Nghiên cứu chế tạo xúc tác Ni-Mo/y-Al1O3 cho phản ứng hydrotreating

Tap chi khoa hgc trffdng Dgi hgc Quy NhOn TQP IV, sd 2 nam 2010<br /> <br /> <br /> <br /> <br /> NGHIEN ClfU CHE TAO XUC xAC Ni-Mo/y-Al^O<br /> CHO P H A N ifNG HYDROTREATING<br /> <br /> LE VAN HI^U*. PHAN THI THUY TRANG^<br /> <br /> I.M6DAU<br /> Hidn nay, 6 nhiim moi trtfdng Id mpt vd'n d l ed'p bdch nhd't dang dtfdc todn nhan<br /> loai quan tdm. Cd rd't nhilu yd'u td ldm dnh htfdng dd'n moi trtfdng vd mpt trong nbtfng<br /> yd'u td quan ti-png dd la chd't Itfdng nhidn bdu dtfng cho dpng cd. Vide sdn xuat nhidn<br /> lieu sach bao gdm loai trtf cdc thanh phan cd hai trong nhidn bdu vd cac loai ca'u tii dpe<br /> hai ti-ong khdi tiidi cua dpng cd, ddc biet la ham Itfdng Itfu huynh, nitd, cdc oxit kim<br /> loai... trong nhidn lieu. Vi nd khdng chi lam dnh btfdng dd'n cha't Itfdng sdn pham, dnh<br /> htfdng dd'n dpng ed may mdc khi suf dung ma cdn cd tde dpng xd'u dd'n moi trtfdng vd stfc<br /> khoe cua eon ngtfdi. Mpt trong eac bidn phap de nang eao chd't Itfdng nhidn bdu la qua<br /> trinh bydrotreating vdi xuc tac Ni-Mo/Y-Al203. He xdc tde cho qua trinh ndy khong<br /> nhffng chi diing trong ede qua trinh chd' bid'n dau ma nd eon dtfdc tfng dung rpng rdi<br /> trong qua trinh xtf ly sdn pham long eua eong nghe chd' bid'n than da.<br /> 2. T H U C N G H I E M<br /> <br /> 2.1. Dung cu va hda chd't<br /> + Chd't mang Y-AI2O3 dang bat tron (Phap).<br /> + Mudi amoni polymolipdat (NH4)gMo,024.4H20 (Nga).<br /> + Mudi niken nitrat Ni(N03)2.6H20 (Trung Qudc).<br /> + Binh tam chdn khong, bdm but chan khong, tu sa'y, 16 nung,...<br /> 2.2. Phvtdng phap nghidn cii'u<br /> Xuc tac Ni-Mo/Y-Al203 dtfdc tdng hdp bang pbtfdng phdp td'm cac pha boat dpng ldn<br /> chd't mang, lan Itfdt hai dung dich cac mudi (NRJ^Mop^^.AHp vd Ni(N03)2.6H20 ldn<br /> b l mat chd't mang Y-AI2O3. Qua binh ngdm tam cdc mudi ndy dtfdc tid'n bdnh nhilu lan,<br /> mdi lan tfng vdi tbi tich chd't long ldn nhd't ma chat mang y-AXp^ hd'p phu bdo boa. Sau<br /> mdi lan ngdm tam tid'n hanh sa'y vd nung d cdc nhiet dp khae nhau brong khodng thdi gian<br /> nha't dinh. Trtfdc kbitid'nbdnh phdn tfng, xuc tde dtfdc boat hda d dilu kidn ngbidn ctfu.<br /> 2.3. Cac phiAftig phap xac dinh d^c triAig cua xuc tac<br /> Pbtfdng phdp TPR dtfdc tid'n bdnh trdn may Autochem II2902 Micromeritics tai<br /> phong tbi nghidm Ipc boa dau vd vdt lieu xuc tac, Dai hpc Bdch khoa Hd Npi.<br /> - Phd XRD cua cdc mau dtfdc chup trdn may PCM-Bruker D8 (Dtfc) tai Khoa<br /> Hoa hpc, Dai hpc Khoa hpc Ttf nhidn, Dai hpc Quo'e gia Hd Npi.<br /> 12 Lfe VAN HI^U, PHAN THI THUY TRANG<br /> <br /> - Didn tich bl mdt dtfdc do bdng pbtfdng phdp BET trdn mdy Micromerictics ASAP<br /> 2010 tai Phdng thi nghidm cdng ngh^ Ipc hda diu vd vdt li^u xdc tde, Dai hpc Bdch<br /> khoa Hd Ndi.<br /> Hinh dnh SEM vd EDS dtfdc chup trdn mdy Hitachi S4800 tai Phong tbi nghidm<br /> trpng did'm qudc gia vat lipu vd linh kidn difn tii, Vi^n Khoa hoc vdt bdu.<br /> Hinh dnh TEM dtfdc chup trdn mdy JEM 1010/JEOL(Nhat) tai Vidn v$ sinh dich<br /> te Trung tfdng.<br /> Pbtfdng phdp nghidn ctfu boat tinh xuc tde dtfdc tbtfc hidn d he phdn tfng vi ddng<br /> Microaetivity Test Unit MAT 5000 cda Zeton (Canada) vd hd thong phdn tfng dp suat<br /> eao ciia Vinci Technologies (Phdp), Trtfdng Dai hpc Bdch khoa Hd Npi.<br /> 2.4. Cac phtfdhg phap danh gid chi tidu chd't \\i(fng cua nguydn li^u vd san ph^m<br /> - Pbtfdng phdp bu^'nb quang tia X (XRF-X Ray Fluorescence) xdc djnh bdm Itfdng<br /> Itfu huynh ciia nguydn bdu vd cdc mau sdn pham tai Trung tdm hda nghidm xdng dau<br /> quan dpi Ha N6i.<br /> - Pbtfdng phdp diim anilin xdc dinh hdm Itfdng bydrocacbon tiidm, pbtfdng phdp<br /> xac dinh dd sang ciia nhidn bdu ldng vd tinh ehi sd diesel cua nhidn bdu long dtfdc tiiifc<br /> bidn tai Phong tbi nghidm cdng nghe Ipc hda dau vd vat bdu xuc tde, Khoa Cong nghe<br /> hda bpe, Dai bpe Bach khoa Hd Npi.<br /> 3. KET QUA VA THAO LUAN<br /> 3.1. D$c triAig cua cha't mang va xuc tac<br /> 3.1.1. Di$n tich be mgt rieng cua chat mang J-AiPj sff dung<br /> Bang pbtfdng phdp do hd'p phu vat ly, difa trdn dtfdng hd'p phu vd nhd hd'p phu<br /> nitd kd't hdp vdi pbtfdng trinh hd'p phu dang nhiet BET xdc dinh dtfdc didn tich b l mat<br /> ridng eiia Y-Al^O, Id 200,5641 mVg. Dtfdng kinh Id xd'p khoang 1(>4,1647A°. Kd't qua<br /> ndy cho thd'y y-Mp^ Id vat bdu khd xdp, b l mat ridng ttfdng ddi ldn tiuch hdp diing lam<br /> chat mang cho phdn tfng bydrotreating.<br /> 3.1.2. Gian dd TPR cda xdc tac Ni-MotfAipp%mO-l2%MoOJ^Aip^<br /> Ttf kd't qud d dd tiii cho tha'y mlu<br /> Ni-Mo/Y-Al203 xud't hidn 4 pic kbii tai nhidt<br /> dp 180°C, 4060C, 542,3°C vd 598,2°C. Qud<br /> tiinh khuf bat dau tai nhidt dp khodng 150°C<br /> dien ra qud trinh khii Mo^ tiidnh Mo^+vd<br /> kd't thuc tai nhidt dp 598,2°C tfng vdi qud<br /> trinh khtf cua NiO, NiAip^. Pic khi^ tai<br /> nhidt dp la 406°C xud't bidn pic ddc tiiftig<br /> cho qua trinh khuf ciia pha NiMoO .<br /> Vdy chpn nhidt dp boat boa xdc tac<br /> cho qud trinh hydroti-eating id 400°C. r^ u i n?. A> TI^T> ^ - .<br /> Hinh 1. Gidn do TPR cua xuc tde Ni-Mo/^-Al 0<br /> NGHlfeN ctfu CH^ TAP XUC TAC Ni-Mo/y-AiPj CHO PHAN LfNG HYDROTREATING 13<br /> <br /> 3.1.3. Gian do nhieu XQ tiaX cua hf xdc tac Ni-Mo/y-Alflj<br /> A • •<br /> <br /> <br /> <br /> <br /> 2%NiO-12%Mo03/yAhO. S^'AiW^^<br /> I<br /> 12%Mo03/iAhO: ,^^^^h^,<br /> <br /> /,<br /> .h.^<br /> Ai^YA<br /> V..u^\A.^*"^'<br /> 70 80<br /> <br /> <br /> <br /> Hinh 2. Gidn do nhieu xa tinh thi cua mdu y-AiPy 12%MoO/iAiPy 2%NiO-<br /> I2%Mo0^t{Aip^ (#); -^Aipy f ^ ) ; NiMoO^<br /> Phd XRD eiia mdu 12%Mo03 cho thd'y chi xud't bidn ede pie ddc trtfng cho<br /> Y-AI2O3 md khdng cd ede pic ddc trtfng cho M0O3. Dilu do chtfng td rang Mo phdn tan<br /> tdt trdn bl mat chd't mang bode kich thtfde tinh the M0O3 r^t be (d thi 4: Ty trgng vd chi sd diesel cda sdn phdm theo thdi gian khi %NiO thay ddi<br /> <br /> Dd thi trdn cho tha'y tai gid tri 2%NiO cho chi sd diesel eao nha't. Dilu ndy pbii<br /> hdp vdi quy ludt bid'n ddi eua mat dp quang, diim anibn vd ty trpng. Thdng qua chi sd<br /> diesel biet dtfdc cdc thdnh phan eua bydrocacbon no nhtf parafinic vd naphtenic tdng<br /> ldn. Dilu dd chtfng to rang tai hdm Itfdng 2%NiO phdn tfng hydro boa xdy ra manh vd<br /> nang eao dtfdc chi sd diesel.<br /> Vdy cdc kd't qud trdn cho thay rang xuc tac Ni-Mo/Y-Al203 cho boat tinh tdt nhd't<br /> [ khi CO hdm Itfdng 12%Mo03 vd 2%NiO.<br /> 4. KET LUAN<br /> Qua qud tiinh tdng hdp xtfc tde Ni-Mo/Y-Al203 vdi mue dich siJ dung cho qua trinh<br /> bydrotreating di ndng ed'p ede phan doan dau mo da. thu dtfdc mpt sd kd't qud sau:<br /> -I- Dilu chd' dtfdc xtfc tde Ni-Mo/Y-Al203 vdi bdm Itfdng NiO, M6O3 tiiay ddi vd<br /> tim ra dtfdc tiidnh pbIn tditfUciia no la 2%NiO vd 12%MoO,.<br /> + Khdo sat dtfdc cdc ddc tiiTng boa ly eua cha't mang vd hd xuc tde 2%NiO-<br /> 18 Lfe VAN m i u , PHAN THI THUY TRANG<br /> <br /> 12%Mo03/Y-Al203qua cdc kd't qud phdn tich TPR, XRD, SEM, EDS vd TEM. Qua do<br /> tao dtfdc pha NiMoO^ Id tiln chd't di tao ra pha NiMoS. Nhtf vdy, dd tdng hdp dtfdc xuc<br /> tde 2%NiO-12%Mo03/g-Al203 c6 boat tinh tdt cho qud trinh hydroti-eating.<br /> <br /> <br /> TAI LifeU THAM KHAO<br /> [1] D. V. Ttfdng, D^ng hgc xiic tde, Trtfdng Dai hpc Bdch khoa Hd Npi, Nhd xua't bdn<br /> Khoa hoe vd Ky thudt (2006).<br /> [2] T. Kabe, A. Ishihara, W. Qian, Hydrodesulfurization and Hydrodenitrogenation<br /> Chemistry and Engineering, Kodansha Ltd, Tokyo (Japan), WILEY-VCH Verlag<br /> GmbH, Weinheim (Federal Republic of Germany), (1999).<br /> [3] M. A. Dominguez-Crespo, E.M.Aree-Estrada, A.M.Torres-Huerta, L.Diaz-Garcia,<br /> M. T. Cortez de la Paz, Support effects on bydrotreating activity of NiMo catalysts,<br /> Materials Characterization (2006).<br /> [4] L. Carolina, A. Jorge, S. R. Mohan, M. Gustavo, A comparative study on the effect of<br /> promoter content of hydrodesulfurization catalyst at different evaluation scales. Fuel<br /> 86 (2007), 1232-1239.<br /> <br /> <br /> SUMMARY<br /> RESEARCH ON THE PREPARATION OF NiMo/Y-AiPj CATALYSTS<br /> FOR HYDROTREATING REACTION<br /> <br /> Le Van Hieu. Phan Thi Thuy Trang<br /> <br /> Hydrotreating catalysts are used to remove sulfur, niu-ogen and otiier contaminants<br /> from refinery feedstocks and petroleum products. NiMo catalysts supported on Y-Al 0,<br /> with different textural properties have been studied in the hydrotreating. The catalysts<br /> containing l-4%NiO and 8-12%Mo03 o" Y'Aip, were prepared by impregnation method<br /> The catalysts were characterized by BET, X-ray diffraction (XRD). TPR studies of the<br /> NiMo were analysed to correlate tiieir hydrotreating properties. TEM and SEM-EDS studies<br /> support the synergetie interaction between Ni sites and MoOx species. The results showed<br /> that NiMo/Y-Aip3 catalysts had grateful activity for tiie hydrotreating processes.<br /> <br /> <br /> "Khoa H6a hoc, Tnfdng Dai hoc Bdch khoa Ha N6i<br /> •"Khoa H6a hoc, Tnrdng Dai hoc Quy Nhdn<br /> Ngay nhan bai: 05/02/2010; Ngay nhSn dSng: 12/03/2010.<br /> Tap chi khoa hgc trUdng Dgi hgc Quy NhOn Tgp IV, sd 2 ndm 2010<br /> <br /> <br /> <br /> <br /> ^ AP DUNG PHlTCfNG PHAP DAY HQC KIEN TAO-XUCfNG TAC<br /> DE REN LUY|:N KI NANG THIET KE KE HOACH BAI D ^ Y H 6 A HQC<br /> CHO SINH VIEN KHOA H 6 A HQC CAC TRl/dNG DAI HQC<br /> <br /> NGUYIN THI KIM ANH», DANG THI OANH"<br /> <br /> ^<br /> l.DAT VANDE<br /> Mue tidu ciia vide ddi mdi pbtfdng phdp day bpe d cdc trtfdng DHSP noi chung vd<br /> khoa Hoa bpe noi ridng la ddo tao sinh vidn sau ndy ra trtfdng trd thdnh nbtfng thay co<br /> gido ttfdng lai, ngodi vide trang bi cho sinh vidn (SV) nhffng Idd'n tbtfc ed bdn ve mon<br /> Hoa hpc con trang bi cho SV ede ki nang nghi: Mpt trong nhffng kl ndng nghi quan<br /> trpng la Id ndng day bpe. Nbtfhg tbtfc td' bien nay, d ede trtfdng phd thong nhilu giao<br /> vidn vd sinh vidn stf pham ndm cuo'i ebtfa nam dtfdc bdn chd't eua cac pbtfdng phap day<br /> bpe tich ctfc (day bpe theo li tiiuye't boat dpng, day bpe theo H thuyd't kid'n tao, stf pham<br /> ttfdng tac, day bpe theo b thuye't khdm phd,...) theo dung bdn chd't vd cae dinh htfdng<br /> ciia chung. Do vdy, vide td ehtfe cac boat dpng bpe tap eua bpe sinh can dung mtfc de<br /> the hidn dung net ddc thii vd phat buy tich ctfc cac pbtfdng phdp day bpe ndy.<br /> Trong ren luydn ki nang day hpc cho sinh vidn eo rat nhieu Id nang, vi du: Ddt<br /> va'n di eiia bdi gidng. Id nang bilu didn tbi nghidm kd't hdp vdi ldi noi ciia gido vidn,<br /> tdp thid't kd'bdi day (soan gido dn), dtf gid vd bid't each phdn tich mpt gid day ddng thdi<br /> tap gidng day mpt trich doan bdi day bode tid't bpe bp mdn,.... Tuy nhidn, trong cae Id<br /> nang day hpc can ren luydn cho sinh vidn trtfdng stf pham, theo chung toi vide bid't each<br /> phan tich mpt gid day vd thid't kd' kd' hoach bai bpe eo stf dung cae pbtfdng phap day bpe<br /> xac dinh Id quan trpng vd can thid't de tiitfc hidn vd ren cae Id ndng day bpe tie'p theo.<br /> Pbtfdng phdp day hpc kid'n tao-ttfdng tac Id mpt pbtfdng phdp tftf vidt trong vide<br /> ren ki ndng thid't kd' kd' hoach bdi day cho sinh vidn.<br /> 2. NOI DUNG<br /> 2.1. To chii'c cho sinh vidn nghidn cuTu cd sd li ludn ciia phtfdng phap d^y hpc kid'n<br /> t^o-ttfdng tac<br /> Cdn ctf vdo npi dung eiia phtfdng phap day bpe kid'n tao-ttfdng tac, sinh vidn cin<br /> ngbidn ctfu cd sd b ludn eiia pbtfdng phap vd trao ddi nhdm theo cac vd'n d l sau:<br /> a) Bdn chd't ciia phtfdng phdp kid'n tao-ttfdng tde, net ddc tiiii ciia pbtfdng phap,...<br /> (ndu va'n d l cho smb vidn thdo ludn, cdc npi dung ed ban vl pbtfdng phap can nam vffng).<br /> b) D l xud't cdc bidn phap de tim hieu cac kid'n tbtfc da cd ciia hpc sinh vl bai bpe<br /> (sinh vidn can xdc dinh cac kid'n tbtfc bdn quan dd'n bdi hpc da dtfdc hpc d trtfdng trung<br /> bpe cd sd, d cae cbtfdng trtfdc do, bai trtfdc do, d l xud't eac phid'u dilu ti-a, eac cdu hoi<br /> Idem tra mtfc dp nam cac idd'n tiitfc lidn quan dd'n bdi hpc ma bpe sinh da dtfdc hpc,...).<br />  NGUYIN THI KIM ANH, DANG THI OANH<br /> 20<br /> <br /> c) Dl xud't cdc bidn phdp dl tim hiiu cdc btfdng vl kid'n tbtfc hpc sinh mudn bi^t<br /> theo chu di cua bdi bpe vd cdc tdi lidu c6 tbi tim bilu npi dung cin thid't.<br /> d) Cdc mditiTTdnghpc tap cin chuan bi dl giiip hpc sinh ki^n tao ki^n tbtfc.<br /> Cbu£n bi cdc tbtf mue, tdi bdu tham khdo cho bdi day theo phtfdng phdp day hpc kien<br /> tao-ttfdng tde (vi du nhtf trang web hpc t$p); cdc kid'n tbtfc, ki ndng, thi nghidm, phtfdng<br /> tidn tnjfe quan, pbIn mim,...<br /> e) Dtf kid'n ede boat ddng bpe tdp (cbinb, chu y^u) cin td chtfc cho hpc sinh ti-ong<br /> mdt gid hpc hda bpe theo cdc dang bdi hpc thuyd't, dinh ludt; nguydn td vd chat; 6n tap,<br /> luydn tap; bdi tbifc bdnh vd cdc boat ddng hpc tap cin dtfdc td chtfc theo phtfdng phdp<br /> day bpe kid'n tao-ttfdng tde.<br /> 2.2. Giang vidn tid'n hanh cho sinh vidn thao ludn nhdm<br /> Nbtfng bpe pbIn dp dung pbtfdng phdp day hpc ki^n tao-ttfdng tde gidp rdn luydn<br /> ki ndng thid't ke kd' hoach bdi day nhtf:<br /> - Hpc phan Pbtfdng phdp day bpe cu the (gidng day cdc cbtfdng mue d trtfdng phd<br /> tiidng) vd bpe phan Thi nghidm tbtfc bdnh pbtfdng phdp day hpc hda hpc. Dtfdc dp dung<br /> cho sinh vidn nam tbtf 3 trong vide thid't kd'tilebdoan bdi day.<br /> Hpc phan ren luydn nghidp vu stf phamti-ongday bpe hda hpc dtiiTdngphd<br /> thdng dtfdc dp dung cho sinh vidn ndm tbtf 4 trong vide thid't ke tid't hpc bode bdi day.<br /> Trong mdi td thtfdng gdm 16 dd'n 20 sinh vidn.<br /> De td ehtfe cho sinh vidn thdo ludn cdc vd'n dl trdn, chung toi dp dung thii thuat<br /> trong bpe tap ddng dang, bpe tap phdi hdp vd hpc tap hdp tde vd siJf dung ed'u tnic<br /> Jigsaw. Gidng vidntid'nhanh chia nhdm (mdi td cd 16 sinh vidn dtfdc chia thdnh 4 nhdm,<br /> mdi nhom cd 4 thdnh vidn) vd td chtfc cho sinh vidn gidi quyd't 4 vd'n di ndu ra theo cac<br /> btfdc ldm vide nhtf sau:<br /> HOAT DQNG Ctx G I A N G VIEN HOAT DQNG CUA SINH VIEN<br /> 1. Thanh lap nhdm hdp tac mpt each ngau Tham gia vdo cdc nhdm vd phdn chia danh<br /> nhidn vd nhdm ndy gpi Id nbdmgd'c. sdeh tiieo sdtiitfttf 1, 2, 3,4.<br /> 2. Phdt cho mdi thdnh vidn trong nhdm Cdc tiidnh vidn 1, 2, 3, 4 nhdn nhiem vu<br /> mpt vd'n dl thdo luan. Thdng bdo thdi vd ttf ngbidn ctfu npi dung vd'n dl dtfdc<br /> gian ddnh cho sinh vidn ttf nghidn ctfu. phdt.<br /> 3. Thanh lap nhdm chuydn gia. Thdng Thdnh vidn ttf cdc nhdm khae nhau cd<br /> bdo thdi gian thdo luan trong nhdm chung chii dl gap nhau de thao luan trong<br /> chuydn gia. Lln Itfdt theo doi stf thdo mpt nhdm mdi.<br /> luan trong cdc nhdm de cd nhffng gdi y, Trong khi thdo ludn, cdc thdnh vidn trao<br /> dinh btfdng trpng tdm kid'n tbtfc cho cdc ddi vd tap luydn vl edch tiinh bay npi ,<br /> chuydn gia, giup dd sinh vidn vl npi dung ngbidn ctfu cho nhdm gd'c cda minh.<br /> dung pbtfdng phdp trinh bdy.<br />