MC LC

LI CM N ............................................................................................................. 4 LI M U ............................................................................................................. 5 Chng 1 - TNG QUAN ......................................................................................... 6 1.1. Than hot tnh v cu trc b mt ....................................................................... 6 1.1.1 Than hot tnh .............................................................................................. 6 1.1.2 Cu trc xp ca b mt than hot tnh ........................................................ 9 1.1.3 Cu trc ha hc ca b mt ...................................................................... 12 1.2 Nhm Cacbon-oxy trn b mt than hot tnh ................................................... 13 1.2.1 Nghin cu nhit gii hp ........................................................................... 16 1.2.2 Trung ha kim........................................................................................... 18 1.3 nh hng ca nhm b mt cacbon-oxi ln tnh cht hp ph ......................... 19 1.3.1 Tnh axit b mt ca cacbon. ...................................................................... 20 1.3.2 Tnh k nc ............................................................................................... 20 1.3.3 S hp ph hi phn cc ............................................................................ 21 1.3.4 S hp ph t cc dung dch ....................................................................... 23 1.3.5 S hp ph u tin. ..................................................................................... 24 1.4. Tm hot ng trn b mt than ....................................................................... 25 1.5 Bin tnh b mt than hot tnh .......................................................................... 29 1.5.1 Bin tnh tnh than hot tnh bng N2 .......................................................... 30 1.5.2 Bin tnh b mt than bng halogen............................................................ 31 1.5.3 Bin tnh b mt than bng s lu hunh ha. ............................................ 31 1.5.4 Bin tnh than hot tnh bng cch tm....................................................... 33

Chng 2 - THC NGHIM .................................................................................. 35 2.1 i tng nghin cu........................................................................................ 35 2.2 Mc tiu nghin cu.......................................................................................... 35 2.3 Danh mc thit b, ha cht cn thit cho nghin cu. ....................................... 35 2.4 Phng php nghin cu ................................................................................... 36 2.4.1 Phng php bin tnh than hot tnh ......................................................... 36 2.4.2. Phng php kho st cc c trng ca than bin tnh ............................ 37 2.4.3. Phng php xc nh cc ion trong dung dch ......................................... 40 2.5 Phng php tnh ton ti trng hp ph ca vt liu ........................................ 43 Chng 3 - KT QU V THO LUN ............................................................... 45 3.1 Oxi ha than hot tnh nhit thng .......................................................... 45 3.1.1 Kho st kh nng hp ph amoni ca than hot tnh ................................. 45 3.1.2 Kho st kh nng hp ph ca than hot tnh c oxi ha trong cc khong thi gian khc nhau ................................................................................ 45 3.1.3 Trung ha than oxi ha bng NaOH .......................................................... 47 3.1.4 Kho st kh nng hp ph ca than hot tnh bin tnh vi cc nng axit khc nhau ............................................................................................................ 49 3.2 Kho st kh nng hp ph amoni ca than c bin tnh nhit 700C. ..... 53 3.3 Kho st kh nng hp ph ca than oxi ha bng HNO 3 nhit 1000C ....... 55 3.4 Kho st kh nng hp ph mt s kim loi nng ca than bin tnh ................. 58 3.4.1.Kh nng hp ph Mangan......................................................................... 58 3.4.2. Kh nng hp ph cadimi (Cd2+) ............................................................... 60 3.5 Xc nh mt s c trng ca than bin tnh .................................................... 61 3.5.1 Xc nh din tch b mt ring ca than .................................................... 61

3.5.2 Xc nh cc nhm chc c th c trn b mt cc loi than ...................... 64 3.5.3 Xc nh tng s tm axit trn b mt than ................................................. 65 3.5.4 Kho st pHpzc ca cc loi than. .............................................................. 68 3.5.5 Bc u nghin cu c ch hp ph amoni ca than bin tnh.................. 69 3.6 Kho st kh nng x l amoni bng m hnh ng .......................................... 72 3.6.1 Kho st kh nng trao i ca than bin tnh vi amoni ........................... 72 3.6.2 Kho st kh nng ti sinh ca vt liu....................................................... 73 KT LUN ............................................................................................................... 75 TI LIU THAM KHO ........................................................................................ 77

LI CM N
Vi lng bit n su sc, em xin gi li cm n chn thnh ti thy gio Trn Hng Cn giao ti v nhit tnh gip , cho em nhng kin thc qu bu trong qu trnh nghin cu. Cm n cc phng th nghim trong Khoa Ha hc Trng i hc Khoa hc T nhin to iu kin gip ti trong qu trnh lm thc nghim. Chn thnh cm n cc bn hc vin, sinh vin lm vic trong phng th nghim ha mi trng gip ti trong qu trnh tm ti liu v hon thin lun vn. hon thnh bn lun vn ny, ngoi s n lc tm ti, nghin cu ca bn thn, s gip ca nhng ngi xung quanh, c bit l nhng ngi thy, ng nghip ng gp mt phn khng nh trong nghin cu ny. Ti xin chn thnh cm n!

Hc vin cao hc

Trnh Xun i

LI M U
Hin nay, tnh hnh nhim ngun nc ni chung v ngun nc sinh hot ni ring bi cc cation kim loi nng l vn ton x hi quan tm khi nhu cu v cht lng cuc sng ngy cng cao. Theo cc phng tin thng tin i chng gn y a tin, ngi dn H ni ang s dng cc ngun nc nhim, c bit l nhim amoni, ngay c ngun nc ca cc nh my nc, hm lng amoni xc nh c cng vt ch tiu cho php n 6 ln hoc cao hn. Than hot tnh t lu c s dng lm sch nc. Tuy nhin, ng dng ca n trong x l nc mi ch dng li vic loi b cc hp cht hu c v mt s cc thnh phn khng phn cc c hm lng nh trong nc. Vi mc ch khai thc tim nng ng dng ca than hot tnh trong vic x l nc sinh hot, c bit mt lnh vc cn rt mi l loi b cc cation v anion trong nc; chng ti chn v thc hin ti Nghin cu bin tnh than hot tnh lm vt liu hp ph x l amoni v kim loi nng trong nc.

Chng 1 - TNG QUAN

1.1. Than hot tnh v cu trc b mt ca than hot tnh 1.1.1 Than hot tnh C rt nhiu nh ngha v than hot tnh, tuy nhin c th ni chung rng, than hot tnh l mt dng ca cacbon c x l mang li mt cu trc rt xp, do c din tch b mt rt ln. Than hot tnh dng than g hot ha c s dng t nhiu th k trc. Ngi Ai cp s dng than g t khong 1500 trc cng nguyn lm cht hp ph cho mc ch cha bnh. Ngi Hindu c n lm sch nc ung ca h bng cch lc qua than g. Vic sn xut than hot tnh trong cng nghip bt u t khong nm 1900 v c s dng lm vt liu tinh ch ng. Than hot tnh ny c sn xut bng cch than ha hn hp cc nguyn liu c ngun gc t thc vt trong s c mt ca hi nc hoc CO2. Than hot tnh c s dng sut chin tranh th gii th nht trong cc mt n phng c bo v binh lnh khi cc kh c nguy him[5]. Than hot tnh l cht hp ph qu v linh hot, c s dng rng ri cho nhiu mc ch nh loi b mu, mi, v khng mong mun v cc tp cht hu c, v c trong nc thi cng nghip v sinh hot, thu hi dung mi, lm sch khng kh, trong kim sot nhim khng kh t kh thi cng nghip v kh thi ng c, trong lm sch nhiu ha cht, dc phm, sn phm thc phm v nhiu ng dng trong pha kh. Chng c s dng ngy cng nhiu trong lnh vc luyn kim thu hi vng, bc, v cc kim loi khc, lm cht mang xc tc. Chng cng c bit n trong nhiu ng dng trong y hc, c s dng loi b cc c t v vi khun ca mt s bnh nht nh. Cacbon l thnh phn ch yu ca than hot tnh vi hm lng khong 85 95%. Bn cnh than hot tnh cn cha cc nguyn t khc nh hidro, nit, lu hunh v oxi. Cc nguyn t khc loi ny c to ra t ngun nguyn liu ban u

hoc lin kt vi cacbon trong sut qu trnh hot ha v cc qu trnh khc. Thnh phn cc nguyn t trong than hot tnh thng l 88% C, 0.5% H, 0.5% N, 1%S, 6 7% O. Tuy nhin hm lng oxy trong than hot tnh c th thay i t 1 - 20% ph thuc vo ngun nguyn liu ban u, cch iu ch. Than hot tnh thng c din tch b mt nm trong khong 800 n 1500m2/g v th tch l xp t 0.2 n 0.6cm3/g. Din tch b mt than hot tnh ch yu l do l nh c bn knh nh hn 2nm. Than hot tnh ch yu c iu ch bng cch nhit phn nguyn liu th cha cacbon nhit nh hn 10000C. Qu trnh iu ch gm 2 bc: Than ha nhit di 8000C trong mi trng tr v s hot ha sn phm ca qu trnh than ha nhit khong 9500 10000C. Qu trnh than ha l dng nhit phn hy nguyn liu, a n v dng cacbon, ng thi lm bay hi mt s cht hu c nh to l xp ban u cho than, chnh l xp ny l i tng cho qu trnh hot ha than. Qu trnh than ha c th xy ra trong pha rn, lng v kh [13]. Qu trnh than ha pha rn: Nguyn liu ban u hu nh lun lun l h phn t ln do s tng hp hoc qu trnh t nhin. Phn hy nguyn liu u bng cch tng nhit x l, qu trnh xy ra cng vi s gii phng kh v cht lng c khi lng phn t thp. Do , than thu c l dng khc ca nguyn liu ban u c th ln hn hoc nh hn hnh dng ban u nhng n c t trng thp hn. Khi tng nhit x l s to ra cu trc trung gian bn hn. Trong qu trnh than ha, khi h i phn t ban u phn hy, cc nguyn t cacbon cn li trong mng i phn t di chuyn khong ngn (c th < 1nm) trong mng ti v tr bn hn, thm ch to ra mng cc nguyn t cacbon(c hydro lin kt vi n). Thnh phn ca nguyn liu ban u khc nhau s phn hy theo nhng cch ring, to ra cc dng than khc nhau. Khong cch (kch thc nguyn t) c m ra bi s thot ra ca cc nguyn t

khc, s di tr ca nguyn t cacbon v cc lin kt ca chng to ra mng xp c thnh phn l cc nguyn t cacbon. Mi loi than c c trng xp khc nhau. Than ha trong pha lng: Cc nguyn liu nh vng thm, hc n cho php to thnh cacbon c th graphit ha v c bn l than khng xp. Do to ra mt loi than xp t nhng nguyn liu ny cn 1 phn ng tc ng ln cc lp graphen. Qu trnh than ha trong pha lng c c ch hon ton khc vi trong pha rn. Bng s than ha pha lng, dng c th graphit ha c to thnh. Cacbon ha trong pha kh cn phi c kim sot cn thn ngun nguyn liu u vo. Nguyn liu c th l metan, propan hoc benzen nhng quan trng nht l qu trnh cacbon ha (b gy hoc nhit phn) nguyn liu kh p sut tng i thp thng c pha long vi kh heli. Mnh v t qu trnh nhit phn nguyn liu ban u tng tc vi cht nn thch hp v bng mt c ch bao gm s chuyn ng cc nguyn t cacbon, cu trc phin 6 cnh ca graphit c hnh thnh [13]. Hot ha l qu trnh bo mn mng li tinh th cacbon di tc dng ca nhit v tc nhn hot ha, to xp cho than bng mt h thng l c kch thc khc nhau, ngoi ra cn to cc tm hot ng trn b mt [24]. C th hot ha bng phng php ha hc hoc bng hi nc. Hot ha ha hc ch yu c s dng cho hot ha than g. Phng php ny khc vi hot ha bng hi; trong qu trnh than ha v qu trnh hot ha xy ra ng thi. Nguyn liu th thng s dng l g c trn vi cht hot ha v cht ht nc thng c s dng l axit photphoric hoc ZnCl2. S hot ha thng xy ra nhit 5000C, nhng i khi cng c khi ln ti 8000C. Axit photphoric lm cho g phnh ra v m cu trc cenlulose ca g. Trong sut qu trnh hot ha axit photphoric hot ng nh 1 cht n nh v m bo rng than khng b xp tr li. Kt qu l than rt xp v cha y axit photphoric. Sau than c ra v tip tc bc sn xut tip theo.

Hot ha bng hi nc c s dng cho tt c cc than c ngun gc t than bn, than , go da, g Trc ht nguyn liu th c chuyn ha thnh cacbon bng nhit. Khi than c s dng lm nguyn liu trong hot ha, hi nc 1300C c thi vo nhit khong 10000C. Mt s ti kh tr thnh dng kh v thot ra khi l xp. Hnh thc ny ph thuc ln vo nguyn liu c s dng. Mt nguyn liu cng nh l go da to ra nhiu l nh trong khi nguyn liu mm nh than bn lun to ra nhiu l trung. Nu tip tc thi hi nc trong 1 thi gian di, nhiu hn rt nhiu cc ti kh to thnh dng kh v li cc l trng. u tin chng ta thu c l nh. Khi tip tc qu trnh, xung quanh ti kh cng chuyn thnh kh v l xp pht trin thnh l trung v nu tip tc th s to thnh l ln. Do , ta khng nn ko di qu trnh hot ha. Tt c cc nguyn liu cha cacbon u c th chuyn thnh than hot tnh, tt nhin sn phm thu c s c s khc nhau ph thuc vo bn cht ca nguyn liu c s dng, bn cht ca tc nhn hot ha v iu kin hot ha. Trong qu trnh hot ha hu ht cc nguyn t khc trong nguyn liu to thnh sn phm kh v bay hi bi nhit phn hy nguyn liu ban u. Cc nguyn t cacbon s nhm li vi nhau thnh cc lp thm lin kt vi nhau mt cch ngu nhin. S sp xp ca cc lp thm ny khng tun theo qui lut do li cc ch trng gia cc lp. Cc ch trng ny tng ln thnh l xp lm than hot tnh thnh cht hp ph tuyt vi. 1.1.2 Cu trc xp ca b mt than hot tnh[5] Than hot tnh vi s sp xp ngu nhin ca cc vi tinh th v vi lin kt ngang bn gia chng, lm cho than hot tnh c mt cu trc l xp kh pht trin. Chng c t trng tng i thp (nh hn 2g/cm3) v mc graphit ha thp. Cu trc b mt ny c to ra trong qu trnh than ha v pht trin hn trong qu trnh hot ha, khi lm sch nha ng v cc cht cha cacbon khc trong khong trng

gia cc tinh th. Qu trnh hot ha lm tng th tch v lm rng ng knh l. Cu trc l v s phn b cu trc l ca chng c quyt nh ch yu t bn cht nguyn liu ban u v phng php than ha. S hot ha cng loi b cacbon khng phi trong cu trc, lm l ra cc tinh th di s hot ng ca cc tc nhn hot ha v cho php pht trin cu trc vi l xp. Trong pha sau cng ca phn ng, s m rng ca cc l tn ti v s to thnh cc l ln bng s t chy cc vch ngn gia cc l cnh nhau c din ra. iu ny lm cho cc l trng c chc nng vn chuyn v cc l ln tng ln, dn n lm gim th tch vi l. Theo Dubinin v Zaveria, than hot tnh vi l xp c to ra khi mc t chy (burn-off) nh hn 50% v than hot tnh l macro khi mc t chy l ln hn 75% . Khi mc t chy trong khong 50 75% sn phm c hn hp cu trc l xp cha tt c cc loi l. Ni chung than hot tnh c b mt ring pht trin v thng c c trng bng cu trc nhiu ng mao dn phn tn, to nn t cc l vi kch thc v hnh dng khc nhau. Ngi ta kh c th a ra thng tin chnh xc v hnh dng ca l xp. C vi phng php c s dng xc nh hnh dng ca l, cc phng php ny xc nh than thng c dng mao dn m c hai u hoc c mt u kn, thng thng c dng rnh, dng ch V v nhiu dng khc. Than hot tnh c l xp t 1 nm n vi nghn nm. Dubinin xut mt cch phn loi l xp c IUPAC chp nhn. S phn loi ny da trn chiu rng ca chng, th hin khong cch gia cc thnh ca mt l xp hnh rnh hoc bn knh ca l dng ng. Cc l c chia thnh 3 nhm, l nh, l trung v l ln. L nh (Micropores) c kch thc c phn t, bn knh hiu dng nh hn 2nm. S hp ph trong cc l ny xy ra theo c ch lp y th tch l, v khng xy ra s ngng t mao qun. Nng lng hp ph trong cc l ny ln hn rt nhiu so vi l trung hay b mt khng xp v s nhn i ca lc hp ph t cc vch i din nhau ca vi l. Ni chung chng c th tch l t 0.15 0.7cm3/g. Din tch b mt

10

ring ca l nh chim 95% tng din tch b mt ca than hot tnh. Dubinin cn xut thm rng cu trc vi l c th chia nh thnh 2 cu trc vi l bao gm cc vi l c trng vi bn knh hiu dng nh hn 0.6 0.7nm v siu vi l vi bn knh hiu dng t 0.7 n 1.6nm. Cu trc vi l ca than hot tnh c xc nh r hn bng hp ph kh v hi v cng ngh tia X. L trung (Mesopore) hay cn gi l l vn chuyn c bn knh hiu dng t 2 n 50 nm, th tch ca chng thng t 0.1 n 0.2cm3/g. Din tch b mt ca l ny chim khng qu 5% tng din tch b mt ca than. Tuy nhin, bng phng php c bit ngi ta c th to ra than hot tnh c l trung ln hn, th tch ca l trung t c t 0.2 0.65cm3/g v din tch b mt ca chng t 200m2 /g. Cc l ny c trng bng s ngng t mao qun ca cht hp ph vi s to thnh mt khum ca cht lng b hp ph. L ln (Macropore) khng c nhiu ngha trong qu trnh hp ph ca than hot tnh bi v chng c din tch b mt rt nh v khng vt qu 0.5m2/g. Chng c bn knh hiu dng ln hn 50nm v thng trong khong 500- 2000nm vi th tch l t 0.2 0.4cm3 /g. Chng hot ng nh mt knh cho cht b hp ph vo trong l nh v l trung. Cc l ln khng c lp y bng s ngng t mao qun. Do , cu trc l xp ca than hot tnh c 3 loi bao gm l nh, l trung v l ln. Mi nhm ny th hin mt vai tr nht nh trong qu trnh hp ph. L nh chim 1 din tch b mt v th tch ln do ng gp ln vo kh nng hp ph ca than hot tnh, min l kch thc phn t ca cht b hp ph khng qu ln i vo l nh. L nh c lp y p sut hi tng i thp trc khi bt u ngng t mao qun. Mt khc, l trung c lp y p sut hi tng i cao vi s xy ra ngng t mao qun. L ln c th cho phn t cht b hp ph di chuyn nhanh ti l nh hn

11

1.1.3 Cu trc ha hc ca b mt[5] Cu trc tinh th ca than c tc ng ng k n hot tnh ha hc. Tuy nhin, hot tnh ha hc ca cc tm mt tinh th c s t hn nhiu so vi tm cnh hay cc v tr khuyt. Do , cacbon c graphit ha cao vi b mt ng nht cha ch yu mt c s t hot ng hn cacbon v nh hnh. Grisdale v Hennig thy rng tc oxy ha ca nguyn t cacbon tm nm cnh ln hn 17 n 20 ln b mt c s. Bn cnh cu trc tinh th v cu trc l xp, than hot tnh cng c cu trc ha hc. Kh nng hp ph ca than hot tnh c quyt nh bi cu trc vt l v l xp ca chng nhng cng b nh hng mnh bi cu trc ha hc. Thnh phn quyt nh ca lc hp ph ln b mt than l thnh phn khng tp trung ca lc Van der Walls. Trong graphit, qu trnh hp ph c quyt nh ch yu bi thnh phn phn tn ca lc London. Trong trng hp than hot tnh, s phc tp ca cc cu trc vi tinh th, do s c mt ca cc lp graphit chy khng hon ton trong cu trc, gy ra bin i v s sp xp cc electron trong khung cacbon v kt qu l to ra cc electron c thn v ha tr khng bo ha iu ny nh hng n c im hp ph ca than hot tnh c bit l i vi cc hp cht phn cc v c th phn cc. Than hot tnh hu ht c lin kt vi mt lng c th xc nh oxy v hydro. Cc nguyn t khc loi ny c to ra t nguyn liu ban u v tr thnh mt phn cu trc ha hc l kt qu ca qu trnh than ha khng hon ho hoc tr thnh lin kt ha hc vi b mt trong qu trnh hot ha hoc trong cc qu trnh x l sau . Cng c trng hp than hp ph cc loi phn t xc nh nh amin, nitrobenzen, phenol v cc loi cation khc. Nghin cu nhiu x tia X cho thy rng cc nguyn t khc loi hoc cc loi phn t c lin kt vi cnh hoc gc ca cc lp thm hoc vi cc nguyn t cacbon cc v tr khuyt lm tng cc hp cht cacbon oxy, cacbon hydro, cacbon nitr, cacbon lu hunh, cacbon halogen trn b mt, chng c bit n nh l

12

cc nhm b mt hoc cc phc b mt. Cc nguyn t khc loi ny c th sp nhp trong lp cacbon to ra h thng cc vng khc loi. Do cc cnh ny cha cc tm hp ph chnh, s c mt ca cc hp cht b mt hay cc loi phn t lm bin i c tnh b mt v c im ca than hot tnh. 1.2 Nhm Cacbon-oxy trn b mt than hot tnh[5] Nhm cacbon oxy b mt l nhng nhm quan trng nht nh hng n c trng b mt nh tnh a nc, phn cc, tnh acid, v c im ha l nh kh nng xc tc, dn in v kh nng phn ng ca cc vt liu ny. Thc t, oxy kt hp thng c bit l yu t lm cho than tr nn hu ch v hiu qu trong mt s lnh vc ng dng nht nh. V d, oxy c tc ng quan trng n kh nng hp ph nc v cc kh v hi c cc khc, nh hng n s hp ph cht in phn, ln than s dng lm cht lc trong cao su v nha, ln nht ca graphit cng nh ln tnh cht ca n khi l mt thnh phn trong phn ng ht nhn. Trong trng hp ca si cacbon, nhm b mt quyt nh kh nng bm dnh ca n vo cht nn l nha v sau l c im vt liu composite. Theo Kipling, cc nguyn t oxy v hydro l nhng thnh phn cn thit ca than hot tnh vi c im hp ph tt, v b mt ca vt liu ny c nghin cu nh mt b mt hydrocacbon bin i mt s tnh cht bng nguyn t oxy. Mc d vic xc nh s lng v bn cht ca cc nhm ha hc b mt ny bt u t hn 50 nm trc, bn cht chnh xc ca nhm chc vn cn cha c chng minh y . Nhng chng c c a ra t cc nghin cu khc nhau s dng cc cng ngh khc nhau v b mt cacbon l rt phc tp v kh m phng. Cc nhm chc b mt khng th c x l nh cc cht hu c thng thng v chng tng tc khc nhau trong mi trng khc nhau. Ph eletron cho phn tch ha hc cho thy s chuyn i bt thun nghch ca chc b mt xy ra khi cc phng php ha hc hu c c in c s dng xc nh v chng minh chng. Do ngi ta mong rng vic p dng ca nhiu cng ngh tinh vi hn nh ph FTIR, XPS, NMR

13

v nghin cu lng vt phng x s gp phn quan trng hiu bit chnh xc hn v cc nhm ha hc b mt ny. Than hot tnh c nhiu xu hng m rng lp oxy c hp th ha hc ny v nhiu cc phn ng ca chng xy ra do xu hng ny. V d, than hot tnh c th phn hy cc kh oxy ha nh ozone v oxit ca nit. Chng cng phn hy dung dich mui bc, halogen, st(III)clorua, KMnO4, amonipersunfat, axit nitricTrong mi trng hp, c s hp ph ha hc oxy v s to thnh hp cht cacbon oxy b mt. Than hot tnh cng c th c oxy ha bng nhit trong khng kh, CO2 hoc oxy. Bn cht v lng nhm oxy - cacbon b mt to thnh t cc s oxy ha khc nhau ph thuc vo bn cht b mt than v cch to ra n, din tch b mt ca n, bn cht cht oxy ha v nhit qu trnh. Phn ng ca than hot tnh vi oxi nhit di 4000C ch yu to ra s hp ph ha hc oxy v s to thnh hp cht cacbon oxy b mt, khi nhit trn 4000C, s phn hy hp cht b mt v kh ha cacbon l cc phn ng tri hn hn. C C + + O2 O2 C(O) (<4000C) s to thnh hp cht b mt S kh ha S phn hy hp cht b mt (>4000C) CO + CO2 (>4000C) CO + CO2

C(O)

Trong trng hp s oxy ha xy ra trong dung dch, phn ng chnh l s to thnh hp cht b mt, mc d mt vi qu trnh kh ha cng c th xy ra ph thuc mnh ca cht oxy ha v s khc nghit ca iu kin th nghim. S to thnh hp cht cacbon oxy b mt s dng than khc nhau. Than hot tnh v mui than s dng nhiu cch oxy ha trong pha kh v pha lng c nghin cu nhiu hn. i nhng than c c trng axit baz, nhiu nh khoa hc b cng sc nghin cu gp phn tm hiu nguyn nhn v c ch than c bn cht acid hay baz. Mt vi thuyt, v d thuyt in ha hc ca Burstein v Frumkin,, thuyt oxit ca Shilov v trng ca ng, thuyt pyron ca Voll v Boehm c a ra gii thch cho c trng acid baz ca than. Cc thuyt ny v cc nghin cu lin quan

14

 c xem xt li mt cch k lng v c xem xt trong mt vi bi bo tng kt. By gi ngi ta chp nhn rng c trng acid baz ca than l kt qu ca qu trnh oxi ha b mt, ph thuc vo cch to thnh v nhit ca qu trnh oxi ha. Dng nhm cacbon oxy b mt (acid, baz, trung ha) c xc nh, cc nhm axit b mt l rt c trng v c to thnh khi than c x l vi oxy nhit trn 4000C hoc bng phn ng vi dung dch oxy ha nhit phng. Cc nhm chc ny t bn nhit v phn hy khi x l nhit trong chn khng hoc trong mi trng kh tr nhit t 3500C n 7500C v gii phng CO2. Cc nhm chc axit b mt ny lm cho b mt than a nc v phn cc, cc nhm ny l caboxylic, lacton, phenol. Nhm oxy baz trn b mt t c trng hn v c to ra khi mt b mt than khng cn bt k nhm oxy b mt no khi x l nhit trong chn khng hoc trong mi trng tr nhit 10000C sau lm ngui nhit phng, c tip xc vi kh oxy. Garten v Weiss xut cu trc dng pyron cho nhm chc bazo, nhm chc ny cng c bit nh cu trc chromene. Cu trc ny c vng cha oxy vi nhm hot ha - CH2 , - CHR. Theo Voll v Boehm, cc nguyn t oxy trong cu trc kiu pyron c nh v trong hai vng khc nhau ca lp graphit. Tuy nhin, cu trc ca cc nhm oxy baz trn b mt cng ang cn tranh ci. Cc nhm oxy trung ha trn b mt c to ra do qu trnh hp ph ha hc khng thun nghch oxy cc tm khng bo ha dng etylen c mt trn b mt than. Cc hp cht b mt b phn hy thnh CO2 khi x l nhit. Cc nhm trung ha trn b mt bn hn so vi cc nhm axit v bt u phn hy trong khong nhit 5000 6000C v b loi b hon ton 9500C. Mt dng ca b mt than hot tnh c oxy ha c cng b bi Tarkovskya hnh di y.

15

Nhiu n lc ca nhiu nh nghin cu xc nh v nh lng cc nhm oxi- cacbon b mt s dng cc phng php vt l, ha hc v ha l gii hp lp oxit, trung ha vi kim, chun in th, phng php ph nh ph IR, X-ray. Cc nghin cu ny ch ra s tn ti ca vi nhm chc, quan trng hn c l cc nhm carboxyl, lacton, phenol, quinin v hydroquinon. Tuy nhin, cc phng php ny khng a ra cc kt qu c th so snh vi nhau v nhiu khi khng gii thch c ton b lng oxi kt hp. 1.2.1 Nghin cu nhit gii hp Cc nhm oxi cacbon trn b mt trn than do qu trnh iu ch hoc c to thnh t kt qu tng tc vi oxi hay vi cc dung dch hay kh oxi ha, c cc cn bng nhit khc nhau v chng c to thnh nhng tm khc nhau, lin kt vi cc nng lng khc nhau. V d, nhm cacboxyl phn hy nhit thp hn so vi phenol hay nhm quinone. Do , khi mu than c x l nhit trong chn khng hay trong mi trng tr, cc nhm b mt khc nhau phn hy cc khong nhit khc nhau. Ni chung, ngi ta thy rng cc nhm b mt ny bn nhit nhit di 2000C, c lp vi nhit chng c to thnh. Phng php chung lin quan n qu trnh gia nhit mu than trong chn khng hoc trong dng kh tr mt chng trnh tc gia nhit. Cc nhm cha oxi b mt gii hp dng cc sn phm kh d bay hi v c phn tch bng nhng phng php thng thng nh trng lng, ph khi lng, sc k kh v ph IR. V cacbon c hot tnh cao vi oxi, cc nhm chc b mt ni chung to ra CO2 , CO v

16

hi nc, lng mi loi kh ph thuc vo bn cht ca than, phng php tin x l v nhit gii hp ca n. V d, CO2 c to ra bng s phn hy cacboxylic v lactomic nhit trong khong 3500 7500C, CO b phn hy t cc nhm quinone v nhm phenolic trong khong nhit t 5000-9500C, hi nc t s phn hy carboxyl, phenol trong khong nhit t 2000 6000C. nhit thp, nc b hp ph vt l v hp ph ha hc cng c th b gii hp. Kh H2 to thnh bi s kt hp li t cc nguyn t hydro c gii phng ra l kt qu ca s t lin kt C-H c gii hp nhit khong 5000-10000C. iu ny c th gii thch khong 25-30% hydro nguyn t cn li lin kt vi cc nguyn t cacbon, thm ch sau khi kh kh 10000C. Nhiu nghin cu trn nhit gii hp ca cc loi than khc nhau c cng b, Puri v Basal thc hin nhit phn chn khng mui than, than g v than hot tnh v xc nh lng oxi gii phng ra dng CO2, CO v hi nc. Tng oxi trong 3 loi hon ton ging vi tng oxi to ra bng nhng phn tch c bn. S gii hp oxi dng CO2 v CO trong chn khng iu kin tng t t nhit ch ra rng cc kh ny c to ra trong nhng khong thi gian khc nhau, iu ny ngha l cc nhm chc cha oxi trn b mt c thnh phn khc nhau lin quan n s khc nhau v tm hot ng c lin kt vi cc nng lng khc nhau. Thnh phn ca kh thot ra trong cc khong nhit ring bit ph thuc vo bn cht nhm chc b mt phn hy trong khong nhit . Bansal v cng s cng nghin cu s phn hy cc nhm cacbon oxi trn b mt c to ra trong qu trnh oxi ha nhit thp b mt siu sch ca graphon hot tnh s dng ph khi lng v thy rng c CO2 v CO l sn phm ch yu c to ra t s phn hy cc nhm chc oxi khc nhau t cc tm hot ng khc nhau trn b mt than. Bn cht ca cc loi kh thot ra trong qu trnh gii hp bng nhit cc nhm chc trn b mt than v c ch thot ra ca chng cng c nghin cu bi Van

17

Driel s dng sc k kh, bi Lang v Magnier s dng IR v sc k kh, bi Bonnetain v cc cng s. Cc nh nghin cu ny thy rng thnh phn chnh ca nhm b mt phn hy trong khong nhit 6000-8000C v hu nh hon ton 10000C. Lng oxi thot ra c th hon ton c gii thch do s thot ra ca kh CO v CO2. Nng lng hot ha cho s gii hp tng ln vi s gim mc che ph b mt, cho thy s thot ra ca cc kh khc nhau lin quan n s phn hy cc loi hp cht b mt khc nhau. Trembley v cng s o nng lng gii hp ca nhm oxi - cacbon b mt trn graphon, s dng phng php gii hp bng nhit thay i tuyn tnh v thy rng nng lng gii hp l mt hm ca mc che ph b mt, iu ni ln rng cc phc oxi b mt bao gm mt vi dng nhm chc v phn hy cc nhit khc nhau. Matsumoto va Setaka thc hin phn hy bng nhit than hot tnh, kim cng, v than ch c oxi ha nhit 9500C s dng ph khi lng. Ph gii hp ca cc mu ch ra rng c hai cc i khc nhau cho CO v CO2 nh 1 hm ca nhit , t cho thy c trn mt ln cc kh c gii hp bng s phn hy cc hp cht b mt khc nhau. Cc chng c r rng t cc nghin cu phn hy nhit l c 2 dng cu trc ha hc b mt lin quan n cc tm khc nhau c nng lng khc nhau v do CO v CO2 c gii phng ra bi s phn hy hai dng nhm b mt ny. Cc nhm b mt gii phng ra CO2 km b hn v phn hy nhit khng ln hn 3500C. Cc nhm ha hc khc m gii phng ra CO bn hn v b phn hy trn 5000C. Gii thch cho kt qu ny ni chung l kh v cc nhm b mt tng tc khc nhau trong cc mi trng khc nhau. Chng c th tng tc trc tip vi cc nhm tng t hoc khc nhau ln cn. Ni chung, cc nghin cu gii hp bng nhit u thu c cc thng tin gi tr cung cp cc kt qu t nhng phng php nghin cu c lp. 1.2.2 Trung ha kim Chun vi kim l mt trong nhng phng php n gin v d nht c

18

s dng xc nh bn cht v lng nhm c tnh axit trn b mt ca than. Ngy nay, ngi ta nhn ra rng kh nng trung ha kim ca than c th c xc nh sau qu trnh kh kh 1500C cho n khng cn bt c hi hay kh b hp ph vt l no trn b mt. Mu than sau cho tip xc vi dung dch kim 0.1 n 0.2N trong 24 hoc 72h. Thi gian tip xc c th gim xung 1 vi gi nu than v kim c un hi lu. Cc iu kin ny c thc hin bng nhiu nghin cu. Puri v cng s kho st mt lng ln than trc v sau kh kh, v oxi ha trong kh oxi cng nh cc dung dch oxi ha, v th kh nng trung ha kim ca than vi oxi thot ra dng CO2 trong chn khng. Ngi ta thy rng trong mi trng hp lng kim trung ha gn vi lng CO2 thot ra trong chn khng. V lng phc CO2 gim trong iu kin kh kh hoc tng trong s oxi ha, kh nng trung ha kim ca than cng gim v tng tng ng. Khi ton b lng phc c loi b trong s kh kh iu kin quanh 7500C, than mt hu nh ton b kh nng trung ha kim ca n, thm ch n vn cha mt lng ng k oxy lin kt. Boehm phn bit cc nhm axit b mt trn than oxi ha bng phng php trung ha chn lc s dng baz c mnh yu khc nhau gm, NaHCO3, Na2CO3, NaOH v C2H5ONa. 1.3 nh hng ca nhm b mt cacbon-oxi ln tnh cht hp ph[5, 13] Ngi ta bit rng than hot tnh cha mt lng ng k oxi v hidro c hp ph ha hc, chng c dng phc b mt cacbon-oxi. Mt vi gi thuyt v cu trc c a ra cho nhng cht phc b mt ny. Da vo cc phng php vt l, ha hc v ha l, s tn ti ca cc nhm chc nh cacbonyl, cacboxyl, lacton, quinon, hydroquinon, v phenol c a ra. Tuy nhin, cc phng php nh gi khc nhau khng cung cp cc kt qu c th so snh c, thm ch quan trng hn l ton b lng oxi lin kt khng c gii thch. V th, vn ny khng c lm sng t mt cch ph hp, cng nh cc cu trc, c ch khc nhau. Tuy nhin, cc nghin cu cng b t cc phng th nghim v cc ni khc ch ra rng hu nh chc chn

19

cc nhm hay phc b mt xc nh c th to ra CO2 v tng t c s tn ti b mt phn bit c th to ra CO trong qu trnh x l nhit trong chn khng hoc mi trng tr. Bt k l cc oxit b mt ny c bn cht v cu trc chnh xc th u c mt cht nghi vn rng oxi hp ph ha hc c mt ch yu ti cnh v gc ph, nn nhng nhm oxi ny nh hng nhiu ti cc c trng b mt v tnh cht b mt ca than hot tnh. 1.3.1 Tnh axit b mt ca than. Tnh axit b mt ca than hot tnh v mui than l i tng ban u ca mt s lng ln cc nghin cu do tm quan trng ca n trong vic xc nh mt vi phn ng phn hy, phn ng xc tc, v cc tnh cht hp ph ca nhng vt liu ny. Trong trng hp ca mui than, Wiegand s dng tnh axit b mt phn loi cc h ca mui than chng c tnh axit mnh hoc c tnh cht kim hoc axit yu. Tnh axit b mt ca than c o bi kh nng hp ph baz ca n ( hoc s trung ha baz), kh nng ny c tnh bng lng cation kim trao i cho cc ion hidro c cung cp bi cc oxit axit trn b mt than. Tnh axit b mt l do cu trc ha hc ca cacbon-oxi b mt c cng nhn nh cacboxyl hay lacton. Cc cu trc ha hc b mt ny to ra CO2 trong qu trnh x l nhit trong chn khng hay trong mi trng tr nhit 300-7500C. Kh nng trung ha baz ca than gim khi ht chn khng hoc loi kh bng cch tng nhit mt cch t t, v gim ti bt k nhit no, tng ng vi lng CO2 c to ra ti nhit . Hn na, khi nhit vt cao qu, kh nng trung ha baz ca than gim, cng nhit cao c s gii phng CO2 t b mt than. Do , tnh axit b mt ca than ph thuc vo s c mt ca nhm ha hc b mt cacbon-oxi. 1.3.2 Tnh k nc Cacbon nguyn cht l cht k nc. Tnh k nc cng gim th tnh a nc ca than cng tng, do lng oxi lin kt vi cacbon b mt tng. T lu ta bit rng

20

mui than vi hm lng oxi cao c th d dng b lm t bi nc. V vy, oxi ha nhit thp mui than thng c s dng lm tng c im a nc ca chng. Tng t, cc si cacbon hiu nng cao thng k nc c oxi ha mt cch thch hp to thnh nhm chc b mt cacbon-oxi lm tng tnh a nc ca chng, chng ln lt ci thin s bm dnh vi cc vt liu nn trong composite c bn cao. Fitzer cng b mi quan h trc tip gia s lng nhm axit trn b mt si cacbon c to bi s oxi ha v bn ca composite trong trng hp ca nha phenola cng nh nha epoxi lm vt liu nn. nh hng ca nhm oxi a ln b mt si cacbon bng qu trnh oxi ha trong khng kh ti 7000C v cc tnh cht composit c ngin cu. Trong trng hp than hot tnh, s c mt ca nhm axit b mt lm cho b mt than a nc v phn cc, theo ci tin tnh cht hp ph kh v hi phn cc. 1.3.3 S hp ph hi phn cc Nhiu nghin cu cng b nh hng ca nhm b mt cacbon-oxi ln kh nng hp ph hi nc. Lawson v King thy rng s c mt ca oxi lin kt trong than lm tng kh nng hp ph p sut thp hi nc v chuyn dch ng ng nhit ti p sut thp hn. Pierce thy ng ng nhit hp ph hi nc trn graphon thay i mt cch ng k sau khi graphon trong hi nc ti 80C. im khc bit ny c cho l s tng tc ca hi nc vi graphon, to mt phc b mt cacbon-oxi dn n kh nng hp ph hi nc nhanh hn b mt sch. Pierce v cc ng nghip v Dubinin thy rng cc tm hot ng nht nh trn than hot tnh c to ra nhiu bi nhm b mt cacbon-oxi, cc nhm ny nh l trung tm hp ph ti s hp ph nc xy ra dng nhng m ring bit qua lin kt hidro. Cc m ny sau pht trin theo kch thc khi c nhiu qu trnh hp ph xy ra trn phn t nc do lin kt hidro. Cui cng th chng kt hp vi nhau p sut hi tng i cao hn to thnh cc nt hai chiu ca pha ngng t trn b mt than. Dubinin,

21

Zaverini v Serpinski xut mt phng trnh tnh s tm hp ph ch yu ca chng. Phng trnh c dng sau: K1 (a0 a) (1 Ka)h = K2a Vi a0 l s tm hp ph ch yu v a ( c 2 biu thc c n v mmol/g) l lng hp ph ti p sut tng ng p/p0. Trong phng trnh, (a-a0) biu din tng s tm hp ph, v (1-Ka) k n s gim s tm hp ph hot ng vi s tng trong qu trnh hp ph. Tham s k c th c tnh t iu kin a=as khi p/p0 = 1, vi as l ch s hp ph bo ha. Puri v cc ng nghip nghin cu s hp ph hi nc trn than kt hp vi mt lng thay i nhm b mt cacbon-oxi v thy rng l s c mt oxy trong phc CO2(oxy c th to ra CO2 khi thc hin gii hp) cung cp cc tm hot ng cho s hp ph hi nc v ng ng nhit hp ph v gii hp khng cn, thm ch ti p sut 0 tng i, min l phc CO2 c mt. iu ny c cho l s c nh ca mt lng nc nht nh trn tm phc CO2 bi lin kt hidro; lng nc c nh tng ng vi 1 mol nc cho mi mol phc CO2. Phn cn li ca oxy hp ph ha hc c nh hng t ti s hp ph hi nc. Khi phc CO2 c tng cng bng s oxi ha v c gii phng bi s kh kh than, s hp ph nc c tng ln hay gim i mt cch tng ng. Barton thy rng s hp ph hi nc ln than hot tnh BPL trc v sau oxi ha cc cp khc nhau vi axit nitric b nh hng khng qu ln bi kch thc l, m ch yu l do s c mt ca cc tm a nc c to ra bi nhm oxy axit. Bansal nghin cu s hp ph hi nc trn vi than polyme c xp khc nhau, lin kt vi nhng lng oxy khng ging nhau. Than lin kt vi nhng lng ging nhau oxy lin kt nhng s hu xp khc nhau cho thy kh nng hp ph tng t nhau ti p sut tng i thp, nhng khc nhau ng k v gi tr hp ph

22

ti p sut hi tng i cao, iu ny cho thy s nh hng ca oxy lin kt v rng ln kh nng hp ph hai khong ca p sut tng i. Khi hm lng oxy lin kt trn than gim, ng ng nhit cho thy s hp ph ca hi nc gim lin tc khi cng nhiu oxy lin kt b gii phng khi mu. Tuy nhin, qu trnh gim ny b gii hn khi s hp ph ti p sut tng i thp (p<p0). Khi lng oxy lin kt trn mu than tng bi s oxi ha, cho thy hp ph hi nc tng. S c mt ca nhm cacbon-oxy cng nh hng ti s hp ph ca cc hp cht phn cc hoc c kh nng phn cc nh methanol, ethanol, amoniac v amin, thuc nhum v cc cht b mt. Puri v cc ng nghip v Bansal nghin cu ng ng nhit ca methanol trn than vi lng thay i nhm cacbon-oxy thy rng hp ph tng hoc gim ng vi s thay i ca nhm oxy b mt. ng hp ph-gii hp khng xut hin ti khi phc CO2 c mt. Lng methanol c gi li bi tng tc c trng trn b mt ca than tng ng vi 1/2 mol cho mi mol phc CO2.. Gi tr ti trng hp ph nh hn trong trng hp ca methanol so vi nc c th do bn knh ln hn ca nhm khng phn cc trong methanol. Mt nhm metyl c bn knh 0.2 nm b hp ph trn mt nguyn t oxy c ng knh 0.13 nm, nm phng, c th cn tr s tip cn ca nhm metyl ti cc nguyn t oxy ln cn. Tng t, s hp ph ca cc amin bi than hot tnh c xc nh bng lng nhm b mt cacbon-oxy mang tnh axit. Khi nhng nhm b mt ny b ri khi b mt, hp ph ca amin cng gim. 1.3.4 S hp ph t cc dung dch S hp ph nhng hp cht hu c v v c t cc dung dch ca chng cng cho thy kh nng hp ph ca than b nh hng bi vic c mt ca cc nhm oxi cacbon. Nhiu nh khoa hc nghin cu s hp ph ca mt vi thuc nhum cation v anion trn than ch cng nh cc loi mui than khc nhau, thy rng s hp ph , mc d c xc nh bi din tch mt ca cacbon, vn b nh hng mnh bi s

23

hin din ca cc oxit c tnh axit trn b mt. Kh nng hp ph nhng cht nhum cation tng cng vi s tng s lng ca nhm oxi b mt trong qu trnh xi ha than v gim khi nhng xit b mt ny b loi b trong qu trnh gii hp bng nhit trong chn khng. Trong trng hp ca nhng thuc nhum anion, s hp ph gim theo mc xi ha, gim ny ty thuc vo s tng v s lng ca cc nhm axit b mt. Goyal v nhng cng s cng nghin cu s nh hng ca cc nhm oxy cacbon ti kh nng hp ph mt vi ion kim loi nh Cr(III), Cr(VI), Co(II), Cu(II), v Ni(II) trn mt vi cacbon hot tnh c s khc nhau v din tch b mt v khc nhau v s nhm chc oxy - cacbon trn b mt. Nhng nh khoa hc ny tm ra rng s hp ph ny khng ch lin quan n din tch b mt, m cn ph thuc vo s lng ca cc nhm oxi v c th l mt vi nhm oxit acid khc. S hp ph cation tng i vi trng hp than thc hin qu trnh xy ha v gim trong qu trnh loi kh, kt qu ny c gii thch l qu trnh oxi ha to thnh cc nhm axit b mt m s ion ha trong nc c th to ra ion H+, chuyn trc tip vo pha lng, li b mt than c cc tm tch in, s hp ph cc cation c th xy ra. Khi cc tm tch in m c loi tr bng loi kh, th b mt than s gim xu hng hp ph cation. S hp ph ca nhng hp cht hu c nh phenol v P. nitrophenol cng b nh hng bi nhng nhm oxi - cacbon ny. Mc d s c mt ca nhng nhm oxi axit lm gim i s hp ph phenol, nhng s c mt ca nhng nhm quinon li lm tng cng kh nng hp ph. 1.3.5 S hp ph u tin. Kipling v cc cng s, trong khi nghin cu s hp ph t nhng hn hp hai cht trong pha lng, thy rng s c mt ca oxi b hp ph ha hc, mang tnh phn cc ca n ln than chng hp ph u tin hn i vi thnh phn phn cc hn trong hn hp. Nh vy, Spheron-6 cha oxi lin kt, metanol c u tin hn trong dung dch cha n so vi benzen. Graphon c bn l khng cha oxi, li u tin

24

benzen hn. Tng t, Spheron-6 u tin benzen hn trong dung dch ca n vi nheptan, v graphon u tin n-heptan hn. S tng tc ny c cho l do s c mt ca cc nhm oxy - cacbon, chng tng tc vi thnh phn phn cc hn trong dung dch cha hai cht khc nhau. Puri v cc ng s, v Bansal v Dhami, trong khi nghin cu ng ng nhit hp ph cc dung dch benzen-metanol, benzen-etanol trn nhng loi than ch khc nhau vi lng oxi lin kt khc nhau, ch ra bn cht ca nhng nhm oxi thm ch quan trng hn tng lng oxi trong vic xc nh tng tc b mt ca than vi cc cht tan trong nhng trng hp trn. Nhng ng ng nhit trong hp ph hn hp benzen-metanol ca than ch c ngun gc t go da khc nhau, cho thy than ch ban u c lng CO2 thot ra trn b mt ln hn cho thy s u tin hn i vi ethanol v methanol phn cc hn benzen. V mt phn ca cc nhm b mt ny c loi b trong chn khng ti 400C, nn kh nng hp ph ru cng gim xung ng k. Khi cc nhm ny c loi b hon ton bng s loi kh than ch ti 750 C, th gn nh s c mt s o ngc ca qu trnh u tin bi v benzen c u tin mc d kh nh, hn l etanol hay metanol. Than ch c loi kh ti 750C vn gi li mt lng ng k oxi c kt hp c kh nng to ra CO. Than ch khng hp ph u tin etanol v metanol, v u tin hn vi benzen i vi nhng mu than loi kh 100C, khi m chng gn nh l khng cn oxi. iu c v l nhng nhm quinon to thnh mt phn cc nhm bay hi CO y mnh qu trnh u tin cho cc nhm benzen. Nh vy, mt phn ca oxi lin kt (c coi nh l mt phc cht ca CO2) y mnh s hp ph u tin cc nhm ru , v mt phn khc ging nh l mt phc cht ca CO li y mnh s hp ph u tin benzen. Nh vy, iu cn xc nh y khng ch l tng lng oxi m cn c dng ca n c th nh gi mt cch chnh xc tnh c trng v trng thi b mt ca nhm cacbon - oxy. 1.4. Tm hot ng trn b mt than[5, 13] Than hot tnh c cu trc gm nhiu lp ca nhng h vng thm ngng t

25

nh vi nhau trong nhng lp khng phn cc. Nhng lp ny c nhng kch thc gii hn, do to thnh cc gc. Bn cnh , nhng lp ny c nhng ch khuyt, bin d vo gin on. Nhng nguyn t carbon nhng v tr ny c nhng cp electron khng ghp i v nhng ha tr tha ra, c th nng cao hn. Do , nhng nguyn t cacbon ny c hot tnh cao, to thnh nhng tm hot ng. Rt nhiu nghin cu tp trung vo tm hiu s lng v bn cht ca cc tm hot ng ny v nhng tm hot ng ny quyt nh hot ng ca b mt, nhng phn ng b mt v kh nng xc tc ca than hot tnh. Bi v xu hng cacbon hp ph ha hc oxy ln hn cc cht khc nn nhiu nghin cu kt lun tm hot ng ny l t s hp ph ha hc oxy. Gi thit u tin l than hot tnh gn vi nhiu loi khc nhau nhng tm hot ng, t nghin cu ca Rideal v Wright s oxi ha b mt than vi kh oxy, h thy 3 loi tm hot ng khc nhau tng tc khc nhau nhng p sut khc nhau v cho thy tc hp ph ha hc khc nhau oxy 200C. Allardice khi nghin cu ng hc ca hp ph ha hc oxy trn than ch nhit gia khong 25C v 300C di p sut 100 n 700 torr, thy mt qu trnh hp ph c 2 bc m ng cho rng c s hin din ca 2 loi tm hot ng khc nhau. Dietz v Mc Farlane trong khi nghin cu s hp ph ha hc oxy trn than hot tnh c b mt ln nhit gia 100C v 300C v p sut oxy l bc ca 100 millitor, quan st thy mt qu trnh hp ph ban u nhanh v sau l mt qu trnh hp ph chm hn nhiu. Carpenter v nhng ng nghip oxy ha rt nhiu loi than nhng nhit khc nhau, nhn thy hp ph ha hc oxy ch tun theo phng trnh Elovich trong thi gian 5 pht u tin. Khi thi gian oxy ha tng ln, lng oxy hp ph ha hc vt qu lng c tnh t phng trnh Elovich. Vic ny c th l do s to thnh ca nhng tm hp ph mi bi qu trnh gii hp oxy khi CO2, CO v hi nc c gii phng. Puri v Bansal, khi nghin cu s clo ha than ng v than go da nhng nhit khc nhau trong khong 30 n 1200C, nhn thy rng hydro b hp ph ha hc c

26

gii phng mt s bc, ph thuc vo nhit . Nhng nh nghin cu ny cho rng hydro trong than ch c lin kt vi nhng dng tm khc nhau bng nng lng hot ha. Lussow v cc ng nghip nghin cu ng hc qu trnh hp ph ca oxy trn mt mt graphon hot ha ti nhng mc t chy trong khong 0-35% trong khong nhit 450C n 675C. Lng oxy hp ph ha hc tng kh mnh nhit trn 400C, ln hn gn 2 hoc 3 ln. Ngi ta cng thy rng khi p sut oxy tng t 0.5 n 700 torr, lng oxy hp ph ha hc gn nh l tng gp i. Nhng kt qu ny ch ra s tn ti ca nhiu hn 1 loi vng nng lng hot ha. nhng nghin cu sau ny, Walker v cc cng s khi nghin cu tc hp ph ha hc ca oxy trn graphon hot ha, vi 14.4% b t chy nhit trong khong 300C ti 625C vi p sut oxy l 0.5 torr, quan st thy 2 tc hp ph khc nhau , mt trn v mt di 250C. Hn na cn c s tng nhanh lng oxy bo ha nhit trn 250oC hay trong khong thi gian di hn. iu ny ch ra s c mt ca 2 loi tm hot ng khc nhau nng lng hot ha ca chng. Nng lng hot ha ca qu trnh hp ph nhng tm tng i hot ng hn c tm ra l khong 30 kJ/Mol. Bansal nghin cu ng hc ca qu trnh hp ph ha hc ca hydro trn cng mu graphon vi p sut oxy v nhit hp ph. Tc hp ph ha hc ca hydro l rt thp so vi oxy. Ch 4 loi tm hot ng c tm ra khi nhit hp ph l 600oC. Nhng th nghim hp ph ha hc hydro khng th thc hin c nhit cao v mt graphon b t chy sinh ra kh c th lm nhiu php o ng hc. Puri v cc ng nghip v Bansal thu c nhng chng c kh thuyt phc cho s tn ti ca nhng tm hot ng hon ton khc nhau, chng c gi l tm cha bo ha. Nhng tm ny c th c xc nh bi s tng tc ca than vi dung dch ha tan brom trong KBr. Nhng tm ny c to ra khi nhng nhm oxy cacbon to ra CO2 b loi khi b mt than bng s loi kh nhit trong khong 350 oC n 750oC. Mt mol tm khng bo ha c to ra bng vic loi b 2 mol oxy hp ph ha hc dng CO2.

27

Nng ca nhng tm hot ng trn b mt than hot tnh c o theo ngn ng din tch mt phng hat ng (ASA). ASA, theo cc nh khoa hc, l mt ch s ca hot ng ha hc ca b mt than, quyt nh kh nng xc tc v phn ng b mt ca than. ASA c xc nh t lng oxy hp ph ha hc 300oC trong 24h p sut oxy ban u l 0.5 torr. Gi s rng mt phn t oxy c hp ph ha hc ti mi nguyn t carbon, m mi nguyn t carbon chim din tch 0.083 nm, lng oxy hp ph ha hc c th c chuyn i sang ASA. Cc nh khoa hc ny hot ha graphon vi nhng mc t chy khc nhau to ra mt lng tng ng ASA v thy rng ASA tng cng vi t chy v c th lin h hot ng ca graphon vi oxy. Tuy nhin, ngy nay ngi ta tm ra rng than c gn vi vi loi nhm tm hot ng, mi nhm li gn vi mt lng ph thuc nng lng hot ha. Tm li, cn thu c d liu t nhng iu kin thch hp c th chc chn rng nhng s hot ng ca b mt khng phi l khng chu nh hng bi phn ng trn nhng vng t hot ng hn. Hoffman khi nghin cu s hp ph ha hc mt vi hydrocarbon nh propylen, ethylen, propan v methan trn graphon hot ng, nhn thy rng hp ph ca mi hydrocarbon tng ng vi cc graphon c mc t chy nhiu hn, do tng ASA ca graphon. Tuy nhin, ASA nhng hydrocarbon ny nh hn nhiu khi so vi ASA bi oxy mi mc t chy. Hn na, propylen c ASA ln hn ethylen, methan v n-butan. iu ny c th do kch c ln hn ca nhng phn t hydrocarbon ny, khi c hp ph trn mt tm hot ng nh l che nhng tm bn cnh, lm chng khng th tham gia hp ph ha hc. Do vy, ASA c ngha duy nht lin quan n s hp ph ha hc ca nhng thnh phn ring bit. Dentzer nghin cu kh nng hp ph v gii hp cc phc bc diamin t dung dch amoni trn graphit c hot ha vi nhng mc chy khc nhau v thy rng lng bc hp ph tng khi mc t chy tng. Mt quan h tuyn tnh gia lng bc b hp ph v ASA nh c xc nh bng phng php Walker. iu ny c th

28

do nhng tng tc kh ca bc diamin vi nhng tm hat ng trn than to ra bc kim loi b hp ph trn nhng tm hot ng. Bansal v cc cng s cho rng s tn ti nhng tm hot ng ny l do s khc nhau trong s sp xp khng gian ca nhng nguyn t carbon b mt. Khi b mt than c cc phn t kh i vo, nhng phc hot ng c to ra gia nhng nguyn t kh v nhng nguyn t cacbon trn 2 b mt c th c cu hnh th nng khc nhau, ph thuc vo khong cch gia nhng nguyn t carbon, to ra s ph thuc ca nng lng hot ha ca qu trnh hp ph ha hc. Sherman v Eyring tnh ton l thuyt nng lng hot ng ca hp ph ha hc hydro trn mt than v tm ra gi tr ph thuc vo khong cch C-C. Mt php so snh nhng gi tr l thuyt ca Sherman v Eyring v gi tr thc nghim thu c bi Bansal c a ra. S thng nht gia gi tr thc nghim v l thuyt cho thy mt iu rng khong cch C c tc ng nh cc loi tm hot ng khc nhau trn s hp ph ha hc c th xy ra. 1.5 Bin tnh b mt than hot tnh[5, 13, 24] c im quan trng v th v nht ca than hot tnh l b mt c th bin tnh thch hp thay i c im hp ph v lm cho than tr nn thch hp hn trong cc ng dng c bit . S bin tnh b mt than hot tnh c th c thc hin bng s to thnh cc dng nhm chc b mt khc nhau. Cc nhm chc ny bao gm cc nhm chc oxy cacbon c to thnh khi oxy ha b mt than vi cc kh hoc cc dung dch oxy ha. Nhm chc b mt cacbon hydro to thnh bng qu trnh x l than hot tnh vi kh hydro nhit cao. Nhm chc cacbon lu hunh bng qu trnh x l than hot tnh vi lu hunh nguyn t, CS2, H2S, SO2. Cacbon nit trong qu trnh x l than hot tnh vi amoniac. Cacbon halogen c to thnh bng qu trnh x l than hot tnh vi halogen trong pha kh hoc dung dch. V cc nhm chc ny c lin kt v c gi cnh v gc ca lp vng thm, v bi v thnh phn cc cnh v gc ny ch yu l b mt hp ph, nn ngi ta hi vng khi bin tnh than

29

hot tnh s thay i c trng hp ph v tng tc hp ph ca cc than hot tnh ny. Thm vo , s bin tnh b mt than cng c thc hin bng qu trnh kh kh v bng vic mang kim loi ln b mt. nh hng ca cc nhm chc b mt oxy cacbon ln c trng v tnh cht b mt c tho lun 1.3. Trong phn ny ch yu cp n nh hng ca cc bin tnh khc ln c im cht hp ph ca than hot tnh. 1.5.1 Bin tnh tnh than hot tnh bng N2 Than hot tnh cha lng khng ng k nhm chc nit. Tuy nhin, phn ng pha kh vi dimethylamin 1500C trong 1h, hoc vi NH3 kh 3000C hoc hn, to ra mt lng ng k nhm chc C-N trn b mt. Boehm v cc cng s cng nh Rivera-Utrilla v cc cng s, thy rng khi than hot tnh oxy ha c un nng vi NH3 kh, nhm nit c to thnh trn b mt. nhit thp s c nh Nit cn bng vi s nhm oxy axit trn b mt v c cho l s to thnh mui amoni. Tuy nhin, nhit cao s thay th cc nhm hydroxyl bng nhm amin c tha nhn, than tr nn k nc v gim ng k kh nng hp ph xanh methylen. Puri v Mahajan thy rng s tng tc gia than ng vi kh NH3 kh lin quan n s trung ha nhm chc axit trn b mt v s c nh thm mt s lng NH3 dng khng th thy phn. Nhng nhng nh nghin cu khng cho rng s c nh NH3 vi nhm bt k no trn b mt than. Tuy nhin, Puri v Bansal thy rng qu trnh x l than ng kh trng clo vi NH3 nhit 3000C thu c s thay th mt phn clo bng nhm amin. Than thu c th hin kh nng hp ph tng i vi axit. S tng ln v kh nng hp ph axit tng ng vi lng nit c c nh, ch ra mt s trao i C-Cl bng lin kt C-NH2. S tng tc ca kh NH3 vi si cacbon trc v sau oxi ha cho thy rng NH3 phn ng vi nhm lacton v anhydrid, dn n s to thnh cu trc imid. Zwadski x l than vi NH3 trc v sau s oxi ha vi HNO3, v s dng ph IR, thy rng khng c s hp ph nhm amide, ph IR cng ch ra c phn ng ca NH3 vi cu trc lactone trn lp cacbon.

30

1.5.2 Bin tnh b mt than bng halogen c im b mt ca than, than hot tnh v mui c bin tnh bng mt s phng php x l vi halogen. S hp ph halogen gm c hp ph vt l v hp ph ha hc, qu trnh thng qua mt s c ch bao gm cng hp cc tm cha bo ha, trao i vi H2, hp ph ha hc v s oxi ha b mt than. Cc c ch ph thuc vo bn cht ca b mt than, hm lng oxy, hydro ca than, iu kin th nghim v bn cht ca tng loi halogen. Halogen c c nh trn b mt than dng hp cht cacbon-halogen c bn nhit cao v khng th loi b bng x l nhit trong chn khng cho ti 10000C nu than khng cn d hydro. Tuy nhin, mt phn halogen c th trao i vi nhm OH khi x l vi kim v trao i vi nhm NH2 khi x l vi kh NH3. Do , cc dng hp ph ha hc hay hp ph vt l ny c th bin tnh hon ton c im b mt v phn ng b mt ca than. V d, s c nh Clo hoc Brom c th to ra s phn cc nhng khng phi l lin kt hydro m l tng t vi lin kt ph bin trn than l lin kt vi nhm oxi b mt. Lin kt C-Cl hoc C-Br c th trao i vi cc nhm chc khc to ra loi hp cht b mt mi. Puri v Bansal nghin cu c trng b mt v tng tc b mt ca than ng, than go da c bin tnh vi halogen. T khi ca than tng tuyn tnh khi tng lng clo c nh trn than. Tuy nhin, axit b mt ca than cn li nhiu hoc t thay i. Ngi ta thy rng s c nh clo dn n nhiu dng cu trc l xp v s phn b kch thc mao qun, hoc s thay i v tr hoc mt tm hot ng. Thay th clo hp th trn b mt bng cc nhm chc khc c Puri v cc cng s v Boehm nghin cu bng cch un hi lu than clo ha vi NaOH 2,5M v x l vi amoniac thay th nhm clo bng nhm amin. S c mt ca nhm amin lm b mt than c tnh cht kim, iu ny lm tng ng k kh nng hp ph axit. 1.5.3 Bin tnh b mt than bng s lu hunh ha. Cc hp cht cacbon-lu hunh trn b mt c nghin cu rng ri trn than

31

g, than hot tnh, mui than. Cc hp cht ny c to thnh trong sut hoc sau qu trnh to thnh than. Trong trng hp ca cacbon hot tnh, chng thng thng c to thnh bi un nng than trong s c mt lu hunh nguyn t hoc cc cht kh c lu hunh nh CS2, v SO2. Nhng hp cht lu hunh trn b mt ny khng hp thc trong khong rng v thnh phn ph thuc vo bn cht than, cc iu kin thc nghim, v ln ca b mt than. Nhng hp cht ny thng cha mt lng ng k lu hunh, c th ln ti 40-50%. Nhng hp cht lu hunh trn b mt ny khng th chit vi cc dung mi hoc b phn hy mt cch hon ton bng x l nhit trong mi trng tr, tuy nhin chng c th b loi b hu nh hon ton khi c x l trong khong 500-700 C vi H2. S hp ph ha hc lu hunh ln b mt than bao gm s lin kt vi cc nguyn t cacbon bn ngoi, cng ti v tr ni i, thm nhp vo bn trong cu trc mng, v trao i ly hydro cng nh oxygen cn lin kt vi b mt cacbon. Nh cc nguyn t cacbon ngoi vi, do cc ha tr khng tha mn ca chng quyt nh cc c im hp ph ca than hot tnh, l l do tin rng s c mt ca cc cht lu hunh b mt s nh hng ti tnh cht b mt ca nhng vt liu ny. S nh hng ca cc hp cht lu hunh b mt ln s hp ph cc cht hi phn cc v khng phn cc c kch thc phn t thay i c nghin cu bi Puri v Hazra. S hp ph hi nc tng mt cc ng k khi p sut tng i thp hn 0.4 v gim p sut cao hn. Lng lu hunh lin kt tng lm tng nh hng v c cho l do thay i s phn b kch thc l xp gy ra bi c nh lu hunh dc theo thnh l. ng ng nhit hp ph hi metanol v hi benzen ch ra rng cc phn t ln hn ny tm cc b mt cng cng nh v cng nhiu lu hunh c lin kt trong l. Cacbon Saran lu ha than ha ti 900 C v thm vo nhng lng lu hunh khc nhau trong khong 1-12 % c s dng bi Sinha v Walker loi b hi thy ngn t khng kh hay hi nc. Khi hi nc b nhim bn c a qua

32

lp than ti 150 C v lng thy ngn tch ly trong dng hi nc rt thp so vi than cha lu ha. iu ny dn ti phn ng gia thy ngn vi lu hunh trn b mt than, to thnh thy ngn sunphua. Cc nh nghin cu Lopez-Gonzalev pht hin ra rng than hot tnh c lu ha l cc cht hp ph tt hn loi b HgCl2 khi dung dch nc. 1.5.4 Bin tnh than hot tnh bng cch tm Than hot tnh c tm kim loi v cc oxit ca chng phn tn dng cc ht nh v ang c s dng rng ri trong mt vi phn ng pha kh c trong cng nghip v bo v con ngi chng li cc kh v hi c. Nhng loi than ny c s dng ln u tin trong chin tranh th gii th nht bo v h h hp ca cc binh lnh chng li chin tranh kh. Hn na, vic mang cc kim loi ln cc vt liu c cacbon lm gim cc c im kh ha v thay i cu trc l ca cc sn phm cacbon cui cng. V vy, vic mang cc cht ln than hot tnh nh vy cng c s dng thu c than hot tnh c mt cu trc vi l xc nh. Than hot tnh c tm KI v cc hp cht tng t, vi amine, bao gm pyridin c s dng rng ri trong cng nghip ht nhn duy tr cc hp cht phng x ca iot t cc tc nhn lm lnh v h thng thng gi. KI mang trn than hot tnh phn ng vi nhm oxi - cacbon trn b mt than v thay i trng thi hp ph ca chng, do ci thin kh nng ca than hot tnh duy tr metyliot phng x. Tnh cht hp ph ca than hot tnh c lm thay i khi mang ln n 5 pyridin. Kh nng phn ng ca than c mang clo-xianua tng cng vi vic tng lng cht mang. Tuy nhin, kh nng phn ng thay i t pyridin ny ti pyridine khc nhng khng nht thit theo th t tnh nucleophilv tnh baz ca chng. Barnir v Aharoni so snh s hp ph clo-xianua trn than hot tnh trc v sau khi mang ln Cu(II), Cr(VI), Ag(I), v NH4+ trong mt t l cho trc. S hp ph clo-xianua l thun nghch trong trng hp ca than hot tnh, tr thnh khng thun nghch sau khi tm mc d kh nng hp ph khng i. Reucroft v Chion cng

33

so snh trng thi hp ph ca than hot tnh BPL trc v sau khi tm vi Cu(II), CrO42-, v Ag(I) cho clorofor, cynogen chlorua, phosgen v hydrogen xyanua. Cacbon c tm cho thy c kh nng hp ph ha hc v kh nng hp ph vt l, kh nng hp ph ha hc c gii thch r hn trong phosgen, cynogen clorua v hygro xyanua. Tt c cc than c tm u gi li lng ng k ba cht c mang ln sau khi qua sy chn khng 1500C. S hp ph hi nc m hn hp hi nc vi HCN tng gp mi ln so vi than hot tnh thng thng.

34

Chng 2 - THC NGHIM

2.1 i tng nghin cu i tng nghin cu trong lun vn ny l than hot tnh t go da do Cng ty C phn Tr Bc sn xut. 2.2 Mc tiu nghin cu Bin tnh than hot tnh t bn cht b mt khng phn cc thnh b mt phn cc, c kh nng hp ph cc cation trong nc. Trong nghin cu ny chng ti tp trung vo x l amoni trong nc, s dng phng php hp ph, trao i ion bng than hot tnh bin tnh. Than hot tnh oxi ha l sn phm oxi ha than hot tnh bng axit HNO3 trong cc iu kin khc nhau v nng axit, thi gian v nhit oxi ha, nhm mang ln trn b mt than hot tnh cc nhm chc c tnh axit, c kh nng trao i ion vi ion amoni v cc cation trong nc. Than oxi ha sau khi c la chn x l amoni trong nc, s c kho st kh nng x l cc ion kim loi nng trong nc nh Mn2+, Cd2+. 2.3 Danh mc thit b, ha cht cn thit cho nghin cu. Bng 1. danh mc dng c thit b cn thit cho nghin cu STT Tn Dng c, thit B 1 2 3 4 5 T ht Bp in My iu nhit T sy ht chn khng My lc Mc ch Oxi ha than un Gi nhit phn ng khng i Sy vt liu Kho st kh nng hp ph ca vt liu bng phng php hp ph tnh 6 My o quang Xc nh nng NH4+, Mn2+

35

My AAS

Xc nh nng dung dch, Cd2+ v cc kim loi khc

8 9 10

My o Ph hng ngoi My o BET

Xc nh cc nhm chc trn b mt vt liu Xc nh din tch b mt than

Cc dng c thy tinh ph Tin hnh cc th nghim ph tr bin trong PTN

Bng 2. danh mc cc Ha cht cn thit cho nghin cu STT 1 2 3 4 5 6 7 8 9 10 11 Tn ha cht HNO3 NaOH H2SO4 AgNO3 2CdSO4.3H2O MnSO4.H2O NH4Cl KOH KI HgI2 Mc ch Oxi ha than Trung ha b mt vt liu Xc nh nng Mangan v axit ha Xc nh Mangan Kho st kh nng x l Cd2+ ca vt liu Kho st kh nng x l Mn2+ ca vt liu Kho st kh nng x l amoni ca than bin tnh Xc nh nng amoni trong dung dch Xc nh nng amoni trong dung dch Xc nh nng amoni trong dung dch

2.4 Phng php nghin cu 2.4.1 Phng php bin tnh than hot tnh Than hot tnh mua t Cng ty c Phn Tr Bc c gi thnh ht c kch thc 0.5 1mm, sau c ra v sy kh trong t ht chn khng. Than sau khi sy c oxi ha bng axit nitric trong cc iu kin nhit , nng v thi gian

36

khc nhau. Sau khi tip xc vi axit, than c ra n ht axit v c sy kh trong t sy ht chn khng, ta thu c than oxi ha. 2.4.2. Phng php kho st cc c trng ca than bin tnh 2.4.2.1 Xc nh din tch b mt ca than Din tch b mt ring ca than c th c xc nh theo phng php BET, Langmuir, phng php n im. Theo phng php BET, xut pht t phng trnh hp ph ng nhit BET:
p 1 (c 1) p v( p0 p ) v m c vm c p0

Trong : p, p0 p sut, p sut hi bo ha ca cht b hp ph trng thi lng. v,vm th tch cht b hp ph, th tch lp hp ph n phn t trn ton b b mt. c hng s. Nu dng th p/v(p0-p) ph thuc p/p0 ta thu c th c dng:
p/v(p0-p)

th c dc s = (c-1)/vmc v ct trc tung ti i = 1/vmc. Bit s v i suy ra:

vm 1 si

v
c s 1 i
p/p0

Hnh 1. Dng th ng thng BET

37

Nu vm l th tch hp ph cc i, ng vi s che ph 1 lp n phn t trn ton b b mt ca mt gam cht hp ph v biu din bng cm3 kh 00C v 1atm, th din tch b mt ring S(m2/g), c tnh theo cng thc:
S vm 2 N 0 Am .10 20 (m /g) 22414

(2-1)

Trong : N0 s Avogadro. Am din tch m mt phn t cht b hp ph chim trn b mt 2.4.2.2. Xc nh cc nhm chc c th c trn b mt than. C th d on s tn ti ca cc nhm chc trn b mt than bng phng php ph hng ngoi. Nu cho mt chm tia hng ngoi i qua mt mu cht no th mt phn nng lng ca n s b hp th kch thch s chuyn mc dao ng ca cc phn t trong mu. Nu ghi s ph thuc ca hp th quang vo s sng ta thu c ph hng ngoi ca mu. C s ca phng php ph hng ngoi l nh lut Lambert Beer. I = I .10- Cl (2 - 2)
0

Trong : I0 Cng ca tia sng n sc i qua cht. I Cng ca tia sng sau khi i qua cht H s hp th phn t, l hng s mt bc sng nht nh, n ph thuc vo bn cht ca cht, bn cht dung mi, bc sng v nhit . n v ca l l/mol.cm. C l nng dung dch (mol/l). l dy ca cuvet (cm). Thc t ngi ta thng dng i lng mt quang D:

38

D = lg(I0/I) = Cl truyn qua T. T = (I/I0).100% hoc D vo s sng . 2.4.2.3 Xc nh tng s tm axit trn b mt than.

(2 - 3)

Trong ph hng ngoi, hp th nh sng thng c o bng i lng

(2 - 4)

Cc my quang ph hin i thng cho ph biu th s ph thuc ca T

Trn b mt than oxi ha c cc nhm chc axit yu, axit mnh tham gia vo qu trnh to phc b mt, trao i vi cc ion trong nc thi. Do vic xc nh lng nhm chc c tnh axit trn b mt than c ngha trong vic nh gi kh nng hp ph ion ca than thu c. Tng s tm axit trn b mt than oxi ha c xc nh bng cch trung ha vi lng d NaOH 0.018M. Phn kim d c chun li bng dung dch HCl 0.021M vi ch th phenolphtalein. Tng s tm axit c xc nh bng cng thc sau:
3

V (C 0 C ).10 a= m

(tm/g)

(2 - 5)

trong : V Th tch dung dch NaOH tiu tn trung ha (ml). C0, C Tng ng l nng NaOH ban u v khi cn bng(M). m khi lng ca than (mg).

2.4.2.4 Xc nh pHpzc[6,7] Point of zero charge (pzc) ca b mt mt cht l gi tr pH ti b mt vt liu trung ha v in. Phng php xc nh da trn gi thit l cc proton H+ v cc nhm hydroxyl OH- l cc ion quyt nh in tch, cc ht than trong dung dch s hp th H + hoc

39

OH-. in tch b mt ca than ph thuc vo pH ca dung dch. Cc nhm chc trn b mt c th lin kt hoc ph lin kt vi proton ca dung dch ph thuc vo c im ca than v pH ca dung dch. Do , b mt tch in dng khi kt hp vi proton ca dung dch trong mi trng axit v tch in m khi mt proton trong mi trng kim. Phng php xc nh pH pzc: Cn 0.25gam than cn nghin cu cho vo 25ml dung dch KCl 0.1M, pH ca dung dch c iu chnh t 2 12 bng dung dch KOH 0.1M hoc HCl 0.1M. Lc trong 4h, sau xc nh li pH sau ca dung dch. Bng th ta xc nh c pHpzc ca than cn nghin cu. 2.4.3. Phng php xc nh cc ion trong dung dch 2.4.3.1. Xc nh nng amoni Nng amoni trong nc c xc nh bng phng php o mu vi thuc th nessler. Nguyn tc chung: Trong mi trng kim NH4+ tc dng vi thuc th nessler to thnh phc c mu t vng n nu, ph thuc vo nng amoni trong dung dch. Yu t cn tr: St gy cn tr xc nh, c loi b bng mui xenhet comlexon (III). Cc hp cht hu c, cc alcol, aldehyt, cc amin bo v thm, cc cloramin phn ng c vi thuc th Nessler, khi c mt chng trong nc phi chng ct tch amoniac trc khi xc nh. Trong trng hp nc c phi x l bng dung dch km sunfat 25%. Cch xc nh: Ly 5ml mu, thm tng ng 0.2ml xennhet v 0.5ml nessler. yn 10 pht sau tin hnh o hp th quang bc sng 420nm. Xy dng ng chun:

40

Pha dung dch amoni c nng 5mg/l t dung dch amoni nng 1g/l. Ly vo cc ng nghim cc lng nc ct v dung dch amoni 5mg/l tng ng nh sau.

NH4+(ml) Nc ct(ml)

0.5 4.5
0.6 0.5 0.4 0.3 0.2 0.1 0 0

1 4 Abs

1.5 3.5

2 3

3 2

4 1

y = 0.1337x + 0.0044 R2 = 0.9994

C(mg/l)
1 2 3 4 5

Hnh 2. ng chun xc nh nng NH4+ 2.4.3.2 Xc nh nng mangan Nng mangan trong dung dch c xc nh bng phng php Persunphat. Nguyn tc: Persunphat oxi ha cc hp cht tan ca mangan to permanganat trong s c mt ca AgNO3. Mu to thnh bn t nht trong 24h nu d persunphat v khng c hp cht hu c. Yu t cn tr: Ion clo (Cl-) gy cn tr xc nh, loi b c bng cch thm dung dch bc nitrat, lc b kt ta s loi c clo-. Nu c nhiu cht hu c, loi b bng cch v c ha, loi tr bng cch thm vi git axit photphoric. Cc cht c mu khc c loi tr bng cch dng mu trng.

41

Cch xc nh: Ly 9.5ml mu cn phn tch, thm 0.5ml dung dch H2SO4 c, thm 2, 3 git AgNO3 cui cng thm 1g (NH4)2S2O8 tinh th. un si trong 10 pht sau ngui v o hp th quang bc sng 525nm. Xy dng ng chun Mn2+. Pha dung dch Mn2+ c nng 5mg/l t dung dch Mn2+ c nng 1g/l ht vo ng nghim cc lng nc ct v dung dch Mn2+ (5mg/l) tng ng nh sau Mn2+(ml) 0.5 Nc ct(ml) 9 1 8.5 1.5 8 2 7.5 2.5 7 3 6

0.14 0.12 0.1 0.08 0.06 0.04 0.02

Abs

y = 0.0392x + 0.0005 R2 = 0.9984

C(mg/l)
0 0 0.5 1 1.5 2 2.5 3 3.5

Hnh 3. ng chun xc nh nng Mn2+ 2.4.3.3 Xc nh nng Cd2+ Nng cadimi trong dung dch c xc nh bng phng php ph hp th nguyn t. Ly cc dung dch Cd2+ c cc nng t 0.5 n 2ppm, xc nh ph hp th nguyn t ca cc dung dch Cd2+ ta thu c ng chun xc nh nng Cd2+. Kt qu c th hin hnh 4.

42

0.25 0.2 0.15 0.1

Abs

y = 0.1151x - 0.011 0.05 0 0 -0.05 0.5 1 1.5 R = 0.9908 2 C(mg/l) 2.5

2

Hnh 4. ng chun xc nh nng Cd2+ 2.5 Phng php tnh ton ti trng hp ph ca vt liu M hnh tnh ton cho cc phng php hp ph, trao i ion thng s dng l phng trnh Langmuir hoc Frendlich Khi thit lp phng trnh hp ph Langmuir, ngi ta xut pht t cc gi thit sau: - Tiu phn b hp ph lin kt vi b mt ti nhng trung tm xc nh - Mi trung tm ch hp ph mt tiu phn. - B mt cht hp ph l ng nht, ngha l nng lng hp ph trn cc trung tm l nh nhau v khng ph thuc vo s c mt ca cc tiu phn hp ph trn cc trung tm bn cnh. Thuyt hp ph Langmuir c m t bi phng trnh:
m . bC 1 b.C

(2-6)

Trong :
, m : dung lng v dung lng hp ph cc i (mg/g)

C : nng dung dch ti thi im cn bng b: h s ca phng trnh Langmuir (c xc nh t thc nghim)

43

Hnh 5. ng hp ph ng nhit Langmuir xc nh cc hng s trong phng trnh Langmuir, ta c th vit phng trnh ny dng:
C C 1 b.m m

(2-7)

ng biu din C/ ph thuc vo C l ng thng c dc 1/ m v ct trc tung ti 1/b. m . Do :

m 1 tg

(2-8)
C/

tg

1 m

1 b.m

Hnh 6. th xc nh cc hng s trong phng trnh Langmuir

44

Chng 3 - KT QU V THO LUN

3.1 Oxi ha than hot tnh nhit thng 3.1.1 Kho st kh nng hp ph amoni ca than hot tnh nguyn liu Ly 0.5g than hot tnh cho vo 50ml dung dch NH4+ c cc nng khc nhau. Tin hnh lc n thi gian cn bng hp ph. Ti trng hp ph ca than hot tnh i vi amoni c tnh qua th sau.
3.5 3 2.5 2 1.5 1 0.5 0 0 100 200 300 400 500 600

(mg/g)

C(mg/l)

Hnh 7. th ng hp ph ng nhit Langmuir ca amoni trn than hot tnh T th ta c th thy ti trng hp ph cc i amoni ln than hot tnh l 3mg/g. Kt qu cho thy kh nng hp ph amoni ca than hot tnh l tng i km, do b mt than hot tnh c bn cht khng phn cc, c i lc km i vi cc ion trong nc. V th tng kh nng hp ph cc ion trong nc ca than hot tnh, vic bin tnh b mt than hot tnh thnh b mt phn cc l cn thit. 3.1.2 Kho st kh nng hp ph ca than hot tnh c oxi ha trong cc khong thi gian khc nhau Ngm than hot tnh trong dung dch HNO3 3M trong cc khong thi gian khc

45

nhau 8h, 16h, 24h, sau ra than bng nc ct n pH khng i, tin hnh th kh nng hp ph amoni ca than thu c (t nay gi l than oxi ha). Kt qu kho st kh nng hp ph amoni ca than sau khi ngm trong HNO3 3M ta thu c bng kt qu sau: Bng 1: Kt qu x l amoni ca than hot tnh bin tnh nhit thng
+ + Thi gian ngm Nng NH4 Nng NH4 khi Ti trng hp ph

than

ban u (mg/l) 100 200

cn bng(mg/l) 88.70 185.93 286.9 377.86 496.03 81.97 183.69 287.65 389.8 567.83 9.51 18.93 27.46 38.83 48.85 57.08 94.18

(mg/g) 1.12 1.40 1.30 2.21 0.396 1.80 1.63 1.23 1.01 3.21 0.0487 0.107 0.254 0.117 0.115 0.292 0.582

8h

300 400 500 100 200

16h

300 40 600 10 20 30

24h

40 50 60 100

T bng kt qu ta nhn thy kh nng x l amoni ca cc than hot tnh ngm

46

trong axit nitric 3M rt km. C th do HNO3 3M oxi ha than cha mnh lit c th mang ln trn b mt than hot tnh nhng nhm chc cha oxi cng nh lng nhm chc nh mong mun. Cng c th nhng nhm axit trn b mt l nhng axit yu, do kh nng phn ly thnh ion H+ trong dung dch, dn n kh nng trao i ion ca than thu c vi ion amoni rt km. 3.1.3 Trung ha than oxi ha bng NaOH T kh nng trao i ca than sau khi oxi ha than hot tnh bng HNO 3 vi amoni l km, chng ti tin hnh bin tnh than oxi ha bng NaOH nhm bin nhm chc axit trn b mt than oxi ha thnh mui natri ca cc nhm chc axit trn b mt tng kh nng phn ly cng nh kh nng trao i ion vi cc ion trong nc. Than hot tnh sau khi ngm trong HNO3 c ra sch, sy kh. Sau ngm trong dung dch NaOH 0.1M trong thi gian 24h. Sau khi trung ha bng kim than oxi ha c ra sch n pH khng i, sy kh ta thu c than c b mt trung tnh (t nay gi l than hot tnh bin tnh) Kho st kh nng hp ph NH4+ ca than thu c, ta c bng kt qu trn bng 2. Bng 2: Kt qu x l NH4+ ca than hot tnh bin tnh Nng Nng NH4+ khi cn bng (mg/l) 0.987 6.37 12.05 19.23 28.51 38.83
0.90 1.96 1.79 2.07 2.14 2.11

Ti trng hp ph (mg/g)

Cch x l

NH4+ ban u (mg/l) 10

Than ngm trong axit 8h sau ngm trong NaOH

20 30 40 50 60

47

100

72.34

2.76

T bng 1 v bng 2 ta thy kh nng x l amoni ca than hot tnh bin tnh tt hn so vi than hot tnh oxi ha, c th do trn b mt than oxi ha ch yu cha cc nhm axit yu, kh nng phn li yu do kh nng trao i gia ion NH4+ trong dung dch vi ion H+ trn b mt than l km. Ngc li, khi to thnh mui trn b mt do trung ha cc nhm axit bng kim, kh nng phn li thnh Na+ d hn dn n kh nng trao i vi ion NH4+ tt hn. T kt qu trn bng 2 chng ti dng th theo phng trnh Langmuir bin i (2-7). th c dng ng thng tuyn tnh nh trn hnh 8. T th ny xc nh c ti trng hp ph cc i ca vt liu thng qua h s gc
tg 1 m

Suy ra:

1 1 2.74(mg / g ) tg 0.3646

30 25 20 15 10 5

C/

y = 0.3646x + 1.7407 R2 = 0.9703

C(mg/l)
0 0 10 20 30 40 50 60 70 80

Hnh 8. th phng trnh Langmuir bin i ca than oxi ha bin tnh

48

T kt qu trn, trong lun vn ny chng ti s bin tnh than theo qui trnh: Than sau khi oxi ha trong HNO3 s c ngm trong NaOH nhm bin cc nhm axit trn b mt thnh mui lm tng kh nng phn li cng l tng kh nng trao i vi cation trong dung dch. 3.1.4 Kho st kh nng hp ph ca than hot tnh bin tnh vi cc nng axit khc nhau 3.1.4.1 Oxi ha than bng dung dch HNO3 5M Than hot tnh c ngm vi HNO3 5M trong cc thi gian 8h, 16h v 24h. Sau khi ra sch v sy kh, than c ngm trong NaOH trong thi gian 24h. Cui cng than c ra n pH khng i, sy kh v kho st kh nng hp ph NH4+ i vi than ngm trong HNO3 5M trong thi gian 8h. T th phng trnh Langmuir ta thu c gi tr ti trng hp ph cc i
m 1 2.78mg / g 0.3594

16 14 12 10 8 6 4 2 0 0 5 10 15 20 25 30 35 40 y = 0.3594x + 1.0295 R2 = 0.9784

C/

C(mg/l)

Hnh 9. th phng trnh Langmuir ca than bin tnh bng HNO3 5M trong 8h. i vi than ngm trong HNO3 5M trong thi gian 16h ta thu c kt qu trn hnh 10.

49

1 2.73mg / g 0.3668

14 12 10 8 6

C/

y = 0.3668x + 0.5475 4 2 0 0 5 10 15 20 25 30 35 R = 0.994

2

C(mg/l)

Hnh 10. th phng trnh Langmuir ca than bin tnh bng HNO3 5M trong 16h Qua 2 th trn ta thy, khi tng nng axit HNO3 ln 5M, kh nng x l amoni trong nc ca than hot tnh bin tnh cha c s thay i r rt so vi khi s dng axit 3M trong cng iu kin thi gian v nhit . V kh nng x l amoni ca than bin tnh cn mc thp. 3.1.4.2 Oxi ha than bng dung dch HNO3 7M Thc hin oxi ha than hot tnh iu kin oxi ha mnh hn bng cch ngm than trong HNO3 7M trong cc khong thi gian 8h, 16h. Sau ngm trong NaOH, ra v sy kh. Kho st kh nng x l amoni ca than thu c. i vi than ngm trong HNO3 7M trong 8h, t hnh 11 v cng thc tnh ti trng cc i ta thu c:
m 1 3.54mg / g 0.2827

50

160 140 120 100 80 60 40 20 0 0

C/

y = 0.2827x + 0.019 R2 = 0.9788

C(mg/l)
100 200 300 400 500

Hnh 11. th phng trnh Langmuir ca than bin tnh bng HNO3 7M trong 8h i vi than ngm vi axit 7M trong thi gian 16h ta thu c kt qu nhu trn hnh 12.
14 12 10 8 6 4 2 0 0 10 20 30 40 50 60 y = 0.1669x + 3.2334 R2 = 0.978

C/

C(mg/l)

Hnh 12. th phng trnh Langmuir ca than bin tnh bng HNO3 7M trong 16h T hnh 12 v cng thc (2-8) ta c:
m 1 5.99mg / g 0.1669

So snh than ngm trong axit cc nng khc nhau cho thy, than c bin tnh trong axit c nng cao hn c kh nng x l amoni cao hn. C s khc nhau kt qu thu c ca 2 loi than l do trong mi trng axit c hn, kh nng oxi ha

51

than hot tnh mnh hn do to ra trn b mt than hot tnh nhiu nhm chc c tnh axit hn. Kt qu l than thu c c kh nng hp ph tt hn. 3.1.4.3 Kho st kh nng hp ph amoni ca than bin tnh trong HNO3 c Tng nng axit HNO3 oxi ha than thnh axit c, tin hnh ngm than hot tnh trong HNO3 c trong cc khong thi gian khc nhau. Than oxi ha sau khi ra v sy kh c ngm trong dung dch NaOH, sau khi ra v sy trong t ht chn khng, than bin tnh c em kho st kh nng x l amoni trong nc. i vi than bin tnh c ngm trong HNO3 c trong thi gian 8h, ta c kt qu nh trn hnh 13. V ti trng hp ph cc i ca than trong trng hp ny l:
m
90 80 70 60 50 40 30 20 10 0 0 100 200 300 400 500 y = 0.1598x + 9.3872 R2 = 0.9275

1 6.257mg / g 0.1598

C/

C(mg/l)

Hnh 13. th phng trnh langmuir ca than bin tnh bng HNO3 c trong 8h i vi than ngm trong thi gian 24h, theo hnh 14 v cng thc (2-8) ta tnh c ti trng hp ph cc i:
m 1 5.93mg / g 0.1686

52

90 80 70 60 50 40 30 20 10 0 0

C/

y = 0.1686x + 4.4306 R2 = 0.9975

C(mg/l)
100 200 300 400 500

Hnh14. th phng trnh langmuir ca than bin tnh trong HNO3 c trong 24h Kt qu bin tnh than hot tnh nhit thng cho thy, than bin tnh c kh nng x l amoni tt hn than hot tnh thng thng nhng vn hiu qu vn cha vt tri. Bn cnh , khi oxi ha than hot tnh nhng iu kin mnh lit hn s thu c than c hiu qu x l tt hn do iu kin oxi ha cng mnh cng nhiu nhm chc axit c to thnh trn b mt. iu ny cho php d on rng khi nhit oxi ha than tng ln, s thu c than bin tnh c kh nng x l amoni tt hn. 3.2 Kho st kh nng hp ph amoni ca than c bin tnh nhit 700C. Cho 20g than hot tnh vo 100ml dung dch HNO3 c, t hn hp phn ng vo bnh iu nhit ti 700C trong cc thi gian 4h, 6h v 8h. Sau khi ra v sy kh than c ngm trong dung dch NaOH. Sau khi ra v sy kh, ta kho st kh nng x l tng loi than bin tnh thu c Kt qu hp ph ca than bin tnh 700C trong thi gian 4h, kt qu th hin trn hnh 15 v ti trng hp ph cc i l:
m 1 14.43mg / g 0.0693

53

70 60 50 40 30 20 10 0 0

C/

y = 0.0693x + 3.5608 R2 = 0.9982

C(mg/l)
200 400 600 800 1000

Hnh15. th Langmuir ca than bin tnh nhit 700C trong thi gian 4h i vi than bin tnh nhit 700C trong thi gian 6h ta c kt qu trn hnh 16. T cng thc (2-8) v hnh 16 ta tnh c:
m 1 17.15mg / g 0.0583

45 40 35 30 25 20 15 10 5 0 0

C/

y = 0.0583x + 2.2715 R = 0.9873

2

C(mg/l)
600 700

100

200

300

400

500

Hnh 16. th Langmuir ca than bin tnh nhit 700C trong thi gian 6h i vi than bin tnh nhit 700C trong thi gian 8h, kt qu th hin trn hnh 17

54

50 45 40 35 30 25 20 15 10 5 0 0

C/

y = 0.0505x + 4.9702 R2 = 0.9725

C(mg/l)
200 400 600 800 1000

Hnh 17. th Langmuir ca than bin tnh nhit 700C trong thi gian 8h T cng thc (2-8) v hnh 17 ta c:
m 1 19.80mg / g 0.0505

T 3 kt qu trn ta thy, khi tng nhit ca qu trnh oxi ha than, kh nng x l amoni trong nc ca than thu c tng r rt so vi than oxi ha nhit thng 3.3 Kho st kh nng hp ph ca than oxi ha bng HNO3 nhit 1000C Than hot tnh c un cch thy vi HNO3 trong cc khong thi gian khc nhau. Sau khi ra n pH khng i, than c ngm trong NaOH 24h, ra v sy kh than trong t sy chn khng. Kho st kh nng hp ph amoni ca than bin tnh thu c, ta c cc kt qu nh di y. i vi than un cch thy vi HNO 3 trong thi gian 2h, kt qu thu c nh trn hnh 18.

55

50 C/ 45 40 35 30 25 20 15 10 5 0 0

y = 0.0545x + 1.7819 R = 0.998

2

C(mg/l)
200 400 600 800 1000

Hnh18. th phng trnh Langmuir ca than bin tnh 1000C trong 2h Theo cng thc (2 - 8) ta tnh c:
m 1 18.35mg / g 0.0545

Khi un cch thy vi HNO 3 trong thi gian 6h, kh nng x l amoni ca than thu c c xc nh qua th hnh 19. T hnh 19 v cng thc (2 - 8) ta tnh c ti trng hp ph amoni ca than bin tnh bng un cch thy trong 6h l:
m 1 23.3mg / g 0.043

56

40 35 30 25 20 15 10 5 0 0

C/

y = 0.0429x + 2.0278 R = 0.9906

2

C(mg/l)
200 400 600 800 1000

Hnh 19. th phng trnh Langmuir ca than bin tnh 1000C trong 6h Khi un cch thy hn hp phn ng trong thi gian 4h, kt qu c th hin hnh 20.
35 30 25 20 15 10 5 0 0 200 400 600 800 y = 0.0387x + 2.2426 2 R = 0.9946

C/

C(mg/l)

Hnh 20. th phng trnh Langmuir ca than bin tnh 1000C trong 4h T hnh 20 ta thu c ti trng hp ph cc i ca than i vi amoni l
m 1 25.84mg / g 0.0387

T cc kt qu trn ta thy kh nng x l amoni ca than hot tnh bin tnh tng khi iu kin oxi ha than mnh lit hn. Tuy nhin khi un cch thy hn hp than vi HNO3, thi gian oxi ha tng s lm tng s nhm chc axit trn b mt, bn

57

cnh l qu trnh ph hy mao qun, lm cho kch thc mao qun ln hn, ngha l din tch b mt than gim so vi khi un thi gian ngn hn. n mt mc oxi ha no , din tch b mt than hot tnh gim s ko theo s tm axit trn b mt ca than oxi ha thu c cng gim theo, th hin than c un trong thi gian 6h (23.3mg/g) v trong thi gian 4h (25.84mg/g). Do , iu kin bin tnh ti u ca than c rt ra t nhng kt qu nghin cu trn l: un cch thy than vi axit HNO3 c theo t l khi lng than so vi th tch axit l 1:5 trong khong thi gian 4h. Sau khi ra n pH khng i v sy kh than, than s ngm trong dung dch NaOH 0.5M trong thi gian 24h, ra v sy trong t sy ht chn khng ta thu c than bin tnh. 3.4 Kho st kh nng hp ph mt s kim loi nng ca than bin tnh T kt qu nghin cu kh nng x l amoni ca cc loi than bin tnh, chng ti ly than bin tnh vi qui trnh bin tnh ti u nu trn, kho st kh nng x l mt s kim loi nng. 3.4.1.Kh nng hp ph Mangan a, Xc nh thi gian cn bng hp ph Mangan Ly 50ml dung dch Mn2+ c nng 100ppm vo cc bnh nn khac nhau, cho vo mi bnh 0,5g than bin tnh. Lc trong cc khong thi gian khc nhau. Thi gian cn bng hp ph l thi gian dung dch sau hp ph c nng khng i.

58

120 100 80 60 40 20

C(mg/l)

t(pht)
0 0 10 20 30 40 50

Hnh 21. th biu din s ph thuc nng Mn2+ dung dch vo thi gian hp ph T th ta thy, thi gian cn bng hp ph nm trong khong 20 n 30 pht, iu cho thy kh nng x l Mn2+ ca than bin tnh rt nhanh. Sau thi gian 10 pht, than hp ph c 90% lng Mn2+ trong dung dch. b, Kho st ti trng hp ph cc i Mn2+ ca than bin tnh Ly vo bnh nn 50ml dung dch Mn2+ c cc nng khc nhau. Cho vo mi bnh nn 0,5g than bin tnh. Tin hnh lc n thi gian cn bng hp ph. Xc nh li nng cc dung dch trong bnh. Kt qu c biu din bng th
18 16 14 12 10 8 6 4 2 0 0 100 200 300 400 500

C/

y = 0.0259x + 0.0502 R2 = 0.9995

C(mg/l)
600 700

Hnh 22. th phng trnh hp ph Langmuir ca than bin tnh hp ph Mn2+

59

T hnh 22 v cng thc tnh ti trng hp ph cc i ta c

m 1 38.61mg / g 0.026

T kt qu ta thy kh nng x l mangan ca than bin tnh rt tt 3.4.2. Kh nng hp ph cadimi (Cd2+) Hm lng Cadimi trong dung dch trc v sau hp ph c xc nh bng phng php o AAS a, Kho st thi gian cn bng hp ph Ly vo cc bnh nn khc nhau 50ml dung dch Cd2+ 200mg/l, cho vo cc bnh nn 0,5g than bin tnh. Tin hnh lc trong cc khong thi gian khc nhau. n khi nng dung dch sau hp ph khng i, ta c thi gian cn bng hp ph Cu2+ ca than bin tnh. T hnh 23 ta thy thi gian cn bng hp ph trong trng hp ny nm trong khong t 20 n 30 pht.
250 200 150 100 50 0 0 10 20 30 40 50 60 70

C(mg/l)

t(pht)

Hnh 23. th biu din s ph thuc nng Cd2+dung dch vo thi gian hp ph b, Xc nh ti trng hp ph cc i Cd2+ ca than bin tnh Cho 0,5g than hot tnh bin tnh vo bnh nn cha 50ml dung dch Cd2+ c cc nng khc nhau. Tin hnh lc n thi gian cn bng hp ph. Xc nh li cc nng sau hp ph. Ta c th sau

60

14 12 10 8 6 4 2 0 0

C/

y = 0.0132x + 0.2329 R2 = 0.9991

C(mg/l)
200 400 600 800 1000

Hnh 24. th phng trnh hp ph Langmuir ca than bin tnh hp ph Cd2+ T hnh 24 v cng thc (2 - 8) ta tnh c ti trng cc i trong trng hp ny l:
m 1 76.92mg / g 0.0132

Kt qu v ny cho thy, kh nng x l Cd2+ ca than bin tnh l rt tt 3.5 Kho st cc c trng ca than bin tnh 3.5.1 Xc nh din tch b mt ring ca than Din tch b mt ca than c xc nh bng s hp ph kh N2. ng hp ph ng nhit ca N2 c xc nh vng p sut tng i t 0 ti 1 v nhit 77.35K. Din tch b mt c xc nh t th BET trong vng p sut tng i t 0 0.3.

61

Hnh 25. th ng hp ph ng nhit BET ca N2 trn than hot tnh.

Hnh 26. th biu din theo ta BET ca than hot tnh hp ph N2.

62

Hnh 27. th ng hp ph ng nhit BET ca ca N2 than oxi ha

Hnh 28. th biu din theo ta BET ca than oxi ha hp ph N2

63

T cc th BET ta thu c kt qu: than hot tnh c din tch b mt l 1767,16m2/g trong khi than oxi ha c din tch b mt l 750,6m2/g. Din tch b mt than oxi ha thu c nh hn nhiu so vi din tch b mt than hot tnh ban u. S d nh vy l do trong qu trnh bin tnh than hot tnh, HNO3 c tnh oxi ha mnh ph hy cu trc l xp ca than, lm cho mt l nh gim xung ng thi lm tng mt l c kch thc ln dn n din tch b mt than oxi ha gim. iu ny lm gim kh nng hp ph vt l ca than hot tnh bin tnh so vi than hot tnh. 3.5.2 Xc nh cc nhm chc c th c trn b mt cc loi than Cc nhm chc tn ti trn than hot tnh v than hot tnh oxi ha c xc nh bng ph hp th hng ngoi. Do mu dng rn thng khuch tn nh sng mnh, nn c mt lp khuch tn nh sng t, thun li cho qu trnh o ngi ta dng phng php nghin cht vi bt KBr tinh khit. KBr khng hp th trong vng trn 400cm-1 v vy c th nghin cu cht trong vng hp th rng

Hnh 29. Ph hng ngoi ca than hot tnh

64

Hnh 30. Ph hng ngoi ca than oxi ha T kt qu ph hng ngoi cho thy trn than oxi ha tn ti cc lin kt OH(3421cm-1), -C=O(1717cm-1), -COO-(1569cm-1), -C-O(1159cm-1), cc lin kt ny c gi thit l do trn b mt than oxi ha c tn ti nhm chc COOH ca axit cacboxylic c to ra trong qu trnh oxi ha than bng HNO3, C0 b oxi ha thnh C+1 trong nhm COOH. T ph hng ngoi ca than oxi ha ta cng thy rng khng tn ti nhm chc NO3-(1410 1340cm-1), chng t rng trong qu trnh ra than chng ti loi b c hon ton lng axit d sau khi bin tnh. Trong than hot tnh bnh thng ta thy khng c cc s sng nh trn nn trn b mt than hot tnh khng tn ti nhm chc COOH. 3.5.3 Xc nh tng s tm axit trn b mt than Tng s tm axit trn b mt than oxi ha c xc nh bng phng php trung ha vi dung dch NaOH. V NaOH l baz mnh nn c th tc dng c tt c cc nhm chc c tnh axit v vy kt qu thu c l tng s tm axit trn b mt than oxi ha.

65

Ly 50ml dung dch NaOH 0.0184M v 0.25g than vo bnh nn c bt kn, tin hnh lc trong cc khong thi gian khc nhau m bo lng axit trn b mt than c trung ha ht. tnh n lng NaOH c th b mt i do tc dng vi CO2 trong khng kh, chng ti tin hnh lc ng thi vi mt bnh nn c bt kn cha 50ml dung dch NaOH. Lng NaOH cn d sau khi lc vi than bin tnh c xc nh bng phng php chun bng axit oxalic 0.01M vi ch th phenolphtalein. i vi than hot tnh thng
0.00025 0.0002 0.00015 0.0001 0.00005

S mol NaOH

Thi gian(h)
0 0 1 2 3 4 5 6 7 8

Hnh 31. th biu din s ph thuc s mol NaOH phn ng vo thi gian

T hnh 31 ta thy, ch sau 2h cc tm axit trn b mt than hot tnh b trung ha ht bi NaOH, t cng thc (2-5) ta tnh c s tm axit trn b mt than l: 1,2.1020(tm/g) i vi than hot tnh c un cch thy vi HNO3 c trong thi gian 2h, ta c kt qu nh trn hnh 32.

66

0.0025 0.002 0.0015 0.001 0.0005 0

S mol NaOH

Thi gian(h)
0 2 4 6 8 10 12

Hnh 32. th biu din s ph thuc s mol NaOH phn ng vo thi gian T cng thc (2-5), tng s tm axit trn b mt than kho st l: 1,2.1021(tm/g). i vi than hot tnh un cch thy vi HNO3 c trong thi gian 4h, kt qu c th hin nh trn hnh 33
0.00295 0.0029 0.00285 0.0028 0.00275 0.0027 0.00265 0.0026 0.00255 0.0025 0.00245 0.0024 0

S mol NaOH

Thi gian(h)
2 4 6 8 10 12 14 16

Hnh 33. th biu din s ph thuc s mol NaOH phn ng vo thi gian Tng s tm axit trn b mt than nghin cu l: 1,68.1021 (tm/g).

67

T cc kt qu kho st tng s tm axit trn b mt than ta thy than hot tnh c s tm axit thp hn hn so vi cc than c bin tnh bng axit. Kt qu tm axit ca than hot tnh un cch thy vi HNO3 c trong thi gian 4h v thi gian 2h cng ph hp vi kt qu v kh nng hp ph amoni ca chng, ngha l than bin tnh c s tm axit ln hn s c kh nng trao i vi ion amoni trong nc tt hn. 3.5.4 Kho st pHpzc ca cc loi than. Ly 0.25g mi loi than cho vo 25ml dung dch KCl 0.01M, iu chnh pH ban u n cc gi tr pH = 2, 4, 6 ,8 ,10, 12 bng cc dung dch HCl 0.01M hoc KOH 0.01M. Lc n thi gian cn bng. o pH sau ca hn hp, bng phng php th ta tnh c gi tr pH ti b mt than nghin cu khng mang in. i vi than hot tnh oxi ha. T hnh 34 ta thy pHpzc ca than l 2,35. S d pHpzc ca than hat tnh oxi ha thp nh vy l do trn b mt than oxi ha c cha cc nhm chc oxi cacbon c tnh cht axit, lm cho b mt than mang tnh axit.
3.5 3 2.5 2 1.5 1 0.5 0 0 2 4 6 8 10 12 14

pHsau

pHban u

Hnh 34. th biu th quan h gia pH sau v pH ban u ca dung dch KCl lc vi than oxi ha i vi than hot tnh bin tnh, t hnh 35 ta thy pHpzc ca n l 6,1. iu cho thy bn cht b mt ca than bin tnh c s thay i so vi b mt than hot

68

tnh oxi ha. Khi th cc ion H+ trn b mt than oxi ha bng ion Na+, b mt than bin tnh mang tnh trung tnh. T kt qu cho php d on rng, than oxi ha c kh nng hp ph cc anion pH nh hn 2,35. pH trn 2,35 than oxi ha c kh nng hp ph cc cation. Thc t cho thy khi hp ph amoni t dung dch (pH ~ 6), kh nng hp ph ca than oxi ha rt km.
9 8 7 6 5 4 3 2 1 0 0 2 4 6 8 10 12 14

pHsau

pHban u

Hnh 35. th biu th quan h gia pH sau v pH ban u ca dung dch KCl lc vi than hot tnh bin tnh i vi than bin tnh, kh nng hp ph anion s tt pH nh hn 6,1. pH ln hn 6,1 kh nng hp ph cation s chim u th. 3.5.5 Bc u nghin cu c ch hp ph amoni ca than bin tnh 3.5.5.1 Kho st pH ti u ca than bin tnh trong qu trnh x l amoni Ly 50ml dung dch NH4+ 60ppm vo cc bnh nn khc nhau, iu chnh pH ca cc dung dch bng dung dch HCl 0.01M hoc dung dch KOH 0.01M. Tin hnh lc trong thi gian 2h, xc nh nng NH4+ cn li trong cc dung dch. Ta thu c th biu th s ph thuc ca nng NH4+ cn li vo pH ca dung dch. T hnh 36 ta thy ngoi tr pH qu thp kh nng x l amoni ca than bin tnh l km, ng vi l thuyt ca pHpzc (pHpzc ca than bin tnh l 6,1). T pH 5 tr ln, c th thy kh nng x l amoni ca than bin tnh khng c s khc bit. iu

69

 chng t c ch x l amoni ca than bin tnh khng ch l qu trnh hp ph thun ty m c c qu trnh trao i cht xy ra trn b mt phn cch pha.
20 18 16 14 12 10 8 6 4 2 0 0 2 4 6 8 10

C(mg/l)

pH

Hnh 36. th biu th nng dung dch sau x l vo pH 3.5.5.2. nh gi lng amoni b hp ph vi lng Na+ b gii hp Ly 50ml cc dung dch NH4+ c cc nng khc nhau vo bnh nn, cho vo mi bnh nn 0,5g than bin tnh. Tin hnh lc n thi gian cn bng hp ph. Xc nh li nng NH4+ khi cn bng v phn tch nng Na+ gii phng ra dung dch ta thu c mi quan h c th hin qua th sau.
1.4 1.2 1 0.8 0.6 0.4 0.2 0 1 2 3 4 5 6 S mmol ion Na b gii hp S mmol amoni b gi li trn b mt

mmol

Hnh 37. th biu din s tng quan gia s lng Amoni b hp ph v lng Na+ b gii hp

70

T th ta thy lng NH4+ b hp ph v lng Na+ b gii hp l tng i bng nhau, iu ny c th ni ln rng vi mi ion NH4+ c hp ph ln b mt than bin tnh th s c mt ion Na+ i ra khi b mt than bin tnh. Do , c th ni rng c ch x l cation ca than bin tnh l c ch trao i ion. Bn cnh , khi so snh s mol in tch than bin tnh c th x l c gia cc cation khc nhau, ta cng thu c s tng quan nh th di y

2: S mmol in tch ion Amoni. 3: S mmol in tch ion Mn(II). 4: S mmol in tch ion Cd(II) 1.5 mmol in
tch

1 2 0.5 0 1 1 3 4

Hnh 38. th biu th mi tng quan s mmol in tch ca cc cation khc nhau m than bin tnh x l c. T th ta thy s mmol in tch cc cation NH4+ (1.39mmol), Mn2+ (1.404mmol), Cd2+(1.37mmol) b gi li trn b mt than bin tnh l gn nh nhau, iu ny ch c th xy ra khi c ch trao i trn b mt than bin tnh l c ch trao i ion gia Na+ trn b mt than bin tnh vi cc cation trong dung dch. T cc kt qu thu c cng cho php d on mt cch gn ng kh nng trao i ion ca than vi mt s cc cation khc trong dung dch.

71

3.6 Kho st kh nng x l amoni bng m hnh ng 3.6.1 Kho st kh nng trao i ca than bin tnh vi amoni Ly 1g than hot tnh bin tnh cho vo ct c ng knh trong l 1cm. Chodung dch NH4+ 5mg/l chy qua ct vi tc 1ml/pht. Xc nh nng NH4+ u ra. Ta thu c th biu din s ph thuc ca nng dung dch u ra vo th tch ca dung dch sau khi qua ct. T th ta c:S bed volume x l c l: VB =
3800 1652 (bed volume) 2.3

Ti trng trao i ion trong trng hp ny l : 19.49mg/g

6 5 4 3 2 1

C(mg/l)

V(ml)
0 0 1000 2000 3000 4000 5000 6000

Hnh 39. th biudin nng ng vi th tch dung dch qua ct Khi thay i nng dung dch ban u ln 20mg/l, v gim tc dung dch qua ct xung 0,5ml/ pht, ta thu c th biu din s ph thuc nng dung dch sau x l vo th tch dung dch u ra. T hnh 43 ta thu c : VB =
950 413 (bed volume) 2.3

Ti trng hp ph ca than trong trng hp ny l : 22.9mg

72

20 18 16 14 12 10 8 6 4 2 0 0

C(mg/l)

V(ml)
500 1000 1500 2000 2500

Hnh 40. th biu din nng ng vi th tch dung dch qua ct T hai th nghim trn ta thy thi gian tip xc cn thit (EBCT) ca than bin tnh x l amoni l tng i thp. C th l 2,5 pht trong trng hp u tin v 5 pht trong th nghim th 2.Ti trng hp ph amoni ca than trong m hnh hp ph ng nh hn trong m hnh hp ph tnh, nhng s chnh lch ny l khng cao. 3.6.2 Kho st kh nng ti sinh ca vt liu Vt liu trong ct sau khi bo ha amoni c tin hnh gii hp bng dung dch NaOH 0.1M trong thi gian 8h. Sau ra li vt liu bng nc ct n pH khng i v cho dung dch NH4+ 5mg/l chy qua ct vi tc 0.5ml/pht. T th ta thy than bin tnh c kh nng ti sinh rt tt, kh nng x l amoni ca than sau ti sinh gn tng ng vi than bin tnh trc khi ti sinh. VB 3780 1643 (bed volume)
2. 3

73

6 5 4 3 2 1

C(mg/l)

V(ml)
0 0 2000 4000 6000 8000

Hnh 41. th biu din nng ng vi th tch dung dch qua ct Nh vy, than bin tnh qua trao i ion vi amoni c th ti sinh rt tt bng cch cho dung dch NaOH 0,1M chy qua ct trong thi gian 8h. Sau khi ra li bng nc ct, than sau ti sinh c ti trng trao i ion gn nh bng than bin tnh ban u.

74

KT LUN
Sau qu trnh lm lun vn, chng ti rt ra mt s kt lun v kh nng bin tnh than hot tnh lm vt liu x l amoni v kim loi nng trong nc nh sau. 1. tin hnh kho st cc yu t nh hng n kh nng bin tnh than hot tnh l nng axit HNO3, thi gian bin tnh v nhit oxi ha than hot tnh. iu kin bin tnh ti u trong cc trng hp nghin cu l un cch thy than hot tnh vi HNO3 c vi t l khi lng cht rn (g) trn th tch cht lng(ml) l 1:5, trong thi gian 4h. Sau ngm than oxi ha bng dung dch NaOH 0,5M trong thi gian 24h. 2. Qu trnh bin tnh than hot tnh lm din tch b mt than gim so vi din tch b mt than ban u, do qu trnh oxi ha than hot tnh bng HNO3 ph hy cu trc l xp, lm tng lng macropores. 3. Nghin cu b mt bng ph hng ngoi, cho thy trn b mt than bin tnh c cha nhm chc cacboxylic (- COOH), l nhm chc to ra cc tm hot ng c th tham gia qu trnh trao i vi cc cation trong nc 4. Qu trnh bin tnh than hot tnh cng lm cho s lng nhm chc c tnh axit trn b mt than tng ln mt cch ng k so vi s lng nhm chc c tnh axit trn b mt than ban u. 5. Tin hnh kho st kh nng x l amoni v cc cation ca than bin tnh thu c cc kt qu kh cao, c th ti trng hp ph cc i ca than bin tnh i vi cc cation NH4+, Mn2+, Cd2+ ln lt l 1.39mmol/g, 0.702mmol/g, 0.687mmol/g. 6. Bc u nghin cu c ch x l cation ca than bin tnh cho thy y ch yu l c ch trao i ion gia cc cation trong dung dch v ion Na+ trn b mt than bin tnh.

75

7. Nghin cu kh nng trao i ion gia than bin tnh v ion amoni theo m hnh hp ph ng cng thu c kt qu rt tt vi nng dung dich amoni ban u l 5mg/l, thi gian tip xc cn thit l 2,5 pht, than bin tnh x l c 1652 (bed volume). iu th v hn l than bin tnh sau khi tham gia trao i ion vi amoni gn nh c ti sinh hon ton bng dung dch NaOH.

76

TI LIU THAM KHO

Ti liu ting Vit 1. V Ngc Ban(2007), Gio trnh thc tp Ha l, Nh xut bn i hc quc gia H ni. 2. Phm Nguyn Chng(ch bin)( 2002), Ha K Thut, Nh xut bn khoa hc k thut. 3. Trn Vn Nhn, Nguyn Thc Su, Nguyn Vn Tu(2004), Ha l. Tp hai. Nh xut bn gio dc. 4. Nguyn nh Triu(1999), Cc phng php vt l ng dng trong ha hc. Nh xut bn i hc quc gia H Ni. Ti liu ting Anh 5. Bansal R.C. , Goyal M.(2005), Activated Carbon Adsorption, Taylor & Francis Group,USA. 6. Biniak S.(1997), The characterization of activated carbons with oxygen and nitrogen surface groups, Carbon, Vol. 35(12), pp.1799-1810. 7. Cerovic Lj.S. et al(2007), Point of zero charge of different carbides, Colloids and surfaces A, 297, pp.1 6. 8. Chen J. P. et al(2003), Surface modication of a granular activated carbon by citric acid for enhancement of copper adsorption, Carbon,41, pp. 19791986. 9. Chingombe P., Saha B., Wakeman R.J. (2005), Surface modication and characterisation of a coal-based activated carbon, Carbon, 43, pp. 31323143.
10. Figueiredo J.L., Pereira M.F.R., Freitas M.M.A., Orfao J.J.M.( 1999), Modication of the surface chemistry of activated carbons, Carbon, 37, pp.1379

1389.

77

11. Li Y.H., Lee C.W., Gullett B.K.( 2003), Importance of activated carbons oxygen surface functional groups on elemental mercury adsorption, Fuel, 82, pp. 451457. 12. Liu S.X., Chen X., Chen X.Y., Liu Z.F., Wang H.L.( 2007), Activated carbon with excellent chromium(VI) adsorption performance prepared by acidbase surface modication, Journal of Hazardous Materials, 141, pp. 315319. 13. Marsh Harry, Rodriguez-Reinoso Francisco(2006), Activated Carbon, Elsevier, Spain. 14. Matsumoto Masafumi et al(l994), Surface modification of carbon whiskers by oxidation treatment, Carbon, Vol. 32 (I), pp. 111-118. 15. Mei S.X., et al(2008), Effect of surface modification of activated carbon on its adsorption capacity for NH3, J China Univ Mining & Technol, (18), pp. 0261 0265. 16. Milonjic. S.K., et al(1975), The Heat of immersion of natural magnetite in aqueous solutions, Thermochimica Acta, 11, pp. 261-266. 17. Moreno C. (2000), Changes in surface chemistry of activated carbons by wet oxidation, Carbon, 38, pp. 19952001. 18. Park Geun Il, Lee Jae Kwang, Ryu Seung Kon, Kim Joon Hyung(2002), Effect of Two-step Surface Modification of Activated Carbon on the Adsorption Characteristics of Metal Ions in Wastewater, Carbon Science, Vol. 3(4), pp. 219225. 19. Reynolds Tom D., Richards Paul A(1996). Unitoperations and processes in environmental engineering, PSW, USA. 20. Shen Wenzhong, Liand Zhijie, Liu Yihong(2008), Surface Chemical Functional Groups Modification of Porous Carbon, Recent Patents on Chemical Engineering, 1, pp.27-40.

78

21.Tao XU, Xiaoqin Liu(2008), Peanut Shell Activated Carbon: Characterization,

Surface Modification and Adsorption of Pb2+ from Aqueous Solution, Chinese Journal of Chemical Engineering, 16(3), pp. 401- 406. 22. Vassileva P., Tzvetkova P., Nickolov R. (2008), Removal of ammonium ions from aqueous solutions with coal-based activated carbons modied by oxidation, Fuel, 88, pp. 387390. 23. Vasu A.dwin(2008), Surface Modification of Activated Carbon for Enhancement of Nickel(II) Adsorption, Journal of Chemistry, 5(4), pp. 814-819. 24. Yin Chun Yang, Aroua Mohd Kheireddine(2007), Review of modications of activated carbon for enhancing contaminant uptakes from aqueous solutions, Separation and Purication Technology, 52, pp. 403415.

79