BI Gi NG

XC TC TRONG
CNG NGH LC DU
TS. Nguyn Th Linh
B m n l c - h a du
1
Cc khi nim c bn v cht xc tc d th, cht xc
tc s dng trong cng ngh lc du
Cc cht xc tc kim loi, cht xc tc axit- baz
c s dng trong cng ngh lc du
Nm c bn cht ca cc qu trnh xc tc trong
cng ngh lc du (xc tc cho qu trnh cracking,
reforming, isome ha, alkyl ha, hydrotreating
Nm c cc phng php ch to, nguyn tc la
chn cht xc tc v ng dng trong cng nghip
MC CH MN HC
2
Nguyn Th Linh, DKLD 4060326, 2013-2014
NI DUNG MN HC
CHNG 1. MT S KHI NIM V CHT XC TC
TRONG CNG NGH LC DU
CHNG 2. XC TC CHO QU TRNH CRACKING
CHNG 3. XC TC CHO QU TRNH REFORMING
CHNG 4. XC TC CHO QU TRNH ISOME HA
CHNG 5 CHT XC TC CHO QU TRNH ALKYL HA
3
Nguyn Th Linh, DKLD 4060326, 2013-2014
NI DUNG MN HC
CHNG 6. CHT XC TC CHO CC QU TRNH
HYDRO HA V DEHYDRO HA
CHNG 7. CHT XC TC CHO QU TRNH
HYDROPROCESSING
CHNG 8. CC PHNG PHP CH TO, LA
CHN CHT XC TC V TRIN KHAI CNG NGHIP
4
Nguyn Th Linh, DKLD 4060326, 2013-2014


CHNG 1
CHNG 1
MT S KHI NIM V CHT XC TC
TRONG CNG NGH LC DU
5
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
6
1.1. Cc khi nim v xc tc trong cng ngh lc du
Tnh c th
Tnh a nng
Tnh a dng
Tnh khng thay i trng thi nhit ng
Qu trnh xc tc l qu trnh lm thay i tc ca cc
phn ng ho hc do nh hng ca cht xc tc; nhng
cht ny tham gia nhiu ln vo tng tc ho hc trung gian
vi cc tc nhn phn ng v sau mi chu trnh tng tc
trung gian li phc hi thnh phn ho hc ban u.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
7
Tnh c th: Mt cht xc tc c hot tnh i vi mt
s phn ng nht nh.
Tnh a nng: Cht xc tc c hot tnh i vi mt s
cc phn ng ha hc khc nhau.
Xc tc axit rn cho cc phn ng cracking, isome
ha, alkyl ha, thy phn, hydrat ha
Xc tc kim loi cho cc phn ng hydro ha
dehydro ha
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
8
Tnh a dng: Thnh phn ha hc ca cc cht xc tc
a dng, c th l nguyn t, hp cht hay phc cht.
Tnh khng thay i trng thi nhit ng: Cht xc
tc khng b tiu hao trong qu trnh phn ng, cht xc tc
khng lm thay i v tr cn bng ca phn ng ho hc.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
9
Cc giai
on trong
phn ng
xc tc d
th
Tng
tc trung
gian
Hp ph
Phn
ng
Nh
hp
ph
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
10
Tng tc trung gian: S tng tc gia tc nhn tham gia
phn ng v b mt cht xc tc.
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tng tc trung gian gia tc nhn tham gia phn ng
v b mt dn n s gia tng nng mt s cht trn
b mt xc tc.
Trong tng tc trung gian, lin kt ca cc nguyn t
b mt v cc nguyn t di lp b mt ca xc tc
khng b t hon ton, m hnh thnh hp cht trung
gian, phc cht hot ng.
CHNG 1
11
Hp ph: S tng tc v gia tng nng tc nhn
phn ng trn b mt cht xc tc.
Hp ph ha hc: xy ra s tng tc ha hc gia tc
nhn phn ng v b mt cht xc tc
Hp ph vt l l trng thi trung gian trc khi xy ra hp
ph ha hc. Xc nh c c im ca hp ph vt l
c th kt lun c mt s c trng b mt, kch thc,
hnh dngmao qun ca cht xc tc.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
12
Phn ng: l qu trnh tng tc ca cc tc nhn tham
gia phn ng c hp ph trn b mt cht xc tc v
hnh thnh sn phm.
Phn ng xy ra gia tc nhn v phc cht hot
ng hnh thnh trn b mt xc tc.
Phn ng trn b mt cht xc tc c nng lng
thp hn so vi phn ng cng loi khng c xc
tc.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
13
Nh hp ph:
Nguyn Th Linh, DKLD 4060326, 2013-2014
S gii phng sn phm v tc nhn tham gia phn ng ra
mi trng.
CHNG 1
14
Mt s i lng c trng cho kh nng ca cht xc tc
Hot cht xc tc (activity): l i lng nh gi
cht rn c phi l cht xc tc hay khng, c c
trng bng chuyn ha v hng s tc phn ng.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
15
chn lc ca cht xc tc (Selectivity): L kh nng
thc y phn ng theo mt chiu hng nht nh, dn n
s to thnh nhiu sn phm mong mun, t cc sn phm
ph.
Nguyn Th Linh, DKLD 4060326, 2013-2014
- chn lc thng c biu din bng t s gia tc
to thnh sn phm chnh v tng tc ca cc phn ng
xy ra.
Hoc xc nh bi t s ca hiu sut sn phm mong mun
q v tng cc sn phm c to thnh q
i
.
(1.1)
(1.2)
CHNG 1
16
Tui th ca cht xc tc: biu th kh nng lm vic ca
cht xc tc trong iu kin vn hnh qu trnh phn ng.
Nguyn Th Linh, DKLD 4060326, 2013-2014
-Tui th ca cht xc tc ph thuc v mi trng phn
ng v iu kin vn hnh.
- Tui th ca cht xc tc th hin bn c hc v
ha hc.
CHNG 1
17
Cc loi cht xc tc trong cng ngh lc du
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Cht xc tc ng th: l cht xc tc cng pha vi tc
nhn phn ng (thng l dng lng).
Cht xc tc ng th lm vic di iu kin mm hn so
vi xc tc d th.
Cht xc tc ng th kh thu hi (kh tch ra khi hn hp
sau phn ng).
CHNG 1
18
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Cht xc tc d th:
Xc tc ng th c th c xc nh cu trc bng cc
phng php ha l, thun li cho nghin cu ng hc ca
phn ng.
Xc tc ng th c ng dng nhiu trong cng nghip
do cng ngh n gin, thc hin lin tc, d thu hi v ti
sinh.
D bin tnh, c chn lc cao, hot tnh cao, n nh
nhit v thy nhit.
Gi thnh cao, iu kin phn ng kh khn.
CHNG 1
19
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Cht xc tc ng th d th ha:
Hot tnh cao
Tm hot tnh l ng th
D thu hi v ti sinh
C tnh n nh nhit
CHNG 1
20
Hp cht phi tr trong xc tc
Nguyn Th Linh, DKLD 4060326, 2013-2014
Hp cht phi tr trong xc tc to h cht xc tc phc vi
s lin kt ca cc phi t (ligan) vi nguyn t kim loi.
Cu trc ca hexol
CHNG 1
21
Nguyn Th Linh, DKLD 4060326, 2013-2014
S phi tr trong cht xc tc hnh thnh theo cc nguyn l sau:
- Nguyn l lin kt cng ha tr:
+ Lin kt gia kim loi v ligan l do phn ng ca baz Lewis (ligan)
v mt axit Lewis (kim loi).
+ S hnh thnh lin kt kim loi-ligan do s nhng cp in t c thn
ca ligan cho orbital trng ca kim loi.
+ Nguyn t kim loi thng c cc orbital lai ha, s lai ha nng cao
kh nng nh hng ca orbital v lm cho lin kt gia KL-Ligan trt t
v n nh hn.
+ Cu trc ca cc phi tr l 8 mt (lai ha d
2
sp
3
) i vi phc phi tr 6,
l 3 (sp
3
) hoc 4 mt (dsp
3
) i vi phc phi tr 4.
CHNG 1
22
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Nguyn l tnh in n gin:
M t s hnh thnh lin kt gia kim loi (hoc ion KL) vi cc
ligan bng tng tc tnh in ca cc in tch dng tm
nguyn t kim loi v in tch m ca cc nguyn t ligan.
- Nguyn l trng tinh th:
Biu din s tng tc tnh in gia ca nguyn t kim loi v
in t ca ligan gn.
- Nguyn l orbital phn t:
S lin kt gia cc orbital nguyn t ca nguyn t kim loi cha
cp in t c thn trn tm nhng in t ca ligan vi cc
in t trng c mc nng lng thp trn ligan.
CHNG 1
23
Nguyn Th Linh, DKLD 4060326, 2013-2014
1.2. Xc tc Axit Baz
Cht xc tc axit l nhng cht xc tc c kh nng nhng
proton (axit Bonsted) hoc nhn in t (axit Lewis). V vy,
chng c kh nng xc tc cho cc tc nhn mang tnh baz.
Cc tm axit tham gia vo s hnh thnh cc hp cht trung gian
trong qu trnh chuyn ha ha hc trn b mt cht xc tc l
nhng axit rn.
Phn ng c s tham gia ca cht xc tc axit hnh thnh
cacbocation theo 4 c ch sau:
CHNG 1
24
Nguyn Th Linh, DKLD 4060326, 2013-2014
(1) Cng cation vo phn t cha no
Qu trnh ny ph thuc vo lc axit v cc yu t khc nh cu t
lm bn cacbocation, tr ha hc v hng s in mi ca mi
trng.
Hydrocacbon c tnh baz yu th cn tm axit mnh.
CHNG 1
25
Nguyn Th Linh, DKLD 4060326, 2013-2014
(2) Cng proton vo phn t no
L, R
1
+
: tm axit Lewis, ion cacbeni
mnh
C
7
H
16
+ H
+
(3) Loi b mt in t trung ha
(4) D li phn t
CHNG 1
26
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc phn ng ca cacbocation
Chuyn v in tch:
Ion 2,4- dimetyl pentyl Chuyn v 1-3
CHNG 1
27
Nguyn Th Linh, DKLD 4060326, 2013-2014
Chuyn v 1-3
ng phn ha cu trc
Xy ra do s chuyn v nhm metyl dn n s hnh thnh ion cacbeni c
cu trc nhnh nhiu hn.
CHNG 1
28
Nguyn Th Linh, DKLD 4060326, 2013-2014
Chuyn v hydrua
Xy ra gia ion cacbeni v phn t ankan
Chuyn v nhm alkyl
Hnh thnh v ct t lin kt C-C
CHNG 1
29
Nguyn Th Linh, DKLD 4060326, 2013-2014
V d v phn ng alkyl ha
CHNG 1
30
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tt mch:
CHNG 1
31
Nguyn Th Linh, DKLD 4060326, 2013-2014
V d v phn ng ct mch C C:
CHNG 1
32
Nguyn Th Linh, DKLD 4060326, 2013-2014
V d v phn ng ct mch C C:
V d v phn ng bt cn i toluen
CHNG 1
33
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc loi tm axit
Tm axit Lewis v Bronsted
- V d v cht xc tc dng aluminosilicat
Cng thc ha hc ca aluminosilicat: Na
2
O.Al
2
O
3
.nSiO
2
trong n biu th t l SiO
2
/Al
2
O
3
CHNG 1
34
Nguyn Th Linh, DKLD 4060326, 2013-2014
S bin tnh, chuyn pha gia tm axit Lewis v
Bronsted trong aluminosilicat
CHNG 1
35
Nguyn Th Linh, DKLD 4060326, 2013-2014
1.3. Mt s thnh phn v tnh cht ca du m
Thnh phn cc nguyn t trong du m:
Du m cha thnh phn cc nguyn t bao gm ch yu l C
(83-87%) v H (11-14%), ngoi ra cn c S, O, N v cc kim loi
nng nh V, Ni, Fe, Cu, Ca, Na, As
Thnh phn ha hc ca du m:
-Cc hp cht hydrocacbon l nhng hp cht trong thnh phn
ch cha nguyn t C v H.
- Cc hp cht d nguyn t l nhng hp cht ngoi thnh phn
gm nguyn t C v H cn cha cc d nguyn t nh S, O, N.
CHNG 1
36
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc hp cht hydrocacbon trong du m
Cc hp cht parafin
Cc hp cht vng no (Naphten)
Cc hp cht thm (Aromatic)
Cc hydrocacbon
- S cacbon ca cc hp cht hydrocacbon trong du m t C
5
-C
60
(t C
1
-C
4
nm trong kh).
CHNG 1
37
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
38
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
39
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc hp cht parafin trong du m
CHNG 1
40
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
41
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc hp cht naphten trong du m
Cc hp cht aromatic trong du m
CHNG 1
42
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc hydrocacbon lai hp
Cc hp cht d nguyn t
- Cc hp cht cha lu hunh:
CHNG 1
43
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 1
44
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Cc hp cht cha nit:
CHNG 1
45
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Cc hp cht cha oxi: gm cc axit (-COOH), cc xeton
(-C=O), cc phenol v lacton.
Cc kim loi trong du m:
- Thng tn ti di dng phc ca kim loi v hp cht
hu c (c-kim).
CHNG 1
46
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc cht nha v asphalten trong du m:
- Cc cht nha v asphalten trong du m c thnh phn
HC v ng thi cha cc d nguyn t O, N, S, c KLPT
ln c 500-600, c mt trong phn on si cao v phn
cn ca du m.
Phn loi du m theo t trng
-Du nh: c t trng < 0,828
- Du trung bnh: c t trng 0,828 < d < 0,884
- Du nng: c t trng > 0,884
1.3. Cc qu trnh trong nh my lc du
Qu trnh vt l Qu trnh ha hc
S dng nhit
C s dng CXT
Chng ct
Chit
Loi sp bng
propan
Loi sp bng
dung mi
Trn
Gim nht
Loi cc
Cracking xc tc
Reforming xc tc
Hydrotreating
Hydrocracking
Loi sp
Alkyl ha
Polyme ha
Isome ha
47
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn on
c im cc phn on
im si (
o
C) S nguyn t C
Kh
Xng
Naphta
Kerosin (nhin liu phn
lc)
Diesel, Fuel oil
Gasoil kh quyn
Fuel oil nng
Cn chng ct kh quyn
Cn chng ct chn khng
< 30
30 210
100 - 200
150 - 250
160 - 400
220 - 345
315 - 540
540
> 615
1 - 4
5 - 12
8 - 12
11 - 13
13 17
20 - 45
30
> 60
48
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
Sn phm sch (khng cha N, S, O, cc kim loi
Thu nhiu xng hn (ON cao)
Thu nhiu diesel hn (CN cao)
Cc sn phm c gi tr (cc hp cht thm, anken)
t cn
Yu cu v cc sn phm lc du
Bin php p ng ?
S dng phng php chng ct tinh vi hn
S dng cc phng php vt l
S dng cc phng php ha hc
49
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
n- pentan
2-metyl pentan
cyclopentan
n-hexan
2,2-dimetyl butan
benzen
cyclohexan
n-octan
2,2,3-trimetyl pentan
metyl-tert- butyl ete
Xng mch thng
Xng nh FCC
Xng alkylat
Xng reformat (CCR)
Tr s Octan v im si ca mt s hp cht
62
90
85
26
93
> 100
77
0
100
118
68 67 (MON)
93 82
95 92
99 88
309
301
322
342
323
353
354
399
372
328
50
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
Hp cht ON
Nhit si
n- ankan
n-hexadecan (cetan)
iso ankan
anken
cycloankan
alkylbenzen
naphtalen
-metyl naphtalen
Xng mch thng
cycle oil FCC
Xng nhit phn
Gas oil hydrocracking
Tr s Cetan ca mt s hp cht
100 - 110
100
30 70
40 60
40 70
20 60
0 20
0
40 50
0 25
30 50
55 60
51
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
Th trng cht xc tc
52
CHNG 1
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 2
CHNG 2
CHT XC TC CHO
QU TRNH CRACKING
53
Nguyn Th Linh, DKLD 4060326, 2013-2014
2.1. Qu trnh cracking xc tc tng si (Fluid Catalytic
Cracking- FCC)
54
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mc ch ca qu trnh cracking
- Sn xut xng c tr s octan cao, cc olefin nh, phn on
nh (LPG, FO)
Nguyn liu cho qu trnh cracking
- Phn on Gas-Oil, cc phn on nng ca qu trnh
chng ct du th.
S nh my lc du hin i
55
Phn xng FCC hin i:
thit b phn ng ng nng
56
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
FCC: Thit b phn ng tng si v thit b ti sinh cht xc tc
57
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn ng ct lin kt C-C
Phn ng isome ha
Phn ng proton ha/loi proton
Phn ng alkyl ha
Phn ng polyme ha
Phn ng vng ha, ngng t to cc
Phn ng cracking xc tc
58
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc phn ng xy ra trong qu trnh cracking
Cracking anken to ion cacbeni
C ch phn ng cracking xc tc
Cracking ankan to ion cacboni
Hoc nu c mt ca ion cacbeni
59
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn ng cracking xc tc n-octan
Ion cacbeni u tin
60
CHNG 2
Xem xt c ch trn sai u?
Ion cacbeni u tin
61
CHNG 2
Phn ng isome ha (ng phn ha)
62
CHNG 2
Phn ng to cc
Ion cacbeni u tin
63
CHNG 2
64
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn b sn phm cracking nhit v cracking xc tc
65
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Theo c ch phn ng cracking xc tc:
- Cht xc tc phi c kh nng nhng H
+
hoc nhn H
-
2.2. Cht xc tc cho qu trnh FCC
Cht xc tc cha tm axit
Cht xc tc th h u tin:
Dung dch AlCl
3
- Gy n mn thit b
- C trong nc thi
Cht xc tc th h sau:
Khong st ( x l axit)
Aluminosilicat v nh hnh
- Tnh n nh v tnh chn lc cao hn
- Chu mi mn c hc tt hn
Zeolit
-Hot tnh v tnh n nh cu trc cao
- t to cc, n nh nhit cao hn
66
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Xc tc cho qu trnh FCC
Tm axit yu
Tm axit mnh
67
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Thnh phn ca cht xc tc FCC
68
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Zeolit Cht mang Ph gia
RE- USY
Vt liu mao qun
Sb, Sn, CaTiO
2
MgO, Pt/Al
2
O
3
, CeO
2
ZSM-5
Zeolit
69
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cu trc ca zeolit:
- n v cu trc c s ca zeolit l
nhng t din Si v Al
- Cc zeolit cha cc mng li cu
trc mao qun vi kch thc rt
nh (zeolit cho xc tc FCC c kch
thc mao qun khong 8 ).
70
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
71
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mt s loi zeolit tng hp ng dng cho sn xut
cht xc tc FCC:
- Zeolit X
- Zeolit Y
- Zeolit ZSM-5
72
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cht mang
- Cc vt liu mao qun vi kch thc trung bnh (2-
50nm) n ln (>50nm)
- Dn cc phn t ln i n tm hot tnh
- Khuch tn tc nhn phn ng vo v ra khi b mt
cht xc tc
- Chng li s u c cht xc tc
73
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Ph gia
- Cht xc tin nhm Pt
- Nhm oxit kim loi (MgO, CeO
2
)
- ZSM-5
- Ph gia th ng ha kim loi (Antimon)
Quy trnh tng hp cht xc tc FCC
74
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Silic v nh
hnh
Natrialuminat NaOH
Mm tinh th
zeolit NaY
Gel natrialuminosilicat
Hn hp Zeolit NaY
Zeolit NaY
Zeolit H-NaY
Gi ha (kt tinh)
Lc, ra
Trao i ion
NH
4
OH
Sn xut cht xc tc FCC
75
CHNG 2
Phn b sn phm ca qu trnh cracking Gas oil
76
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tnh chn lc hnh dng
77
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tnh chn lc hnh dng
78
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Pht trin cht xc tc mi cho qu trnh FCC
0.51 0,55nm
Cht xc tc FCC cha ZSM-5:
- Sn xut olefin nh (C
3
=
, C
4
=
) lm
nguyn liu cho ha du v sn xut
MTBE, ETBE
79
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
2.3. S mt hot tnh v ti sinh cht xc tc FCC
80
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
Nguyn nhn gy mt hot tnh cht xc tc
Mt hot tnh do thay i cu trc ca cht xc tc
Mt hot tnh do s hnh thnh cc
Mt hot tnh do kim loi nng
81
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch ca s mt hot tnh cht xc tc FCC
C ch hnh thnh cc
82
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch hnh thnh cc
83
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch tch t kim loi nng
84
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch tch t kim loi nng
85
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
nh gi tnh cht cht xc tc FCC mi
86
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
nh gi tnh cht cht xc tc FCC cn bng
MAT
wt %
G.F.
H2
YLD
SCFB
C.F.
SA
m/g
Z-SA
m/g
M-SA
m/g
Z/M SA/K
Ni
ppm
V
ppm
Ni/V
Na
wt %
Sb
ppm
Sb/Ni
UCS

RE2O3
wt %
Al2O3
wt %
CaO
wt %
Fe
wt %
74 3.4 171 1.2 155 89 66 1.3 53 3508 822 4.27 0.24 42 0.01 1.76 49.8 0.241 0.58
K2O
wt %
MgO
ppm
P2O5
wt %
Pb
ppm
TiO2
wt %
C
wt %
ABD
g/cc
PV
cc/g
0-
20
%
0-
40
%
0-
80
%
40-
80
%
APS
Umb/
Umf
0.08 3462 0.151 26 0.75 0.04 0 6 62 56 71
2.4. Ti sinh cht xc tc FCC
87
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch loi b cc
88
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch loi b kim loi nng
Mt s pht thi kh trong qu trnh ti sinh cht xc tc
v bin php thu hi
89
CHNG 2
Nguyn Th Linh, DKLD 4060326, 2013-2014
- c dch ti liu
- Trao i Tho lun
CHNG 3
CHNG 3
CHT XC TC
CHO QU TRNH
REFORMING
90
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.1. Reforming xc tc
91
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mc ch ca qu trnh reforming xc tc
Sn xut xng c tr s octan cao
Sn xut ha cht c bn (Benzen, Toluen, Xylen-
BTX)
Reforming xc tc l qu trnh sp xp li cu trc ca
cc hp phn hydrocacbon c tr s octan thp trong
phn on thnh cc hydrocacbon c tr s octan cao m
khng lm thnh i vng nhit si ca phn on
92
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Nguyn liu cho qu trnh reforming xc tc
Phn on Naphta ca qu trnh chng ct du th,
qu trnh cracking xc tc.
- Phn on Naphta (C
5
-C
12
) c vng nhit si t
30
o
C 200
o
C (naphta nng t 90 200
o
C).
Thnh phn ca phn on Naphta:
Parafin: n- v iso-parafin
Olefin: mch thng hoc nhnh cha 1 hoc nhiu ni i
Naphten: Cycloankan
Aromatic: cc hp cht cha vng thm
93
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Hp cht cha lu hunh trong phn on Naphta:
94
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Hp cht cha nit trong phn on Naphta:
95
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mt s phn ng xy ra trong qu trnh reforming xc
tc phn on Naphta:
96
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.2. Cht xc tc cho qu trnh reforming
Cht xc tc th h u tin: Cr
2
O
3
, MoO
3
/Al
2
O
3
Cht xc tc th h th hai: Pt/Al
2
O
3
Cht xc tc th h th ba: Pt-Re(Ir, Rh, Ge)/Al
2
O
3
- Hp phn kim loi xc tc cho qu trnh hydro v dehydro
ha
- Cht mang Al
2
O
3
(c tnh axit) xc tc cho cc qu trnh
thm ha, vng ha, isome ha.
97
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Thnh phn ca mt s cht xc tc reforming in hnh
98
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Vai tr ca cht xc tc lng chc
C ch qu trnh isome ha metylcycolpentan
99
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
C ch lng chc trong phn ng isome ha o-xylen thnh
etylbenzen
100
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
nh hng ca nhit v p sut n qu trnh thm ha cyclohexan
101
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
nh hng ca t l H
2
/HC nguyn liu n qu trnh thm
ha cyclohexan
102
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc loi thit b phn ng reforming
103
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cng ngh reforming xc tc bn ti sinh (SRR)
104
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cng ngh reforming xc tc ti sinh lin tc (CRR)
105
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.3. S mt hot tnh ca cht xc tc
Mt hot tnh do s tch t cc
Mt hot tnh do s u c bi hp cht cha lu hunh
Do thnh phn nguyn liu
Hnh thnh nhit thp
Khi nhit > 400
o
C hnh
thnh lp graphit Pt-C bao
ph b mt xc tc
106
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.4. Ti sinh cht xc tc
t cc c s dng dng kh tr loi b hydrocacbon,
hydro.
Kim sot nhit t cc > 450
o
C
Oxi ha v oxiclo ha n phn tn kim loi trn cht mang
v hot ha tm axit.
Lm kh
Kh b mt kim loi nhit 700
o
C
Sulfit ha b mt kim loi (0,05-0,06%wt S)
107
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.5. Cng ngh ti sinh cht xc tc
Cng ngh bn ti sinh xc tc
Cng ngh ti sinh tun hon
Cng ngh ti sinh lin tc (CCR)
108
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
3.6. Thu hi kim loi t xc tc reforming s dng
- X l vi axit v kim
Re nm trong dung dch, Pt, Ir trong phn cn rn
109
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Thu hi Pt:
Hoc dng qu trnh in ha:
- Ha tan Pt:
- Kt ta mui Pt:
- Nung mui Pt:
110
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Thu hi Re
Ha phn dung dch ca qu trnh x l axit v kim vi ion
amoni
- Trao i ion:
- X l vi amoni:
CHNG 4
CHNG 4
XC TC CHO QU TRNH
ISOME HA
111
Nguyn Th Linh, DKLD 4060326, 2013-2014
112
4.1. Qu trnh isome ha
Mc ch:
Tng ON cho xng
Gim nhit ng c ca cc phn on nng
(DO, FO)
Thu cc sn phm ha cht c bn
Qu trnh isome ha l qu trnh ha hc lm thay i cu trc
ca hp cht hu c.
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Nguyn liu: Phn on Naphta C
5
/C
6
, n-butan (phn on
kh), phn on C
8
thm t reformate, phn on nng (DO, FO).
113
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
4.2. Phn ng isome ha cc nguyn liu in hnh
114
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Sn xut MTBE, ETBE t isobuten
115
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Vit c ch Isome ha n-buten trn cht xc tc cha
tm axit
116
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
C ch phn ng isome ha xy ra trn tm axit
117
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
C ch phn ng isome ha n-pentan xy ra trn tm axit
118
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Qu trnh isome ha thu p-xylen t phn on C
8
ca reforming
119
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
4.3. Cht xc tc cho qu trnh isome ha
Cht xc tc axit: Nhm clorua khan, c tnh axit rt mnh, c
hot tnh cao cho qu trnh.
-Gy n mn mnh, kh thu hi
Cht xc tc HF-BF
3
:
- Thc hin iu kin mm
- Gy n mn
120
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Cht xc tc lng chc:
Pt/Al
2
O
3
:
-Cn lm sch nguyn liu
- Phi clo ha xc tc
- Gy n mn
Pt/zeolit:
-Khng cn clo ha
- Khng nhy cm vi cc hp cht d nguyn t
- C cu trc mao qun (5,2-5,8 )
- Tnh chn lc hnh dng cao
121
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
Tnh chn lc hnh dng ca cht xc tc
122
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 4
4.4. S mt hot tnh v ti sinh cht xc tc
Sinh vin t nghin cu thuyt trnh
Trao i Tho lun
CHNG 5
CHNG 5
XC TC CHO QU TRNH
ALKYL HA
123
Nguyn Th Linh, DKLD 4060326, 2013-2014
124
5.1. Qu trnh alkyl ha
Mc ch: tng ON cho xng nh qu trnh alkyl ha cc
n-parafin vi cc olefin.
Qu trnh alkyl ha l qu trnh nhm chuyn ha anken,
ankan thnh isoankan
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
Nguyn liu:
- Isobutan (t FCC, hydrocracking, chng ct)
- Propen, buten (t FCC)
125
Cc phn ng trong qu trnh alkyl ha
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
126
Cc phn ng trong qu trnh alkyl ha
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
127
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
128
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
129
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
130
C ch phn ng trong qu trnh alkyl ha: c ch ion
cacbeni
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
131
C ch trn cht xc tc HF
- Khi mo:
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
132
C ch trn cht xc tc HF
- Pht trin mch:
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
133
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
Cc phn ng xy ra trong qu trnh alkyl ha
- Isome ha alkyl ha:
2,2,4- trimetylpentan
134
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
135
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
Tng qut:
136
5.3. Cht xc tc cho qu trnh alkyl ha
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
Cht xc tc cho qu trnh alkyl ha thng thng s dng:
- Cht xc tc th h u:
H
2
SO
4
10
o
C
100 (kg axit/tn sn phm)
HF
30
o
C
0,5 (kg axit/tn sn phm)
-Th h xc tc ngy nay: H
2
SO
4
/HF/AlCl
3
-HCl
- iu kin lm vic: 25
o
C, 8bar
137
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
So snh cht xc tc H
2
SO
4
v HF
Qu trnh s dng H
2
SO
4
Qu trnh s dng HF
Nhit (K) 277-283 298-313
p sut (bar) 2-6 8-20
Thi giam lu (pht) 20-30 5-20
T l nguyn liu isobutan/buten 8-12 10-20
Nng axit (%KL) 88-95 80-95
Lng axit trong nh tng (%V) 40-60 25-80
Lng cht xc tc s dng 70-100 0.4-1
axit/sn phm (kg/t)
138
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
Mt s hn ch ca cht xc tc alkyl ha:
-Cht xc tc H
2
SO
4
c hot tnh cao nhng to nhiu sn
phm ph
- Cht xc tc HF hot tnh thp hn nhng gy nhim v
c hi
- Cc cht xc tc kh thu hi, mt mt trong sn xut
- Gy n mn mnh
139
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
S qu trnh alkyl ha vi cht xc tc H
2
SO
4
140
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 5
CHNG 6
CHNG 6
CHT XC TC HYDRO V
DEHYDRO HA
141
Nguyn Th Linh, DKLD 4060326, 2013-2014
Sinh vin t nghin cu
142
CHNG 6
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 7
CHNG 7
CHT XC TC
HYDROPROCESSING
143
Nguyn Th Linh, DKLD 4060326, 2013-2014
7.1. Qu trnh Hydroprocessing
144
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mc ch ca qu trnh hydroprocessing
Hydroprocessing l qu trnh x l v ch bin du th v
cc phn on nng bng qu trnh c s dng H
2
, trong
bao gm cc qu trnh Hydrocracking, Hydro loi asphalten
(HDAs), hydro loi kim loi nng (HDM), hydro loi lu
hunh (HDS), hydro loi nit (HDN), hydro loi oxi (HDO).
145
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mc ch ca qu trnh hydroprocessing
- X l cc nguyn liu, phn on cha nhiu hp phn gy
ng c v mt hot tnh cht xc tc trong qu trnh ch bin
nh asphalten, kim loi nng (V, Ni), hp cht d nguyn t
ca lu hunh, oxi, nit
Nguyn liu cho qu trnh hydroprocessing
- Du chua, du nng, cc phn on nng ca qu trnh
chng ct du th.
146
Nguyn Th Linh, DKLD 4060326, 2013-2014
S nh my lc du hin i
147
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Cc phn ng xy ra trong cc qu trnh hydroprocessing
Phn ng tch loi lu hunh
148
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn ng tch loi nit
149
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phn ng tch loi oxi
150
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tch kim loi nng: Cc hp cht c kim cha As, Pb, V, Ni
c by vo cc l trng trn b mt cht xc tc.
151
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
7.2. Cht xc tc cho qu trnh hydroprocessing
Thnh phn ca cht xc tc:
Cht mang: -Al
2
O
3
Pha hot ng: l sulfua ca cc kim loi Mo, W c xc
tin bi Co, Ni, c s dng di dng hn hp ca
CoMo, NiMo, NiW.
-Thnh phn CoMo dng cho qu trnh HDS
- Thnh phn NiMo dng cho qu trnh HDN, HDO
- Thnh phn NiW dng cho qu trnh HDM, HDO
152
CHNG 3
Nguyn Th Linh, DKLD 4060326, 2013-2014
Hnh dng ht xc tc cng nghip
153
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phng php chun b cht xc tc hydroprocessing
-Dng mui ca cc kim loi trong pha hot ng tm ln
cht mang.
- Hot ha pha hot ng nh qu trnh sulfat ha:
154
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
- a thm cht xc tin nh Co, Ni nhm lm thay i
lin kt gia kim loi v S, to l trng trong mng tnh
th, tng cng s hp ph cc phn t hp cht hu c.
- C th a thm photpho nhm tng kh nng phn tn
ca pha hot ng trn cht mang.
- Cht mang c din tch b mt 120-150m
2
/g, c tnh axit
h tr phn ng HDT, gim ng cn trn b mt cht xc
tc.
155
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
7.3. S mt hot tnh ca cht xc tc
- Mt hot tnh do thay i cu trc: Di iu kin nhit
cao (400
o
C, 6Mpa), tinh th MoS
2
v WS
2
chuyn pha.
- Mt hot tnh do s hnh thnh cc: Tc hnh thnh cc
tng nhanh khi iu kin lm vic 450
o
C, 3Mpa.
- Asphalten v kim loi nng: hm lng kim loi khng
vt qu 50ppb
156
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
7.4. Cc yu t nh hng n hot tnh cht xc tc
-Nguyn liu u: cha nhiu asphalten, nha d gy mt
hot tnh cht xc tc.
- Kim loi nng: gy ng c cht xc tc
- Nhit v p sut H
2
: p sut H
2
tng t 2-15MPa s
lm gim s hnh thnh cc t 10-40%, cht xc tc n nh
400
o
C.
- Tc dng c hc:
157
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
-Chu k lm vic ca cht xc tc ph thuc vo nguyn liu
u vo
158
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
7.5. Ti sinh cht xc tc
-Ti sinh bng qu trnh oxi ha: dng cc cht oxi ha mnh nh
O
3
, N
2
O, H
2
O
2
., dng oxi t cc.
- Ti sinh bng qu trnh kh: Dng dng H
2
iu kin nhit
730
o
C, cc c hydro kh ha to CH
4
. Thu c din tch b
mt ln hn nhng c th lm chuyn pha ca cht mang.
- Ti sinh bng CO
2
: CO
2
+ C = 2CO
159
CHNG 7
Nguyn Th Linh, DKLD 4060326, 2013-2014
Tiu lun mn hc
CHNG 8
CHNG 8
CC PHNG PHP CH TO,
LA CHN CHT XC TC CNG NGHIP
160
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
161
Qu trnh tng hp cht xc tc bao gm cc giai on:
- iu ch cc tin cht rn
- Chuyn ha cc cht u thnh thnh phn ca cht xc
tc bng cc qu trnh thch hp (phn hy nhit, kim
ha)
- Thay i thnh phn cht xc tc (bin tnh xc tc)
Nguyn Th Linh, DKLD 4060326, 2013-2014
8.1. K thut tng hp cht xc tc
CHNG 8
162
Nguyn Th Linh, DKLD 4060326, 2013-2014
Mt s n v o c trng cho tnh cht cht xc tc:
- Hot tnh ca cht xc tc (activity), a:
- Tc th tch dng kh (gas hourly space velocity- GHSV):
CHNG 8
163
Nguyn Th Linh, DKLD 4060326, 2013-2014
- Tc th tch dng lng (Liquid hourly space velocity- LHSV):
- chuyn ha % (Conversion- C):
- Hiu sut % (A):
CHNG 8
164
Nguyn Th Linh, DKLD 4060326, 2013-2014
- chn lc (Selectivity- S):
- Hiu sut khng gian (Space time yield- STY)
- Thi gian sng ca cht xc tc (Catalyst lifetime- Z):
- Thi lu (residence time- t):
CHNG 8
165
Cc phng php ch to cht xc tc
Phng php kt ta:
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
166
Phng php kt ta:
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
167
Phng php tm trn cht mang
Nguyn Th Linh, DKLD 4060326, 2013-2014
ui kh ra khi l
xp cht mang
X l cht mang
bng dung dch
Loi dung mi d
Sy kh v nung
CHNG 8
168
Cc phng php tm:
- Phng php nhng
- Phng php phun
-Tm km theo bay hi dung dch
- Tm mui nng chy
Phng php trn c hc
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
169
Cc nguyn tc c bn trong ch to xc tc
Ch to xc tc kim loi trn cht mang
Xc tc Pt/cht mang:
Ch to cht xc tc oxit kim loi/cht mang
-Phng php ch to: ng kt ta, tm, hp thu
- Tin cht ban u: mui natri, cacbonat, axetat ca cc kim loi
Ch to xc tc HDS, HDN:
-Tin cht ban u: mui ca cc kim loi Mo, Co, W, Ni, Al
2
O
3
- Phng php: tm
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
170
Ch to xc tc zeolit
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHNG 8
171
Tng hp cht xc tc zeolit
Nguyn Th Linh, DKLD 4060326, 2013-2014
Qu trnh chun b gel v kt tinh zeolit t hn hp phn ng
Na
2
O- Al
2
O
3
- SiO
2
- H
2
O xy ra nh sau:
CHNG 8
172
8.2. La chn cht xc tc cng nghip
Nguyn Th Linh, DKLD 4060326, 2013-2014
Yu cu i vi xc tc cng nghip:
-Hot cao
- chn lc cao
- Nhit khi ng
- bn nhit
- dn nhit tt
- chc rn, bn c hc
- bn chng bo mn: 1-3%/thng (tng si), 10% thng (lp c
nh)
- bn vi cht u c
- Gi thnh thp
CHNG 8
173
8.3. Cc phng php thc nghim trong TH xc tc
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phng php xc nh tnh cht vt l ca cht xc tc
CHNG 8
174
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phng php xc nh tnh cht ha hc
CHNG 8
175
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phng php xc nh tnh cht b mt cht xc tc
CHNG 8
176
Nguyn Th Linh, DKLD 4060326, 2013-2014
TEM, SEM Xc inh cu trc b mt
CHNG 8
177
Nguyn Th Linh, DKLD 4060326, 2013-2014
Phng php xc nh hot tnh xc tc:
- Th hot tnh ca cht xc tc bng h thit b phn ng vi
dng
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Nguyn Th Linh, DKLD 4060326, 2013-2014