1

MC LC
M U .................................................................................................................................................. 3
CHNG I: TNG QUAN V QU TRNH HDS3
I. QU TRNH HYDRODESUNFUR HA ........................................................................................... 4
1.1.Gii thiu chung v qu trnh hydrodesunfur ha (HDS) .................................................................. 4
1.2. Vai tr ca qu trnh hydrodesunfur ha: .......................................................................................... 5
1.3. ng dng ca qu trnh hydrodesulfure ha: .................................................................................... 5
II. C S CA QU TRNH HYDRODESULFURE HA ................................................................. 7
2.1. C s ha hc-ha l ca qu trnh HDS: ......................................................................................... 7
2.1.1. Phng trnh phn ng tng qut hydrodesunfur ha .................................................................... 7
2.1.2. C ch ca phn ng Hydrodesurfur ha: ...................................................................................... 7
2.1.2.1. C ch phn ng Hydrodesunfur ha ca Mercaptanes: ........................................................... 7
2.1.2.2. C ch phn ng Hydrodesunfur ha ca Thiophene: ............................................................... 8
2.2 Cc yu t nh hng n qu trnh hydrodesulfure ha: ................................................................ 10
2.2.1. p sut ring phn ca H
2
(PPH). ................................................................................................ 10
2.2.2 Nhit phn ng ......................................................................................................................... 12
2.2.3. Ch s tun hon H
2
...................................................................................................................... 12
2.2.4. p sut ring phn ca H
2
S. ......................................................................................................... 12
III. XC TC HYDRODESUNFUR HA........................................................................................... 15
3.1. Xc tc hydrodesunfur ha trong cng nghip: .............................................................................. 15
3.2.Gim hot tnh xc tc ..................................................................................................................... 16
3.2.1. S gim hot tnh xc tc do ngng t cc .................................................................................. 17
3.2.2. Bin php ngn nga s to cc: .................................................................................................. 18
3.3. Ti sinh xc tc ............................................................................................................................... 18
3.3.1. S th i c cht xc tc trong qu trnh vic. ................................................................. 18
3.3.2.Phng php ti sinh xc tc......................................................................................................... 19
CHNG 2: S DY CHUYN CNG NGH.20
I. Cng ngh Prime-D ca Axens ....................................................................................................... 21
II. Cng ngh CDHdro CD-HDS ca CDTech ............................................................................ 23
III. Cng ngh Distillate HDS/HDA ca Haldor Topsoe ................................................................... 24
IV.Cng ngh REDAR ca Shaw Group/BASF ................................................................................ 26
2

V.Cng ngh Unisarca UOP ............................................................................................................ 27
CHNG 3: CU TO THIT B HDS...............................................................................................29
I.Thp dc trc.29
II.Thp xun t31
III.Thp tng si...33
KT LUN ............................................................................................................................................ 35
DANH MC TI LIU THAM KHO ............................................................................................... 36


3

M U

Lu hunh (S) l nguyn t ph binnhttrong du th v v thn , h
ng u hunh l mt ch tiu nh gi cht ng du th. Hu ht cc phn
on du m su khi chng ct khng th s dng c ngay v chng ln rt
nhiu tp cht v cc hp cht gy ng c vi xc tc, gi bn v lm
xui cht ng sn phm, gim hiu qu ca qu trnh ch bin, gy thit hi
v kinh t. V vy loi b u hunh trong cc sn phm du m l mt nhim v
cp bch hin nay. Chnh v vy m qu trnh hydrodesunfur ha (HDS) r i
nhm loi b u hunh ra khi du m v cc sn phm du m.
HDS l mt qu trnh c ngh qun trng c bit trong ch bin du
kh.Cng vi s pht trin mnh m ca cng nghip ha cht-du kh, ngy nay
vic x u hunh tr nn ph bin v d dng hn rt nhiu.Vi thnh qu
ca nghin cung hc v xc tc ca qu trnh HDS, cc nh nghin cu
r cc cht xc tc thc y qu trnh ny trong cng nghip, cng vi
l s tm ra ngy mt nhiu hngi i trong xc tcHDS nhm tiu ha,
gim gi thnh v nng cao hiu qu cht ng qu trnh.
Vi mong mun hiu su hn, c ci nhn tng quan v qu
trnhHydrodesulfur h v cc xc tc trong qu trnh, chng e thc hin
tiu lun: Tm hiu qu trnh Hdrodesufur h.
Do hn ch v mt thi gin cng nh kin thc, nn bi tiu lun khng
trnh khi nhng thiu st. Chng em mong nhn c s gp c c bi
tiu lun thm hon chnh.
Chng em xin chn thnh c n ThS. Vng Thnh Hun tn tnh
hng dn v gip chng em hon thnh bi tiu lun ny!

4

CHNG 1: TNG QUAN V QU TRNH HDS

I. QU TRNH HYDRODESUNFUR HA
1.1.Gii thiu chung v qu trnh hydrodesunfur ha (HDS)
Qu trnh Hydrodesulfure ha l mt qu trnh xc tc ha hc c s
dng rng ri loi b u hunh (S) ra khi kh t nhin, cc sn phm du
m c tinh ch nh xng, nhin iu phn lc, du ha, nhin liu diesel, du
nhin liu.
Trong qu trnh hydrodesunfur ha, mt hn hp ca cc nguyn liu du
v kh hdro c un nng n 300-400 C v c b di p sut n n
130atm vo mt l phn ng hydrodesulfurization . , hn hp i qu cht
xc tc ph v cc lin kt u hunh - carbon (C-S) , cho php u hunh phn
ng vi hdro to thnh hydro sunfit H
2
S. H
2
S ra khi l phn ng, cng vi
hdro d, c sng thit b loi b H
2
S, tch H
2
ra, cho php H
2
c tun
hon trli.
Qu trnh ny bao gm cc phn ng nh:
+Vi hp cht mercaptan:
R-SH + H
2
RH + H
2
S
+Vi hp cht thiophen:

+ H
2
C=C-C=C +H
2
S
+ H
2
+H
2
S
+ Lu hunh dng t do (S) cng c phn ng tng t:
S + H
2
H
2
S
5

Sau qu trnh hydrodesunfur ha, S c tch ra khi cc cu t cha S
lm gi h ng S c trong sn phm n h ng cho php.
1.2. Vai tr ca qu trnh hydrodesunfur ha:
Qu trnh hydrodesunfur hng vi tr v cng qun trng trong qu
trnh sn xut cc sn phm du m. Rt nhiu qu trnh sn xut cc sn phm
du m c s dng xc tc. Lu hunh trong nguyn liu du m c th lm
gim hiu qu ca cc cht xc tc c s dng chuyn i nguyn liu du
m thnh cc sn phm khc. N to cc hp cht bn vi pha hot tnh lm mt
hot tnh cht xc tc gi l ng c xc tc. Do qu trnh HDS c vai tr
nhm to ra sn phm nhin liu hoc nguyn liu c cht ng tt hn, hm
ng u hunh thp hn, trnh hin tng ng c xc tc, gi bn v lm
xui cht ng sn phm, gim hiu qu ca qu trnh ch bin, gy thit hi
v kinh t.
Qu trnh hydrodesunfur h cng ng vi tr gp phn gim thiu
nhi i trng, vi mc ch chnh vic loi b u hunh (S) l gim
ng u hunh i--xt (SO
2
) - kh thi gy ra cc vn h hp v l tc nhn
g r xit. SO
2
l kh thi ca kt qu t nhng vic s dng nguyn liu
trong xe t, b, u my xe l ng st, tu ga, hoc cc nh in
t du, cc khu cng nghip, v cc hnh thc khc ca vic t chy nhin
liu.
1.3. ng dng ca qu trnh hydrodesulfure ha:
Sn xut axit sunfuric H
2
SO
4
t u hunh v cc sn phm ph c ly
t cc nh my lc du.Lu hunh su khi c loi b khi npht c kt
hp vi hdro to kh hydrogen sulfide (H
2
S).Trong cc nh my lc du, kh
hydrogen sulfide su khi c to thnh th c chuyn thnh cc sn phm
ph c u hunh hoc axit sunfuric H
2
SO
4
. Thc t, phn ln 64 triu tn u
6

hunh c sn xut trn ton th gii n 2005 c sn xut t u hunh v
sn phm ph ca cc nh my lc du.
ng dng HDS sn xut nhin liu ng c. Trong qu trnh HDS
distilat du lin kt C-S b ph hu hon ton, lin kt C-C hu nh khng b b
gy tc l khng c qu trnh ph hu nguyn liu. iu n c chng minh
bi hiu sut hdro ho t 95%-99% cn chuyn ho desunfur t 90%-
99.5%.
ng dng HDS cho phn on xng ct trc tip v c xng t cc qu
trnh th cp, c s dng cho qu trnh reforing. Su khi HDS su xng t
cc qu trnh th cp, chng thch hp lm nguyn liu cho qu trnh reforming
xc tc thu c thnh phn xng c tr s octan 82-85(MON) v 92-
95(RON) vi hiu sut sn phm l 80%.
HDS phn on kerosene chng ct trc tip nhn c nhin liu phn
lc cht ng cao bn cnh cng nhn c du ho.
HDS su du bi trn lm sng mu sn phm, gi cc, axit v
to nh tng v gi h ng u hunh.
HDS distilat lm nguyn liu cho qu trinh crcking xc tc v thu c
nhin liu t t u hunh.
Mt s hp cht u hunh c nhiu vng th ngng t nh dibenzo
thiophen (DBTP), dimetylbiphenyl(DMBP), dimetylxyclehexylbenzen
(DMCHB), dietdixcohex (DMDCH) rt kh kh bng cc phng
php thng thng do u hunh nm su trong vng, lin kt gia chng v gc
hydrocacbon bn vng, v vy phi s dng cng ngh hydrodesunfur ho c
bit trn xc tc c hot tnh cao, cng ngh gi l kh u hunh su. Cng
ngh n thng p dng i vi vic kh u hunh trong xng v izen.

7

II. C S CA QU TRNH HYDRODESULFURE HA

2.1. C s ha hc-ha l ca qu trnh HDS:
2.1.1. Phng trnh phn ng tng qut hydrodesunfur ha
a. Mercaptanes:
R-SH + H
2
RH + H
2
S
b. Sulphides:
R
2
S + 2H
2
2RH + H
2
S
c. Disulphides:
(RS)
2
+ 3H
2
2RH + 2H
2
S
d.Thiophenes:

+ H
2
C=C-C=C + H
2
S

+ H
2
+ H
2
S

2.1.2. C ch ca phn ng Hydrodesurfur ha:
Vic nghin cu c ch ca phn ng hydrodesunfur ha ph thuc vo
bn cht phn ng, ng nhit hc ca qu trnh, xc tc s dng.Tin trnh
phn ng hydrodesulfure ha c th din ra 1 phn ng trc tip hay gin tip
qua cc hp cht trung gin. Su xt c ch ca mt s phn ng
2.1.2.1. C ch phn ng Hydrodesunfur ha ca Mercaptanes:
Phng trnh phn ng:
R-SH + H
2
RH + H
2
S
Xc tc s dng Moipden sufur: MoS
2

8

Cu trc ca xc tc MoS
2
:

Hnh 2.1. Cu trc b mt ca MoS
2

C ch phn ng qu 5 gi on:
1. Hydro b hp ph ln b mt cht rn MoS2:

2. Mercaptane b hp ph ln b mt xc tc:

3. S kh Hydro lm b gy lin kt C-S trong mch:

4. Nhhp ph ca Hydrocacbon:

5. Nhhp ph H
2
S trn b mt xc tc:


2.1.2.2. C ch phn ng Hydrodesunfur ha ca Thiophene:
Phng trnh phn ng tng qut:
+Vi hp cht thiophen:

+ H
2
C=C-C=C + H
2
S
9


+ H
2
+ H
2
S
Xc tc s dng CoMoS (Coban Molyden)

Hnh 2.2. Chu trnh phn ng tng qut HDS ca thiophene
C ch phn ng HDS Thiophene c ch do Langmuir-Hinshelwood xut
+ Hydro b hp ph ln b mt xc tc
+ Thiophene b hp ph ln b mt xc tc
+ Qu trnh hydro ha xy ra, b gy lin kt C-S
+ Qu trnh nh hp ph to C
4
H
10

+ Nh hp ph H
2
S, ti sinh xc tc
10


Hnh 2.3. C ch phn ng HDS ca Thiophene

2.2 Cc yu t nh hng n qu trnh hydrodesulfure ha:
2.2.1. p sut ring phn ca H
2
(PPH).
S gi tng p sut ring phn c hdro tng tc HDS v lm
gim than cc bm trn cht xc tc, do gim t l nhim cht xc tc
c thi gian vo hot ng, v tng tui th cht xc tc. Th i trong hydro
p sut ring phn cng dn n s th i trong c ch phn ng cho hai tuyn
ng phn ng HDS khc nhau.V d, kh u hunh trc tip c th xy ra
11

p sut hdro tng i thp, trong khi cc con ng hdro c chung ti
mt p sut ring phn hydro cao.

Bng: L phn ng p lc hydro v yu cu loi cht xc tc cho cc loi ch
tiu khc nhau

Ch tiu
Mc
Thp Trung bnh Cao

p sut (MPa)

p sut H
2
(MPa)

LHSV (h
-1
)

TGR, SCF/B

Khuyt im H
2
,SCF/B

Xc tc

2,7 4,1

1,4 3,1

0,5 1,5

< 1000

< 250

CoMo
3,4 5,5

2,7 4,5

0,5 1,5

1000 3000

250 500

CoMo/NiMo/CoNiMo
4,8 8,9

4,5 6,5

0,5 1,0

2500 -
6000
> 500

NiMo

n v p lc cao c hiu qu i ph vi ngun cp d liu chu la,
chng hn nh ngun iu nt (v d nh LCO, CGO, ...) c cha nng cao
ca cht cn tr hp cht u hunh alkyl DBT, cht th v cc oi nit.
Nickel-molypden cht xc tc c chung trong trng hp n to iu
kin cho vic loi b cc cn tr sterically hp cht u hunh alkyl DBT qua
con ng HYD v loi b hiu qu hn cc oi nit c th c ch cc phn
12

ng kh u hunh. Hot ng p lc co cho nhiu li ch trong kh u
hunh trong nguyn liu du diesel cp u hunh cc k thp.Tuy nhin, n
tng c tiu th hydro v chi ph hot ng ng k v gii hn mc s
dng ca n.

2.2.2 Nhit phn ng
Nhit ca nguyn liu vo phn ng c vai tr quan trng thc y
phn ng hydro ha lm sch. Qu trnh desunfu h tng khi nhit gim.
Trong iu kin thc t th nhit thng l 325
0
C.

2.2.3. Ch s tun hon H
2
T l mol H
2
trong kh tun hon trn mol nguyn liu (H
2
/HR) xc nh
nng ca hydrocacbon trong vng phn ng, t l mol H
2
s dng n nh do
np kh cha H
2
cho tun hon tr li t qu trnh phn ng.
Chn t s tun hon kh H
2
c qu nh bi cc yu t: thnh phn
phn on ca nguyn liu, kht khe ca qu trnh v tr s octan ca sn
ph xng. T l H
2
trn nguyn liu cng cao th tc to cc trn xc tc
cng nh v thi gian lm vic ca xc tc cng ko di, song nu tng t l s
dn n tiu tn mt ng nhit ng k, ng thi tng tr lc th ng
v th tch ca thit b, ng dn. V vy cn phi iu chnh t l H
2
trn nguyn
liu sao cho ph hp vi yu cu sn phm.

2.2.4. p sut ring phn ca H
2
S.
H
2
S l sn phm ph to c ra trong qu trinh HDS, p sut ring
phn thp H
2
S ng vi tr qun trng trong vic duy tr qu trnh sunfit.
13


Hnh 2.4. nh hng ca p sut ring phn ca H
2
S ti phn ng HDS
thiophen trn xc tc CoMoS/Al
2
O
3
Hnh 2.4 cho ta bit nh hng ca p sut n phn ng HDS, khi
p sut ring phn ca H
2
S tng th hot tnh ca xc tc gim. Tuy nhin vi
mt nng rt thp H
2
S li tng ng sn phm cho qu trnh HDS. iu
ny c th l kt qu ca vic gia tng cc nh S-H trn b mt xc tc b phn
li t H
2
S n Mo ch bo h(Hnh 2.5)

Hnh 2.5. S hp ph H
2
S ln b mt xc tc
14

H
2
S hp ph ln trn b mt Mo.Do vy qu trnh c ch xc tc ph
thuc vo nng ca H
2
S.Ty theo phn ng v ty loi xc tc m hot tnh
xc tc gi khng ng u th hin hnh 2.6

Hnh 2.6. nh hng ca p sut ring phn H
2
S n hng s tc ca phn
ng HDS 4,6-DMDBT (a) v DBT (b) trn cc xc tc
NiMo/-Al
2
O
3
, CoMo/-Al
2
O
3
, Mo/-Al
2
O
3







15

III. XC TC HYDRODESUNFUR HA

3.1. Xc tc hydrodesunfur ha trong cng nghip:
Do qu trnh HDS oi b u hunh r khi hp cht, nn cn phi la
chn xc tc bn vi u hunh. Trc , ngi t s dng nhiu cc sufu
c Motrn cht mang xp(nh oxit) xc tc cho HDS.
Ng n, xc tc cobn-oibden trn nh oxit c s dng rng ri
trong cng nghip. Xc tc ny c hot cao trong phn ng ct t lin kt C-
S v bn nhit co, do c tui th co. N cng c hot tnh tng i cao
trong phn ng no h hdroccbon khng no v t lin kt C-N v C-O.Ngoi
r xc tc cng cn c hot thp i vi nhng phn ng t lin kt C-
C, ngh hot ph hy cu trc hydrocacbon phi thp.Trong iu kin
thng thng ca qu trnh lm sch bng hydro hot tnh ca xc tc alumo-
coban-molibden trong phn ng polymer ha hoc ngng t l thp.
Xc tc n c h ng coban v molibden (III), t l gia s nguyn t
Co v Mo cng nh h ng tng ca hai kim loi, din tch b mt ring v
cc ch s khc khc nhu. Chng cng khc nhu v hnh dng hnh hc. Xc
tc c dng dng vin, ng hoc vin cu c np mthay vi lp trong l
phn ng.Trn qun im cng ngh v kinh t t l Co v Mo trong xc tc c
ngh qun trng. T thc t cho thy t l Co: Mo l 0,20.T l ny cho php
xc tc c hot cao nht trong phn ng HDS, xc tc c chn lc cao, cn
phn ng hydrocracking lien kt C-C v no h vng th hu nh khng xy
ra.
u im ln ca xc tc ny l n hu nh khng nhy cm vi cc cht
u c xc tc, c hot hydrodesulfur cao v sc bn c hc cao. Nu cn
tng bn c hc ca xc tc nn thm 5 10% oxit silic .
16

Trong nhng n su n xc tc uo-niken- oibden cng c s
dng rng ri. Xc tc ny c hot lm sch distit trung bnh tng t xc
tc alumina - coban -oibden, nhng c chung hn trong sch
nguyn liu ca cracking xc tcdo c mc hydro ha hp cht nit v
hdroccbon th vng. Xc tc lumo- niken -oibden cng r hn. Hin
nay xc tc tt nht c iu ch dng ht kch thc 1,5 x 3 mm hoc nh
hn. u th ca xc tc ny cho ch bin sn phm du nng l do chng c hot
co hn xc tc dng vin.

Hnh 3.1. Hng s tc ca phn ng desulfur ha (dds) v phn ng hydro
ha (hyd) trn xc tc Co-MoS/-Al
2
O
3
v xc tc NiMoS/-Al
2
O
3

Ta c th th, i vi hu ht cc cht, hng s tc ca phn ng
desulfur ha v phn ng hydro ha c xc tc NiMoS/-Al
2
O
3
u ln hn.
iu y cho thy s tng hot tnh r rt ca xc tc.
Cc xc tc coban - molibden v niken - molibden mang trn nhm oxit
cng nh xc tc hn hp trong phn ln trng hp lm vic c thi gian
sdng l 8 thng.
3.2.Gim hot tnh xc tc
Nguyn nhn ch yu lm gim hot tnh xc tc l do ng c xc tc.
Cc cng trnh nghin cu cho thy hp cht H
2
S b hp ph mnh c bit trn
kim loi niken. Hp cht to thnh gia H
2
S v Ni c tnh n nh cao v tnh
ng c thun nghch thp.
17

V vy khi s dng Ni h Co ngi ta cho thm Mo vo th s gim hot
tnh ca xc tc kim loi ch hn nhiu.

3.2.1. S gim hot tnh xc tc do ngng t cc
- C th chia thnh 2 dng ngng t cc:
Loi 1: Hp ph thun nghch cc hdroccbon th v qu trnh cc ha
- Qu trnh cc ha :


Hnh 3.6. Qu trnh cc ha
+ Hp ph cc trn b mt trng hoc sunfit :

Hnh 3.7. S hp ph cc ln b mt xc tc
Loi 2: Ct mch bng nhit ca cc dy asphalten v hp th trn trung tm S
b mt.Cc asphanten sa lng hp ph thun ngch:

18

Hnh 3.8. Qu trnh cc asphanten sa lng

3.2.2. Bin php ngn nga s to cc:
gim bt qu trnh to cc chng ta phi phn tch nguyn nhn,ngun
gc to ra cc nhm loi tr gim tc to thnh chng.Phi r c
phng php gim tc to ra cc tin t to cc,bng cch s dng cc
nguyn t c th ph v gc t do,hoc bng cch vo cc kh nh
H
2
,H
2
O,hoc pha long kh phn ng
S dng xc tc trn cht mang c mao qun ln gim thiu hin tng
lp kn cc mao qun do cc v cacbon. Cc cht mang phi c bn c hc
khi kt ta cc khng ph v cu trc ca n.
S ngng t cacbon v cc trn cc xc tc oxit hay cc sunfua xy ra ch
yu trn cc tm axit, v vy phi c bin php gi ng tm axit mnh bng
cch cho thm cc ph gia MgO,K
2
O.

3.3. Ti sinh xc tc
3.3.1. S th i c cht xc tc trong qu trnh vic.
Trong qu trnh vic th cht xc tc b th i tnh cht v do
hot tnh cng nh chn c gi i. Nhng s th i n do s to cc
trn b t xc tc do nh hng c nhit co, do cc tp cht c trong
ngun iu v kh tun hon. S th i tnh cht c xc tc c th chi 2
oi su:
Nhng th i c th khi phc c. cc th i do s ng c
xc tc h s to cc thun nghch bi cc hp cht c oxi, nito, u hunh.
Nhng th i vnh vin: s th i vnh vin do th i b t ring
c xc tc h th i trng thi phn tn c xc tc ki oi trn b t cht
mang.
19

3.3..Phng php ti sinh xc tc
phng php ti sinh xc tc bng cch t ch cc b trn b
t xc tc bng ox khng kh nhit 300 500
o
C . dng dng kh nng
ch t 2-15 ox t cc v gi khong nhit trn trnh tn hi
n t ki oi Mo, Co. cht xc tc su ti sinh ch t hn 2 cc
Qu trnh t cc :
C
x
H
y
+ O
2
CO
2
+H
2
O +Q
T th qu trnh n t nhit, c nh hng ti bn nhit c xc tc.
Nhit qu co dn ti s gi phn tn c t ki oi do cc phn t n
b t ch. Nhit qu co cng cht ng
2
O
3
th i cu trc. V v
ngi t t cch gi nhit xung c cho php trnh g nh hng ti
xc tc.

20

21

CHNG : S DY CHUYN CNG NGH

I. Cng ngh Prime-D ca Axens

Hnh 4:Cng ngh Prime-D ca Axens
Hng cng ngh xens c hn 30 n kinh nghim viqutrnh x l
phn ct trung bnh ca du bng hydro v p t 100 phn xng HDT
trn th gii. Cng ngh Prime-D da trn qu trnh HDS v HDA nhm sn
xut Diesel vi vic gim thiu h ng Aromatic, nng cao ch s xetan v
gi h ng u hunh xung di 15ppm.
Dng nguyn liu cng dng kh H
2
v dng kh tun hon su khi c
tro i nhit vi dng sn phm phn ng v tip tc c vo t gia
nhit ti nhit phn ng cn thit s c vo thit b phn ng.
gm 2 thit b ni tip nhau, thit b u tin xy ra phn ng HD v su n
phn ng HDS thit b th 2. Dng sn ph i r su khi tro i nhit vi
dng nguyn liu phn ng c qu thit b lm mt bng khng kh. Ri
i vo thp tch ph, vi dng kh ra khi thp tch ph c i x l hp
22

th bng dung dch amin nhm loi b H
2
S v tun hon kh ch phn ng (ch
yu l H
2
). Dng lng ra t thp tch ph c vo thp chng ct nhm
tch Off-Gas v Diesel sn phm.
Ngoi ra, Cng ngh Prime-D cn pht trin cc cng ngh tng t ch
khc nhau cm thit b phn ng nh: UD-HDS (Utral-Deep HDS) ch x l
su u hunh, Single-Stage HDS/ HDA tc l cng ngh gm 2 phn ng l
HDS v HD nhng trong cng 1 gii on, v cui cng Two-Stage HDS/
HDA tc l cng ngh gm 2 phn ng l HDS v HD nhng trong cng 2 gii
on nh trn. So snh v tnh cht ca sn phm v tnh kinh t ca 3 loi
cng ngh trn qua bng 5 sau:
Ch tiu Utral-Deep HDS
Single-Stage
HDS/ HAD
Two-Stage HDS/
HDA
Sn phm
Sunfua, ppm <10 <10 <5
T trng <0.84 <0.834 <0.825
Aromatic,%wt <2-3 <2 <1-2
Ch s xetan 55 58 58
Tnh kinh t
p sut(MPa) 1.7 2.5 1.7
LHSV (h
-1
) 0.4 0.25 0.4
Bng 5: So snh 3 cng ngh Prime-D ca Axens
23

II. Cng ngh CHdro C-HDS ca CDTech

Hnh 5: Cng ngh CDHdro CD-HDS ca CDTech
C 21 phn xng CDHydro/CD-HDS ng vn hnh x xng FCC
v hn 12 phn xng ngx dng. Vitng cngsut t c 1.3 triu
thng/ngy. Bn qun cng ngh thuc v CDTech (Catalytic Distillation
Technologies).
Cng ngh bo g 2 qu trnh CDHdro CD-HDS c s dng ring
r tch u hunh trong xng FCC vi s gim tr s octan thp nht. Sn
phm c qu trnh xng FCC vi hm ng S rt thp v gi i nhiu nht
olefin cng nh tr s octan.
LCN, MCN, HCNc x ring trong iu kin ti u cho i phn.
Lu hunh gim trong tonb phn xng FCC bt u vi phn tch naphtha nh
trong thp CDHdro. Lu hunh mercaptan phn ng vilng diolefin d
sn xut cc hp cht lu hunh nng hn, cc dioefin cn i mt phn bo ha
oefin bng phn ng vi hdro.Phn y ca thp CDHydro c cha cc
mercaptans phn ng c n thp CD-HDS, ti MCN v HCN m
xc tc kh S trong 2 khu ring bit. iu kin qu trnh HDS c ti u ha
cho tng phn t c mong un gi u hunhvi bo ha olefin ti
thiu. Olefin c tp trung pha trn cng ca thp ni c iu kin m,trong
24

khi u hunhi tp trung pha di ni cc iu kin c cao ca
qu trnh HDS.
Khngc phn ng cracking iu kin m, do thit hi v nng
sut c th c gim n c ti thiu. Ba dng sn phm c n nh cng
nhau hoc ringr ty theo mong un, kt qu dng sn phm thch hp cho
c ch s dng tip theo ca chng.Hai thp c tch hp nhit gim
thiu nhu cu v nng ng. H ng u hunhtrong sn ph xng su x
l t ch tiu cht ng s cho php pha ch xng du p ng cc quy nh
hin hnh h trong tng i.
Xc tc chng ct v c bn oi b s tch t bnxc tc dooi b cc
tin cc nng t khu vc xc tc, trc khi cc c th hnh thnh v bt kn cc
mao qun xc tc. Do d, tui th ca xc tc trongchngctxctcc tng n
ng k so vi xc tc c nh in hnh. Qu trnh CDHydro /CD-HDS c th
hot ng trong sut t chu k ca phn xng FCC ln n 6 n
khngcn dng hot ng ti sinh hay thay th xc tc, tit ki nng ng
cho nh y.
III. Cng ngh Distillate HDS/HDA ca Haldor Topsoe

25

Hnh 6: Cng ngh Distillate HDS/HDA ca Haldor Topsoe
Cng ngh Haldor Topsoe s dng x su h ng u hunh v
Aromatic trong sn phm diesel bng hydro hoc x l nguyn liu s b cho
qu trnh FCC, hydrocracker.
Cng ngh Distillate HDS/HDA ca Haldor Topsoe trn vi 2 thit b
phn ng l HDS v HDA gip gim mc u hunh v Aromatic, ci thin t
trng ng thi nng cao tr s xetan sn phm diesel. Vi thit b phn ng u
tin hot ng ti p sut 2060 kg/cm
2
v nhit t 320400
o
C xy ra qu
trnh kh su HDS v HDN trn xc tc kim loi. Dng sn phm ra t thit b
phn ng HDS c vo thp chng tch nhm loi b H
2
S v NH
3
. Kh
Off-Gas(ch yu l H
2
) c i ra bng dung dch in, su cng vi
dng sn ph thp chng c vo thit bi phn ng HDA th hi, ni
m cc hp cht rotic c bo ha bi H
2
trn xc tc.Phn ng n cng
thc hin ti p sut 2060 kg/cm
2
nhng ti nhit 260-300
o
C. Sn phm ra
c lm mt bng khng kh su vo thp tch ph tun hon li kh
ch phn ng. Sn phm lng c i chng tch y sn phm diesel vi
h ng Aromatic nh hn 3 khi ng v tng ch s xetan thm 11
n v.
26

IV.Cng ngh REDAR ca Shaw Group/BASF

Hnh 7: Cng ngh REDAR ca Shaw Group/BASF
Cng ngh REDAR (Raytheon/Engelhard DeAromatization) thc hin
trong cc phn xng hdrotreter sn xut diesel vi tng h ng
Aromatic nh hn 5 khi ng. Trong qu trnh hu nh ton b ng u
hunh b loi b hon ton, t trng ca sn ph c ci thin ng thi lm
tng ch s xetn n 5 n v.
Xc tc c s dng trong cng ngh l kt hp ca 2 kim loi Pt/Pd trn
cht mang l SiO
2
v -Al
2
O
3
khng cn cht kt dnh. Xc tc s c hot tnh
mnh hn khi s dng cht kt dnh, cho php cng ngh hot ng iu kin
m hn ti 45-50
o
C, tc th tch co hn, v p sut cho qu trnh gim
xung.
Nguyn liu sau khi qua cc thit b tro i nhit, trn vi kh t thp
tch ph v c gia nhit n nhit cn thit trong t trc khi vo
thit b phn ng HDS. Dng sn ph i r tip tc c vo phn ng
HDA vi 2 dng i ngc chiu. Sau phn ng sn ph c i chng
27

tch ly diesel. Cn cc kh sau phn ng c i ra bng nc v hp th
bng dung dch in tr li kh tun hon (ch yu cha H
2
) cho phn ng.
Ngoi ra cng ngh cn c th dng nng cp phn on LCO sn xut
diesel bng vic s dng xc tc Ni-Mo trong thit b phn ng HDS/HDNu
tin.
V.Cng ngh Unisarca UOP
UOP mt trong cc hng ln cng ngh trong vic x l nguyn liu hay
nng cp sn phm du m. Ty vo vic x l cc ngun nguyn liu khc nhau
hng c r cc cng ngh x tng ng. Ch yu nh x l cc phn
on ct trung bnh, VGO...nhm sn xut cc sn phm trng theo nhu cu.
Ngoi r, UOP cng sn xut cung cp cc loi xc tc mi cho qu trnh.

Hnh 8: Cng ngh Unisar ca UOP
Cng ngh Unisar c UOP s dng xc tc kim loi qu trn cht
ng bo ha cc Aromatic trong cc phn on ct trung bnh nh Nphth,
28

Kerosene, Diesel. Cng ngh hot ng vi ch xc tc c nh vi xc tc
mi AS-250 thay th cho xc tc c S-100. Hn 20 phn xng cng ngh
Unisar c UOP c lp t trn ton th gii, sn phm sau khi c x l
gip lm gi h ng Aromatic t 26% khi ng xung cn nh hn 1
khi ng trong nguyn liu.
Cng ngh cng c 2 phn ng x chnh HDS v HD nhng trong
cng mt thit b phn ng c chia lm nhiu tng. Nguyn liu c trn vi
kh H
2
sch v kh tun hon, sau khi gia nhit c vo thit b phn ng.
Do cc phn ng c Hdrotreting t nhit rt nh nn ngi t thng chi
xc tc thnh nhiu tng khc nhu ( c th iu chnh nhit su i tng,
v c th b xung th dng H
2
nu cn thit), hoc c nhiu thit b ni tip
nhau.
Trn cc tng xc tc thng c cc tng Ceric bo v xc tc.
gia cc tng c cc thit b thu nhit v cc thit b thu hi v phn tn u li
dng nguyn liu trc khi c sng tng xc tc khc.
Dng sn ph su khi i r khi thit b phn ng s c lm lnh, v
qua thit b tch kh-lng c th tch cc kh (ch yu l H
2
ch phn ng,
H
2
S, NH
3
, v mt s hydrocacbon nh) ra khi sn phm.
Dng kh s c qua mt thp hp ph bng Amin iu kin nhit
v p sut co c th lm sch H
2
S, NH
3
ra khi dng kh, trc khi c
tun hon quay tr li thit b phn ng.
Dng sn ph c i vo t thp tch, c th tch trit cc kh
H
2
S, NH
3
, v t s kh nh khc r khi sn ph cui cng.



29

CHNG 3: CU TO THIT B HDS
I.Thp dc trc
Cu to:
Thp hnh tr, c ng knh khng c nh D= 2-3, chiu co H=10-20m.
Ngun khi, v d 90-100, c ch to t cc p thp c chiu d t
10-20 c it nng di p c co i vs nhu. Cc p bn ngoi thp
thng, thp bn trong thp inox.c ch to bng cc vt iu t bit c
kh nng chu c p sut co ~ 40t.Bn ngoi c p cch nhit bng Ceric
hoc b tong phun c b d t 150-200.C b phn phn phi hi
bo ngun iu tip xc tt vi xc tc.Thng s dng t 4 6 chic pin nhit
in o nhit ti tng vng trong thit b nh gi kh nng n n
hidro.
Thp phn ng dc trc thp hnh tr, cu to in khi. ng knh th i
theo cng sut. V thp bng thp crbon c ch to bng cch it
nng cc p thp vo nhau, p trong cng l p thp khng g, chu
nhit cao (p thp dy 10-15mm). Bn ngoi c p cch nhit d t
200 v thng p t bng btng phun. Trong thp ch xc tc,
ph trn v ph di p xc tc p s xc tc khng b ng theo
dng kh, p s n c cc kch thc khc nhu, gn xc tc c kch thc
to hn, v nh dn.
30


Hot ng:
Trong thit b phn ng dc trc, khi kh ngun iu nng chun ng
qua p xc tc dc theo hng trc thp phn ng, khi qu xc tc s c s
chun h v h hc x r, dng kh su khi i r khi p xc tc c
ra ngoi.
c im:
+ R tin, cu to n gin
+ Khi tng cng sut th ng knh v chiu co thit b tng tng ng
xc tc nn dng cho thp dc trc c cng sut nh ( ng knh t 2-3m, cao
t 8 n 20m)
+ Lng xc tc dng nhiu hn. OK
+ Thi gin phn ng di hn
+ Tr c n
31

II.Thp xuyn tm
Cu to:
Cc thng s thp nh thit b dc trc, nhng bo khi kh ngun iu
chun ng qu xc tc theo hng bn knh th
Thit b phn ng xun t cng c cu trc hnh tr, v cng c p t
bng btng phun. Nhng to chun ng hng t c dng hi kh,
ngi t b tr ph trong thit b t cc hi v hnh tr bng thp c c
thnh, gi hi p v c cc ch xc tc.
C ng dn ngun iu vo v ng trung t dng sn ph r, ngoi r
cn c cc ng xc tc vo v r khi cc hi v.



32

Hot ng:
Hn hp hi kh i t ng tip iu s qu cc thnh cc hi v, qu p xc
tc theo phng vung gc vi trc c ri i vo ng trung t v i r
ngoi.
c im:
+ Cu to phc tp, t tin.
+ Khi tng cng sut th tng chiu co thp nn khng b chi phi nhiu bi
ng knh thp. V ng knh thp n qu th d x r hin tng tr c cc
b h qu nhit cc b.
+ Thi gin phn ng ngn
+ Lng xc tc cn t hn ( Lng xc tc ch c t hn)
+ Tr c nh
Do nhng u i v nhc i ng n thit b phn ng
dc trc khng cn c s dng n v c th th bng thit b phn
ng xuyn tm.Tuy nhin, ta vn c th dng c 2 oi thp n ng thi.
V d nh phn ng reforing, bn u thnh phn ngun iu d phn ng s
phn ng nhnh nn cn t xc tc t c th dng thp phn ng oi xun t,
cng v su ngun iu cng kh phn ng cn nhiu xc tc hn, thi gin
phn ng di hn th t c th chn thit b dc trc hoc thit b xun t kch
thc n hn.
Thit b dng xun t vn u vit hn c v n gi c hin tng qu
nhit cc b khi xc tc, g t hot tnh xc tc.





33

III.Thit b tng si ( Ebuted-Bed Reactor )

S cng ngh


Cu to thit b

34

Dng ngun iu v kh hdro i t di n ( hdrogen nd feed) sc vo p
xc tc x r qu trnh phn ng hdrodesunfu h.Su dng sn ph i
n trn thit b phn ng ri c thu go vo thit b go sn ph ri c
b tun hon b tr i thit b tip tc din r phn ng tng hiu sut
phn ng.Cui cng,sn ph c tch trn nh thp nh thit b tch,dng
kh thu c bn trn,cn dng sn ph thu c di thit b.


35

KT LUN

Qua vic tm hiu cc qu trnh hydrodesulfur ha nh chng e thu
c mt s kin thc rt b ch v xc tc hydrodesulfurization ni ring v
xc tc cng nghip ni chung. Bit cch tm ti liu, c v dch ti liu chuyn
ngnh nc ngoi qu tng th hiu bit v k nng. Vic lm vic nhm
cng gpi cht kh khn song nh bit thng nht v gip nhau cng
lm bi tiu lun.Qu cng th c tc dng ca lm vic nhm kt hp
hc tp v nghin cu.Mong rng s c thm nhiu hn na cc mn hc cc bi
tp ln i hi vic tm ti v lm vic nhm nhiu hn n chng em hon
thin bn thn nng cao k nng v kin thc hc tp nghin cu v lm vic
sau ny.

36

DANH MC TI LIU THAM KHO
[1]. L Vn Hiu, Cng ngh ch bin du m, NXB Khoa hc v k thut, H
Ni, 2006
[2]. o Vn Tng, ng hc xc tc, NXB Khoa hc v k thut, H Ni,
2006.
[3]. inh Th Ng, Ha hc du m v kh, ti bn ln th t NXB Kho hc v
k thut, H Ni, 2008.
[4]. inh Th Ng, Nhin liu sch v cc qu trnh x l trong Ha Du, ti bn
v b sung ln hai, NXB Khoa hc v k thut, H Ni, 2008.
[5].TS. Nguyn Thnh Sn, Qu trnh kh lu hunh trong phn on du m.
[6] [Desulfurization ]James G. Speight The Desulfurization of Heavy Oils and
Residua Chemical Industries 1999
[7] [Petroleum] Handbook Of Petroleum Refining Processes-McGraw-Hill
Professional (2003) (1)