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M u
Hin nay, trn th gii, mt hng xng du l mt mt hng quan trng
v c bit quan trng .N chnh l mu huyt ca nn kinh t quc dn v
quc phng cho bt k mt quc gia no.
V Vit Nam ,nhu cu tiu th sn phm du kh ang tng ln cng
vi s tng trng ca nn kinh t quc dn v quc phng.Tuy nhin sn
phm xng Vit Nam hin nay u c nhp khu t nc ngoi.Phn ln
t Singapore vi ba u ni tip nhn l H Ch Minh, Nng v Qung
Ninh. V t ba u ni tip nhn ny ,sn phm c phn phi ti cc kho
trung chuyn trn ton quc. Trong tng lai vic nhp sn phm xng du l
diu khng c li cho nn kinh t ca c nc. V vy m c th p ng
nhu cu xng cho ngi tiu dng th nht thit phi c nh my lc v ch
bin ,trong quan trng hn c l phi c phn xng sn xut xng du [8].
Ngi ta c th sn xut xng bng nhiu cc qu trnh ch bin khc
nhau nh l cracking xc tc, Reforming xc tc, izome ha ...V..V...trong
cracking xc tc l qu trnh ch yu sn xut xng . Tiu chun quan
trng ca nhin liu dng cho ng c xng l ch s octan . Ch s ny cng
cao th kh nng chng kch n cng cao. Thot tin th ngi ta thc hin
cracking phn on du m c nhit si trong khong 490 800 K bng
nhit , nhng vi phng php ny th hiu qu rt thp v sn phm cha
nhiu hydrocacbon phn t thp . n khong nhng nm 1930 , qu trnh
cracking nhit c thay th bng cracking xc tc , vi cht xc tc l
Aluminosilicat t nhin. V u tin ngi ta s dng lp xc tc tnh nhng
m n cng cha mang li hiu sut v cht lng xng cao nh mong mun ,
n li c qa nhiu nhc im chnh v nhng l do nh vy cho nn ngi ta
thay th n bng qu trnh Cracking c lp xc tc chuyn ng .
C rt nhiu cng ngh khc nhau cho qu trnh Cracking c lp xc tc
chuyn ng. Nhng ngy nay ngi ta dng ph bin l cng ngh ca FCC.
Vi cng ngh ny cho ngi ta thu c nhiu xng v cht lng cng tt
hn rt nhiu , phn no cng p ng c nhu cu xng du hin nay.
Nguyn Vit Hun
1
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Phn I
Tng quan l thuyt qu trnh
cracking xc tc
Trong cng ngh ch bin du m cc qu trnh chuyn ha ha hc
di tc dng ca cht xc tc chim mt t l rt ln v ng vai tr v cng
quan trng . Cht xc tc trong qu trnh chuyn c kh nng lm gim nng
lng hot ha ca phn ng v vy m tng tc phn ng ln rt nhiu .
Mc khc , khi c mt cht xc tc th phn ng c kh nng tin hnh nhit
thp hn iu ny rt quan trng i vi nhng phn ng c hiu ng
dung nh phn ng hydro ha , alkyl ha , polime ha v.v...
S c mt cht xc tc va thc y nhanh qu trnh chuyn ha ha
hc , va c kh nng to ra nhng nng cn bng cao nht , c ngha l
tng hiu sut ca qu trnh .iu quan trng nht l cht xc tc c kh nng
tng nhanh khng ng u gia cc loi phn ng m v phng din nhit
ng l chng xy ra cng lc trong qu trnh , trong iu kin nh nhau ,
ngi ta gi y l tnh cht chn la ca xc tc. Ngi ta nghin cu rt
nhiu loi cht xc tc v ngi ta cng li dng tnh cht chn la ca n m
hng phn ng ca qu trnh ch bin theo chiu c li nhm thu c
nhng sn phm chnh t hiu sut v cht lng tt nh mong mun.
Chnh v l do cho nn p ng ngy cng nhiu nhu cu dng
xng du th ngi ta nghin cu v ci tin dn qu trnh cracking xc tc
. Qu trnh cracking xc tc vi dy chuyn cng ngh FCC l u im hn
c.
2
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Chng I
Mc ch v ngha Bn Cht Ha Hc
vc ch phn ng
I. Mc ch v ngha ca qu trnh cracking xc tc
3
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CmH2m + CpH2p+2 (n = m + p)
CmH2m + CpH2p
(n = m + p)
ArCmH2m+1 + CpH2p (n = m + p)
CmH2m + CpH2p
naphten
olefin
CnH2n
(n = m + p)
olefin
xyclohexan olefin
olefin
izo-olefin
n-parafin
izo-parafin
hydrocacbon thm
+ parafin
4. Phn ng trng hp
Ch yu xy ra vi hydrocacbon i.
Nguyn Vit Hun
4
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CnH2n + CmH2m
CpH2p
(n + m = p)
ArH
CnH2n
Hydrocacbon thm
olefin
Aromat CnH2n+1
alkyl thm
H2
2 H2
cc phn t
5
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+H2
CH3-CH2-CH2-CH2-CH2-CH3
CnH2n+1
H2
CnH2n+3
CmH2m+1 + CpH2p
R1 CH C R2
H
+ (xt)
6
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hoc l
RH +
olefin
Al O Si
H Al O Si
CnH2n + H+
Cn+H2n+1
CnH2n + L
C+nH2n+1 + LH
Ion cacboni to thnh trong cc phn ng tun theo quy tc nht nh.
Nh khi olefin tc dng vi H+(xt) th xc sut to alkyl bc 2 ln hn alkyl
+
bc mt.
CH3 CH2 CH CH2 + H + (xt)
CH3
CH3 CH C CH3
+ H + (xt)
CH3 CH CH CH3
CH3
T hydrocacbon naphten:
Khi hydrocacbon naphten tc dng vi tm axit ca xc tc hay cc ion
cacboni khc s to ra cc ion cacboni mi tng t nh qu trnh xy ra vi
parafin.
T hydrocacbon thm :ngi ta quan st thy s to thnh ion
cacbonil s kt hp trc tip ca H+ vo nhn thm
CH2 CH3
H+
CH2 CH3
H
7
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R CH2 CH CH3
CCCCR
+
R CH CH2
R C CH2
CH3
CH3
C3 + (bc 1)
CnH2n
+ C+mH2m+1
C+nH2n+1 + CmH2m+2
CnH2n+2 + C+mH2m+1
8
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[B]
+
R C C C C C C
C
[C]
CH3 CH CH2 R
CH3 CH CH2 + R
C C
C
C C
+
C C
CH C
C
9
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10
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n tt nghip
11
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t C, xc tc
C4H10
CH4 + C3H6
(60%)
C2H6 + C2H4
(30%)
C4H6 + H2
(10%)
Hydrocacbon
nC6H14
nC7H16
n-C8H18
E kcal/mol
36
29
24
12
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Bng 2:
Hydrocacbon
n-C5H12
n-C7H16
n-C12H26
% cracking
18
n-C12H26
42
t oC, xc tc
t oC, xc tc
C9H20 + C5H10
C5H12 + C4H8
n-C8H18
t C, xc tc
o
izo-C8H18 t C, xc tc
C4H8
+ C4H10
(phn hu 42%)
izo-C4H10 + C4H8
(phn hu 49%)
13
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Bng 3:
% chuyn ho
C6
CCCCCC
14
CCCCC
25
C
25
CCCCC
C
12
CCCC
C C
C
10
CCCC
C
H2
CH4
C2
C3
C4
C5
%V
12
19
49
8,5
1,6
14
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RH
+ R 1H
R2
R1
olefin
izo-C5H11
n- C5H11
izo-C5H11 + C4H10
izo-C5H12 + C4H9
RCH2CHCH2CH2R1
+
CH3CH2R1
Nguyn Vit Hun
+ H+
+
RCH2CH=CH2 + CH2CH2R1
R1CH=CH2 + H2
15
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CH3CH=CH2 +
2C5
C7
C10
CH3CHCH2CH2CH3
CH2CH3
C3 + C7
C3 + C4
C3 + C4
(vi C3/C4 = 1)
CH3
CH3 CH CH CH3
16
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CH3(CH2)5 CH CH2
CH2 CH CH2 CH3
CH2 CH CH CH2
Cc olefin cn phn ng vi hydro to thnh parafin:
R CH2 CH2 + H2
R CH2 CH3
Cc olefin trong qu trnh cracking xc tc cn tham gia phn ng ngng
H2
H2
H2
+ 3H2
+ C3H8 + 2 H2
+ 3 H2
n tt nghip
CH3
CH3
CH3
CH3
Sn phm khi cracking naphten c tnh cht no nhiu hn so vi cracking
18
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Bng 5:
Loi hydrocacbon thm
C6H5C2H5
50
C6H5C4H9
34
C6H5CHCH2CH3
19
CH3
C6H5CHCH3
17,5
CH3
C6H6 + CH3CH=CH2
C6H5CH3 + CH2=CH2
CH3
CH3
t C, xc tc
t C, xc tc
CH3
CH3
CH3
para-xylen
meta-xylen
octo-xylen
19
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CH3
CH3
t C, xc tc
+
CH3
CH3
CH3
t C, xc tc
+ 5 H2
H2
2 H2
hay
+
CH2 CH2
20
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Olefin v parafin
Parafin
Olefin v hydro
izo-parafin
Cc hp cht olefin c trng lng thp
Parafin v dien
Olefin
Naphten
Xyclohexan v olefin
Hydrocacbon thm
Olefin
Parafin v alkyl thm c mch bn ngn
Hydrocacbon thm
(alkyl thm)
Sn phm ngng t, cc
Sn phm ngng t, cc
21
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Gazoil
LCO
HCO
Xng
C4 v kh
Cc
Hnh 1
Nhn s phn ng chng ta thy rng, cc sn phm ph l LCO v
HCO cn phi to iu kin thun li chng chuyn ho tip thnh xng,
ng thi c gng hn ch qu trnh to kh v cc. S hnh thnh cc l
khng mong mun, v cc bm trn tm hot tnh ca xc tc, dn n lm
gim hot tnh ca xc tc. Sn phm cc c to ra l mt h vng thm c
ngng t cao, nn khc vi cacbon t do. S hnh thnh cc c th do cc
nguyn nhn sau:
Do bn cht ca nguyn liu cracking
Do cht xc tc ca qu trnh c chn lc khng cao
Do ch cng ngh cha ti u.
22
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chng II
xc tc ca qu trnh Cracking
Xc tc l mt trong nhng lnh vc khoa hc k thut lun c nhiu
23
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dng trong cng nghip cracking sut 30 nm. Tuy vy, hin nay vic ci
thin xc tc vn khng ngng pht trin v n cui thp nin 60 ca th k
20, ngi ta chuyn sang ch yu dng xc tc cha zeolit.
M vo nm 1972 s dng khong 80% cht xc tc cha zeolit cho
qu trnh cracking xc tc. Hng nm M tiu th 130 nghn tn xc tc,
trong ch c 14 nghn tn l khng cha zeolit.
I. Vai tr ca xc tc trong qu trnh cracking (1,2,3,12,14)
qu trnh cracking.
V mc ch ca cracking l nhn xng, nn phng php dng hiu sut
xng thu c nh gi hot ng ca xc tc s n gin hn, hot tnh
ca xc tc cng cao s cho hiu sut xng cng ln. Do vy, hot tnh ca
xc tc thng c biu din thng qua ch s hot tnh. l gi tr ca
hiu sut xng (%KL) khi cracking nguyn liu mu trong iu kin phng th
nghim.
Hot tnh xc tc ph thuc vo tnh cht vt l - ha hc ca xc tc,
m trc ht l ph thuc vo thnh phn ha hc ca xc tc cng nh ph
thuc vo iu kin cng ngh ca qu trnh. Trong thc t sn xut, da vo
hot tnh ca xc tc, ngi ta phn xc tc thnh cc loi nh sau:
+ Xc tc c hot tnh cao, hiu sut xng > 45%
Nguyn Vit Hun
24
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13
Oxyt silic
87
24
Oxyt natri
0,02 0,2
0,8 0,9
hot tnh n nh
55 60
75 80
bn do mi mn, %
94 96
<23
n 40 m
15 25
n 100 m
96 98
B mt ring, m2/g
400 450
25
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chn lc) sau mt thi gian lm vic lu di. Cht xc tc c thi gian lm
vic lu di th gi thnh chi cho cht xc tc cng thp ( cho d tin mua xc
tc c t ) hn so vi khi mua xc tc r m thi gian lm vic ngn.
n nh xc tc c trng cho kh nng khng thay i cc tnh cht
trong qu trnh lm vic. Xc tc c n nh cng cao cng tt trong qu
trnh s dng.
4. m bo bn c v bn nhit: [3]
Trong qu trnh lm vic, xc tc c xt vi nhau v c xt vi thnh
26
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cu v sn xut.
III. zeolit v xc tc cha Zeolit
1. Xc tc Zeolit [1,2,3,12,13,14]
Zeolit l hp cht ca alumino - silic, l cht tinh th c cu trc c bit.
27
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Trong :
x,y - l cc h s tng ng
z
O2Si4+
O2-
O2-
O2Al3+
O2-
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O2
HnhAl4.3+n v c bn ca zeolit
Zeolit A
Zeolit X
29
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Zeolit
Thnh phn ho hc
Na2O.Al2O3.2SiO2.4,5H2O
3,6 3,9
Na2O.Al2O3.2,5SiO2.6H2O
7,4
Na2O.Al2O3.4,8SiO2.8,9H2O
7,4
Na8O(Al2O3)8(SiO2)40.24H2O
Mordenit
5,4 5,6
ZSM-5 v 11
n tt nghip
31
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32
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[1-trang122]
Xc tc cracking trong qu trnh lm vic b gim hot tnh v chn
lc. Hin tng ny ngi ta gi l qu trnh tr ho xc tc. Qu trnh tr ho
xc tc cng nhanh nu ta tin hnh qu trnh iu kin cng ngh kh
khn, kht khe tng (v d nhit qu cao, thi gian tip xc qu di,
nguyn liu xu). Ngoi ra cn xy ra cc qu trnh khc lm tng tc tr
ho. Chng ta c th phn qu trnh tr ho xc tc lm hai qu trnh chnh,
l s tr ho do tc dng ca cc cht lm ng c xc tc v s tr ho do
tc dng lm thay i cc tnh cht l - ho ca xc tc.
Nguyn nhn ca s tr ho xc tc c th l do:
Tc dng ca cc c t nh NH3, CO2 ca cc hp cht lu
nng ca xc tc.
S tc ng ca nhit cao v hi nc.
chn lc nh hi nc.
- Nhm lm gim chn lc ca xc tc (H2S nhit trn
33
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34
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V. Ti sinh xc tc [1,2,3]
CO
CO + 1O2
CO2
2
1O2
2
H2O
O2
SO2
SO2 +
O2
SO3
MeO +
SO3
MeSO4
C + O2
C +
H2 +
S +
1
O
2 2
MeSO4 + 4H2
35
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E
RT
Trong :
V - tc ti sinh
PO2, PH2O - p sut ring phn ca oxy v hi nc
C - hm lng cc bm trn xc tc
n - bc phn ng theo cacbon
K1, K2 - hng s.
Vy tng tc ti sinh th ta phi tng nhit ti sinh (hiu qu
nht vng ng hc), tng p sut ring phn ca oxy trong khng kh, gim
ng knh cc ht xc tc.
Xc tc c ng knh l xp cng ln v ng u th qu trnh ti sinh
cng nhanh v oxy d khuch tn. Tuy vy iu ny b gii hn bi bn ca
xc tc v mt s tnh cht khc ca n.
Qu trnh ti sinh xc tc bng phng php t cc cha gii quyt
c vic kh cc kim loi nng hp ph trn xc tc. V vy hon thin
qu trnh ti sinh ngi ta tin hnh thm qu trnh trao i ion kh cc
kim loi nng, iu ny gii quyt c s nng cao c hiu qu ca qu
trnh ti sinh xc tc.
36
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Xc tc dng bi:
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CHng III
NGuyn Liu V Sn PHm
Ca QuTRnh Cracking Xc Tc
I. Nguyn liu ca qu trnh cracking xc tc: [1,2,3,4,5,6,7]
38
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39
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t 210 5000C.
Nhm 4: l nhm nguyn liu c nhit si t 300 4500C.
[1-trang 125]
Bng 8:c tnh 4 nhm nguyn liu ca qu trnh cracking xc tc
Ch tiu
Nhm 1
Nhm 2
Nhm 3
Nhm 4
T trng
0,8300,870
0,8300,920
0,8700,885
0,8700,875
t0 si u (0C)
200 215
300 315
225 235
n 250
t0 si 10% (V)
225 240
335 355
290 305
275 300
t0 si 50%
260 270
420 445
390 400
335 375
490 500
385 450
Thnh
phn
phn on
t0 si 80%
t0 si 90%
290 320
520 540
t0 si cui
315 360
540 550
515 520
420 490
(95%)
(95%)
(95%)
0,6 1,8
0,35 0,75
0,5 1,4
0,2 0,9
0,2 0,3
0,05 0,2
Hm lng S
(%) TL
0,2 0,6
cc % TL
40
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% khi lng
C1 C2
10 25
C3
25 30
C4
30 50
C5
10 20
thu c t 30 55% lng nguyn liu em cracking. Hiu sut xng v cht
lng xng ph thuc vo cht lng nguyn liu, xc tc v ch cng ngh.
Nu nguyn liu c hm lng hydrocacbon naphten th cho hiu sut v
cht lng xng cao. Nu nguyn liu c hm lng ln parafin th nhn c
Nguyn Vit Hun
41
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d 20
4
Hm lng S (% KL)
Tr s octan (sch)
RON
MON
Thnh phn hydrocacbon (%)
Hydrocacbon thm
OlefHin
Naphten
Parafin
0,01 0,20
87 95
78 85
25 40
15 30
2 10
35 60
(izo-parafin chim phn chnh)
42
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Ch tiu
195 270
270 350
350 420
> 420
d 20
4
0,860,95
1 11
Nhit ng c, 0C
40 60 20 50 0 5
Tr s xetan
20 35
Tr s it, g/100 g
10 20
5 10
35
Hydrocacbon thm, % V
60 80
50 75
cc ho conradson, % KL
0,05 1,0
5 10
1025
43
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44
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Phn II
Tnh Ton V Thit K Dy Chuyn
Cng Ngh CrackingXc Tc
Chng I.
Cc yu t nh hng n
qu trnh cracking xc tc
45
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10
20
8
6
10
0
Ch s octan
95
NC (sch), %
30
100
90
60
85
50
chuyn ho
80
70
%V
n tt nghip
425
450 475
40
500 5250C
Hnh 6
Bng 12. nh hng ca hydrocacbon n hiu sut v cht lng ca sn
phm vi nguyn liu l phn on xola (du m Lin X)
Nhit trung bnh trong TBP
Cc thng s
415
452
480
513
2,31
Kh bo
5,00
5,13
8,34
18,80
Xng
30,29
7,49
9,41
9,45
Gazoil nh
59,20
30,72
32,45
37,42
53,30
46,30
28,10
Gazoil nng
Cc
3,20
3,30
3,50
6,60
Tng cng
100,00
100,00
100,00
100,00
40,80
46,70
53,70
71,90
khng c pha ch
84,10
91,70
93,70
94,40
93,00
98,20
98,20
98,50
0,748
0,748
0,757
su chuyn ho (%TL)
Tr s octan ca xng (RON)
46
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n tt nghip
Nhit , 0C
C, % KILN
SP tng, %KL
Xng, %KILN
Kh, %KL
Cc, %KL
Cn, %KL
Mt mt, %KL
RH no, %V
RHO, %V
RHa, %V
400
64,5
81,5
49,2
11,6
3,7
32,3
3,2
66,8
7,7
25,3
420
70,2
76,7
49,7
16,0
4,5
27,0
2,8
61,9
8,5
29,6
435
72,1
74,4
49,1
18,2
4,8
25,3
2,6
56,5
9,6
33,9
450
75,5
69,9
47,5
22,2
5,8
22,4
2,1
50,8
10,8 38,4
470
74,4
61,9
38,6
29,5
6,5
22,5
2,9
39,6
13,9 46,5
485
74,9
59,7
33,2
32,6
7,8
24,7
2,4
28,6
15,0 56,4
500
73,8
52,5
31,3
37,2
7,2
21,0
3,2
28,6
14,8 56,4
47
Ho Du K44-QN HBK HN
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n tt nghip
%V
NO
50
95
% xng
90
40
% NO
30
20
85
80
48
Ho Du K44-QN HBK HN
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n tt nghip
C
P.K
=
100 C
M/H/M
Phng trnh biu din p dng rt ng vi trng hp xc tc c nh,
y khng xy ra s chuyn ng ri hay s xo trn ca hi nguyn liu v
sn phm. Trong trng hp cracking xc tc vi lp si ca xc tc (FCC),
chuyn ho C l ph hp vi cng thc sau:
C
C
100 1
100
P.K
M/H/M
chuyn ho
70
50
% xng
%KL %V
80
10
60
40
20
30
Cc
10
0,2
1,0
chuyn
2,0
3,0
M/H/M
nh hng ca tc np liu ring
%KL
10
% xng
Cc
2
2
10
X/RH
nh hng ca t l X/RH
Hnh 8.
49
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n tt nghip
Khi dng xc tc cha zeolit, cho php gim t l X/RH xung cn 10/1
so vi xc tc v nh hnh l 20/1. Nu khi dng cng ngh xc tc chuyn
ng vi kch thc ht xc tc t 3 5 mm, t l X/RH cn thp hn na, ch
khong 2/1 5/1.
Khi thay i t l X/RH s lm thay i nhit ca reactor, thay i
thi gian lu ca xc tc trong reactor v l ti sinh, ng thi cng lm thay
i c lng cc bm trn xc tc trong mt chu trnh.
Nu ch n nh, tng t l X/RH s lm tng chuyn ho, tng
hiu sut cc/nguyn liu, nhng hm lng cc bm trn xc tc li gim
xung. iu ny c gii thch l do lng cc c dn ra mt lng
xc tc ln hn. Khi gi tc np liu M/H/M l khng i, nu tng t l
X/RH th thi gian tip xc gia xc tc v nguyn liu gim, v nh vy
hot tnh trung bnh ca xc tc tng ln. l l do t hiu qu cao ca qu
trnh vi xc tc lp si (FCC). Nh t hiu qu cao m cho php gim kch
thc ca thit b. Nhng d dng nhn thy rng, nu tng cao qu mc
tun hon xc tc s lm nh hng n qu trnh tch hi bm trn xc tc v
lm nh hng n qu trnh ti sinh l ti sinh v cc trang thit b km
theo.
Nguyn Vit Hun
50
Ho Du K44-QN HBK HN
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n tt nghip
51
Ho Du K44-QN HBK HN
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n tt nghip
Chng II
I. Lch s pht trin cng ngh cracking xc tc [1,2,3]
52
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n tt nghip
Qua lch s pht trin ca qu trnh cracking xc tc, ng thi qua phn
tch nh gi cc yu cu khc nh ch lm vic, nguyn liu xc tc... ta
Nguyn Vit Hun
53
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n tt nghip
54
Ho Du K44-QN HBK HN
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n tt nghip
Chun b
x l
L
phn ng
Xc tc
lm vic
Sn phm
qua chng tch
Xc tc
ti sinh
L ti sinh
xc tc
Reactor
Ti sinh v vn dng nhit ca kh khi
Phn on phn chia sn phm.
55
Ho Du K44-QN HBK HN
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n tt nghip
1.
15.
2.
Bm
16.
ng dn hi sn phm
3.
Van tit lu
17.
4.
L t
18.
Thp ti bay hi
5.
19.
B phn ng ng
6.
B cha sn phm
20.
Xyclon 2 cp
7.
21.
Thit b ti sinh xc tc
8.
Van l
9.
23.
10.
24.
Ni hi tn dng nhit
11.
B lng tch
25.
12.
Thp tch kh
26.
My nn kh
13.
Thp n nh
14.
Nguyn liu mi t b cha nguyn liu (1) c cho qua thit b trao
i nhit ng chm, nguyn liu mi c th c trn vi phn tun hon
(HCO) (6),(l phn on du nng ca qu trnh cracking xc tc ) v cn y
thit b (5), sau cho qua l t nng nguyn liu cracking Nguyn liu
cracking c tip xc vi xc tc nng ti sinh i vo y ca ng
ng(19), khi nguyn liu bay hi cng vi hn hp ca hi nng v xc
tc c i ln pha trn ti nh ca ng ng, ng thi xy ra cc phn ng
cracking xc tc. Hu ht nguyn liu u tham gia phn ng v chuyn ho
trong ng ng, cn reactor c dng nh mt thit b tch xc tc v hi
hydrocacbon.
56
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n tt nghip
57
Ho Du K44-QN HBK HN
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n tt nghip
58
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n tt nghip
59
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n tt nghip
Sn phm
T trngkg/m3
Kh
17
1.22
Xng
48
0.764
Gazoil nh
17
0.933
Gazoil nng
13
0.942
Cc
60
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n tt nghip
2400.000 1000
=285714,286 kg/h
350 24
- Lng kh crackinh l
Gk=Gnl 0.17 = 2857140,286 0.17 = 48571.429 kg/h
- Lng xng l
Gx=Gnl 0.48 =285714,286 0.48 =137142,857 kg/h
- Lng gazoil nh l
Gg= Gnl 0.17 =285714,286 0.17 =48571,429 kg/h
- Lng gazoil nng l
Gn= Gnl 0.13 =28571 4,286 0.13 =37142,857 kg/h
- Lng cc l
Gc=Gnl 0.05 =285714,286 0.05 =14285,286 kg/h
Vy tng sn phm l
Gk + Gx + Gg + Gn +Gc = 48571,429 +137142,857 +48571,429
+37142,857 + 14285,714 =285714,286 kg/h
* tng hiu sut xng ca qu trnh th ngi ta cho tun hon mt phn
Gazoil nngv h s tun hon khong 0,3 .Vy lng Gazoil tun han li
l :
Gth = Gn 0.03 =37142,857 0.03 =11142,857 kg/h
- Tiu hao hi nc l
Gn =Gnl ( 0.03 + 0.05) =285714,286 0.08 =22857,143 kg/h
61
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n tt nghip
Sn phm
S lng (kg/h)
285714,286
11142,857
* Tng vo
296857,143
*Dng sn phm ra
+kh
48571,429
+xng
137142,857
+Gazoil nh
48571,429
+Gazoil nng
37142,857
+ Cc
14285,714
11142,857
* Tng ra
296857,143
1. Xc nh nhit chy ca cc
q = a1. qCO2 + a2.qCO + a3.qH2O kcal/kg
Trong :
a1 :l phn cacbon trong cc c t chy thnh CO2
a 2 : l phn cacbon trong cc c t chy thnh CO
a 3 : hm lng hydro trong cc
qCO2 : lng nhit ta ra khi t chy 1kg cc thnh CO2
qCO2=6137 kcal/kg
qCO2 :lng nhit ta ra khi t chy 1kg cc thnh CO
qCO=2450 kcal/kg
qH2o :lng nhit ta ra khi t chy 1kg cc thnh nc
Nguyn Vit Hun
62
Ho Du K44-QN HBK HN
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n tt nghip
1
(0,403t + 0,000405 t2)
qdt=
Trong :
1
(0,043 .485 + 0,000405 .4852)
0,764
=322,633
qg485=
kcal/kg
1
(0,043.485 + 0,000405 4852)
0,933
= 301 kcal/kg
qn485 =
1
(0,403 .485 + 0,000405 .4852)
0,942
=299,4 kcal/kg
63
Ho Du K44-QN HBK HN
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n tt nghip
qth485=
1
( 0,403 .485 + 0,000405 .4852)
0,934
=300,83 kcal/kg
Hm nhit ca hi nc qu nhit 485 0 C l ;:
q H2O485 =833,6 kcal/kg
t nhit ca kh crackinh l Ck=0,38 kcal/kg 0 C
Vy :
Q/1 = 48571,429 . 0,38 . 485 +137142,857 . 332,633
+48571,429 .301 +37142,857 .299,4 + 11142,857 .300,83
+285714,286 .833,6 = 321834060,3 kcal/kg
b) do xc tc lm vic v cc mang ra :
Q/2 = (Gxt.C1 +Gc .C2)t
Trong :
C1 : l t nhit ca xc tc C1 = 0,27 kcal/kg 0 C
C2 : l tt nhit ca cc
C2 = 0,6
kcal/kg 0 C
kg/h
Vi n l bi s tun hon
kg/h
Vy :
Q/2 = (2785. 0,27 + 14285,714 .0,6)485
=4521838,524 kcal/h
c) do tiu hao cho phn ng crackinh xc tc :
Q/3 =Gx .i kcal/h
Trong :
i : l nhit ca phn ng crackinh xc tc i = 105 kcal/1 kg xng
Gx : lng xng to thnh
Nguyn Vit Hun
64
Ho Du K44-QN HBK HN
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n tt nghip
Suy ra :
Q/3 = 137142,857 .105 =14399999,99 kcal/h
d) Nhit mt mt vo mi trng ly bng 5% lng nhit cn bng
Q/4 = ( Q/1 + Q/2 + Q/3 ) 0,05 =2673131,59 kcal/h
* Nhit mang vo phn ng gm c
a) Do nguyn liu nng : Q1= Gnl . qnl kcal/h
trong :
Gnl : lng nguyn liu ban u kg/h
Qnl: hm nhit ca nguyn lu
b) Do xc tc ti sinh
Q2 = Gnl .n .C1.t2 kcal /h
Trong :
Gnl : lng nguyu n liu ban u
kg/h
1
(0,043t2 + 0,000405 t22)
65
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n tt nghip
1
(0,043 .290 + 0,000405 . 2902)
0,934
=156,172 kcal/kg
trong :
t2 : nhit ca xc tc tun hon li
suy ra :
Q4 = 11142,857 .156,172 =1740202,263 kcal/h
Vy lng nhit mang vo l phn ng l
Q1 + Q2 + Q3 +Q4=Q1 + 246857202,6 kcal/h
T phng trnh cn bng nhit lng ca l phn ng ta c
Q1 +Q2 + Q3 + Q4 = Q/1 + Q /2 + Q/3 + Q/4
Q1 306978560,8
=
= 1074,425
Qnl
285714,268
kcal/kg
D = 1,128 s
(m)
Trong :
S : l din tch tit din ngang ca l phn ng (m2)
S=
V
3600.
(m2)
66
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n tt nghip
22,4
V=
Gi
(273 + t p )
Mi
273p
Gi
:Lu lng hi trong l phn ng.
Mi
Gi
ta phi xc nh dc trng lng phn t
Mi
48571,429
= 33,27
1460
Suy ra:
Vy V =
22857,143 11142,857
+
= 4432,91
18
248
Kcal / h
137852,13
= 63,8 m2
3600 x 0,6
67
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n tt nghip
h2 = 6m
68
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n tt nghip
Vp
S
(m)
trong ;
Vp : l th tch ca khnh gian phn ng
Vp =
(m3)
Gk
Trong :
Gk : lng xc tc c trong khong khng gian phn ng ca l phn ng
(kg)
Gc
285714,286 + 11142,857
= 156240,60 ( kg )
1,9
Vp =
156240,60
= 312,48
500
H=
312,48
= 4,9 (m)
63,8
(m3 )
69
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n tt nghip
h/2 =
D1 D 2 9 4,5
=
= 2,25 (m)
2
2
(m)
1. Cc s liu ban u
+ lng xc tc tun hon li : Gth = 1428,57 T/h
= 500 kg/h
70
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n tt nghip
Thnh phn
Hm lng ( %)
Cacbon
87
Hydr
Lu hunh
-T l th tch CO2/ CO = 1,85 .Ta tnh lng cacbon trong 1kg cc khi chy
c to thnh CO2 v CO v xc nh lng sn phm c to thnh :
+ 1kg cc cha 0,87 kg cacbon nn:
GCO2 + GCO = 0,87
GCO2 v GCO : tng ng vi lng cacbon to thnh CO2 v CO
Bit rng khi t 1kmol C cn 1 kmol CO2 ( tnh ra kg/kg cc)
mco2 = GCO2 +
Gco
.32 = 3,67 GCO2 (kg/kg)
12
Tng t ta c lng CO :
mco = GCO +
Gco
.1/2 .32 =2,34 GCO (kg/kg)
12
VCO2 =
3,67Gco
.22,4 = 1,87 GCO2 m3/kg
44
VCO =
2,34 Gco
.22,4 =1,87 GCO
28
m3/kg
Vco 1,87Gco
=
= 1,87
Vco 1,87Gco
ta c h phng trnh sau:
Nguyn Vit Hun
71
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n tt nghip
Gco
= 1,87
Gco
* Gii ra ta c:
V/N 2 = 3,76.V/O 2 = 3,76. 0,13= 0,49 m3/ kg
m /N 2 =
VN
22,4
.28 =
0,49
.28 = 0,61 kg/kg
22,4
sp
+ VN 2 +V/N 2 + V/O 2
+ mN 2 + m/O 2 + m/N 2
kg/kg
Thnh phn ca kh ti
t chy 1kg cc
m3/kg
kg/kg
kh
CO2
1,043
2,048
10,59
17,25
CO
0,565
0,707
5,73
5,95
SO2
0,028
0,08
0,28
0,67
N2
7,08
8,85
71,85
74,5
O2
0,13
0,19
1,32
1,6
8,846
11,87
89,77
100,00
1,008
0,81
10,23
9,854
12,65
100,00
Tng cng kh kh
H2O
Tng cng kh m
72
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n tt nghip
m3/kg
+ Lng N2 tng ng l :
mN 2 + m/N 2 = 8,85 + 0,61 =9,46
kg/kg
m3/kg
L
12,3
=
=1,07
L o 11,49
g d = g - g o = 20 5,57 = 14,43 kg
- Lng khng kh dng t cc:
Gkk= 12,3 . 14,43 = 1774890 kg/h
- Lng kh ti sinh m:
73
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n tt nghip
3. Tiu hao hi nc kh hp ph
* Ngi ta dng hi nc qu nhit kh hp ca hi sn phm ti sinh
K hiu
S lng ( kg/h)
+ xc tc tun hon
Gth
1428571
+ cc
20000
+ khng kh
Gkk
210822
+ hi nc vn chuyn xc
Gh
4130
Go
7142,85
* a vo
tc
+ hi nc kh hp ph
* Cng
1670665,85
* Ly ra
+xc tc
Gth
1428571
+ cc cn li
g 0
2860
+ kh ti sinh m
Ga
227962
+ hi nc vn chuyn xc
Gh
4130
Go
7142,85
tc
+ hi nc kh hp ph
* Cng
1670665,85
74
Ho Du K44-QN HBK HN
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n tt nghip
Cu t
Nhit hm ( kcal/kg )
Ring
Ring phn
+ CO2
10,59
149,0
15,78
+CO
5,73
155,6
8,92
+SO2
0,28
90,5
0,25
+N2
71,85
154,2
110,79
+O2
1,32
142,3
1,88
+H2O
10,23
287,9
29,45
* Tng cng
1000,0
167,07
( kcal/kg)
( kcal/kg)
trong :
C : t nhit ca xc tc hay cc kcal/kg
t : nhit ca cc hay xc tc
kcal/kg
QCO 2 ,QCO,, QH 2 O, QSO 2 : hiu ng nhit ca phn ng Oxi ha, cacbon ,hydro
v lu hunh
QHp = 0,558.8137 + 0,302.2452,6 + 0,09.28905 + 0,04.2181
= 7969,82
Nguyn Vit Hun
kcal/kg
75
Ho Du K44-QN HBK HN
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n tt nghip
S
lng(kg/h)
Nhit
0
(C)
Nhit
hm
(kcal/kg)
Lng nhit
(kcal/kg)
1428571
482
130,3
186142801,3
+ cc
20000
482
289
5780000
+ khng kh
210822
80
19,24
4056215,28
4130
482
824
3403120
7142,85
230
700
4999995
17140
7969,82
136602714,8
* a vo
+ xc tc
+ hi nc vn
chuyn xc tc
+ hi nc kh
hp ph
+nhit chy ca cc
* Tng cng
340984846,4
* Ly ra
+ xc tc
+ cc
+ kh m
+hi nc vn
1428571
600
162,2
231714216,2
2860
600
360
1029600
227962
600
160,6
36473920
4130
600
884
3650920
7142,85
600
884
6314279,4
chuyn xc tc
+ hi nc kh
hp ph
+ mt mt
* Cng
+ Lng nhit d (ly
theo hiu s )
* Tng cng
ly bng
2000000
279182935,6
61801910,2
340984846,4
76
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n tt nghip
77
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n tt nghip
Nhit
S lng
nhit hm
S lng nhit
0C
kg/h
kcal/kg
kcal/h
+ Q1
482
1428571
130
185714230
+ Q2
480
20000
289
5780000
+ Q3
80
12,3.x
19,24
236,625.x
+ Q4
482
4130
824
3403120
+ Q5
7855
7855.x
Tng cng Qa
+ Q 1/
600
1428571
162,2
231714216,2
+ Q 2/
600
20000 - x
360
3200000 - 360.x
+ Q 3/
600
12,65.x
160,6
2031,59.x
+ Q 4/
600
4130
884
3650920
+ Q 5/
tha
500000
K hiu
* a vo
194897350 + 8091,65.x
* Ly ra
nhn
Tng cng Qb
239065136,2 +
1671,59.x
( kg/h )
78
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n tt nghip
( kg/h )
( kg/ h )
Vng 1
phn
- Xc tc
- cc
- khng kh
- hi nc
Vng 2
Vng tch
vo (kg/h)
ra( kg/h)
vo (kg/h)
ra (kg/h)
vo (kg/h)
ra (kg/h)
1428571
1428571
1428571
1428571
1428571
1428571
20000
13120,35
13120,35
2860
2860
2860
84619,69
126202,3
4130
4130
4130
4130
4130
4130
87027,57
140934,4
7142,85
7142,85
1537320,
1532848,
1572023,
1576495,
1442703,
1442703,
vn
chuyn xc
tc
- kh m ti
sinh
- hi nc
kh hp
ph
* Tng
cng
79
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n tt nghip
v
3600.
m2
- trong :
v : th tch hi v kh i qua tit din cho ca l ti sinh ( trn lp gi
si ) m3/h
: tc cho php ca kh trong tit din t do ( m/s )
22,4.
G (273 + t p
M
273.P
-Trong :
80
Ho Du K44-QN HBK HN
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n tt nghip
G
: lng hn hp kh kmol/h
12,65
= 28,76
9,854
* Khi :
a) i vi l ti sinh
Ga
G
G
227962
7182,45
=
+ 0 =
+
= 8259,79
M
M H2 O
9,854
M
29
kmol/h
b) i vi vng th nht
G1
G
87027,57
= ts =
= 3000,95 kmol/h
M
M
29
c) i vi vng th hai
G 2 140934,43
G
= ts =
= 4859,81 kmol/h
M
M
29
d) i vi vng tch ( kh hp ph )
G
G
7182,45
=
=
= 399,03
M
M H 2O
18
kmol/h
m/s
s ( m2 )
- L ti sinh
257241,5
0,55
129,92
- Vng 1
93461
0,55
47,20
- Vng 2
151353
0,55
76,44
- Vng tch
12427,32
0,80
4,32
Tit din
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D1=
4.4,32
= 2,35 (m)
3,14
4.S 2 + .D12
+ 2.d =
4.76,44 + 3,14.2,35 2
+ 2.0,06 = 10,26 (m)
3,14
Dl = D1 =
+ 2. =
4.47,20 + 3,14.10,26 2
+ 2. 0,02
3,14
=12,9 ( m)
7. Chiu Cao L Ti Sinh V Cc Vng Ca N
a) chiu cao vng th nht bng chiu cao lp gi si ca xc tc :
V1
S1
h1 =
( m)
- trong :
V1 : th tch lp gi si ( m3)
S1 : tit din ngang ca vng th nht ( m2 )
+ Xc nh lp gi si theo ng thc sau :
V1 =
G1
(m3)
trong :
G1 : lng xc tc c trong vng th nht
( kg/h )
: t trng ca lp gi si
( kg/m3 )
- Xc nh lng G1:
G1 =
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6879,65
= 125,085 T = 125085 kg
55
V1 =
146576
= 250,17 ( m3)
500
h1 =
250,17
= 5,3
47,20
( m)
b) chiu cao vng th hai bng chiu cao ca tm ngn hnh tr .Xc nh
chiu cao vng th hai tng t nh xc nh chiu cao vng th nht :
G2 =
10260,35
= 146,576 T = 146576 kg
70
V2 =
146576
= 293,15 ( m3 )
500
h2 =
293,15
= 3,84
76,76,44
( m)
( m)
- th tch ca lp ny :
Vc = h3 .S 2 = 1,46.76,44 = 111,6 (m3)
- lng xc tc gi si trong lp ny
Gc = Vc. c = 111,6.500 = 5580,2 kg
d) chiu cao h4 di li phn phi : ta ly h4 = 5 ( m)
e) chiu cao vng tch h5 = 8( m) ( tinh c chiu cao t xyclon )
Vy chiu cao chung ca l ti sinh l ;
Hts= h1 +h4 + h5 = 5,3 + 5 + 8 = 18,3 (m)
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Phn IV
xy dng
I. Chn a im xy dng
1. Nhng c s xc nh a im xy dng
Do phn xng cracking xc tc l mt phn ca nh my lc du, v vy
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50%, din tch dnh cho d tr 30%, cn li dnh cho trng cy xanh v b tr
cc hng mc khc.
S nguyn tc dy chuyn ca phn xng:
Nguyn tc:
Nguyn liu
L phn ng
L ti sinh xc tc
Thp tch kh
Cn
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460 m
250 m
F = 115.000 m2
27.820 + 10.000
100 = 32,9%
115.000
A+B
100
F
A+B+C
100
F
Theo tiu chun Vit Nam th cc ch tiu kinh t k thut xy dng Kxd
v Ksd ca phn xng cracking xc tc hon ton tho mn v m bo yu
cu quy nh.
Do qu trnh sn xut hu ht c tin hnh trong cc thit b kn, kch
thc thit b rt cao v to, vn chuyn bng ng ng, cc qu trnh c c
kh ho t ng ho ton b, vic iu khin c tin hnh trong phng iu
khin trung tm. Do thit k nh sn xut l thin - bn l thin.
- Nh sn xut l thin - bn l thin c thit k bng khung thp. Bn
trong c nh iu khin trung tm v t cc thit b ph tr cho qu trnh sn
xut nh thit b lm lnh ni hi, bm, cc thit b chnh nh thit b phn
ng, thit b ti sinh, thit b tch sn phm c t ngoi tri.
+ Nhp nh L1 = 6 m, L2 = 6 m.
+ Bc ct B = 6 m.
+ Chiu cao nh: H = 6 m.
Nguyn Vit Hun
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Phn V
Nguyn Vit Hun
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Tnh ton kinh t l phn quan trng trong thit k phng n xy dng
nh my. N quyt nh phng n thit k c a vo sn xut hay khng.
Mt phng n c thit k ti u nht phi m bo v trnh m
thut, sn xut, cht lng sn phm ng thi em li hiu qu kinh t cho
nh sn xut.
Tnh ton kinh t l tnh hiu qu kinh t ca phng n thit k. Nu
vn kinh t c tho mn th bn thit k c a vo sn xut, khi ta
s bit c vn u t cho nh my, bit c li nhun m nh my thu
c hng nm v thi gian thu hi vn ca d n.
II. Ch cng tc ca phn xng
12
= 0,6
20
1.000
= 11,1 (thng)
90
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* i vi sn phm xng: d 20
4 = 0,75
1 thng 150 lt s cha c: 150 0,75 = 112,5 (kg xng)
1 tn xng s cha c trong:
1.000
= 8,89 (thng)
112,5
1000
= 7,169 (thng)
139,5
1000
= 7,092(thng)
141
Tn/nm
Thng/nm
Thng/gi
Kh
390514,28
4334708,59
539,143
Xng
110268,5
80286,96
9,986
Gazoil nh
390514,28
2799596,8
384,209
Gazoil nng
298628,57
2117873,8
263,417
Cc
114858,29
Tng
1304783,9
14,286( T/h)
9332466
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1.000
= 7,75 (thng)
129
(USD)
(USD)
17
17,051
Cn du
thng
1,003
Hi nc
m3
4,5
0,35
1,575
Nc
m3
0,8
0,07
0,056
in
kWh
0,9
0,8
0,72
Nng lng
tn
0,01
10
tin
0,1
Tng chi ph nguyn liu v nng lng cho 1 thng sn phm 19,502
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3 ngi
Th c kh
3 ngi
2 ngi
Cn b k thut
2 ngi
Qun c
1 ngi
Ph qun c
1 ngi
36 ngi
Lng 1
nm
Bm + my nn
150
900
10.800
Thit b nhit
150
900
10.800
Cc thit b chnh
12
150
1.800
21.600
Th in
180
540
6.480
Th c kh
180
540
6.480
Hnh chnh
160
320
3.840
K thut
210
420
5.040
Qun c
225
225
2.700
Ph qun c
220
220
2.640
10
70.380
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Vt =
Vxd + Vtb
50.000.000 + 300.000.000
=
1 0,05
0,95
= 368.421.052,6 (USD)
- Tnh khu hao ph c bn:
+ Nh sn xut c thi gian khu hao l 20 nm, do mc khu hao
theo ti sn l:
50.000.000
= 2.500.000 (USD/nm)
20
+ Thit b c thi gian lm vic chung l 20 nm, do mc khu hao
trong 1 nm l:
300.000.000
= 15.000.000 (USD/nm)
20
+ Khu hao sa cha ly 5% khu hao c bn:
0,05 (2.500.000 + 15.000.000) = 875.000 (USD/nm)
Tng mc khu hao trong mt nm l:
2.500.000 + 15.000.000 + 875.000 = 18.375.000 (USD/nm)
Mc khu hao trn 1 thng sn phm l:
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CPSX
20,91
=
= 21,34 (USD/thng sn phm)
1 0,02
0,98
19,502
0,013
Khu hao
0,98
Chi ph khc
0,418
Chi ph sn xut
20,91
0,43
21,34
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STT
Tn sn
phm
c trong 1 nm
(USD)
(thng)
Kh
15
3.496.501
52.477.515
Xng
30
8.001.000
240.030.000
Gazoil nh
25
2.710.125
67.753.125
Gazoil nng 20
4.533.750
90.675.000
Cc
90.000 (tn/nm)
9.000.000
100 (USD/tn)
459.905.640
LN
Vsx
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Vy
DL =
36.969.394,2
= 0,048
768.362.016,4
Vsx
LN + KH
768.362.016,4
= 13,8
36.969.394,2 + 0,98 18.741.376
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- 5 m (chu la tt)
- 10 m (chu la km)
n tt nghip
n tt nghip
Khi s dng cn phi dng dng in an ton, cch ly dy dn, che chn
c hc, cc thit b in u phi c dy ni t, phi s dng gng v ng
bng cao su.
n tt nghip
Kt lun
Sau hn 4 thng thc hin ti cng vi s c gng ca bn thn cng
nh tm ti ti liu v s hng dn ca thy c, n nay bn n ca em
hon thnh.
Qua bn n ny gip em hiu c vic a mt thnh qu ca vic
p dng nghin cu vo sn xut l mt qu trnh ht sc phc tp, n i hi
phi c s lin quan n qu trnh sn xut. V phn l thuyt cn phi nm
c cc tnh cht ca nguyn liu v sn phm, nm c yu cu v xc tc,
hiu c c ch phn ng cng nh cc yu t nh hng n qu trnh. Da
trn c s l thuyt kt hp vi cc ti liu v thit k cho ta phng hng
la chn cng ngh thch hp.
Hin nay trn th gii, vic nghin cu cc phng php sn xut
xng c tr s octan cao v cht lng tt vn l vn quan trng. Nhiu
hng cho ra cc dng cng ngh khc nhau. ng thi trn th trng tiu
th xng ngy cng tng, sn phm xng c ng dng rng ri trong kinh
t, an ninh quc phng. Do nhu cu s dng xng ngy cng tng cho nn vic
sn xut xng l mt yu cu quan trng, khng ch cho ra loi xng thng
m phi sn xut ra loi xng c tr s octan cao v cht lng tt. cng l
mt trong nhng nguyn nhn m nc ta quyt nh xy dng nh my
lc du Dung Qut Qung Ngi v s 2 Nghi Sn Thanh Ho.
Bn n ny c hon thnh nhng v iu kin cng nh ti liu
tham kho cn hn ch, hn na Vit Nam ngnh ho du l mt trong
nhng ngnh mi v v bc u lm quen vi cng tc thit k phn xng
cho nn chc hn cn thiu st l iu khng th trnh khi. Vy em rt mong
c s ch bo cng nhng kin ng gp ca cc thy c v cc bn ng
nghip bn n c hon thin hn.
n tt nghip
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Mc lc
Trang
M u
....................................................................................................................... 1
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1.
Xc tc Zeolit ................................................................................... 27
1. Sn phm kh ........................................................................................ 41
2. Xng cracking xc tc .......................................................................... 41
3. Phn on si cao hn 1950C ............................................................... 42
Phn II: Tnh Ton V Thit K Dy Chuyn Cng Ngh
CrackingXc Tc ............................................................................... 45
Chng I. Cc yu t nh hng n qu trnh cracking xc
tc ............................................................................................................... 45
I. Nhit ................................................................................................... 45
II. p sut ................................................................................................... 47
III. Mc chuyn ho C ......................................................................... 48
IV. Tc np liu ring ......................................................................... 48
V. T l lng xc tc/nguyn liu (X/RH) hay bi s tun hon xc tc
..................................................................................................................... 50
VI. Hiu ng nhit ..................................................................................... 51
Nguyn Vit Hun
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Chng II ..................................................................................................................... 52
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I. Mc ch.................................................................................................. 91
II. Ch cng tc ca phn xng......................................................... 91
III. Nhu cu v nguyn liu v nng lng ............................................. 93
................................................................................................................... 103