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MC LC

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MC LC ................................................................................................................................... 1
GII THIU V MUN ............................................................................................................ 3
CC HNH THC HC TP CHNH TRONG MUN .............................................................. 4
YU CU NH GI HON THNH MUN ........................................................................... 5
BI 1. VAI TR CA QU TRNH CRACKING XC TC .......................................................... 6
M bi: HD E1 ............................................................................................................................ 6
1.1. Nhu cu v s lng v cht lng ca xng nhin liu ..................................................... 6
1.1.1. Nhu cu tng s lng ..................................................................................................... 6
1.1.2. Yu cu tng cht lng v cc cng ngh sn xut xng ............................................... 8
1.2.Cc phn on nng t du th, S cn thit phi c qu trnh Cracking ............................ 9
1.2.1. Cc phn on nng t du th........................................................................................ 9
1.2.2.S cn thit phi c qu trnh Cracking ........................................................................... 10
1.2.3. Sn xut xng t v xng my bay ............................................................................... 11
1.3. Cu hi .............................................................................................................................. 12
BI 2. BN CHT HA HC CA CRACKING XC TC ....................................................... 13
M bi:HD E2 ........................................................................................................................... 13
2.1. C s ha hc ca Cracking ............................................................................................. 13
2.2. C ch phn ng cracking ................................................................................................. 13
2.3. Cracking hydrocacbon parafin, naphten, aromat ................................................................ 15
2.4. Cc phn ng ph km theo phn ng cracking xc tc ................................................... 17
2.5. Vai tr ca phn ng cracking xc tc ............................................................................... 18
2.6. Cu hi .............................................................................................................................. 18
BI 3. LCH S PHT TRIN CA XC TC ZEOLIT ............................................................ 19
M bi: HD E3 .......................................................................................................................... 19
3.1. Lch s pht trin xc tc ................................................................................................... 19
3.2. Xc tc zeolit v xc tc cha zeolit .................................................................................. 20
3.3. Phng php iu ch xc tc zeolit ................................................................................. 22
3.4. Xc nh cc c trng ca xc tc zeolit .......................................................................... 22
3.5. Phn thc hnh ................................................................................................................. 23
3.6. Cu hi .............................................................................................................................. 23
BI 4. NGUYN LIU V SN PHM THU ............................................................................. 25
M bi: HD E4 .......................................................................................................................... 25
4.1. Cc ngun nguyn liu v tnh cht ca mi loi ............................................................... 25
4.2. Cc loi sn phm thu c t qu trnh cracking xc tc ................................................ 26
4.3. c im cc sn phm kh v lng thu c t qu trnh cracking xc tc ...................... 27
4.3.1. Kh hydroccbon ............................................................................................................. 27
4.3.2. Phn on xng .............................................................................................................. 28
4.3.3. Cc phn on 200350oC ............................................................................................. 28
4.4. Phn thc hnh ................................................................................................................. 28
4.5. Cu hi .............................................................................................................................. 29

BI 5. CC LOI CNG NGH CRACKING XC TC ........................................................... 30


M bi: HD E5 .......................................................................................................................... 30
5.1. Cracking vi lp xc tc c nh ........................................................................................ 30
5.2. Cracking vi lp xc tc tng si ....................................................................................... 30
5.3. Cng ngh FCC ngy nay .................................................................................................. 32
5.3.1. Qu trnh ca hng UOP................................................................................................. 33
5.3.2. Qu trnh ca Kellog ....................................................................................................... 34
5.3.3. Qu trnh ca hng SHELL ............................................................................................. 35
5.3.4. Qu trnh IFP Total v Stone & Webster ...................................................................... 36
5.3.5. Qu trnh Exxon .............................................................................................................. 37
5.4. So snh cc loi cng ngh ............................................................................................... 38
5.5. Cu hi .............................................................................................................................. 40
BI 6. VN HNH CNG NGH CRACKING .......................................................................... 41
M bi: HD E6 .......................................................................................................................... 41
6.1. c im ca s cng ngh FCC ................................................................................. 41
6.1.1. chuyn ha ................................................................................................................ 41
6.1.2. Tc np liu ............................................................................................................... 42
6.1.3. T l xc tc/Nguyn liu ................................................................................................ 42
6.1.4. Nhit .......................................................................................................................... 42
6.1.5. p sut ........................................................................................................................... 42
6.2. Ti sinh xc tc cracking .................................................................................................... 42
6.3. Vn hnh s cng ngh cracking .................................................................................. 43
6.3.1. L phn ng ................................................................................................................... 43
6.3.2. L ti sinh ....................................................................................................................... 44
6.3.3. B phn phn on sn phm ........................................................................................ 44
6.4. Phn thc hnh ................................................................................................................. 44
6.5. Cu hi .............................................................................................................................. 44
BI 7. C IM CA XNG CRACKING XC TC .............................................................. 46
M bi: HD E7 .......................................................................................................................... 46
7.1. c im v thnh phn ha hc....................................................................................... 46
7.2. c im v tr s c tan.................................................................................................... 46
7.3. ng dng ca xng cracking xc tc ................................................................................. 47
7.4. Phn thc hnh ................................................................................................................. 47
7.5. Cu hi .............................................................................................................................. 48
TM TT NI DUNG MODUN ................................................................................................. 49
Mc ch ca qu trnh cracking xc tc ................................................................................... 49
Cc phn ng ha hc sy ra trong qu trnh cracking xc tc................................................. 49
Cc sn phm ca qu trnh cracking xc tc ........................................................................... 49
C ch ca qu trnh cracking xc tc ...................................................................................... 49
Cht xc tc ca qu trnh cracking .......................................................................................... 49
c trng quan trng ca cht xc tc ..................................................................................... 50
Quy trnh vn hnh ca thit b cracking xc tc cng nghip ................................................... 50
KIM TRA, NH GI HON THNH MN HC ................................................................... 50
CC THUT NG CHUYN MN ........................................................................................... 52

GII THIU V MUN


V tr, ngha, vai tr mun
Cracking xc tc l mt qu trnh cng ngh c bit quan trng trong cng
nghip ch bin du m. Thc hin cng ngh cracking nhm tng t l khi
lng cc sn phm nh nh, xng t, du ha, nhin liu Diezen...c bit l
cho xng t t cht lng thng phm. Cng qua qu trnh crc kinh xc tc
cn cho ta nhng lfin nh lm nguyn liu c bn cho ha du nh Etylen,
Propylen.
Mc tiu ca mun
Hc mn ny hc sinh cn phi:
1. Hiu bit v nm vng bn cht ha hc v vai tr xc tc trong qu trnh
cracking
2. iu ch c xc tc zeolit v xc tc cha zeolit.
3. Thc hin phn ng cracking xc tc trong PTN
4. Xc nh cc ch tiu ca xng cracking xc tc thu c.
Mc tiu thc hin ca mun
Hc xong mun ny hc vin c kh nng:
1. M t c bn cht ha hc v xc tc ca cracking xc tc.
2. iu ch c xc tc cracking: Xc tc zeolit.
3. Xc nh cc c trng ca xc tc iu ch
4. Thc hin phn ng cracking xc tc trn s PTN
5. Xc nh c ch tiu ca sn phm xng cracking xc tc
6. Thc hin cc th nghim lm trong PTN chuyn ha du.
Ni dung chnh/cc bi ca mun
1. Vai tr ca qu trnh cracking xc tc trong lc ha du.
2.
3.
4.
5.
6.
7.
8.

Bn cht ha hc ca cracking xc tc.


Lch s pht trin xc tc.
Xc tc zeolit
Nguyn liu v sn phm thu
Cc loi cng ngh cracking xc tc
Vn hnh s cng ngh cracking
c im ca xng cracking xc tc.

CC HNH THC HC TP CHNH TRONG MUN


1. Hc trn lp v cc ni dung chnh ca mun
2. Thm quan phng cng ngh lc ha du v phng nghin cu xc tc ti
Trung tm Nghin cu & Pht trin Ch bin du kh(tm hiu s
cracking hi nc, xem thit b nh gi xc tc cracking MAT)
3. Thm quan h thng chng ct du m, xem mu du m, cc phn on
chng ct c t du m v tm hiu nguyn liu cho qu trnh cracking
xc tc, cc thit b phn tch cht lng cc sn phm (Xng t)
4. Thc hnh cng ngh cracking (s trong phng th nghim)
5. Thc hnh phn tch cc ch tiu cht lng ca xng (ch tiu ha l).
Thc hnh phn tch thnh phn hydrocacbon trong sn phm cracking
bng phng php xc k.
6. Nghe chuyn gia nghnh du kh ni v cng ngh cracking xc tc cn
du (RFCC) ca nh my lc du Dung qutQung ngi.

YU CU NH GI HON THNH MUN


V kin thc
-

Hiu bit v nm vng bn cht ha hc v vai tr xc tc trong qu


trnh cracking trong cng nghip ch bin du m.

- Vai tr, v tr ca cracking xc tc trong cng nghip ch bin du m


- Sn phm ca qu trnh cracking xc tc.
V k nng
-

Bit phn tch mt s ch tiu cht lng sn phm xng trong phng

th nghim
Nm c cch thc hin quy trnh cracking xc tc quy m thit b
phng th nghim.

- Bit xc nh mt s c trnng ca xc tc zeolit


V thi
-

Hc trn lp nghim tc
Chun b chu o cho cc hat ng tham quan, nghe ngai kha

Lin h, chun b chu o cho cc bui thc hnh th nghim (vt t,


ha phm, cc iu kin hat ng ca thit b phn tch)
- Nhc nh thc an ton lao ng trong phng th nghim, vn
phng nga v chng chy,n trong PTN.
Phng php nh gi mdun
-

TT

Phng php nh gi

S ln nh gi

Trng s(%)

Kim tra gia k

20

Thc hnh th nghim

30

Thi cui k

50

BI 1. VAI TR CA QU TRNH CRACKING XC TC


M bi: HD E1
Gii thiu
Yu cu v s lng v cht lng cc sn phm nh, nguyn liu cho
cc ngnh cng nghip ho hc l rt ln, nu ch chng ct trc tip t du
th th khng th p ng nhu cu. Do cracking xc tc ng vai tr quan
trng chuyn ho cc phn nng ca du thnh cc sn phm nh v to
nguyn liu cho ho du.
Mc tiu thc hin
Hc song bi ny hc sinh c kh nng:
- M t nhu cu v s lng v cht lng ca xng nhin liu
- M t qu trnh sn xut xng.
Ni dung
1.1. Nhu cu v s lng v cht lng ca xng nhin liu
1.1.1. Nhu cu tng s lng
Nhin liu sn xut t du m gm c:
- Nhin liu kh (FG)
- Xng t, xng my bay
- Nhin liu phn lc v du ha dn dng (Jet/Kero)
- Nhin liu Diezen (DO)
- Nhin liu cho cc l t cg nghip (FO)
Nhin liu cho giao thng vn ti c 2 loi chnh l xng t v nhin liu
iezen. S pht trin khng ngng ca nn kinh t th gii, nhin liu s
dng cho giao thng vn ti cng tng lin tc do yu cu v s lng
xng nhin liu cng tng ln dn n tng nhu cu du m. Trong bng.1.1.
cho thy nhu cu du m th gii t 19702020.
Bng 1.1. Tiu th du th gii 19902020 (International Energy Outlook)
Khu
vc

Nm
1990

1995

Tng TB
nm,%

D bo
1996

2000

2005

2010

215

2020

Cc nc cng nghip pht trin


Bc M

1050,6

1094,3

1128,3

1216,2

1305,9

1419,5

1491,5

1551,7

1,4

Ty u

664,4

724,4

733,4

733,8

744,8

766,3

781,8

739,7

0,3

Chu

319,3

359,7

364,1

395,1

413,2

442,3

473,2

505,2

1,4

Tng

2034,2

2178,2

2225,8

2340,0

2489,3

2628,1

2741,3

2850,8

1,1

ng u v Lin x (c)

Nm

Khu
vc

Tng TB
nm,%

D bo

1990

1995

1996

2000

2005

2010

215

2020

515,0

303,1

292,3

302,8

341,8

401,2

462,9

520,7

2,2

Cc nc ang pht trin


Chu

391,4

580,5

610,3

682,5

851,9

1023,5

1224,1

1474,4

3,8

Tr.
ng

175,1

210,6

215,4

225,8

255,1

288,0

324,0

366,0

2,2

Chu
Phi

108,2

118,2

123,1

159,1

188,7

210,9

236,6

262,9

3,2

Trung
NamM

175,1

200,4

205,1

266,8

316,3

175,4

437,2

505,2

3,8

Tng

849,8

1109,7

1153,9

1334,2

1611,9

1897,8

2221,8

2806,5

3,5

Tng
th gii

3399

3591

3672

3977

4443

4927

4526

5980

2,1

C cu nhin liu c sn xut t du m c th hin ttrong bng 1.2.


Bng 1.2. C cu sn phm nhin liu t du m c s dng Vit Nam
(19901998)
t l
% khi lng

Loi sn phm

STT

Nhin liu
1

Nhin liu kh (F.G),LPG

810

Xng t, xng my bay

2225

Nhin liu phn lc v du ha dn dng


(Jet/Kero)

1115

Nhin liu Diezen (D.O)

4045

Nhin liu cho cc l t cg nghip(F.O)

1520

Phi nhin liu


6

Du nhn

23

Bng 1.3. Tnh hnh tiu th sn phm du Vit Nam (19901998)


Tiu th sn
phm du,tn

1990

1995

1996

1997

1998

LPG

1.000

55.000

76.000

249.000

177.000

Xng

700.800

Du ha

229.000

260.000

324.000

269.000

300.000

Nhin liu Phn


lc

120.000

229.000

237.000

391.000

300.000

1.378.100 1.310.000 1.376.000 1.564.000

Nhin liu iezen

1.353.000 2.724.000 3.103.000 3.347.000 3.642.000

Nhin liu t l

568.000

891.000

1.072.000

961.000

1.321.000

Du nhn

65.210

122.000

142.000

155.000

167.000

Nha ng

36.000

104.000

163.000

142.000

155.000

Tng cc sn
phm du

3.072.000 5.763.000 6.427.000 6.890.000 7.626..000

Ngun: Statistic General Department, B Thng Mi,Tng cc Hi quan,


Kinh t Vit nam v Th gii(9899)
Vi nhng s liu c th nu trong bng 1.2, v 1.3.cho thy s gia tng
nhu cu v s lng cc sn phm du ni chung v xng t ni ring.
Vit nam nm 1990 mi ch s dng c 700.000 tn xng nhng n nm
1998 tiu th ti 1.564.000 tn.
1.1.2. Yu cu tng cht lng v cc cng ngh sn xut xng
Do s tin b ca cng nghip ch to t, tng cng sut ng c
ngi ta ch to cc ng c c t s nn ngy cng cao, cc loi xe i
c trc (1980) xe thng c t s nn t 78.Nhng ngy nay cc xe i
mi c sn xut c t s nn 910. Do s tng cht lng cc loi xe t
nn cng i hi cht lng xng nhin liu phi thay i cho ph hp.Nhng
loi xe i c c t s nn thp ch cn s dng loi xng c tr s ctan RON
8385. Cc loi xe i mi yu cu xng c tr s ctan RON 90, RON 92,
RON 95 v RON 98.
Xng chng ct trc tip t du m t v khi lng li cn km v
cht lng. Nhiu gii php cng ngh ra i nhm lm tng tr s cctan
RON nh cng ngh crackking, reforming, isome ha, alkyl ha.Ngoi ra cn
tm cc loi ph gia cho thm vo xng tng tr s ctan nh Tetra Etyl Ch,
MtylTerbutylEter(MTBE), vv..
Mt s qu trnh cng ngh nng cao c tr s c tan nhng cc
cht lm tng tr s ctan nh cc hp cht thm c bit l Benzen rt c hi
cho sc khe con ngi.
Tiu chun cho php hm lng Benzen trong xng trc cho php ti
5% th tch, nhng nay yu cu phi < 1% th tch. Cc loi ph gia cho
vo xng tng tr s ctan nh Tetra Etyl Ch, MBTE th hin nay cng
cm s dng nh xng ch, v MBTE cng ch s dng mt cch gii hn.
Cc cht gy nhim khng kh nh lu hynh cng yu cu phi gim
nhiu ch cho php lu hynh trong xng < 10 phn triu.

Nh vy cng ngh ch bin du m phi khng ngng pht trin gia


tng tha mn yu cu c v s lng v cht lng i vi xng nhin liu
p ng yu cu ca k thut i vi ng c v yu cu kht khe bo v
mi trng.
1.2.Cc phn on nng t du th, S cn thit phi c qu trnh
Cracking
1.2.1. Cc phn on nng t du th
Cc phn on nng c nhit si trn 360oC c trong phn cn cn li
ca chng ct kh quyn thng chim t l cao, trung bnh t 3070% ty
theo tng loi du nh, du nng khc nhau. Xem bng 1.4.
- Trong bng 1.4.cho thy 02 loi du:
-

Du nh c t trng 35oAPI, du nng 25oAPI v thnh phn t nhin


ca du cho sn phm tng ng l kh, xng, cc phn on trung
bnh (diezen) v cc phn on nng. Tng ng c cu nhu cu sn

phm thc t yu cu th trng


Ta thy loi du nh c ti 68% cho xng v cc phn ct trung bnh
(diezen), ch c ~30% thuc phn on nng.Trong khi loi du nng th ch c
29% cho xng v cc phn ct trung bnh (diezen) v ti 70% thuc cc phn
on du nng.
Bng 1.4.Thnh phn t nhin chng ct trc tip t du m
Du nh
(35o API)

Du nng
(25oAPI)

Yu cu sn
phm ca th
trng

Nhin liu kh,%

02

01

510

Xng nhin liu,%

30

19

2530

Phn on chng ct trung


bnh(diezen),%

38

10

40

Phn on du nng,%

30

70

1520

Phn on sn phm

Ngun: The fuels Quality Training Seminar on 2527 October 2003 Sydney,
Australia.
Bng1.5..Cc phn on t du th Bch H v i hng ca Vit nam
Phn on sn phm

Du th Bch h

Du th i
hng

Cc phn on Napta sn xut


xng nhin liu;

3570oC,%Khi lng

2,81

1,05

70140oC,%Khi lng
35190oC,%Khi lng

8,21
18,57

6,54
13,08

7,55
19,78

5,60
17,30

230360oC,%Khi lng

26,98

22,42

Cc phn on nng:
360540oC,%Khi lng

32,15

31,78

>540oC,%Khi lng

16,35

20,76

Cc phn on sn xut du ha v
nhin liu phn lc:
190230oC,%Khi lng
140260oC,%Khi lng
Cc phn on trung bnh sn xut
nhin liu diezen:

Ngun:International Symposium on Technology Transfer and


Implementation for Refining and Petrochemical Industries in Vitnam
1.2.2.S cn thit phi c qu trnh Cracking
-

Project

Nhu cu cc phn on nh v trung bnh sn xut xng, du ha,


nhin liu phn lc v iezen nhiu hn s lng hin c nu ch
chng ct trc tip t du th.
Do nhu cu v nguyn liu cho ha du nh etylen, propylen, benzen,

toluen, xylen...
- Do yu cu cht lng xng phi c ch s c tan cao.
Nhng yu cu trn i hi phi c qu trnh cracking. Qu trnh cracking
bin i cc phn on nng thnh cc phn on nh gip ta tng hiu sut
v s lng cc sn phm nh, tng tr s ctan ca xng v to ngun
nguyn liu cho ha du.
T ban u, khi m ngi ta bit chng ct du m vi mc tiu l ly
du ha thp sng. Phn nh trong du m cha bit dng vo vic g.
Nhng khi c ng c t trong ra i, phn nh t du m c s dng
lm nhin liu v t loi xng nhin liu c ra i. S lng, chng loi
cc ng c t trong lin tc tng khng ngng cho ti ngy nay. Cc loi
ng c t trong s dng xng lm nhin liu chim t l ch yu l cc loi
xe t trong vn chuyn, c bit l cc loi xe hi c nhn.T l xng cho
ng c my bay th lin tc gim v khi ng c phn lc ra i, do c nhiu
u im nn ngnh hng khng chuyn sang s dng my bay phn lc
v dng phn on du ha sn xut nhin liu phn lc.
10

Phn nh chng ct trc tip t du th thng ch c khong t


1520% khi lng. Nhng nhu cu v xng t chim t 2530%. Vi s
tng lin tc cc loi xe s dng xng, mc d sn lng khai thc du th
cng tng ln nhanh chng nhng nu ch c cng ngh chng ct trc tip
du th th khng th p ng nhu cu v xng.
Cc phn on nh t du th c s dng sn xut xng, du ha,
nhin liu phn lc v nhin liu diezen. Cc phn on ny c nhit si
ti 350360oC. Trong cng nghip c thc hin chng ct iu kin p
sut kh quyn gi l(chng kh quyn).
Qu trnh cracking c thc hin i vi cc phn on nng c nhit
si trong khong 350540oC. Qu trnh cracking quyen thuc l crking xc
tac gi si FCC. Trng hp du th c t tp cht, loi du parafin c ch s
cc Conradson thp c th tin hnh cracking xc tc trc tip cn chng ct
kh quyn m khng cn qua chng ct chn khng c cc phn on
nng lm nguyn liu cho qu trnh cracking.
1.2.3. Sn xut xng t v xng my bay
Xng t v xng my bay u l nhin liu cho ng c t trong (c
bugi nh la). Ngoi t du lch, xng cn c dng cho cc xe ti, tu
thuyn. Xng my bay l loi khc vi xng t.Thnh phn v c tnh ca
hai loi ny c khc nhau. Loi xng my bay tiu th ngy cng t v chuyn
sang dng loi ng c phn lc dng loi nhin liu l du ha phn lc.
c trng th hin cht lng quan trng i vi xng cc loi l: bc hi,
ng cong chng ct tiu chun, tr s ctan v n nh ha hc.
bc hi c o p sut bo ha (phng php Reid), v ng
cong chng ct tiu chun(ASTM D86).Tr s ctan th hin tnh chng kch
n ca nhin liu i vi ng c c o bng loi ng c tiu chun l
my o tr s ctan. Thnh phn ca xng l hn hp cc loi hydrocacbon t
C4 n C10, C11 v c khong nhit t 40180oC. Xng c sn xut qua
pha trn t nhiu cu t ca cc qu trnh cng ngh khc nhau nh:
- Phn on chng ct trc tip t du
- Qu trnh cracking nhit, cracking xc tc
- Qu trnh reforming xc tc,
-

Qu trnh alkyl ha, Izome ha,


Qu trnh hydrocracking
Butan.

11

Xng t c cc loi khc nhau ty theo loi ng c, cc quy nh theo


tiu chun ca tng quc gia, tng khu vc lin quan n cc vn an ton
cho sc khe, mi trng v iu kin a l ca tng khu vc. ng c my
bay hat ng trong iu kin khc nghit hn so vi t do cht lng
xng my bay cn c s m bo nghim ngt. ng c my bay khi lm vic
c 2 qu trnh: Qu trnhh ct cnh s dng cng sut ti a, lng xng
trong hn hp ha kh cng tng ti a (hn hp giu). Trong khi bay ng c
c khi gim cng sut lng xng trong hn hp ha kh cng gim theo (hn
hp ngho).
Ch s ctan ca xng my bay bng hoc ln hn 100. Trng hp tr
s c tan trong hn hp giu cn gi l tr s ctan phm . Ngi ta biu th
tr s ctan ca xng my bay bng phn s, trong t s l tr s ctan cn
mu s l tr s phm .
Xng my bay c khong nhit chng ct 30170oC, khng cha
butan nh trong xng t v butan c bc hi cao, d to cc nt hi trong
ng dn nhin liu gy tc xng. Trong xng my bay thnh phn
hydrocacbon nParafin v lfin v Benzen (Benzen c nhit ng c l
6oC),cn c gii hn thp trong thnh phn. Nparafin c kh nng kt tinh,
lfin d to keo, benzen d ng c lm tc ng dn, v phin lc xng
khi my bay bay cao nhit xung rt thp. Tiu chun i vi xng my
bay quy nh im kt tinh, ng c phi thp hn 60oC.
Nh vy xng t v xng my bay hin nay thc cht c sn xut
qua qu trnh pha trn cc cu t ca cc qu trnh cng ngh khc nhau theo
yu cu tiu chun c quy nh c th.
1.3. Cu hi
1. Nhng phn on chng ct c bn t du m sn xut cc loi nhin
liu l phn on no?, khong nnhit si ca cc phn on ?
2. Cho bit t l cc loi nhin liu c s dng trong thc t?, Xng cho
ng c t trong?, nhin liu cho ng c diezen?.
3. Tnh hnh tiu th nhin liu Vit nam hin nay th no?.
4. Ti sao trong cng ngh lc du phi tin hnh qu trnh cracking?
5. Xng t v xng my bay c g khc nhau?.

12

BI 2. BN CHT HA HC CA CRACKING XC TC
M bi:HD E2
Gii thiu
Bit c vai tr ca qu trnh cracking xc tc, hc sinh phi bit r bn
cht ho hc ca qu trnh cracking.
Mc tiu thc hin
Hc bi ny hc sinh bit:
- M t c s ho hc ca qu trnh cracking
- M t c ch cracking i vi cc loi hydrocacbon.
Ni dung
2.1. C s ha hc ca Cracking
Qu trnh cracking xc tc c tin hnh iu kin:
-

Nhit : 470550oC,

p sut: 23MPa
Tc khng gian th tch: t 1120m3/m3.h (ty theo dy chuyn

cng ngh.
Nhiu phn ng ha hc s sy ra trong qu trnh v cc phn ng ny
s quyt nh cht lng v hiu sut ca qu trnh, l:
- Phn ng phn hy ct mch (b gy), phn ng cracking
- Phn ng ng phn ha,
- Phn ng chuyn v tr ca hydro, phn ng ngng t, polyme ha v
phn ng to cc.
Cc phn ng phn hy l phn ng thu nhit mnh, phn ng ng
phn ha, chuyn v hydro, polyme ha v phn ng ngng t l cc phn
ng ta nhit yu.
2.2. C ch phn ng cracking
C ch phn ng cracking xc tc l c ch ion cacboni.Cc tm hat
tnh l ion ccboni c to ra khi cc phn t hydrocacbon ca nguyn liu
tc dng vi tm axt ca xc tc.
- Tm axt xc tc c 2 loi: Loi Bronsted (H+) v Lewis (L).
- Tm Bronsted l khi tham gia phn ng c kh nng cho proton hat
ng (H+) cn tm Lewis th thiu electron nn c xu hng nhn
thm in t.
Phn ng cracking xc tc sy ra theo cc giai on sau:
Giai on 1: to ion cacboni
13

V d: trong trng hp i vi cc hydrocacbon mch thng (alkan):

CnH2n+2 +
L(H+)
+CnH 2n+1 +
Trng hp phn hy izopropylbenzen:
-

Trn tm axt kiu xc tc Lewis:


C3H7C6H5

LH

H:L +

[C6H5]
+
H:L C6H6
+
Trn tm axt kiu xc tc Bronsted:

C3H6

[C6H+5]

C3H7C6H5
+
HB [C3H+7] +
C6H6
+
+

[C3H 7] +
B
C3H6
+
HB
Giai on 2:.Cc phn ng ca ion cacboni to cc sn phm

Khi cc ion cacboni c tao ra s lp tc tham gia vo cc phn ng


bin i khc nh
-

Phn ng ng phn ha
[RCH2CH2CH2+]

[RCH2CH+CH3]

Phn ng ct mch theo quy tc

(ct mch v tr

so vi ccbon

mang in tch)

CH3C+H2

H2

CH3CH3 + H+

Cc ion tip tc tham gia cc phn ng ng phn ha, ct mch


tip,alkyl ha hay ngng t. Bin i cc ion cacboni tip din cho n khi c
cu trc bn vng nht.
bn ca cc ion cacboni c th xp xp theo th t:
ion ccboni bc 3 > ion ccboni bc 2 > ion ccboni bc 1

14

bn ca cacboni s quyt nh mc tham gia cc phn ng tip


theo ca chng.Cht lng sn phm c quyt nh bi cc phn ng ca
cc ion cacboni, c bit l phn ng phn hy, ng phn ha v chuyn v
hydro.
Giai on 3: giai on dng phn ng
Khi cc ion cacboni kt hp vi nhau, nhng hay nhn nguyn t hydro
ca xc tc to thnh phn t trung ha v chng chnh l cu t ca sn
phm cracking xc tc.
2.3. Cracking hydrocacbon parafin, naphten, aromat
Cracking hydrocacbon parafin
Parafin l thnh phn quan trong ca cc phn on gasoil. Nng lng
hat ha ca phn ng cracking parafin gim dn theo chiu di ca mch
parafin tng. V vy khi cracking mch hydrocacbon parafin cng di th cng
d b gy.
S phn nhnh v s lng nhnh ca parafin l rt quan trng trong
qu trnh cracking, chng lin quan n s to thnh ion cacboni v do
quyt nh n tc to thnh sn phm.
V d trng hp chuyn ha parafin nC6 (nhecxan) khi cracking trn
xc tc aluminosilicat:
CCCCCC
Chuyn ha 14%
Chuyn ha 25%
Chuyn ha 25%
Chuyn ha 32%

Chuyn ha 10%

Phn ng chnh to sn phm ph thuc vo s tng quan gia phn


ng cracking theo quy tc v phn ng chuyn hydro ca ion cacboni.

15

Cracking hydrocacbon Naphten


Trong qu trnh cracking xc tc naphten chuyn ha thnh olefin C3 v
C4.Cc naphten c mch bn di hn thng b ct nhnh to thnh
cyclohexan v olefin. Vng naphten tip tc c th b kh hydro to thnh
hydrocacbon thm.
R

+L

R-C+-R

+H

ion cacboni b ng phn v cracking to thnh izoparafin.(L l tm


axit Lewis v H l tm axit Bronsted).
Cracking cyclohexan:

Nh vy qua cracking c th thu c sn phm l vng nh hn hoc


vng i v cho nhiu sn phm lng hn. Do vy ngi ta cho rng naphten
l thnh phn u im nht i vi nguyn liu cracking xc tc.
Cracking hydrocacbon thm (aromat)
Do cc hp cht alkyl thm c vng thm rt bn nn khi cracking, qu
trnh s ct nhnh alkyl trc. Toluen c bn rt ln v khng th tch
nhm metyl hay etyl trong iu kin cracking.Mch alkyl cng di th cng d
b b gy v nu mch alkyl li c nhnh th tc ct nhnh cng ln.
V d khi cracking xc tc propylbenzen, phn ng nh sau:
C6H5CH2CH2CH3
C6H6
+
CH3CH=CH2
- Phn ng ng phn ha i vi hydroccbon thm:
Para Xylen
Meta Xylen
Orto Xylen
Phn ng khp vng to ra hydrocacbon thm a vng v v cui
cng hydrocacbon thm a vng tham gia phn ng ngng t to cc.
Tm tt qu trnh cracking xc tc i vi hydrocacbon ring l nh sau:
-

16

Sn phm qu trnh cracking xc tc

Hydrocacbon

Parafin

Olefin v parafin

Olefin v hydro
izoparafin

Cc hp cht olefin c trng lng phn t


thp

Parafin v ien

Parafin, naphten v hydrocacbon thm

Polyme, cc

Olefin

Xyclohexan v olefin
Hydrocacbon thm

Parafin v alkyl c mch bn ngn

ng phn ha, chuyn v nhm alkyl


Sn phm ngng t v cc.

Phn ng bc 2:

Hydrocacbon thm

Naphten + Olefin

Parafin

Hydrocacbon thm +Olefin

Sn phm ngng t v cc

Olefin

Naphten

Hydrocacbon thm
(alkyl thm)

2.4. Cc phn ng ph km theo phn ng cracking xc tc


-

Vi nguyn liu l parafin ngoi phn ng chnh l ct mch cn km


theo phn ng dehydho ha
V d:
C4H10
C4H10
C4H10

t oC , xctc
t oC , xctc
t oC , xctc

CH4

C3H6

C2H6

C2H4

C4H8

H2

Vi nguyn liu l olefin th ngoi phn ng cracking cn c phn ng


trng hp
2CH3CH2CH=CH2
CH3(CH2)5CH=CH2
Phn ng ng phn ha

Phn ng kt hp hydro to parafin

RCH=CH2

H2

RCH2CH3
17

Phn ng khp vng sau c th b kh H2 thnh cc Aren


CH2=CH-CH2-CH2-CH2-CH3

-3H2

CH 2-CH 2-CH 2-CH 3

toC, xuc tac


+ 5H2

CH 2- CH 2 -CH 2 -CH 3

Ngoi ra cn sy ra phn ng ngng t v to cc

Trong qu trnh cracking xc tc, phn ng to cc cn tm gii php hn


ch v chng lm gim hat tnh ca cht xc tc.
Phn ng to kh (C1, C2) cng cn gii hn, v mc tiu chnh ca cracking
xc tc l sn xut xng t c ch s ctan cao.
2.5. Vai tr ca phn ng cracking xc tc
Phn ng cracking xc tc nhm tng khi lng xng c sn xut
nhm p ng nhu cu tiu th xng cho t du lch v vn ti ngy cng cao,
trong khi xng c th thu c trc tip t chng ct du ch chim t l thp,
khng p ng yu cu v khi lng v cht lng. Phn ng ccracking xc
tc cn to ra cc olefin (etylen, propylen) l nguyn liu c bn rt quan
trng cho cng nghip ha du.
2.6. Cu hi
1. Cho bit c ch phn ng cracking?
2. Cc phn ng ha hc no sy ra trong qu trnh cracking? Vai tr ca
mi phn ng i vi qu trnh?
3. Cracking i vi mi nhm hydrocacbon? (parafin, naphten, aromat?)

18

BI 3. LCH S PHT TRIN CA XC TC ZEOLIT


M bi: HD E3
Gii thiu
Qu trnh xc tc cracking c p dng t lu v hin nay t
c nhng tin b rt quan trng c bit l cht xc tc. Chng ta c ng
cn phi bit nhng mc quan trng ca s pht trin khoa hc trong lnh vc
cracking xc tc.
Mc tiu
Truyn t hc sinh bit v lch s pht trin ca xc tc, nhng mc
quan trng ca s pht trin.
Bit xc nh c trng ca xc tc geolit.
Ni dung
3.1. Lch s pht trin xc tc
Trong qu trnh cracking, tc dng xc tc ca cc halogen cua hp cht
vi kim loi nh nhm clorua, km clorua., cc khong st hc cc cht tng
hp tng t trong thnh phn c cha silic, nhm, oxy(alumino silicat).
Tc dng xc tc cu nhm clorua khi cracking phn on ca du m, c
N.D.Zelinski pht hin nm 1918 trong khi nghin cu sn xut xng my bay
cho lc lng hng qun trong chin tranh v quc.Rt nhiu nghin cu
nhm gim bt lng nhm clorua nhng khng t kt qu tt.
Nm 1911, Ubbelhode v Voronin pht hin tc dngxc tc ca
khong st. Nhiu nghin cu tip theo c thc hin do Gurvici v
S.V.Lebedev theo hng lm gim s to cc trn b mt xc tc nhng
khng t kt qu mong mun.
Qu trnh cng ngh cracking c thc hin quy m cng nghip nm
1936 do k s ngi Php l Houdry v gii php loi b lp cc trn xc tc
bng qu trnh ti sinh xc tc trong khong thi gian ngn(1015 pht). Qu
trnh Houdry c thc hin trn lp xc tc c nh. Nguyn tc ca qu
trnh cracking xc tc l loi xc tc aluminosilicat v ti sinh xc tc trong
khong thi gian ngn qua s t chy cc bao ph trn xc tc.
Nhiu cng trnh nghin cu trong nhng nm tip theo, tp trung vo
cu trc ca khong st, cu trc ca aluminosilicat tng hp v l bn cht
t nhin ca cc tm axit. S nghin cu ny khng nhng ch quan trng v
l thuyt m cn lin quan cht tr n c ch tc dng ca cht xc tc v
vn hat ha cht xc tc.
19

c trng axt ca khong st t nhin c V.I.Vernadski pht hin


t 1891. Tc dng xc tc tng t nh axt sunfuric, axit phosphoric v
nhm clorua c A.V.Frost v B.A.Cazanski chng minh. Ngy nay hu
ht nghin cu u tp trung gii thch v tc dng xc tc ca khong st,
aluminosilicat tng hp v c trng axit ca chng.
Thomas thy phn cht xc tc vi t l Al/Si thay i trong dung dch
nc, cn etylic hn hp etyl ortosilicat vi etyl hoc nhm izopropylat v
thy rng: hat tnh xc tc ti a khi t s Al/Si =1.Khi tng ng vi s
lin kt ti a Al O Si.Thomas a ra s gii thch mt cch tha mn
s tn ti cc tm axit trn mng tinh th nhng li khng ph hp vi nhiu
nghin cu sau , nht l i vi khong st t nhin nh st montmorilonit.
Chng c th biu th di dng: Al2.4SiO2. H2O+nH2O.
Nh vy xc tc cracking c dng rn, xp, ban u l cc khong st t
nhin hay tng hp.
Xc tc cracking ban u l khong st thin nhin c tnh axit
(montmorillonit) sau c thay bng aluminosilicat c hat tnh v chn
lc cao hn. Cui thp nin ca th k 20 chuyn sang dng xc tc cha
zeolit. Zeolit l hp cht aluminosilic, l tinh th c cu trc c bit. Xc tc
cha zeolit c hat tnh cao, chn lc tt.
3.2. Xc tc zeolit v xc tc cha zeolit
Cc cht zeolit c cng ch to cng vi xc tc aluminosilicat hay vi
khong st thin nhin ri sau s l bng cc phng php c bit
thnh xc tc zeolit.
V thnh phn ha hc ca zeolt c biu din bng cng thc:
M2/nO.AL2O3xSiO2yH2O
y: x > 2 v n l ha tr ca cation kim loi M
Zeolit c to thnh t cc n v cu trc (hnh 1.1)

Hnh 1.1. n v cu trc c bn ca zeolit

20

Hnh 1.2.Cu trc c bn ca Aluminosilicat


Khi cc n v cu trc c bn ni vi nhau theo cc mt 4 cnh ta c
loi zeolit A, nu ni vi nhau theo cc mt 6 cnh ta c loi zeolit X hoc Y
c cu trc tng t.(Hnh 1.3)

Zeolit A

Zeolit X, Y

Hnh 1.3. Cu trc ca zeolit A v X, Y


Ngy nay ngi ta ch c nhiu loi zeolit c kch thc ca s
khc nhau.
Khi ch to xc tc cracking lng Na cn gim ti mc cc tiu v khi
nhit cao, c mt ca hi nc Na s lm gim hat tnh v chn lc
ca xc tc. Tnh cht hp ph ca zeolt xut hin sau khi chng c tch
m (bng cch sy kh 300350oC) v trong qu trnh tng hp cc l rng
ca tinh th b cht y cc phn t nc. Mng tinh th sau khi sy vn
c bo ton v c dung lng hp ph rt ln.
Qu trnh cracking xc tc thng dng loi zeolit X, Y c ch cc
nguyn t trong t him hay dng trao i ion v c s l bng cc
phng php c bit kt hp vi cc hp phn lm tng bn c, bn

21

nhit, hay iu chnh kch thc l xp. Zeolit c hat tnh cao nn ngi ta
thng dng n dng hn hp vi xc tc v nh hnh hay aluminosilicat
tinh th v c gi l xc tc cha zeolit.
3.3. Phng php iu ch xc tc zeolit
Trong cng nghip xc tc zeolit c ch to di hai dng chnh l
dng cu v dng bt.
Ngoi yu cu v hat tnh cao, xc tc cracking cn phi p ng cc
yu cu khc nh bn nht, bn c, khng gy n mn hay mi mn thit
b v m bo d khuch tn nguyn liu ti cc tm hat tnh v sn phm t
b mt ra bn ngoi. m bo s khuch tn ca xy ti b mt xc tc d
t chy cc khi ti sinh, v m bo gi thnh sn xut xc tc c th chp
nhn c.
Xut pht t cc yu cu trn m ngi ta phi chn cc hp phn thch
hp ch to xc tc.
Trong zeolit c 2 loi kch thc l xp: kch thc ca s v kch thc
l ln.Khi a chng trn vi aluminosilicat ta s iu chnh c cu trc l
ca chng trong gii hn thch hp. V d nh xc tc cha zeolit A c kch
thc l trong khong 45Ao
Xc tc zeolit loi X v Y c kch thc l 810Ao c dng cracking
nguyn liu c thnh phn phn on rng. Khi cc phn t ln ca
nguyn liu c th d dng ti b mt ca xc tc v cc phn t nh hn th
c th tip xc vi cc tm hat tnh b mt trong ca xc tc. Cn cc l
loi cao phn t nn chng bm mt ngoi ca xc tc s thun li trong
qu trnh t chy khi ti sinh xc tc.
3.4. Xc nh cc c trng ca xc tc zeolit
3.4.1. hat tnh ca xc tc cracking
Cc phng php u da vo thit b tiu chun v nguyn liu mu
cng cc iu kin cng ngh ca phng th nghim, xc nh hiu sut
sn phm.(xng, phn ct, kh v cc).V mc ch chnh ca qu trnh
cracking l sn xut xng nn phng php dng hiu sut xng thu c
nh gi hat ng ca xc tc l n gin hn.Nh vy hat tnh ca
xc tc thng biu din qua ch s hat tnh, l hiu sut xng(%kl) khi
cracking nguyn liu mu trong iu kin phng th nghim.Hat tnh ca xc
tc ph thuc vo cc tnh cht l, ha ca xc tc, vo thnh phn ha hc
ca xc tc v cng ngh ca qu trnh.
3.4.2. chn lc ca xc tc
22

Kh nng lm tng tc cc phn ng c li v ng thi lm gim tc


cc phn ng khng mong i chnh l chn lc ca xc tc. Trong
qu trnh cracking xc tc, chn lc ca xc tc quyt nh n s to
thnh xng vi cc cu t c tr s octan cao. chn lc ca xc tc c
nh gi qua t l gia hiu sut xng v cc (hay kh) cng mc bin
i.
3.4.3. S thay i tnh cht ca xc tc khi s dng
Khi lm vic hat tnh v chn lc ca xc tc cracking b gim i
n khi ht tc dng (tr ha) do cc nguyn nhn:
- Nhit qu cao,
- Thi gian tip xc qu di,
- Nguyn liu xu.
S tr ha ca xc tc qua 2 qu trnh l tr ha do cc cht lm ng c
xc tc v tc dng lm thay i tnh cht l, ha ca xc tc.
S tr ha do cc nguyn nhn trc tip l:
- Tc dng ca cc c t nh NH3, CO2, cc hp cht lu hynh c
bit l H2S khi nhit cao.
- S tch t cc kim loi nng di dng cc oxyt lm thay i chc
nng ca xc tc.
- S tc ng ca nhit cao v hi nc.
Cc hp cht c kim, cc hp cht cha nit trong nguyn liu l cc
cht lm gi nhanh xc tc. S c mt ca nit trong nguyn liu lm gim
hiu xut xng v cc sn phm trng.
Cc kim loi nng lm ng c xc tc nhanh, lm gim hat tnh, gim
su cracking, gim hiu sut xng v tng nhanh qu trnh to cc. Trong
cc phn nng ca du m c nhiu lu hynh thng c nhiu nha,
asphalten th cng c nhiu kim loi nng nh vanadi, niken.
3.5. Phn thc hnh
Hc sinh thc hin xc nh mt s c trng ca xc tc geolit ti phng
th nghim xc tc ca Trung tm nghin cu v pht trin ch bin du kh
(RDCPP), Thi gian thc hnh 08 gi, do cn b ca phng th nghim cung
cp quy trnh v hng dn th hnh.
3.6. Cu hi
1. im qua cc mc quan trng trong lch s pht trin ca xc tc
crackinng?
2. Ngi ta iu ch xc tc nh th no?
23

3. chn lc ca xc tc l g?, lm th no nh gi c chn lc?


4. Cch xc nh hat tnh ca xc tc?
5. Xc tc b mt hat tnh do nguyn nhn no?.

24

BI 4. NGUYN LIU V SN PHM THU


M bi: HD E4
Gii thiu
Bi ny gii thiu v cc ngun nguyn liu cho qu trnh cracking xc
tc v nhng sn phm thu c t qu trnh.
Mc tiu
Phn l thuyt hc sinh phi bit c cc ngun nguyn liu v tnh cht
ca nguyn liu ca qu trnh cracking xc tc.
Phn thc hnh: Phn tch mt s ch tiu ca xng cracking nh: Thnh
phn ct phn on, p sut hi bo ho, t trng...
Ni dung
Ging bi trn lp:
4.1. Cc ngun nguyn liu v tnh cht ca mi loi
Nguyn liu cho qu trnh cracking xc tc truyn thng c khong nhit
si t 300550oC v nhit si trung bnh l 400oC.
Cc phn on thng c t cc ngun:
- Cc phn ct chn khng (380550oC)
- Mt s phn ct t chng ct kh quyn.
- Cn chng ct kh quyn (>360oC) trong trng hp t kim loi, c ch
s ccConradson thp
- Cc phn ct t qu trnh cc ha
- Cc phn ct t qu trnh Visbrackinh
- Nhng phn cn chn khng kh asphalten(>550oC)
Qua cc cng trnh nghin cu ch ra:
- Nguyn liu l nhng phn ct nh s cho sn phm c hiu sut C3,
C4 tng cn H2 v cc gim. Nhng phn on nh (200 360oC)
nhn c t chng ct trc tip l nguyn liu tt nht sn xut
xng t v xng my bay.
- Nguyn liu t cc phn on nng (cc gasoil) chn khng l ph
bin nht trong qu trnh cracking xc tc. Nhm ny cho sn phm l
xng v cc phn on sn phm trng, qua chng ct chn khng
lm gim nhng cu t v hp cht c hi cho qu trnh cracking.
Thc t l thnh phn nhng kim loi nng lm nhim c xc tc
nh vanadi, niken thng c trong cc hp cht c kim, trong thnh
phn ca nha, asphalten l nhng phn t ln, c nhit si cao,
25

khi chng ct chn khng nhng cht ny s li phn cn ca


chng ct chn khng, chnh v vy m cc phn ct c lm
sch, c loi v c gim cc cht gy nhim c xc tc. Cng
chnh cc hp cht nha, asphalten khng nhng cha cc kim loi
nng m chng cn l ngun chuyn thnh cc nhiu nht, lm gim
hat tnh ca xc tc.
Thnh phn ha hc ca nguyn liu nh hng rt ln n hiu sut
ca qu trnh. Vi nhm hydrocacbon parafin s cho hiu qu chuyn ha cao
nht.Nhm hydrocacbon thm cho hiu sut xng km hn v li tng mc
chuyn ha to cc. Nhng cht phi hydrocacbon l c hi cho qu trnh
cracking xc tc, chng gy ng c cho xc tc v cn chuyn vo sn phm
lm gim cht lng sn phm nh cc hp cht lu hynh.
Trong thc t vi s tin b ca cng ngh, qu trnh cracking xc tc c
th s dng cn chng ct kh quyn lm nguyn liu trc tip cho qu trnh
m khng phi qua chng ct chn khng. Qu trnh ny gi l qu trnh
cracking xc tc cn (RFCC).Nhng loi du th parafin, t lu hynh thng
c t cc cht gy nhim c xc tc v ch s cc Conradson thp rt thun
li cho vic dng thng cn chng ct kh quyn lm nguyn liu cho qu
trnh RFCC.
tng ngun nguyn liu, ngay c cn chng ct chn khng cng
c lm nguyn liu cho qu trnh cracking xc tc sau khi kh nha v
asphalten.
4.2. Cc loi sn phm thu c t qu trnh cracking xc tc
Cht lng ca sn phm cracking xc tc thay i trong phm vi rt
rng ph thuc vo rt nhiu yu t nh nguyn liu, loi xc tc v cc thng
s cng ngh ca qu trnh.Hn hp sn phm ca qu trnh cracking c
chuyn tip n thit b chng ct phn ra cc phn on sn phm:
- Sn phm kh,
- Cc phn on xng, du ha,
- Cc phn on gasoil nh v nng.
- Phn on cn dng lm nhin liu t l... Trong bng 4.1. th hin
hiu sut v cht lng ca sn phm cracking ph thuc vo tnh
cht ca nguyn liu:
Bng 4.1. nh hng ca nguyn liu i vi cht lng v s phn b sn
phm

26

loi nguyn liu


c trng

Nguyn liu:
- Hng s c trng KUOP
- Gii hn chng ct, oC

Parafin

Naphten

Aromat

C
nhiu
lu
hynh

12,2
11,9
11,3
12,0
280540 250466 220462 245570

C nhiu
Nit

11,5
218471

Thnh phn nhm hydrocacbon:


- Parafin,% th tch
- Aromat+olefin,% th tch
- Naphten,% th tch
- S,% trng lng
- N,% trng lng

60
14
26
0,17
-

49
28
23
-

24
40
36
-

2,14
0,07

0,7
0,25

Hiu sut:
- H2S, % trng lng
- H2 , % trng lng
- CH4 , % trng lng
- C2H4 , % trng lng
- C2H6 , % trng lng
- C3H6 , % trng lng
- C3H8 , % trng lng
- i-C4H10 , % th tch
- n-C4H10 , % th tch
- C4H8 , % th tch

0,05
0,7
0,6
0,6
3,8
1,6
7,2
1,7
6,9

0,02
0,7
0,6
0,6
3,6
1,9
8,5
1,9
5,7

0,03
0,6
0,6
0,5
3,0
1,3
7,7
1,1
5,0

0,9
0,05
0,8
0,4
0,8
2,6
2,4
7,1
1,8
3,6

0,3
0,1
1,2
0,5
1,0
1,9
1,8
5,3
1,7
3,6

- Xng(C5+), %th tch

39,3

36,7

41,4

39,3

38,7

- Gasoil nh, %th tch


- Cc, %trng lng
- Tr s octan ca xng(RON)

45,0
3,1
93

45,0
4,3
94,5

45,0
3,8
97,2

45,0
6,5
89,8

45,0
8,0
97,0

4.3. c im cc sn phm kh v lng thu c t qu trnh cracking


xc tc
4.3.1. Kh hydroccbon
Hiu sut kh c th t 1025% nguyn liu ph thuc vo nguyn liu v
iu kin cracking.
Trong iu kin nhit cao, tc nguyn liu nh, bi s tun hon
xc tc ln th hiu sut sn phm kh s ln v ngc li th hiu sut kh
nh.Nguyn liu c hm lng lu hynh cao th sn phm kh c nhiu kh
H2S v khi nguyn liu c nhiu nit th sn phm kh cracking c nhiu NH3.
27

Thnh phn kh cracking cn ph thuc bi loi xc tc c s dng.(v d


nh trong bng 4.2).
Bng 4.2. Thnh phn kh cracking ph thuc bi loi xc tc c s dng.
Cu t hydrocacbon Xc tc cha zeolit

Xc tc cha aluminosilicat

H2S

4,9

3,6

H2
CH4

0,1
1,6

3,1
8,0

C2H4

2,7

6,9

C2H6

1,8

2,8

C3H6
C3H8

23,1
7,9

25,6
5,7

nC4H8
iC4H8
nC4H10
iC4H10

16,6
5,7
6,4
28,1

16,0
10,1
3,0
15,2

Sn phm kh, kh kh c dng lm nhin liu kh, etylen v propylen


l nguyn liu cho sn xut nha polyetylen (PE) v polypropylen (PP),
Propanpropen lm nguyn liu cho qu trnh polyme ha v sn sut cc
cht hat ng b mt v lm nhin liu t (LPG).
Propanpropen, butanbuten cn lm nguyn liu cho qu trnh alkyl ha
nhn cu t c tr s octan cao pha vo xng, v lm nguyn liu cho cc
qu trnh tng hp ha du.
4.3.2. Phn on xng
Phn on xng thng c nhit 40200oC, phn on ny l cu t
c bn pha trn vi nhng cu t khc t cc qu trnh Reforming,
alkylha, v cc phn on naphta t qu trnh chng ct trc tip sn
xut cc loi xng t, xng my bay.
Phn on xng t qu trnh cracking xc tc khc vi cc phn on c
cng khong nhit si t qu trnh chng ct trc tip l c tr s ctan cao
hn v cc bit l c thm thnh phn hydrocacbon olefin.
4.3.3. Cc phn on 200350oC
Phn on 200280oC dng lm du ha v phn on 200350oC c
dng pha trn v sn xut nhin liu diezen
Cc phn on > 350oC c dng lm nhin liu t l FO hay c
dng lm nguyn liu cho qu trnh cc ha.
4.4. Phn thc hnh
28

Phn thc hnh trong phng th nghim ca Trung tm nghin cu v


pht trin ch bin du kh (RDCPP), Thi gian thc hnh 08 gi, do cn b
ca phng th nghim cung cp quy trnh v hng dn thc hnh. S thc
hnh xc nh thnh phn chng ct theo tiu chun ASTM D86, xc nh t
trng v o p sut hi bo ho.
4.5. Cu hi
1. Cho bit cc ngun nguyn liu cho qu trnh cracking xc tc?.
2. Cc loi sn phm chnh thu c t qu trnh cracking xc tc?
3. Tnh cht ca nguyn liu nh hng nh th no n hiu sut v cht
lng cc sn phm thu c t qu trnh cracking?

29

BI 5. CC LOI CNG NGH CRACKING XC TC


M bi: HD E5
Gii thiu
Trong cng nghip lc du v ang p dng nhiu cng ngh cracking
khc nhau theo bn quyn ca cc hng. Chng ta cn bit nhng nt c bn
khc nhau ca mi loai cng ngh ny.
Mc tiu
Khi hc song hc sinh phi:
- M t c bn cht ca cc loi cngg ngh cracking
- So snh u, nhc im ca cc loi cng ngh.
Ni dung
5.1. Cracking vi lp xc tc c nh
Dy truyn cracking xc tc u tin do Houdry,mt k s ngi Php
thit k c a vo cng nghip ch bin du t nm 1936.Cng ngh ny
hat ng theo kiu gin on vi lp xc tc c nh. Nhc im ca cng
ngh ny l hat ng gin on v vy rt phc tp trong vn hnh. Hai chu
k l phn ng xc tc cho sn phm v chu k ti sinh xc tc trong cng
mt thit b. Dy truyn ny nhanh chng c ci tin v ch nm nm sau,
nm 1941 xut hin qu trnh cracking vi lp xc tc chuyn ng.
5.2. Cracking vi lp xc tc tng si
Qu trnh cracking c lp xc tc chuyn ng thay th qu trnh
Houdry. Qu trnh phn ng xc tc v ti sinh xc tc c thc hin cc
thit b ring bit: thit b phn ng(l phn ng) v thit b ti sinh xc tc.(l
ti sinh). Xc tc lm vic c cha cc chy t l phn ng vo l ti sinh
v sau khi ti sinh li ngc v l phn ng (hoc bng t chy hoc bng
cng bc) to thnh mt chu trnh lin tc. Nm 1942 quy trnh cracking xc
tc gi si (FCC) u tin c a vo hat ng c tn l Up Flow (model
I) hnh 5.1
Nm 1944 ngi ta tng ng knh ca l phn ng v l ti sinh, tch
hi sn phm c thc hin ngay trong l phn ng v ti sinh xc tc
dng tng si v qu trnh thi cho xc tc chuyn ng t pha di v ly ra
ngoi y l. Dy truyn hat ng nh vy c tn l Dow Flow (Model II)
hnh 5.2. Ngi ta lin tc ci tin thit b v c hng dng ca xc tc.
Hnh dng xc tc ph bin l dng vin hnh cu nhm lm gim s mt mt
xc tc v gim s mi mn thit b v nng cao hiu qu tch ca xyclon.
30

Hnh 5.1. S FCC Model I


Model I, t l xc tc/nguyn liu ch t ti a l 3 nhng model II c th
tng ti a l 10. Hng M.B.Kellog thit k loi cn bng p sut Model III
nm 1946, hnh 5.3.

Hnh 5.2. S FCC Model II


Hng StandardOil (New Jersey) thit k loi FCC mi (Model IV)
hnh 5.4. t ci tin ca Model II v a vo hat ng t 1952.

31

Cng ngh FCC ngy cng c ci tin nhm t hiu sut v cht
lng xng cao hn, vi cht lng nguyn liu ngy cng xu hn.

Hnh 5.3. S FCC Model III

1.Kh, 2. Hi nc, 3. L ti sinh, 4.Kh, khi, 5.Nguyn liu, 6. L phn ng,


7. Ct chng ct phn on, 8.Xng v kh, 9.Hi lu nh, 10.Hi lu,
11. ct bay hi ph, 12.Gasoil nh, 13. Gasoil nng, 14.Cn
Hnh 5.4. S cng ngh FCC Model IV
5.3. Cng ngh FCC ngy nay
Qu trnh FCC ca mt s hng cng nghip ni ting gm c:

32

5.3.1. Qu trnh ca hng UOP


Qua cc bc ci tin lin tc, hin nay cng ngh FCC ca UOP cng
p dngg cracking nhm chuyn ha cn du nng. Qu trnh ca UPOP
c cng ty Ashland OilCo pht trin. Chnh hng UOP thit k 2 loi
FCC:
- Loi l ti sinh t chy hon ton 1 cp (hnh 5.5)
-

Loi ti sinh hai cp.(hnh 5.6)

Hnh 5.5. S RCC ti sinh 1 cp ca hng UOP

33

Hnh 5.6. S RCC loi ti sinh 2 cp ca hng UOP


5.3.2. Qu trnh ca Kellog
S vn chuyn xc tc c thc hin theo phng thng ng rt
thun li v c th dng van chn iu khin qu trnh tun hon ca xc
tc. Qu trnh cracking c thc hin hon ton trong l phn ng dng ng
ng.(l ng ng). H thng xyclon c t ngay ca ra ca ng ng.
Trong l ti sinh xc tc v khng kh tip xc ngc chiu nhau. Kiu RFCC
c trnh by trong hnh 5.7. c im chnh ca model ny l vi phun
nguyn liu c ci tin nhm tng cng s tip xc gia xc tc v
nguyn liu, b phn lm ngui c thay i bng cch t t pha c
thay cho pha lang trong l ti sinh trnh n mn, mi mn trang thit b do
34

xc tc v nhm lm tng tc truyn nhit. Hnh dng b phn lm ngui


xc tc do Kellog thit k cng tng t ca UOP ch khc l cch b tr cc
ng trao i nhit t ngc chiu.

Hnh 5.7. S RFCC ca hng Kellog


5.3.3. Qu trnh ca hng SHELL
Shell c nhiu ng gp trong vic pht trin cracking xc tc phn cn
nng (RFCC). Qu trnh Shell LRFCC(Long Residue FCC) cracking xc tc
cn nng v rng, c b phn lm ngui xc tc trnh s t chy qu
nhit. Thit b trnh by trong hnh 5.8.

35

Hnh 5.8. S RFCC ca hng Sheell


5.3.4. Qu trnh IFP Total v Stone & Webster
Hai hng cng nghip ny hp tc tht k qu trnh RFCC vi ti sinh
xc tc 2 cp. Qu trnh nhm cracking xc tc cn nng v c tn l R.2.R
Process. Qu trnh cng c trang b b phn lm ngui xc tc, h thng kim
tra v iu khin nhit ca khi l phn ng.
c im ca cng ngh R.2.R l l ng, ti sinh 2 cp, c s ci tin
thit b phun nguyn liu trc tip vo dng xc tc mng. (hnh 5.9).

36

Hnh 5.9. Qu trnh R.2.R ca IFP


5.3.5. Qu trnh Exxon

Hnh 5.10. Qu trnh RFCC ca hng Exxon

37

Exxon lin tc nghin cu ci tin cng ngh FCC,t khi a ra model IV


v n nay a ra loi model IIIR, cracking c c tnh linh hat.C th s
dng nguyn liu khc nhau t cc phn ct chn khng n cc loi cn
nng (hnh 5.10).
5.4. So snh cc loi cng ngh
Trong nphn m t cng ngh chung nu c im chnh ca tng
loi. Qua m t ny ta c th so snh s ging nhau v cc c trng khc
nhau gia cc cng ngh. Mi loi cng ngh c nhng u im v s hn
ch. Ty theo mc tiu ca nh u t, mc ch s dng nguyn liu g
c th quyt nh chn cng ngh no?
Thc t tnh ti nm 1994, nhng bn quyn cng ngh c cc
nh u t chn v c xy dng.(bng 5.1)*
Bng 5.1. Bn quyn cng ngh c nh u t chn
Ngun: Idemisu Kosan.Co.LTD. 1994
Nh bn quyn

S cng ngh c chn, trin


khai trong cc nh my trn th gii

UOP

KELLOG

STONE&WEBSTER

16

IFP/TOTAL

SHELL

Sau y l c th nhng ni mua bn quyn cng ngh ca cc hng,


ni xy dng v thi gian a vo vn hnh.
Bng 5.2. Cc n v mua bn quyn cng ngh v a im xy d
Khch hng mua bn
quyn

Ni xy dng

Nm a vo
hot ng

Catlettsburg,Kentuka, USA
Mongstat, Nauy
Ohita, Nht bn
Bologan, Indonesia

1983
1989
1991
1994

Chu u
Hn quc
Hn quc

thit k(1994)
1996
1996

ICng ngh RFCC ca UOP


1.Ashland Oil
2.Statoil
3.Kyushu Oil
4.Pertamina
5.Undesclosed
6.Yukong
7.Kuyng In Energy

38

Khch hng mua bn

Ni xy dng

quyn

Nm a vo
hot ng

II Cng ngh RFCC ca KELLOG


1.Phillip Petroleum
2.Phillip Petroleum
3.Valero Refining Co.
4.Chinese Petroleum Corp.

Borger, Texas, USA


Sweeny, Texas, USA

1961
1981

Corpus Chiristi,Texas, USA


Ta lin Pu, i loan

1983
1991

Sen dai, Nht bn

1992

Chiba, Nht bn

1995

Arkansas,Kansas,USA
Ardmore,Oklahoma, USA
Montreal, Canada

1881(nng cp)
1982
1985

Montreal, Canada
Kwinana,Australia
Wuhan. Trung Quc

1987
1987
1987(nng cp)

Changling,Trung Quc
Guangzhou,Trung Quc
Zhenhai,Trung Quc
Nanjing,Trung Quc

1989
1990
1990(nng cp)
1991

PortAthur,Texas,USA
Negishi,Nht bn
Yeochum, Hn quc
Sanfrancisco,USA

1991(nng cp)
1992
1994
1994

Singapore
Thi lan

1996
1996

Aichi,Nht bn
Musi,Indonesia
Ulsan, Hn quc
Hokkaido, Nht bn
Montenvideo, Urugoay

1987
1993
1993
1994
1994(nng cp)

Barrancebermeyja, Columbia

1995(nng cp)

5.Misubishi Oil
6.Kyokuto Petroleum Ind.
IIICng ngh RFCC ca S&W
1.Total Petroleum
2.Total Petroleum
3.Petro Canada
4.Shel Canada
5.BPAustralia
6.SINOPEC
7.SINOPEC
8.SINOPEC
9.SINOPEC
10.SINOPEC
11.Chevron USA.Inc.
12.Nipon Petrpoleum
13.Honam Oil
14.Pacific Refining
15.Singapore.Refining
16.Star Petroeum Refinery

IVCng ngh R.2.R.ca IFP/TOTAL


1.Idemisu Kosan
2.Pertamina
3.Sang Yong Oil
4.Idemisu Cosan
5.Ancap
6.Ecopetrol

VCng ngh LRFCC ca Shell


1.Shell UK

Stanlow, Anh quc

1989

39

Khch hng mua bn

Nm a vo

Ni xy dng

quyn
2.Shell Singapore
3.Shell Australia

hot ng

Pulau Bukom, Singapore


Geelong, Australia

1990
1992

Norco, Lousiana

1992

Yokkaichi, Nht bn

1995

4.Shell Oil
5.Showa Yokkaichi Sekiyu

Bng 5.3.So snh cng ngh


Nh bn
quyn

IFP

SW

UOP

KELLOG

SHELL

Tn cng
ngh

R.2.R

S&W
FCC

RCC

Kellog&MobilFCC

ShellLR
FCC

Phun

Vi p

Vi p

Vi p

Vi p sut thp

Vi p sut

sut

sut cao

sut thp

Bn

Bn

Bn trong

Bn trong

Bn trong

ngoi

ngoi

H thng
ti sinh

Hai cp

Hai cp

1
cp/2cp

1 cp

1 cp

Lm ngui
xc tc

Khng

Hat ng
ca h
thng

H
thng
m

H thng
m

H thng
ng

H thng ng

h thng
m

nguyn liu

thp

cao
Xyclon

Xyclon
5.5. Cu hi
1. M t, trnh by v nguyn l hat ng ca 1 loi cng ngh cracking xc
tc gi si?
2. Cng ngh FCC ngy nay, nu nhng c im khc nhau ca cng ngh
FCC gia cc hng?

40

BI 6. VN HNH CNG NGH CRACKING


M bi: HD E6
Gii thiu
Nm c nguyn l vn hnh s cng ngh cracking l vic phi bit
i vi hc sinh. Mi cng ngh khc nhau c nhng im ging v khc
nhau, hc sinh cng cn phi bit.
Mc tiu
- Hc sinh cn phi nm c c im ca s cngg ngh FCC.
- Bit c nhng vn quan trng trong ti sinh xc tc
- c thc hnh thit b nh gi hot tnh xc tc trn thit b MAT.
Ni dung
6.1. c im ca s cng ngh FCC
c im cng ngh FCC l qu trnh cracking xc tc lp si (gi si),
qu trnh thc hin trn dng xc tc chuyn ng lin tc trong l phn ng
cng nguyn liu v sang l ti sinh thc hin vic t cc cng vi oxy
khng kh trn xc tc tham gia phn ng ri li sang l phn ng, c th
xc tc lin tc chuyn ng.
Cng ngh FCC hat ng vi nhng thng s quan trng sau::
- chuyn ha.
- Tc np liu,
- T l xc tc/Nguyn liu
- Nhit
- p sut
6.1.1. chuyn ha
chuyn ha C c tnh bng:
C = Tng hiu sut (kh +Xng +Cc)
C = 100 y(100z)
y: l% th tch ca sn phm c nhit si cui cao hn im si
cui ca xng
z: l% th tch xng c trong nguyn liu

41

6.1.2. Tc np liu
L t s gia lng nguyn liu c np trong mt n v thi gian trn
lng xc tc trong l phn ng.v c k hiu bng M/H/M
Khi tng tc np liu s lm gim chuyn ho v ngc li v tc
np liu l i lng ngc vi thi gian phn ng. Khi s dng xc tc c
hat tnh cao ta c th tng tc np liu khi y s tng nng sut ca
thit b.
6.1.3. T l xc tc/Nguyn liu
T l xc tc zeolit/nguyn liu,cn gi l bi s tun hon xc tc
(X/RH). Vi loi xc tc zeolt th X/RH=10/1 cn xc tc v nh hnh
X/RH=20/1. Khi thay i t l X/RH s lm thay i thi gian lu ca xc tc
trong l phn ng v l ti sinh v thay i c lng cc bm trn xc tc.
ch n nh t l X/RH tng s lm tng chuyn ha v gim hm lng
cc bm trn xc tc, khi thi gian tip xc gia xc tc v nguyn liu
gim nhng hat tnh trung bnh ca xc tc li tng ln.
6.1.4. Nhit
Nhit trong l phn ng khi vn hnh trong khong 470540oC. Khi
nhit tng ln th tc phn ng phn hy nhanh hn nhng cng thc
y cc phn bc 2 nh kh hydro tng ln dn n tng hiu sut
hydrocacbon thm v olefin. Khi C1C3 trong kh tng, C4 gim, t trng v
tr s octan ca xng tng ln.
Khi nhit cao hiu sut xng gim, hiu sut kh tng v cc khng
tng.
6.1.5. p sut
Khi p sut tng th hiu sut xng tng ln, hiu sut C 1C3 gim, hm
lng olefin v hydrocacbon thm gim dn ti tr s octan ca xng gim.
6.2. Ti sinh xc tc cracking

42

s dng xc tc c lu, trong cng ngh phi thc hin vic ti


sinh xc tc. Nguyn nhn chnh lm mt hat tnh ca xc tc l do cc
to thnh bm kn b mt hat tnh ca xc tc.
ti sinh xc tc ngi ta tin hnh t cc bng khng kh nng
trong l ti sinh.
Khi t cc s to thnh CO, CO2, cc phn ng kh cc hp cht lu
hynh.
O2

CO2

C +
CO +
H2 +

O2
O2
O2

CO
CO2
H2O

S
+
SO2 +

O2
O2

SO2
SO3

MeO+

SO3

MeSO4

MeSO4 + 4H2
MeO
+
H2S
+
3H2O
Nhit lng ta ra c dng cp nhit cho xc tc mang vo l phn
ng.
6.3. Vn hnh s cng ngh cracking
Sau y trnh by s vn hnh ca mt dy truyn cng ngh FCC thng
dng (hnh 6.1) t cc b phn chnh:
6.3.1. L phn ng
Nguyn liu mi t b cha (1), i qua cc thit b trao i nhit ng
chm, nguyn liu mi c th c trn vi phn tun hon (HCO)(2) v cn
y (3), sau cho qua l t nng nguyn liu cracking.Nguyn liu cracking
(5)c tip xc vi xc tc nng ti sinh (6) y ca l ng, lc ny
nguyn liu c bay hi, v hn hp vi hi nng cng xc tc i ln pha
trn ti nh ca ng ng, trong qu trnh i ln trong ng th hu ht cc
phn ng cracking xc tc sy ra, cn phn l pha trn lm nhim v tch
xc tc v hi hydroccbon.Mt b phn c thit k b tr gn van chn,
dng hi nc thi xc tc v du nhm hn ch ti a hin tng quay
tr li ca xc tc v hi kh lm vic. Hi sn phm nng (7) c chuyn
ti ct phn on. Xc tc lm vic (8) cho qua vng tch hi bng cch
thi hi nc.B phn lm sch khng nhng ch lm nhim v ui ht
hydrocacbon hp ph trn xc tc m cn lm ti cc ht xc tc trc khi
sang l ti sinh.Vic thi hi nc c b iu chnh tc hi mt cch thch
hp, kim tra cht ch thi gian lu ca xc tc trong b phn ra nhm trnh
43

phi dng qu nhiu khng kh trong l ti sinh.p sut trong l phn ng


c bng b phn iu chnh p sut ca ct phn on.
6.3.2. L ti sinh
Xc tc lm vic b bm cc (8) c chuyn qua van iu khin v b
khng ch bi b kim tra mc xc tc trong l phn ng sau i vo l ti
sinh. Theo hung tip tuyn vi thnh l. Vic t cc trn xc tc trong l
ti sinh bng oxy khng kh to thnh CO v CO2 v xc tc c ti sinh.
Khng kh t sau khi nn uc cho vo l ti sinh qua li phn phi
trn khng kh v xc tc.S chy ca cc c thc hin trong lp si, mun
t iu ny tc cca khng kh phi ln hn 1m/s.Xc tc ti sinh
c chuyn vo ng ng sau khi i sch kh nh mt van t
ng ca l ti sinh ri sau xc tc c trn vi nguyn liu cracking v
hon thnh mt chu trnh. Ngi ta tho xc tc bn gi ha ra, b sung
xc tc mi m bo hat tnh ca xc tc n nh trong thi gian
lm vic.Kh to thnh qua s chy cc cng cc ht xc tc b cun theo ln
nh l ti sinh s qua hai cp xyclon gi li cc ht x tc, Kh v khi
c qua bung lng tch tip bi xc tc ri qua b phn tn dng nhit
(12), tip tc c lm sch bng lc in ri i ra ngoi theo ng khi.
6.3.3. B phn phn on sn phm
Hi sn phm (7) c np vo ct phn on chia thnh cc sn
phm khc nhaunh: xng v phn nh hn c di qua b phn ngng t
ri vo b phn tch kh.Sau khi tch kh nhn c phn on C1, C2 s
(16). Phn on ny c dng lm kh nhin liu.
Phn on C3, C4 cha nhiu propylen v buten (17) c dng lm
nguyn liu cho qu trnh alkyl ha v tip l phn on xng kh butan
(18). T ct phn on chnh cn nhn c cc phn on Naphta nng
(19), LCO (20), HCO(21). Phn HCO c th cho tun hon li ng ng ca l
phn ng qua ng (22) v cui cng l du cn c lm sch (24).
6.4. Phn thc hnh
Phn thc hnh trong phng th nghim ca Trung tm nghin cu v
pht trin ch bin du kh (RDCPP), Thi gian thc hnh 08 gi, do cn b
ca phng th nghim cung cp quy trnh v hng dn thc hnh. S thc
hnh trn thit b nh gi hot tnh ca xc tc trn thit b MAT
6.5. Cu hi
1. Nhng thng s k thut quan trng ca qu trnh cng ngh cracking xc
tc khi vn hnh? nh hng ca tng thng s i vi qu trnh?
44

2. Mc chuyn ha c tnh nh th no?


3. Ti sinh xc tc trong cng nghip nh th no? sn phm to thnh trong
qu trnh ti sinh?
4. M t, trnh by qu trnh vn hnh 1 s cng ngh FCC thng (hnh
6.1).

45

BI 7. C IM CA XNG CRACKING XC TC
M bi: HD E7
Gii thiu
Qu trnh cracking xc tc cho sn phm xng c cht lng khc nhau
tu theo loi nguyn liu v c im ca tng loi cng ngh vi cc bn
quyn khc nhau.
Mc tiu
Sau khi hc bi ny hc sinh phi:
- Gii thiu c c im ca xng cracking
- Xc nh c thnh phn ca xng cracking.
Ni dung
7.1. c im v thnh phn ha hc
Xng cracking xc tc l sn phm chnh ca qu trnh cracking xc tc.
Ty theo loi nguyn liu s dng v cc ch khi thc hin cng ngh (xc
tc, nhit , p xut...) dn n thnh phn ha hc ca xng thu c cng
thay i. Hiu sut xng t qu trnh cracking xc tc thng khong 3035%
lng nguyn liu.
Thnh phn ha hc ca xng cracking:
Hydrocacbon thm: 2540%
Olefin: 1530%
Naphten: 210%
Parafin: 3560%
- Hm lng lu hynh: 0,010,02%khi lng
Hiu sut v cht lng ca xng ph thuc vo cht lng nguyn
liu,xc tc v ch cng ngh.
Nguyn liu c nhiu naphten th xng c cht lng cao, nguyn liu c
nhiu parafin th xng thu c c tr s ctan thp hn.
Xng cracking c t trng trong khong 0,720,77.
Xng cracking c dng pha ch sn xut xng t v xng my bay.
Xng cracking xc tc c lng olefin cao, dn ti tnh n nh ca xng km,
trong tn cha v s dng d b to nha, gy tc kim phun nhin liu, nh
hng ti cht lng xng.
7.2. c im v tr s c tan

46

Ty theo bn cht nguyn liu v cc iu kin ca qu trnh cng ngh


thc hin cracking xc tc s cho sn phm xng c tr s ctan trong khong
di y:
Tr s ctan,

RON: 8795
MON: 7885
Tr s ctan ph thuc vo thnh phn ha hc ca xng. Khi thnh phn
hydrocacbon thm, v izoparafin cao s cho tr s ctan cao.
Tr s c tan ca xng cracking cng ch mc p ng cho xng t thng
thng, khi cn xng cho cc loi t i mi hat ng vi tr s nn cao v
cho xng my bay, cn phi pha trn vi nhng loi xng t qu trnh ng
phn ha, alkyl ha hoc qu trnh reforming.
7.3. ng dng ca xng cracking xc tc
Xng cracking xc tc l cu t quan trng i vi vic sn xut xng
nhin liu nhm p ng yu cu ngy cng cao v s lng v cht lng.
Nu ch c xng chng ct trc tip t du th th khng p ng c yu
cu v s lng. Qua qu trnh cracking xc tc bin chuyn t phn nng
km gi tr s dng v t yu cu thnh cc sn phm nh c gi tr s dng
cao hn, c bit l xng cracking.
Vi s i hi cht lng xng c cht lng cao hn, xng cracking
cn phi pha trn cng vi nhng cu t khc sn xut xng thng
phm. Xng cracking c hm lng hydrocacbon thm, olefin cao cho tr s
ctan cao nhng i hi v v sinh mi trng ch cho php gii hn thnh
phn ny. Nhiu olefin cn lm cho xng km n nh, d b oxy ha to thnh
cc cht nha gy tc h thng phun xng ca ng c.Hm lng
hydrocacbon thm cao, nht l benzen gy hi cho sc khe ngi s dng.
Trong thc t cc nh my ch bin du hin i cn c nhng cng ngh
khc nhm tng tr s ctan ca xng nhng hn ch nhng cu t olefin v
hydrocacbon thm.Nhng cng ngh thng l qu trnh ng phn ha,
alkyl ho. Vi xng ct trc tip t du th thng c tr s ctan thp s
c qua qu trnh reforming xc tc nng cao ch s c tan. sn xut
cc loi xng t, xng my bay c phm cht theo tiu chun yu cu th
xng ca qu trnh cracking xc tc l thnh phn chnh pha trn vi
nhng loi xng chng ct trc tip, xng alkyl ha, xng ng phn ha...
7.4. Phn thc hnh
Phn thc hnh trong phng th nghim ca Trung tm nghin cu v
pht trin ch bin du kh (RDCPP), Thi gian thc hnh 08 gi, do cn b
47

ca phng th nghim cung cp quy trnh v hng dn thc hnh xc nh


thnh phn nhm hydrocacbon
7.5. Cu hi
1. c im, thnh phn ha hc ca xng cracking xc tc
2. ng dng ca xng cracking xc tc, Xng cracking xc tc c nhng u
im, nhc im g khi pha trn v sn sut xng thng phm.

48

TM TT NI DUNG MODUN
Ni dung trng tm ca modun ny
Mc ch ca qu trnh cracking xc tc
-

S ra i cng ngh cracking xc tc nhm p ng yu cu sn


phm nh t du ngy cng cao nht l xng cho t m nu ch
chng ct du th th khng tha mn nhu cu.

Qu trnh cracking xc tc cn cho cc olefin nh lm nguyn liu cho


ha du.

Cracking thng thc hin i vi phn cn chng ct kh quyn (si


trn 350oC), thng c gi tr thp hn du th, nn cn cracking (ch
bin su) thu cc sn phm nh c gi tr cao v qua lm tng

hiu qu kinh t ca nh my lc du.


Cc phn ng ha hc sy ra trong qu trnh cracking xc tc
-

Phn ng phn hy ct mh CC (phn ng cracking)


Phn ng ng phn ha

- Phn ng chuyn v hydro


- Phn ng ngng t
- Phn ng polyme ha
- Phn ng to cc.
Cc sn phm ca qu trnh cracking xc tc
-

Sn phm kh: Sn phm kh quan trng l cc olefin nh nh etylen,


propylen, butadien...l nguyn liu c bn cho cng nghip ha du,
Sn phm lng: c xng cracking, du ha, gasoil, trong quan

trng nht l xng cracking.


C ch ca qu trnh cracking xc tc
C ch ca qu trnh cracking xc tc l c ch ion cacboni. C s l
thuyt ny da vo cc tm hat tnh l cc ion cacboni, chng c to ra
khi cc phn t hydrocacbon ca nguyn liu tc dng vi cc tm axt ca
cht xc tc loi Bronsted(H+) hay Lewis (L).
Cht xc tc ca qu trnh cracking
-

Zeolit v xc tc cha zeolit. Zeolit l hp cht ca aluminosilic dng


tinh th c cu trc c bit, c cc l rng, rnh nh thng vi nhau
Cc cht zeolit c ch to cng vi cc xc tc aluminosilicat hay
vi t st thin nhin ri sau c s l bng cc phng php
c bit to thnh xc tc cha zeolit.
49

c trng quan trng ca cht xc tc


-

hat tnh ca xc tc: thng c biu din thng qua ch s


hat tnh, l gi tr ca hiu sut xng (% khi lng) khi cracking
nguyn liu mu trong iu kin phng th nghim
chn lc ca xc tc: l kh nng lm tng tc cc phn ng c
li v ng thi lm gim tc cc phn ng khng c li, qua
lm tng hiu sut v cht lng ca sn phm thu c.
bn ca xc tc: Trong qu trnh tham gia phn ng, hat tnh ca
cht xc tc b gim i v s ht tc dng do b cc bm kn b mt, b
nhim c bi cc c t nh NH3, CO2, H2S,v s tch t cc kim loi
nng di dng oxit lm thay i chc nng ca xc tc. Ngi ta
nghin cu nhiu phng php tng bn tng thi gian s dng
ca xc tc. Bin php quan trng nht v ch yu trong cng nghip
l phi ti sinh xc tc.

Qu trnh cng nghip cracking xc tc l qu trnh tham gia phn ng


v ti sinh lin tc theo chu trnh khp kn.
Quy trnh vn hnh ca thit b cracking xc tc cng nghip
-

Ty theo cng ngh ca cc hng khc nhau c cch vn hnh khc


nhau nhng u qua chu trnh.
a nguyn liu v cht xc tc ti sinh vo l phn ng vi c mt
h thng iu khin phc tp. Xc tc v nguyn liu qua l phn ng s cho
sn phm dng hi c tch v that khi l ti h thng phn tch sn
phm v xc tc tham gia phn ng i sang l ti sinh ri li i tr li l
phn ng cng vi dng nguyn liu mi. Qu trnh nh vy din ra lin tc
di s iu khin t ng ca h thng m bo cc iu kin phn ng
nh p sut, nhit , cc ch ti sinh, phn tch sn phm....
KIM TRA, NH GI HON THNH MN HC
Kim tra gia k 02 ln mi ln 30 pht, gio vin chn bt k bi no
trong s cc bi ging. Chm theo thang im 10. (trng s im l 20%)
bi kim tra cui k 01 ln, bt buc i vi hc vin. bi gio vin s
t la chn, mc ch l kim tra s tip thu caa hc sinh i vi nhng vn
rt c bn ca modun ny. Bi kim tra cui k rt quan trng, cng chm
theo thang im 10, v trng s trong ton modun l 50%.
im thc hnh trong phng th nghim s do ngi hng dn trong
phng th nghim, kt hp vi gio vin cho im khi thc hin th nghim(ch

50

v k nng v tinh thn, thi ca hc sinh). Mi ln c thc hnh, gio


vin cho im theo thang im 10, trong s ca thc hnh l 30%.
Sau y l mt s th d thi kim tra cui k:
Cu hi 1
1. Ti sao trong cng ngh lc du phi tin hnh qu trnh cracking?
2. Cc phn ng sy ra trong qu trnh cracking phn ng c ch cn tng
cng? Phn ng khng c li cn hn ch?
3. Cc thng s quan trng ca cng ngh cracking xc tc, ngha ca
cc thng s ny?
Cu hi 2
1. C ch phn ng ca qu trnh cracking xc tc?
2. Gii thiu mt s cng ngh ca cc hng ln v nhng khc bit gia
cc cng ngh :
nh gi kt qu kim tra theo sch hng dn gio vin

51

CC THUT NG CHUYN MN
Cracking: S phn hy ct mch cu to CC trong phn t hydrocacon
F.G: nhin liu kh
Jet/kero: nhin liu phn lc v du ha
D.O: nhin liu cho ng c iezen
F.O: Nhin liu cho l t cng nghip
Gasoil: phn on chng ct t du th c nhit si (280 540oC)
PE: Polyetylen (nha PE)
PP: Polypropylen(Nha PP)
MTBE: Metyl ter butyleter

52

TI LIU THAM KHO


[1]. PGS.TS. inh Th Ng, Ha hc du m & kh. Nh xut bn khoa hc
v k thut,H ni,2001
[2]. PGS.TS. L Vn Hiu, Cng ngh ch bin du m, Nh xut bn khoa
hc v k thut,H ni,2000
[3]. Ch.Marchilly, Catalytic cracking, ENSPMFormation Industrie 1991
[4]. Dr.Docent. ing.Rdulescu.G.A. Fabricarea Produselor Petroliere, Editura
Tehnical.
[5]. Prof.ing.S.D.Raseev. Procese Distructive de Prelucrare a Titeiului.Editura
Tehnic
[6]. 6.Statistic General Department, B Thng Mi,Tng cc Hi quan, Kinh
t Vit nam v Th gii (9899)

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