c s thay i cc tnh nng c l ca ht (t trng, kim, trng n, kh nng trao i ion, hp ph, ch s keo, ). Da vo ngi ta c th phn bentonite t nhin thnh hai loi: (i) Bentonite kim (Na, K); cation trao i ch yu l Na+, K+; c trng n cao, bn nhit km. (ii) Bentonite kim th (Ca, Mg); cation trao i ch yu l Ca2+, Mg2+; c trng n km nhng c bn nhit cao hn [1]. 1.1.3. Tnh cht ha l Kh nng trng n Khong cch c bn gia hai lp trong mng li tinh th ca bentonite c th thay i, chiu dy ny bin thin nhiu hay t ty thuc vo lng nc lin kt nm gia khong khng gian hai lp tc ng vo - Yu t quyt nh n tnh trng n ca bentonite. Tnh trng n ca bentonite ty thuc vo in tch m ca cc tm v s solvat ha ca cc cation kim loi nm gia cc tm . Bentonite hp ph qua s solvat ha ca cc cation lm cho th tch cc lp tng ln. Th tch bentonite tng khong 10 - 15 ln so vi th tch ban u khi n bo ha nc. Kh nng hydrat ha ca cation cng mnh, lng nc hp ph vo gia cc lp cng nhiu, tnh trng n cng ln [1]. Kh nng trao i ion Kh nng trao i ion l c trng c bn ca bentonite, c hai nguyn nhn gy nn kh nng trao i ion ca bentonite: - S thay th ng hnh Si4+ bng Al3+ hoc Fe3+ trong mng t din, thay th Al3+ bng Mg2+ trong mng bt din lm xut hin in tch m trong mng li cu trc tinh th. Dung lng trao i ion ca bentonite c quyt nh bi s lng in tch m trn lp b mt.

- Trong mng li tinh th lun tn ti nhm OH lin kt vi cc cation Al3+ hoc Mg2+ trong mng bt din. Nguyn t H ca nhm ny trong iu kin nht nh c th tham gia phn ng trao i. Cc nhm OH nm cui mt trn ca tinh th lin kt vi nguyn t Si c xem nh nhm OH trn b mt Si. im ng in ca Si vng pH = 1,7; pH nh hn, nhm OH ny tham gia vo phn ng trao i anion; pH ln hn, ion H+ ca nhm ny tham gia vo phn ng trao i cation. - Cc cation trao i c lin kt tnh in vi MMT v dung lng trao i cation (CEC) ph thuc vo nng cation trao i trn b mt MMT. 80% dung lng trao i ion l do s thay th ng hnh to nn cn 20% l do nhng nguyn nhn khc. - Kh nng trao i ion ca bentonite ph thuc vo ha tr v bn knh ca cc cation trao i, cc cation ha tr nh d b trao i hn cc cation ha tr ln, theo th t Me+ > Me2+ > Me3+. i vi cc cation cng ha tr th bn knh ion cng nh, kh nng trao i cng ln: Na+ > K+ > Mg2+ > Ca2+ > Fe2+ > Al3+. - Gi tr CEC phn nh hai tnh cht c bn ca bentonite l din tch b mt v lng in tch m trong mng li tinh th. B mt tinh th gm b mt trong v b mt ngoi: + Dung lng trao i b mt ngoi phn nh kch thc tinh th, ph thuc vo s gy lin kt v khuyt tt b mt. Kch thc ht cng nh th dung lng trao i cng ln. + Dung lng trao i ion b mt trong phn nh lng in tch m trong mng li, kh nng hp ph ca bentonite v s ph thuc vo s lng cc cation b tr trong mng li. S lng cation cng ln th dung lng trao i cng ln [1]. Kh nng hp ph Bentonite c kh nng hp ph rt ln. Kh nng hp ph ca bentonite c quyt nh bi c tnh b mt v cu trc xp. Qu trnh hp ph xy ra trn c b

mt trong ln b mt ngoi ca bentonite. l s tng tc ca cc cht b hp ph vi cc tm hot tnh trn b mt bentonite. - B mt trong c xc nh bi b mt ca khong khng gian gia cc lp trong cu trc tinh th. Nh trn cho thy khong cch c bn gia cc lp b thay i ph thuc vo loi cation trao i, ph thuc vo cu trc v tnh cht ca cht b hp ph. - B mt ngoi c xc nh bi b mt cc mao qun chuyn tip c to nn do s tip xc ca cc ht bentonite. Ht cng nh th din tch b mt cng ln v kch thc mao qun chuyn tip cng nh. CEC ca bentonite ln hn dung lng trao i anion, do bentonite hp ph ch yu l cc cation trong mi trng kim [1]. 1.1.4. ng dng ca bentonite Bentonite c bit n v s dng t lu vi nhng tnh cht a dng ca n. Bentonite c s dng trong cc lnh vc chnh sau: - Lm vt liu ty, lc trong nhiu ngnh cng nghip ha hc nh: lc du, ha du, dc phm, thc phm, dt nhum, cht ty ra, - Cht kt dnh, khun c trong cng nghip luyn kim - Kh cht thi phng x, x l kim loi nng c hi trong nc v x l nc thi cc vng cng nghip, chng nhim mi trng - Ph gia trong cc ngnh cng nghip cao su, giy, thuc tr su, phn bn sinh ha, sn, gm s, lm dung dch khoan su - Lm cht xc tc; cht mang xc tc trong cc phn ng tng hp v oxy ho hon ton cc cht hu c [2]. 1.1.5. Khong st bentonite Vit Nam Cc vng phn b bentonite Vit nam Cng nh mt s nc trn th gii, tim nng khong sn bentonite Vit Nam rt ln, phn b khp cc vng min t Bc vo Nam vi hai chng loi bentonite kim v kim th. Cc a phng c khong bentonite vi tr lng rt ln, in hnh l Di Linh - Lm ng, C nh Thanh Ho, Tuy Phong Bnh

Thun, Gia Quy B Ra Vng Tu, Kin Bnh An Giang, Long t ng Nai Tr lng v thnh phn ca khong bentonite Vit Nam p ng c cho s trin khai cc ng dng vo cng nghip, nng nghip v gp phn bo v mi trng sinh thi. Bentonite Di Linh Lm ng Bentonite Di Linh khai thc t m st Tam B thuc thn Hip Thnh, x Gia Hip, huyn Di Linh, tnh Lm ng; cch th trn Di Linh 17 km. Thnh phn khong st Di Linh gm khong 60% MMT, 40% thch anh, kaolinite v mt s tp cht phi st khc, st c mu da cam sng, thuc loi bentonite kim th (giu Mg). Laurent Duclaux v cc cng s Lm ng: Bng 1.1. Thnh phn ho hc ca Bentonite Di Linh-Lm ng [14]
(Phn trm khi lng cc oxide)
SiO2 57,7-62,6 Al2O3 17,5-21,1 Fe2O3 6,4-8,9 TiO2 0,87 FeO <0,1 MgO 1,77-3,56 CaO 0,36-1,40 Na2O K2O
[14]

kho st

thnh phn ho hc (bng 1.1) v tnh cht ho l ca khong bentonite Di Linh

0,19-0,69 0,72-1,23

- Dung lng trao i cation CEC = 0,59 meq g-1. - Din tch b mt SBET = 64 m2 .g-1. - Din tch l xp = 19 m2 .g-1. - Tng th tch l xp = 0,07 cm3 .g-1. - S lp trung bnh trong ht st l 7. 1.2. St chng v st chng nhm st 1.2.1. Vt liu st chng t st chng [Pillared interlayer clay (PILC)] l vt liu rn siu xp, c cu trc v tnh cht c o, c hnh thnh bi cc polycation kim loi chn vo gia cc lp ca khong st trng n, c bit l smectite. Nung nhit cao (300 - 500C), cc polycation chn gia c chuyn thnh cc cm oxide kim loi thng qua qu trnh dehydrat v dehydroxy. Bng cch chng cc lp silicate,

cc oxide kim loi c tnh nng nh ct chng gia cc lp, to ra cc l xp kch c meso v micro. Cc polycation kim loi chn gia cc lp lm tng khong cch c bn v din tch b mt ring ca t st t nhin [10], [13]. Cc PILC khng c tnh trng n; duy tr xp ca n trong qu trnh hydrat ha hoc dehydrat ho (hnh 1.2). y l c tnh quan trng v khc bit ca PILC so vi smectite ban u c tnh trng n v khi nung nhit cao, c s sp cc lp lm cho b mt trong ca smectite khng cn s dng c cho cc qu trnh ho hc.

Hnh 1.2. M hnh qu trnh hydrat v dehydrat smectite v st chng [10] Ty thuc vo polycation kim loi lm tc nhn chng thu c cc PILC c kch thc ct chng v kch c l xp khc nhau, t c th iu chnh xp ca vt liu. xp ny kt hp vi cc tnh cht ca ct chng v t st nn, chng ng vai tr quan trng cho cc ng dng nht nh ca vt liu nh hp ph chn lc kh, cc phn ng xc tc [10] Nh vy, vt liu PILC phi p ng ng thi t nht ba tiu ch: (i) n nh ho hc v bn nhit. (ii) Mt lp chc chn c sp xp th t cho php xc nh r t nht mt khong cch c bn d001 v (iii) Mt lng ln cc phn t nh nh N2 c th vo c khng gian gia cc lp v v th, ng ng nhit hp ph gii hp ca N2 c xc nh [8]. 1.2.2. Nhng yu cu c bn v t st nn v tc nhn chng

- t st nn c CEC va phi v cation chng c in tch dng cao. - St trng n trong dung mi phn cc v cation chng ha tan c trong dung mi . - Cation gia cc lp silicate trao i c d dng v kch thc gia cc lp st phi thch hp bn sau khi c chng. Theo , khong st Na-MMT v tc nhn chng polycation kim loi c u tin la chn v s dng rng ri trong hai thp k qua: 1.2.2.1. Khong st lp: Na-Montmorillonite Khong st lp Na-MMT vi cation trao i ch yu l Na+ gia cc lp, p ng tt nht cho vt liu st chng do: - Ion Na+ bn knh nh, in tch nh trao i d dng vi cc cation khc, c bit l vi cc chui cation chng in tch ln hn - Kh nng hydrat ca Na+ cao lm cho cc lp st trng n. MMT trng n trong nc nhng khng tch lp trong huyn ph - MMT c CEC va phi (0,80 - 1,60 meq/g MMT) - Kch thc ht va nh (<2 m) qu trnh chng ng nht va ln sn phm tr nn cng, bn - Na-MMT r tin [10], [26]. Thc t khong bentonite c ln nhng tp cht nh l calcite, feldspath, thch anh cc loi oxide st v nhng cht hu c l nhng thnh phn tn ti chung vi khong bentonite trong t st, lm gim hm lng v cht lng MMT, do cn phi tinh ch lm giu MMT [8]: - X l c hc thu c cc ht c kch thc < 2 m (ch yu l khong MMT) bng phng php ly tm, siu m v sa lng; Sa lng phn on to thun li cho vic loi b cc tp cht c kch thc ln hn st (nh thch anh) c th b mc kt gia cc cht kt t khng tch lp. - Carbonate phi c loi b, c bit l khi cc loi t st tinh khit c s dng trong cc nghin cu ha cht keo. iu ny l do cc ion canxi v magi trong carbonate cn tr hon thnh vic gii keo ca st v phn lp ca smectite.

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Tp cht carbonate c loi b thng qua vic x l bng acid acetic. - S hin din ca hydroxide/ oxide ngn cn phn tn ti a ca khong st v sa lng phn on, bi v cc cation ha tr 3 t cc hydroxide hoc oxide gy ra ng t mnh. Ngoi ra, pH ph thuc s tng tc ca hydroxide/ oxide vi cc khong st dn n kt t; cng nh cc tp cht v c ny gy nhiu vi tia X khi nhn dng khong st. Hn na, s hin din ca silica v nh hnh, tc ng nh mt tc nhn kt dnh, cn tr s trng n v phn tn ca st. Cc loi oxide/ hydroxide st thng c loi b bng qu trnh kh xung Fe2+ v to phc vi citrate. - Hp cht hu c phi c loi b v lng mn cao ca khong, kt hp ch yu vi t st, c th khin X-ray nhn dng kh khn. Cht hu c, ngay c mt lng nh, cng c th pht huy nh hng rt ln n tnh cht c l, bn, v lu lng phn tn thp ca st. Loi b cc tp cht hu c bng qu trnh oxy ho bi dung dch hydrogen peroxide. - Thc hin trao i nhiu ln ion Na+ ng nht cc khoang st. St th c phn tn cn thn trong dung dch NaCl 1M bng cch khuy trong khong 12 gi, v tch ra bng my li tm. Qu trnh ny c lp li nhiu ln (t nht l 5 ln vi st kim th). - St phn tn thu c sau qu trnh x l ho hc nh trn thng cha mt lng ng k mui NaCl. Lng mui d ny thng c loi b bng mt lng ln nc ct; tuy nhin vic ra sch nhiu ln bng nc gy nn s gii keo ca cc ht st. Theo l thuyt v s tuyn rn, s lc l khng thc t bi v bn st hnh thnh mt lp rt mng lm nc hu nh khng th thm qua mng lc; S ly tm i hi my c tc ln v thc hin nhiu ln trong thi gian di. Thc t c th loi b mui d bng thm tch, qu trnh thm tch c thc hin trong nhiu ngy nhng khng nn ko di n mc khng cn thit v c th dn n s keo t cc ht st, c bit khi pH gim xung di 7. Ti pH 6 cc ht st bt u kt t, nn cn gi pH ca nc bn ngoi mng thm khong 7,5 8,0 bng cch thm vo mt lng nh dung dch NaOH long.

11

Ngoi ra, tu theo yu cu thc t st th c th c tinh ch m khng p dng phng php x l ha cht loi b carbonate, hydroxide, oxide, v hp cht hu c. Phng php tinh ch n gin gentle (van Olphen, 1963) bao gm s thay th cc cation c th trao i cng vi ion Na+ tip theo l ra bng nc. Ra (bng ly tm) loi b mui d tha v lm sch cc tp cht (Annabi Bergaya, 1978; Benna et al., 1999). 1.2.2.2. Tc nhn chng: Cc polycation kim loi Vt liu st chng bi tc nhn polycation, polyoxocation hay polyhydroxocation kim loi (cc oligome v c) c s dng rng ri, do cc cation tin cht c polyme ha d dng in hnh l [Al13O4(OH)24(H2O)12]7+, [Zr4(OH)8(H2O)16]8+, [(TiO)8(OH)12]4+, [Crn(OH)m](3n-m)+ c quan tm nht v: - Cc polycation kim loi trao i cation tt vi MMT do c in tch ln. - Kch thc ln ca polycation kim loi to c khong cch ln gia cc lp khi a vo trong cu trc MMT. - Cc polycation kim loi d chuyn sang dng oxide bn vng bng qu trnh x l nhit, v d: [Al13O4(OH)24(H2O)12]7+ 6,5 Al2O3 + 7 H+ + 20,5 H2O [Zr4(OH)8(H2O)16]8+ 4 ZrO2 + 8 H+ + 16 H2O cc oxide ny to thnh ct chng lin kt tt vi cc lp cu trc ca MMT [10]. Cc polycation kim loi c tng hp bng phng php sol-gel. - Phng php sol-gel: Tng hp polycation kim loi Sol gel l mt loi phng php tng hp vt liu rn, thc hin trong cht lng nhit thp (< 1000C). Ha hc v vt l ca qu trnh sol-gel c tng quan chi tit trong nhiu ti liu (bi bo, sch chuyn kho vv), cc cht rn c cp n y l cc cht v c; phn ln cc oxide hoc hydroxide c to thnh do s bin i ha hc ca cc cht tan ha hc c gi l cc tin cht. Cht rn c hnh thnh nh l kt qu ca qu trnh polyme ha, bao gm s xc lp cc cu ni M-OH-M hoc M-O-M gia nguyn t kim loi M ca cc phn t tin cht. Qu trnh bin i ny hon ton tng ng vi qu trnh polyme ha

12

vi s to thnh cc lin kt trc tip gia cc nguyn t carbon ca tin cht hu c. bc u tin ca qu trnh sol-gel, cc ht keo rn c lp l cc ht nano oxide kim loi (kch thc <1 m) c hnh thnh trong cht lng. C mi ht keo c cu trc cu ni ni tng i dy c (hnh 1.7a), iu ny lm cho cc ht rn d dng duy tr trng thi phn tn trong dung mi, trong trng hp cc huyn ph keo hay cn gi l sol c hnh thnh.

Hnh 1.3. Qu trnh sol-gel [24] bc th hai, cc ht keo c th to nn cc cu ni lin kt vi nhau trong khi vn cn trong dung mi, c nh vy to nn mt mng ba chiu h gi l gel (hnh 1.7b). S bin i t sol sang gel to thnh qu trnh gel ha, kt qu l thu c cc gel hay cn gi l gel keo (colloidal gel). Mt khc, hon ton c th trc tip to ra mt s gel t cc polyme thng hnh thnh t dung dch tin cht m khng c s xut hin cc ht ring l. Khi xut hin iu ny cc gel to thnh c gi l gel cao phn t (polymeric gel)[24]. - C ch ca qu trnh sol-gel Cc tin cht u tin c s dng trong qu trnh sol gel l cc mui kim loi dng MXn, trong cation kim loi M lin kt vi anion X. Trong dung dch m dung mi l nc cc tin cht ny hin din nh l cation solvat ha M[H2O]Nz+. Cc phn ng hnh thnh ht sol v gel bao gm: (i) cc phn ng

13

thy phn, trong cc ligand H2O c thay th bi cc ligand OH lm mt proton; (ii) cc phn ng ngng t, trong cc phn t nc b loi ra v to nn cc cu ni OH M hay gi l ni ol hoc cu ni M O M hay gi l cu ni oxo. Livage v cc cng s[24] ngh c ch cho qu trnh ny nh sau: u tin, mt ligand nc c th b thay th trc tip bi mt OH- theo c ch trao i proton thng qua s chuyn lin kt hydrogen nh m t trong phng trnh 1.

K tip, cc phn ng ngng t khc nhau c th dn n s hnh thnh cc cu ni ol v oxo, theo c ch phn ng m t trong phng trnh 2.

Ni chung, Livage pht trin khi nim chuyn in t ca Sanderson v ngh m hnh in tch ring phn (partial charge). M hnh ny c th xc minh mt cch c l hn cc d on v s hnh thnh cc phc cht trong dung dch. Nh vo trng thi chuyn tip hnh thnh bi cc tc cht thn nhn hoc thn in t ko theo s sp sp li m my in t (tc l lm bin i phn cc ca tng lin kt) trong tt c cc nguyn t trong trng thi chuyn tip cho. Kt

14

qu l in tch ring phn cng nh m in ca mi mt nguyn t trong trng thi chuyn tip ny b bin i. Khi mt nhm cc nguyn t k cnh trong trng thi chuyn tip t n in tch ring phn thm, th nhm nguyn t ny tr nn t in v tch ra thnh nhm tch ri. Nhm tch ra ny c th l mt anion, cation hay phn t trung ha nh H2O khi in tch ring phn cng thm (2H + O) t n 0. S dng mui kim loi lm tin cht trong qu trnh sol gel vi vic dng dung dch hu c, m mt s cht hu c c dng lm cht bt proton (proton scavanger) chm ha tan trong . Mui ion kim loi phi dng hydrat ha, dung mi hu c c th l ethanol. Cation hydrat [M(H2O)N]z+ phi c tnh acid cho phn ng proton ha xy ra vi cht bt proton. Cht bt b proton ha m bo cho phn ng m vng bt thun nghch vi anion ca mui kim loi, trong khi cation b solvat ha chuyn thnh dng aquo hydroxo [M(OH)x(H2O)N-x](z-x)+ m bo cho phn ng ngng t v sau. Cc alkoxide M(OR)n hin nay c s dng rng ri lm tin cht trong tng hp sol-gel. c trng ca cc tin cht ny l trong phn t c s tn ti ca cc ni cng ha tr c cc M O. Trong thc t, chng t hoc nhiu c kh nng to thnh dng phc polyme nh, trong dung mi alcohol m ROH, S bin i chng xy ra trong dung mi hu c v nc tr thnh tc nhn c thm vo vi mt t l c kim sot. Phn ng sol gel xy ra l phn ng thy phn (phng trnh 3), trong ligand OR c thay th bi mt nhm OH, ni tip bi phn ng ngng t; tng t nh xy ra vi mui kim loi.

(3)

15

Kt qu ca phn ng thy phn v ngng t, cc oligome (polyme vi mt s lng tng i nh nguyn t kim loi) dn dn c hnh thnh, l cc cluster c sp xp tng i trt t, in hnh nh cluster trung gian [Al13O4(OH)24(H2O)12]7+ (Al137+) l dn xut cho tt c gel nhm oxit. Bng cch ny c th iu ch c cc khi gel t hon ho (gel monoliths) vi Cr, Fe, Al, Zr v cc cation khc. - Al-polycation: Al137+ (Al-Keggin) Ion Al137+ ( -Keggin -Johansson) c dng hnh cu thun (prolate spheroid), gm mt khi t din AlO4 trung tm, bao quanh bi mi hai bt din ca nhm hydroxide (hnh 1.4). Mi bt din chia s vi nhau 3 cnh qua cu ni l oxy trn nh t din, cc nhm hydroxyl hoc cc phn t nc. Khong cch gia cc tm (Al3+) ca cc bt din u bng nhau v c tnh i xng qua khi t din. Trc ng cho t oxy pha trn xung oxy pha di ca ion Al137+ l 8,8 , nu tnh thm chiu di ca lin kt O-H th c gi tr khong 10 [26].

Hnh 1.4. Cu trc ca ion Al137+ [24] Theo M.Wang v M.Muhammed

[29]

, ion Al-Keggin c th tng hp bng

cch thu phn c kim sot ion Al3+ trong dung dch; ti mt nhit nht nh ion Al137+ chim u th trong khong pH c th, khi nhit tng v pH chuyn sang pha acid hn th s chim u th Al137+ s gim. Mc d v mt nhit ng hc th ion Al137+n nh hn nhit thp hn, iu gy kh khn cho tin trnh hnh thnh do ng hc thp. Nhit thu phn c ngh l 700C vi gi tr pH trong khong 5 - 6. Tc gi cng ch ra rng iu quan trng cho qu trnh tng hp

16

l phi kim sot cn thn tc kim a vo dung dch mui, cng vi cc iu kin th nghim khc duy tr pH trong khong hp.
(a) b

Hnh 1.5. Gin XRD chun (a)[29] v nh SEM (b) ca Al-Keggin sulfate [25] Ion Al137+ c kh nng kt hp vi cc ion SO42-, C2O42- to thnh cc kt ta mu trng nh tinh th hnh cu Al-Keggin oxalate, tinh th t din Al-Keggin sulfate [29], cu trc t din ny c trng bi ph XRD v nh SEM (hnh 1.5). Trong vi thp k qua, nhiu nghin cu cho thy rng c th tch hp cc ion ca cc kim loi Zr, Ga, Cr, Fe, Cu, Mo, Ru v nhm Lantan vo cu trc ion Al137+ to thnh cc polyoxocation cha 2 hoc 3 kim loi v c s dng trong cc lnh vc khc nhau [8]. AlFe-polycation chn vo gia cc lp silicate to thnh vt liu st chng c s dng trong cc lnh vc hp ph v xc tc. - AlFe- polycation (AlFe-Keggin) Ion AlFe-Keggin c hnh thnh nh s tch hp ion Fe3+ vo cu trc ion Keggin Al137+. S tch hp ny xy ra khi thc hin phn ng gia hn hp mui Al3+ v Fe3+ v dung dch kim, qua qu trnh thu phn v ngng t dung dch keo to thnh cha Fe(OH)2+, Fe(OH)2+, Fe2(OH)42+, [Al2(OH)2(H2O)4]4+, [Al3(OH)4(H2O)9]5+ v [Al13-xFex(OH)24(H2O)12]7+ [27], [28], [29]. Hm lng ion AlFe-Keggin ph thuc nhiu vo cc t l mol OH-/(Al3+ + Fe3+), Fe3+/Al3+, nhit v thi gian gi ho dung dch keo.Theo E.Ts. Dashinamzhilova v cc cng s, vic tng t l mol OH-/(Al3+ + Fe3+) v gim hm lng ca ion Fe3+ th lng polyhydroxocation c hnh thnh trong dung

17

dch nhiu hn. t l mol OH-/(Al3+ + Fe3+) t 2,0 2,4 c s tch hp cc ion Fe3+ vo cu trc ca ion Keggin Al137+; t l Al3+/Fe3+ cng b th d dn n s ph v mng cu trc ion Keggin do s kt t ring bit ion Al3+ v Fe3+. ng thi lng st d trong cu trc tr thnh cc tc nhn phn ng khng mong mun gy nh hng n tnh cht ha l ca vt liu st chng. Thi gian gi ha c ngh ln hn 7 ngy 250C [27]. Vaughan[18] cho rng st c th c thay th ng hnh c Al v tr tm t din (Al(4) ) v Al tm bt din (Al(6)) trong cu trc ca ion Al137+; nhng Kiricsi v cc cng s[23] li thng bo rng khng c s thay th v tr t din, ch mt phn nh Al3+ trong v tr bt din c th c thay th bng ion Fe3+. Da vo bn knh ca Al(4) (0,53 ), Al(6) (0,68 ), Fe3+ (0,67 ) v phn tch Mssbauer, N.R.Sanabria, M.A.Centeno, R. Molina v S.Moreno[25] (2009) cho thy s ph hp khi cc ion Fe3+ thay th ion Al3+ v tr tm bt din. Tuy nhin kh nng thay th ny vn cn l mt vn v ang tip tc c nghin cu. 1.2.3. Cc qu trnh tng hp vt liu st chng Qu trnh chn polycation kim loi vo gia cc lp st - Qu trnh chn (intercalation) cc polycation kim loi vo gia cc lp st thng qua phn ng trao i (hnh 1.6); Qu trnh ny c th thc hin trong s phn tn long (Pillaring in Dilute Dispersions) hoc trong mi trng m c (Pillaring in Concentrated Medium) ca tc nhn chng v t st nn [8].

Hnh 1.6. S qu trnh chn cc polycation vo gia cc lp st [5] Qu trnh trao i cation ph thuc nhiu vo tc khuy trn, kch thc ht, nhit , bn cht ca polycation v tui ca dung dch chng. Kch thc ht

18

ng vai tr quan trng trong qu trnh ny, c bit l nh hng n trng thi bn nhit ca sn phm cui. Ni chung, kch thc ht < 2 m l kch thc tt t c t st chng c cu trc siu xp v n nh [26]. Din tch b mt v th tch l xp tng ln cng vi thi gian gi ha tc nhn chng[27]. - Sau khi thc hin qu trnh trao i cation, cn phi loi b phn d ca dung dch chng, tch ly phn t st bng ly tm hoc lc t st sau khi chng. Ra t st bng nc ct loi b cc mui tan. Ra sch t st s tng cng cht lng ca t st chng, qu trnh ra lm cho s phn b cc ion chng ng nht hn v khong cch c bn ln hn. - Trc khi nung, t st chng c sy loi b lng nc l hc. Cc phng php sy c s dng l: phi trong khng kh, lm kh bng cch ng lnh ri cho bay hi nc trong chn khng, sy phun hoc dng t sy. Ch c phng php phi trong khng kh l k thut sy tng i chm cc ht st t t n nh trong s nh hng song song v ng nht (hnh 1.7a), to sn phm c tinh th v xp cao. Cc phng php khc to st chng nh hng ngu nhin (hnh 1.7b) c cu trc xp trung bnh v tinh th thp [10], [26].

(a)

(b)

Hnh 1.7. M hnh biu din t st chng theo k thut sy khc nhau [10] Qu trnh nung nh hnh cu trc Nung khong nhit 300-500oC chuyn i tin cht chng thnh dng oxide kim loi cng, bn (hnh 1.8). Nu t st chng khng c nung th cu trc d b sp qua s thy phn tinh th bn trong cu trc. Qu trnh nung tt s p ng nhng iu kin sau:

19

- Cc cation kim loi chng trong cc lp t st s khng trao i vi cc cation khc na. - Sn phm cui s khng trng n thm trong cc dung mi phn cc. - Nhit nung khng c qu cao nhm ngn s gim cp v mt cu trc siu xp (nh sp mng cu trc hoc kt khi sn phm).

Hnh 1.8. S qu trnh nung nh hnh cu trc [5] Trong sut qu trnh gia nhit, cc oligome ln lt qua qu trnh dehydrat ri dehydroxy. S tng tc mnh gia cht chng dehydroxy v cc lp st to ra lc lin kt nh tng tc van de Waals hoc thm ch l lin kt phi tr gia cc v tr cha bo ha v lp oxy hnh thnh h thng hp nht bn vng [26]. 1.2.4. Hai phng php tng hp vt liu st chng Phng php chng phn tn long y l phng php chng c in, st c phn tn trong nc to huyn ph long (2%), thc hin chn tc nhn chng vo gia cc lp silicate bng cch thm t t mt dung dch long ca tc nhn chng c chun b trc vo huyn ph st (kiu Ex-situ) (hnh 1.9a); hoc thm cng lc 2 dung dch long ca mui kim loi v base ng thi vo dung dch long ca huyn ph st (kiu Insitu) (hnh 1.9b). u im ca phng php In-situ ny l t tn thi gian hn phng php Ex-situ v khng c s chun b ring bit dung dch chng, tc nhn chng c cho l hnh thnh trc tip trong huyn ph st. Tuy nhin, kh thc hin thnh cng do phi kim sot tc thm hai dung dch sao cho gi tr pH cui cng khng thay i nhiu so vi vic thm tng git ca hai thnh phn. Yamanaka, Brindley (1978) v Brindley, Kao(1980) ci tin phng php

20

(a)

(b)

Hnh 1.9. S m t phng php chng phn tn long [8] chng lin quan n s thy phn kiu In-situ ca cc cation trao i trong khng gian xen gia cc lp, theo cn phi trao i trc khong st cng vi mt cation ph hp nhng cng khng mang li mt sn phm mong mun. Mt s phng php chng ci tin khc nh: Thc hin qu trnh chn gia nhit thng, kt hp nh siu m trong vng 20 pht cho Ca2+- MMT vi chlorhydrol (Al2(OH)5Cl) thu c vt liu st chng vi ci thin c tnh kt cu v tnh n nh cao hn (Katdare v cng s, 1997, 2000.). Hoc s dng bc x vi sng nh mt bin php nhanh gim thi gian chn gia cc lp silicate theo yu cu ca phng php truyn thng (Fetter v cng s, 1996.). Nhn chung phng php chng c in cng nh cc phng php ci tin khc tn nhiu thi gian, cn mt ln lng th tch cht lng v phn tch nhiu ln mt lng rt ln huyn ph st bi ly tm hoc lc. Do phng php chng pht trin trong phng th nghim rt kh m rng ti quy m cng nghip [8]. Phng php chng trong mi trng m c sn xut vt liu st chng quy m cng nghip, phng php chng phi c n gin ha. c bit, th tch ca tt c cc cht phn ng cn phi c gim ng k. Trong thp k qua, thng tin v cc phng php s dng cht phn ng m c, kt hp vi ti thm tch l c gi tr. Cc phng php ny c tm tt trong s hnh 1.10 (Aouad v cng s, 2005)[8].

21

Hnh 1.10. S m t phng php chng trong mi trng m c [8] Vaughan (1988) l ngi u tin thnh cng to ra vt liu st chng bng cch thm bt st vo dung dch chng cho ti mt lng bn t n 40%. Khi nng cao, khong st khng phn lp hoc keo ha. Phng php Ex-situ cng c th thc hin bng cch cho huyn ph st c trong ti thm tch v t trong mt dung dch long tc nhn chng (Schoonheydt v Leeman, 1992; Sanchez v Montes, 1998). Frini v cng s (1997) so snh kt qu thu c t mt phng php c in phn tn long vi cc phng php s dng bt t st 'v bn st c trong ti thm tch. t st sau khi b chn gia c ra nhiu ln, ly tm v em nung, t st chng c iu ch bng hai phng php sau d nghin hn sn phm thu c t phng php c in. Vic s dng st dng phn tn c hoc bt nho v thm tch, to iu kin cho vic thu hi huyn ph chn gia (Molina,1992; Del Riego, 1994; Schoonheydt, 1994 v cng cc cng s), ng thi gim c s ln ra vt liu. Tuy vy, tt c cc phng php ny vn cn s dng dung dch long ca tc nhn chng vi mt lng ln cht lng. Vt liu st chng c sn xut th im (> 1 kg mi ln tng hp) ti N.T.U.A (Athens) v Tolsa (Madrid), bt st kh c cho vo dung dch long cha tc nhn chng thng mi (chlorhydrol) v st phn tn c ra trong mt my p lc (Moreno v cng s, 1997); So vi vt liu st chng tng hp phng th nghim (mt l khong 100 g) u cho thy hot tnh xc tc tng t. Storaro

22

v cng s (1996) s dng dung dch tc nhn chng chlorhydrol thng mi (50% khi lng) v huyn ph st (50% khi lng ) trong nc hoc acetone; Vic huyn ph st trong acetone t dnh v d thao tc hn so vi huyn ph trong nc; Bin php ny c th thu c lng st chng tng gp nhiu ln. Storaro v cc cng s (1998) ci tin hn na bng cch trn chlorhydrol rn vi cc khong st khc nhau trong acetone. Mt bin php tng t c s dng bi Salerno v Mendioroz (2002) bng cch trn huyn ph t st th trong acetone vi Locron (mt hydroxychloride nhm thng mi cha 47% cation Keggin). Phng php c xut bi Fetter v cng s (1997) bao gm trn mt dung dch chlorhydrol nng cao (50% theo khi lng; 2,5 M) vi mt huyn ph st c 50% theo khi lng v s dng bc x vi sng cho bc chn gia. Phng php tng hp vi hm lng st cao nht v tiu ph lng nc v thi gian t nht c thc hin thnh cng bi Aouad v cng s (2005); Phng php ny cung cp kh nng m rng vi quy m cng nghip. y, 1 gam hn hp bt st th v Al13 rn c thm tch nm ln vi 5 ml nc. n nay, phn ng gia solid solid thc s vn cha kim sot c. Bin php thm tch dng nh quyt nh cho qu trnh chng. S cn thit phi c nhiu nghin cu c bn hiu cc phn ng v nhng c ch lin quan [8]. 1.3. Xc tc Fenton-like 1.3.1. Cc qu trnh Fenton Phn ng Fenton ban u c cng b bi Fenton (1894) cho qu trnh oxy ha acid tartaric, t n nay c nhiu nh nghin cu s dng phn hy v loi b cc hydrocarbon; thuc nhum hu c; thuc khng sinh; thuc tr su; nc thi; vt liu n; phenol cng nh loi b vi khun Qu trnh Fenton lin quan n phn ng ca Fe (II) vi H2O2, sinh ra cc gc hydroxyl (OH*) nh phng trnh (1). Phn ng xc tc ny tip din bng vic kh Fe (III) thnh Fe (II) c din t qua phng trnh (2) cng vi s hnh thnh cc gc t do theo cc phng trnh t (3) n (5).

23

Fe2+ + H2O2 Fe3+ + OH- + OH* Ea = 39,5 kj mol-1 ; k1 = 76 M-1S-1 (1) Fe3+ + H2O2 Fe2+ + HO2* + H+ Ea = 126 kj mol-1 ; k2 = 10-3-10-2 M-1S-1 (2) Fe2+ + HO2* Fe3+ + HO2Fe3+ + HO2* Fe2+ + O2 + H+ Ea = 42,0 kj mol-1 ; k3 = 1,3106 M-1S-1 (3) Ea = 33,0 kj mol-1 ; k4 = 1,2106 M-1S-1 (4)
H2O2 + HO* HO2 + H2O
*

Ea = 14,0 kj mol-1 ; k5 = 2,7107 M-1S-1 (5)

S hnh thnh cc gc hydroxyl trong phn ng Fenton v ang c s dng trong mt lot cc qu trnh: (i) Fenton ng th, lin quan n cc mui st(II) trong mi trng acid (ii) Xc tc d th (iii) Kh Fe (III) thnh Fe (II) nh bc x t ngoi (Qu trnh photo-Fenton) (iv) Qu trnh oxy ha in phn v quang in ho (v) Xc tc nano - Qu trnh Fenton ng th c nghin cu rng ri; y l qu trnh n gin, s dng thit b thng dng v hot ng nhit v p sut thng. Tuy nhin, c mt vi hn ch ch yu l s hnh thnh cc phc cht Fe (III) do s thay i pH ca dung dch. pH ti u cho qu trnh Fenton ng th khong 2,8, khi st trong dung dch mt phn l Fe (III) v mt phn l Fe (III)(OH)2+ l cc tiu phn c hot tnh quang ho; di pH ny, cc gc hydroxyl b loi tr bi proton v nng ca Fe(III)(OH)2+ gim, trong khi trn pH ny, Fe (III) kt ta nh mt oxyhydroxide. duy tr pH ~ 3, mt lng ln axit (thng l H2SO4) phi c thm vo mi trng phn ng. Do , khng thc t khi p dng quy trnh Fenton ng th lm sch mi trng do (khng iu chnh pH) lng ln cn hydroxide st s to ra, pht sinh cc vn x l mi trng khc [13].

24

- Phn ng Fenton trn cc cht rn xc tc d th c th iu chnh gi tr pH trong mt phm vi rng. Ngoi vic hn ch s chit cc ion st ra mi trng phn ng, cht xc tc c th d dng c phc hi sau khi phn ng v vn gi nguyn hot tnh xc tc trong nhiu ln s dng. Hiu qu xc tc ca cht xc tc rn Fenton d th trong s phn hy cc cht hu c gy nhim chu nh hng ca cc yu t nh hm lng v loi cht xc tc, din tch b mt ca cht xc tc, nng hydrogen peroxide, nhit mi trng, pH dung dch v cu trc ca cht gy nhim. Cc cht rn xc tc d th c s dng trong phn ng Fenton-like nh cacbon hot tnh c tm st v ng oxide; nha thng b tr Fe(II) hoc Fe(III); st c cha tro; st ph trn cc ht bt; zeolite t nhin v tng hp trao i vi cc ion st hoc ng, khong st oxide v t st chng chn gia cc lp [13] 1.3.2. t st chng vi phn ng Fenton-like t st chng c cha cc oxocation ng (Cu-PILC) hoc st (Fe-PILC) cng vi Al-PILC c gn thm cc ion st v ng , c s dng rng ri nh l cht xc tc cho s ph hu cc hp cht hu c kh phn hu thng qua cc phn ng Fenton-like, photo-Fenton. St chng lm cht xc tc rt n nh, cho thy cc dng kim loi chn gia cc lp tch ra dung dch bn ngoi l t nht. Do vy, nhng vt liu ny c th c s dng nhiu ln nhng hot tnh xc tc vn t b suy gim, p ng c vn x l cht thi lin quan n nhim ngun nc bi cc kim loi ha tan. Hn th, quy trnh tng hp qua cc giai on tng i ngn l mt li th na ca vic s dng PILC lm cht xc tc [13]. pH ti u cho cc qu trnh Fenton v photo-Fenton khong 3 nhng qu trnh Fenton-like vi vt liu AlFe-PILC, AlFeCu-PILC cho thy kh nng hot ng ti pH rng hn t 3,7 - 5,5 [12] v pH gn trung tnh [28]. iu ny l v cc dng Fe (III) phn ln c "c nh" trong khng gian xen gia cc lp ca khong st, do st trong PILC bn, hn ch s tch chit ra mi trng phn ng khi pH ca dung dch thay i . Trong qu trnh phn ng, pH dung dch gim do s

25

hnh thnh cc acid trung gian (nh acetic , oxalic), nhng acid c th chim ly bt k ion st c tch ra t cht xc tc, hnh thnh cc phc cht tan v thc y qu trnh Fenton ng th. Khi cc acid trung gian b oxy ha n CO2 v H2O, cc ion st c th hp ph li trn b mt PILC, hnh thnh mt chu trnh Fe(III) [13]. Xc tc Fenton-like l mt trong cc ng dng quan trng ca vt liu AlFePILC. y l loi xc tc rn Fenton d th Fe(III)/H2O2, oxy ho cc cht hu c kh b phn hu, c bit l cc hp cht cha lin kt C=C, -N=N- v hp cht d vng [6], [12], [13], [22], [27]. Bng 1.2. Bng tng hp mt s nghin cu st chng nhm st
t st nn Bentonite
Greek[7] (2000)

Phng php Ex-situ

lng + lng (hnh 1.9a)

T l mol
OH /(Al+Fe)

% s mol
Fe/(Al+Fe)

T l
(Al+Fe)/ 1g st

Tnung ( C)
0

d001
(nm)

SBET
2 -1 (m .g )

1.9

10

3,8 mmol

500

1,84

240

Na-MMT
Colombia[9] (2005)

Ex-situ
lng + lng (hnh 1.9a)

2.0

10

20 meq

400

1,70

130

Na-MMT
China[17] (2006) MMT
Wyoming[16]

Ex-situ
lng + lng (hnh 1.9a)

1.9

10

10 mmol

400

1,88

194

Ex-situ
lng + lng (hnh 1.9a)

2.0

7 13

10 meq

500

1,67 1,67

234 198

(2008)

Ca-MMT
Colombia[25]

Ex-situ
rn + rn (hnh 1.10)

2.46

20 meq

400

1,82

145

(2009)

Na-MMT
Bogovina[6] (2009)

Ex-situ
lng + lng (hnh 1.9a)

2.0

10 15

20 mmol

300

1,64 1,56

172 175

26

Trong nhiu thp k qua c nhiu nghin cu tng hp vt liu AlFePILC bng nhiu phng php khc nhau, thu c cc vt liu c hot tnh xc tc tt. Cc phng php tng hp v mt s c trng ca vt liu AlFe-PILC nghin cu trong 10 nm gn y c nu trong bng 1.2. Theo , phng php chng ch yu l cho dung dch tc nhn chng vo huyn ph st (phng php phn tn long). Cc iu kin phn ng thng c kho st nh sau: T l mol Fe3+/(Al3+ + Fe3+) l 10% v OH-/(Al3+ + Fe3+) l 2,0; hm lng (Al + Fe) trn 1 gam st t 1,4 20 meq; nhit nung nh hnh cu trc 4000C. Nh vy: Tng hp st chng vi polycation kim loi ni chung hay AlFepolycation ni ring v cc c trng ca vt liu thu c nh bn nhit, khong cch c bn, din tch b mt ring, din tch v th tch l xp micro ph thuc vo: - Bn cht ca polycation kim loi v loi khong st nn - Kch thc ht st - Thi gian gi ho dung dch tc nhn chng - Cch thc chn polycation kim loi vo gia cc lp st, nh cho dung dch tc nhn vo huyn ph st lng-lng, cho bt st vo dung dch tc nhn rn-lng hay trn bt st vi bt polycation rn-rn - S khuyy trn hoc khng, x l bng sng siu m hoc thm tch v nhit trong qu trnh chn gia - Cch thc ra: Ra st chn gia bng ly tm, lc, hoc thm tch - K thut sy: Phi st chn gia trong khng kh, sy nhit thp trong l sy, sy ng kh hoc kt hp cc phng php sy - Ch nung nh hnh cu trc bao gm nhit nung, thi gian nung, tc gia nhit v thi gian lu nhit.