MC LC

mc Trang

LI TA ........................................................... Error! Bookmark not defined. MC LC ......................................................................................................... 1 GII THIU V M UN ................................................................................. 2 V tr, ngha, vai tr m un: ........................................................................... 2 Mc tiu ca m un: ....................................................................................... 2 Mc tiu thc hin ca m un: ....................................................................... 2 Ni dung chnh cc bi ca m un: ................................................................ 2 CC HNH THC HC TP CHNH TRONG M UN .................................. 3 YU CU V NH GI HON THNH M UN ......................................... 3 BI 1. VAI TR CA QU TRNH REFORMING XC TC ........................... 5 BI 2. BN CHT CA QU TRNH REFORMING XC TC ..................... 11 BI 3. XC TC LNG CHC NNG ....................................................... 18 BI 4. NGUYN LIU V CC SN PHM THU .......................................... 37 BI 5. CC LOI CNG NGH REFORMING XC TC ............................. 49 BI 6. S TIN B CA REFORMING XC TC........................................ 66 BI 7. C IM CA XNG REFORMING XC TC ................................ 70 KIM TRA, NH GI HON THNH MN HC ........................................ 75 CC THUT NG CHUYN MN ................................................................ 76 TI LIU THAM KHO ................................................................................... 77

GII THIU V M UN
V tr, ngha, vai tr m un: Reforming xc tc l mt trong nhng qu trnh quan trng nht ca cng nghip ch bin du m. T qu trnh ny thu c mt khi lng ln reformat-hp phn ch yu pha xng thng phm c ch s octan cao. y cng l mt qu trnh c bn thu BTX-mt trong nhng nguyn liu ch yu ca ha du. M un ny trang b kin thc chuyn ngnh cn thit cho cc hc vin sau ny tham gia vn hnh trong nh my lc du cng nh lm vic trong cc lnh vc lin quan n nghin cu ch bin du kh. Mc tiu ca m un: Hc xong m un ny, hc sinh phi t c: 1. Hiu bit v nm vng bn cht ha hc, c ch phn ng ca qu trnh reforming xc tc. 2. Bit iu ch c xc tc reforming 3. Xc nh c mt s c trng ha l ca xc tc iu ch c. 4. Vn hnh s reforming xc tc trong PTN 5. Xc nh cc ch tiu ca xng reforming xc tc. Mc tiu thc hin ca m un: 1. M t c bn cht ha hc, nguyn liu v sn phm thu ca qu trnh reforming xc tc. 2. iu ch c xc tc hai chc nng. 3. Xc nh c c trng ca xc tc iu ch bng cc phng php ha l hin i. 4. Thc hin c phn ng reforming xc tc trn s qui m phng th nghim. 5. Phn tch xc nh c cc ch tiu ca xng reforming xc tc. 6. Cc th nghim ca m un lm trong PTN ha du. Ni dung chnh cc bi ca m un: Bi 1: Vai tr ca qu trnh reforming xc tc trong lc ha du Bi 2: Bn cht ha hc ca reforming xc tc Bi 3: Xc tc hai chc nng Bi 4: Nguyn liu v sn phm thu Bi 5: Cc loi cng ngh v thit b reforming xc tc Bi 6: S tin b ca qu trnh reforming xc tc trong lc du ngy nay Bi 7: c im ca xng reforming xc tc
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CC HNH THC HC TP CHNH TRONG M UN

Hc trn lp v cc ni dung chnh ca m un. T nghin cu ti liu lin quan n bi ging do gio vin hng dn. Tham quan, thc tp trn s reforming xc tc qui m PTN v cc phng php iu ch xc tc reforming, cc phng php c trng xc tc ti cc PTN Trung tm Nghin cu & Pht trin Ch bin Du kh thuc TCT DK v Vin Ha Cng ngh thuc TT KH- CN QG. Thc hnh phn tch cc ch tiu ca xng reforming v xngthng phm. Thc hnh phn tch thnh phn hydrocacbon PONA v hm lng benzen ca xng reforming bng phng php sc k kh. Nghe bo co chuyn v cng ngh reforming xc tc ca nh my lc du s 1 VN. YU CU V NH GI HON THNH M UN V kin thc Hiu bit c vai tr quan trng v v tr ca reforming xc tc trong nh my lc du v trong cng nghip ha du. Nm c bn cht ha hc ca qu trnh reforming v vai tr ca cht xc tc i vi qu trnh. nh hng nguyn liu-sn phm v cc thng s quan trng n qu trnh. Hiu bit v nguyn tc v cc bc c bn trong iu ch xc tc reforming v cc phng php xc nh c trng xc tc. V k nng Bit cch vn hnh s reforming xc tc trong PTN. Bit phn tch cc thnh phn, tnh cht ha l v cc ch tiu cht lng quan trng ca nguyn liu v sn phm reforming. Bit xc nh mt vi c trng ca xc tc a chc nng (b mt ring, phn b l xp, thnh phn kim loi)

V thi Tip thu nghim tc bi ging trn lp. Chun b chu o, tch cc, ch ng trong cc bui thc hnh th nghim, thc tp ngoi kha v nghe ging chuyn . Tun th ni qui, an ton phng th nghim ti cc PTN ca trng v cc ni n thc tp. Phng php kim tra, nh gi Kim tra gia k Kim tra cui k Bo co kt qu thc tp PTN Tham d y cc tit hc, ch ng tch cc trong cc bui tho lun

BI 1. VAI TR CA QU TRNH REFORMING XC TC M bi: HD F1

Gii thiu Bi hc nhm gip hc vin nhn thc c vai tr quan trng ca qu trnh reforming xc tc trong nh my lc du hin i. Qu trnh nhm cung cp xng cht lng cao (RON t 90-95) v ngun nguyn liu qu (BTX) cho ha du. Mc tiu thc hin Hc vin phi nm c vai tr, v tr ca qu trnh reforming trong nh my lc du. ngha ca qu trnh reforming i vi vic sn xut xng cht lng cao v p ng yu cu v mi trng. Nm c cc khi nim v xng thng phm, thnh phn v cht lng ch s octan RON, MON. Ni dung chnh Nhu cu v xng cht lng cao cho ng c S cn thit ca qu trnh reforing xc tc cho sn xut xng 1. Nhu cu v xng cht lng cao cho ng c T sau nm 1900, t ra i thc y vic sn xut xng t nh my lc du. Lc xng ch yu ch ly t chng ct trc tip. n khong 1912 th chng ct trc tip khng cn tho mn vi nhu cu v xng ngy mt tng cao. Mt khc xng loi ny cha mt lng ng k kh t C1-C4 lm cho bay hi ca xng tng v kh nng chng kch n khng cao (th hin qua ch s octan ch xp x 60). T cc nh lc du nghin cu v pht trin mt lot cc qu trnh ch bin du nhm sn xut ra xng c cht lng cao hn. V c bn xng thng phm ngy nay c pha trn t cc sn phm ca cc qu trnh sau: xng chng ct trc tip t du th, xng t cracking nhit v cracking xc tc, xng reforming xc tc, xng t ng phn ha, alkyl ha, c th c thm cc hp phn t hyrdocracking, t polymer ho. Ngy nay vic s dng cc ng c c h s nn cao i hi cht lng nhin liu, c bit l ch s octan cao. p ng yu cu , ngi ta pha trn vo xng cc ph gia hoc tng cng cc hp phn hydrocacbon cho ch s octan cao. Hin ti vi cc tiu chun nghim ngt v mi trng mt loi ph gia truyn thng l tetraetyl ch, tuy lm tng ch s octan ln 15-20 s nhng li gy
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c hi i vi sc khe con ngi, nn gn nh c loi b hon ton. i vi cc ph gia thay th hu hiu nh MTBE, TAME cng c mt s kin nghi ng v kh nng chm phn hy ca chng trong mi trng. Hin ti Vit nam xut hin mt s ph gia mi cha Mn, Fe c th thay th tm thi cc ph gia truyn thng. Nhng cc ph gia trn c s kim loi ny cng cn gy nhiu tranh lun, cn c tip tc lm sng t v kh nng nhim mi trng. Ngi ta c xu hng la chn phng n th hai, tng cng cc hp phn pha ch t cc qu trnh ch bin su nh cracking, reforming, ng phn haCc hp phn ny cho ch s octan cao hn nhiu so vi xng t chng ct trc tip, m li t gy nhim mi trng. Xng pha trn nhm mc ch t nhng ch tiu quan trng sau: - p sut hi bo ha (RVP- Reid Vapor Pressure): o p sut hi ca cc hydrocacbon, cn thit cho s khi ng ca ng c. - Ch s octan: o mc chng kch n ca xng, ch tiu quan trng v ng c kch n thp s hot ng hiu qu hn v tit kim c nng lng. - c hi: o cc hp phn c hi trong xng. Cc nh my lc du thng ch n hm lng benzen, olefin, lu hunh. Ch s octan l i lng c quan tm hn c v thng c la chn nh gi v iu chnh cht lng xng. Ty thuc vo ch s octan m ngi ta c th chia thnh xng thng (regular) hoc xng cht lng cao (premium). nhiu nc, cc phng tin vn ti la chn mc cht lng xng theo ch s octan theo s hng dn ca cc nh ch to ng c. C 2 mc cht lng 87 v 89, thng s dng mc 87 hn. Cn hiu y l gi tri trung bnh gia ch s octan o theo phng php nghin cu v ch s octan o theo phng php m t: (RON+MON)/2. cc cy xng VN ngi ta nim yt gi xng theo ch s RON. Ch s octan ca mt nhin liu em th nghim trn mt ng c trong phng th nghim c xc nh bng cch so snh kh nng chng kch n (ghi trn b knockmeter) ca nguyn liu vi nguyn liu chun cha hn hp isooctan v heptan (qui c ch s octan ca isooctan = 100, ca heptan = 0) trong cng iu kin th nghim. Phn trm th tch ca octan trong nguyn liu chun cho kch n tng ng vi nguyn liu em th nghim chnh l ch s octan ca nguyn liu . V d nguyn liu em th s c ch s octan l 70
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nu kh nng chng kch n ca n tng ng vi hn hp nhin liu chun cha 70% t.t. isooctan v 30% t.t. n-heptan. Tu thuc vo loi ng c th nghim m ngi ta c c ch s octan RON hay MON. Do MON c xc nh trong iu kin khc nghit hn (s vng quay ca ng c ln hn) so vi RON nn RON thng ln hn khong 8 n v i vi cng mt nhin liu. Ch s octan c ghi trn cc bm xng c tnh trung bnh gia RON v MON: (R+M)/2. S ph thuc ca ch s octan vo nhit si ca cc hydrocacbon ri ng r v nhm hydrocacbon c m t trn hnh 1.

Hnh 1. Ph thuc ch s octan vo nhit si v nhm hydrocacbon C th thy i vi phn on xng nh (T s-80oC) tng i kh c th ci thin ch s octan bng cc chuyn ha ho hc, ngoi tr mt qu trnh duy nht c th p dng, l ng phn ha, trong cc n-parafin c chuyn thnh cc isoparafin, lm tng ng k ch s octan. Vi cc phn on xng nng (Ts >80oC) giu parafin v naphten c th lm tng ch s octan nu chuyn ha chng thnh cc hydrocacbon thm (aromatics). y chnh l nguyn tc ca qu trnh reforming xc tc. Hm lng hydrocacbon thm c nh hng kh quan trng i vi ch s octan MON ca cc hp phn xng pha trn (Hnh 2).

MON

Hnh 2. Ph thuc ch s MON vo hm lng aromat ca cc xng hp phn 2. S cn thit ca qu trnh reforming xc tc cho sn xut xng C th nh ngha: Reforming xc tc l qu trnh lc du nhm chuyn ha phn on naphta nng c chng ct trc tip t du th hoc t mt s qu trnh ch bin th cp khc nh FCC, hidrocracking, visbreaking, c ch s octan thp (RON =30-50) thnh hp phn c s ca xng thng phm c ch s octan cao (RON =95-104). V mt bn cht ha hc y l qu trnh chuyn ha cc n-parafin v naphten c mt trong phn on thnh cc hydrocacbon thm. Chnh cc hydrocacbon thm vi ch s octan rt cao lm cho xng reforming c ch s octan cao ng hng u trong s cc xng thnh phn (Hnh 2). Thnh phn xng thng dng hin nay trn th gii thng cha: - Xng cracking xc tc (m ch yu l xng FCC) : 35% t.t - Xng reforming xc tc : 30% t.t - Xng alkyl ha : 20% t.t - Xng isomer ha : 15% t.t Xng Php c thnh phn a dng hn, trong hp phn alkyl ha thng t hn: - Xng FCC : 40% - Xng reforming xc tc : 33%
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- Xng isomer ha - Xng nhit phn

: 10% : 6%

- Xng alkyl ha : 5% - Butan : 4% - Hp cht cha oxy : 2% T cc s liu trn cho thy, xng reforming ng th 2 trong xng thng phm, ch sau xng cracking. Thm ch mt s khu vc nh M, Ty u, xng reformirng c phn vt tri (hnh 3,4).
United States

3% 10% 3% 5% 12%

Butane Isomerate FCC gasoline Polymerisation gasoline reformate

36% 1%

30%

Ether Alkylate HYC gasoline

Hnh 3. Phn b thnh phn xngthng mi M

Europe

5%

5%

5% 30%

Isomerate FCC gasoline Butane Reformate Ether

50%

5%

Alkylate

Hnh 4. Phn b thnh phn xng thng mi chu u

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Thnh phn sn phm ca qu trnh reforming v hiu sut thng dng nm trong khong: Reformat (C5+) C4 C3 Kh nhin liu C1-C2 Hidro Mt s tnh cht ca reformat: : 80-92% : 3-11% : 2-9% : 2-4% : 1,5 -3,5%

Thnh phn ct: thng thng t 35 190oC T trng: 0,76 0,78

- Ch s octan RON: 94 103 (tu thuc iu kin cng ngh) Do v tr quan trng ca xng reforming trong thnh phn xng thng phm, c bit l xng cht lng cao m hin nay trong mi nh my lc du trn th gii thng c ti thiu l mt phn xng reforming xc tc. Cng sut ch bin nm trong khong 40 tn/gi n 150 tn/gi. Tng cng sut ca cc phn xng reforming xc tc trong tt c cc nh my lc du Php ln ti 18 triu tn trong mt nm. Cu hi Bi 1: 1. Nu s cn thit phi s dng xng cht lng cao hin nay trn th gii. Cc gii php to xng cht lng cao. 2. nh ngha ch s octan RON, MON. nh hng cc nhm hydrocacbon n CSOCT. 3. Mc ch qu trnh reforming xc tc. Vai tr ca reforming xc tc trong nh my lc ha du. 4. Thnh phn c bn ca xng thng phm hin nay. V tr ca xng reforming trong xng thng phm. Nu v d.

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BI 2. BN CHT CA QU TRNH REFORMING XC TC M bi: HD F2

Gii thiu Reforming xc tc l mt qu trnh phc tp bao gm nhiu phn ng khc nhau xy ra ng thi. Hiu bit c bn cht ha hc ca qu trnh v cc yu t nh hng c th gip la chn iu kin thun li cho cc sn phm chnh v hn ch cc sn phm khng mong mun. Mc tiu thc hin Hc vin phi nm c bn cht ha hc ca qu trnh reforming xc tc. Phn bit c nhm cc sn phm chnh v sn phm ph. Hiu c nh hng ca cc yu t nhit ng hc v ng hc n c ch ca qu trnh reforming. Ni dung chnh Cc nhm phn ng chnh v phn ng ph ca qa trnh. Cc yu t ng hc v nhit ng hc nh hng n c ch qu trnh. nh hng ca c ch phn ng i vi s gia tng ch s octan

Nguyn liu ban u cho reforming ch yu l phn on naphta nng, c nhit si nm trong khong 80-180oC, cha nhiu parafin v naphten, di tc ng ca nhit cao (khong 480-540oC), xc tc a chc nng v mt p sut va phi (5 30 atm), c th xy ra cc hng chuyn ha c bn sau:

Chi tit hn, chng ta chia cc phn ng xy ra lm 2 nhm nh sau: 1. Nhm cc phn ng chnh Dehydro ha naphten thnh hydrocacbon thm:

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Dehydro ng vng ha parafin thnh hydrocacbon thm:

ng phn ha n-parafin thnh iso-parafin:

Dehydro ng phn ha naphten thnh hydroccbon thm:

Dehydro ha prafin thnh olefin: CH3-(CH2)4-CH 3 Pt CH3-CH=CH-CH2-CH2-CH3 Bn phn ng u tin ng vai tr quan trng hn c trong qu trnh reforming, lm tng ch s octan ca h nh cc sn phm thm v isoparafin. Phn ng th 5 xy ra yu trong iu kin reforming, nhng l phn ng cn thit v olefin c coi l hp cht trung gian trong qu trnh vng ha to cc sn phm thm. 2.Nhm cc phn ng ph: Hydrocracking parafin v naphten:

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Hydrodealkyl ha hydrocacbon thm:

Bt cn i ha:

Qu trnh cc ha: qu trnh trng ngng cc hyrocacbon thm a vng (sinh ra t cc qu trnh alkyl ha v ng vng ha) to cc sn phm rn giu cacbon, c th che ph ln xc tc. Qu trnh ny thun li nhit cao v p sut thp. Cc phn ng trn dn ti lm gim hiu sut sn phm reformat v hidrogen, lm tng im si cui ca reformat (do to cc hydrocacbon thm a vng, cc olefin mch di v bn thn cc) v lm gim hot tnh xc tc. Phn ng hydrocracking to nhit (H = -10 kcal/mol) v iu kin reforming thun li cho hydrocracking, mc d qu trnh xy ra chm. nhit cao phn ng xy ra p o so vi ng phn ha v dehydro ho parafin. Sn phm cracking ch yu l cc hydrocacbon nh C1 C5, mch thng v mch nhnh. V phng din no qu trnh ny thun li c th to thnh cc sn phm isoparafin c ch s octan cao hn so vi cc sn phm ca qu trnh ng phn ha trong iu kin reforming. V d, n-octan c ch s octan cc thp (<0), trong iu kin reforming ch cho ra hn hp cn bng ng phn C8 vi ch s octan = 35, trong lc hydrocracking C8 thnh isopentan v propan, cho ch s octan xp x 90 i vi hp phn C5. 3. C ch phn ng reforming v s tng ch s octan 3.1. nh hng nhit ng hc n c ch phn ng: Nhit phn ng ca mt s phn ng chnh trong qu trnh reforming c nu trong bng sau:

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Bng 1. Nhit phn ng ca mt s qu trnh Phn ng 1 2 3 4 5 Dehydro ha parafin Dehydro ha naphten Dehydro vng ha parafin ng phn ha parafin Hydrocracking H (Kcal/mol) 31,5 52,8 63,6 -1 -5 -10

Dehydro ha naphten v dehydro vng ha parafin l cc phn ng thu nhit mnh (endothermic), dehyro ha parafin thu nhit va phi, cn ng phn ha parafin to nhit nh (exothermic). Ba phn ng u xy ra thun nghch, c s gia tng s phn t trong sn phm phn ng (do hnh thnh H2), nn thun li nhit cao, p sut thp. Bng 2. Ph thuc nhit cn bng t chuyn ha 90% vo p sut Phn ng 1. Dehydro ha: Cyclohexan Benzene + 3H2 MethylCyclohexan Toluene + 3H2 2. Dehydro vng ha: n-Hexan Benzene + 4H2 n-Heptan Toluene + 4H2 3. Dehydro ng phn ho: MethylCyclopentane Benzene+ 3H2 Nhit cn bng chuyn ha 90%, oC 1 atm 294 315 354 305 315 10 atm 355 391 487 428 391 15 atm 443 492 562 496 492 50 atm 487 540 623 550 540

T bng 2, iu kin l thuyt thun li v p sut v nhit c th t chuyn ha 90% cho cc phn ng thm ha l 1atm v khng qu 350oC. Tuy nhin trong thc t ngi ta khng tin hnh qu trnh reforming iu kin trn, l do ti sao chng ta s xem xt tip theo trong phn ng hc. nh hng ca nhit v p sut n cn bng nhit ng gia parafin v aromatic t C6 n C9 c biu din trn hnh 5. T hnh 5 chng ta thy, nu tng p sut H2 ln qu cao (30atm) s lm gim hm lng cc hydrocacbon thm to thnh, c bit i vi cc hydocacbon c s C thp hn. Chng ta cng thy, i vi hydrocacbon no c
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trng lng phn t cng cao th hiu ng thun li ca nhit v p sut cng r rt. Ngha l trong cng mt iu kin, cc hydrocacbon mch di hn (c s nguyn t cacbon cao hn) s d chuyn ha thnh sn phm thm hn.
Xi 1.0 PH2 = 10 Bars
AR iP iP

PH2 = 30 Bars

AR

0.5

C6

nP

nP AR AR iP

1.0
iP NA nP

0.5

Maxi

C7

nP AR iP AR

1.0

0.5

iP nP nP AR AR iP nP 450 500T C 350 400 450 500T C

C8

Hnh 5. Cn bng nhit ng hc cc phn ng ca qu trnh reforming. (nh hng nhit , p sut)

1.0

0.5

C9

iP nP 350 400

3.2. ng hc v c ch phn ng: Trong bng 3 l vn tc tng i ca mt s phn ng chnh ca cc hydrocacbon C6-C7 trong qu trnh reforming ( iu kin khc nghit ha cao). Bng 3. Vn tc tng i ca cc chuyn ha hydrocacbon C6-C7 Phn ng ng phn ha Dehydro vng ha Dehydro ha Hydrocracking Parafin C6 10 1 3 C7 13 4 4 Naphten vng 5 cnh Naphten vng 6 cnh C6 10 C7 13 C6 100 C7 120 15

T bng 3 c th sp xp vn tc phn ng theo th t sau: Dehydro ha > ng phn ha > Hydrocracking > Dehydro vng ha Nghin cu nh hng nhit v p sut n tc cc phn ng khng mong mun l cc ha v cracking, ngi ta nhn thy: -Tc hnh thnh cc gim khi tng p sut H2 v gim nhit phn ng. -Tc cracking gim khi gim p sut H2 v gim nhit phn ng. Mt khc, nh phn nhit ng hc nu, vic tng p sut hoc lm gim nhit u nh hng khng thun li n qu trnh chnh to cc sn phm thm. V vy, trong thc t ngi ta cn c s la chn cc thng s vn hnh ti u tha mn c 2 yu t nhit ng hc v ng hc, ngha l bo m cho hiu sut cc phn ng thm ha cao ng thi hn ch cc sn phm cracking v cc ha (v d t 3-4% cc trn trng lng xc tc trong khong 612 thng). Trong cng ngh bn ti sinh ngi ta chn p sut vn hnh khong 10-20 atm, trong cng ngh CCR chn p sut t 3,5-4 atm v nhit phn ng l 500oC. 3.3. C ch phn ng v s gia tng ch s octan Nh trn nu, trong iu kin reforming, thun li cho cc phn ng chnh l dehydro ha naphten, dehydro ng vng ha parafin, dehydro ng phn ha naphten v ng phn ha parafin. Ba phn ng u to nn cc sn phm l hydrocacbon thm v phn ng cui cho sn phm l cc parafin mch nhnh. Chnh cc sn phm ny ng gp vai tr chnh lm cho ch s octan ca xng thu c sau qu trnh reforming (cn gi l reformat) tng ln rt nhiu so vi nguyn liu naphta ban u. RON nguyn liu = 40-60 RON sn phm = 95-105 Ty thuc vo hiu sut reformat thu c m ch s octan c th cao hn hay thp hn. V d, reforming vi cng ngh bn ti sinh cho hiu sut xng ~ 80% th RON t ~90, cng ngh ti sinh lin tc cho hiu sut reformat ~ 90% cho RON ~100. Cu hi Bi 2: 1. Nu bn cht ha hc ca qu trnh reforming xc tc. 2. Cc nhm phn ng chnh v cc nhm phn ng ph xy ra trong qu trnh reforming xc tc.
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3. Ti sao theo l thuyt qu trnh reforming xy ra thun li p sut thp nhng trong thc t cng nghip qu trnh li c vn hnh p sut tng i cao? 4. C ch phn ng reforming lin quan n s gia tng CSOCT nh th no?

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BI 3. XC TC LNG CHC NNG M bi: HD F3

Gii thiu Xc tc ng vai tr v cng quan trng trong cng ngh reforming. Hiu bit v xc tc reforming gip hon thin kin thc v cng ngh reforming. Mc tiu thc hin Hiu c vai tr ca xc tc lng chc nng i vi qu trnh reforming. Nm c cc phng php iu ch xc tc reforming lng chc nng. Xc nh c c trng ca xc tc iu ch bng cc phng php ha l hin i. Ni dung chnh Lch s pht trin xc tc reforming Vai tr ca xc tc lng chc nng i vi qu trnh reforming nh hng ca cc kim loi ph gia S mt hot tnh xc tc v s ti sinh xc tc Cc phng php iu ch xc tc. Cc phng php c trng xc tc

Mt s khi nim lin quan n tnh nng xc tc: Hot tnh xc tc: Kh nng ca cht xc tc nhm bo m tnh nng nhit thp nht c th. la chn: Kh nng cht xc tc to ra cc sn phm mong mun (trong trng hp qu trnh reforming l hydro v reformat). bn ( n nh): Kh nng ca cht xc tc c th lm vic lu theo thi gian gia 2 ln ti sinh lin k. phc hi: Kh nng cht xc tc lp li cc tnh nng ban u sau khi ti sinh.. 1. Lch s pht trin xc tc reforming Th h u tin ca xc tc reforming c ch to trn c s oxyt crom v oxyt molypen (10%) mang trn oxyt nhm. Loi xc tc ny c u im l kh

18

bn vi cc tp cht cha lu hunh, nhng cho hot tnh xc tc thp v reformat thu c c cht lng thp. Sau chin tranh th gii th hai vi s pht trin ca k ngh xe hi yu cu xng c cht lng cao, cng ngh reforming c nhng bc tin ng k, nht l trong lnh vc ci tin cht xc tc. T nhng nm 50, xut hin nhng th h xc tc mi l kim loi qu Pt mang trn oxyt nhm c b mt ring ln v tm thm Cl. So vi th h xc tc c th Pt hn hn v hot tnh xc tc, la chn phn ng thm ha nhng li d b u c (hnh 6).

Cui thp nin 60 th h xc tc th 3 ra i: cc xc tc lng kim loi. Bn cnh Pt ng vai tr chnh, ngi ta a thm kim loi th 2: Re, Ir, Ge, In, Sn...Vic a thm cc kim loi ny vo gip lm tng n nh ca xc tc v cng lm tng hot tnh xc tc theo hng tng cc sn phm thm, nh m p sut vn hnh cng gim ng k.Vic thay th mt phn Pt bng kim loi ph gia cn lm cho gi thnh xc tc gim v tit kim c mt phn Pt l kim loi qu v t tin. 2. Vai tr ca xc tc lng chc nng trong qu trnh reforming Xc tc reforming l xc tc lng chc nng do trong thnh phn ca n cha 2 pha c th thc hin 2 chc nng chnh sau: - Chc nng hydro-dehydro ha c thc hin bi cc kim loi dng phn tn.

19

- Chc nng axit nhm sp xp li cc mch cacbon (ng phn ha, ng vng ha...) c thc hin bi oxyt nhm c b mt ring ln v c clo ha iu chnh lc axit thch hp. Chc nng kim loi ng vai tr chnh, gip hnh thnh cc hp cht hydrocacbon khng no v dehydro ho cc naphten. Cn thit lp c s cn bng gia 2 chc nng c th c hot tnh xc tc cao v la chn tt. Nu xc tc qu axt s d xy ra cracking lm gim nhanh hot tnh xc tc. Trong cng nghip ngi ta lun kim tra hm lng Cl- a vo m bo cn bng trn lun n nh. S di y m t tng qut cc phn ng chnh xy ra trong qu trnh reforming vi s tham gia ca 2 loi tm xc tc:

3. Vai tr ca cc kim loi ph gia Nghin cu cc phn ng dehydro ha v dehydro ng vng ha cc hydrocacbon ring r nh cyclohexan, n-heptan... ngi ta thy vic a cc kim loi ph gia nh Re, Sn, Ir, Ge (cn gi l cc cht xc tin) lm tng tc phn ng dehydro ha v dehydro vng ha (nht l vng p sut thp) ca h xc tc lng kim so vi xc tc ch cha Pt (hnh 7 v hnh 8).

20

+ 3 H2
activity (mole/h/g) x 102 40 5 % coke

30

PtIr

PtRe 20 Pt 10 PtSn 0 0 5 10 15 20 pH2 (bar)

Hnh 7. nh hung ca kim loi th 2 n qu trnh dehydro ha Cyclohexan

vng p sut thp (5-10 bar), cc kim loi ph gia (Re, Sn) cng ng vai tr quan trng trong vic gim hydro phn (hydrogenolysis) v cracking (hnh 9 v hnh 10) t lm gim kh nng to cc v tng hiu sut sn phm chnh.

21

(n + i) C6
hydrogenolysis activity (Carbon converted wt %) 40

H2

C5350C WHSV = 2.5 h-1

30

PtRe (Re/Pt=2)

20

PtRe (Re/Pt=1)

10

Pt (0.40%)

PtSn 0 0 5 10 15

PtRe-S (Re/Pt=1) 20 25 pH2 (bar)

Hnh 9.nh hng ca cc kim loi ph gia n qu trnh hydro phn (hydrogenolysis)

Nu nh thp nin 70 ch khong 30% reformat thu c t h xc tc lng kim th n nhng nm 80 th phn ln ti 80%. Trong s cc h xc tc lng kim, chng ta thy hai h xc tc Pt-Sn v PtRe t ra u vit hn c, chng cho php lm vic p sut thp (<10 atm) m
22

vn bo m hot tnh dehydro ha v dehydro ng vng ha cao. Ring h xc tc Pt-Sn hi c bit, ch th hin hot tnh cao vng p sut thp. Ln hn 5 atm, h xc tc ny khng pht huy c tc dng tch cc so vi Pt v cc h lng kim khc trong phn ng dehydro v dehydro vng ha. Chng ta xem xt k hn v vai tr ca 2 kim loi ph gia c a vo xc tc reforming cng nghip hin nay l Re (Renium) v Sn (Thic). Ngi ta nhn thy Re c cc chc nng sau: - thay i c ch to cc v c tc dng bo v kim loi chnh Pt Lm tng bn v tui th xc tc, t lm tng chu k hot ng ca xc tc. Cn Sn th li c cc vai tr sau: Lin kt vi Pt lm thay i c ch phn ng theo hng c li. Cho hiu sut v la chn theo reformat cao iu kin p sut thp (< 5 atm). Tuy nhin loi xc tc ny km bn hn so vi xc tc cha Re.

Vi cc c im trn, ngi ta thng s dng Re trong cng ngh bn ti sinh v Sn trong cng ngh ti sinh lin tc (CCR).

Hnh 11. So snh c tnh xc tc ca 2 loi xc tc ca Php CR 201 (cha PtSn) v RG 482 (cha Pt-Re)
23

C th lit k mt s mc xc tc lng kim mi ca cc hng xc tc tn tui trn th gii: UOP (M): IFP (Php): Criterion (M): Exxon: Bn ti sinh: R-56, R-62, R-72 Ti sinh lin tc (CCR): R-132, R-134 Bn ti sinh: RG-102, RG-104, RG- 482 CCR: CR- 201 Bn ti sinh: PR- 8, PR- 28 CCR: PS- 20, PS- 40 KX-120, KX-130, KX-190, KX-200

Amoco: PHF-5, PRHP-30, PRHP-35, PRHP-50, PRHP-58 Engelhard (M): RD- 150, E- 501, E- 601 IMP (Mexico): RNA- 1, RNA- 2, RNA- 4, RNA- 4M Lin x (c): A- 56, A- 64, KP-108, KP-110 4. S mt hot tnh v ti sinh xc tc 4.1. nh hng u c xc tc Cc cht xc tc reforming rt nhy vi cc tp cht c trong nguyn liu v kh tun hon (H2, N2). nh hng u c c th l thun nghch v khng thun nghch. nh hng thun nghch Nu sau khi cht c thi tc dng, bng bin php x l c bit (qu trnh ti sinh xc tc), b mt v tnh cht xc tc c phc hi tr li. nh hng khng thun nghch (vnh vin) B mt v tnh cht xc tc khng th khi phc li c. 4.1.1. Cc cht u c thun nghch a. Nc v cc hp cht cha oxy: Nc tc dng vi clo c trong xc tc lm gim tnh axit ca xc tc:

T dn ti lm gim hot tnh xc tc. Cc hp cht cha oxy th li d dng to thnh nc trong iu kin reforming. Cn bng H2O/Cl cn c quan
24

tm gi axit n nh cho xc tc. vic a thm Cl vo h trong qu trnh vn hnh l cn thit. Ngoi ra nc cn gy n mn thit b. C th s b loi b nc bng cch cho qua cc ct hp ph cha ry phn t (zeolit 5A). Lng nc cho php trong nguyn liu ti a l 4 ppm. b. Hp cht cha lu hunh: trong iu kin reforming s d dng chuyn ha thnh H2S, u c chc nng kim loi do hnh thnh sulfua platin.

T , chc nng quan trng nht ca xc tc l dehydro, dehydro ng vng ha b u c. Trong s cc hp cht cha lu hunh th mecaptan (R-S-H) v H2S c nh hng u c ln hn c, lm gim hiu sut v cht lng reformat, lm tng t trng kh cha hydro, tng mc lng ng cc. H2S c tnh axit nn cn gy n mn thit b. Hm lng cho php: 0,5 ppm. c. Cc hp cht cha nit: Cc hp cht nit hu c d dng chuyn ha thnh amoniac trong iu kin reforming. Cht ny s tc dng vi Cl trong xc tc to NH4Cl, lm gim chc nng axit ca cht xc tc, ko theo s gim hot tnh xc tc, lm tng s hnh thnh hydro. NH4Cl li d bay hi trong vng phn ng lm tng nhit thit b. Mt khc, NH4Cl d kt tinh nhng phn lnh hn ca h thng, gy h hng thit b:

25

4.1.2. Cc cht u c khng thun nghch Cc kim loi kim v kim th lm trung ha tnh axit ca cht mang (Al2O3), to thnh hp cht aluminat kh bn. Cc kim loi As, Cu, Pb, Zn, Hg, Si, Fe kt hp vi Pt to mi lin kt bn, u c vnh vin tm kim loi khng phc hi li c.T d lm mt chc nng chnh l hydo- dehydro ho ca xc tc. Cc kim loi ny cn tch t trong c 4 l phn ng, lm gim nhit vng phn ng, dn ti mt hot tnh xc tc tng th. Hm lng cho php i vi mi kim loi: ti a 5 ppb. bo v hu hiu cc cht xc tc reforming bin php bt buc v hiu qu trong cng ngh l phi c phn xng x l s b nguyn liu bng hydro (hydrotreating) nhm loi b cc cht c thun nghch v khng thun nghch trn, nht l trong trng hp c s dng nguyn liu t cc ngun ch bin th cp khc (hydrocracking, FCC, visbreaking...) c hm lng ng k cc cht u c trn so vi nguyn liu naphta t ngun du th. 4.2. Qu trnh ti sinh xc tc 4.2.1. Cc phng php hot ha (ti sinh) xc tc: Trong qu trnh lm vic xc tc c th b mt mt phn hot tnh xc tc do nh hng ca s lng ng cc trn b mt xc tc, do nh hng ca cc cht u c... Mt iu cn lu l, chng ta cng c gng la chn iu kin vn hnh cho hiu sut xng cao nht hoc ch s octan tt nht (v d, tng nhit hoc gim p sut) th s lng ng cc cng tr nn trm trng hn (xem phn c trng ng hc ca qu trnh reforming). Vi mt lng cc qu
26

ln, s che ph v lm gim ng k s lng cc tm hot ng. Lc , tu thuc vo cu to cht xc tc, s mt i mt phn hoc ton b cc chc nng xc tc. Cn thit phi c qu trnh ti sinh xc tc tr v trng thi hot ng ban u. Qu trnh ny c th c tin hnh bng mt s phng php sau: a. Phng php oxy ha (phng php t) Cc lng ng trn b mt cht xc tc c loi b bng cch t chy trong dng khng kh pha long vi Nit nhit 350 500oC. cn ch trnh hin tng qu nhit cc b lm gim b mt, gim bn c hc c a cht mang hoc lm tng qu trnh thiu kt lm gim phn tn kim loi. Chu k ti sinh xc tc ph thuc vo iu kin vn hnh h thng, nhng thng khong 6 thng mt ln. Sau mi ln ti sinh, hot tnh xc tc tr v trng thi ban u, nhng sau nhiu chu k ti sinh xc tc s gi ha v gim kh nng xc tc. Vic ti sinh xc tc s tr nn thng xuyn hn., cho n khi cn phi thay th xc tc mi. Thi gian tn ti ca xc tc reforming thng khong vi nm. Qu trnh t cc c biu din bng phong trnh sau: CnHm + O2 CO2 + H2O + Q y l qu trnh ta nhit, nhng khi nh hng n cht lng xc tc cn gim thiu lng nhit ta ra (T 0oC). iu ny cn thit v: nhit cao lm gim din tch b mt v c th lm thay i pha ca oxyt nhm Al2O3, nhit cao cng lm xy ra qu trnh thiu kt lm gim phn tn ca Pt. Trong cng ngh CCR (ti sinh xc tc lin tc) qu trnh oxy ha c thc hin trong vng t (Burn Zone). b. Phng php kh Thc t cho thy, cc hp cht lu hunh khng c loi b hon ton bng qu trnh oxy ha, cn tn ti ch yu cc hp cht dng sunfat. Phng php kh c tin hnh nhm loi b trit cc dng hp cht ny v.cc kim loi tp c hi trong xc tc, quan trng hn c l kh Pt oxyt v dng Pt n cht. Trong cng ngh CCR, qu trnh kh xy ra ti vng kh (Reduction Zone). c. Phng php clo ha

27

Trong qu trnh lm vic axit ca xc tc gim, mt phn do cc lng ng che ph b mt oxit nhm, mt phn do lng clo trong xc tc gim do nh hng ca H2O trong nguyn liu v trong kh tun hon. Clo cng c th mt do cun theo sn phm phn ng. Do cn phi b sung axit cho h xc tc bng cch bm thm mt lng nh Cl hu c. Lng Cl trn xc tc c gi mc 1% khi lng. 4.2.2. Qui trnh ti sinh xc tc Qui trnh ti sinh hon chnh cht xc tc gm cc bc sau: 1. Trng ra h thng: Dng dng nit thi sch cc hydrocacbon cn st li sau phn ng. 2. t cc: t bng dng khng kh pha long vi N 2 (c kim sot hm lng oxy trong kh) v nng dn nhit t theo chng trnh: -Nhit : t 370oC n 480oC -Oxy: t 0,5 n 2,0 % th tch 3. Oxy-clo ha: Bm cc tc nhn cha Cl vo h nhm gi n nh lng Cl cn thit cho xc tc (1% trng lng). -Nhit : 510oC -Oxy: 5% th tch 4. Qu trnh nung: Mc ch lm kh xc tc v phn tn li platin -Nhit : 510oC -Lng oxy: 8% th tch -Thi gian: 4 gi 5. Qu trnh kh: chuyn Pt t dng b oxit ha v dng kh (dng hot ng). Loi oxy bng cch trng vi nit. Sau a hydro vo h. -Nhit : 480oC -Hm lng H2: ti thiu 50% th tch -Thi gian: 4 gi 5. iu ch xc tc reforming C th hnh dung tng th thnh phn cu to xc tc reforming hin i vi cc chc nng ca cc thnh phn qua s di y:

28

Nh trn nu, xc tc reforming bao gm 2 hp phn chnh: + Oxit nhm (dng ) c chc nng axit, to thun li cho cc qu trnh ng phn ha, ng vng ha, cracking, ng thi ng vai tr cht mang, do c b mt ring ln n gip tng ti a din tch b mt ca pha hot tnh. Lc axit ca cht mang c iu chnh bng ion Cl c a vo trong qu trnh iu ch xc tc v a thm trong qu trnh vn hnh xc tc. + Pt (hoc a phn l Pt kt hp vi mt s cht xc tin nh Re, Ir, Sn, Ge...) ng vai tr pha kim loi (pha hot tnh), thc y cc qu trnh dehydro ha parafin, naphten, hidro phn, cc ha.. m bo vai tr cht mang, oxyt nhm cn c cc tnh cht sau: - Hm lng tp cht cho php: Na < 50 ppm Fe < 200 - Cu to: T trng ht 1.1 g/cm3 180-220 m2/g Tng th tch l xp 0.60 cm3/g - Tnh cht c hc: T trng nhi 0.6-0.7 g/cm3 B mt ring Kch thc ht 1-2 mm
29

Lc nghin nt

> 1 MPa

ng thi phi thun tin cho vic nh v pha kim loi v khng thay i tnh cht trong thi gian s dng. Oxyt nhm c th c ch to bng cc phng php to ht bng thit b to ht dng a (Pan granulation), phng php p n (Extrusion) v phng php to git trong du (Oil drop). Pha kim loi (Pt v cc kim loi ph gia) thng c mang ln cht mang bng phng php tm: thng dng dung dch mui [PtCl6]2- rt y ln cht mang, quay u, sau dung mi c tch ra khi cht mang bng phng php bay hi. Nh vy trn b mt cht mang to cc vi tinh th mui platin, sau khi kh trong dng H2 s to c cc ht Pt ring r. Cc phn ng xy ra trong qu trnh tm:

Trong cng nghip, ngi ta iu ch xc tc reforming theo cc bc sau (hnh 12): -a Cl- vo h

30

Hnh 12. Cc bc iu ch xc tc reforming trong cng nghip

Hnh 13. M hnh thit b tm trong cng nghip a kim loi ln cht mang
31

(a)

(b)

(c)

Hnh 14. Cc phng php to ht oxyt nhm trong cng nghip Trn hnh 13 gii thiu m hnh phng php tm kim loi hot tnh ln cht mang. Hnh 14 m t 3 phng php thng dng to ht cho cht mang ca xc tc reforming: to ht trn thit b dng a (a), to ht ri trong du (b), n vin (c). 6. Nghin cu cc c trng ca xc tc reforming 6.1. Xc nh b mt xc tc bng phng php hp ph vt l Nhm so snh cc cht xc tc khc nhau hoc nh gi nh hng qu trnh x l n tnh cht xc tc, ngi ta thng xc nh thng s b mt ca cht xc tc rn. Nguyn tc ca phng php o b mt tng ca cht xc tc l o hp ph vt l cc phn t kh hoc lng ln b mt xc tc.
32

Theo Emmet v Brunauer, nu hp ph kh bi lc Van Der Waals ti nhit si ca kh (hp ph vt l) ta s c, p sut tng i cao, hp ph a phn t v ngng t mao qun. Hin nay phng trnh BET, c xy dng trn c s hp ph a phn t, tuy cn phi t ra mt s gi thit, nhng c coi nh mt phng php tiu chun nh gi b mt ring ca cht xc tc. Phng trnh BET c ng dng thc t dng:

Vi P-p sut cn bng ca kh hp ph Po-p sut hi bo ha ca kh b hp ph V- th tch b hp ph p sut P Vm-th tch b hp ph ca mt lp n phn t C-H s c nh ph thuc vo nng lng hp ph y l dng phng trnh tuyn tnh vi: 1 / Vm.C l tung v C -1 / Vm.C l h s gc. T c th d dng tnh c Vm. B mt ring xc nh theo phng trnh BET l tch s ca s phn t b hp ph nhn vi b mt ct ca mt phn t b hp ph chim ch trn b mt cht rn. Ngi ta thng dng nit lm cht b hp ph xc nh b mt ring. Lc ta c phng trnh n gin: SBET = 4,3.Vm Phng trnh BET c th p dng xc nh b mt ring ca tt c cc cht rn, vi iu kin p sut tng i (P/Po) nm trong khong 0,05 n 0,3 v hng s C >1. 6.2. Xc nh phn tn kim loi bng phng php hp ph ho hc Xc tc thng cha pha kim loi hot ng mang trn cht mang th ng (v d, xc tc reforming thng cha Pt kim loi mang trn oxyt nhm). Tng hm lng kim loi hot ng a ln cht mang c xc nh trong qu trnh iu ch xc tc. Tuy nhin, trong qu trnh nung, x l xc tc hoc qu trnh phn ng thng xy ra nhit cao, lm cho mt s tm kim loi hot ng tr nn khng thun li hoc mt hot tnh i vi phn t cht phn ng, do chng di
33

chuyn vo trong th tch cht mang hoc thiu kt to nn cc phn t ln hn.... T dn ti lm gim b mt ring hot ng. Rt cn thit phi nh lng s tm hot ng hu dng thc t v chng lin quan n tnh nng ca cht xc tc ni chung v hiu qu hot ng xc tc. phn tn-T l cc tm kim loi hot ng, thun li cho tc nhn phn ng trn tng s lng cc tm hot ng.

phn tn cao lm tng hot tnh ca cht xc tc. Cc cht mang c b mt ring ln (xc nh bng phng php hp ph vt l) cho php iu ch cc cht xc tc vi phn tn cao hn. Ngi ta thng dng phng php hp ph ha hc xc nh phn tn ca kim loi. Hp ph ha hc c phn bit vi hp ph vt l bi nhit hp ph (hp ph ha hc ta nhit mnh, nhit hp ph c th ln ti 500 kcal/mol) v c thc hin vi cc kh hp ph nh H2, CO... nhit cao hn so vi hp ph vt l (thng nhit phng), tu thuc i lc ca kh i vi kim loi v bc phn ly t lng. T phng trnh ng nhit hp ph ha hc Langmuir ngi ta c th tnh c s lng cc tm kim loi hot ng hu dng Ns, t xc nh c phn tn. Phng trnh Langmuir:

Vi N-S lng cc tm b chim bi phn t kh b hp ph Ns-Tng s lng cc tm hu dng b-H s, ph thuc vo H v T Va-Th tch b hp ph Vm-Th tch hp ph lp n Ns c th nhn c t th ph thuc P/N = f (P)
34

Ngoi ra ngi ta cn c th s dng phng php ph hng ngoi xc nh phn tn ca kim loi. Ngi ta bit kh CO d to phc vi hu ht cc kim loi chuyn tip vi cc dng lin kt khc nhau. Tn dng c im ny, ngi ta cho CO hp ph ln tm kim loi ca xc tc v tin hnh o ph hng ngoi ca CO, s tnh c s lng phn t CO hp ph v tm c cc dng lin kt khc nhau gia kim loi v CO. T c th xc nh c phn tn ca kim loi. V d, ngi ta c cc s liu IR trn bng sau, khi cho CO hp ph ln cc kim loi khc nhau: Kim loi Pt Cht mang SiO2 di bc sng (cm-1) 2075 1850 Lin kt Pt =C =O Pt C=O Pt Pd SiO2 2050 1900 1830 Pd Ni SiO2 2030 1905 Ni =C =O Ni C=O Ni Pd =C =O Pd C=O

6.3. o phn b kch thc ht bng phng php nhiu x tia X (phng php Rn ghen) Phng php nhiu x tia X cho php xc nh b rng ca cc vch nhiu x ca cc ht nh hn 50 nm (do khi chiu tia nhiu x cc vch ny b dn rng), t c th tnh ton kch thc trung bnh ca ht theo phng trnh Sherrer: Bc = Kc. /d. cos (Bc- rng ca vch, Kc-hng s = 0,893, - di sng, d-kch thc tinh th, -gc Bragg).
35

T ngi ta c th xc nh c s phn b kch thc ht. Tuy nhin phng php ny khng nhy vi cc ht 5 nm v vch b dn qu ln. 6.4. Xc nh trng thi ha tr ca kim loi bng phng php rn ghen. Xc tc d th thng c hnh thnh t mt hay nhiu pha kim loi trn cht mang. V d, xc tc reforming c th dng n kim loi Ni/Al2O3, hoc cha ng thi Ni v Rh mang trn oxyt nhm. Bng phng php nhiu x tia X, ngi ta xc nh c xc tc n kim loi (Ni) cha 2 pha: Ni kim loi v dng spinel lin kt vi cht mang NiAl2O4. pha sau t c hot tnh xc tc so vi pha u. Ngi ta cng thy trn xc tc lng kim Ni-Ru/Al2O3, ngoi cc pha oxyt kim loi ring r, cn c s to thnh hp kim dng Ni-Rh trn xc tc lng kim, v dng ny c hot ng xc tc. Cu hi Bi 3: 1. Th no l xc tc a chc nng. Nu v d trong trng hp xc tc reforming. 2. Vai tr ca kim loi ph gia trong xc tc lng kim. Gii thch vai tr c th ca Re v Sn trong cng ngh bn ti sinh v cng ngh CCR. 3. Phn bit u c xc tc thun nghch v khng thun nghch. Cho v d trong trng hp xc tc reforming. 4. Ti sinh xc tc nhm mc ch g. Cc bin php ti sinh xc tc reforming trong cng nghip. 5. Hy nu s tng qut iu ch xc tc reforming trong cng nghip. 6. Lit k v nu nguyn tc cc phng php nghin cu c trng xc tc reforming.

36

BI 4. NGUYN LIU V CC SN PHM THU M bi: HD F4

Gii thiu Hiu bit v nguyn liu v cc sn phm ca qu trnh reforming gip la chn iu kin vn hnh thch hp vi cc nh hng sn phm c th ca cng ngh reforming trong tng nh my lc du. Mc tiu thc hin Nm c c im v nguyn liu ca qu trnh. nh hng ca thnh phn, tnh cht nguyn liu n qu trnh. Nm c cc sn phm thu c t qu trnh reforming, hng ng dng. Nm c nh hng cc thng s vn hnh (nhit , p sut, t t H2/ HC tc np liu) n hiu sut, cht lng sn phm chnh. Ni dung chnh Nguyn liu ca qu trnh Cc yu t nh hng n qu trnh reforming xc tc Sn phm ca qu trnh reforming xc tc 1. Nguyn liu ca qu trnh Xut x: Xng t chng ct trc tip Xng t qu trnh Visbreaking, Hydrocracking Phn on gia ca sn phm FCC Thnh phn: Hn hp hydrocarbon t C7 n C11 (trong trng hp nh my khng c phn xng isomerisation c th s dng P C5 n C11) Tnh cht: Khong chng ct: T trng: Trng lng phn t trung bnh: 100-110 RON: 40-60 Thnh phn nhm: paraffin: 40-60 wt%
37

60-180C 0.7-0.8 g/cm3

olefin: naphtene: -

0 wt% 20-30 wt%

aromatic: 10-15 wt% Hm lng tp cht: cn thit phi lm

Xc tc rt nhy vi cc cht c c trong nguyn liu

sch nguyn liu (dng cc cng ngh lm sch HDS, HDN, HDM) Gii hn tp cht cho php trong nguyn liu (sau khi lm sch): S < 1ppm N (hu c) 1 ppm H2O (v cc hp cht cha oxy) 4 ppm Kim loi (As, Cu, Pb...) 15 ppb Olefin v cc diolefin = 0 Halogen (F) 1 ppm 1.1.Gii hn nhit chng ct ca nguyn liu: V nguyn tc ngi ta c th s dng phn on naphta t 60 180oC tin hnh qu trnh reforming. Nhng ngy nay ngi ta thng s dng cc phn on c gii hn si u 80oC lm nguyn liu. Gii hn si u uc thit lp nh vy nhm loi bt cc hp phn C6 d chuyn ha thnh benzen l mt hp cht c hi, cn tin ti loi b theo tiu chun mi v mi trng. Cc hnh 15, 16 cho thy nh hng la chn nhit si u n hiu sut reformat, cht lng reformat (th hin qua ch s RON) v n hm lng benzen to thnh.

38

Hnh 16. nh hng nhit si u n hm lng benzen v ch s Octan. Gii hn si cui ca nguyn liu thng c chn trong khong 1650C 180oC. Gii hn si cui ca nguyn liu khng nn cao qu 180oC v xng reforming cha nhiu hydrocacbon thm, c nhit si ln hn nguyn liu khong 20oC. M gii hn si cui ca xng thnh phm (cha t 40-50% reformat) theo tiu chun th gii ch cho php n 200 205oC. Ngoi ra nu im si cui ca nguyn liu qu cao s dn ti qu trnh cc ha cc hydrocacbon nng, lm gim hot tnh xc tc. nh hng chiu di mch cacbon (lin quan n im si cui ca nguyn liu) n chuyn ha naphten t thy r v phn ng xy ra nhanh. i vi parafin, chiu di mch cng tng (trng lng phn t cng cao) th qu trnh dehydro vng ho cng thun li. Tuy nhin mch cacbon cng cng d gy hn do cracking. (hnh 17).

39

Hnh 17. nh hng s nguyn t C n qu trnh dehydro vng ha parafin v cracking. 1.2. Thnh phn hydrocacbon ca nguyn liu Nh trong bi 2 trnh by, phn ng dehydro ha naphten thnh hp cht thm xy ra d dng, vi vn tc ln hn nhiu so vi phn ng dehydro vng ha parafin thnh hp cht thm. Nh vy, nguyn liu cng giu parafin cng kh chuyn ha thnh reformat so vi nguyn liu giu naphten. C th m t nh tnh s chuyn ha trn 2 phn on nh trn hnh 18. V vy, t uc cht lng sn phm mong mun (v d, vi RON nh trc) nguyn liu giu parafin i hi nhit phn ng cao hn (tng khc nghit ha ca qu trnh).

Hnh 18. Ph thuc thnh phn sn phm vo tnh cht nguyn liu
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Trong cng nghip ngi ta thng nh gi kh nng chuyn ha ca nguyn liu thnh sn phm thm da vo gi tr N + 2A (N, A-% trng lng ca naphten v aromat tng ng c trong nguyn liu). Gi tr ny cng cao th kh nng thm ha cng ln, khc nghit ca qu trnh vn hnh cng gim. Ch s N+2A bin thin trong khong 30- 80. Hng UOP (M) c a ra h s KUOP c lin quan n ch s N+2A theo cng thc sau: KUOP = 12,6 (N+2A)/100. Trn bng 4 gii thiu mt s nguyn liu tiu biu ca du th th gii thng c la chn cho qu trnh reforming xc tc. Bng 4. Thnh phn v tnh cht ca mt s nguyn liu reforming Naphta trung bnh t hydrocrackin g ASDTM D86, oC IBP 10% 30% 50% 70% 90% FBP Thnh phn,% V Parafin Naphten Aromatic N+2A RON d415 98 115 127 140 157 180 201 33 55 12 79 62 0,775 Naphta Trung ng Naphta giu parafin ( rp) Naphta giu naphten (Nigeria) 88 107 115 123 132 145 161 29,3 61,9 8,8 79,6 66 0,779

81 105 113 119 129 143 166 45 45 10 65 55 0,754

92 106 115 123 132 147 155 66,8 21,8 11,4 44,6 50 0,716

Tu thuc vo tnh cht du th m cc phn on nguyn liu ny cng rt khc nhau v thnh phn v tnh cht. V d, du th nhiu parafin cho ch s octan ca nguyn liu v ch s N+ 2A thp hn nhiu so vi du naphten.

41

Vi mc ch sn xut BTX cho ha du th vic la chn ngun nguyn liu v gii hn im ct phn on ng vai tr quan trng. thu tng BTX ngi ta thng chn phn on 60- 145oC. Nu ch thu benzen chn P 65-85oC. Thu toluen chn P 85-120oC. Thu xylen chn P 120-145oC. 1.3. Hm lng tp cht trong nguyn liu: Cc hp cht khng phi hydrocacbon, nht l cc hp cht cha lu hunh v nit cn gim ti gii hn cho php. Gii hn cho php cc tp cht: S: 0,5 ppm , N (hu c): 1 ppm H2O (v cc HC cha oxy): 4 ppm, As: 5 ppb Olefin: khng c c , diolefin: khng c c Kim loi: 5 ppb , halogen (F,Cl): 1 ppm 1.4. X l s b nguyn liu reforming: Trong cng nghip y l khu cn thit v bt buc, nhm mc ch sau: - Loi tr cc cht u c xc tc reforming (hp cht S, N, nc, cc kim loi) - iu chnh im ct nguyn liu ph hp C th tm tt cc bc x l s b nguyn liu nh sau: Cho nguyn liu v hidro i qua l phn ng c cha xc tc NiMo(hoc CoMo) nhm loi tr cc kim loi, cc hp cht cha lu

hunh v hp cht cha nit (gi chung l cc qu trnh x l dng hidro). - Trong trng hp nguyn liu l cc phn on xng cracking cn thm giai on x l lm no ha olefin nhm loi tr kh nng to nha. - Tip theo cho nguyn liu qua ct tch loi H2S v nc. - Trong nhiu trng hp, cn tch phn on xng nh (a vo phn xng isomer C5/C6) ra khi phn on xng nng (dng cho reforming xc tc). 2. Cc yu t nh hng n qu trnh reforming xc tc - Nhit thit b phn ng - p sut thit b phn ng - Tc np liu - T l mol H2/ nguyn liu
42

- Cht lng nguyn liu 2.1. nh hng nhit Trong cng nghip ng nht vic nh gi hot tnh xc tc vi nhit c cung cp u vo thit b phn ng (i vi nguyn liu c th, RON cho trc). Nhit c th thay i nhm iu chnh cht lng sn phm, v d: Thay i ch s octan ca reformat Ph thuc cht lng ca nguyn liu np B tr s gi ha xc tc (gim hot tnh xc tc) qua nhiu chu k hot ng

- B tr mt hot tnh xc tc tm thi do cc tp cht gy ra. Nhit tng lm tng kh nng chuyn ha thnh sn phm thm dn ti tng ch s octan nhng li lm gim hiu sut xng. Ngc li nhit gim c li cho hiu sut xng, gim kh, gim hiu sut to cc. Nhit thng c chn trong cng ngh: 490-540oC 2.2. Tc np liu (tc th tch hoc tc khi lng) c xc nh bng lu lng dng nguyn liu (th tch hoc trng lng) i qua trong 1 gi trn 1 n v xc tc (trng lng hoc th tch lp xc tc). Khi tng lu lng nguyn liu hay gim lng xc tc u lm tng tc np liu, ni cch khc l lm gim thi gian tip xc ca cc cht tham gia phn ng vi lp xc tc. Hu qu dn ti lm tng hiu sut reformat (do gim kh), nhng ng thi lm gim cht lung reformat v gim ch s octan. iu ny cng d hiu v cc qu trnh c tc chm nh dehydro ng vng to thm, hydrocracking, dealkyl ha s kh xy ra hn nu thi gian tip xc t. Hiu ng ny c th c b tr nu tng nhit l phn ng. Trong thc t, hn ch bt hyrdrocracking v cc sn phn cc ha ngi ta thng p dng nguyn tc sau: - gim tc th tch: gim nhit u vo cc l phn ng sau gim lu lng liu np. - tng tc th tch: tng lu lng liu np sau tng nhit l phn ng. C th gim tc th tch tng ch s octan. Tuy nhin trong vn hnh ngi ta khng c php gim tc trn nh hn mt na so vi thit k
43

hoc < 0,75 h-1. V nh vy s khng kinh t, lm tng tc kh hot tnh xc tc. Tc c la chn ph thuc vo cc iu kin cng ngh c th: p sut vn hnh, t l mol H2/ nguyn liu, thnh phn nguyn liu a vo v cht lng reformat mong mun. V d cng ngh CCR mi thng chn V = 1,5 -2,5 h-1. 2.3. p sut vn hnh Cc phn ng chnh c li cho reforming u xy ra thun li p sut thp. p sut cng thp hiu sut reformat v hidro cng cao. Tuy nhin nh hng cc s cng trm trng hn. Do cn la chn p sut thch hp va hn ch qu trnh to cc va t nh hng n hiu sut to xng. p sut vn hnh i vi mt phn xng cng ngh c th l gi tr c nh m ngi ta la chn trc nhm tho mn cht lng sn phm nht nh. Ngy nay nh ci tin cng ngh (s dng cng ngh ti sinh lin tc) v ci tin xc tc (tm c cc h xc tc c th lm vic p sut thp, cho hiu sut xng v RON cao) m ngi ta c th vn hnh qu trnh p sut thp nht m vn p ng yu cu v cht lng sn phm, vn u t v hiu qu kinh t. Cng ngh CCR tin tin nht (PLATFORMING, OCTANIZING) s dng xc tc Pt-Sn/ Al2O3 cho php vn hnh p sut t 3-5 atm (trc y cn vi chc atm) 2.4. T l H2/ nguyn liu Xc nh bng t l gia lu lng (mol/h) hydro tun hon v lu lng nguyn liu np (mol/h). Thm mt lng ln kh tun hon cha H2 (80-90% tl) nhm lm gim s lng ng ca cc trn b mt xc tc (do tng qu trnh hydro ha cc hp cht khng no trung gian l tin cht to cc). T l H2/NL thay i trong khong rng (1-10). Gii hn di ph thuc lng H2 yu cu nh nht nhm duy tr p sut ring phn ca H2 trong h thng. Gii hn trn xc nh bi cng sut my nn, kch thc l phn ng v tnh kinh t qu trnh. Thay i t l ny t lm thay i cht lng sn phm. Mt khc vi cc cng ngh CCR hin nay p sut thc hin ch >3 atm, gim t l H2/NL trong trng hp ny tng ng vi vic lm

44

gim p sut ring phn ca H2 nn c tc ng thun li n hiu sut sn phm. V d cng ngh OCTANIZING vn hnh vi t l H2/NL =1-4, ty thuc loi nguyn liu v gi tr RON yu cu. C th tm tt nh hng cc thng s vn hnh (p sut, nhit , tc khi, t l H2 / nguyn liu, tnh cht nguyn liu) n hiu sut v cht lng sn phm nh bng 5. Bng 5. nh hng cc thng s vn hnh n hiu sut v cht lng sn phm S gia tng cc thng s p sut (atm) Nhit (oC) Tc khi (h-1) H2 / nguyn liu 0,85N +A Nguyn im si u liu im si cui 3. Sn phm ca qu trnh reforming xc tc C th m t mi tng quan gia nguyn liu v sn phm ca qu trnh reforming xc tc theo gin sau:
Reformat RON > 95 Naphtha 40<RON<60
CATALYTIC REFORMING

RON reformat

Hiu sut reformat

Hm lng cc

Aromatics BTX Hydrogen

Nh vy, t naphta nng ban u vi ch s octan thp sau khi tin hnhreforming xc tc, ngi ta thu c cc sn phm vi hiu sut sau: Reformat (xng C5+): 80-92% C4: 3-11%
45

C3:

2-9%

Kh nhin liu C1-C2: 2-4% Hidro: 1,5 -3,5% Trong cc sn phm quan trng hn c l reformat (xng C5+), cc hydrocacbon thm-m ch yu l benzen, toluen, xylen (BTX) v kh hydro k thut. 3.1. Sn phm xng reforming xc tc Mt s tnh cht ca xng (reformat): - Thnh phn ct: thng thng t 35 190oC - T trng: 0,76 0,78 - Ch s octan RON: 94 103 - Thnh phn hydrocacbon: ch yu l aromatic v parafin, naphten ch chim < 10%, olefin khng ng k. Do c cht lng cao (ch s octan cao nht trong s cc xng thnh phn , thu c t qu trnh lc du), hm lng olefin li rt thp nn xng reforming c th s dng lm xng my bay. S thay i thnh phn v tnh cht ca xng reformat trong cc gii hn nu trn ph thuc vo nguyn liu ban u, iu kin cng ngh, cht xc tc. V d tng quan gia nguyn liu l naptha Trung ng v sn phm reforming trnh by trong bng 6. Thnh phn parafin trong nguyn liu kh nh hng n cht lng xng C5+. Bng 6. So snh Nguyn liu Sn phm reforming t du th Trung ng ASTM D86 d415 IBP Nguyn liu 0,754 Sn phm C5+ 0,701 81 60 10 % 105 93 50 % 119 118 90 % 143 152 FB P 166 185 Thnh phn, %V P N A N+2A 65 115 RON 55 95

45 45 10 40 5 55

Nu ch s dng ton b reformat lm xng thng phm s khng kinh t, do hm lng hydrocacbon thm qu cao, to nhiu cn trong ng c v gy nhim mi trng. Xng ny li c p sut hi bo ha thp, lm cho ng c

46

kh khi ng. Chnh v vy ngi ta a vo xng thng phm cc hp phn khc nh xng ng phn ha, xng alkylat, butan, MTBE... 3.2. Cc sn phm kh: hydro v cc kh nh 3.2.1. Kh giu hydro y l sn phm kh quan trng ca qu trnh reforming xc tc. Hm lng hydro trong kh chim 70 90%. Thnh phn nguyn liu, cht xc tc v iu kin cng ngh cng nh hng n hm lng hydro trong kh. Kh ny mt phn c s dng li cho qu trnh reforming, cn phn ln c s dng cho cc qu trnh lm sch bng hydro (HDS, HDN, HDM...) hoc cc qu trnh chuyn ha c hydro (hydrocraking, hydroisomer ha). y l ngun thu hydro kh r, hiu sut cao (thu c khong 90 120 Nm3/ m3 nguyn liu) v c th lm sch tu mc ch s dng. Vic ci tin cng ngh, xc tc cho qu trnh reforming nhm lm tng hiu sut xng th cng ko theo s gia tng hm lng H2 trong sn phm v thc y thm s pht trin cc qu trnh s dng hydro. 3.2.2. Kh ho lng LPG Kh ha lng thu c sau khi cho sn phm i qua thp n nh xng, bao gm ch yu propan v butan. Hiu sut kh ph thuc vo tnh cht ca cht xc tc m trc tin l axit. y l sn phm khng mong mun trong iu kin reforming, v s lm gim hiu sut ca sn phm chnh l reformat. 3.3. Sn phm hydrocacbon thm Qu trnh reforming cn cung cp ngun nguyn liu BTX (benzen-toluenxylen) cho ha du. Cc sn phm thm trong qu trnh ny chim ti 65-75% trong tng sn phm lng hoc c th cao hn na vi cc cng ngh v xc tc hin i. Trong c bit quan trng l paraxylen-nguyn liu cho sn xut cht do, si tng hp, cao su nhn to, nguyn liu cho cng nghip dc phm, m phm, thuc nhum Cu hi Bi 4: 1. Ngun nguyn liu cho qu trnh reforming xc tc. c im chung v thnh phn v tnh cht nguyn liu. Ti sao ngy nay ngi ta thng s dng cc phn on si c gii hn si u 80oC lm nguyn liu? 2. Thnh phn v tnh cht nguyn liu nh hng th no n hiu sut v
47

cht lng sn phm? Trong CN ngi ta thng da vo i lng no nh gi kh nng chuyn ha thnh sn phm thm ca nguyn liu? 3. Cc loi sn phm chnh thu c t qu trnh reforming xc tc? 4. Cc thng s vn hnh (nhit , p sut, tc np liu, t l H2/NL) nh hng nh th no n hiu sut v cht lng sn phm?

48

BI 5. CC LOI CNG NGH REFORMING XC TC

M bi: HD F5 Gii thiu Mc ch bi ny nhm gip hc vin tip cn vi nhng cng ngh reformimg thng dng v tin tin nht trn th gii hin nay. Mc tiu thc hin Nm c cc c im v thit b, xc tc, iu kin vn hnh v cht lng sn phm ca 2 loi cng ngh reforming xc tc hin nay. So snh u, nhc im ca cng ngh bn ti sinh v cng ngh ti sinh lin tc xc tc. Bit cch vn hnh s reforming xc tc qui m phng th nghim, nm c phng php phn tch sn phm v cch tnh ton kt qu thc nghim. Ni dung chnh Cng ngh bn ti sinh xc tc Cng ngh ti sinh xc tc lin tc c im thit b xc tc trong cng ngh ti sinh lin tc nh gi hiu qu kinh t ca qu trnh reforming xc tc Cng ngh reforming s dng cho mc ch ha du (sn xut BTX) Vn hnh s reforming qui m phng th nghim

Hin nay trn th gii tn ti 2 loi cng ngh reforming ch yu: cng ngh bn ti sinh v cng ngh ti sinh lin tc (CCR). 1. Cng ngh bn ti sinh Mt s c im c bn: Lp xc tc c nh H thng dng nguyn liu c chuyn ng t thit b phn ng ny sang thit b phn ng khc. Ngng hot ng ton b h thng ti sinh cht xc tc ti ch, ngay trong thit b phn ng, khi lng cc trn lp xc tc chim 15-20% trng lng. Thng th chu k lm vic ca xc tc trong khong 6 thng n 1 nm. 49

Thi gian ti sinh xc tc mt khong 2 tun l. Trong mt s cng ngh bn ti sinh ngi ta s dng cc thit b phn ng (reactor) c cc van ng m c lp, hoc lp thm mt thit b phn ng d tr, cho php ti sinh xc tc tng thit b ring bit m khng cn dng ton b h thng. Tuy nhin vn hnh cng ngh cng tr nn phc tp hn. Cng ngh bn ti sinh tng i lu i (cng ngh truyn thng), cc ci tin ch yu ch tp trung vo xc tc. T nhng nm 1949-1950 cht xc tc trn c s Pt (xc tc n kim loi) c a vo s dng cho xc tc tng c nh. Loi xc tc ny tuy cho hot tnh xc tc cao, nhng c nhc im l rt d b cc ha nn phi vn hnh trong iu kin p sut hidro kh cao (xp x 40 atm). Khong nhng nm 60, mt s kim loi ph gia c a thm vo h xc tc Pt (xc tc lng kim), khc phc tnh trng gim nhanh hot tnh xc tc. Cht xc tc tr nn bn hn vi qu trnh cc ha, gip qu trnh cng ngh c vn hnh p sut thp hn (khong t 15 n 30 atm). S n gin ca cng ngh bn ti sinh c trnh by trn hnh 19. M t hot ng ca s Nguyn liu (phn on naphta nng) c lm sch t qu trnh hydro ha, c trn vi kh hydro t my nn, sau khi qua cc thit b trao i nhit c dn ln lt vo cc l phn ng (c th t 3-4 l) c cha lp xc tc c nh. Cc sn phm c to thnh sau khi ra khi h thng phn ng, qua thit b trao i nhit, thit b t nng v thit b lm lnh. Qua thit b ngng t, sn phm lng gi li, kh khng ngng c s a vo thit b tch kh . Phn ln kh c nn li nh my nn kh v tun hon tr li l phn ng. Phn kh cn li c dn sang b phn tch kh. Hydro c tch ra t y c th c s dng cho cc qu trnh lm sch dng hydro. Phn lng tch ra c a vo thp n nh, thc cht l mt thp chng ct vi mc ch tch phnnh (LPG) nhm tng n nh ca xng v gim p sut hi bo ha.

50

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LPG tch ra c a vo thit b ngng t. Xng sn phm ra y thp, mt phn c un nng v hi lu tr li thp n nh, phn ln c lm lnh v a vo b cha. Cng ngh bn ti sinh hin nay vn cn rt thnh hnh Php v mt s nc khc. V d, Vin du m Php ((IFP) lp t c 600 phn xng bn ti sinh trn th gii so vi 120 phn xng CCR. 2. Cng ngh ti sinh lin tc (continuous regenerative-vit tt CCR) c im: Lp xc tc c chuyn dng nh nhng, lin tc trong h thng thit b phn ng vi vn tc va phi (trong khong 3- 10 ngy).

Ton b h thng c vn hnh lin tc. Lp xc tc sau khi ra khi h thng phn ng c a ra ngoi ti sinh trong mt h thng ti sinh ring. Sau c quay tr li h thng phn ng. Cu to mt l phn ng dng ng thng vi lp xc tc chuyn ng dng trong cng ngh CCR c m t trn hnh 20.

Hnh 20. Cu to theo mt ct dc l phn ng reforming xc tc

52

61

Kch thc l phn ng thay i trong khong: ng knh 1,5 3,5 m, Chiu cao 4 12 m, Th tch lp xc tc: 6 80 m3. Chi tit hn chng ta thy cm h thng thit b phn ng bao gm 3-4 l phn ng c kch thc, iu kin vn hnh, lng xc tc np vo khng ging nhau, t phn b thnh phn sn phm ra t mi l cng khng ging nhau (hnh 21). H thng cu to t nhiu l phn ng gip cho dng hn hp nguyn liu v kh giu hidro (kh tun hon) t c nhit phn ng v b tr nhit nng t cc phn ng ha hc xy ra trong qu trnh reforming. Nhit gim nhanh trong l th nht do s xut hin ca cc phn ng thu nhit quan trng (ch yu l phn ng dehydro ha naphten), lng xc tc tiu th cho giai on ny chim 10-15% trng lng. l phn ng th 2 nhit gim t hn, lng xc tc tiu th chim 20-30%. Ti l phn ng cui cng, nhit gn nh n nh do c s b tr nhit gia cc phn ng thu nhit nh vi cc phn ng ta nhit kiu nh hydrocracking

Hnh 21. S thay i thng s vn hnh v phn b sn phm theo v tr l Phn ng

53

Hin nay c 2 kiu lp t h thng phn ng trong s cng ngh CCR (hnh 22 v hnh 23): 1. S cng ngh PLATFORMING ca UOP (M): Thit b phn ng c xp chng ln nhau. Xc tc i t trn xung qua h thng thit b phn ng, sau tp trung li v c nng ln thit b ti sinh nh kh nng. Sau khi ti sinh, cht xc tc c a tr li thit b phn ng th nht. Nh c ly ra tng phn v ti sinh lin tc m hot tnh xc tc n nh cao hn so vi trong trng hp lp xc tc c nh (cng ngh bn ti sinh). Cng ngh ny hin nay c s dng ph bin hn c (chim 70% th phn cng ngh CCR trn th gii). Tuy nhin cng c nhc im l vn hnh kh khn do chiu cao h thng thit b phn ng (hnh 22). 2. S cng ngh OCTANIZING ca IFP (Php): H thng thit b phn ng c sp xp theo hng ngang. Tuy khc phc c nhc im v chiu cao nhng li tn din tch xy dng v ng ng dn ln dn n tng gi thnh xy dng v chi ph vn hnh cao (hnh 23). Ngoi ra c th k n cng ngh ti sinh lin tc POWERFORMING (Anh) v cng ngh hn hp DUALFORMING (Php), trong kt hp 2 h thng bn ti sinh v ti sinh lin tc vi 2 loi xc tc khc nhau. Phn xng reforming xc tc ca nh my lc du s 1 Dung qut Vit nam c lp t theo cng ngh Platforming ca UOP (M). Phn xng ny c nhim v cung cp hp phn pha xng (reformat) cht lng cao v p ng mt phn nguyn liu (BTX) cho ha du.

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3. c im ca thit b xc tc chuyn ng v ti sinh lin tc So vi qu trnh bn ti sinh (semiregenerative) hoc ti sinh tun hon (cyclic regenerative)-trong ln lt tng thit b phn ng c th dng ti sinh xc tc m khng nh hng n vn hnh chung ca h thng, th qu trnh ti sinh lin tc cho hiu sut reformat (xng C5+) lun n nh theo thi gian (hnh 24).

Hnh 24. S tng quan gia c th cng ngh v hiu sut sn phm reformat.

57

S khc bit v cc c trng k thut (p sut vn hnh, t l H2 /nguyn liu, loi xc tc, chu k ti sinh xc tc) v hiu sut, cht lng sn phm gia 2 cng ngh bn ti sinh v ti sinh lin tc c trnh by trn bng 7 v hnh 25. Cng ngh ti sinh lin tc t ra u vit hn v hiu sut v cht lng sn phm v vn hnh p sut thp hn. Xu hng cng ngh hin nay trn th gii thin v s dng cng ngh reforming ti sinh xc tc lin tc vi p sut thp nht.Tuy nhin cng ngh ny cng c hn ch l chu k hot ng ngn hn do phi ti sinh xc tc lin tc, i hi chi ph nng lng v chi ph u t cao hn. Bng 7. So snh cc c trng cng ngh v cht lng sn phm gia 2 cng ngh bn ti sinh v ti sinh lin tuc Bn ti sinh p sut (bar) H2/HC (mol) Xc tc Chu k hot ng C5+ (wt %) H2 (wt %) RON MON 12-25 5-7 Pt-Re 6-15 thng 75-84 1.5-2 % 95-98 85-88 Ti sinh lin tc 3 -10 1.5-4 Pt-Sn 3-10 ngy 85-92 2-3.6 % 100-102 90-92

58

H2/HC (mol/mol) 9 8 7

Semi-Reg

Pt
6
Semi-Reg

5
CCR

4 3 2 1 0

Pt - Sn
3

Pt - Re

10

15

20

25

30

35 P (bar)

Hnh 25. Tng quan gia cc c trng cng ngh v cht xc tc gia 2 cng ngh bn ti sinh v ti sinh lin tc. 4. nh gi hiu qu kinh t ca qu trnh reforming xc tc: Di y phn tch cc s liu kinh t ca mt cm CCR (cng ngh Php) vi cng sut 25.000 thng/ ngy: Cn bng vt cht nguyn liu sn phm: Thnh phn (kg/gi) H2 C1 C2 C3 IC4 nC4 C5+ Tng Nguyn liu 121.850 121.850 Kh giu H2 4.604 917 1.208 869 288 253 309 8.448 Sau khi lm sch h thng 26 54 241 161 35 20 27 564 LPG 4 242 1.285 840 634 115 3.020 Reformat 55 1.043 108.720 109.818

* Tng gi tr sn phm tng ng 200 triu Franc trong 1 nm Chi ph vn hnh:

59

Tiu hao nhin liu: 6 tn /gi Hi nc p sut cao: 18 tn/gi Tiu th in nng: 1700 kwh/gi Cht xc tc: 16 tn/nm Tng chi ph hng nm: 32 triu Franc /nm u t: Thit b: 500 triu Franc Platin (xc tc): 20 triu Franc Thi gian thu hi vn: Vn u t thu hi sau khong 3 nm. 5. Cng ngh reforming s dng cho mc ch ha du (sn xut BTX): Cc sn phm thm Benzen Toluen Xylen, m c bit l p Xylen c nhiu ng dng quan trng trong cng nghip ha du. T qu trnh reforming xc tc c th thu c khong 80% BTX. V nguyn tc, cc cng ngh reforming xc tc u c th s dng cho sn xut BTX. Hin nay xu hng chnh l dng cng ngh CCR sn xut BTX v ch to mt s cht xc tc c hiu nhm lm tng la chn theo BTX (c bit xc tin qu trnh dehydro vng ha parafin). V d IFP c cng ngh AROMIZING vi cc xc tc h AR-401, AR- 405. Criterion c cc xc tc PS-20, PS-40. Vi mc ch sn xut BTX th vic la chn ngun nguyn liu v gii hn khong nhit chng ct ng vai tr quan trng. V d: sn xut tng BTX chn P 60 145oC, nhm mc ch thu benzen chn 65 85oC, thu toluen chn 85 120oC, thu xylen chn P 120 145oC. 6. Cng ngh reforming vi gii php kh Benzen trong xng: Benzen hin nay c bit n nh mt tc nhn rt c hi, gy ung th cho con ngi. Hin nay cc nc tin tin khng ch hm lng benzen trong xng thng phm xung < 1%. Vi mc ch sn xut xng th vic loi tr hp phn benzen ra khi thnh phn sn phm reformat l iu m cc nh cng ngh hin nay rt quan tm n. loi tr ti a benzen ra khi nguyn liu, ngi ta nng im si u ca nguyn liu ln 85oC. Tuy nhin benzen vn lun l sn phm ca qu trnh dehydro ha naphten cha 6 cacbon v dealkyl ha cc hydrocacbon thm mch di hn. Yu cu v khc nghit ha ca cng ngh cng cao (th hin qua yu cu cao v RON) th hm lng
60

benzen trong sn phm to thnh cng nhiu hn. Cc nh cng ngh ngh mt s gii php sau y cho vic gim thiu hm lng benzen trong sn phm: Loi tr benzen v cc tin cht to benzen (cc naphten cha 6 C), bng cch tch xng nh ra khi nguyn liu reforming. Sau a vo s dng cho cm ng phn ha. Ti y benzen c no ha trc khi vo h thng ng phn ha. Cch ny c th lm gim bt 1 ch s RON ca xng reforming nhng kh c th lm gim benzen xung mc 1% theo tiu chun mi trng. Cch th 2 l lp thm mt ct ct pha sau loi tr cc reformat nh (cha benzen sn phm) v hydro ha benzen thnh hydrocacbon no. Cch ny c th gip gim benzen xung 1%, tuy nhin lm mt 1,5 ch s RON. 7. Vn hnh s reforming qui m phng th nghim: tin hnh qu trnh reforming xc tc iu kin gn vi cng nghip, ngha l trong iu kin p sut hidro, c th s dng m hnh thc nghim c lp t ti Trung tm nghin cu v pht trin Ch bin Du kh (xem hnh 26). 7.1. Cu to s : S gm 3 phn chnh: a. B phn np liu: Bnh cha nguyn liu lng v bm nh lng chu p vi chnh xc cao. My pht H2 v b o tc dng H2 cung cp cho h thng duy tr p sut v phc v cho mc ch kh xc tc sau khi lm vic. H thng kh (khng kh, nit) cho mc ch ti sinh xc tc v trng ra h thng. b. B phn phn ng: L gia nhit c h thng iu khin t ng nhit vi n nh nhit cao (T = 2oC). Bnh phn ng chu p sut (4 atm) l ni din ra cc qu trnh phn ng. Bnh cu to hnh ch U nhm lm tng thi gian tip xc ca dng nguyn liu vi vng nhit phn ng trc khi dn vo lp xc tc. c. B phn ngng, tch sn phm v ly mu phn tch: Cc h thng sinh hn, bnh ngng v cyclon tch lng kh. Cc b phn ly mu lng, kh em phn tch.
61

7.2. Qui trnh vn hnh: Nh bm vi lng c chnh xc cao dng nguyn liu c a vo bnh phn ng vi cc tc n nh. C th thay i tc (khi lng) np liu bng cch thay i tc dng nguyn liu hoc thay i khi lng cht xc tc. Dng kh hidro vi tc v p sut n nh c pha trn vi nguyn liu trc khi a vo h thng phn ng. Ti y xy ra qu trnh phn ng, cc sn phm lng v kh c to thnh. Phn ng c kho st vi cc nhit nm trong khong 450 520oC. Sau khi ra khi bnh phn ng, sn phm lng c ngng li nh h thng sinh hn, bnh ngng v c ly i phn tch. Sn phm kh qua h thng o lu lng kh thot ra ngoi v ly i phn tch. 7.3. Phng php phn tch thnh phn nguyn liu v sn phm: Thnh phn nguyn liu v sn phm c xc nh bng phng php sc k kh. My sc k kh hiu HP 6890 Plus (M) vi phn mm chuyn dng AC/DHA (dng cho phn tch cc sn phm du m) cho php xc nh chnh xc thnh phn (%tl, %tt, % mol) v tnh ton mt s tnh cht khc ca h nh ch s octan RON, trng lng phn t trung bnh, t trng... Cc iu kin phn tch nh sau: Kh mang: He Detect: Ion ha ngn la FID

- Ct: HP-1, 100 m x 250 m x 0,5 m - Nhit detect: 280oC, Nhit bung bm mu: 250oC - Lng mu bm: 0,5 l, t l chia dng 1/100 M t phn mm AC DHA: a) Phm vi ng dng: - Chng trnh AC DHA dng xc nh thnh phn hydrocacbon ca cc hn hp hydrocarbon nh nh: naptha, reformate, alkylate, xng cracking, condensate vi khong si ln n 225oC - C th c dng nhn bit v phn tch chnh xc vi cc cu t c hm lng t 0,01-30% khi lng. - C th ng dng cho cc hydrocarbon lng cha olefin nh hn 25% khi lng, c bit l cc phn on nh ca sn phm cracking xc tc. b) Nguyn tc s dng phn mm nhn danh AC-DHA:
62

- Nhn danh cc cu t - Tnh ch s index cho mi peak sc k - So snh vi bng tham kho Quy trnh t ng xc nh cc thnh phn: i vi mi peak sau khi tnh ch s, phn mm s t ng tm trong file tham kho cho vng nhn danh m ch s index nm trong . Tip theo l i chiu peak vi tn cu t. Chng trnh phn mm sau s t sp xp, a ra bng bo co nhn danh cc cu t theo nhm ha hc. D liu tnh tan cho mi peak bao gm: thi gian lu, ch s index, % din tch tng ng vi % khi lng (% th tch, % mol). C th biu din thnh s khi nh sau:

c) Tnh ton cc thng s vt l da trn kt qa sc k kh: Xc nh trc tip tc qu trnh tnh tan cc thng s vt l nh t trng, khi lng phn t trung bnh, p sut hi da vo thnh phn % cc cu t c trong mu. Phng php ny c li im l nhanh, cn lng mu t, kh chnh xc, c th so snh vi cc phng php tiu chun. Xc nh gin tip tc vic xc nh cc thng s vt l nh RON v MON c thc hin thng qua phng trnh tan hc. RON = A + kiCI
63

A, kI: hng s xc nh bng thc nghim CI: % khi lng. 7.4. X l kt qu thc nghim Cc s liu sc k kh c trnh by di dng cc bng kt qu reforming, ph thuc vo s thay i cc thng s nh nhit phn ng, tc np liu, t l H2/nguyn liu. T c th nh gi v hiu sut reformat, chn lc theo sn phm thm v ngh cc iu kin vn hnh ti u ca qu trnh cho mt loi nguyn liu v mt loi xc tc c th. V d, trn bng 8 trnh by kt qu reforming phn on nguyn liu 85165 C ca du th Bch h, nhit phn ng 500oC, xc tc R-134 (M) trn
o

s PTN Trung tm NC&PTCB Du kh: Bng 8. Hiu sut v thnh phn sn phm reforming P 85-165oC t du th BH. % khi lng . Hiu sut sn phm kh . Hiu sut reformat C5+ Trong : Tng aromat Tng naphten Tng parafin Tng olefin RON (tnh ton) Cu hi bi 5: 1. c im ca cng ngh reforming bn ti sinh xc tc. V s , m t hot ng ca qu trnh. 2. Trnh by c im, m t s n gin cng ngh ti sinh lin tc xc tc reforming CCR. 3. So snh s khc bit gia 2 cng ngh bn ti sinh v ti sinh lin tc. 4. c im ca cng ngh reforming s dng cho mc ch ha du. 5. V 1 s reforming qui m phng th nghim. M t qui trnh vn hnh v nu phng php phn tch thnh phn v sn phm qu trnh. 74,9 3,4 18,4 3,3 102 16,0 84,0

64

65

BI 6. S TIN B CA REFORMING XC TC M bi HD F6
Gii thiu Bi ny gip hc vin thy c ngha ca vic ci tin cng ngh, xc tc i vi vic nng cao cht lng sn phm mong mun v p ng yu cu kht khe hn v mi trng. Mc tiu thc hin Nm c cc ci tin ca cng ngh reforming trong thi gian qua. Cc nh hng ci tin trong tng lai v cc yu t rng buc. Ni dung chnh Cc ci tin t c trong thi gian qua ca cng ngh reforming (thay i v xc tc, thit b cng ngh, iu kin vn hnh) Xu hng ci tin trong tng lai v cc iu kin rng buc (th phn sn phm, yu t mi trng, hng pht trin ha du)

Cng ngh reforming tri qua nhiu thp nin pht trin c ci tin theo cc hng sau: - Gim p sut vn hnh lm tng hiu sut reformat v hydrogen. - Tm ra cc loi xc tc mi bn hn, c tui th cao hn (t b tc ng cc ha trong iu kin gim p sut), v c la chn theo sn phm thm cao hn. - Thay i s cng ngh trong xc tc c tun hon v c ti sinh lin tc. S ci tin cng ngh v xc tc reforming nh trn dn ti s tin b ng k v cht lng sn phm reforming (bng 9). Bng 9. S tin b v cht lng sn phm reforming Sn phm, (%tl) H2 C1 + C 2 C3 + C 4 C5+ (reformat)
66

1960 2,0 4,4 13,1 80,5

1970 2,7 3,1 10,4 83,8

1980 3,2 1,2 8,0 87,6

1990 3,3 1,1 6,9 88,7

1998 3,8 88,0

RON Yu cu xc tc

RON = l tng:

100-102 H2 = 5%, C5+ = 95%

Vi nhng tiu chun nghim ngt mi v mi trng, vic loi b hon ton hp phn ph gia ch c trong xng m vn phi bo m cht lng xng thng phm (ch s octan cao) cng cho thy vai tr quan trng ca reforming trong cng nghp lc du. Cc s liu mi nht v thnh phn xng thng phm th gii c trnh by trn bng 10. Bng 10. Thnh phn xng thng phm th gii Thnh phn, %tl - Butan - Xng nhit phn - Xng nh - Xng ng phn ha - Xng alkyl ha - Xng FCC - Xng reforming - Hp cht cha oxy (MTBE, etanol) Bng 10 cho thy M, Php hp phn xng reforming trong xng thng phm ch thua km khng ng k so vi xng cracking, cn Ty u, xng reforming chim phn p o (phn na th phn). Trong nhiu trng hp, thu c xng thng phm khng ch RON 95 v RON 98 ngi ta a vo hp phn xng reforming ln ti 60%-80%. Php 4,0 6,0 10,0 5,0 40,0 33,0 2,0 M 5,5 4,0 4,7 13,0 36,1 34,6 2,1 Ty u 5,7 7,6 5,0 5,9 27,1 46,9 1,8

67

Xng khng ch RON 98

Xng khng ch RON 95

Hnh 27. Thnh phn mt s loi xng thng phm cao cp khng ch Trong tng lai sp ti, ngi ta s phi tip tc ci tin cng ngh reforming hn na nhm tho mn cc yu cu cao hn v cht lng sn
68

phm. Tuy nhin cc khuynh hng ci tin v pht trin cng ngh cn ph thuc vo nhiu yu t: - Khuynh hng th trng xng du - Khuynh hng cht lng xng: yu cu v ch s octan, yu cu gim thnh phn thm (c bit benzen, t 2005 nhiu nc khng ch thp hn 0,5%), xu hng s dng nhin liu hn hp (xng, alcol tng hp) cho ch s octan siu cao. - S thay i phn b th phn cc sn phm du m theo xu hng tng lng sn phm nh. Mt s hp phn xng t cc qu trnh cc ha, cracking, visbreaking s c a vo reformat trc khi pha trn - Kh nng pht trin cng ngh reforming theo hng ha du (to ngun hydrocacbon thm). Cu hi Bi 6: 1. Nu cc tin b v cng ngh reforming xc tc hin nay. 2. Khuynh hng ci tin v pht trin cng ngh reforming trong tng lai ph thuc vo cc yu t no ?

69

BI 7. C IM CA XNG REFORMING XC TC
M bi: HD F7 Gii thiu Xng reforming l sn phm ch yu ca qu trnh reforming v l mt trong nhng hp phn quan trng nht pha xng thng phm. V vy hiu bit k v cc c im ca xng reforming l cn thit i vi hc vin. Mc tiu thc hin Nm c cc c im v thnh phn ha hc v tnh cht ca xng reforming. Nm c cc gii php nhm lm tng cht lng xng reforming Ni dung chnh Thnh phn ha hc ca xng reforming xc tc Ch s octan ca xng reforming xc tc Tnh cht ca xng reforming xc tc nh hng ca tin b v cng ngh, thit b v xc tc n cht lng xng reforming ngy nay. 1. Thnh phn ha hc ca xng reforming xc tc Xng reforming xc tc c thnh phn ha hc ch yu l cc hydrocacbon thm v cc parafin, hm lng naphten chim di 10%, olefin hu nh khng ng k (0-2%). Nh trn nu, thnh phn v cht lng ca reformat (xng C5+) ph thuc vo nguyn liu ban u, cht xc tc, qui trnh cng ngh. C th tham kho bng di y (bng 11) thy nh hng thnh phn parafin ca nguyn liu n thnh phn ha hc v tnh cht ca xng. Bng 11. nh hng nguyn liu n cht lng xng reforming Thnh phn v tnh cht xng T trng d 420 Hm lng parafin trong nguyn liu (%tl) > 65% 0,785 0,735 0,796 <40% 0,772

70

Thnh phn ct, oC: Nhit si u 10% tt 50% tt 90% tt Nhit si cui Thnh %tl: phn hydrocacbon, 59,0 38,8 2,2 80,0 89,0 65,4 33,7 0,9 85,0 95,5 62,0 37 1,0 80,0 89,0 68,5 31,1 0,5 85,0 95,5 49 82 135 172 202 42 76 137 170 214 58 97 141 171 199 58 110 141 168 205

aromatic Parafin+ naphten olefin Ch s octan: MON RON

Bng 11 cho thy, khi xng thu c c cng ch s octan, nguyn liu t parafin s cho xng c thnh phn ct nng hn so vi nguyn liu nhiu parafin. Cc kt qu kho st phn nguyn liu (trang 34, hnh 18) cng cho thy nguyn liu giu naphten (t parafin) s cho xng giu aromat hn, ngha l xng c cht lng cao hn so vi nguyn liu giu parafin. Cho n nay, phng php hu hiu nht xc nh thnh phn ha hc ca xng reforming vn l sc k kh. Vi s ci tin khng ngng v k thut sc k kh (h thng t ng ha, iu khin in t, cc loi ct mao qun c tch cao....) kt hp s dng cc phn mm chuyn dng cho phn tch sn phm du kh, lm cho vic xc nh thnh phn sn phm reforming tr nn d dng v chnh xc hn nhiu so vi trc y. C th k n h thng sc k kh HP-6890 ca hng Agilent (M) kt hp vi phn mm phn tch chuyn dng AC DHAca hng AC (M) t ti Trung tm nghin cu v pht trin ch bin Du kh ( c m t trong phn S thc nghim reforming) nh mt v d v loi thit b phn tch cao cp, p ng yu cu phn tch thnh phn xng reformat. 2. Tr s octan ca xng reforming xc tc

71

Thnh phn hydrocacbon thm cao ng vai tr quyt nh n ch s octan cao ca xng reforming. Ch s RON ca reformat thu c nm trong khong 95 -103, tu thuc nguyn liu ban u v khc nghit ha ca iu kin vn hnh. Trong cc cng ngh reforming xc tc hin i RON thng t 100-103. Tuy nhin, s phn b khng ng u ca ch s octan theo cc im ct phn on xng, do hydrocacbon thm tp trung ch yu cc phn on si cao, nn ngi ta thng pha thm cc hp phn si nh, c ch s octan cao thu c t cc qu trnh ch bin khc, ci thin nhc im ny. Tr s octan ca xng reforming xc tc ni ring, cng nh tr s octan ca xng thng phm v cc xng thnh phn khc u c xc nh theo 2 phng php tiu chun l: phng php nghin cu (Research Method ASTM D 2699) o ch s RON v phng php m t (Motor Method ASTM D 2700). C hai phng php ny nhm o kh nng chng kch n ca xng t. i vi mt loi ng c nht nh, vn hnh trong iu kin n nh th kh nng chng kch n ch ph thuc duy nht vo cht lng nhin liu (xng) m thi. RON v MON ch khc nhau c bn s vng quay ca m t th nghim (600 vng/ pht i vi RON v 900 vng /pht i vi MON). i vi cc phn on sn phm du m, MON thng thp hn RON vi n v. Ngi ta cng thng quan tm n hiu s gia gi tr RON v MON nhy cm (Gasoline Sensitivity). i lng ny lin quan n bn cht ha hc ca xng v xng c nhy cm thp s cho hiu qu s dng tt hn khi dng cho t. Trn bng 12 so snh tng i s khc bit v t trng, ch s RON v nhy cm gia cc nhm hydrocacbon. Xt theo nhy th xng reforming do nhiu hydrocacbon aromatic s khng t hiu sut cao nh cc loi xng c thnh phn parafin cao, nn ngi ta thng phi pha thm cc xng khc giu i-parafin nh xng ng phn ha, alkyl ha... Bng 12. Tng quan tng i ch s octan vo cu trc nhm hydrocacbon Tnh cht n-Parafin T trng lng ch s octan RON nhy RON- MON thp rt thp rt thp i- Parafin thp cao rt thp Hydrocacbon Naphten trung bnh trung bnh thp Aromatic cao rt cao cao Olefin thp cao rt cao

72

 xc nh ch s octan, ngoi phng php tiu chun nu trn, phc v cho mc ch nghin cu hoc trong cc phng k thut nh my lc du nhm mc ch s b nh hng thnh phn octan trong pha trn xng, ngi ta cn s dng cc phng php sc k kh, ph hng ngoi. Tuy cha c cng nhn l phng php tiu chun nh gi ch tiu k thut ca xng v t nhy vi xng pha ph gia, nhng cc phng php ny c nhng li im nh phn tch nhanh, lng mu cn rt t, chnh xc chp nhn c nn hin nay thng c s dng cho cc mc ch nu trn. 3. Cc tnh cht ca xng reforming xc tc Ngoi ch s octan, ngi ta cn quan tm n cc c im k thut sau y ca xng reforming: - Khong chng ct theo ASTM D 86: im si cui: gii hn cc i l o 205 C (do gii hn qui nh im si cui ca xng thng phm). im si u: nm trong khong 35-60oC, nhng thng l 50 60oC (do mc ch reforming hin nay nhm chuyn ha cc hp phn >C6 trong nguyn liu vi Tsd>80oC). - T trng ring: Nm trong khong 0,760-0,780. c trng ny thng cao do thnh phn hydroccbon trong sn phm cao (>50%) - p sut hi bo ho RVP: Gii hn trn khng vt qu 30 kPa - Hm lng olefin: Lin quan n tnh n nh ca xng, khng ch < 2%tt. Hin nay trong nhiu cng ngh reforming hu nh loi tr olefin trong sn phm xng - Hm lng benzen: Do tnh c hi ca benzen i vi mi trng m benzen cn gim thiu trong xng reforming. Loi tr benzen bng cc gii php: tng nhit si u ca nguyn liu ln >80oC, s b tch benzen v cyclohexan ra khi sn phm. Cng ngh CCR vi xc tc Pt Sn khng ch benzen trong xng khong 2%tl. 4. nh hng ca tin b v cng ngh, thit b v xc tc n cht lng ca xng reforming xc tc ngy nay Nh trn nu, vic a cc h xc tc lng kim loi, m i din l cc h xc tc Pt-Re / Al2O3, Pt-Sn / Al2O3, gip tng bn v tui th ca cht xc tc, t tng chu k hot ng ca cht xc tc (trng hp Re) hoc gip
73

lm tng hiu sut reformat v la chn theo sn phm thm (trng hp Sn) tc l lm tng cht lng ca xng reforming. Vic a cc h xc tc lng kim mi cng lm gim p sut vn hnh ca thit b, gim t l kh H2 tun hon. Cc ci tin v cng ngh, c bit l vic a cng ngh ti sinh lin tc CCR, trong lp xc tc chuyn ng v c ti sinh lin tc, gip hot tnh xc tc c n nh mc cao, t n nh hiu sut v tng cht lng xng reforming. u im ca cng ngh ti sinh lin tc so vi cng ngh bn ti sinh c th hin rt r qua cc c im di y: Bn ti sinh p sut (bar) H2/HC (mol) C5+ (wt %) H2 (wt %) RON MON 12-25 5-7 75-84 1.5-2 % 95-98 85-88 Ti sinh lin tc 3 -10 1.5-4 85-92 2-3.6 % 100-102 90-92

Tuy nhin cng ngh ny cng rt ngn chu k hot ng ca xc tc, do xc tc lm vic p sut thp s to thnh cc tr nn mnh m hn, cn c chu k ti sinh lin tc hn. Cu hi Bi 7 1. Thnh phn hydrocacbon trong xng nh hng th no i vi thnh phn v tnh cht ca xng thng phm ? 2. Cho bit phng php ch yu phn tch thnh phn xng reforming. 3. Ch s octan (CSOCT) ca xng reforming nm trong khong no ? c im no cn lu i vi CSOCT RON, MON ca xng reforming. Cc phng php xc nh. 4. Nu mt s c im k thut ca xng reforming. 5. Cht lng xng reforming hin nay c ci tin nh cc yu t cng ngh no ?

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KIM TRA, NH GI HON THNH MN HC

y l bi kim tra quan trng nht nh gi kt qu hon thnh m un. Bi kim tra nn thc hin trong 60 pht. Di y l 2 kim tra mu gio vin tham kho (c th phn hoc cho sinh vin la chn). p n c trong gio trnh v trong phn tr li cu hi mi cui bi trong gio trnh ny. 1. (10 im) 1. Mc ch qu trnh reforming xc tc. Vai tr reforming xc tc trong cng nghip lc ha du. (2 im) 2. Nu vai tr ca cht xc tc a chc nng i vi qu trnh reforming. Nu 2 loi cht xc tc thng dng hin nay ca qu trnh bn ti sinh v ti sinh lin tc. Vai tr ca cc ph gia chnh (Re, Sn). (3 im) 3. nh hng cc thng s vn hnh (nhit , p sut, tc np liu, t l H2/nguyn liu) n hiu sut v cht lng sn phm. (3 im) 4. So snh s khc bit gia 2 cng ngh bn ti sinh v ti sinh lin tc. (2 im)

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CC THUT NG CHUYN MN
Catalytic Reforming: Qu trnh chuyn ha (reform-ci thin, ci cch) c xc tc nhm nng cao cht lng phn on naphta c ch s octan thp thnh hp phn pha xng c ch s octan cao. Reformate: Sn phm (lng) ca qu trnh reforming. CCR (continuous catalyst regeneration)- Cng ngh reforming vi ch ti sinh xc tc lin tc. 4. 5. 6. 7. PONA: Php phn tch thnh phn nhm hydrocacbon Parafin-OlefinNaphten-Aromatic trong nguyn liu. Ch s octan (RON, MON): Gi tr bng s, ch c tnh chng kch n tng i ca xng. Hot tnh (Activity): thut ng dng trong cng ngh reforming, ch nhit phi t cho u vo l phn ng (reactor) t c RON theo yu cu. n nh (Stability): thut ng cng ngh, p dng cho hot tnh, ch tc tng nhit u vo l phn ng nhm duy tr gi tr octan cho trc. Hoc p dng cho la chn, ch mc thay i hiu sut so vi gi tr ban u. khc nghit (Severity): thut ng cng ngh, thng th hin thng qua gi tri octan. la chn (Selectivity): thut ng cng ngh, ch kh nng ca cht xc tc cho ti a hm lng hydro hoc/v hm lng C5+ reformate.

1.

2. 3.

8. 9.

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Hnh 27. Thnh phn mt s loi xng thng phm cao cp khng ch

TI LIU THAM KHO

1. 2. 3. 4. 5.

inh th Ng, Ha hc du m v kh, Nh xut bn KHKT, H ni, 2004 L vn Hiu, Cng ngh ch bin du, Nh xut bn KHKT, H ni, 2000 Berthelin, Catalytic Reforming, ENSPM Formation Industrie 1991 G. Margaret Wells, Handbook of Petrochemical Processes (1997) Lp hc chuyn Php-Vit v Xc tc-ng hc-Lc du, H ni, 2005

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