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NGHIN CU C TRNG V NH GI HOT TNH XC TC MOF-Co CHO PHN NG TNG HP FISCHER - TROPSCH
ThS. ng Ngc Long1, ThS. Th Thanh H2, KS. Nguyn Vit Linh1 TS. Nguyn Anh V1, PGS. TS. Nguyn Hng Lin1, PGS. TS. Phm Thanh Huyn1 1 Vin K thut Ha hc - i hc Bch khoa H Ni 2 i hc Xy dng

Tm tt Trong bi bo ny, nhm tc gi nghin cu tng hp xc tc MOF-Co10, MOF-Co50 v MOF-Co100 bng phng php kt tinh dung mi nhit. Theo kt qu kho st bng cc phng php nghin cu c trng xc tc (nh XRD, TG/DSC, BET, FT-IR, SEM), MOF-Co10 c n nh nhit vt tri (ln n 300oC), b mt ring ln (665,58m2/g), xp ln, c th tham gia lm xc tc cho phn ng Fischer - Tropsch v cc phn ng d th khc nhit di 300oC. Kt qu nghin cu hot tnh xc tc bng phn ng tng hp Fischer - Tropsch ( 200oC, p sut 10at, trong 16 gi) cho thy mu MOF-Co10 c kh nng xc tc cho phn ng tt hn mu MOF-Co50. Phn tch sn phm phn ng bng GC-MS cho thy, hm lng cc hydrocarbon thu c trong phn on xng rt cao, m ra kh nng ng dng MOF-Co10 lm xc tc cho qu trnh tng hp Fischer - Tropsch sn xut xng.

1. Gii thiu Vt liu khung kim loi hu c (metal - organic framework - MOF) l cc hp cht tinh th m phn t bao gm mt hoc mt nhm cc ion kim loi lin kt vi cc phn t cht hu c (gi l cc linker) to thnh cc cu trc (mt, hai hoc ba chiu), t lin kt to thnh cc mao qun (Hnh 1). MOF vi cu trc mao qun ng u, xp ln, din tch b mt ring ln [1 - 9] v c kh nng hp ph tt nn c ng dng nhiu lm cht hp ph v lu tr kh. Kh nng s dng MOF lm xc tc vn cn hn ch do 2 nguyn nhn ch yu: (1) s n nh

ca vt liu theo nhit , m, cht phn ng, tp cht km hn vt liu mao qun tinh th v c nh zeolite, lin kt kim loi - hu c (me - linker) cng yu hn lin kt Si - O ca zeolite; (2) trong cu trc ca MOF th cc linker bao quanh ion kim loi, lm gim kh nng xc tc v hp ph ha hc [2]. Gn y, mt s phng n tng hp c nghin cu v pht trin khc phc nhng hn ch trn. Tm kim loi thng b bao quanh bi cc lin kt phi tr, tuy nhin c mt s linker b tch ra, li cc v tr phi tr trng trn kim loi. Vt liu MOF vi cc tm kim loi cha

Hnh 1. Cu trc ca MOF-5 [9] v Co-MOF-74 [10] (nguyn t C mu xm, O mu , Co mu vng, t din ZnO4 mu xanh)

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bo ha lin kt phi tr c th c ng dng lm xc tc c kh nng hp ph v phn ng cao, do kh nng tng tc gia kim loi v cht b hp ph. Vic tn ti cc tm kim loi cha bo ha c ngha rt quan trng i vi kh nng xc tc cng nh kh nng hp ph tn cha kh. Do , cc vt liu c tng hp dng cho hp ph cng c kh nng s dng trong qu trnh xc tc hoc ngc li. Do s thiu ht ngun cung du m, kh t nhin c chuyn ha thnh nhin liu lng (gas to liquid - GTL) thng qua qu trnh tng hp Fischer - Tropsch [11, 12]. Qu trnh tng hp Fischer - Tropsch gm nhiu phn ng ha hc c xc tc, trong hn hp kh CO v H2 c bin i thnh hydrocarbon theo phng trnh tng qut sau [11, 13]: n(CO + 2H2) - (CH2)n - + nH2O H = - 167kJ/mol Theo , CO v H2 phn ng vi cc t l khc nhau, to ra cc sn phm phong ph v a dng. Cc oxide ca kim loi chuyn tip nhm VIII (Ru, Fe, Ni, Co, Rh, Pd, Pt) c th c dng lm xc tc cho qu trnh ny. Trong , Fe v Co l 2 ngun xc tc chnh cho qu trnh tng hp Fischer - Tropsch. Xc tc Co t hn 230 ln so vi xc tc Fe nhng vn c ng dng nhiu do c hot tnh tt trong iu kin tng hp p sut thp, vi chi ph vn hnh thp. V vy, trong bi bo ny, nhm tc gi tp trung nghin cu, iu ch xc tc MOF-Co bn nhit trn c s MOF-5, c kh nng ng dng cho phn ng tng hp Fischer - Tropsch. 2. Thc nghim 2.1. Tng hp xc tc MOF-Co Cc mu xc tc c tng hp t mui Co(NO3)2 v Zn(NO3)2 c hm lng khc nhau bng phng php kt tinh dung mi nhit. Ha tan 0,049g acid terephthalic trong 3ml dung mi dimethylformamide (DMF). Lng mui Co v Zn tng ng t l mol Co/Zn = 100/0 (MOFCo100), 50/50 (MOF-Co50), 10/90 (MOF-Co10) v ha tan trong 4,5ml DMF trong l dung tch 8ml. Siu m 10 pht nhit 50oC cho tan hon ton. l mui vo l acid ri siu m thm 10 pht na nhit 50oC. a hn hp vo ni hp (autoclave) v gia nhit nhit 105oC trong 20 gi, sau ngui n nhit phng. Tip theo tin hnh lc v ngm tinh th trong 3ml DMF trong

3 ngy, mi ngy thay dung mi mt ln. Lc ly tinh th v sy nhit 105oC trong 18 gi. 2.2. nh gi c trng ha l ca xc tc Nhiu x tia X c tin hnh trn my D8 Advance - Bruker vi ng pht x n sc Cu - K ( = 1,54). Ph hng ngoi c thc hin trn my Thermo Nicolet 6700 FT-IR. My NETZSCH STA409 PC/PG c s dng phn tch nhit TG/DSC, mi mu 10mg c gia nhit vi tc 10oC/pht n 600oC trong dng khng kh (30ml/ pht). Cc ng ng nhit hp ph - nh hp ph nit c o bng thit b Micromeritics ASAP 2010 v d liu thu c ti nhit ca nit lng, 77K. Cc mu c loi kh 300oC trong 24 gi v p sut l 10-5 Pa trc khi o. nh hin vi in t qut (SEM) c chp trn my Hitachi S-4800. 2.3. Th nghim hot tnh xc tc v phn tch thnh phn sn phm phn ng Phn ng tng hp Fischer - Tropsch c tin hnh trn h thit b phn ng vi dng vi lp xc tc c nh. Kh tng hp a vo theo t l H2/CO = 2/1. Qu trnh chuyn ha kh tng hp c tin hnh nhit 200C, p sut 10at trong 16 gi, tc gia nhit 1oC/pht, vn tc khng gian th tch 255h-1. Kh nguyn liu v cc kh sn phm c phn tch trc tip bng sc k kh (GC ultra thermo finnigan) detector dn nhit (TCD) v detector ion ha ngn la (FID). Sn phm lng c phn tch bng GC-MS. 3. Kt qu v tho lun 3.1. c trng ha l ca xc tc 3.1.1. Cu trc tinh th ca xc tc Gin nhiu x tia X (XRD) ca cc mu MOF-5 (100% Zn), MOF-Co100, MOF-Co50 v MOF-Co10 c trnh by ln lt trong Hnh 2 (a, b, c, d). Theo gin XRD ca mu MOF-5 (Hnh 2a) ti gc 2 = 7o v 10o xut hin nh (peak) c trng cho MOF-5 c cng ln, ng nn ph thp cho thy sn phm to thnh c tinh th cao, t pha v nh hnh. Khi tin hnh thay th 100% Zn bng Co th gin XRD ca mu MOF-Co100 (Hnh 2b) vn xut hin cc nh c trng tng t MOF-5 ti gc 2 = 7o v 10o. Gin c ng nn cao chng t c nhiu pha v nh hnh. Trn Hnh 2c vn xut hin cc nh c trng ti gc 2 = 7o v 10o, ng nn thp hn so vi mu MOFDU KH - S 4/2013

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(a)

(c)

(b)

(d)

Trong gin phn tch nhit (Hnh 4), nh thu nhit ti 308,7oC v gim 11,58% trng lng, nguyn nhn c th do qu trnh bay hi dung mi trong mao qun. nh ta nhit ti 396,5oC gim 23% trng lng, c th l do linker hu c b phn hy. Nh vy, mu MOF-Co10 c bn nhit tt (n 300oC), do c th lm xc tc cho phn ng tng hp Fischer - Tropsch nhit trn 200oC.

Theo kt qu phn tch ng ng nhit hp ph (Hnh 5), mu MOF-Co10 c dng I (theo IUPAC) c Hnh 2. Gin XRD ca cc mu MOF-5, MOF-Co100, MOF-Co50 v MOF-Co10 trng cho vt liu vi mao qun vi din tch b mt 665,58m2/g. Mu MOF-Co50 c Co100, chng t mu MOF-Co50 c t pha v nh hnh din tch b mt thp hn (480,95m2/g). So vi vt liu hn mu MOF-Co100. Tuy nhin, ng nn vn cao nn MOF-5, cc mu ny c din tch b mt ring khng ln, n nh tinh th cha tt. V vy, nhm tc gi tip tc nguyn nhn c th do s thay th 10% v 50% Zn bng thay th bng mu cha 10% Co. Co lm thay i cu trc ca vt liu hoc do iu kin Trong Hnh 2d vn xut hin cc peak c trng ti tng hp cha tt. Tuy nhin, din tch b mt ca mu gc 2 = 7o v 10o, ng nn rt thp, chng t mu tng ng din tch b mt ca mt s zeolite dng MOF-Co10 c t pha v nh hnh v n nh tinh th lm xc tc trong cc phn ng lc ha du. tt hn so vi mu MOF-Co100 v MOF-Co50. Trong nh hin vi in t qut ca mu MOF-Co10 Trong gin XRD ca cc mu MOF-5 v MOF-Co, (Hnh 6), mu xc tc c dng hnh que, cu trc xp lp, ngoi cc nh c trng cho vt liu MOF, nhm tc gi xp kh ln. Kt qu ny tng t kt qu nghin cu khng thy xut hin cc nh c trng cho dng tn ti ca tc gi C.E.Phillips [14]. khc ca Zn v Co. iu ny cho thy ton b lng Zn v Co nm trong mng tinh th ca MOF, s cn li c 3.1.3. Ph hng ngoi loi b trong qu trnh ngm ra vi dung mi DMF. Ph hng ngoi (IR) ca mu MOF-Co10 v acid 3.1.2. Kho st bn nhit v din tch b mt ca vt liu terephthalic, tin cht ng vai tr to linker hu c MOF-Co10 trong qu trnh tng hp MOF (Hnh 7). MOF-Co10 sau 15 gi kt tinh xut hin dao ng vi cng mnh nghin cu bn nhit ca mu MOF-Co100, ti s sng 1.660,2cm-1, thp hn dao ng c trng ca nhm tc gi nung mu n nhit 300oC. Theo kt qu nhm C=O trong acid terephthalic t do vi s sng l phn tch XRD (Hnh 3), mu sau khi nung trng thi v 1.683,3cm-1. y c th l bin dng ca nhm C=O trong nh hnh, b sp khung, khng cn pha tinh th, chng -COO- sau khi xy ra qu trnh proton b thay th bi ion t mu khng bn nhit. Do , nhm tc gi tip tc Zn2+ v Co2+. Ph hng ngoi ca mu MOF-5 (ch c Zn2+) thay th 50% Zn bng Co (khng thay th hon ton Zn c nghin cu trong cng trnh [1] cho thy dao ng bng Co). ny li v s sng 1.593,2cm-1. Nh vy, khi thay th mt Gin phn tch nhit v ng ng nhit hp ph phn Zn2+ bng Co2+ c s thay i nh c trng ca ca mu MOF-Co10 c trnh by trong Hnh 4 v 5. dao ng bin dng ca nhm C=O. 38
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Hnh 3. Gin XRD ca mu MOF-Co100 nung 300oC

Nhm dao ng bin dng c s sng 1.489,5 1.391,0cm-1 v nhm dao ng bin dng c s sng 1.615,5 - 1.567,9cm-1 c trng cho dao ng ca nhm C = C vng benzen. Nhm dao ng bin dng c s sng 879,4 - 654,2cm-1 l bin dng c trng ca nhm C-H trong vng thm (un). Nhm dao ng bin dng c s sng 3.064,2 - 2.937,6cm-1 l bin dng c trng ca nhm C-H trong vng thm. Nhm dao ng bin dng c s sng 3.506,0cm-1 l bin dng c trng ca H2O v trong qu trnh tng hp MOF-Co c s hnh thnh ca nc, do c th vn cn nc trong mao qun ca vt liu. Ngoi ra, nhm tc gi cn thy xut hin cc nhm dao ng bin dng c s sng 1.249,9 - 1.086,4cm-1; 2.830 - 2.695cm-1; 3.064,2 - 2.937,6cm-1 ln lt l bin dng c trng ca nhm C-N, C-H aldehyde, C-H alkan. iu ny chng t mu MOF-Co10 sau 15 gi kt tinh vn cn dung mi DMF ((CH3)2NCHO), ph hp vi gi thit trong phn phn tch nhit. T phn tch trn cho thy MOF-Co10 c bn nhit tt ( 300oC), ph hp vi iu kin ca qu trnh tng hp Fischer - Tropsch iu kin mm (< 280oC). Ngoi ra, mu c din tch b mt ring ln, c nhng tm hot tnh Co, do c kh nng ng dng lm xc tc trong phn ng tng hp Fischer - Tropsch. 3.2. Hot tnh v chn lc ca xc tc 3.2.1. nh hng ca hm lng Co ti chuyn ha Thc hin phn ng Fischer - Tropsch t 2 mu xc tc l MOF-Co10 v MOF-Co50 vi lng xc tc bng nhau nhit 200oC, p sut 10at. Theo kt qu (Hnh 8), chuyn ha ca phn ng khi s dng xc tc MOF-Co10 (khong trn 20%/g xc tc) cao hn so vi chuyn ha ca phn ng khi s dng xc tc MOF-Co50 (trn 10%/g xc tc).

Hnh 4. Gin TG/DSC ca mu MOF-Co10

Dung lng hp ph (cm3/g STP)

p sut tng i (P/Po)

Hnh 5. ng ng nhit hp ph ca mu MOF-Co10

chuyn ha CO ca phn ng khi dng xc tc MOF-Co10 tng dn ri t cc i 26%/g xc tc sau 3

Hnh 6. nh hin vi in t qut ca mu MOF-Co10

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Nh vy, kh nng xc tc ca mu MOF-Co10 tt hn so vi mu MOF-Co50. iu ny hon ton ph hp vi cc c trng ca cc mu xc tc. Do mu MOF-Co50 c nhiu pha v nh hnh nn din tch b mt v bn nhit km hn mu MOF-Co10, dn n hot tnh xc tc thp hn. Mc d c hot tnh thp hn nhng mu xc tc MOFCo50 li c bn hot tnh cao hn mu MOF-Co10. 3.2.2. Phn b sn phm ca qu trnh chuyn ha Fischer - Tropsch Vic nh gi s phn b sn phm ca qu trnh chuyn ha Fischer - Tropsch c thc hin da trn s lng nguyn t C c trong cc phn t hnh thnh (phn tch bng GC-MS). Qu trnh tin hnh phn ng Fischer - Tropsch vi mu xc tc MOF-Co10 cho cc sn phm C5 - C17, trong C8 v C9 chim t l cao nht v khng c sn phm nh hn C5. Do , s dng xc tc MOFCo10 trong phn ng tng hp nhin liu lng t kh tng hp c th thu c sn phm gm cc hydrocarbon nm phn ln phn on xng (Hnh 9). Khi tin hnh phn ng trong iu kin tng t s dng xc tc Co/-Al2O3, sn phm nhn c ch yu trong phn on diesel [12]. Nguyn nhn do s khc bit v kch thc mao qun ca MOF-Co v Co/-Al2O3. Xc tc MOF-Co10 l vt liu vi mao qun nn c kch thc ph hp vi kch thc ca cc hydrocarbon trong phn on xng, sn phm to thnh ch yu l cc hydrocarbon C5 C9. Trong khi , nu s dng xc tc -Al2O3 c kch thc mao qun trung bnh s cho sn phm ch yu trong phn on diesel. 4. Kt lun - Nhm tc gi nghin cu, tng hp thnh cng vt liu MOF-Co10, MOF-Co50, MOF-Co100, trong tiu biu l mu MOF-Co10 vi n nh nhit vt tri, c th tham gia xc tc cho phn ng Fischer - Tropsch v cc phn ng xc tc d th khc nhit 300oC; - nh gi kh nng xc tc cho qu trnh Fischer Tropsch, xc tc ca mu MOF-Co10 tt hn so vi mu MOF-Co50. Mu MOF-Co10 t chuyn ha CO cao nht l 26%/g xc tc, cn mu MOF-Co50 ch t chuyn ha CO cao nht l 12%/g xc tc; - Kt qu phn tch GC-MS sn phm ca phn ng Fischer - Tropsch s dng xc tc MOF-Co10 cho hm lng C8, C9 nm trong phn on xng cao, gi m hng nghin cu mi sn xut xng da trn phn ng tng hp Fischer - Tropsch s dng xc tc vi mao qun.

% truyn qua

S sng, cm-1

Hnh 7. Ph hng ngoi ca mu MOF-Co10 sau 15 gi kt tinh v tin cht acid terephthalic

Hnh 8. chuyn ha ca CO trn mu xc tc MOF-Co10 v MOF-Co50

Hnh 9. S phn b sn phm vi xc tc MOF-Co10

gi tin hnh phn ng, sau xc tc bt u gim hot tnh v chuyn ha. Tuy nhin, sau khi tin hnh phn ng khong 12 gi tr i, chuyn ha CO c xu hng n nh khong 16%/g xc tc. i vi mu xc tc MOF-Co50, chuyn ha CO ban u thp do h cha n nh, sau tip tc tng v t cc i 12%/g xc tc ti thi im sau gn 8 gi tin hnh phn ng. Tuy nhin, sau khi tin hnh phn ng khong 12 gi tr i, chuyn ha gim v c xu hng n nh 8%/g xc tc.

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Ti liu tham kho 1. Vng Thanh Huyn, Phan Th T Nga, Phan Th Thanh Loan, Ng Th Nga, Nguyn Vn Quyn, Phm Thanh Huyn. Nghin cu mt s yu t nh hng n qu trnh kt tinh MOF-5. Tp ch Ha hc. 49(5): p. 665 - 669. 2. A.Corma, H.Garca, F.X.Llabrs I Xamena. Engineering metal organic frameworks for heterogeneous catalysis. Chemical Review. 2010; 110: p. 4606 - 4655. 3. Alexander U.Czaja, Natalia Trukhan, Ulrich Mueller. Industrial applications of metal-organic frameworks. Chemical Society Review. 2009; 38: p. 1284 - 1293. 4. Shilun Qiu, Guangshan Zhu. Molecular engineering for synthesizing novel structures of metal-organic frameworks with multifunctional properties. Coordination Chemistry Reviews. 2009; 253: p. 2891 - 2911. 5. Scott T.Meek, Jeffery A.Greathouse, Mark D.Allendorf. Metal-Organic Frameworks: A rapidly growing class of versatile nanoporous materials. Adv. Mater. 2011; 23: p. 249 - 267. 6. U.Mueller, M.Schubert, F.Teich, H.Puetter, K.Schierle-Arndt, J.Pastre. Metal-organic frameworks prospective industrial applications. J. Mater. Chem. 2006; 16: p. 626 - 636. 7. Ulrich Mueller. WO (2005)/049892. 8. Q.Fang, J.Sculley, H-C.J.Zhou, G.Zhu. Porous metal organic frameworks. Elsevier B.V. 2011.

9. A.K.Cheetham, C.N.R.Rao, R.K.Feller. Structural diversity and chemical trends in hybrid inorganic-organic framework materials. Chemical Communications. 2006: p. 4780 - 4795. 10. H.Y.Cho, D.A.Yang, J.Kim, S.Y.Jeong, W.S.Ahn. CO2 adsorption and catalytic application of Co-MOF-74 synthesized by microwave heating. Catalysis Today. 2012;185: p. 35 - 40. 11. C.Perego, R.Bortolo, R.Zennaro. Gas to liquids technologies for natural gas reserves valorization: The Eni experience. Catalysis Today. 2009; 142: p. 9 - 16. 12. Nguyen Hong Lien, Do Thi Thanh Ha, Nguyen Anh Vu, Pham Thanh Huyen. Study on conversion of syngas into liquid fuel over modified Co/g-Al2O3 catalyst. Procedding of The 5th AUN/SEED-Net Regional Conference on New/ Renewable Energy. 2012: p. 368 - 372. 13. Carlo Giorgio Visconti, Enrico Tronconi, Luca Lietti, Roberto Zennaro, Pio Forzatti. Development of a complete kinetic model for the Fischer - Tropsch synthesis over Co/Al2O3 catalysts. Chemical Engineering Science. 2007; 62: p.5338 - 5343. 14. C.E.Phillips. COBALT MOF-5: A novel catalyst for CO2 conversion to carbonates. Master thesis, University of Louisville. 2012.

Characterisation and evaluation of catalytic activity of MOF-Co catalyst for Fischer-Tropsch synthesis
Dang Ngoc Long1, Do Thi Thanh Ha2, Nguyen Viet Linh1 Nguyen Anh Vu1, Nguyen Hong Lien1, Pham Thanh Huyen1 1 School of Chemical Engineering, Hanoi University of Science and Technology 2 National University of Civil Engineering

Summary Metal-organic framework materials (MOF-Co10, MOF-Co50 and MOF-Co100) were synthesised by solvothermal method. The catalysts were characterised by XRD, TG/DSC, BET, FT-IR and SEM. The results show that MOF-Co10 has good thermal stability (up to 300oC), high surface area of 665,58m2/g, and high porosity. MOF-Co can be used as catalyst for the FischerTropsch synthesis (FTS) and other catalytic reactions which are carried out at temperature less than 300oC. The results obtained from the FTS at 200oC, 10 atm in 16 hours prove that the catalytic activity of MOF-Co10 is better than that of MOF-Co50. The reaction products (analysed by GC-MS) are mainly hydrocarbons in gasoline fraction. This opens a trend to use MOF-Co10 as catalysts for gasoline production by FTS.

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