Bg Xuc Tac Trong Cnld-In

BI GiNG

XC TC TRONG

CNG NGH LC DU

TS. Nguyn Th Linh

B mn lc- ha du

1

Cc khi nim c bn v cht xc tc d th, cht xc tc s dng trong cng ngh lc du

Cc cht xc tc kim loi, cht xc tc axit- baz c s dng trong cng ngh lc du

Nm c bn cht ca cc qu trnh xc tc trongcng ngh lc du (xc tc cho qu trnh cracking, reforming, isome ha, alkyl ha, hydrotreating

Nm c cc phng php ch to, nguyn tc la chn cht xc tc v ng dng trong cng nghip

MC CH MN HC

2Nguyn Th Linh, DKLD 4060326, 2013-2014

NI DUNG MN HC

CHNG 1. MT S KHI NIM V CHT XC TC

TRONG CNG NGH LC DU

CHNG 2. XC TC CHO QU TRNH CRACKING

CHNG 3. XC TC CHO QU TRNH REFORMING

CHNG 4. XC TC CHO QU TRNH ISOME HA

CHNG 5 CHT XC TC CHO QU TRNH ALKYL HA


NI DUNG MN HC

CHNG 6. CHT XC TC CHO CC QU TRNH

HYDRO HA V DEHYDRO HA

CHNG 7. CHT XC TC CHO QU TRNH

HYDROPROCESSING

CHNG 8. CC PHNG PHP CH TO, LA

CHN CHT XC TC V TRIN KHAI CNG NGHIP


CHNG 1

CHNG 1

MT S KHI NIM V CHT XC TC

TRONG CNG NGH LC DU


CHNG 1

6

1.1. Cc khi nim v xc tc trong cng ngh lc du

Tnh c th Tnh a nng Tnh a dng Tnh khng thay i trng thi nhit ng

Qu trnh xc tc l qu trnh lm thay i tc ca cc phn ng ho hc do nh hng ca cht xc tc; nhng

cht ny tham gia nhiu ln vo tng tc ho hc trung gian

vi cc tc nhn phn ng v sau mi chu trnh tng tc

trung gian li phc hi thnh phn ho hc ban u.

Nguyn Th Linh, DKLD 4060326, 2013-2014

CHNG 1

7

Tnh c th: Mt cht xc tc c hot tnh i vi mts phn ng nht nh.

Tnh a nng: Cht xc tc c hot tnh i vi mt s cc phn ng ha hc khc nhau.

Xc tc axit rn cho cc phn ng cracking, isomeha, alkyl ha, thy phn, hydrat ha Xc tc kim loi cho cc phn ng hydro hadehydro ha


CHNG 1

8

Tnh a dng: Thnh phn ha hc ca cc cht xc tca dng, c th l nguyn t, hp cht hay phc cht.

Tnh khng thay i trng thi nhit ng: Cht xctc khng b tiu hao trong qu trnh phn ng, cht xc tckhng lm thay i v tr cn bng ca phn ng ho hc.


CHNG 1

9

Cc giai on trong phn ng xc tc d

th

Tng tc trung

gian

Hp ph

Phn ng

Nh hp ph


CHNG 1

10

Tng tc trung gian: S tng tc gia tc nhn tham giaphn ng v b mt cht xc tc.


Tng tc trung gian gia tc nhn tham gia phn ngv b mt dn n s gia tng nng mt s cht trnb mt xc tc. Trong tng tc trung gian, lin kt ca cc nguyn tb mt v cc nguyn t di lp b mt ca xc tckhng b t hon ton, m hnh thnh hp cht trunggian, phc cht hot ng.

CHNG 1

11

Hp ph: S tng tc v gia tng nng tc nhnphn ng trn b mt cht xc tc.

Hp ph ha hc: xy ra s tng tc ha hc gia tcnhn phn ng v b mt cht xc tc Hp ph vt l l trng thi trung gian trc khi xy ra hpph ha hc. Xc nh c c im ca hp ph vt lc th kt lun c mt s c trng b mt, kch thc,hnh dngmao qun ca cht xc tc.


CHNG 1

12

Phn ng: l qu trnh tng tc ca cc tc nhn thamgia phn ng c hp ph trn b mt cht xc tc vhnh thnh sn phm.

Phn ng xy ra gia tc nhn v phc cht hotng hnh thnh trn b mt xc tc. Phn ng trn b mt cht xc tc c nng lngthp hn so vi phn ng cng loi khng c xctc.


CHNG 1

13

Nh hp ph:


S gii phng sn phm v tc nhn tham gia phn ng ra

mi trng.

CHNG 1

14

Mt s i lng c trng cho kh nng ca cht xc tc

Hot cht xc tc (activity): l i lng nh gicht rn c phi l cht xc tc hay khng, c ctrng bng chuyn ha v hng s tc phn ng.


CHNG 1

15

chn lc ca cht xc tc (Selectivity): L kh nngthc y phn ng theo mt chiu hng nht nh, dn ns to thnh nhiu sn phm mong mun, t cc sn phmph.


- chn lc thng c biu din bng t s gia tc to thnh sn phm chnh v tng tc ca cc phn ng xy ra.

Hoc xc nh bi t s ca hiu sut sn phm mong mun q v tng cc sn phm c to thnh qi.

(1.1)

(1.2)

CHNG 1

16

Tui th ca cht xc tc: biu th kh nng lm vic ca cht xc tc trong iu kin vn hnh qu trnh phn ng.


-Tui th ca cht xc tc ph thuc v mi trng phn ng v iu kin vn hnh.

- Tui th ca cht xc tc th hin bn c hc v ha hc.

CHNG 1

17

Cc loi cht xc tc trong cng ngh lc du


- Cht xc tc ng th: l cht xc tc cng pha vi tc nhn phn ng (thng l dng lng).

Cht xc tc ng th lm vic di iu kin mm hn so vi xc tc d th.

Cht xc tc ng th kh thu hi (kh tch ra khi hn hp sau phn ng).

CHNG 1


- Cht xc tc d th: Xc tc ng th c th c xc nh cu trc bng cc phng php ha l, thun li cho nghin cu ng hc ca

phn ng.

Xc tc ng th c ng dng nhiu trong cng nghip do cng ngh n gin, thc hin lin tc, d thu hi v ti

sinh. D bin tnh, c chn lc cao, hot tnh cao, n nh nhit v thy nhit.

Gi thnh cao, iu kin phn ng kh khn.

CHNG 1


- Cht xc tc ng th d th ha: Hot tnh cao Tm hot tnh l ng th D thu hi v ti sinh C tnh n nh nhit

CHNG 1

20

Hp cht phi tr trong xc tc


Hp cht phi tr trong xc tc to h cht xc tc phc vi s lin kt ca cc phi t (ligan) vi nguyn t kim loi.

Cu trc ca hexol

CHNG 1


S phi tr trong cht xc tc hnh thnh theo cc nguyn l sau:- Nguyn l lin kt cng ha tr:+ Lin kt gia kim loi v ligan l do phn ng ca baz Lewis (ligan)

v mt axit Lewis (kim loi).

+ S hnh thnh lin kt kim loi-ligan do s nhng cp in t c thn ca ligan cho orbital trng ca kim loi.

+ Nguyn t kim loi thng c cc orbital lai ha, s lai ha nng cao

kh nng nh hng ca orbital v lm cho lin kt gia KL-Ligan trt t v n nh hn.

+ Cu trc ca cc phi tr l 8 mt (lai ha d2sp3) i vi phc phi tr 6, l 3 (sp3) hoc 4 mt (dsp3) i vi phc phi tr 4.

CHNG 1


- Nguyn l tnh in n gin:M t s hnh thnh lin kt gia kim loi (hoc ion KL) vi cc

ligan bng tng tc tnh in ca cc in tch dng tm

nguyn t kim loi v in tch m ca cc nguyn t ligan.- Nguyn l trng tinh th: Biu din s tng tc tnh in gia ca nguyn t kim loi v

in t ca ligan gn.- Nguyn l orbital phn t:S lin kt gia cc orbital nguyn t ca nguyn t kim loi cha cp in t c thn trn tm nhng in t ca ligan vi cc

in t trng c mc nng lng thp trn ligan.

CHNG 1


1.2. Xc tc Axit Baz

Cht xc tc axit l nhng cht xc tc c kh nng nhng

proton (axit Bonsted) hoc nhn in t (axit Lewis). V vy,

chng c kh nng xc tc cho cc tc nhn mang tnh baz.

Cc tm axit tham gia vo s hnh thnh cc hp cht trung gian trong qu trnh chuyn ha ha hc trn b mt cht xc tc l

nhng axit rn.

Phn ng c s tham gia ca cht xc tc axit hnh thnh cacbocation theo 4 c ch sau:

CHNG 1


(1) Cng cation vo phn t cha no

Qu trnh ny ph thuc vo lc axit v cc yu t khc nh cu t lm bn cacbocation, tr ha hc v hng s in mi ca mi

trng. Hydrocacbon c tnh baz yu th cn tm axit mnh.

CHNG 1


(2) Cng proton vo phn t no

L, R1+: tm axit Lewis, ion cacbeni mnh

C7 H16 + H+

(3) Loi b mt in t trung ha

(4) D li phn t

CHNG 1


Cc phn ng ca cacbocation

Chuyn v in tch:

Ion 2,4- dimetyl pentyl Chuyn v 1-3

CHNG 1


Chuyn v 1-3

ng phn ha cu trc

Xy ra do s chuyn v nhm metyl dn n s hnh thnh ion cacbeni c

cu trc nhnh nhiu hn.

CHNG 1


Chuyn v hydrua

Xy ra gia ion cacbeni v phn t ankan

Chuyn v nhm alkyl

Hnh thnh v ct t lin kt C-C

CHNG 1


V d v phn ng alkyl ha

CHNG 1


Tt mch:

CHNG 1


V d v phn ng ct mch C C:

CHNG 1


V d v phn ng ct mch C C:

V d v phn ng bt cn i toluen

CHNG 1


Cc loi tm axit Tm axit Lewis v Bronsted- V d v cht xc tc dng aluminosilicatCng thc ha hc ca aluminosilicat: Na2O.Al2O3.nSiO2 trong n biu th t l SiO2/Al2O3

CHNG 1


S bin tnh, chuyn pha gia tm axit Lewis v Bronsted trong aluminosilicat

CHNG 1


1.3. Mt s thnh phn v tnh cht ca du m Thnh phn cc nguyn t trong du m: Du m cha thnh phn cc nguyn t bao gm ch yu l C

(83-87%) v H (11-14%), ngoi ra cn c S, O, N v cc kim loi nng nh V, Ni, Fe, Cu, Ca, Na, As

Thnh phn ha hc ca du m:-Cc hp cht hydrocacbon l nhng hp cht trong thnh phn ch cha nguyn t C v H.

- Cc hp cht d nguyn t l nhng hp cht ngoi thnh phn gm nguyn t C v H cn cha cc d nguyn t nh S, O, N.

CHNG 1


Cc hp cht hydrocacbon trong du m

Cc hp cht parafin

Cc hp cht vng no (Naphten)

Cc hp cht thm (Aromatic)

Cc hydrocacbon

- S cacbon ca cc hp cht hydrocacbon trong du m t C5-C60(t C1-C4 nm trong kh).

CHNG 1


CHNG 1


CHNG 1


Cc hp cht parafin trong du m

CHNG 1


CHNG 1


Cc hp cht naphten trong du m

Cc hp cht aromatic trong du m

CHNG 1


Cc hydrocacbon lai hp

Cc hp cht d nguyn t

- Cc hp cht cha lu hunh:

CHNG 1


CHNG 1


- Cc hp cht cha nit:

CHNG 1


- Cc hp cht cha oxi: gm cc axit (-COOH), cc xeton (-C=O), cc phenol v lacton.

Cc kim loi trong du m:

- Thng tn ti di dng phc ca kim loi v hp cht hu c (c-kim).

CHNG 1


Cc cht nha v asphalten trong du m:

- Cc cht nha v asphalten trong du m c thnh phn HC v ng thi cha cc d nguyn t O, N, S, c KLPT ln c 500-600, c mt trong phn on si cao v phn cn ca du m.

Phn loi du m theo t trng-Du nh: c t trng < 0,828- Du trung bnh: c t trng 0,828 < d < 0,884- Du nng: c t trng > 0,884

1.3. Cc qu trnh trong nh my lc du

Qu trnh vt l Qu trnh ha hc

S dng nhit C s dng CXT

Chng ct Chit Loi sp bng propan

Loi sp bng dung mi

Trn

Gim nht Loi cc

Cracking xc tc Reforming xc tc Hydrotreating Hydrocracking Loi sp Alkyl ha Polyme ha Isome ha 47

CHNG 1


Phn onc im cc phn on

im si (oC) S nguyn t C

Kh Xng Naphta Kerosin (nhin liu phn lc) Diesel, Fuel oil Gasoil kh quyn Fuel oil nng Cn chng ct kh quyn Cn chng ct chn khng

< 3030 210100 - 200150 - 250

160 - 400220 - 345315 - 540

540> 615

1 - 45 - 128 - 1211 - 13

13 17

20 - 4530

> 60

48

CHNG 1


Sn phm sch (khng cha N, S, O, cc kim loi Thu nhiu xng hn (ON cao) Thu nhiu diesel hn (CN cao) Cc sn phm c gi tr (cc hp cht thm, anken) t cn

Yu cu v cc sn phm lc du

Bin php p ng ?

S dng phng php chng ct tinh vi hn S dng cc phng php vt l S dng cc phng php ha hc

49

CHNG 1


n- pentan 2-metyl pentan cyclopentan n-hexan 2,2-dimetyl butan benzen cyclohexan n-octan 2,2,3-trimetyl pentan metyl-tert- butyl ete Xng mch thng Xng nh FCC Xng alkylat Xng reformat (CCR)

Tr s Octan v im si ca mt s hp cht

62 90 85 26 93 > 100 77 0 100 118 68 67 (MON) 93 82 95 92 99 88

309 301 322 342 323 353 354 399 372 328

50

CHNG 1


Hp cht ON Nhit si

n- ankan n-hexadecan (cetan) iso ankan anken cycloankan alkylbenzen naphtalen -metyl naphtalen Xng mch thng cycle oil FCC Xng nhit phn Gas oil hydrocracking

Tr s Cetan ca mt s hp cht 100 - 110 100 30 70 40 60 40 70 20 60 0 20 0 40 50 0 25 30 50 55 60

51

CHNG 1


Th trng cht xc tc

52

CHNG 1


CHNG 2

CHNG 2

CHT XC TC CHO

QU TRNH CRACKING


2.1. Qu trnh cracking xc tc tng si (Fluid Catalytic Cracking- FCC)

54

CHNG 2


Mc ch ca qu trnh cracking

- Sn xut xng c tr s octan cao, cc olefin nh, phn on nh (LPG, FO) Nguyn liu cho qu trnh cracking

- Phn on Gas-Oil, cc phn on nng ca qu trnh chng ct du th.

S nh my lc du hin i

55

Phn xng FCC hin i:thit b phn ng ng nng

56

CHNG 2


FCC: Thit b phn ng tng si v thit b ti sinh cht xc tc

57

CHNG 2


Phn ng ct lin kt C-C Phn ng isome ha Phn ng proton ha/loi proton Phn ng alkyl ha Phn ng polyme ha Phn ng vng ha, ngng t to cc

Phn ng cracking xc tc

58

CHNG 2


Cc phn ng xy ra trong qu trnh cracking

Cracking anken to ion cacbeniC ch phn ng cracking xc tc

Cracking ankan to ion cacboni

Hoc nu c mt ca ion cacbeni

59

CHNG 2


Phn ng cracking xc tc n-octan

Ion cacbeni u tin

60

CHNG 2

Xem xt c ch trn sai u?

Ion cacbeni u tin

61

CHNG 2

Phn ng isome ha (ng phn ha)

62

CHNG 2

Phn ng to cc

Ion cacbeni u tin

63

CHNG 2

64

CHNG 2


Phn b sn phm cracking nhit v cracking xc tc

65

CHNG 2


Theo c ch phn ng cracking xc tc:- Cht xc tc phi c kh nng nhng H+ hoc nhn H-

2.2. Cht xc tc cho qu trnh FCC

Cht xc tc cha tm axit Cht xc tc th h u tin: Dung dch AlCl3- Gy n mn thit b- C trong nc thi

Cht xc tc th h sau: Khong st ( x l axit) Aluminosilicat v nh hnh- Tnh n nh v tnh chn lc cao hn- Chu mi mn c hc tt hn Zeolit-Hot tnh v tnh n nh cu trc cao- t to cc, n nh nhit cao hn

66

CHNG 2


Xc tc cho qu trnh FCC

Tm axit yu

Tm axit mnh67

CHNG 2


Thnh phn ca cht xc tc FCC

68

CHNG 2


Zeolit Cht mang Ph gia

RE- USY Vt liu mao qunSb, Sn, CaTiO2

MgO, Pt/Al2O3, CeO2ZSM-5

Zeolit

69

CHNG 2


Cu trc ca zeolit:- n v cu trc c s ca zeolit lnhng t din Si v Al- Cc zeolit cha cc mng li cutrc mao qun vi kch thc rtnh (zeolit cho xc tc FCC c kchthc mao qun khong 8 ).

70

CHNG 2


71

CHNG 2


Mt s loi zeolit tng hp ng dng cho sn xutcht xc tc FCC:

- Zeolit X- Zeolit Y- Zeolit ZSM-5

72

CHNG 2


Cht mang

- Cc vt liu mao qun vi kch thc trung bnh (2-50nm) n ln (>50nm)- Dn cc phn t ln i n tm hot tnh- Khuch tn tc nhn phn ng vo v ra khi b mtcht xc tc- Chng li s u c cht xc tc

73

CHNG 2


Ph gia

- Cht xc tin nhm Pt- Nhm oxit kim loi (MgO, CeO2)- ZSM-5- Ph gia th ng ha kim loi (Antimon)

Quy trnh tng hp cht xc tc FCC

74

CHNG 2


Silic v nh hnh Natrialuminat NaOH

Mm tinh th zeolit NaY

Gel natrialuminosilicat

Hn hp Zeolit NaY

Zeolit NaY

Zeolit H-NaY

Gi ha (kt tinh)

Lc, ra

Trao i ion

NH4OH

Sn xut cht xc tc FCC

75

CHNG 2Phn b sn phm ca qu trnh cracking Gas oil

76

CHNG 2


Tnh chn lc hnh dng

77

CHNG 2


Tnh chn lc hnh dng

78

CHNG 2


Pht trin cht xc tc mi cho qu trnh FCC

0.51 0,55nmCht xc tc FCC cha ZSM-5:- Sn xut olefin nh (C3=, C4=) lmnguyn liu cho ha du v sn xutMTBE, ETBE

79

CHNG 2


2.3. S mt hot tnh v ti sinh cht xc tc FCC

80

CHNG 2


Nguyn nhn gy mt hot tnh cht xc tc

Mt hot tnh do thay i cu trc ca cht xc tc

Mt hot tnh do s hnh thnh cc

Mt hot tnh do kim loi nng

81

CHNG 2


C ch ca s mt hot tnh cht xc tc FCC

C ch hnh thnh cc

82

CHNG 2


C ch hnh thnh cc

83

CHNG 2


C ch tch t kim loi nng

84

CHNG 2


C ch tch t kim loi nng

85

CHNG 2


nh gi tnh cht cht xc tc FCC mi

86

CHNG 2


nh gi tnh cht cht xc tc FCC cn bng

MAT wt % G.F.

H2 YLD

SCFBC.F. SA m/g

Z-SA m/g

M-SA m/g Z/M SA/K

Ni ppm

V ppm Ni/V

Na wt %

Sb ppm Sb/Ni

UCS

RE2O3 wt %

Al2O3 wt %

CaO wt %

Fe wt %

74 3.4 171 1.2 155 89 66 1.3 53 3508 822 4.27 0.24 42 0.01 1.76 49.8 0.241 0.58

K2O wt %

MgO ppm

P2O5 wt %

Pb ppm

TiO2 wt %

C wt %

ABD g/cc

PV cc/g

0-20 %

0-40 %

0-80 %

40-80 %

APS Umb/Umf

0.08 3462 0.151 26 0.75 0.04 0 6 62 56 71

2.4. Ti sinh cht xc tc FCC

87

CHNG 2


C ch loi b cc

88

CHNG 2


C ch loi b kim loi nng

Mt s pht thi kh trong qu trnh ti sinh cht xc tc

v bin php thu hi

89

CHNG 2


- c dch ti liu- Trao i Tho lun

CHNG 3

CHNG 3

CHT XC TC

CHO QU TRNH

REFORMING


3.1. Reforming xc tc

91

CHNG 3


Mc ch ca qu trnh reforming xc tc Sn xut xng c tr s octan cao Sn xut ha cht c bn (Benzen, Toluen, Xylen-BTX)

Reforming xc tc l qu trnh sp xp li cu trc cacc hp phn hydrocacbon c tr s octan thp trongphn on thnh cc hydrocacbon c tr s octan cao mkhng lm thnh i vng nhit si ca phn on

92

CHNG 3


Nguyn liu cho qu trnh reforming xc tc Phn on Naphta ca qu trnh chng ct du th,qu trnh cracking xc tc.- Phn on Naphta (C5-C12) c vng nhit si t30oC 200oC (naphta nng t 90 200oC).

Thnh phn ca phn on Naphta:

Parafin: n- v iso-parafin Olefin: mch thng hoc nhnh cha 1 hoc nhiu ni i Naphten: Cycloankan Aromatic: cc hp cht cha vng thm

93

CHNG 3


Hp cht cha lu hunh trong phn on Naphta:

94

CHNG 3


Hp cht cha nit trong phn on Naphta:

95

CHNG 3


Mt s phn ng xy ra trong qu trnh reforming xc tc phn on Naphta:

96

CHNG 3


3.2. Cht xc tc cho qu trnh reforming

Cht xc tc th h u tin: Cr2O3, MoO3/Al2O3 Cht xc tc th h th hai: Pt/Al2O3 Cht xc tc th h th ba: Pt-Re(Ir, Rh, Ge)/Al2O3

- Hp phn kim loi xc tc cho qu trnh hydro v dehydro ha- Cht mang Al2O3 (c tnh axit) xc tc cho cc qu trnh thm ha, vng ha, isome ha.

97

CHNG 3


Thnh phn ca mt s cht xc tc reforming in hnh

98

CHNG 3


Vai tr ca cht xc tc lng chc

C ch qu trnh isome ha metylcycolpentan

99

CHNG 3


C ch lng chc trong phn ng isome ha o-xylen thnh etylbenzen

100

CHNG 3


nh hng ca nhit v p sut n qu trnh thm ha cyclohexan

101

CHNG 3


nh hng ca t l H2/HC nguyn liu n qu trnh thm

ha cyclohexan

102

CHNG 3


Cc loi thit b phn ng reforming

103

CHNG 3


Cng ngh reforming xc tc bn ti sinh (SRR)

104

CHNG 3


Cng ngh reforming xc tc ti sinh lin tc (CRR)

105

CHNG 3


3.3. S mt hot tnh ca cht xc tc

Mt hot tnh do s tch t cc Mt hot tnh do s u c bi hp cht cha lu hunh Do thnh phn nguyn liu

Hnh thnh nhit thp

Khi nhit > 400oC hnh thnh lp graphit Pt-C bao ph b mt xc tc

106

CHNG 3


3.4. Ti sinh cht xc tc

t cc c s dng dng kh tr loi b hydrocacbon, hydro. Kim sot nhit t cc > 450oC Oxi ha v oxiclo ha n phn tn kim loi trn cht mang v hot ha tm axit.

Lm kh Kh b mt kim loi nhit 700oC

Sulfit ha b mt kim loi (0,05-0,06%wt S)

107

CHNG 3


3.5. Cng ngh ti sinh cht xc tc

Cng ngh bn ti sinh xc tc Cng ngh ti sinh tun hon Cng ngh ti sinh lin tc (CCR)

108

CHNG 3


3.6. Thu hi kim loi t xc tc reforming s dng

- X l vi axit v kim

Re nm trong dung dch, Pt, Ir trong phn cn rn

109

CHNG 3


Thu hi Pt:

Hoc dng qu trnh in ha:

- Ha tan Pt:

- Kt ta mui Pt:

- Nung mui Pt:

110

CHNG 3


Thu hi Re

Ha phn dung dch ca qu trnh x l axit v kim vi ion amoni

- Trao i ion:

- X l vi amoni:

CHNG 4

CHNG 4

XC TC CHO QU TRNH

ISOME HA


112

4.1. Qu trnh isome ha

Mc ch: Tng ON cho xng Gim nhit ng c ca cc phn on nng (DO, FO) Thu cc sn phm ha cht c bn

Qu trnh isome ha l qu trnh ha hc lm thay i cu trc

ca hp cht hu c.


CHNG 4

Nguyn liu: Phn on Naphta C5/C6, n-butan (phn on kh), phn on C8 thm t reformate, phn on nng (DO, FO).


CHNG 4

4.2. Phn ng isome ha cc nguyn liu in hnh


CHNG 4

Sn xut MTBE, ETBE t isobuten


CHNG 4

Vit c ch Isome ha n-buten trn cht xc tc cha tm axit


CHNG 4

C ch phn ng isome ha xy ra trn tm axit


CHNG 4

C ch phn ng isome ha n-pentan xy ra trn tm axit


CHNG 4

Qu trnh isome ha thu p-xylen t phn on C8 ca reforming


CHNG 4

4.3. Cht xc tc cho qu trnh isome ha

Cht xc tc axit: Nhm clorua khan, c tnh axit rt mnh, c hot tnh cao cho qu trnh.

-Gy n mn mnh, kh thu hi Cht xc tc HF-BF3: - Thc hin iu kin mm- Gy n mn


CHNG 4

Cht xc tc lng chc: Pt/Al2O3:-Cn lm sch nguyn liu- Phi clo ha xc tc- Gy n mn Pt/zeolit:-Khng cn clo ha- Khng nhy cm vi cc hp cht d nguyn t- C cu trc mao qun (5,2-5,8 )- Tnh chn lc hnh dng cao


CHNG 4

Tnh chn lc hnh dng ca cht xc tc


CHNG 4

4.4. S mt hot tnh v ti sinh cht xc tc

Sinh vin t nghin cu thuyt trnh Trao i Tho lun

CHNG 5

CHNG 5

XC TC CHO QU TRNH

ALKYL HA


124

5.1. Qu trnh alkyl ha

Mc ch: tng ON cho xng nh qu trnh alkyl ha cc n-parafin vi cc olefin.

Qu trnh alkyl ha l qu trnh nhm chuyn ha anken,

ankan thnh isoankan


CHNG 5

Nguyn liu: - Isobutan (t FCC, hydrocracking, chng ct)- Propen, buten (t FCC)

125

Cc phn ng trong qu trnh alkyl ha


CHNG 5

126

Cc phn ng trong qu trnh alkyl ha


CHNG 5


CHNG 5


CHNG 5


CHNG 5

130

C ch phn ng trong qu trnh alkyl ha: c ch ion cacbeni


CHNG 5

131

C ch trn cht xc tc HF- Khi mo:


CHNG 5

132

C ch trn cht xc tc HF- Pht trin mch:


CHNG 5


CHNG 5 Cc phn ng xy ra trong qu trnh alkyl ha- Isome ha alkyl ha:

2,2,4- trimetylpentan


CHNG 5


CHNG 5

Tng qut:

136

5.3. Cht xc tc cho qu trnh alkyl ha


CHNG 5

Cht xc tc cho qu trnh alkyl ha thng thng s dng:- Cht xc tc th h u:

H2SO410oC

100 (kg axit/tn sn phm)

HF30oC

0,5 (kg axit/tn sn phm)

-Th h xc tc ngy nay: H2SO4/HF/AlCl3-HCl- iu kin lm vic: 25oC, 8bar


CHNG 5

So snh cht xc tc H2SO4 v HF

Qu trnh s dng H2SO4 Qu trnh s dng HF

Nhit (K) 277-283 298-313p sut (bar) 2-6 8-20Thi giam lu (pht) 20-30 5-20

T l nguyn liu isobutan/buten 8-12 10-20Nng axit (%KL) 88-95 80-95Lng axit trong nh tng (%V) 40-60 25-80Lng cht xc tc s dng 70-100 0.4-1axit/sn phm (kg/t)


CHNG 5

Mt s hn ch ca cht xc tc alkyl ha:

-Cht xc tc H2SO4 c hot tnh cao nhng to nhiu sn phm ph

- Cht xc tc HF hot tnh thp hn nhng gy nhim v c hi

- Cc cht xc tc kh thu hi, mt mt trong sn xut- Gy n mn mnh


CHNG 5S qu trnh alkyl ha vi cht xc tc H2SO4


CHNG 5

CHNG 6

CHNG 6

CHT XC TC HYDRO V

DEHYDRO HA


Sinh vin t nghin cu

142

CHNG 6


CHNG 7

CHNG 7

CHT XC TC

HYDROPROCESSING


7.1. Qu trnh Hydroprocessing

144

CHNG 7


Mc ch ca qu trnh hydroprocessing

Hydroprocessing l qu trnh x l v ch bin du th vcc phn on nng bng qu trnh c s dng H2, trong bao gm cc qu trnh Hydrocracking, Hydro loi asphalten(HDAs), hydro loi kim loi nng (HDM), hydro loi luhunh (HDS), hydro loi nit (HDN), hydro loi oxi (HDO).

145

CHNG 7


Mc ch ca qu trnh hydroprocessing- X l cc nguyn liu, phn on cha nhiu hp phn gy ng c v mt hot tnh cht xc tc trong qu trnh ch bin

nh asphalten, kim loi nng (V, Ni), hp cht d nguyn t

ca lu hunh, oxi, nit

Nguyn liu cho qu trnh hydroprocessing

- Du chua, du nng, cc phn on nng ca qu trnh chng ct du th.


S nh my lc du hin i

147

CHNG 7


Cc phn ng xy ra trong cc qu trnh hydroprocessing Phn ng tch loi lu hunh

148

CHNG 7


Phn ng tch loi nit

149

CHNG 7


Phn ng tch loi oxi

150

CHNG 7


Tch kim loi nng: Cc hp cht c kim cha As, Pb, V, Ni c by vo cc l trng trn b mt cht xc tc.

151

CHNG 7


7.2. Cht xc tc cho qu trnh hydroprocessing

Thnh phn ca cht xc tc: Cht mang: -Al2O3 Pha hot ng: l sulfua ca cc kim loi Mo, W c xctin bi Co, Ni, c s dng di dng hn hp caCoMo, NiMo, NiW.

-Thnh phn CoMo dng cho qu trnh HDS- Thnh phn NiMo dng cho qu trnh HDN, HDO- Thnh phn NiW dng cho qu trnh HDM, HDO

152

CHNG 3


Hnh dng ht xc tc cng nghip

153

CHNG 7


Phng php chun b cht xc tc hydroprocessing-Dng mui ca cc kim loi trong pha hot ng tm lncht mang.- Hot ha pha hot ng nh qu trnh sulfat ha:

154

CHNG 7


- a thm cht xc tin nh Co, Ni nhm lm thay ilin kt gia kim loi v S, to l trng trong mng tnhth, tng cng s hp ph cc phn t hp cht hu c.- C th a thm photpho nhm tng kh nng phn tnca pha hot ng trn cht mang.- Cht mang c din tch b mt 120-150m2/g, c tnh axith tr phn ng HDT, gim ng cn trn b mt cht xctc.

155

CHNG 7


7.3. S mt hot tnh ca cht xc tc

- Mt hot tnh do thay i cu trc: Di iu kin nhit cao (400o C, 6Mpa), tinh th MoS2 v WS2 chuyn pha.- Mt hot tnh do s hnh thnh cc: Tc hnh thnh cctng nhanh khi iu kin lm vic 450oC, 3Mpa.- Asphalten v kim loi nng: hm lng kim loi khngvt qu 50ppb

156

CHNG 7


7.4. Cc yu t nh hng n hot tnh cht xc tc-Nguyn liu u: cha nhiu asphalten, nha d gy mthot tnh cht xc tc.- Kim loi nng: gy ng c cht xc tc- Nhit v p sut H2 : p sut H2 tng t 2-15MPa slm gim s hnh thnh cc t 10-40%, cht xc tc n nh 400oC.- Tc dng c hc:

157

CHNG 7


-Chu k lm vic ca cht xc tc ph thuc vo nguyn liuu vo

158

CHNG 7


7.5. Ti sinh cht xc tc

-Ti sinh bng qu trnh oxi ha: dng cc cht oxi ha mnh nhO3, N2O, H2O2., dng oxi t cc.

- Ti sinh bng qu trnh kh: Dng dng H2 iu kin nhit 730oC, cc c hydro kh ha to CH4. Thu c din tch bmt ln hn nhng c th lm chuyn pha ca cht mang.- Ti sinh bng CO2 : CO2 + C = 2CO

159

CHNG 7


Tiu lun mn hc

CHNG 8

CHNG 8CC PHNG PHP CH TO,

LA CHN CHT XC TC CNG NGHIP


CHNG 8

161

Qu trnh tng hp cht xc tc bao gm cc giai on:- iu ch cc tin cht rn- Chuyn ha cc cht u thnh thnh phn ca cht xc tc bng cc qu trnh thch hp (phn hy nhit, kim

ha)- Thay i thnh phn cht xc tc (bin tnh xc tc)


8.1. K thut tng hp cht xc tc

CHNG 8


Mt s n v o c trng cho tnh cht cht xc tc:- Hot tnh ca cht xc tc (activity), a:

- Tc th tch dng kh (gas hourly space velocity- GHSV):

CHNG 8


- Tc th tch dng lng (Liquid hourly space velocity- LHSV):

- chuyn ha % (Conversion- C):

- Hiu sut % (A):

CHNG 8


- chn lc (Selectivity- S):

- Hiu sut khng gian (Space time yield- STY)

- Thi gian sng ca cht xc tc (Catalyst lifetime- Z):

- Thi lu (residence time- t):

CHNG 8

165

Cc phng php ch to cht xc tc Phng php kt ta:


CHNG 8

166

Phng php kt ta:


CHNG 8

167

Phng php tm trn cht mang


ui kh ra khi l

xp cht mang X l cht mang

bng dung dch

Loi dung mi d

Sy kh v nung

CHNG 8

168

Cc phng php tm:- Phng php nhng- Phng php phun-Tm km theo bay hi dung dch- Tm mui nng chy Phng php trn c hc


CHNG 8

169

Cc nguyn tc c bn trong ch to xc tc Ch to xc tc kim loi trn cht mangXc tc Pt/cht mang:

Ch to cht xc tc oxit kim loi/cht mang-Phng php ch to: ng kt ta, tm, hp thu- Tin cht ban u: mui natri, cacbonat, axetat ca cc kim loi Ch to xc tc HDS, HDN:-Tin cht ban u: mui ca cc kim loi Mo, Co, W, Ni, Al2O3 - Phng php: tm


CHNG 8

170

Ch to xc tc zeolit


CHNG 8

171

Tng hp cht xc tc zeolit


Qu trnh chun b gel v kt tinh zeolit t hn hp phn ng

Na2O- Al2O3- SiO2- H2O xy ra nh sau:

CHNG 8

172

8.2. La chn cht xc tc cng nghip


Yu cu i vi xc tc cng nghip:

-Hot cao- chn lc cao- Nhit khi ng- bn nhit- dn nhit tt- chc rn, bn c hc- bn chng bo mn: 1-3%/thng (tng si), 10% thng (lp c nh)

- bn vi cht u c- Gi thnh thp

CHNG 8

173

8.3. Cc phng php thc nghim trong TH xc tc


Phng php xc nh tnh cht vt l ca cht xc tc

CHNG 8


Phng php xc nh tnh cht ha hc

CHNG 8


Phng php xc nh tnh cht b mt cht xc tc

CHNG 8


TEM, SEM Xc inh cu trc b mt

CHNG 8


Phng php xc nh hot tnh xc tc:- Th hot tnh ca cht xc tc bng h thit b phn ng vi dng


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