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BI TIU LUN
MN: CNG NGH LC DU
GVHD: NGUYN HU SN
TP. HCM, THNG 10 NM 2012
MC LC
I)
CRAKING NHIT..............................................................................................1
1)
TNG QUAN...................................................................................................1
2)
C S L THUYT........................................................................................1
a)
S bin i paraffin......................................................................................1
b)
Bin i ca olefin.......................................................................................1
c)
Bin i ca naphten....................................................................................1
d)
e)
3)
Nguyn liu..................................................................................................1
b)
4)
Cc yu t nh hng...................................................................................1
b)
II) CC HA (COKING)........................................................................................1
1)
Mc ch......................................................................................................1
b)
Khi nim.....................................................................................................1
2)
PHN LOI.....................................................................................................1
a)
Cc ho gin on........................................................................................1
b)
Cc ha chm...............................................................................................1
c)
d)
Cc ha tng si...........................................................................................1
3)
CC YU T NH HNG..........................................................................1
a)
Nhit :.......................................................................................................1
b)
p sut.........................................................................................................1
MC CH QU TRNH................................................................................1
2)
C IM QU TRNH................................................................................1
3)
LNG HI NC........................................................................................1
2
4)
NGUYN LIU................................................................................................1
5)
6)
9)
10)
11)
IV) VIS-BREAKING.................................................................................................1
1)
TNG QUAN...................................................................................................1
2)
NGUYN LIU................................................................................................1
3)
SN PHM......................................................................................................1
4)
5)
CC YU T NH HNG..........................................................................1
6)
a)
Nguyn liu..................................................................................................1
b)
Nhit ........................................................................................................1
CC S CNG NGH IN HNH........................................................1
Nguyn
liu
Sn phm chn
Nhit ,
o
p sut,
kg/cm3
Cracking hi
Etan
Axetylen
1000 1400
0,2 0,5
Cracking hi
Etan
Propanbutan
Etylen
800 850
0,2 2
Etylen propa
770 800
0,2 2
720 770
0,5 2
720 -750
0,5 2
Cracking hi
n
Cracking hi
Xng nh
Etylen
propylen
Cracking hi
Gasoil nh
Etylen
propylen
Cracking nhit
Gasoil nh
Xng
469 510
20 70
Cc ho
Cn nng
Cc
480 530
1 10
Vibreking
Cn nng
Gim tc nht
440 - 480
20 70
Qu trnh cc ha
Qu trnh visbreaking
y l cc qu trnh bin i nguyn liu du m di tc dng ca nhit
cao thnh cc sn phm rn, lng, kh. Thnh phn v s lng cng nh cht
lng ca sn phm cui c quyt nh bi cc thng s cng ngheejcuar qu trnh
nh:nhit , p sut, thi gian phn ng.
Trong qu trnh ch bin nhit kh cu trc c hai vn quan trng cn gii
quyt:
trn th qu trnh cracking nhit chim mt v tr tng i quan trng trong cng
ngh lc du.
2) C S L THUYT
Bn cht ca cracking l s b gy mch cacbon, thu c nhng phn t
mch cabon ngn hn ph hp vi yu cu .
L phn ng thu nhit,nn i hi iu kin nhit thch hp.
L qu trnh phc tp v nguyn liu gm s lng ln cc cu t ring bit,
di nhit cao dn n s bin i rt phc tp nn kh theo di
5
a) S bin i paraffin
CnH2n+2
CmH2m + CpH2p+2
Khi n 4 th lin kt C C bn hn C H
xy ra hin tng t
lin kt C H to H2.
Nhit cao, p thpnhiu sn phm kh.
Nhit va phi (450 530 oC), p sut caot gia mchnhiu sn
phm lng.
C ch: Theo Rice n xy ra theo c ch gc t do:
b) Bin i ca olefin
Nhit thp, p sut cao olefin d trng hp. Nhit tng phn ng
phn hu tng. Ngoi ra,olefin cn tham gia phn ng ngng t, ankyl ho vi
naphten to thnh nha v cc.
6
c) Bin i ca naphten
u tin xy ra cc phn ng sau:
Kh nhnh ankyl
Kh nhnh ankyl.
Olefin
Aren
Naphten
Parafin
12
26
62
25-35
12-1
5-8
40-45
40-45
18-20
15-20
20-25
19-20
14-16
27-32
33-37
Nhit cng cao, p sut cng thp th pha kh s cng nhiu, tc dng
trong l ng cng ln v cho php gim s lng ng cc trong cc ng xon ca l.
Nhng trong qu trnh vibreaking, nh hng ca p sut khng ln, tng p sut ch
c th lm tng mt cht t nng sut ca thit b. p sut cao thng lm tng nng
ca cc tc nhn phn ng trongpha hi, iu s to iu kin cho cc phn ng
kt hp nh phn ng polymer ha, alkyl ha v hydro ha.
(3) Nguyn liu
Nguyn liu ca cracking nhit ph bin nht l phn on mazt ca chng
ct trc tip, phn on gasoil nng ca qu trnh cracking xc tc hay cn nng ca
qu trnh lm sch. Cht lng ca nguyn liu l mt thng s quan trng xc nh
cht lng sn phm. khi iu kin cracking khng thay i, nu ta dung nguyn liu
c thnh pn khc nhau s cho cc kt qu khc nhau. Khi tng gii hn nhit si
ca nguyn liu, tc phn ng cng tng ln:
Nguyn liu
Phn on ligroil
Phn on Kerosen
Phn don gasoil
Phn on xola
Gii hn si, oC
180 220
220 270
270 300
300 350
10
12
p sut
MPa
L t 1
L t 2
Vo
Ra
Vo
Ra
400 410
450 490
380 390
540 550
470 500
L phn ng 3
Thit b bay hi p sut cao 4
nh thp
y thp
Thp tinh ct 8
nh thp
Gia thp
y thp
Thp bay hi p sut thp 9
nh thp
Gia thp
y thp
4.0 5.5
2.2 2.7
4.0 4.5
2.2 2.8
1.5 2.5
415 430
410 420
0.8 1.2
190 210
275 320
380 410
0.15 0.35
190 195
290 310
380 410
II)CC HA (COKING)
1 GII THIU QU TRNH CC HA
a) Mc ch
Qa trnh cc ho nhm sn xut cc cc t du m t cc nguyn liu l cn
nng nh gudron ,cn ca qu trnh cracking nhit hay cracking xc tc . Qa trnh
ny c tin hnh iu kin nhit t 450-520 oC . Sn phm chnh l cc ,c
dng cho cng nghip luyn nhm , ch to in cc , cho nghnh cng nghip khc
nh cng ngh in t , vin thng. Ngoi ra ta cng thu c cc sn phm khc
nh kh ,xng v gasoil cc ho.
13
b) Khi nim
Qa trnh cc ho l mt dng ca qu trnh cracking nhit .S to thnh cc
l do cc phn ng ngng t cc hydrocacbon to thnh cc hp cht cao phn t c
ngng t vng thm cao . Nh vy nu nh nguyn liu cha nhiu vng no ,
nhiu vng thm ngng t c mch bn di ,l cc cu t d tham gia phn ng ngng
t , s cho hiu sut v cht lng cc tt nht .Kh nng to cc v hiu sut c
nh gi thong qua i lng gi l cc ho Conradson. cc ho ca nguyn
liu cng cao cng cho php nhn nhiu cc hn.
2 PHN LOI
Trong thc t ,cc dy chuyn cng ngh cc ho c phn loi thnh cc ho
gin on , cc ho bn lin tc (cc ho chm) v cc ho lin tc trong lp si
ca cc ht cc.
c) Cc ho gin on.
Cc ha gin on l loi c in v n gin nht. Dy chuyn gm 1 thit b
chnh l ni cc ha, hnh tr c t nm ngang, ng knh t 2-4m v chiu di
10-12m. Nguyn liu c cho vo ni ri c t trc tip nhm nng nhit ,
tch phn nh v to cc. Khi t ti 450-460 oC, sau gim nhit tch phn
nh. Sau tip tc gia nhit t 700-750oC. Khi thy nhit gim th ngng gia
14
nhit v duy tr thm thi gian na hon thnh to cc. Sau c lm lnh n
250oC v tho cc. Chu k lm vic khong 25-35h. Nng sut ti a khong 5 tn.
d) Cc ha chm
*Mt s h thng s cc ha chm.
Hnh 1.1:
Hnh1.2:
bung khc. S hot ng theo kiu bn lin tc.c m t chi tit trong s
sau:
Nguyn liu c chia lm 2 dng, nh bm bm qua cc thit b trao i nhit
a vo l ng 1 ri t a vo ct tinh ct. Ti y nguyn liu c tip xc vi
sn phm hi kh t bung cc ha sang vi nhit khong 425oC, nguyn liu c
t nng ti 400oC. Sn phm nng v phn tun hon c trn cng vi nguyn liu
mi to thnh nguyn liu cho vo bung cc ha. T y ct 3, nguyn liu c
bm qua l ng 2 nng nhit ln 510 oC v tip tc c np vo bung cc ha
4 ang sn sng lm vic (trong chu k np liu). Cc bun khc ang tho cc hoc
ang tho d cc. Gasoil nng t y ca ct tch c bm qua l t 1, y n
c t n nhit 510 520oC, qua van trn vi nguyn liu cc ha v c np
vo bung cc ha. Ti nh ct 3, kh v hi xng cng vi hi nc c cho qua
thit b lm lnh bng khng kh, tip theo lm lnh bng nc thit b 8 ti 40 oC
sau a ti thit b tch kh 9. Nc t y thit b tch kh c cho vo b 10, t
bm qua cc thit b trao i nhit n 150oC ri vo l 1 v 2. Gasoil nh t ct
tch hi 11 c bm qua thit b trao i nhit, sau qua thit b lm lnh ri ra
khi dy chuyn thnh sn phm. Phn gasoil nng t y ct 11 c bm qua thit
bj trao i nhit, vo thit b un nng cp nhit cho y thp n nh ri cng
c cho qua thit b t sn xut hi nc vi p sut t 1 1.4 MPa, sau
c lm lnh trong thit b ngng t ri a ra khi dy chuyn. Kh bo(C3 C4)
t thit b phn tch kh 12 cng c a ra ngoi lm sn phm. Xng cha n inh
c bm phn ln, a vo thit b trao i nhit sau cho vo ct n nh 13.
Di p sut 0.6 MPa, qu trnh kh butan c thc hin. Hi t thit b 13 c
a qua thit b lm lnh, sau c a i phn tch kh 17 nhn C1,C2 . Xng
n nh thit b 13 c cho qua thit b trao i nhit, thit b lm lnh ri a
vo b cha. Khi tho d cc, thit b c lm lnh bng hi nc n 400 oC. Hi
tch ra c da vo thp tch 3, sau lm lnh bng khng kh v bng nc ri
a vo b cha 16 tch hydrocacbon nng. Cc trong bung c tho bng
phng php thy lc, nc tch ra c a vo thit b lng lc 16 v c a tr
li chu trnh.
16
Nga
Cn cracking
Cn du m
Gudron
Du
Ty
Xibia
California
Trung
ng
Craking
nhit
T trng
0.9540
1.040
0.9861
0.984
1.083
Hm lng S,%
0.51
2.4
1.6
0.38
0.56
cc ho
8.0
21.0
9.6
11.3
8.6
Kh
9.1
5.0
12.0
6.5
18.1
Xng
10.4
3.0
15.7
16.0
0.9
Gasoil nh
24.7
29.2
35.2
56.5
21.1
Gasoil nng
37.8
27.8
15.5
Cc
18.0
35.0
21.6
21.0
59.9
487
505
496
488
502
0.18
0.4
0.41
0.2
0.34
Thng s
iu kin lm vic
Nhit ra khi l t 0
o
C
p sut trong bung
cc ,MPa
e) Qa trnh cc ha tip xc
Qa trnh ny c m phng bng s cng ngh sau
17
Nguyn liu
Nng sut
16 tn cc / ngy
Gasoil
19.8
16.2
53.5
24
11.4
12.5
49.6
20
14.6
20.0
43.0
T
trng
cc
kh
1.1011
19
1.055
1.028
70 tn cc/ ngy
900 nghn tn cc/nm
f) Cc ha tng si
19
Cn
19.5
36.5
22.4
I: nguyn liu, II: xng v kh, III: Gasoil nh,IV: Gasoil nng
Cng ngh cc ha lp si p dng qu trnh lp si ca cc ht cc c nhit
cao khong 480-540oC trong l phn ng S thit b: Nguyn liu i vo oc chia
lm 2 phn, mt phn vo thit b phn ng, mt phn vo thp ra, cc trng thi
tng si c nhit cao t l t sang. Trong thit b phn ng xy ra cc phn ng
cracking nhit v cc ha. Hn hp kh, xng, gasoil t thit b phn ng vo cyclon
tch nhng ht mn v hn hp hi i ln thp ra ra cc ht bi cha tch
c cyclon (thp ra ngc chiu tng hiu sut chuyn ha). Sau hn hp
hi c a vo thp chng ct. nh thp chng ct thu c xng v kh; y
thu c gasoil nng v gia thu c gasoil nh. Cc t thit b phn ng c a
qua l t ( trng thi tng si) nng ln nhit 600 620 oC. Cc ht ln c
cho qua thit b tch, lm ngui v a ra ngoi. Cc mn bay ln theo gp O 2 t my
nn kh cung cp nhit cao cho thit b phn ng. Nhit khi l t cao tn
dng nhit sinh cng.
20
3 CC YU T NH HNG
g) Nhit :
h) p sut
1) C IM QU TRNH
21
2) LNG HI NC
Gasoil : H = 0.8 1
3) NGUYN LIU
NAPHTA
T trng
ng cong chng ct
PI
PF
Thnh phn
n-P
i-P
N
Ar
Nh
Trung
Bnh
Nng
0.65
0.68
0.71
C
C
35
90
44
125
60
175
%m
%m
%m
%m
52
39
7
2
46
31
18
5
32
29
31
8
0
0
22
C3
n-Buthane
i-Buthane
Buthane
BUTHANE
%m
%m
%m
%m
2
58
27
13
t mch:
5) C CH TO THNH SN PHM PH
Cc dng phn ng ph c bn:
Polime ha.
23
To vng v ngng t.
24
Nh
C2
C2H 4
C3H 6
Coupe C4
Butadiene
Coupe C5+
Benzene
Huite
20
34
18
9.5
4.5
17
6
1.5
Trung bnh
17
32
17
9
4.5
22.5
8
2.5 25
Nng
17
29
15
9
4.5
26
10
4
10)
Hi nc
Fuel gas
in
Ch s nng
lng tiu th
/TC2H4
/T nguyn liu
Thp
-2 000
6 700
1
T l C3=/C2=
Trung bnh
-2 050
6 400
0.94
cao
-1 950
6 200
0.88
6 600
1 760
6 325
1 850
6 100
1 900
IV) VIS-BREAKING
1 TNG QUAN
Visbreaking l mt qu trnh s dng nhit nhm chuyn ha cn ca qu trnh
chng ct kh quyn (RA: residue atmospherique) hoc cn ca qu trnh chng ct
chn khng (RSV: residue sous-vide) theo con ng cracking nhit thnh kh, xng,
cc sn phm trung bnh v cn c lm gim nht. Cn RA v RSV c np
liu vo thit b gim nht thng thng gim nht ca nhin liu (fuel oil) v
tng hiu sut thu cc sn phm trung bnh trong nh my lc du.
Qa trnh visbreaking thng b gy cc phn t gia mch nhit
khong 4500C vi khong thi gian rt ngn.Cc phn t parafin mch di s b b
gy thnh cc phn t mch ngn hn,phn ng dealkyl s gip b gy cc mch
nhnh ca cc phn t hydrocacbon thm.
i vi cc nh my lc du ngy nay nu ch bin du th nng hn v c
nhu cu cao hn v sn phm th visbreaking cung cp kh nng chuyn ho chi ph
thp m vn tng c sn lng kh ,xng v cc sn phm khc;ng thi lm gim
nht ca sn phm nng FO.y cng l mc ch chnh ca qu trnh visbreaking.
Mc tiu visbreaking:
1) NGUYN LIU
Cn ca qu trnh chng ct kh quyn (RA: residue atmosphrique) hoc cn
ca qu trnh chng ct chn khng (RSV: residue sous-vide).
2) SN PHM
Kh, xng, cc sn phm trung bnh v cn c lm gim nht.
C cu sn phm theo ngun nguyn liu t cn du th Rp
Sn phm
Xng
Gasoil
LPG
Tar
%khi lng
6
15
3
76
Trc
visbreaking
28
Sau
visbreaking
nht
1000C(centistok
es)
T trng(kg/l)
930
115
1,020
1,048
29
qu
liu
c np vo
thit b gia
thit
nhit
ca
gim
nht
(visbreaker
heater), ti y
nguyn liu c gia nhit n nhit cao, gy ra s ha hi mt phn v s
cracking nh. Dng ra ca thit b ny c lm lnh vi dng gas oil hoc nhng
nhng sn phm y ca thit b phn on lm ngng li cc phn ng cracking.
Hn hp lng hi i vo thit b phn on phn tch thnh kh, xng, gas oil v
cn gim nht (tar). nhng sn phm y sau c trn vi nhng nguyn liu
nh hn (cutter stock) p ng cc tiu chun ca nhin liu trong cc l t. Gas
oil t thit b ny thng c s dng lm cutter stock phi trn vi cn gim
nht.
4) CC YU T NH HNG
a) Nguyn liu
S chuyn ho sn phm cn thnh sn phm nh hn b hn ch bi mt s
c tnh nguyn liu, chng hn nh hm lng asphaltene, natri v hm lng carbon
Conradson. Mt nguyn liu vi hm lng asphaltene cao s cho hiu sut chuyn
ho thp. Ngoi ra ,s c mt ca natri cng nh hm lng cao Conradson carbon, c
th tng t l to cc trong ng gia nhit. Gim thiu hm lng natri v Conradson
carbon s ko di c chu trnh lm vic ca h thng.
30
Chiu di quy trnh , chuyn ho theo cht lng ngun nguyn liu
31
b) Nhit
33
dng
hi
c gom
li ti thit
b
gom
condensate.
34
35