GS. TS.

Nguyn Hu Ph

Cracking xc tc
Ho hc
Cht xc tc
Qu trnh cng ngh

Nh xut bn Khoa hc v K thut

H Ni

Tc gi: GS. TS. Nguyn Hu Ph

Chu trch nhim xut bn:

Bin tp v sa bi:

PGS. TS. T ng Hi
ThS. Nguyn Huy Tin
Ngc Linh
hng Lan

Trnh by ba:

Nh xut bn khoa hc v k thut

70 Trn Hng o H Ni

54 541
546 17 05
KHKT 05

In 700 cun, kh 19 27 cm, ti

Giy php xut bn s: 546 17 20/5/2005
In xong v np lu chiu thng 6 nm 2005.

Li ni u

Vit Nam ang bt u xy dng cc nh my lc du v lc ho du.

Trong mt nh my lc du, qu trnh cracking xc tc chim mt v tr
kh quan trng. Do , cc kin thc c bn v ho hc qu trnh cracking xc
tc, v bn cht v cc phng php tng hp cht xc tc v v cng ngh qu
trnh cracking l ht sc quan trng i vi nhng ai , ang v s lm vic
(hc tp, nghin cu v vn hnh sn xut) trong lnh vc lc ho du.
Ti vit cun sch ny vi s chn thnh mun ng gp phn kin thc
t i ca mnh cho s pht trin ngnh Du kh cn non tr ca Vit Nam.
Hy vng rng, cun sch s em li nhng iu c ch cho cc sinh vin,
bn b v ng nghip ca ti ang hc tp, nghin cu v cng tc trong cc
trng i hc, vin nghin cu v cc c s sn xut.
Ti xin thnh thc cm n cc li nhn xt, gp ca c gi v cun
sch ny.

GS. TS. Nguyn Hu Ph

Phng Ho l B mt
Vin Ho hc, Vin Khoa hc v Cng ngh Vit Nam
18 Hong Quc Vit, Cu Giy, H Ni

Bng cc ch vit tt v k hiu

Cc ch vit tt v k hiu c ch thch ngay ln u tin xut hin trong cun
sch. Tuy nhin, cho thun tin, nht l i vi cc c gi ch c tng phn, chng ti
nhc li tt c cc ch vit tt v k hiu trong bng ny d dng theo di.

~
Me

Chuyn dch nhm metyl (alkyl)

~
H

Chuyn dch hydro (hydrua)

%kl

Phn trm khi lng

%LV

Phn trm th tch lng

%tt

Phn trm th tch

G*

~
~
Bin thin th ng p (nng lng t do) ca giai on chuyn dch ( Me , H )

Gpu

Bin thin th ng p ca phn ng

Hpu

Bin thin entanpy ca phn ng

Hht

Bin thin entanpy hnh thnh (nhit sinh)

Spu

Bit thin entropy ca phn ng

ABD

Mt khi trung bnh (average bulk density)

AFS

Fluosilicat amoni

AFSY

Zeolit Y c x l vi (NH4)2SiF6

Al (E)

Nhm ngoi mng tinh th

Al (T)

Nhm trong mng li tinh th

AP

im anilin, aniline point

ASTM

U ban Th nghim v Vt liu ca M (American Society for Testing and

Materials)

ATB

Sn phm giu aromat y thp

Tm Brnsted

BPSD
C3
C3

Thng du/ngy hot ng (barrels per calendar day)

Hydrocacbon c mch cacbon nh hn 3
Hydrocacbon olefin c mch 3 cacbon (propylen)

C5+

Hydrocacbon c mch cacbon ln hn 5

CA

Phn trm trng lng cacbon ca aromat; phn trm trng lng aromat

CCR

Cn cacbon Condrason

CD

Mt ln cht (compacted density)

CI

Ch s cetan, cetane index

CN

Phn trm trng lng cacbon ca naphten, phn trm trng lng naphten

Cn

Phn hydrocacbon c mch cacbon nh hn n

Cn

Phn hydrocacbon c mch cacbon ln hn n

CO

Kh oxit cacbon

CO

Du giu hydrocacbon vng thm (cycle oil)

CO

Phn trm trng lng cacbon ca olefin, phn trm trng lng olefin

COC

M hnh suy gim hot tnh xc tc do s hnh thnh cc (coke on catalyst)

CP

Phn trm trng lng cacbon ca parafin, phn trm trng lng parafin

cSt

n v o nht, xenti stoke (St)

T trng

DCC

Cracking xc tc su (deep catalytic cracking)

DHA

Hydrodealkyl ho

DMO

Du x l kim loi (demetallized oil)

DO

Du gn (decanted oil)

EBP

im si cui (end boiling point)

EDTA

Etylen diamin tetra axetic (ethylenediaminetetraacetic acid)

ESP

My lc kh tnh in (electrostatic precipitaion)

EXT

Chit tch aromat

FAU

Faujazit (Faujasite): cu trc tinh th ca zeolit Y

FCC

Cracking xc tc pha lu th (fluid catalytic cracking)

FGSV

Van iu chnh kh bung hon nguyn

GCRON

RON xc nh bng phng php sc k kh

HCO

Du giu hydrocacbon vng thm nng (heavy cycle oil)

HSY

Zeolit Y c hm lng silic cao (high silic Y zeolite)

IBP

im si u (initial boiling point)

IUPAC

Union International of the pure and applied chemistry

Kpu

Hng s cn bng ca phn ng

Tm Lewis

LCO

Du giu hydrocacbon vng thm nh (light cycle oil)

LHSV

Tc khng gian theo th tch cht lng theo n v thi gian gi (liquid

hourly space velocity)

LPG

Kh du m ho lng (liquified petroleum gas)

MAS NMR Phng php cng hng t ht nhn vt liu rn (magic angle spinning nuclear
magnetic resonance)
MAT

Php o hot tnh xc tc trong thit b MAT (th hot tnh dng vi lng,
micro activity test)

MON

Tr s octan ng c

MONC

Tr s MON c xc nh vi xng khng pha ch

MTBE

Metyl tectiary butyl ete, methyl tertiary buthyl ether

MTC

H hn hp khng ch nht

N&TN

Nhit v thu nhit ( bn nhit v thu nhit)

NSTB

Nhit si trung bnh

NOx

Cc oxit nit (NO2, NO...)

API

i lng o mt ca du m

Nhit theo thang Rankine

Poise, n v o nht

PONA

Parafin, olefin, naphten v aromat

PP

Polypropylen

Nhm alkyl

RCC

Cracking xc tc nguyn liu du cn (residue catalytic cracking)

RE

Cation t him

RFCC

Cracking xc tc pha lu th du cn

RON

Tr s octan nghin cu

RONC

Tr s RON c xc nh vi xng pha ch

ROT

Nhit u ra ca react (raiz)

RPT

Ry phn t (vt liu ry phn t)

SA

Aluminosilicat

SAP

Hydro ho chn lc

SBU

n v cu trc th cp (secondary unit building)

SC

Hi nc - cracking (steam cracking)

SCR

Kh xc tc chn lc (selective catalytic reduction)

SFV

Viscomet Furol Saybolt

SIMDIS

Phng php chng ct m phng nhit thp

SIMS

Phng php ph khi lng ion th cp (secondary ion mass spectroscopy)

7

SUV

Viscomet vn nng Saybolt

TBP

im si thc (true boiling point)

TO4

T din gm 1 tm T v 4 oxy lin kt

TOS

M hnh suy gim hot tnh xc tc theo thi gian phn ng trong dng

USY

Zeolit Y dng siu bn (ultra stabilized Y zeolite)

VGO

Vacuum gas oil, gas oil chn khng

V/V

T s th tch/th tch

VPI-5

Tn ca mt vt liu h aluminophosphat

VRDS

Du cn chn khng c kh lu hunh

VTB

Sn phm y thp chng ct chn khng

WHSV

Tc khng gian trng lng tnh vi n v thi gian gi (weigh hourly

space velocity)

xt/d

T s cht xc tc/du

Zeolit kiu Y dng faujazit (Faujasite)

ZSM-11

Zeolit ZSM-11 c m cu trc quc t l MEL

ZSM-5

Zeolit ZSM-5 c m cu trc quc t l MFI

Chng 1

M u
Hu ht cc phn ng ho hc c p dng quy m cng nghip u l cc phn
ng xc tc. Rt nhiu qu trnh cng ngh c ci tin, hon thin l nh nhng pht
minh v cht xc tc mi. Mt trong nhng qu trnh c quy m cng nghip ln nht l qu
trnh cracking xc tc. Cracking l s chuyn ho cc phn t ln ca du m thnh cc
phn t hydrocacbon nh hn thuc phn on gasolin (xng).
1.1. Gii thiu tng qut v cng ngh cracking
Cc qu trnh cracking, thot tin, c thc hin khng c mt cht xc tc, nhng
v sau, trong 4-5 thp k gn y, nhiu cht xc tc cracking lin tc xut hin v ci tin.
Hu ht cht xc tc cracking l xc tc axit. Thnh tu quan trng nht trong cng ngh
cracking xc tc trong hn 4 thp k qua l s pht minh v s pht trin lin tc ca xc
tc zeolit.
Cc zeolit (dng axit, H-zeolit) xc tc cho phn ng cracking du m nhanh hn,
hiu qu hn rt nhiu so vi cht xc tc dng aluminosilicat v nh hnh trc kia, n
mc ngi ta phi thay i c thit k ca cc thit b cracking c, dng lp xc tc n nh,
hoc dng lp xc tc ng (tng si n nh) thnh cc react ng nh thng ng (reactor
- riser). Trong react riser, cc ht xc tc c kch thc nh c chuyn qua react rt
nhanh nh dng hydrocacbon ho hi trong trng thi lu th (fluid), cht xc tc v
hydrocacbon c tip xc nhau trong khong thi gian rt ngn, khong 5 - 10 giy*.
C th ni, xt v mt ho hc ca nhiu qu trnh lc - ho du (cracking, reforming,
izome ho...) th qu trnh cracking c nghin cu nhiu nht v t c nhiu thnh
tu nht. l ho hc v axit mnh, hydrocacbon, cacbocation v v zeolit.
Zeolit l vt liu aluminosilicat tinh th, bn trong n cha nhng h mao qun ng
nht c kch thc c phn t. Cu trc tinh th v tnh cht b mt ca zeolit c xc nh
kh chnh xc v r rng, trong khi cc tham s cu trc ca cc cht xc tc rn khc
dng v nh hnh li hay thay i v kh xc nh.
Ho hc ca qu trnh cracking xc tc s c trnh by t m trong mt chng
ring. Tuy nhin, hnh dung ho hc cracking xc tc trong ng cnh ca thc t cng
nghip, chng ta c th theo di mt s khi qut ca mt qu trnh cng nghip nh sau:
* V qu trnh cracking xy ra trong trng thi lu th (fluid) ca cht xc tcv hydrocacbon, nn qu
trnh xc tc ny thng c gi l Fluid Catalytic Cracking vit tt l FCC (cracking xc tc pha lu th)

675oC
2,4 atm

Kh t

H2 - C4

(25 - 200oC)
Naphta

Kh chy n bnh t CO
o
675 C; 2,1 atm

Du nhiu (200 - 340oC)

hydrocacbon
aromat nh
(Light Cycle Oil, LCO)

Khng kh

o
Du nhiu (340 - 429 C)
hydrocacbon
aromat nng
(Heavy Cycle Oil, HCO)

Hi nc
Khng kh

Gas oil

Du cn
(>425oC)

Thit b hon nguyn

Thit b phn ng xc tc

Thit b phn ring

(chng ct phn on)

Hnh 1.1. S nguyn tc ca qu trnh cracking xc tc cng nghip.

S gm mt react cha lp xc tc ng, cng vi mt b phn tch ht xc tc
v sn phm (thit b phn ng xc tc); mt thit b hon nguyn xc tc, trong cc sn phm cacbon phn t lng cao, c t chy phc hi hot tnh xc tc v mt
thit b chng ct tch sn phm cracking thnh cc phn on c nhit si khc nhau
v mt phn du nng c hon lu tr li react cracking. Cc tham s cng ngh ca qu
trnh cracking xc tc thng xy ra trong react ng ng nh sau (bng 1.1):
Bng 1.1. Cc tham s qu trnh cracking xc tc
React ng ng
Nhit oC
- y
- nh
p sut, atm
T s cht xc tc/du
Thi gian lu, s

550
510
3
6
57
Thit b hon nguyn xc tc

Nhit trong xyclon C

T s CO/CO2 (mol/mol)
p sut y ca tng xc tc ng, atm
Tc dng pha kh, m/s
Thi gian lu ca cht xc tc rn, s
Hm lng cc ca cht xc tc (%kl)
- Li vo
- Li ra

10

650 760
0,7 1,3 : 1
3,5
60
30
0,8
< 0,1

Bng 1.2 trnh by hiu sut sn phm ca mt qu trnh cracking xc tc vi cc cht

xc tc khc nhau: zeolit v aluminosilicat.
Bng 1.2. Cc tham s cng ngh v hiu sut sn phm cracking xc tc
Tham s cng ngh
Nhit hi nguyn liu vo, oC
Nhit xc tc vo, oC
Nhit sn phm ra, oC

Tc khng gian th tch, h 1

T s cht xc tc/du (%tt)
th tch xc tc hon nguy n
T s hon nguyn
th tch cht xc tc mi
Hm lng hi nc trong nguyn liu, %kl
Cng sut thit b xc tc bbl/ngy*
Tc tun hon cht xc tc, kg/h
Tc t chy cc, kg/h
Khong nhit si ca dng nguyn liu hon lu, oC
chuyn ho, % th tch
Hiu sut cracking, %

Durabead5(a)
476
548
474
1,0
1,9
0,84

Durabead1(b)
476
549
471
0,9
2,0
0,82

3,6
12900
136065
2267
215-332
73,4

3,5
13400
136065
1542
232-327
49,5

77,6

77,3

th tch gasolin
100
th tch du d chuyn ho

%tt
13,7
12,9
56,9
13,4
2,1
6,5
4,8
13,4
1,35
3,8
4,1
7,9
-

Hiu sut
%kl
%tt
15,2
21,3
13,3
29,2
48,7
38,3
8,5
8,5
8,9
5,4
100
1,3
1,1
4,0
2,9
3,2
4,5
8,5
8,5
0,64
2,1
2,4
2,4
3,7
4,5
6,1
1,3
0,6
1,8
0,1
0,6
4,4
-

%kl
Sn phm y thp chng ct
22,3
Du t
29,4
32,4
Gasolin (khng c C4)
Cc butan
5,4
6,6
Kh kh (C3 v kh nh khc)
Cc
3,4
Tng cng
100
n-butan
0,6
Isobutan
1,8
Buten
3,0
5,4
Tng C4
T s i-C4/C4
Propan
1,3
Propylen
2,1
3,4
Tng C3
Etan
1,0
Etylen
0,4
Metan
1,2
Hydro
0,1
Sulfua hydro
0,5
3,2
Tng C2 v nh hn
* bbl: barrel, n v o th tch du m thng dng trong giao dch thng mi, 1bbl = 165 lit.
(a): xc tc zeolit REHY trong pha nn aluminosilicat v nh hnh; (b): xc tc aluminosilicat v
nh hnh; %tt: phn trm tnh theo th tch; %kl: phn trm tnh theo khi lng

11

Hin nay cc thit b cracking xc tc c nhiu hng ch to v ci tin (s trnh

by phn qu trnh cng ngh). Tuy nhin, hnh dung nguyn tc ca react dng ng
ng (reactor - riser) chng ta kho st mt s react c in nh trn hnh 1-2.
Gas oil c a vo phn y ca reactor - riser vi dng hi nc rt phn tn, c
ho trn vi cht xc tc dng ht mn n t phn y thit b hon nguyn xc tc. ng
knh ca react tng dn theo chiu cao gi cho tc lu chuyn cht xc tc hu nh
khng thay i, bi v p sut thu tnh trong ng ng gim dn n u ra.

Thit b tch
hydrocacbon strip

Hi nc
React
(reactor)

Thit b hon nguyn cht xc

tc, regenerat (regenerator)
Thi

Cht xc tc b sung
Khng kh

Hi nc
Gas oil

Hi nc

Hnh 1.2. Thit b craking xc tc FCC.

Sau react, cht xc tc c tch ra khi sn phm nh thit b tch xyclon. Hydrocacbon c tch bng hi nc khi cht xc tc b cc ho trong vng trn ca thit b
tch xyclon. Trong thit b hon nguyn xc tc, cc c t chy, gii phng cht xc tc
cho chu trnh chuyn ho tip theo.

12

1.2. Gii thiu s chung ca cc phn ng cracking

Cc phn ng cracking hydrocacbon c thc hin bi cc cht xc tc axit v xy
ra theo c ch cc hp cht trung gian cacbocation. V ho hc, cc phn ng cacbocation
chng ta s xt sau, cn v mt cng ngh qu trnh, c th hnh dung trong mt thit b
phn ng xc tc, phn ng cracking gas oil c miu t nh s n gin sau y:
O

k1

k2

k3
Gas oil O, Gasolin G v sn phm ph X.
Qua s , nhn thy rng, tng hiu sut gasolin cn hn ch cc phn ng
cracking su, chuyn ho G thnh X. Vic s dng react - riser, chnh l gim thiu s
cracking su ca gasolin. Mt khc, cng c th nhn thy rng, cc sn phm ph X nhn
c khng ch t gasolin m cn trc tip t gas oil.
1.3. Gii thiu chung v cht xc tc cracking cng nghip
Cc xc tc cng nghip thng c iu ch t 3 - 25% (kl) ca zeolit tinh th
(ng knh ht tinh th zeolit c 1 m) trong mt cht nn (matrix) l aluminosilicat v
nh hnh v/hoc khong st. bo m ch lm vic trng thi lu th (fluid) trong
dng hi hydrocacbon, kch thc ht xc tc phi nm trong khong 20 n 60 m (ng
knh ht). Zeolit phi c phn tn vo trong pha nn aluminosilicat v nh hnh trnh
cc hiu ng nhit cc b, n nh hot tnh xc tc ca zeolit, nh cu trc xp v
axit khc nhau gia zeolit v pha v nh hnh.
Nh s khc nhau m xc tc zeolit c hot tnh cracking gas oil v chn lc
gasolin cao hn nhiu so vi xc tc aluminosilicat v nh hnh (xem bng 1.2). Ngy nay ,
trong cht xc tc FCC, ngoi cc hp phn c bn l zeolit Y(Faujasite) dng USY v pha
nn aluminosilicat v nh hnh, ngi ta cn thm vo cc zeolit ph gia (vi hm lng t
1 n 10% khi lng) H-ZSM-5, HZSM-11, H-Bta... gia tng ch s octan ca gasolin
hoc gia tng hm lng olefin nh trong thnh phn kh cracking, v thm mt s ph gia
th ng ho kim loi (xem mc cht xc tc cracking).
1.4. Cc c trng v nguyn liu cho cracking xc tc (FCC)
Cc nh lc du phi ch bin nhiu loi du th khc nhau. Cht lng ca du th
thng b bin i theo tng vng khc nhau, do , ngi ta phi xc nh r cc tnh cht
c trng ca tng loi nguyn liu m bo s vn hnh n nh ca cc cng on ch
bin (cracking, reforming...) trong mt nh my lc du.

13

c trng nguyn liu FCC l mt nhim v rt quan trng cho s hot ng ca cng
on FCC. Nh , ngi ta c th chn cht xc tc, x l cc s c, ti u ho qu trnh
cracking xc tc.
Hai yu t quan trng nht nh hng n cht lng ca nguyn liu FCC l:
- cc hydrocacbon;
- cc tp cht;
cha trong nguyn liu FCC.
1.4.1. Phn loi cc hydrocacbon
Cc hydrocacbon trong nguyn liu FCC thng c phn thnh parafin, olefin,
naphten v cc aromat (hydrocacbon cha vng thm) vit tt l PONA.
Parafin: parafin l cc hydrocacbon mch thng hoc mch nhnh c cng thc ho
hc l CnH2n+2.
Ni chung, nguyn liu FCC cha ch yu cc hydrocacbon parafin. Hm lng ca
cacbon trong parafin chim khong 50 n 65% khi lng ca nguyn liu. Parafin d b
cracking v to ra lng sn phm lng nhiu nht. Parafin to ra gasolin nhiu nht, kh
nhin liu t nht, nhng cng c gi tr octan thp nht.
Olefin: olefin l cc hydrocacbon cha bo ho, c cng thc l CnH2n. So vi
parafin, olefin l hp cht km bn hn v c th phn ng vi nhau hoc vi cc cht khc
nh oxy, v vi dung dch brom. Olefin khng tn ti trong t nhin, n c mt trong
nguyn liu FCC l do cc qu trnh x l trc , v d nh, do cracking nhit, hoc do
cracking xc tc...
Olefin khng phi l hp phn mong mun trong nguyn liu FCC v olefin thng b
polyme ho to ra cc sn phm nh cc v nha. Hm lng olefin ti a trong nguyn liu
FCC l 5%kl.
Naphten: Naphten c cng thc CnH2n cng nh cng thc ho hc ca olefin.
Olefin c cu trc mch thng (chnh xc hn l mch h), cn naphten l parafin c cu
trc mch vng. Naphten l hp cht bo ho. V d, cc naphten nh xyclopentan,
xylcohexan, metyl-xyclohexan c cu trc vng nh sau:
CH3

Xyclo pentan
C5H10

Xyclo hexan
C6H12

Metyl xyclo hexan

C7H14

Naphten cng l hp phn mong mun trong nguyn liu FCC v chng to ra gasolin
c gi tr octan cao. Gasolin c to ra t naphten c nhiu aromat hn, v l gasolin nng
hn so vi gasolin c sn xut t cracking parafin.
14

 Aromat: aromat (CnH2n-6) tng t nh naphten, nhng cha vng cacbon cha bo
ho v kh n nh. Aromat l cc hp cht cha t nht mt vng benzen. Vng benzen rt
bn v khng b cracking. Cc aromat l hp phn mong mun cho nguyn liu FCC hin
nay, v s to ra gasolin c gi tr octan cao.
Cracking cc aromat thng xy ra s phn ct cc mch nhnh v to ra cc hydrocacbon phn t nh. Ngoi ra, mt s t hp cht aromat a vng c th to ra nhng mng
cacbon nm li trn b mt cht xc tc (cc), hoc cc sn phm a phn t khc (nha).
Trong tng lai, khi hm lng benzen trong gasolin b hn ch ngt ngho th c l
aromat khng phi l hp phn a chung cho nguyn liu FCC.
1.4.2. Cc tnh cht vt l ca nguyn liu FCC
c trng nguyn liu FCC bao gm vic xc nh cc tnh cht ho hc v vt l ca
nguyn liu. Song, cc k thut phn tch qu nhy v chnh xc nh ph khi l khng
thch hp cho cc hot ng cng ngh thng ngy, do ngi ta thng phi s dng cc
tnh cht vt l nh gi nhanh cht lng nguyn liu. Cc phng th nghim ca cc
nh my lc du thng c trang b cc dng c, thit b cn thit thc hin vic th
nghim cc tnh cht vt l thng thng ca nguyn liu nh:
-

T trng, oAPI;
Chng ct nguyn liu;
im anilin;
Ch s khc x (RI);
S brom (BN) v ch s brom (BI);
nht;
Cacbon Conradson, Ramsbottom, Micro-cacbon v cacbon khng tan trong heptan.

T trng, oAPI
T trng (density, D) l mt i lng o mt cht lng: D ca cht lng l t s ca
trng lng mt th tch cht lng vi trng lng ca th tch nc tng ng, ti mt nhit
cho, v d nhit 15,5oC. oAPI l i lng o mt ca hydrocacbon lng.
So vi t trng, oAPI xc nh cc thay i mt ca cht lng mc nh hn
(nhy hn). V d, t 24oAPI n 26oAPI tng ng vi s thay i ca t trng l 0,011.
Vi s thay i 2oAPI c th nh hng ng k n hiu sut sn phm cracking.
Gia D15,5 v oAPI c mi lin h sau y:

D
o

15,5 C

API =

141,5
131,5+ o API

141,5
131,5
D o

(1.1)
(1.2)

15,5 C

15

V mt tnh theo oAPI t l nghch vi t trng D, nn oAPI cng cao th cht lng
cng nh. Trong ch bin du m, oAPI thng c o hng ngy i vi mi nguyn liu
v sn phm. Phng php tiu chun ASTM D-287 l php th c thc hin hng ngy
bi mt k thut vin ca phng th nghim hoc bi mt cng nhn vn hnh phn xng.
Ngi ta dng mt t trng k (hydrometer) khc oAPI cm vo mt ng ong ng hn hp
cn o, c gi tr oAPI v nhit ca cht lng. Sau cn c vo cc bng chun quy
i v oAPI 15,5oC.
i vi nguyn liu giu parafin (sp nn), ngi ta phi gia nhit n ~49oC trc
khi nhng t trng k. Gia nhit lm cho sp nng chy v c chnh xc. Theo di
o
API hng ngy gip cho cng nhn vn hnh hiu c tnh hnh hot ng ca phn xng
cracking. Cng mt khong nhit chng ct nh nhau, phn on c 26oAPI d b
cracking hn so vi phn on 24oAPI, v nguyn liu vi 26oAPI nhiu parafin mch thng
di hn. Khi tip xc vi cht xc tc nhit ~700oC, chng d b phn ct thnh cc sn
phm c gi tr.
Parafin mch thng di rt c li cho cracking v n d b cracking, to ra nhiu
gasolin v LPG (kh du m, liquified petroleum gas), to ra ti thiu cc sn phm nha v
kh kh.
Cc gi tr oAPI cung cp nhng thng tin quan trng v phm cht nguyn liu. Tuy
nhin s dch chuyn cc gi tr oAPI cng cn lin quan n nhiu tnh cht khc ca
nguyn liu nh dng cacbon, im anilin, do , ngi ta phi o cc tham s khc c
trng y tnh cht ca nguyn liu.
Chng ct nguyn liu
Cc s liu v khong nhit chng ct cung cp cc thng tin quan trng v phm
cht v thnh phn ca nguyn liu. Nguyn liu cho cng on cracking xc tc l mt hn
hp c pha trn t nhiu gas oil ca cc cng on chng ct du th, chng ct chn
khng, x l nha ng bng dung mi, v t l cc. Mt s nh lc du cn mua thm
nguyn liu FCC bn ngoi nh my m bo thnh phn nguyn liu t cht lng
thch hp. Mt s nh lc du ch bin du cn t chng ct kh quyn v chng ct chn
khng. Trong nhng nm gn y, ngi ta c khuynh hng ch bin gas oil nng v du
cn. Du cn l phn du ng vi im si trn 565oC. Mi mt nguyn liu FCC c nhng
c tnh ring ca mnh.
S lng v phng php th nghim i vi tng m nguyn liu tu thuc vo cc
nh lc du. Mt s nh lc du tin hnh phn tch hng ngy, mt s khc t mt n 3
ln mt tun v mt s khc na mt ln mt tun. S ln phn tch ph thuc vo cc kt
qu chng ct, s bin i ngun du th, v tnh hnh nhn s ca phng th nghim nh
my.

16

Chng ct phn on du th trong phng th nghim c tin hnh bng cch o

nhit ca hi chng ct im si ban u (IBP, initial boiling point) ng vi cc phn
on, % th tch: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 v 95; v im si cui cng (EBP,
end boiling point). Ba phng php tiu chun ASTM thng c s dng o im si
D-86, D-1160 v D-2887.
D-86 l phng php ph bin nht trong cc nh my lc du. Chng ct c thc
hin p sut kh quyn, khi mu c EBP thp hn 400oC. Trn nhit , mu bt u b
cracking nhit. S cracking nhit c biu hin bi s st gim nhit ca hi chng ct,
c khi nu xut hin v p sut ca h tng. Hu ht cc nguyn liu cho FCC hin nay u
nng, khng thch hp vi phng php D-86, phng php ny c s dng cho cc sn
phm nh.
Phng php D-1160 c thc hin iu kin chn khng (1mmHg). Cc kt qu
o c chuyn i v iu kin p sut thng bng bng cho sn. Mt s thit b mi sn
xut c phn mm chuyn i t ng. D-1160 c gii hn cc i EBP khong 538oC p
sut kh quyn. Cao hn nhit , mu bt u b cracking nhit.
D-2887 l phng php chng ct m phng nhit thp (SIMDIS. Simulated
distillation), ngi ta o % th tch ca phn on c nhit si thc (TBP, true boiling
point) bng phng php sc k kh (GC, gas chromatography). Tng t nh D-1160,
phng php D-2887 b gii hn nhit si cc i ~538oC. Tuy nhin, vi cc h GC
mi, ngi ta c th o c cc nhit si cao n 750oC. Nh phng php ny, ngi
ta c th o c nhit si ca cc nguyn liu nng cha du cn v c trng cc du
th. So vi phng php D-1160, phng php SIMDIS c thao tc n gin hn, lp li
tt hn v o im IBP v nhit si ca im 5% v 10% chnh xc hn.
Cc s liu chng ct cung cp cc thng tin v phn on nguyn liu nh c nhit
si thp hn 343oC. Cc nguyn liu nh ny thng cho hiu sut LCO cao v
chuyn ho thp. Cc ngun nguyn liu nh thng l cc gas oil ca cc cng on chng
ct kh quyn, chng ct chn khng nh v sn phm nh ca l cc. Nguyn liu nh c
chuyn ho thp v cc l do sau y:
- Cc sn phm hydrocacbon nh thng kh b cracking hn.
- Gas oil nh t l cc cha rt nhiu aromat.
- Aromat nh c mch bn th phn mch bn d b cracking.
Ni chung, nguyn liu nh c s dng rt hn ch. Tuy nhin gas oil nh trong
nguyn liu FCC lm gim lng cc trn cht xc tc, c ngha l lm gim nhit hon
nguyn xc tc.
Cc s liu chng ct cho bit thng tin v phn nguyn liu c nhit si trn
482 C. Phn nguyn liu ny c khuynh hng to cc b mt v cha nhiu tp cht nh
cc hp cht cha kim loi v nit, to ra sn phm lng t hn, cn cc v kh th nhiu hn.
o

17

 im anilin
Anilin l mt amin thm (C6H5NH2). Khi c s dng lm dung mi, anilin ho tan
chn lc cc phn t aromat nhit thp, cn parafin v naphten nhit cao hn.
Anilin c s dng xc nh hm lng cc hydrocacbon thm ( aromat) ca cc sn
phm du m, trong c nguyn liu cho FCC. im anilin (AP) l nhit ti thiu
ho tan hon ton mt mu du vo anilin.
Phng php ASTM D-611 c thc hin bng cch gia nhit mt hn hp 50/50
mu v anilin cho n khi thnh mt pha ng th. Sau , hn hp c lm lnh; nhit
ti hn hp bt u xut hin mu c, l im anilin. Php th c tin hnh nh mt
ngun sng chiu qua mu.
AP tng vi s tng hm lng parafin ( parafin) v gim vi aromat. im
anilin cng tng theo trng lng phn t. Naphten v olefin c gi tr nm gia parafin v
aromat. im anilin cao hn 93oC c trng cho nguyn liu parafin, thp hn 65oC c
trng cho aromat.
im anilin c dng xc nh aromat ca gas oil v cc nguyn liu nh.
Gia AP v ch s khc x c mi quan h tng h. Do , ngi ta cn s dng ch s
khc x c trng nguyn liu FCC.
Ch s khc x
Tng t nh im anilin, ch s khc x (RI, refractive index) cho bit hm lng
aromat ca mu. RI cng cao, aromat cng nhiu v mu cng kh b cracking. Mt mu c
RI bng 1,5105 b cracking kh hn mu RI 1,4990. Ch s khc x c o bi phng
php thc nghim (ASTM D-1218) hoc c xc nh theo quan h chuyn i theo h
thc TOTAL t AP. Trong phng th nghim , ngi ta o RI bng khc x k. i vi
nhng mu du c mu ti v nht cao, c AP v RI u b hn ch v chnh xc v
kh nng s dng.
S brom v ch s brom
S brom (ASTM D-1159) v ch s brom (ASTM D-2710) l cc phng php nh
tnh xc nh s tm phn ng ca mu. Brom phn ng khng ch vi cc lin kt olefin m
cn vi cc phn t baz cha nit v vi mt s dn xut aromat cha sulfua. Tuy nhin,
olefin l cc tm phn ng ch yu nht, nn s Brom c dng nh gi hm lng
olefin ( olefin) trong nguyn liu.
S brom l s gam brom c dng tc dng vi 100 g mu. Cc s brom in
hnh l:
- Nh hn 5 i vi nguyn liu qua hydro - x l.
- 10 i vi gas oil nng t cng on chng ct chn khng.
- 50 i vi gas oil t l cc.
18

Theo kinh nghim thc t, phn olefin ca mu bng mt na s brom.

Ch s brom l s mg ca brom c dng tc dng vi 100 g mu. Ch s ny c
dng trong cng ngh ho hc i vi cc ngun nguyn liu c hm lng olefin rt thp.
nht
nht biu th thnh phn ho hc ca mt mu du. Khi nht ca mu tng,
hm lng parafin tng, hm lng hydro tng v hm lng aromat gim.
nht c o 2 nhit khc nhau, c bit 38oC v 99oC. i vi nhiu
nguyn liu FCC, mu du kh c v st 38oC nn mu c gia nhit khong 50oC. Cc
s liu v nht c tm thy trn biu "nhit - nht" (trong cc s tay lc - ho
du). nht khng bin i tuyn tnh vi nhit , nhng trn cc biu , ngi ta
hiu chnh c quan h tuyn tnh.
nht l mt thc o bn chy ca mt cht lng. n v o nht tuyt i
l poise (P). Song vic xc nh nht tuyt i thng khng n gin, do , ngi ta
thng s dng nht ng (kinematic (flowing) viscosity). nht ng c xc nh
bng cch o thi gian cht lng chy qua mt ng dng mao qun c ng knh v di
quy nh. n v o nht ng l stoke (st).
Gia nht tuyt i v nht ng c quan h:
St = P
d
2
trong , P = 0,1 Ns/m = 1 dyn.s/cm2 = 1 g/cm.s;

(1-3)

St = 1 cm2/s;
d = khi lng ring, g/cm3.
nht Saybolt (ASTM D-88) l i lng c s dng ph bin nht o nht
ca du m, ca nguyn liu FCC. Phng php Saybolt c hai dng:
- Viscomet vn nng Saybolt (SUV, Saybolt universal viscometer) p dng cho du nh.
- Viscomet furol Saybolt (SFV) dng cho du nng.
C hai cch u da trn nguyn tc o thi gian chy ca mt th tch mu c nh
qua mt ng mao qun mt nhit cho.
S khc nhau gia hai dng c o ni trn l ng knh bn trong ca ng chy khc
nhau. SUV c ng knh trong ca ng l 0,176 cm, ca SFV l 0,315 cm. SUV c dng
cho cc mu c thi gian chy ln hn 600 sec. i vi cc gas oil thng thng nht, thi
gian chy l ngn nn c o bng SUV. Kch thc ca ng trong hai phng php o
c chn sao cho nht Furol ca du bng 1/10 nht Universal cng mt nhit .
Cacbon: Conradson, Ramsbottom, Micro-cacbon v cacbon khng tan trong heptan
Mt vn hin nay vn cha c nghin cu mt cch y trong cng ngh
cracking xc tc l cn cacbon ca nguyn liu. Ngi ta cha c cch xc nh chnh xc
19

v nh hng ca n n vic to cc.

Cn cacbon c nh ngha l cn c to ra sau khi mu b phn hu nhit.
Cc thit b cracking xc tc thng c kh nng gii hn t chy cc, do s c
mt ca cn cacbon trong nguyn liu s to ra lng cc nhiu hn v lm gim r rt nng
sut ca thit b FCC. Gas oil thng thng dng lm nguyn liu FCC c t hn 0,5% khi
lng cn cacbon, nhng nguyn liu cha du cn, hm lng cn cacbon ln n 15%
khi lng.
Hin nay c 4 phng php c s dng xc nh cn cacbon trong nguyn liu
FCC:
- Conradson
- Ramsbottom
- Micro-cacbon
- Khng tan trong heptan
Cc phng php ch ra c trng s hnh thnh cc dng cc ca nguyn liu. Mi
mt phng php c nhng u im v nhc im ca mnh, v khng mt phng php
no c th cung cp mt nh ngha chnh xc v cn cacbon hoc v cn asphalten.
Xc nh cn Conradson theo phng php ASTM D-189 bng cch o cn cacbon
sau khi bay hi mu bng phn hu nhit. Mu c cho vo a cn sn. Sau c gia
nhit bng n ga cho n khi hi ca mu ngng chy v khng thy khi xm bc ra. Sau
khi lm ngui, a ng mu c cn li tnh ton % cn cacbon. Php th mc d
kh n gin v ph bin, song khng cho kt qu tt v c im hnh thnh cc ca
nguyn liu FCC, bi v n ch cho bit cn to ra do hiu ng nhit ch khng phi do hiu
ng xc tc. Ngoi ra, phng php ny c lp li khng cao, tn cng v kh ph thuc
vo ngi thc hin.
Phng php Ramsbottom ASTM D-524 c dng xc nh cn cacbon. Mu
c cho vo mt bnh cu thu tinh cn trc, sau lp bnh cu vo bp gia nhit
trong 20 pht. Nhit ca bp gi 553oC. Sau 20 pht, bnh cu c lm ngui v cn.
So vi phng php Conradson, th phng php Ramsbottom chnh xc hn v lp li tt
hn.
C hai phng php u cho cc kt qu tng t nhau v c mi tng quan vi nhau
(hnh 1.3).
Phng php xc nh microcacbon hin nay cn gi l phng php micro s dng
mt dng c o cacbon Conradson. Phng php micro (ASTM D-4530) cho cc kt qu
cng tng t nh phng php Conradson (ASTM D-189).
Phng php khng tan trong heptan (ASTM D-3279) c s dng ph bin xc
nh hm lng asphalten trong nguyn liu. Asphalten l cc cm vt liu c to ra t
20

Cn cacbon Ramsbottom, %kl

100

10

0,1

0,01
0,01

0,1

1
10
Cn cacbon Conradson, %kl

100

Hnh 1.3. Mi quan h gia cn cacbon Ramsbottom v Conradson.

cc mng aromat a nhn, nhng cho n nay ngi ta vn cha hiu c mt cch r rng
v cu trc phn t ca chng. Cc asphalten khng tan trong cc parafin C5 - C7. Lng cc
asphalten b kt lng lun thay i t dung mi ny n dung mi khc. Do , iu quan
trng l: gi tr asphalten o c phi tng ng vi mt dung mi tng ng. Ngi ta
thng dng phng php khng tan trong heptan v pentan xc nh asphalten. Mc d
c hai cch ny khng cho mt nh ngha r rng v asphalten, nhng chng to ra mt gii
php thc t nh gi cc cht khi u to ra cc trong cc ngun nguyn liu cho FCC.
Xin lu rng, theo nh ngha truyn thng th lng cn khng tan trong heptan
c gi l asphalten v nha (resin). Hiu s ca lng cn khng tan trong pentan v
heptan l resin. Resin l tp hp cc phn t ln hn aromat v nh hn asphalten.
1.4.3. Cc tp cht
Trong nhng nm gn y, cc nh lc du phi ch bin cc ngun du th nng hn,
lm cho li nhun t lc du tr nn t hn. Nhng nh ngi ta ni: t cn hn khng, do
cc thit b cracking - mt trong nhng cng on ch yu trong nh my lc du, c
thit k a nng p ng mi ngun nguyn liu khc nhau. Cc ngun nguyn liu FCC
hin nay u l nguyn liu nng v cha nhiu tp cht lu hunh, nit v kim loi. Cc tp
cht nh hng xu n s hot ng ca thit b. Hiu r bn cht v tc hi ca cc tp
cht l iu rt quan trng x l cc s c trong vn hnh nh my.
21

Hu ht cc tp cht trong nguyn liu FCC u nm trong thnh phn cc cht hu

c phn t ln, di dng cc hp cht cha:
- Nit;
- Lu hunh;
- Niken;
- Vanadi;
- Natri.
Cc tp cht trn gy ra nhim c cht xc tc FCC, lm mt hot tnh i vi cc
phn ng to ra cc sn phm c gi tr. Lu hunh trong nguyn liu lm tng gi thnh
ch bin v cn phi c cc phng tin x l nguyn liu v sn phm p ng tiu
chun mi trng.
Nit
Nit trong nguyn liu FCC tn ti di dng cc hp cht hu c cha nit. Hm
lng nit trong nguyn liu FCC thng c nh gi di hai dng: nit baz v nit
tng. Nit tng l tng nit baz v nit khng baz. Nit baz thng bng 1/4 n 1/2
nit tng. T baz ng cho cc phn t c kh nng phn ng vi axit. Cc hp cht nit
baz s trung ho cc tm axit ca cht xc tc v lm gim chuyn ho. Tuy nhin, hp
cht nit l cht ng c xc tc tm thi. Trong thit b hon nguyn, hp cht nit b t
chy, hot tnh cht xc tc c hi phc, khong 70 - 90% nit trong cc c chuyn
thnh N2, phn cn li c chuyn thnh oxyt nit (NOx). NOx thot ra mi trng cng
vi kh thi.
S ng c xc tc do cc hp cht nit khc trong nguyn liu FCC l kh ln. Tuy
nhin, s quan tm nhm gim thiu tc hi ny l cha thch ng. Ngi ta bit rng, 100
ppm nit dng baz trong nguyn liu lm gim khong 1% hiu sut gasolin. khc phc
tc hi ca hp cht nit baz, ngi ta phi nng cao nhit phn ng v s dng cc cht
xc tc c hm lng zeolit cao v pha nn hot tnh.
Trong mt s nh my lc du, nguyn liu c hydro-x l (hydrotreating) t
hiu qu kinh t cao hn. Ni chung, cc nguyn liu c hm lng nit cao u cha thm
cc tp cht khc. Do , kh m nh gi ring r hiu ng tc hi ca nit i vi cht
xc tc. Hydro-x l nguyn liu lm gim khng ch hm lng nit m cn gim hu ht
cc nhim khc.
Ngoi tc hi ng c cht xc tc, hp cht nit cn c tc dng xu i vi mt s b
phn khc. Chng hn, trong react ng ng (riser), hp cht nit c th chuyn thnh amoniac
v xyanid (HCN). Xyanid tng nhanh qu trnh n mn ca cc thit b trong phn xng kh,
s n mn to ra hydro nguyn t v do dn n s n mn vy cc chi tit thit b
kim loi. S hnh thnh xyanid c khuynh hng tng theo khc nghit ca qu trnh.
22

Ngoi ra, mt s hp cht nit cng c mt trong du nh (LCO) nh pyrol (pyrolle)

v piridin. Nhng hp cht ny d b oxy ho v s lm i mu ca sn phm. Lng cc
hp cht nit trong LCO ph thuc vo chuyn ho. chuyn ho tng, hm lng nit
trong LCO gim.
Xut x v mt ca ngun du th nh hng kh ln n hm lng nit trong
nguyn liu FCC (bng 1.3)
Bng 1.3. oAPI, hm lng nit v du cn ca mt s ngun du m
o

Xut x
Maga
Cao nguyn bc Alaska
Du trung bnh rp
Forcados
Cabinda
Du nh rp
Du trung bnh Bonny
Brent
Min trung nguyn ty Texas
Forties

API

21,6
28,4
28,7
29,5
32,5
32,7
35,1
38,4
38,7
39,0

Phn du y chng ct
chn khng %LV
33,5
20,4
23,4
7,6
23,1
17,2
5,3
11,4
10,6
10,1

Hm lng nit ca
gas oil chn khng, ppm*
2498
1845
829
1746
1504
1047
1964
1450
957
1407

* Hm lng nit thay i theo ngun du th v hm lng du cn.

Ni chung, du th nng cha nhiu nit hn du th nh. Ngoi ra, hm lng nit
c khuynh hng gia tng theo phn cn trong du th.
Mt s hp cht nit trong du th:
A. Hp cht trung tnh
H

Indol

Cacbazol

B. Hp cht nit baz

N
Pyridin

N
Quinolin

N
Acridin

N
Phenanthridin

C. Hp cht nit baz yu

N OH
Hydroxyl pyridin

N OH
Hydroxyl quinolin

23

Phng php ca UOP 313 thng c s dng ph bin xc nh hm lng nit

baz trong nguyn liu FCC. Mu nguyn liu, trc ht c trn vi axit axetic theo t l
50/50 sau chun vi axit percloric.
Phng php ASTM D-3228 (hoc detect hunh quang ho hc) c s dng ph
bin o nit tng, v bng cch chuyn tt c cc dng nit trong nguyn liu thnh
amoniac v sau chun amoniac vi axit sulfuric. Mt phng php khc ASTM
D-4629 c s dng o nit tng thng qua t chy oxy ho v detect hunh quang
ho hc.
Lu hunh
Nguyn liu FCC cha lu hunh di dng cc hp cht hu c - sulfua nh
mercaptan, sulfua v thiofen. Thng thng khi hm lng cn trong du th tng ln th
hm lng lu hunh cng tng. Hm lng lu hunh tng trong nguyn liu FCC c
xc nh bng phng php ph hunh quang tia X sng di (ASTM D-2622). Cc kt qu
c tnh i sang hm lng lu hunh nguyn t.
Mc d desulfua ho khng phi l mc ch ca qu trnh cracking xc tc, song
trong khi cracking, khong 50% lu hunh trong nguyn liu c chuyn ho thnh H2S.
Ngoi ra, cc hp cht lu hunh cn li trong cc sn phm FCC c loi b trong qu
trnh x l hydro-desulfua ho p sut thng.
Trong qu trnh cracking FCC, H2S c hnh thnh ch yu t phn ng phn hu
xc tc ca cc hp cht khng cha vng thm.
S phn b lu hunh trong cc sn phm FCC khc nhau ph thuc vo nhiu yu t:
ngun nguyn liu, kiu cht xc tc, chuyn ho v ch vn hnh.
i vi nguyn liu khng c hydro-x l, ng vi chuyn ho 78%, khong
50% khi lng lu hunh trong nguyn liu c chuyn ho thnh H2S. Phn cn li c
phn b nh sau:
- 6% trong gasolin;
- 23% trong du nh (LCO);
- 15% trong du gn (DO);
- 6% trong cc.
Cc hp cht lu hunh dng thiofen (dng vng) b cracking chm, v cc thiofen
khng b cracking chuyn vo trong gasolin, du nh v du gn.
Hydro-x l lm gim lng lu hunh trong mi sn phm. Vi nguyn liu c
hydro-x l, lng lu hunh trong nguyn liu c chuyn vo cc v sn phm nng
nhiu hn. Lng lu hunh l ra c chuyn thnh H2S trong cracking FCC th nh
hydro-x l m c loi b. Phn cn li kh loi b hn. Nguyn liu cng nng, cng
giu aromat th hm lng lu hunh trong cc cng cao.
24

Mc du hydro-x l lm tng hm lng lu hunh trong cc v trong cn nha,

nhng lng lu hunh thc t t hn ng k so vi lng lu hunh trong nguyn liu
cha x l. Lu hunh khng nh hng n nhit chuyn ho v hiu sut sn phm.
Tc ng xu ca lu hunh l rt nh trong qu trnh ch bin du m. Mt s hp cht
hu c cha lu hunh khng b chuyn ho cng tng t nh nhiu hp cht aromat khc.
Chng s lm gim phn no chuyn ho v hiu sut sn phm cc i.
Cc kim loi
Cc kim loi nh niken, vanadi v natri c trong du th.
Cc kim loi l cht xc tc v tr xc tc cho nhiu phn ng khng mong mun,
nh dehydro ho v ngng t, lm cho hiu sut hydro v cc tng ln v hiu sut gasolin
gim. Kim loi lm gim hot tnh xc tc i vi cc sn phm mong mun.
Hu nh tt c cc kim loi trong nguyn liu FCC u b gi li trn cc cht xc tc
cracking. Nguyn liu giu parafin cha nhiu niken hn vanadi. Mi mt kim loi c mt
tc hi nht nh.
Niken (Ni)
Nh mc 1.3, cht xc tc cracking cng nghip c hai phn ch yu:
- Pha hot ng xc tc l zeolit Y.
- Cht nn: ch yu l khong st, aluminosilicat v nh hnh.
Khi tip xc vi cht xc tc, niken lng ng trn pha nn. Niken tr xc tc cho
phn ng dehydro ho, tch hydro t cc hp cht bn v to ra cc olefin khng bn. Cc
olefin ny c th polyme ho to ra cc hydrocacbon nng. Cc phn ng ny dn n
hiu sut cao ca hydro v cc. Lng cc trn b mt cht xc tc tng lm cho nhit
hon nguyn cao hn. Nh vy, cn gim t s cht xc tc/du v do gim chuyn ho.
Hm lng niken cao l iu thng thy khi ch bin nguyn liu nng. To ra nhiu
hydro hoc nhit hon nguyn cao l iu khng mong mun i vi cc nh lc du.
Ngi ta nhn thy rng, da vo s liu xc nh lng kim loi trn cht xc tc
lm vic n nh (cht xc tc cn bng) c th tnh ton lng kim loi trong nguyn liu
mt cch chnh xc hn so vi s phn tch trc tip t nguyn liu. Nu niken l kim loi
thng xuyn c mt trong nguyn liu, th c th s dng cht th ng hn ch nh
hng ca niken. Thng thng, ngi ta s dng antimon th ng ho niken. Bin php
ny l kh d nu hm lng niken trong cht xc tc cn bng ln hn 1.000 ppm.
Vanadi (V)
Vanadi cng l kim loi cho cc phn ng dehydro ho, nhng yu hn so vi niken.
Phn ng gp to ra hydro ca vanadi ch bng 20% n 50% so vi niken. Khng ging
niken, vanadi khng b gi li trn b mt cht xc tc . Thc vy, n di chuyn vo bn

25

trong cht xc tc (zeolit) v ph hoi cu trc tinh th ca zeolit. B mt ring ca cht xc

tc v hot tnh xc tc gim dn.
Vanadi c mt trong cc phn t hu c kim loi (c kim) c phn t lng cao, khi
nhng phn t nng ny b cracking, cn cc cha vanadi b gi li trn cht xc tc. Trong
qu trnh hon nguyn, cc b chy v vanadi c chuyn thnh oxyt vanadi V2O5.
V2O5 nng chy 690oC v ph v cu trc tinh th zeolit. V2O5 kh linh ng nn
c th di chuyn t ht tinh th ny n ht tinh th khc.
Hin nay, c mt vi l thuyt v ho hc ng c ca vanadi. Trong , l thuyt ph
bin nht cho rng, V2O5 chuyn ho thnh axit vanadic (H3VO4) trong iu kin hon
nguyn xc tc. Axit vanadic tch nhm t din (Al) trong mng cu trc tinh th zeolit v
do lm sp khung tinh th.
Tc dng ng c ca vanadi ph thuc vo cc yu t sau y:
- Nng vanadi: ni chung, nng vanadi trn 2.000 ppm trong cht xc tc cn
bng cn p dng bin php th ng ho hn ch tc hi ca vanadi.
- Nhit thit b hon nguyn xc tc: nhit thit b hon nguyn cht xc tc
(>677 C) vt qu im nng chy ca oxyt vanadi lm gia tng kh nng linh ng ca
V2O5 di chuyn n cc tinh th zeolit.
o

- Cch t chy cc: ch t chy cc hon ton to ra cht xc tc "sch" lm

tng s hnh thnh V2O5 v nh c mt oxy d.
- Natri: natri v vanadi tc dng vi nhau to ra vanadat natri. Hp cht ny c im
nng chy thp (649oC) v lm tng kh nng linh ng ca vanadi.
- Hi nc: hi nc tc dng vi V2O5 to ra axit vanadic bay hi. Axit vanadic
thng qua s thu phn, gy ra s sp khung tinh th zeolit.
- Kiu cht xc tc: hm lng nhm, lng nguyn t t him, kiu v lng zeolit
nh hng n bn ng c ca cht xc tc i vi vanadi.
- Ch b sung cht xc tc: vic b sung cht xc tc cng nhiu cng lm gim
nng kim loi trong cht xc tc v lm rt ngn thi gian vanadi kp oxy ho hon ton.
Kim loi kim: natri
Natri l kim loi c hi cho cht xc tc FCC. Natri lm mt hot tnh xc tc v n
trung ho cc tm axit. Trong thit b hon nguyn, natri kt hp vi vanadi lm sp khung
tinh th ca zeolit. Natri c xut x t hai ngun chnh:
- natri trong cht xc tc ban u;
- natri trong nguyn liu.
Cht xc tc ban u cha natri v do qu trnh sn xut cht xc tc (xem chng
cht xc tc FCC).
26

Natri trong nguyn liu c gi l natri b sung. nh hng bt li ca cc dng

natri u nh nhau bt k t u.
1.4.4. Cc gi tr v h thc kinh nghim
Phng th nghim ca nh my lc du khng th trang b mt cch y cc thit
b tin hnh phn tch hm lng ca PONA (parafin/olefin/naphten/aromat) v cc phn
tch ho hc khc ca nguyn liu mt cch tc thi v thng xuyn.
Tuy nhin, cc tnh cht vt l nh oAPI, s liu chng ct c th o c d dng. Do
, ngi ta tm ra cc i lng kinh nghim p dng cho cng nghip nhm xc nh
nhanh cc tnh cht ho hc t cc tham s vt l.
c trng y nguyn liu FCC cho php chng ta nh gi mt cch nh tnh v
nh lng v tnh hnh hot ng ca nh my lc du. M hnh ho qu trnh c thc
hin da vo cc tnh cht ca nguyn liu, tin on hiu sut sn phm FCC v cht
lng ca cc sn phm. M hnh cng ngh c s dng hng ngy theo di hot ng
ca phn xng, nh gi cht xc tc, ti u ho qu trnh.
Hin nay, khng c mt i lng kinh nghim tiu chun no. Tuy nhin, mt s t
hng ra cc i lng kinh nghim ring ca mnh, iu cng rt c li cho vic nh
gi cht lng nguyn liu v hiu sut sn phm. Ni chung, cc i lng kinh nghim
u bao gm hu ht hoc mt s tnh cht vt l nh nhau. Hin nay, ngi ta thng hay
dng cc i lng kinh nghim: tha s K, h thc TOTAL, phng php n-d-M, phng
php API.
Tha s K
Tha s K l mt ch s rt hu ch xt on kh nng cracking ca mt nguyn
liu. K lin h vi hm lng hydro ca nguyn liu: K c tnh ton da vo cc s liu
chng ct v mt ca nguyn liu. Tha s K cng cao, cng th hin parafin cao v
kh nng cracking tt. Gi tr K hn 12,0 chng t nguyn liu l parafin, thp hn 11,0,
nguyn liu l aromat.
Tng t nh im anilin, tha s K thay i t nguyn liu giu parafin n nguyn
liu giu aromat. Tuy nhin, trong mt khong hp (K = 11,5 - 12,0) K khng c mi quan
h no gia aromat v naphten. Thc vy, trong khong , K bin i rt tuyn tnh vi
hm lng parafin. Tha s K khng cho bit cc thng tin v t s hm lng gia naphten
v parafin. T s c th thay i ng k i vi mt gi tr K no .
K c tnh ton t nhit si v mt ca nguyn liu. Hin nay, ngi ta s
dng hai phng php kinh nghim tnh K: KW v KUOP.
KW =

( MeABP + 460)1 / 3
D

(1.4)

(CABP + 460 )
D

(1.5)

K UOP =

1/ 3

27

trong :
MeABP: im si trung bnh, oF;
D: t trng 60oF (15,5oC);
CABP = (Fvi x TBi1/3)3;
vi:
Fvi: phn th tch ca cu t i;
TBi: nhit si tiu chun ca cu t i, oF.
Cc h thc TOTAL
Cc h thc TOTAL cho php tnh ton hm lng cc cacbon aromat, trng lng
phn t v ch s khc x da trn cc th nghim thng thng phng th nghim. Cc h
thc ny nh sau:
Hm lng cacbon aromat (%kl):
CA = 814,136 + 635,192.RI(20) 129,266.D + 0,1013.MW 0,304.S 0,872.ln()
Hm lng hydro (%kl):
H2 = 52,825 14,26.RI(20) 21,329.D 0,0024.MW 0,052.S + 0,757.ln()

(1.6)

Trng lng phn t (MW):

MW = 7,8312.10 3.D

0,0976

.AP0,1238

(1-7)

Ch s khc x 20 C RI(20):
RI(20) = 1 + 0,8447.D1,2392.(VABPoC + 273,16)

0,0557

.MW

0,0044

(1-8)

Ch s khc x 60 C RI(60):
RI(60) = 1 + 0,8156.D1,2392x(VABPoC + 273,16)

0,0576

.MW

0,0007

(1-9)

trong :
S : hm lng ca lu hunh % khi lng;
: nht 100oC;
AP,oC: im anilin oC;
D: t trng 20oC;
VABP: nhit si trung bnh theo th tch chng ct, oC;
T (10%) + T (50%) + T (90%)
VABP =
5

vi T(a%): nhit si ca phn th tch chng ct ng vi a%, oC.

H thc n-d-M*
H thc n-d-M l mt phng php (ASTM D-3238) nh gi s phn b cacbon
* Cc k hiu n, d, M c gi theo tn gi truyn thng ca phng php.

28

tng loi hydrocacbon trong cacbon tng s. H thc kinh nghim ny da trn cc ch s
khc x (n), t trng (d) v trng lng phn t trung bnh (MW) v hm lng lu hunh
(S). Ch s khc x v t trng u c o 20oC. Lu rng h thc n-d-M cho php tnh
ton phn trm cacbon trong cu trc ca vng aromat. V d, nu c toluen trong nguyn
liu th phng php n-d-M cho s liu cacbon aromat l 85%, ngha l tng ng vi 6
cacbon trong vng benzen, khng k 1 cacbon mch bn: 6/7 = 0,85 (85%).
Phng php n-d-M rt nhy vi ch s khc x v mt . Phng php da vo
cc php o ch s khc x 20oC. Song, hu ht cc nguyn liu FCC 20oC u trng
thi rn, do , khc x k khng th o ch s khc x v mt nhit . s dng
phng php n-d-M, ch s khc x 20oC cn c xc nh bng cc h thc khc
c cng b. V th phng php n-d-M thng c s dng kt hp vi cc h thc khc,
nh h thc TOTAL.
Phng php API
Phng php API l mt phng php tng qut nhm nh gi phn mol ca cc cht
parafin, naphten hoc aromat i vi mt nguyn liu khng cha olefin. S thit lp cc
phng php tnh da trn c s chia hydrocacbon thnh hai dng phn t: phn hydrocacbon
nng, trng lng phn t MW < 600 v phn hydrocacbon nh 70 < MW < 200. Cc cng
thc API c cng b trong cc s tay lc ho du.
Nh vy, nguyn liu cho FCC bao gm cc dng hydrocacbon khc nhau: parafin,
olefin, naphten v aromat (PONA); v mt s tp cht cha N, S, cc kim loi (Ni, V,
Na...). Vic xc nh chnh xc cc hp phn PONA v cc tp cht trong nguyn liu FCC
l iu ht sc quan trng khng nhng cho cc tnh ton thit k thit b, la chn cht xc
tc, xc nh hiu sut sn phm m cn cn thit nhm x l kp thi cc s c trong qu
trnh vn hnh sn xut.
Thnh phn ho hc ca nguyn liu thng lin quan cht ch vi cc tnh cht vt
l: nhit si, ch s khc x, mt nguyn liu... Do , nhiu khi khng th v khng
cn xc nh trc tip thnh phn ho hc, ngi ta c th s dng cc tham s vt l v
thng qua cc h thc kinh nghim: K, TOTAL, n-d-M c trng nguyn liu mt cch
thun tin, nhanh chng.
1.5. Cc sn phm ca FCC

Cracking xc tc l mt qu trnh nhm chuyn ho gas oil thnh cc sn phm c gi

tr hn. Mc ch chnh ca cc phn xng FCC l chuyn ho cc i gas oil thnh
gasolin v LPG.
Cc sn phm ch yu ca cng on FCC l: kh kh, LPG, gasolin, LCO, HCO, du
gn v cc.

29

 Kh kh
Cc kh nh (C2 v nh hn) thot ra t thp hp th du c gi l kh kh. Cc cu
t chnh ca kh kh l hydro, metan, etan, etylen v H2S. Ngay sau khi c x l vi amin
tch H2S v cc kh axit khc, kh c trn vo h kh nhin liu (fuel gas) ca nh my
lc du. Tu thuc vo thnh phn ca hydro trong kh kh, mt s nh lc du thu hi
hydro bng cc k thut nh lm lnh, hp th di p sut thay i (pressure-swing
absorption) hoc mng phn ring. Hydro thu hi c s dng trong cc qu trnh hydro x l.
Kh kh l mt sn phm khng mong mun ca phn xng FCC, kh kh nhiu qu
gy ra qu ti my nn kh t (WGC, wet gas compressor) v thng gy bt li. Kh kh
c to ra ch yu do cracking nhit, dehydro ho trn tp cht kim loi, v do cracking
xc tc khng chn lc (cht xc tc c lc axit qu cao ...).
LPG
Dng sn phm thot ra t phn trn thp tch butan hoc thp n nh l mt hn hp
cc hydrocacbon C3 v C4 thng c gi l kh ho lng t du m LPG (liquefied
petroleum gas). LPG cha nhiu olefin, propylen v butylen. Cc olefin nh ny ng vai
tr quan trng trong vic sn xut gasolin ci bin, RFG (reformulated gasoline). Tu thuc
vo c cu ca nh my lc du, LPG ca FCC c s dng trong cc dng sau y :
- Sn phm ho cht: LPG c tch thnh hydrocacbon C3 v C4. C3 c bn di
dng propylen c sch ho cht hoc sch cng nghip. Cc olefin C4 c s dng
polyme ho hoc ankyl ho.
- Pha trn trc tip: Cc hydrocacbon C4 c pha trn vo gasolin iu chnh p
sut hi v thay i gi tr octan. Tuy nhin, cc tiu chun cht lng mi v gasolin yu
cu phi gim p sut hi bo ho, do mt lng ln C4 c s dng vo cc mc ch
khc thch hp hn.
- Ankyl ho: Olefin tc dng vi isobutan to ra cc sn phm rt tt cho pha trn
gasolin. Cc ankylat (sn phm ankyl ho) l cc hp phn pha trn gasolin rt a chung v
chng khng cha aromat v sulfua, v c p sut hi thp, im si thp v c gi tr octan
cao.
- MTBE : isobutylen tc dng vi metanol to ra mt oxygenat lm ph gia rt tt
cho gasolin thng c gi l MTBE (methyl tertiary buthyl ether). MTBE c thm vo
gasolin p ng nhu cu ti thiu cho gasolin ci bin.

Gasolin
Gasolin FCC l mt sn phm ch yu v c gi tr ca phn xng FCC. Hiu sut
gasolin c th gia tng nh:

30

- Tng t s cht xc tc/ du bng cch gim nhit gia nhit nguyn liu.
- Tng hot tnh xc tc bng cch tng lng cht xc tc mi hoc bng cht xc
tc c hot tnh cao.
- Tng nhit si cui ca gasolin bng cch gim tc hi lu nh thp chng
ct chnh.
- Tng nhit react (nu khng dn n s cracking su).

Cht lng gasolin ch yu c nh gi bi gi tr octan.

- RON v MON: gi tr octan ca gasolin l thc o c tnh kch n ca gasolin v
c xc nh theo phng php tiu chun ASTM. Gi tr octan cng cao kh nng chng
kch n cng tt, ngha l n ca ng c cng gim.

Ngi ta o gi tr octan thng qua cc php th n ca cc ng c n xylanh

trong phng th nghim vi s vng quay khc nhau nhit khng kh 49oC. Vi ng c
600 vng/pht, gi tr octan o c gi l RON (tr s octan nghin cu, research octane
number), vi 900 vng/pht gi l MON (tr s octan ng c, motor octane number).
RON c o theo tiu chun ASTM-2669, cn MON theo ASTM-2700. Nh vy, s khc
nhau gia RON v MON thc cht l m hnh hot ng ca ng c trong hai iu kin
khc nghit khc nhau.
Tr s octan ca mt gasolin c th c xc nh bng cch pha trn n-heptan (c tr
s octan bng 0) v iso-octan (2,2,4 trimetyl pentan, c tr s octan bng 100) theo mt t l
no ri th n vi ng c. V d, mt gasolin c n ng c tng ng vi
n ca hn hp cha 85% iso-octan v 15% n -heptan, th mu gasolin c tr s octan
l 85%.
- nhy octan: tr mt vi ngoi l, ni chung gi tr RON cao hn gi tr MON.
i vi cc hydrocacbon sch, s chnh lch l t 0 n 15 n v. Hiu s gia RON v
MON c gi l nhy octan. nhy octan cng thp cng tt.
- Octan xa l (road octane) l gi tr trung bnh ca MON v RON, (R+M)/2. Gi tr
trung bnh ny c s dng ti cc trm bm xng cnh ng, nn gi l octan xa l. Cc
ng c t c t s nn cao i hi nhin liu c ch s octan xa l cao.
- GC-RON: l RON gasolin c xc nh bng phng php sc k kh, GC-RON
(gas chromatographic method). Phng php ny c xy dng bi Anderson (P.C.
Anderson et al, J. Inst. Petr., 58, 83, 1972) v sau c ci tin trong nhiu phng th
nghim khc nhau. Theo phng php ny, gi tr octan c th c tnh ton t hm lng
hydrocacbon ca sn phm lng, theo cc s liu sc k kh.
- Octan - barrel: octan - barrel l tch s gia phn gasolin tnh theo barrel nhn c
trong qu trnh cracking v gi tr (M+R)/2 ca gasolin . Thng thng, cc nh lc du
quan tm n vic t ti a octan - barrel hn l i vi tr s octan ca gasolin.

31

 LCO (light cycle oil)

Nhiu khi, do quan tm n sn phm gasolin m ngi ta thng khng ch n
cc sn phm khc ca FCC, c th l i vi LCO.
LCO l phn sn phm thu c thp chng ct sn phm FCC. N c khong nhit
si cao hn gasolin, t 220 - 350oC. LCO l ch vit tt ca nhm t light cycle oil, sn
phm ny cha cc vng thm nh. LCO c hm lng aromat cao, c t 50 - 75%kl. Trong
, 30 - 50% aromat tn ti di dng cc phn t cha 2 v 3 vng thm.
LCO c s dng rng ri nh l mt sn phm pha trn vo du t v nhin liu
diezen, nht l trong ma ng, gi bn LCO nhiu khi li cao hn gasolin. Do , cc nh
lc du thng iu chnh hot ng ca cng on FCC to ra hiu sut gasolin v LCO
hp l, p ng nhu cu th trng.
Cht lng ca LCO c nh gi qua gi tr xetan v hm lng lu hunh.
Cn c vo hai ch s ny, ngi ta mi bit c lng LCO c php pha vo du
t v diezen m bo tiu chun cht lng t ra.
Xetan

Tr s xetan l gi tr bng s c trng cho tnh bt la ca nhin liu. Octan v xetan

l 2 i lng ngc nhau c trng cho tnh cht chy ca nhin liu. Cc cht lm tng tr
s octan s lm gim tr s xetan. V d, hydrocacbon parafin mch thng c tr s octan
thp nhng li c tr s xetan cao; aromat c tr s octan cao nhng c tr s xetan thp.
Tr s xetan c o bng ng c n xylanh trong phng th nghim. Trong thc t,
ngi ta hay dng i lng gi l ch s xetan CI (cetane index). Ch s xetan CI c tnh
ton t cc phng trnh kinh nghim. Hu ht cc nh lc du u dng cch tnh ca
ASTM D-976-80 nh sau:
CI = 65,011(logT)2 + [0,192(oAPI).logT] + 0,16 (oAPI)2 0,0001809(T)2 420,34 (1-10)
trong , T l nhit ti im si 50%, oF.
o

API c xc nh 60oF (15,5oC).

V d:

T = 550oF (288oC), oAPI = 19

Tnh ra CI = 28,9

LCO thng c ch s xetan thp, CI = 20 - 30.

Hydro-x l LCO c th tng tr s xetan. Mc ci thin tr s xetan ca LCO tu
thuc vo iu kin khc nghit ca qu trnh hydro-x l.
HCO v du gn (DO)
HCO l sn phm nhn c t thp chng ct sn phm FCC, c khong nhit si
nm gia LCO v DO (du gn, decanted oil). HCO l tn vit tt ca heavy cylce oil, du

32

(cha) nhiu vng thm nng. HCO thng c s dng nh dng hi lu ca thp chng
ct nhm truyn nhit cho nguyn liu mi v/hoc cho b phn gia nhit ca thp tch C4.
HCO c th c x l tip trong cng on hydrocracking, hoc c dng pha trn vi
du gn.
Du gn (DO) l sn phm nng nht ca cng on cracking xc tc. DO cn c
gi l du st, du y v du cn FCC.
DO l sn phm c gi tr kinh t thp nht, nn ngi ta c gng hn ch hiu sut
DO. Hiu sut DO ph thuc nhiu vo cht lng nguyn liu cracking v chuyn ho.
Nguyn liu giu naphten v aromat c xu hng to ra nhiu DO hn nguyn liu giu
parafin. Nu chuyn ho thp n trung bnh, khi tng t s cht xc tc/du hoc s
dng cht xc tc c pha nn hot ng th c th dn n gim hiu sut DO. Tng
chuyn ho, lm gim hiu sut sn phm y.
Cc (coke)
Trong qu trnh cracking, mt phn nguyn liu b chuyn ho thnh cc do cc phn
ng cracking th cp, polyme ho, ngng t... Cc c hnh thnh trn b mt cht xc tc
dn n s suy gim hot tnh cht xc tc. Do vy, hon nguyn hot tnh ca cht xc
tc, ngi ta phi t chy cc trong thit b hon nguyn (regenerator). Tuy nhin, cc l
mt sn phm ph cn thit cho s hot ng bnh thng cho cng on FCC, bi v nhit
thot ra t phn ng t chy cc li bo m ch nhit (nhit ) cho react cracking.
S hnh thnh, bn cht, nh hng ca cc n hot tnh xc tc c xem xt k
trong chng 2 v 3.
Sau khi cracking cc sn phm ca cng on FCC c phn ring theo khong
nhit si: kh kh, LPG, gasolin, LCO, HCO, DO v cc. Trong , gasolin l sn phm
quan trng v c gi tr nht. Hiu sut cc sn phm FCC ph thuc vo nhiu yu t:
ngun nguyn liu, bn cht v kiu loi cht xc tc, iu kin vn hnh v kinh t
cng ngh ca nh lc du.

33

Chng 2

Ho hc qu trnh cracking xc tc

2.1. M u
Cc phn ng cracking thc hin cc phn ct lin kt CC, v v l cc phn ng
thu nhit nn xt v mt nhit ng hc, chng c tin hnh thun li nhit cao.
Qu trnh cracking hydrocacbon c th bao gm cc phn ng c th sau y:
1. Parafin b cracking cho olefin v cc parafin nh hn:
CnH2n+2

CmH2m + CpH2p+2

(2-1)

Olefin
Vi n = m + p
2. Olefin b cracking cho olefin nh hn
CnH2n

CmH2m + CpH2p

(2-2)

Vi n = m + p
3. Cc alkyl hydrocacbon aromat (cc hydrocacbon vng thm vit tt ArCnH2n+1,
trong Ar: gc hydrocacbon aromat, CnH2n+1 gc alkyl)
ArCnH2n+1

ArH

Aromat

CnH2n

(2-3)

Olefin

4. Thay v phn ng dealkyl ho, phn ng cracking mch nhnh ca vng thm c
th xy ra:
ArCnH2n+1

ArCmH2m1

Hydrocacbon vng thm

c mch nhnh olefin

CpH2p+2

(2-4)

Parafin

Vi n = m + p
Cc hydrocacbon aromat khng c nhm th tng i kh b cracking iu kin
cng nghip v s bn vng ca cc vng thm.
5. Cracking naphten (xycloparafin) to ra cc olefin:
CnH2n

CmH2m + CpH2p
Olefin

Vi n = m + p

34

Olefin

(2-5)

Nu parafin mch c cha mt vng xyclo hexan th vng khng b ph v:

CnH2n

C6H12
Xyclohexan

CmH2m

Olefin

CpH2p

(2-6)

Olefin

Vi n = m + p
Cc phn ng th cp xy ra tip sau cc phn ng cracking s cp ng mt vai tr
quan trng trong vic xc lp thnh phn sn phm cui cng trong qu trnh cracking.
Cc phn ng th cp thng l:
6. Chuyn dch hydro*
Naphten + Olefin
Tin cht cc aromat + Olefin

Aromat + Parafin

(2-7)

Cc + Parafin

(2-8)

Isoolefin

(2-9)

7. Isome ho
Olefin
8. Chuyn dch nhm alkyl
C6H4(CH3)2 + C6H6

C6H5(CH3) + C6H5(CH3)

9. Phn ng ngng t (condensation reactions):

CH CH2

+ R1CH CHR2

R2

+ 2H

(2-10)

R1

10. Phn ng ti phn b cc olefin phn t lng thp

2H2C=CHCH2CH3

H2C=CHCH3 + H2C=CHCH2CH2CH3

(2-11)

Trong iu kin cng nghip, cc phn ng cracking chnh khng b hn ch bi cn

bng nhit ng hc, ti cn bng cc hydrocacbon u c th phn hu hon ton thnh
cacbon graphit (C) v hydro (bng 2.1). Ngc li, cc phn ng ph nh isome ho, ti
phn b nhm alkyl, v dealkyl ho cc aromat c th xy ra ch mc nh trong iu
kin cracking cng nghip. Cc phn ng alkyl ho parafin - olefin, hydro ho aromat v
polyme ho olefin (ngoi tr polyme ho etylen) u hon ton khng xy ra.
Cc phn ng cracking thu nhit mnh, isome ho c hiu ng nhit nh, cn phn
ng chuyn dch hydro to nhit. Trong qu trnh cracking, cc phn ng thu nhit lun lun
chim u th, hiu ng nhit ca qu trnh ph thuc vo ngun nguyn liu, cht xc tc v
iu kin phn ng.

* Cn gi l s chuyn dch hydrua, v thc cht l s chuyn i H trong v gia cc phn t

phn ng.

35

Bng 2.1. Hng s cn bng ho hc ca cc phn ng cracking hydrocacbon

Phn ng
CnHm

Hng s cn bng

nC + m/2H2 (tr khi n = 1)

Rt ln

(Graphit)
CnHm

CH4 + Cn-1Hm-4 (tr khi n = 1)

Rt ln

Parafin + Olefin

Rt ln

Parafin ln
Olefin ln
Parafin
Parafin + H2

2 Olefin

Rt ln

Aromatic + H2

Rt ln

2 Parafin nh hn

Hydroaromatic + Olefin

Rt ln

Aromatic + Parafin

ng vng olefin thnh naphten (1-hexen

Rt ln

xyclohexan)

Trung bnh (15,2)

Isome ho olefin (n-buten

isobuten)

Trung bnh

Isome ho parafin (n-butan

isobutan)

Nh (0,51)

Dehydro ho ng vng parafin (n-hexan

xyclohexan + H2)

Nh (0,07)

Cracking nhit
Trc khi pht hin ra cc cht xc tc cracking, ngi ta tin hnh cracking cc
hydrocacbon khng c mt cht xc tc - cracking nhit. Qu trnh n nay vn cn ng
vai tr quan trng trong vic chuyn ho naphta* thnh cc olefin nh v x l cc
nguyn liu nng. Khi khng c mt cht xc tc, nhit cao, cc hydrocacbon b
cracking nhit theo c ch gc t do.
Giai on khi mo ca cracking nhit mt parafin l s phn ct ng ly (homolysis)
ca lin kt cacbon - cacbon:
H H

R1 C C R2

R1 C

H H

C R2

(2-13)

Gc va c hnh thnh c th b phn ct cho etylen v mt gc bc mt c s

nguyn t cacbon t hn 2 (so vi gc ban u). Quy tc kinh nghim phn ct cho rng,
s phn ct lin kt CC v tr i vi cacbon mang electron khng cp i:

RCH2CH2CH2

RCH2 + CH2=CH2

(2-14)

Gc t do bc mt va mi hnh thnh c th tip tc b phn ct theo quy tc

cho etylen v cc gc mi nh hn cho n khi to ra mt gc metyl. Gc metyl kt hp vi
mt gc H ca mt phn t hydrocacbon khc to thnh mt metan v mt gc th cp:
*

Naphta: phn on du nh ca xng, khong C5 - C11, l ngun nguyn liu cho qu trnh hi nc cracking (steam cracking).

36

H3C + RCH2CH2CH2CH2CH2CH2CH3

CH4 + RCH2CH2CH2CH2CHCH2CH3 (2-15)

Gc ny li b phn ct theo quy tc to thnh mt -olefin v mt gc t do bc

mt.

RCH2CH2CH2 CH2CHCH2CH3

RCH2CH2CH2 + H2C=CHCH2CH3

(2-16)

S lp li phn ng ny v cc phn ng (2-14) v (2-15) dn n s hnh thnh mt

lng ln etylen, mt t metan v olefin.

Tng t nh gc metyl, gc RC H2 c th kt hp vi gc H tch t mt parafin

khc to ra mt gc t do bc 2 v mt parafin nh hn, nhng phn ng xy ra vi
tc chm hn so vi CH3 v tnh n nh ca RCH2 cao hn. Ch khong 10% ca cc
chui gc b bin i theo kiu nh th trc khi b phn ct n CH3. Thc vy, lng
parafin c to ra trong cracking nhit rt t, khi nng hydrocacbon cao, phn ng
chuyn chui gc tr nn quan trng hn, v sn phm cracking nhit c nng cao ca
cc parafin phn t ln v cc olefin, c bit, t C3=, n C7=.

R1CH2 + RCH2CH2CH2CH2CH2CH2CH3

R2CH3 + RCH2CH2CH2CH2CH2CHCH3

(2-17)

Cc gc t do khng b isome ho bng cch chuyn dch cc nhm alkyl hoc

chuyn dch cc tm gc t cacbon ny n cacbon khc trong chui. V cc gc t do bc 1
km bn nhit ng hc hn so vi gc bc 2 v gc bc 3, nn cc gc bc 1 chui di c
th t cun li chim ly gc hydro H t cc v tr bc 2 hoc bc 3 ngay trong bn
thn chui gc :
CH3
CH2

CH2 CH2
RCHCH3

CH2

CH2CH2 CH2

RCCH3

CH2

(2-18)

CH2CH2 CH2

Phn ng v phn ng (2-17) l rt quan trng bi v chng to ra cc sn phm t

etylen hn v giu gasolin hn.
Phn ng kt hp gia cc gc t do (2-13) xy ra vi xc sut khng ln lm, bi v
nng ca cc gc t do thp. Cc phn ng ng vng v phn ng ngng t xy ra vi
mc rt khng ng k trong cracking nhit, tng ng vi lng nha aromat thu c
rt t.
T l tng i v kh nng tch gc hydro t cc nguyn t cacbon khc nhau ca
mt parafin c d on theo l thuyt ca Rice v ng s nh sau: i vi nguyn t
cacbon bc mt: 1; i vi nguyn cacbon bc hai: 3,66 v i vi nguyn t cacbon bc ba:
13,4. T l tng i ca tc cracking cc parafin mch thng v mch nhnh c th d
on theo l thuyt , vi gi thuyt l giai on tch nguyn t hydro l chm nht. T
37

cc nghin cu thc nghim v cracking nhit ca nhiu parafin c th nhn thy rng, t l
tch nguyn t hydro l 1 : 3,66 : 14,4. Kt qu kh ph hp vi l thuyt.
S phn b sn phm cracking nhit ca naphta v ca n-hexadecan c trnh by
trong bng 2.2. ng nh d on, hiu sut etylen ca hai trng hp u cao. i vi
n-hexadecan, ngi ta thy c mt mt lng tng t nhau ca cc sn phm C5 v cc hp
cht aromat c phn t lng cao hn.
Bng 2.2. Cracking nhit hydrocacbon
Cracking nhit naphta thit b
cng nghip (a)
Sn phm

Cracking nhit n-hexadecan(b) quy m phng th nghim

(mol/100 mol cracking)

%mol

Sn phm

Thc nghim

Tnh ton

Hydro
Metan
Axetylen
Etylen
Propadien
Propylen
Propan
Butadien
Butylen
Butan
Lng C5+

16,2
25,7
1,4
30,7
2,5
0,8
7,5
0,2
2,4
1,0
11,5(c)

C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11

53
130
60
23
9
24
16
13
10
11
9

61
139
50
27
15
17
14
12
11
10
9

Tng cng

100

C12

C13

C14

H/C ca C5+ =1,0

iC4/C4 = 0,07
(a): Thi gian tip xc trong l ng = 0,05 - 0,1 giy, nhit ~900oC.
(b) Tc khng gian cht lng LHSV = 0,05. React cha lp m thch anh, chuyn ho
31,5% khi lng.
(c) Xc nh trn c s C5H5.

Tm li, nhng c im quan trng ca cc phn ng cracking nhit l: s phn ct

lin kt cacbon - cacbon xy ra v tr i vi nguyn t cacbon c electron cha cp
i; xc sut chuyn i gc t do t hydrocacbon ny sang hydrocacbon khc l khng
ng k; v s chuyn dch electron cha cp i t nguyn t cacbon ny sang nguyn t
cacbon khc l hu nh khng th, ngha l gc t do khng th thc hin cc phn ng
isome ho bng cch chuyn dch nhm metyl. L thuyt cracking nhit rt ph hp vi cc
d on v hiu sut cao ca etylen, hiu sut thp ca metan, ca -olefin, s vng mt ca
cc sn phm isome ho v t s cao ca olefin so vi parafin trong sn phm cracking nhit.
38

2.2. Cracking xc tc
Cc phn ng cracking xy ra nh cc cht xc tc axit theo c ch cacbocation. C
ch ny c xut u tin bi Gayer (F.H. Gayer, Ind. Eng. Chem, 75, 1122, 1935) nm
1933, sau c Hansford (R.C. Hansford, Ind. Eng. Chem. 39:849, 1947), Olah v
Thomas (C. L. Thomas, Ind. Eng. Chem., 41:2004, 1949) ng h, cng c v pht trin. n
nay, c ch cacbocation trong cracking xc tc hu nh c hon ton tha nhn. Do
, nhng hiu bit v bn cht, v s hnh thnh ca cc cacbocation l ht sc cn thit
nghin cu cc phn ng xy ra trong qu trnh cracking xc tc.
2.2.1. Cc kin thc c s v cacbocation
(i) Danh php
Theo danh php ca UIPAC th thut ng cacbocation c dng biu th cho cc
cation hu c c hnh thnh nh thm mt proton (H+) vo mt phn t hu c hoc tch

ra mt ion hydrua (H ) t mt phn t hu c.

Cacbocation gm hai loi ion:
- Ion cacbeni*: l cc cacbocation, trong , cacbon mang in tch dng c s phi
tr ba, v d nh: CH3+, C2H5+, C3H7+, (CH3)3C+...
- Ion cacboni: l cc cabocation, trong , cacbon mang in tch dng c s phi tr
nm, v d nh: CH5+, C6H7+, R1-CH3+-CH2-R2,...
Cc ion cacbeni khc nhau c gi tn theo tn ca gc alkyl tng ng v thm mt
t cation pha trc tn gc alkyl. V d:
+ CH3+: cation metyl, C2H5+ cation etyl, C3H7+ cation propyl, (CH3)3C+ cation tertbutyl,...
Hoc i khi ngi ta c th gi tn theo mt cch khc: gi CH3+ l ion cacbeni, i
vi cc ion khc th chn tn nhm alkyl thay th H ca CH3+ vo gia 2 t ion v cacbeni.
V d:
CH3+: ion cacbeni
CH3CH2+: ion metyl cacbeni
C2H5CH2+: ion etyl cacbeni
CH3C+HCH3: ion dimetyl cacbeni.
(ii) C ch hnh thnh cc cacbocation
C nhiu cch hnh thnh cacbocation. Sau y l mt s trng hp thng gp:
a) Thm mt proton vo mt phn t cha bo ho
* Xin lu rng, hin nay cc ti liu (sch gio khoa, gio trnh...) Vit Nam vn ang dng
danh php c.

39

- Olefin: s hnh thnh cacbocation bng cch thm mt proton vo mt phn t olefin
xy ra nh sau: proton tn cng vo cc electron ; sau , lin kt (CH) c to thnh
vi mt trong 2 cacbon ca lin kt i, v cacbon th 2 mang in tch dng. Ion
cacbeni c to ra nh trn c mt cacbon lai ho kiu sp2 v c mt cu hnh phng xung
quanh cacbon mang in tch dng.
V d:

R1CH CHR2 + HX
axit

R1CH2 CHR2 + X
cacbocation

[ R1 CH CH R2 ] + X

H
H
H

C+

H
C

H
H

(cu hnh ca cation propyl bc 2)

Nhng phn t no c cu trc khng gian cn tr cu hnh phng s to ra cc ion
cacbeni km bn vng.
- Hydrocacbon aromat: s proton ho mt vng aromat xy ra theo c ch tng t
trng hp trn, ngha l, proton tng tc vi cc orbital ca nhn aromat, sau , hnh
thnh mt lin kt (CH). Tuy nhin, khc vi trng hp trc, trong trng hp ny
in tch dng khng nh x ti mt cacbon nht nh m nh x trn c nhn thm.
H H
+ HX

+ X

b) Thm mt proton vo mt phn t bo ho

Proton ho mt hydrocacbon bo ho cn mt axit c lc cho proton rt ln. Ngi
ta tha nhn rng, proton ho mt parafin xy ra qua mt hp cht trung gian c mt cacbon
phi tr 5. S hnh thnh mt ion cacboni xut pht t metan l ion CH5+. Ion gm 3 lin
kt ng ho tr 2 electron, v mt lin kt gm 2 electron v 3 tm, nh s
H
C
H
Proton ho mt alkan cha 2 hoc nhiu nguyn t cacbon c th xy ra lin kt
CH v hnh thnh mt lin kt HH tng i mnh, hoc xy ra lin kt CC, nh s
sau y.
40

H
+

C C

R C

+ H+

+ H

C
H

C H +

C+

R C+ +

H2

R C
H

Nh vy, tnh kim ca cc lin kt CH v CC ca cc alkan s quyt nh kh

nng tn cng ca proton ln cc lin kt .
c) Chuyn dch electron
Cc axit Lewis, ni chung, c kh nng to ra cc ion cacbeni xut pht t cc alkan.
C ch hnh thnh c th nh sau:
Chuyn dch mt electron t alkan n axit Lewis (L)
RH + L

RH+ + L

Tip n, phn hu gc t do cation RH+ thnh R+

RH+ + L

R+ + HL

d) Phn ct d ly mt phn t bo ho
S phn ct d ly ny c thc hin lin kt cacbon-cacbon ca alkan. S phn ct
thc hin do hiu ng nhit thng to ra 2 gc t do, tuy nhin, khi c mt mt axit th c
th to ra mt cp ion, trong c mt ion l cacbeni.
R1+R2

R1R2

(iii) bn nhit ng ca cc ion cacbeni

Nng lng hnh thnh (Hht) cc ion cacbeni tng theo s nguyn t hydro lin kt
vi nguyn t cacbon mang in tch dng. Cc gi tr nng lng hnh thnh tng i
ca cc ion cacbon bc 3, bc 2 v bc 1 nh sau:
Ion

(CH3)3C+

(CH3)2CH+

CH3CH2CH2+

Gi tr tng i ca Hht (kcal/mol)

14

21

T cc s liu trn, c th nhn thy rng, bn nhit ng ca cc ion cacbeni gim

theo trt t sau y:
R3C+ >> R2CH+ > RCH2+ >> CH3+
V d, phn ng
CH3CH2C+HCH3

(CH3)3C+

c bin thin hiu ng nhit phn ng Hpu = 14 kcal/mol

Nh chng ta bit, bin thin nng lng t do ca phn ng l:
41

Gpu = Hpu TSpu

Nu gi thit bin thin entropy ca phn ng l khng ng k th:
Gpu Hpu
V hng s cn bng Kpu ca phn ng 25oC l:
Gpu = RTlnKpu
lnKpu =

G
14000
=
= 23,644
RT
1,987 298

Kpu = 1,85.1010
Ngha l, khi cc cation cha cng mt s nguyn t cacbon nh nhau th hiu sut
chuyn ho t cation bc 3 sang cation bc 2 l rt ln.
Hng s ca phn ng:
R1H + R2+

R1 + + R2H

bng 1 nu cc cation R1+ v R2+ u l 2 ion cacbeni bc 3 (hoc bc 2). Nu R1+ l ion
bc 3 v R2+ l ion bc 2 th hng s cn bng ca phn ng ~1010, v d phn ng:
(CH3)3CH + CH3CH2C+HCH3

nC4H10 + (CH3)3C+

(iv) Cc phn ng ca cacbocation

Tt c cc cacbocation c hnh thnh u c th tham gia cc chuyn ho sao
cho t c trng thi bn vng nhit ng nht, vi tc chuyn ho nhanh nht. Cc
chuyn ho l:
- Chuyn dch hydrua v chuyn dch nhm alkyl.
- Hnh thnh hoc ph v cc lin kt cacbon - cacbon.
Tt c cc chuyn dch c th c thc hin ngay trong bn thn mt phn t hoc
gia cc phn t. Chnh nhng chuyn dch ny l cc giai on cha kho ca cc phn
ng isome ho, polyme ho, ng vng, alkyl ho v cracking ca cc hydrocacbon.
1. Chuyn dch hydrua v chuyn dch nhm alkyl
S chuyn dch ny xy ra bi mt qu trnh chuyn i 1~2, ngha l bi mt s i
ch ca 2 in tch dng ti 2 cacbon cnh nhau. Nu cc ion cacbeni tham gia chuyn i
c bn nhit ng xp x nhau, th bin thin nng lng t do G* nh, thng thng
thp hn 3 kcal/mol v do tc chuyn dch ln*.
V d, i vi ion cacbeni bc 3
Chuyn dch H
* Da theo l thuyt phc cht hot ng (xem trang 256, Gio trnh Ho l - Ho keo, Nguyn Hu Ph,

Nh xut bn KHKT, 2003) th hng s tc phn ng k = kT e G/RT, nu G nh th k ln.

h

42

C C

~
H

C C C C

C C
C C C C

~ nhm metyl)
Chuyn dch nhm alkyl (Me:
~

C C

Me

C C C C

C C

G* = 3 - 3,5 kcal/mol

k = 107 - 108 s 1
(T = 120oC)

C C C C

Nh vy, phn ng chuyn dch hydrua v nhm alkyl gia 2 cacbeni bc 3 xy ra vi

tc rt ln.
i vi cc ion cacbeni bc 2 cng xy ra tng t
Chuyn dch H
H H

C C C C

H H

G* < 3 kcal/kmol

C C C C

Chuyn dch nhm alkyl

H H

Me

C C C C
+

H H

G* ~ 2 kcal/kmol

C C C C
C

Ngc li, khi chuyn t mt ion bc 3 sang mt ion cacbeni bc 2 phi vt qua mt
thm nng lng l 13 kcal/mol. Do , tc chuyn dch l rt nh. V d, phn ng
isome ho cation 2,4,4-trimetylpentyl thnh cation 2,3,4-trimetylpentyl xy ra vi tc rt
nh mc d bn nhit ng hc ca 2 cation xp x nhau. Tuy nhin, thc hin s
isome ho , cn phi vt qua giai on chuyn dch hydrua to ra mt ion cacbeni bc 2
trung gian, chnh giai on ny l giai on chm, quyt nh tc chung ca qu trnh
isome ho.
C H C
C H C
C C C
~
~
Me
H
C C C C C
C C C C C
C C C C C
+

C H

H H

Giai on chm
G* = 13,5 kcal/mol

k = 5.10 4 s 1 (ti 80oC)
2. Sp xp li mch cacbon
S sp xp li mch cacbon ca cc hydrocacbon theo 2 cch: khng phn nhnh v
phn nhnh.

43

 Khng phn nhnh

C ch ca s sp xp li ny da trn cc chuyn dch 1~2 ca cc hydrua v ca cc
nhm alkyl v c mt giai on chuyn qua ion cacbeni bc 2.
Giai on chuyn dch cation bc 3 thnh cation bc 2 lun lm cho tc chung ca
phn ng khng ln
C H

C C C C
+

C C C C

C C C C

H H

H H

Cation bc 3

Me

H C
C C C C
+

Cation bc 2

Giai on chm
Phn ng:
C H

H C

C C C C

C C C C

Vi G* = 14,8 kcal/mol
Xy ra vi tc khng ln, k = 10 s

( 0oC).

Tng t, phn ng
C H

H C
C C C C C

C C C C C
+

Cng c tc nh k = 8.10

H
4 1

( 78oC).

Phn nhnh
Cc sp xp li mch cacbon c phn nhnh xy ra vi tc nh hn so vi tc
ca cc phn ng sp xp li mch cacbon khng phn nhnh v theo mt c ch khc.
V d:
Phn ng
C C

C C C C

C C C C C

C hng s tc phn ng
k = 0,08 s
k = 4.10
Phn ng:
44

0oC

4 1

-45oC

C
C C C C C

C C C C C

k = 600 s

120oC

Phn ng
+

k = 900 s

100oC

Thot tin, c ch ca cc phn ng sp xp li mch cacbon c phn nhnh c

ngh da vo cc chuyn dch 1~2 ca hydrua v ca alkyl.
C
C C C C C
+

C C C C C

C C C C C
+

Theo s trn, th s chuyn ho phi thng qua mt ion cacbeni bc 1, nn tc

ca qu trnh trn rt chm.
Tuy nhin, c ch ny, v sau, b loi b v ngay c trong mi trng super axit phn
ng isome ho n-butan hu nh khng xy ra, trong khi , n-pentan li b oxy ho rt
nhanh. Nh vy, s chuyn i cation n-butyl thnh cation tert-butyl l kh khn hn rt
nhiu so vi s chuyn i cation n-pentyl thnh cation tert-pentyl. iu mu thun vi
c ch c in v chuyn i 1~2 ca hydrua v ca alkyl, ngha l tc ca 2 qu trnh
trn phi tng t nhau.
Do , mt c ch khc c ngh nh da vo mt hp cht trung gian
xyclopropan proton ho:
CH2
+

R CH2

CH

H
C H
H

R CH2

CH2
+
H

CH2

R CH2

CH3
+
C
CH3

Trong c ch ny, cacbon v tr ca C+ trong mch cacbocation kt hp vi C+ to

ra mt vng xyclopropan proton ho. M vng xyclopropan s to ra mt ion cacbeni
mi c cu trc mch cacbon khc vi cu trc mch cacbon ca ion cacbeni ban u: mt
nhnh thnh 2 nhnh mch thng thnh mch nhnh.
V d:
+

C C C C C C

C C

C
+
C C C C C

C
C C

C
+
H
C
H+

C C C

C C

C
+
C C C C C
C C
+
C C C C

45

Da vo c ch , ngi ta c th gii thch c c ch sp xp li mch cacbon

khng phi tri qua hp cht trung gian ion cacbeni bc 1, v cc kt qu thc nghim ca
tc isome ho kh ln ca n-pentan thnh isopentan trong mi trng axit.
3. Phn ng ct mch cacbon v tr (phn ct )
Cc cacbocation c th tham gia phn ng ct mch cacbon CC v tr i vi
cacbon mang in tch dng to ra mt olefin v mt ion cacbeni nh hn.
H

R1CHCH2CH2R2

R1C=CH2 + CH2R2

Tc phn ng ny ph thuc vo bn nhit ng ca ion cacbeni u v ion

cacbeni cui.
Nu cc ion cacbeni u v cui u l bc 3, phn ng ct xy ra rt nhanh. V d,
cation 2,4,4 trimetylpentyl d dng thc hin phn ng:
C

CH3

CCCC C
C

CC C + C=CC

Tc phn ng phn ct ln hn tc phn ng sp xp li c phn nhnh v nh

hn tc phn ng sp xp li khng phn nhnh ca mch hydrocacbon. Do , ion
trimetylpentyl s cn bng vi cc cation trimetylpentyl khc, ch mt trong cc ion thc
hin phn ng ct .
C C
+

C C C C C

C C
+

C C C C C

C
+

C C C C C

ct

C
+

C C C

C
C C C

C C C
+

C C C C C

C C C
+

C C C C C

Phn ng ct ca ion cacbeni 2 nhnh xy ra chm hn so vi phn ng~ ct ca

ion cacbeni 3 nhnh, v s phn ct ny to ra mt ion cacbeni bc 2 t mt ion cacbeni bc
3 (khng thun li v mt nhit ng hc).

46

chm

C C C C C

C C C C C

nhanh

C
+

C C C + C C C

G* < 3 kcal/kmol

C
+

C C C + C C C

Qu trnh phn ct ca ion cacbeni mch thng xy ra vi tc cn chm hn, kh

khn hn, v n to ra mt ion cacbeni bc mt.
Di y l s biu din cc giai on khc nhau xy ra khi cracking n-octan.

n-octan

Cc cation bc 2
n-octyl

Phn ng phn ct
rt chm

rt nhanh

Cc metylheptan
3-etylhexan

Cc cation metylheptyl
v etyl hexyl

Phn ng phn ct
cc k chm

chm

Cc dimetylhexan
metyl etyl pentan

Cc cation dimetylhexyl
v metyl etyl pentyl

Phn ng phn ct
rt chm

chm

Cc trimetylpentan

Cc cation trimetylpentyl
trong c
C
C
+

C C C C C

Phn ng phn ct
nhanh

C
+

C C C + C C C

Qua s trn thy r c im ca cc qu trnh chuyn dch hydrua, nhm alkyl v

phn ct : chiu hng v tc cc qu trnh u ph thuc vo bn nhit ng ca
cc cation cacbeni v gi tr bin thin nng lng ca qu trnh.
S phn ct cc lin kt CC trong mch vng ca cc cation xycloalkyl l mt phn
ng kh khn hn so vi lin kt CC trong mch thng.
V d, cation trimetylxyclopentyl bc 3 tng i bn 0 o C, trong khi cation
2,2,4-trimetylpentyl bc 3 li b phn ct 73oC.
47

k = 10 4s

+
+

0oC

k = 5.10 4s

73oC

Tnh cht xut pht t bn cht ca cu hnh cc orbital trong khng gian. Trong
ion xyclopentyl cc lin kt CC ca mch vng nm trong mt mt phng vung gc vi
orbital trng pz ca cacbon mang in tch dng. Do , s m vng cng vi s hnh
thnh mt lin kt i i hi mt s che ph cc i ca 2 orbital p i vi orbital pz v do
, i hi mt nng lng hot ho cao hn.
Phn ng cracking xc tc xy ra theo c ch cacbocation. Cacbocation bao gm hai
loi: ion cacbeni (cha C+ phi tr 3) v ion cacboni (cha C+ phi tr 5).
Ion cacbeni chuyn ho theo quy tc phn ct lin kt i vi tm C+ to ra mt
olefin v mt ion cacbeni mi, nh hn.
Cc chuyn ho ca cc cacbocation u tun theo quy tc to ra cacbocation bn
vng nhit ng nht (R3C+ >> R2CH+ >> RCH2+ >> CH3+) v vt qua thm nng lng
hot ng nh nht.
2.2.2. Cracking xc tc cc hydrocacbon n l
Nhng cng trnh nghin cu u tin v cracking xc tc l cracking cc hydrocacbon
n l nhm xc nh cc giai on phn ng v c ch xc tc. Mc du trong nhng iu
kin thc nghim ban u cha hin i, nhng nhng nghin cu cng dn n cc kt
qu v ang c tha nhn, v d nh, quy tc cracking , s hnh thnh cc ion cacbeni
bc 1, 2 v 3,...
Tuy nhin, cc nghin cu v cracking xc tc ca hydrocacbon n l, v sau, t
c thc hin v ngi ta nhn thy rng, cht xc tc cracking rt nhanh chng b suy
thoi do s to cc trn b mt cht xc tc.
Trong nhng nm 1970 nh s pht trin ca my tnh v cc l thuyt mi cp
n s suy gim hot tnh xc tc (l thuyt to cc trn b mt cht xc tc, l thuyt phn
ng trong dng) m ngi ta c th p dng cc s liu phng th nghim cho quy m
cng nghip. Chnh v vy, cc nghin cu v cracking hydrocacbon n l li c hi
phc nhm xc nh mt m hnh ng hc v cc tm hot ng ca cht xc tc v do ,
cho php ch to cc cht xc tc cracking tt nht.

48

2.2.2.1. Cracking xc tc parafin

Parafin l mt cu t quan trng ca gas oil, ngun nguyn liu ca nhiu nh my
lc du, v l sn phm cracking s cp ca nh my .
V th, chng ta s tng quan li cc kt qu trc y t c v cp n cc
kt qu mi nht lin quan n cracking xc tc cc hydrocacbon parafin.
Tnh cht cracking
Mt trong nhng nghin cu u tin v cracking xc tc hydrocacbon n l l
cracking n-hexadecan. Bi v kch thc ca phn t ny i din cho nhiu phn t trong
nguyn liu lc du. Tuy nhin cracking xc tc ca cc phn t mch ngn li c nghin
cu mt cch chi tit hn.
T thc nghim, ngi ta nhn thy rng, trong cc iu kin phn ng nh nhau,
di ca chui cacbon nh hng r rt n nng lng hot ho ca phn ng cracking nh
bng 2.3.
Bng 2.3. nh hng ca di chui cacbon n nng lng hot ho cracking
Hydrocacbon

Nng lng hot ho (kcal/g.mol)

n-C6H14

36,6

n-C7H16

29,4

n-C8H18

24,9

T bng 2.3, c th nhn thy rng, s hnh thnh cc cacbocation cng d dng trn
cc nguyn t cacbon cng su bn trong chui. Cc kt qu trn cng tng t nh kt
qu ca Voge khi nghin cu chuyn ho ca cc parafin khc nhau trn xc tc
aluminosilicat - zirconi, 500oC, 1 atm (bng 2.4).
Bng 2.4. nh hng ca di chui cacbon n chuyn ho cracking
Parafin

chuyn ho (%)

n-C5H12

n-C7H16

n-C12H26

18

n-C16H34

42

Mt khc, ngi ta nhn thy rng, mch ca parafin c nh hng rt ln n ng

hc phn ng cracking (bng 2.5).

49

Bng 2.5. nh hng ca mch cacbon n chuyn ho cracking, 550oC, 1 atm

Parafin

chuyn ho

CCCCCC

13,8

24.9

CCCCC
C

25,4

CCCCC
C
CCCC

31,7

C
C
CCCC

9,9

T bng 2.5 c th nhn xt rng, kh nng phn ct ca cc lin kt CC trong mch

ca cc isome l khc nhau. Kt qu thc nghim ny hon ton ph hp vi nhng tnh
ton orbital phn t v ph hp vi cc tnh cht nhit ng hc ca cc cacbocation trong
dung dch.
Nh vy, parafin thng c mch cng di cng d b cracking; parafin c mch
nhnh d b cracking hn mch thng, cng nhiu mch nhnh, cng d b cracking (trong
iu kin khng b hn ch bi kch thc hnh hc xung quanh tm xc tc).
S phn b sn phm cracking
Mt trong nhng kt qu ng quan tm nht ca phn ng cracking l s phn b sn
phm phn ng, trong , sn phm no l s cp v sn phm no c to thnh t cc
phn ng th cp?
y l mt vn ht sc phc tp, bi v qu trnh cracking lun bao gm nhiu
phn ng th cp v cc phn ng ph khc (xem mc 2.1), v chu tc ng ca nhiu yu
t ng hc, nhit ng hc ca phn ng, c im ca cht xc tc s dng,...
Do , khi xem xt s phn b sn phm cracking chng ta cn cn trng nh gi
bn cht ca s phn b , nht l khi so snh cc kt qu c cng b ca cc tc gi
khc nhau.
V d, Greensfelder v Voge (B. S. Greensfelder, H. H. Voge and G. M. Good, Ind.
Eng. Chem. 41:2573, 1949) cng b hiu sut sn phm cracking ca hexadecan
500oC, chuyn ho = 24% trn xc tc SiO2-Al2O3-ZrO2 (Si-Al-Zr) l:
Bng 2.6. Phn b sn phm cracking hexadecan (100 mol) trn xc tc Si-Al-Zr
Hydrocacbon

C1

C2

C3

C4

C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

Mol

12

97

102

64

50

50

T bng 2.6 thy rng, t 100 mol C16H34 chuyn ho 24% ngi ta thu c 359
mol hydrocacbon (cha k 12 mol H2, khng lit k trong bng 2.6). Nh vy, mt s sn
phm trong bng 2.6 khng phi l sn phm s cp, m cn l sn phm c to ra t cc
sn phm phn ng th cp v phn ng cracking nhit. Thc vy, nu l sn phm s cp
th s phn b s tun theo quy lut:
C1
C
C
C
C
C
= 2 = 3 = 4 = 5 = 6 ==1
C 15
C 14
C 13
C 12
C 11
C 10
Ch nhng thc nghim c tin hnh chuyn ho rt thp v thi gian phn
ng (thi gian tip xc gia hydrocacbon v cht xc tc) rt ngn th mi hn ch c s
sai lch do phn ng th cp xy ra. Da vo mt s gi thit (tc hnh thnh cc ion
cacbeni th cp, s phn ct , s cracking ca olefin va c to ra...), Voge tnh ton s
phn b sn phm khi cracking 100 mol hexadecan to ra ~359 mol sn phm v cho kt
qu nh bng 2.7.
Bng 2.7. Phn b sn phm cracking 100 mol hexadecan theo tnh ton ca Voge
Hydrocacbon

C1

C2

C3

C4

C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

Mol

95

97

72

41

Cc kt qu ca bng 2.7 gn tng t nh bng 2.6. iu chng t rng, cc kt

qu thc nghim cracking hexandecan bao gm cc sn phm s cp v th cp.
Hin nay ngi ta dng cc k thut thc nghim hin i nh ph khi, cacbon
phng x... nghin cu phn ng cracking mt cch chnh xc hn v phn b cc sn
phm. n-Hexan l mt hydrocacbon thng c chn lm cht th (test) cho phn ng
cracking quy m phng th nghim.
Cc kt qu cracking n-hexan ca Good v cng s (G. M. Good et al, Ind. Eng.
Chem. 39:1032, 1947) 550oC, 60 pht trong dng, trn aluminosilicat.
Bng 2.8. Phn b sn phm cracking n-hexan trn aluminosilicat v nh hnh
% mol

H2

CH4

C2 tng

C3 tng

C4 tng

C5 tng

9,4

12,5

19,5

9,5

8,5

1,0

T bng 2.8 c th c nhng nhn xt:

- Lng hydro kh ln.
- T s C1/C4 kh ln chng t y l khng phi l mt phn ng cracking n gin.
- T s C1/C5 cng kh cao.
Thc vy, lng hydro, metan v hydrocacbon C2 kh ln chng t trong thc nghim
ny c s tham gia ca phn ng cracking nhit. Hn na, mu c ly 60 pht phn ng,
ti thi im , cht xc tc tri qua bao nhiu bin i (suy gim hot tnh), do , t
51

cc kt qu tc thi kh m a ra mt kt lun chnh xc v bn cht vn c ca cht

xc tc.
C ch phn ng cracking xc tc ca parafin
iu tin quyt cho mt phn ng cracking xc tc l s hnh thnh cacbocation. Sau
, cacbocation b cracking theo quy tc phn ct , to ra mt cacbocation nh hn b
hp ph trn cht xc tc v mt -olefin pha kh.
V d:
RCH2CH2CH2CH2R
Xc tc

RCH2C+HCH2CH2R

RCH2CH=CH2 + RC+H2

Ion cacbeni mi hnh thnh rt khng bn vng nhit ng, nn phi tip nhn H t
tm xc tc v kh hp ph hoc phi isome ho thnh cc ion cacbeni c ion mang in
tch dng nm pha bn trong mch cacbon nhn c trng thi n nh (bn vng
hn).
C ch cracking xc tc parafin nh trn hu nh u c mi ngi tha nhn. Vn
cn li l nguyn nhn to thnh cacbocation. C kin cho rng, trong mi trng supe
axit cc alkan thng to ra cc ion cacboni; trn cht xc tc d th cc ion cacbeni c

hnh thnh t cc tm axit Lewis bng cch nhng li ion hydrua H ca alkan. Trn xc
tc zeolit, c mt s gi thit v s hnh thnh cacbocation nh sau:

1. Ion cacbeni c hnh thnh bng cch tch ion H t alkan trn tm Lewis.

2. Ion cacbeni c hnh thnh bng cch tch ion H ca alkan trn tm axit mnh
Brnsted, ng thi to ra hydro.
3. Ion hnh thnh trc tin l cacboni phi tr nm, do alkan ly thm proton (H+) t
cc tm axit mnh Brnsted.
4. Ion cacbeni c to ra nh hp ph olefin trn tm axit Brnsted. Cc olefin ny
l tp cht trong nguyn liu hoc do cracking nhit.
5. Cacbocation c hnh thnh nh s phn cc ca phn t nguyn liu trong trng
tnh in mnh ca mao qun zeolit.
Ngi ta tin hnh rt nhiu nghin cu thc nghim xc nh chnh xc cc c
ch hnh thnh cacbocation trong giai on khi mo ca phn ng cracking. Trong s
gi thit 4 c tha nhn rng ri nht. Song, c th ni, cho n nay cha c mt gi thit
no c hon ton khng nh, v vn cn mt s kt qu thc nghim cha c sng t

52

khi da vo cc gi thit . Nhng ni chung, ngi ta thng gii thch s hnh thnh
cacbocation bng mt s gi thit ni trn.
Cc phn ng pht trin mch
-

Cc phn ng khi mo
Ion cacboni

Cacking protolyt

m
Alkan T

T
m

Le H wis
m

nh

Phn ct

Ion cacbeni

Olefin (sn phm)

(2)

Alkan (sn phm)

Ph

Olefin (sn phm)

Ion cacbeni
Ph
c

+ Hhi
tm

Lew
is

Alkan (sn phm)

Giai on
Giai on
pht trin phn ng kt thc phn ng

(n + A
gu lk
y an
n
li
u)

-H
nste
Bro
i tm
c h

Giai on
khi mo phn ng

H2, Alkan (sn phm)

(1)

h
n
+ H ted m
ns
Bro
+

Hnh 2.1. S c ch phn ng cracking alkan trn zeolit

Gn y nht, bng tnh ton orbital phn t khi nghin cu tng tc gia proton ca
nhm OH vi n-butan, ngi ta nhn thy rng, phn ng cracking vn xy ra qua cc ion
cacboni (thng c gi l cracking protolyt) rt thun li v mt nng lng. Do , mt
s c ch phn ng cracking ca alkan trn zeolit c ngh nh trn hnh 2.1.
S ny cho php gii thch c s hnh thnh H2 v cc sn phm alkan, olefin
trong phn ng cracking xc tc: S phn b sn phm ph thuc vo bn cht, s tm v
lc axit ca cc cht xc tc.
Giai on quyt nh ca phn ng cracking parafin
Hin nay, rt nhiu ngi cho rng, giai on hnh thnh cc cacbocation l giai on
quyt nh tc phn ng cracking parafin. S d nh th l v, thc nghim xc nhn
rng, s hnh thnh cacbocation t olefin d dng hn t parafin, ng vi tc phn ng
cracking olefin ln hn tc cracking parafin.
Tuy nhin, suy lun nh trn l khng hon ton chnh xc, bi v cch hnh thnh
cacbocation t olefin v t parafin trn hai loi tm axit khc nhau. Thc vy, trn cht xc
tc axit rn, parafin c th b cracking trn c hai tm Lewis v Brnsted, trong khi , ch
tm Brnsted mi xc tc cho phn ng cracking olefin.

53

C kin cho rng, s hnh thnh cacbocation khng phi l giai on quyt nh
(giai on c tc chm nht) trong phn ng cracking m l giai on chuyn ho ca
cc cacbocation ( to ra mt trng thi hot ng nht). Thc vy, khi nghin cu phn
ng cracking heptan ngi ta nhn thy rng, nng lng hot ho khi cracking n-heptan
thnh C2 + C5 v thnh C3 + C4 khc bit nhau 11 kcal/mol, nhng nng lng hnh thnh
cc cacbocation to ra C2 + C5 v C3 + C4 u xp x nhau ~ 1kcal/mol. Do , r rng l,
giai on quyt nh phn ng cracking n-heptan khng phi l giai on hnh thnh
cacbocation.
Nh vy, cho n nay, cc vn v s nh hng ca cu trc phn t parafin n
tc phn ng cracking, v nguyn nhn v bn cht s phn b sn phm phn ng
cracking l hu nh c tha nhn v sng t. Song, cc vn v bn cht ca cc tm
xc tc khi mo cho s hnh thnh cc cacbocation v giai on no l giai on quyt
nh trong phn ng cracking th vn cn c tip tc tho lun v nghin cu.
2.2.2.2. Cracking xc tc olefin
Trong phn ng cracking xc tc olefin, mi ngi u tha nhn rng, s hnh thnh
cacbocation c thc hin bng cch chuyn mt proton t tm axit Brnsted vo lin kt
i ca olefin. Sau khi hnh thnh, cc cacbocation thc hin phn ng cracking theo quy
tc phn ct . S phn ct to ra mt olefin nh hn v mt cacbeni bc 1 nh hn
trng thi hp ph trn tm xc tc. Ion cacbeni s ti phn b li to ra ion cacbeni
bc 2 hoc b kh hp ph.
RCH2CH=CH2CH2CH2R + H+
RCH2C+HCHCH2CH2R

RCH=CH2 + H+
RCH2CH=CH2 + RCH2C+H2

Nh ni trc y, olefin d b cracking hn parafin c mch cacbon v cu trc

phn t tng ng.
i vi cc olefin mch ngn nh C2 - C5, phn ng cracking tin hnh khng thun
li v cc phn ng chuyn dch hydrua v polyme ho to ra nhiu parafin v cc. V d,
400oC cracking etylen trn xc tc aluminosilicat to ra 2% hydrocacbon C3 v C4, 6% etan,
trong khi trn b mt cht xc tc cha khong 9,6% cc; cracking n-buten to ra 7% C3,
7% isobuten v 8% isobutan.
Olefin l ngun ch yu to ra lp ph cacbon trn cht xc tc cracking. Thc vy,
cc olefin mch ngn u tham gian phn ng to cc, m tt c cc phn ng cracking u
sinh ra olefin v theo qu trnh phn ng, cc olefin mch ngn li dn dn c to ra. V
d, c th khong 27% butadien c chuyn thnh cc khi cracking butadien trn xc tc
NaHY. Etylen b hp ph rt mnh trn cc tm axit Brnsted ca xc tc HY zeolit, thm

54

ch nhit thp. Khi nng dn nhit , cc phn ng chuyn dch proton, polyme ho...
xy ra trong lp etylen hp ph, lm nh hng n hot tnh xc tc b mt.
Nh vy, olefin, c bit, olefin mch ngn l ngun gc ch yu gy hin tng to
cc trn b mt cht xc tc. Tuy nhin, iu ng ngc nhin l hin nay vn cn t cc
nghin cu so snh gia cracking olefin v parafin lm sng t hn na v c ch hnh
thnh cc trn cht xc tc cracking.
Cracking olefin C5, C6 v C7
Nhiu kt qu thc nghim chng t rng, cracking n-penten 400oC xy ra ch yu
l, dime ho, tip n cracking C10. chn lc thc nghim ca phn ng cracking cc
olefin C5, C6 v C7 trn xc tc HZSM-5 c trnh by trong bng 2.9.
T bng 2.9 nhn thy rng, C5 olefin b cracking chm nht so vi ng phn ho cu
trc (C), v cc olefin c chui cacbon di hn c sn phm cracking nhiu hn. Mt khc,
cracking C5 theo cch dime ho (lng phn t) sau mi thc hin phn ng phn ct, do
, sn phm phn ng ch l C3 v C4, trong khi , cracking C7 thc hin bng c ch n
phn t (khng dime ho), t s C3/C4 xp x bng 1). Hexen l trng hp trung gian ca 2
trng hp trn, va cracking theo c ch n v lng phn t.
Bng 2.9. chn lc ca phn ng cracking n-alken trn ZSM-5 450oC
Phn mol

1-peten

1-hexen

1-hepten

C3

0,0173

0,0201

0,0468

C4

0,0095

0,0175

0,0509

C5

(ng phn cu trc-C)

0,0130

0,0097

C6

(C)

C7

0,0025

(C)

C8

0,00098

C9

0,0268

0,05408

0,1074

0,9710

0,9444

0,8974

Tng cng

0,9978

0,9985

1,004

Sn phm

Trong sn phm phn ng, chng ta khng thy sn phm C2 l v s khc nhau rt
ln v bn nhit ng ca C3+ v C2+. Sn phm phn ng cng khng cha hydro chng
t rng khng xy ra qu trnh tch ion hydrua t cacbocation bi cc tm axit Brnsted.

55

Hnh 2.2 ch ra s mt mng phn ng isome ho xy ra khi cracking n-hepten trn

zeolit HZSM-5 (con s trong vng n l chn lc (phn mol), cc ch vit tt M = metyl,
H = hepten).
C th nhn thy rng, cc sn phm ch yu nhn c u xut pht t cc ion
cacbeni bc 3, v cc ion bc 3 ca cacbon v tr th 3 bn vng nhit ng hc hn v
tr th 2 ca chui cacbon.
2M1H (0,054)

2M2H (0,125)

C
CCCCCC

CCCCCC

2M3H (0,028)

5M1H (0,001)
C

5M2H (0,040)

CCCCCC

CCCCCC

CCCCCC

C C+ C C C C C

~
Me 1,2

C CC C C C C

C
C C C C+ C C

C C C+ C C C

CC C C C C

C
C C C C C+ C

~
Me 1,2

C C C C+ C C C

C
C C C+ C C C

C
C C+ C C C C

CCCCCC
C

3M1H (0,00)

CCCCCC
C

3M2H (0,445)

C
C C C C+ C C

CCCCCC
C

3M3H (0,116)

C
C C C C C C+

CCCCCC
C

CCCCCC
C

4M2H (0,038)

4 M1H (0.00)

Hnh 2.2. S cc phn ng isome ho cu trc trong qu trnh cracking n-hepten.

Nh vy, cracking olefin d dng hn so vi parafin tng ng, trong qu trnh
cracking, cc olefin mch ngn (C2 - C5) l tc nhn chnh dn n s hnh thnh cc trn
b mt cht xc tc rn; cn cc olefin c mch cacbon ln hn (C5 - C7) va b cracking,
va b isome ho nhng ch yu l b isome ho thnh nhiu sn phm khc nhau.
2.2.2.3. Cracking xc tc alkyl hydrocacbon aromat
Trong qu trnh cracking alkyl hydrocacbon aromat, vng benzen vn khng b bin
i, trong khi , cc mch bn ca vng benzen u b cracking, v to ra olefin tr trng
hp vi toluen.
nh hng ca di v s phn nhnh ca mch bn, ca v tr nhm alkyl n tc
phn ng c minh ho bng 2.10.

56

Bng 2.10. nh hng ca mch bn n nng lng hot ho cracking alkyl benzen
Hydrocabon

Nng lng hot ho (kcal/mol)

C6H5CH2CH3

50

C6H5CH2CH2CH2CH3

34

CH3

19

C6H5CHCH2CH3
CH3

17,5

C6H5CHCH3

Ni chung, tc cracking mch bn tng khi chuyn v tr gn mch bn vo vng

benzen t cacbon bc 1 n bc 2, bc 3, trong cng mt iu kin lin kt gia mch bn
v vng benzen th tc cracking tng khi di chui bn cng tng.
Trong trng hp toluen th phn ng ch yu l bt i ho toluen thnh benzen v
xylen, khng cracking to ra metan. i vi polymetylbenzen, phn ng chnh l isome
ho v bt i ho ca cc phn t phn ng. V d, trn cht xc tc axit dimetylbenzen b
isome ho v bt i ho tng ng vi s sau y:
o-xylen

m-xylen

toluen

p-xylen

trimetylbenzen

i vi etylbenzen, ngi ta thy phn ng transalkyl ho cng vi phn ng cracking

nhit khong 200oC. nhit thp hn, ch c phn ng transalkyl ho xy ra.
Nh vy, i vi cc alkyl hydrocacbon aromat, phn ng cracking bao gi cng xy
ra km theo cc phn ng cnh tranh khc nh transalkyl ho v isome ho.
Cracking cumen (isopropylbenzen)
C th ni, cracking cumen l phn ng c nghin cu nhiu nht, bi v n c
xem nh l mt phn ng test (th nghim) tiu chun nh gi cc cht xc tc cracking
quy m phng th nghim. S d nh th l v: phn ng cracking cumen p ng c hai
yu cu sau y:
i) l phn ng xy ra theo c ch cracking i din cho nhiu cu t trong nguyn
liu du m.
ii) Phn ng to ra mt s sn phm ti thiu, c th xc nh nh lng mt cch d
dng thnh phn phn ng v s din tin ca qu trnh.
Cracking cumen xy ra theo c ch qua cc hp cht trung gian cacbocation, trn c
hai tm axit Lewis v Brnsted, sn phm chnh l benzen v propylen.

57

C9H12

C6 H6 + C3H6

Ngoi benzen v propylen, ngi ta cn tm thy cc sn phm khc nh: toluen,

etylbenze, o-etyltoluen, n-propylbenzen, xymen, m-diisopropylbenzen, p-diisopropylbenzen,
metan, etan, etylen, propan, butan, buten, isobutan,... T , c th nhn xt rng, thc ra
cracking cumen cng l mt phn ng phc tp, tuy nhin bng nhiu thc nghim trn
nhiu cht xc tc axit rn khc nhau, ngi ta phn bit c hai nhm phn ng xy ra
trn hai loi tm khc nhau (Lewis v Brnsted). V d: trn tm Lewis, c cc sn phm
etylbenzen, n-propylbenzen, etyltoluen... Trn tm Brnsted, c cc sn phm: benzen,
propylen, diisopropylbenzen... Da vo cc c im ny ngi ta c th nh gi c s
lng tm axit Lewis v Brnsted trn cc cht xc tc axit rn. V d, nng cc tm axit
trn cc xc tc zeolit HY, LaY, SA (aluminosilicat v nh hnh) l khc nhau (bng 2.11).
Bng 2.11. Nng tng i ca cc tm axit trn cc cht xc tc khc nhau
n v tng i (so snh vi LaY) Loi tm

HY(a)

S tm axit tnh cho 1g cht xc tc

310

100

45

4,51

1,02

0,42

65

100

6,90

1,66

0,22

310

100

45

9,08

2,07

0,42

65

100

13,90

3,37

0,22

S tm axit tnh cho 1m b mt cht

xc tc

LaY(a) 82%LaY(b) SA-25(c) SA-13(c) 36%LaY(b)

B: Brnsted, L: Lewis;
(a) trao i hon ton vi natri;
(b) % trao i lantan vi natri;
(c) % oxyt nhm trong SA.

Nh vy, nghin cu phn ng cracking cumen cho php chng ta nh gi c hot

tnh ca cc tm xc tc.
Ngoi ra, bng cc nghin cu ng hc phn ng, ngi ta kt lun rng, giai
on quyt nh tc phn ng cracking cumen l giai on phn ng cacbocation b mt
thnh benzen pha hi v cation propyl hp ph. Cn giai on hnh thnh ion cacbocation
khng phi l giai on quyt nh phn ng cracking cumen.
Tm li, trong phn ng cracking, vng benzen ca alkyl hydrocacbon aromat vn
khng b bin i, mch bn c th b cracking: mch cng di, v s bc ca cacbon ni
vi vng thm cng ln th cng d b cracking.
2.2.2.4. Cracking xc tc xycloparafin
Sn phm s cp ca phn ng cracking xycloparafin l cc isome olefin tng ng.
i vi cc xycloparafin nh cc sn phm s cp tng i d dng xc nh, v d, sn
phm s cp cracking xylclopropan l propylen. Ngi ta ngh c ch cracking
xyclopropan nh sau:
58

CH2

CH2
CH2

CH3 Z

CH2

+ H Z

CH2

CH2
+

H
Z
CH3
C3H6

CH3 C CH2 +

H Z

Theo c ch ny, propylen l cc sn phm s cp, cn isobuten l sn phm th cp.

Khi cracking xyclopropan trn xc tc NaHY, propylen l sn phm s cp; isobuten,
2-metylbuten v 2-metylpenten l sn phm th cp. Cc xycloparafin C5, C6 v cc xycloparafin ln hn tham gia phn ng cracking vi tc chm hn so vi cracking n-hexan v
olefin bc mt tng ng, trong khi thc nghim cho thy nng lng hot ho cracking
n-hexan v xyclohexan l xp x nhau; i vi n-heptan v metyl xyclohexan cng tng t
nh vy. Tuy nhin, s phn b sn phm trong cracking n-parafin v xycloparafin l hon
ton khc nhau. iu c bit l, trong sn phm cracking xycloparafin c rt nhiu hydro
(27% khi cracking xyclohexan, 6,5% khi cracking n-heptan). Do , dn n mt kt lun
l: hydro c to ra c th t phn ng dehydro ho. l mt kt lun ht sc ng ngc
nhin, bi v cc h xc tc c s dng u hon ton khng cha cc tm hydro - dehydro
ho (tm kim loi). Kh nng to hydro ca xycloparafin khi b cracking hon ton c
nhiu thc nghim xc nhn. Kh nng c s dng trong vic lm gim kh nng to
cc trn xc tc. Tuy nhin, cho n nay, ngi ta vn cha xc nh c loi tm xc tc
c bit no c kh nng dehydro ho trong qu trnh cracking xyclohexan.
C th nhn xt rng, trong qu trnh cracking, xycloparafin b phn ct thnh cc
isome olefin khc nhau. Tc phn ng cracking xycloparafin nh hn so vi cracking
n-parafin v olefin bc mt tng ng. c bit, sn phm cracking xycloparafin cha rt
nhiu hydro so vi parafin.
2.2.2.5. S hnh thnh cc
Tt c mi phn ng ca hydrocacbon xy ra trn cht xc tc axit u to ra mt hp
cht cacbon, thng c gi l cc. Cc l mt vt liu c bit khng tht r rng v
thnh phn v cc cu trc ca n. Cc khng th tch khi b mt cht xc tc bng cch
thi mt dng nit hoc hi nc nhit cao. Trong qu trnh phn ng, cc dn dn
c to ra, che lp cc tm hot ng trn b mt cht xc tc, do , hot tnh xc tc
gim dn v chn lc phn ng cng b bin i.
Cho n nay, s hnh thnh v cu trc ca cc vn l mt vn cha thc s sng
t. Do , chng ta ch nhc li mt s kt qu r rng t c v vn ny.

59

Ni chung, cc l vt liu cha cacbon v hydro, t s H/C thay i trong khong 0,3
0,1. Da vo cc s liu ph, ngi ta nhn thy mt s lin kt trong vt liu cc cng
tng t nh cc lin kt trong hydrocacbon aromat. Cc c hnh thnh l do cc phn
ng ngng t, alkyl ho, ng vng v thm ho cc hydrocacbon, sau chuyn dch
hydro n cc olefin trong pha kh.
Nhiu kin cho rng kh nng to cc ca cc kiu hydrocacbon khc nhau l khng
nh nhau.
Bng 2.12. Lng (gi tr tng i) ca cc dng ng v phng x trong cc
Cc cht ng v phng x

Lng (gi tr tng i) ng v phng x

n-Hexadecan

1,00

Propan

0,07

Benzen

0,55

Toluen

1,71

Etylen

1,75

Propylen

2,65

1-Penten

8,58

Hydrocacbon a nhn aromat, olefin v polyolefin d to cc so vi naphten v

parafin. Hightower v Emmet (J. W. Hightowner and P. H. Emmet, J. Catal., 42:367, 1976)
cracking hexandecan trn aluminosilicat c s dng cht ng v phng x. Lng ng v
phng x trong cc nh bng 2.12.
T bng 2.12 nhn thy rng, olefin tham gia to cc mnh nht, parafin v aromat
khng ng k.
Mt s nghin cu khc nh alkyl ho benzen vi etylen, cracking cumen, u nhn
thy rng, cc c to ra ch yu l do etylen v propylen (t cracking cumen).
Nh vy, olefin l tc nhn d hnh thnh cc. Hydrocacbon a nhn thm cng l
mt tc nhn to cc quan trng. Ngi ta thy nguyn liu cha cng nhiu hydrocacbon
a nhn thm th lng cc to ra cng ln.
C ch hnh thnh cc cng rt phc tp. Trong trng hp cho butadien i qua cht
xc tc NaHY, s hnh thnh cc c gi thit l do s cng hp ni tip kiu Diels Alder, xy ra trn tm axit Lewis.
i vi trng hp propylen trn xc tc NaHY, cc c hnh thnh theo hai c ch
ph thuc vo nhit ca phn ng. nhit thp hn 300oC, s gim hot tnh xc tc
l do s hp ph mnh ca cc hp cht nh xyclo-olefin v dien trong cc mao qun ca
60

zeolit. trn 300oC hydrocacbon aromat c hnh thnh v c th khuch tn ra b mt

ngoi cht xc tc.
S hnh thnh cc cn ph thuc vo cu trc (ng knh mao qun, kiu h mao
qun, t s Si/Al...) ca cht xc tc. Thc vy, cracking n-hexen-1 trn zeolit HY (ng
knh mao qun ~7,5, h mao qun khng gian 3 chiu) v trn zeolit HZSM-5 (ng knh
mao qun ~5,5, h mao qun khng gian 3 chiu) dn n cc kt qu khc nhau v thnh
phn ca cc (hnh 2.3).

2,8
HY

T s C/H

2,0

1,2
ZSM-5

0,4
10

20
30
40
chuyn ho (%kl)

50

Hnh 2.3. T s C/H trong cc ph thuc vo chuyn ho

trong phn ng cracking n-hexen-1.
Lc ban u, cc c hnh thnh trn 2 cht xc tc u c t s C/H ~ 0,5 tng ng
vi thnh phn nguyn liu. Khi chuyn ho tng, cc trn HY cng b dehydro ho t s
C/H tng, trong khi thnh phn cc trn HZSM-5 vn khng thay i, thnh phn sn
phm cracking trn cht xc tc HY giu cc hydrocacbon parafin. Cu hi: lm th no v
ti sao hydro c th chuyn t cc n sn phm trong pha kh trong trng hp i vi
zeolit HY, cn i vi zeolit HZSM-5 th khng? l vn kh phc tp, song ngi ta
c th ngh rng, iu c th c lin quan n cu trc hnh hc v t s Si/Al cao ca
HZSM-5.

Khi cc ion cacbenium chim ot ion hydrua (H ) t cc nhng cc in tch d

(i) khng tn ti trong vt liu cc, ngi ta cho rng, cc l vt dn in, nn cc in
tch d c phn b li, chuyn t cc (cc tm hot ng) n pha nn v c (aluminosilicat, axit...).
Cc c hnh thnh ch yu b mt ngoi cht xc tc, gia cc khe h ca ht
cht xc tc, tuy nhin cc cng c th hnh thnh trong cc mao qun v cc hc c kch
thc ln trong cc cht xc tc. Nguyn Hu Ph v cng s ( ti Cht xc tc cracking
FCC, Trung tm KHTN&CNQG, 2002-2003, H Ni) nghin cu cracking n-hexan trn xc
tc HY v HZSM-5 trong react cha lp xc tc c nh, 500oC nhn thy rng,

61

chuyn ho ca n-hexan trn xc tc HY gim theo thi gian, cn trn xc tc HZSM-5 th

chuyn ho lun lun n nh. Cc tc gi gii thch rng, cc khng hnh thnh trong
mao qun zeolit HZSM-5, cn trong mao qun HY th c th.
T cc kt qu nghin cu trn, c th kt lun rng, s hnh thnh cc l mt qu
trnh phc tp, cn cha xc nh r rng. l do khng ch c qu nhiu phn ng xy ra
trong qu trnh cracking m cn ngay bn thn khi nim cc cng l mt nh ngha cn
cha xc nh.
Mt kt lun chung c th rt ra l: s hnh thnh cc lun gn lin vi s chuyn
dch hydro t cc hp cht cacbon b mt n cc olefin pha ph. Olefin l sn phm b hp
ph nhiu nht hoc b polyme ho trn b mt cht xc tc, to nn ngun hydro cung cp
cho olefin pha kh v l vt liu cacbon c gi l cc. Cc hydrocacbon aromat nh nh
benzen, cumen khng to cc t chnh vng thm ca mnh. a s cc c to ra khng
trc tip t cc tm hot ng xc tc m l bn ngoi cc ht xc tc v trong mt s mao
qun rng. Tnh cht ca cc ht xc tc nh kch thc mao qun, c trng hnh hc mao
qun, thnh phn ho hc, cng nh hng n bn cht v lng cc hnh thnh trong mt
phn ng cho.
2.2.3. Cracking xc tc gas oil
2.2.3.1. Nhc li cc c im c bn v cracking
Trc khi nghin cu cracking xc tc gas oil, chng ta hy dng li v nh gi xem:
nhng kt qu no c cho l chc chn v r rng trong cc nghin cu cracking trc y.
iu c mi ngi tha nhn chc chn l: cacbocation l tc nhn chnh cho
cracking xc tc v cc phn ng lin quan. Cacbocation bao gm hai loi ion cacbeni v
ion cacboni. C hai loi u c hnh thnh t tm axit Brnsted, trong khi trn tm
axit Lewis ch hnh thnh ion cacbeni.
S phn b lc axit cng nh t s cc tm Brnsted/Lewis s nh hng n hot
tnh xc tc ( chuyn ho) v n chn lc ca cc cht xc tc cracking khc nhau.
chn lc thc nghim bin i trn cc cht xc tc khc nhau l do s thay i tc
ca tng phn ng ring r ng vi nng ca cc tm hot ng khc nhau, ch khng
phi do s thay i bn cht tm hot ng xc tc. Mi mt phn ng c tin hnh trn
cc tm xc tc nht nh vi bn cht (Lewis hoc Brnsted) v vi mt gii hn nht nh
ca axit.
V tc phn ng ph thuc vo mt tm xc tc, cn nng lng hot ho ca
cc phn ng khc nhau thay i trong khong t 25 n 30 kcal/mol, do chn lc
phn ng c th thay i ng k (trong mt khong rng) bng cch thay i nhit phn
ng v bng cch ch to cht xc tc c cc tm khc nhau.

62

Tt c mi cht xc tc u suy gim hot tnh. S suy gim thng xy ra rt

nhanh v dn n cc hin tng rt kh cm nhn trc tip v khc vi nhng g xy ra
i vi cc cht xc tc v cc quy lut ng hc c in. Tuy nhin, cc hin tng xy ra
trong cracking xc tc c th xc nh nh lng v c th c m t mt cch r rng
bng l thuyt suy gim hot tnh xc tc trong dng (the time on stream theory, xem phn
cht xc tc cracking). Nh l thuyt ny m chng ta phn bit r rng nhng vn rc
ri trong cracking xc tc: phn bit s khc nhau gia chn lc thc nghim thu c t
cc react vi lp xc tc n nh v cc react cng nghip, cho php xc nh cc h phn
ng xy ra khi cracking tng hydrocacbon ring r, cho php xc nh ngoi suy cc tnh
cht ban u ca cht xc tc ang hot ng.
L thuyt v thc nghim u chng t rng, khi thm olefin vo parafin th tc
phn ng cracking parafin tng ln, cn i vi hn hp parafin th tc phn ng
cracking ca hn hp l tc tng ca cc parafin ring r (khng nhn thy hiu ng hip
tr xc tc - synergistic effect - gia cc parafin).
Chc chn rng, cc hin tng xy ra trong cracking gas oil - mt nguyn liu kh
phc tp, s tun theo cc quy lut c bn nh i vi cc parafin n l, v ngoi ra, cn
phi b chi phi bi nhng quy lut khc do tnh a dng ca nguyn liu cracking.
2.2.3.2. S phn b sn phm trong cracking ga soil
Theo c ch cracking ion cacbeni, sn phm cracking gas oil s l propylen, buten,
cc olefin v parafin c mch cacbon ngn hn ca hydrocacbon trong gas oil ban u. Tuy
nhin, trong thc t ngi ta nhn c khong 5% hydrocacbon C1 v C2 trong sn phm
cracking. iu c gii thch bi phn ng cracking nhit xy ra trong khng gian gia
cc ht xc tc v bi phn ng th cp ca cc sn phm s cp. Ngoi ra, ngi ta cn
nhn c mt lng kh hydro c hnh thnh do phn ng cracking xy ra theo c ch
protolyt (c ch ion cacboni) trn cc tm supe axit v nhit cao.
Nh vy, trong cc sn phm cracking thu c bao gm cc sn phm hnh thnh t
giai on cracking trc tip cc hydrocacbon nguyn liu (thng c gi l sn phm s
cp) v cc sn phm hnh thnh do cc phn ng cracking k tip ca cc sn phm s cp
to ra cc sn phm cracking th cp. Tiu chun nhn bit cc sn phm cracking s
cp l: cc hiu sut sn phm thi im cracking ban u (cht xc tc cn mi) ti cc
chuyn ho khc nhau u nm trn mt ng c h s gc dng v i qua gc to .
Hnh 2.4, 2.5, 2.6, 2.7 v 2.8 biu din mi quan h gia hiu sut ca gasolin C5+ (gm cc
hydrocacbon c s nguyn t cacbon trong phn t ln hn hoc bng 5), olefin, n-butan, v
ca buten tng ng.
Trn hnh 2.4 cc s liu nm trn ng cong v nt m i din cho hiu sut cc
i ca cht xc tc cn mi (thi gian phn ng trong dng rt ngn). ng thng i qua

63

cc gi tr hiu sut cc i cc gi tr chuyn ho thp v i qua gc to (ngoi

suy) chng t l cc sn phm s cp ca phn ng. Cc s liu nm thp hn ng hiu
sut cc i i din cho hiu sut sn phm trong tnh trng cht xc tc b suy gim
hot tnh.

Hiu sut gasolin C5+ (%kl)

Cc s liu trn cc hnh 2.4 - 2.7 chng t rng parafin v olefin (C5+) l cc sn
phm s cp. Cc parafin trong phn on gasolin (hnh 2.4) bt u chu nhng chuyn ho
(cracking) su hn khi chuyn ho vt qu 70%. V do , ng cong c trng cho

chuyn ho (%kl)

Hnh 2.4. chn lc ca gasolin c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC, nguyn liu gas oil giu parafin,
0,01; 0,0034.

Hiu sut olefin trong gasolin C5+ (%kl)

t s cht xc tc/nguyn liu: 0,25; 0,05;

chuyn ho (%kl)

Hnh 2.5. chn lc ca olefin trong gasolin C5+

c xc nh trong react c lp xc tc c nh.
iu kin phn ng: nhit 503oC nguyn liu gas oil giu parafin;
t s cht xc tc/nguyn liu: 0,25; 0,05;

64

0,01; 0,0034.

n-Butan thu dc (%kl)

chuyn ho (%kl)

Hnh 2.6. hiu sut ca n-butan c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC nguyn liu gas oil giu parafin;
0,01; 0,0034.

Buten thu c (%kl)

t s cht xc tc/nguyn liu: 0,25; 0,05;

chuyn ho (%kl)

Hnh 2.7. hiu sut ca n-buten c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC nguyn liu gas oil giu parafin;
t s cht xc tc/nguyn liu: 0,25; 0,05;

0,01; 0,0034.

65

chuyn ho cc i (ng cong nt lin) bt u i xung so vi ng thng i qua gc

to . Xu hng bin i chn lc ca olefin C5+ cng tng t nh ca parafin C5+, tuy
nhin chuyn ho thp hn 40%, v cc olefin C5+ km bn hn cc parafin C5+.
Propylen l sn phm s cp rt bn. Prolylen khng tham gia vo cc chuyn ho th cp
tip theo, ngc li, chuyn ho cao, mt lng propylen c th c to ra t cc phn
ng cracking th cp khc, do , ng c trng chuyn ho cc i ca propylen nng
cao hn ng thng ngoi suy qua gc to (hnh 2.8), tng t nh trng hp ca
n-butan (hnh 2.6).
n-Butan l sn phm s cp (hnh 2.6), chuyn ho cao ca qu trnh cracking
gas oil (> 30%) lng n-butan c gia tng ng k, c th, do qu trnh chuyn dch hydro
gia buten v cc.
Cc phn ng th cp xy ra theo c ch ion cacbeni to ra cc sn phm th cp. Cc
-olefin c to ra (do cracking ion cacbeni v tr ) li tip tc proton ho, ri isome

ho v cracking. Cc ion cacbeni hnh thnh t cc olefin c th tch H t cc phn t

hydrocacbon khc to ra cc parafin. Phn ng chuyn dch hydrua c tc dng lm n
nh cc hydrocacbon trong sn phm cracking, ngn nga s cracking tip tc.

Propylen (%kl)

20

40

60

80

chuyn ho %kl

Hnh 2.8. chn lc trong propylen c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC nguyn liu gas oil giu parafin;
t s cht xc tc/nguyn liu: 0,25; 0,05;

66

0,01; 0,0034.

Theo l thuyt, mt phn ng cracking c bn (elementary step) to ra mt phn t

olefin. Thng thng, mt mol hydrocacbon trong phn on cracking gas oil to thnh 3
mol sn phm. Do , t s olefin/parafin (o/p) trong sn phm cracking bng 2/1. Tuy
nhin, qu trnh cracking xy ra trn xc tc aluminosilicat v nh hnh cho t s o/p thp
hn, trn xc tc zeolit th hu nh rt t olefin. S thiu ht olefin l do phn ng
chuyn dch hydrua to ra parafin (1) t xycloparafin v xycloolefin khi to ra hydrocacbon
aromat, (2) t cc olefin b dehydro ho v ng vng khi to ra cc xycloolefin v (3) t
phn ng dehydro ho cc dng aromat, olefin khi to ra cc. 500oC, phn ng chuyn
dch hydrua thng xy ra chm hn so vi cracking gas oil. nhit thp hn, chuyn
dch hydrua nhanh hn, c l, do nng lng hot ho phn ng cracking cao hn. Do ,
gim nhit cracking lm chuyn dch phn b sn phm v pha trng lng phn t cao
hn, v (1) cc ion cacbeni chuyn thnh parafin do chuyn dch hydrua nhanh hn so vi s
phn ct ca ion cacbeni v (2) chuyn dch hydrua n -olefin nhanh hn cracking.
Thi gian tip xc tng to iu kin thun li cho chuyn dch hydrua, do , lm gim sn
phm olefin. Chnh v th, khi sn xut gasolin my bay (hm lng hydrocacbon no cao),
ngi ta phi tin hnh cracking nhit trung bnh v thi gian tip xc di hn so vi
thi gian cracking to ra gasolin thng thng.
Chuyn dch hydrua l mt phn ng quan trng trong phn ng cracking gas oil, bi
v (1) n lm gim hm lng olefin trong sn phm cracking, (2) nh hng mnh n s
phn b sn phm theo trng lng phn t v (3) thc y qu trnh to cc, lm gim hot
tnh xc tc.
Cc s liu ca John v Woijciechowski c trnh by trn cc hnh 2.9 n 2.11
chng t rng, isobutan, propan v etylen l cc sn phm th cp (ng c trng cho hiu
sut cc i khng i qua gc to ). Isobuten l mt sn phm th cp khng bn c
hnh thnh, c th t buten do phn ng chuyn dch hydrua; tng t, propan c hnh
thnh t propylen hoc t cracking cc hydrocacbon C4 (to ra metan v propylen).
S chuyn dch hydro n buten v cracking buten gii thch s suy gim nhanh
chng hiu sut buten chuyn ho cao (hnh 2.7). Etylen xut hin chuyn ho
khong 20% (hnh 2.11). Etan ch xut hin khi chuyn ho ln hn 50%. Metan, etan
hoc propan xut hin chuyn ho cao v chng c hnh thnh t cc olefin hoc t
cracking cc hydrocacbon mch ngn.
Cc l sn phm khng sao trnh c ca cracking xc tc. S tch t cc trn cht
xc tc dn n s suy gim hot tnh xc tc. Cc cng l ngun hydro cung cp cho
olefin trong pha kh thnh parafin. C 2 nh hng ny u khng mong mun, do , vic
nghin cu v tc v ngun gc hnh thnh cc l nhng vn rt c quan tm. Tuy
nhin, s hnh thnh cc cng mang n mt iu thun li v cng ngh: s t chy cc
trong thit b hon nguyn cung cp nhit cho phn ng cracking quy m cng nghip.
67

Isobuten thu c (%kl)

chuyn ho %kl

Hnh 2.9. chn lc ca isobuten c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC, nguyn liu gas oil giu parafin;
0,01; 0,0034.

Propen thu c (%kl)

t s cht xc tc/nguyn liu 0,25; 0,05;

chuyn ho (%kl)

Hnh 2.10. chn lc ca propylen c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC, nguyn liu gas oil giu parafin;
t s cht xc tc/nguyn liu: 0,25; 0,05;

68

0,01; 0,0034.

Etylen thu c (%kl)

chuyn ho (%kl)

Hnh 2.11. chn lc ca etylen c xc nh trong react c lp xc tc c nh.

iu kin phn ng: nhit 503oC, nguyn liu gas oil giu parafin;
t s cht xc tc/nguyn liu 0,25; 0,05;

0,01; 0,0034.

Cc l sn phm th cp. Cc c hnh thnh ch yu t cc olefin. Nu nguyn liu

cracking l mt hn hp parafin v cc hydrocacbon aromat phc tp th cc c to ra ch
yu t aromat.
Tm li, cracking gas oil trn cht xc tc axit rn xy ra ch yu theo c ch
cacbocation, to ra hai loi sn phm chnh:
- Sn phm s cp, bao gm propylen, n-butan, buten v gasolin (C5 - C14).
- Sn phm th cp, bao gm metan , etan, propan, isobutan, propylen v cc.
C th biu din s cracking ca mt gas oil giu parafin nh trn hnh 2.12.
Gasoil parafin

Propylen

Cc

n-Butan

Metan

Gasolin
C5 - C14

Buten

Etan

Etylen

Propan

Isobutan

Sn phm
s cp

Sn phm
th cp

Hnh 2.12. S cracking gas oil giu parafin.

69

2.2.3.3. ng hc phn ng cracking ga soil

Gas oil l mt hn hp cc hydrocacbon ring l, gia chng c mi quan h v tng
tc phc tp, do , ng hc phn ng gas oil khng th l s cng tnh n gin gia cc
hydrocacbon ring l, m cn tu thuc vo bn cht, thnh phn v mi tng tc gia hp
phn trong gas oil.
phn nh thc t , Reif (H.E. Reif et al., Pet. Refiner, 4015:237, 1961)
ngh mt biu thc v hiu sut sn phm phn ng trong cracking gas oil nh sau:
Hiu sut sn phm = f(NSTB, Cp, CN, CA).
trong : CP, CN, CA l phn trm trng lng ca cacbon trong cc hydrocacbon parafin,
naphten v aromat ca cacbon tng ng ca gas oil;
NSTB l nhit si trung bnh ca gas oil (oR)*.
Biu thc thun tu kinh nghim c gi tr thc dng la chn nguyn liu
cracking cng nghip ph hp vi hiu sut sn phm (gas oil, sn phm kh, cc) c d
tnh.
ng hc phn ng cracking xc tc gas oil l mt vn kh phc tp.
Thc vy, thnh phn nguyn liu v sn phm lun thay i theo chiu dc lp xc
tc n nh, ngay c thnh phn cht xc tc cng b bin i theo thi gian do hin tng
ng c, to cc... Trong cc thit b cracking cng nghip (riser)hoc trong thit b c lp
xc tc linh ng, cc cu t d b cracking nht c chuyn ho trong phn u ca
react, trong cc phn tip theo khng ch l sn phm m bao gm c phn nguyn liu d
kh cracking. Chnh v vy, cc nguyn liu quay vng t cc thit b cracking bao gi
cng kh cracking hn nguyn liu gc ban u.
Cn c vo cc c im phc tp , ngi ta (Kemp v Wojciechowski) a ra mt
phng trnh ng hc cracking gas oil nh sau:

trong :

dC A
= k o C S C A k io X i
d
i =1

(2-19)

kio: hng s tc cracking ca cc cu t trong nguyn liu;

Xi: phn mol ca cu t th i trong nguyn liu;
ko: hng s tc ban u biu kin;
CS: nng tm xc tc;
CA: nng tng cng ca gas oil.

Trong phng trnh trn, s hng kioXi i din cho s nh hng ca thnh phn
gas oil n tc cracking.
* Nhit biu din theo thang o Rankine (oR).
R (oR) = 460 oF; F (oF) = 1,8 oC + 32; K (K) = oC + 273.

70

Cho n nay, phng trnh (2-19) vn c p dng thnh cng cho nhiu t hp
nguyn liu/cht xc tc ca cracking gas oil.
2.2.3.4. Cracking cc nguyn liu nng
Cng ngh lc du ngy cng phi quan tm n ngun nguyn liu. Bi v nhu cu
nhin liu ca x hi ngy cng tng, nhp pht hin cc m du mi ngy cng gim. Do
, ngi ta ch n ngun nguyn liu nng. Ngun nguyn liu ny khng nhng r tin
m cn d kim v cc nhu cu khc s dng ngun nguyn liu nng ngy cng gim dn.
Nguyn liu nng c nhit si cao hn nhin liu nh, bao gm cc polyxycloalkan,
cc hydrocacbon n v a nhn thm, rt nhiu asphalten. Trong nhin liu nng cn c
nhiu phn t cha cc nguyn t khc loi (heteroatom) cha lu hunh (S), t n ~6%
v nit ~0,7%, gy ng c cht xc tc. Ngoi cc hp cht , trong nguyn liu nng cn
cha nhiu kim loi, c khi t n ~2000 ppm trong du th cn ch bin, c hi cho cht
xc tc cracking.
C th c nhng bin php tin x l nh hydro - x l, phn ring ho hc hay vt
l... gim thiu nng cc cu t khng mong mun Tuy nhin thc hin cc cng ngh
tin x l lun lun i hi s lp t thm thit b v gia tng gi thnh ch bin. Do ,
ngay t nhng nm 1960, cc nh lc du mun cracking trc tip du nng bng cc
cht xc tc thch hp.
cracking cc phn t ln, ngi ta phi cn cc cht xc tc c mao qun rng.
Trong khi , zeolit trong cht xc tc cracking ch c kh nng ci thin cht lng sn
phm thng qua cc phn ng cracking th cp. Cc mao qun rng trong pha nn to ra
hot tnh xc tc. Thc vy, ngi ta khng th tm thy cc nguyn liu lng, cc phn t
ln nm bn trong cc mao qun ca zeolit. Do , cracking nguyn liu nng, ngi ta
phi ch to cht xc tc cracking c mao qun rng, ng thi thm cc tc nhn th ng
vo ngun nguyn liu ban u hn ch s ng c cht xc tc bi kim loi. Cc c
tnh ca hp cht lu hunh v nit c th c khng ch bi hm lng ca zeolit b sung
vo cht xc tc, bi v zeolit l vt liu chng chi tt vi cc hp cht d nguyn t .
Mt vn na cn lu trong cracking gas oil l s to cc kh mnh. V nguyn tc,
ngi ta thm mt tc nhn thch hp h tr cho phn ng chuyn dch hydro vo du nng
th c th khng ch c s hnh thnh cc. Tuy nhin, tm ra mt cht c tnh nng nh
th, va r tin v va hiu qu th vn l mt bi ton cha c li gii.
Khuynh hng hin nay l: vn ch to cht xc tc cracking du nng vi hiu sut
to cc cao. Cc c t chy iu kin khc nghit hn so vi cht xc tc c hiu sut
to cc thp. V do , phi cn c mt cht xc tc bn thu nhit hn so vi cc cht xc
tc thng thng, ngha l phi trao i n mc cao nht c th gia cc ion natri trong

71

cht xc tc vi cc cation lm bn cu trc mao qun rng thch hp cht xc tc khng

b bin dng (ph v cu trc) trong thit b hon nguyn.
S to cc mnh trn b mt cht xc tc li dn n s suy gim nhanh hot tnh ca
cht xc tc. nhn c mt chuyn ho hp l, ngi ta phi s dng mt t s cht
xc tc/du cao, v do , phi cn mt tc tun hon cht xc tc cao. Cht xc tc li
phi c mt bn c hc rt tt chng li s bo mn. Pha nn mao qun rng phi
c la chn p ng yu cu .
Trong thit b hon nguyn, dng kh b sung cho hon nguyn xc tc c th lm tn
tht mt lng ln cht xc tc, nu khng c cc xyclon thu hi cc ht xc tc c mt
cao cn thit (v c th). c im ny cng lin quan n c trng ca vt liu matrix
(pha nn) c mao qun rng.
Cracking xc tc nguyn liu nng c tin hnh theo nhng c ch m thc ra cho
n nay ngi ta cha nhn bit mt cch r rng v chnh xc. Bn cht ca qu trnh
ta nh mt qu trnh cc ho bng xc tc. Nhng d sao, s phn b sn phm ca qu
trnh cng tt hn nhiu so vi qu trnh cc ho bng nhit. V t s H/C ca nguyn
liu thp, nn ngi ta ch c th ci thin cht t (khng ng k) v hiu sut sn phm, tr
phi khi ngi ta c th to ra c mt cht xc tc hot ng v chn lc cho cc phn ng
chuyn dch hydro.
Tm tt mc cracking xc tc gas oil:
Gas oil l mt hn hp phc tp ca cc hydrocacbon. Do , ho hc v cng ngh
cracking gas oil l mt trong nhng lnh vc phc tp nht ca cng ngh lc du. Tuy
nhin, da vo cc kin thc c bn v cracking cc hydrocacbon n l, da vo cc quy
lut ng hc cracking gas oil (l thuyt v cng ngh) ngi ta c th xc nh c cc
tham s ti u (thnh phn nguyn liu, nhit , cht xc tc, thi gian tip xc...) thu
c hiu sut cao nht i vi sn phm cracking mong mun.

72

Chng 3

Cht xc tc fcc

3.1. M u
Ngy nay, tt c cc nh my lc du trn th gii u p dng cng ngh cracking
xc tc pha lu th (Fluid Catalytic Cracking, vit tt l FCC). Cht xc tc cho cng ngh
ny c gi l xc tc FCC. V bn cht, cht xc tc FCC l mt axit rn, tuy nhin n
c ci tin rt nhiu so vi cc xc tc axit rn ban u ca cng ngh cracking du m
ca thi k thp k 30, 40 th k trc.
Bng 3.1. Cc cht xc tc trong thi k u ca cng ngh cracking du m
Nm

Qu trnh

H react

Kiu cht xc tc

1920
1939
1940
1942
1945
1942
1946

McAfee
Houdry
Suspensoid
FCC
TCC
FCC
FCC

M
Lp xc tc c nh
t st dng huyn ph
Xc tc trng thi lu th
Lp xc tc ng
Xc tc trng thi lu th
Xc tc trng thi lu th

AlCl3
t st (clay)
t st (clay)
t st (clay)
t st (clay)
SiO2.Al2O3 tng hp
SiO2.Al2O3 tng hp

Dng
Ht
Ht c x l axit
Super Filtril, Dng bt x l axit
Ht trn x l axit
Ht
Ht vi cu

T bng 3.1, c th nhn thy rng, hu ht cc cht xc tc cracking trc kia u

c ch to t t st hot ho axit v cc aluminosilicat v nh hnh. Cc xc tc c
hot tnh, chn lc thp v thi gian hot ng ngn.
Mi n gia nhng nm 60 ca th k trc, cc xc tc cracking cha zeolit mi
c bt u s dng trong cng ngh FCC. T , cc nh lc du mi bt u c c mt
cng ngh FCC vi hiu sut gasolin (xng) cao nh zeolit c hot tnh xc tc v chn
lc tt hn nhiu so vi aluminosilicat v nh hnh, cc oxyt, khong st (clay)... Cht nn
cha cc mao qun trung bnh v ln, cc tm axit yu nn c th cracking s b cc
hydrocacbon phn t ln, to iu kin thun li cho qu trnh khuch tn cht tham gia
phn ng v sn phm phn ng; cht nn h tr qu trnh truyn nhit trong cht xc tc.
Cht nn cn l ni bt gi t xa cc tc nhn ng c zeolit (V, Ni, cc hp cht nit...),
bo v cc pha hot ng xc tc. Trong cht nn cha cc cht c vai tr lin kt gia cc
hp phn xc tc to nn bn c hc cho cht xc tc.
73

Ngoi 2 hp phn chnh (zeolit Y v cht nn) trong xc tc FCC, nhiu khi ngi ta
cn thm vo cc cht ph tr (additive) lm cho cht xc tc FCC t c mc tiu c
th ca cc nh my lc du. V d, thm kim loi Pt xc tin qu trnh CO => CO2,
ngha l gim thiu lng kh thi CO ra mi trng; thm zeolit ZSM-5 gia tng ch
s octan ca gasolin hoc tng hiu sut propylen (dng cho qu trnh sn xut polypropylen, PP)...
C th hnh dung cc hp phn ca cht xc tc FCC nh s sau (hnh 3.1):
Nguyn liu

Sn phm trung gian

Oxyt silic
Oxyt nhm
Hydroxyt natri
----------------Clorua t him
Sulfat amoni

Sn phm cui cng

10-50%
Zeolit
Pha hot ng xc tc

50-90%
Vt liu khong st
Oxyt nhm
Oxyt silic...

Cht nn

Cht xc tc
FCC

Pha n nh cu trc
v c th c hot tnh xc tc

0 - 10%

Bch kim
t him
Zeolit ZSM-5
Antimon...

Cht ph tr

Hnh 3.1. Cc hp phn chnh ca cht xc tc FCC.

3.2. Cc hp phn c bn ca cht xc tc FCC
3.2.1. Zeolit Y
C th ni, zeolit Y l thnh phn quan trng nht trong cht xc tc cracking. Theo
d bo ca mt s nh khoa hc (C. Marcilly, Proceedings of ICZ, Montperllier, France,
7.2001) th trong th k 21, zeolit Y vn l cu t hot ng quan trng nht ca xc tc
FCC m cha c loi zeolit no thay th c.
J c im cu trc ca zeolit Y
Zeolit Y c cu trc tinh th ging nh cu trc ca mt loi zeolit t nhin c tn l
Faujazit (Faujasite). Do , n c mang m hiu quc t (structure type code) l FAU do
U ban danh php ca IUPAC ngh.
Thnh phn ho hc ca mt n v tinh th c bn ca Y l:
Na56[(AlO2)56(SiO2)136].250H2O
74

(3.1)

Tinh th c bn ca Y c cu trc lp phng, thuc nhm i xng Fd3m, khong

cch mng a = 24,7 . Mt vt liu ca Y l 17,7 T/1000 3 (s nguyn t T ca t
din TO4 (T = Si, Al...) trong mt th tch 1000 3) rt thp, chng t Y l zeolit kh
rng, bn trong n cha nhiu th tch trng.
Thc vy, zeolit Y l aluminosilicat tinh th c hnh thnh trong qu trnh kt tinh
bi cc t din SiO4 v AlO4*. Cc t din ny to ra cc n v cu trc th cp SBU
(Secondary Building Unit) 4 v 6 cnh. Sau , cc SBU 4 v 6 cnh ghp li vi nhau thnh
mt bt din ct (sodalit). Cc sodalit ny ghp li vi nhau qua mt 6 cnh, to nn cu
trc faujasit (Y, X) nh hnh 3.2.

Hnh 3.2. M phng s hnh thnh cu trc tinh th ca zeolit Y

S hnh thnh mng li cu trc nh th to ra mt hc ln (-cage) c ng knh
~13 (xem hnh 3.3). Mi hc ln (-cage) thng vi 4 ca s c to ra bi vng 12T vi
ng knh 7,4. Cc hc ln ni vi nhau qua ca s vng 12T to thnh mt h thng
mao qun 3 chiu:
<111>12 7,4xxx
* Trong ti liu ny v nhiu ti liu khc, k hiu cc t din l SiO4 v AlO4 hoc SiO2 v AlO2 u c
ngha tng ng v xem cc t din lin kt vi nhau qua cu oxy, nn oxy l chung cho c 2 t din.

75

(theo k hiu ca U ban Cu trc ca Hi Zeolit Quc t (M. M. Meier and D. H. Olson,
Atlas of zeolite stucture types, 1992):
<111>: cc h mao qun song song vi cc trc tinh th x, y, z.
12: vng ca s 12 cnh (12T hoc 12 oxy)
7,4: kch thc ca s tnh bng .
xxx: h thng knh mao qun khng gian 3 chiu
Hc sodalit (-cage)
Hc ln (-cage)

Lng tr lc gic

Hnh 3.3. Cu trc mng tinh th faujasit o: v tr nh x ca cc oxy

: v tr ca cc cation b tr in tch, OH: nhm OH.
Mi mt sodalit c cu to bi 24 TO4 (t din), gm 8 mt 6 cnh v 6 mt 4 cnh.
Cu trc ca sodalit khng c kht, li vo cc mt 6 cnh c kch thc c 2,4 , ng
knh ca cu rng trong sodalit (hc nh, -cage) ~6,6 .
T cng thc (3.1), chng ta c th bit c mt n v tinh th c s ca zeolit gm

136 + 56
= 8 , trng thi hydrat ho cha 250 phn t nc (~20% khi lng
8 sodalit

24
ca zeolit hydrat ho). Cc phn t H2O ny chim ch trong cc hc nh v hc ln ca
zeolit. Khi b nung nng, nc trong zeolit thot ra (thng gi l qu trnh tch nc hoc
dehydrat ho), thot tin, t cc hc ln, sau mi t cc hc nh nhit tng i cao
(400 500oC). Trn hnh 3.3, m t mt m hnh mng cu trc rng ca zeolit Y trng
thi dehydrat ho hon ton.
Trn hnh 3.3 cn ch ra cc v tr nh x ca cc cation b tr in tch ca mng

cu trc zeolit. Thc vy, v zeolit l t hp cc lin kt cc t din SiO4 v AlO4 :

76

O
Si
O

Na
O - O
Al
OO

OO

O
Si
O

nn thng c cc cation (Na+, K+, Ca2+...) b tr in tch m b mt. V tr ca cc cation

b tr in tch l khc nhau, xt v mt nng lng v hnh hc. T hnh 3.3 nhn thy
rng, v tr SI nm tm ca lng tr 6 cnh l v tr kn nht, sau mi n v tr SI (i
xng vi SI qua mt 6 cnh), ri n v tr U (tm ca sodalit), SII, SII (i xng vi SII qua
mt 6 cnh), SIII v C (tm ca hc ln). R rng l, cc v tr C, SIII, SII rt d tip cn v
kh linh ng (c th d dng x dch v tr). Mt phn t hoc mt cation no nu xm
nhp vo v tr SI, v nht l SI, th phi rt c li th v mt hnh hc (ng knh ng hc
nh) v rt thun li v mt nng lng (c gia nhit...) t -cage vo -cage, v n SI.
Trong mt mng tinh th c bn c 16 v tr SI, 32 v tr SI, SII, SII v 48 v tr SIII.
Trn hnh 3.3, cng gii thiu cc v tr oxy (O) ca t din TO4 trong cu trc tinh
th faujasit. O1 nm tm cnh ca lng tr 6 cnh ni cc sodalit, v tr ca O2, O3 v O4
nh trn hnh 3.3. Tu thuc vo nhiu yu t khc nhau, cc proton H+ c th tn cng vo
cc lin kt Si-O(i)-Al (i = 1, 2, 3 v 4) to ra cc nhm OH
H
SiO(i)Al
c axit v nh hng hnh hc khc nhau. Ngi ta cho rng (D. H. Olson et al, J. catalysis,
13 221, 1969), xc sut to nhm OH gia nhm O1 v O3 l gn nh nhau, tuy nhin, cc
orbital t do ca O1 nh v thun li cho cc nhm hydroxyl hng vo hc ln, d dng
tip cn vi cc tc nhn phn ng. Trong khi , O3 c 4 nh hng ca cc orbital vi xc
sut: 1 hng vo hc ln; 1 hng vo bn trong lng tr 6 cnh v 2 hng vo bn trong
hc nh sodalit.
Nh vy, c im cu trc ca zeolit Y l kh phc tp, nhng hu nh c xc
nh r rng. Da vo cc c im , chng ta c th bit cch tng hp, bin tnh v ng
dng zeolit Y mt cch hiu qu trong vic ch to xc tc cracking.
3.2.2. Cc phng php iu ch zeolit Y c t s Si/Al cao
T cng thc (3.1) c th nhn thy t s Si/Al ca zeolit Y l:
SiO 2
SiO 2
Si
136
=
=
= 2,43 hoc
= 4,86
AlO 2
Al 2 O 3
Al
56
Tuy nhin, thc nghim chng t rng, cc zeolit c cu trc tinh th kiu faujasit
(nh hnh 3.3) c th d dng tng hp trong iu kin thu nhit, vi t s Si/Al bin i
t 1 2,5. Trong , zeolit c t s:

77

1 Si/Al 1,5 c gi l zeolit X

1,5 Si/Al 2,5 c gi l zeolit Y
s phn loi nh th ch c tnh cht quy c, song d gi nn mt c im v bn nhit
v bn thu nhit ca 2 loi zeolit . V lin kt Si-O bn vng hn lin kt Al-O, do ,
khi tng t s Si/Al th cu trc tinh th faujasit bn vng hn nhit cao trong s c mt
ca hi nc.
Chnh v th, trong ch to cht xc tc FCC hin nay, ngi ta khng s dng zeolit
X, v cc zeolit Y c Si/Al thp. Cc zeolit Y c t s Si/Al cao ( 2,5) c quan tm c
bit khi ch to xc tc cracking.
3.2.2.1. Tng hp zeolit c t s Si/Al cao
Sau khi tng hp c zeolit Y c t s Si/Al ~ 2,5, ngi ta thng s dng cc
phng php sau y tng t s Si/Al ca zeolit Y:
- X l nhit v nhit - hi nc
- X l ho hc
- Kt hp x l thu nhit v x l ho hc
- Tng hp trc tip
1. X l nhit v nhit - hi nc
Nung zeolit Y trao i vi ion amoni NH4+ (NH4+Y) trong mi trng hi nc
tch nhm trong t din AlO4 ra khi mng cu trc ca zeolit. Qu trnh c tin
hnh nhit cao nhm thu phn cc lin kt SiOAl, to ra cc dng nhm ngoi
mng v lm tng t s Si/Al trong mng, lm gim kch thc mng c s. Thc vy, v
di lin kt SiO = 1,619 , ca AlO = 1,729 , do , khi t s Si/Al tng th khong
cch mng (a) gim (H. Fichtner Schittler et al, Cryst. Res. Technol. 19, K1, 1984). T
thc nghim, ngi ta xc nh c h thc:
a (nm) =

N Al
+ 2,4191
1152

(3.2)

trong , NAl: s nguyn t nhm trong mt mng c s.

Trong qu trnh tch nhm (dealumination) bng nhit - hi nc c th lm ph v
mt phn cu trc tinh th ca zeolit, to ra mt s dng oxyt nhm, oxyt silic, aluminosilicat v nh hnh. S lng v dng pha v nh hnh to ra ph thuc rt nhiu vo t l
Si/Al ca zeolit ban u, vo iu kin khc nghit ca qu trnh x l (nhit , thi
gian x l, p sut hi nc...). S din tin qu trnh tch nhm nhit - hi nc c th
c theo di bng k thut nhiu x tia X (XRD), v cc pic XRD s chuyn dch v
pha 2 cao hn khi khong cch mng nh hn. Ngi ta cng c th s dng k thut

78

MAS NMR* (cng hng t ht nhn vt liu rn) hoc k thut IR (ph hng ngoi)
theo di cc c trng ca zeolit trong qu trnh x l.
Ho hc qu trnh tch nhm bng nhit - hi nc c th c din t nh sau:
(A) Tch nhm trong t din ca mng cu trc zeolit:

Si

Si

O
Si

Al

Si

+ H2O
(hi nc,
nhit )

OH
Si

OH

HO

Si

+ Al(OH)3 (3-3)

OH
Si

Si

Al(OH)3 + H+Y

Al(OH)2+[Y] + H2O

(3-4)

(B) n nh mng cu trc zeolit:

Si

Si

OH
Si

OH

HO
OH
Si

Si

+ SiO2
(hi nc,
nhit )

Si

Si

Si

+ 2 H2O

(3-5)

O
Si

Nh vy, thot tin ( nhit cao 400oC) hi nc tn cng vo nhm trong mng,
tch nhm ra di dng Al(OH)3, li nhng l trng Al trong mng (3.3). Nu cc l
trng Al qu nhiu, v khng c gn li th cu trc tinh th ca zeolit s b sp (ph
v). Song, rt may l trong vt liu zeolit thng c mt lng nh SiO2 v nh hnh (
dng tp cht), hoc do mt phn nh no ca cu trc tinh th zeolit b ph v dng
SiO2 v nh hnh. Di iu kin nhit cao v c mt hi nc, dng SiO2 ny c th di
chuyn n cc l trng Al v gn li cc l trng bng lin kt SiO4 nh (3.5). Nh
vy, bng phng php tch nhm nhit - hi nc, ngi ta c th to ra cc zeolit Y c t
s Si/Al kh cao (c th t n Si/Al = 3,5 hoc cao hn) rt bn nhit, thng c gi l
zeolit Y siu bn USY (ch vit tt ca thut ng utrastable Y zeolite). Cc zeolit USY c
th bo ton cu trc tinh th ca mnh n nhit khong 1000oC.

MAS NMR l tn vit tt ca phng php cng hng t ht nhn p dng cho vt liu rn:
Magic Angle Spinning Nuclear Magnetic Resonance.

79

Phng php tch nhm bng nhit - hi nc ca zeolit Y thng c tin hnh nh
sau:
Zeolit NaY c trao i vi dung dch mui amoni gim lng natri xung cn
10 - 25% (so vi lng natri trong NaY ban u).
Zeolit c trao i NH4+ (vn cn 10 25% Na) c ra ht mui d, sy v
nung nhit trong khong 200 600oC nhm natri phn b li (natri cc v tr
kn, khi trao i, v d SI, SI... chuyn ra cc v tr h hn nh SII, SII...), nhng ch
khng nn nung nhit qu cao, thi gian qu lu... v c th lm sp cu trc tinh th
zeolit.
Phn natri cn li trong zeolit li c ly i bng cch trao i vi dung dch mui
amoni. V nguyn tc, gim hm lng natri trong zeolit cng thp cng tt. Song cn ch
n s bo ton cu trc tinh th, v trong trng thi ny, zeolit c cu trc rt khng n
nh.
Zeolit c hm lng natri thp (n mc c th) c nung nng nhanh trong mi
trng cha hi m (H2O) n nhit gia 500oC n 800oC (nhit c la chn tu
theo iu kin thc nghim c th: t s Si/Al trong zeolit ban u, hm lng natri cn li,
p sut hi nc...). X l hi nc c th thc hin trong cc react tnh hoc trong cc
react c dng hi nc ng. Thi gian x l ph thuc vo mc tiu t n t s Si/Al
cn thit. Song khng c ph v cu trc tinh th ca zeolit qu 1 1,5%.
Zeolit Y siu bn (USY) c bn nhit v thu nhit ln hn so vi zeolit Y thng
thng, USY c th bo ton cu trc ca n ~1000oC. Do s tch nhm khi mng li,
nn s tm trao i ca USY cng b thay i. S tm axit Bronsted ca USY t hn so vi
zeolit Y thng thng. S khc nhau s c nh hng n hot tnh xc tc v chn
lc ca zeolit USY.
2. X l ho hc
Zeolit Y c t s Si/Al cao c th c iu ch bng cch tch nhm t zeolit Y
thng thng bng cc tc nhn ho hc khc nhau. Trong trng hp ny, s tch nhm
km theo cc phn ng gia zeolit v cc tc nhn ho hc. C th c hai trng hp xy ra:
a. Va tch nhm khi mng va th silic vo mng
i. Tch nhm vi (NH4)2SiF6
Ngi ta x l zeolit vi dung dch fluosilicat amoni (AFS) mt gi tr pH cho php
tch nhm ca zeolit ra khi mng li. Nhm b tch ra di dng mui fluoaluminat
ho tan trong nc, li cc l trng, silic t fluo silicat li in vo l trng, gn lin
cu trc mng zeolit. Qu trnh phn ng c th din ra nh sau:

80

NH4

O
Si

OO

Al

Si

OO

Si

+ (NH4)2SiF6

Si

Si
OO

OO

(NH4)3AlF6

Tc ca giai on tch nhm khi mng tinh th zeolit cao hn tc gn silic

vo mng, do thng vn to mt s l trng trong mng.
Do hm lng silic cao (c th t n t s Si/Al = 12), nn zeolit sau khi x l c
bn thu nhit rt tt. Tuy nhin, ngi ta chng minh bng thc nghim rng, nu tch
nhm qu nhiu (> 34 Al/tinh th c s) th zeolit tr nn khng bn, tinh th thp v c
nhiu l trng trong khung mng zeolit.
ii. Tch nhm bng SiCl4
C th tc dng zeolit Y vi hi SiCl4 nhit cao (gia 450oC v 550oC) tch
Al ra khi mng zeolit v thay th Si vo mng.
+

Na O
Al
O
O

+ SiCl4

Si
O

NaAlCl4

NaAlCl4 c tch bng nc nhit phng. Tuy nhin, mt vi phc cloro nhm
b thu phn to ra cc dng oxyt nhm ngoi mng li. Mc tch nhm ph thuc
vo nhit v thi gian phn ng. Zeolit sau khi tch nhm c t s Si/Al cao, rt bn nhit
v bn axit.
b. Tch nhm nhng khng th silic vo mng.
i. Tch nhm vi cc tc nhn selat (chelating agent)
C th tch nhm ra khi mng tinh th zeolit bng dung dch EDTA (etylenediaminetetraacetic acid and salts) trong iu kin ng (khuy trn hoc tun hon dung
dch EDTA qua lp zeolit). Bng phng php , ngi ta c th tch khong 50% nhm
khi mng di dng phc selat ho tan trong nc m khng lm tn tht tinh th. Nu
tch nhm khong 80% th tinh th ca zeolit ch cn li 60 70% so vi ban u. Mc
d ngi ta nhn thy s hnh thnh cc khuyt tt ca mng li do x l bng EDTA.
Song, zeolit c tch nhm bng phng php ny vn c bn nhit v thu nhit ln
hn so vi zeolit ban u, v kch thc mng c s vn gim. bn vng ca zeolit tch
nhm bng EDTA c th c tng cng thm bng cch trao i vi ion t him.
Axetylaxeton v mt vi selat ca aminoaxit cng c s dng tch nhm t
zeolit Y.
ii. Tch nhm bng cc halogen bay hi
Cc halogen bay hi ny khng cha silic (v d COCl2) tc dng vi zeolit nhit

81

cao tch nhm khi mng zeolit v to ra cc khuyt tt mng. Cc dng dung dch trong
dung mi khng nc cng c th tch nhm t zeolit.
iii. Tch nhm bng fluorin
nhit thng, mt hn hp fluorin - khng kh c th tch nhm khi zeolit nh
to ra cc hp cht nhm - fluorin.
Tch nhm bng cc dung dch axit ch thc hin c vi cc zeolit c hm lng
silic cao nh mordenit, clinoptilolit, erionit... Bin php ny khng thnh cng i vi zeolit
X v Y v cu trc tinh th ca chng khng bn trong mi trng axit.
3. Kt hp x l nhit v x l ho hc
Phng php ny nhm chuyn zeolit Y dng amoni (NH4+Y) ban u thnh dng
siu bn bng cch x l nhit, tip n x l ho hc tch nhm ngoi mng. X l
ho hc c th thc hin bng dung dch axit (v d HCl) baz (v d NaOH), mui (v d
KF) hoc bng mt s cc tc nhn selat (v d EDTA). Nhm ngoi mng cng c th loi
b bng cc phn ng rn - kh vi cc halogenua nhit cao. Tuy nhin, cn ch s
dng nng thch hp, v nng cao, cc tc nhn ho hc ni trn u c th tc dng
vi nhm trong mng zeolit.
4. Tng hp trc tip
Hu ht cc zeolit Y thng mi u c t s Si/Al trong khong 2,5 2,75. T lu,
ngi ta c tng tng hp trc tip zeolit Y c t s Si/Al cao, tuy nhin, tng
khng d dng thc hin, v qu trnh kt tinh zeolit Si/Al cao ph thuc rt nhiu yu t,
nh ngun vt liu (ho cht) ban u, thnh phn gel tng hp, iu kin lm gi gel, nhit
v thi gian kt tinh, cht to cu trc hoc mm kt tinh (lng v bn cht mm...)... V
d, tng t s Si/Al trong gel hoc thi gian kt tinh dn n s gia tng t s Si/Al trong
zeolit. Thm sol silic vo gel aluminosilicat cng c th lm tng t s Si/Al trong zeolit.
Nhiu sng ch cng b v tng hp zeolit Y c t s Si/Al cao hn 2,75. Tuy nhin, cc
zeolit Y c Si/Al cao hn 3 3,25 l cha th thc hin c quy m cng nghip bng
cch tng hp trc tip.
3.2.2.2. Cc tnh cht c bn ca zeolit Y c t s Si/Al cao (HSY - high silica Y)
1. Cc tnh cht chung
So snh vi zeolit Y ban u, zeolit Y c t s Si/Al cao c iu ch bng cc
phng php ni trn u c cc tinh cht chung sau y:
1) T s Si/Al trong mng tinh th ca zeolit cao hn.
2) bn nhit v thu nhit tt hn.
3) Kh nng trao i ion gim.
4) Kch thc mng c s gim.
5) Cc pic nhiu x XRD chuyn dch v pha gi tr 2 cao hn.
82

6) Lin kt Si (oAl)* l ch yu c th hin trong ph 29Si-MAS NMR.

7) S phn b ca Al trong hu ht cc zeolit USY l khng ng nht.

8) Tn s dao ng hng ngoi ca cc lin kt cu trc (400 1200 cm 1)

chuyn v pha gi tr cao hn.
9) Nng ca nhm OH axit trong ph hng ngoi (IR) gim.
10) axit tng cng ca zeolit gim.
11) Lc axit ca zeolit tng.
12) Mt tm axit gim.
Nhng c im chung ca zeolit Y bin tnh l do t s Si/Al trong mng li cao
hn zeolit Y thng thng. Ngc li, da vo mt s tnh cht , ngi ta c th tnh ton
s nguyn t Al trong mng zeolit. V d, da vo hng s mng li, gi tr ca ph IR,
ph 29Si-MAS NMR... ngi ta c th xc nh t s Si/Al ca zeolit.
2. nh hng ca phng php x l n tnh cht ca zeolit HSY
Nhiu tnh cht ca zeolit Y bin tnh c t s Si/Al cao thng c to ra do cc
phng php x l. V d, cc tnh cht cu trc v hp ph ca zeolit HSY c iu ch
bng cc phng php khc nhau c th hin nh trong bng 3.2 v 3.3.
Bng 3.2. nh hng ca phng php x l n tnh cht cu trc
v hp ph ca zeolit HSY
Phng php x l
Tnh cht
Thnh phn
pha rn
Dng Al trong
pha rn (a)

Nhit - hi nc Nhit - hi nc (hi

(hi H2O, ToC)
H2O, ToC) v axit
B mt giu nhm
Al(T) + Al(E)

S phn b Al kh
ng u

SiCl4
B mt giu
nhm

Al(T)

Al(T) + Al(E)

H thng mao
Mao qun nh v Mao qun nh v th Mao qun
qun
th cp trung bnh cp trung bnh
nh
Hp ph N2

ng nhit hp
ph kiu IV

ng nhit hp ph
kiu IV

(NH4)SiF6
B mt ngho
nhm
Al(T)

EDTA
B mt ngho
nhm
Al(T)

Mao qun nh
Mao qun nh v th cp
trung bnh

ng nhit
ng nhit hp ng nhit hp
hp ph kiu I ph kiu I
ph kiu IV

(a): Al(T): nhm trong mng cu trc

Al(E): nhm ngoi mng cu trc

* Si (oAl): Si khng lin kt trc tip vi bt k mt Al no:

Si
O
Si

Si

O Si

O
Si

83

Bng 3.3. So snh mt vi tham s cu trc ca zeolit

trong cc phng php x l khc nhau

Zeolit

SiO2/Al2O3(a) Na2O %kl

B mt ring Hng s mng Nhit ph

m2/g
v cu trc(b)

tinh th
cn li, %(c)

USY

5,8

0,17

734

24,55

1010

59,2

Y x l vi EDTA

8,1

0,42

812

24,62

982

53,7

USY x l axit

8,4

0,05

923

24,58

1032

74,6

Y x l vi
(NH4)2SiF6

11,7

0,05

863

24,42

1104

77,4

(a): Xc nh bng phn tch ho hc.

(b): Xc nh bng phng php DTA.
(c): % tinh th so vi tinh th NH4Y trc khi x l bng hi nc 871oC, 5h, 1atm,
23% hi nc.

Nh vy, sau khi x l bng cc phng php khc nhau, nhiu tnh cht ca zeolit Y
b thay i v do , dn n nhng thay i ng k tnh cht xc tc ca zeolit, chng
ta s xem xt nhng c im ch yu.
i. S hnh thnh cc dng Al ngoi mng
Nh chng ta bit, x l zeolit Y trong dng hi nc nhit cao c th tch Al
trong mng tinh th zeolit thnh nhng dng Al ngoi mng, nm trong cc mao qun zeolit,
ng thi thc hin qu trnh lp y cc l trng Al bng silic. Hin tng hon ton
c xc nhn bng thc nghim nh ph cng hng t ht nhn vt liu rn

29

Si-MAS

NMR.
Hnh 3.4 v 3.5 gii thiu mt ph

29

Si-MAS NMR v

27

Al-MAS NMR ca zeolit

NaY v zeolit Y c x l bng phng php nhit - hi nc.

T hnh 3.4 nhn thy rng, NaY c rt nhiu Al, to ra cc lin kt Si(3Al), Si(2Al)
v Si(oAl), trong , Si(2Al) l nhiu nht v Si(oAl) l t nht. Theo qu trnh x l nhit hi nc v x l axit, Al tch dn ra khi mng zeolit, do , nng ca pic c trng
cho lin kt Si(oAl) tng dn v chim u th (nht l mu USY-B x l vi axit.
T hnh 3.5 nhn thy rng, mu NaY hu nh Al trong zeolit u dng t din,
nm trong mng tinh th zeolit. Khi b x l nhit - hi nc, Al b tch ra khi mng th
hin pic O v pic P. Lng thay i gia cc dng Al ph thuc vo phng php x l v
s khc nghit ca s x l.

84

Hnh 3.4. Ph 29Si-MAS NMR ca

zeolit Y vi cc hm lng nhm khc
nhau trong mng.

Hnh 3.5. Ph 27Al-MAS NMR (a)

NaYZeolit, (b) zeolit Y tch nhm bng
phng php nhit hi nc (T-Al
dng t din, P-Al c phi tr 5, O-Al
dng bt din).

Tch nhm khi mng zeolit bng SiCl4 cng dn n s hnh thnh cc dng nhm
khc n
nhau
hau ngoi mng, phn b trong cc mao qun zeolit. Ngi ta cho rng, nhm ngoi
mng c cu trc pseudo bomit (pseudoboehmite, gi bomit), hoc dng aluminosilicat v
nh hnh. Trong phng php x l bng nhit - hi nc v bng SiCl4, b mt ngoi ca
zeolit giu Al (c nng Al cao hn), do mt s Al ngoi mng di chuyn n b mt.
Ngc li, tch nhm bng cc tc nhn selat (v d EDTA) hoc vi fluosilicat amoni
khng to ra cc dng nhm ngoi mng, v cc hp cht nhm u d tan nn d dng loi
b khi b mt ca zeolit. Hu nh lng nhm cn li u c nh x trong mng zeolit.
Tuy nhin, x l bng EDTA thng to ra cc khuyt tt (l trng cha c lp y)
trong mng, trong khi x l bng (NH4)2SiF6 th cc l trng hu nh c in y
bng cc nguyn t Si.
85

Trc y, ngi ta cho rng, cc dng Al ngoi mng zeolit khng ng vai tr g
trong xc tc axit ca zeolit. Song, gn y c nhng nghin cu (M.L. Oicelli and P. O
Conner, 2001 Elsevier Science) cho rng, cc zeolit Y c t s Si/Al cao nhng khng c
hoc c t Al ngoi mng th th hin hot tnh xc tc axit khng cao; trong khi , zeolit Y
c tch nhm vi t s Si/Al thp hn, nhng c dng Al ngoi mng li rt hot ng vi
xc tc axit (v d cracking), l do s hip tr xc tc gia cc tm axit Bronsted ca
mng zeolit v cc tm Lewis (nhm ngoi mng).
ii. bn thu nhit
bn nhit v thu nhit ca zeolit Y c t s Si/Al cao, ni chung l tt hn so vi
zeolit ban u. bn ph thuc ng k vo phng php x l. V d, bn nhit ca
zeolit m sau khi x l khng c cc khuyt tt mng, ngha l, cc l trng c lp y
bi Si th cao hn so vi zeolit c nhiu khuyt tt mng. Nh vy, zeolit USY c to ra
bng phng php nhit - hi nc, USY x l bng axit, bng (NH4)2SiF6 hoc SiCl4 c
bn tt hn so vi zeolit Y c t s Si/Al cao c x l bng cc tc nhn selat (v d
EDTA) hoc cc halogenua bay hi. bn nhit v thu nhit ny lin quan cht ch n
qu trnh lp y l trng ca Al trong qu trnh tch nhm. i vi zeolit Y x l bng
(NH4)2SiF6, (Y(NH4)2SiF6), ngun silic lp y l trng Al l ngun bn ngoi nn tinh
th c bo ton, trong khi USY nhn c t phng php nhit - hi nc li s dng
ngun silic bn trong (ngha l t bn thn zeolit, mt phn no ca zeolit b bin i)
lp y l trng v ng thi to ra cc mao qun th cp c kch thc mao qun trung
bnh (mesopore). Do , bn nhit v thu nhit ca zeolit Y(NH4)2SiF6 tt hn so vi
zeolit USY c to ra do phng php x l nhit - hi nc.
iii. S phn b ca Al trong zeolit c t s Si/Al cao.
Cn lu rng, t s Si/Al nhn c t php phn tch ho hc cho bit thnh phn
tng th ca zeolit. Song, trong thc t s phn b Al trong mng zeolit thng l khng
ng nht i vi zeolit c t s Si/Al cao. S phn b c th c pht hin bng cc
phng php ph XPS (ph pht x photon tia X, X ray Photoemission Spectroscopy) SIMS
(ph khi lng ion th cp, Secondary Ion Mass Spectroscopy),... Cc kt qu nghin cu
cho thy rng, USY c iu ch bng phng php nhit - hi nc, hoc bng SiCl4 c
b mt giu nhm, cn cc zeolit c x l bng EDTA hoc (NH4)2SiF6 th li ngho Al
b mt. USY c x l va nhit - hi nc va ra axit c s phn b nhm tng i
ng nht.
S phn b Al trong mng zeolit c nh hng ln n axit, c ch phn ng, kh
nng tip cn ca cc tm xc tc vi hydrocacbon,... Do , khi nghin cu v hot tnh
xc tc ca zeolit Y giu silic cn lu n c im ny.

86

iv. H mao qun

Maher v cng s (Adro, Chem, Soc, 101, 206 (1971)) l nhng ngi u tin nhn
thy rng, trong qu trnh to ra zeolit USY, cc l trng li do s tch nhm nhit hi nc c gn li do cc nguyn t Si do chuyn t cc phn tinh th b ph v n
l trng. Mt s sodalit b ph v, to ra ngun silic cho s gn lin mng, ng thi
to ra cc mao qun th cp, c kch thc c 50 - 200Ao. Kch thc v s lng mao qun
th cp tng ln theo mc v thi gian tch nhm. X l axit v sau , x l nhit - hi
nc lm tng ng kch hiu dng ca zeolit, thun li cho s khuych tn ca nhng
phn t hydrocacbon ln vo bn trong cc tinh th zeolit.
Zeolit Y c x l bng EDTA cng c mt s mao qun trung bnh bn cnh cc
mao qun nh. Cn trong zeolit Y c x l bng SiCl4 v (NH4)2SiF6 th khng c loi
mao qun th cp v ngun silic c cung cp t tc nhn x l.
v. Tnh cht axit
Bng hp ph piridin, ngi ta kt lun rng, trong zeolit USY tn ti c hai loi
tm axit: Bronsted v Lewis. axit Bronsted c to ra ch yu l do cc nhm hydroxyl
axit gn vi mng zeolit, trong khi , axit Lewis l do cc dng Al ngoi mng. S c
mt ca mt t aluminosilicat v nh hnh cng ng gp vo axit ca USY. Trong cc
zeolit USY c to ra do va x l nhit - hi nc va x l axit th axit Bronsted v
Lewis u gim.
Nghin cu axit ca nhiu zeolit Y khc nhau dn n kt lun rng, cc zeolit
USY c cc tm axit mnh hn so vi cc zeolit Y ban u (trc khi x l tng t s
Si/Al). Hin hay, mi ngi u tha nhn rng, trong zeolit Y giu silic, mi mt tm
nhm trong mng u gn vi mt tm axit mnh, s c mt ca cc tm nhm ngoi mng
cng nh hng ng k n hot tnh xc tc cracking, izome ho hydrocacbon. Cu hi v
bn cht v vai tr ca nhm ngoi mng n hot tnh xc tc vn l mt thch thc l
thuyt v thc nghim trong nghin cu xc tc zeolit hin nay.
vi. Tnh cht trao i ion
Zeolit Y bin tnh thng c s dng trong ch to cht xc tc FCC di dng trao
i vi cation kim loi. Cc cation ng vai tr nh trong zeolit cation-Y thng thng,
ngha l gia tng bn cu trc v axit ca zeolit. Bng phng php trao i ion, ngi
ta c th thay th hoc loi b cc cation (k c dng nhm ngoi mng) ca zeolit.
Cc ion natri lm suy gim hot tnh xc tc (axit), bn v kh nng gia tng ch s
octan ca zeolit. Cc ion natri thng c loi b bng cch trao i ion vi cc ion amoni
v/hoc vi cation t him. USY cng c trao i vi ion t him khi ch to xc tc
FCC nhm gia tng hot tnh m vn duy tr tng hp l ch s octan ca zeolit. Zeolit Y
trao i vi cation t him c kh nng lm gim s to cc v s hnh thnh kh kh trong

87

qu trnh cracking. Khi hm lng ca t him gim, hiu sut to gasolin ca xc tc

gim, nhng kh nng ci thin ch s octan li tng.
Nh vy, zeolit Y l mt hp phn quan trng trong cng ngh to cht xc tc FCC.
Zeolit Y l mt aluminosilicat tinh th c cu trc mao qun khng gian 3 chiu vi kch
thc mao qun ~7,4 , cha cc hc rng ~13 , do , zeolit Y l mt vt liu rn kh
xp v rng, to ra mt b mt ring kh ln (~700 1000m2/g). Thnh phn ho hc
ca zeolit Y: Me2/nO.AlO2.xSiO2.yH2O, n l ho tr ca cation Me, vi 1,5 x 2,5,
x = Si/Al, t s ny l mt tham s rt quan trng i vi zeolit Y. Khi x tng th bn
nhit, thu nhit, axit ca zeolit HY tng, trong khi hng s mng, kh nng trao i
ion, lng tm axit gim.
Cc phng php x l nhm nhm gia tng gi tr x ca zeolit u phi cn c vo
nhng mi quan h ni trn.
3.2.3. Cht nn
Hp phn quan trng th hai ca cht xc tc FCC l cht nn (matrix). Nhiu pha
nn c thnh phn tng t thnh phn ca cht xc tc cracking c s dng trc y,
khi cha pht hin ra zeolit, trong thi k trc chin tranh th gii ln th II, chng hn
nh t st x l axit v aluminosilicat v nh hnh.
Trong cht xc tc FCC, zeolit c phn tn trong cht nn. Thnh phn ca cht nn
v iu kin ch to cht xc tc c chn la sao cho cht xc tc c hot tnh v bn
c hc thch hp.
3.2.3.1. Chc nng cht nn
1. Chc nng vt l
Cht nn ca cht xc tc m bo mt s chc nng vt l quan trong sau y:
Tc nhn kt dnh: mt trong cc chc nng chnh ca cht nn l lin kt cc tinh
th zeolit trong ht xc tc dng vi cu c to ra bng k thut sy phun. Ht phi c
cng ( bn c hc) thch hp, chu c s va p gia cc ht v gia ht vi thnh (v)
react.
H tr khuch tn: cht nn ng vai tr nh mt tc nhn h tr khuch tn cho cc
phn t nguyn liu v cc sn phm cracking. Cht nn c mt h thng mao qun vi kch
thc kh ln (mao qun rng) nn rt thun li cho s vn chuyn cc hydrocacbon n v
ri khi b mt zeolit. Cc h thng mao qun ca cht nn khng b h hi trong qu
trnh x l nhit, nhit - hi, hon nguyn xc tc.
Mi trng pha long: cht nn c tc dng nh mt mi trng pha long cc
tinh th zeolit trong mt th tch vt liu ln hn nhm iu chnh hp l hot tnh xc
tc ca zeolit v nhm trnh cc phn ng cracking su.
88

 Cht ti nhit: cht nn c chc nng nh l mt vt liu ti nhit trong cc ht xc

tc FCC. Nh kh nng ti nhit tt ca pha nn m khng xy ra hin tng qu nhit cc
b, do , cu trc tinh th ca zeolit khng b ph v trong qu trnh cracking v hon
nguyn xc tc.
Cht thu gom natri: nh chng ta bit, natri l mt tc nhn gy hi cho hot
tnh xc tc, bn nhit v thu nhit ca zeolit. Nh kh nng trao i ion trong pha rn,
cc ion natri trong zeolit c th di chuyn t zeolit n pha nn, v do , lm cho hm
lng natri trong zeolit gim n mc thp nht c th.
2. Chc nng xc tc
Ngoi chc nng vt l, cht nn cn th hin chc nng xc tc. Trong nhng nm
1960 v nhng nm u thp k 70 th k trc, ngi ta nhn thy rng, cht nn cng
ng vai tr quan trong trong vic ci thin tnh cht xc tc ca cc cht xc tc FCC. Do
, cc nh sn xut xc tc s dng cc cht nn hot ng nh oxyt nhm hoc
aluminosilicat v nh hnh b sung vo t st. C th chia cht nn thnh hai loi :
Cht nn c hot tnh thp
Trong cc cht xc tc FCC cng cha mt lng lng zeolit v kiu zeolit nh nhau
th cht xc tc no c pha nn hot tnh thp (v d pha nn l hn hp t st - silicagel) s
to ra t cc v kh hn. nh hng ca pha nn hot tnh thp n gi tr octan ca gasolin
l khng ng k. Tuy nhin, v kh nng to cc v to kh thp nn xc tc FCC ny c
th hot ng trong nhng iu kin khc nghit hn v do c th tng chuyn ho v
ci thin ch s octan gasolin nhiu hn.
Cht nn c hot tnh xc tc cao v trung bnh
Cc cht nn ny c hot tnh xc tc cracking, nhng vn yu hn nhiu so vi zeolit.
Hot tnh ca cht nn c to ra l do b mt ring cao (> 150 m2/g), axit b mt v
kch thc mao qun khong 50 150 .
Mt cht nn hot ng c th thc hin cc chc nng xc tc sau y:
a. Cracking cc phn t ln trong phn on y thp (chng ct), v cc phn t
hydrocacbon khng th khuch tn vo bn trong mao qun zeolit.
b. Ci thin cht lng LCO, light cycle oil (gi tr xetan cao hn) do tng hm lng
hydrocacbon aliphatic, v cc aliphatic nng ca phn on y c cracking d dng nh
cht nn.
c. Nng cao bn ca xc tc i vi kim loi, v cht nn c th cracking cc phn
t nng cha kim loi v lin kt vi kim loi (ch yu vi vanadi), nh , cht nn bo v
c cu trc tinh th ca zeolit trc s tn cng ca vanadi.
d. Ci thin bn ca xc tc i vi cc hp cht nit trong nguyn liu cracking:
nh , zeolit c bo v, khng b ng c (suy gim hot tnh) v cc hp cht cha nit.
89

e. Gim thiu lng pht thi SOx. V d khi pha nn cha oxyt nhm hot tnh th s
pht thi SOx t thit b hon nguyn xc tc c th c gim xung ng k.
f. Ci thin gi tr octan ca xng do hn ch tc phn ng chuyn dch hydro.
Cc cht xc tc FCC c pha nn hot tnh thng c s dng trong cc cng on
FCC, m , ngi ta khng th tin hnh cracking trong nhng iu kin khc nghit.
Di nhng iu kin cracking bnh thng, cht nn hot tnh c th gp phn gia tng
chuyn ho v gi tr octan ca xng. Tuy nhin, cht nn hot tnh cng lm chn lc
cracking gim, lm tng cc, kh kh v cc olefin C3, C4.
3.2.3.2. Phn loi
Cc cht nn c th c phn loi da theo cc tiu chun khc nhau: thnh phn ho
hc, ngun gc ca vt liu (tng hp, bn tng hp, t nhin), chc nng xc tc (hot tnh
thp, trung bnh v cao), tnh cht vt l...
Hu ht cc cht nn u gm 2 hoc 3 hp phn. Mt trong cc hp phn l cht
kt dnh, thng thng l cc oxyt tng hp nh oxyt silic, oxyt nhm, aluminosilicat hoc
magnesio-silicat v nh hnh. Mt hp phn khc l vt liu khong st, thng l cao lanh,
halloysit, hoc montmorillonit. Cc khong st c x l ho hc hoc x l nhit trc
khi c s dng ch to cht xc tc cracking. Chc nng ca khong st ch yu nhm
ci thin bn c hc ca cht xc tc. Cht nn bao gm mt oxyt tng hp ( lm cht
kt dnh) v mt khong st t nhin thng c gi l cht nn bn tng hp.
Cc oxyt tng hp
- Oxyt silic v nh hnh (SiO2)
SiO2 c to ra t hydrosol ca oxyt silic (mt cht lng keo ca SiO2 trong nc).
l mt cht kt dnh tt v c hot tnh thp c s dng khi ch to cht xc tc FCC
bng k thut sy phun. Sol oxyt silic c th c iu ch bng mt s phng php nh:
tc dng silicat natri vi axit trong iu kin thch hp; cho mt dung dch long silicat natri
qua nha trao i ion axit; peptit ho silicagel; thu phn cc hp cht silic... Ngun silic
thng mi l silicat natri dng iu ch sol oxyt silic hoc silicagel c gi l thu
tinh lng, vi t s SiO2/Na2O ~3,3 v cha cc anion silicat c mc polyme ho khc
nhau.
Sol silic c iu ch bng cch axit ho nhanh mt dung dch thu tinh lng vi
axit sulfuric n pH = 2 3 c th dng kt dnh cc ht zeolit v khong st to ra mt
cht xc tc FCC cng v mi mn tt. C th thm mt t sulfat nhm c nh
sol nhng pH mong mun.
Oxyt silic c iu ch t sol oxyt silic c n nh bi amoni (cn gi l dung
dch poly silicat amoni) cng c xem l mt cht k dnh hiu qu, c bit khi kt hp
vi oxyt nhm.
90

Sol silic l mt cht kt dnh rt hiu qu khi va mi iu ch, v khi oxyt silic
(hay ni ng hn, cc phn t axit silicic) c polyme ho thp v cha b gel ho. Sol
oxyt silic ni chung l mt h keo khng bn, theo thi gian h s b gi ho do to gel.
Tng pH thc y s to gel. Mc du hydrogel oxyt silic c iu ch t silicat natri c
xem nh mt cht kt dnh hiu qu cho xc tc zeolit, song n vn khng bng sol oxyt
silic.
Sol oxyt silic to ra cc cht nn c hot tnh xc tc thp, do khng c mt cc nhm
OH axit. Tuy nhin, khi kt hp vi khong st, ngi ta to ra mt cht nn c b mt ring
cao, th tch mao qun tng i ln (> 0,3 ml/g), vi mt lng ln mao qun rng (~50%)
c kch thc c 500 2000 , v do , n rt thch hp cho cracking cc nguyn liu
nng.
- Oxyt nhm
Oxyt nhm l mt cu t quan trng ca nhiu cht xc tc zeolit. Ph thuc vo loi,
khi lng v cch phi tr vo cht nn, oxyt nhm c th ng cc vai tr: (i) tng hot
tnh xc tc ca cht nn, (ii) ci thin bn mi mn ca cht xc tc, (iii) ci thin
bn thu nhit ca cht xc tc, (iv) by kim loi trong cc nguyn liu nng v (v) gim
pht thi SO2 khi ch bin cc nguyn liu giu lu hunh (du chua). Trong mt s trng
hp, oxyt nhm c thm vo cht xc tc nh nhng ht oxyt ring r.
Pxdobomit (Pseudoboehmite) thng c s dng ch to xc tc. Pxdobomit
c b mt ring cao (200 - 300 m2/g), l dng oxyt monohydrat ca nhm, c iu ch
bng mt s phng php: thu phn alkoxit nhm; tc dng aluminat natri vi sulfat nhm;
axit ho aluminat kali hoc thm mt baz vo mt mui nhm. Pxdobomit c c trng
bi mt pic rng trong khong 10o - 18o, nh pic 13,5o (2) ca ph XRD. S c mt ca
oxyt nhm dng pxdobomit trong cht xc tc khng ch lm tng bn v hot tnh
xc tc m cn ci thin mi mn ca cht xc tc. Pxdobomit thng c peptit ho
trong nc axit (axit rt long), trn vi cc hp phn khc ca cht xc tc, tip n, hn
hp c sy phun. tr thnh mt cht kt dnh tt, pxdobomit phi d dng peptit
ho.
Oxyt nhm dehydrat ho c axit ng k. V d, khi nhit nung tng, axit
ca oxyt nhm c iu ch bng thu phn isopropylat nhm, i qua hai gi tr cc i
500oC v 800oC. Theo qu trnh nung pxdobomti chuyn dn thnh -Al2O3 khong
300oC v thnh -Al2O3 khong 870oC. -Al2O3 c nhng nhm OH axit (axit Bronsted)
cng nh cc tm Lewis. l vt liu mao qun trung bnh (mesopore) v mao qun ln
(macropore), trn b mt -Al2O3 c 5 nhm hydroxyl khc nhau ng vi cc axit khc
nhau. Lc axit ca oxyt nhm thp hn lc axit ca aluminosilicat. ng kt ta oxyt nhm
vi mt lng nh cc oxyt khc (v d oxyt Fe, Ca...) ngi ta c th gim cc tm axit
mnh, v tng cc tm axit yu v trung bnh. Cc ion natri bao bc cc tm axit v lm
91

gim hot tnh xc tc ca oxyt nhm. trong qu trnh x l nhit - hi nc, oxyt nhm b
gi ho, b mt ring gim, cc mao qun nh b chp li, mao qun trung bnh tng ln.
Pxdobomit thng c s dng cng vi khong st v mt s hp phn khc to
ra cht nn cho xc tc zeolit. V d, thm mt lng nh ca sol oxyt silic n nh bng
amoni vo hn hp oxyt nhm - t st lm gia tng bn mi mn c hc ca cht xc
tc. Mt vi aluminosilicat v nh hnh c hnh thnh trong qu trnh ch to cht xc
tc. Ngi ta cng c th to ra cht nn t gel aluminosilicat, pxdobomit v khong st.
Ngoi pxdobomit, mt s hp cht khc ca nhm cng c s dng nh l tin
cht ca tc nhn kt dnh dng oxyt nhm. Ngi ta thy rng, oxyt nhm xut pht t
clohydrol nhm l mt cht kt dnh hiu qu cho cht xc tc cha zeolit v khong st.
Clohydrol nhm l polyme ca clohydroxyt nhm t monome Al2(OH)5Cl.2H2O. Nung
clohydrol nhm cha trong xc tc lm thot ra axit HCl v hnh thnh mt cht xc tc rt
bn v chu mi mn.
- Aluminosilicagel
Trc khi pht hin ra xc tc FCC, ngi ta s dng aluminosilicagel nh l cht
xc tc cracking. Trong thi gian , aluminosilicagel rt c ch nghin cu. Nhiu
kin thc kinh nghim t thi k vn c ng dng trong vic ch to cht nn cho xc
tc FCC hin nay.
Phng php iu ch:
Aluminosilicagel tng hp s dng trong cng nghip ch to cht xc tc FCC c th
iu ch bng cc phng php:
i. Kt ta hydroxyt nhm v hydrogel oxit silic.
ii. Phn ng gia sol oxyt silic v oxyt nhm: thm oxyt nhm di dng oxyt nhm
hydrat hoc dung dch mui nhm vo sol oxyt silic.
iii. ng kt ta aluminosilicagel: dung dch thu tinh lng tc dng vi mt vi mui
nhm trong nhng iu kin c th.
iv. Thu phn cc dn xut hu c ca nhm v silic.
Cc aluminosilicagel c iu ch t silicat natri u cha cc mui natri ho tan
trong nc. V tc dng xu ca ion natri i vi xc tc zeolit nn ngi ta phi ra sch
cc mui natri trc khi trn gel vo zeolit v khong st. Mt s ion natri lin kt vi
hydrogel (gel t) c th c loi b bng cch trao i ion vi dung dch amoni.
Tnh cht
Rt nhiu tham s ca qu trnh iu ch aluminosilicagel nh hng n tnh cht
ca hydrogel nh: t s Si/Al, nng oxyt, pH, tc nhn to gel, thi gian v nhit
phn ng, thi gian v nhit lm gi, s hin din ca cc cation...

92

Lng axit
(mmol/m2)x104

Cc aluminosilicagel c hm lng nhm thp (10 15% Al2O3) ni chung c th tch

mao qun thp, ng knh mao qun nh, b mt ring cao v c hot tnh xc tc thp hn
gel cha hm lng oxyt nhm cao (~25% Al2O3). axit ca gel thay i theo hm lng
ca oxyt nhm : axit Bronsted t n cc i khong ~70% SiO2, nh trn hnh 3.6.

A
C

SiO2 (%kl)

Hnh 3.6. axit ca aluminosilicagel bin i theo hm lng ca oxyt silic (%):
A axit tng Ho +1,5; B axit Lewis; C, axit Bronsted (C = A B)
(K. Tanabe, Solid acids and bases, Academic Press, New York, 1970).
Cc tm Bronsted c lc axit c phn b trong mt khong kh rng (3 H 15).
C hai loi tm axit Bronsted v Lewis u c mt trong aluminosilicagel, to ra hot
tnh xc tc ca gel. gii thch s hin din ca cc tm axit, ngi ta gi thit rng,
trong phn ng gia oxyt nhm v oxyt silic, mt s oxyt nhm tr thnh cc cu trc c
phi tr t din nn mang mt in tch m, v c b tr bi mt proton (to ra tm axit
Bronsted). Dehydrat ho bng cch x l nhit (nung) cc tm Bronsted chuyn thnh cc
tm Lewis. Tuy nhin, trong gel Al2O3-SiO2 c hm lng SiO2 cao, t s Lewis/Bronsted
vn khng thay i ng k trong mt khong nhit rng. Ngi ta bit rng, cc mao
qun trung bnh v ln d c hnh thnh khi tng hp aluminosilicagel pH cao, nng
cao v vi s c mt ca cht iu chnh cu trc mao qun.
Cc cu trc khc nhau vi cc tm axit khc nhau c th tn ti trn b mt cc
aluminosilicagel. Bng nghin cu ph cng hng t ht nhn 27Al-MAS-NMR, Gilson v
cng s (J. P. Gilson et al. J. Chem. Soc. Commun 91, 1987) thy rng, gel ca aluminosilicagel (Al2O3-SiO2) va mi tng hp vi t s Si/Al = 2,15 ch yu cha cc dng nhm
t din, trong khi , trong cc gel c x l nhit - hi nc, tn ti ng thi c nhm
dng t din, bt din v lin kt phi tr 5 (hnh 3.7). Trn ph 29Si-MAS-NMR ca
aluminosilicat v nh hnh c mt m ph rng ~110 ppm i din cho oxyt silic.
93

Hnh 3.7. Ph 27Al-MAS-NMR ca gel Al2O3-SiO2 (Si/Al = 2,15); (A) gel mi tng hp;
(B) gel c x l nhit hi nc 427oC, 4h; (C) gel c x l nhit - hi nc
700oC, 4h (T: Al t din, P: Al phi tr 5, O: Al bt din).
Aluminosilicagel c cu to gm cc ht hnh cu nh v trng thi v nh hnh
theo k thut XRD. Gn y, ngi ta pht hin rng c mt s zeolit v nh hnh theo
XRD nhng theo k thut IR th hnh thnh cc tinh th (hoc mm tinh th) rt nh ca
zeolit, do dn n gi thit rng, trong aluminosilicagel cng c nhng cu trc tin
zeolit v do , gel c hot tnh xc tc. Din tch b mt ring ca gel c th thay i t t
100 600m2/g tu thuc vo cc yu t sau y: iu kin iu ch, cch sp xp ca cc
ht gel, kch thc ht gel, khi lng ring, s x l nhit - hi nc... Cc yu t cng
nh n th tch mao qun, s phn b kch thc mao qun trong gel. Nung gel trong hi
nc lm gim din tch b mt v th tch mao qun, lm tng kch thc mao qun l do
s hnh thnh cc ht gel ln t cc ht nh, do s sp (ph v) ca cc mao qun nh (<30).
X l nhit v nhit - hi nc cng c th lm gim axit v hot tnh xc tc ca cht
nn.
Aluminosilicagel cng c kh nng trao i ion nh s hin din ca cc ion Al t
din. Ngi ta cng c th trao i t him vi aluminosilicagel ch to cht nn cho
xc tc FCC nhm gia tng hot tnh xc tc, song cng lm gia tng cc v kh.
94

- Cc oxyt hn hp v c khc
Trong nhiu bng sng ch, ngi ta s dng cc oxyt hn hp v c lm cht nn
cho xc tc FCC (bng 3.4).
Bng 3.4. Mt s oxyt hn hp v c
Oxyt hn hp (%mol)
Al2O3.SiO2 (94:6)

B mt ring, m2/g

Lc axit

270

8,2

440

8,2 7,2

90

8,2 7,2

110

6,4

450

6,4

110

5,6

ZrO2.SiO2 (88:12)

Ga2O3.SiO2 (92,5:7,5)
BeO.SiO2 (85:15)

MgO.SiO2 (70:30)

Y2O3.SiO2 (92,5:7,5)

a
a

80

5,6 3,2

SnO. SiO2 (85:15)

70

Yu hn La2O3,SiO2

PbO. SiO2 (85:15)

100

Yu hn La2O3,SiO2

La2O3. SiO2 (92,5:7,5)

a: Hydrooxyt kim loi c kt ta trn SiO2 mn.

b: Silicat etyl v nitrat zirconi ng kt ta.
c: Silicat etyl v axetat magie ng kt ta.

Ngoi aluminosilicagel, ngi ta cn s dng cc cht nn cha oxyt titan, oxyt

zirconi, oxyt magie... cc gel ca TiO2-SiO2, ZrO2-SiO2, P2O5-SiO2, Al2O3-MgO... Mt vi
cht nn cha phosphat nhm hoc perovskit cng vi SiO2 v/hoc Al2O3.
Cc oxyt hn hp v c c nng axit, b mt ring, th tch mao qun, phn b
kch thc mao qun v cng khc nhau. Chng to ra cc tnh cht vt l v xc tc cn
thit cho xc tc FCC. V d, SiO2.ZrO2 c axit rt mnh (H 8,2) v b mt ring cao
(trn 400m2/g). SiO2.ZrO2 cha cc zirconi phi tr 6 mang in tch 2. B sung perovskit
(CaTiO3) vo xc tc FCC nhm ci thin ch s octan ca gasolin, nhng lm gim hiu
sut gasolin.
Cc vt liu khong st t nhin
- Khong st t nhin
Cc khong st t nhin c s dng hu nh trong mi cht xc tc thng mi,
dng ngm nc hoc dng c x l ho hc hoc x l nhit. dng ngm nc chng
c hot tnh thp, nhng nh hng mnh n cc tnh cht vt l ca cht xc tc. Ni
chung, cht xc tc cha khong st u cng hn, chc hn v c mi mn tt hn so
vi cht xc tc c cht nn tng hp. Cc khong st t nhin cn ng vai tr nh cht
n, v thng thng chng r hn cc cht nn khc.

95

Ni chung st c la chn ch to cht xc tc FCC l kaolinit v halloysit.

Chng c cu trc 2 lp, gm cc mng xen k ca SiO4 (t din) v AlO6 (bt din) nh
trn hnh 3.8. Thnh phn l tng ca kaolinit l 2SiO2.Al2O3.2H2O. Tuy nhin, khong st
t nhin thng cha cc tp cht nh st, manhe, calxi... v mt s tp cht khong khc
(v d quartz). Kaolinit khc vi halloysit trong cch sp xp hnh hc cc lp c s.
Halloysit c th b ehdrat ho khng thun nghch v to thnh metahalloysit. Kh nng
trao i ion ca cc khong st ny thp (1 10 mlg/100g khong st). Ngi ta cho rng
tnh cht trao i ion c to ra l do s thay th ng hnh ca Al3+ trong mng bt din
bi Mg2+ (Mg2+ Al3+).
Oxy
Nhm
Silic
Hydroxyl

OH ti 0,437nm
Al ti 0,327 nm
O,OH ti 0,219 nm

= 91,8o

Si ti 0,06 nm
O ti 0,0 nm

Hnh 3.8. Cu trc lp ca kaolinit nhn theo trc a

C mt s khong st cng c s dng trong ch to cht xc tc FCC, nh
montmorillonit, illit... Montmorillonit l khong st c cu trc 3 lp gin n, gm mt
mng bt din AlO6 nm gia 2 mng t din SiO4. Loi khong st ny c kh nng trao
i ion ln hn (70 - 90 mlg/100g khong st) so vi kaolinit.
Cc khong st dng lm cht nn cho cht xc tc FCC thng phm c tinh
ch (lm sch) v c kch thc trung bnh ca cc ht nh (a s l 2m). Tinh ch loi
b cc tp cht c hi cho hot tnh xc tc (v d Fe) hoc to ra nhng cht nhim mi
trng. Kch thc ht nh, phn tn cao ci thin bn mi mn ca cht xc tc.
Ch vi kaolinit khng cn thm cht ph tr no khc, ngi ta cng c th ch to
c cht xc tc c bn mi mn tt: p n mt hn hp t ca NH4Y v cao lanh,
nung v x l nhit - hi nc 700oC c th to ra mt cht xc tc chu mi mn v rt
hot ng.
- Khong st bin tnh
96

i. X l ho hc
Cc khong st kaolinit, halloysit hoc montmorillonit c x l bng axit l cc vt
liu c hot tnh xc tc tt hn so vi khong st t nhin ban u. Chnh cc khong st
c x l bng axit ny c s dng nh l xc tc cracking trc y khi cha tm ra
zeolit (M. Sitting, Refiner, 31(9), 203, 1952). X l vi mc va phi cc khong st t
nhin bng axit long, v d axit sulfuric long, c th tch b cc tp cht st (tc nhn gia
tng s to cc v hydro). X l axit c th loi bt nhm, magie, kim loi kim th... lm
gia tng xp v b mt ca vt liu, v thay th mt s cation bng proton. Do ,
khong st tr nn hot ng xc tc hn. B sung oxyt nhm hoc aluminosilicat tng hp
vo khong st x l axit lm tng hot tnh xc tc. Nhiu khong st x l axit c s
dng trong ch to cht xc tc FCC.
Mt dng khc ca khong st bin tnh ho hc l st pilla*. Ngi ta th nghim
ch to montmorillonit pilla bng cch a cc oligome ca hydroxy-zirconi hoc hydroxyalumin vo cc khe mng ca montmorillonit to ra mt cht xc tc cracking. Cht xc
tc ny c kh nng gia tng gi tr octan nh zeolit v cho hiu sut LCO cao. Tuy nhin,
nhc im ch yu ca loi st pilla ny l bn nhit v thu nhit thp, do cho n
nay, kt qu vn cha c p dng vo xc tc thng mi. Gn y hn, ngi ta ch
to st pilla dng Al-rectonit. Dng ny c bn thu nhit cao hn v c hot tnh xc tc
cracking tt hn sau khi x l nhit - hi nc.
ii. X l nhit
Trong qu trnh nung, kaolinit tri qua cc giai on bin i pha nh sau:
Kaolinit

580 600oC
H2O

Metakaolinit

950oC

Spinel

> 1000oC

Mullit

-Al2O3 v crystobalit cng c th c hnh thnh nhit nung cao. K thut

DTA (phn tch nhit vi sai, differential thermal analysis) xc nh rng, phn ng thu nhit
dehydrat ho kaolinit xy ra ~600oC, sau mt phn ng to nhit xy ra ~1000oC to ra
spinel/mullit.
Kaolinit nung ~1000oC c s dng trong vic tng hp trc tip zeolit. Hn hp
metakaolinit v silicat natri c th chuyn mt phn thnh zeolit Y.
iii. X l nhit v ho hc
Cc khong st c x l nhit v ho hc c th c dng lm cht nn cho cht
xc tc FCC. V d, ngi ta c th chuyn kaolinit thnh mt hn hp spinel/mullit bng
cch nung 1000oC, sau loi bt SiO2 khi spinel bng xt. Hn hp spinel/mullit x
*

Thut ng ny c dch t pillared clay. l loi khong st c "chn" cc cation kim loi
vo gia cc lp cu trc chng, chn (pillared) lm bn cc lp cu trc . C ngi
dch st chng, st chn.

97

l xt c s dng ch to cht xc tc FCC. Cht xc tc ny c bn thu nhit

tt v rt hiu qu trong phn ng cracking nguyn liu nng (du cn). Xc tc cha
metakaolinit c x l bng axit cng c cc tnh cht tng t.
Tm li, cht nn l mt hp phn kh quan trng trong vic ch to cht xc tc
FCC. Cht nn c nhim v ch yu l tng bn c hc, bn nhit, thu nhit, kh
nng khuch tn v iu chnh hp l tnh cht xc tc ca cht xc tc FCC. Cht nn
thng bao gm cc oxyt, hn hp oxyt tng hp v cc khong st t nhin c x l thch
hp (lm sch, ho hc v nhit). La chn cc hp phn, xc nh thnh phn cht nn v
k thut x l, ch to cht nn l mt vn khoa hc v ngh thut trong cng ngh
sn xut cht xc tc ni chung v cho cht xc tc FCC ni ring. Quy trnh v vt liu
sn xut cht xc tc ph thuc ch yu vo mc ch cn t c ca cc nh lc du.
3.2.4. Cc cht ph tr xc tc
Cng nghip lc du ngy cng phi i mt vi nhiu thch thc quan trng. Trong
c nhng lut l mi trng, yu cu nghim ngt v cht lng ca nhin liu v phng
cch hot ng ca cc nh my lc du. Ngi ta i hi phi sn xut gasolin nhiu hn,
ng thi phi to ra nhiu cc sn phm khc, v d nh cc alken nh nhm phc v cho
cng nghip ho du. Do , trong nhng nm gn y, ngi ta c khuynh hng thm mt
s cht ph tr (additive) vo cht xc tc FCC nh zeolit ZSM-5, zeolit ,... v mt s cht
ph tr khc.
3.2.4.1. Zeolit ZSM-5
Vai tr ph tr xc tc ca ZSM-5 trong cht xc tc FCC (Nguyn Hu Ph, Tp
ch Ho hc, T35, S 36, tr8-22, 1997)
Vic thm ZSM-5 vo cht xc tc FCC l mt phng php quan trng tng lng
alken nh m khng lm tng lng cc v kh. Thm ZSM-5 dn n s gia tng ch s
octan ca gasolin do tng t s iso/normal ca cc alkan v alken v tng nng
hydrocacbon aromat trong gasolin. ng thi, n lm tng hiu sut propen v gim hiu
sut gasolin, lm tng ng thi c isobuten v isobutan. Thm ZSM-5 cng lm gim lng
metylpenten, hexan v heptan. Tng lng cc C5 s lm tng gi tr RVP (p sut hi ca
gasolin, Reid vapor pressure). Hiu qu ca ZSM-5 l lm thay i tnh cht xc tc
cracking C7 v cc alken cao hn. iu tt nhin ko theo s tng thm mt lng alkan
C5 v C6. C6 li c th cracking tip thnh alken nh hn.
Khi ZSM-5 c phi liu trong cht xc tc cracking th s hp ph cc alkyl thm
d dng hn nn dn n tng hiu sut bezen. Vi zeolit USY, t s dealkyl ho v cracking
mch nhnh nh hn so vi ZSM-5. Ngi ta nhn thy rng, vi 20% ZSM-5 trong xc tc
FCC, nhit cao, phn ng chuyn dch hydro cc k chm so vi phn ng cracking,
thi gian tip xc cho phn ng cracking ngn (0,1 - 0,5 sec), do hiu sut propen v
98

buten c th t c n 35% (theo th tch).

Zeolit ZSM-5 thc s l mt cht ph tr hiu qu cho xc tc FCC lm gia tng
gi tr octan ca gasolin v olefin nh, c bit l propen.
Thnh phn ho hc v cu trc ca zeolit ZSM-5
Zeolit ZSM-5 c cc nh nghin cu hng Mobil Oil pht minh nm 1972 (US
patent 3702886). Cng thc ho hc ca ZSM-5 c dng:
NanAlnSiO96-nO192.~16H2O (n < 27)
Zeolit ZSM-5 thuc h vt liu pentasil, m cu trc quc t gi l MFI. Cc d liu
tinh th hc c bn ca ZSM-5 nh sau:
Cu trc tinh th c bn: octorhombic (orthorhombic) thuc nhm i xng Pnma,
a = 20,1; b = 19,9; c = 13,4 . Mng tinh th ca ZSM-5 cha cc t din TO4 (trong T
l nguyn t nm tm t din, c th l Si hoc Al), cc t din lin kt vi nhau thnh
n v cu trc th cp SBU (secondary unit building) dng 5 cnh: 5-1. Cc SBU ny li kt
ni vi nhau to ra 2 h knh mao qun ct nhau, vi ca s mao qun l vng 10 cnh. Mt
h knh mao qun song song vi trc a ca tinh th c s octorhombic, c dng ziczc vi
kch thc ca s gn trn (5,4 - 5,6 ), Mt h knh khc, thng v song song vi trc b,
c dng ca s hnh elip (5,1x5,7 ). Hai h knh ny ct nhau: to ra mt hc rng c kch
thc c 9 v l ni nh x cc tm axit mnh c trng cho hot tnh xc tc ca zeolit
ZSM-5 (P. Dejaitre et al, J. Catal, 63, 331, 1980). Hnh 3.9 l ph XRD ca ZSM-5 dng bt.

Hnh 3.9. Ph XRD dng bt ca ZSM-5.

ZSM-5 l zeolit c hm lng oxyt silic cao, t s SiO2/Al2O3 c th bin i t 20
n 8000. Khi hm lng Al2O3 tin ti khng (vt liu cha hon ton oxyt silic) v vn

99

gi cu trc ca MFI th vt liu c tn gi silicalit. ng dng cc k thut MAS NMR,

XPR v hin vi in t, ngi ta nhn thy rng, nhm trong ZSM-5 phn b khng ng
u, c bit trong cc tinh th ln (> 5 m). B mt tinh th thng giu nhm so vi ton
th tinh th.
Hnh 3.10. Gii thiu cu trc ca ZSM-5.

Hnh 3.10. Cu trc tinh th ca ZSM-5 (a) h knh mao qun (b)
s mng cu trc ca ZSM-5.
Tnh cht
Nhiu tnh cht ca zeolit ZSM-5 thay i theo thnh phn vi t s Si/Al. V d nh:
tnh cht trao i ion, tnh cht k nc v tnh cht xc tc. Cc tnh cht thay i hu
nh tuyn tnh vi hm lng nhm: dung lng trao i ion v hot tnh xc tc tng theo
hm lng nhm, trong khi tnh cht k nc gim. Cc tnh cht vt l nh: cu trc
tinh th, th tch mao qun, mt mng... khng ph thuc vo t s Si/Al.
Trong dng proton, H-ZSM-5 c cc tm axit Bronsted v cc tm axit Lewis. Ph

hng ngoi (IR) ca H-ZSM-5 c mt m dao ng mnh trong vng 3600cm 1, c trng
cho nhm OH nh x trong ch giao nhau ca 2 h knh mao qun. C th ni H-ZSM-5 l

xc tc axit mnh nht so vi cc zeolit HY, H-mordenit... Cc m ph 3720 3740cm 1

l ca cc nhm axit yu, nhm silanol (SiOH) trn b mt tinh th zeolit. Nng ca cc
tm axit Bronsted mnh t l vi nng ca Al trong mng tinh th. Tng nhit nung
ZSM-5 n 400oC dn n qu trnh tch nhm hydroxyl (OH), lm gim cc tm axit
Bronsted v tng cc tm axit Lewis. X l nhit - hi nc gy ra qu trnh tch nhm khi
mng zeolit, lm gim nng cc tm OH axit mnh. un nng mt hn hp m ca ZSM5/Al2O3 hoc x l nhit - hi nc hn hp ZSM-5/Al2O3 c th lm tng hot tnh xc tc
cracking v kh nng trao i ion ca zeolit. Ngi ta gi thit hiu ng l do hiu ng
thm nhp ca Al vo trong mng zeolit.
Ngoi tnh cht axit mnh ca H-ZSM-5, zeolit ny cn c mt tnh cht xc tc ni
bt: l tnh cht chn lc hnh dng.

100

Tnh cht xc tc chn lc hnh dng l yu t then cht lm gia tng ch s octan
ca gasolin khi ZSM-5 c s dng lm cht ph tr cho cht xc tc cracking FCC.
Tnh cht chn lc hnh dng (CLHD) xut pht t kh nng hn ch kch thc v
hnh dng cc phn t khuch tn vo v ra khi knh mao qun ca zeolit.
Tnh cht CLHD c th miu t c th hn: (a) theo cht phn ng, ngha l loi b
cc phn t tham gia phn ng c kch thc ln hn kch thc ca s mao qun ca zeolit.
(b) theo sn phm phn ng, ngha l ch nhng phn t sn phm phn ng c hnh thnh
phi c kch thc nh hn kch thc mao qun zeolit th mi thot (khuch tn) ra ngoi
tinh th zeolit, (c) theo trng thi trung gian, ngha l nhng phn ng thc hin qua nhng
trng thi trung gian cng knh, c kch thc ln hn kch thc mao qun, th khng xy
ra, ch u tin cho cc phn ng xy ra qua cc trng thi trung gian kch thc nh.
Ngoi yu t hnh hc, chn lc hnh dng cn ph thuc vo cc hiu ng tnh
in to ra t tng tc gia trng in tch ca s mao qun v moment lng cc ca
phn t tham gia phn ng. Nhng tng tc c th thun li hay ngn cn s khuch tn
ca cc phn t vo bn trong zeolit. chn lc hnh dng ca zeolit c th thay i nh
cc hiu ng trao i ion, tch nhm khi mng tinh th, thay i t s Si/Al hoc bt k
mt tc ng c nh hng n kch thc v cu trc hnh hc ca mao qun.
Tnh cht chn lc hnh dng ca zeolit thng c c trng bi ch s cn tr.
Ch s c xc nh bi t s tc cracking ca n-hexan v 3-metylpetan. Zeolit c
kch thc mao qun ln nh X, Y, v L c ch s cn tr ln hn 1, zeolit mao qun
trung bnh nh ZSM-5, ZSM-11 hoc ZSM-22 c ch s cn tr gia 1 v 12, v cc zeolit
mao qun nh, ch s cao hn 12. Ch s cn tr gim khi nhit tng.
3.2.4.2. Cc vt liu ry phn t (RPT) dn xut t AlPO4: SAPO, MeAPO,
MeAPSO.
Theo mt s bng pht minh (Eur. Pat. Appl. 208,409, 1987, US Pat. 4,764,269, 1988,
US Pat. 4,734,285, 1988), vt liu ry phn t dng aluminophosphat v dn xut c thm
vo cht xc tc FCC lm tng ch s octan ca gasolin. Mc du cho n nay, cc xc
tc cha c thng mi ho, song chng ti cng trnh by mt s c im c bn ca
vt liu .
AlPO4-n
Trong nhng nm u ca thp k 80 th k trc, mt h vt liu RPT mi c pht
hin bi cc nh nghin cu ca hng Union Carbide, Wilson v cng s (S. T. Wilson et al.
J. Am. Chem. Soc. 104, 1146, 1982, US Pat. 4,310440, 1982). H tng hp thnh cng
cc aluminophosphat tinh th AlPO4 c cu trc mao qun nh bng phng php thu
nhit, xut pht t oxyt nhm hydrat, axit phosphoric v cht to cu trc hu c, nh amin
v mui amoni bc 4. Thnh phn ho hc ca vt liu l:
101

xR.Al2O3.1,0-1,2P2O5.4H2O
trong , R l cht to cu trc hu c.
Cc vt liu RPT ny c to ra t cc t din AlO2 v PO2 ni vi nhau thnh mt
mng tinh th khng gian 3 chiu v trung ho in tch, cu trc ca tng loi aluminophosphat tu thuc vo iu kin iu ch. Trong mng cu trc khng tn ti cc lin kt
Al-O-Al, P-O-P. Cc cht to cu trc hu c ng vai tr rt quan trng trong vic hnh
thnh cu trc tinh th. Khong 20 cu trc AlPO4 khc nhau c pht hin, trong 13
cu trc l vt liu mao qun nh. Danh php ca cc vt liu ny l AlPO4-n, trong n
biu th kiu cu trc. V d, ngi ta bit AlPO4-17 (c cu trc erionit) hoc AlPO4-20
(c cu trc sodalit).
AlPO4-5 c cu trc gm cc vng 4 v 6 cnh, ni vi nhau to ra cc knh mao
qun vi 12 cnh v ng knh c ~8 (hnh 3.11).

Hnh 3.11. Cu trc ca vt liu RPT AlPO4: (a) s mng ca AlPO4-5 (b)
s mng ca VPI-5.
rng cu trc ca vt liu RPT AlPO4 bin i t cc h mao qun nh (~3) n h
mao qun rng (~8 ): t 0,04 n 0,35 cm3/g. V mng cu trc ca AlPO4-n trung ho in
tch nn chng khng c kh nng trao i ion. Tuy nhin cc vt liu ny tng i bn
nhit v thu nhit. Vt liu AlPO4-n c axit b mt rt nh, do b hn ch trong ch
to cht xc tc cracking.
Cc vt liu SAPO, MeAPO, MeAPSO
Xut pht t vt liu aluminophosphat tinh th c mao qun, ngi ta c th iu ch
mt h vt liu RPT mi c cu trc tinh th bng cch thay th ng hnh mt s nguyn t
khc nhau vo mng AlPO4. Cc nguyn t th ng hnh c th l cc cation c ho tr 1+
n ho tr 5+. C Al v P u c th b thay th ng hnh, song ch Al c th bi cc ion
ho tr 2 v P bi cc ion ho tr 4 th mi to ra cc vt liu c kh nng trao i ion v mi
to ra axit Bronsted ng k. Sau y l mt s v d minh ho.

102

Thm silic vo mng cu trc ca h aluminophosphat c th to ra mt vt liu RPT

mi l silico aluminophosphat (SAPO). Vt liu ny c tng hp thu nhit t mt hn
hp cha oxyt nhm hydrat, axit phosphoric, sol oxyt silic v cht to cu trc. Cu trc ca
SAPO c cng cu trc vi AlPO4 tng ng. 13 cu trc SAPO c tng hp, trong s
c mt s cu trc tng t cu trc zeolit. SAPO dng khan c thnh phn 0 0,3R
(SixAlyPz)O2, trong R l cht to cu trc, x = 0,04 0,80. Tnh cht hp ph, kch thc
mao qun, bn nhit v thu nhit ca SAPO tng t nh ca AlPO4. SAPO c a
nc (hydrophilic) va phi, c axit t thp n trung bnh, tu thuc vo nng ca
silic v kiu cu trc hnh thnh. Nhiu vt liu SAPO c hm lng silic cao nhng hot
tnh xc tc vn thp hn so vi zeolit. Tuy nhin, ngi ta nhn thy rng, vt liu SAPO37 l mt xc tc cracking rt tt. Ngoi ra, cc SAPO-5, SAPO-40 cng c s dng trong
mt s bng pht minh ch to xc tc FCC tng ch s octan.
Vic thay i ng hnh mt s ion kim loi vo mng cu trc AlPO4 c th to ra
cc aluminophosphat kim loi (MeAPO), cn thay th ng hnh mt s ion kim loi vo
mng cu trc SAPO th li to ra vt liu silico aluminosilicat kim loi (MeAPSO). Cc vt
liu MeAPO, MeAPSO c tng hp thu nhit t mt h gel hot ng ca
aluminophosphat cha cc nguyn t thay th ng hnh, cc amin hu c hoc cc mui
amoni bc 4. Thnh phn ho hc ca vt liu MeAPO l 0-0,3R(MexAlyPz)O2, trong R
l cht to cu trc, x = 0,01 0,25. Cc tnh cht ca vt liu MeAPO cng tng t nh
ca vt liu AlPO4-n ban u. bn nhit v thu nhit ca MeAPO thp hn mt t so vi
AlPO4 v SAPO tng ng. MeAPO c xem nh l vt liu to ra t s thay th ng hnh
ca cc kim loi ho tr 2 hoc 3 cho Al to ra mt mng cha in tch m (khi th vi
Me2+) hoc mng trung ho in (khi th vi Me3+). in tch m b mt ca vt liu
MeAPO to ra tnh cht trao i ion v do c th to ra cc tm axit Bronsted.
Nm 1988, Davis v cng s (Davis et al, Nature 331(6158), 698, 1988) tm ra mt
loi vt liu RPT AlPO4 c ca s mao qun l vng 12 cnh, ng knh 12 13. l ca
s c ng knh ln hn bt k mt loi ca s no khc ca cc zeolit hin c. Cu trc
mi c t tn l VPI-5 (xem hnh 3.11b). Nu vt liu ny c bn nhit v thu
nhit tt th n cng s c vai tr rt quan trng trong ch to xc tc FCC.
3.2.4.3. Cc loi vt liu khc
Trong vi thp k va qua v hin nay, cc nh khoa hc ang ht sc quan tm
nghin cu ch to cc vt liu RPT c kch thc mao qun ln hn kch thc mao qun
ca zeolit Y (~7,4), c bn nhit v thu nhit tt v c axit b mt cao xc tc cho
qu trnh chuyn ho cc hydrocacbon trong phn du cn, ngha l tn dng ti a
ngun du m hin c.
Ngi ta dng zeolit mordenit hoc mordenit cng vi zeolit USY gia tng ch

103

s octan ca gasolin. Ngoi ZSM-5, ngi ta cn dng cc zeolit khc ZSM-11, ZSM-22,
ZSM-35, ZSM-38, , offrerit... lm cht ph tr xc tc cho cht xc tc FCC.
c bit gn y nht, mt s cng b ca S. Kaliaguine v Trng n (Trong On
D., S. Kaliaguine et al, Appl. Catal A: General, 222, 299-357, 2001; Do Trong - On,
Research signport 37/661 Fort P.O, Trivanchum - 695023 Khala, India, 2003) tng hp
cc vt liu mao qun trung bnh m thnh mao qun c tinh th ho gia tng bn
nhit, thu nhit v axit ca vt liu. Mt trong nhng ca cc tc gi l ch to
cc cht xc tc cracking cho cc hydrocacbon phn t ln.
Mc d c rt nhiu tng v th nghim ch to cht xc tc cracking vi cc
zeolit ph tr khc nhau v cc vt liu RPT mi. Song cho ti nay, vn cha c mt h xc
tc no c thng mi ho v ni tri hn h xc tc ZSM-5/Y/pha nn ang c s
dng quy m cng nghip cho cc qu trnh cracking to ra gasolin c ch s octan cao v
nhiu olefin nh.
Tm li, do yu cu nng cao cht lng ca gasolin v mt s sn phm cracking
khc, ngi ta thng b sung mt s cht ph tr xc tc vo cht xc tc FCC.
Hin nay, zeolit ZSM-5 l mt cht ph tr xc tc c hiu qu nht cho zeolit Y trong
cht xc tc FCC thng mi. Cc cht ph tr khc nh mordenit, VPI-5, zeolit v mt
s h vt liu mao qun trung bnh khc ang l mc tiu nghin cu ch to ra cc cht
xc tc FCC mi nhm tn dng ti a ngun du m v nng cao cht lng sn phm
cracking.
3.3. Ch to cht xc tc FCC
C rt nhiu phng php ch to cht xc tc FCC c cng b trong rt nhiu
bng sng ch pht minh. Trong mc ny, chng ta ch xem xt mt s phng php thng
hay c cc nh sn xut xc tc s dng nht.
3.3.1. Phn loi cc phng php sn xut cht xc tc FCC
Cht xc tc FCC c th c sn xut theo hai phng php chnh:
i. Cc zeolit c tng hp trc, sau mi phi trn vo cht nn.
ii. Zeolit c hnh thnh (kt tinh) trong pha nn khong st t nhin.
Phng php th nht hu nh c tt c cc nh sn xut cht xc tc FCC s dng.
Vi phng php ny c hai iu khc bit:
- Zeolit c trao i ion vi cc cation cn thit, sau mi phi trn vo cht nn (I).
- Zeolit c trao i ion sau khi phi trn vi pha nn (II).
Sn xut cht xc tc FCC theo cch (I) thng gm cc bc: (a) tng hp, trao i
ion v bin tnh cu trc zeolit, (b) phi trn zeolit vi pha nn v (c) sy phun hn hp xc
104

tc (zeolit + pha nn); theo cch (II), zeolit sau khi tng hp c trn vo pha nn v sy
phun, tip n tin hnh trao i ion.
3.3.2. Ch to cc zeolit
3.3.2.1. Zeolit Y
Hnh 3.12 gii thiu mt s kt tinh, trao i ion v bin tnh cu trc ca zeolit Y.
Silicat natri

Aluminosilicat

Mm NaY

NaOH

Trn
Gen
aluminosilicat
natri
Kt tinh
NaY v nc t
(A) Lc
(B) Ra vi nc
Zeolit NaY
Trao i NH4

Trao i NH4

Trao i RE
RE, NaY

NH4NaY

NH4NaY

Na-USY

AFSY

Nung ~540oC
RE, NaY nung

(A) Trao i NH4

(A) Trao i RE
(B) Ra vi nc
(B) Ra vi nc
(A) X l vi axit
RE, NH4Y
(B) Trao i RE
(C) Ra vi nc

(A) Trao i NH4

(B) Ra vi nc

RE-AFSY

NH4-USY

RE-USY
RE-USY

Hnh 3.12. S kt tinh, trao i ion v bin tnh cu trc zeolit Y

(RE: cation nguyn t t him).
Zeolit Y thng c iu ch dng NaY t ngun silic (ch yu l silicat natri),
ngun nhm (aluminat natri) v hydroxyt natri. Mt s cht mm khi mo cho qu
trnh kt tinh NaY cng c thm vo hn hp gel tng hp zeolit. S kt tinh thng c
tin hnh trong mt thit b kt tinh ln, ko di t 8 gi cho n vi ngy, tu thuc vo
ngun nguyn liu ban u, iu kin kt tinh, tinh th ca zeolit v thnh phn ho hc
105

ca zeolit sn phm.
Zeolit sau khi kt tinh c tch ra khi pha lng bng cc my lc ly tm v ra
bng nc. NaY c cht lng tt phi c t s SiO2/Al2O3 5, b mt ring khong
800m2/g, tinh th cao (so vi zeolit chun). Tp cht khng ng k (pht hin bng
XRD), kch thc ht c 1 5m.
3.3.2.2. Trao i ion
NH4

NaY sau khi tng hp c trao i ion vi cc cation t him (RE) hoc/v vi
chuyn zeolit NaY v dng hot ng v bn thu nhit.

S trao i ion c thc hin trong mt thng trao i ion hoc trong mt my lc
vt ngang. Trong thng, zeolit c ngm vi dung dch cha ion trao i nhit , pH,
nng , thi gian... quy nh. Sau , zeolit trao i ion c lc v ra bng nc.
Trong my lc, zeolit c cho vo cc ngn lc vi dung dch trao i ion sau c ry
kh v ra nc.
Cc mui t him dng cho trao i ion thng c s dng dng clorua ca hai
loi qung t nhin l bastnasit v monazit. Cc t him t nhin thng gm xeri, lantan,
neodym v paraseodym v mt lng t hn ca samari, gadolini... (bng 3.5)
Bng 3.5. Thnh phn ca qung t him
t him
Xeri
Lantan
Neodym
Paraseodym
Samari
Gadolini
Khc

Nomazit (%)

Bastnactic (%)

46
24
17
6
3
2
2

50
33
12
4
0,5
0,2
0,3

sn xut cht xc tc FCC, nhiu nh sn xut thng tch bt xeri. S trao i ion
c thc hin trong dung dch axit vi pH = 3,5 5,0 trnh s kt ta ca cc ion t
him trong qu trnh trao i v hn ch s oxy ho Ce3+ thnh Ce4+.
Sau khi trao i vi cc ion t him, zeolit Y vn cn cha 3 6% Na2O. loi b
ht cc ion natri cn li, zeolit li c sy nhanh, nung t 425 760oC trong l quay v sau
li trao i vi dung dch sulfat amoni. Khi mun iu ch zeolit Y c mc trao i
ion cao vi cc ion t him, ngi ta c th trao i ion 2 ln vi dung dch t him, sau
mi ln trao i, zeolit c sy, nung nhit cao, cc ion t him c th thm nhp
vo cc v tr kh trao i SI, SI. Zeolit dng RE-NH4Y c th c iu ch bng cch
trao i ng thi vi dung dch cha ion NH4+ v t him.

106

Dng cui cng ca zeolit trao i (RE-NH4Y) cha khong 16% oxyt t him, t
hn 1% Na2O (dng kh). Trong thc t, hm lng t him trong xc tc FCC bin i
tu theo yu cu sn xut, v hm lng t him tc ng n hot tnh, chn lc xc
tc, bn cng nh ch s octan ca gasolin. Sau khi nung, dng RE-NH4Y chuyn thnh
dng RE-HY.
3.3.2.3. Bin tnh cu trc ca zeolit Y
Trong sn xut cht xc tc FCC, zeolit Y thng c s dng dng siu bn
(ultrastable) USY. Zeolit USY c iu ch bng cc phng php nh trnh by mc
3.2.2.1.
Zeolit USY
iu ch zeolit USY, NaY c trao i amoni gim hm lng natri n 3
hoc 4% Na2O. Zeolit c trao i mt phn vi NH4+ sau c nung nhit cao
(~760oC) vi hi nc n nh cu trc zeolit v gim bt lng natri cn li. Trong sn
xut cng nghip, zeolit c nung trong cc l quay. S trao i ion vi NH4+ c thc
hin tip tc cho n khi hm lng natri trong zeolit t n mc thp hn 1% Na2O v c
kch thc mng tinh th c s khong 24,55 0,02 . T s SiO2/Al2O3 cao, kch thc
tinh th c s thp v hm lng natri nh l cc tiu chun c bn trong vic iu ch xc
tc FCC gia tng gi tr octan.
iu ch zeolit Y c hot tnh xc tc cao hn, ngi ta thng trao i vi t
him, c th l, vi dung dch cc mui clorua t him. Hm lng t him a vo zeolit
tu thuc vo mi quan h gia hot tnh, chn lc gasolin v s bin i ch s octan.
X l zeolit USY bng axit
Zeolit USY c x l axit nhm tch Al ngoi mng v cc ion natri cn li. Vic x
l c th c thc hin bng mt dung dch axit hoc bng mt cht (nha) trao i dng
H+. iu kin x l c la chn (nng axit, nhit , thi gian x l...) t n mt
hm lng thp ca Al ngoi mng. Thng thng, ngi ta x l axit to ra mt zeolit
c t s SiO2/Al2O3: 6,5 12 ng vi hot tnh xc tc tt nht, hm lng natri gim xung
khong 0,1% Na2O. USY sau khi c x l axit c th c trao i vi cc cation t
him tng hot tnh xc tc.
Zeolit AFSY
l zeolit Y c x l (NH4)2SiF6 thng c k hiu l AFSY. Zeolit ny c
ch to bi hng Union Carbide (Union Carbide Company) v c hng Katalistiks Company
s dng lm cht xc tc FCC di nhn hiu thng mi l LZ-210. AFSY c iu
ch bng cch x l zeolit Y vi dung dch (NH4)2SiF6 pH xc nh. V qu trnh tch
nhm khi mng li nhanh hn qu trnh silic lp y l trng trong mng, nn tinh
th ca zeolit gim. S suy gim tinh th ca zeolit c th hn ch mc ti thiu bng
107

cch khng ch cht ch iu kin thc hin phn ng. Bng cch tng pH phn ng (trong
khong 3 7) v gim nng (NH4)2SiF6, tc tch nhm c th gim. Tng nhit
phn ng lm tng tc lp y l trng mng bng silic.
Hp cht (NH4)3AlF6 c to ra v phi loi khi zeolit bng cch ra nc mt cch
cn thn. Bi v hp cht rt c hi cho bn nhit ca zeolit. T s SiO2/Al2O3 c th
t c 6 15, tu thuc vo iu kin x l. Zeolit AFSY, sau , c th trao i vi cc
cation thch hp, thng l cc cation t him.
Gi thnh ch to AFSY cao hn zeolit bnh thng.
Zeolit ph tr (ZSM-5)
ZSM-5 l zeolit ng vai tr cht ph tr cho cht xc tc FCC lm gia tng ch s
octan ca gasolin. ZSM-5 c a vo cht nn ca cht xc tc trc khi c trn u v
sy phun. ZSM-5 thng c s dng dng trao i vi NH4+, i khi cng dng ZnZSM-5, Cd-ZSM-5...
Ngi ta c th s dng ZSM-5 dng mt cht ph tr ring r. Trong trng hp
ny, ZSM-5 c trn vi mt cht kt dnh tr ri sy phun. V d, mt cht ph tr xc
tc ZSM-5 thng mi c iu ch vi 25% ZSM-5 trong cht kt dnh tr, c cc tnh
cht vt l sau y: kch thc ht = 74 m, ch s mi mn Davison = 5, b mt ring =
100 m2/g, th tch mao qun = 0,41 ml/g (Intercat, Technical data sheet for z-cat, 1988).
Xc tc cha hn hp zeolit
Ngoi cc zeolit Y c hm lng silic cao (vit tt l HSY), cn c mt s xc tc
FCC gia tng ch s octan c ch to vi mt hn hp gm 2 hoc nhiu zeolit, v d nh
RE, HY + USY; RE, HY + RE-USY; RE, HY + USY x l axit. Ngoi zeolit Y, cht xc tc
cn cha zeolit ZSM-5, mordenit v mt s zeolit mao qun trung bnh v mao qun nh
khc. Bng cch , cc nh sn xut c th d dng iu chnh thnh phn ca xc tc sao
cho ph hp vi yu cu ca cht lng sn phm ra. V d, khi mc ch tng ch s
octan l ch yu th zeolit USY l hp phn chnh ca cht xc tc. Khi cn tng gi tr
octan-barrel, hm lng ca zeolit RE, HY hoc HSY trao i RE l ch yu. Tuy nhin v
cc zeolit c mc suy gim hot tnh khc nhau do ngi ta cn phi lu n s bin
i hot tnh v chn lc xc tc ca ca cc cht xc tc ny trong khi s dng.
3.3.3. Cht nn v quy trnh ch to cht xc tc FCC
Hu ht cc cht nn sn xut cht xc tc FCC u l cc oxyt v c tng hp
(ch yu l oxyt nhm) v cc hp phn t nhin - khong st. Zeolit c phn tn tt
trong cc hp phn ca pha nn ri c sy phun. Mt s sn xut cht xc tc FCC
c gii thiu hnh 3.13.

108

Alumina
t natri

(NH4)2SO4

NaOH
Mm

Silicat
natri

Ra

H2O

My lc

Sy phun
NaY

NH4,NaY

H2O

L nung

Trao i ion

Tc nhn trao i, H2O

Khong st

My lc

Na-USY

Al2O3

xc tc
FCC bn
thnh phm

SiO2

My sy nhanh

NH4,NaY

Cht ph tr,
nu cn

H2O
Xc tc FCC

Hnh 3.13. S sn xut cht xc tc FCC:

zeolit USY c trao i ion sau khi phi trn vi cht nn.
C rt nhiu s liu v thnh phn ca cht nn ca xc tc FCC. Sau y l mt vi
v d minh ho.
3.3.3.1. Cht xc tc vi cht nn hot tnh thp
Cht nn t sol SiO2
Axit

Silicat natri

Sol nc ca SiO2,
pH 3,0
Khong st
Trn

NaY
hoc Na-HSY

Hn hp t
SiO2/khong st
Trn

Hn hp zeolit/
khong st/SiO2
(>40% vt liu rn)
Sy phun

Xc tc
bn thnh phm
Trao i ion
Ra nc

Xc tc t

Sy nhanh

Xc tc FCC

Hnh 3.14. S sn xut cht xc tc FCC vi cht nn

l sol-nc ca oxyt silic (silicasol).
Mt sol-nc (hydrosol) ca oxyt silic c iu ch bng cch axit ho dung dch
silicat natri n pH ~ 3,0. Zeolit v khong st dng ht mn (NaY, HSY) c cho vo
hydrosol v khuy trn. Sau khi sy phun, sn phm c c trao i ion vi NH4+ hoc
109

ion t him tch b ion natri, chuyn zeolit v dng hot ng xc tc. sau , tin hnh
ra, lc v sy kh vt liu nhn c. Quy trnh iu ch c m t nh trn hnh 3.14.
Thnh phn cha zeolit - t him v cht nn gm SiO2 v nh hnh v khong st.
Cht xc tc ny c gi thnh khng cao, c mi mn tt, nhng cht nn c mao qun
nh v b mt ring thp, v do khng tc ng ng k n hot tnh xc tc cracking.
Cht nn khong st
Ngi ta c th iu ch cht xc tc FCC vi cht nn khong st theo s sau (hnh
3.15): (i) st kaolinit mn dng hydrat c nung khong 1000oC, khi st chuyn thnh
dng spinel, (ii) st nung c ho vi mui v mt t st kaolinit hydrat, silicat natri v
mm zeolit. (iii) Hn hp t c sy v cc ht vi cu c nung 732oC chuyn
kaolinit hydrat thnh metakaolinit. Hai dng st nung (spinel v metakaolinit) lin kt vi
nhau trong ht vi cu bi cht kt dnh silicat natri. (iv) Cc ht vi cu sau khi nung c
zeolit ho vi dung dch silicat natri v xt 90 95oC khong 20 h, trong qu trnh c
s hnh thnh zeolit bn trong cc ht vt liu vi cu. (v) Cc ht vi cu c zeolit ho mt
phn li c trao i ion vi cc cation cn thit.
Kao lanh
L nung, T~1000o

Silicat natri

Kao lanh
Mm zeolit
My trn

Sy phun
Vi ht
H2O

L nung, ~732Co

Silicat natri
NaOH

Vi ht nung
Kt tinh,
~95Co, 10-24h

H2O ra

Vi ht zeolit ho
Lc

RE3+ v/
hoc NH4+

Vi ht ra
Trao i ion
Vi ht trao i
RE/NH4
Sy kh nhanh
Ph gia
Xc tc FCC

Hnh 3.15. S sn xut cht xc tc FCC theo quy trnh kt tinh zeolit ti ch (in situ).

110

Zeolit kt tinh trong ht vi cu c th c bin tnh cu trc bng cc x l nhit hi nc. Mun th, ngi ta tin hnh trao i ion cc ht vi cu vi NH4+, sau nung
di hi m. S n nh cu trc cng c th thc hin bng cch nung cc ht vi cu trong
hn hp hi nc v amoniac. Mt s ion Al c th b tch ra ngoi mng zeolit v c
ra sch khi b mt zeolit bng cch x l axit. Cht nn bng t st nung khng c nh
hng ng k n gi tr octan ca xng.
Mt s khong st c x l ho hc, x l nhit (hoc khng x l nhit) cng c
s dng lm cht nn iu ch cht xc tc. V d, kaolin nung nhit cao, x l bng
kim (xt) c dng lm cht nn cho xc tc cha zeolit.
3.3.3.2. Cht xc tc vi cht nn hot tnh
Cht nn t sol oxyt nhm
Ch to mt cht xc tc vi cht nn t sol oxyt nhm v mt t oxyt silic v nh
hnh c thc hin nh s hnh 3.16. Cu t hot ng ca cht nn l oxyt nhm v
nh hnh, mc du c mt t aluminosilicat v nh hnh c to thnh.
St t

Nhm

RE, HY; HSY

Nhm/St
Trn

Silica sol

Zeolit/Nhm/St
Trn
Zeolit/St/SiO2-Al2O3
Sy kh
Xc tc FCC

Hnh 3.16. S sn xut cht xc tc FCC vi cht nn l sol aluminosilicat.

Zeolit c trao i ion v bin tnh trc khi phi trn vi cht nn. Oxyt nhm dng
pxdobomit c peptit ho vi axit, sau trn vi khong st v zeolit Y chun b sn.
Mt lng nh sol oxyt silic hoc axit polysilic c thm vo ci thin tnh cht kt
dnh ca cht nn. Sn phm c sy phun, c hot tnh xc tc tt, cht nn c b mt
ring cao. Cht xc tc ny kh hiu qu cho cracking du cn cho ch s octan cao.

111

Cht xc tc FCC vi cht nn ch yu l oxyt nhm cng c th c iu ch t

clohydrol nhm (clohydroxyt nhm dng polyme). Mc du l mt cht kt dnh tt, cht
nn c b mt ring thp v hot tnh xc tc khng cao so vi cht nn t pxdobomit.
Pxsdobomit cng c s dng kt hp vi aluminosilicat v nh hnh ch to
cht nn cho xc tc cha zeolit.
Cht nn t aluminosilicat v nh hnh
Cht nn c th c iu ch t aluminosilicat v nh hnh. Loi cht nn ny thay
i ng k hot tnh xc tc v gi tr octan ca gasolin. Cht khi u cho aluminosilicat
v nh hnh l aluminosilicagel hoc hydrosol ca oxyt nhm v oxyt silic. Aluminosilicat
dng gel t c th c iu ch nh trong mc 3.2.2. Cht xc tc FCC c ch to vi
cht nn aluminosilicat c m t nh cc s hnh 3.12 - 3.16.
Ngun oxyt silic c th l sol oxyt silic hoc dung dch silicat natri c trung ho vi
axit, ngun oxyt nhm l cc hp cht nhm nh sulfat nhm, aluminat natri hoc oxyt
nhm dng hydrat ho. Nc "t" nhn c sau khi kt tinh zeolit Y c th c dng lm
ngun silic. Bng cch thay i nng ca cc tc nhn phn ng, pH ca hn hp t ch
to xc tc, thi gian v nhit to gel, thi gian v nhit lm gi gel, ngi ta c th
iu chnh c cu trc mao qun ca cc pha nn. Zeolit c thm vo hn hp t to
cht xc tc sau khi gel c hnh thnh. Vt liu sy phun c trao i ion v ra
bng nc loi b cc ion natri v cc mui cn li. Sn phm c ra, sy nhit
200 260oC trong thit b sy quay (sy nhanh).
Cht xc tc vi cht nn t hydrosol aluminosilicat c th c iu ch theo s
hnh 3.14, nhng axit thm vo dung dch silicat c thay bng dung dch ca mt mui
nhm.
Mt s cht nn khc
Cho n nay, cc cht nn c trnh by trn u cha oxyt silic v/hoc oxyt
nhm cng vi khong st. Mt s cht nn khc cha cc oxyt, thng gm 2 hoc 3 oxyt
hn hp. Tuy nhin, chng cha c gi tr thng mi, ch tr cht nn t magnesiosilicat.
3.4.4. So snh cc quy trnh sn xut xc tc khc nhau
Mi mt quy trnh sn xut cht xc tc trn c nhng u im v nhc im nht
nh.
Phng php kt tinh zeolit ring r khng c mt ca cht nn c nhng u im sau
y:
- D dng iu chnh thnh phn cht xc tc: v ngi ta c th phi trn zeolit vi
cc cht nn khc nhau, cng nh c th phi trn cc zeolit khc nhau vo trong mt cht
xc tc.

112

- Khng ch tt hn qu trnh kt tinh zeolit.

- S bin tnh zeolit (x l nhit hoc x l ho hc) khng nh hng n cht nn.
Tuy nhin phng php ny hn ch lng zeolit trong ht xc tc FCC v khi hm
lng zeolit t n 40 50% th ht xc tc c bn mi mn km.
u im ca phng php kt tinh zeolit ti ch (in situ) l mi mn ca ht xc
tc rt cao, thm ch vi hm lng zeolit cao. Ngoi ra phng php ny khng cn cng
on phi trn zeolit vo cht nn. Tuy nhin, nhc im ca phng php l khng th
iu chnh thnh phn v tnh cht ca pha nn, khng th kt hp c nhiu zeolit trong
pha nn, vic bin tnh zeolit s b hn ch v nh hng n pha nn. Phng php ny cng
i hi nhiu nng lng hn v phi nung ht xc tc nhit cao.
Gn y, ngi ta khc phc nhc im trn bng cch pha trn cc ht xc tc c
thnh phn v tnh cht khc nhau: cc ht xc tc c iu ch bng phng php kt tinh
zeolit ti ch (c hm lng zeolit cao) vi mt s ht xc tc cha cc cht nn, cc cht
ph tr khc nhau nh Al2O3, ZSM-5,... S pha trn c hc cc ht xc tc to ra mt s
linh hot cn thit cho vic sn xut xc tc.
Nh vy, sn xut mt cht xc tc FCC, ngi ta cn c cc hp phn: zeolit Y
(thng l dng HSY), cht nn, cht kt dnh v mt s cht ph tr hot tnh. Cc hp
phn c th c iu ch, bin tnh ring r theo mc ch d nh, sau phi trn vi
nhau to ra ht xc tc c bn c hc, bn nhit v thu nhit, c hot tnh xc tc
cn thit (phng php t hp). Hoc zeolit Y c kt tinh t pha nn v cc hp cht c
trong pha nn ca ht xc tc (phng php kt tinh ti ch)
Hu ht cc xc tc thng mi c sn xut theo phng php t hp v d to ra
cc cht xc tc mong mun. Phng php kt tinh ti ch to ra cc ht xc tc rt bn
c hc, chu mi mn tt, tuy nhin tnh cht ho l ca cht xc tc li khng d dng iu
chnh.
3.4. Cc tnh cht vt l quan trng ca cht xc tc FCC
Nhng tnh cht vt l quan trng ca cht xc tc FCC l bn nhit v thu nhit,
b mt ring, khi lng ring, tinh th (theo XRD).
Cc tnh cht nh b mt ring, phn b kch thc mao qun, tinh th, bn
nhit v thu nhit nh hng n tnh cht xc tc ca vt liu. Mt s tnh cht khc nh
bn mi mn, phn b kch thc ht v khi lng tc ng trc tip n tnh cht c
hc ca cht xc tc FCC.
3.4.1. bn mi mn
l mt tnh cht rt quan trng v: (a) bn mi mn quyt nh t l b sung xc
tc mi v xc tc ang hot ng, do , nh hng n tnh kinh t ca cng ngh; (b)
113

mc nh hng n mi trng: v xc tc c mi mn km c th b ph v v thi

mt lng bi ng k vo mi trng, (c) nh hng n tnh cht linh ng ca cht xc
tc trong thit b v s phn b kch thc khng hp l.
Hm lng zeolit, cng nh kiu v hm lng ca cht nn tc ng trc tip n
bn mi mn ca cht xc tc FCC. Ni chung, tng hm lng zeolit dn n gim bn
mi mn. iu th hin rt r khi hm lng zeolit t n gi tr ti hn ~35% (zeolit),
khi cht xc tc FCC c sn xut theo phng php t hp (xem mc 3.3). sn xut
cht xc tc FCC gia tng gi tr octan, ngi ta thng cn hm lng cao ca zeolit HSY,
song bn mi mn li hn ch hm lng zeolit trong ht xc tc. Bng phng php kt
tinh ti ch ngi ta c th sn xut cht xc tc FCC vi hm lng zeolit t n 70%.
Kch thc tinh th zeolit nh v phn tn cao ca zeolit trong pha nn to ra
bn mi mn tt cho ht xc tc. Hnh th hc ca cc tinh th zeolit cng c th nh hng
n bn mi mn. V d, ngi ta c th thay th cc tinh th zeolit Y dng tm mt
thng thng bng cc tinh th zeolit Y dng a dt (kt tinh khi c mt ion K+) gia tng
mi mn ca ht xc tc (G. Edwards et al. US. Pat. No 4,175,059, 1979).
Chng loi v lng cht kt dnh cng nh phng php phi trn cht kt dnh vo
cht xc tc cng c nh hng ng k n bn mi mn. Ni chung, tng lng cht
kt dnh trong ht xc tc lm tng bn mi mn. Tuy nhin, iu cn ph thuc vo
gi thnh hoc vo cc tnh cht vt l v xc tc khc ca sn phm. Oxytsilic, oxyt nhm
v nh hnh v aluminosilicagel thng l cc cht kt dnh thng dng ca cht xc tc
FCC. Cn lu rng, cht khi u (precursor) v phng php phi trn cht kt dnh cng
rt c nh hng n mi mn. V d, oxyt nhm l cht kt dnh hiu qu hn khi cht
khi u l pxdobomit c peptit ho so vi pxdobomit khng c kh nng peptit ho.
Cc loi oxyt nhm khc (v d, bayerit, hoc gibbsit) u khng hiu qu bng
pxdobomit.
Chng loi v hnh th hc ca khong st dng to dng ht xc tc cng nh
hng n bn mi mn. Kaolin dng hnh a dt tng sc bn cho ht xc tc, c bit
khi khong st dng ht mn. X l nhit v thu nhit trong qu trnh iu ch cht xc
tc cng ci thin mi mn.
bn mi mn lin h mt thit vi cc tnh cht vt l ca cht xc tc. V d, cht
xc tc c khi lng ring thp v th tch mao qun cao thng khng cng v c
bn mi mn thp.
Cc iu kin sy phun cng nh hng n bn mi mn ca sn phm. V d,
nhit u ra ca thit b sy phun cao v nng hn hp c c tc dng tt tng bn
mi mn. Trong mt vi trng hp, nng ca hn hp c tng cng bng cch s
dng cc cht ph gia gim nht, nn lm tng lng pha rn trong vt liu sy phun v

114

do to ra mt cht xc tc c bn mi mn cc k tt.
bn mi mn ca ht xc tc c c trng nh lng bi ch s mi mn, c
xc nh bng mt trong cc phng php do cc nh sn xut ngh. Mt trong cc
phng php tiu chun l ASTM D4058.
3.4.2. Th tch mao qun v s phn b kch thc mao qun
Th tch mao qun v s phn b kch thc mao qun ph thuc vo thnh phn,
phng php iu ch v s x l nhit v thu nhit cht xc tc. Dubinin (M. M. Dubinin,
Chem. Rev., 60, 235, 1960) ngh phn loi cc vt liu mao qun theo kch thc
trung bnh ca mao qun: vt liu mao qun nh ( < 20), vt liu mao qun trung bnh
(= 20 200) v vt liu mao qun ln ( > 200). Da vo tiu chun phn loi , zeolit Y
ch cha cc mao qun nh ( = 8), trong khi zeolit USY c c 2 loi mao qun v ng
vai tr quyt nh to ra th tch mao qun v s phn b kch thc mao qun ca cht xc
tc. V d, cc cht xc tc c iu ch bng phng php bin tnh ti ch t khong
st x l nhit c th tch mao qun thp (nh hn 0,2 ml/g trong vng kch thc mao qun
t 35 20.000). Cc xc tc c sn xut bng phng php t hp c th tch mao qun
rng hn. Cc xc tc iu ch theo phng php ny c khong bin i rng v th tch
mao qun v phn b kch thc mao qun.
S phn b kch thc mao qun trong pha nn cht xc tc ng vai tr quan trng
trong s nh hnh tnh cht xc tc. nu cht nn cha nhiu mao qun tng i hp
(<100) th c th xy ra s bt tc mao qun do s hnh thnh cc v do , gy cn tr
khuch tn, ng thi bn thu nhit ca vt liu khng cao. Nu cht nn cha nhiu
mao qun tng i rng ( > 200) th thng c b mt ring thp, v do , lm gim vai
tr xc tc ca cht nn, ng thi cng lm gim bn mi mn ca ht xc tc. Theo
Beck v cng s (H. W. Beck et al., US Pat. No 4,480,047, 1984) s phn b kch thc mao
qun ti u l s phn b cn bng gia cc mao qun hp v mao qun rng cn tu thuc
vo ngun nguyn liu v cc iu kin cracking cc nguyn liu nng (du cn).
S phn b kch thc mao qun ca cht nn b bin i khi thm cc cht khc vo
cht nn. V d, thm 35% 40% kaolin vo aluminosilicagel th ngi ta nhn c mt
vt liu c cu trc mao qun rng. Aluminosilicagel c thnh phn ho hc khc nhau cng
c kch thc v th tch mao qun khc nhau. Chng hn, tng hm lng Al2O3 trong gel
t 13 25% c th lm tng th tch v ng knh mao qun trung bnh ca vt liu.
Cc iu kin iu ch cht nn cng nh hng n cu trc mao qun. Nng ca
hn hp t, pH, nhit phn ng, nhit v thi gian lm gi, s hin din ca cc
cation khc nhau u nh hng n th tch mao qun ca cht nn. V d, thay th cc ion
Na+ bng NH4+ khi gel ho sol aluminosilicat s dn n mt loi gel c b mt ring ln v
mao qun nh. Khi iu ch gel aluminosilicat t sulfat nhm v silicat natri, kt hp vic

115

thm mui nhm vi s lm gi gel lm tng th tch mao qun v kch thc mao qun
trung bnh ca gel. S hnh thnh cc mao qun rng trong gel aluminosilicat xy ra thun
li pH cao v nng cao vi s c mt ca cc tc nhn iu chnh cu trc mao qun
trong dung dch iu ch gel. S lm gi gel t trc khi thc hin cc x l tip theo cng
rt c li cho s pht trin mao qun rng. Nung gel trong hi nc lm gim b mt ring
v th tch mao qun, lm tng bn knh mao qun v m rng vng phn b bn knh mao
qun. V th, cc cht xc tc tham gia phn ng t n trng thi cn bng (v cu trc,
hot tnh xc tc...) thng c gi tt l cht xc tc cn bng, thng c bn knh mao
qun ln hn v s phn b kch thc mao qun rng hn so vi cht xc tc cn mi
nguyn (cha tham gia phn ng).
Cc polyme hu c v mui than c thm vo cc ht xc tc vi cu, sau khi t
chy, ngi ta nhn c cc vt liu c mao qun tng i rng. V d, thm mui than
vo hn hp t cha zeolit REY, pxdobomit peptit ho, khong st v polysilicat amoni.
Sau sy phun hn hp t, t chy cht ph gia ngi ta nhn c mt cht xc tc c
th tch mao qun tng ng k v c nhiu mao qun nm trong khong 100 200 .
Th tch mao qun t 20 600 c xc nh bng phng php ng nhit hp ph
nit (ASTM D-4222 v D-4641), trong khi th tch cc mao qun c kch thc t 600
20.000 c xc nh bng phng php porosimet thu ngn (ASTM D-4284). Th tch
mao qun cng c th o bng phng php hp ph nc.
3.4.3. bn nhit v bn thu nhit
Vic duy tr n nh hot tnh v chn lc xc tc trong qu trnh hon nguyn
khc nghit i hi bn nhit v bn thu nhit (N&TN) cao ca cht xc tc FCC, ngha
l, ca zeolit v ca cht nn. bn N&TN ca zeolit Y chu tc ng ca t s
SiO2/Al2O3, tinh th, dng ion trao i, hm lng ion natri cn li, v kch thc tinh
th. bn N&TN ca zeolit tng vi t s SiO2/Al2O3 tng, tinh th cao v kch thc
ht tinh th ln. Ni chung, cc cation a ho tr to ra bn N&TN ln hn so vi ion ho
tr mt. Zeolit Y trao i vi cation t him l zeolit bn nht trong cc zeolit Y. Ion natri
nh hng xu n bn N&TN ca zeolit, hm lng ca ion natri trong zeolit cn gim
n mc thp nht c th. Nh t s SiO2/Al2O3 cao m zeolit HSY c bn N&TN cao
hn cc zeolit Y thng thng.
Cht nn bn vng m bo mt xp n nh cho cht xc tc trong qu trnh
hon nguyn, ngha l, bo m mt s khuch tn tt cho cc phn t nguyn liu v cc
kh hon nguyn n tn cc tinh th zeolit. Cht nn tng hp cha nhiu mao qun nh
km n nh hn so vi cht nn cha t mao qun nh. Cc cht nn hot tnh c bn tt
duy tr mt cch n nh b mt ring sau cc x l nhit v thu nhit, do , m bo s
n nh ca hot tnh xc tc.

116

 bn N&TN ca mt cht xc tc c xc nh trong phng th nghim bng cch

x l nhit v thu nhit cht xc tc trong nhng iu kin khc nghit khc nhau. Sau khi
x l, cc tnh cht vt l ( tinh th, b mt ring, phn b mao qun v tnh cht xc tc)
ca cht xc tc c xc nh.
S suy gim hot tnh ca mt cht xc tc, di tc ng ca nhit , hi nc c
xc nh theo phng php ASTM D-4463. B mt ring ca cht xc tc c to ra t b
mt ring ca zeolit v ca cht nn. Trong khi b mt ring ca zeolit Y ban u rt cao
(thng n 800 m2/g, i vi zeolit Y thng thng, trn 600 m2/g i vi zeolit USY), b
mt ring ca cht nn c th thay i t mt vi chc m2/g i vi khong st n mt vi
trm m2/g i vi cht nn tng hp.
Cc cht xc tc gia tng gi tr octan c b mt ring cao ch yu nh hm lng cao
ca zeolit Y bin tnh. X l nhit - hi nc mt cht xc tc lm gim b mt ring ca
n. l do gim mt phn tinh th ca zeolit v do lm thay i cu trc mao qun v
th tch mao qun ca cht nn tng hp hoc bn tng hp. Trong x l nhit - hi nc,
cc mao qun nh b ph v v cc mao qun ln pht trin dn n s suy gim b mt
ring. Do nhng bin i nh th, cc cht xc tc cn bng c b mt ring thp hn cht
xc tc mi. S x l nhit v nhit - hi nc khng nh hng ng k n tnh cht b
mt ca khong st trong cht nn.
Cc cht xc tc c cht nn hot ng (c hot tnh xc tc) thng c b mt ring
ln, trong b mt ring ca cht nn cng tng i ln. Tng b mt ring ca cht nn
do tng hm lng oxyt nhm dn n s gia tng cht lng sn phm y v hiu sut
LCO. Ci thin cc phn ng cracking trong pha nn cng lm cho gi tr octan tng. Tng
hot tnh ca cht nn khi tng b mt ring l do gia tng s tm axit trn mt n v khi
lng cht xc tc. Tuy nhin, b mt ring cao (tng ng vi mao qun hp) ca cht nn
lm tng kh nng hp ph hydrocacbon v c th dn n cc qu trnh cracking su,
cracking th cp. Do , la chn cht nn c b mt ring va phi l tt hn c.
B mt ring ca cht xc tc thng c xc nh bng phng php BET da trn
c s hp ph ng nhit nit theo phng php ASTM D-3663.
3.4.4. Phn b kch thc ht
Sau khi sy phun, ngi ta nhn c cc ht xc tc c kch thc nm trong phn b
Gauss vi cc i khong 60 80 m. Cc ht c ng knh nh hn 40 m v c bit,
nh hn 20 m (ht mn) hu nh rt t, bi v chng s khng lu li trong thit b FCC.
Cc ht rt ln (trn 140 m) khng tt cho s lun chuyn trong trng thi lu th.
Cc iu kin sy phun quyt nh phn ln s phn b kch thc ht xc tc. V d,
tng hm lng pha rn v nht ca nguyn liu sy phun lm tng kch thc ht, khi
tng p sut hoc tng tc ca a phn tn lm gim kch thc ht. Bng cch thay i
117

iu kin sy phun, vi cht xc tc c thnh phn ho hc nh nhau nhng ngi ta c th

nhn c s phn b kch thc ht khc nhau, p ng yu cu c th ca tng nh my
lc du.
S phn b kch thc ht ca cht xc tc mi (cha tham gia cracking) v cht xc
tc cn bng ( tham gia cracking nhiu ln) l khc nhau. Ngoi phn "bi" (ht mn) c
mt sn trong xc tc ban u, mt s "bi" c to thnh trong qu trnh cracking do tc
ng mi mn ca cc ht xc tc ln. Do , kch thc trung bnh ca cc ht gim dn.
Hu ht cc ht mn u b loi b v thu hi trong cc xyclon ca thit b hon nguyn. S
hnh thnh qu nhiu cc ht mn c th gy ra s pht thi bi vo kh quyn v gy tc hi
xu cho mi trng. Bi ny nh hng n tnh linh ng ca cht xc tc trong cc thit
b cracking. Tng bn mi mn ca cht xc tc FCC c th lm gim s hnh thnh bi
ht v do gim thiu s nhim mi trng.
Trong cng nghip, s phn b kch thc ht c xc nh vi cc b ry phn loi
cc kch thc ht t 20 150 m (ASTM D-4513). Gn y, s phn b kch thc ht
c o da trn mi quan h gia cng nh sng laze (laser) vi kch thc ht (ASTM
D-4464) hoc bng k thut in t (ASTM D-4438).
3.4.5. Khi lng ring
Khi lng ring ca cht xc tc ph thuc vo thnh phn v phng php iu ch.
Cht xc tc c iu ch theo phng php kt tinh "ti ch" t khong st nung c khi
lng ring cao hn so vi cht xc tc c iu ch vi cht nn bn tng hp. Cht xc
tc vi cht lin kt xut pht t sol oxyt silic hoc t clohydrol nhm c khi lng ring
cao hn so vi cht xc tc cha cht kt dnh aluminosilicat v nh hnh.
iu kin sy phun c nh hng mnh n khi lng ring cht xc tc vi cht nn
bn tng hp. V d, tng nng pha rn trong nguyn liu sy phun hoc tng nhit
u ra lm tng khi lng ring ca sn phm sy phun.
Khi lng ring cao thng biu hin mt bn tt ca cht xc tc, cng nh
xp v th tch mao qun khng cao. Do , khi lng ring cng l mt c trng vt l
quan trng ca cht xc tc FCC.
Khi lng ring ca cht xc tc l khi lng ca mt n v th tch cht xc tc
c th c biu din nh l mt khi trung bnh ABD (average bulk density) hoc mt
ln cht CD (compacted density), chng c xc nh theo cc phng php ASTM
D-4164 v D-4512
3.4.6. tinh th XRD
tinh th XRD l thut ng din t tinh th ca vt liu c xc nh theo
phng php nhiu x tia X (XRD).

118

 tinh th XRD biu hin hm lng ca zeolit trong cht xc tc FCC. Ngi ta o
din tch ca mt hoc mt vi pic trong ph nhiu x tia X ca cht xc tc v tnh ton
phn trm din tch so vi din tch ca cc pic tng ng ca zeolit chun (thng l
NaY kt tinh tt) (hnh 3.17).

Hnh 3.17. Ph XRD ca (a) NaY chun v (b) cht xc tc cracking.

Cc mi tn ch ra cc pic c la chn xc nh tinh th.
tinh th XRD tng khi hm lng zeolit trong cht xc tc FCC tng v khi tng
mc hon thin qu trnh kt tinh zeolit. So snh vi tinh th XRD ca mu xc tc
cn bng v mu xc tc mi c th bit c s ph v cu trc v bn ca cht xc tc.
Xc nh tinh th XRD thng c thc hin bng phng php ASTM D-3906. Cc
nh my lc du thng s dng phng php ny theo di cht lng v tnh nng ca
cc cht xc tc FCC mi hoc lm vic lu (cn bng).
Tm li, cht xc tc FCC cn c nhng tnh cht vt l cn thit m bo bn
c hc v thc cht, m bo bn ho hc v xc tc ca cht xc tc. Cc tnh cht
vt l quan trng ca cht xc tc l: bn mi mn, bn nhit v thu nhit, kch
thc mao qun, phn b kch thc mao qun, kch thc ht v phn b kch thc ht
xc tc, b mt ring, khi lng ring v tinh th ca zeolit.
Cc tham s vt l ny lun ng vai tr pht trin, bo v v tng tnh hiu qu ca
cc tm xc tc trong qu trnh thc hin phn ng cracking v hon nguyn cht xc tc.

119

3.5. Mi quan h gia thnh phn v tnh cht xc tc

3.5.1. Cc c trng c bn ca cht xc tc FCC
So vi cht xc tc aluminosilicat v nh hnh, ngi ta thy cht xc tc FCC cha
zeolit c nhng tnh cht c trng c bn sau y:
a. hot tnh xc tc cao;
b. bn hot tnh tt, ngha l thi gian lm vic ca cht xc tc kh di;
c. bn nhit v thu nhit cao;
d. hiu sut gasolin cao;
e. hiu sut to cc v kh thp (bng 3.6);
f. bn mi mn tt.
Bng 3.6. So snh hiu sut sn phm mc to cc nh nhau
trn hai xc tc zeolit v aluminosilicat v nh hnh
Sn phm
Cc, %kl
chuyn ho, %tt
H2, %kl
C1+C2, %tt
C3, %tt
C3=, %tt
i-C4, %tt
n-C4, %tt
C4=, %tt
C5+ gasolin, %tt
LCO, %tt
HCO, %tt
RON

Aluminosilicat v nh hnh SiO2 - Al2O3

Zeolit

Sai khc

5,0
77,0
0,07
3,1
1,4
14,2
6,8
0,6
9,9
55,5
5,0
18,0
94,0

5,0
86,0
0,04
2,7
1,6
14,0
8,9
0,8
8,5
65,5
4,3
9,7
91,0

0
+9
0,03
0,4
+0,2
0,2
+2,1
+0,2
1,4
+10,0
0,7
8,3
3,0

Mt s cht xc tc cha zeolit c bn ng c tt vi kim loi, cc hp cht

sulfua v nit. Cht xc tc FCC cn c th cha cc cht ph tr khng c chc nng
cracking m c chc nng x l cc nhim, v d, tr xc tc cho qu trnh chy CO thnh
CO2, SO2 thnh SO3 v to ra cc mui sulfat, nhm gim thiu pht thi CO v SO2. Vic
la chn cht xc tc FCC ph hp cho mt cng ngh cracking c th ph thuc vo cc
yu t: ngun nguyn liu, yu cu sn phm, bin php tin x l nguyn liu, iu kin
vn hnh cho php, tiu chun mi trng quy nh v gi thnh cht xc tc. V cc tham
s tin hnh qu trnh cracking tc ng mnh n cc tnh cht xc tc, nn s so snh cht
lng gia cc cht xc tc phi c tin hnh trong cc iu kin nh nhau.

120

Hiu sut sn phm

(% tt hoc %kl

Gasolin

Kh
HCO
LCO
Cc
40

60
80
100
chuyn ho (%kl)

Hnh 3.18. Mi quan h gia hiu sut sn phm v chuyn ho.

Mi quan h gia hiu sut sn phm v chuyn ho ca cht xc tc FCC c
minh ho nh trn hnh 3.18.
T hnh 3.18 nhn thy rng, khi chuyn ho tng, hiu sut gasolin tri qua mt
cc i, sau gim v xy ra hin tng cracking su. S thay i hiu sut LCO tng t
nh i vi hiu sut gasolin. Hiu sut to cc v kh tng, trong khi hiu sut HCO
gim khi chuyn ho tng.
S bin i cht lng gasolin vi chuyn ho c miu t nh trn hnh 3.19.
Olefin (O)
Aromat (A)
Parafin (P)
Naphten (N)

P/O/N/A (%tt)

chuyn ho (%tt)

chuyn ho (%kl)

Hnh 3.19. nh hng ca chuyn ho n cht lng ca gasolin (a) thnh phn PONA
(parafin, olefin, naphten v aromat) trong gasolin, (b) RON ca gasolin, (c) MON ca gasolin.

121

Khi chuyn ho tng, cc thnh phn PONA trong gasolin thay i khc nhau:
trc khong 60% chuyn ho, hm lng olefin, aromat tng trong khi naphten gim.
Khi chuyn ho ln hn 60%, hm lng olefin gim, aromat vn tip tc tng, naphten
vn tip tc gim. Parafin tng vi chuyn ho do to ra cc isome phn nhnh. S bin
i thnh phn PONA trong gasolin vi chuyn ho c phn nh trong s gia tng gi
tr RON v MON ca gasolin.
Cc cht xc tc tng gi tr octan, ni chung, c hot tnh thp hn v hiu sut
gasolin thp hn so vi cc cht xc tc cha zeolit REY. Hot tnh v chn lc ca cht
xc tc FCC tng gi tr octan ph thuc rt nhiu vo hm lng v kiu zeolit. Mt zeolit
thng c c trng bi cu trc, t s SiO2/Al2O3, dng ion trao i, mc trao i ion,
hm lng ion natri cn li trong zeolit, mc v phng php tch nhm, kch thc
mng c s, tinh th v bn nhit.
Hot tnh xc tc v chn lc sn phm ca cht xc tc cng b nh hng phn
no bi thnh phn v tnh cht ho l ca cht nn ( axit, din tch b mt, th tch mao
qun, phn b mao qun, khi lng ring). Cc cht ph tr gia tng ch s octan c th
cng nh hng n tnh cht xc tc.
3.5.2. nh hng ca zeolit n tnh cht xc tc FCC
Tng hm lng zeolit dn n s gia tng hot tnh xc tc, bt k loi zeolit Y no
(Y thng thng hay USY). nh hng ca zeolit REY n hiu sut sn phm ti
chuyn ho khng i (70%) nh hnh 3.20.

Hiu sut sn phm (n v quy c)

Gasolin, %tt

Tin x l xc tc: 827oC/12h/20% hi nc

Nguyn liu: gas oil Ty Texas
iu kin phn ng: 493oC, xt/d: 4,0 (thay i WHSV)
Gim thi gian lu
RON

LCO, %tt

H2, %kl
C3= - C4=, %tt
Cc,%kl

%tt: phn trm th tch

%kl: phn trm khi lng

% REY

Hnh 3.20. nh hng ca hm lng zeolit n hiu sut sn phm ti chuyn ho

khng i (70%tt) (ch s cnh cc ng cong l hiu sut sn phm tng ng).
122

T hnh 3.20 nhn thy rng, khi hm lng zeolit REY tng, hiu sut gasolin v
LCO tng, trong khi hiu sut hydro, olefin C3= - C4=, v cc gim.
HSY c nng tm axit nh hn so vi REY do , hot tnh xc tc ca HYS nh
hn ca REY. b tr cho hot tnh xc tc thp, ngi ta phi dng zeolit HSY nhiu gp
2 3 ln so vi zeolit REY khi iu ch cht xc tc cracking. Nh chng ta thy mc
3.2, vic tch nhm khi mng zeolit dn n t s Si/Al tng ln, kch thc mng tinh
th gim i, v kh nng trao i ion nh hn so vi zeolit ban u (hnh 3.21).

T s Si/Al

T s SiO2/Al2O3

Do , ngi ta cho rng, c mt mi lin quan cht ch gia cc tham s ho l v

tnh cht xc tc ca zeolit.

Kch thc mng c s (

Hnh 3.21. Mi quan h gia kch thc mng c s ca zeolit v t s Si/Al.

3.5.2.1. nh hng t s Si/Al ca zeolit n hot tnh xc tc v chn lc

Llng tng tng i

ca zeolit (ln)

Khi t s SiO2/Al2O3 tng th kch thc mng c s gim (hnh 3.21). Mt khc,
chng ta bit rng, khi t s SiO2/Al2O3 tng th lng tm axit trong zeolit gim, do ,
hot tnh xc tc cracking gim. Nh vy, duy tr mt chuyn ho khng i, lng
ca zeolit phi tng khi t s Si/Al tng (hay kch thc mng c s gim (hnh 3.22)).

Kch thc mng c s (

Hnh 3.22. Quan h gia s gia tng lng tng i ca zeolit v kch thc mng c s ca
zeolit chuyn ho khng i (65%tt). iu kin phn ng: xc tc/d = 4, WHSV = 30, 510oC.
123

S tng t ngt lng zeolit gi tr kch thc mng c s rt thp l do s tng

t ngt ca t s Si/Al (ngha l do s gim t ngt ca hot tnh xc tc ca zeolit). Mc
d vy, cn lu rng, cht xc tc cha zeolit vi hm lng silic cao, v d nh USY, c
hot tnh thp hn so vi cht xc tc cha zeolit REY cng hm lng zeolit, nhng di
iu kin x l nhit hi nc khc nghit th cht xc tc cha USY vn gi c % hot
tnh cn li cao hn so vi xc tc cha REY, v USY c bn thu nhit tt hn.
chn lc sn phm ca cht xc tc b tc ng mnh bi hiu ng tch nhm.
Bng 3.7. Cc s liu cracking trn 2 cht xc tc cha zeolit REY v USY
trong thit b MAT (micro activity test)
Xc tc cha REY (iu kin x l
s b S-13,5stm(a)

Xc tc cha USY. iu kin x l

s b, S-20 stm(b)

iu kin thc nghim: 40WHSV, 4 xt/du, 510oC, nguyn liu NWR(c)

chuyn ho
Hydro, %kl
C1+C2, %kl
Tng C3, %tt
C3=, %tt
Tng C4, %tt
T s C4=/i-C4
Gasolin C5+
Ch s octan
RON
MON
Mt , oAPI
im anilin, oC
Ch s brom
LCO, %
Mt , oAPI
im anilin, oC
Du cn ti 338oC
Mt , oAPI
im anilin, oC
Cc, %kl

72,5
0,020
1,28
7,9
6,0
13,6
0,83
59,0

72,5
0,020
1,13
9,0
7,6
15,1
0,91
58,0

86,0
78,0
57,4
31,7
31,0
18,1
18,4
16,7
9,4
3,6
39,4
4,6

90,4
80,0
57,3
26,7
50,0
19,5
20,1
23,9
8,0
3,1
34,4
4,0

a: 732oC, 8 h, 100% hi nc, 15 atm;

b: 827oC, 12 h, 20% hi nc trong khng kh;
c: nguyn liu: 23,9oAPI, im anilin 92oC, tha s K UOP 11,9, IBP 201oC, FBP: 552oC.

124

 ti mt chuyn ho nh nhau, tng t s Si/Al (gim kch thc mng c s)

ca zeolit dn n chn lc LPG (liquefied petroleum gas, gm propan v butan thng
mi) cao hn, sn phm olefin trong LPG cao hn, v s to cc nh hn. i vi sn phm
lng, chn lc gasolin gim rt t, trong khi LCO (phn du cha nhiu aromat nh)
tng, DO (decanted oil, phn du cn li sau im si 338oC) gim vi s gim ca kch
thc mng c s ca zeolit. iu chng t rng, vic gim kch thc mng c s
lm thun li cho s chuyn ho ca phn on du nng (phn sn phm y (bottom))
thnh LCO. Nh vy, nh kch thc mng gim, ngi ta c th tin hnh phn ng
cracking trong cc iu kin khc nghit hn, v do , t c chuyn ho cao cho d
zeolit c hot tnh thp.
Tnh cht xc tc ca cht xc tc cha zeolit AFSY cng c cc c im tng t.
Cc s liu thc nghim quy m pilot ca cht xc tc FCC cha zeolit LZ-210 (tn thng
mi ca zeolit AFSY) v ca cht xc tc cha zeolit REY c trnh by bng 3.8.
Bng 3.8. So snh tnh cht xc tc ca cc cht xc tc cracking cha zeolit REY
v cha zeolit LZ-210 trao i ion RE (s liu pilot, US Pat. 4,744,886. 1988)
Cht xc tc REY (a)

Cht xc tc vi LZ 210(a)

Thnh phn cht xc tc

SiO2, %kl
47,65
52,62
Al2O3, %kl
48,31
46,63
RE2O3, %kl
1,52
0,41
Na2O, %kl
0,17
0,12
Hm lng zeolit
16,0
18,0
iu kin th nghim
WHSV
15,1
14,6
T s xc tc/du (xt/d)
4,1
4,3
Nhit cracking oC
482
482
chn lc sn phm (b)
chuyn ho, %kl
70,7
71,3
H2, %kl
0,08
0,07
C1+C2, %kl
1,4
1,4
=
C3 , %kl
4,3
4,5
Tng C3, %kl
5,0
5,0
Tng C4, %kl
8,6
9,2
Gasolin, %kl
52,5
52,8
RON
87,6
89,6
MON
75,9
76,2
LCO, %kl
18,2
19,1
HCO, %kl
11,2
9,5
Cc, %kl
2,8
2,5
a: x l s b: 100% hi nc 813oC, 2 h;
b: nguyn liu: mt 24,6oAPI, IBP = 332oC, FBP= 559oC, tha s K, UOP = 12,0.

125

Vi chuyn ho tng t, cht xc tc cha zeolit LZ-210 c chn lc LPG cao

hn v cc thp hn, chn lc gasolin cao hn mt t. Cht xc tc cha LZ-210 cho hiu
sut ca LCO cao hn v DO thp hn so vi cht xc tc cha zeolit REY. Mc d s bin
i chn lc ca zeolit AFSY v USY so vi REY c khuynh hng ging nhau, nhng
chn lc ca 2 zeolit HSY l khc nhau.
3.5.2.2. nh hng ca zeolit n cht lng gasolin
Cht lng ca gasolin b nh hng bi t s Si/Al ca zeolit. S nh hng c
minh ho trong bng 3.9.
Bng 3.9. Thnh phn v hiu sut ca gasolin (react th nghim vi lp xc tc tng si)
lng cht xc tc c nh nhng lun trng thi lu th n nh G. C. Edwards et
al. ACS Symposium Series, 375,101 1988).
Cht xc tc(a)
10% REY, 90% cht nn tr

20% USY 80% cht nn tr

6,0
20,0
510,0
24,46
52,0

4,0
30,0
510,0
24,26
53,0

Parafin thng
Isoparafin
Olefin
C7 C8

1,4
12,5
13,3

1,1
8,9
19,9

Parafin thng
Isoparafin
Olefin
Aromatic

1,6
10,7
8,7
8,2

1,4
8,0
14,3
6,9

11,4
14,1

10,0
13,3

37,5
21,9
12,6
22,4
88,6
77,4

29,3
34,2
12,1
20,1
92,6
80,0

Cht xc tc/du
WHSV
T, oC
Kch thc mng zeolit,
chuyn ho, %kl
C5 - C6

C9+
Parafin
Aromatic
Tng
Parafin
Olefin
Naphten
Aromat
RON
MON

a: x l s b, 816oC, 4h, 100% hi nc

b: nguyn liu: gas oil Ty Texas (M)

126

So snh vi REY, xc tc cha zeolit USY lm gim hm lng parafin tng olefin v
gim nh aromat trong gasolin.

MON

RON

Gim kch thc mng c s ca zeolit dn n s gia tng RON v MON, ng

thi lm ch s brom cao hn v im anilin thp hn (hnh 3.23)

mng c s ()

Ch s brom

im anilin ca gasolin(F)

mng c s ()

mng c s (

mng c s ()

Hnh 3.23. nh hng ca kch thc mng c s ca tinh th zeolit

n cht lng gasolin chuyn ho khng i (65%tt).
iu kin phn ng: xc tc/du = 4, WHSV = 30, nhit : 510 oC.

Gi tr octan tng mnh nht khi kch thc mng c s nh (nh hn 24, 30 ),
trong min ch tn ti ch yu cc tm axit mnh. Tuy nhin, trong iu kin , th
chn lc ca gasolin li gim mnh. S brom tr nn cao hn l do tng hm lng olefin,
im anilin thp hn chng t aromat tng. Theo Leuenberger et al. (E. L. Leuenberger
et al., NPRA Annual Mtg., March 1989, San Francisco, CA, AM-89-50) th cht xc tc ti
u cho octan - barrel nn cha cc zeolit tinh th nh vi kch thc mng c s khng
qu 24,50 ) i vi zeolit mi (cha tham gia cracking), v khong 24,3 , i vi zeolit
Y trng thi cn bng.
Vic xc nh ch s octan kt hp vi s phn tch parafin, olefin, naphten v aromat
(PONA) chng t rng, s ci thin ch s octan trong phn gasolin nh (C5, 127oC) l do
hm lng olefin tng, trong khi trong phn gasolin nng (127 220oC) l do olefin khi
chuyn ho thp (~50%) v do aromat khi chuyn ho cao (70 75%).
127

Gim kch thc mng c s t 24,44 24,26 dn n tng RON ca gasolin

khong 3 n v v tng MON khong mt n v. Mi quan h gia im si, ch s octan,
s phn b hydrocacbon trong cc phn on khc nhau ca gasolin FCC i vi mt s xc
tc c nu ln trong bng 3.10.
Bng 3.10. Tnh cht ca cc phn on gasolin c to ra do FCC
Tnh cht

Nguyn liu VGO (vacuum gas oil)

Mt , oAPI

21,3
2,3
260,0
61,2
16,3
0
22,5

Lu hunh, %kl
Trng lng phn t trung bnh
Hm lng parafin, Cp, %
Hm lng naphten Cn, %
Hm lng olefin Co, %
Hm lng aromat Ca, %
D1160, oC
5%
50%
90%

319,0
425,5
524,0
Cc phn on gas oil

Phn on
RON
MON
Khong nhit si, oC
Ch s Brom
Cp
Cn
Co
Ca

96,3
82,2
33 48

93,7
79,1
49 89

90,0
79,0
90 130

94,5
82,3
131 186

92,7
80,8
187 221

99,0
40,0
0,1
60,0
0,1

109,0
35,0
7,0
45,0
4,0

94,0
24,0
15,0
48,0
13,0

41,0
14,0
12,0
28,0
46,0

20,0
21,0
24,0
5,0
50,0

D1160: phng php chng ct tiu chun ASTM D1160.

Xin lu rng, khi s dng gi tr kch thc mng c s tinh th zeolit nh gi

cht lng octan ca gasolin cn phi thn trng i vi cc cht xc tc cn bng ( s
dng nhiu ln), bi v mu xc tc cn bng l mt hn hp cc xc tc cha cc loi zeolit
Y khc nhau v hot tnh xc tc, v mc tch nhm (REY, REHY, USY...), kch thc
mng c s o c l mt gi tr kch thc pha trn khng phn nh bn cht thc s
ca tng n v cu trc ca zeolit v do khng phn nh ng tnh cht xc tc ca cht
xc tc. Tuy nhin, cc gi tr kch thc mng pha trn nh th ch c th c s dng
gii thch v tin on nhng kt qu v cht lng sn phm cracking m thi.
128

3.5.2.3. nh hng ca ion natri

S c mt ca ion natri trong zeolit Y tch nhm cn tr s hnh thnh gasolin c ch
s octan cao (hnh 3.24).
95

RON

94

mng c s:
24,22-24,25

93
92
91
90
0,0

1,0

2,0
3,0
4,0
Na2O, %kl trn zeolit

5,0

Hnh 3.24. nh hng ca ion natri n RON ca gasolin.

Ngi ta cho rng, cc ion natri trung ho cc tm axit mnh nht trong zeolit. Tuy
nhin, ch natri cn li trong zeolit do qu trnh iu ch, sn xut cht xc tc mi nh
hng n cht lng octan ca gasolin, cn natri c trong nguyn liu th nh hng rt t
n hiu ng , m ch yu, ch c tc dng lm gim hot tnh xc tc.
3.5.2.4. nh hng ca phng php iu ch zeolit HSY

Hng s tc
(n v quy c)

Phng php iu ch zeolit cng nh hng n tnh cht xc tc ca zeolit trong

phn ng cracking gas oil. Cc zeolit Y c x l theo cc phng php khc nhau (nung
trong lp zeolit dy, x l bng nhit hi nc, x l bng SiCl4 v x l bng (NH4)2SiF6 )
c hot tnh xc tc khc nhau. S nh hng c th c minh ho nh trn hnh 3.25.

Kch thc mng c s, (

Hnh 3.25. S nh hng ca kch thc mng c s ca tinh th zeolit n hot tnh
cracking gas oil ca cc zeolit c tch nhm bng cc phng php khc nhau: (o) nung
trong lp dy, () x l bng nhit hi nc, () x l bng SiCl4, () x l SiCl4 v nhit hi nc.

129

Cc ng cong nhn c u c hot tnh cc i 24,59, 24.35 v 24,35

tng ng vi cc phng php x l zeolit bng nung, x l nhit - hi nc v x l SiCl4.
T hnh 3.25 nhn thy rng, zeolit c x l bng nhit - hi nc c hot tnh xc
tc cao nht v ng vi mc tch nhm va phi. Mt khc, trong hnh 3.25 cho thy
rng, cng mt kch thc mng c s nhng cc zeolit c x l (iu ch) bng cc
phng php khc nhau s c hot tnh xc tc khc nhau.

chn lc

Trn hnh 3.26 trnh by nh hng ca cc phng php iu ch zeolit HSY n

chn lc sn phm cracking gas oil.
a) Gasolin

b) LCO

c) Tng kh

a) C1 - C2

b) Cc

c) Buten/butan

Kch thc mng c s (

Hnh 3.26. nh hng ca kch thc mng c s tinh th zeolit n

chn lc sn phm cracking gas oil trn cc zeolit: (o) nung trong lp dy,
() x l bng nhit hi nc, () x l bng SiCl4, () x l SiCl4 v nhit hi nc.

Zeolit tch nhm bng cc phng php khc nhau c s phn b khc nhau ca nhm
trong mng tinh th. V nng nhm trn b mt khc vi bn trong tinh th. V v cc
phn t ca gas oil khng th xm nhp su nh nhau vo bn trong cc mao qun ca
zeolit, do , hot tnh xc tc b khng ch ch yu bi t s Si/Al b mt ngoi hoc gn
b mt ngoi ca ht zeolit. iu gii thch v sao mc d thnh phn xc tc nh nhau
(v d, Si/Al = const) nhng zeolit c iu ch bng cc quy trnh khc nhau s dn n
hot tnh xc tc v chn lc sn phm cracking khc nhau.
Zeolit HSY mi iu ch bng phng php x l (NH4)2SiF6 (zeolit AFSY) c hot
tnh v chn lc khc vi zeolit USY trong cracking gas oil (A. Corma et al., Prepr. Div. Petr.
Chem., ACS Mtg., New Orleans, LA, Aug. 1987). Zeolit AFSY c rt t Al ngoi mng (tinh
th) v t tm axit Lewis, khc vi zeolit USY. S phn b kch thc mao qun ca 2 zeolit
cng khc nhau (xem mc iu ch zeolit). Nhng s khc nhau c th l nguyn nhn
to ra s khc nhau v chn lc ca 2 zeolit USY v AFSY trong cracking gas oil (hnh 3.27).
130

gasolin

DIEsel

c1 - c2

cc

c4 / c4

Hiu sut, %

Kh

chuyn ho, %

Hnh 3.27. Hiu sut cc sn phm cracking gas oil 482oC.

ng m: USY, ng chm chm: AFSY, (o): x l USY bng axit xitric

USY cho nhiu gasolin hn, kh C1 + C2 t hn v sn phm y t hn, nhng cng

to cc nhiu hn. Al ngoi mng l nguyn nhn to ra cc nhiu hn trn xc tc USY.
X l zeolit USY vi axit xitric c th loi b (tch) cc dng nhm ngoi mng khi
b mt zeolit. Do , tnh cht xc tc ca USY - x l axit xitric tng t nh ca zeolit
AFSY, v AFSY khng c hoc c rt t dng nhm ngoi mng (hnh 3.26). Zeolit Y c
ngm ra vi axit v c cng c s dng trong cng ngh sn xut xc tc.
Nhiu nghin cu xc nhn rng, tch nhm ngoi mng bng ngm ra vi axit lm
gim hot tnh xc tc v hiu sut gasolin, nhng li tng hm lng olefin trong LPG v
tng t s i-C4/n-C4 trong sn phm cracking, thm ch nhn xt cng ng vi zeolit
dng trao i t him.
X l nhit - hi nc ca zeolit USY cng c th tip tc tch nhm khi mng (n
80 hoc 85%), x l nhit hi zeolit AFSY cng c th dn n s hnh thnh nhm ngoi
mng. Tng t nh vi USY, hot tnh xc tc ca zeolit AFSY c x l nhit hi nc
cng tri qua mt cc i khi t s Si/Al tng. S khc nhau v chn lc sn phm
cracking gas oil ca 2 zeolit sau khi x l nhit - hi nc l rt nh, khng ng k so vi
trc khi x l. l v do s c mt ca nhm ngoi mng c trong 2 zeolit. Theo
131

Beyerlein v cng s (R. A. Beyerlein et al, J. Phys. Chem., 92, 1967, 1988), nhm ngoi
mng trong zeolit AFSY x l nhit - hi nc c kh nng gia tng hot tnh xc tc, v cc
tm axit Bronsted v cc tm Lewis lin kt vi nhm ngoi mng. Cc tm axit mnh nh
th thng tn ti trong zeolit USY. C ngi cho rng, zeolit USY v AFSY c x l
nhit - hi nc u c chn lc nh nhau v u to ra gasolin c thnh phn nh nhau
(G. C. Edwards et al., ACS Symposium Series, 375, 101, 1988). Song cng c ngi cho
rng, cht xc tc cha zeolit AFSY x l nhit - hi nc c chn lc gasolin v LCO
cao hn v t to cc hn so vi cht xc tc ch to t USY tiu chun. Cc s liu thc
nghim (MAT) chng t rng, zeolit AFSY x l nhit - hi nc c bn thu nhit cao
hn v c nng cc vt l ngoi mng t hn (oxy nhm, aluminosilicat v nh hnh).
Cc "vt l" trong zeolit USY l nguyn nhn chnh gy ra cc phn ng cracking th cp
(cracking su) v dn n s to cc nhiu hn v hiu sut gasolin thp hn.
3.5.2.5. nh hng ca s trao i ion t him vi zeolit HSY
Nh chng ta bit, zeolit HSY (siu bn v giu silic) l xc tc c kh nng gia
tng ch s octan ca gasolin trong qu trnh cracking gas oil khi zeolit dng H-zeolit
(zeolit dng trao i vi NH4+, sau c nung bin thnh dng H-zeolit, NH4zeolit
H-zeolit + NH3). Tuy nhin, hot tnh xc tc ca H-HSY thng thp hn so vi REHSY. Thc nghim chng t rng, bng cch trao i ion vi t him, zeolit HSY dng
RE-HSY c hot tnh v chn lc cao hn v ch s octan ca gasolin vn khng gim.
Mt s nh sn xut xc tc thng trao i zeolit Y (SiO2/Al2O3 = 5) vi ion t
him vi mc thp hn so vi zeolit REY (zeolit ny cng c iu ch t Y thng
thng nhng vi mc trao i ion vi RE cao to ra cht xc tc tng hiu sut
gasolin). Sau zeolit RENaY c trao i tip vi NH4+ to ra zeolit REHY. Zeolit
ny li c x l nhit - hi nc tch nhm, to ra mt zeolit tng t zeolit REUSY.
Trong cng on FCC, khi t n trng thi lm vic cn bng, cc zeolit USY c
kch thc mng c s khong 24,20 , trong khi cc zeolit REUSY khong 24,26 n
24,32 . Kch thc mng c s tng vi hm lng ion t him, v do dn n tng
hiu sut gasolin v gim ch s octan.
Cc tnh cht xc tc c trng ca cc zeolit Y khc nhau trao i vi ion t him
c tng kt trong bng 3.11.
nh hng ca hm lng t him trong cht xc tc n chuyn ho v n
RON (ch s octan nghin cu, xem mc 1.5 Gasolin) c th hin trn hnh 3.28.
Trong khi ch s octan RON gim mnh vi hm lng t him trong zeolit USY
tng, th MON thot tin tng v sau gim (hnh 3.29).

132

Bng 3.11. chn lc cc sn phm cracking trn cc cht xc tc Y khc nhau

Hiu sut kh kh
Hiu sut C3 - C4
Hiu sut olefin C3= - C4=
Hiu sut cc
Hiu sut gasolin
Gi tr octan
Hot tnh cracking
343 - 482oC
482oC
bn vi hi nc, V, Na

USY

REUSY

REHY

REY

Thp
Cao
Cao
Rt thp
Trung bnh
Cao

Thp
Trung bnh
Trung bnh
Rt thp
Cao
Trung bnh

Thp
Trung bnh
Trung bnh
Thp
Cao
Thp

Thp
Thp
Thp
Trung bnh
Cao
Thp

Cao
Trung bnh
Trung bnh

Cao
Trung bnh
Trung bnh

Cao
Thp
Thp

Cao
Thp
Thp

RON

chuyn ho, (%)

chuyn ho 65%

RE2O3 trong xc tc (%)

Hnh 3.28. nh hng ca hm

lng t him trong xc tc n
chuyn ho v ch s octan.

RE2O3, %kl trn zeolit

Hnh 3.29. S ph thuc ca ch s octan

RON v MON vo hm lng t him
trong zeolit, chuyn ho 65%kl.

Do nhu cu tng barrel-octan hn so vi octan ca gasolin nn nhiu nh my lc du

s dng xc tc FCC vi zeolit giu oxyt silic trao i vi ion t him.
3.5.3. nh hng ca pha nn
Ngoi chc nng vt l trong cht xc tc FCC (mc 3.2.3.1), cht nn cn c chc
nng xc tc. Trong nhng nm 60 v 70 ca th k trc, vai tr xc tc ca cht nn
thng c xem l khng quan trng. By gi, nhiu cht xc tc thng mi c cht nn
vi hot tnh xc tc v b mt ring thp. V sau, cc nh sn xut xc tc mi nhn thy
vai tr quan trng ca cht nn trong vic ci thin tnh cht xc tc. Do , ngi ta ch
133

n vic sn xut cc cht xc tc c cht nn hot ng cha oxyt nhm hoc aluminosilicat v nh hnh cng vi khong st.
Nh ni trc y, trong cc cht xc tc FCC c cng hm lng v kiu zeolit
tng t, th cc cht xc tc vi cht nn t hot tnh (v d, vi cht nn silicagel - khong
st) to ra t cc v kh hn. nh hng ca cc cht nn n ch s octan ca gasolin l
khng ng k. Tuy nhin, do s hnh thnh cc v kh t nn qu trnh cracking c th thc
hin iu kin khc nghit hn, do ci thin ch s octan gasolin v cracking sn phm
nng do chuyn ho tng.

(a)

Hiu sut gasolin (%kl)

Cc cht xc tc FCC c cht nn hot ng thng c ng dng trong cc phn

xng FCC m ngi ta khng th tng chuyn ho v ch s octan ca gasolin bng
cch s dng iu kin vn hnh khc nghit. Trong trng hp , cht nn hot ng lm
tng chuyn ho v ch s octan trong iu kin vn hnh mt cch va phi. Tuy nhin,
cht nn hot ng cng to ra mt vi bt li: lng cc nhiu, kh kh tng, cc olefin
C3 C4 tng, v do , dn n gim chn lc gasolin. nh hng ca cht nn n tc
chn lc gasolin v s to cc c th hin trn hnh 3.30.

Hiu sut cc (%kl)

(b)

chuyn ho (%kl)

Hnh 3.30. nh hng ca pha nn n chc lc gasolin v cc,

k hiu y: cht nn hot ng, k hiu rng: cht nn khng hot ng, (a) hiu
sut gasolin, (b) hiu sut cc (CREY: zeolit REY c nung)

134

Cc kt qu trn hnh 3.30 ch ra rng, i vi cc cht xc tc c pha nn hot ng

th chn lc gasolin thp hn v hiu sut to cc cao hn. c mt cht xc tc ti u,
ngi ta phi la chn khng ch pha nn m cn phi ch la chn t s zeolit/pha nn
mt cch thch hp.
3.5.4. nh hng ca t s zeolit/cht nn

Hiu sut SP y
o
338 C (%kl)

Hiu sut LCO

(%)kl

Hiu sut Hiu sut gasolin Hiu sut C3/C4

(%)kl
(%)kl
cc(%)kl

Hiu sut kh kh
(n v quy c)

Khi chuyn t aluminosilicat v nh hnh (pha nn) n zeolit tinh th, chn lc
ca sn phm phn ng bin i nh trn hnh 3.31. Vi t s zeolit/pha nn cao, chn

T s zeolit/cht nn

Hnh 3.31. nh hng ca t s zeolit/cht nn n hiu sut sn phm ti

chuyn ho 60% (s liu xc nh theo MAT).
iu kin thc nghim: xc tc/du = 3, WHSV = 16,
nhit phn ng 500oC, nguyn liu 22,5oAPI/11,5 UOP K.

135

lc sn phm tin dn n chn lc ca zeolit, trong khi vi t s zeolit/cht nn thp,

chn lc ch yu quyt nh bi pha nn.
Ni chung, khi t s zeolit/cht nn hot ng thay i, ngi ta nhn thy mt s c
im sau y:
(a) Khi hm lng zeolit khng i, tng hot tnh ca cht nn dn n s gia tng
hot tnh xc tc.
(b) Khi gi hot tnh cht xc tc khng i, gim t s zeolit/cht nn hot ng dn
n tng hiu sut LCO, cc v kh kh (C2), v gim hiu sut sn phm y.
(c) T s olefin/parafin ca LPG tng khi hot tnh ca cht nn tng v hot tnh ca
zeolit gim.
(d) Khi hm lng zeolit cao, hiu sut gasolin khng b bin i ng k do hot tnh
ca cht nn tng. Tuy nhin, khi hm lng zeolit thp, tng hot tnh ca cht nn dn n
chn lc gasolin tng v hm lng olefin trong gasolin tng (ch s octan cao hn).
Gia zeolit v cht nn, lun lun xut hin hiu ng hip tr xc tc (catalytic
synergism), ngha l hiu sut sn phm trn xc tc gia zeolit v pha nn bao gi cng ln
hn tng hiu sut sn phm trn zeolit v trn pha nn ring r.
3.5.5. nh hng ca cht ph tr
Zeolit ZSM-5
Thm mt lng nh (1 3%) zeolit ZSM-5 vo cht xc tc FCC lm tng gi tr octan
ca gasolin FCC v lm gim mt t hiu sut gasolin. ZSM-5 c th s dng di dng cc
ht ring r thm vo cht xc tc REY hoc di dng mt cht ph gia trn vo cc ht
xc tc. ZSM-5 cng c th c s dng kt hp vi zeolit Y tng gi tr octan, nh USY.
Cc s liu MAT i vi cht xc tc zeolit thng thng REY c v khng c cht
ph tr ZSM-5 c nu ln trong bng 3.12.
Ti mt chuyn ho nh nhau, cht xc tc c cht ph tr ZSM-5 to ra kh kh
v hydrocacbon C3, C4 nhiu hn, nhng c chn lc gasolin thp hn. Tuy nhin, hiu
sut gasolin v alkylat to ra cho cc olefin C3=, C4= l cao hn i vi cht xc tc c
ZSM-5, ch s RON cng cao hn. Hiu sut cc cng tng nh.
Cc kt qu th nghim quy m cng nghip i vi xc tc REY c v khng c cht
ph tr c trnh by trong bng 3.13.
Cc s liu th nghim cng nghip cng cho kt qu tng t nh s liu th nghim
vi MAT. Ngoi ra, c th nhn thy, vi s liu cng nghip cc hiu sut cc, LCO v sn

phm y l khng thay i, hiu sut i-C4 v C2 (H2 + CH4 + C2H4 + C2H6) cng nh
MON tng hn. Tuy nhin, cc s liu cng nghip gn y chng t khng c s gia tng

hiu sut C2 .
136

Bng 3.12. nh hng ca cht ph tr ZSM-5 n chn lc sn phm

v gi tr octan ca gasolin
Cht xc tc

Super D

Super D + 0,25% ZSM-5

S sai khc

Lng ZSM-5, %

0,0

0,25

chuyn ho, %tt

72,8

72,8

Kh kh, %kl

8,9

11,0

2,1

C3 , %tt

7,3

10,4

3,1

Tng C3, %tt

10,7

14,4

3,7

C4 , %tt

6,4

7,7

1,3

Tng C4, %tt

17,0

19,7

2,7

Gasolin, %tt

55,7

50,8

(4,9)

RON

89,2

92,1

2,9

Cc, %kl

4,2

4,4

0,2

78,5

80,9

2,4

Gasolin + alkytal, %tt

Bng 3.13. Cc kt qu th nghim cng nghip

Cht xc tc

REY (Filtrol)

REY + ZSM-5

S sai khc

73,2
51,6
26,5
0,3
5,4
1,4
9,0
2,3
7,0
2,6

2,3

Tng C2 , %tt

73,2
53,9
26,5
0,3
5,1
1,4
7,9
2,3
6,2
2,4

Cc, %kl
RON
MON
(R+M)/2
Gasolin + alkylat, %tt

6,7
87,3
78,1
85,0
78,8

6,7
89,0
78,7
86,3
79,9

chuyn ho
Gasolin (196oC, 90%), %tt
LCO (324oC, 90%), %tt
Sn phm y, %tt
Isobutan, %tt
n-Butan, %tt
Tng buten, %tt
Propan, %tt
Propen, %tt

0,2

1,7
0,6
1,3
1,1

Zeolit ZSM-5 ci thin gi tr octan ca gasolin FCC, trong phn on C5 - C6 nng

cc olefin tng, trong khi , trong phn on C7 - C13 nng ca cc cu t c gi tr
octan thp li gim.
Cc sn phm to ra do cracking cc parafin l cc hydrocacbon c phn t lng nh,
trong c cc phn t nm ngoi khong nhit si ca gasolin, do , dn n vic
137

gim hiu sut gasolin v cng nh vic gia tng cc olefin nh C3, C4. Nu nh my lc du
c cng on alkyl ho th cc olefin C3 - C4 c th c s dng trong sn xut cc alkylat
c gi tr octan cao. Thm cc alkylat vo gasolin c th b tr cho s gim bt hiu sut
gasolin. Hn na, zeolit ZSM-5 cng lm tng hiu sut isobuten v isopenten, chng c
s dng nh l nguyn liu cho sn xut cht gia tng tr s octan nh MTBE (methyl
tertiary butyl ether) v TAME (tertiaryamylmethylether). Cc th nghim quy m phng
th nghim v quy m cng nghip cc cht xc tc cha ZSM-5 chng t rng, hiu sut
gasolin gim khong 2%tt ng vi s gia tng 1 gi tr RON. S gia tng cc alkylat c th
b tr cho s hao ht hiu sut gasolin. MON ca gasolin tng khong t 20 50% s gia
tng ca RON. MON tng ln hn i vi gasolin cng vi alkylat.
Cu trc hnh hc ca zeolit ZSM-5 ngn cn s hnh thnh cc sn phm mch vng
v a vng, cc sn phm ny thng b dehydro ho v polyme ho to ra cc. Do ,
cc hnh thnh rt t trn ZSM-5, m ch to ra trn cht nn v trn zeolit Y. Cc tinh th
ln ca ZSM-5 l tc nhn hiu qu gia tng gi tr octan ca gasolin hn l cc tinh th
nh.
Zeolit ZSM-5 c ng dng thng mi trong nhiu nh my lc du. S dng
cht ph tr ZSM-5 cho cng on FCC c mt s u im tri hn so vi cht xc tc FCC
ch cha zeolit Y, nh sau: (a) nh my lc du c th d dng gia tng gi tr octan ca
gasolin v sn phm olefin nh; (b) ch trong thi gian t 1 n 7 ngy, ngi ta c th xc
nh c gi tr octan mong mun, trong khi , vi cht xc tc Y c th phi hng thng;
(c) s gia tng cc sn phm olefin C3 v C4 c th ngng trong mt tun k t khi khng
thm ZSM-5 na. iu rt quan trng i vi trng hp khng c nhu cu v kh cho
sn xut alkylat hoc cho ho du (polyme); (d) ZSM-5 c th gia tng tr s octan nghin
cu v m t khi nng ca ZSM-5 thp.
Tm tt
Hot tnh xc tc ca cht xc tc FCC ph thuc rt nhiu vo 3 hp phn to nn
n: zeolit, cht nn v cht ph tr xc tc.
Zeolit (REY, HSY) l pha tinh th c hot tnh xc tc cao, gia tng hiu sut gasolin
hoc gi tr octan, gim hiu sut to cc v to kh.
Pha nn (aluminosilicat, oxyt silic, oxyt nhm,) c hot tnh xc tc thp hn, c h
mao qun rng, c bn nhit v thu nhit cao, do , pha nn ng gp phn quan
trng ca mnh to ra bn mi mn, bn hot tnh tt cho cht xc tc.
Cht ph tr xc tc (ZSM-5, cht gim ng c) c vai tr gia tng gi tr sn
phm cracking theo hng mong mun (ch s octan, hm lng olefin nh), gim thiu
tc hi ca cc tc nhn gy nhim trong nguyn liu cracking, nh vo tnh cht xc tc
chn lc hnh hc v tnh cht hp ph chn lc ca n.

138

Cht xc tc FCC khng phi l mt hn hp c hc ca 3 hp phn ni trn, m

thc cht l mt tp hp kh ng nht. Thc vy, gia cc hp phn lun lun c s
hip tr gia cc tm xc tc v gia cc phn ng c bn xy ra trong h to ra
nhng tnh cht vt l, ho hc v xc tc vt tri so vi s t hp cng tnh ca tng hp
phn ring r.
3.6. Nghin cu hot tnh xc tc cracking
Cracking xc tc l mt qu trnh rt phc tp. Vic nh gi hot tnh ca mt cht
xc tc thng gp rt nhiu kh khn v ngoi cc phn ng cracking s cp cn c nhiu
phn ng th cp, b mt cht xc tc li b che chn bi mt lp ph cc lun bin i.
Hot xc tc b suy gim lin tc theo thi gian phn ng. Do , nhiu khi cc s liu
nh gi cht xc tc quy m phng th nghim (PTN) v th nghim cng nghip khng
ph hp nhau.
Trong nhng nm 70 ca th k trc, cc nh nghin cu xy dng cc m hnh
v suy gim hot tnh cht xc tc da trn l thuyt ton hc v cc phng tin my tnh
mnh x l nh lng cc d liu thc nghim. Nh , ngi ta c th hiu r hn bn
cht s suy gim hot tnh cht xc tc. Trong , c hai loi m hnh c tha nhn ph
bin nht l:
- M hnh suy gim hot tnh cht xc tc do s hnh thnh cc.
- M hnh suy gim hot tnh cht xc tc theo thi gian phn ng trong dng (decay
model based on time on stream).
3.6.1. Nguyn nhn suy gim hot tnh xc tc
Ni chung, s suy gim hot tnh xc tc c th chia thnh hai loi: nguyn nhn ho
hc v nguyn nhn vt l.
Cc nguyn nhn vt l bao gm s t hp cc tm xc tc, s bt tc cc mao qun,
tn tht (gim) b mt ring... Cc cht xc tc thng mi hot ng tt u rt bn vng
trong cc iu kin vn hnh cng nghip. iu ny cng hon ton ng vi cht xc tc
cracking, nh bn vt l tt m cht xc tc cracking c th lm vic trong nhiu tun
hoc nhiu thng.
Nguyn nhn ho hc thng phc tp hn, c th chia thnh:
Ng c thun nghch: do s hp ph cnh tranh ca cc tp cht trong nguyn liu.
V s hp ph c tnh cht thun nghch nn s suy gim hot tnh do nguyn nhn ny cng
c tnh "thun nghch", ngha l c th khi phc tnh cht xc tc bng cch kh hp ph
cht ng c nh thi kh nit, x l nhit...
Ng c khng thun nghch bi cc tp cht trong nguyn liu. Ng c bi cc
kim loi trong cracking xc tc l mt v d in hnh v ng c khng thun nghch. S

139

suy gim hot tnh ca cht xc tc do ng c bt thun nghch khng th phc hi bng
cc x l vt l hoc ho hc.
T ng c: l s suy gim hot tnh xc tc do cc phn ng mong mun xy ra.
y l nguyn nhn chnh ca s suy gim hot tnh ca cht xc tc cracking v do
cng l l do pht trin cc dng thit k khc nhau v react v thit b hon nguyn cht
xc tc cracking.
Hin tng ng c cht xc tc cracking xy ra do s che ph mt lp vt liu
cacbon ho trn b mt v bn trong cc mao qun cht xc tc. Vt liu cc l sn
phm khng mong mun. Thnh phn ho hc ca cc lun bin i t t s H/C bng 2
gim dn n 0,3 0,1, tnh cht ca cc lun bin i v ph thuc vo bn cht cht xc
tc, ngun nguyn liu, iu kin phn ng,... Ngi ta phn bit s to cc theo cc c ch
khc nhau.
1. Cc do cn: c to ra do dehydro ho cc phn cn khng bay hi ca nguyn
liu (cc Condrason).
2. Cc do tp cht kim loi: loi ny c to ra do cc tp cht kim loi trong
nguyn liu bm vo b mt cht xc tc, ri tr thnh cc tm to cc.
3. Cc xc tc: c hnh thnh do cc qu trnh xc tc to ra mt s sn phm v
mt l do no (kch thc hnh hc, kh nng khuch tn...) phi nm li trn
b mt xc tc.
4. Cc do nguyn liu: mt s nguyn liu khng kp cracking ng li trong cc
mao qun cht xc tc.
S phn chia bn loi cc nh th khng cho chng ta bit nhng c tnh khc nhau
gia chng, song, c th bit c ngun gc xut x ca chng. V d nh bng 3.14.
Bng 3.14. Ngun gc ca cc trn cht xc tc FCC
Loi cc (xut pht t)
Condrason
Tp cht kim loi
Do nguyn liu
Phn ng xc tc

% khi lng chim trong tng lng cc

5
30
20
45

T bng 3.14 nhn thy rng, phn ch yu ca cc c to ra l do cc phn ng

xc tc. Mt khc, chng ta c th nhn xt mt cch nh tnh rng, s suy gim hot tnh
xc tc l do s hnh thnh cc trn cht xc tc. Tuy nhin, mt s cu hi c t ra l:
c phi cc l nguyn nhn duy nht dn n s suy gim hot tnh xc tc? S suy gim
hot tnh l do mao qun b bt tc, do che ph b mt cht xc tc, do tr lc khuch tn,
hoc do chnh bn thn cc tm xc tc b mt dn hot tnh.
140

 c rt nhiu nghin cu c xut v thc hin tr li cc cu hi . Song,

n nay, c hai m hnh m t s suy gim hot tnh ca cht xc tc FCC c tha nhn
nht. l: m hnh to cc v m hnh phn ng trong dng.
3.6.2. M hnh suy gim hot tnh xc tc do s hnh thnh cc trn cht
xc tc (m hnh COC, coke on catalyst)
M hnh COC c Froment ngh (G. F. Froment, Stud. Surf. Sci. Catal. (Catal.
Deact.), 6:1, 1980) da trn c s m t ng hc s suy gim hot tnh xc tc. M hnh
ny l s n gin ho ca mt thc t rt phc tp v suy gim hot tnh cht xc tc. Theo
Froment, trong qu trnh cracking, mt hydrocacbon n l X no bao gm phn ng
cracking X v phn ng to cc. Gi s, hot tnh cht xc tc cracking hydrocacbon X l
aHC v hot tnh to cc l aC, th tc phn ng cracking X v phn ng to cc l:

dC HC
= k oHC .a HC
dt
dC C
o
= k C .a C
dt

(3.10)
(3.11)

trong : CHC: nng ca hydrocacbon sn phm;

CC: lng cc hnh thnh trong phn ng;
k oHC , k oC : hng s (tc phn ng cracking v to cc tng ng ti thi im

t = 0, cha to cc).
aHC v aC l cc hm s kinh nghim ph thuc vo m hnh la chn (sao cho cc s
liu thc nghim ph hp vi ng cong m phng). Chng hn, ngi ta c th cho rng,
hot tnh cracking v hot tnh to cc u ph thuc vo s to cc b mt.
aHC = exp(HCCC,bm)

(3.12)

aC = exp(CCC,bm)

(3.13)

trong , HC, c: cc h s;
Cc,bm: hm lng cc b mt (lng cc tnh cho n v b mt).
Thay (3-12) vo (3-10) v (3-13) vo (3-11) v tch phn s nhn c:

C HC =

1
HC

ln(1 + HC k oHC t )

C C = 1 ln(1 + C k oC t )
C

(3.14)
(3.15)

Cc phng trnh (3-14) v (3-15) m t s suy gim hot tnh cracking v s hnh
thnh cc da trn m hnh to cc b mt. T cc phng trnh , bng cch t chc cc
thc nghim cn thit, chng ta c th bit c s din bin ca hot tnh xc tc v s

141

hnh thnh cc trong qu trnh cracking.

Tuy nhin, m hnh COC ny khng ni ln c bn cht phc tp ca cc lm suy
gim hot tnh ca cht xc tc. Mt khc, vic xc nh cc l vn khng d dng, mt
nhiu thi gian v d sai s. Do , m hnh COC t c ng dng trong thc t. D sao,
phng php ca Froment cng l s ng gp u tin c gi tr trong vic m t s hnh
thnh cc trn cht xc tc cracking.
3.6.7. M hnh suy gim hot tnh xc tc theo thi gian phn ng trong
dng (time on stream, TOS)
trnh nhng kh khn gp phi khi s dng m hnh COC, ngi ta a ra mt s
quy lut nht nh trong qu trnh phn ng. Chng hn, hot tnh cht xc tc (a) ph thuc
vo thi gian phn ng trong dng t v theo quan h tuyn tnh:
a = ao At

(3.16)

da
=A
dt

(3.17)

hoc

A: hng s.
hoc di dng ph thuc bc 1:

da
= Aa
dt

a = a o exp(At)

(3.18)
(3.19)

hoc ph thuc dng bc 2:

da
= Aa 2
dt

(3.20)

1 1
=
+ At
a ao

(3.21)

hoc di dng ph thuc khc nh Blanding (F. H. Blanding, Ind. Eng. Chem., 45:1186,
1953) v Voorhier (A. Voorhiers, Jr. Ind. Eng. Chem. 37:318, 1945) s dng.
1

da
= BA 2 a ( B +1) / B
dt

(3.22)

1/ B

1

a

= const1 + const 2 (t )

(3.23)

B: hng s.
Tt c nhng dng ph thuc ni trn c p dng thnh cng trong mt s
trng hp c th. c bit, dng hm m (3.19) c p dng cho mt m hnh cracking
xc tc vi cc kt qu nhn c kh hp l.
142

C th t hp cc hm suy gim hot tnh ni trn trong mt dng tng qut ca l

thuyt TOS (H. Heinemann, Ind. Eng. Chem. 43:2098, 1950). L thuyt cho rng, hot
tnh ca mt cht xc tc c lin h trc tip vi nng cc tm hot ng xc tc, Cs, trn
b mt cht xc tc.

dC S
2
m
= k od + k 1 d C S + k 2d C S + ... + k md C S
dt

(3.24)

Phng trnh (3.24) bao gm cc dng suy gim hot tnh khc nhau nh do ng c
xc tc, do cn tr khuch tn... c biu din bi cc s hng cha hm m khc nhau, v
vi gi thit rng, cc qu trnh xy ra ng thi.
Trong phng trnh (3-24) c mt gi thit quan trng l: s suy gim hot tnh khng
ph thuc vo nng ca cht tham gia phn ng v ca sn phm phn ng. R rng gi
thit ni chung khng thc t. Song, ngi ta cho rng cht tham gia phn ng v sn
phm phn ng u tham gia vo qu trnh ng c xc tc vi mc ng k nh nhau.
Ni chung, phng trnh (3.24) m t kh tt cc kt qu thc nghim, k c nhng trng
hp kh phc tp.
Phng trnh (3.24) c th c vit di dng :

=
trong ,

CS
C So

CS: s tm hot ng;

CSo: s tm hot ng ban u;

d
= k o d + k1d + k 2 d2 + ... + k mdm
dt

(3.25)

m 1

trong , k md = k md C So .
Phng trnh (3.25) c th vit di dng n gin hn:

d
= k d m
dt

(3.26)

vi gi thit m l cc gi tr khng tch phn (nonin tegral values).

Tch phn phng trnh (3.26), chng ta thu c:

1
=

1 + Gt
trong ,

(3.27)

G = (m 1)kd

N=

1
,m1
m 1

Phng trnh (3.27) c p dng kh thnh cng cho nhiu dng phn ng cracking
v dehydro ho, v l c s gii thch cc tnh cht ca cht xc tc cracking. c bit,
143

n cung cp nhng hiu bit cn thit v chn lc ca cc cht xc tc b suy gim hot
tnh mt cch nhanh chng.
3.6.4. chn lc sn phm trong phn ng cracking xc tc
Trong phn ng cracking, hot tnh cht xc tc thng b suy gim rt nhanh, do ,
chn lc sn phm phn ng l mt vn kh phc tp, kh nhn bit bng trc gic. V
th, ngi ta thng d b nhm ln khi nh gi v chn lc sn phm phn ng
cracking.
hiu vn mt cch y hn, chng ta cn bit rng:
- Ti mt chuyn ho nht nh, chn lc thc nghim phn ng cracking lun
ph thuc vo kiu react.
- Trong mt react c lp xc tc n nh, chn lc thc nghim ti mt chuyn
ho nht nh ph thuc vo tc khng gian v t s cht xc tc/du.
Cc nhn xt l hon ton ng vi bt c cht xc tc no: b suy gim hot tnh
chn lc hay khng chn lc trong phn ng cracking.
3.6.4.1. chn lc sn phm trong cc react c lp xc tc n nh
By gi, chng ta xt mt phn ng xy ra theo mt s n gin:
A

minh ho cho s bin i chn lc sn phm khi phn ng cracking xy ra trong mt

lp n nh ca cht xc tc.
Nu s suy gim hot tnh xy ra chm so vi thi gian tip xc ca nguyn liu trong
react, th mi phn nguyn liu qua lp xc tc c xem nh c cng mt chuyn ho.
chuyn ho ca phn nguyn liu ph thuc vo hot tnh xc tc tng ng. Cc
phn nguyn liu tip theo s c chuyn ho dn dn thp hn v cht xc tc b suy gim
hot tnh dn dn.
Nu chng ta xt cho mt s n gin hn
A

th c th biu din tc phn ng cho bt c mt phn nguyn liu no, nh sau:

trong ,

dA
= kCSCA
d

(3.28)

CS: nng tm xc tc;

CA: nng ca cht A (nguyn liu);
: thi gian tip xc;
= bPtf
vi,

144

b: h s (ph thuc n v o);

(3.29)

tf: thi gian thc hin phn ng;

P: t s cht xc tc/nguyn liu.
Tch phn phng trnh (3.28), chng ta nhn c:

CA
= 1 XA = exp(kCS)
C Ao
trong ,

(3.30)

CA: nng tc thi ca cht A;

CAo: nng ban u ca cht A;
XA: chuyn ho ca cht A;
: thi gian tip xc.

Phng trnh (3.30) l bin thin chuyn ho tc thi ca phn nguyn liu c
cracking. nhn c gi tr trung bnh ca phn nguyn liu chuyn qua lp xc tc
trong khong thi gian trong dng t 0 n tf, chng ta thc hin:
1
XA =
tf

tt

X A dt

(3.31)

thay phng trnh (3.27) vo (3.30) v (3.31), nhn c:

XA = 1

trong ,

1
tf

exp[ k o (1 + Gt )

tf

) dt

(3.32)

ko = kCSo;
cc k hiu G, N, , tf nh trc y.

Thay (3.29) vo (3.32):

1
XA = 1
tf

Nh vy:

exp[ k o (1 + Gt )

tf

(bPt f ) dt

(3.33)

X A = f(ko, G, N, b, P, tf)

(3.34)

Trong phng trnh (3.34) ko, G, N v b l nhng tham s khng i c trng cho
mi mt h nghin cu, trong khi P v tf l cc bin s thc nghim.
nghin cu mt phn ng, chng ta phi thay i c P v tf hoc da theo phng
trnh (3.29), c th thay i bt k 2 trong cc bin s , P v tf. Thng thng, ngi ta hay
tin hnh thc nghim theo cch c nh P v thay i (v do , thay i tf) trong mt
khong thc nghim cho php. Sau , chn mt gi tr P khc v li thay i .
Trong mt lot thc nghim nh th ng vi mt t s cht xc tc/du khng i,
chng ta s tm c quan h XA = X B cho phn ng c c ch n gin ang xt.
V X A + X B = 1 do nu lp mt biu biu din quan h X B v 1 X A th s
nhn c mt quan h tuyn tnh. iu hon ton d nhn thy, thm ch bng trc gic.
145

Tuy nhin, vn s tr nn phc tp hn nu chng ta tr li vi s phn ng:

A
Ta c:
V:

k1

k2

dC A
= k 1 CS1CA
d

(3.35)

dC B
= k 1 CS1CA k 2 CS2CB
d

(3.36)

Gii cc phng trnh vi phn (3.35) v (3.36) chng ta c:

CA
= 1 XA = exp( k 1 CS1)
C Ao
CB
k 1 C S1
[exp( k 1 C S1 ) exp( k 2 C S 2 )]
= XB =
C Ao
k 2 C S 2 k 1 C S1

(3.37)
(3.38)

CC
= X C = 1 XA X B
C Ao

(3.39)

Da vo phng trnh (3.27) v nh ngha = CS/CSo tnh CS, thay vo cc phng

trnh (3.37) n (3.39), trong , t l thi gian phn ng trong dng, CS1 l nng cc tm
xc tc cho phn ng 1 v CS2 - cho phn ng 2. Hai loi tm c nng khc nhau v
tnh cht suy gim hot tnh khc nhau:
CS1 CS2
1 = (1 + G1t )

N1

2 = (1 + G 2 t )

N 2

(3.40)

T cc gi thit nh trn, chng ta c:

X B = f1 (k10 , k 20 , G1 , G 2 , N1 , N 2 , b, P, t tf )

(3.41)

X C = f2 (k10 , k 20 , G1 , G 2 , N1, N 2 , b, P, t tf )

(3.42)

Cc kt qu tnh ton m phng bng my tnh chng t rng, trong iu kin lp

xc tc n nh, ngi ta khng phn bit mt cch r rng gia 2 trng hp suy thoi hot
tnh chn lc hay khng chn lc. Do , chng ta kho st chn lc ch trong trng
hp cht xc tc b suy gim hot tnh khng chn lc (G1 = G2 =..., N1 = N2 =...,)
Lp th biu din quan h X B v X C vi to (1 XA ) nh trn hnh 3.32 v
3.33 ng vi cc trng hp N > 1 (loi I), N = 1 (loi II) v N < 1 (loi III).
Sau y, chng ta xt cho trng hp cht xc tc lm vic trong trng hp III. Cc
trng hp I v II cng c xem xt tng t.
Trc ht, chng ta thy rng, c cc ng cong gii hn bao gm cc gi tr P
khng i (vng ng P, constant P loop) v vng ng P ti u c k hiu OPE
146

(optimum performance envelope) v vng ng P ti thiu MPE (minimum performance

envolope). Hai ng cong ng P ny xc nh hai gii hn cho php ca chn lc. Gia
hai ng cong OPE v MPE l min thc nghim cho php, vi iu kin l: mi mt im
trong min ch i din cho mt kt qu ring duy nht cho mt tp hp cc iu kin
phn ng. Khng th c hai tp hp iu kin phn ng khc nhau cho cng mt im kt
qu trong vng .

Tng tf

Tng tf

Tng tf
Tng P

Tng P

Tng P

Hnh 3.32. chn lc l thuyt ca sn phm C trong phn ng A B C

i vi cht xc tc (a) loi I, (b) loi II v (c) loi III.
1
(N =
, m 1; N > 1 khi m > 2; N = 1 khi m = 2 v N < 1 khi m < 2)
m 1

Tng P

XB

Tng P

chn lc
ban u

XB

chn lc
ban u

Tng tf

Tng tf

Vng ng P

a)

XA

XA

b)
Tng P
XB

chn lc
ban u
Tng tf

c)

XA

Hnh 3.33. chn lc l thuyt ca sn phm B trong phn ng A B C

i vi cht xc tc (a) loi I, (b) loi II v (c) loi III.
147

Nu xt cc im nm trn ng thng ng vi mt chuyn ho khng i, chng

ta nhn thy rng, c th c cc chn lc khc nhau cho mt sn phm no bng cch
chn cc iu kin phn ng khc nhau. V d, ti thi im ca thi gian trong dng rt
ngn, chn lc ca B ( X B ) v ca C ( X C ) u nm trn OPE (nh trn hnh 3.34). Trong
khi , ti thi im thi gian trong dng di, c X B v X C u MPE.
T hnh 3.34 c th nhn thy rng, t s X C / X B lun thay i theo tf. Thc vy, khi
tf tng, ti mt chuyn ho nht nh ( = 1 XA ) th X C tng (im X C (tf,P) i ln),
cn X B gim (im X B (tf,P) i xung). Nu chng ta tin hnh mt lot thc nghim vi P
v tf thay i v gi nguyn chuyn ho ( = 1 XA = const, ng chm chm hnh
3.34) th chng ta s nhn c s bin i X C / X B nh trn hnh 3.35.
tf nh

tf ln

tf ln

tf nh

Hnh 3.34. chn lc sn phm ca phn ng ni tip A B C

trong trng hp xc tc loi III.
Vng thi gian trong dng rt ngn
Vng thc nghim
tf , P thay i,
XA khng i
XC/XB
Vng khng nghin cu

tf

Hnh 3.35. nh hng ca thi gian trong dng (TOS) n t s hiu sut
sn phm ng vi mt chuyn ho khng i ca phn ng A B C.
148

T hnh 3.35 nhn thy rng, trong min thi gian trong dng tf rt ngn v min thi
gian thc nghim thng thng t s X C / X B lun lun tng.
S gia tng ca X C so vi X B , r rng l khng phi do s ng c chn lc ca cc
tm xc tc, v chng ta chn trng hp G1 = G2 v N1 = N2, m chnh l do bn cht
ca s to thnh sn phm theo cc quy lut din bin trong dng:

X B = f1 (k10 , k 20 , G, N, b, P, t tf )

(3.43)

X C = f2 (k 10 , k 20 , G, N, b, P, t tf )

(3.44)

(3.43) v (3.44) c suy t (3.41) v (3.42), tng ng.

Do , trong nghin cu xc tc, chng ta thng d hay ng nhn cho rng, cc kt
qu nhn c nh trn hnh 3.35 l do s ng c chn lc ca cc tm xc tc to ra sn
phm B m khng suy xt v quy lut din bin phn ng trong dng.
T cc s xem xt trn c th dn n mt kt lun quan trng l: cc react loi lp
xc tc n nh khng th cho nhng kt qu thc nghim ni ln s suy gim hot tnh xc
tc do hin tng ng c chn lc cc tm xc tc.
3.6.4.2. chn lc sn phm trong cc react cracking xc tc trng thi
lu th - react thng mi
Cc kt qu thc nghim v chn lc sn phm cracking trong cc react lp xc
tc n nh khng trng vi cc kt qu trong cc react lin tc, vi h ht xc tc trng
thi lu th chuyn ng.
lm sng t iu , chng ta xt trng hp mt h lu th l tng gm cc ht
v dng cht phn ng c trn ln hon ho. Trong mt react nh th, thi gian lu ca
ht xc tc c xc nh:

1
t
E( t ) = exp
t
t

(3.45)

trong , t l thi gian trong dng ca mt ht xc tc ring r;

t l thi gian lu trung bnh ca tt c cc ht xc tc, tng ng vi tf trong

phng trnh (3.29).
Mt khc, ti mt thi im t, ht xc tc c hot xc tc tng ng:
kot = ko(1 + Gt)

(3.46)

trong , ko c gi l hng s tc ban u;

kot c gi l hng s tc ti thi im t bt k.
Hng s tc trung bnh ca ht:

1
k
t
k = k o (1 + Gt ) N exp dt = o
t
t
t
0

exp( t / t )

(1 + Gt )N

dt

(3.47)

149

Nu s suy gim hot tnh l khng chn lc, mi mt hng s tc trong mt h

phn ng s bin i theo mt quy lut nh nhau theo phng trnh (3.47). Trong trng hp
, hiu sut trung bnh X B v X C trong phn ng A B C s nhn c nh phng
trnh (3.37), (3.38) v (3.39) vi kCS c thay th bi k .

X A = exp( k)
XB =

(3.48)

k10
exp( k1 exp( k 2 )
k 20 k10

XC = 1 X A + X B

(3.49)
(3.50)

Ngi ta chng minh rng, cc im to ra t cc phng trnh (3.48) n (3.50)

u nm trn ng OPE ca cc im thuc cc phng trnh (3.37) n (3.39). Nh vy,
mt h xc tc trng thi lu th l tng lun lun hot ng ch OPE khi s suy
gim hot tnh l khng chn lc, v c cht xc tc, nguyn liu u c trn ln trong
dng mt cch ho ho.
Khi ch trn ln khng t c mc l tng th da theo m hnh trn,
chn lc sn phm c th dch chuyn t ng biu din OPE vo min c php bn
trong din tch OPE v MPE. Mc trn ln cng km th cc im kt qu ( chn lc)
cng nm bn trong din tch OPE v MPE.
V trng thi lu th ca cc ht xc tc l mt m hnh l tng, do cng khng
d dng thc hin trong mi iu kin. Nhiu khi, ngi ta s dng cc react c h xc tc
trng thi ng (tng si n nh), dng cht tham gia phn ng v sn phm phn ng d
dng t n ch ti u.
Trong cc react, thay i P v nhng gi nguyn t , ngi ta c th nhn c
ng cong chn lc sn phm t = const trong khong chuyn ho cho php. Nu
s suy gim hot tnh xc tc l khng chn lc th ng cong chn lc sn phm s trng
vi ng OPE ca h xc tc n nh, vi bt c gi tr t no. Nu s suy gim hot tnh
ca cht xc tc l chn lc th ng cong chn lc sn phm cracking trong react c h
xc tc ng s khc nhau vi cc t khc nhau.
Vic nghin cu chn lc sn phm trong react c h xc tc ng rt c ngha
phn bit s suy gim hot tnh l chn lc hay khng chn lc.
S sai khc v chn lc sn phm gia react lp xc tc n nh v react c cht
xc tc trng thi chuyn ng l kh ln, v do , nhiu khi dn n cc kt lun v gii
thch khng hp l. Tuy nhin, hu ht cc th nghim xc tc cracking cc phng th
nghim hin nay u thc hin vi thi gian trong dng rt ngn, do , u t n chn
lc sn phm ti u ti OPE. iu to ra mt kh nng thc t nh gi cc cht xc tc
thng mi, mc d chng ta cha hiu mt cch tng tn cc hnh vi ca cht xc tc
trong qu trnh phn ng.

150

3.6.4.3. Xc nh hot tnh cht xc tc cracking quy m phng th nghim

(PTN)

Hot tnh xc tc, s to cc v to kh l cc tham s quan trng khi nh gi tnh

cht xc tc ca mt cht xc tc.
Hin nay quy m PTN ngi ta thng s dng thit b MAT (micro activity test)
nh gi hot tnh xc tc. S thit b nh trn hnh 3.36.
Bm xi - ranh

3
2
Cc b t
Van 3 ng
L phn ng
Lu lng k

iu khin nhit
vng tin gia nhit

N2 lm sch

iu khin nhit

vng xc tc
Mu kh sn phm

iu khin nhit

5
Xc tc s dng ti My
phn tch Leco xc nh cc

Lm lnh

Thu kh

Sn phm lng ti sc k kh
phn tch hydrocacbon v chng
ctm phng

My tnh

- Cn bng vt cht
- Hiu sut
- Hot tnh
- Tc nhn kh, tc nhn cc
- H2/CH4

Hnh 3.36. S thit b MAT.

Cht xc tc mi hoc lm vic (cht xc tc cn bng) c a vo react 1.

Cht xc tc cn bng c lm sch cc (t chy trong dng khng kh) trc khi o hot
tnh xc tc. Nguyn liu cracking c a vo bnh 2, nh bm y dng xy-ranh
(syringe) a nguyn liu gas oil vo react 1. Nguyn liu c gia nhit bng lp vt liu
ht thch anh, sau qua lp xc tc. Hn hp nguyn liu cha cracking v sn phm
cracking i vo bnh 4. Ti , mt s hydrocacbon c im si cao b ngng t do lm lnh
(sn phm lng), phn cn li khng ngng t i qua bnh 5. Trong bnh 5, c mt dung
dch mui ( lm gim tan ca kh) c gi mt p sut cn bng nht nh. Khi p
151

sut kh trong bnh 5 ln hn p sut cn bng th cht lng vo bnh 6. o lng cht lng
thu c, chng ta bit lng sn phm kh to ra trong qu trnh cracking. Ti 7, mu sn
phm kh c a n sc k kh phn tch thnh phn ho hc. Thnh phn sn phm
kh, sn phm lng v lng cc to thnh t xc tc lm vic c phn tch. Cc s liu
c chuyn n my tnh xc nh cn bng vt liu, hiu sut sn phm: hiu sut
gasolin, cc, sn phm kh, cc kh H2/CH4...
Cht lng nguyn liu, nhit phn ng (react), t s cht xc tc/du v tc
khng gian l 4 tham s quan trng nh hng trc tip n kt qu ca MAT.
Cc nh sn xut c th s dng cc iu kin sau thc nghim sau y nh gi
cht xc tc (bng 3.15).
Bng 3.15. Cc iu kin th nghim MAT
Hng sn xut
xc tc

Nhit
(oC)

T s xc
tc/du

Davison
Engelhard

527
488

4,0
5,0

WHSV, h
30
15

Thi gian
phn ng tf, s

Ngun
nguyn liu

Kiu react

30
48

(1)
(2)

ng nhit
ng nhit

(1) Gas oil nng, chua nhp khu.

(2) Trung cn ng.

Nh chng ta thy mc 3.6.4.1 v 3.6.4.2, khi cc th nghim xc tc trong react

lp xc tc n nh c thc hin vi thi gian trong dng rt ngn th cc gi tr c
u nm ch OPE v c th tng t nh c o trong ch cht xc tc trng thi
lu th, do , cc thit b MAT c s dng rng ri khng nhng cc phng th nghim
nghin cu xc tc cracking m cn c s dng cc phng th nghim ca cc nh my
lc du.
S sai lch gia s liu MAT v s liu cng nghip thng do phm cht nguyn liu
ban u khc nhau v do s xc nh hm lng cc trong phng php MAT c chnh
xc khng cao.
Do , ngi ta a ra mt khi nim v hot tnh ng nh gi xc tc cng
nghip t s liu ca MAT mt cch ph hp hn.
chuyn ho bc 2
(3.51)
Hot tnh ng =
Hiu sut cc, %kl
trong ,
chuyn ho bc 2 =

chuyn ho MAT, %tt

100 chuyn ho MAT, %tt

(3.52)

V d: chuyn ho MAT ca mt cht xc tc l 70%tt v hiu sut cc l 3%kl.

Ta c:
152

 chuyn ho bc 2 =

70
70
=
= 2,33.
100 70 30

Hot tnh ng ca cht xc tc l: Ad =

70
= 0,78.
30.3

Hin nay, trong phiu cho hng bn cht xc tc, cc nh sn xut cng gii thiu
s liu v hot tnh ng A cc nh lc du tham kho.
Tm li, cracking xc tc l mt qu trnh rt phc tp. Trong qu trnh cracking,
hot tnh cht xc tc lun b suy gim. S suy gim l do s ng c thun nghch v
khng thun nghch ca mt s tp cht c trong nguyn liu cracking, do s che ph ca
ca cc, do ng c bi cc tm xc tc trong qu trnh phn ng. S suy gim c th
hin bng mt trong nhng m hnh ph bin nht l m hnh "suy gim hot tnh trong
dng".
Da vo m hnh , chng ta c th nhn thy rng:

Cc sn phm s cp ca phn ng cracking lun nm trn ng thng i qua gc

to ca th "hiu sut sn phm - chuyn ho", trong khong chuyn ho thp.
i vi cc react lp xc tc n nh, khi thi gian phn ng trong dng nh,
chn lc sn phm cracking lun nhn c ch ti u OPE.
i vi cc react xc tc m cht xc tc trng thi lu th, chn lc sn
phm lun lun t n ti u, nh ch OPE ca react - lp xc tc n nh vi thi
gian trong dng ngn.
Cc s liu nh gi hot tnh ca cht xc tc quy m phng th nghim bng cc
react lp xc tc n nh MAT nhn c thi gian trong dng ngn cng c th c s
dng la chn kim tra v theo di tnh cht xc tc ca cc cht xc tc thng mi.

153

Chng 4

Cng ngh qu trnh cracking xc tc

4.1. M u
Cracking xc tc pha lu th FCC (fluid catalytic cracking) l mt qu trnh chuyn
ho gas oil chng ct trc tip di p sut kh quyn, gas oil chn khng, mt s du cn
v du nng ca nhiu cng on khc nhau trong nh my lc du to ra gasolin c gi
tr octan cao hn, du t v cc kh giu olefin nh. c im ca qu trnh FCC l: vn
u t tng i thp, hot ng lu di kh n nh v kh a dng (ngha l nh my lc
du c th iu chnh hiu sut cc sn phm theo nhu cu th trng bng cch thay i cc
tham s vn hnh. Gasolin ca FCC c gi tr octan kh tt. Ngoi ra, cc gasolin cn
c b sung cc alkylat sn xut t cc kh giu olefin. Cc alkylat c gi tr octan kh cao
v nhy octan kh tt.
Trong mt h thng FCC in hnh, cc phn ng cracking u c thc hin trong
mt react ng ng (vertical reactor riser), trong riser (raiz) mt dng nguyn liu lng
c tip xc vi cht xc tc nng, dng bt. Nguyn liu (gas oil) b ho hi v cracking
thnh cc sn phm nh khi di chuyn t di ln pha trn react v mang theo cht xc tc
bt. Cc phn ng xy ra rt nhanh ch trong vi giy, ng thi cc cng c hnh thnh,
bm vo b mt cht xc tc lm cho hot tnh xc tc gim dn. Cht xc tc tham gia
phn ng v cc sn phm cracking c phn ring. Cht xc tc c chuyn qua thit b
hon nguyn t chy cc v phc hi hot tnh xc tc. Sau , cht xc tc li c
chuyn n y ca react ng ng tip tc thc hin mt chu trnh cracking xc tc
tip theo. t c mt quy trnh hon ho nh trn, cng ngh cracking xc tc phi tri
qua bao nhiu thi gian th thch, ci tin v hon thin dn.
Mt vi nt v lch s pht trin cng ngh FCC
Cracking xc tc bt u pht trin trong nhng nm cui ca thp k 30 th k trc.
Trong th chin th II, do yu cu quc phng cng ngh ny c u tin pht trin c
bit, hn 30 c s cracking c xy dng v hot ng.
Phn xng FCC quy m cng ngh u tin c a vo vn hnh M thng 51942 theo mu thit k s 1 (khng gii thiu y). Mu ny nhanh chng c thay th
bi mu s 2 (hnh 4.1).
S ny gm mt react dng thng rng c t gn mt sn v mt thit b hon
nguyn cht xc tc v tr cao hn react mt t. Cht xc tc v hydrocacbon c ho

154

hi i vo react c lp xc tc n nh. Cc van iu chnh c lp t nhiu v tr khc

nhau trong h thng duy tr p sut thp hn trong thit b hon nguyn so vi react.
Thc t cng ngh chng t rng, mc d chuyn ho ca cc sn phm cracking xc
tc ny vn cn thp (40 n 50% th tch lng, %LV: % liquid volume) nhng phn ln cc
phn ng cracking xy ra trong mt khong thi gian tip xc rt ngn gia xc tc v
hydrocacbon.
Kh x sau
hon nguyn

Xyclon a cp
Ni hi tn
dng nhit
thi

Thit b hon
nguyn

n thit b phn
on chng ct

React
Thit b
thu hi bi
Hi nc lm
sch cht xc tc
Du
nguyn liu

Khng kh

Sn phm y chng ct

Hnh 4.1. S h thng cracking xc tc theo mu thit k s 2.

Bung gim p
Kh
Reactor
B phn lm sch cht xc tc
(bng hi nc)
Hi nc x l cht xc tc
Thit b hon
nguyn

Du lng gn
Du st
Khng kh

Hi nc
Nc
x l

Ni hi

Kh v xng

Ct chng ct chnh
LCO
HCO

Nguyn liu

Hnh 4.2. S h thng FCC theo thit k ca m hnh "ni tip"

(gia react v regenerat).
155

Sau chin tranh, mu thit k h thng FCC dng ni tip c trin khai (hnh 4.2)
S ny gm mt react p sut thp kt ni trc tip phn pha trn ca thit b
hon nguyn cht xc tc c p sut cao hn. Mu thit k ny l mt bc chuyn tip
quan trng t cng ngh cracking trong lp cht xc tc n nh n cracking trong h xc
tc pha lu th. Gia thp k 50 th k trc mu thit k kiu react ng ng (reactor
riser) c gii thiu (hnh 4.3).
Kh x n
l t CO
Kh v xng

Bung gim p

Reactor

B phn lm
sch cht xc tc
(bng hi nc)

LCO
Ct chng ct
HCO

Thit b hon
nguyn

Hi nc

Du lng gn
Du st

Khng kh
Nguyn liu

Hnh 4.3. H thng FCC theo m hnh"song song" ca UOP.

Trong mu thit k ny, thit b hon nguyn xc tc c t gn mt sn v react
v tr cao hn bn cnh. Cht xc tc hon nguyn, nguyn liu mi v nguyn liu hon
lu c a vo react bng mt ng ng di pha di react. So vi thit k trc, th
hiu sut v chn lc ca mu thit k ny c ci thin ng k.
Gia thp k 1960 vic ng dng cht xc tc zeolit quy m cng nghip to ra
mt bc nhy vt trong cng ngh xc tc cho cc qu trnh lc du. Cc cht xc tc
zeolit c hot tnh, chn lc gasolin v n nh ( bn xc tc) rt cao so vi cht
xc tc aluminosilicat v nh hnh. Nh nhng u im ni bt ca cht xc tc zeolit m
t n nay, nhiu sng ch v ci tin quy trnh cng ngh cracking xc tc lin tc
trin khai. Nm 1971, UOP thng mi ho mt mu thit k mi, c gi l mu riser
cracking (cc phn ng cracking c thc hin trong mt react ng ng cha hi
hydrocacbon v bt xc tc c chuyn ng trong trng thi lu th). S cng ngh
FCC nhanh chng c trin khai trong cc nh my lc du mi xy dng v thm ch c
thay th cho cc s FCC c ang tn ti. Thc t chng t rng, cracking react ng ng
(riser cracking) em li chn lc gasolin cao hn, kh v cc gim hn, ngha l hn
ch mt cch rt hiu qu cc phn ng cracking th cp.
156

Trong nhiu nm, ngi ta ht sc quan tm n vic hon thin mt h react

cracking, bao gm: ng phn ng, h xyclon, u phun nguyn liu,... Mi ci tin u
nhm tng cng s tip xc tt gia nguyn liu cracking v cht xc tc, thc hin phn
ng cracking hon ton trong ng phn ng (riser), nng cao hiu sut sn phm mong
mun, gim thiu cc sn phm ph khng cn thit.
Bn cnh s quan tm ci tin react phn ng, ngi ta cn ch ci tin h thng
hon nguyn xc tc. Trong thi k u (khong 20 nm) hot ng ca cc nh my lc
du, cc thit b hon nguyn xc tc u pht ra kh x cha ch yu CO v CO2. Vi bin
php t chy khng hon ton, cht xc tc sau khi hon nguyn cn cha hng chc phn
trm lng cacbon trn b mt ca n. Trong nhng nm u ca thp k 1970 ngi ta phi
ci tin vic ch to cht xc tc v lp t thm cc thit b ph tr (l t CO) chuyn
ho CO thnh CO2, nhm gim thiu c hi ca kh thi. Nm 1973, mt h thng FCC
ca UOP c lp t thit b hon nguyn xc tc mi, c hiu qu cao trong vic chuyn
ho trc tip CO thnh CO2. T v sau, cc c s FCC u c thit k theo cng ngh
hon nguyn xc tc ci tin, do , hiu sut cc gim, pht thi CO thp hn (p ng tiu
chun mi trng) v ci thin cht lng, chn lc sn phm.
Sn phm phn ng

React ng ng
Kh x sau hon nguyn

Thit b hon nguyn

xc tc 2 giai on

Khng kh s cp
Nguyn liu v
pha phn tn

Khng kh th cp
Khng kh th cp

Pha phn tn

Hnh 4.4. S cng ngh RCC.

157

Vo cui nhng nm 1980, do kh khn v ngun du th, cc nh lc du bt u

quan tm n vic ch bin ngun du nng, c bit l du cn t chng ct p sut kh
quyn. ch bin hiu qu du cn cha nhiu tp cht, 2 hng UOP v Ashland Oil
hp tc vi nhau trin khai mt cng ngh cracking xc tc cho nhiu dng nguyn liu
khc nhau. Nm 1983, cng ngh ch bin du th nng RCC c p dng quy m cng
nghip. T v sau, vic x l du cn dn dn pht trin, hn mt na cc nh my mi
u c xy dng theo cng ngh x l du cn hoc du cha nhiu hp phn nng. Hnh
4.4 gii thiu mt m hnh h thng RCC c thit k nm 1983.
Trong s c nhiu ci tin so vi cng ngh FCC thng thng, c bit l s
ci tin v thit b hon nguyn hai giai on nhm t chy tt hn lng cc nhiu hn t
nguyn liu du cn. Thit b hon nguyn xc tc ny khng ch tt hn s cn bng nhit
ca qu trnh, bi v mt giai on hot ng trong ch chy hon ton, v mt giai on
khc trong ch chy khng hon ton. B phn lm ngui cht xc tc cng l mt ci
tin ca cng ngh RCC. N khng nhng gp phn vo vic khng ch nhit hon
nguyn m cn duy tr s tun hon cht xc tc trong iu kin phn ng khc nghit.
Nhn chung, trong 4 - 5 thp k va qua cng ngh cracking xc tc lun c ci tin
v hon thin.Do thc trng ngy cng kh khn v ngun nguyn liu, do nhu cu sn
phm v yu cu nghim ngt v bo v mi trng m cng ngh cracking xc tc ang
c pht trin theo ba hng sau y:
- C kh nng ch bin cc ngun nguyn liu a dng.
- Quan tm c bit n cng ngh ch bin du nng.
- Cracking su to ra ngun olefin cho sn xut vt liu Polyme.
Do trong chng ny chng ti gii thiu mt s cng ngh i din cho ba xu
hng .
4.2. Cng ngh FCC ca UOP
4.2.1.Gii thiu cng ngh FCC ca UOP
Mt h thng FCC ca UOP bao gm cc b phn ch yu sau y: Cm thit b phn
ng (reactor) v hon nguyn xc tc (regenerator); thp chng ct chnh v phn xng kh
(hnh 4.5).
Tu thuc vo mc ch ca nh lc du, c th mt phn du nng c hon lu tr
li react to ra hiu sut sn phm mong mun.
chuyn ho c nh ngha l: 100% - % th tch lng ca cc sn phm nng
hn gasolin.
Ni chung chuyn ho khng bao gi t n 100%. Mt s sn phm y thp
chng ct c gi l du lng gn (clarified oil) hoc du st (slurry oil) thng c s

158

dng trong vic pha ch du t. LCO thng c dng lm du t cho gia nh, mt
phn khc dng cho ngun nhin liu diesel.
Phn xng kh
n h x l kh x
React
Ti sinh

Thp chng
ct chnh

Kh t
(kh nhin liu)
C3 - C 4
Xng loi butan

Naphta
LCO
HCO
Sn phm y
thp chng ct chnh

Khng kh

Nguyn liu mi

Hnh 4.5. S chung ca h thng FCC ca UOP.

Mt h thng FCC hin i bao gi cng gn lin vi mt h thng x l kh x (kh
sau thit b hon nguyn). Kh x cha nhiu nhit d, bi-xc tc, nit, oxyt cacbon (CO,
CO2), oxyt sulfua, oxyt nit v hi nc.
Sau thit b hon nguyn kh cn c nhit 700 780oC, p sut: 0,7 2,8 atm.
Nhit ca kh c th c s dng trong sn xut hi nc chy tuabin pht in. CO
c t chy thnh CO2 l t CO. Bi xc tc c loi b bng my lc bi tnh in.
Cm thit b phn ng Cracking- Hon nguyn xc tc
Qu tim ca cng ngh FCC l cm thit b phn ng v hon nguyn xc tc
(React-Regenerat, hnh 4.6).
Trong khi vn hnh, nguyn liu ban u v mt phn du nng hon lu (tu thuc
vo mc tiu sn phm) c a vo ng phn ng riser cng vi mt lng nht nh cht
xc tc hon nguyn. Nguyn liu c th c gia nhit bng cch trao i nhit hoc
bng l t nhin liu. Cht xc tc sau khi hon nguyn c nhit cao lm bay hi
nguyn liu. Hi hydrocacbon mang theo cht xc tc di chuyn trong ng phn ng t di
ln trn. nh ng riser cc phn ng cracking cn thit c thc hin, cht xc tc li
nhanh chng c tch ra khi hi hydrocacbon hn ch cc phn ng cracking th cp.
Hn hp cht xc tc, hydrocacnbon di chuyn ra phn bn ngoi ca react,i qua mt b
phn tch hydrocacbon khi cht xc tc. S phn tch cht xc tc v sn phm cracking
trng thi hi c thc hin bc cui cng bi h xyclon.
159

Kh thot ra t react cracking

React
Kh x t thit b
hon nguyn
React kiu
ng ng

Thit b hon nguyn

Tch hydrocacbon
khi cht xc tc

Bung t kiu ng ng

B phn lm ngui
cht xc tc

ng dn cht xc tc
tham gia phn ng

Bung t

ng dn cht
xc tc ti sinh

ng dn cht
xc tc tun hon

Nguyn liu

ng dn cht
xc tc ngui

Khng kh
oxy ho cc

Kh y

Hnh 4.6. S thit b phn ng v hon nguyn xc tc ca cng ngh UOP.

Cc sn phm cracking c dn n thp chng ct chnh phn chia thnh kh
olefin nh, gasolin FCC v cc sn phm nng hn. Cht xc tc tham gia phn ng ri t
phn bao ngoi ca react vo b phn stripp (stripper, tch kh hydrocacbon khi cht xc
tc bng hi nc), mt dng hi nc ngc chiu tch b phn hydrocacbon cn hp
ph trn b mt cht xc tc. Sau , cht xc tc c chuyn n thit b hon nguyn.
Trong qu trnh cracking, cc hnh thnh, v tch t trn b mt cht xc tc ri c t

160

chy trong thit b hon nguyn. Nhim v chnh ca thit b hon nguyn l hot ho cht
xc tc n c th tip tc xc tc cho phn ng cracking khi tr v react. Regenerat t
chy cc to ra cc sn phm kh ng thi ng vai tr cung cp nhit cho react cracking
(vn cn bng nhit s c trnh by phn sau).
Tu thuc vo iu kin c th, thit b hon nguyn c th hot ng theo ch oxy
ho hon ton cacbon thnh CO2 hoc oxy ho khng hon ton, hoc chuyn ho CO thnh
CO2 bng mt l t CO bn ngoi regenerat. Nu t chy CO thnh CO2 bn trong
regenerat th nhit ca kh x c cung cp cho l hi. Kh x sau regenerat i qua
xyclon gim lng cht xc tc b cun theo trc khi b thi ra mi trng.
duy tr hot tnh cht xc tc mc cn thit v b li lng cht xc tc b
mt trong h thng kh x, mt lng cht xc tc mi c b sung vo h thng cung cp
cht xc tc. Ngoi ngn ng cht xc tc mi, cn c mt ngn khc ly ra cht xc
tc hot ng nhm m bo hot tnh xc tc cn thit cho phn ng cracking v tho
ton b cht xc tc khi h thng ngng hot ng sa cha, bo dng v.v...
S cn bng nhit
S cn bng nhit trong cng ngh FCC c m t nh trn hnh 4.7

Kh x

Ti sinh

Xc tc s dng
QSC

React
QP

QFG

QL2
Tn tht
QL1
nhit

QRG

QRX

Nhit t
chy cc

Nhit phn ng

QRC
QA

QFD

Xc tc ti sinh

Sn phm
Tn tht nhit

Hi lu
Nguyn liu mi

Khng kh cho ti sinh

Gia nhit s b

Hnh 4.7. S cn bng nhit ca t hp FCC.

Ging nh mi qu trnh cng ngh khc, h thng FCC v c bn l on nhit. Biu
thc cn bng nhit tng qut c th c vit nh sau:
QRG = (QP QFD) + (QFG QA) + QRX + (Q L 1 + Q L 2 )

(4.1)

161

trong :
QRG : nhit thot ra do t chy cc;
QP QFD: bin thin entanpy gia sn phm v nguyn liu;
QFG QA: bin thin entanpy gia kh x v khng kh a vo hon nguyn;
QRX: nhit phn ng;
Q L 1 + Q L 2 : cc tn tht nhit.
Biu thc (4.1) l s n gin ho m t cc thnh phn nhit tham gia trong h
react-regenerat. Nhit lng to ra do qa trnh t chy cc m bo cho cc nhu cu
nhit ca react v regenerat. Nhit cn tiu tn :
- Nng nhit ca nguyn liu n nhit phn ng;
- Ho hi nguyn liu;
- Cung cp cho cc phn ng thu nhit cho cc yu cu nhit ca cc b phn ph tr
v cho tn tht;
- Nng nhit khng kh n nhit ca kh x v cc tn tht nhit ca
regenerat;
S lun chuyn ca cht xc tc chnh l c ch vn chuyn nhit lng t regenerat
n react. Nh vy ton b nhit lng cung cp cho react l do bin thin entanpy gia
cht xc tc hon nguyn v phn ng (QRC QSC).
Do , tc lun chuyn cht xc tc l mt tham s vn hnh quan trng v quyt
nh, v n khng ch cung cp nhit m cn tc ng n chuyn ho thng qua nng
ca cht xc tc v nng nguyn liu (thng c biu din di thut ng t s cht
xc tc/du). Trong thc t, t s khng phi l mt tham s c khng ch trc tip: s
thay i t s cht xc tc/du l h qu ca cc thay i ca cc tham s vn hnh khc. V
d, tng t s cht xc tc/du l do s gia tng nhit ca react, do s gim nhit
trong regenerat hoc do s tng nhit ban u ca nguyn liu. Cc iu kin qu trnh
thay i lm cho t s cht xc tc/du tng th chuyn ho ca qu trnh cracking xc
tc cng tng theo.

Thit b chng ct chnh

Sn phm cracking dng hi c dn vo thit b chng ct chnh phn ring
thnh cc hp phn. Ti gasolin v cc sn phm nh giu olefin v mt s sn phm nh
khc c tch ra t nh thp v dn n phn xng kh. LCO c x l tch ring cc
sn phm nh v phn cn li c lu gi kho. Cc sn phm y thp l du st hoc
du lng gn. V hiu qu phn tch hydrocacbon v cht xc tc rt cao i vi cc h
thng FCC hin i ca UOP nn lng cht xc tc b cun theo n thp chng ct phn
on l rt nh. Cc sn phm nng cn li y thp thc ra khng cn phi lng gn, tr

162

phi cn phi s dng trong cc cng ngh c bit, v d nh, sn xut mui than,
ngi ta yu cu hm lng cht rn rt thp. Trong mt s trng hp, sn phm nng y
thp c hon lu a v react cracking.
Ti thp chng ct chnh ngi ta rt quan tm n vic tn dng cc ngun nhit c
th c. V d: LCO v HCO c s dng trong phn xng kh vi mc ch trao i nhit,
v dng sn phm y thp c tun hon trao i nhit sn xut hi nc.

Phn xng kh
Phn xng kh l mt tp hp cc thp hp th v chng ct phn on phn ring
cc sn phm nh thp ca thit b chng ct chnh thnh gasolin v cc sn phm nh
khc. i khi cc kh olefin t cc cng on khc, cng c chuyn n phn xng kh
ca h thng FCC.
Mt phn xng kh in hnh gm 4 thp nh hnh 4-8.

Kh nhin liu
Thp hp th s cp
Bnh cha
p sut cao

Kh nh
thp chnh

n bnh cha
ca thp chnh

Thp hp
th th cp
thp tch C4

Thp tch

LCO n v i t
h thng FCC

Gasolin c cht
lng n nh
kh C4

gasolin c cht lng cha

n nh n t bnh cha
sn phm nh thp chnh

Hnh 4.8. S mt phn xng kh FCC.

Kh t bnh cha sn phm nh thp chnh c nn v a vo bnh cha p sut cao

cng vi sn phm y ca thp hp th s cp v kh nh thp tch (stripper). Kh t bnh
cha p sut cao c dn n thp hp th s cp, ti kh tip xc vi gasolin cha
n nh n t bnh cha ca thp chnh. Kt qu ca s tip xc l phn ring cc

phn on C3+ v C2 trong phn kh n thp hp th s cp. Kh thot ra t thp hp th

s cp c a vo thp hp th th cp hoc thp hp th "vt liu bt", ti dng LCO
tun hon hp th hu ht cc sn phm C5+ ca dng nguyn liu n thp hp th th cp.
163

Mt s sn phm C3 v C4 cng b hp th. Du thu c sau thp hp th th cp c quay

v thp chng ct chnh. Sn phm nh thp hp th th cp l C3+ v kh H2S, c chuyn
n b phn kh nhin liu hoc b phn ch bin khc.
Sn phm lng t bnh cha p sut cao c dn n thp tch, ti hu ht cc C2

c tch ra nh thp v chuyn tr v bnh cha (bnh tch) p sut cao. Sn phm lng
y thp tch c a n thp kh C4, ti sn phm olefin C3 - C4 c tch ra nh
thp c dn n b phn akylho hoc ngng t xc tc sn xut gasolin. Sn phm
y thp kh C4 l gasolin c cht lng n nh, c chuyn n b phn x l tip theo
(nu cn) hoc n kho lu tr.
Trn y l s ti thiu ca mt phn xng kh. i khi trong phn xng ny
cn c thm thp tch gasolin, phn chia gasolin thnh phn on nh v nng. Kh H2S
trong kh nhin liu hoc trong sn phm C3 - C4 c th c loi b bng hp th trong mt
h cha amin. Do phn xng kh c th gm 6 hoc 7 thp x l.
4.2.2. Phn tch cc u im ca h thng FCC-UOP hin i

Mt h thng FCC hin i phn nh s kt hp ti u nht cc c im c kh v

cng ngh qu trnh.
C s l thuyt v lu th ho, dng lu th, truyn nhit, chuyn khi, ng hc,
nhit ng hc phn ng v cc vn xc tc khc c p dng v c kt hp vi kinh
nghim thc tin v thit k c kh to ra mt t hp FCC cc k n nh hp l v a
nng.

React
u im ca h phn ng l thi gian tip xc ngn nn c trng cho mt thit k
react hin i (hnh 4.6). Reat ny rt thch hp cho cht xc tc zeolit c hot tnh v
chn lc rt cao. S tip xc gia cht xc tc v nguyn liu c m bo kh hon ho
do ch thu ng hc ca lu th. Sn phm phn ng v cht xc tc c tch ra nhanh
chng trc khi a vo h hon nguyn. Phn ng cracking hon ton trong ng ng
(riser) to ra hiu sut cao cho gasolin v olefin nh C3 - C4. Nhit phn ng cao cng

c p dng tng gi tr octan ca gasolin v hiu sut olefin nh cho alkyl ho v ete
ho v sau.
Nhng ci tin v reat khng ch c thc hin trong cc nh my lc du mi thit
k. Ngay c trong rt nhiu phn xng FCC c, mt hoc nhiu khu quan trng trong dy
chuyn cng ngh cng c ci tin nh: tng cng kh nng tip xc gia cht xc tc nguyn liu phn cui ca riser, hoc b phn lm sch (tch hydrocacbon) cht xc tc.
ng react, ng dn cht xc tc v cc van iu chnh c thay th khi cc nh my c
cn nng cao cng sut hot ng ca mnh.
164

 Thit b hon nguyn (regenerator)

Cng ngh FCC hin i ca UOP c mt h hon nguyn rt hiu qu, thng c
gi l h hon nguyn oxy ho hon ton (combustor-regenerator). H combustorregenerator c kh nng phn b ng u khng kh v cc, v ci thin ng k ch
chy hon ton ca cc. Trong regenerator c hai vng t chy: vng t lp tng si n
nh ca cht xc tc cn t cc, v vng t trong ng ng (combustor riser) c trao i
nhit v tc chuyn vn cao ca cht xc tc. S kt hp hai ch t chy cc m
bo hiu sut bo ton cht xc tc kh cao v nhit nh nhau ca kh x v cht xc tc
hon nguyn. Nh ci thin hiu qu thit b hon nguyn m lng cht xc tc b mt
gim ng k. iu khng nhng c ngha kinh t ln i vi s tiu hao cht xc tc
ton b m cn gim s hao ph lng cht xc tc hng ngy. M hnh thit b hon nguyn
kiu combust c trin khai trong nhng nm 1970. Trc , cc thit b hon nguyn
hot ng ch yu da trn ch chy cc khng hon ton. Mt phn cc, khong vi
chc phn trm, cn bm li trn cht xc tc hon nguyn. Kh x thot ra sau hon
nguyn cn cha mt lng CO v CO2 tng ng nhau. Ngi ta phi s dngl t CO
b sung gim mc tc hi ca CO p ng tiu chun mi trng v kh thi. Nhit
to ra do s t chy CO thnh CO2 cng c tc ng ng k n cn bng nhit ca t hp
FCC. Ch chy hon ton cn lm cho nhit ca thit b hon nguyn cao hn, v do
lng cht xc tc t regenerat n react cng t hn do nhit react tng v do s
chy hon ton hn nn lng cc bon lu li trn b mt cht xc tc gim xung. Lng
cacbon cn li cng thp th hot tnh xc tc cng cao. Nh vy, s chy hon ton ca cc
dn n gim tc tun hon ca cht xc tc nhng li lm tng hot tnh xc tc. V
lng cc cn thit cho cn bng nhit gim, hiu sut cc gim dn n s gia tng cc sn
phm FCC. h tr cho s chy ca CO, ngi ta thng cho mt lng nh cc kim loi
qu vo cht xc tc FCC. Cc cht tr xc tc c s dng rng ri ch to cc
cht xc tc cho nhiu nh my lc du c, xem nh l mt bin php trung gian lm cho c
ch chy cc hon ton hn. Trong cc nh my mi vi thit b hon nguyn kiu
combust, cc c oxy ho trong ch chy hon ton khng cn phi s dng cht tr
xc tc t tin (kim loi qu Pt).
Thit b hon nguyn - oxy ho hon ton (regenerator-combustor) chng t s u
vit ca n tri qua thi gian lm vic lu di. N th hin l mt thit b rt hiu qu t
chy cacbon v to ra mt lng CO rt nh. Cho d mt nh my nh hay ln, ngi ta u
phi quan tm hng ngy n cht lng kh x sau hon nguyn v cht xc tc hon
nguyn.

S a dng v hiu sut sn phm

Mt trong cc th mnh ca cng ngh FCC l kh nng a dng cc hiu sut sn
phm mong mun da trn c s iu chnh cc tham s vn hnh. Mc d hu ht cc nh
165

my c thit k sn sut ra gasolin, nhng UOP thit k cc c s cracking theo mt

trong ba m hnh hot ng chnh sau y:
- Phng n sn phm gasolin: phng n hot ng ph bin nht ca mt h thng
FCC l sn xut ti a sn phm gasolin. Phng n ny c thc hin trong cc iu kin
thch hp sao cho hiu sut gasolin cao nht li c tr s octan ca gasolin tt nht.

iu kin phn ng phi c khng ch mt cch nghim ngt chuyn ho phn

ln nguyn liu, nhng khng nh hng xu n cht lng gasolin to ra. Yu cu
thng t c bng cch s dng cc cht xc tc rt hot ng v chn lc, v nhit
phn ng cao to ra gi tr octan mong mun. Tc lu chuyn cht xc tc cng
c khng ch thch hp thi gian tip xc ngn.
Trong iu kin phn ng nghim ngt nh th, vic hon lu cc sn phm cracking
ni chung l khng cn thit.
- Phng n LPG

Nu thc hin phn ng trong iu kin khc nghit hn, th s to ra nhiu olefin nh
v gi tr octan ca gasolin cao hn. Do phng n sn phm ny c gi l phng n
LPG (liquefied petroleum gas) hay l phng n iu kin khc nghit cao (hoc i khi cn
gi l phng n FCC ho du). Bi v phng n ny gia tng lng cc sn phm nh v
tng aromat trong gasolin.
Nu isobutan c akyl ho vi olefin nh hoc nu cc olefin c ete ha v
polyme ha thnh cc sn phm c nhit si ca gasolin, th hiu sut tng cng ca
gasolin v gi tr octan nhn c l kh cao.
- Phng n sn phm chng ct

Nu mt t hp FCC khng th vn hnh trong iu kin phn ng khc nghit th

ngi ta c th sn xut theo phng n cc sn phm chng ct. Thay i cc iu kin vn
hnh c th chuyn dch t s phn b sn phm gasolin bnh thng n mt phn b v
lng gasolin xp x vi lng LCO v HCO. thc hin phng n , ngi ta gim
nhit si cui ca gasolin chuyn mt phn sn phm vo phn du LCO.
Gii hn s iu chnh c quyt nh bi im chp chy ca phn du CO
(cycle oil)
S phn b in hnh cho ba phng n c dn ra trong bng 4.1.
Ngun nguyn liu cho ba phng n sn phm trn l gas oil chn khng Trung
ng. Cc hiu sut sn phm c trng cho mt ngun nguyn liu c th. Ni chung,
s phn b hiu sut sn phm FCC lun ph thuc vo tnh cht ca nguyn liu. V d:
nguyn liu vi tha s KUOP thp hn, hm lng hydro thp hn th kh cracking hn v
c s phn b sn phm hn ch hn.

166

Bng 4.1. S phn b cc sn phm v tnh cht sn phm

Phng n cc sn phm chng
ct

Phng n
Gasolin

Phng n
olefin nh

Gasolin ti a

Gasolin ti thiu

Hiu sut sn phm

H2S (%kl)

0,7

0,7

1,0

1,0

C2 (%kl)

2,6

2,6

3,2

4,7

C3 (%LV)
C4 (%LV)
Gasolin C+5 (%LV)

6,9
9,8
43,4
37,5
7,6
4,9

6,9
9,8
33,3
47,6
7,6
4,9

10,7
15,4
60,0
13,9
9,2
5,0

16,1
20,5
55,2
10,1
70
6,4

3,4
1,6

3,2
1,8

3,6
2,1

132
270
91,3
79,3

193
380
93,2
80,4

193
380
94,8
82,1

354
670
97 (207)
3,7
2,9
34,3

354
670
55 (132)
2,4
2,4
31,8

316
600
97 (207)
3,1
3,4
24,3

316
600
97 (207)
3,2
3,7
20,6

10,9
5,1

10,9
5,1

9,0
6,0

10,1
6,8

LCO (%LV)
CO (%LV)
Cc (%kl)
Tnh cht sn phm

LPG(%LV)
C3=/C3 no
C4=/C4 no

3,4
1,6
Gasolin

ASTM im si 90% (oC)

ASTM im si 90% (oF)
RONC
MONC

193
380
90,5
78,8
LCO

ASTM im si 90% ( C)
ASTM im si 90% (oF)
im chp chy, oC (oF)
nht, cSt 50oC (100oF)
Lu hunh (%kl)
Ch s xetan
Du gn
nht, cSt 50oC (100oF)
Lu hunh (%kl)

Ghi ch:
ASTM: American Society for Testing and Material.
RONC: RON clear, gi tr RON trong php th ca xng khng ch.
MONC: MON clear, gi tr MON trong php th ca xng khng ch.
V/V: t l th tch /th tch (%).
Ngun s liu ly t: D.A.Lomas v cng s, Controlled catalytic cracking, UOP 1990
Technology conference.

167

Cc s liu trong bng 4.1 ch ra mt vi nhn xt:

Khi khc nghit cracking tng t thp n cao th cc v cc sn phm nh tng,
octan ca gasolin tng v ni chung sn phm lng cng ngho hydro hn. Nh vy, khc
nghit phn ng cao dn n cracking su mt lng gasolin thnh cc sn phm C3 - C4.
4.2.3. Kh nng ch bin cc ngun nguyn liu a dng

Cc h thng FCC trc y c thit k ch bin gas oil chn khng (VGO).
l mt ngun nguyn liu c tha s KUOP bng 12 hoc ln hn, nn d cracking. Gia
nhng nm 1990 rt nhiu nh lc du phi ch bin cc ngun nguyn liu ti hn. Thc
vy, cc nh lc du ngy cng mun ch bin nhiu hn phn du khng chng ct c
tng cng kh nng cnh tranh ca mnh.
Trong phn ny chng ta xt hai vn quan trng: hydro-x l (hydro treating) cc
nguyn liu cho FCC nhm ci thin hiu sut sn phm v gim thiu nhim mi trng;
v cracking cc du cn, du c tch chit bng cc dung mi khc nhau.
Hydro-x l cc nguyn liu FCC
Bng 4.2. Hydro-x l nguyn liu FCC
Nguyn liu ban u Kh lu hunh va phi
Mt ,oAPI
Tha s KUOP
o

Hydro-x l va phi

18,4 (0,944)

22,3 (0,920)

26,3 (0,897)

11,28

11,48

11,67

275 (527)

266 (510)

249 (481)

410 (770)
498 (928)
1,30

399 (750)
497 (926)
0,21

375 (707)
467 (873)
0,04

0,43
11,42

0,32
12,07

0,05
12,74

66,1
46,0
6,1

82,5
55,6
5,6

Chng ct D-1160, C ( F)
5%
50%
95%
Lu hunh, %kl
Nit, %kl
Hydro, %kl

Hiu qu cracking trong iu kin pilot nh sau:

chuyn ho, %LV
Gasolin, %LV
Cc, %LV

59,0
41,1
8,8

V nguyn liu FCC c th cha cc hp cht lu hunh, nn cc sn phm FCC k c

kh x sau thit b hon nguyn u cha lu hunh di cc dng khc nhau. Do , ngi
ta phi xy dng nhiu h x l kh x hoc phi ch to cht xc tc c bit hoc phi
hydro-x l nguyn liu gim thiu mc pht thi lu hunh. Trong cc bin php ,
ch hydro-x l l hu hiu hn c v vi s c mt ca hydro kh nng cracking ca nhiu

168

loi nguyn liu c th gia tng. Bin php thc s c gi tr khi nguyn liu ban u c
cht lng km hoc nhiu tp cht. Bng 4-2 dn ra cc kt qu v hydro-x l mt nguyn
liu cht lng thp hai ch H2 khc nhau.
Khi cht lng nguyn liu ban u cng xu v vn x l lu hunh cn c quan
tm th b phn hydro-x l s ng vai tr ngy cng quan trng hn.
Cracking cc nguyn liu c nhit si cao
Khi cc nh lc du tm cch m rng khong cht lng ca nguyn liu cracking th
ngi ta thng gp nhng dng nguyn liu nng nh sau:
- Phn on chng ct su thp chng ct chn khng.
- Cc du chit bng dung mi ca sn phm nh thp chn khng.
- Du cn chng ct kh quyn.
Bt c xut pht t dng nguyn liu no ni trn, ngi ta phi gii quyt nhng vn
c bn sau y: (tuy nhin vi mc khc nhau tu thuc vo tng dng nguyn liu c
th):
Lng cc tng: nguyn liu nng lun c nng tp cht cao, hm lng cacbon
Conradson cao. Cc tp cht ny to ra mt lng cc trn cht xc tc ln hn so vi
cracking nguyn liu bnh thng. Vic t chy cc i hi mt lng khng kh tng
cng cho thit b hon nguyn. Trong nhng h thng FCC thng thng, vic hon
nguyn dn n st gim nng sut thit b.
Cn phi hn ch tp cht kim loi
Kim loi trong nguyn liu nng hu nh u lng ng trn cht xc tc. Cc kim
loi to ra hai hiu ng quan trng.
(i) Xc tc cho cc phn ng dehydro ho,to ra nhiu kh nh (H2,..) v to thm mt
lng cc.
(ii) Kim loi u c cc tm hot tnh xc tc, dn n s suy gim hot tnh xc tc.
khc phc hiu ng ny ngi ta phi thay th dn dn cht xc tc (thm v ly bt cht
xc tc) trong qu trnh cracking.
Tp cht lu hunh v nit
Hm lng cc hp cht lu hunh v nit trong cc sn phm FCC, trong cht thi,
v trong kh x tng ln ng k khi ch bin nguyn liu c nhit si cao v tp cht lu
hunh v nit trong cc nguyn liu cao hn nhiu so vi nguyn liu thng thng. Tuy
nhin trong trng hp i vi nit, vn khng ch l nng cao ca hp cht nit trong
sn phm, m ch yu l do mt phn nit tn ti di dng hp cht nit baz, cc hp cht
ny s u c cc tm axit v do lm suy gim hot tnh ca cht xc tc.

169

 Vn cn bng nhit: khng ch cn bng nhit l vn u tin phi i ph v

l rc ri nht khi ch bin nguyn liu nng. V lng cc dng cacbon tp cht tng ln,
nn nhit ca thit b hon nguyn gia tng r rt.
Ngi ta c th iu chnh cc tham s vn hnh khng ch nhit ca thit b
hon nguyn xc tc. Song khi nhit t qu cao so vi nhit hot ng ca cht xc
tc th ngi ta phi b sung thm cc b phn tn nhit ph tr bn ngoi gim nhit
ca regenerator, chng hn nh, phi c b phn lm ngui cht xc tc (catalyst cooler).
Hin nay khong 25 h thng FCC ca UOP s dng ngun nguyn liu c nhit
si cao. Vy m cht lng sn phm ca cc h thng FCC khng khc g cht lng
ca sn phm c ch bin t cc gas oil thng thng. Ni chung gi tr octan ca gasolin
tt,cht lng cc du CO (cycle oil) cng tng t, cc phn du t nng c nht thp
v hm lng kim loa thp.
Du x l kim loi (demetallized oil)
Trong khong mt vi nm gn y,du x l kim loi (DMO, demetallized oil) l
mt hp phn chnh ca nguyn liu trong mt vi h thng FCC c thit k bi UOP.
Du DMO ny nhn c t s chit tch dng sn phm y thp ct chn khng
bng dung mi parafin nh. Qu trnh chit tch dung mi hin i to ra hiu sut DMO
cao hn so vi qu trnh tch asphalten bng propan c s dng trong nhiu nm v
nhiu ni sn xut nguyn liu cho FCC. Du DMO cn cha kh nhiu tp cht.
Ni chung, cc du DMO l ngun nguyn liu tt cho cracking, tuy nhin cc du
cn c hydro - x l tip tc gim mc tp cht kim loi v tng hm lng hydro
ca du.
Du cn chng ct kh quyn (atmopheric residue)
Nhiu nh lc du la chn du cn chng ct kh quyn lm nguyn liu b sung
cho cc h thng FCC c. S la chn xut pht t mun chuyn ho ht cc
phn nng nht ca du th. Du cn t chng ct kh quyn c b sung t mt lng
tng i nh vo ngun nguyn liu tng n thay th ton b. ci thin qu trnh ch
bin ngun nguyn liu c nhit si cao , mt s nh my c sa cha nng cp
cng ngh. Mt s nh my tin hnh b sung dn dn lng du cn nh bin i cc
iu kin vn hnh v k thut ch bin, v nh cn c vo cc kinh nghim tch ly c
trong qu trnh cracking du c nhit si cao.
Thc vy, hin nay trong cc nh my c thit k theo cng ngh cracking gas oil
thng thng, ngi ta tin hnh ch bin ngun nguyn liu c thnh phn bin i
trong mt khong kh rng. Bng 4.3 gii thiu mt cng thc pha ch nguyn liu gm bn
loi: t ngun du ngt, du chua n du nhiu tp cht thm ch c n 4% cacbon
conradson.
170

Bng 4.3. Nguyn liu cracking pha ch

Mt , API (t trng)
Tha s KUOP
Lu hunh, %kl.
Cn cacbon Conradson, %kl
Kim loi, ppm(kl)
Niken
Vanadi
Phnkhngchng ct c 65oC (1050oF), %LV

28,2
(0,886)
12,1
0,98
1,01

24,5
(0,907)
1l,75
1,58
1,25

26,4
(0,896)
12,1
0,35
2,47

22,4
(0,919)
11,95
0,77
3,95

0,2
0,8
10

1,6
2,3
8

0,7
0,5
13

2,8
3,5
23

Cng ngh RCC (cng ngh cracking xc tc du cn, residue catalytic cracking)
Khi ngun nguyn liu c nng tp cht cao c s dng ch bin th cc vn
nh ci to thit k v iu hnh ch nhit tr nn quan trng hng u. Mt vi v d
v cc kiu nguyn liu cho cng ngh RCC c nu ln trong bng 4.4.
Bng 4.4. Cc nguyn liu cho cng ngh RCC
A

21,3
(0,9260)
11,8

19,1
(0,9396)
11,7

21,2
(0,9267)
11,9

22,4
(0,9194)
12,2

Lu hunh, %kl
Nit, %kl
Cn cacbon Conradson, %kl

1,1
0,14

2,1

0,55
0,19
3,8

0,1
0,23
5,6

Cn cacbon Rambottom, %kl

Kim loi, ppm (kl)
Niken
Vanadi

5,0

5,5

13
31

15
45

2,5
3,7

Mt , API
Tha s KUOP

2,2
1

Theo bng 4.4 thy rng: cng ngh RCC c th ch bin c nhng ngun nguyn liu
rt kh x l, cha hm lng cacbon Conradson v kim loi tp cht kh cao. Trn b mt
cht xc tc cn bng c khi hm lng kim loi t n 10.000 ppm ca niken v vanadi,
i khi c th ln n 15.000 ppm.
4.2.4. Gi thnh cng ngh

Vn u t cho mt h thng cng ngh FCC c cng sut 35.000 thng du/ngy lm
vic (BPSD: barrels per stream day), hot ng trong ch cc 5,5%kl, nguyn liu mi,
c dn ra trong bng 4.5.
171

Bng 4.5. Vn u t
Thit b qu trnh gm

Gi thnh lp t c tnh*, triu USD

Reactor-regenerator, phn xng kh, h thng chng ct v

thit b lc bi tnh in
Cc thit b trn + h thng thu hi nng lng

103
114

* Gi chnh xc

40% .

Chi ph vn hnh v thu hi nng lng

Chi ph vn hnh ca h thng FCC c th gim ng k nh thc hin thu hi nng

lng. Cc nh lc du t lu bit tn dng ngun nng lng tim nng trong kh x.
Sau mt s nm nghin cu, mt h thng thu hi nng lng c trin khai chuyn
nhit nng ca kh x thnh c nng bng mt tuabin gim p (expander turbine). Nng
lng thu hi ph thuc vo gim p qua tuabin. Cng sut ca tuabin c th c tnh
ton theo phng trnh sau y (m lc: ml):
K 1

PE K
K

ml = 2,808(EGT)

K 1 P1

(4.2)

trong E: tha s hiu dng (0,8);

G: lu lng kh x (s mol ca mt pao kh x (pound = 0,454 kg) trong n v
thi gian, mol/s);
R: hng s kh;
T: nhit , oR;
K: tha s on nhit (1,313 i vi kh x);
PE: p sut kh sau tuabin;
PI: p sut vo tuabin.
Theo cc thit k hin nay, trong cc h thng FCC hin i, nng lng thu hi c
chuyn ho thnh in nng hoc d tha cung cp cho h thng vn chuyn khng
kh. Ngoi vn thu hi nng lng, h thng FCC c th c thit k sn xut ra mt
lng ln hi nc p sut cao (42 bar). Ngun hi nc ch yu c to ra t nhit trao
i ca cc sn phm y ca ct chng ct chnh v t ni hi tn dng nhit ca kh x
sau hon nguyn.
Chi ph vn hnh in hnh ca h thng FCC c v khng c thu hi nng lng c
trnh by trong bng 4.6. Cc s liu nhn c t h thng ch bin du VGO Trung ng
theo phng n sn phm gasolin vi phn xng kh c 5 thp x l, lc bi tnh in v
ni hi.

172

Bng 4.6. Chi ph vn hnh in hnh

Thu hi nng lng

Khng thu hi nng lng

300
12
14

1200
32
14

2,3
34
175

2,3
34
175

0,16

0,16

Thit b in, kWh/1000 thng

Hi nc:
42 bar
10,5 bar
3,2 bar
Nc x l
Nc lm lnh
Vt liu:
Cht xc tc
Gi tr dng:tiu th.
Gi th m: thu hi.

4.2.5. Tnh hnh th trng

FCC l mt trong nhng qu trnh c p dng rng ri nht trong cc nh my lc

du. Hn 450 h thng FCC c xy dng nhiu ni trn th gii k t khi cng ngh
ny c thng mi ho. Vo cui nm 1994, khong 350 h thng ang hot ng v
khong 20 h thng mi ang c thit k v xy dng. Cng sut hot ng ca cc c s
FCC c gii thiu trong bng 4.7.
Bng 4.7. Cng sut ca cc h thng FCC trn th gii
Cng sut du th,

Cracking xc tc

Triu BPCD

Triu BPCD*

Bc M

18,8

6,0

Chu v khu vc Thi Bnh Dng

14,4

2,1

Ty u

14,2

2,1

ng u v cc nc thuc Lin X (trc y)

12,9

0,7

Nam M v vng Caribe

5,8

1,0

Trung ng

5,3

0,3

Chu M

0,8

0,2

Tng cng

74,2

12,4

* BPCD: barrel/ngy (theo lch), ngun ti liu tham kho: Oil and Gas Journal, December 1994.

Ni chung, cng sut cc h thng FCC bng khong 1/3 cng sut du th ch bin,
v hu nh n tng ng vi phn th tch ca VGO trong du th. Cng sut c th cao
hn nu phn du cn chn khng c b sung vo nguyn liu cho FCC. Ngoi ra, mt s
nh lc du li mun bn trc tip VGO di dng sn phm nhin liu trong trng hp
ny cng sut ca FCC cn thp hn nhiu.
173

FCC r rng l mt qu trnh chuyn ha c u tin la chn trong hon cnh m

gasolin, hoc ng hn, sn phm chng ct trung bnh c chn l sn phm mong mun.
Trong bng 4.7, chng ta thy cng sut FCC cc vng Bc M l kh ln v
ngi ta cn sn phm chng ct trung bnh nhiu hn.
Ni chung hiu sut v tnh cht ca nhin liu tn la hoc diesel t hydrocracking l
tt hn so vi t FCC.
4.3. Qu trnh RFCC ca S&W IFP

Tp on cng nghip Stone&Webster (S&W) kt hp vi Vin Du m Php IFP

(Institut Franais de Ptrole) sng ch ra cng ngh cracking xc tc pha lu th RFCC
(residual fluid catalytic cracking) p dng c bit cho nguyn liu nng. H thng RFCC
c trin khai trong nhiu nm u ca thp k 1980 bi hng du m Total ti cc nh
my lc du Kansas, Oklahama,... V nhiu ni khc trn th gii (bng 4.8).
Bng 4.8. Cc h thng RFCC ca S&W-IFP xy dng
Nh my lc du

a im

Cng sut, BPSD

Hot ng t nm

A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
S
T
U
V
W

Kansas
Oklahoma
Canada
Nht Bn
Australia
Canada
Trung Quc
Trung Quc
Trung Quc
Trung Quc
Trung Quc
Nht Bn
Nht Bn
Uruguay
California
Singapore
Hn Quc
Hn Quc
Thi Lan
Malaysia
Thi Lan
n
n

20.000
25.000/40.000*
19.000
40.000
25.000
25.000
23.000
21.000
28.000
21.000
21.000
30.000
31.600
9.000
31.000
24.000
50.000
30.000
37.000
55.000
14.000
15.000
60.000

1981
1982
1985
1987
1987
1987
1987
1989
1990
1990
1991
1992
1994
1994

* Cng sut thit k 40.000 BPSD, ang hot ng 25.000 BPSD.barrel/ngy).

174

1995
1995
1995
1996

1997
1998

Nh ni phn 4.1, cc nh lc du ngy cng quan tm ch bin cc nguyn liu

nng. Do chng ti gii thiu qu trnh RFCC c gi Vit Nam quan tm tham kho.
4.3.1. Gii thiu qu trnh RFCC (S&W-IFP)

C hai m hnh c bn ca RFCC c gii thiu. M hnh th nht l ph bin nht

v c thit k theo cu hnh thit b hon nguyn ni tip (connected) nh trn hnh 4.9.
M hnh ny i hi din tch lp t nh. M hnh th hai theo cu hnh thit b hon
nguyn song song (side-by-side) c p dng i mi cc h FCC c thnh RFCC.
Trong hnh 4.9 gii thiu s cng ngh ca m hnh regenerator "ni tip trong h
RFCC.
H thng FCC gm react-ng ng (riser-reactor), b phn tch (lm sch) cht xc
tc (catalyst stripper), bung hon nguyn cht xc tc giai on 1, bung hon nguyn cht
xc tc giai on 2, v cc ng dn xc tc. S dy chuyn cng ngh hon nguyn theo
m hnh song song cng hon ton tng t nh m hnh ni tip", ch khc nhau v s lu
chuyn cht xc tc gia hai b phn hon nguyn cht xc tc giai on 1 v giai on 2.
Nguyn liu ban u c phn tn rt u v mn vi hi nc ri c phun vo ng
ng bng cc u phun nguyn liu. Cc ht nh nguyn liu tip xc vi cht xc tc
nng va mi hon nguyn v lp tc ho hi. Cc phn t du ho trn rt ng u vi cc
ht xc tc v b cracking thnh cc sn phm nh c gi tr hn.
Cc u phun khng ch nhit ca hn hp (cht xc tc v nguyn liu) bng cch
phun mt lng thch hp sn phm hon lu lm ngui cht xc tc v hi nguyn liu.
Nh cch , ngi ta c th khng ch c nhit trong vng phn ng gia cht xc
tc nguyn liu. Nhit u ra ca ng phn ng (ROT, riser outlet temperature) c
khng ch bng van iu tit cht xc tc sau khi hon nguyn.
Hn hp phn ng di chuyn ln pha trn ng phn ng, sau cht xc tc, hi nc
v hydrocacbon chuyn qua mt b phn cui ca ng phn ng (c gi l b phn
Ramshorn do S&W-IFP sng ch). B phn ny nhanh chng tch cht xc tc khi hi
nc v hi hydrocacbon. Hi c lm ngui nhanh bn trong ng thot kh ca Ramshorn
gim thiu cc phn ng phn hu nhit cc sn phm phn ng.
Cht xc tc v khng kh t chy cc i ngc chiu nhau trong khu vc hon
nguyn giai on 1. Khng kh chy c phn phi vo bung hon nguyn bng cc vng
cp khng kh. Khng kh phn tn u qua lp xc tc to ra mt "lp si" (tng si) v
phn ng chy cc. Cht xc tc c hon nguyn mt phn i ra khi bung hon nguyn
giai on 1 qua mt van phn pha y, van ny cn c nhim v gi n nh mc (lp)
cht xc tc trong bung hon nguyn, cht xc tc c chuyn n khu vc hon nguyn
giai on 2 trong mt ng dn bng khng kh phun qua cc l van. Kh chy i vo bung
hon nguyn giai on 2. iu kin chy trong bung hon nguyn giai on 1 khng khc
175

176

Thi

Hi nc

Du t

Kh t

T-101
Tuabin thi
khng kh

sung c bit

Hi nc b

BFW

Hi nc p sut cao

Khng kh

Vng loi kh
km cht lng

Khng kh
lm sch

Khng kh

Kh x sau hon nguyn giai on 2

(1) H thng lm ngui xc tc v ti sinh hi nc

ch s dung cho nguyn liu c CRC > 7%kl

NNF = Thng khng c dng

= S dng hi nc

Hi lu n nh

Hi lu b sung
phn tn

Nguyn liu

Th ng
ho kim loi

Hi lu MTC

Hi nc lm
sch xc tc

n kh x sau hon nguyn giai on 1

Kh x sau react

n van kh x sau hon nguyn giai on 1

Hnh 4.9. S cng ngh ca RFCC ca S&W-IFP theo m hnh ni tip

T-101
My thi
khng kh

Khng kh

Khng kh

Khng kh

Khng kh to
dng lu th

Khng kh

Van kh x sau hon

nguyn giai on 2

Hnh 4.9 ngang

177

ngui cht xc

tc (1)

hon nguyn

khng kh

V-105

xc tc).

on 1.

regenerator

cp ca

HC: van khng ch nhit.

PC: kim tra p sut;

LC: kim tra mc lu th;

PDC: kim tra chnh lch p sut;

FC: kim tra dng chy;

TC: kim tra nhit ;

Bung tho
vt liu (cht

B phn

regenerator giai

H xyclon th

V-104

on 1.

regenerator giai

cp cho

H xyclon s

CY-101

ngui cht
xc tc (1).

thit b lm

nc cp cho

cht xc tc (1)

V-101

2 giai on.

P-101
Bm tun hon

thit b lm ngui

bng nhit t

ngui hi nc

B phn lm

CY-104

giai on 2

E-101

Thit b lm

H-102

Thit b gia nhit

on 2.

regenerator giai

cpcho

H xyclon th

CY-102

on hai

nguyn giai

khng kh hon

Thit b gia nhit

H-101:

react.

H xyclon ca

CY-105

giai on 2.

regenerator

B phn

V-102

Hnh 4.9. S cng ngh ca RFCC ca S&W - IFP theo m hnh ni tip (tip theo)

CY-103

React

V-103

hai giai on

regenerator

cp ca

H xyclon s

nghit v ngi ta mun thc hin mt s t chy cc khng hon ton. Nhit thp bo
m duy tr b mt ring v tnh cht xc tc ca vt liu rn, phn cn li c t chy
bung hon nguyn giai on 2. Nh , h thng RFCC c kh nng ch bin a dng cc
nguyn liu khc nhau t du cn n du gas oil bnh thng. i vi nguyn liu nng,
70% lng cc c t chy trong bung hon nguyn giai on 1, trong khi , ch 50%
cc c t chy i vi gas oil. Hu nh ton b hydro ca cc c chy trong bung
hon nguyn giai on 1 nhit thp nn hn ch ti a s suy gim hot tnh xc tc
v tc ng thu nhit.
Trong bung hon nguyn giai on 2, phn cacbon cn li trn cht xc tc c t
chy hon ton trong iu kin d oxy, lm cho nhit cao hn bung hon nguyn giai
on 1. Vng phn phi khng kh ca bung hon nguyn th 2 cung cp mt phn khng
kh t chy cc, mt phn khc l khng kh c cp vo chuyn cht xc tc t
bung 1 ln bung 2. V hu ht hydro ca cc chy ht trong giai on 1 nn hm lng
m trong giai on 2 rt thp. Do , nhit hon nguyn giai on 2 cao hn m khng
gy ra s ph v cu trc tinh th ca zeolit do tc ng ca mi trng thu nhit (hi nc
nhit cao).
Bung hon nguyn giai on 2 c th tch ti thiu hn ch s gia tng nhit .
Kh x sau hon nguyn i qua ng ln nh ca react gn li vo xyclon, cht xc tc
b gt li qua ng gp (dipleg) ca b phn Ramshorn vo b phn lm sch cht xc tc
bng hi nc (steam stripper). Khong dch chuyn hn hp sau phn ng khng di, nn
thi gian lu ca hi hydrocacbon rt ngn, hn ch cc phn ng nhit khng mong mun
trong khng gian react. Sn phm phn ng, kh tr, hi nc v mt lng rt nh cht
xc tc cn li c dn n y thp chng ct chnh phn ring thnh cc sn phm
khc nhau.
Bn di cc ng gp cht xc tc (dipleg), hi nc c cp vo nhanh chng tch
b hydrocacbon bm vo cht xc tc. Nu khng x l nhanh nh th th hydrocacbon hp
ph c th polyme ho to thnh cc. Khng gian ca b phn tch (stripper) ny b ngn
ra thnh 4 bi cc tm chn. Hi nc t vng phn phi chnh lm cho lp xc tc linh
ng dng tng si, li cun cc hydrocacbon, tch b hydrocacbon bm vo cht xc tc
trc khi cht xc tc i vo thit b hon nguyn. Mt vng phn phi hi nc kh mn
c t y stripp (stripper) gi cho cht xc tc trng thi kh linh ng, v d
chy qua ng dn vo regenerat.
Cht xc tc c tch sch hydrocacbon chy vo mt on ng nghing 45o, vo mt
on ng thng ng, ri li vo mt on ng nghin 45o th 2, ni vi regenerat giai
on 1. Van iu chnh lng xc tc sau phn ng c t on cui ng nghing 45o v
khng ch lng xc tc trong stripper. Cc ng dn xc tc c cp kh (khng kh)
bo m dng cht xc tc chy u n. Tc dng kh c iu chnh duy tr mt
178

cht xc tc n nh trong cc ng phn ng khi thay i tc lun chuyn hoc thay i

cht xc tc. Cht xc tc i vo khu vc hon nguyn giai on mt qua h xyclon 2 cp
t bn ngoi bung hon nguyn. Cht xc tc c gi li ri quay v bung hon
nguyn, kh x c dn n cc b phn thu hi nhit,
Nu cn cacbon Conradson ln hn 7% th bung hon nguyn giai on 2 cn c s
h tr ca b phn lm ngui cht xc tc (nh trong hnh 4.9) lm gim nhit hon
nguyn xung di 760oC. Cht xc tc c a vo thit b lm ngui trng thi mt
cao, sau chuyn qua ng nng bng khng kh quay tr v hon nguyn. Nhit thu hi do
lm ngui cht xc tc dng to ra hi nc bo ho p sut cao. Nng lc lm ngui c
th thay i bng cch iu chnh tc lu chuyn cht xc tc qua thit b lm ngui.
Cht xc tc hon nguyn v cn nng t bung hon nguyn giai on 2 chy vo
mt thng cha xc tc. Thng ny iu chnh mt cht xc tc trc khi vo ng thng
ng (di thng cha). Thit k nh vy bo m s di chuyn u n, tun t ca cht
xc tc khi vo ng phn ng cracking. Cc mo kh (khng kh) c t cc v tr khc
nhau ca ng ng pha di thng cha bo m s cung cp khng kh theo cc ch
lu chuyn khc nhau ca cht xc tc hoc khi thay i chng loi cht xc tc. Cht xc
tc i qua van iu chnh, van ny khng ch nhit react bng cch iu chnh lng
cht xc tc. Sau , cht xc tc i qua mt on ng nghing 45o ni vi y ng phn
ng. y c cc mo phun hi nc n nh lm phn tn cht xc tc, trc khi n vng
phun nguyn liu. B phn pha di cc vi phun nguyn liu c nhim v n nh dng
cht xc tc v ngn khng cho nguyn liu chuyn ng ngc dng.
4.3.2. Cc vn cng ngh

Vn kh x
H thng kh x ca cng ngh RFCC hu nh khng hon ton nh nhau gia c s
ny vi c s khc, bi v cn ph thuc vo cc yu cu v tiu chun mi trng tng a
phng v vo cch la chn ca nh lc du. Mt v d v h thng kh x c trnh by
trn hnh 4.10. Mi mt ng dn kh x c mt van iu chnh v mt bung rng. Van
iu chnh kh ca bung hon nguyn giai on 1 (FGSV, flue gas slide valve) iu chnh
s chnh lch p sut gia hai bung hon nguyn, trong khi FGSV ca bung hon
nguyn giai on 2 khng ch trc tip p sut ca bung 2. Mi mt bung rng c nhim
v gim p ca h thng.
L t CO c t v tr ngay sau bung rng ca bung hon nguyn giai on
1, ti CO c oxyho thnh CO2 bng kh t v khng kh. Nhit ra xp x 980oC
vi 1% O2. Kh t l t CO kt hp vi kh x ca bung hon nguyn giai on 2 i vo
bung lm ngui. Nhit c thu hi y cung cp cho hi nc p sut cao. Cui cng
kh x c phn tn vo kh quyn qua ng khi nh my.

179

B phn khng
ch p sut
T b phn hon
nguyn giai on 2

n ng khi

V-108

n b phn sn
xut hi nc p
sut cao
V-106

B phn khng
ch p sut

P-102
V-107

T b phn hon
nguyn giai on 1
T b phn lm
ngui cht xc tc

E-102
H-103

Kh x

Nc cp cho ni hi

Hnh 4.10. S cng ngh qu trnh x l kh x

V-107: bung rng ca kh x hon nguyn giai on 1;
V-108: bung rng ca kh x hon nguyn giai on 2;
H-103: l t CO;
E-102: h lm lnh kh x;
V-106: thnglm lnh kh x bng hi nc;
P-102: bm tun hon ca h lm ngui kh x.

Cc h thng RFCC c cng sut ln c th s dng mt dy thit b thu hi nng

lng v h xyclon 3 cp trn ng dn kh x sau bung hon nguyn giai on 1 cung
cp cho cc my thi kh. Tu thuc vo tiu chun kh thi ca tng a phng, mt my
lc bi tnh in (ESP, electro static precipitator), hoc cc thit b thu hi bi kiu khc
nh h xyclon 3 cp, khi kh x cha nhiu SOx v NOx th ngi ta cn phi c thm cc
bin php khc nh thm cht ph tr xc tc gim SOx hoc cc qu trnh thu hi SOx
v/hoc kh chn lc xc tc (CSR) loi tr NOx.
H iu hnh cht xc tc
H iu hnh cht xc tc c ba chc nng ring bit:
- Lu gi v v tho b cht xc tc s dng.
- Lu gi cht xc tc mi v b sung.
- Lu gi cht xc tc cn bng v b sung.
Ngn ng cht xc tc s dng nhn trc tip cht xc tc nng t bung hon
nguyn giai on 2 nhm duy tr mt lng n nh cht xc tc trong qu trnh hot ng.
Ngoi ra ngn ng xc tc s dng cn c dng gim bt lng xc tc hoc lu
tr cht xc tc trong thi k sa cha hng hc.
180

Ngn ng cht xc tc mi l ni cp cht xc tc hng ngy. Lng xc tc mi

c b sung vo sao cho m bo hot tnh ti u ca cht xc tc.
i vi h thng RFCC cn c thm mt ngn th ba dnh cho cht xc tc cn bng.
Tng t nh ngn xc tc mi, ngn ng cht xc tc cn bng c nhim v d tr v
cung cp cht xc tc hng ngy. Cht xc tc cn bng khng ng gp nhiu cho vic gia
tng hot tnh xc tc m c nhim v thu gom kim loi khi x l cc ngun nguyn liu
nng c hm lng kim loi cao. Do , liu lng ca cht xc tc cn bng c thm vo
c xc nh da trn hm lng kim loi c php trn mt n v cht xc tc cn bng.
Cc t l cht xc tc mi b sung c cn c vo hot tnh xc tc cn phi duy tr cho
phn ng cracking.
Nguyn liu cho RFCC
u im ni bt nht ca h thng RFCC l kh nng ch bin a dng cc ngun
nguyn liu. Bng 4.9 dn ra mt s tnh cht ca ngun nguyn liu c ch bin thnh
cng bng h thng RFCC: S&W-IFP.

Nguyn liu cho RFCC c th c nhiu dng, t gas oil chn khng c hydro x
l (VGO) n cc sn phm y thp chng ct kh quyn giu aromat (ATB, aromatic
tower bottoms), v d nh ATB nh Arp. Nguyn liu cho RFCC cng c th l mt t hp
pha trn ca nhiu ngun nguyn liu khc nhau nh VGO kt hp vi gas oil chn khng
ca l cc, vi VTB (sn phm y thp chng ct chn khng,vacuum tower bottoms), vi
du tch asphalt (DAO, deasphalted oil), sp th hoc du chit. Trong thc t, c th c
rt nhiu dng, nhiu hp phn nguyn liu cho RFCC v khng th lit k ht c.
V sao RFCC li c th ch bin nhiu dng nguyn liu nh vy? l v RFCC c
h hon nguyn 2 giai on. Ch s c trng cho nguyn liu c kh nng to ra nhiu cc
l cn cacbon conradson (CCR, conradson carbon residue).
Bng 4.9. c trng c bn ca ngun nguyn liu cho RFCC
Tnh cht
o

Mt , API
Cn cacbon Conradson, %kl
Sunfua, %kl
Nit, %kl
Kim loi (Ni+V) ppm (kl)
Cc cu t si trn 540oC, %tt

Khong tham s
19 29
08
0,2 2,4
0,05 0,30
0 50
0 58

Khi hm lng cn trong nguyn liu tng th lng CCR cng tng. Bng 4,10 so
snh mc CCR cc i c th ch bin trong h thng c thit b hon nguyn 1 giai on v
2 giai on.

181

Bng 4.10. Kh nng ch bin nguyn liu nng

trong cc h thng c thit b hon nguyn khc nhau
H thng

Hm lng cacbon Conradson, %kl

Thit b hon nguyn 1 giai on

Chy hon ton

2,5

Chy khng hon ton

3,5

Chy khng hon ton + MTC

4,0

H lm ngui cht xc tc

Khng
Thit b hon nguyn 2 giai on

Khng c MTC

6,0

Vi MTC

7,0

H lm ngui cht xc tc

Khng

Ghi ch, MTC: h khng ch nhit hn hp (mix temperature control).

Gn y, nhu cu chuyn ho cc sn phm y ngy cng tng to ra nhin liu

sch cho vn ti (hm lng lu hunh thp) kt hp vi s suy gim ngun du ngt nn
ngi ta mi quan tm n cc qu trnh hydro desulfua ho v hydro desulfua ho du cn
tng ln. Ngi ta nhn thy rng l mt cng ngh kh thi nng cp cht lng VTB
bng cch s dng qu trnh hydro desulfua ho du cn chn khng (VRDS) cho nguyn
liu dng cho h thng RFCC kiu S&W-IFP. Ch bin 100% VTB trong h thng RFCC l
hiu qu hn so vi cc cng ngh truyn thng.
Cc iu kin vn hnh
Cng nh cc h thng FCC truyn thng, cng ngh RFCC S&W-IFP c th hot
ng theo cc ch khc nhau: sn phm chng cht cc i, gasolin cc i hoc olefin
cc i. chuyn ho gim trong ch sn phm chng ct cc i v tng trong ch
olefin cc i c iu chnh bng cch khng ch nhit u ra ca ng phn ng
(ROT, riser outlet temperature) v hot tnh cht xc tc, khong lm vic in hnh i vi
3 ch ni trn l: sn phm chng ct cc i, 510oC ROT ti thiu; gasolin cc i, 510
530oC ROT; v olefin cc i 530 550oC ROT, i vi ch sn phm chng ct cc
i, s khng ch nhit hn hp ( MTC, Mix temprature control) l quan trng duy tr
nhit i hi cho s ho hi nguyn liu cn khi ROT thp hn. Tng t, cng ngh lm
ngui hi cht phn ng l mt khu quan trng trong ch olefin cc i nhm gim
cracking nhit khi nhit react cao. Cc iu kin vn hnh in hnh khc ca RFCC
c nu ra trong bng 4,11. Cc v d v hiu sut sn phm ca RFCC S&W - IFP c
dn ra t bng 4.12.
182

Bng 4.11. Cc iu kin vn hnh in hnh ca RFCC

React
p sut, kg/ cm
Nhit , oC

1,1 2,1
510 550
10 25
3,0 7,0
3,0 5,0

MTC hi lu, % th tch nguyn liu

Hi nc phn tn vo nguyn liu, %kl nguyn liu
Hi nc tch sch, kg / 100 kg xc tc
Hi nc dng mixel %kl nguyn liu

1,5

Hon nguyn xc tc giai on mt

p sut, kg/cm
Nhit , oC

1,4 2,5 *
620 690

CO/CO2

0,3 1,0

O2, % th tch

0,2
50 70

Cc chy, %kl
Hon nguyn xc tc giai on hai
p sut, kg/cm2
Nhit , oC
O2, % th tch

0,7 1,4
675 760
2,0
30 50

Cc chy, %kl

* p sut ca bung hon nguyn giai on 2 phn nh cu to thit b hon nguyn ni

tip. i vi thit b hon nguyn song song, p sut trong giai on 2 tng t nh p sut
trong giai on 1.

Bng 4.12. Hiu sut sn phm RFCC

n v (nm)
Tnh cht nguyn liu
540oC +
Cc cu t, LV %
CRC, %kl
Mt , oAPI
Hiu sut
Kh kh, %kl
C3 - C4, LV%
Gasolin, LV%
LCO, LV%
Du st, LV%
Cc, %kl
chuyn ho, LV%

A (1987)

B (1993)

36

58

5,9
22,3

4,9
25,1

4,3
24,9
60,2
17,5
6,6
7,8

3,2
30,5
61,5
14,0
4,9
8,0

75,9

81,1

183

 Cht xc tc cho RFCC

Chng loi xc tc

S hot ng bnh thng ca RFCC ph thuc khng ch vo thit k c kh ca thit

b chuyn ho m cn ph thuc vo s la chn cht xc tc. x l nguyn liu RFCC
c lng cn ti a, cn la chn mt cht xc tc c hm lng cc delta thp.
Cc delta c nh ngha nh sau:
Cc delta = %kl cacbon trn cht xc tc phn ng - %kl CRC
y CRC: cacbon trn cht xc tc hon nguyn, hoc c nh ngha:

Cc delta =

% nguyn liu to cc
t s cht xc tc/nguyn liu

Cc delta l mt ch s rt ph cp, khi cc delta tng c th dn n s gia tng ng

k nhit ca thit b hon nguyn.
Khi ch bin nguyn liu cn, cc to ra t ngun nguyn liu ng gp phn ch yu
cho cc delta. gim bt dng cc delta trong vn hnh h thng RFCC, S&W-IFP, ngi
ta khuyn co nn la chon cht xc tc sau y:
- Zeolit Y siu bn (USY) c hm lng t him thp.
- Hot tnh xc tc cn bng theo MAT: 60 65.
- Pha nn c cc delta thp.
Khi hm lng kim loi cao (trong nguyn liu), ngi vn hnh c th xem xt kh
nng s dng cht xc tc c tc nhn by vanadi.
B sung cht xc tc

Cc nguyn liu cn thng cha nhiu kim loi. Trong qu trnh cracking, cc kim
loi u lng ng ln b mt cht xc tc.V ch hon nguyn 2 giai on khng khc
nghit nn hm lng kim loi ca cht xc tc c th t c 10.000 ppm (kl) i vi
(Ni+V) m hiu sut sn phm cha thy b nh hng ng k. i vi ch RFCC, vic
b sung cht xc tc da trn c s duy tr n nh hot tnh v lng kim loi trn cht xc
tc. Bin php hiu qu nht duy tr mc hot tnh vi hm lng kim loi cho php l b
sung c cht xc tc mi v cht xc tc lm vic lu (t cn bng). Cht xc tc cn
bng l tc nhn phn tn kim loi rt hiu qu, tuy nhin, n khng nh hng g n
hot tnh xc tc cracking. Do , cht xc tc cn bng c b sung vo cht xc tc mi
khng ch rt nhy v hiu qu hot tnh ring v hm lng kim loi trn mt n v
cht xc tc.
Ch hon nguyn 2 giai on

Trong ch hon nguyn 2 giai on ca cng ngh RFCC, cht xc tc c hon

nguyn trong 2 giai on: 50 70% trong giai on 1 v t cn bng trong giai on 2.
184

S hon nguyn cht xc tc trong giai on 1 c thc hin trong mi trng thiu
oxy to ra mt lng CO ng k. V nhit chy ca cacbon thnh CO nh hn 1/3 nhit
chy thnh CO2 nn nhit chuyn vo cht xc tc t hn rt nhiu so vi ch hon
nguyn chy hon ton 1 giai on. V d, mt h thng RFCC nng sut 30.000 thng
du/ngy hot ng (BPSD barels per stream day: thng du/ngy hot ng) vi nguyn
liu c 22,5oAPI v hiu sut cc l 7,5%kl vi 60% cc c t chy trong giai on 1
lm gim bt mt lng nhit truyn cho cht xc tc khong 25.106 kcal/h so vi hon
nguyn t chy hon ton mt giai on.
Phn cacbon cn li c t chy giai on 2 trong ch chy hon ton. V
nhit cao nn cc xyclon c thit k bn ngoi gim thiu th tch ca bung hon
nguyn v c th s dng thp - cacbon.
So snh s hon nguyn 2 giai on v hon nguyn n-mt giai on c b

phn lm ngui cht xc tc

Nguyn l lm vic ca hai h trn l khc nhau. u im ca h hon nguyn 2 giai

on c th hin r khi ch bin cc nguyn liu nng v hm lng kim loi cao.
Sau y l mt vi so snh gia hai h hon nguyn ni trn.
- Nhit ca h xc tc thp hn.
Vi h hon nguyn mt giai on, nhit to ra trong thit b hon nguyn c tch
ra bng b phn lm ngui cht xc tc, trong khi vi h hon nguyn 2 giai on, nhit
to ra t hn. V th, nhit ca cc ht xc tc khng cao v do s suy gim hot tnh
ca ht xc tc cng c hn ch. V s chy cc xy ra trong 2 giai on nn khc
nghit ca phn ng oxy ho trong mi mt giai on u khng cao. Trong giai on 1,
cht xc tc vo tng phn t nh qua b phn phn phi xc tc, trong khi khng kh
chy i vo di y ca bung hon nguyn. S di chuyn ngc chiu ca cht xc
tc v khng kh ngn nga s tip xc ca xc tc tham gia phn ng (nhiu cacbon) vi
khng kh mi cho vo cha 21% oxy.
Kt qu l, nhit ht xc tc thp hn v s suy gim hot tnh xc tc do tc dng
nhit nh hn trong thit b hon nguyn 2 giai on.
- S suy gim hot tnh xc tc do tc ng thu nhit thp hn
Trong giai on 1, cht xc tc ch c hon nguyn mt phn, hu ht nc hnh
thnh bi phn ng chy hydro ca cc c thc hin trong giai on 1. Hnh 4.11 ch ra %
hydro ca cc b chy ph thuc vo hm lng cacbon b oxy ho.
V nhit ca bung hon nguyn giai on 1thp, s suy gim hot tnh xc tc do
tc ng thu nhit c hn ch r rt. Trong bung hon nguyn giai on 2, nhit
khng cao, m l cc tiu, v do , khng c nguy c suy gim hot tnh do thu nhit
i vi cht xc tc.
185

100

% H2 chy

80
Giai on 2

60
Giai on 1
40
20
0

50
% cacbon chy

100

Hnh 4.11. Mc chy ca hydro v hydrocacbon trong h hon nguyn 2 giai on.

- bn hot tnh i vi kim loi tt hn.

Khi cc nh lc du s dng cc nguyn liu cha nhiu kim loi, th iu hp l nht
l c th vn hnh trong iu kin cht xc tc c bn cao i vi kim loi (ngha l vi
hm lng kim loi cao trn b mt m cht xc tc vn cn hot tnh xc tc tt). Cc kt
qu nghin cu chng t rng lng kim loi cao (c bit i vi Vanadi) dn n s
suy gim hot tnh ng k ca cht xc tc khi c mt hi nc v oxy. V hu ht hi nc
trong thit b hon nguyn c to ra t hydro ca cc, nn hm lng hi m c th tnh
ton trc tip. i vi h hon nguyn mt giai on hm lng thng ln hn 10%.
Khi c mt oxy, hi nc v Vanadi phn ng vi nhau to thnh axit vanadic. Axit ny tn
cng vo nhm trong cu trc ca zeolit. S tch nhm pht trin s lm sp cu trc
zeolit v xc tc tr nn mt hot tnh.
2V +

5
O2
2

V2O5 + H2 O

V2O5
2VO(OH)3
Axit vanadic

Do , cht xc tc trong thit b hon nguyn mt giai on hot ng trong iu

kin d oxy v hi m thng b axit vanadic ph v cu trc.
Phn chia s hon nguyn thnh 2 giai on c th ci thin tnh hnh ni trn. Trong
giai on mt, hu ht hydro (v do , hi nc) c gii phng nhit thp v khng
c oxy. Trong giai on 2, s chy cc xy ra trong ch oxy ho hon ton, d oxy,
nhng hm lng m rt t. S ph v cu trc ca zeolit do vanadi c hn ch ti a, v
trong giai on 1 thiu oxy v nhit thp nn V2O5 rt t, cn trong giai on 2 th axit
vanadic cng kh hnh thnh v rt t H2O. Ni mt cch khc phn ng

186

2V + 5 O2
2

V2O5

xy ra rt chm trong bung hon nguyn giai on 1v thiu oxy, v phn ng

V2O5 + H2 O

2VO(OH)3

xy ra khng d dng trong bung hon nguyn giai on 2 v hm lng hi m nh.

Hon nguyn 2 giai on r rng l t khc nghit hn kt hp vi cc th h mi cht
xc tc (th ng ho vanadi...) s cho php cc nh lc du ch bin cc du nng mt cch
c hiu qu hn m trc y cha tng t c.
H lm ngui cht xc tc
Trong dy chuyn cng ngh RFCC S&W-IFP c thit k mt h thng lm ngui
cht xc tc khi nguyn liu c hm lng CCR ln hn 6% hoc 7%kl. Cc h lm ngui
cht xc tc ny c th lp t cho cc thit b hon nguyn ca cc c s FCC c.
Khong hn mt chc c s ang s dng thit k ny, v mt s c s khc ang trong giai
on xy dng.
Mt vi c im ca h lm ngui cht xc tc ca S&W nh sau:
- Mt pha xc tc ln (dense phase), dng cht xc tc i xung
- S lu chuyn cht xc tc c khng ch bi cc van iu chnh
- Kh nng iu chnh t 0 n 100%.
- Khng cn h thng ng dn phc tp.
- chnh xc c kh cao.
- V thit b ngui.
- Vt liu bng thp - cacbon.
- truyn nhit cao - nhit thnh ng thp.
Nng lc lm ngui c th t t thp ~2.106 kcal/h n cao ~35.106 kcal/h. Trong
trng hp cn t mc lm ngui ln hn 35.106 kcal/h th c th ng dng cc b lm
ngui kt hp.
S lp t ca h lm ngui vi thit b hon nguyn 2 giai on nh trn hnh
4.12.
Mc xc tc bn trong h lm ngui c khng ch bi van iu khin cht xc tc
u vo. Khng ch s b nhit ca thit b hon nguyn t c bng van iu chnh
cht xc tc y. Khng ch nhit chnh xc bng khng kh lu th ho vo h lm
ngui.

187

Bung to
hi nc

Hi nc
p sut cao

Thit b
hon nguyn

Nc cp

H lm ngui
cht xc tc

Khng kh
lu th ho
Khng kh nng

Hnh 4.12. S lp t h lm ngui cht xc tc.

Mt vi c im ca cng ngh S&W-IFP

Cng ngh S&W-IFP c nhng c im ci tin v chn lc sn phm, cng sut
thit b v kh nng vn hnh ca h thng RFCC. Chnh nhng c im cng c th tc
dng nng cp cho cc h cracking FCC truyn thng. Thc vy, nhiu vn cng ngh
ca S&W-IFP c ng dng hn 50 c s FCC c nng cp. Sau y l cc ci tin
ng ch :
(i) H phun nguyn liu
H phun nguyn liu v b phn pha di ca ng dn nguyn liu l phn quan
trng nht ca RFCC/FCC.
H phun nguyn liu ca cng ngh S&W-IFP c nhng c im chnh sau y:
- Trc im phun nguyn liu, dng cht xc tc trng thi mt cao nh s dng
mt lng nh hi nc n nh dng xc tc v duy tr dng xc tc kh ng u i
qua ng phn ng.
- S phn tn nguyn liu vo trong ng phn ng bng hi nc nh s dng mt u
phun 2 bung chy n gin nhng rt hiu qu.

188

- a nguyn liu vo dng cht xc tc trng thi mt cao ang di chuyn ln

pha trn sao cho t c lan truyn v trn ln cn thit gia cht xc tc v nguyn
liu, ngha l sao cho t c s truyn nhit nhanh chng t ht xc tc nng n cc git
du li ti, lm ho hi tc khc.
Bng 4.12 dn ra cc kt qu ci thin v hiu sut sn phm sau khi thay th h phun
nguyn liu c bng h phun nguyn liu S&W-IFP.
Bng 4.12. S sai khc hiu sut sn phm gia h phun nguyn liu
ca S&W-IFP v h c
Sn phm
Kh kh, %kl
C3 v C4, %LV
Gasolin, %LV
LCO, %LV
Du st, %LV
Cc, %kl
chuyn ho, %LV

Chnh lch hiu sut

C s A

C s B

0,0
+1,5
+3,4
+1,6
6,5

1,3
1,5

0,0
+4,9

+6,2
4,5
0,3
0,1
+4,8

u phun nguyn liu ca S&W-IFP c gii thiu nh trn hnh 4.13.

M

L dn du

a chn
L dn hi nc

Hnh 4.13. u phun nguyn liu theo thit k S&W-IFP.

u phun nguyn liu - 2 lung (lung hi nc, lung du) hot ng bng cch
phun du c p lc ngc vi a chn phn tn du thnh mng du mn, hi nc phun
qua lp du to ra sng m du. Dng sng ny c phun vo ng phn ng nh mt u
phun (m) c thit k c bit m bo lng du phn tn cc i m khng va p
mnh vo thnh v gy h hng thnh ng phn ng.
H phun nguyn liu ny c trin khai cho nhiu c s RFCC, du cn c
nht cao v rt kh phn tn. to ra s phn tn tt cho cc du nng, vic thit k
189

u phun nguyn liu ny phi la chn cc p sut ca du, ca hi nc v t l hi nc/

du thch hp. i vi nguyn liu l gas oil chn khng, d dng phn tn hn, p sut du
v t l hi nc c th gim xung so vi khi vn hnh vi du cn.
(ii) H khng ch nhit hn hp phn ng
Mt vn c quan tm nhiu khi ch bin nguyn liu nng c lng du cn
nhiu l m bo s ho hi nhanh chng ca nguyn liu. l iu cc k quan trng
gim thiu s to cc do s ho hi khng hon ton. Tuy nhin, trong cc thit k thng
thng, nhit hn hp li ph thuc ch yu vo nhit u ra ca ng phn ng.
Thng thng, nhit hn hp phn ng cao hn khong 20 40oC so vi nhit u ra
ca ng phn ng v nhit ch c th thay i nh thay i t s cht xc tc/du.
Trong rt nhiu trng hp, vic nng cao nhit u ra ca ng phn ng iu
chnh nhit ca hn hp phn ng l khng thch hp, v thng dn n cc phn ng
cracking khng chn lc v to ra nhiu kh kh. Vn tr nn nan gii hn khi ch bin
theo ch sn phm chng ct cc i, ngha l, iu kin phn ng khng th khc
nghit, nhit phn ng khng qu cao. gii quyt vn , nhit u ra ca ng
phn ng c iu chnh mt cch c lp. IFP- Total sng ch v trin khai mt h
khng ch nhit hn hp phn ng (MTC, Mix Temperature Control) cho cc react
cracking.
MTC hot ng da trn c s hon lu mt phn cht lng vo pha sau vng phun
nguyn liu mi. N phn chia ng phn ng thnh hai vng phn ng:
- Vng pha trc c nhit cao, t s cht xc tc/du cao v thi gian tip xc rt
ngn.
- Vng pha sau, phn ng xy ra di iu kin cracking bnh thng v n ho
hn.
Vic tao ra hai vng cracking trong ng phn ng cho php iu chnh mt cch
chnh xc s ho hi ca nguyn liu v phn ng cracking to ra sn phm mong mun.
Nh h MTC, ngi ta c th nng nhit hn hp phn ng trong khi vn gi nguyn
hoc thm ch cn gim nhit u ra ca ng phn ng. Hnh 4.14 minh ha cch b tr
h MTC v ba vng nhit .
Mc ch s mt ca h MTC l to ra mt phng cch khng ch nhit hn hp
phn ng mt cch c lp (tu ). Tuy nhin, ging nh mt h h nhit tng t nh h
lm ngui cht xc tc, h thng MTC c th c s dng tng lng nguyn liu cn
cn phi ch bin trong mi c s lc du.

190

T3

MTC

T2
Du phn tn mn

Du
Xc tc
T1

Phun nguyn liu

Hi nc

Hnh 4.14. Khng ch nhit vng phn ng.

T1, T2, T3 : cc vng nhit khc nhau;
MTC: khng ch nhit hn hp phn ng.

(iii) C cu phn cui ng phn ng

Rt nhiu nghin cu chng minh rng, thi gian lu ca hi sau ng phn ng to
ra s cracking nhit v tip tc cracking xc tc trong bung react. c bit, cc phn ng
trong pha hi u l cc phn ng khng chn lc mong mun v dn n s suy gim
cht lng sn phm cracking, to ra nhiu kh kh v thc y phn ng chuyn dch hydro
trong olefin ca LPG ( chn lc olefin thp).
Cc yu t gy ra hin tng trn l: nhit , thi gian v din tch b mt.
S&W-IFP thit k ch to mt cu hnh c bit ca ng phn ng khng ch 3
tham s .
C cu phn cui ng phn ng Rawshorn theo thit k ca S&W-IFP c dn ra
trn hnh 4.15.
Nh c cu , cht xc tc v hi hydrocacbon c tch khi nhau mt cch nhanh
chng. Hi phn ng c dn n gn cc xyclon gim thi gian lu ca hi trong vng
phn ng. Gia cc xyclon v u ra ca ng phn ng khng ni nhau trc tip, nn lng
cht xc tc b cun theo hi gim ng k. Cc vn khc nh qu nhit react, gia tng
kim loi v to cc cng c loi b.

191

......
-----

Hi
Xc tc

Hnh 4.15. C cu phn cui ng phn ng Rawshorn.

(iv) H Amoco lm ngui hi sn phm

Cng ngh ny c pht minh v trin khai bi Amoco c p dng vo cng
nghip S&W-IFP.
Bng 4.13. nh hng ca k thut lm ngui hi sn phm n hiu sut
C s A

C s B

u ra ng phn ng
Sau khi lm ngui:

513
484

549
529

Thay i hiu sut, %kim loi

Kh kh:
Gasolin:

0,23

0,82

+0,43

+1,80

Nhit , C

Cht phn ng dng hi, khi ri khi on cui ca ng phn ng v tch khi
cht xc tc, c lm ngui bi LCO. Bng k thut lm ngui, cc phn ng khng chn
lc do tc dng nhit b hn ch, dn n hiu sut gasolin cao hn v kh kh thp hn.
Ngoi ra, s dng k thut lm ngui hi sn phm cn bo v c hm lng olefin trong
LPG, gi tr octan ca gasolin, gim thiu s hnh thnh diolefin v ci thin tnh n nh
ca gasolin.
Hiu qu ca k thut lm ngui hi sn phm c th hin bng 4.13.
Cc s liu bng 4.13 chng t rng, hiu sut kh kh gim.
ng nh d on, nh hng ca k thut lm ngui n hiu sut ca kh kh v
ca gasolin th hin cng r khi nhit cng cao.
192

S kt hp gia cu hnh c bit phn cui ng phn ng v k thut lm ngui

Amoco loi b kh hiu qu cc phn ng khng mong mun sau ng phn ng.
Ci to cc c s FCC thnh RFCC (thm thit b hon nguyn giai on 2)
B sung mt thit b hon nguyn giai on 2 l bin php hiu qu chuyn cc c
s FCC ang c thnh cc c s ch bin nguyn liu nng m khng lm gim nng sut.
Cho n nay 3 c s FCC c ci to, lp t thm mt thit b hon nguyn giai on 2
v do c th ch bin cc nguyn liu nng. Cc thit k gi li cc thit b hon
nguyn c lm thnh thit b hon nguyn giai on 1v gi li react/stripp. Mt thit
b mi hon nguyn giai on 2, cc ng dn cht xc tc v l t CO; mt my thi kh
mi hoc b sung, sa cha b phn kh x l cc vn cn gii quyt khi ci to h FCC
thnh RFCC. Khi vn hnh thit b hon nguyn giai on 1 theo ch chy khng hon
ton, nu hm lng CCR ca nguyn liu khng cao hn 6%kl th khng cn thit b ly
nhit b sung (nh trnh by trc y).
Hnh 4.16 ch ra cch thc ci to mt c s FCC thnh RFCC, trong c ghi r
thit b v cc chi tit c kh mi v c.
Xyclon (mi)

Xyclon (mi)
H thng hon
nguyn (c)

H thng hon
nguyn giai
on 2 (mi)
B
phn
phn
phi (mi)

Thng tho xc tc
hon nguyn giai
on 1 (mi)

Vng kh
(mi)

Khuu ni ch Y (mi)

Mo cp nguyn liu (mi)

Hnh 4.16. S ci to c s FCC thnh RFCC

theo m hnh react - regenerat lp ghp "song - song".

193

4.4. Cracking xc tc su- sn xut olefin nh

4.4.1. M u

Cracking xc tc pha lu th (FCC) l qu trnh chuyn ho du th c p dng ph

bin nht v quan trng nht trong mt nh my lc du hin i. Trc y cc c s FCC
thng hot ng theo ch to ra sn phm gasolin cc i v sn phm chng ct cc
i, tu theo yu cu tng thi v hoc theo nhu cu a phng. Gn y, vi s xut hin
ca mt hng gasolin ci bin (reformulated gasoline) m cc c s FCC ang hng s sn
xut ca mnh theo ch sn phm olefin cc i.
Isoolefin nh, isobutylen v isoamylen t cng ngh FCC l cc ngun nguyn liu
cn thit sn xut metyl tectiary butyl ete (MTBE, metyl tertiary butyl ether) v tectiary
amyl metyl ete (TAME, tertiary amyl metyl ether). l nhng hp cht cha oxy
(oxygenated compounds) c dng pha ch cc gasolin ci bin. Nhu cu v cc alkylat
cng gia tng p ng cho vic sn xut gasolin ci bin, do , ngun olefin nh cng
ngy cng i hi nhiu hn.
Cng vi nhng bin i trong cng nghip lc du, trong cng nghip ho du
nhu cu v propylen cng ang tng ln sn xut ra cc sn phm polypropylen. Gn mt
na lng polypropylen dng trong cng nghip ho hc c sn xut t cc nh my lc
du, v phn cn li t cng ngh hi nc-cracking (SC, steam cracking). Do , nhu cu
v propylen t c hai cng ngh trn FCC v SC u tng.
Theo d on, nhu cu v isoolefin ch to cc hp cht oxygenat s tip tc tng
cho n cui th k. Ngoi ra, nhu cu propylen cho alkylho cng nh cho polypropylen
cng tip tc gia tng.
Nh vy, cng ngh FCC v SC phi c nhng thay i ng k p ng i hi
ca th trng. R rng l cn phi c mt cng ngh sn xut olefin nh mt cch kinh t
p ng ngun olefin nh (C3-C5) ni trn.
DCC l cng ngh cracking xc tc su (Deep catalytic cracking) sn xut cc
olefin nh (C3-C5) t ngun gas oil chn khng (VGO), cng ngh ny c to ra do s hp
tc ca 3 i tc: tp on cng ngh Stone&Webster, Vin nghin cu ch bin du m
(RIPP) v tp on quc t Sinopec (hai i tc sau Trung Quc).
C s DCC u tin c xy dng v th nghim thnh cng ti nh my lc du
Jinan Sinopec (Trung Quc). Trong , c ba c s khc c trin khai Trung Quc v
Thi Lan (bng 4.14).

194

Bng 4.14. Tnh hnh khi u ca DCC

a im
Jina, Trung Quc
Anquing, Trung Quc
Daging, Trung Quc
Rayon, Thi Lan

Nng sut nguyn liu MTY*

Thi gian khi hnh

150.000
400.000
120.000
725.000

1994
1995
1995
1997

* Tn/nm.
+ Thit k bi S&W.

Hnh 4.17 l nh chp mt c s DCC Trung Quc.

Hnh 4.17. Cc thit b chnh ca cng ngh DCC Trung Quc

(t tri sang phi: thp hon nguyn xc tc, l phn ng v thp phn on chnh).

195

4.4.2. M t qu trnh

DDC l cng ngh cracking xc tc pha lu th c p dng cracking chn lc

nhiu dng nguyn liu thnh olefin nh.
Mt c s DDC c th hot ng theo mt trong hai ch : propylen cc i (cch I)
v isoolefin cc i (cch II). Mi mt ch lm vic s dng mt loi xc tc v mt b
iu kin vn hnh khc nhau.Sn phm ca DCC l olefin nh, gasolin octan cao, du vng
thm nh, kh kh v cc. Mt lng nh ca du st cng c to ra.
Ch vn hnh to ra olefin cc i (cch I) s dng c k thut cracking xc tc
pha lu th (trong ng phn ng riser) v cracking lp xc tc n nh vi iu kin phn
ng khc nghit. Ch vn hnh vi isoolefin cc i (cch II) ch s dng k thut
cracking pha lu th ging nh trong mi c s FCC hin i, trong iu kin t khc nghit
hn so vi cch I.
n b phn kh x

n b phn thu hi kh
31Z001
31R001

31K001
31Z002
31D002

Kh nhin liu
31B001

Du st hi lu

31D001
Nguyn liu mi

Khng
kh

Hi nc

Hi nc

Hi nc n nh

Hnh 4.18. S cng ngh DCC I propylen cc i:

31B001: gia nhit khng kh;

31R001: react;

31Z002: cc xyclon ca thit b hon nguyn;

31Z001: xyclon ca react;

31D001: thit b hon nguyn;

31K001: h kh nn;

31D002: thng tho liu ca thit b hon nguyn.

Hnh 4.18 m t s cng ngh DCC cch I. Lu rng, bn thit k ca DCC I v

DCC II ch khc nhau mt ng phn ng (riser) c lp tng cng pha trn react xc tc
lp n nh.
196

Nguyn liu ban u c phn tn mn bi hi nc v c phun vo ng phn ng

bng u phun ca S&W, phun vo pha xc tc n nh. Du nguyn liu lp tc c trn
ln vi cht xc tc v bt u phn ng cracking to ra cc sn phm nh hn. Cng ngh
DCC cn c u phun nguyn liu rt tt bo m ho hi nhanh v cracking chn lc.
Hi nc cho ng phn ng c phun vo ngay trn im phun nguyn liu tng
cng s phn tn cho nguyn liu v tch hydrocacbon khi b mt cht xc tc nhm
m bo mt p sut ring phn ti thiu cho phn ng trong h DCC. u phun hi nc
thng thng c s dng phun hi nc vo ng phn ng.
Khi cn thit mt lng du st (slurry oil) c phun vo ngay pha trn u phun
hi nc. Dng du hon lu khng c tc dng lm tng chuyn ho chung ca phn
ng m ti u ho ch nhit ca h thng, bi v sn phm ch yu ca cracking du
st l cc.
nh ng phn ng, cht xc tc, hi nc v hydrocacbon i qua phn cui ng
phn ng c t v tr thp hn mc lp xc tc n nh. chuyn ho ca nguyn liu
c iu chnh bng cao ca lp xc tc n nh (tc khng gian trng lng gi ca
hydrocacbon, WHSV). Cc xyclon ca react c ch to theo cu hnh hai giai on,c
hiu sut phn ring cao cht xc tc v hi sn phm. Cc sn phm, kh tr, hi nc v
mt lng nh cht xc tc c dn n y thp phn on.

Van iu chnh lng cht xc tc hon nguyn c th khng ch nhit ca lp

xc tc reat bng cch thay i lng cht xc tc nng hon nguyn i vo ng xc
tc. Nhit v p sut ca react c lit k trong bng iu kin phn ng di y
(bng 4.15).
B phn stripp ca bung phn ng gm cc khoang c tm chn v lm sch
hydrocacbon khi b mt cht xc tc theo tng giai on. Mt vi phun hi nc c t
di tm ngn th nht tch cc hydrocacbon d bay hi ngay khi xc tc i vo stripp.
Nu khng c s tch s b th hydrocacbon d bay hi s hp ph trn xc tc v c th
phn ng vi nhau to ra cc polyme khi cht xc tc tip tc i xung pha di stripp.
Hi nc t vng phun chnh lu th ho lp xc tc n nh, cun theo hydrocacbon
tch ra v tip tc tch sch hydrocacbon ang b hp ph trn cht xc tc trc khi cht
xc tc vo thit b hon nguyn. Mt vng phun hi nc khc t y ca stripp,
gi cho cht xc tc trng thi lu th (linh ng), bo m to ra mt dng cht tun t
chy vo ng dn cht xc tc phn ng.
Cht xc tc s dng ra khi stripp qua mt ng nghing. Cc mo kh t cch
nhau di ng nghing thng kh cho cht xc tc v b sung th tch kh b mt do nn.
Van iu chnh cht xc tc s dng c t cnh v tr m ng nghing ni vo thit b
hon nguyn. Van ny gi cho lp cht xc tc n nh trong react/stripp. Mc lp xc
tc n nh c ti u ho theo chuyn ho v kh nng vn hnh ca h thng.

197

Cht xc tc tham gia phn ng cracking c phn tn vo bn trong thit b hon

nguyn bng cc h phn phi xc tc t ngay trn cc vng khng kh chy. Cc vng
khng kh ny phn phi khng kh qua lp xc tc hon nguyn to ra s lu th ho v
chy. Thit b hon nguyn hot ng theo c ch oxy ho hon ton v 2%tt oxy d. Kh x
t thit b hon nguyn i ra,qua cc xyclon - 2 cp tch cc ht xc tc ko theo kh x.
Nhit ca regenerat thng xp x 700oC. p sut chnh lch gia react /regenerat
c khng ch bi van iu chnh kh x.
Cht xc tc va hon nguyn cn nng c tho ra v tr thp hn mc lp xc t
n nh trong thit b hon nguyn chy vo ngn ng xc tc. Ngn tho xc tc l ni
cht xc tc x kh t n mt cht xc tc trong ng dn trc khi vo ng thng ng
dnh cho cht xc tc hon nguyn. Mt vng nh phn phi khng kh trong ngn cha
xc tc nhm gi cho cht xc tc trng thi linh ng. Cc mo kh (khng kh) t cch
nhau theo ng dn xc tc c nhim v np kh v b p th tch kh mt do nn. Cht xc
tc chuyn qua van iu chnh cht xc tc hon nguyn, van ny khng ch nhit ca
react bng cch iu chnh lng xc tc nng i vo ng phn ng v bung react. Phn
ng ng pha di cc u phun nguyn liu c nhim v n nh cht xc tc v ng vai
tr nh van mt chiu, cn khng cho dng du chy ngc li vo thit b hon nguyn.
Trong on ng ny, cc u phun hi nc lm n nh v ti phn b cht xc tc, duy tr
mt mt cao ca pha xc tc, trc khi vo vng phun nguyn liu.
B phn thu hi kh ca DCC l mt thp phn on chnh c h ngng t hi lu nh
thp ngng t hi nc. Mt my nn kh cng sut ln so vi qu trnh FCC c lp t
bi v trong cng ngh ny lng kh kh v kh du m ho lng (LPG) rt ln. Thp hp
th v cc ct tch sch (stripp) t sau my nn c thit k c bit ci thin kh
nng thu hi C3 v mt s cu t gasolin nh. Sau cc thp tch C4 debutaniz v C3
depropaniz loi b tp cht nh trong cc h thu hi kh truyn thng, trong cng ngh
ny cn c thp deetaniz (deethanizer) v thp tch C3 splitt (splitter) to ra propylen
c sch cao sn xut polyme cao cp. i vi cc c s DCC trong hoc gn cc t
hp ho du, mt h thu hi etylen theo k thut lm lnh tin tin ARS (advanced recovery
system) ca hng S&W c s dng thu hi etylen v ch yu thu hi hon ton
propylen.
H thng iu hnh kh x sau thit b hon nguyn DCC cng tng t nh i vi h
FCC. H iu hnh ny bao gm mt van iu chnh kh x khng ch p sut chnh lch
gia react v regenerat, tip n l mt bung rng. Nhit c thu hi bng thit b lm
ngui kh x trong dng hi qu nhit p sut cao. Tu thuc vo tiu chun kh thi ca
tng a phng, h thng c th c mt xyclon 3-cp t trc van iu chnh kh x hoc
mt thit b lc bi tnh in (ESP, electrostatic precipitator) t trc ng khi. SOx hoc
NOx nu cn thit c x l bng k tht ph gia xc tc loi b SOx v bng k thut
kh chn lc xc tc (SRC) loi b NOx.
198

4.4.3. Cc vn cng ngh

Cht xc tc
Phn quan trng nht ca cng ngh DCC l cht xc tc.Cc c gng nghin cu v
trin khai ca RIPP to ra mt s cht xc tc chuyn dng, mi mt cht xc tc u
lin quan n cc zeolit. Tt c mi cht xc tc u c c trng vt l tng t nh ca
xc tc FCC.
Cht xc tc k hiu CRP-1 c ch to cho cng nghip DCC1, propylen cc i.
CRP c hot tnh tng i thp nhm bo m chn lc olefin cao v phn ng chuyn
dch hydro khng ng k. Cht xc tc cng th hin bn thy nhit cao v chn lc
cc thp.
CS-1 v CZ-1 c ch to sn xut isobutylen v isoamylen vi chn lc cao.
Cc xc tc ny cng c tnh cht hn ch phn ng chuyn dch hydro v c bn thu
nhit tt, chn lc cc thp.
C ba loi xc tc trn ang c sn xut c s sn xut xc tc ca Cng ty Ho
du Qilu Trung quc. Tp on Stone & Webster l nh cung cp xc tc th hai cho cng
ngh DCC ngoi Trung Quc.
Ngun nguyn liu
Cng ngh DCC c p dng cho nhiu dng nguyn liu VGO khc nhau cho sn
xut propylen v isoolefin. Ngun nguyn liu c th bao gm sp, naphta v du cn.Du
th parafin l tt nht, tuy nhin cc th nghim pilot thnh cng vi cc nguyn liu
naphten v aromat hydro-x l.
Cc iu kin vn hnh
Nhng iu kin vn hnh in hnh cho 2 ch :ch I (propylen cc i), ch
II (isoolefin cc i) c dn ra bng 4.15.
Bng 4.15. iu kin vn hnh ca DCC, FCC v SC
DCCI Max C3

DCC II Max isoolefin

FCC

SC

550 565

525 550

510 550

760 870

670 700

670 700

670 730

0,7 1,0*

1,0 1,4

1,4 2,1

1,0

Thi gian phn ng, s

9 15

2 (ng phn ng)

2 (ng phn ng)

0,1 0,2

Cht xc tc/du (kl/kl)

9-15

7 11

58

20 30

10 15

27

30 80

Nhit , C
React
Regenerat
2

p sut react (kG/cm )

Hi nc, %kl nguyn liu

* Thi gian lu trong ng phn ng ~2s + 2-8h

(WHSV) trong react lp n nh.

199

 Hiu sut sn phm DCC

Propylen cc i, DCC I

Bng hiu sut sn phm ca ch DCC i vi VGO Daging giu parafin c dn

ra bng 4.16.
Bng 4.16. Hiu sut sn phm DCC, FCC v SC
Sn phm
H2
Kh kh (C1 - C2)
LPG (C3 - C4)
Naphta (C5 - 205oC)
LCO (205 330oC)
Du st (330oC (+))
Cc
Olefin nh
C2
C3
C4

%kl ca nguyn liu

DCCI

FCC

SC

0,3
12,6
42,3
20,2
7,9
7,3
9,4

0,1
3,8
27,5
47,9
8,7
5,9
6,1

0,6
44,0
245,7
19,3
4,7
5,7

5,7
20,4
15,7

0,9
8,2
13,1

28,2
15,0
4,1

Ngun ti liu: Lark Chapin and Warren Letzseh "Deep Catalytic Cracking, Maximize
Olefin Production" NPRA Annual Meeting, AM-94-43, March 20-23, 1994.

so snh, hiu sut olefin cc i ca cng ngh FCC v SC ca cng mt dng

nguyn liu cng c dn ra bng 4.16.
Propylen c hm lng cao trong sn phm LPG v cao hn ng k so vi cng ngh
FCC. LPG ca DCC cng cha mt lng ln butylen.Trong phn isobutylen trong
butylen tng cao hn so vi FCC (38 42% so vi 17 33%). Do , s sn xut MTBE
cng c ci thin ng k so vi cng ngh FCC do lng isobutylen tng. Hiu sut
olefin cao t c l do cracking su chn lc i vi naphta.
Mt lng ln kh kh cng c to ra trong cng ngh DCC v nhit ca react
cao.Kh kh ca DCC rt giu olefin, rt cn thit cho cng nghip ho du. Tuy nhin,
cng ngh DCC to ra t kh kh v nhiu LPG hn so vi cng ngh SC. Sn phm chnh
ca DCC l propylen.Trong khi etylen l sn phm chnh ca SC (SC l phn ng
cracking nhit, trong khi DCC ch yu l cracking xc tc).
V chuyn ho cao, nn cc sn phm lng C5+ ca DCC hu nh l aromat. Do ,
gi tr octan ca naphta ca DCC rt cao. Vi hiu sut sn phm nh trn, ngi ta xc nh
c MONC l 84.7 v RONC l 99.3. Naphata DCC C5+ c hn 25% benzen, toluen v
xylen (BTX). V hm lng diolefin cao nn naphta DCC thng phi c hydro x l chn
lc t cht lng n nh m khng lm gim gi tr octan.
200

Cc cng c to ra nhiu hn so vi FCC. Nhit ca phn ng chuyn ho nguyn

liu thnh sn phm cao nn i hi nhit ca react cao, do hiu sut cc ln.
nhy v hiu sut olefin i vi 3 nguyn liu VGO c dn ra bng 4.17.
Bng 4.17. Hiu sut olefin ca DCCI i vi cc VGO khc nhau
Daqing

VGO nh Arp

Iran

Mt

0,84

0,88

0,91

K, UOP

12,4

11,9

11,7

Hiu sut olefin,%nguyn liu

C2
C3
C4

6,1
21,1
14,3

4,3
16,7
12,7

3,5
13,6
10,1

VGO Daqing l nguyn liu parafinic, VGO Iran giu aromat. Hit sut propylen v
butylen rt cao i vi nguyn liu parafin v gim t t i vi nguyn liu aromat. Cc s
liu cho c thc hin ti RIPP trn thit b pilot vi cng sut 2BPD (barrel/ngy).
DCC II isoolefin cc i
Hiu sut olefin cc i ca DCC II c dn ra bng 4.18
Bng 4.18. Hiu sut sn phm ca DCC II
Hiu sut,% nguyn liu
C2

C3 - C4
Naphta C5+
LCO
HCO
Cc
Tn tht
Olefin nh
C2=
C3=
C4=
i-C4=
C5=
i-C5=

5,59
34,49
39,00
9,77
5,84
4,31
1,00
2,26
14,29
14,65
6,13
9,77
6,77

Ngun ti liu: Z. T. Li W. Y. Shi, N. Pan, F. K. Jaing, DCC flexibility for isoolefins

production Advances in fluid catalytic cracking, ACS vol 3 pp 581-583.

201

Bng 4.19. S phn b cc isome olefin theo ch DCCII

DCCII

Gi tr cn bng
Isome ca butylen
1.buten,%kl.
t-2-buten, %kl
c-2-buten,%kl
isobuten, %kl
Isome ca amylen
1-penten, %kl
t-2-penten,%kl
c-2-penten,%kl
isoamylen, %kl

14,7
24,5
16,7
44,1

12,8
26,7
18,6
41,9

5,2
12,2
2,0
70,6

5,2
17,6
7,9
6,93

Ngun ti liu: Z. T. Li W. Y. Shi, N. Pan, F. K. Jaing, DCC flexibility for isoolefins

production Advances in fluid catalytic cracking, ACS vol 3 pp 581-583.

Hiu sut olefin cao c to ra bi cracking su naphta trong iu kin khc nghit
hn DCC I. chn lc cao ca olefin chng t tc phn ng chuyn dch hydro rt
thp. Butylen v cc amylen bao gm nhiu cc isome nh bng 4.19.
Lu rng, isoolefin trong DCC II c gi tr gn nh gi tr cn bng nhit ng hc.
Do , hiu sut ca isobutylen v isoamylen l rt cao, khong 6,0%kl.
Trin khai cng ngh DCC

C th lp t mt h thng DCC trong mt c s ho du vi mt vi kch bn sau y:

ng dng cng ngh DCC gia tng sn xut propylen trong mt c s sn xut
etylen. Sn phm naphta DCC, etan, propan v butan c s dng cho SC sn xut etylen.

Mt h DCC c th c lp t trong mt c s lc du sn xut polypropylen v

styren. Mt v d nh th c gii thiu trn hnh 4.18.
Kh t
EXT + HDA
C2=
C3=

EB +
Styren

POLY

Styren

Polypropylen

C4
VGO
DCC
SHP
LCO
X l nguyn
liu

DO

Hnh 4.18. S sn xut polypropylen v styren:

(EXT = chit tch aromat, DHA = hydro dealkyl ho, SHP = hydro ho chn lc,
EB = etyl benzen, POLY = polypropylen).

202

Mt v d khc v trin khai cng ngh DCC l thc y s sn xut gasolin ci bin,
nh trn hnh 4.19. Mt h thng thu hi etylen theo cng ngh ARS (lm lnh ca hng
Stone & Wegster) c a vo s sn xut etylen v propylen.

Kh t
Etylen

Thu hi kh
ERU

Propylen
Ru

C4=
Metanol

Alkylat
oxygenat,...

VGO

Cu t pha
trn xng
cao cp

C5-

DCC
C5+
Naphta

Gasolin

SHU

HT

LCO
DO

Hnh 4.19. S sn xut gasolin ci bin:

ERU: b phn thu hi etylen (ethylene recovery unit);
SHU: b phn hydro ho chn lc (selective hydrocarbon unit);
HT: b phn hydro-x l (hydro-treating).

Trn y l mt s cng ngh in hnh ca FCC c la chn gii thiu: cng ngh
FCC ca UOP, cng ngh RFCC ca Stone &Webster kt hp vi IFP (Institute Franaise de
Ptrole) v cng ngh DCC ca Stone&Webster lin kt vi RIPP v Sinopec International
(Trung Quc).
Ngoi cc cng ngh ra, chng ta cn c bit rt nhiu cng ngh khc nh:
cng ngh FCC IIIR ca Exxon, cng ngh FCC ca tp on M.W. Kellogg...
Mi mt cng ngh u th hin nhng u im c bn ca mnh cho tng trng hp
c th (ph thuc vo rt nhiu yu t: ngun nguyn liu, trnh cng ngh, kh nng ti
chnh, mc tiu sn phm...). Tuy nhin tt c cc cng ngh u hng ti: vic s dng
a dng ngun nguyn liu, c bit quan tm n nguyn liu nng, tnh a dng ca sn
phm v trang b cc thit b hin i, t ng ho v gi thnh h.
Mi ci tin cng ngh (v thit b v cht xc tc) u nhm tn dng ti a v
khng ph phm ngun ti nguyn du m m chng ta v cc nh lc du u bit rng,
khng phi l ngun ti nguyn v hn v trong tng lai khng xa n s cn kit. Cu hi:
203

Ci g sau du m? l cha ai tr li c, song mi ngi u thc rng, phi tm cch

ko di thi k nng lng du m cng lu cng tt, trc ht bng khoa hc v cng
ngh v sau mi n chnh sch v thc con ngi!

204

Ti liu tham kho

1. Bruce C. Gates, James R. Kater, G.C.A. Schuit, Chemistry of catalytic processes,
McGraw - Hill Book Company, 1979.
2. C. Naccache, Catalyseur solides acides, cole de catalyse au Vietnam, (1995).
3. C. Naccache, P. Mriaudeau, Nguyen Huu Phu, cole de catalyse au Vietnam, (1996).
4. Donald W Breck, Zeolite Molecular Sieves, Wiley - Interscience Publication, 1974.
5. J. Dwyer and D.J. Rawlence, Fluid catalytic cracking: chemistry and catalyst particle
design, Catal. Today, vol. 18, No 4 (487-509) (1993).
6. J. P. Mikkola et al., Future Trends in the Worldwide Oil Refining Industry. NATO
Science Series, II Mathematics, Physics and Chemistry, vol. 69 (2002).
7. Julius Scherzer, Octane - Enhancing, Zeolite FCC catalysts: Scientific and Technical
Aspects, Catal. Review, Sci. Eng 313) 215-354 (1989).
8. M. L. Occelli and P. O'connor, Fluid catalytic cracking materials and Technological
innovations, Studies in Surface Science and Catalysis 134, Elsevier 2001.
9. Nguyn Hu Ph, Ho l-Ho keo, Nh xut bn Khoa hc v K thut H Ni, 2003.
10. Nguyn Hu Ph, Xc tc v Hp ph trn b mt vt liu v c mao qun, Nh xut bn
Khoa hc v K thut H Ni, 1998.
11. R. J. Farrauto and Bartholomew Fundametals of Industrial Catalytic Processes, Blackie
Academic & Professional, 1997.
12. Reza Sadeghbeigi, Fluid Catalytic Cracking Handbook, Crulf Publishing Company
Houston, Texas (2000).
13. Robert A. Meyer, Handbook of Petroleum Refining Processes, McGraw - Hill, 1997.
14. Bohdan W. Wojciechowski and Avelino Corma, Catalytic cracking: Catalysts, Chemistry
and Kinetics, Marcel Dekker, Inc. New York. Basel, 1986.

205

Mc lc
Li ni u ......................................................................................................................

Bng cc ch ci vit tt v cc k hiu ........................................................................

Chng 1: M u..........................................................................................................

1.1. Gii thiu tng qut v cng ngh cracking............................................................

1.2. Gii thiu s chung ca cc phn ng cracking ................................................. 13

1.3. Gii thiu chung v cht xc tc cracking cng nghip .......................................... 13
1.4. Cc c trng v nguyn liu cho cracking xc tc (FCC)...................................... 13
1.4.1. Phn loi cc hydrocacbon ............................................................................... 14
1.4.2. Cc tnh cht vt l ca nguyn liu FCC ......................................................... 15
1.4.3. Cc tp cht ...................................................................................................... 21
1.4.4. Cc gi tr v h thc kinh nghim ................................................................... 27
1.5. Cc sn phm ca FCC ........................................................................................... 29
Chng 2: Ho hc qu trnh cracking xc tc ............................................................ 34
2.1. M u ................................................................................................................... 34
2.2. Cracking xc tc..................................................................................................... 39
2.2.1. Cc kin thc c s v cacbocation .................................................................. 39
2.2.2. Cracking xc tc cc hydrocacbon n l......................................................... 48
2.2.2.1. Cracking xc tc parafin............................................................................. 49
2.2.2.2. Cracking xc tc olefin............................................................................... 54
2.2.2.3. Cracking xc tc alkyl hydrocacbon aromat ............................................... 56
2.2.2.4. Cracking xc tc xycloparafin .................................................................... 58
2.2.2.5. S hnh thnh cc ....................................................................................... 59
2.2.3. Cracking xc tc gas oil ................................................................................... 62
2.2.3.1. Nhc li cc c im c bn v cracking .................................................. 62
2.2.3.2. S phn b sn phm trong cracking gas oil ............................................... 63
2.2.3.3. ng hc phn ng cracking gas oil ........................................................... 70
2.2.3.4. Cracking cc nguyn liu nng ................................................................... 71

206

Chng 3: Cht xc tc FCC......................................................................................... 73

3.1. M u ...................................................................................................................
3.2. Cc hp phn c bn ca cht xc tc FCC ............................................................
3.2.1. Zeolit Y ............................................................................................................
3.2.2. Cc phng php iu ch zeolit Y c t s Si/Al cao .......................................
3.2.2.1. Tng hp zeolit c t s Si/Al cao ...............................................................
3.2.2.2. Cc tnh cht c bn ca zeolit Y c t s Si/Al cao (HSY - high silica Y) .
3.2.3. Cht nn ...........................................................................................................
3.2.3.1. Chc nng cht nn ....................................................................................
3.2.3.2. Phn loi.....................................................................................................
3.2.4. Cc cht ph tr xc tc ...................................................................................
3.2.4.1. Zeolit ZSM-5 ..............................................................................................
3.2.4.2. Cc vt liu ry phn t (RPT) dn xut t AlPO4: SAPO, MeAPO,

73
74
74
77
78
82
88
88
90
98
98

MeAPSO ...................................................................................................... 101

3.2.4.3. Cc loi vt liu khc ................................................................................. 103
3.3. Ch to cht xc tc FCC ....................................................................................... 104
3.3.1. Phn loi cc phng php sn xut cht xc tc FCC...................................... 104
3.3.2. Ch to cc zeolit ............................................................................................. 105
3.3.2.1. Zeolit Y ...................................................................................................... 105
3.3.2.2. Trao i ion ................................................................................................ 106
3.3.2.3. Bin tnh cu trc ca zeolit Y.................................................................... 107
3.3.3. Cht nn v quy trnh ch to cht xc tc FCC................................................ 108
3.3.3.1. Cht xc tc vi cht nn hot tnh thp ..................................................... 109
3.3.3.2. Cht xc tc vi cht nn hot tnh ............................................................. 111
3.4.4. So snh cc quy trnh sn xut xc tc khc nhau............................................. 112
3.4. Cc tnh cht vt l quan trng ca cht xc tc FCC............................................. 113
3.4.1. bn mi mn ............................................................................................... 113
3.4.2. Th tch mao qun v s phn b kch thc mao qun .................................... 115
3.4.3. bn nhit v bn thu nhit ......................................................................... 116
3.4.4. Phn b kch thc ht ..................................................................................... 117
3.4.5. Khi lng ring .............................................................................................. 118
3.4.6. tinh th XRD .............................................................................................. 118
3.5. Mi quan h gia thnh phn v tnh cht xc tc .................................................. 120
3.5.1. Cc c trng c bn ca cht xc tc FCC ...................................................... 120
3.5.2. nh hng ca zeolit n tnh cht xc tc FCC .............................................. 122
3.5.2.1. nh hng t s Si/Al ca zeolit n hot tnh xc tc v chn lc........ 123
3.5.2.2. nh hng ca zeolit n cht lng gasolin ............................................. 126
207

3.5.2.3. nh hng ca ion natri ............................................................................. 129

3.5.2.4. nh hng ca phng php iu ch zeolit HSY ...................................... 129
3.5.2.5. nh hng ca s trao i ion t him vi zeolit HSY ............................. 132
3.5.3. nh hng ca pha nn .................................................................................... 133
3.5.4. nh hng ca t s zeolit/cht nn.................................................................. 135
3.5.5. nh hng ca cht ph tr.............................................................................. 136
3.6. Nghin cu hot tnh xc tc cracking.................................................................... 139
3.6.1. Nguyn nhn suy gim hot tnh xc tc .......................................................... 139
3.6.2. M hnh suy gim hot tnh xc tc do s hnh thnh cc trn cht xc tc
(m hnh COC, coke on catalyst)...................................................................... 141
3.6.7. M hnh suy gim hot tnh xc tc theo thi gian phn ng trong dng
(time on stream, TOS) ...................................................................................... 142
3.6.4. chn lc sn phm trong phn ng cracking xc tc ................................... 144
3.6.4.1. chn lc sn phm trong cc react c lp xc tc n nh................... 144
3.6.4.2. chn lc sn phm trong cc react cracking xc tc trng thi
lu th - react thng mi ......................................................................... 149
3.6.4.3. Xc nh hot tnh cht xc tc cracking quy m phng th nghim (PTN) 151
Chng 4: Cng ngh qu trnh cracking xc tc........................................................ 154
4.1. M u ................................................................................................................... 154
4.2. Cng ngh FCC ca UOP ....................................................................................... 158
4.2.1. Gii thiu cng ngh FCC ca UOP ................................................................. 158
4.2.2. Phn tch cc u im ca h thng FCC-UOP hin i ................................... 164
4.2.3. Kh nng ch bin cc ngun nguyn liu a dng .......................................... 168
4.2.4. Gi thnh cng ngh......................................................................................... 171
4.2.5. Tnh hnh th trng.......................................................................................... 173
4.3. Qu trnh RFCC ca S&W-IFP............................................................................... 174
4.3.1. Gii thiu qu trnh RFCC(S&W-IFP).............................................................. 175
4.3.2. Cc vn cng ngh ....................................................................................... 179
4.4. Cracking xc tc su - sn xut olefin nh ............................................................. 194
4.4.1. M u ............................................................................................................. 194
4.4.2. M t qu trnh................................................................................................. 196
4.4.3. Cc vn cng ngh ....................................................................................... 199
Ti liu tham kho ......................................................................................................... 205

208