Tap chi khoa hgc trffdng Dgi hgc Quy NhOn TQP IV, sd 2 nam 2010 NGHIEN ClfU CHE TAO XUC xAC Ni Mo/y Al̂ O CHO P H A N ifNG HYDROTREATING LE VAN HI^U* PHAN THI THUY TRANĜ I M 6 D A U Hidn nay, 6 nhiim[.]
Tap chi khoa hgc trffdng Dgi hgc Quy NhOn TQP IV, sd nam 2010 NGHIEN ClfU CHE TAO XUC xAC Ni-Mo/y-Al^O CHO P H A N ifNG HYDROTREATING LE VAN HI^U* PHAN THI THUY TRANG^ I.M6DAU Hidn nay, nhiim moi trtfdng Id mpt vd'n d l ed'p bdch nhd't dang dtfdc todn nhan loai quan tdm Cd rd't nhilu yd'u td ldm dnh htfdng dd'n moi trtfdng vd mpt nbtfng yd'u td quan ti-png dd la chd't Itfdng nhidn bdu dtfng cho dpng cd Vide sdn xuat nhidn lieu sach bao gdm loai trtf cdc phan cd hai nhidn bdu vd cac loai ca'u tii dpe hai ti-ong khdi tiidi cua dpng cd, ddc biet la ham Itfdng Itfu huynh, nitd, cdc oxit kim loai nhidn lieu Vi nd khdng chi lam dnh btfdng dd'n cha't Itfdng sdn pham, dnh htfdng dd'n dpng ed may mdc suf dung ma cdn cd tde dpng xd'u dd'n moi trtfdng vd stfc khoe cua eon ngtfdi Mpt eac bidn phap de nang eao chd't Itfdng nhidn bdu la qua trinh bydrotreating vdi xuc tac Ni-Mo/Y-Al203 He xdc tde cho qua trinh ndy khong nhffng chi diing ede qua trinh chd' bid'n dau ma nd eon dtfdc tfng dung rpng rdi qua trinh xtf ly sdn pham long eua eong nghe chd' bid'n than da T H U C N G H I E M 2.1 Dung cu va hda chd't + Chd't mang Y-AI2O3 dang bat tron (Phap) + Mudi amoni polymolipdat (NH4)gMo,024.4H20 (Nga) + Mudi niken nitrat Ni(N03)2.6H20 (Trung Qudc) + Binh tam chdn khong, bdm but chan khong, tu sa'y, 16 nung, 2.2 Phvtdng phap nghidn cii'u Xuc tac Ni-Mo/Y-Al203 dtfdc tdng hdp bang pbtfdng phdp td'm cac pha boat dpng ldn chd't mang, lan Itfdt hai dung dich cac mudi (NRJ^Mop^^.AHp vd Ni(N03)2.6H20 ldn b l mat chd't mang Y-AI2O3 Qua binh ngdm tam cdc mudi ndy dtfdc tid'n bdnh nhilu lan, mdi lan tfng vdi tbi tich chd't long ldn nhd't ma chat mang y-AXp^ hd'p phu bdo boa Sau mdi lan ngdm tam tid'n hanh sa'y vd nung d cdc nhiet dp khae brong khodng thdi gian nha't dinh Trtfdc kbitid'nbdnh phdn tfng, xuc tde dtfdc boat hda d dilu kidn ngbidn ctfu 2.3 Cac phiAftig phap xac dinh d^c triAig cua xuc tac Pbtfdng phdp TPR dtfdc tid'n bdnh trdn may Autochem II2902 Micromeritics tai phong tbi nghidm Ipc boa dau vd vdt lieu xuc tac, Dai hpc Bdch khoa Hd Npi - Phd XRD cua cdc mau dtfdc chup trdn may PCM-Bruker D8 (Dtfc) tai Khoa Hoa hpc, Dai hpc Khoa hpc Ttf nhidn, Dai hpc Quo'e gia Hd Npi Lfe VAN HI^U, PHAN THI THUY TRANG 12 - Didn tich bl mdt dtfdc bdng pbtfdng phdp BET trdn mdy Micromerictics ASAP 2010 tai Phdng thi nghidm cdng ngh^ Ipc hda diu vd vdt li^u xdc tde, Dai hpc Bdch khoa Hd Ndi Hinh dnh SEM vd EDS dtfdc chup trdn mdy Hitachi S4800 tai Phong tbi nghidm trpng did'm qudc gia vat lipu vd linh kidn difn tii, Vi^n Khoa hoc vdt bdu Hinh dnh TEM dtfdc chup trdn mdy JEM 1010/JEOL(Nhat) tai Vidn v$ sinh dich te Trung tfdng Pbtfdng phdp nghidn ctfu boat tinh xuc tde dtfdc tbtfc hidn d he phdn tfng vi ddng Microaetivity Test Unit MAT 5000 cda Zeton (Canada) vd hd thong phdn tfng dp suat eao ciia Vinci Technologies (Phdp), Trtfdng Dai hpc Bdch khoa Hd Npi 2.4 Cac phtfdhg phap danh gid chi tidu chd't \\i(fng cua nguydn li^u vd san ph^m - Pbtfdng phdp bu^'nb quang tia X (XRF-X Ray Fluorescence) xdc djnh bdm Itfdng Itfu huynh ciia nguydn bdu vd cdc mau sdn pham tai Trung tdm hda nghidm xdng dau quan dpi Ha N6i - Pbtfdng phdp diim anilin xdc dinh hdm Itfdng bydrocacbon tiidm, pbtfdng phdp xac dinh dd sang ciia nhidn bdu ldng vd tinh ehi sd diesel cua nhidn bdu long dtfdc tiiifc bidn tai Phong tbi nghidm cdng nghe Ipc hda dau vd vat bdu xuc tde, Khoa Cong nghe hda bpe, Dai bpe Bach khoa Hd Npi KET QUA VA THAO LUAN 3.1 D$c triAig cua cha't mang va xuc tac 3.1.1 Di$n tich be mgt rieng cua chat mang J-AiPj sff dung Bang pbtfdng phdp hd'p phu vat ly, difa trdn dtfdng hd'p phu vd nhd hd'p phu nitd kd't hdp vdi pbtfdng trinh hd'p phu dang nhiet BET xdc dinh dtfdc didn tich b l mat ridng eiia Y-Al^O, Id 200,5641 mVg Dtfdng kinh Id xd'p khoang 1(>4,1647A° Kd't qua ndy cho thd'y y-Mp^ Id vat bdu khd xdp, b l mat ridng ttfdng ddi ldn tiuch hdp diing lam chat mang cho phdn tfng bydrotreating 3.1.2 Gian dd TPR cda xdc tac Ni-MotfAipp%mO-l2%MoOJ^Aip^ Ttf kd't qud d dd tiii cho tha'y mlu Ni-Mo/Y-Al203 xud't hidn pic kbii tai nhidt dp 180°C, 4060C, 542,3°C vd 598,2°C Qud tiinh khuf bat dau tai nhidt dp khodng 150°C dien qud trinh khii Mo^ tiidnh Mo^+vd kd't thuc tai nhidt dp 598,2°C tfng vdi qud trinh khtf cua NiO, NiAip^ Pic khi^ tai nhidt dp la 406°C xud't bidn pic ddc tiiftig cho qua trinh khuf ciia pha NiMoO Vdy chpn nhidt dp boat boa xdc tac cho qud trinh hydroti-eating id 400°C r^ u i n? A> TI^T> ^ - Hinh Gidn TPR cua xuc tde Ni-Mo/^-Al NGHlfeN ctfu CH^ TAP XUC TAC Ni-Mo/y-AiPj CHO PHAN LfNG HYDROTREATING 13 3.1.3 Gian nhieu XQ tiaX cua hf xdc tac Ni-Mo/y-Alflj A • • S^'AiW^^ 2%NiO-12%Mo03/yAhO I 12%Mo03/iAhO: ,^^^^h^, h.^ /, Ai^YA V u^\A.^*"^' 70 80 Hinh Gidn nhieu xa tinh thi cua mdu y-AiPy 12%MoO/iAiPy 2%NiOI2%Mo0^t{Aip^ (#); -^Aipy f ^ ) ; NiMoO^ Phd XRD eiia mdu 12%Mo03 cho thd'y chi xud't bidn ede pie ddc trtfng cho Y-AI2O3 md khdng cd ede pic ddc trtfng cho M0O3 Dilu chtfng td rang Mo phdn tan 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 %NiO thay ddi Dd thi trdn cho tha'y tai gid tri 2%NiO cho chi sd diesel eao nha't Dilu ndy pbii hdp vdi quy ludt bid'n ddi eua mat dp quang, diim anibn vd ty trpng Thdng qua chi sd diesel biet dtfdc cdc thdnh phan eua bydrocacbon no nhtf parafinic vd naphtenic tdng ldn Dilu dd chtfng to rang tai hdm Itfdng 2%NiO phdn tfng hydro boa xdy manh vd nang eao dtfdc chi sd diesel Vdy cdc kd't qud trdn cho thay rang xuc tac Ni-Mo/Y-Al203 cho boat tinh tdt nhd't [ CO hdm Itfdng 12%Mo03 vd 2%NiO KET LUAN Qua qud tiinh tdng hdp xtfc tde Ni-Mo/Y-Al203 vdi mue dich siJ dung cho qua trinh bydrotreating di ndng ed'p ede phan doan dau mo da thu dtfdc mpt sd kd't qud sau: -I- Dilu chd' dtfdc xtfc tde Ni-Mo/Y-Al203 vdi bdm Itfdng NiO, M6O3 tiiay ddi vd tim dtfdc tiidnh pbIn tditfUciia no la 2%NiO vd 12%MoO, + Khdo sat dtfdc cdc ddc tiiTng boa ly eua cha't mang vd hd xuc tde 2%NiO- 18 Lfe VAN m i u , PHAN THI THUY TRANG 12%Mo03/Y-Al203qua cdc kd't qud phdn tich TPR, XRD, SEM, EDS vd TEM Qua tao dtfdc pha NiMoO^ Id tiln chd't di tao pha NiMoS Nhtf vdy, dd tdng hdp dtfdc xuc tde 2%NiO-12%Mo03/g-Al203 c6 boat tinh tdt cho qud trinh hydroti-eating TAI LifeU THAM KHAO [1] D V Ttfdng, D^ng hgc xiic tde, Trtfdng Dai hpc Bdch khoa Hd Npi, Nhd xua't bdn Khoa hoe vd Ky thudt (2006) [2] T Kabe, A Ishihara, W Qian, Hydrodesulfurization and Hydrodenitrogenation Chemistry and Engineering, Kodansha Ltd, Tokyo (Japan), WILEY-VCH Verlag GmbH, Weinheim (Federal Republic of Germany), (1999) [3] M A Dominguez-Crespo, E.M.Aree-Estrada, A.M.Torres-Huerta, L.Diaz-Garcia, M T Cortez de la Paz, Support effects on bydrotreating activity of NiMo catalysts, Materials Characterization (2006) [4] L Carolina, A Jorge, S R Mohan, M Gustavo, A comparative study on the effect of promoter content of hydrodesulfurization catalyst at different evaluation scales Fuel 86 (2007), 1232-1239 SUMMARY RESEARCH ON THE PREPARATION OF NiMo/Y-AiPj CATALYSTS FOR HYDROTREATING REACTION Le Van Hieu Phan Thi Thuy Trang Hydrotreating catalysts are used to remove sulfur, niu-ogen and otiier contaminants from refinery feedstocks and petroleum products NiMo catalysts supported on Y-Al 0, with different textural properties have been studied in the hydrotreating The catalysts containing l-4%NiO and 8-12%Mo03 o" Y'Aip, were prepared by impregnation method The catalysts were characterized by BET, X-ray diffraction (XRD) TPR studies of the NiMo were analysed to correlate tiieir hydrotreating properties TEM and SEM-EDS studies support the synergetie interaction between Ni sites and MoOx species The results showed that NiMo/Y-Aip3 catalysts had grateful activity for tiie hydrotreating processes "Khoa H6a hoc, Tnfdng Dai hoc Bdch khoa Ha N6i •"Khoa H6a hoc, Tnrdng Dai hoc Quy Nhdn Ngay nhan bai: 05/02/2010; Ngay nhSn dSng: 12/03/2010 Tap chi khoa hgc trUdng Dgi hgc Quy NhOn Tgp IV, sd ndm 2010 ^ AP DUNG PHlTCfNG PHAP DAY HQC KIEN TAO-XUCfNG TAC DE REN LUY|:N KI NANG THIET KE KE HOACH BAI D ^ Y H A HQC CHO SINH VIEN KHOA H A HQC CAC TRl/dNG DAI HQC NGUYIN THI KIM ANH», DANG THI OANH" ^ l.DAT VANDE Mue tidu ciia vide ddi mdi pbtfdng phdp day bpe d cdc trtfdng DHSP noi chung vd khoa Hoa bpe noi ridng la ddo tao sinh vidn sau ndy trtfdng trd thdnh nbtfng thay co gido ttfdng lai, ngodi vide trang bi cho sinh vidn (SV) nhffng Idd'n tbtfc ed bdn ve mon Hoa hpc trang bi cho SV ede ki nang nghi: Mpt nhffng kl ndng nghi quan trpng la Id ndng day bpe Nbtfhg tbtfc td' bien nay, d ede trtfdng phd thong nhilu giao vidn vd sinh vidn stf pham ndm cuo'i ebtfa nam dtfdc bdn chd't eua cac pbtfdng phap day bpe tich ctfc (day bpe theo li tiiuye't boat dpng, day bpe theo H thuyd't kid'n tao, stf pham ttfdng tac, day bpe theo b thuye't khdm phd, ) theo dung bdn chd't vd cae dinh htfdng ciia chung Do vdy, vide td ehtfe cac boat dpng bpe tap eua bpe sinh can dung mtfc de the hidn dung net ddc thii vd phat buy tich ctfc cac pbtfdng phdp day bpe ndy Trong ren luydn ki nang day hpc cho sinh vidn eo rat nhieu Id nang, vi du: Ddt va'n di eiia bdi gidng Id nang bilu didn tbi nghidm kd't hdp vdi ldi noi ciia gido vidn, tdp thid't kd'bdi day (soan gido dn), dtf gid vd bid't each phdn tich mpt gid day ddng thdi tap gidng day mpt trich doan bdi day bode tid't bpe bp mdn, Tuy nhidn, cae Id nang day hpc can ren luydn cho sinh vidn trtfdng stf pham, theo chung toi vide bid't each phan tich mpt gid day vd thid't kd' kd' hoach bai bpe eo stf dung cae pbtfdng phap day bpe xac dinh Id quan trpng vd can thid't de tiitfc hidn vd ren cae Id ndng day bpe tie'p theo Pbtfdng phdp day hpc kid'n tao-ttfdng tac Id mpt pbtfdng phdp tftf vidt vide ren ki ndng thid't kd' kd' hoach bdi day cho sinh vidn NOI DUNG 2.1 To chii'c cho sinh vidn nghidn cuTu cd sd li ludn ciia phtfdng phap d^y hpc kid'n t^o-ttfdng tac Cdn ctf vdo npi dung eiia phtfdng phap day bpe kid'n tao-ttfdng tac, sinh vidn cin ngbidn ctfu cd sd b ludn eiia pbtfdng phap vd trao ddi nhdm theo cac vd'n d l sau: a) Bdn chd't ciia phtfdng phdp kid'n tao-ttfdng tde, net ddc tiiii ciia pbtfdng phap, (ndu va'n d l cho smb vidn thdo ludn, cdc npi dung ed ban vl pbtfdng phap can nam vffng) b) D l xud't cdc bidn phap de tim hieu cac kid'n tbtfc da cd ciia hpc sinh vl bai bpe (sinh vidn can xdc dinh cac kid'n tbtfc bdn quan dd'n bdi hpc da dtfdc hpc d trtfdng trung bpe cd sd, d cae cbtfdng trtfdc do, bai trtfdc do, d l xud't eac phid'u dilu ti-a, eac cdu hoi Idem tra mtfc dp nam cac idd'n tiitfc lidn quan dd'n bdi hpc ma bpe sinh da dtfdc hpc, ) NGUYIN THI KIM ANH, DANG THI OANH 20 c) Dl xud't cdc bidn phdp dl tim hiiu cdc btfdng vl kid'n tbtfc hpc sinh mudn bi^t theo chu di cua bdi bpe vd cdc tdi lidu c6 tbi tim bilu npi dung cin thid't d) Cdc mditiTTdnghpc tap cin chuan bi dl giiip hpc sinh ki^n tao ki^n tbtfc Cbu£n bi cdc tbtf mue, tdi bdu tham khdo cho bdi day theo phtfdng phdp day hpc kien tao-ttfdng tde (vi du nhtf trang web hpc t$p); cdc kid'n tbtfc, ki ndng, thi nghidm, phtfdng tidn tnjfe quan, pbIn mim, e) Dtf kid'n ede boat ddng bpe tdp (cbinb, chu y^u) cin td chtfc cho hpc sinh ti-ong mdt gid hpc hda bpe theo cdc dang bdi hpc thuyd't, dinh ludt; nguydn td vd chat; 6n tap, luydn tap; bdi tbifc bdnh vd cdc boat ddng hpc tap cin dtfdc td chtfc theo phtfdng phdp day bpe kid'n tao-ttfdng tde 2.2 Giang vidn tid'n hanh cho sinh vidn thao ludn nhdm Nbtfng bpe pbIn dp dung pbtfdng phdp day hpc ki^n tao-ttfdng tde gidp rdn luydn ki ndng thid't ke kd' hoach bdi day nhtf: - Hpc phan Pbtfdng phdp day bpe cu the (gidng day cdc cbtfdng mue d trtfdng phd tiidng) vd bpe phan Thi nghidm tbtfc bdnh pbtfdng phdp day hpc hda hpc Dtfdc dp dung cho sinh vidn nam tbtf vide thid't kd'tilebdoan bdi day Hpc phan ren luydn nghidp vu stf phamti-ongday bpe hda hpc dtiiTdngphd thdng dtfdc dp dung cho sinh vidn ndm tbtf vide thid't ke tid't hpc bode bdi day Trong mdi td thtfdng gdm 16 dd'n 20 sinh vidn De td ehtfe cho sinh vidn thdo ludn cdc vd'n dl trdn, chung toi dp dung thii thuat bpe tap ddng dang, bpe tap phdi hdp vd hpc tap hdp tde vd siJf dung ed'u tnic Jigsaw Gidng vidntid'nhanh chia nhdm (mdi td cd 16 sinh vidn dtfdc chia thdnh nhdm, mdi nhom cd thdnh vidn) vd td chtfc cho sinh vidn gidi quyd't vd'n di ndu theo cac btfdc ldm vide nhtf sau: HOAT DQNG Ctx G I A N G VIEN Thanh lap nhdm hdp tac mpt each ngau nhidn vd nhdm ndy gpi Id nbdmgd'c Phdt cho mdi thdnh vidn nhdm mpt vd'n dl thdo luan Thdng bdo thdi gian ddnh cho sinh vidn ttf nghidn ctfu Thanh lap nhdm chuydn gia Thdng bdo thdi gian thdo luan nhdm chuydn gia Lln Itfdt theo doi stf thdo luan cdc nhdm de cd nhffng gdi y, dinh btfdng trpng tdm kid'n tbtfc cho cdc chuydn gia, giup dd sinh vidn vl npi dung pbtfdng phdp trinh bdy HOAT DQNG CUA SINH VIEN Tham gia vdo cdc nhdm vd phdn chia danh sdeh tiieo sdtiitfttf 1, 2, 3,4 Cdc tiidnh vidn 1, 2, 3, nhdn nhiem vu vd ttf ngbidn ctfu npi dung vd'n dl dtfdc phdt Thdnh vidn ttf cdc nhdm khae cd chung chii dl gap de thao luan mpt nhdm mdi Trong thdo ludn, cdc thdnh vidn trao ddi vd tap luydn vl edch tiinh bay npi , dung ngbidn ctfu cho nhdm gd'c cda minh ... xuc tde Ni- Mo/ ^-Al NGHlfeN ctfu CH^ TAP XUC TAC Ni- Mo/ y- AiPj CHO PHAN LfNG HYDROTREATING 13 3.1.3 Gian nhieu XQ tiaX cua hf xdc tac Ni- Mo/ y- Alflj A • • S^''AiW^^ 2%NiO-12 %Mo0 3/yAhO I 12 %Mo0 3/iAhO:... ,^^^^h^, h.^ /, Ai^YA V u^\A.^*"^'' 70 80 Hinh Gidn nhieu xa tinh thi cua mdu y- AiPy 12%MoO/iAiPy 2%NiOI2 %Mo0 ^t{Aip^ (#); -^Aipy f ^ ) ; NiMoO^ Phd XRD eiia mdu 12 %Mo0 3 cho thd ''y chi xud''t bidn... parafinic vd naphtenic tdng ldn Dilu dd chtfng to rang tai hdm Itfdng 2%NiO phdn tfng hydro boa xdy manh vd nang eao dtfdc chi sd diesel Vdy cdc kd''t qud trdn cho thay rang xuc tac Ni- Mo/ Y- Al203 cho