Lun vn tt nghip

Qu trnh iu ch st hu c t bentonit Bnh Thun

M U
Bentonit l loi khong st t nhin, thuc nhm smectit gm montmorilonit v mt s khong khc. Bentonit c cc tnh cht c trng l trng n, kt dnh, h p ph, tr, nht v do [1,3,4,35,37]. Do nhng tnh cht n y m bentonit c ng dng t xa xa nh lm gia dng (bt a, ni, chum, vi) v ngy nay c s dng lm cht xc tc [2,8,10,20,39], cht to huyn ph trong sn, thuc nhum, vecni, lm cht hp ph trong x l nc thi [11,17,20,26,27], kh giy, mc, lm cht u ch to nanocompozit [7,14] St hu c l sn phm ca qu trnh tng tc gia st bentonit v cc hp cht hu c phn cc hoc cc cation hu c, c bit l cc amin b c 1, bc 2, bc 3, bc 4 c mch thng, nhnh v vng [9,11,25,31]. St hu c c tnh cht c bit nh a hu c, nht, hp ph. Do c nhng tnh cht trn m st hu c c ng dng lm cht chng sa lng trong sn, du nhn, mc in, v gn y l iu ch vt liu nanocompozit, lm cht hp ph cc cht hu c v du m trong x l mi trng nc [17,20,26,27,30]. Do c nhiu ng dng trong cc lnh vc khc nhau, st hu c v ang c cc nh khoa hc trn th gii nghin cu ngy cng nhiu. Vit Nam c mt tr lng khong st di do song mi c khai thc trong phm vi nh v m i c s dng lm vt liu gm, vt liu xy dng, x l mi trng, m cha c nghin cu nhiu nng cao tnh nng s dng. Do vic nghin cu s dng mt cch c hiu qu ngun khong st Vit Nam l nhim v cp thit, c ngh a khoa hc v thc tin ca cc nh khoa hc Vit Nam. ng gp mt phn nh vo vic nghin cu v bentonit v iu ch st hu c t bentonit Vit Nam, trong lun vn ny chng ti trnh by cc kt qu kho st qu trnh iu ch st hu c t bentonit Bnh Thun hm lng MMT >90% vi cetyl trimetyl amoni bromua v dodecyl amoni clorua, sau tin hnh xc nh cu trc v tnh cht ca sn phm st hu c iu ch c.

CHNG I. TNG QUAN

1.1. Gii thiu v bentonit [1,3,4]
Bentonit l lo i khong st t nhin thnh ph n chnh l montmorilonit (MMT) v vy n cn c tn l MMT. Cng thc n gin nht ca MMT l Al2O3.4SiO2.nH2O ng vi na t bo n v cu trc. Trong trng hp l tng, cng thc ca MMT l Si8Al4O20(OH)4 ng vi mt n v cu trc. Tuy nhin thnh phn ca MMT lun khc vi thnh phn biu din l thuyt do c s thay th ng hnh ca ion kim loi Al3+, Fe3+, Fe2+, Mg2+ vi ion Si4+ trong t din SiO4 v Al3+ trong bt din AlO6. Nh vy thnh phn ha hc ca MMT ngo i s c mt ca Si v Al cn thy cc nguyn t khc nh Fe, Zn, Mg, Na, K trong t l Al2O3 : SiO2 t 1: 2 n 1: 4 [1,3 -6]. Ngoi thnh ph n chnh l MMT, trong bentonit cn cha mt s khong st khc nh hectorit, saponit, beidelit, nontronit, v mt s khong phi st nh canxit, pirit, manhetit, mt s mui kim loi kim khc v hp cht hu c. 1.1.1. Cu trc ca bentonit Cu trc khng gian m ng li ca montmorilonit c trnh by trn hnh 1.

Hnh 1.1. Cu trc khng gian mng li ca montmorilonit Trong trng hp l tng, cc nguyn t Si nm tm ca cc t din, cn cc nguyn t Al nm tm cc bt din ca MMT. Do MMT c cu trc 2:1 dng diocta nn cu trc lp ca MMT c hnh thnh t hai l t din lin kt vi mt l bt din gia to nn mt lp aluminosilicat. Gia cc lp aluminosilicat l cc cation c kh nng trao i b hydrat ha. Khong cch gia cc lp trong cu trc c bn ca MMT l 9,6, khong cch ny b thay i t hay nhiu ty thuc vo s lng, bn cht cc cation trao i v lng nc b hp ph, thng c th n 15. S cu trc khng gian mng li ca MMT h nh 1.1 l cu trc trung ha in. Nu Si4+ tm t din hay Al3+ tm bt din b thay th ng hnh bi cc cation dng c in tch nh hn th cc mng li tch in m. in tch m ca mng li s c b tr bng cc cation mang in tch dng nh Na+, K+, Ca2+, Fe2+, Mg2+... khong khng gian gia cc lp. Cc cation ny c kh nng trao i vi cc cation kim loi ho c cation hu c khc. Nh vy dung lng trao i cation ca MMT tng ng vi in tch ca cc lp. 1.1.2. Tnh cht ca bentonit 1.1.2.1. Tnh cht trao i ion [10]

c trng c bn ca bentonit l kh nng trao i ion do trn b mt ca cc lp st c cc trung tm (O, OH) mang in tch m c kh nng hp ph v trao i cation. ng thi, tnh ch t c c l do s thay th ng h nh ca cc cation. V d nh khi Si4+ trong mng t din b thay th bi Al3+ ho c Fe3+, hoc Al3+ trong m ng bt din b thay th bi Mg2+, Fe3+, Cr3+, Zn2+..., th s thay th cc ion in tch cao ny bng cc ion in tch thp hn s gy ra s thiu ht in tch dng trong cu trc t din v bt din to ra in tch m trn b mt phin st. i vi bentonit, s th ay th ng hnh ch yu xy ra trong lp bt din, gia hai lp t din ca phin st. Do lin kt ca cation vi b mt lp st l lin kt yu v cc cation c th b thay th bi cc cation khc. Kh nng trao i mnh hay yu ph thuc vo lng in tch m b mt v s lng ion trao i. Nu s lng in tch m cng ln, s lng cation trao i cng ln th dung lng trao i cng ln. Kh nng trao i ion ca lp aluminosilicat cn ph thuc vo in tch v bn knh ion ca cation trao i. Cation c in tch thp d trao i hn cation c in tch cao: Me+ > Me2+ > Me3+ i vi cation cng in tch, bn knh ion cng nh th kh nng trao i cng ln, c th sp xp theo trt t sau: Li+ > Na+ > K+ > Cu2+ > Fe2+ > Al3+ Tuy nhin kh nng trao i ca bentonit ch yu vn ph thuc vo in tch m b mt v in tch m trong mng li. B mt ca bentonit gm b mt trong v b mt ngoi. Kh nng trao i ion b mt ngoi phn nh kch thc h t tinh th , ph thuc vo s t gy lin kt v khuyt tt b mt. Kch thc ht cng nh th kh nng trao i cng ln. Kh nng trao i ion b mt trong phn nh lng in tch m trn m ng li v kh nng hp ph ca bentonit. N ph thuc vo lng cation b tr trong mng li. S lng cation cng ln th kh nng trao i

cng ln. Dung lng cation trao i dao ng t 80 n 150 meq/100g. Dung lng trao i anion dao ng t 15 n 40 meq/100g. S trao i ion ca bentonit cn lin quan n s thay th cc nguyn t hyro trong cc nhm hyroxyl ca montmorilonit. Theo mt s nghin cu th nh ca cc t din SiO2 hng ra ngo i ca lp cu trc, cc nguyn t oxi c thay th bi cc nhm hiroxyl v cc nhm ny m nhim vic duy tr lin kt yu gia cc lp v gp phn vo s cn bng in tch. Ngoi ra trong cu trc ca bentonit cn c cc nhm hiroxyl khc nm nh cc bt din. Trong su nh ca bt din c hai nh l nhm OH cn bn nh kia l oxi, trong nhm hiroxyl ca lin kt Si OH khng c kh nng trao i hiro. Nhm hiroxyl ca lin kt Al OH c tnh axit yu nn kh nng trao i yu. Nhm Si O Al c tnh trao i mnh nn c tnh quyt nh n trao i cation H+. 1.1.2.2. Tnh cht trng n [9,37] Khi nc, cc phn t phn cc hoc cc cation b hp ph vo khe trng gia cc lp s lm tng chiu dy lp cu trc, tnh cht n y gi l tnh cht trng n. Mc trng n ph thuc vo bn cht khong st, cation trao i, s thay th ng hnh ca cc ion trong cc lp v s c mt ca cc ion, cc phn t phn cc trong mi trng phn tn. Lng nc c hp ph vo gia cc lp st ph thuc vo kh nng hydrat ha ca cc cation trao i. Khi bentonit hp ph hi nc hay tip xc vi nc, cc phn t nc phn cc s thm nhp vo bn trong cc lp, lm kho ng cch ny tng ln t nht 1415 ty thuc vo loi bentonit v lng nc b hp ph. S tng khong cch d 001 c gii thch l do s hydrat ha ca cc cation gia cc lp. trng n ca bentonit ph thuc vo bn cht cation trao i trn b mt lp st. V d, ion Na+ vi in tch +1 c th lin kt vi mt tm tch in m trn m t lp st. Do vy khi b hyrat ha, bentonit Na c kh nng trng n t khong cch ban u gia 2 phin st l t 9,2 n t nh t 17. Trong mi trng kim

bentonit-Na b hirat ha mnh hn, lp nc hp ph tng mnh. Do vy trong mi trng kim, huyn ph bentonit-Na rt bn vng. Cation Ca2+ lin kt vi 2 tm tch in m trn 2 phin st do vy khi bentonit-Ca b hydrat ha, khong cch gia 2 phin st ch tng t 12,1 n 17. iu n y h n ch s trng n hay kh nng to nht ca bentonit-Ca. trng n ca bentonit-Ca t 100 n 150%, i vi bentonit-Na trng n ln hn. 1.1.2.3. Tnh hp ph [1,7] Tnh cht hp ph ca bentonit c quyt nh bi c tnh b mt v cu trc lp ca chng. Vi kch thc ht nh hn 2m v c cu trc mng tinh th dng lp nn bentonit c b mt ring ln. Din tch b mt ca bentonit gm din tch b m t ngoi v din tch b mt trong. Din tch b mt trong c xc nh bi b m t ca khong khng gian gia cc lp trong cu trc tinh th. B mt ngoi ph thuc vo kch thc ht. S hp ph b mt trong ca bentonit c th xy ra vi cht b hp ph l cc ion v c, cc cht hu c dng ion hoc cht hu c phn cc. Cc cht hu c phn cc c kch thc v khi lng nh b hp ph bng cch to lin kt trc tip vi cc cation trao i nm gia cc lp hoc lin kt vi cc cation qua lin kt vi nc hoc lin kt vi cc trung tm mang in tch trn b mt cc lp st. Nu cc cht hu c phn cc c kch thc v khi lng phn t ln, chng c th kt hp trc tip vo v tr oxi y ca t din trong mng li tinh th bng lc Van der Walls hoc lin kt hiro. S hp ph cc cht hu c khng phn cc, cc polime v c bit l vi khun ch xy ra trn b mt ngo i ca bentonit [5,6]. Do bentonit c cu trc lp v phn tn cao nn c cu trc xp phc tp v b mt ring ln. Cu trc xp nh hng rt ln n tnh cht hp ph ca cc khong st, c trng ca n l tnh chn lc i vi cht b hp ph. Ch c phn t no c ng knh nh so vi l xp th mi chui vo c. Da vo iu ny

ngi ta c th dng bentonit hot ha lm vt liu tch cht. y cng l m t im khc nhau gia bentonit v cc cht hp ph khc. 1.1.2.4. Tnh kt dnh Khi trn vi nc, bentonit s c kh nng kt dnh mnh nn t thi xa xa con ngi bit s dng loi st ny nn th nh cc vt dng nhm mc ch phc v i sng. Li dng tnh cht kt dnh ny, trong cc xng c gang, bentonit c dng lm ch t kt dnh v qu ng bt thnh vin trc khi a vo l nung, hoc lm cht kt dnh trong khun ct c. 1.1.2.5. Tnh tr Bentonit tr v bn ha hc nn khng c, c th n c. Ngi ta dng bentonit lm cht n trong dc phm, thc n gia sc, m phm, lm ch t lc sch v ty mu cho bia, ru vang v m t ong... 1.1.2.6. Tnh nht v do Do c cu trc lp, c xp cao, c kh nng trng n mnh trong nc nn bentonit c tnh nht v do. Do c cc tnh cht n y m bentonit c s dng lm ph gia bi trn mi khoan, gia c thnh ca l khoan, lm ph gia trong xi mng Portland, ch va v ch t dnh kt c bit. 1.1.3. ng dng ca bentonit 1.1.3.1. Lm cht xc tc trong cc qu trnh tng hp hu c [1,10,12,28] Do c axit cao nn bentonit c th c dng lm cht xc tc trong cc phn ng hu c. B mt ca bentonit mang in tch m do s thay th ng hnh ca cc ion Si4+ bng ion Al3+ tm t din v ion Mg2+ thay th ion Al3+ tm bt din. Cc ion thay th Al3+, Mg2+ c kh nng cho in t nu ti in tch m ca chng khng c b tr bi cc ion dng. Do vy tm axit Lewis c to thnh t ion Al3+ v ion Mg2+ cc nh, cc ch gy nt v cc khuyt tt trn b m t bentonit. Nu lng Al3+ v Mg2+ tng ln b mt bentonit s lm tng axit Lewis ca chng.

Trn b mt bentonit tn ti cc nhm hiroxyl. Cc nhm hiroxyl c kh nng nhng proton hnh thnh trn b mt bentonit nhng tm axit Bronsted. S lng nhm hiroxyl c kh nng tch proton tng ln s lm tng axit trn b mt ca bentonit. Trong cc vt liu st chng (pillared clays), gia ct chng v cc lp aluminosilicat ca bentonit c nh ng lin kt cng ha tr thc s. Cc lin kt ny d n n s gii phng cc phn t nc v proton lm tng axit v b n ha cu trc ca bentonit chng. Vic b in tnh bentonit bng phng php trao i cation kim loi a ha tr nh Ti4+, Zr4+, Al3+, Si4+,... to ra vt liu st chng c axit v xp cao hn, c kh nng xc tc cho mt s phn ng hu c. V d ; vic s dng st chng lm cht xc tc axit rn trong phn ng hu c pha lng thun li hn nhiu so vi axit lng. Sau khi kt thc phn ng ch cn lc hn hp phn ng c th tch ch t xc tc rn ra khi hn hp phn ng. Ngoi ra, do bentonit c kh nng hp ph cao nn c th hp ph cc cht xc tc trn b mt trong gia cc lp. V vy, bentonit c s dng lm cht mang xc tc cho nhiu phn ng tng hp hu c. 1.1.3.2. Lm vt liu hp ph [18] Bentonit c dng rng ri lm ch t hp ph trong nhiu ngnh cng nghip. Trong cng nghip lc du, lng bentonit c s dng vi lng rt ln, bao gm bentonit t nhin v bentonit hot ha. Lng bentonit t nhin tiu tn cho qu trnh lc du l 25% khi lng du v lng bentonit ho t ha bng 10% khi lng du. Vic s dng bentonit lm cht hp ph u vit hn hn phng php c l phng php ra kim. Lng bentonit m t i trong qu trnh tinh ch ch bng 0,5% lng du c tinh ch. Ngoi ra, phng php dng bentonit cn c mc hao ph du thp do trnh c phn ng thy phn. Trong cng nghip ha than, bentonit c s dng tinh ch benzen th v cc bn sn phm khc.

Vi t cch l mt cht hp ph c bit tt, bentonit c th to ra cc dung d ch khoan vi cht lng c bit cao v chi ph nguyn liu thp. V th, cng vi s pht trin ca ngnh thm d v khai thc du, lng bentonit c s dng trong vic ch to dung dch khoan ngy cng tng. Ngy nay M, lng bentonit c s dng lm dung dch khoan chim ti 40% tng sn lng bentonit ca nc ny. Cc ch c nng quan trng ca bentonit trong dung dch khoan l: + Lm tng kh n ng lu chuyn ca dung dch khoan do c nht cao ngay c khi nng cht rn thp. + To huyn ph vi cc tc nhn v mn khoan gy lng khi ngng lu chuyn dung dch khoan v mt l do no . + Ngn cn s mt dung dch vo cc tng c p su t thp, thm nc nh vic to nn lp bnh lc khng thm nc trn thnh l khoan. Lp bnh lc ny khng ch ngn khi b mt dung dch m cn c tc dng nh mt ci mng cng lm bn thnh l khoan. Ngoi ra, do c kh nng hp ph tt n n bentonit cn c s dng lm ch t h p ph cc cht hu c v du m trong x l mi trng 1.1.3.3. Lm vt liu iu ch st hu c v nanocompozit [4,13] Gn y vi s pht trin mnh m ca cng ngh nano, nhiu ngnh cng nghip s dng bentonit ngy cng nhiu. Cng ngh nano s dng st hu c trn vi cc cht khc ch to ra cc vt liu mi. V d, st hu c c trn vi cc polime ch to cc nanocompozit, gi l composit-nano-bentonit. Cc polime c th c trn th m cc ht nanobentonit khi c ko th nh mng s cho m ng kn hn rt nhiu so vi polime khng trn v khi ko, cn, cc l nanobentonit ny n m song song vi b mt, c kh nng ngn cn hiu qu nhiu loi phn t i qua. Cc ht nanobentonit ny trn vi polime khng nhng kn m cn bn hn nhiu, do p ng yu cu lm cc ng mm truyn dn thuc, dn mu trong y t.

10

1.1.3.4. Dng trong mt s lnh vc khc Mt lng ln bentonit c s dng lm cht n trong cng nghip sn xut vt liu tng hp (x phng, vi si...). c bit trong cng nghip sn xut giy, vic trn thm bentonit lm tng hm lng cao lanh, gim lng xenlulo cn c trong giy, lm tng ng k cht lng v gim gi thnh ca giy. Trong cng nghip bia, ru, bentonit hp ph cc cht hu c, cc cht bo, cc sn phm ph khng mong mun trong qu trnh ln men, ng thi hp ph c ion st, ng v cc tc nhn gy b nh ca ru, li khng lm mt hng v ca ru, bia. Bentonit cn c s dng lm sch ngun nc mt. Do bentonit lm kt ta cc vn c, hp ph cc ion gy c, mt lng ln vi khun gy bnh v ch t hu c c trong nc vi gi thnh tng i r. Do c c tnh tr, khng c hi n n bentonit cn c dng lm ph gia trong thuc tiu ha thc n v gip iu tit axit cho ng vt, lm ph gia dc phm. 1.1.4. Lm giu, lm sch bentonit Cc m bentonit kim trn th gii thng c hm lng MMT cao, nn cc cng trnh nghin cu v lm giu, lm sch bentonit kim nng cao hm lng MMT-Na ca cc tc gi trn th gii khng nhiu. i vi nhng m bentonit kim c hm lng MMT cao nh bentonit kim Wyoming (M) ngi ta c th trc tip s dng m khng cn qua giai on lm giu, ho c bin tnh n thu c sn phm cho nhng mc ch khc nhau. Tuy nhin i vi loi qung bentonit c hm lng MMT thp - nh bentonit Tuy Phong, Bnh Thun ca Vit Nam, ngi ta phi s dng phng php tuyn trng lc nh ca cc tc gi cng trnh [2] hoc phng php t nh ca cc tc gi M cc cng trnh [3,4]. Theo phng php ny, bentonit c pha vi nc theo mt t l thch hp. S dng cht phn tn Na(PO3)6 lm lng cc khong

11

phi st theo nhiu giai on, sau huyn ph mn c lc, sy kh v nghin mn thu sn phm. Mt s tc gi khc s dng phng php tuyn thy xyclon, x l nhit v ha hc nng cao hm lng MMT trong bentonit. Trn th gii s lng khong bentonit kim th (cha cc cation Ca+2, Mg+2, ) vi hm lng MMT cao tng i nhiu, nhng dng bentonit kim li mang li nhiu ng dng hn trong nhiu lnh vc, v vy c rt nhiu nghin cu chuyn ha bentonit kim th v dng bentonit kim. Nhng nghin cu ny c t trc nhng nm 1950 ti nhiu nc nh M, Lin X c, ...[1,2,...]. Ngy nay cng ngh chuyn ha bentonit kim th sang dng bentonit kim c a vo nhiu nh my vn hnh v sn xut ra hng trm ngh n tn sn phm cho nhng lnh vc khc nhau, nh Hn Quc mi nm sn xut hn 800 ngh n tn sn phm bentonit hot ha cho nhng mc ch khc nhau. Phng php hot ha chuyn bentonit kim th v dng bentonit kim nh sau: qung bentonit kim th c phn cp, p, nghin n c ht thch hp. Sau qung c trn u vi tc nhn ho t ha (l cc mui ca natri nh Na2CO3, NaCl, ...) theo mt t l thch hp v nung hn hp trong l quay vi nhit trong khong 300500oC, sn phm hot ha sau y c ng bao v a i s dng. Mt iu ng lu y l qung bentonit kim th trn th gii thng c hm lng MMT cao nn qu ng c a vo hot ha ngay m khng qua giai on lm giu, cn i vi qung bentonit kim th Di Linh -Lm ng ca chng ta, do hm lng MMT khng cao (khong 3040%) nn s dng cho mt s mc ch ch to vt liu st hu c th trc khi hot ha nn lm giu qung nng hm lng MMT. Ngi ta cng s dng cc tc nhn hot ha khc nh axit v c (H2SO4, HNO3, HCl) v cc ch t hu c khc hot ha bentonit kim v bentonit kim th nhm thu nhanh cc sn phm hot ha cho nhng mc ch s dng khc nhau. 1.1.5. Gii thiu v bentonit Bnh Thun Vit Nam nc ta bentonit c pht hin nhiu ni: C nh (Thanh Ha), Di Linh (Lm ng), Bnh Thun, Mc Chu v.v... vi tr lng di do. Trong m

12

bentonit Bnh Thu n c tr lng ln hng trm triu tn, mi c tm th y nm 1987. Bnh Thun c c trng bi kh hu kh nng, lng ma t v l ni phn b rng ri magma giu kim (giu Na v K). Vi nhng c im trn bentonit to thnh b i hai qu trnh thy phn v qu trnh hp ph trao i cation. Tr lng c th khai thc c Nha M khong 42 triu tn cn thung lng Vnh Ho khong 33 triu tn [6]. Hm lng MMT-Na trong st Bnh Thun kh thp, khong t 12% n 20%. Tp cht ch yu trong khong st l canxit, th ch anh vi tinh th , phenspat, cao lanh. Trn bng 1.1 a ra thnh phn ha hc ca bentonit Bnh Thu n [3,6]. Trong thc t, ty theo mc ch s dng cho tng lnh vc m i hi v hm lng montmorilonit cng khc nhau, nh khi dng lm khun c trong ngnh thp hoc s dng trong nng nghip th c th dng bentonit nguyn khai hay ch qua khu x l qung s b, cn nu dng cho mc ch lm cht xc tc, s dng trong ngnh y, dng sn xut st hu c th i hi phi lm sch, lm giu bentonit nng hm lng montmorilonit trong bentonit ln cao. C hai phng php ho t ha bentonit thng c s dng l hot ha bng kim, hot ha bng axit. Bng 1.1. Thnh phn ha hc ca bentonit Bnh Thun Thnh ph n ha hc Hm lng (% trng lng) SiO2 Al2O3 Fe2O3 TiO2 FeO 68,4 9,26 2,1 0,49 0,48 CaO MgO K2O Na2O CO2 5,8 1,51 1,26 1,87 3,31

1.2. Gii thiu v st hu c [15]

St hu c l sn phm c to th nh bi s thay th cation v c trong mt s st thuc nhm smectit c th trao i vi cation hu c ca nhiu dng khc nhau. Cation hu c c s dng gm cc cation amoni hu c (bc 1, bc 2, bc 3, bc 4, mch thng, mch nhnh, mch vng), cc aminoaxit, ancol, trong

13

cc cation amoni hu c bc 4 c dng ph bin nht. C th l cc loi khong st montmorilonit, beidelit v nontronit c ch ha vi cc dung dch mui amoni hu c khc nhau. Khong st hp ph cc cation h u c, lm tng khong cch gia cc lp so vi cng loi khong st c lm bo ha bi cation nh hn nh canxi hoc hydro. Lin kt ca cc cation hu c vi lp silicat ca montmorilonit to thnh mt tp hp hu c - v c, c tnh cht c bit l a hu c, nn c kh nng hp ph cc hp ch t hu c trong mi trng lng tri hn h n khin chng tr th nh tim nng hu ch trong nhiu ng dng. Cc nghin cu v tng tc gia cc khong st v cc h p cht hu c c thc hin t nhng nm u ca th k XX v tng ln khng ngng v s lng v a dng v ti. Nghin cu s thm nhp ca cc phn t hu c vo khong cch gia cc lp ca cc khong st t nhin cng c bt u t nhng nm 20 ca th k XX, sau khi xut hin phng php nhiu x tia X vo nm 1913. Mt trong nhng b i bo sm nht l ca Smith vo nm 1934 thng bo v s tng tc ca khong st vi nicotin. Tuy nhin, vic ng dng cc khong st lm vt liu hp ph hu c th c con ngi thc hin sm nht l khong 7.000 nm trc cng nguyn. Hin nay, ng dng quan trng ca cc st hu c l trong lnh vc iu ch cc polime nanocompozit. Vic thm st hu c vo mi trng polime s lm tng cc tnh cht ha hc, vt l v c hc ca mi trng v lm gim gi th nh trong mt s trng hp. in hnh l st hu c thay th cc cht n (fillers) talc hoc thy tinh t l 3:1. V d, vic s dng 5% st hu c c th thay th cho 1550% cht n nh canxi cacbonat lm gim gi thnh v lm tng cc tnh cht c hc. St hu c l vt liu thng mi u th nht iu ch cc polime nanocompozit, chim khong 70% khi lng s dng [28]. St hu c cng c s dng trong nhiu lnh vc khc nhau. Cc ng dng ny bao gm cc cht hp ph, cc tc nhn kim sot tnh lu bin trong sn, du

14

m , m phm, cc sn phm chm sc dnh cho c nhn, cht lng khoan ging d u, lm cht hp ph du trn trn bin,... Trong s cc khong st, smectit, c bit l montmorilonit c s dng rng ri iu ch cc st hu c v cc tnh ch t c bit ca n, chng hn nh dung lng trao i ion cao, c kh nng trng n mnh, c cc tnh cht h p ph cao v din tch b mt ln. Ngoi montmorilonit, cc khong st khc cng c s dng, nh hectorit (Vougaris v Petridis, 2002), fluoro-hectorit tng hp nhn to (Gorassi v cc cng s, 2003), sepiollit (Akyz v Akyz, 2003),... 1.2.1. Cu trc ca st hu c [21-24,28] S tng tc ca khong st vi cc hp cht hu c c nhiu nh khoa hc nghin cu. Bn cht ca s tng tc ny l hp ph cc cht hu c phn cc nh ancol v lin kt ion gia cc cation v anion trn b mt v ra cnh ca cc lp st. Tuy nhin s hp ph cc phn t hu c ln cc trung tm in tch dng phn b b mt cnh v ra cc phin st thng rt nh nn t c xem xt. S hp ph cc cht hu c phn cc nh ru bc thp, glycol v cc amin trn b mt phin st c cha cc trung tm mang in tch m cng tng t nh h p ph nc cng mt mc nng lng hp ph nh nhau. V vy cc hp cht hu c phn cc khi tip xc vi cc khong st s d dng y v chim ch cc phn t nc n m khong khng gian gia 2 lp st to thnh st hu c. Cc phn t lin kt yu vi oxi b mt ca nh t din n v cu trc trong st bng lc Van der Walls. Do vy cc phn t hu c phn cc trn b mt lp st rt linh dng v d dng b thay th bng cc phn t khc. S nh hng ca cc ion amoni hu c trong cc khong st ln u tin c Lagaly v Weiss (1989) xut v c a ra trn hnh 1.2.

15

Hnh 1.2. Cc s nh hng ca cc ion ankyl amoni trong cc khong cch gia cc lp silicat: a) lp n; b) lp kp; c) lp gi tam phn t; v d), e) sp xp kiu parafin ca cc ion ankyl amoni vi gc nghing khc nhau ca cc mch ankyl. S sp xp khc nhau ca cc phn t hu c gia cc lp aluminosilicat ph thuc vo in tch ca lp st v di mch ca cc ion hu c. Nh c th thy trong hnh 1.2, cc ion hu c c th nm song song vi nhau trn b mt lp alumino silicat hnh thnh mt lp n, lp kp hoc gi tam phn t. Bn cnh mt cu trc nghing kiu parafin vi cc ui cha ra xa khi b mt c th c hnh thnh ph thuc vo m t sp xp v di mch. Trong cc lp gi tam phn t, mt s ui mch cacbon c th chuyn v tr ln mt lp khc, v vy s gin cch c xc nh bng d y ca ba mch ankyl ([Lagaly v Weiss, 1969], [Lagaly, 1981], [Lagaly, 1986] v [Bergaya v cc cng s. 2006]). S hnh thnh cc lp n, lp kp v lp gi tam phn t ca cc ion ankyl amoni gia cc lp aluminosilicat ca montmorilonit c Lagaly v cc cng s (1976) nghin cu. Khong cch gia cc lp aluminosilicat ca montmorilonit cha ankyl amoni thay i theo d i ca ankyl amoni (hnh 1.3).

16

Hnh 1.3. S thay i khong cch gia cc lp aluminosilicat ca montmorilonit cha ankyl amoni theo di mch cacbon (nc) do s to thnh cc lp n, cc lp kp, v cc lp gi tam phn t ca cc ion ankyl amoni Cu trc lp n c c trng bi khong cch gia cc lp aluminosilicat vo kho ng 1,35nm. S hnh thnh cu trc lp n l c th nu Ac(=), l din tch i hi cho cc cation sp xp nm dc theo lp vi nc nguyn t cacbon trong m ch, tr nn ln hn so vi din tch ng lng Ae, l din tch c th s dng c i vi mi cation c ha tr 1 trong mt lp n gia hai lp silicat. Nu nh Ac(=) > Ae, th ph n cu i ca cc mch ankyl s bt buc phi nm trong phm vi lp n. Khi xm phm gii hn Ac(=) = Ae, cc lp kp ca cc ion ankyl amoni n m phng s c hnh thnh vi cc khong khng c s khon g 1,75 nm. Cc cu trc lp kp khng th tn ti nu Ac(=) > 2 Ae. V cu trc 3 lp ca cc ion ankyl amoni l rt khng bn do s y in tch, cu trc cc mch ankyl s c hnh thnh theo kiu parafin. Trong cu trc theo kiu parafin, cc gc gia cc m ch v lp silicat tng ln khi tng in tch lp. V th , mc tng trung bnh ca khong cch gia cc lp aluminosilicat khi tng di m ch ca cation s bin i theo mt in tch ca b mt lp (Lagaly v Weiss, 1989).

17

Trong mt s trng hp, cc mch ankyl c xu hng hnh thnh cu trc theo kiu parafin hn l cc lp gi tam phn t. Xu hng n y do s t hp kiu parafin khin cc nhm amoni ph hp vi cc nguyn t oxi trn b mt hn so vi trng hp cc mch sp xp c kht trong cc lp gi tam phn t (Lagaly, 1986). Vi cu trc ca cc mch ankyl cng c th c m t theo thut ng ca cc vng v nh hnh v kt tinh tinh th ging nh m hnh hai pha ca polime, y s sp xp cc mch trong vng v nh h nh l thp hn khong 1020% so vi trong vng kt tinh (Lagaly v cc cng s 1976 ). Vaia v cc cng s (1994) ngh mt cch m t thc t hn da trn cc thc nghim v XRD v FTIR thm d cu trc gia cc lp v cu trc pha ca ankyl amoni. Bng cch theo di s chuyn d ch tn s dao ng ca nhm CH2 (giao ng ko cng v giao ng bt cho) nh l mt hm s ca sp xp c kht gia cc lp, d i m ch v nhit , h pht hin thy rng cc phn t thm nhp tn ti cc trng thi vi mc trt t khc nhau. Cc trng thi phn t bin i t ging pha rn sang ging pha lng. S c mt ca trng thi mt trt t c cu trc ging vi cht lng l ph bin hn trong khi mt trng thi c trt t (cu hnh tt c u l trans) ch c mt trong cc trng hp c bit. Ni chung, khi mt sp xp gia cc lp hoc di m ch gim xung ho c khi nhit tng ln th cc mch thm nhp s chp nhn mt cu trc ging cht lng mt trt t hn do s tng t s cu hnh gauche/trans. Khi gi tr din tch b mt/mol nm trong mt khong no cc chui mch ankyl c sp t khng hon ton mt trt t m gi li mt vi kiu sp t c trt t v nh hng nht nh, ging vi trng thi tinh th lng. V cc mch trong trng thi ging vi trng thi lng c t do chuyn ng v ti nh hng nn chng c th t n cn bng nhanh hn nhiu so vi khi chng trong trng thi rn.

18

Hnh 1.4 a ra cc kiu tp hp ui ankyl c Vaia v cc cng s (1994) a ra. Khi s cc nguyn t cacbon tng ln th s sp xp cc mch tun theo nhng cu trc c trt t hn.

Hnh 1.4. Cc cch tp hp ui ankyl c Vaia v cc cng s (1994) a ra: a) di mch ngn, lp n bn; b) di mch trung b nh, mt trt t trong mt phng v an vo nhau hnh thnh kiu lp kp; c) mch di: trt t gia cc lp tng ln dn n to thnh mt mi trng polime tinh th lng. Hackett v cc cng s (1998) s dng s m phng phn t nghin cu cc s nh hng ca cc ui ankyl trong cc khong st c bin tnh hu c. Hnh 1.5 a ra cc hnh nh ca cc phn t cht hot ng b mt trn cc lp aluminosilicat. S sp xp bn l mt lp n vi khong cch gia cc lp aluminosilicat l 1,32nm, trong khi lp kp v lp ba th tng ng vi cc kho ng cch gia cc lp aluminosilicat l 1,80nm v 2,27nm. Cc s m phng ch ra rng s sp xp mt trt t ca cc mch cacbon trng thi ging vi cht lng khng nm phng nh lp n thay vo li qun vo cc m ch trong lp i din. Trong lp kp, gn nh mt na s nhm CH2 trong lp i din vi nhm amoni, trong khi trong lp ba cc nhm CH2 c tr ng i s nhy vo lp gia nhng tng i t s lng ca nhm ny s c tm thy trong lp i din cui mch. Khi mt cation hu c tng cao, s tng di m ch cacbon lm tng tuyn tnh khong cch gia cc lp aluminosilicat, thng th cc cu trc vi khong cch gia cc lp aluminosilicat c sai lch ti thiu so vi khong cch trong cc cu trc lp n hoc lp kp s c hnh thnh. Cc ankan mch di to thnh cc cu trc vi mt s phn b rng ri ca khong cch gia cc lp lm

19

tng chiu rng ca cc pic XRD, mc d khong cch gia cc lp aluminosilicat vn rt gn vi mt lp n hoc lp kp.

Hnh 1.5. Mu phn t ca cc cht hot ng b mt vi cc di mch khc nhau thm nhp vo trong cc st c dung tch trao i cation khc nhau vi: a) lp n (C9, CEC = 0,9 meq/g); b) lp kp (C11, CEC = 1,0 meq/g); c) lp ba (C19, CEC = 1,5 meq/g) Mt phng php m t s sp xp mch cacbon ca cht hot ng b mt l thng qua s cc cu h nh trans v gauche. S phn trm cu hnh trans tng ln mt cch t ngt c quan h mt thit vi di m ch cc i trc khi h thng chuyn t lp n sang lp kp, bi v ti im ny, cc phn t cht hot ng b m t thch cu h nh tt c trans hn sp xp mt cch hiu qu nht v cung cp mt s cao nht cc nhm CH2 v CH3 trong phm vi mt lp n. Lin kt hyro gia cc phn t hu c vi khong st c th l quan trng, c bit i vi cc phn t c cha cc nhm OH, NH2, v NH3 (Moore v Reynolds, 1997). Trong ti ny chng ti s dng dodecyl ammoni clorua v cetyl trimetyl amoni bromua lm tc nhn hu c khuch tn vo khong khng gia cc lp trong cu trc ca bentonit.

20

1.2.2. Tnh cht v ng dng ca st hu c [17,21,29] 1.2.2.1. Tnh cht ca st hu c * Tnh hp ph Trong cu to ca st hu c c cc gc hirocacbon l nhm a du, m nn st hu c c kh nng hp ph cc cht hu c. V vy c nhiu cng trnh nghin cu s dng st hu c hp ph du trn trn bin, loi b cc cht hu c khi mi trng nc. * Tnh lu bin St hu c c kh nng trng n tt trong cc dung mi hu c, l cht a hu c. Khi c phn tn vo mi trng l cc ch t hu c n lm tng phn tn ca cc cht hu c. Do c ng dng trong nhiu lnh vc khc nhau nh trong lm ch t chng sa lng trong sn, trong mc in, lm sch nc b nhim bi d u m. 1.2.2.2. ng dng ca st hu c * Lm cht hp ph [25] St h u c c chc nng tng t nh cacbon hot tnh, nha trao i ion v mng lc tch du/nc. Bt st a du c th l 1 hp phn hoc nguyn liu chnh ca bt st ng t. Chng l cht hp ph cc mnh loi b du, cht hot ng b mt, v cc dung mi, bao gm metyl etyl xeton, t-butyl ancol (TBA) v cc cht khc. Do loi b du v du nhn t l th tch/khi lng cao, st a hu c c th tit kim ti 50% chi ph hoc hn. St hu c c th dng trong pha trn nhin liu nh my nha ng hoc lm cht n nh. ng dng mi trng ca st a h u c bao gm: lm sch nc b mt b i rc c v h cha nc ngm. ng dng trong cng nghip bao gm my nn khng kh, lm lnh nc, my nn kh. * Lm cht chng sa lng trong mi trng hu c [25,26]

21

Khc vi bentonit thng thng, st hu c trng n v to gel trong dung mi hu c. Nh vy st hu c ng dng trong nhiu lnh vc khc nhau. V d, trong cng nghip du kh st hu c c dng lm cht to cu trc cho dung d ch khoan, trong sn lu ha nhit, cht lm sch du trong nh tng du/nc. Ngoi ra, st hu c va c kh nng tan trong nc va c kh nng tan trong dung mi hu c nn khi kt hp vi cc phn t trong sn s to huyn ph. St hu c c cu trc rt n nh ngay c khi trong dung dch c mt mt lng ln cc cation kim lo i. bn ca cc st hu c cha cc cation amin b c 4 mt phn l do lc Van der Walls gia cc mch hirocacbon vi b mt st. V vy, huyn ph bentonit hu c trong du kh n nh nhit, iu ny cho php st hu c c ng dng trong vic lm ch t chng sa lng trong mi trng hu c nh sn, du, mc in, du nhn * Lm nguyn liu iu ch nanocompozit [7,9,16] Vt liu st hu c c th cho vo polime, cht do, nha to ra vt liu nanocompozit c sc bn cu trc c nng cao. Cng c th s dng st hu c lm ph gia lu bin nh cht c ch s chy. Vt liu st stevensit - h u c c tnh cht thun li l d th v d dng to ra do to thnh sn phm cui. Hn na, tnh cht ca vt liu ny l d phn tn hn nhiu, v d trong polime, do s phn b in tch thch hp hn, tnh cht k nc, s tch lp, s sp xp v kch thc thch hp hn. 1.2.3. Cc phng php iu ch st hu c [32,33,38] Qu trnh tng hp st hu c da trn cc c ch ca cc phn ng m khong st c th c vi cc hp cht hu c. iu ch st hu c, ngi ta thng dng hai phng php ch yu sau: 1.2.3.1. Phng php t

22

Phng php t l phng php trao i gia cation hu c vi bentonit hot ha trong mi trng nc. C ba phng php iu ch st hu c trn c s phng php t: * Phng php khuch tn trong mi trng nc Phng php ny da trn s khuch tn ca cc cht hu c v bentonit trong mi trng nc. S khuch tn c thc hin nh khuy lin tc hn hp bentonit v cc tc nhn hu c trong mi trng nc iu kin (nhit , pH, t l hu c/st,..) nht nh. u im ca phng php ny l n gin, thc hin d dng v chi ph thp. y l phng php c s dng ph bin nht Vit Nam cng nh trn th gii. Mt dng thit b iu ch st hu c trong phng th nghim m chng ti s dng iu ch st hu c c a ra trn h nh 1.6.

Hnh 1.6. Thit b iu ch st hu c theo phng php khuych tn trong nc trong phng th nghim c dung tch 2 lt v 10 lt

* Phng php l vi sng Tng t phng php khuch tn th phng php l vi sng cng c thc hin trong mi trng nc, tuy nhin phng php ny da trn nguyn tc s dng vi sng tc dng ln hn hp phn ng v c thc hin trong l vi sng. u

23

im ca phng php ny l cho hiu sut cao hn phng php khuch tn, tuy nhin do chi ph ln v thit b v nng lng nn phng php n y cha c ng dng rng ri. * Phng php thy nhit Trong phng php ny, qu trnh iu ch st hu c c thc hin trong thit b thy nhit, c th thc hin phn ng nhit cao v p sut cao. Phng php thy nhit c nhiu u im: - Cho php iu ch sn phm c tnh ng nht cao, vi thnh phn ha hc c iu chnh mt cch d dng: qu trnh cho php ly nhng lng chnh xc cht u trn vi nhau theo t l ha hc ca sn phm t c nh mong mun. iu ny c bit quan trng trong vic tng hp cc vt liu cao cp, i hi t l chnh xc ca cc cu t trong vt liu. - Cho php iu chnh c tnh ch t ca sn phm thng qua iu chnh cc iu kin phn ng nh: pH, nhit , nng , tc , thi gian ca s thy phn, s kt tinh nh hng hnh thi hc, ln v tnh cht ca cc ht sn phm cui cng. Tuy nhin phng php ny cha c s dng rng ri v thit b s dng trong phng php thy nhit rt t tin v dung lng nh. 1.2.3.2. Phng php kh Theo phng php ny, phn ng trao i gia cation vi bentonit c thc hin bng cch trn ln chng trong thit b trn c bit kiu warning type blender cng vi nh mt lng nh nc v dung mi phn cc khng cha proton nh propylencacbonat, etylencacbonat... Ngoi ra mt tc gi ngh thm mt lng nh (< 1%) Na2CO3 vo hn hp tng hiu qu phn ng. Cc phn t hu c c th thm nhp vo trong cc khong st kh b ng phn ng pha rn m khng cn dng dung mi. S vng mt cc dung mi trong qu

24

trnh iu ch l mi trng tt v lm cho qu trnh iu ch ph h p hn vi vic cng nghip ha. S thm nhp ca cc hp cht trung tnh vo st kh montmorilonit v vermiculit kh l v d khng cn thit phi c gii thch bng s vn chuyn chng gia cc lp st. Cc cation c th duy tr s tip xc vi mt lp st, ngha l cc nguyn t oxi ca b mt silicat chim c cc v tr phi tr ca cc cation. Th i gian phn ng theo phng php kh thng ngn hn so vi phng php t. Tuy nhin trong thc t nu sn xut bentonit hu c theo phng php kh m c hp ph thay th bng cc cation hu c ch t c gi tr cc i l 80% trn b mt lp st [34]. Do vy trong thc t ngi ta t p dng phng php kh sn xut bentonit hu c. Trong qu trnh nghin cu xy dng quy trnh iu ch st hu c trong phng th nghim, chng ti s dng phng php khuch tn trong dung dch nc v ph ng php ny d thc hin, trang thit b n gin v c bit l n d trin khai vi quy m sn xut ln trong thc t sau ny.

1.3. Mc ch v ni dung nghin cu ca lun vn

1.3.1. Mc ch Tm c cc iu kin thch hp v t l cht hu c/bentonit, nhit huyn ph, pH huyn ph v thi gian khuy trn cho qu trnh iu ch st hu c t bentonit Bnh Thun hm lng >90% vi dodecylamoni clorua v cetyl trimetyl amoni bromua. T xy dng c quy trnh chu n iu ch st hu c t bentonit Bnh Thun >90% v hai amin trn vi quy m phng th nghim. 1.3.2. Ni dung nghin cu t c mc ch nu trn chng ti s thc hin nhng n i dung nghin cu sau:

25

* iu ch st hu c t bentonit Bnh Thun hm lng >90% v cetyl trimetyl amoni bromua (CTAB) - Kho st nh hng ca t l cetyl trimetyl amoni bromua/bentonit - Kho st nh hng ca nhit huyn ph - Kho st nh hng ca pH huyn ph - Kho st nh hng ca thi gian khuy trn - Xy d ng quy trnh iu ch chun - p dng iu ch sn phm st hu c c cht lng cao * iu ch st hu c t bentonit Bnh Thu n hm lng >90% v dodecyl amoni clorua (DAC) - Kho st nh hng ca t l dodecyl amoni clorua/bentonit - Kho st nh hng ca nhit huyn ph - Kho st nh hng ca pH huyn ph - Kho st nh hng ca thi gian khuy trn - Xy d ng quy trnh iu ch chun - p dng iu ch sn phm st hu c c cht lng cao

26

CHNG II. THC NGHIM

2.1. Ha cht, dng c v thit b
2.1.1. Ha cht * Bentonit Bnh Thun (Vit Nam) qua tinh ch, lm giu v hot ha bng axit, c hm lng bentonit >90% v c dung lng hp ph >90mlg/100g st. * Tc nhn hu c: - Cetyl trimetyl amoni clorua (k hiu l CTAB) l thng phm ca h ng Merk (CHLB c), c cng thc C19H42NBr, l cht bt mu trng, c khi lng phn t 364,46 g/mol, nhit nng chy 250-256oC. - Dodecylamin (DA) l thng phm ca hng Merck, c cng th c phn t C12H27N, l ch t rn mu trng, khi lng phn t 185,346 g/mol, nhit nng chy 28-30 oC, nhit si 247-249oC, khi lng ring 0,806 g/cm3. * Ha ch t ph tr khc: - Etanol (Merck) - Axit HCl (China) - NaOH (China) 2.1.2. Dng c - Cc chu nhit 250 ml, 1lt, 2 lt - a, th a thy tinh - Pipet 5 ml, 2 ml - ng ong 100 ml - Ph u lc chn khng bng thy tinh c mng lc bng s. - Ci nghin s ng knh = 15cm 2.1.3. Thit b - My khu y t gia nhit Veia ca Cole Parmer Instrument Company - T sy chn khng Memmert (c) - My nhiu x tia X D8 Advanced Brucker (c).

27

- Cn Mettler Tolledo (Thy S) c chnh xc 0,0001g - My phn tch nhit Labsys TG/DSC SETARAM (Php).

2.2. Phng php iu ch st hu c

2.2.1. Chuyn dodecylamin thnh mui dodecyl amoni clorua Dodecylamin s dng trong ti ny l amin m ch di t tan trong nc, mt khc s h nh thnh st hu c l s thay th cc cation v c gia cc lp st bng cc cation hu c, v vy qu trnh iu ch t hiu qu cao chng ti chuyn amin ny thnh d ng mui amoni d tan. Di y l cc bc chuyn dodecylamin thnh mui dodecyl amoni clorua (DAC): - Cn lng chnh xc dodecylamin, cho vo cc 250 ml. - Ha tan amin bng etanol 96%. - Thm t t HCl c (d 10%), va thm va khuy u cho phn ng hon ton. - C cn ui axit d

2.2.2. Qui trnh iu ch st hu c

Qu trnh iu ch st hu c c th c tin hnh theo cc phng php t hoc kh. Tuy nhin hin ti chng ti khng c thit b nghin trn km gia nhit thch hp cho vic iu ch st hu c theo phng php kh, nn chng ti chn phng php t da vo qu trnh trao i cation amoni hu c vi cc cation c trong lp st v trn b mt st trong dung dch nc trong iu kin thng. Trong lun vn ny chng ti tin hnh iu ch st hu c t bentonit Bnh Thun v hai tc nhn hu c l cetyl trimetyl amoni clorua (k hiu l CTAB) v mui dodecyl amoni clorua (DAC) b ng phng php khuch tn trong mi trng nc. Cc bc iu ch gm: - Cn lng chnh xc bentonit bng cn in t c chnh xc 0,0001g. Ha vo mt th tch nc ct thch hp trong cc chu nhit. Khuy mnh nhit khong 70oC trong 2h st trng n ti a, to huyn ph bentonit.

28

- Cn chnh xc lng mui amoni hu c bng cn in t c chnh xc 0,0001g. Ha tan lng mui ny vo m t th tch nc ct nht nh. iu nhit dung dch trong 1h. - iu chnh pH ca c hai dung d ch n gi tr ph hp (s dng cc dung d ch HCl v NaOH long v giy ch th pH ca hng Merk). - t t dung dch mui amin vo huyn ph bentonit, ng thi khuy lin tc trong mt khong thi gian nht nh trn my khuy t gia nhit Veia ca Cole Parmer Instrument Company. Kim tra pH, nhit ca dung dch phn ng v gi n nh trong sut thi gian tin hnh phn ng. - Lc nng bng phu lc c bm ht chn khng. Ra sn phm t nht 3 ln b ng nc ct nng. - Sy sn phm trong t sy chn khng trong 24h 800C. Ly sn phm ra nghin bng ci s thnh bt mn. - Xc nh cu trc v tnh cht ca sn phm bng cc phng php: phng php nhiu x tia X; phng php phn tch nhit.

2.3. Cc phng php nghin cu cu trc v tnh cht vt liu

Trong ti ny chng ti s dng cc phng php: phng php nhiu x tia X; phng php phn tch nhit xc nh cu trc v tnh ca sn phm. 2.3.1. Phng php nhiu x tia X Cc m u bentonit v cc sn phm st hu c c xc nh cu trc bng phng php nhiu x tia X. Gin XRD ca cc mu c ghi trn nhiu x k Advanced Brucker (CHLB c) ti Khoa Ha hc, Trng i Hc Khoa Hc T Nhin. Vi cc iu kin ghi nh sau: + UAK = 40 KV, IAK = 40mA. + ng anot bng Cu c bc sng Cu K: 1,54056. + Bc ghi: 0.030/step. + Thi gian ghi cho mi bc: 0.6s/step. + Khong ghi 2: t 0.50 n 10 0. + Mi trng khng kh.

29

Cu trc lp ca bentonit v kho ng cch gia cc lp (d001) c xc nh da vo v tr pic nhiu x trn gin XRD. 2.3.2. Phng php phn tch nhit Cc sn phm st hu c v mu bentonit Bnh Thun (dng so snh) c tin h nh ghi gin phn tch nhit trn my Labsys TG/DSC SETARAM (Php), ti Khoa Ha Hc, Trng i Hc Khoa Hc T Nhin. Vi cc ch ghi nh sau: + Khong ghi nhit : t nhit phng n 8000C. + Tc nng nhit : 5 0/pht. + Mi trng khng kh. Hm lng hu c trong st hu c (%) ca cation amoni hu c vo bentonit c xc nh bng hiu cc pic mt khi lng trn gin phn tch nhit ca m u st c ch ha khi c mt v khng c m t mui amoni. C th, ly hai mu bentonit c khi lng bng nhau trong mt mu l bentonit khng c tc nhn hu c v mt mu l st hu c c iu ch theo quy trnh 2.2.2. Sau tin hnh ghi gin phn tch nhit ca hai mu trn. Hm lng cation amoni hu c trong st hu c c xc nh theo cng thc: m(%) = mhc(%) - mbent (%) Trong : m(%): hm lng hu c trong st hu c m hc(%): tng % cc pic mt khi lng ca mu st hu c m bent (%): tng % cc pic mt khi lng ca mu bentonit c ch ha khng c tc nhn hu c.

30

CHNG III. KT QU NGHIN CU V THO LUN

Khi c khu y trn vi bentonit, cc cation amoni hu c trong dung dch mui amin s thm nhp v trao i vi cc cation vng khng gian gia cc lp st. Qu trnh ny lm tng kho ng cch gia cc lp st, tc lm tng gi tr d001 hay tng ng lm gim gi tr gc 2 ng vi pic cc i trn gin . Hm lng amoni hu c trong sn phm st hu c thu c th hin mc thm nhp ca cc cation amoni hu c vo khong khng gian gia cc lp st. C rt nhiu yu t nh hng ti s thm nhp ca cc cation amoni hu c vo gia cc lp st. Trong lu n vn ny chng ti kho st bn yu t nh hng n khong cch gia cc lp st (d 001) v hm lng hu c trong sn phm, theo chng ti l quan trng nht, l: t l mui amoni hu c/bentonit; nhit huyn ph; pH ca dung d ch; thi gian phn ng.

3.1. Kho st qu trnh iu ch st hu c t bentonit v CTAB

3.1.1. Kho st cc yu t nh hng trong qu trnh iu ch n gi tr d001 v hm lng amoni hu c trong st hu c t bentonit v CTAB 3.1.1.1. nh hng ca t l cation amoni hu c/bentonit T l CTAB/bentonit s dng trong vic iu ch st hu c l mt yu t rt quan trng. T l ny nh s d n n hm lng hu c trong sn phm st hu c th p, khong cch gia cc lp st thp, cn nu qu ln th s b d tha gy lng ph ha ch t, khng c hiu qu kinh t. V vy, trc tin chng ti t vn kho st nh hng ca t l CTAB/bentonit n cht lng st hu c c nh gi thng qua gi trh d001 v hm lng hu c c trong sn phm. Cc m u st hu c c iu ch theo quy trnh nu mc 2.2.2 vi cc iu kin c th nh sau : huyn ph (bentonit v mui amoni hu c) c iu chnh n pH bng 7, nhit 600C v c khuy trn trong thi gian 5h, tc khuy n nh 500 vng/pht, t l CTAB/bentonit c bin i t 90 n 170mmol/100g bentonit kh. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2 v khong cch

31

gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c, t nh gi c mc thm nhp ca cation amoni hu c vo bentonit, tm c mc nh hng ca yu t ang kho st n gi tr d001 ca sn phm st hu c v hm lng hu c trong sn phm. Cui cng xc nh c iu kin thch hp nh t cho qu trnh iu ch st hu c. T gin nhiu x tia X v gin phn tch nhit, chng ti a ra kt qu kho st nh hng ca t l CTAB/bentonit n gi tr d001 v hm lng cation cetyl trimetyl amoni trong sn phm trong bng 3.1. Bng 3.1. Kt qu kho st nh hng ca t l CTAB/bentonit n gi tr d001 v hm lng cation cetyl trimetyl amoni trong sn phm
T l CTAB/bentonit (mmol/g) d 001 () Hm lng hu c trong sn phm (%) 90 100 110 120 130 140 150 160 170

30,74 34,85 36,52 38,47 39,53 40,65 39,85 39,57 39,02 18,46 21,32 24,74 26,23 27,71 28,20 28,12 26,56 24,29

* nh hng ca t l CTAB/bentonit n gi tr d001 Gin XRD ca mu st hu c c iu ch t CTAB v bentonit Bnh Thun hm lng >90% t l CTAB/bentonit l 140mmol/100g c a ra trn hnh 3.1.

Hnh 3.1. Gin XRD ca mu st h u c iu ch t CTAB v bentonit Bnh Thun hm lng >90% t l CTAB/bentonit l 140mmol/100g

32

T gin trn ta thy r, st hu c iu ch c c cu trc lp vi gi tr d 001 = 40,650 tng ng gc 2 ~ 2,17 o. Gin XRD ca cc mu st hu c iu ch vi cc t l CTAB/bentonit (mmol/100g) khc nhau c a ra h nh 3.2.

Hnh 3.2. Gin XRD ca cc mu st hu c c iu ch cc t l CTAB/bentonit khc nhau (mmol/100g bentonit kh) T cc gin XRD trn hnh 3.2 c th thy, cc m u st hu c iu ch c u c cu trc lp vi gi tr d001 kh ln thay i t ~30 n ~ 40 . th s ph thuc ca gi tr d001 vo t l CTAB/bentonit (mmol/100g) c a ra h nh 3.3. T cc gin XRD thu c trn hnh 3.2 v th trn hnh 3.3 c th thy, khi lng CTAB trong dung dch tng, tng ng vi t l CTAB/bentonit (mmol/100g) tng t 90 n 140, th khong cch gia cc lp st tng ln, th hin gi tr d001 tng ln t 30,74 n 40,65 ; gi tr 2 ca pic cc i gim t 2,87o xung 2,17o.

33

45

40

Gi tr d(001), angstron

35

30

25

20 80 90 1 00 1 1 0 1 20 1 30 1 40 1 50 1 60 1 70 1 80

T l CTAB/bentonite (m m ol/100g)

Hnh 3.3. S ph thuc gi tr d 001 vo t l CTAB/bentonit Tuy nhin sau th s tng lng CTAB trong dung dch c xu hng lm gim khong cch d 001. iu ny c th c gii thch nh sau: thi im u , tng ng vi s tng t l CTAB/bentonit, s trao i gia cation hu c vi cc cation v c c m t gia cc lp st xy ra m nh hn nn gi tr d001 tng ln ; nhng khi t l CTAB/100g bentonit t n gi tr 140mmol/100g th nng cation amoni hu c trong huyn ph st c th coi l t bo ha. Khi t l CTAB/bentonit vt qu gi tr 140mmol/100g th cc ui hu c ca cc ion amoni hu c trong dung dch nc c xu hng tp hp li thnh ht keo, cc ht keo c b mt tch in d ng, c kch thc ln nn khng c kh nng thm nhp nn qu trnh trao i ca cc cation hu c vi cation v c gim ; v vy gi tr d001 dn gim xung, tng ng vi gi tr 2 ca pic cc i tng ln. Nh vy, khi tin hnh kho st s ph thuc ca gi tr d001 vo dy t l CTAB/bentonit, chng ti nh n thy rng ti t l CTAB/bentonit bng 140mmol/100g, gi tr d001 ln nht, tc khong cch gia cc lp st hu c l ln nht. V vy, chng ti c th kt lun, t l CTAB/bentonit thch hp nht thu c sn phm st hu c c khong cch gia cc lp st cao l 140mmol/100g, ti

34

t l ny, gi tr d 001 t ~40 . Gi tr t l ny c s dng trong cc nghin cu tip sau. * nh hng ca t l CTAB/bentonit n hm lng hu c trong sn ph m xc nh hm lng cc cation amoni h u c trong sn phm, chng ti tin h nh ghi gin phn tch nhit ca cc mu bentonit c ch ha khi c mt v khng c mt cc mui amoni hu c. Trong hnh 3.4 l v d v gin phn tch nhit c a mt mu st hu c iu ch t CTAB v bentonit Bnh Thun hm lng >90% ti t l CTAB/bentonit l 140mmol/100g.
Figure: Labsys TG TG/% 40 Peak :106.54 C 30 10 Experiment: Thuy Anh-CTAB-140 30 ----> 800C (10C.min-1) (Zone 2) HeatFlow/V Exo Crucible: PT 100 l Atmosphere: Air Mass (mg): 56.242 0 04/07/2009 Procedure:

dTG/%/min

20

Peak :282.88 C Peak :446.31 C

-4

10 Peak 1 :65.72 C Peak 2 :110.64 C 0 Mass variation: -3.79 % -10 Mass variation: -17.31 % -20

-8 -10

-12 -30 Mass variation: -18.60 % -20

-40

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.4. Gin phn tch nhit ca mu st hu c iu ch t CTAB v bentonit Bnh Thun hm lng >90% t l CTAB/bentonit l 140mmol/100g Hnh 3.4 cho thy c 3 hiu ng mt khi lng ti 106,54 oC (-3,79%), ti 282,88oC (-17,31%) v 446,31 oC (-18,60%). Cc hiu ng ny u c km theo hiu ng thu nhit trn ng DTA v c chng ti quy gn cho qu trnh m t nc cu trc v phn hy ca cetyl trimetyl amoni trong mu. Tng khi lng m t khi nung ca mu st hu c tnh c l 39,70%.

35

Vi mu st c ch ha tng t nhng khng c tc nhn hu c, gin phn tch nhit c a ra trn hnh 3.5. Trn gin 3.5 c xut hin cc pic 140,26oC (-7,44%) v 670,36oC (-4,06%) tng ng vi tng khi lng mt khi nung l 11,50%.
Figure: Labsys TG 30/05/2009 Experiment: Procedure: Bentonit Binh Thuan >90% 30 ----> 800C (10 C.min-1) (Zone 2) Crucible: PT 100 l Atmosphere: Air Mass (mg): 53.47

TG/%

HeatFlow/V Exo
Peak :670.35 C

d TG/%/min 10

7 0 -2

Peak :140.26 C

-10 -4

Mass variation: -7.44 %

-20

-7 -30
Mass variation: -4.06 %

-6

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.5. Gin phn tch nhit ca mu st c ch ha tng t nhng khng c tc nhn hu c Hm lng amoni hu c trong sn phm st hu c c tnh ton theo cng thc nu mc 2.3.2. m(%) = mhc(%) - mbent (%) Vy hm lng cation cetyltrimetylamoni trong sn phm st hu c iu ch t CTAB v bentonit Bnh Thu n t l CTAB/bentonit l 140mmol/100g bng: 39,70% - 11,50% = 28,2%. Hm lng cation cetyl trimetyl amoni trong cc mu st h u c iu ch t CTAB v bentonit Bnh Thun cc t l CTAB/bentonit khc cng c cn c theo gin phn tch nhit v c xc nh tng t.

36

Kt qu kho st nh hng ca t l CTAB/bentonit n hm lng cation cetyl trimetyl amoni trong sn phm c a ra trong bng 3.1. th s ph thuc ca hm lng hu c trong sn phm vo t l CTAB/bentonit (mmol/100g) c a ra hnh 3.6.
30 28

Hm lng hu c trong st,%

26 24 22 20 1 8 1 6 1 4 1 2 1 0 80 90 1 00 1 1 0 1 20 1 30 1 40 1 50 1 60 1 70 1 80

T l CTAB/bentonite (m m ol/100g)

Hnh 3.6. S ph thuc ca hm lng hu c trong sn phm st h u c iu ch c vo t l CTAB/bentonit T th trn hnh 3.6 c th thy, khi nng CTAB trong huyn ph st tng tng ng vi t l CTAB/bentonit thay i t 90 n 140mmol/100g, hm lng cation cetyl trimetyl amoni trong sn phm tng ln v t cc i l 28,20% ti t l CTAB/bentonit l 140mmol/100g. Tuy nhin sau th s tng nng CTAB trong huyn ph bentonit khng lm bin i ng k hm lng amoni hu c trong sn phm na. iu n y c th c gii thch tng t nh i vi gi tr d001. Tc l ti t l CTAB/bentonit b ng 140mmol/100g, nng cation cetyl trimetyl trong huyn ph st cng nh hm lng ca n trong khng gian gia cc lp st coi nh t bo ha. Nu t l CTAB/bentonit tng vt qu gi tr 140mmol/100g th hm lng cation amoni hu c trong sn phm gim xung do cc ui hu c ca amin c xu hng tp h p thnh cc h t keo khng c kh nng thm nhp vo gia cc lp st. Kt lun:

37

Qua kt qu kho st mc nh hng ca t l CTAB/bentonit n gi tr d 001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi tin hnh khuy trn huyn ph (CTAB v bentonit) trong thi gian 5h, nhit huyn ph l 60oC, pH b n g 7 th ti t l CTAB/bentonit l 140mmol/100g, gi tr d001 t cc i bng 40,65 v hm lng cation cetyl trimetyl amoni cng t cc i b ng 28,20%. Nh vy theo chng ti, t l CTAB/bentonit thch h p iu ch st h u c t CTAB v bentonit Bnh Thu n hm lng >90% l 140mmol/100g. Chng ti duy tr iu kin n y trong cc th nghim tip theo. 3.1.1.2. nh hng ca nhit huyn ph Theo cc cng trnh khoa hc [25,26] cng b th nhit c nh hng kh ln n qu trnh iu ch st hu c. Nu nhit qu thp th s thm nhp ca cc cation hu c vo bentonit thp. V vy yu t th hai m chng ti tin hnh kh o st l nh hng ca nhit huyn ph, t tm ra nhit thch hp cho qu trnh iu ch st hu c t bentonit Bnh Thun v CTAB. Cc m u st hu c c iu ch theo quy trnh nu mc 2.2.2 vi cc iu kin c th nh sau: huyn ph (bentonit v mui amoni hu c) c t l CTAB/bentonit l 140mmol/100g c iu chnh n pH bng 7 v c khuy trn trong thi gian 5h, tc khuy n nh 500 vng/pht. Nhit huyn ph c bin i t 30 n 90oC. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2 v khong cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c, t nh gi c mc thm nhp ca cation amoni hu c vo bentonit, tm c mc nh hng ca yu t ang kho st n gi tr d 001 ca sn phm st hu c v hm lng hu c trong sn phm. Cui cng xc nh c iu kin thch hp nht cho qu trnh iu ch st hu c.

38

T gin nhiu x tia X v gin phn tch nhit, chng ti a ra kt qu kho st nh hng ca nhit huyn ph n gi tr d001 v hm lng cation cetyl trimetyl amoni trong sn phm trong bng 3.2. Bng 3.2. Kt qu kho st nh hng ca nhit huyn ph n gi tr d 001 v hm lng cation cetyl trimetyl amoni trong sn phm
Nhit huyn ph (oC) d 001 () Hm lng hu c trong sn phm (%) 30 29,125 18,57 40 34,217 21,13 50 60 70 80 90 40,953 26,40

37,192 40,057 23,24 25,64

40,168 40,621 26,10 26,35

* nh hng ca nhit huyn ph n gi tr d001 Gin XRD ca mt mu st tiu biu c a ra trn h nh 3.7.

Hnh 3.7. Gin XRD ca mu st hu c iu ch t CTAB v bentonit Bnh Thun hm lng >90% nhit huyn ph bng 60oC T gin trn ta thy r, st hu c iu ch c c cu trc lp vi gi tr d 001 = 40,057 tng ng gc 2 ~ 2,20o. Gin XRD ca cc mu st hu c c iu ch cc nhit huyn ph khc nhau c a ra hnh 3.8. T cc gin XRD trn hnh 3.8, c th thy

39

cc mu st hu c iu ch c u c cu trc lp vi gi tr d001 kh ln thay i t ~29 n ~40.

Hnh 3.8. Gin XRD ca cc mu st hu c c iu ch cc nhit huyn ph khc nhau th s ph thuc ca gi tr d001 vo nhit huyn ph c a ra hnh 3.9. T cc gin XRD thu c trn hnh 3.8 v th trn hnh 3.9 c th thy, khi nhit huyn ph tng t 30 n 60 oC, th khong cch gia cc lp st tng ln kh nhanh, th hin gi tr d001 tng ln t 29,125 n 40,057; gi tr 2 ca pic cc i gim t 3,03 xung 2,203o. Nu tip tc tng nhit th gi tr d001 vn tng ln nhng mc tng gim xung, s bin i n y c th c gii thch l do khi tng nhit huyn ph, tc chuyn ng ca cc ion trao i tng ln, nn qu trnh trao i gia cc cation hu c v v c din ra mnh hn. Tuy nhin, kh nng trao i cng ch tng n mt mc nht nh, v vy nhit cao hn 60oC, nh hng ca nhit ln gi tr d001 l khng ng k.

40

43 41 39

Gi tr d(001), angstron

37 35 33 31 29 27 25 20 30 40 50 60 70 80 90 1 00

Nhit huyn ph (oC)

Hnh 3.9. S ph thuc gi tr d001 ca sn phm st hu c vo nhit huyn ph Chng ti c th kt lun, nhit huyn ph thch hp nht thu c sn phm st hu c c khong cch gia cc lp st cao l 60oC, ti nhit ny, gi tr d001 t ~40. * nh hng ca nhit huyn ph n hm lng hu c trong sn phm
29

27

Hm lng hu c trong st,%

25

23

21

1 9

1 7

1 5 20 30 40 50 60 70 80 90 1 00

Nhit huyn ph (oC)

Hnh 3.10. S ph thuc ca hm lng cation cetyl trimetyl amoni trong sn phm vo nhit huyn ph

41

 xc nh hm lng cc cation amoni hu c trong sn phm, chng ti tin h nh ghi gin phn tch nhit ca cc mu bentonit c ch ha khi c mt v khng c m t cc mui amoni hu c. Hm lng amoni hu c trong sn phm st hu c c tnh ton theo cng thc nu mc 2.3.2. Kt qu kho st nh hng ca nhit huyn ph n hm lng cation cetyl trimetyl amoni trong sn phm c a ra trong b ng 3.2. th s ph thuc ca h m lng cation cetyl trimetyl amoni trong sn phm vo nhit huyn ph c a ra hnh 3.10. T th trn hnh 3.10, c th thy rng, khi nhit huyn ph tng t 30 n 60oC, hm lng cation amoni h u c trong sn phm st tng dn, t cc i nhit huyn ph 60 oC b ng 25,64%. Nu tip tc tng nhit huyn ph ln cao hn 60 oC, hm lng hu c trong sn phm vn tng ln, nhng tc tng rt chm, c th coi l khng thay i. V vy, chng ti cho rng nhit huyn ph thch hp nht iu ch sn phm st hu c c hm lng cation cetyl trimetyl amoni tng i cao l 60oC. Kt lun: Qua kt qu kho st mc nh hng ca nhit huyn ph n gi tr d 001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi khuy trn huyn ph (CTAB v bentonit) c t l CTAB/bentonit l 140mmol/100g trong 5h, pH bng 7, th khong cch lp c bn d 001 t gi tr cao b ng 40,057 v hm lng cation cetyl trimetyl amoni cng t gi tr cao b ng 25,64% khi duy tr nhit huyn ph 60 oC. Nu tin h nh ph n ng nhit cao hn, th gi tr d001 v hm lng cation amoni cng tng ln, tuy nhin s thay i l khng ng k. Nh vy theo chng ti, nhit thch hp cho qu trnh iu ch st hu c t CTAB v bentonit Bnh Thun >90% l 60oC. 3.1.1.3. nh hng ca thi gian khuy trn Thi gian khuy trn c nh hng n cht lng st hu c. Bn cht ca s tng tc gia phn t hu c vi bentonit l s khuch tn cc cation hu c

42

vo gia hai lp st. Thi gian khuy trn cng lu, kh nng khuch tn ca cation hu c vo cc lp bentonit cng ln, khong cch c bn d001 cng tng. kho st nh hng ca yu t thi gian khuy trn, chng ti tin hnh hnh th nghim theo qui trnh nu 2.2.2 trong nhng iu kin c th sau: huyn ph (bentonit v mui amoni hu c) c t l CTAB/bentonit l 140mmol/100g c iu chnh n pH bng 7, nhit 600C v c khuy trn tc khuy n nh 500 vng/pht. Thi gian khuy trn c thay i t 1h n 8h. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2 v khong cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c, t nh gi c mc thm nhp ca cation amoni hu c vo bentonit, tm c mc nh hng ca yu t ang kho st n gi tr d 001 ca sn phm st hu c v hm lng hu c trong sn phm. Cui cng xc nh c iu kin thch hp nht cho qu trnh iu ch st hu c. T gin nhiu x tia X v gin phn tch nhit, chng ti a ra kt qu kho st nh hng ca thi gian khuy trn n gi tr d001 v hm lng cation cetyl trimetyl amoni trong sn phm trong bng 3.3. Bng 3.3. Kt qu kho st nh hng ca thi gian khuy trn n gi tr d001 v hm lng hu c trong sn phm st hu c
Thi gian (h) d001 () Hm lng hu c trong sn phm (%) 1 22,8 18,76 2 28,41 22,0 3 31,16 25,41 4 33,42 27,30 5 34,65 28,35 6 34,70 28,35 7 35,08 28,42 8 35,21 28,47

* nh hng ca thi gian khuy trn n gi tr d001 Gin XRD ca mu st tiu biu c iu ch vi thi gian khu y trn l 5h c a ra trn h nh 3.11. T gin trn hnh 3.11 ta thy r, st hu c iu ch c c cu trc lp vi gi tr d001 = 34,651 tng ng gc 2 ~ 2,54 o.

43

Gin XRD ca cc m u st hu c iu ch trong cc thi gian khuy trn khc nhau c a ra hnh 3.12. T cc gin XRD trn hnh 3.12, c th thy cc mu st hu c iu ch c u c cu trc lp vi gi tr d001 kh ln thay i t ~22 n ~35.

Hnh 3.11. Gin XRD ca mu st hu c iu ch t CTAB v bentonit Bnh Thun hm lng >90% trong thi gian khuy trn l 5h

Hnh 3.12. Gin XRD ca cc mu st hu c c iu ch trong cc thi gian khuy trn khc nhau

44

36 34 32 30 28 26 24 22 20 0 1 2 3 4 5 6 7 8 9

Gi tr d(001), angstron

Thi gian khuy trn (h)

Hnh 3.13. S ph thuc gi tr d001 vo thi gian khuy trn th s ph thuc ca gi tr d001 vo thi gian khuy trn c a ra hnh 3.13. T hnh 3.12 v 3.13 c th thy, khi thi gian khuy trn tng t 1h n 5h, th gi tr d001 tng ln r rt t 22,8 n 34,65; nhng khi tip tc tng thi gian khuy trn th gi tr d001 bin i khng nhiu na. iu n y c th c gii thch nh sau: ban u khi thi gian khuy trn tng ln, kh nng khuch tn v trao i ca cation hu c vo cc lp bentonit tng ln, lm khong cch c bn d001 tng, gi tr 2 ca pic nhiu x cc i gim xung. Nhng khi th i gian khu y trn c 5h th qu trnh khu ch tn v trao i ca cc cation t n trng thi cn bng v khi nu tip tc tng thi gian phn ng th gi tr d 001 bin i khng ng k na. Nh vy, thun tin cho qu trnh iu ch, chng ti thy rng thi gian khuy trn thch hp nht l ~5h v iu kin ny c duy tr cc th nghim sau. * nh hng ca thi gian khuy trn n hm lng hu c trong sn phm xc nh hm lng cc cation amoni hu c trong sn phm, chng ti tin h nh ghi gin phn tch nhit ca cc mu bentonit c ch ha khi c mt

45

v khng c m t cc mui amoni hu c. Hm lng amoni hu c trong sn phm st hu c c tnh ton theo cng thc nu mc 2.3.2.
31 29

Hm lng hu c trong st,%

27 25

23 21 1 9 1 7 1 5 0 1 2 3 4 5 6 7 8 9

Thi gian khuy trn (h)

Hnh 3.14. S ph thuc ca hm lng cation cetyl trimetyl amoni trong sn phm vo thi gian khuy trn Kt qu kho st nh hng ca th i gian khuy trn n hm lng cation cetyl trimetyl amoni trong sn phm c a ra trong b ng 3.3. th s ph thuc ca hm lng cation amoni hu c trong sn phm vo th i gian khuy trn c a ra hnh 3.14. T h nh 3.14 chng ti nh n thy hm lng cation amoni hu c trong sn phm ph thuc vo thi gian khuy trn tng t nh s ph thuc ca gi tr d001. Khi th i gian khuy trn tng dn t 1h n 5h, hm lng cation cetyl trimetyl amoni trong sn phm tng ln v t cc i l 28,35% ti thi gian khuy trn 5h. Cc m u sn phm st c khuy trn trong thi gian 5h, 6h, 7h, 8h c hm lng cation hu c trong sn phm khc nhau khng ng k, ch dao ng t 28,35 n 28,47%. Tc l khi thi gian khuy trn t 5h th gn nh qu trnh khuch tn v trao i ca cc cation t n trng thi cn bng v khi nu tip tc tng thi gian phn ng th hm lng cation cetyl trimetyl amoni trong sn phm bin i khng ng k na.

46

Kt lun: Qua kt qu kho st mc nh hng ca thi gian khuy trn n gi tr d 001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi khuy trn huyn ph (CTAB v bentonit) c t l CTAB/bentonit l 140mmol/100g nhit 60oC, pH bng 7, th khong cch lp c bn d001 t gi tr cao bng 34,65 v hm lng cation cetyl trimetyl amoni cng t gi tr cao b ng 28,35% khi tin hnh trong thi gian khuy trn l 5h. Nu tip tc tng thi gian khu y trn, hiu qu thu c khng cao m ch tn thi gian. V vy, theo chng ti, thi gian khuy trn thch h p iu ch st hu c t CTAB v bentonit Bnh Thun hm lng >90% l 5h. Chng ti duy tr iu kin ny trong cc th nghim tip theo. 3.1.1.4. nh hng ca pH huyn ph Ngoi cc yu t v t l CTAB/bentonit, nhit huyn ph, thi gian khuy trn, th yu t pH huyn ph cng nh hng kh ln n qu trnh iu ch st hu c. Tin hnh iu ch st gi tr pH ph hp s thu c hiu qu cao, ngc li khi pH qu cao hoc qu thp s nh hng xu n cht lng sn phm. V vy yu t th t m chng ti tin h nh kho st l nh hng ca pH n qu trnh iu ch st hu c t CTAB v bentonit Bnh Thu n hm lng >90%. Cc mu st hu c c iu ch theo quy trnh nu mc 2.2.2 vi cc iu kin c th nh sau: t l CTAB/bentonit c c nh 140mmol/100g, thi gian khu y l 5h, iu nhit ti nhit 60oC, pH ca dung dch c thay i t 6.0, 6.5, 7.0, 7.5, 8.0, 8.5; 9.0; 9.5; 10.0 v 10.5. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2theta v kho ng cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c, t nh gi c mc thm nhp ca cation amoni hu c vo bentonit, tm c mc nh hng ca yu t ang kho st n gi tr d001 ca sn phm st hu c v hm lng hu c trong sn phm. Cui cng xc nh c iu kin thch hp nht cho qu trnh iu ch st hu c.

47

T gin nhiu x tia X v gin phn tch nhit, chng ti a ra kt qu kho st nh hng ca pH huyn ph n gi tr d 001 v hm lng cation cetyl trimetyl amoni trong sn phm trong bng 3.4. Bng 3.4. Kt qu kho st nh hng ca pH huyn ph n gi tr d 001 v hm lng cation cetyl trimetyl amoni trong sn phm
pH 6 6,5 7 7,5 8 8,5 9 9,5 10 10,5 d001 () 30,74 32,46 33,23 35,05 36,03 36,59 37,18 36,98 36,76 36,52 Hm lng hu c 26,23 27,42 29,15 30,03 30,83 31,21 31,03 30,73 30,33 29,73 trong sn phm (%)

* nh hng ca pH huyn ph n gi tr d001 Gin XRD ca mt mu st tiu biu c iu ch iu kin pH dung d ch l 9.0 a ra trn hnh 3.15.

Hnh 3.15. Gin XRD ca mu st h u c iu ch t CTAB v bentonit Bnh Thun hm lng >90% pH huyn ph bng 9,0

48

Hnh 3.16. Gin XRD ca cc mu sn phm st hu c c iu ch t CTAB v bentonit Bnh thun >90% cc pH huyn ph khc nhau T gin trn ta thy r, st hu c iu ch c c cu trc lp vi gi tr d 001 = 37,183 tng ng gc 2 ~ 2,37o. Gin XRD ca cc mu st hu c c iu ch cc gi tr pH huyn ph khc nhau c a ra hnh 3.16. T cc gin XRD trn hnh 3.16, c th thy cc mu st hu c iu ch c u c cu trc lp vi gi tr d001 kh ln thay i t ~30 n ~36. th s ph thuc ca gi tr d 001 vo gi tr pH huyn ph c a ra hnh 3.17. T gin XRD trn hnh 3.16 v th trn hnh 3.17 c th thy rng, trong khong pH thay i t 6.0 n 10.5, gi tr d001 thay i khng ng k, ch t 30,74 n 36,52, c ngha gi tr d001 t b nh hng khi pH thay i. Chng ti cho rng, cn c vo gi tr pH sn c ca dung dch mui amoni v dung dch st ban u khong 7-8, th gi tr pH thch hp nht cho qu trnh iu ch st hu c t CTAB thu c sn phm c khong cch lp c bn d001 ln l 9,0.

49

39

37

Gi tr d(001), angstron

35

33

31

29

27 5.5 6 6.5 7 7.5 8 8.5 9 9.5 1 0 1 0.5 1 1

pH huyn ph

Hnh 3.17. S ph thuc gi tr d001 vo pH huyn ph * nh hng ca pH huyn ph n hm lng cation amoni hu c trong st xc nh hm lng cc cation amoni hu c trong sn phm, chng ti tin h nh ghi gin phn tch nhit ca cc mu bentonit c ch ha khi c mt v khng c m t cc mui amoni hu c. Hm lng amoni hu c trong sn phm st hu c c tnh ton theo cng thc nu mc 2.3.2.
34

Hm lng hu c trong st,%

32

30

28

26

24

22 5.5 6 6.5 7 7.5 8 8.5 9 9.5 1 0 1 0.5 1 1

pH huyn ph

Hnh 3.18. S ph thuc ca hm lng cation amoni hu c trong sn phm vo pH huyn ph

50

Kt qu kho st nh hng ca pH huyn ph n hm lng cation cetyl trimetyl amoni trong sn phm c a ra trong b ng 3.4. th s ph thuc ca h m lng cation cetyl trimetyl amoni trong sn phm vo pH huyn ph c a ra hnh 3.18. Hnh 3.18 c th cho ta thy r rng, khi pH thay i t 6,0 n 10,5 hm lng cation amoni hu c trong sn phm c thay i, nhng s thay i l nh, ch t 26 n 31%. Nh vy, pH cng nh hng khng nhiu n hm lng cation cetyl trimetyl amoni trong sn phm. Tuy nhin, trong s cc im pH chng ti kho st, th pH t 8 ,0-9,0, hm lng cation cetyl trimetyl amoni trong sn phm t cao nht ~31%. V vy, kho ng pH t 8,0-9,0 l ph hp nht iu ch ra sn phm st hu c t CTAB v bentonit Bnh Thun c hm lng hu c cao. Kt lun: Qua kt qu kho st mc nh hng ca pH huyn ph n gi tr d001 v hm lng cation amoni hu c trong sn phm , chng ti thy rng, tuy pH t nh hng ti gi tr d 001 v hm lng hu c trong sn phm; nhng nu khuy trn huyn ph (CTAB v bentonit) c t l CTAB/bentonit l 140mmol/100g trong 5h, nhit huyn ph l 60oC, th khong cch lp c bn d001 t gi tr cao v hm lng cation cetyl trimetyl amoni trong sn phm cng t gi tr cao khi pH huyn ph c duy tr gi tr bng 9,0. Nh vy theo chng ti, pH huyn ph thch hp nht cho qu trnh iu ch st hu c t CTAB v bentonit Bnh Thun >90% l 9,0. 3.1.2. Xy dng quy trnh iu ch st hu c t bentonit v CTAB 3.1.2.1. Quy trnh iu ch st hu c t bentonit Bnh Thun v cetyl trimetyl amoni bromua: c trnh by trn hnh 3.19. 3.1.2.2. Thuyt minh quy trnh - Cn chnh xc mt lng bentonit b ng cn in t c chnh xc 0,0001g vo mt cc chu nhit 250ml. Ha thm vo mt th tch nc ct thch hp ri khuy mnh c gia nhit, trong mt khong thi gian nht nh to huyn ph bentonit.

51

Hnh 3.19. S khi quy trnh iu ch st hu c t bentonit Bnh Thun v CTAB

Nc ct

Cn chnh xc mt lng CTAB

Dung dch mui CTAB, pH = 9

CTAB/bentonit = 140mmol/100g

t t, khuy u

Nc ct

Cn chnh xc mt lng bentonit

Huyn ph bentonit, pH = 9

Khuy mnh

Huyn ph bentonit + CTAB

Khuy mnh 5h, 60oC

Huyn ph

Lc nng

Ra nng 3 ln

Sy 80oC trong 24h

Xc nh cu trc, tnh ch t

ST HU C

Nghin mn

52

- Cn chnh xc mt lng CTAB (sao cho t l CTAB/bentonit l 140mmol/100g) bng cn in t c chnh xc 0,0001g. Ha tan lng mui ny vo mt th tch nc ct thch hp nh trn ri khuy c gia nhit trong mt khong thi gian CTAB tan ht, to thnh dung dch mui CTAB. - iu chnh pH ca c hai dung dch n 9,0 (s dng cc dung dch HCl v NaOH long v giy ch th pH ca h ng Merk). - t t dung dch mui amin vo dung dch bentonit, ng thi khuy lin tc trong 5h trn my khuy t gia nhit Veia ca Cole Parmer Instrument Company. Kim tra pH, nhit ca dung dch phn ng v gi n nh trong sut th i gian tin hnh ph n ng. - Lc nng bng phu lc c bm ht chn khng. Ra sn phm t nht 3 ln b ng nc ct nng. - Sy sn phm trong t sy chn khng trong 24h 800C. Ly sn phm ra nghin bng ci s thnh bt mn. - Xc nh cu trc v tnh cht ca sn phm bng cc phng php: phng php nhiu x tia X; phng php phn tch nhit. 3.1.2.3. Kt qu iu ch p dng quy trnh 3.19 iu ch st hu c t bentonit Bnh Thun c hm lng MMT > 90% v CTAB. Gin nhiu x ca sn phm st hu c c a ra trn hnh 3.20. T hnh 3.20, chng ta c th thy rng sn phm st hu c iu ch c c cu trc lp vi khong cch gia cc lp st cao, d 001 = 43,021, tng ng vi gc 2theta ca pic cc i nhiu x bng 2,052o. Chng ti tin hnh ghi gin ph n tch nhit v so snh vi gin phn tch nhit ca mu bentonit c ch ha tng t khng c tc nhn hu c xc nh hm lng cation cetyl trimetyl amoni trong sn phm. Gin phn tch nhit ca mu st hu c c iu ch t bentonit Bnh Thun loi c hm lng >90% vi CTAB theo quy trnh 3.19 c a ra trn hnh 3.21. Hnh 3.21 cho thy, c 3 hiu ng mt khi lng ti 112,47oC (-2,63%), ti 293,97oC (-15,71%) v ti 436,39oC (-27,73%).

53

Hnh 3.20. Gin XRD ca mu st hu c c iu ch t bentonit Bnh Thun loi c hm lng >90% vi CTAB theo quy trnh 3.19
Figure: Labsys TG TG/% Peak :112.47 C 40 19/8/2009 Experiment: Thuy Anh-CTAB Procedure: 30 ----> 800C (10C.min-1) (Zone 2) HeatFlow/V Exo Crucible: PT 100 l Atmosphere: Air Mass (mg): d 51.14

Peak :293.97 C 20 Peak :436.39 C

20 -4

Mass variation: -2.63 % Mass variation: -15.71 %

-20

-8

-20

Mass variation: -27.73 %

-60

-12

-40

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.21. Gin phn tch nhit ca mu st hu c c iu ch theo quy trnh 3.19 t bentonit Bnh Thun loi c hm lng >90% vi CTAB

54

Cc hiu ng ny u c km theo hiu ng thu nhit trn ng DTA v c quy gn cho qu trnh mt nc cu trc v phn hy ca cetyl trimetyl amoni trong m u. Tng khi lng mt khi nung l: 2,63% + 15,71% + 27,73% = 46,07%, tng ng vi hm lng cation cetyl trimetyl amoni trong sn phm l 34,57%.

3.2. iu ch st hu c t bentonit v dodecylamoni clorua (DAC)

Tc nhn h u c tip theo c chng ti s dng trong ti ny l dodecyl amin. V nhng l do nu trong mc 2.2.1, nn chng ti chuyn amin ny thnh mui dodecyl amoni clorua (DAC). Phng php chuyn amin th nh mui nu mc 2.2.1. Sau chng ti tin h nh kh o st cc yu t nh hng n qu trnh iu ch st hu c t bentonit Bnh Thun v DAC, gm: t l cation amoni hu c/bentonit, nhit huyn ph, th i gian khuy trn, pH huyn ph. T tm iu kin thch hp nht v xy dng quy trnh chun iu ch st hu c t bentonit Bnh Thun 90% v DAC. 3.2.1. Kho st cc yu t nh hng trong qu trnh iu ch n gi tr d001 v hm lng amoni hu c trong st hu c t bentonit v DAC 3.2.1.1. nh hng ca t l cation hu c/bentonit Nh ni mc 3.1.1.1, t l cation amoni hu c/bentonit (mmol/100g) c nh hng quan trng n gi tr d001 v hm lng cation amoni hu c trong sn phm, do yu t nh hng ny c chng ti t vn kho st trc tin. Cc m u st hu c c iu ch theo quy trnh nu mc 2.2.2 vi cc iu kin c th nh sau: huyn ph (bentonit v mui amoni hu c) c iu chnh n pH bng 7, nhit 600C v c khuy trn trong thi gian 5h, tc khuy n nh 500 vng/pht, t l DAC/bentonit c bin i t 150 n 330mmol/100g bentonit kh. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2theta v kho ng cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c, t nh gi c mc thm nhp ca cation amoni hu c vo bentonit, tm c mc nh hng ca yu t ang kho st n gi tr d001 ca sn phm

55

st h u c v hm lng hu c trong sn phm. Cui cng xc nh c iu kin thch hp nht cho qu trnh iu ch st hu c. Bng 3.5. Kt qu kho st nh hng ca t l DAC/bentonit n gi tr d 001 v hm lng cation dodecyl amoni trong sn phm
T l DAC/bentonit (mmol/g) d 001 () Hm lng hu c trong sn phm (%) 150 170 190 210 230 250 270 290 310 330

15,8 17,98 19,71 21,15 24,01 25,06 25,44 25,54 25,87 25,97 14 15,29 16,38 17,8 19,33 20,29 19,52 17,47 15,29 14,52

T gin nhiu x tia X v gin phn tch nhit, chng ti a ra kt qu kho st nh hng ca t l DAC/bentonit n gi tr d 001 v hm lng cation dodecyl amoni trong sn phm trong bng 3.5. * nh hng ca t l DAC/bentonit n gi tr d001 Gin XRD ca mt mu st tiu biu c a ra trn h nh 3.22.

Hnh 3.22. Gin XRD ca mu st hu c iu ch t DAC v bentonit Bnh Thun hm lng >90% t l DAC/bentonit l 250mmol/100g

56

T gin trn ta thy r, st hu c iu ch c c cu trc lp vi gi tr d 001 = 25,059Ao tng ng gc 2 ~ 3,523o. Cc gin XRD ca cc mu st hu c iu ch vi t l DAC/bentonit (mmol/100g) khc nhau c trnh by trn hnh 3.23. T hnh 3.23 thy rng, gin XRD ca cc mu st hu c iu ch c u c pic c trng cho cu trc lp vi gi tr d001 kh ln thay i t ~16 n ~26Ao, tng ng gc 2theta ca pic nhiu gim t 5,519o n 3,39o. th s ph thuc ca gi tr d 001 vo t l DAC/bentonit (mmol/100g) c a ra hnh 3.24.

Hnh 3.23. Gin XRD ca cc mu sn phm st hu c c iu ch t DAC v bentonit Bnh thun >90% cc t l DAC/bentonit khc nhau T hnh 3.24, chng ti thy rng, trong khong t l DAC/bentonit t 150 n 250 (mmol/100g), gi tr d001 tng r rt t 15 n 25Ao v t cc i t l DAC/bentonit bng 250mmol DAC/100g. Khi tip tc tng t l n y, d001 vn tng

57

ln nhng mc tng gim xung, sau gn nh khng thay i. V vy m ti cc t l DAC/bentonit bng 250, 270, 290, 310, 330 mmol/100g cc gi tr d 001 xp x nhau, u ~25Ao.
28 26 24 22 20 1 8 1 6 1 4 1 2 1 0 1 30 1 50 1 70 1 90 21 0 230 250 270 290 31 0 330 350

Gi tr d(001), angstron

T l am oni hu c/bentonite, m m ol/100g

Hnh 3.24. S ph thuc ca gi tr d001 vo t l DAC/bentonit iu ny c th c gii thch nh sau: thi im u, vi s tng t l DAC/bentonit, s trao i gia cation hu c vi cc cation v c c m t gia cc lp st xy ra mnh hn nn gi tr d001 tng ln; nhng khi t l DAC/100g bentonit t n gi tr 250mmol/100g th nng cation amoni hu c trong huyn ph st c th coi l t b o ha; V th nu tip tc tng t l ln th gi tr d 001 thay i rt t. V n thi im no , chng ti cn d on gi tr d001 gim xung, do khi nng cation amoni hu c trong huyn ph st t bo ha, th cc ui hu c ca cc amin trong dung dch nc c xu hng tp hp li th nh ht keo, cc h t keo khng c kh nng thm nhp n n qu trnh trao i ca cc cation hu c vi cation v c gim; v vy gi tr d001 d n gim xung. V vy, trnh lng ph ha cht, chng ti cho rng t l DAC/bentonit thch h p cho qu trnh iu ch st hu c t dodecyl amoni clorua v bentonit Bnh Thun hm lng >90% l 250mmol/100g. * nh hng ca t l DAC/bentonit n hm lng hu c trong sn phm

58

 xc nh hm lng ca cc cation amoni trong sn phm, chng ti tin hnh ghi gin phn tch nhit ca cc mu bentonit c ch ha khi c mt v khng c m t DAC. Di y l v d gin phn tch nhit ca mt mu st hu c iu ch t DAC v bentonit Bnh Thu n hm lng >90% ti t l DAC/bentonit l 250mmol/100g.
Figure: Labsys TG TG/% Experiment: Thuy Anh - DAC-250 Crucible: PT 100 l Atmosphere: Air Mass (mg): HeatFlow/V Exo 30 Peak :631.77 C 20 Peak :405.65 C 20 10 -4 0 0 40 -2 42.61 28/07/2009 Procedure: 30 ----> 800C (10 C.min-1) (Zone 2) d TG/%/min

-10

Mass variation: -21.56% -20

-6

-20 Mass variation: -10.23 % -40 -30 -8

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.25. Gin phn tch nhit ca mu st hu c iu ch t DAC v bentonit Bnh Thun hm lng >90% t l DAC/bentonit l 250mmol/100g Hnh 3.25 cho thy c 2 hiu ng mt khi lng ti 406,605oC (-21,56%) v ti 631,77oC (-10,23%). Cc hiu ng ny u c km theo hiu ng thu nhit trn ng DTA v c quy gn cho qu trnh mt nc cu trc v phn hy ca dodecyl amoni trong mu. Tng khi lng mt khi nung ca mu st hu c tnh c l 31,79%. Gin phn tch nhit ca m u st c ch ha tng t nhng khng c tc nhn hu c c a ra trn hnh 3.5. T gin 3.5, chng ti tnh ton c tng khi lng mt khi nung l 11,5%. Hm lng amoni hu c trong sn phm st hu c c tnh ton theo cng thc nu mc 2.3.2.

59

m(%) = mhc(%) - mbent (%) Vy hm lng cation dodecyl amoni trong sn phm st hu c iu ch t DAC v bentonit Bnh Thun t l DAC/bentonit l 250mmol/100g bng: 31,79% - 11,50% = 20,29%. Hm lng cation dodecyl amoni trong cc m u st h u c iu ch t DAC v bentonit Bnh Thu n cc t l DAC/bentonit khc cng c cn c theo gin phn tch nhit v c xc nh tng t. Kt qu kho st nh hng ca t l DAC/bentonit n hm lng cation dodecyl amoni trong sn phm c a ra trong b ng 3.5. th s ph thuc ca hm lng hu c trong sn phm vo t l DAC/bentonit (mmol/100g) c a ra hnh 3.26.
23 21

Hm lng hu c trong st,%

1 9 1 7 1 5 1 3 1 1 9 7 5 1 30 1 50 1 70 1 90 21 0 230 250 270 290 31 0 330 350

T l am oni hu c/bentonite,m m ol/100g

Hnh 3.26. S ph thuc ca hm lng hu c vo t l DAC/bentonit Hnh 3.26 cho thy, khi tng t l DAC/bentonit t 150 n 250mmol/100g, hm lng cation dodecyl amoni trong sn phm tng ln r rt v t cc i t l 250mmol/100g tng t nh d001. Nhng nu tip tc tng th hm lng ny c xu hng gim. iu ny c gii thch tng t nh vi d001, ngha l khi t l DAC/bentonit t n 250mmol/100g, th nng cation dodecyl coi nh t bo ha, nu t l vt qu 250mmol/100g, cc ui hu c ca cc amin trong dung dch nc tp hp li thnh ht keo. Cc ht keo khng c kh nng thm

60

nhp vo bentonit nn lm gim nng cation hu c trong nc v d n n lm gim hm lng hu c trong sn phm. Kt lun: Qua kt qu kho st mc nh hng ca t l DAC/bentonit n gi tr d001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi tin hnh khuy trn huyn ph (DAC v bentonit) trong th i gian 5h, nhit huyn ph l 60 oC, pH bng 7 th ti t l DAC/bentonit l 250mmol/100g, gi tr d001 t gi tr cao b ng 25,06Ao v hm lng cation dodecyl amoni t cc i bng 20,29%. Nh vy theo chng ti, t l DAC/bentonit thch hp iu ch st hu c t DAC v bentonit Bnh Thun hm lng >90% l 250mmol/100g. Chng ti duy tr iu kin ny trong cc th nghim tip theo. 3.2.1.2. nh hng ca nhit huyn ph Yu t tip theo chng ti tin h nh kh o st l s nh hng ca nhit ti qu trnh iu ch. Nhit cng l mt yu t nh hng rt quan trng. Cc th nghim c chng ti tin hnh theo quy trnh nu mc 2.2.2, trong nhng iu kin c th sau: t l DAC/bentonit bng 250mmol/100g bentonit, pH huyn ph b ng 7, thi gian phn ng l 5h, tc khuy 500 vng/pht. Nhit huyn ph c thay i t 30 n 90oC. Bng 3.6. Kt qu kho st nh hng ca nhit huyn ph n gi tr d001 v hm lng hu c trong sn phm
Nhit huyn ph (oC) d 001 () Hm lng hu c trong sn phm (%) 30 17,751 8,7 40 21,07 14,2 50 60 70 80 90 15,838 10,4

24,594 26,866 18,7 19,8

25,042 22,267 19,1 15,5

Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2theta v kho ng cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu

61

c. Cc kt qu thu c t gin nhiu x tia X v gin phn tch nhit c a ra trong bng 3.6. * nh hng ca nhit huyn ph n gi tr d001

Hnh 3.27. Gin XRD ca mu st h u c iu ch t DAC v bentonit Bnh Thun hm lng >90% nhit huyn ph bng 60oC

Hnh 3.28. Gin XRD ca cc mu st hu c c iu ch t DAC v bentonit Bnh Thun >90% ti cc nhit huyn ph khc nhau

62

Gin XRD ca mt mu st tiu biu c a ra trn h nh 3.27. T hnh 3.27 ta thy r, st h u c iu ch c c cu trc lp vi gi tr d001 = 26,866Ao tng ng gc 2 ~ 3,28 o. Gin XRD ca cc mu st hu c c iu ch cc nhit huyn ph khc nhau c a ra hnh 3.28. T cc gin XRD trn hnh 3.28, c th thy cc mu st hu c iu ch c u c cu trc lp vi gi tr d001 thay i t ~15 n ~29Ao.
30

25

Gi tr d(001), angstron

20

1 5

1 0

5 20 30 40 50 60 70 80 90 1 00

Nhit huyn ph,oC

Hnh 3.29. S ph thuc ca gi tr d001vo nhit huyn ph T hnh 3.28 v 3.29, c th th y khi tng nhit huyn ph, gi tr d001 tng kh nhanh v t cc i ti nhit 60 oC, gi tr d001 tng ng bng 26,866Ao. Nu tip tc tng nhit ln trn 60oC, gi tr d 001 gim xung. iu n y c th c gii thch l khi nhit huyn ph tng th s chuyn ng ca cc cation amoni hu c v cation v c trong bentonit tng do s trao i din ra nhanh hn, cn khi nhit huyn ph qu cao th cc cation amoni hu c c th b thy phn tr thnh amin ban u (l cht t tan) do s trao i gim xung. Do khong cch lp st thay i khng ng k so vi mu st ban u cha c ch ha vi tc nhn hu c.

63

Chng ti ngh rng, nhit huyn ph thch hp nht thu c sn phm st hu c c khong cch gia cc lp st cao l 60oC, ti nhit ny, gi tr d001 c th t ~27. * nh hng ca nhit huyn ph n hm lng hu c trong sn phm Hnh 3.30 a ra th biu din s ph thuc ca hm lng hu c trong sn phm vo nhit huyn ph khi phn ng.
25

Hm lng hu c trong st,%

20

1 5

1 0

0 20 30 40 50 60 70 80 90 1 00

Nhit huyn ph, oC

Hnh 2.30. S ph thuc ca hm lng cation dodecyl amoni trong sn phm vo nhit huyn ph T h nh 2.30 ta thy rng, hm lng cation amoni hu c trong sn phm tng dn khi nhit huyn ph tng, v cng t gi tr cc i ti nhit 60 oC (l 19,8%). Khi tip tc tng nhit , hm lng ny li gim xung. S bin i ny rt ph hp v c gii thch tng t nh s bin i ca gi tr d001. Kt lun: Qua kt qu kho st mc nh hng ca nhit huyn ph n gi tr d 001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi khuy trn huyn ph (DAC v bentonit) c t l DAC/bentonit l 25mmol/100g trong 5h, pH bng 7, th kho ng cch lp c bn d001 t gi tr cc i bng 26,866Ao v hm lng cation dodecyl amoni cng t gi tr cc i bng 19,8% khi duy tr nhit huyn ph 60oC. V vy, chng ti cho rng nhit huyn

64

ph thch h p iu ch st hu c t DAC v bentonit Bnh Thun >90% l 60oC. 3.2.1.3. nh hng ca thi gian khuy trn Vic tm c thi gian khuy trn thch hp s tit kim c thi gian v nng lng s dng trong qu trnh iu ch. V vy, yu t tip theo m chng ti kho st l nh hng ca thi gian khuy trn n qu trnh iu ch st hu c. Cc th nghim c tin hnh theo quy trnh nu mc 2.2.2. Cc iu kin c th nh sau: t l DAC/bentonit l 250mmol amoni h u c/100g bentonit kh, pH huyn ph l 7, nhit huyn ph bng 60 oC, thi gian khuy trn c thay i t 1h n 8h. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2theta v kho ng cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c. Cc kt qu thu c t gin nhiu x tia X v gin phn tch nhit c a ra trong bng 3.7. Bng 3.7. Kt qu kho st s nh hng ca thi gian khuy trn vo gi tr d 001 v hm lng cation amoni hu c trong sn phm
Thi gian (h) d001 () Hm lng hu c trong sn p hm (%) 14 16,7 20,6 23,7 25 25,57 25,7 25,7 1 15,84 2 19.72 3 23,95 4 23,97 5 24.87 6 24,88 7 25,06 8 25.20

* nh hng ca thi gian khuy trn n gi tr d001 Gin XRD ca mt mu st tiu biu c a ra trn h nh 3.31. T hnh 3.31 ta thy r, st h u c iu ch c c cu trc lp vi gi tr d001 = 24,568Ao tng ng gc 2 ~ 3,59 o. Gin XRD ca cc mu sn phm st hu c c iu ch cc thi gian khuy trn khc nhau c a ra trn hnh 3.32.

65

Hnh 3.31. Gin XRD ca mu st hu c iu ch t DAC v bentonit Bnh Thun hm lng >90% trong th i gian khuy trn l 5h

Hnh 3.32. Gin XRD ca cc mu st hu c iu ch t bentonit Bnh Thun v DAC trong cc thi gian khuy trn khc nhau

66

Hnh 3.32 cho ta thy cc mu st hu c iu ch c c cu trc lp th hin vic xut hin cc pic nhiu x c trng cho cu trc lp. Gin XRD ca m u st c khuy trn trong 1h khng c pic c trng, chng t thi gian 1h l cha h nh thnh cu trc lp sn phm st hu c. th s ph thuc ca gi tr d001 vo thi gian khuy trn c a ra hnh 3.33.
26

24

Gi tr d(001),angstron

22

20

1 8

1 6

1 4

1 2 0 1 2 3 4 5 6 7 8 9

Thi gian khuy trn,h

Hnh 3.33. S ph thuc ca gi tr d001 vo thi gian khuy trn T hnh 3.32 v 3.33, ta c th thy r, khi thi gian khuy trn tng t 1h n 5h, khong cch gia cc lp st d001 tng ln t 15,84 ln 24,87Ao. Nhng khi tng tip thi gian khuy trn th gi tr d001 gn nh khng thay i. iu n y c th gii thch nh sau: khi khu y trn huyn ph DAC v bentonit trong thi gian ngn, s trao i ca cation hu c vi cation v c l cha nhiu, n u tip tc cho phn ng th s trao i tip tc xy ra. Khi khuy trn hn hp phn ng c 5h th qu trnh trao i gn nh t n trng thi cn bng, do n u ta c tip tc khuy trn na th d001 cng bin i khng nhiu, nh vy s gy lng ph thi gian m khng em li hiu qu ng k.

67

Chng ti cho rng thi gian khuy trn ph hp nht cho qu trnh iu ch st hu c t DAC v bentonit Bnh Thu n >90% iu kin ny c duy tr cc th nghim sau. * nh hng ca thi gian khuy trn n hm lng hu c trong sn phm Kt qu kho st s ph thuc ca hm lng cation dodecyl amoni trong sn phm vo thi gian khuy trn c a ra trong bng 3.7. th s ph thuc ca hm lng cation amoni hu c trong sn phm vo th i gian khuy trn c a ra hnh 3.34.
30

Hm lng hu c trong st,%

25

20

1 5

1 0

5 0 1 2 3 4 5 6 7 8 9

Thi gian khuy trn,h

Hnh 3.34. S ph thuc ca hm lng cation amoni hu c trong sn phm vo thi gian khuy trn Hnh 3.34 cho thy khi tng thi gian khuy trn t 1 n 5h, hm lng cation amoni hu c trong sn phm tng ln r rt t 14 n 25%. Tip tc tng th i gian khuy trn, hm lng cation dodecyl amoni cng tng ln nhng khng ng k. iu ny cng c th gii thch tng t nh vi d 001, tc l khi th i gian khuy trn c 5h th gn nh s trao i gia cation hu c v v c t ti trng thi cn bng, hm lng hu c trong sn phm coi nh khng b nh hng b i thi gian khuy trn na. Ta nn d ng phn ng li tit kim thi gian v nng lng.

68

Kt lun: Qua kt qu kho st mc nh hng ca thi gian khuy trn n gi tr d 001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khi khuy trn huyn ph (DAC v bentonit) c t l DAC/bentonit l 250mmol/100g nhit 60oC, pH b ng 7, th khong cch lp c bn d001 t gi tr kh cao bng 24,87Ao v hm lng cation dodecyl amoni cng t gi tr kh cao bng 25,5% khi tin hnh trong th i gian khuy trn l 5h. Nu tip tc tng thi gian khuy trn, ch lng ph thi gian m khng c hiu qu kinh t. V vy, theo chng ti, th i gian khuy trn thch hp iu ch st hu c t DAC v bentonit Bnh Thun hm lng >90% l 5h. Chng ti duy tr iu kin ny trong cc th nghim tip theo. 3.2.1.4. nh hng ca pH huyn ph Gi tr pH huyn ph c nh hng rt ln n qu trnh iu ch st. kho st nh hng ca pH huyn ph n cht lng st hu c, chng ti tin hnh th nghim theo qui trnh 2.2.2 cc iu kin sau: t l DAC/bentonit c c nh 250mmol/100g bentonit kh, th i gian khuy trn l 5h, iu nhit n nh 60oC. pH ca dung dch c thay i t 6; 6,5; 7; 7,5; 8; 8,5; 9; 9,5; 10; 10,5. Sn phm st hu c iu ch c c chp gin nhiu x tia X xc nh cu trc lp ca sn phm, gi tr 2theta v kho ng cch gia cc lp st (d001); ghi gin phn tch nhit xc nh hm lng hu c trong sn phm st hu c. Bng 3.8. Kt qu kho st nh hng ca pH huyn ph n gi tr d001 v hm lng cation amoni hu c trong sn phm
pH d001 () Hm lng hu c trong sn phm (%) 6 6,5 7 7,5 8 8,5 9 9,5 10 10,5

13,87 15,84 17,75 20,39 22,27 24,72 25,36 25,06 24,50 23,96 13.71 15.62 17,94 19,26 20 20,4 20,83 20,2 19,2 18,3

69

T gin nhiu x tia X v gin phn tch nhit, chng ti xc nh c cc gi tr khong cch lp d001 v hm lng hu c trong sn phm, cc kt qu c a ra trong bng 3.8. * nh hng ca pH huyn ph n gi tr d001 Gin XRD ca mt mu st tiu biu c a ra trn h nh 3.35. T gin trn ta thy r, st hu c iu ch c c cu trc lp vi gi tr d 001 = 25,358Ao tng ng gc 2 ~ 3,48o.

Hnh 3.35. Gin XRD ca mu st hu c iu ch t DAC v bentonit Bnh Thun hm lng >90% pH huyn ph bng 9,0 Gin XRD ca cc mu st hu c c iu ch cc gi tr pH huyn ph khc nhau c a ra hnh 3.36. Hnh 3.36 cho th y cc mu st hu c iu ch c c cu trc lp vi gi tr d 001 thay i t ~14 n ~24Ao. th s ph thuc ca gi tr d 001 vo gi tr pH huyn ph c a ra hnh 3.37. T hnh 3.36 v 3.37, ta c th th y rng, gi tr d001 rt thp khi pH huyn ph th p, khi pH huyn ph tng t 6,0 n 9,0, gi tr d 001 tng ln t 13,87 n 25,36Ao v t cc i (d001 = 25,36Ao) ti pH huyn ph bng 9,0. Khi tip tc tng pH huyn ph, gi tr d 001 dn gim xung, v gim r rt pH = 10,5.

70

Hnh 3.36. Gin nhiu x XRD ca cc mu st hu c iu ch t bentonit Bnh Thun v DAC cc pH huyn ph khc nhau
30

25

Gi tr d(001),angstron

20

1 5

1 0

5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 1 0 1 0.5 1 1

pH dung dch

Hnh 3.37. S ph thuc ca gi tr d001 vo pH huyn ph iu n y c th c gii thch nh sau: pH thp, nng ion H3O+ ln, cn tr s trao i ca cation amoni hu c vi cc cation v c trong bentonit, cn pH cao, cc cation dodecyl amoni c xu hng thy phn thnh dodecyl amin ban u, l hp cht t tan n n s khuch tn v trao i ca cc cation cng b gim

71

xung. S khuch tn trao i ca cc cation dodecyl amoni vi cc cation v c gim xung lm kho ng cch gia cc lp st gim, th p hn r rt so vi trng h p pH huyn ph bng 9,0. V vy, chng ti cho rng, pH huyn ph thch h p nht cho qu trnh iu ch st hu c t DAC v bentonit Bnh Thu n hm lng >90% l 9,0. * nh hng ca pH huyn ph n hm lng hu c trong sn phm T gin phn tch nhit ca cc mu bentonit c ch ha khi c mt v khng c mt DAC v tnh ton hm lng amoni hu c trong sn phm st hu c theo cng th c nu mc 2.3.2, chng ti thu c cc kt qu kho st s nh hng ca pH huyn ph n hm lng cation dodecyl amoni trong sn phm v a ra trong bng 3.8. th s ph thuc ca hm lng cation dodecyl amoni trong sn phm vo pH huyn ph c a ra hnh 3.38.
23

Hm lng hu c trong st,%

21

1 9

1 7

1 5

1 3

1 1 5.5 6 6.5 7 7.5 8 8.5 9 9.5 1 0 1 0.5 1 1

pH dung dch

Hnh 3.38. S ph thuc ca hm lng cation dodecyl amoni trong sn phm vo pH huyn ph T hnh 3.38, chng ti nhn thy rng, khi thay i pH huyn ph t 6,0 n 9,0, hm lng cation dodecyl amoni trong sn phm tng dn 13,71 n 20,83%. Nhng t pH huyn ph b ng 9,5 tr i, hm lng cation dodecyl amoni trong sn phm bt u gim dn. Nh vy hm lng cation dodecyl amoni trong sn phm t cc i ti pH huyn ph bng 9,0. cc pH thp hn hoc cao hn 9,0, gi tr

72

ny u gim so vi pH bng 9,0. S bin i n y rt ph hp vi s bin i ca gi tr d001 v c gii thch tng t nh vi d001. Kt lun: Qua kt qu kho st mc nh hng ca pH huyn ph n gi tr d001 v hm lng cation amoni hu c trong sn phm, chng ti thy rng, khc vi trng hp CTAB, st hu c iu ch t DAC v bentonit Bnh Thun b nh hng r rt bi pH huyn ph. Khi khu y trn huyn ph (DAC v bentonit) c t l DAC/bentonit l 250mmol/100g trong 5h, nhit huyn ph l 60oC, th khong cch lp c bn d 001 t gi tr cc i bng 25,36Ao v hm lng cation dodecyl amoni trong sn phm cng t gi tr cc i bng 20,83% khi pH huyn ph c duy tr gi tr bng 9,0. Nh vy theo chng ti, pH huyn ph thch hp nht cho qu trnh iu ch st hu c t DAC v bentonit Bnh Thun >90% l 9,0. 3.2.2. Xy dng quy trnh iu ch st hu c t bentonit v DAC 3.2.2.1. Quy trnh iu ch st hu c t bentonit Bnh Thun v dodecylamin: c trnh by trn hnh 3.37. 3.2.2.2. Thuyt minh quy trnh - Chuyn dodecylamin thnh dodecyl amoni clorua (DAC) nh mc 2.2.1 - Cn chnh xc mt lng bentonit bng cn in t (0,0001g) vo mt cc chu nhit 250ml. Ha thm vo mt th tch nc ct thch hp ri khuy mnh c gia nhit, trong mt khong thi gian nht nh to huyn ph bentonit. - Cn chnh xc mt lng DAC (sao cho t l DAC/bentonit l 250mmol/100g) bng cn in t c chnh xc 0,0001g. Ha tan lng mui ny vo mt th tch nc ct thch hp nh trn ri khuy c gia nhit trong mt khong thi gian DAC tan ht, to thnh dung d ch mui DAC. - iu chnh pH ca c hai dung dch n 9,0 (s dng cc dung d ch HCl v NaOH long v giy ch th pH ca h ng Merk). - t t dung dch mui amin vo dung dch bentonit, ng thi khuy lin tc trong 5h trn my khuy t gia nhit Veia ca Cole Parmer Instrument Company.

73

Hnh 3.39. S khi quy trnh iu ch st hu c t bentonit Bnh Thun v DAC

Nc ct

Cn chnh xc mt lng DAC

Dung dch mui DAC, pH = 9

DAC/bentonit = 140mmol/100g

t t, khuy u

Nc ct

Cn chnh xc mt lng bentonit

Huyn ph bentonit, pH = 9

Khuy mnh

Huyn ph bentonit + DAC

Khuy mnh 5h, 60oC

Huyn ph

Lc nng

Ra nng 3 ln

Sy 80oC trong 24h

Xc nh cu trc, tnh cht

ST HU C

Nghin mn

74

- Kim tra pH, nhit ca dung dch phn ng v gi n nh trong sut thi gian tin hnh ph n ng. - Lc nng bng phu lc c bm ht chn khng. Ra sn phm t nht 3 ln b ng nc ct nng. - Sy sn phm trong t sy chn khng trong 24h 800C. Ly sn phm ra nghin bng ci s thnh bt mn. - Xc nh cu trc v tnh cht ca sn phm bng cc phng php: phng php nhiu x tia X; phng php phn tch nhit. 3.2.2.3. Kt qu iu ch p dng quy trnh 3.39 iu ch st hu c t bentonit Bnh Thun c hm lng MMT > 90% v DAC. Gin nhiu x ca sn phm st hu c c a ra trn hnh 3.40.

Hnh 3.41. Gin XRD ca mu st hu c c iu ch t bentonit Bnh Thun loi c hm lng >90% vi DAc theo quy trnh 3.39 T gin trn, chng ta c th thy rng sn phm st hu c iu ch c c cu trc lp vi khong cch gia cc lp st kh cao, d001 = 27,012, tng ng vi gc 2theta ca pic cc i nhiu x bng 3,26 o.

75

Gin phn tch nhit ca mu st hu c c iu ch t bentonit Bnh Thun loi c hm lng >90% vi DAC theo quy trnh 3.39 c a ra trn hnh 3.42.
Figure: Labsys TG 23/08/2009 Experiment: Thuy Anh DAC Procedure: 30 ----> 800C (10 C.min-1) (Zone 2) Crucible: PT 100 l Atmosphere: Air Mass (mg): 49.15

TG/%

HeatFlow/V Exo

dTG/%/min

30
Peak :631.52 C

20
Peak :410.37 C

30

-2

10 -4 0 0

-10
Mass variation: -23.75 %

-6

-20

-30 -8
Mass variation: -8.72 %

-30

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.42. Gin phn tch nhit ca mu st hu c iu ch theo quy trnh 3.39 t bentonit Bnh Thun loi c hm lng >90% v DAC Hnh 3.42 cho thy c hai hiu ng mt khi lng ti 410,37oC (-23,75%) v ti 631,52 oC (-8,72%). Cc hiu ng ny u c km theo hiu ng thu nhit trn ng DTA v c quy gn cho qu trnh mt nc cu trc v phn h y ca dodecyl amoni trong mu. Vi mu st c ch ha tng t nhng khng c tc nhn hu c (gin phn tch nhit c a ra trn hnh 3.20) th c tng khi lng mt khi nung l 11,50%. Nh vy, hm lng cation dodecyl amoni trong sn phm st hu c l ~20,97%.

76

KT LUN
1. Cc kt qu thc nghim thu c cho thy, p hng php t c hiu qu tt trong vic iu ch st hu c t bentonit Bnh Thu n v cc mui amoni hu c. Cc m u st hu c iu ch c c cc gi tr d001 ln v hm lng hu c trong sn phm cao, p ng tt yu cu ca cc ng dng khc nhau (lm cht u iu ch vt liu nanocompozit v s dng trong sn xut sn). Cc kt qu thc nghim cng kh ng nh rng, bentonit Bnh Thun sau khi c lm sch v lm giu c th s dng lm nguyn liu u iu ch st hu c cho cc nhu cu khc nhau. 2. Trng hp s dng CTAB lm tc nhn hu c, kho st c cc yu t nh hng n qu trnh iu ch st hu c t bentonit Bnh Thun (Vit Nam) c hm lng MMT >90% v CTAB vi cc iu kin thch hp nh sau: t l CTAB/bentonit l 140 mmol/100g bentonit kh, nhit huyn ph l 60-70oC, thi gian khuy l 5h, pH huyn ph l 9,0. T cc iu kin kh o st c, tin hnh xy dng quy trnh iu ch st hu c t bentonit Bnh Thun v CTAB. Sn phm iu ch c theo quy trnh c cht lng tt, vi gi tr d001 ~40, hm lng hu c trong sn phm l ~35%. 3 . kho st c cc yu t nh hng n qu trnh iu ch st hu c t bentonit Bnh Thun (Vit Nam) hm lng >90% v DAC vi cc iu kin thch h p nh sau: t l DAC/bentonit l 250 mmol/100g bentonit kh, nhit huyn ph l 60oC, thi gian khuy l 5h, pH huyn ph l 9,0. T cc iu kin kh o st c, tin hnh xy dng quy trnh iu ch st hu c t bentonit Bnh Thun v DAC. Sn ph m iu ch c theo quy trnh c cht lng tng i tt, vi gi tr d 001 ~ 27, hm lng hu c trong sn phm l ~21%. 4. Kt hp kt qu nghin cu vi cc mui amoni l CTAB v DAC trong lu n vn ny v mt s kt qu nghin cu vi cc mui amoni khc c tin hnh trong phng th nghim Vt liu m i, s b so snh kh nng to st hu c

77

ca cc amin khc nhau v nh n thy rng, amin c bc cng cao, di mch cng di th kh nng to st hu c (d001 v hm lng cation amoni hu c trong sn phm cng ln) cng ln.

78

TI LIU THAM KHO

Ting Vit
1. Nguyn Vn Bnh, Hot tnh xc tc ca bentonit Thun Hi c bin tnh trong phn ng chuyn ha mt s hp cht hu c, Lun n tin s Ha hc, HKHTN, 1999. 2 . V nh C, Nguyn Xun Chnh (2001), Cng ngh nano iu khin n tng phn t, nguyn t, NXBKH- KT H Ni 2001. 3. Thn Vn Lin, Nghin cu qui trnh x l, hot ho bentonit Vit Nam sn xut bentonit xp , Bo co kt qu nghin cu ti hp tc theo ngh nh th vi Hn Quc, H Ni, thng 5, 2005. 4. Thn Vn Lin v cng s, Lm giu, lm sch v ho t ho bentonit Di Linh Lm ng v bentonit Tuy Phong, Bnh Thun, Hi ngh Khoa hc v Cng ngh ht nhn ton quc ln th VI, Lt thng 10 nm 2005. 5. Ng S Lng, Nguyn Trng Ngha, Thn Vn Lin, iu ch st hu c t bentonit Bnh Thun v cetyl trimetyl amoni bromua, Tp ch ho hc T46, s 2A, 2008. 6. Nguyn Vit Lc, L i Th (1999), Bentonit Thun Hi, NXB H Ni. 7. Nguyn c Ngha (2007), Ha hc nano cng ngh nn v vt liu ngun, Nh xut bn Khoa Hc T nhin v Cng Ngh H Ni. 8. Nguyn Hong Ngh , L thuyt nhiu x tia X, Nh xut bn H Ni, 2002. 9. Trn Xun Phng, Nghin cu tng hp bentonit hu c lm cht to cu trc cho dung dch khoan gc du, Lu n vn thc s, HQGHN, 2004. 10. Ng Th Thun, Trn Nh Mai, Nguyn Th Thanh Bo, Mt s kin nh hng cu trc l xp n phn ng phn b li bt i xng toluen, Tuyn tp cc cng trnh hi ngh ha hc ln th 3, 1998.

Ting Anh
11. Anatolie Pushniak (2003), Method for acidic activation of bentonite. MD 2 739 F1. 14.01.2003.

79

12. Antonio Gonzales, Kevin L. Nichols (1998), Oganoclay compositions, US Patent 5,780,376, Jul. 14, 1998. 13. Bauer Carl (1997), Formulations including improved organoclay compositions, WO 97/09375. 13.03.97. 14. Bekh N. I (2001), Method for preparation of activated bentonite, (Russia) RU 2 196 117 C1. 06.08.2001. 15. Charles A. Cody, Edward D.Magauran (1992), Method of treating waste water for organic containminatnts with water dispersible organically modified smectite clay compositions, US Patent 5,130,028, Jul.14, 1992. 16. Chuen-Shyong Chou, Dennis Paul Lorah, Aqueous nano composite dispersions, US 2002/0086908 A1, Jul.4, 2002. 17. David E. W. Vaughan (1999), Pillared interlayered clays materials useful as catalysts and sorbents, U.S. Patent. 4,176,090, Date of Patent: Nov. 27.1999. 18. David Jarus (2005), Nanoclay-containing composites and methods of making them. WO 2005/056644 A2. Jun. 23, 2005. 19. Emmanuel P. Glennelis, Composite of high melting polymer and nanoclay with enhanced properties. US 2005/0137287 A1. Jun. 23, 2005. 20. Fethi Kooli, Yan Liu, Solhe F. Alshahateet, Mouslim Messali, Faiza Bergaya (2009), Reaction of acid activated montmorillonites with hexadecyl trimethylammonium bromide solution, Applied Clay Science 43 (2009) 357 363. 21. George R. Alther (2000), Granular organoclay for high temperature applications. US Patent 6,093,241. Jul. 25, 2000. 22. Harry Ryan Dennis (1996), Improved organoclay products containing a branched chain alkyl quaternary amonium ion . WO 96/ 35764. Nov. 14, 1996. 23. Hemi N. Nae (1994), Organoclay compositions prepared with a mixture of two organic cations and their use in non-aqueous systems, US 5,336,647. Aug. 9, 1994. 24. James Gadbery (1986), Improved organoclay compositions, WO 97/09285. Mar.13, 1997.4,631,091. Dec. 23, 1986.

80

25. John P. Tatum, Robert Christopher Wight, Organoclay materials, UK Patent Application GB 2 151 219 A. 55R. 26. Jules Roelofs, Synthetic nanoclay materials, WO 2005/026049 A2. Mar 24, 2005. 27. Leandro Pizzatto, Analice Lizot, Rudinei Fiorio, Cntia L. Amorim, Giovanna Machado, Marcelo Giovanela, Ademir J. Zattera, Janaina S. Crespo (2009), Synthesis and characterization of novel organo-montmorillonites, Materials Science and Engineering C 29 (2009) 474478 28. Lucilene Betega de Paiva, Ana Rita Morales, Francisco R. Valenzuela Daz (2008), Organoclays: Properties, preparation and applications Applied Clay Science 42 (2008) 824. 29. Pavlidoua S., C.D. Papaspyridesb (2008), A review on polymerlayered silicate nanocomposites, Progress in Polymer Science 33 (2008) 11191198. 30. Qin Zhou, Ray L. Frost, Hongping He, Yunfei Xi (2007), Changes in the surfaces of adsorbed para-nitrophenol on HDTMA organoclay - The XRD and TG study Journal of Colloid and Interface Science 307 (2007) 5055. 31. Rajkiran R. Tiwari, Kartic C. Khilar, Upendra Natarajan (2008), Synthesis and characterization of novel organo-montmorillonites, Applied Clay Science 38 (2008) 203208. 32. Roelofs J.C., P.H. Berben (2006), Preparation and performance of synthetic organoclays, Applied Clay Science 33 (2006) 1320. 33. Rui Liu, Ray L. Frosta, Wayde N. Martens, Yong Yuana (2008), Synthesis, characterization of mono, di and tri alkyl surfactant intercalated Wyoming montmorillonite for the removal of phenol from aqueous systems, Journal of Colloid and Interface Science 327 (2008) 287294. 34. Sfung Yeop Lee & Soo Jin Kim, Transimission electron microscopy of hexadecyltrimetylamonium- exchanged smetite claymineral, 2002. 35. Soo Bin Bae, Chang Kee Kim, Kwanghyon Kim, In Jae Chung (2008), The effect of organic modifiers with different chain lengths on the dispersion of clay layers in HTPB (hydroxyl terminated polybutadiene), European Polymer Journal 44 (2008), 33853392. 36. Steven D. Landau. Nickel (1991), pillared interlayered clays, US Patent 5,037,787. Aug. 6,1991.24.

81

37. S.Y.LEE & S.J.KIM, dehydration behaviour of hexa decyltri metylamonium exchanged, smectit, clay mineral, 2003. 38. Vechiugov Alekxandr Viacheslavovich (2001), Method for activation of bentonite clay. RU 2 199 504 C1. 16.07.2001. 39. Youngjae Yoo, D.R. Paul (2008), Effect of organoclay structure on morphology and properties of nanocomposites based on an amorphous polyamide, Polymer 49 (2008) 37953804.

82

PH LC

83

84

85

86

87

88

89

90

91

92

Figure: Labsys TG 19/6/2009

Experiment: Thuy Anh-CTAB-tg-5 Procedure: 30 ----> 800C (10C.min-1) (Zone 2)

Crucible: PT 100 l

Atmosphere: Air Mass (mg): 59.76

TG/% 36
Peak :116.67 C Peak :432.66 C

HeatFlow/V Exo 20

dTG/%/min

27

Peak :243.73 C

-5
Peak :292.46 C

18

10

9 0 0
Peak :67.54 C Mass variation: -2.67 %

-10

-10 -9
Mass variation: -21.78 %

-15

-18

-20

-27
Mass variation: -15.40 %

-20 -30

-36 0 100 200 300 400 500 600 700 Furnace temperature /C

Hm lng hu c trong sn phm t 28,35%

Figure: Labsys TG 03/07/2009

Experiment: Procedure:

Thuy Anh CTAB-pH9 30 ----> 800C (10C.min-1) (Zone 2)

Crucible:

PT 100 l

Atmosphere: Mass (mg):

Air 48.55

TG/% 40
Peak :107.47C

HeatFlow/V Exo

d TG/%/min

30

Peak :287.88 C

10

-4

20

Peak :573.35 C

10

Peak 1 :69.29 C Peak 2 :106.63 C

-8

0
Mass variation: -3.14 %

-10
Mass variation: -21.81 %

-10

-12

-20

-30
Mass variation: -17.58 %

-20

-16

-40 0 100 200 300 400 500 600 700 Furnace temperature /C

Hm lng hu c trong sn phm t 31,03%

93

Figure: Labsys TG TG/% 36 14/7/2009

Experiment: Thuy Anh-CTAB-t-60 Procedure: 30 ----> 800C (10C.min-1) (Zone 2)

Crucible: PT 100 l

Atmosphere:Air Mass (mg): 54.42

HeatFlow/V Exo Peak :108.72 C 20

dTG/%/min

27 Peak :293.54 C Peak :416.89 C 18 10 -4

9 0 Peak :67.71 C 0 Mass variation: -1.62 % Mass variation: -10.78 % -10 -8

-9

-18 Mass variation: -24.74 % -27

-20 -12

-30 -36 0 100 200 300 400 500 600 700 Furnace temperature /C

Hm lng hu c trong sn phm t 25,64%

Figure: Labsys TG 25/05/2009 Experiment: Thuy Anh-CTAB-150 Procedure: 30 ----> 800C (10C.min-1) (Zone 2) Crucible: PT 100 l Atmosphere: Air Mass (mg): 32.52

TG/% 40
Peak :96.94 C

HeatFlow/V Exo 20

d TG/%/min

30

20

Peak :277.08 C Peak :450.49 C

10

-4

10
Peak 1 :67.93 C Peak 2 :103.70 C

0
Mass variation: -3.63 %

-8 -10

-10
Mass variation: -19.12 %

-20

-20 -12

-30

Mass variation: -16.87 %

-30 -40 0 100 200 300 400 500 600 700 Furnace temperature /C

Hm lng hu c trong sn phm t 28,12%

94

Figure: Labsys TG TG/%

Experiment: Thuy Anh-DAC-t5

Crucible:PT 100 l

Atmosphere: Air Mass (mg): 45.65

28/07/2009 Procedure: 30 ----> 800C (10 C.min-1) (Zone 2) HeatFlow/V Exo

d TG/%/min

30 Peak :632.67 C 20 Peak :404.74 C 20 10 -4 0 0 40 -2

-10

Mass variation: -25.07 % -20

-6

-20 Mass variation: -11.43 % -40 -30 -8

100

200

300

400

500

600

700

Furnace temperature /C

Hm lng hu c trong sn phm t 25%

Figure: Labsys TG TG/% 28 22/08/2009 Experiment: Thuy Anh-DAC-pH9 Procedure: 30 ----> 800C (10 C.min-1) (Zone 2) HeatFlow/V Exo 70 Crucible: PT 100 l Atmosphere:Air Mass (mg): 44.98 dTG/%/min 0

21 Peak :404.9 2C 14

Peak :636.91 C

30

-3

0 -10 -7 Mass variation: -22.16 % -14 -50 -21 Mass variation: -10.17 % -28 0 100 200 300 400 500 600 700 Furnace temperature /C -9 -6

Hm lng hu c trong sn phm t 20,83%

95

Figure: Labsys TG TG/%

Experiment: Thuy Anh-DAC-270

Crucible: PT 100 l

Atmosphere: Air Mass (mg): 49.15

23/07/2009 Procedure: 30 ----> 800C (10 C.min-1) (Zone 2) HeatFlow/V Exo

dTG/%/min

30 Peak :630.81 C 20 Peak :411.27 C 10 -4 0 0 30 -2

-10 Mass variation: -22.24 %

-6

-20

-30 -8 Mass variation: -8.78 %

-30

100

200

300

400

500

600

700

Furnace temperature /C

Hm lng hu c trong sn phm t 19,52%

Figure: Labsys TG 23/07/2008 Experiment: Procedure: Thuy Anh DAC-t-60 30 ----> 800C (10 C.min-1) (Zone 2) Crucible: PT 100 l Atmosphere: Air Mass (mg): 49.15

TG/%

HeatFlow/V Exo

dTG/%/min

30
Peak :630.81 C

20
Peak :411.27 C

30

-2

10 -4 0 0

-10
Mass variation: -21.69 %

-6

-20

-30 -8
Mass variation: -9.61 %

-30

100

200

300

400

500

600

700

Furnace temperature /C

Hm lng hu c trong sn phm t 19,80%

96

MC LC
M U ................................................................................................................ 1 CHNG I. TNG QUAN .................................................................................. 3 1.1. Gii thiu v bentonit .................................................................................... 3 1.1.1. Cu trc ca bentonit .................................................................................. 3 1.1.2. Tnh cht ca bentonit ................................................................................. 4 1.1.2.1. Tnh cht trao i ion .............................................................................. 4 1.1.2.2. Tnh cht trng n ................................................................................ 6 1.1.2.3. Tnh hp ph ............................................................................................ 7 1.1.2.4. Tnh kt dnh ............................................................................................. 8 1.1.2.5. Tnh tr ..................................................................................................... 8 1.1.2.6. Tnh nht v do ....................................................................................... 8 1.1.3. ng dng ca bentonit ................................................................................ 8 1.1.3.1. Lm cht xc tc trong cc qu trnh tng hp hu c ......................... 8 1.1.3.2. Lm vt liu hp ph ............................................................................... 9 1.1.3.3. Lm vt liu iu ch st hu c v nanocompozit .............................. 10 1.1.3.4. Dng trong mt s lnh vc khc ........................................................... 11 1.1.4. Lm giu, lm sch bentonit ..................................................................... 11 1.1.5. Gii thiu v bentonit Bnh Thun Vit Nam ........................................ 12 1.2. Gii thiu v st hu c ................................................................................ 13 1.2.1. Cu trc ca st hu c ............................................................................. 15 1.2.2. Tnh cht v ng dng ca st hu c ...................................................... 21 1.2.2.1. Tnh cht ca st hu c......................................................................... 21 1.2.2.2. ng dng ca st hu c ........................................................................ 21 1.2.3. Cc phng php iu ch st hu c ...................................................... 22 1.2.3.1. Phng php t .................................................................................... 22 1.2.3.2. Phng php kh ................................................................................... 24 1.3. Mc ch v ni dung nghin cu ca lun vn .......................................... 25 1.3.1. Mc ch ..................................................................................................... 25

97

1.3.2. Ni dung nghin cu .................................................................................. 25 CHNG II. THC NGHIM ......................................................................... 27 2.1. Ha cht, dng c v thit b........................................................................ 27 2.1.1. Ha cht ..................................................................................................... 27 2.1.2. Dng c ...................................................................................................... 27 2.1.3. Thit b ....................................................................................................... 27 2.2. Phng php iu ch st hu c ................................................................ 28 2.2.1. Chuyn dodecylamin thnh mui dodecyl amoni clorua ......................... 28 2.2.2. Qui trnh iu ch st hu c .................................................................... 28 2.3. Cc phng php nghin cu cu trc v tnh cht vt liu ...................... 29 2.3.1. Phng php nhiu x tia X ...................................................................... 29 2.3.2. Phng php phn tch nhit .................................................................... 30 CHNG III. KT QU NGHIN CU V THO LUN .......................... 31 3.1. Kho st qu trnh iu ch st hu c t bentonit v CTAB.................... 31 3.1.1. Kho st cc yu t nh hng trong qu trnh iu ch n gi tr d001 v hm lng amoni hu c trong st hu c t bentonit v CTAB ................ 31 3.1.1.1. nh hng ca t l cation amoni hu c/bentonit .............................. 31 3.1.1.2. nh hng ca nhit huyn ph ....................................................... 38 3.1.1.3. nh hng ca thi gian khuy trn ..................................................... 42 3.1.1.4. nh hng ca pH huyn ph ............................................................... 47 3.1.2. Xy dng quy trnh iu ch st hu c t bentonit v CTAB ............... 51 3.1.2.1. Quy trnh iu ch st hu c t bentonit Bnh Thun v cetyl trimetyl amoni bromua...................................................................................................... 51 3.1.2.2. Thuyt minh quy trnh ........................................................................... 51 3.1.2.3. Kt qu iu ch...................................................................................... 53 3.2. iu ch st hu c t bentonit v dodecylamoni clorua (DAC)................ 55 3.2.1. Kho st cc yu t nh hng trong qu trnh iu ch n gi tr d001 v hm lng amoni hu c trong st hu c t bentonit v DAC .................. 55 3.2.1.1. nh hng ca t l cation hu c/bentonit.......................................... 55

98

3.2.1.2. nh hng ca nhit huyn ph ....................................................... 61 3.2.1.3. nh hng ca thi gian khuy trn ..................................................... 65 3.2.1.4. nh hng ca pH huyn ph ............................................................... 69 3.2.2. Xy dng quy trnh iu ch st hu c t bentonit v DAC.................. 73 3.2.2.1. Quy trnh iu ch st hu c t bentonit Bnh Thun v dodecylamin .............................................................................................................................. 73 3.2.2.2. Thuyt minh quy trnh ........................................................................... 73 3.2.2.3. Kt qu iu ch...................................................................................... 75 K T LUN .......................................................................................................... 77 TI LIU THAM KHO ................................................................................... 79 PH LC............................................................................................................. 83

99