HON HOP NICKEL CHLORIT DIHYDRAT &
NICKEL-NHOM OXIT - XUC TAC HYDRO HOA MOI
'^Ho So-n Long.^Tran Boi Chau/Huynh Thanh C6ng,'V6 D6 Minh Hoang ' "Ho Son Lam
(1); Viin Khoa hgc Vdt lieu Lfng dung. (2): Trudng Dgi hoc Tdn Dire Thdng Tom tat:
Xiie tdc mdi trin ca sd nhdm clorit vd nickel clorit dugc tdng hgp qua giai dogn tgo phuc, sau dd thiiu kit a nhiit do 550°C. Cdc kit qud phdn tich xiic tde bdng IR, X-ray, BET, SEM cho thdy ed nhiiu diim tuang ddng giua xiic tdc mdi vdi xuc tdc Raney-Nickel chudn cita hdng Merk. Cd hai logi xiic tdc dugc tiin hdnh phdn ung hydro hda trong pha khi (dp sudt thudng) vd trong pha Idng (dp sudt 2 atm) trin ciing mdt ddi tugng Id linh ddu sd cd hdm lugng cilral 86%. Sdn phdm cua phdn ung dugc phdn tich trin GC/MS HP 6890 vdi cdt HP5MS vdi khi mang la helium. Sdn phdm ciia phdn itng cho thdy hiiu qud hydro hda ciia xuc tdc mdi khdng nhiing khdng thua kem xiic tdc Raney-Nickel chudn, md cdn tga rg nhiiu sdn phdm qui khdc, ddc biel khi hydro hda trong pha Idng vdi dp sudt 2 at.
Tir khda: Xuc tdc, Raney-Nickel, hydro hda Abstract:
New catalyst based on AlClj and NiCh that is synthesized by complexing, then sintering al 550°C. Analysing by IR, X-Ray, BET, SEM shows similarity between this new catalyst and Raney-Nickel catalyst of Merck. Hydrogenation of these t^vo catalysts in gas phase (normal pressure) and in liquid phase (pressure 2 atm) on citronella oil which contains 86% of cilral. The products are analysed with GC/MS HP 6890 on HP5 MS column with helium as gas carrier. These products show that the new catalyst not only has Ihe same properties with Raney-Nickel catalyst of Merck, but also create many precious substances, especially in hydrogenation in liquid phase with pressure 2 atm.
Key words : Catalyst, Raney-Nickel, Hydrogenation
I. DAT VAN DE
Xuc tac ddng vai trd quan trong trong phan ung hydro hda. Mot sd xuc tac kim loai quy hiem dac biet la Platinum, Palladium, Rhodium, cd boat tinh xiic tac cao, thudng xay ra khi nhiet dp va ap suat H2 thap, tuy nhien, gia thanh cua cac loai xiic tac nay tuong ddi cao.
Xiic tac dung nhihig kim loai khdng quy hiem, dac biet la nhung loai xiic tac dugc lam dua tren Nickel (nhu Urushibara Nickel, Raney-Nickel) mang tinh kinh te ban, nhung ddi hdi nhiet dp cao ban [2].
Xiic tac thudng dugc su dung trong cdng nghiep cho cac qua trinh hydro hda la xiic tac di the, thudng d dang ran, khdng ddng nhat vdi chat nen trong dung mdi, hoac la dugc su dung trong trudng hgp chat nen d dang khi [1,3].
Xiic tac Raney-Nickel dugc su dung nhilu d VN cho cong nghiep san xudt ddu thuc vat. Hang nam lugng xiic tac nay phai nhap khdu la rdt Idn, lam cho gia thanh san phdm tang, kha nang canh tranh tren thi tmdng cua hang Viet Nam giam.
Dinh hudng cua de tai la tdng hgp mgt loai xiic tac hydro hda mdi theo dilu kien va cdng nghe Viet Nam, sao cho hieu qua tuong duong vdi xiic tac nhap, nhung cd thS san xudt
Tieu ban Khoa hoc vdt liiu ISBN: 978-604-913-0
De lam co sd khoa hoc cho cac nghien cuu ciia minh, chiing tdi da sir dung xuc tac Raney-Nickel ciia hang Merck lam chat ddi chung trong phan iing hydro hda.
II. PHAN THUC NGHIEM
Xiic tac mdi dugc tdng hgp tren ca sd mudi chlorit cua Nikel (NiCh) va nhdm chlorit (AICI3) d dang hda chdt P. Sau khi thu dugc phiic chat dang chlorin, san pham dugc tien hanh thieu ket trong ddng khi tra d nhiet do 550°C. nhan dugc hon hgp Nickel chlorit dihydrat va Nickel aluminium oxh tinh the.
Ca hai loai xiic tac (Raney-Nickel ciia Hang Merk va xiic tac mdi) dugc tien hanh phan tich IR, X-ray, BET, SEM. Ca hai xiic tac dugc tiln hanh phan iing hydro hda tren thiet bi hydro hda trong pha khi va thilt bi trong pha Idng cd ap suat. Ddi tugng hydro hda la tinh dau sa cd ham lugng Citral chiem 86%).
IH. KET QUA VA THAO LUAN III.l Ket qua phan tich xuc tac:
III.l.1: Phan tich IR: Khi phan tich IR cac mau xiic tac,nhan thay cau tnic ciia nd cd viing dac trung d 3385 (nhdm OH hydrat), vung 1615 (O2) va vung 632(Cl).Ca hai mau cd hinh dang tuong tu nhau.
III.1.2: Phan tich X-ray: Kit qua xac dinh X-ray cua hai mau xiic tac cho thay:
- Xiic tac mdi (CM): 6 budc sdng 38 tren thang 2-Theta da xac dinh dugc hai san phdm cung tdn tai, dd la Nikelchloride dihydrat (NiCl2(H20)2) vdi ham lugng 13,17% va Nikel-Aluminium Oxide (NiAl203) vdi ham lugng 7,54%. Nhu vay, tuy chua hinh thanh hgp kim Al - Ni, nhung xiic tac nhan dugc da cd su thay ddi hda tri, tu Ni"^^ sang Ni""^ va Chlor trong AICI3 da chuyen sang AI2O3.
- Xiic tac Raney-Nickel ciia hang Merck (CRN) : Ket qua phan tich X-Ray cho thay thanh phan cua xiic tac nay la NiO, Ni, ngoai ra cdn cd cac hgp chat khac ciia Nickel nhu la NiC, FeNi3 va tat ca cac hgp chat nay deu nam dudi dang tinh the.
III.1.3: Phan tich BET:
Kit qua phan tich dien tieh be mat cua hai mau xiic tac cho thay : dien tich bl mat ciia xiic tac mdi (CM) la 21.605 m^/g, ciia xiic tac Raney-Nickel (CRN) ciia hang Merck la 30.132 m'/g.
in.1.4: Phan tich SEM:
Kit qua do SEM hai mau xiic tac Raney-Nickel CRN va CM:
Htnh 1: Hinh chup SEM cita mdu Raney- Nickel ciia hdng Merck C^v
Hinh 2: Hinh chup SEM cua mdu xuc tdc mdi
(CM)
Qua hinh SEM ciia hai mau xiic tac tren, cd the nhan thay cd su gidng nhau vl mat cdu tnic ciia chiing. Xiic tac Raney-Nickel ciia Merk (CRN) hinh thanh theo dang ban mdne tung ldp. tao thanh Id xdp dang vien gach dng. Xiic tac mdi (CM) cung cd cau tao tuang ty 'ihung mdng ban. Do day mang ciia ca hai xiic tac rat nhd va nam trong khoang < 50 nm.
Ve mat cam quan, xiic tac mdi nhe va xdp hon, ed do sang ban so vdi xiic tac Raney- Nickel (CRN).
'' .-4
I f ^
Htnh 3'. Xiic tdc Raney-Nickel (CRA) dgng bdt Hinh 4: Xuc tdc mdi (CM) a dgng bdt vd sou vd sau khi ep viin khi ep viin
III.2 Ket qua phan ung hydro hda trong pha khi khong co ap suSt:
Phan ling tiln hanh vdi nhiing dilu kien cd dinh cho tdt ca cac nghien ciiu nhu sau:
- The tich Id phdn img: 90ml, khdi lugng xiic tdc: 10 gram - Van tdc khi hydro: 7 lit/gid, van toe ngp nguyen lieu: 30ml/gid - Nhiit do phdn itng: trong vung tu 295 °C din 335 °C.
San pham thu dugc d dang Idng dem phan tich sdc ki khi GC va GC/MS.
III.2.1 Phan iing hydro hoa su dung xiic tac Raney-Nickel cua hang Merck : Trong tdng sd 75,61 % nguyen lieu chuyin hda thanh san phdm mdi, cd:
+ 58,28 % thanh hydroeacbon khdng chiia oxy.
+ 14,23%) thanh san pham chiia oxy:
+ 3,1%) hao hut do hinh thanh cac san phdm khi, nude va sai sd.
Xiic tac Raney-Nickel ciia hang Merck xiic tiln phan iing hydro hda rdt manh va khdng nhung the, nd cdn cdt mach C-C dl tao thanh hydroeacbon thdp. 77% san phdm mdi la hydrocarbon khdng chiia oxy da chiing minh dilu dd:
+ 2,6-dimethyl, 3-heptene, C9H,8(3,07%) +2,6-dimethylheptane, C9H2o(10,l%) +2,6-dimethylheptene, C9H,8(4,21%) +2,6-dimethyl,2-heptene, C9H,8(11,32%) +2,6-dimethyl, 1,5-heptadiene C9H16 (14,09%)
III.2.2 Phan iing hydro hoa su dung xiic tac moi:
Trong tdng sd 74,54 % nguyen lieu da chuyin hda, hinh thanh:
+ 58,22% hydrocarbon vdng khdng chiia oxy: chiim 81,62% tdng san phdm mdi, trong dd, Cymene chiem 50%).
+ 12,56 %) hydroeacbon vdng cd chiia oxy.
+ 3,0%) hao hut do hinh thanh cac san phdm khi, nude va sai sd.
Xiic tac mdi la mgt xiic tac cd kha nang khdng chi hydro hda ma cdn cd kha nang ddng vdng hydroeacbon rat tdt. Hdu hit cac san phdm diu dugc ddng vdng dl tao ra nhilu hgp chat cd gia tri nhu:
+ 1,4-Cyclohexadiene, 1-methyl- C7H10 (9,13%)
, + m-Cymene.C,oH,4 (33,15%) + p-Isopropenyl toluen, C,oH,2 (14,76%) + Trans-Carveol, CoH.eO (0.86%) + Piperitone. C,oH,eO (1,16%)
Tiiu ban Khoa hoc vdt liiu ISBN: 978-604-913-011-3
-I- 5-Hydroxymethyl-1,1,4a-trimethyl-6-methylenedecah>'dronaphthalen (1.16%o)
III.3 Ket qua phan irng hydro hoa trong pha long CO ap suat:
Autoclave sii dung la thiet bi phan iing khep kin, chiu dugc nhiet do \'a ap suat cao, lam bang thep khdng gi, cd dang hinh tru. dudng kinh 6.4 cm, chieu cao 7 cm va be day 0.8 cm. Trong long ndi phan ling cd gan cap nhiet diet de dieu chinh nhiet do.
Nhiet do phan img ISO^'C, ap suat 2 at.
* Cac san pham mdi hydro hda trong khi
Autoclave vdi xuc tac la
STT 1 2 3 5 6 S
10 11 13 IP
20
I T
23 24
25
25
27
2S
Ten SP-CTPT 6-Eial:yl-5-h^€E-2-OEa, C j H u O [RT : r2.4Sl{MS: 43 35 69 93 lOS 125}
2,<S-Dia.€thyl-1.3,5,7-KtaKftia2E5, C;oHt4 [RT:
12.?2] {Ms': "7 91 105 119 134}
1.3,5-p-M€Etha£i=r-; C^oH-.j [RT:13.S41.{MS: 77 91 119 134}
[RT : 19.«1.{MS: 41 55 59 Sl 95 109 121}
CitiOL-UaL CLCHISO
[RT : 20.051.{MS: 41 55 69 95 U l 121}
tiaiis-Car\*»l C^cHidO
[RT: 21.24] {MS:41 S3 S4 93 lOS 119 137}
CitiOL^llaL CLCHLSO
[RT: ••\301.{MS:41 55 59 95 111 121}
Cydoh^xatol, 2-ci5tiyla:-5-5-lniaiylai.5Lyl- C';H:,;0.[RT:a2.54]'{MS:41 S4 91 lOJ 119 137}
2,6o::tadia:-l-ol, 3.7-cJi:i5ftl:yl-. CicHiiO [RT: 25.14].{MS:41 59 S4 94 i w } p-Is<vpfoj>=Lyl tol;:3: CicH;:
[RT: 50.09]'{MS: 41 69 91 105 119 143 157 225}
P«iocar!>-"-3i-3-OL5,13.lHta-ni€tliyl-13-',-ii:yl- C:oHi.:d.[RT: 52.25].{MS: 41 69 79 91 1 0 5 ' l l 9 135 255}
RstinoL C;cHi.;0
[RT:53.55].{MS: 59 91 105 119 133 157 199}
P&do:ar[>-"-2E-3-ori 13 .bna.-Elalyl-13-\•^ty^
C:oHJoO.[RT: 55.32].{laS: 41 59 91 105 119 225}
1,5,10,14-He!ai?c31etia3:-3-ol, 3,7,11,15- tettamahyl-, (E,E>, CioHj40
[RT: 55.92].{MS: 41 59 91 107 119 134 } CopaiHric azii. C:;:H3:Oi
[RT:5S,44].{MS:
2-[4-Ei?thyl-5-;2,5,5-taa^ykydol:€!;-l- aLyl)h^xa-l,3,5-taa;yl];ydoh3;- 1-a:- Icaiboxaldivdc C;3Hj:0
[RT: 52.70],{MS: 43 69 93 119 13" 229 3'04}
5.alpLa.-Ardio;taL-l".l»ta.-ol, 2,alpha., 3.alpLa.,3.alpha.-=!poxy-3-in^yl-, CicHj.O:
[RT: 59.05].{MS: 43 69 93 119 13" 229 3-04}
13alpLKi-?lta;2)-cihydfoabiet!C acid C:,:Hj:0:
[RT: 59.31.{MS: 43 69 93 119 137 229 3-M}
KllOBg XT
- - - - -
5.52 1.64 3.52
1.25
- - - - - - -
- -
Cnx 0.61
- -
2.26 5.20 S.4S 1.90 4.29
1.22
- - - - - - -
0.25
0.4i CM
-
5.23 7.45
- -
2 . J 3
-
2.24
-
3.97 2.12 2,09
5.35 1.25
1.27
1.21
1.55
3.21
Phdn ung hydro hda khi khdng ed xuc tde;
- Tdng cac chat la 13 chat, trong dd 4 chat mdi:
(6,8,11,13)
Phdn itng hydro hda khi ed xiie tdc C/i\;
- Tdng cac chat la 18 chat, trong dd cd 9 chat mdi (1,5,6,8.^10. 11.13.27,28)
Phdn irng hydro hda khi cd xiic tdc CM :
- Tdng cac chat la 20, trong dd cd 13 chat mdi:
(2,3.8,11,19,20, 22, 23, 24, 25,26,27,28)
+ Cac chdt 4.7.9,12,14,15,16,17,18.21 la nguyen lieu ban ddu (trong dd chdt 12,14 la hai dang cis va trans ciia Citral, chiem 86%)) khdng the hien trong bang.
+ Nhimg chdt mdi hinh thanh (20, 22. 23, 24, 25, 26, 27, 28 ) Id phdt hien mdi cun cdng Irinh ndy. Tam chat mdi nay chiem 47% trong tdng sd 13 chdt mdi va cd cdu true hoan toan khac. tuong tu cac chat cd boat tinh sinh hoc cd gia tri cao nhu Retinol,[C2oH3oO](chilni 8%). Podocarp-7-en-3-one, 13.beta.-methyl-13-vinyl-[C2oH3oO] (cdn cd ten Ir'v Sandraeapimgric gcid) (chiem 7,53%o).
Hinh 5 ; Bgng sgnphdm mdi Irong qud trinh hydro hda ed dp sudi
IV. KET LUAN
1. Kit qua phan tich X-ray, BET, IR, SEM cho thdy xiic tac mdi(CM) cd nhiing thanh phan hda hgc khac vdi xiic tac chuan ciia hang Merck.
2. Kit qua khao sat phan iing hydro hda trong pha khi khdng cd ap suat tren hai xiic tac cho thay:
+ Xiic Idc Raney-Nickel ciia hdng Merck la mgt chat xuc tien hydro hda rat manh va khdng nbirng thi, nd cdn cdt mach C-C de tao thanh mach hydroeacbon thap. 77%o san pham mdi la hydrocarbon khdng chira oxy da chimg minh dieu dd.
+ Xuc tdc mdi (CM) la mdt xiic tac cd kha nang khdng chi hydro hda ma cdn cd kha nang ddng vdng hydroeacbon rat tdt. Hau bet cac san pham deu dugc ddng vdng. Dac biet sir hinh thanh m-Cymene cd gia tri Idn (33,15 %)) va do chgn lgc cao (50%)). Kha nang hydro hda ciia xiic tac nay khdng thua kem xiic tac Raney-Nickel ciia hang Merck va cd nliung dac tinh trgi hon.
3. Ket qua khao sat phan img hydro hda trong pha Idng cd ap suat:
-I- Xiic tdc Raney-Nickel cua hdng Merck cho 9 chat mdi, tuang tu nhu trong phan img hydro hda khdng cd ap suat.
"I" Xiic tdc mdi (CM) da hinh thanh 5 chat tuong tu nhu khi hydro hda khdng cd ap suat va 8 chat mdi Id phdt hiin mdi ciia cdng Irinh ndy. Tam chat mdi nay chiem 47 %o trong tdng sd 13 chat mdi va cd cau tnic boan toan khac, tuong tir cac chat cd boat tinh sinh hgc cd gia tri cao nhu Retinal, fC2oHsoO] (chiem %%), Podocarp-7-en-3-one, 13.beta.-methyl-13- vinyl-[C2oH3oO] (cdn cd ten la Sandracopimaric acid, chiem 7,53%)). Day la nhimg chat cd gia tri cao trong viec san xuat tbudc chiia benh. Neu cac chat cd boat tinh sinh hgc trong thuc vat chiem tir 0,5-1%), dugc xem la ngudn nguyen lieu cd kha nang khai thac cdng nghiep, thi nhiing chat tren day, hoan toan dap img dieu dd va md ra kha nang tdng hgp chiing.
4. Phan ca che hinh thanh cac san pham mdi se cdng bd trong bai tiep theo.
TAI LIEU THAM KHAO
1. R. L. Augustine: Heterogeneous Catalysis for the Synthetic Chemist Marcel Decker, New York 1995.
2. BOITIAUX J.-P. COSYNS J. {Institut Frangais du Pelrole(l))Cata\yi\c Hydrogenation from Basic Research to Industrial Applications Revue de I'lnstitut Frangais du Petrole 1988. Volume 43, n° 06, p. 855 - 871
3. Fine Chemical though Heterogeneous Catalysis. Ed. R.A. Sheldon and H.Van Beckum, Viley-VCH Weinheim 2000.
4. G.W. Huber, J.W. Shabaker. J.A. Dumesic: Raney-NiSn catalyst for H2 production from biomass-derived. Science vol 300 (pp. 2075-2077) 2003.
5. A. Rehman et.al: Selective hydrogenation of menthone on raney nickel catalysts Indian.), of Chem.Tech. Vol 13 (pp 584-590) 2006
6. Beatriz Zeifert et al. Raney-Nickel catalysts produced by Mechanical alloying.
Rev.Adv.Mater.Sci 18,632-638 (2008)
