NGHIN CU PHN NG ANKYL HA BENZEN BNG ETANOL TRN XC TC ZEOLIT Y BIN TNH n Ta son 2-3-2004 Ng Th Thun 1 , Cao Hi Thng 2 1 Khoa Ha hc, Tr!ng i hc Khoa hc T nhin - i hc Quc gia H* Ni 2 Khoa Ha-L k thut, Hc vin K thut Qun s
Summary This paper presents the benzene alkylation with ethanol catalysed on the Y and ZSM-5 zeolite. The experimental results have shown that 30%H-ZSM-5/HY sample is the best for forming ethylbenzene. On this sample the reaction has been carried out by central composite orthogone design at the second level for three factors reaction temperature, flow speed and the molar ratio of ethanol/benzene. The target function for the productivity of ethylbenzene has been yielded. By checking the experimental and mathematic results we observed that current equation is suitable.
I - t vn Trong vi thp k gn y, vai tr ca cht xc tc !c khng nh trong cng nghip lc - ha du, c bit l xc tc zeolit c rt nhiu c tnh !u vit hn so vi cc loi xc tc khc bi hot xc tc, n nh v chn lc cao v nht l gii quyt !c cc p lc v mi tr!ng. Ankyl ha l mt trong nhng phn ng !c s dng xc tc axit, cc xc tc truyn thng !c thay th bi xc tc axit rn zeolit. Hin nay, h!ng nghin cu ch yu ca phn ng ankyl ha l to ra cumen, etylantraquinon, etylbenzen... trong etylbenzen l ngun nguyn liu ch yu iu ch styren cng nghip. V vy, vi mc ch iu ch etylbenzen chng ti tin hnh phn ng ankyl ha benzen bng etanol trn xc tc zeolit Y v ZSM-5 ng thi s dng ph!ng php qui hoch ha thc nghim tm iu kin ti !u cho qu trnh to thnh etylbenzen. II - thc nghim 1. Chun b xc tc Zeolit Y !c s dng l zeolit ca tr!ng HBK t l SiO 2 /A1 2 O 3 = 2,8 v zeolit ZSM-5 c t l Si/A1 = 39 !c chuyn v dng H-Y v H-ZSM-5 bng cch trao i vi dung dch NH 4 NO 3 ri em nung nhit 500 - 600 o C. Mu xc tc HY !c bin tnh bng cch !a thm zeolit H-ZSM-5 theo cc hm l!ng tnh ton tr!c bng cch trn c hc trn my lc trong vng 5 gi, sau em nung v p vin theo kch c ht nh sn. 2. Phn ng ankyl ha benzen bng etanol Phn ng !c thc hin trong pha kh theo ph!ng php dng trong l ng d!i p sut th!ng. Ly xc tc vi c ht nh sn (1 ml) ri np vo ng thch anh, pha trn l lp thch anh c kch th!c c ht ln hn. Thch anh tr!c khi s dng !c un vi axit, ra sch ri sy kh. Nhit ca h phn ng !c xc nh bi pin nhit in Cromen-Alumen gn vi b hin s in t c rle t ngt. Xc tc tr!c khi tin hnh phn ng !c hot ha nhit 500 - 600 o C c dng khng kh i qua trong vng 4 gi v sau cho dng kh tr N 2 i qua. 158 Cht phn ng pha theo t l nh sn ri !c !a vo l vi tc dng khc nhau. Khi cht phn ng i vo ng phn ng, qua lp thch anh pha trn hp th nhit chuyn sang th hi; hi cht tip tc i vo vng xc tc v ti y xy ra qu trnh chuyn ha. Sn phm ca phn ng !c ng!ng t li dng lng qua sinh hn ri em i phn tch trn my sc k kh Shimadzu GC-14B vi ct tch DB-1, kh mang nit p sut 160 kPa. 3. Xc nh axit ca xc tc Dng ph!ng php hp ph v gii hp NH 3 theo ch!ng trnh nhit (NH 3 -TPD) xc nh lc v l!ng cc tm axit trn xc tc. Cc mu xc tc sau khi hp ph cn bng NH 3 d!i iu kin xc nh s !c gia nhit theo ch!ng trnh nhit . Khi nng l!ng nhit cung cp ln hn nng l!ng hp ph cc phn t NH 3 s gii hp khi b mt xc tc v !c kh mang !a qua etector xc nh nh l!ng. III - Kt qu v) tho lun 1. c tnh ca xc tc Trn c s trn, chng ti iu ch !c cc mu xc tc t!ng ng vi 10, 20, 30, 40%H-ZSM-5/HY ng thi tin hnh phn ng trn cc mu xc tc ny. Kt qu !c trnh by bng 1. T bng 1 cho thy, mu xc tc 30%H-ZSM-5/HY l !u vit nht v chuyn ha benzen, chn lc sn phm etylbenzen kh cao. Thc hin o tnh axit ca cc mu xc tc, kt qu thu !c trong bng 2. Bng 1: nh h!ng ca hm l!ng zeolit H-ZSM-5 trn HY khi t l mol etanol/benzen = 1 : 1, nhit 400 o C, tc th tch 3 h -1 Mu xc tc chuyn ha benzen, % chn lc etylbenzen, % Hiu sut etylbenzen, % HY 34,32 37,01 12,70 10%H-ZSM-5/HY 75,81 35,89 27,21 20%H-ZSM-5/HY 82,87 47,41 39,29 30%H-ZSM-5/HY 83,12 55,24 45,92 40%H-ZSM-5/HY 84,34 52,94 44,65 H-ZSM-5 65,48 46,27 30,29 Bng 2: axit ca cc mu xc tc STT Mu xc tc axit, mol NH 3 /g xt
1 HY 156 2 30%H-ZSM-5/HY 391 3 H-ZSM-5 820 T kt qu trn thy rng axit ca cc mu xc tc !c sp xp theo th t HY < 30%H-ZSM-5/HY < H-ZSM-5. 2. Ph'ng php qui hoch ha thc nghim [1] v2 kt qu th nghim Trn mu xc tc 30%H-ZSM-5/HY chng ti tin hnh qui hoch ha thc nghim bc hai tm trc giao vi 3 yu t nh h!ng l: tc dng, t l mol etanol/benzen v nhit phn ng cho hm mc tiu l hiu sut to thnh sn phm etylbenzen. Trong m hnh ha thc nghim bc hai tm trc giao vi ba yu t nh h!ng hm mc tiu !c m t bng a thc: y = b 0 x 0 + b 1 x 1 + b 2 x 2 + b 3 x 3 + b 12 x 1 x 2 + b 13 x 1 x 3 + b 23 x 2 x 3 + b 11 x 2 1 - ) + b 22 (x 2 2 - ) + b 33 (x 3 2 - ) Ph!ng trnh hm mc tiu nhm m t nh h!ng ca tt c cc yu t ln mt qu trnh bng mt ph!ng trnh. Chng ta s tnh !c gi tr ca hm mc tiu tc l tnh !c kt qu nghin cu m khng cn tin hnh th nghim. Trong = 0,73 l h s hiu chnh, d = 159 1,215 l khong cch t tm n im sao i vi loi m hnh ny; b i , b ii , b ij l cc h s hi qui. M ha cc yu t: x 1 l tc dng, x 2 l t l mol etanol/benzen, x 3 l nhit phn ng, x 0 l mc gc. Trong qu trnh tin hnh thc nghim thc hin theo cc mc bng 3. T cc mc thc nghim trn tin hnh 17 th nghim theo cc iu kin khc nhau trn mu xc tc 30%H-ZSM-5/HY (th nghim tm !c tin hnh 3 ln tnh sai s v coi l sai s th nghim). Kt qu !c trnh by trong bng 4.
Bng 3: Cc mc tin hnh thc nghim Cc mc th nghim x 1 x 2 x 3 Mc gc 3 1 400 Khong bin thin 1,5 0,5 50 Mc cao (+) 4,5 1,5 450 Mc thp (-) 1,5 0,5 350 +d 4,82 1,61 461 -d 1,18 0,39 339 Bng 4: Kt qu th nghim STT Tc dng, h -1 T l mol etanol/benzen Nhit phn ng, o C chuyn ha benzen, % chn lc sn phm etylbenzen, % Hiu sut sn phm etylbenzen, % 1 1,5 0,5 350 74,64 41,24 30,78 2 4,5 0,5 350 96,81 54,89 53,14 3 1,5 1,5 350 87,71 32,14 28,19 4 4,5 1,5 350 73,90 40,73 30,10 5 1,5 0,5 450 60,60 57,00 34,54 6 4,5 0,5 450 65,31 53,86 35,18 7 1,5 1,5 450 85,17 48,20 41,05 8 4,5 1,5 450 75,31 54,23 40,84 9 4,82 1,0 400 69,52 52,67 36,17 10 1,18 1,0 400 96,31 44,59 42,94 11 3,0 1,61 400 91,21 28,19 25,71 12 3,0 0,39 400 95,03 50,26 47,76 13 3,0 1,0 461 91,45 46,37 42,41 14 3,0 1,0 339 87,22 40,32 35,17 15 3,0 1,0 400 83,12 55,24 45,92 16 3,0 1,0 400 82,19 56,72 46,62 17 3,0 1,0 400 82,56 54,77 45,22 160 T cc gi tr thc nghim v tm !c tnh h s hi qui b i , b ii , b ij t!ng ng. So snh vi gi tr t tnh thu !c trn vi gi tr t bng (95%, 2) = 4,03 v loi b nhng h s hi qui khng c ngha (c gi tr t < t bng ) thu !c ph!ng trnh hi qui cho hiu sut to thnh etylbenzen nh! sau: y = 37,99 + 1,50x 1 - 3,68x 2 + 1,66x 3 - 2,66x 12 - 2,98x 13 + 4,73x 23 - 3,19x 2 2 - 1,80x 3 2 (1) Tnh ton gi tr l thuyt theo ph!ng trnh hi qui trn ri so snh vi gi tr thc nghim nh gi tnh ph hp ca ph!ng trnh hi qui theo chun Fisher: F tnh = 17,65 < F bng (95%, 9, 2) = 19,33. Nh! vy, s sai khc gia gi tr l thuyt v gi tr thc nghim l khng ng k tc l ph!ng trnh hi qui thu !c trn l thch ng. Trn c s hm mc tiu tm !c, tm iu kin ti !u bng ph!ng php ly o hm ring theo tng yu t: 0x 1 + 2,66x 2 + 2,98x 3 = 1,50 -2,66x 1 - 6,38x 2 + 4,73x 3 = 3,68 -2,98x 1 + 4,73x 2 - 3,60x 3 = -1,66 Gii h ph!ng trnh v qui v gi tr thc chng ti thu !c iu kin ti !u cho qu trnh l: x 1 = - 0,226 tc dng l 2,66h -1
x 2 = - 0,066 t l mol etanol/benzen l 0,97 x 3 = 0,562 nhit phn ng l 428 o C Tin hnh phn ng ti iu kin ti !u va tm !c th hiu sut etylbenzen l 53,87% so vi kt qu tnh theo ph!ng trnh hi qui l 54,02%. S sai khc ny l nm trong khong sai s th nghim nn ph!ng trnh thu !c trn l ph hp. Tho lun Nh! vy, hiu sut to thnh sn phm etylbenzen ca phn ng ankyl ha benzen bng etanol trn xc tc 30%H-ZSM-5/HY theo ph!ng trnh hi qui (1) v thy rng: - C 3 yu t tc dng, t l mol etanol/benzen v nhit phn ng u nh h!ng n qu trnh phn ng. - Cc yu t nh h!ng kh phc tp, khng nhng khng tc ng c lp m cn c mi lin h ng thi vi nhau nh h!ng n hiu sut phn ng. Nhit l mt trong nhng yu t quan trng i vi phn ng ankyl ha. S thay i nhit s lm thay i s l!ng ca cc tm axit Bronstet [2] v thay i kh nng ehirat ha ca tc nhn etanol. S thay i nh h!ng n chuyn ha v chn lc sn phm ca phn ng; ng thi qu trnh lm thay i kh nng to cc trn xc tc lm thay i hot tnh xc tc [3]. Nhit thch hp cho qu trnh chuyn ha ny l 300 450 o C. Tc dng cng nh h!ng rt ln n chuyn ha benzen v chn lc sn phm etylbenzen. Khi tc dng nh, thi gian tip xc ca cht phn ng vi xc tc ln, hi cht i su vo cc l xp ca xc tc lm tng kh nng tip xc vi cc trung tm hot ng do lm tng chuyn ha benzen v lm gim chn lc sn phm etylbenzen v sn phm ny d dng i vo phn ng hn so vi benzen. Khi tc dng ln hn, hi cht i qua vng xc tc nhanh hn lm gim thi gian tip xc ca cht vi cc tm hot ng do lm gim chuyn ha benzen nh!ng s lm tng chn lc sn phm etylbenzen. Nh! vy, hiu sut to thnh sn phm etylbenzen cao th tc dng phi c cc gi tr thch hp. T l mol gia etanol v benzen cng l mt trong nhng yu t quyt nh cho hiu sut sn phm etylbenzen. Nu t l mol ln tc l l!ng tc nhn ln, do chuyn ha benzen cao nh!ng chn lc etylbenzen gim v ng!c li. Kt qu cho thy chuyn ha benzen tng khi t l mol etanol/benzen tng. Nh! vy, phn ng khng tun theo c ch Langmuir- Hinshelwood cn c ch Rideal-Eley li gii thch kh tt trong tr!ng hp ny [2, 3]. T l mol etanol/benzen tng nn l!ng etilen v cacbocation to thnh tng do chuyn ha benzen tng; ng thi qu trnh thun li cho vic xy ra cc phn ng th cp to poliankylbenzen nn chn lc sn phm etylbenzen gim. Mt im ph hp na trong tr!ng hp ny l c ch Rideal-Eley ch xy ra i vi cc zeolit c kch th!c l ln cc phn t hirocacbon thm d dng khuch tn v phn ng pha kh vi tc nhn phn ng trong cc l ca zeolit. Nh! vy, c th ngh 161 rng phn ng ankyl ha benzen bng etanol trn xc tc 30%H-ZSM-5/HY chy theo c ch Rideal-Eley. Hm l!ng xc tc H-ZSM-5 mang ln zeolit HY cng nh h!ng n qu trnh phn ng. Qua kt qu thc nghim thu !c nh! trn thy rng mu xc tc 30%H-ZSM-5/HY l tt nht cho qu trnh to thnh etylbenzen. iu ny !c gii thch l do tnh axit ca mu xc tc ny thch ng cho phn ng ankyl ha. Cn cc zeolit ban u c tnh axit yu (HY) hoc c tnh axit qu mnh (H-ZSM-5) nh! nu phn trn l khng thun li cho phn ng ankyl ha v nht l cho qu trnh to sn phm etylbenzen. Do c kch th!c l ln nn xc tc 30%H-ZSM-5/HY to ra nhiu sn phm ph poliankylbenzen hn so vi ZSM-5. Tuy nhin, mt iu c bit l th l trong sn phm ph hm l!ng cc sn phm ietylbenzen, trietylbenzen kh cao; cc cht ny u l sn phm c gi tr, d dng chuyn ha thnh etylbenzen bng phn ng phn b li vi benzen. IV - Kt lun 1. kho st nh h!ng ca hm l!ng H- ZSM-5 mang ln zeolit HY cho phn ng ankyl ha benzen bng etanol. Kt qu cho thy 30%H-ZSM-5/HY l xc tc c tnh !u vit nht cho qu trnh iu ch etylbenzen. ng thi xc nh !c v lc axit ca mu xc tc 30%H-ZSM-5/HY bng ph!ng php gii hp NH 3 -TPD. Kt qu cho thy rng xc tc 30%H-ZSM-5/HY ch cha cc tm axit trung bnh v yu; axit ca cc xc tc theo th t HY < 30%H-ZSM-5/HY < H-ZSM-5. 2. dng ph!ng php k hoch ha thc nghim tm iu kin ti !u cho phn ng ankyl ha benzen bng etanol to thnh etylbenzen trn cc mu xc tc iu ch !c. Kt qu tm !c ph!ng trnh hi qui cho hm mc tiu; iu kin ti !u cho qu trnh l nhit 428 o C, tc dng 2,66 h -1 , t l mol etanol/benzen 0,967. kim tra li phn ng iu kin ti !u va tm !c v xc nhn rng ph!ng trnh hi qui thu !c m t ng th nghim cho. Mt khc, ngh c ch phn ng ankyl ha benzen bng etanol trn xc tc 30%H-ZSM-5/HY theo c ch Rideal-Eley. T)i liu tham kho 1. L c Ngc. X l s liu v k hoch ha thc nghim, i hc Khoa hc T nhin-i hc Quc gia H Ni (2000). 2. K. A. Becker, H. G. Karge, W. D. Streubel. J. Catal. Vol. 28, P. 403 - 413 (1973). 3. Pierre Leveque, Le H. Dao. Appl. Catal. A, Vol. 53, P. 47 - 59 (1996). 4. G. Panagiotis, Smirniotis, Eli Ruskenstein. Ind. Eng. Chem., Vol. 34(