n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Mc lc
Mc lc .......................................................................................................... 1 Danh mc cc bng ....................................................................................... 3 Danh mc cc hnh ........................................................................................ 4 Li ni u .................................................................................................... 6 Chng 1: Tng quan l thuyt..................................................................... 7 1.1. 1.2. 1.3. M u:......................................................................................... 7 Lch s pht trin ca qu trnh tng hp Fischer Tropsch ...... 9 Cc phn ng trong qu trnh FTS ............................................. 10 Cc giai on v c im cng ngh ca qu trnh .......... 10 Cc phn ng xy ra trong qu trnh ................................... 12 C ch ca qu trnh ............................................................ 12 ng hc ca phn ng ....................................................... 14

1.3.1. 1.3.2. 1.3.3. 1.3.4. 1.4.

Xc tc ca qu trnh .................................................................. 15 Tng quan v xc tc FTS ................................................... 15 Cc loi xc tc.................................................................... 16 Phng php tng hp xc tc ............................................ 19 Cc yu t nh hng n hot tnh xc tc........................ 21

1.4.1. 1.4.2. 1.4.3. 1.4.4. 1.5. 1.6.

Thit b phn ng FTS................................................................ 24 Cc cng ngh FT trn th gii .................................................. 26 CN ca Sasol ( Sasolburg and Secunda, South Africa) ....... 27 Cng ngh ca PetroSA/Mossgas(Mossel Bay South Africa ) 28 Cng ngh ca Shell SMDS ( Bintulu, Malaysia) ............... 29

1.6.1. 1.6.2. 1.6.3.

Chng 2: Thc nghim.............................................................................. 31

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 1

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

2.1.

Tng hp xc tc ........................................................................ 31 Ha cht, dng c v thit b s dng ................................. 31 Qu trnh tng hp xc tc .................................................. 31

2.1.1. 2.1.2. 2.2.

Nghin cu c trng ca xc tc .............................................. 33

2.2.1. Phng php xc nh din tch b mt ring v phn b cu trc l xp bng hp ph vt l nit [1, 6, 8] .......................................... 33 2.2.2. Phng php xc nh phn tn kim loi trn cht mang bng hp ph ha hc [6, 8] .................................................................... 35 2.2.3. Phng php xc nh hm lng kim loi trong xc tc bng phng php ph hp thu nguyn t [21] ............................................... 37 2.2.4. Phng php nhiu x tia X (XRD-X Ray Diffraction) nghin cu nh tnh cu trc pha tinh th. [5, 6, 7,8] ........................................ 38 2.3. Nghin cu th nghim hot tnh xc tc cho phn ng FT ...... 41 c trng ha l ca xc tc ...................................................... 45 Hm lng kim loi trong xc tc ....................................... 45 Chng 3: Kt qu v tho lun .................................................................. 45 3.1.

3.1.1.

3.1.2. Din tch b mt ring v cu trc mao qun ca cht mang v xc tc ............................................................................................ 45 3.1.3. 3.1.4. 3.2. c trng pha tinh th ca cht mang v xc tc ................ 49 phn tn ca kim loi trn cht mang ............................ 50

nh gi hot tnh ca xc tc ................................................... 51

Kt lun ....................................................................................................... 64 Ti liu tham kho ....................................................................................... 65 Ph lc ........................................................................................................ 67

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 2

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Danh mc cc bng
Bng 1.1: So snh gi thnh ca cc kim loi lm xc tc FTS ................. 19 Bng 1.2: Hm lng tp cht cho php trong nguyn liu syngas ............ 22 Bng 1.3: Phn b sn phm ca hai kiu cng ngh LTFT v HTFT ....... 27 Bng 2.1: Cc mu xc tc tng hp ...................................................... 33 Bng 3.1: Hm lng kim loi c trong cc mu xc tc ........................... 45 Bng 3.2: Kt qu o phn tn Co-K/ -Al2O3 ..................................... 51 Bng 3.3: Phn b sn phm ca phn ng FT vi xc tc N1 10% Co0,2%K/ -Al2O3 ............................................................................... 55 Bng 3.4: Phn b sn phm ca phn ng FT vi xc tc N2 20% Co0,2%K/ -Al2O3 ............................................................................... 59

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 3

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Danh mc cc hnh
Hnh 1.1: Cc sn phm thu c t syngas ................................................. 7 Hnh 1.2: Cc giai on ca qu trnh tng hp FT ...................................... 8 Hnh 1.3: th ph thuc phn trm khi lng sn phm - xc sut pht trin mch ........................................................................... 15 Hnh 1.4: Phn b sn phm trn xc tc Fe 30 bars, 280oC ................... 18 Hnh 1.5: Phn b sn phm trn xc tc Co 30 bars, 240oC ................. 18 Hnh 1.6: S cng ngh lm sch kh Rectisol ca Lurgi ...................... 23 Hnh 1.7: Cc loi reactor trong cng ngh FTS......................................... 24 Hnh 1.8: S cng ngh ca Sasol .......................................................... 27 Hnh 1.9: S cng ngh ca Petrol SA/Mossgas ................................... 28 Hnh 1.10: S cng ngh ca Shell SMDS ............................................ 30 Hnh 2.1: S qui trnh tng hp xc tc Co,K/ -Al2O3 ........................ 32 Hnh 2.2: S phn ng FT ...................................................................... 42 Hnh 2.3: Mt ct dc ng phn ng ........................................................... 43 Hnh 2.4: Cu to bnh phn tch sn phm ................................................ 43 Hnh 3.1: ng ng nhit hp ph v nh hp ph N2 ca cht mang Al2O3 ..................................................................................... 46 Hnh 3.2: Phn b l xp ca cht mang -Al2O3 ...................................... 47 Hnh 3.3: ng ng nhit hp ph v nh hp ph N2 ca mu xc tc N2 .......................................................................................... 48 Hnh 3.4: Phn b l xp ca cht xc tc N2 ............................................ 48 Hnh 3.5: Ph XRD ca cht mang -Al2O3 .............................................. 49 Hnh 3.6: Ph XRD ca mu xc tc N3 (25% Co- 0,2%K/ -Al2O3) ...... 50 Hnh 3.7: chuyn ha ca Co trong phn ng FT khi s dng xc tc 10% Co- 0,2% K/ -Al2O3 ................................................... 52 Hnh 3.8: chuyn ha ca Co trong phn ng FT khi s dng xc tc 20% Co- 0,2% K/ -Al2O3 ................................................... 52 Hnh 3.9: chuyn ha ca Co trn mu N1 v N2 ................................. 53 Hnh 3.10: Phn b s C trong sn phm ca mu xc tc 10% Co- 0,2%K/ -Al2O3 ................................................................................. 54

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 4

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
Hnh 3.11: Ph GCMS phn tch thnh phn sn phm phn ng FT trn xc tc N1 (10% Co- 0,2%K/ -Al2O3) ............................... 56 Hnh 3.12: Cc loi hp cht c mt trong thnh phn sn phm phn ng trn xc tc N1 (10% Co- 0,2%K/ -Al2O3) ....................... 58 Hnh 3.13: Ph GCMS phn tch thnh phn sn phm phn ng FT trn xc tc N2 (20% Co- 0,2%K/ -Al2O3) ............................... 60 Hnh 3.14: Cc loi hp cht c mt trong thnh phn sn phm phn ng trn xc tc N2 (20% Co- 0,2%K/ -Al2O3) ........................ 62 Hnh 3.15: Phn b s C trong sn phm ca mu xc tc N2 20% Co0,2%K/ -Al2O3 .................................................................... 63

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 5

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Li ni u
Ngy nay, khi nn cng nghip pht trin mnh m th nhu cu v nhin liu l mt nhu cu thit yu. Tuy nhin, khi du m ngy cng cn kit th chng ta phi tm ra mt hng mi to ra nhin liu. Fischer- Tropsch l mt hng nh th. T qu trnh ny chng ta c th tn dng c ngun kh t nhin, than , nhin liu sinh khi to ra xng, diezen phc v cho cc ngnh cng nghip, giao thng vn ti. Hn na, vi cch lm ny, chng ta c th hn ch c vic t than trc tip - nguyn nhn gy ra nhim mi trng, hiu ng nh knh. y l mt trong nhng vn ang c quan tm hng u ngy nay. Vi cc l do trn, em tin hnh thc hin ti: Nghin cu tng hp xc tc Co/ - Al2O3 i t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng. n bao gm 3 phn chnh: Chng 1: Tng quan l thuyt, cp n lch s, c im cng ngh ca qu trnh cng nh xc tc ca qu trnh Chng 2: M t cc thc nghim tin hnh Chng 3: Trnh by v tho lun v cc kt qu thu c hon thnh c bn n ny, em xin chn thnh cm n T.S. Nguyn Hng Lin, ngi trc tip hng dn em trong qu trnh nghin cu. ng thi em cng xin gi li cm n n Th.S. Chu Th Hi Nam cng ton th cc thy c trong PTN CN Lc du v vt liu xc tc ch bo, gip em rt nhiu trong qu trnh nghin cu ti PTN. Cui cng em xin gi li cm n n gia nh, bn b, nhng ngi h tr cho em rt nhiu trong qu trnh thc hin n. H ni, ngy 03 thng 06 nm 2010. GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 6

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Chng 1: Tng quan l thuyt

1.1. M u: Tng hp Fischer-Tropsch (FTS) l qu trnh chuyn ha kh tng hp thnh cc hydrocacbon lng v cc sn phm phi nhin liu khc nh sp trn cc xc tc kim loi chuyn tip. Qu trnh FTS c th c ng dng sn xut ra nhin liu lng nh xng v diesel, ngoi ra cn tng hp sp, du nhn, phenol v cresol, kerosene, alcohols, ammonia, Nguyn liu ca qu trnh l kh tng hp c thnh phn gm ch yu l CO v H2. Kh tng hp c sn xut t qu trnh kh ha cc nguyn liu nh kh thin nhin, than , cc sn phm du m hoc sinh khi. Trong qu trnh sn xut syngas, nhit thng trn 1100 o F vi s c mt ca O2 (trong dng khng kh, xy tinh khit hay trong hi nc) nhng lng xy t hn lng cn thit xy ha hon ton. T ngun nguyn liu kh tng hp ta c th tng hp nn nhiu sn phm c gi tr, th hin s hnh 1.1:

Hnh 1.1: Cc sn phm thu c t syngas [18] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 7

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Xc tc cho qu trnh FTS l cc kim loi chuyn tip nhng c nhc n nhiu nht l Fe, Co, Ni v Ru. Mi loi xc tc c nhng u nhc im khc nhau, u tin to thnh cc sn phm cui khc nhau. Fe r nht v u tin cho nhiu sn phm xng qu trnh FTS nhit cao v ng dng sn xut sp qu trnh nhit thp. Xc tc Co t tin hn Fe nhng cho bn hot tnh cao hn nhiu v cho nhiu sn phm diesel qu trnh FTS nhit thp. Trong khi Ru d c hot tnh FTS cao nht nhng li qu t nn khng c ng dng trong cng nghip m ch yu phc v cc mc ch nghin cu. Cng ngh FTS bao gm ba bc chnh l: chun b nguyn liu; tng hp FTS v nng cp sn phm (hnh 1.2).\

Hnh 1.2: Cc giai on ca qu trnh tng hp FT [9] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 8

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng 1.2. Lch s pht trin ca qu trnh tng hp Fischer Tropsch Qu trnh chuyn ha kh tng hp thnh cc hydrocacbon lng da trn xc tc kim loi c pht hin bi Franz Fischer v Hans Tropsch vo nm 1923. H chng minh c rng vic hydro ha CO da trn xc tc Fe, Co, hay Ni 180- 250oC v p sut kh quyn th thu c sn phm l hn hp cc hydrocacbon mch thng. Nguyn l c bn ca qu trnh l phng trnh phn ng ha hc sau: (2n+1)H2 + nCO = CnH2n+2 + nH2O

Nhng tc cht ban u trong phn ng trn (CO v H2) c th sn xut c t vic nung than hay nguyn liu sinh khi theo phn ng: C + H2O = H2 + CO Vo thi im , d n trin khai phng php ny b ct vo ngn ko do gi thnh sn phm qu t so vi gi du ha v vic t than trc tip cha lm cho con ngi kinh hi bi nhim. Nm 1935, ln u tin phn ng FT nhit thp din ra trong thit b xc tc c nh p sut kh quyn. Fischer v Pichler sau pht trin cng ngh vi vic s dng xc tc Co v p sut thng vi sn phm chnh l khong gia sn phm chng ct v sp. Cng ngh quan trng ny c nc c s dng sut thi k chin tranh th gii th 2. Cng ngh s dng xc tc Fe iu kin p sut thng cng c Fischer v Pichler pht hin ra, sau c cng nghip ha bi hng GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 9

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Ruhrchemie v hng Lurgi v c cng c bi hng Sasol Sasolburg, Nam Phi nm 1955. Nm 1946 nh du mt bc ngot ln khi ngi ta pht hin ra rng s dng nguyn liu kh t nhin tt hn than trong vic sn xut ra cc hydro cacbon lng. Cui thp nin 1940, Cng ty Sasol c thnh lp di tn gi Cng ty Than v Du kh Nam Phi, vi mc ch p dng phng php Fischer-Tropsch gip Nam Phi c th t cung t cp nhin liu mc cao nht thng qua cc nh my kh ha than. Gia thp nin 1950, khi chnh sch phn bit chng tc khin cho nc ny ngy cng b c lp vi th gii, nh my kh ha than theo phng php Fischer-Tropsch vi quy m thng mi u tin c khnh thnh ti Sasolburg. Gn 80 nm sau ngy c sng ch, nm 1999, nhin liu lng c t phng php Fischer-Tropsch c khng lc Hoa K mt ti trc tnh hnh gi du th tng v phi i mt vi nhng tnh ton: ring khng lc Hoa K ngn n 2,6 t gallon nhin liu my bay hng nm, tr gi 4,5 t USD, cn cc hng hng khng dn s Hoa K th tiu th mi ngy 53 triu gallon, nu nhn cho 365 ngy = 19 t 345 triu gallon, qu l mt con s khng l. Kt qu l vo ngy 27/9/2006, khng lc Hoa K ln u tin th nghim loi nhin liu tng hp ny trn mt pho i bay B-52, song ch 2/8 ng c m thi v vi t l pha 50-50 (nhin liu tng hpxng). Kim nh mi trng, kt qu l gim 50% kh thi so vi trc y. Tip n, vo ngy 15/12/2006, khng lc Hoa K thng bo hon tt chuyn bay th nghim ca my bay B-52 vi tm ng c c s dng loi nhin liu mi: hn hp nhin liu tng hp theo phng php Fischer-Tropsch. 1.3. Cc phn ng trong qu trnh FTS 1.3.1. Cc giai on v c im cng ngh ca qu trnh Qu trnh tri qua ba giai on chnh: Trang 10

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng - Giai on chun b nguyn liu - Giai on tng hp FT - Giai on nng cp sn phm c im cng ngh ca qu trnh: Trong cng ngh FTS, qu trnh n thun reforming t nhit hoc kt hp vi reforming hi, ni chung hay c ng dng cho qu trnh sn xut syngas t kh thin nhin t c t l H2:CO mong mun v cng kinh t hn khi thit k cc thit b tch kh. Nu i t than , syngas c tng hp t qu trnh kh ha nhit cao trong dng kh O2 v hi nc. Nhit ca qu trnh FTS lun c gi thp hn 4000C lm gim ti thiu lng CH4 to thnh. Thit b phn ng FTS hot ng trong khong p sut t 10 40 bars (145 580 psi). Khong 20% lng cc cht cha C trong kh thin nhin c chuyn ha thnh CO2 trong qu trnh reforming, trong kh khong 50% lng hp cht C trong than c chuyn ha thnh CO2 do hm lng H trong than thp hn trong kh thin nhin. Kh ha than cho syngas c t l H2:CO khong 0.67, nh vy theo l thuyt th chuyn ha CO thnh cc sn phm FTS cao nht l 33% (khng c phn ng chuyn ha CO WGS. chuyn ha cao nht theo l thuyt ca kh thin nhin thnh paraffins l 78% trn c s qu trnh nhit thp LHV (low heat value). chn lc sn phm ph thuc vo nhit v p sut phn ng, thnh phn kh nguyn liu, loi xc tc s dng v thnh phn xc tc (cht mang, cht tr xc tc). Da vo tnh ton cc sn phm FTS mong mun m ta c th s dng qu trnh FTS nhit thp (200 2400C) hay FTS nhit cao (300 3500C) cng nh l xc tc Co hoc Fe. Tng hp nhit thp cho nhiu sn phm c khi lng phn t ln mch thng nh sp cn tng hp nhit cao cho hiu sut cc sn phm xng v olefin phn t lng nh cao hn. Hiu sut thu xng s cao nht trong qu trnh tng hp nhit cao s dng xc tc Fe vi thit b phn ng xc tc c nh (fixed bed reactor). chuyn ha l thuyt cao nht ca syngas l 48%. Cn GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 11

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

hiu sut to diesel s t max trong qu trnh tng hp nhit thp s dng xc tc Co vi thit b phn ng dng slurry (slurry reactor), chuyn ha syngas t gn 40%. Qu trnh nng cp sn phm cui cng bao gm hydrotreating, hydrocracking, hydroizomerization v chng tch sn phm. 1.3.2. Cc phn ng xy ra trong qu trnh Cc phn ng chnh: CnH2n+2 + nH2O CnH2n + nH2O CO2 + H2 CnH2n+2O + (n-1)H2O C + CO2 (1) (2) (3) (4) (5)

To Parafin: (2n+1)H2 + nCO To olefin: 2nH2 + nCO Phn ng WGS: CO + H2O Cc phn ng ph: To alcol: 2nH2 + nCO Phn ng: 2CO -

Cc phn ng bin i ca xc tc: Phn ng oxy ha, kh xc tc: MxOy + yH2 yH2O + xM (6)

MxOy + yCO -

yCO2 + xM

(7)

Phn ng to cacbua kim loi yC + xM MxCy (8)

1.3.3. C ch ca qu trnh GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 12

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng C ch ca qu trnh nh sau: Giai on khi mo hay s to thnh hp cht C1

Pht trin mch hydrocacbon

t mch

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 13

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng 1.3.4. ng hc ca phn ng ng hc qu trnh FTS l phn ng polymer ha gm cc bc sau: - Hp ph cht phn ng (CO) ln b mt xc tc. - Phn ng khi mo do qu trnh phn tch ca phn t CO (CO dissociation) khi b mt xc tc v lin sau l qu trnh hydro ha (hydrogenation). - Pht trin mch. - Ct mch polymer. - Nh hp ph sn phm khi b mt xc tc. Cc hp cht methyl b hp ph ha hc trn b mt xc tc do s phn tch ca cc phn t CO v km sau l qu trnh hydro ha ln lt bi s xut hin ca cc nguyn t H. Cc hp cht methyl (CH2- ) ny c th hydro ha to thnh CH4 hoc tr thnh cht khi mo cho cc phn ng pht trin mch polymer. Qu trnh pht trin mch din ra nh s thm vo ln lt cc nhm (-CH2- ), trong khi c mch alkyl vn b hp ph trn b mt xc tc v tr ca nhm methyl cui cng. S t mch polyme c th xy ra ti bt c thi im no ca qu trnh pht trin mch to thnh sn phm l olefin hay n-paraffin sau khi nh hp ph. Tng hp FTS l qu trnh c th khng ch ng hc c v ng hc ca phn ng l qu trnh pht trin mch lin tc (polymer ha ca nhm (-CH2- ) trn b mt xc tc). Tc phn ng polymer ha hay ng hc phn ng khng ph thuc vo cc sn phm to thnh m c xc nh bi hot tnh ca xc tc xc tin cho qu trnh pht trin mch-qu trnh ngt mch. Xc sut pht trin mch v ngt mch khng ph thuc vo di mch C v v th ta c th d on c kh nng to thnh cc sn phm khc nhau da vo quan h gia xc sut pht trin mch v s nguyn t C. M hnh ng hc qu trnh polymer ha (m hnh Anderson-Shulz-Flory) c th hin phng trnh (9), da vo phng trnh thc nghim ny ta c th d on c s phn b cc sn phm FTS. Phng trnh( 9) cn

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 14

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

c th hin trn th ph thuc gia phn trm khi lng sn phm-xc sut pht trin mch hnh. Wn = n(1- )2 n-1 (9) Wn l phn trm khi lng sn phm cha n nguyn t C cn l xc sut pht trin mch.

Hnh 1.3: th ph thuc phn trm khi lng sn phm-xc sut pht trin mch [18] 1.4. Xc tc ca qu trnh 1.4.1. Tng quan v xc tc FTS Xc tc ng mt vai tr thit yu trong cc phn ng chuyn ha syngas. Khi nim c bn v phn ng c xc tc l cht phn ng c hp ph ln trn b mt cht xc tc, c sp xp li v kt hp to thnh sn phm. Sn phm phn ng sau nh hp ph ra khi b mt xc tc v khuch tn ra ngoi. Mt trong nhng im khc bit c bn v chc nng ca xc tc cho phn ng chuyn ha syngas l c hay khng s phn ly ca phn t CO ra khi b mt xc tc. GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 15

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

i vi phn ng FTS hay tng hp alcohol cao hn th s phn ly ca CO l mt iu kin cn thit cho phn ng. Cc oxit ca kim loi chuyn tip nhm VIII (Ru, Fe, Ni, Co, Rh, Pd, Pt) c th c dng lm xc tc cho qu trnh hydro ha CO. Trong s th Fe v Co l hai ngun xc tc chnh cho tng hp FT. 1.4.2. Cc loi xc tc a. Xc tc Fe Fe l kim loi rt hot ng, n c th lp tc to carbide, nitride v carbonitride vi cc kim loi khc cng c hot tnh FTS. Vi xc tc Fe c xy ra phn ng chuyn ha CO. Tuy nhin, xc tc Fe c xu hng to nhiu carbon ngng t trn b mt xc tc v lm gim hot tnh xc tc hn l cc kim loi khc nh Ni hay Co. Vic thm cc cht tr xc tc v cht mang vo thnh phn xc tc Fe cng rt quan trng lm tng hot tnh ca xc tc. Kali thng c dng lm cht tr xc tc v n thc y qu trnh hp ph ca CO ln b mt xc tc do tng tnh kim ca b mt xc tc v cng l ngun electrons c tch ra t CO bi Fe. Ngoi ra, khi thm kali oxit vo xc tc Fe cn lm gim s hydro ha cc hp cht cha C b hp ph trn b mt xc tc, to ra nhiu sn phm olefin c khi lng phn t ln hn. Tuy nhin, s c mt ca cht xc tin kali cng lm tng phn ng chuyn ha CO dn n s ngng t cc trn b mt xc tc din ra mnh hn v xc tc mt hot tnh cng nhanh hn. Ngoi K, Cu cng c th s dng lm cht xc tin cho xc tc Fe. Cht tr xc tc Cu lm tng tc chuyn ha, gim tc phn ng chuyn ha CO v thc y s kh ha Fe. Xc tc c cha Cu s cho sn phm c khi lng phn t trung bnh ln hn, d khng ln hn qu nhiu so vi khi dng xc tc cha K. S kt hp ca cc xyt kim loi chuyn tip nh nh MnO vi Fe lm tng chn lc olefin nh cho phn ng FTS. Xc tc Fe/Mn/K cho chn lc C2-C4 olefins t 85-90%. GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 16

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hin nay trong cng nghip thng s dng cc loi xc tc Fe nh Fe/Cu/K/Al2O3; Fe/Cu/K/Si O2; Fe/Mn/K/Al2 O3 Xc tc Fe thch hp cho nguyn liu c t l H2/CO thp do c hot tnh WGS mnh, t l H2/CO c th thp n 0.5 1.3, thng t ngun kh ha than . b. Xc tc Co Xc tc Co c bn cao hn xc tc Fe v khng c hot tnh WGS (khng xy ra phn ng chuyn ha CO ), cho nn chuyn ha tng ln do khng to thnh CO2. Trong tng hp FTS, xc tc Co cho sn phm ch yu l cc hp cht hydrocarbon mch thng ch khng phi nhiu sn phm cha oxy nh vi xc tc Fe. Xc tc Co t hn xc tc Fe gp 230 ln nhng vn c ng dng trong thc t v xc tc Co vn th hin hot tnh tt trong iu kin tng hp p sut thp nn chi ph u t cao cho xc tc c b p bi chi ph vn hnh thp. Xc tc Co khng qu nhy cm vi s c mt ca cht xc tin, mt vi nghin cu cho thy khi thm vo ThO2 s lm tng hiu sut to sp p sut thng nhng p sut cao th s ci thin l khng ng k. Nu thm vo cc kim loi qu th hot tnh FTS tng ln nhng chn lc khng thay i. Do xc tc Co khng c hot tnh WGS nn ch thch hp vi nguyn liu c t l H2/CO t 2.0 n 2.3, thng ly t ngun kh t nhin. So snh s chn lc sn phm gia xc tc Fe v xc tc Co: Xc tc Fe 30 bars, 2800C: theo hnh 1.4 th sn phm hydrocarbons c s C trong khong t 10 n 18 chim s lng ln, cho thy vi xc tc Fe th FTS s cho hiu sut xng cao hn. Xc tc Co 30 bars, 2400C: theo hnh 1.5 th sn phm hydrocarbons c s phn b khi lng ng u hn so vi xc tc Fe, cho thy vi xc tc Co th hiu sut to diesel tng ln.

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 17

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

% wt sn phm

S C trong phn t Hnh 1.4: Phn b sn phm trn xc tc Fe 30 bars, 2800C [15] % wt sn phm mm

S C trong phn t Hnh 1.5: Phn b sn phm trn xc tc Co 30 bars, 2400C [15] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 18

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

c.

Xc tc khc

Vi qu trnh FTS, cc loi xc tc khc cng c nghin cu nh Ni, Ru. Ni v c bn l xc tc cho qu trnh mtan ha (methanation) v khng c chn lc rng nh cc xc tc FTS khc. Cn Ru cho thy c hot tnh v chn lc rt ln vi cc sn phm phn t lng ln trong iu kin phn ng nhit thp, nhng Ru li qu t c th ng dng trong thc t, khi m Ru t hn Fe n gn 5x104 ln (Fe l xc tc FTS r tin nht). Bng 1.1: So snh gi thnh ca cc kim loi lm xc tc FTS [9] Kim loi Fe Ni Co Ru T gi (so vi Fe) 1 250 1000 48000

1.4.3. Phng php tng hp xc tc Cc tnh cht quan trng nht ca cht xc tc quyt nh hiu qu kinh t khi s dng chng trong cng nghip l hot tnh, chn lc v bn ca xc tc. Do nhng tnh cht ny ph thuc ch yu vo thnh phn v phng php ch to xc tc cho nn c s khoa hc v cng ngh tng hp xc tc c coi l nhng vn rt quan trng v c ngha thc t ln. Qu trnh hnh thnh cht xc tc bao gm nhng giai on: iu ch cc tin cht rn trong bn cnh cc hp phn ca xc tc cn c mt s cht phi loi ra khi cht xc tc trong cc giai on sau. Chuyn ha cc hp cht l thnh phn c bit ca xc tc. T cc cht ban u, bng cch phn hy nhit, kim ha hoc bng cc phng php khc loi b cc cht tha. Sau giai on ny cht xc tc tn ti pha tinh th c lp. Khi x l nhit mui ca Fe, Co hay GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 19

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ni s hnh thnh cc oxit d kh, cn cc mui ca Cr, Al hay Zn s cho oxit kh kh. Thay i thnh phn xc tc sau khi tng tc vi mi trng v di tc dng ca iu kin phn ng. C nhiu phng php ch to xc tc nhng phi k n l phng php ng kt ta, phng php ngm tm, phng php trn c hc, phng php solgel do tnh n gin, hiu qu v ph dng ca chng. Di y em xin a ra hai phng php thng c s dng. a. Phng php ngm tm

Phng php ngm tm c thc hin qua cc bc sau: Ngm tm, sy, nung, kh, v hot ha bng H2. Trong qu trnh tm dung dch mui kim loi hot ng c in y vo cc mao qun ca cht mang. Khi h mao qun ca cht mang c ph y dung dch mui kim loi. Sau khi dung dch bay hi ht, cc tinh th mui nm li trn thnh mao qun ca cht mang. Khi tin hnh kh trong dng H2, cc tinh th y s to ra cc ht kim loi, chnh l cc tm hot tnh ca xc tc. Phng php ngm tm l mt phng php c s dng kh ph bin do n c mt s cc u im nh: vi phng php ny ta c th a ton b lng kim loi ln cht mang, hn ch c s mt mt, hn na qu trnh thc hin li tng i n gin, nhanh gn Tuy nhin, c th nhn thy trong phng php ny, gia kim loi v cht mang khng hnh thnh lin kt ha hc m ch thun ty l bm dnh thng thng do phn tn ca kim loi trn cht mang khng cao. b. Phng php sol-gel

Phng php a cc tiu phn kim loi vo cht mang solgel c nh hng mnh n tnh cht ca xc tc. Mt trong nhng cch hay c s dng l a mui kim loi hoc phc vo sol nhm oxit trc khi c c, chuyn ha sol thnh xerogel hoc aerogel, tip theo GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 20

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

l kh tin cht kim loi thnh kim loi. Cc ht kim loi ny do b che ph mt phn bi oxit nhm nn bn vng vi thiu kt, hn na cc xc tc tng hp t qu trnh ny cng t b u c bi cc. Phng php ny khng nhng cho php ch to c cc loi xc tc c bn cao m cn kim sot c cc tm kim loi, tuy nhin y l mt phng php tng i phc tp v cha ph bin vi nhiu loi cht mang. V vy, trong cc phng php tng hp trn th phng php ngm tm l phng php c dng ph bin nht v l phng php ph hp tng hp xc tc Co,K/ -Al2O3 1.4.4. Cc yu t nh hng n hot tnh xc tc a. Cc nguyn nhn gy gim hot tnh xc tc Xc tc FTS mt hot tnh do mt s nguyn nhn sau: cc tm hot tnh kim loi b chuyn thnh cc tm oxit khng c hot tnh, xc tc b thiu kt, gim b mt hot tnh do ngng t cc hay ng c ha hc. Mt s loi hnh gim hot tnh xc tc l khng th trnh khi, cn li c th trnh c hoc gim thiu ti a bng cch m bo hm lng tp cht trong nguyn liu syngas l chp nhn c i vi mt qu trnh cng ngh FTS nht nh. nh hng ca s to cc: S ngng t cc trn b mt xc tc l qu trnh gim hot tnh xc tc quan trng nht. Cc yu t nh hng n s to cc nh s c mt ca cht tr xc tc, nhit phn ng v p sut phn ng. y l s gim hot tnh khng th trnh khi trong phn ng FTS v v th, qu trnh phi c tin hnh trong iu kin c th dung ha gia hiu sut sn phm, chi ph thay th v ti sinh xc tc. Do c hot tnh ln hn nn s to cc trn xc tc Fe s nhanh hn trn xc tc Co v v th xc tc Co c tui th cao hn so vi xc tc Fe. nh hng ca tp cht:

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 21

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Bn cnh s mt hot tnh do cc, cc tm kim loi b mt hot tnh cn do nh hng ca tp cht c mt trong nguyn liu syngas. Sulfur l c t ln nht i vi xc tc c mt trong c kh thin nhin v than , c chuyn ha thnh H2S v cc hp cht hu c cha S trong qu trnh reforming hi hay kh ha than . Hp cht cha S lm mt hot tnh nhanh chng c xc tc Fe ln xc tc Co do to ra cc hp cht cha lu hunh vi tm kim loi. Trong , xc tc Co nhy cm hn vi s ng c bi lu hunh so vi xc tc Fe. Cc tp cht khc trong syngas c th gy ng c xc tc FTS nh hp cht cha halogen hay hp cht cha N (NH3, NOx v HCN). Ngoi ra phi k n nh hng ca nc, nc xy ha c hai loi xc tc Fe v Co. Nc cn lm c ch hot tnh ca xc tc Fe do chnh nh hng ca hot tnh WGS ca xc tc Fe. Bng sau cho thy mc tp cht c th chp nhn c trong nguyn liu syngas: Bng 1.2: Hm lng tp cht cho php trong nguyn liu syngas [19]

b.

Phng php m bo hot tnh xc tc

Hin nay c nhiu cng ngh thng mi ng dng lm sch nguyn liu syngas t c tinh khit cn thit. Cng ngh Rectisol s dng methanol nhit thp phn tch NH3, H2S, v CO2 ra khi nguyn liu syngas. Cc cng ngh hp th khc nh cng ngh dng kali carbonate hay alkanolamine (MEA - monoethanolamine hoc DEA diethanolamine) tch t (wet scrubbing).Mc lm sch kh cn thit cng phi cn bng gia chi ph lm sch v chi ph tiu GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 22

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

tn do xc tc mt hot tnh. Ta bit c gi c tng i ca Fe v Co cho nn vic lm sch kh cn phi tt hn nu qu trnh FTS s dng xc tc Co. Trng tm ca vic pht trin xc tc l nng cp hot tnh, chn lc v tui th ca xc tc, nhng yu t ny b nh hng bi cu trc v thnh phn cht tr xc tc, qu trnh chun b v to hnh xc tc, tin x l v kh ha xc tc hay ng c chn lc Qu trnh chun b v tng hp xc tc c nh hng n kh nng lm vic ca xc tc. Xc tc Fe c th c tng hp bng phng php kt ta trn cht mang nh SiO2 hay Al2O3 hoc nh Fe lng khi tng hp bng phng php nng chy Fe, lm ngui v nghin. Vai tr ca cht mang vi xc tc Co cng quan trng, v Co t hn Fe nn kt ta mt nng va trn cht mang c th gip gim gi thnh xc tc trong khi vn c th gi hot tnh v bn ti a.

Hnh 1.6: S cng ngh lm sch kh Rectisol ca Lurgi [20] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 23

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng 1.5. Thit b phn ng FTS Do qu trnh FTS ta nhit ln nn thit k thit b phn ng v pht trin cng ngh tp trung ch yu vo vic thu hi lng nhit ta ra ny v iu khin nhit ca phn ng. Nu lm mt khng hiu qu s dn n qu nhit cc b trong thit b, y mnh qu trnh cc ha trn b mt xc tc dn n lm gim hot tnh xc tc. Bn cnh s cc ha, nhit tng cao cng lm tng hiu sut to methane v nh vy lm gim hiu sut cc sn phm mong mun. V th thit k thit b FTS quan trng nht l quy trnh ly nhit i v iu khin nhit ti u ha c chn lc sn phm v bn ca xc tc. Trong thc t cng nghip c bn loi thit b phn ng FTS chnh: Thit b ng chm vi xc tc c nh (multi-tubular fixed bed), Thit b phn ng nhit cao c tun hon xc tc (circulating fluidized bed), Thit b phn ng xc tc dng gi lng Sasol Advanced Synthol (fixed fluidized bed), Thit b phn ng dng slurry (fixed slurry bed):

Hnh 1.7: Cc loi reactor trong cng ngh FTS [18] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 24

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Thit b ng chm vi xc tc c nh l mt trong nhng thit k thit b phn ng FTS ra i u tin. Sau nhiu nm pht trin, Ruhrchemie v Lurgi ci tin thit k ny thnh FTS reactor cng sut ln ARGE v loi thit b ny c s dng trong rt nhiu nm sau . Mi thit b phn ng bao gm 2050 ng ng kch thc 50 mm i.d v di 12 m. Mi ng cha khong 20 l xc tc Fe. Nhit thit b c khng ch thng qua p sut. Syngas vo t nh thit b phn ng v i vo cc ng phn ng v sn phm ra y thit b. Sp chim khong 50% sn phm, chuyn ha hiu qu trn 70%. Thit b ny lm vic khong p sut 20-30 bar v nhit trong khong 220-260C. Ngoi ra, nhit cn c iu khin nh s dng vn tc dng kh ln v tun hon kh lin tc. T l kh tun hon trn kh mi vo l khong 2.5. Tui th ca xc tc t 70-100 ngy v vic thay th xc tc tng i kh khn. Thit b phn ng nhit cao c tun hon xc tc c thit k dnh cho sn xut xng v cc olefin nh. Nhng thit b ny c bit n vi ci tn Synthol reactor, hot ng 25 bar v 350 0C. C kh mi v kh tun hon u vo pha di ca thit b v cun theo xc tc chy t trn ng ng xung, qua van trt (slide valve). Dng kh vo vi vn tc ln cun theo xc tc vo cung phn ng, ti y din ra phn ng cn nhit c ly ra ngoi qua thit b trao i nhit. Kh sn phm cng xc tc i vo b tch sn phm, xc tc lng xung di cn kh qua cyclone ra ngoi. Thit b phn ng dng Synthol ny rt thnh cng trong nhiu nm lin nhng c nhc im c to phc tp v li nhanh b mi mn do dng xc tc chuyn ng nhanh trong thit b, v b gii hn v nng sut (7,500 BPD) . Thit b phn ng xc tc dng gi lng Sasol Advanced Synthol reactor c thit k thay th thit b Synthol. Dng kh c dn vo qua b phn phi kh v sc bong bng qua lp xc tc. Nhit c ly i nh mt thit b trao i nhit c b tr trong thit b phn ng. iu kin hot ng ca thit b dng ny tng ng vi thit b Synthol. Thit b phn ng ci tin ny c cng nng sut vi GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 25

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Synthol, c hiu sut trao i nhit tt hn vi gradient nhit n nh hn v s gim p trong thit b cng nh hn, nhng gi thnh v kch thc li gim i mt na so vi Synthol. Bn cnh th chi ph sn xut cng thp hn, linh hot ca qu trnh cao hn v cho php nng nng sut ln n 20,000 BPD. Thit b phn ng dng slurry hot ng nhit thp ln u c pht trin vo thp nin 50 bi Kolbel. Thit b phn ng 3 pha ny bao gm lp xc tc rn dng huyn ph v c phn tn trong cht lng c nhit dung ln (thng l chnh sn phm sp ca FTS). Syngas c sc bong bng qua pha lng v tip xc pha vi xc tc, ngoi ra cng gip cc ht xc tc c phn tn tt hn tng din tch tip xc b mt. Slurry reactors c ti u ha cho qu trnh FTS nhit thp, sn phm ch yu l sp lng vi lng methane thp. So vi thit b xc tc c nh th thit b dng slurry c u im l d iu chnh nhit hn, lng xc tc cn dng t hn, v bo mn xc tc cng thp hn nhiu. iu kin ng nhit ca thit b slurry cho php tng nhit trung bnh ca phn ng ln v do tng chuyn ha syngas thnh cc sn phm mong mun. V so snh vi thit b phn ng dng ng chm th thit b slurry c phn b p sut trong ton thit b ng u hn nn gim c chi ph cho nn kh cng nh gim lng tiu hao xc tc, hot ng nhit cao hn v c chuyn ha cao hn. Thit b slurry cng c gi thnh sn xut thp hn. Nhc im ln nht ca thit b slurry l cc c cht xut hin trong dng kh nguyn liu s nh hng n ton b lng xc tc trong thit b, cn trong thit b dng ng th chng s ch nh hng ti lng xc tc gn dng nguyn liu vo. Cng ngh dng thit b slurry ca Sasol c hiu sut nhit khong 60% v chuyn ha carbon vo khong 75%. 1.6. Cc cng ngh FT trn th gii C hai loi hnh cng ngh FTS: cng ngh FTS nhit thp (LTFTS) v cng ngh FTS nhit cao (HTFTS): + LTFTS: 2000C 2400C (xc tc Co v Fe) GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 26

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

+ HTFTS: 3000C 3500C (xc tc Fe) Nhit phn ng tng ln s lm gim chiu di mch C sn phm, ngha l phn ng ct mch s tri hn phn ng polymer ha v sn phm thu c nhiu xng v olefin hn. Bng 1.3: Phn b sn phm ca hai kiu cng ngh LTFT v HTFT [9]

1.6.1. CN ca Sasol ( Sasolburg and Secunda, South Africa)

Hnh 1.8: S cng ngh ca Sasol [9]

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 27

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hin ti hng Sasolburg s dng nguyn liu l kh tng hp nguyn cht c cung cp bi cc thit b phn ng LTFT. C 5 thit b ng chm v mt thit b pha huyn ph vi cng sut ln. Cc thit b phn ng c hot ng iu kin m u tin ti a sn phm cc ankan, anken mch thng v sp. Sasol l nh cung cp cc sp parafin ln nht th gii. Cc sn phm ny c lm no ha chuyn i tt c cc anken v cc hp cht cha oxy thnh cc ankan. Sau khi tch LPG t phn kh cui ca qu trnh FT, th hydro c tch tng hp amoniac.
1.6.2. Cng ngh ca PetroSA/Mossgas(Mossel Bay South Africa )

Di y l s khi cng ngh ca hng Mossgas/PetroSA. Sn phm chnh ca hng l nhin liu du v diezen. Kh tng hp c sn xut t kh t nhin ngoi bin.Kh tng hp c cung cp cho thit b phn ng tng si c tun hon, xc tc s dng cho cc thit b phn ng loi ny l xc tc Fe. Ru, xeton v andehit ha tan trong pha nc ca qu trnh FT c chit,sau xeton v andehit c hydro ha thnh ru. Phn C3 v phn hydrocacbon nng ca qu trnh FT c thu hi li trong thit b lm lnh.

Hnh 1.9: S cng ngh ca PetroSA/ Mossgas [9] GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 28

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Phn cn li ca kh cha kh tng hp cha chuyn ha, CO2, CH4, C2H4, v C2H6 c a tun hon li thit b refoming ph. Butan t kh t nhin c isomer ha thnh iso-butan sau c alkyl ha cng vi cc anken C3, C4 ca qu trnh FT to thnh xng c tr s octan cao. Lng d cc anken C3+ ca phn kh cui c oligomer ha vi xc tc l zeolit c tnh chn lc hnh dng to thnh sn phm l diezen v xng. Tt c cc xng trn u c x l bng hydro, cc ankan C5/ C6 c isomen ha v cc ankan C7+ th c a vo qu trnh reforming xc tc (Pt) sn xut xng c tr s octan cao. Tt c cc diezen cng c x l bng hydro. Tng sn lng nhin liu l 1020x103 tn/nm. 1.6.3. Cng ngh ca Shell SMDS ( Bintulu, Malaysia) Kh tng hp c sn xut bng cch oxi ha mt phn khng s dng xc tc p sut cao v nhit khong 1400oC. Kh tng hp to ra theo cch ny tuy t hiu qu cao nhng t l H2/CO thp, ch t khong 1,7 trong khi s dng cho phn ng FT vi xc tc Co th t l yu cu cn khong 2,1; do phi thm vo kh tng hp ny kh giu hydro. Phn ng FT s dng thit b phn ng loi ng chm ging nh thit b phn ng sn xut metanol ca hng Lurgi. Phn ng din ra iu kin 3 Mpa v 200 230oC. S chuyn ha t khong 80% v chn lc C5+ t 85% yu cu. Mc ch ca qu trnh l sn xut sp. Sau khi ngng t nc, du lng v sp th kh cui c th cha tt c cc sn phm t C1- C4 v cng c th ln mt cht C5+, chng c a n thit b reforming hi nc c xc tc to ra kh tng hp cung cp cho phn ng FT.

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 29

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hnh 1.10: S cng ngh ca Shell SMDS [9]

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 30

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Chng 2: Thc nghim

2.1. Tng hp xc tc 2.1.1. Ha cht, dng c v thit b s dng Ha cht tng hp xc tc: (CH3COO)2Co.4H2O CH3COOK -Al2O3 Nc ct 2 ln Dng c: Cc thy tinh c m: loi 50ml, 100ml Pipet, micropipet Bnh ht m Chn nung Thit b: My khuy t T sy L nung Cn phn tch

2.1.2. Qu trnh tng hp xc tc Qu trnh tng hp xc tc c trnh by tm tt hnh 2.1 di y: Qui trnh ny bao gm cc giai on sau: - Chun b cht mang: Cht mang v-Al2O3 c nghin mn v sng qua sng c kch thc. Sau -Al2O3 c em nung 300oC

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 31

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng trong vng 2h, tc gia nhit l 5oC/ pht.em bo qun -Al2O3 trong bnh ht m.

Hnh 2.1: S qui trnh tng hp xc tc Co,K/ -Al2O3 - Chun b dung dch tm: + Cn mt lng mui (CH3COO)2Co.4H2O v CH3COOK cn thit, sau ha tan mui bng nc ct hai ln sao cho dung dch to thnh c nng 0,5M. + Cn mt lng mui CH3COOK cn thit, sau ha tan mui bng nc ct hai ln sao cho dung dch to thnh c nng 0,05M - Ngm tm: Cht mang c tm dung dch mui cha kim loi iu kin thng theo hai bc: GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 32

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

+ Dng micropipet ly chnh xc th tch dung dch (CH3COO)2Co v dung dch CH3COOK theo t l tnh ton cho vo cc c cha Al2O3 sau em khuy bng my khuy t nhit thng trong 3h. + Tng nhit ln 55 oC v khuy cho ti khi kh b mt mu xc tc th ngng khuy. - em xc tc sau khi ngm tm sy nhit 120 oC qua m. - Sau khi sy, xc tc c em i nung 300 oC, tc 1 oC/ pht. Gi 300 oC trong 4h. - Kh H2 Trong nghin cu ny tng hp 4 mu xc tc Co,K/ -Al2O3 vi cc nng khc nhau ca Co. Chi tit cc mu tng hp c a ra trong bng 2.1 sau: Bng 2.1: Cc mu xc tc tng hp STT 1 2 3 4 K hiu mu N1 N2 N3 N4 %mCo/ -Al2O3 10 20 25 30 %mK/ -Al2O3 0,2 0,2 0,2 0,2

2.2.

Nghin cu c trng ca xc tc

2.2.1. Phng php xc nh din tch b mt ring v phn b cu trc l xp bng hp ph vt l nit [1, 6, 8]

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 33

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Din tch b mt ring c nhiu ngha khc nhau vi vt liu rn xp v qkhng xp. Vi vt liu rn khng xp th din tch b mt ring l tng din tch bn ngoi cc ht hay khi vt liu. Cn i vi cc vt liu rn xp th b mt ring l tng din tch bn ngoi v tng din tch cc mt trong ca cc l xp c gi tr ln hn rt nhiu so vi din tch b mt ngoi. Phng php thng dng xc nh din tch b mt ring ca mt vt liu rn l o mc hp ph ca nit hoc mt s kh khc c kh nng thm nhp vo tt c cc mao qun nh: Ar, CO2, Kr, v tnh ton din tch b mt ring da vo ng ng nhit hp ph. Nguyn tc: Vt liu c hp ph kh N2 ti nhit N2 l 77 oK. S dng phng trnh BET:

C 1 P P 1 Va Pa P VmC VmC Po
Trong : Va: S mol kh b hp ph p sut Pa (mol/g) C: Hng s BET Vm: Th tch cn thit hnh thnh n lp hp ph trn b mt (mol/g) P: p sut kh (mmHg) Po: p sut hi bo ha ca cht b hp ph ti nhit cho (mmHg) C th xy dng c th biu din mi quan h l mt ng thng trong khong
P Po
P V Po P

P , Po

= 0,05

0,3. Da vo h s
Trang 34

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng gc v im ct trc tung ca ng thng biu th mi quan h gia
P Va Pa P

P , xc nh c Vm v t tnh c din tch b Po

mt ring S (m2/g) theo cng thc:

S = Vm.an.Na.10-20
Trong : an: Tit din ngang ca phn t Ni ( ) Na: S Avogadro, Na= 6,023.1023 mol-1 Thc nghim: Trong nghin cu ny hp ph vt l nit c p dng xc nh b mt ring v cu trc xp ca cht mang -Al2O3. ng ng nhit hp ph nit c ghi trn my Micromerictics ASAP 2010 (M) ti PTN CN lc ha du v vt liu xc tc - HBK H Ni. Trc khi o mu c lm sch trong dng kh heli nhit 350 C trong 90 pht vi tc gia nhit l 5 oC/ pht. Qu trnh hp ph c tin hnh nhit -196 oC (77K), p sut 770mmHg trong dng kh mang vi lu lng l 25ml/ pht.
o

2.2.2. Phng php xc nh phn tn kim loi trn cht mang bng hp ph ha hc [6, 8] Ngi ta xc nh phn tn ca kim loi trn b mt cht mang bng phng php chun b mt, dng kh CO (hoc H2 ) Nguyn tc : o lng kh CO (hoc H2) hp ph ln kim loi trn b mt mu phn tch (trong trng hp ny th kim loi l Cobalt), da vo ta o lng kh CO (hoc H2) b hp ph bi kim loi Cobalt trn b mt mu phn tch v t ta c th tnh c s phn b kim loi trn b mt cht mang GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 35

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Thc nghim: Trong nghin cu ny, hp ph ha hc CO c s dng xc nh phn tn ca kim loi Co trn cht mang -Al2O3. Trc tin mu c lm sch bng kh heli 150 oC trong 1h, sau h nhit xung nhit phng bng cch cho kh heli i qua trong 10 pht. Tip theo a dng H2 vo kh Co oxit v dng kim loi, qu trnh kh ny din ra 350 oC trong 1h, sau a heli vo ui ht H2 ra trong vng 30 pht v i h xung nhit hp ph l 35 oC, trong khi i h nhit th dng heli vn tip tc c a vo. Sau chuyn dng kh cho CO vo phn tch, lng CO l 10,2%CO/H2 theo tng xung (loop 0,5ml) 35oC v i n nh trong khong 15 pht, sau bt u qu trnh phn tch trong khong 2h (ti khi bo ha). Kt thc qu trnh hp ph, a kh heli qua h phn tch mu v h nhit xung nhit phng. Qu trnh ny c thc hin trn my Autochem II 2920, PTN CN Lc ha du v vt liu xc tc, khoa Cng ngh ha hc, trng HBK H Ni. Tnh ton hp ph: Th tch kh CO hp ph ln cc tm kim loi c tnh ton theo cng thc sau:

V
Trong :

Ac Ai 273 P Vc Ac 273 T 760

V: th tch ca kh CO/H2 c hp ph, cm3 Ac: trung bnh ca ln bm khng hp ph Ai: vng hp ph ring phn ca ln bm Vc: th tch ca kh CO hoc H2 bm vo GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 36

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng T: nhit phng, oC P: p sut phng, mmHg phn tn ca mt kim loi D trn b mt cht mang c tnh theo cng thc:

2.2.3. Phng php xc nh hm lng kim loi trong xc tc bng phng php ph hp thu nguyn t [21] Phng php ph hp thu nguyn t (Atomic Absorption Spectrophoto-metric), vit tt l phng php AAS. Cc nguyn t trng thi bnh thng th chng khng hp thu hay bc x nng lng nhng khi chng trng thi t do di dng nhng m hi nguyn t th chng hp thu v bc x nng lng. Mi nguyn t ch hp thu nhng bc x nht nh tng ng vi nhng bc x m chng c th pht ra trong qu trnh pht x ca chng. Khi nguyn t nhn nng lng chng chuyn ln mc nng lng cao hn gi l trng thi kch thch. Qu trnh gi l qu trnh hp thu nng lng ca nguyn t t do trng thi hi v to ra ph ca nguyn t . Ph sinh ra trong qu trnh ny gi l ph hp thu nguyn t. Thit b: Ngun pht ra bc x n sc Chn h thng n catot rng (HCl). n ny c cu to gm ba phn chnh: * Thn n v ca s * Cc in cc catot v anot * Kh trong n. l kh tr He

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 37

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Anot c cu to bng kim loi tr v bn nhit nh W hay Pt. Catot c ch to c dng hnh xylanh hay hnh ng rng c ng knh t 3-5 mm. Di 5-6 mm v chnh bng kim loi cn phn tch vi tinh khit cao (t nht 99.9%). Dy dn ca catot cng l kim loi W hay Pt. c hai in cc c gn cht trn b ca thn n v cc catot phi nm ng trc xuyn tm ca n. Ngun nui l ngun mt chiu c th 220-240 V. Nguyn tc lm vic Khi n lm vic, catot c nung , gia catot v anot xy ra s phng in lin tc. Do s phng in m mt s phn t kh b ion ha. Cc ion va c sinh ra s tn cng vo catot lm b mt catot nng v mt s nguyn t kim loi trn b mt catot b ha hi v n tr thnh nhng nguyn t kim loi t do. Khi di tc dng ca nhit trong n HCl ang c t nng , cc nguyn t kim loi ny b kch thch v pht ra ph pht x ca n. chnh l ph vch ca chnh kim loi lm catot rng. Nhng v trong iu kin lm vic c bit ca mi trng kh tr c p sut thp, nn ph pht x ch bao gm cc vch nhy ca kim loi . Tnh ton: Dng ng chun: Pha mt dy cc dung dch chun c nng xc nh (thng pha tuyn tnh theo cp s nhn), em o AAS thu c hp th A, t dng c ng chun. em mu cn phn tch o AAS, thu c hp th A, t hp th , ging vo ng chun ta s xc nh c nng kim loi c trong mu. 2.2.4. Phng php nhiu x tia X (XRD-X Ray Diffraction) nghin cu nh tnh cu trc pha tinh th. [5, 6, 7,8] Phng php nhiu x tia X l mt phng php ph bin v hin i c ng dng nghin cu cc vt liu c cu trc tinh GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 38

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng th. Nhng kt qu thu c t phng php ny gip nhn din nhanh chng v chnh xc cu trc tinh th, c n pha v a pha, ng thi cng gip phn tch nh lng pha tinh th vi tin cy cao. Phn tch nh tnh pha tinh th l pht hin s c mt ca mt pha tinh th no trong i tng kho st. Tng t nh cc phng php phn tch khc, mt pha tinh th no khng c pht hin c th hiu l khng c hoc c nhng hm lng nm di gii hn nhn bit. Gii hn pht hin cc pha tinh th ca phng php nhiu x tia X ph thuc vo cc nguyn t ha hc trong vt liu , h tinh th, kt tinh, thay i t 1% n 20%. Nguyn tc: Theo thuyt cu to tinh th, mng tinh th c cu to t cc ion hay cc nguyn t, c phn b mt cch u n v trt t trong khng gian theo mt quy lut xc nh. Khong cch gia cc nguyn t hay ion trong mng li tinh th khong vi hay xp x bc sng ca tia Rownghen (tia X). Khi chm tia X p vo pha b ngoi mt tinh th v xuyn su vo trong do tia X c nng lng cao, th mng tinh th vi cc mt phng nguyn t song song s ng cai tr l mt cch t nhiu x c bit. Cc nguyn t hay ion trong mng tinh th s b kch thch bi chm tia X s tr thnh cc tm pht x pht ra nhng tia sng th cp (tia tn x). Do cc nguyn t hay ion ny c phn b trn cc mt phng song song ( mt phng nguyn t) nn hiu quang trnh ca hai tia phn x bt k trn hai mt phng song song cnh nhau c tnh nh sau:

Trong : GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 39

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

d: khong cch gia hai mt phng song song : gc gia chm tia Rnghen v tia phn x T iu kin giao thoa, cc gc phn x trn hai mt phng song song cng pha ch khi hiu quang trnhf ca chng bng s nguyn ln bc sng, ngha l tun theo nh lut Vulf- Bragg: (n l cc s nguyn dng) H thc Vulf- Bragg l phng trnh c bn cho nghin cu cu to mng tinh th. Da vo cc cc i nhiu x trn gin Rnghen s tm ra gc , t suy ra c gi tr d theo h thc Vulf- Bragg. So snh gi tr d va tm c vi gi tr d chun s xc nh c thnh phn cu trc mng tinh th ca cht cn phn tch.

tinh th ca cht cn phn tch c xc nh theo cng thc:

tinh th (%) = 100.A/B

Trong : A: cng peak c trng ca mu phn tch B: cng peak c trng ca mu chun chn lc ca pha tinh th c xc nh theo cng thc:

chn lc tinh th (%) = 100.C.D

Trong : C: phn trm cng peak c trng cho tinh th cn xc nh D: tng phn trm cng peak c trng cho tt c cc tinh th c mt trong mu do my nhiu x xc nh. GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga Trang 40

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Thc nghim: Trong nghin cu ny, phng php nhiu x tia X c s dng xc nh nh tnh pha tinh th ca cht mang v xc tc sau qu trnh ngm tm. Ph nhiu x tia X ca mu nghin cu c ghi trn my Bruker D8 Advance (c), ng pht tia Rnghen bng Cu, bc sng 1,540 ;gc qut thay i t 10o n 60o, 70o; tc qut 0,05o/ pht ti PTN CN Lc ha du v vt liu xc tc- trng HBK H Ni. Nghin cu th nghim hot tnh xc tc cho phn ng FT Hot tnh ca xc tc Co,K/ -Al2O3 c th nghim cho phn ng FT trn s c m t nh trong hnh 2.2. 2.3. Thuyt minh s : Qu trnh c tin hnh trn s dng vi lng vi 1gam xc tc v 4gam silicagel lm cht n. Phn ng din ra 210oC, p sut 10 bar, t l H2/CO l 2:1. Kh H2, CO, N2 c a vo ng phn ng 1 theo t l nh sn nh b iu chnh lu lng MFC 2(Mass Flow Controller). ng phn ng 1 cha xc tc v c t trong l phn ng 3. Nhit ca l phn ng c duy tr bi b iu khin nhit . Cc cht sau phn ng c a qua bnh phn tch kh lng 7. Kh i ra t nh ca bnh 7 c qua b lc kh 9 ri i vo sc k kh phn tch chuyn ha. Sn phm lng i ra y bnh 7 c tho ra qua van 15, em i phn tch GCMS xc nh thnh phn. Cc ng phn ng c lm bng thp khng g (Swagelok 316, 0,028) v c hn mt que thm nhit chnh gia ng c tc dng gi lp xc tc v cm u d nhit (hnh 2.3).

GVHD: TS. Nguyn Hng Lin SVTH: Phm Th Nga

Trang 41

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hnh 2.2: S phn ng FT

trong : 1: ng phn ng 2: b iu chnh lu lng dng 3: l t 4: p k 5: van ng m 6: van mt chiu 7: bnh phn tch kh lng 8: van x p 9: lc kh 10: b iu chnh p sut 11: van tinh chnh 12: ng x kh 13, 14: ng ra sc k 15: ng tho sn phm

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 42

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Pha di ng phn ng l mt thit b phn tch kh lng lm bng thp khng g (th tch 60 ml), c tc dng phn tch cc sn phm lng v kh (hnh 2.4). Nhit ca bnh phn tch c gi 10oC bng hn hp mui + trnh cc sn phm lng bay hi.

Hnh 2.3: Mt ct dc ng phn ng

600

600

150

Hnh 2.4: Cu to bnh phn tch sn phm GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 43

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Nguyn tc ca phng php sc k kh: Khi dng dng kh mang a mt hn hp cc cht i qua mt cht hp ph, do tc ng ca dng kh mang , cc cht trong hn hp s chuyn ng vi cc vn tc khc nhau, ty thuc vo kh nng hp ph ca cht hp ph vi cht phn tch, hay ty thuc vo i lc ca cht phn tch vi ct tch. Kh nng hp ph ca cht hp ph vi cht phn tch c c trng bng thng s thi gian lu. Trong cng mt ch sc k th cc cht khc nhau c thi gian lu khc nhau, cht no b hp ph mnh th thi gian lu di,v ngc li. Ngi ta cng c th a cht chun vo mu phn tch v ghi li cc peak chun so snh vi cc cht trong mu phn tch. Trong phn tch nh tnh, ngi ta tin hnh so snh cc kt qu thu c vi cc bng s liu trong s tay hoc so snh vi thi gian lu ca mu chun c thc hin trong cng mt iu kin. Trong phn tch nh lng, ngi ta tin hnh xc nh lng mi cht da v vic o cc tham s ca cc peak sc k nh chiu cao peak, din tch peak. Thc nghim: Hot tnh xc tc c nh gi qua hm lng nguyn liu v sn phm trong hn hp nguyn liu trc v sau phn ng. chuyn ha C c tnh theo cng thc: = Lng nguyn liu tham gia phn ng 100 Lng nguyn liu ban u
o

Lng nguyn liu c tnh theo din tch peak o c qua phn tch bng sc k kh, ct ca sc k l ct ry phn t 5 A .

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 44

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Chng 3: Kt qu v tho lun

3.1. c trng ha l ca xc tc 3.1.1. Hm lng kim loi trong xc tc

Hm lng kim loi trong xc tc c xc nh theo phng php ph hp th nguyn t AAS. Kt qu thu c nh sau: Bng 3.1: Hm lng kim loi c trong cc mu xc tc STT Mu xc tc 1 2 3 4
N1 Thnh phn xtc (%mAl2O3) 10% Co 0,2% K 20% Co 0,2% K 25% Co 0,2% K 30% Co 0,2% K

Hm Hm Hm Hm lng Co lng Co lng K lng K l thuyt thc t l thuyt thc t (mg/L) (mg/L) (mg/L) (mg/L) 181,4 100,36 3,62 1,86 362,8 453,5 544,2 254,51 322,90 411,93 3.32 3,2 3.0 1.76 1,53 1,48

N2

N3

N4

Nhn xt: T bng trn ta thy hm lng kim loi thc t trong xc tc t c khong 55 70% so vi hm lng kim loi d kin a vo xc tc theo l thuyt. Nh vy,ta thy hiu sut mang kim loi ln xc tc cng tng i cao trong phng php ngm tm thng. 3.1.2. Din tch b mt ring v cu trc mao qun ca cht mang v xc tc xc nh din tch b mt ring v cu trc l xp ca cht mang -Al2O3 v xc tc (mu N2) ta tin hnh phn tch theo phng GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 45

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng php ng nhit hp ph v nh hp ph vt l N2. Kt qu thu c nh sau: Vi cht mang -Al2O3

- Din tch b mt ring theo BET: 239,5761m2/g - Din tch b mt ring theo Langmuir: 317,5993 m2/g - Th tch l xp: 0.512366 cm3/g ng ng nhit hp ph v nh hp ph c th hin trn hnh 3.1

Hnh 3.1: ng ng nhit hp ph v nh hp ph N2 ca cht mang -Al2O3 Quan st trn hnh 3.1 ta thy, ng hp ph v ng nh hp ph khng trng nhau v to thnh mt vng tr, hnh dng ca vng tr ny c trng cho vt liu mao qun trung bnh c kch thc mao
o

qun t 200 500 A .

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 46

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hnh 3.2: Phn b l xp ca cht mang -Al2O3 Hnh 3.2 cho thy -Al2O3 c kch thc mao qun trung bnh tp trung 30 A . Vi mu xc tc N2
O

- Din tch b mt ring theo BET: 194.3835 m2/g - Din tch b mt ring theo Langmuir : 259.9539 m2/g - Th tch l xp: 0.488522 cm3/g ng ng nhit hp ph v nh hp ph c th hin trn hnh 3.3. ng ng nhit hp ph v nh hp ph vt l N2 ca mu xc tc N2 (20%Co-0,2%K/ -Al2O3) cho thy mu hnh tng t nh cht mang -Al2O3. Nh vy vic tm kim loi ln cht mang khng lm nh hng n loi cu trc mao qun trung bnh ca vt liu. GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 47

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hnh 3.3: ng ng nhit hp ph v nh hp ph N2 ca mu xc tc N2

Hnh 3.4: Phn b l xp ca cht xc tc N2 GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 48

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Phn b l xp ca xc tc N2 (20%Co-0,2%K/ -Al2O3) cng cho thy, xc tc mi hnh thnh cng c kch thc mao qun trung bnh tp trung ti khong 30 A nh cht mang. Nh vy vic a kim loi ln cht mang khng lm thay i ng knh l xp ca vt liu. 3.1.3. c trng pha tinh th ca cht mang v xc tc Cu trc pha tinh th ca cht mang -Al2O3 v mu xc tc N3 c xc nh bng phng php nhiu x tia X (XRD). Kt qu phn tch c a ra trong hnh 3.5.
O

Hnh 3.5: Ph XRD ca cht mang -Al2O3 Quan st gin XRD hnh 3.5 ta thy, cc pha tinh th c trng cho cu trc -Al2O3 c th hin r ti 4 vng peak c trng gc qut 2 t 3637o, t 3940o, t 4546o, t 6668o

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 49

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 25%Co-0,2%K-gama Al2O3

1000

900

700

600

Lin (Cps)

500

400

300

200

100

0 20 30 40 50 60 70 80

d=2.738

d=2.327

800

2-Theta - Scale
File: Thi BK mau 25%Co-0,2%K-gama Al2O3.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 12 s - 2-Theta: 20.000 - Th 00-010-0458 (D) - Cobalt Aluminum Oxide - CoAl2O4/CoOAl2O3 - Y: 89.32 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.10300 - b 8.10300 - c 8.10300 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-cente 00-002-0770 (Q) - Cobalt Oxide - Co2O3 - Y: 80.14 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 4.64000 - b 4.64000 - c 5.75000 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P (0) - 2 - 107.210

Hnh 3.6: Ph XRD ca mu xc tc N3 (25%Co- 0,2%K/ -Al2O3) Vi mu xc tc N3, quan st trn hnh 3.6 ta thy vi hm lng kim loi tm trn cht mang l 25%Co- 0,2%K, xut hin cc tn hiu c trng cho tinh th Co tn ti di dng oxit Co2O3 ti gc qut 2 ~ 28o, 31o, 39o, 51o, 56o, 67o v dng CoAl2O4/ CoO_Al2O3 gc qut 2 ~ 37o. 3.1.4. phn tn ca kim loi trn cht mang phn tn ca kim loi trn cht mang c nh gi qua phng php hp ph xung CO. Kt qu o 2 mu N1 (10%Co0,2%K/ -Al2O3) v mu N2 (20%Co-0,2%K/ -Al2O3) c a ra trong bng 3.2 sau:

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

d=1.437 d=1.424

d=2.443

Trang 50

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Bng 3.2: Kt qu o phn tn Co-K/ -Al2O3 Mu Hm lng kim loi trn phn tn (%) cht mang (%) Hm lng Hm lng phn tn ca Kch thc Co K Co ht(nm) 10 0,2 0,5171 158,6429 20 0,2 0,4040 243,1245 25 0,2 0,2831 351,9256 30 0,2 0,2056 484,7206

N1 N2 N3 N4

Nhn xt: T bng 3.2 trn ta thy, khi hm lng Co tng th phn tn gim, iu ny c th gii thch l khi tng lng Co tm th do s lng tm kim loi nhiu nn d xy ra hin tng co cm lm gim phn tn ca Co. iu ny cn c minh chng bng kch thc tm hot tnh ca tng xc tc, ta thy rng khi tng lng Co tm th kch thc cc cm tm hot tnh cng tng ln ng k. 3.2. nh gi hot tnh ca xc tc Hot tnh xc tc l thng s quan trng nht trong vic nghin cu pha hot ng ca xc tc v l thng s u tin cn phi tm hiu khi tin hnh nghin cu mt xc tc mi. 3.2.1. Th hot tnh xc tc Hot tnh ca xc tc Co- K/ Al2O3 c th nghim trn phn ng FT vi nguyn liu l kh tng hp vi t l H2/CO l 2:1. Xc tc c th nghim l hai mu N1 (10%Co-0,2%K/ -Al2O3) v mu N2 (20%Co-0,2%K/ -Al2O3). Phn ng c tin hnh 210 o C, p sut 10 bar, tc dng ca nguyn liu l 200ml/ pht. Kt qu phn tch chuyn ha c a ra trong cc th sau: GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 51

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
12.00% 10.00% Do chuyen hoa, % 8.00% 6.00% 4.00% 2.00% 0.00% 0 60 120 180 240 300 360 420 480 540 Thoi gian, phut 10%

Hnh 3.7: chuyn ha ca CO trong phn ng FT khi s dng xc tc 10% Co-0,2%K/ -Al2O3

8.00% Do chuyen hoa, % 7.00% 6.00% 5.00% 4.00% 3.00% 2.00% 1.00% 0.00% 0 60 120 180 240 300 360 420 480 540 600 Thoi gian, phut 20%

Hnh 3.8: chuyn ha ca CO trong phn ng FT khi s dng xc tc 20% Co-0,2%K/ -Al2O3 GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 52

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Nhn xt: Quan st hnh nh v chuyn ha ca CO trong phn ng FT khi s dng hai mu xc tc N1 v N2 trn ta thy: c hai mu xc tc, chuyn ha ca CO trong phn ng khng cao, ch t khong 5 10%, v c hai mu chuyn ha ca CO u t mc cao nht ti thi im pht th 300, 360 ca phn ng. 3.2.2. nh hng ca hm lng kim loi chnh trn cht mang n hot tnh xc tc a. nh hng n chuyn ha i vi loi xc tc kim loi trn cht mang, hm lng kim loi trn cht mang nh hng rt ln n hot tnh xc tc, thi gian lm vic cng nh gi thnh ca xc tc. Chnh v vy vic ti u ha hm lng kim loi a vo hp phn xc tc lun l mt vn rt c ch trng v quan tm i vi cc nh nghin cu v sn xut xc tc. C hai mu N1 (10%Co-0,2%K/ -Al2O3) v mu N2 (20%Co-0,2%K/ -Al2O3) u c th nghim cng mt iu kin phn ng, kt qu phn tch chuyn ha ca CO khi s dng hai xc tc ny c a ra hnh 3.9:
12.00% Do chuyen hoa, % 10.00% 8.00% 6.00% 4.00% 2.00% 0.00% 0 60 120 180 240 300 360 420 480 540 10% 20%

Thoi gian, phut

Hnh 3.9: chuyn ha ca CO trn mu N1 v N2 GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 53

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Kt qu cho chuyn ha ca CO trn hnh 3.9 cho thy s khc nhau: Mu N1 (10%Co-0,2%K/ -Al2O3) cho chuyn ha cao hn mu N2 (20%Co-0,2%K/ -Al2O3). Nh vy khi hm lng Co trn xc tc thp th chuyn ha ca CO trong phn ng FT li cao hn trong trng hp hm lng Co cao. iu ny c th c gii thch trn c s phn tn tm hot tnh cao hn i vi mu c lng Co thp hn. b. nh hng n s phn b sn phm S phn b sn phm ca xc tc 10% Co-0,2%K/ -Al2O3 T s liu bng 3.3 ta c th xy dng biu v s phn b sn phm phn ng vi xc tc 10% Co-0,2%K/ -Al2O3 nh hnh 3.10:

%m
30

25 % Khoi luong san pham

20

15 %m 10

0 C6 C8 C14 C16 C21

So nguyen tu C trong phan tu

Hnh 3.10: Phn b s C trong sn phm ca mu xc tc 10% Co-0,2%K/ -Al2O3 GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 54

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Bng 3.3: Phn b sn phm ca phn ng FT vi xc tc N1 10% Co-0,2%K/ -Al2O3
STT 1 2 3 4 5 6 7 8 9 10 V tr peak Phi HC HC 6,9 7,72 9,26 10,16 10,20 10,32 10,72 23,34 26,40 29.3 X X X X X X X X X X Cng thc C8H16O C8H16O C8H14O C14H24O C14H24O C14H24O C6H10O2 C16H34 C16H34 C21H44 S C C8 C8 C8 C14 C14 C14 C6 C16 C16 C21 %m 3,3 2,73 3,83 4,85 7,94 3,13 21,46 5,46 18,95 10,57

Hm lng hydrocacbon tng = 34,98%m Cc hydrocacbon thu c trong sn phm khi s dng xc tc N1 ch yu l cc ankan mch thng, di c s C t 16 n 22. Lng hydrocacbon pht hin c nhiu nht pht th 26,40 vi ch yu l cc cu t nh n-cetan, pentadecane, n-nonadecane, hexadecane, ntetradecan, hay 10-methylnonadecane. GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 55

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Hnh 3.11. Ph GCMS phn tch thnh phn sn phm phn ng FT trn xc tc N1 (10% Co-0,2%K/ -Al2O3) Compound Structure
Hexadecane n-Cetane
Relative Abund anc e
100 39 28 0 71 97 99

Delta
Raw dat a - Library ent ry 41

154

212

286

-100

100 m/ z

200

296

Hexadecane n-Cet ane 100

Raw dat a - Library ent ry 41 39 28 0 71 97 99

Relative Abund anc e

154

212

286

-100

100 m/ z

200

296

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 56

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
10-M et hylnonadecane 100 41 Raw dat a - Library ent ry

Relative Abund anc e

71 82 0

140 169 212

286

-100

100 m/ z

200

296

pent adecane 100

Raw dat a - Library ent ry 41 43

Relative Abund anc e

71 97 99 126 168

265 286

-100

100 m/ z

200

296

Nonadecane n-Nonadecane

Raw dat a - Library ent ry 1 00 41

Relative Abund anc e

82 0

1 26

1 67

21 2

286

-1 00

1 00 m/ z

200

296

Pent adecane n-Pent adecane 100

Raw dat a - Library ent ry 41

Relative Abund anc e

39 28 0

71 82 97 126 167 265 286

-100

100 m/ z

200

296

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 57

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
Hexad ecane (CA S) n-Hexad ecane

Raw d at a - Lib rary ent ry 1 0 0 41

Relative Abund ance

71 85 0 97 1 6 1 9 2 6 265 286

-1 0 0

1 0 0 m/ z

200

296

Pent adecane n-Pent adecane

1 00 41

Raw dat a - Library ent ry

Relative Abund ance

71

85 97 1 26 0

1 67

265 286

-1 00

1 00 m/ z

200

296

Pent adecane (CAS) n-Pent adecane 1 00 41

Raw dat a - Library ent ry

Relative Abund anc e

71 0

85 97 1 26 1 67 265 286

-1 00

1 00 m/ z

200

296

Tet radecane n-Tet radecane 100 41

Raw dat a - Library ent ry

Relative Abund anc e

71 0

85

97

126

168 212

286

-100

100 m/ z

200

296

Hnh 3.12.Cc loi hp cht c mt trong thnh phn sn phm (phn tch bng GCMS)phn ng trn xc tc N1 (10% Co-0,2%K/ -Al2O3)

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 58

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng S phn b sn phm ca xc tc 20% Co-0,2%K/ -Al2O3 Bng 3.4: Phn b sn phm ca phn ng FT vi xc tc N2 20% Co-0,2%K/ -Al2O3
STT V tr peak Phi HC HC 1 2 3 4 5 6 7 8 9 10 7,72 9,26 10,16 10,21 10,31 10,72 11,64 29,3 32,06 34,68 X X X X X X X X X X Cng thc C8H16O C8H14O C7H14O C14H24O C6H10O2 C8H16O C 16H30O2 C22H46 C17H36 C21H44, C23H48, C25H52, C28H60 S C C8 C8 C7 C14 C6 C8 C16 C22 C17 C21, C23, C25, C28 %m 2,69 4,03 4,93 8,98 5,31 22,08 2,02 5,32 9,47 8,28

Hm lng hydrocacbon tng = 23,07%m

Cc hydrocacbon thu c trong sn phm khi s dng xc tc N2 ch yu l cc ankan mch thng, di c s C t 17 n 28. Lng hydrocacbon pht hin c nhiu nht pht th 29,3; pht th 32,06 v pht th 34,68. Di y l cc cu t tm thy pht th 32,06

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 59

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
RT: 31.50 - 32.66 SM: 3G 100 80 60 40 20 31.56 0 31.6 31.8 32.0 32.2 Time (min) 32.4 32.6 31.71 31.89 32.31 32.43 32.58 RT: 32.06 NL: 5.08E5 TIC F: + c Full ms [ 25.00300.00] MS FT_Nga_29_ 5

Relative Abundance

Hnh 3.13. Ph GCMS phn tch thnh phn sn phm phn ng FT trn xc tc N2 (20% Co-0,2%K/ -Al2O3) Compound Structure
Nonadecane n-Nonadecane 100 41

Delta
Raw dat a - Library ent ry

Relative Abund anc e

71 0

99

111 126 182 210 263

-100

100 m/ z

200

299

Hept adecane n-Hept adecane 100 41

Raw dat a - Library ent ry

Relative Abund anc e

71 85 0 97 111

139 185

263

-100

100 m/ z

200

299

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 60

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
Hept adecane (CAS) n-Hept adecane 100 41 71 85 0 97 111 Raw dat a - Library ent ry

Relative Abund anc e

139 185

263

-100

100 m/ z

200

299

Hexadecane (CAS) n-Hexadecane 100 41

Raw dat a - Library ent ry 71

Relative Abund anc e

97 0

99

127 168 210 263

-100

100 m/ z

200

299

Hexadecane n-Cet ane

Raw dat a - Library ent ry 1 00 41 71 97 99 1 27 0 1 39 1 82 240

Relative Abund anc e

-1 00

1 00 m/ z

200

299

Hexadecane n-Cet ane 100

Raw dat a - Library ent ry 41 71 97 99 127 0 139 182 240

Relative Abund anc e

-100

100 m/ z

200

299

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 61

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng
Oct ad ecane (CA S) n-Oct ad ecane 1 0 0 41 71 83 0 97 1 1 1 Raw d at a - Lib rary ent ry

Relative Abund ance

1 8 6

240

263

-1 0 0

1 0 0 m/ z

200

299

Oct adecane n-Oct adecane

1 00 41

Raw dat a - Library ent ry

Relative Abund ance

71 82 1 1 1 1 26 1 52

240 263

-1 00

1 00 m/ z

200

299

Pent aco sane (CA S) n-Pent aco sane

1 0 0 41

Raw d at a - Lib rary ent ry

71 85 99

Relative Abund ance

57 0

11 1

1 8 1 5 6 8

263

-1 0 0

1 0 0 m/ z

200

299

Hept adecane (CAS) n-Hept adecane 100

Raw dat a - Library ent ry

41 71 85 99 111 168 210 263

Relative Abund anc e

-100

100 m/ z

200

299

Hnh 3.14.Cc loi hp cht c mt trong thnh phn sn phm (phn tch bng GCMS)phn ng trn xc tc N2 (20% Co-0,2%K/ -Al2O3)

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 62

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng T bng s liu trn ta c th xy dng biu v s phn b sn phm phn ng vi xc tc 20% Co-0,2%K/ -Al2O3 nh hnh 3.15:

%m
35 30 25 20 15 10 5 0 C6 C7 C8 C14 C16 C17 C21 C22 C23 C25 C28 %m

Hnh 3.15: Phn b s C trong sn phm ca mu xc tc N2 20% Co-0,2%K/ -Al2O3 Nhn xt T cc kt qu trn ta thy, trong c hai trng hp khi s dng xc tc N1 v N2 th sn phm thu c c hm lng hydrocacbon tng i cao t 23,07 34,98%, v cc hydrocacbon tp trung ch yu trong phn on diezen. Tuy nhin, trng hp mu xc tc N2 (20% Co-0,2%K/ -Al2O3) th hm lng hydrocacbon tng thu c thp hn mu N1(10%Co-0,2%K/ -Al2O3). Nh vy c th ni rng, hm lng Co mang trn cht mang mc 10%m l tng i tt, thch hp cho cc nghin cu chuyn ha Fischer Tropsch to nguyn liu lng. GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 63

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Kt lun
Sau 5 thng thc hin nghin cu xc tc Co/ -Al2O3 cho qu trnh chuyn ha kh tng hp thnh nhin liu lng, em rt ra mt s kt lun sau: 1. Vic ngm tm Co ln cht mang -Al2O3 vi lng 10 20% khng lm thay i cu trc xp v h mao qun trung bnh ca vt liu ban u. 2. Qu trnh ngm tm t hiu sut trung bnh 60 70% lng kim loi so vi l thuyt. 3. Khi lng Co a vo tng t 10 20% phn tn cc tm kim loi gim v ng knh ht hot ng tng dn ti lm gim hot tnh xc tc cho phn ng FT. 4. chn lc sn phm FT ph thuc vo lng Co kim loi c trong hp phn xc tc. Loi xc tc cha 10% Co cho chuyn ha CO 10% nhng rt chn lc sn phm hydrocacbon mch di (>C16), ph hp cho sn xut nhin liu diezen. Do thi gian nghin cu khng , nn cha c iu kin th hot tnh xc tc vi 2 mu cn li. Tuy nhin cc kt qu nghin cu trn y ch ra kh nng rt tt tng hp nhin liu diezen t kh tng hp trn c s s dng xc tc Co/ -Al2O3.

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 64

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Ti liu tham kho

[1] H S Thong,Lu Cm Lc, Chuyn ha hydrocacbon v cacbon oxit trn cc h xc tc kim loi v oxit kim loi, NXB Khoa Hc T Nhin v Cng Ngh, 2007. [2] o Vn Tng, ng hc xc tc, NXB Khoa hc v k thut, 2006 [3] Nguyn Th Minh Hin,Hp ph- xc tc [4] Nguyn Anh V, Bi ging cc phng php phn tch cu trc [5] L Cng Dng, K thut phn tch cu trc bng tia Rnghen, NXB Khoa hc v k thut, 1984 [6] T Vn Mc, Phn tch ha l, NXB Khoa hc v k thut, 1999 [7] Nguyn nh Triu, Cc phng php phn tch vt l v ha l, NXB Khoa hc v k thut, 2001 [8] Chu Th Hi Nam, Nghin cu tng hp xc tc Pd/ -Al2O3 cho qu trnh x l hp cht hu c cha clo, lun vn thc s khoa hc, 2008 [9] Andre Steynberg, Mark Dry, Fischer- Tropsch tecnology [10] Xiaoping Dai, Changchun Yu, Characterization and catalytic performance of CeO2-Co/SiO2 catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratory scale fixed-bed reactor, China. [11] Carlo Giorgio Viscontia, Enrico Tronconia, Luca Liettia, Roberto Zennarob, Pio Forzattia, Development of a complete kinetic model for the Fischer-Tropsch synthesis over Co/Al2O3 catalysts [12] Carlo Giorgio Visconti a, Luca Lietti a, Pio Forzatti a, Roberto Zennaro, Fischer- Tropsch synthesis on sulphur poisoned Co/Al2O3 catalyst [13] Rune Myrstad, Sigrid Eri b, Peter Pfeifer c, Erling Rytter b, Anders Holmen, Fischer- Tropsch synthesis in a microstructured reactor [14] http://www.patentstorm.us/patents/7351679/description.html [15] http://www.tuwien.ac.at - Vienna University of Technology GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga Trang 65

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng [16] www.sarvco.ir/productsCAT.html [17] Xiangdong Ma, et al. Journal of Natural Gas Chemistry. (2009) [18] http://www.nrel.gov National Renewable Energy Laboratory [19] http://bioweb.sungrant.org SunGrant BioWeb-Online Resource for Bioenergy and Bioproducts [20] http://www.lurgi.com LURGI GmbH [21] http://vi.wikipedia.org

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 66

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng

Ph lc
Ph lc 1: Kt qu phn tch chuyn ha CO trong phn ng FT trn my sc k kh khi s dng mu xc tc N1(10%Co-0,2%K/ -Al2O3).

t (pht) Din tch peak chuyn ha 0 1802904 0.00% 15 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 1753773 1739919 1726230 1705971 1697215 1682940 1675905 1676847 1688511 1666016 1651173 1649021 1668029 1651126 1653226 1645311 1643540 2.73% 3.49% 4.25% 5.38% 5.86% 6.65% 7.04% 6.99% 6.34% 7.59% 8.42% 8.54% 7.48% 8.42% 8.30% 8.74% 8.84%

t (pht) Din tch peak chuyn ha 270 1641215 8.97% 285 300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 1625700 1632233 1624827 1630107 1638019 1633267 1636095 1637209 1636788 1628599 1631551 1630336 1626169 1631106 1628638 1626153 1626906 1636084 9.83% 9.47% 9.88% 9.58% 9.15% 9.41% 9.25% 9.19% 9.21% 9.67% 9.50% 9.57% 9.80% 9.53% 9.67% 9.80% 9.76% 9.25%

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 67

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ph lc 2: Kt qu phn tch chuyn ha CO trong phn ng FT trn my sc k kh khi s dng mu xc tc N2(20%Co-0,2%K/ -Al2O3).

t (pht) 0 15 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300

Din tch peak chuyn ha 1870180 0.00% 1828864 2.21% 1805450 3.46% 1798620 3.83% 1790590 4.26% 1782060 4.71% 1778990 4.88% 1776552 5.01% 1766609 5.54% 1762300 5.77% 1761716 5.80% 1761169 5.83% 1759871 5.90% 1767296 5.50% 1762436 5.76% 1754073 6.21% 1748773 6.49% 1762537 5.76% 1759756 5.90% 1748424 6.51% 1747422 6.56%

t (pht) Din tch peak chuyn ha 315 1745918 6.64% 330 1754707 6.17% 345 1746813 6.60% 360 1751680 6.34% 375 1754328 6.19% 390 1750117 6.42% 405 1745647 6.66% 420 1753447 6.24% 435 1757346 6.03% 450 1744680 6.71% 465 1759609 5.91% 480 1754667 6.18% 495 1747476 6.56% 510 1751848 6.33% 525 1754654 6.18% 540 1749098 6.47% 555 1752203 6.31% 570 1749635 6.45% 585 1747068 6.58% 600 1751285 6.36% 615 1753013 6.27%

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 68

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ph lc 3: Kt qu o phn tn Co bng hp ph xung CO ca mu N1(10%Co-0,2%K/ -Al2O3).

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 69

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ph lc 4: Kt qu o phn tn Co bng hp ph xung CO ca mu N1(20%Co-0,2%K/ -Al2O3).

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 70

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ph lc 5: Kt qu o phn tn Co bng hp ph xung CO ca mu N1(25%Co-0,2%K/ -Al2O3).

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 71

 n tt nghip: Nghin cu tng hp xc tc Co/Al2O3 t ngun mui acetate cho qu trnh chuyn ha kh tng hp thnh nhin liu lng Ph lc 6: Kt qu o phn tn Co bng hp ph xung CO ca mu N1(30%Co-0,2%K/ -Al2O3).

GVHD: TS. Phm Hng Lin SVTH: Phm Th Nga

Trang 72