Xúc tác dùng trong lọc hóa dầu

MC CH MN HC
Cc khi nim c bn v cht xc tc d th, cht xc

tc s dng trong cng ngh lc du
B m n l c - h a d u
BI Gi NG
Cc cht xc tc kim loi, cht xc tc axit- baz

c s dng trong cng ngh lc du
XC TC TRONG
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
CNG NGH LC DU
Nm c cc phng php ch to, nguyn tc la

chn cht xc tc v ng dng trong cng nghip
TS. Nguyn Th Linh

1
NI DUNG MN HC
NI DUNG MN HC
CHNG 6. CHT XC TC CHO CC QU TRNH
CHNG 1. MT S KHI NIM V CHT XC TC
HYDRO HA V DEHYDRO HA
TRONG CNG NGH LC DU
CHNG 7. CHT XC TC CHO QU TRNH
CHNG 2. XC TC CHO QU TRNH CRACKING
HYDROPROCESSING
CHNG 3. XC TC CHO QU TRNH REFORMING
CHNG 8. CC PHNG PHP CH TO, LA
CHNG 4. XC TC CHO QU TRNH ISOME HA

CHNG 5 CHT XC TC CHO QU TRNH ALKYL HA
Nguyn Th Linh, DKLD 4060326, 2013-2014
CHN CHT XC TC V TRIN KHAI CNG NGHIP
CHNG 1
CHNG 1
1.1. Cc khi nim v xc tc trong cng ngh lc du

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
CHNG 1
cht ny tham gia nhiu ln vo tng tc ho hc trung gian
MT S KHI NIM V CHT XC TC
vi cc tc nhn phn ng v sau mi chu trnh tng tc

trung gian li phc hi thnh phn ho hc ban u.
TRONG CNG NGH LC DU
Tnh c th
Tnh a nng
Tnh a dng
Tnh khng thay i trng thi nhit ng
5
CHNG 1
CHNG 1
Tnh c th: Mt cht xc tc c hot tnh i vi mt
Tnh a dng: Thnh phn ha hc ca cc cht xc tc
s phn ng nht nh.
a dng, c th l nguyn t, hp cht hay phc cht.
Tnh a nng: Cht xc tc c hot tnh i vi mt s
Tnh khng thay i trng thi nhit ng: Cht xc
cc phn ng ha hc khc nhau.
tc khng b tiu hao trong qu trnh phn ng, cht xc tc
Xc tc axit rn cho cc phn ng cracking, isome
khng lm thay i v tr cn bng ca phn ng ho hc.
ha, alkyl ha, thy phn, hydrat ha

Xc tc kim loi cho cc phn ng hydro ha
dehydro ha
CHNG 1
CHNG 1
Tng tc trung gian: S tng tc gia tc nhn tham gia
Tng
tc trung
gian
Nh
hp
ph
Cc giai
on trong
phn ng
xc tc d
th
phn ng v b mt cht xc tc.

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.
Hp ph
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
Phn
ng
gian, phc cht hot ng.

9
CHNG 1
CHNG 1
Phn ng: l qu trnh tng tc ca cc tc nhn tham
Hp ph: S tng tc v gia tng nng tc nhn
gia phn ng c hp ph trn b mt cht xc tc v
phn ng trn b mt cht xc tc.

Hp ph ha hc: xy ra s tng tc ha hc gia tc
hnh thnh sn phm.
nhn phn ng v b mt cht xc tc
Phn ng xy ra gia tc nhn v phc cht hot
Hp ph vt l l trng thi trung gian trc khi xy ra hp
ng hnh thnh trn b mt xc tc.
ph ha hc. Xc nh c c im ca hp ph vt l
Phn ng trn b mt cht xc tc c nng lng
c th kt lun c mt s c trng b mt, kch thc,
thp hn so vi phn ng cng loi khng c xc
hnh dngmao qun ca cht xc tc.
tc.
10
11
12
CHNG 1
CHNG 1
Mt s i lng c trng cho kh nng ca cht xc tc
Nh hp ph:
S gii phng sn phm v tc nhn tham gia phn ng ra
mi trng.
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.
13
CHNG 1
14
CHNG 1
chn lc ca cht xc tc (Selectivity): L kh nng
Tui th ca cht xc tc: biu th kh nng lm vic ca
thc y phn ng theo mt chiu hng nht nh, dn n
cht xc tc trong iu kin vn hnh qu trnh phn ng.
s to thnh nhiu sn phm mong mun, t cc sn phm
-Tui th ca cht xc tc ph thuc v mi trng phn
ph.
ng v iu kin vn hnh.
- 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.
(1.1)
- Tui th ca cht xc tc th hin bn c hc v

ha hc.
Hoc xc nh bi t s ca hiu sut sn phm mong mun

q v tng cc sn phm c to thnh qi.
(1.2)
15
16
CHNG 1
CHNG 1
Cc loi cht xc tc trong cng ngh lc du
- Cht xc tc d th:
Xc tc ng th c th c xc nh cu trc bng cc
- Cht xc tc ng th: l cht xc tc cng pha vi tc
phng php ha l, thun li cho nghin cu ng hc ca
nhn phn ng (thng l dng lng).
phn ng.
Cht xc tc ng th lm vic di iu kin mm hn so
Xc tc ng th c ng dng nhiu trong cng nghip
vi xc tc d th.
Cht xc tc ng th kh thu hi (kh tch ra khi hn hp
sau phn ng).
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.
17
CHNG 1
18
CHNG 1
Hp cht phi tr trong xc tc
- Cht xc tc ng th d th ha:
Hot tnh cao
Hp cht phi tr trong xc tc to h cht xc tc phc vi
Tm hot tnh l ng th
s lin kt ca cc phi t (ligan) vi nguyn t kim loi.
D thu hi v ti sinh
C tnh n nh nhit
Cu trc ca hexol
19
20
CHNG 1
CHNG 1
S phi tr trong cht xc tc hnh thnh theo cc nguyn l sau:
- Nguyn l tnh in n gin:
- Nguyn l lin kt cng ha tr:
M t s hnh thnh lin kt gia kim loi (hoc ion KL) vi cc
+ Lin kt gia kim loi v ligan l do phn ng ca baz Lewis (ligan)
ligan bng tng tc tnh in ca cc in tch dng tm
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 d2sp3) i vi phc phi tr 6,
l 3 (sp3) hoc 4 mt (dsp3) i vi phc phi tr 4.
21
CHNG 1
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.
22
CHNG 1
1.2. Xc tc Axit Baz
(1) Cng cation vo phn t cha no
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.
Qu trnh ny ph thuc vo lc axit v cc yu t khc nh cu t
Phn ng c s tham gia ca cht xc tc axit hnh thnh
lm bn cacbocation, tr ha hc v hng s in mi ca mi
cacbocation theo 4 c ch sau:
trng.
Hydrocacbon c tnh baz yu th cn tm axit mnh.
23
24
CHNG 1
CHNG 1
Cc phn ng ca cacbocation
(2) Cng proton vo phn t no
Chuyn v in tch:
C7 H16 + H+
(3) Loi b mt in t trung ha

L, R1+: tm axit Lewis, ion cacbeni
mnh
Ion 2,4- dimetyl pentyl
Chuyn v 1-3
(4) D li phn t
25
CHNG 1
26
CHNG 1
ng phn ha cu trc
Chuyn v hydrua
Xy ra do s chuyn v nhm metyl dn n s hnh thnh ion cacbeni c
Xy ra gia ion cacbeni v phn t ankan
cu trc nhnh nhiu hn.

Chuyn v nhm alkyl
Hnh thnh v ct t lin kt C-C
Chuyn v 1-3
27
28
CHNG 1
CHNG 1
V d v phn ng alkyl ha
Tt mch:
29
CHNG 1
30
CHNG 1
V d v phn ng ct mch C C:
V d v phn ng ct mch C C:
V d v phn ng bt cn i toluen
31
32
CHNG 1
CHNG 1
Cc loi tm axit
S bin tnh, chuyn pha gia tm axit Lewis v

Bronsted trong aluminosilicat
Tm axit Lewis v Bronsted

- V d v cht xc tc dng aluminosilicat
Cng thc ha hc ca aluminosilicat: Na2O.Al2O3.nSiO2
trong n biu th t l SiO2/Al2O3
33
CHNG 1
34
CHNG 1
Cc hp cht hydrocacbon trong du m
1.3. Mt s thnh phn v tnh cht ca du m

Thnh phn cc nguyn t trong du m:
Cc hp cht parafin
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
Cc hydrocacbon
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.
Cc hp cht vng no (Naphten)

Cc hp cht thm (Aromatic)
- S cacbon ca cc hp cht hydrocacbon trong du m t C5-C60

(t C1-C4 nm trong kh).
35
36
CHNG 1
CHNG 1
37
CHNG 1
38
CHNG 1
Cc hp cht parafin trong du m
39
40
CHNG 1
CHNG 1
Cc hp cht naphten trong du m
Cc hydrocacbon lai hp
Cc hp cht aromatic trong du m
Cc hp cht d nguyn t
- Cc hp cht cha lu hunh:
41
CHNG 1
42
CHNG 1
- Cc hp cht cha nit:
43
44
CHNG 1
CHNG 1
- Cc hp cht cha oxi: gm cc axit (-COOH), cc xeton
Cc cht nha v asphalten trong du m:
(-C=O), cc phenol v lacton.
- 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
Cc kim loi trong du m:
-Du nh: c t trng < 0,828
- Thng tn ti di dng phc ca kim loi v hp cht
- Du trung bnh: c t trng 0,828 < d < 0,884
hu c (c-kim).
- Du nng: c t trng > 0,884

45
CHNG 1
46
CHNG 1
1.3. Cc qu trnh trong nh my lc du

Qu trnh vt l
Qu trnh ha hc
S dng nhit
Phn on
C s dng CXT
Chng ct
Gim nht
Cracking xc tc
Chit
Loi cc
Reforming xc tc
Loi sp bng
propan
Loi sp bng
dung mi
Trn
Hydrotreating
Hydrocracking
Loi sp
Alkyl ha
Polyme ha
Isome ha
47
c im cc phn on
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
im si (oC)
S nguyn t C
< 30
30 210
100 - 200
150 - 250
1-4
5 - 12
8 - 12
11 - 13
160 - 400
220 - 345
315 - 540
540
13 17
> 615
> 60
20 - 45
30
48
CHNG 1
CHNG 1
Yu cu v cc sn phm lc du
Tr s Octan v im si ca mt s hp cht
Nhit si
Hp cht
ON
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
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)
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
50
Th trng cht xc tc
Tr s Cetan ca mt s hp cht
309
301
322
342
323
353
354
399
372
328
CHNG 1
CHNG 1
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
62
90
85
26
93
> 100
77
0
100
118
68
67 (MON)
93
82
95
92
99
88
100 - 110
100
30 70
40 60
40 70
20 60
0 20
0
40 50
0 25
30 50
55 60
51
52
CHNG 2
CHNG 2
2.1. Qu trnh cracking xc tc tng si (Fluid Catalytic
Cracking- FCC)
Mc ch ca qu trnh cracking
CHNG 2
- Sn xut xng c tr s octan cao, cc olefin nh, phn on
CHT XC TC CHO
nh (LPG, FO)
Nguyn liu cho qu trnh cracking

- Phn on Gas-Oil, cc phn on nng ca qu trnh
QU TRNH CRACKING
chng ct du th.
53
54
CHNG 2
S nh my lc du hin i
Phn xng FCC hin i:

thit b phn ng ng nng
55
56
CHNG 2
CHNG 2
FCC: Thit b phn ng tng si v thit b ti sinh cht xc tc
Cc phn ng xy ra trong qu trnh cracking
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
57
CHNG 2
58
CHNG 2
C ch phn ng cracking xc tc
Cracking anken to ion cacbeni
Phn ng cracking xc tc n-octan
Cracking ankan to ion cacboni
Ion cacbeni u tin
Hoc nu c mt ca ion cacbeni
Xem xt c ch trn sai u?
59
60
CHNG 2
CHNG 2
Phn ng to cc
Phn ng isome ha (ng phn ha)
Ion cacbeni u tin
62
61
CHNG 2
CHNG 2
Ion cacbeni u tin
63
64
CHNG 2
CHNG 2
Phn b sn phm cracking nhit v cracking xc tc
2.2. Cht xc tc cho qu trnh FCC
Theo c ch phn ng cracking xc tc:

- Cht xc tc phi c kh nng nhng H+ hoc nhn HCht xc tc cha tm axit
Cht xc tc th h u tin:
Dung dch AlCl3
Cht xc tc th h sau:
Khong st ( x l axit)
- Gy n mn thit b
Aluminosilicat v nh hnh
- C trong nc thi
- 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
65
CHNG 2
- t to cc, n nh nhit cao hn

66
CHNG 2
Thnh phn ca cht xc tc FCC
Xc tc cho qu trnh FCC
Zeolit
Cht mang
RE- USY
Vt liu mao qun
Ph gia
Tm axit yu
Sb, Sn, CaTiO2

MgO, Pt/Al2O3, CeO2
ZSM-5
Tm axit mnh
67
68
CHNG 2
CHNG 2
Zeolit
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 ).
69
CHNG 2
70
CHNG 2
Mt s loi zeolit tng hp ng dng cho sn xut
Cht mang
cht xc tc FCC:
- Cc vt liu mao qun vi kch thc trung bnh (2-
- Zeolit X
50nm) n ln (>50nm)
- Zeolit Y
- Dn cc phn t ln i n tm hot tnh
- Zeolit ZSM-5
- Khuch tn tc nhn phn ng vo v ra khi b mt

cht xc tc
- Chng li s u c cht xc tc
71
72
CHNG 2
CHNG 2
Quy trnh tng hp cht xc tc FCC

Mm tinh th
Silic v nh
Natrialuminat
NaOH
zeolit NaY
hnh
Ph gia
- Cht xc tin nhm Pt
- Nhm oxit kim loi (MgO, CeO2)
- ZSM-5
Gel natrialuminosilicat
- Ph gia th ng ha kim loi (Antimon)
Gi ha (kt tinh)
Hn hp Zeolit NaY
Lc, ra
NH4OH
Zeolit NaY
Trao i ion
Zeolit H-NaY
73
CHNG 2
74
CHNG 2
Sn xut cht xc tc FCC
Phn b sn phm ca qu trnh cracking Gas oil
75
76
CHNG 2
CHNG 2
Tnh chn lc hnh dng
Tnh chn lc hnh dng
77
78
CHNG 2
CHNG 2
Pht trin cht xc tc mi cho qu trnh FCC
Cht xc tc FCC cha ZSM-5:
2.3. S mt hot tnh v ti sinh cht xc tc FCC

Nguyn nhn gy mt hot tnh cht xc tc
0.51 0,55nm
Mt hot tnh do thay i cu trc ca cht xc tc
- Sn xut olefin nh (C3=, C4=) lm
Mt hot tnh do s hnh thnh cc
nguyn liu cho ha du v sn xut
Mt hot tnh do kim loi nng
MTBE, ETBE
79
80
CHNG 2
CHNG 2
C ch ca s mt hot tnh cht xc tc FCC
C ch hnh thnh cc
C ch hnh thnh cc
81
82
CHNG 2
CHNG 2
C ch tch t kim loi nng
C ch tch t kim loi nng
83
84
CHNG 2
CHNG 2
nh gi tnh cht cht xc tc FCC mi
nh gi tnh cht cht xc tc FCC cn bng

MAT
wt %
G.F.
H2
YLD
SCFB
C.F.
SA
m/g
74
3.4
171
1.2
155
Z-SA M-SA
m/g m/g
89
66
Z/M
SA/K
1.3
53
Ni
ppm
V
ppm
3508 822
Ni/V
Na
wt %
4.27 0.24
Sb
ppm
Sb/Ni
42
0.01
UCS RE2O3 Al2O3 CaO
wt % wt % wt %
Fe
wt %
1.76 49.8 0.241 0.58
00- 400K2O MgO P2O5 Pb TiO2 C ABD PV

Umb/
20 40 80 80 APS
wt % ppm wt % ppm wt % wt % g/cc cc/g
Umf
%
%
%
%
0.08 3462 0.151 26 0.75 0.04
0
6
62
56
71
85
86
CHNG 2
CHNG 2
2.4. Ti sinh cht xc tc FCC
C ch loi b cc
C ch loi b kim loi nng
87
88
CHNG 2
CHNG 3
Mt s pht thi kh trong qu trnh ti sinh cht xc tc

v bin php thu hi
CHNG 3
CHT XC TC
- c dch ti liu
- Trao i Tho lun
CHO QU TRNH
REFORMING
89
90
CHNG 3
CHNG 3
Nguyn liu cho qu trnh reforming xc tc
3.1. Reforming xc tc
Phn on Naphta ca qu trnh chng ct du th,
Reforming xc tc l qu trnh sp xp li cu trc ca
qu trnh cracking xc tc.
cc hp phn hydrocacbon c tr s octan thp trong
- Phn on Naphta (C5-C12) c vng nhit si t
phn on thnh cc hydrocacbon c tr s octan cao m
30oC 200oC (naphta nng t 90 200oC).
khng lm thnh i vng nhit si ca phn on
Thnh phn ca phn on Naphta:
Mc ch ca qu trnh reforming xc tc
Parafin: n- v iso-parafin
Sn xut xng c tr s octan cao
Olefin: mch thng hoc nhnh cha 1 hoc nhiu ni i
Sn xut ha cht c bn (Benzen, Toluen, Xylen-
Naphten: Cycloankan
BTX)
Aromatic: cc hp cht cha vng thm

91
92
CHNG 3
CHNG 3
Hp cht cha lu hunh trong phn on Naphta:
Hp cht cha nit trong phn on Naphta:
93
94
CHNG 3
CHNG 3
Mt s phn ng xy ra trong qu trnh reforming xc
3.2. Cht xc tc cho qu trnh reforming
tc phn on Naphta:
Cht xc tc th h u tin: Cr2O3, MoO3/Al2O3

Cht xc tc th h th hai: Pt/Al2O3
Cht xc tc th h th ba: Pt-Re(Ir, Rh, Ge)/Al2O3
- Hp phn kim loi xc tc cho qu trnh hydro v dehydro
ha
- Cht mang Al2O3 (c tnh axit) xc tc cho cc qu trnh
thm ha, vng ha, isome ha.
95
96
CHNG 3
CHNG 3
Thnh phn ca mt s cht xc tc reforming in hnh
Vai tr ca cht xc tc lng chc

C ch qu trnh isome ha metylcycolpentan
97
98
CHNG 3
CHNG 3
C ch lng chc trong phn ng isome ha o-xylen thnh
nh hng ca nhit v p sut n qu trnh thm ha cyclohexan
etylbenzen
99
100
CHNG 3
CHNG 3
nh hng ca t l H2/HC nguyn liu n qu trnh thm
Cc loi thit b phn ng reforming
ha cyclohexan
101
CHNG 3
102
CHNG 3
Cng ngh reforming xc tc bn ti sinh (SRR)
Cng ngh reforming xc tc ti sinh lin tc (CRR)
103
104
CHNG 3
CHNG 3
3.3. S mt hot tnh ca cht xc tc
3.4. Ti sinh cht xc tc
Mt hot tnh do s tch t cc
t cc c s dng dng kh tr loi b hydrocacbon,
Mt hot tnh do s u c bi hp cht cha lu hunh
hydro.
Do thnh phn nguyn liu
Kim sot nhit t cc > 450oC

Oxi ha v oxiclo ha n phn tn kim loi trn cht mang
Hnh thnh nhit thp
v hot ha tm axit.
Khi nhit > 400oC hnh
Lm kh
thnh lp graphit Pt-C bao
Kh b mt kim loi nhit 700oC
ph b mt xc tc
Sulfit ha b mt kim loi (0,05-0,06%wt S)

105
CHNG 3
CHNG 3
3.5. Cng ngh ti sinh cht xc tc
3.6. Thu hi kim loi t xc tc reforming s dng
Cng ngh bn ti sinh xc tc
106
- X l vi axit v kim
Cng ngh ti sinh tun hon

Cng ngh ti sinh lin tc (CCR)
Re nm trong dung dch, Pt, Ir trong phn cn rn
107
108
CHNG 3
CHNG 3
Thu hi Pt:
Thu hi Re
- Ha tan Pt:
Ha phn dung dch ca qu trnh x l axit v kim vi ion

amoni
- X l vi amoni:
- Kt ta mui Pt:
- Nung mui Pt:
- Trao i ion:
Hoc dng qu trnh in ha:
109
110
CHNG 4
CHNG 4
4.1. Qu trnh isome ha

Qu trnh isome ha l qu trnh ha hc lm thay i cu trc
ca hp cht hu c.
Mc ch:
CHNG 4
Tng ON cho xng
XC TC CHO QU TRNH
Gim nhit ng c ca cc phn on nng

(DO, FO)
ISOME HA
Thu cc sn phm ha cht c bn

Nguyn liu: Phn on Naphta C5/C6, n-butan (phn on
kh), phn on C8 thm t reformate, phn on nng (DO, FO).
111
112
CHNG 4
CHNG 4
4.2. Phn ng isome ha cc nguyn liu in hnh
Sn xut MTBE, ETBE t isobuten
113
114
CHNG 4
CHNG 4
Vit c ch Isome ha n-buten trn cht xc tc cha

tm axit
C ch phn ng isome ha xy ra trn tm axit
115
116
CHNG 4
CHNG 4
Qu trnh isome ha thu p-xylen t phn on C8 ca reforming
C ch phn ng isome ha n-pentan xy ra trn tm axit
117
CHNG 4
118
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
Cht xc tc lng chc:

Pt/Al2O3:
hot tnh cao cho qu trnh.
-Cn lm sch nguyn liu
-Gy n mn mnh, kh thu hi
- Phi clo ha xc tc
Cht xc tc HF-BF3:
- Gy n mn
- Thc hin iu kin mm
Pt/zeolit:
- Gy n mn
-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
119
120
CHNG 4
CHNG 4
Tnh chn lc hnh dng ca cht xc tc
4.4. S mt hot tnh v ti sinh cht xc tc
Sinh
vin t nghin cu thuyt trnh
Trao i Tho lun
121
122
CHNG 5
CHNG 5
5.1. Qu trnh alkyl ha

Qu trnh alkyl ha l qu trnh nhm chuyn ha anken,
ankan thnh isoankan
CHNG 5
Mc ch: tng ON cho xng nh qu trnh alkyl ha cc

n-parafin vi cc olefin.
XC TC CHO QU TRNH
Nguyn liu:
ALKYL HA
- Isobutan (t FCC, hydrocracking, chng ct)

- Propen, buten (t FCC)
123
124
CHNG 5
CHNG 5
Cc phn ng trong qu trnh alkyl ha
Cc phn ng trong qu trnh alkyl ha
125
126
CHNG 5
CHNG 5
127
128
CHNG 5
CHNG 5
C ch phn ng trong qu trnh alkyl ha: c ch ion

cacbeni
129
CHNG 5
130
CHNG 5
C ch trn cht xc tc HF
- Khi mo:
C ch trn cht xc tc HF
- Pht trin mch:
131
132
CHNG 5
CHNG 5
Cc phn ng xy ra trong qu trnh alkyl ha

- Isome ha alkyl ha:
2,2,4- trimetylpentan
133
134
CHNG 5
CHNG 5
5.3. Cht xc tc cho qu trnh alkyl ha

Cht xc tc cho qu trnh alkyl ha thng thng s dng:
- Cht xc tc th h u:
H2SO4
10oC
100 (kg axit/tn sn phm)
30oC
0,5 (kg axit/tn sn phm)
-Th h xc tc ngy nay: H2SO4/HF/AlCl3-HCl
Tng qut:
HF
- iu kin lm vic: 25oC, 8bar

135
136
CHNG 5
CHNG 5
Mt s hn ch ca cht xc tc alkyl ha:
So snh cht xc tc H2SO4 v HF

Qu trnh s dng H2SO4
Nhit (K)
Qu trnh s dng HF
-Cht xc tc H2SO4 c hot tnh cao nhng to nhiu sn

phm ph
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
- Cc cht xc tc kh thu hi, mt mt trong sn xut
Nng axit (%KL)
- Gy n mn mnh
88-95
80-95
Lng axit trong nh tng (%V) 40-60
25-80
Lng cht xc tc s dng

axit/sn phm (kg/t)
0.4-1
70-100
- Cht xc tc HF hot tnh thp hn nhng gy nhim v

c hi
137
138
CHNG 5
CHNG 5
S qu trnh alkyl ha vi cht xc tc H2SO4
139
140
CHNG 6
CHNG 6
CHNG 6
Sinh vin t nghin cu
CHT XC TC HYDRO V
DEHYDRO HA
141
142
CHNG 7
CHNG 7
7.1. Qu trnh Hydroprocessing

Hydroprocessing l qu trnh x l v ch bin du th v
CHNG 7
cc phn on nng bng qu trnh c s dng H2, trong

bao gm cc qu trnh Hydrocracking, Hydro loi asphalten
Mc ch ca qu trnh hydroprocessing
(HDAs), hydro loi kim loi nng (HDM), hydro loi lu
CHT XC TC
hunh (HDS), hydro loi nit (HDN), hydro loi oxi (HDO).
HYDROPROCESSING
143
144
CHNG 7
S nh my lc du hin i
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.
145
CHNG 7
Cc phn ng xy ra trong cc qu trnh hydroprocessing
146
CHNG 7
Phn ng tch loi nit
Phn ng tch loi lu hunh
147
148
CHNG 7
CHNG 7
Phn ng tch loi oxi
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.
149
CHNG 7
150
CHNG 3
Hnh dng ht xc tc cng nghip
7.2. Cht xc tc cho qu trnh hydroprocessing

Thnh phn ca cht xc tc:
Cht mang: -Al2O3
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
151
152
CHNG 7
CHNG 7
Phng php chun b cht xc tc hydroprocessing

-Dng mui ca cc kim loi trong pha hot ng tm ln
- 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
cht mang.
th, tng cng s hp ph cc phn t hp cht hu c.
- Hot ha pha hot ng nh qu trnh sulfat ha:
- 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 120-150m2/g, c tnh axit
h tr phn ng HDT, gim ng cn trn b mt cht xc
tc.
153
154
CHNG 7
CHNG 7
7.3. S mt hot tnh ca cht xc tc
7.4. Cc yu t nh hng n hot tnh cht xc tc
- Mt hot tnh do thay i cu trc: Di iu kin nhit
-Nguyn liu u: cha nhiu asphalten, nha d gy mt
cao
(400o C,
hot tnh cht xc tc.
6Mpa), tinh th MoS2 v WS2 chuyn pha.
- Mt hot tnh do s hnh thnh cc: Tc hnh thnh cc
- Kim loi nng: gy ng c cht xc tc
tng nhanh khi iu kin lm vic 450oC, 3Mpa.
- Nhit v p sut H2 : p sut H2 tng t 2-15MPa s
- Asphalten v kim loi nng: hm lng kim loi khng
lm gim s hnh thnh cc t 10-40%, cht xc tc n nh
vt qu 50ppb
400oC.
- Tc dng c hc:
155
156
CHNG 7
CHNG 7
7.5. Ti sinh cht xc tc
-Chu k lm vic ca cht xc tc ph thuc vo nguyn liu
-Ti sinh bng qu trnh oxi ha: dng cc cht oxi ha mnh nh
u vo
O3, N2O, H2O2., dng oxi t cc.
- Ti sinh bng qu trnh kh: Dng dng H2 iu kin nhit

730oC, cc c hydro kh ha to CH4. Thu c din tch b
mt ln hn nhng c th lm chuyn pha ca cht mang.
- Ti sinh bng CO2 : CO2 + C = 2CO
157
CHNG 7
158
CHNG 8
Tiu lun mn hc
CHNG 8
CC PHNG PHP CH TO,
LA CHN CHT XC TC CNG NGHIP
159
160
CHNG 8
CHNG 8
8.1. K thut tng hp cht xc tc
Qu trnh tng hp cht xc tc bao gm cc giai on:

- iu ch cc tin cht rn
Mt s n v o c trng cho tnh cht cht xc tc:

- Hot tnh ca cht xc tc (activity), a:
- Chuyn ha cc cht u thnh thnh phn ca cht xc

tc bng cc qu trnh thch hp (phn hy nhit, kim
- Tc th tch dng kh (gas hourly space velocity- GHSV):
ha)
- Thay i thnh phn cht xc tc (bin tnh xc tc)
161
162
CHNG 8
CHNG 8
- Tc th tch dng lng (Liquid hourly space velocity- LHSV):
- chn lc (Selectivity- S):
- Hiu sut khng gian (Space time yield- STY)
- Hiu sut % (A):
- Thi gian sng ca cht xc tc (Catalyst lifetime- Z):

- chuyn ha % (Conversion- C):
- Thi lu (residence time- t):

163
164
CHNG 8
CHNG 8
Cc phng php ch to cht xc tc

Phng php kt ta:
Phng php kt ta:
165
166
CHNG 8
CHNG 8
Phng php tm trn cht mang
Cc phng php tm:

- Phng php nhng
ui kh ra khi l
- Phng php phun

-Tm km theo bay hi dung dch
- Tm mui nng chy
Phng php trn c hc
xp cht mang
X l cht mang
bng dung dch
Loi dung mi d
Sy kh v nung
167
168
CHNG 8
CHNG 8
Ch to xc tc zeolit
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, Al2O3
- Phng php: tm
169
CHNG 8
170
CHNG 8
Tng hp cht xc tc zeolit
8.2. La chn cht xc tc cng nghip

Yu cu i vi xc tc cng nghip:
Qu trnh chun b gel v kt tinh zeolit t hn hp phn ng
-Hot cao
Na2O- Al2O3- SiO2- H2O xy ra nh sau:
- 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
171
- Gi thnh thp
172
CHNG 8
8.3. Cc phng php thc nghim trong TH xc tc
Phng php xc nh tnh cht vt l ca cht xc tc
173
CHNG 8
CHNG 8
Phng php xc nh tnh cht ha hc
CHNG 8
Phng php xc nh tnh cht b mt cht xc tc
TEM, SEM
174
175
Xc inh cu trc b mt
176
CHNG 8
Phng php xc nh hot tnh xc tc:
- Th hot tnh ca cht xc tc bng h thit b phn ng vi
dng
177
178

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MC CH MN HC

Cc khi nim c bn v cht xc tc d th, cht xc

Cc cht xc tc kim loi, cht xc tc axit- baz

Nm c bn cht ca cc qu trnh xc tc trong

Nm c cc phng php ch to, nguyn tc la

TS. Nguyn Th Linh

CHNG 6. CHT XC TC CHO CC QU TRNH

CHNG 1. MT S KHI NIM V CHT XC TC

TRONG CNG NGH LC DU

CHNG 7. CHT XC TC CHO QU TRNH

CHNG 2. XC TC CHO QU TRNH CRACKING

CHNG 3. XC TC CHO QU TRNH REFORMING

CHNG 8. CC PHNG PHP CH TO, LA

CHNG 4. XC TC CHO QU TRNH ISOME HA

Nguyn Th Linh, DKLD 4060326, 2013-2014

Nguyn Th Linh, DKLD 4060326, 2013-2014

CHN CHT XC TC V TRIN KHAI CNG NGHIP

Nguyn Th Linh, DKLD 4060326, 2013-2014

1.1. Cc khi nim v xc tc trong cng ngh lc du

cht ny tham gia nhiu ln vo tng tc ho hc trung gian

MT S KHI NIM V CHT XC TC

vi cc tc nhn phn ng v sau mi chu trnh tng tc

TRONG CNG NGH LC DU

Nguyn Th Linh, DKLD 4060326, 2013-2014

Nguyn Th Linh, DKLD 4060326, 2013-2014

Tnh c th: Mt cht xc tc c hot tnh i vi mt

Tnh a dng: Thnh phn ha hc ca cc cht xc tc

s phn ng nht nh.

a dng, c th l nguyn t, hp cht hay phc cht.

Tnh a nng: Cht xc tc c hot tnh i vi mt s

Tnh khng thay i trng thi nhit ng: Cht xc

cc phn ng ha hc khc nhau.

tc khng b tiu hao trong qu trnh phn ng, cht xc tc

Xc tc axit rn cho cc phn ng cracking, isome

khng lm thay i v tr cn bng ca phn ng ho hc.

ha, alkyl ha, thy phn, hydrat ha

Nguyn Th Linh, DKLD 4060326, 2013-2014

phn ng v b mt cht xc tc.

Trong tng tc trung gian, lin kt ca cc nguyn t

gian, phc cht hot ng.

Nguyn Th Linh, DKLD 4060326, 2013-2014

Phn ng: l qu trnh tng tc ca cc tc nhn tham

Hp ph: S tng tc v gia tng nng tc nhn

gia phn ng c hp ph trn b mt cht xc tc v

phn ng trn b mt cht xc tc.

hnh thnh sn phm.

nhn phn ng v b mt cht xc tc

Phn ng xy ra gia tc nhn v phc cht hot

Hp ph vt l l trng thi trung gian trc khi xy ra hp

ng hnh thnh trn b mt xc tc.

Phn ng trn b mt cht xc tc c nng lng

c th kt lun c mt s c trng b mt, kch thc,

thp hn so vi phn ng cng loi khng c xc

hnh dngmao qun ca cht xc tc.

Nguyn Th Linh, DKLD 4060326, 2013-2014

Nguyn Th Linh, DKLD 4060326, 2013-2014

Mt s i lng c trng cho kh nng ca cht xc tc

Hot cht xc tc (activity): l i lng nh gi

Nguyn Th Linh, DKLD 4060326, 2013-2014

Nguyn Th Linh, DKLD 4060326, 2013-2014

chn lc ca cht xc tc (Selectivity): L kh nng

Tui th ca cht xc tc: biu th kh nng lm vic ca

thc y phn ng theo mt chiu hng nht nh, dn n

cht xc tc trong iu kin vn hnh qu trnh phn ng.