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 H2 (PPH). ................................................................................................ 10
2.2.2 Nhit phn ng ......................................................................................................................... 12
2.2.3. Ch s tun hon H2 ...................................................................................................................... 12
2.2.4. p sut ring phn ca H2S.......................................................................................................... 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. C ng ngh CDH dro

CD-HDS ca CDTech ............................................................................ 23

III. Cng ngh Distillate HDS/HDA ca Haldor Topsoe ................................................................... 24

IV.Cng ngh REDAR ca Shaw Group/BASF ................................................................................ 26
1

V.Cng ngh Unisarca UOP ............................................................................................................ 27

CHNG 3: CU TO THIT B HDS...............................................................................................29
I.Thp dc trc.29
II.Thp xu n t 31
III.Thp tng s i...33
KT LUN ............................................................................................................................................ 35
DANH MC TI LIU THAM KHO ............................................................................................... 36

M U
Lu hunh (S) l nguyn t ph binnhttrong du th v v th n , h
ng u hunh l mt ch tiu nh gi cht ng du th. Hu ht cc phn
on du m s u 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 qu n 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 d ng 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 H drodesu fur h .

Do hn ch v mt thi gi n 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 Th nh Hu n tn tnh

hng dn v gip chng em hon thnh bi tiu lun ny!

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 h dro 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 h dro to thnh hydro sunfit H2S. H2S ra khi l phn ng, cng vi
h dro d, c s ng thit b loi b H2S, tch H2 ra, cho php H2 c tun
hon trli.
Qu trnh ny bao gm cc phn ng nh:
+Vi hp cht mercaptan:
R-SH + H2 RH + H2S
+Vi hp cht thiophen:

+ H2

+ H2

C=C-C=C +H2S

+H2S

+ Lu hunh dng t do (S) cng c phn ng tng t:

S + H2

H2S

Sau qu trnh hydrodesunfur ha, S c tch ra khi cc cu t cha S

lm gi

ng S c trong sn phm n h

ng cho php.

1.2. Vai tr ca qu trnh hydrodesunfur ha:

Qu trnh hydrodesunfur h ng v i tr v cng qu n 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 v i tr gp phn gim thiu
i trng, vi mc ch chnh

nhi

vic loi b u hunh (S) l gim

ng u hunh i--xt (SO2) - kh thi gy ra cc vn h hp v l tc nhn

g r

trong xe

xit. SO2 l kh thi ca kt qu t nhng vic s dng nguyn liu

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 H2SO4 t u hunh v cc sn phm ph c ly
t cc nh my lc du.Lu hunh s u khi c loi b khi n pht c kt
hp vi h dro to kh hydrogen sulfide (H2S).Trong cc nh my lc du, kh
hydrogen sulfide s u khi c to th nh th c chuyn thnh cc sn phm
ph c

u hunh hoc axit sunfuric H2SO4. Thc t, phn ln 64 triu tn u

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 kh ng b b
gy tc l khng c qu trnh ph hu nguyn liu. iu n

c chng minh

bi hiu sut h dro 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 refor ing. S u 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 9295(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 b i trn lm sng mu sn phm, gi
to nh tng v gi

cc, axit v

ng u hunh.

HDS distilat lm nguyn liu cho qu trinh cr cking xc tc v thu c

nhin liu t t u hunh.
Mt s hp cht u hunh c nhiu vng th
thiophen

(DBTP),

dimetylbiphenyl(DMBP),

(DMCHB), di et dix c ohex

ngng t nh dibenzo
dimetylxyclehexylbenzen

(DMDCH) rt kh kh bng cc phng

php th ng 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.

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 + H2 RH + H2S
b. Sulphides:
R2S + 2H2 2RH + H2S
c. Disulphides:
(RS)2 + 3H2 2RH + 2H2S
d.Thiophenes:

+ H2 C=C-C=C + H2S

+ H2

+ H2S

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 gi n. S u 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 + H2

RH + H2S

Xc tc s dng

Mo ipden su fur: MoS2

7

Cu trc ca xc tc MoS2:

Hnh 2.1. Cu trc b mt ca MoS2

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 H2S 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:

+ H2

C=C-C=C + H2S
8

+ H2

+ H2S

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 C4H10
+ Nh hp ph H2S, ti sinh xc tc

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 H2 (PPH).
S gi tng p sut ring phn c h dro
gim than cc bm trn cht xc tc, do

tng tc HDS v lm

gim t l nhim cht xc tc

c thi gian vo hot ng, v tng tui th cht xc tc. Th

p sut ring phn cng dn n s th

i trong hydro

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

10

p sut h dro tng i thp, trong khi cc con ng h dro 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
Mc
Ch tiu

Thp

Trung bnh

Cao

p sut (MPa)

2,7 4,1

3,4 5,5

4,8 8,9

p sut H2 (MPa)

1,4 3,1

2,7 4,5

4,5 6,5

LHSV (h-1 )

0,5 1,5

0,5 1,5

0,5 1,0

TGR, SCF/B

< 1000

1000 3000

2500

6000
Khuyt im H2 ,SCF/B < 250

250 500

> 500

Xc tc

CoMo/NiMo/CoNiMo

NiMo

CoMo

n v p lc cao c hiu qu i ph vi ngun cp d liu chu la,

chng hn nh ngu n 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
11

ng kh u hunh. Hot ng p lc c o 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 0C.

2.2.3. Ch s tun hon H2

T l mol H2 trong kh tun hon trn mol nguyn liu (H2 /HR) xc nh
nng ca hydrocacbon trong vng phn ng, t l mol H2 s dng n nh do
np kh cha H2 cho tun hon tr li t qu trnh phn ng.
Chn t s tun hon kh H2 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 H2 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 H2 trn nguyn

liu sao cho ph hp vi yu cu sn phm.

2.2.4. p sut ring phn ca H2S.

H2S l sn phm ph to c ra trong qu trinh HDS, p sut ring
phn thp H2S ng v i tr qu n trng trong vic duy tr qu trnh sunfit.

12

Hnh 2.4. nh hng ca p sut ring phn ca H2S ti phn ng HDS

thiophen trn xc tc CoMoS/Al2O3
Hnh 2.4 cho ta bit nh hng ca p sut n phn ng HDS,

khi

p sut ring phn ca H2S tng th hot tnh ca xc tc gim. Tuy nhin vi
mt nng rt thp H2S 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 H2S n Mo ch bo h (Hnh 2.5)

Hnh 2.5. S hp ph H2S ln b mt xc tc

13

H2 S hp ph ln trn b mt Mo.Do vy qu trnh c ch xc tc ph

thuc vo nng ca H2S.Ty theo phn ng v ty loi xc tc m hot tnh
xc tc gi

kh ng ng u th hin hnh 2.6

Hnh 2.6. nh hng ca p sut ring phn H2S n hng s tc ca phn

ng HDS 4,6-DMDBT (a) v DBT (b) trn cc xc tc
NiMo/-Al2O3, CoMo/-Al2O3, Mo/-Al2O3

14

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
Ng

oxit)

xc tc cho HDS.

n , xc tc cob n- o ibden trn nh

oxit c s dng rng ri

trong cng nghip. Xc tc ny c hot cao trong phn ng ct t lin kt CS v bn nhit c o, do c tui th c o. N cng c hot tnh tng i cao
trong phn ng no h h droc cbon kh ng no v t lin kt C-N v C-O.Ngoi
r xc tc cng cn c hot thp i vi nhng phn ng
C, ngh

t lin kt C-

hot ph hy cu trc hydrocacbon phi thp.Trong iu kin

th ng thng ca qu trnh lm sch bng hydro hot tnh ca xc tc alumocoban-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 nh u. Chng cng khc nh u 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 qu n im cng ngh v kinh t t l Co v Mo trong xc tc c
ngh qu n 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 kh ng xy

ra.
u im ln ca xc tc ny l n hu nh kh ng 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 .

15

Trong nhng n

s un

xc tc

u o-niken-

o ibden cng c s

dng rng ri. Xc tc ny c hot lm sch disti t trung bnh tng t xc

tc alumina - coban - o ibden, nhng c chung hn trong

sch

nguyn liu ca cracking xc tcdo c mc hydro ha hp cht nit v

h droc cbon th

vng. Xc tc lumo- niken - o ibden 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
c o 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/-Al2O3 v xc tc NiMoS/-Al2O3
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/-Al2O3 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 H2S b hp ph mnh c bit trn
kim loi niken. Hp cht to thnh gia H2S v Ni c tnh n nh cao v tnh
ng c thun nghch thp.
16

V vy khi s dng Ni h
tnh ca xc tc kim loi ch

Co ngi ta cho thm Mo vo th s gim hot

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 h droc cbon 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:

17

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 v o cc kh nh
H2,H2O,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
ng tm axit mnh bng

yu trn cc tm axit, v vy phi c bin php gi

cch cho thm cc ph gia MgO,K2O.
3.3. Ti sinh xc tc
3.3.1. S th

i c cht xc tc trong qu trnh

Trong qu trnh

vic th cht xc tc b th

hot tnh cng nh chn c gi

trn b

vic.

i. Nhng s th

i tnh cht v do
i n

do s to cc

t xc tc do nh hng c nhit c o, do cc tp cht c trong

ngu n iu v kh tun ho n. S th

i tnh cht c xc tc c th chi

oi s u:
Nhng th
xc tc h

i c th kh i phc c.

cc th

i do s ng c

s to cc thun nghch bi cc hp cht c oxi, nito, u hunh.

Nhng th
c xc tc h

i vnh vin: s th
th

i vnh vin do th

i trng thi phn tn c xc tc ki

mang.
18

i b
oi trn b

t ring
t cht

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 kh ng kh nhit 300 500 oC . dng dng kh nng

ch t 2-15
n t

ki

ox t cc v gi khong nhit trn trnh

oi Mo, Co. cht xc tc s u ti sinh ch t hn 2

tn hi
cc

Qu trnh t cc :
CxHy + O2 CO2 +H2O +Q
T th qu trnh n

t nhit, c nh hng ti bn nhit c xc tc.

Nhit qu c o dn ti s gi

phn tn c t

b t ch . Nhit qu c o cng
ngi t t

cch gi

cht

nhit xung

ng

ki
2O3

oi do cc phn t n
th

i cu trc. V v

c cho php trnh g nh hng ti

xc tc.

19

20

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
phn ct trung bnh ca du

kinh nghim viqutrnh x l

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
gi

ng Aromatic, nng cao ch s xetan v

ng u hunh xung di 15ppm.

Dng nguyn liu cng dng kh H2v dng kh tun hon s u khi c
tr o i nhit vi dng sn phm phn ng v tip tc c v o

t gia

nhit ti nhit phn ng cn thit s c v o thit b phn ng.

gm 2 thit b ni tip nhau, thit b u tin xy ra phn ng HD v s u n
phn ng HDS thit b th 2. Dng sn ph

i r s u khi tr o i nhit vi

dng nguyn liu phn ng c qu thit b lm mt bng khng kh. Ri

i v o thp tch ph , vi dng kh ra khi thp tch ph c i x l hp
21

th bng dung dch amin nhm loi b H2S v tun ho n kh ch phn ng (ch
yu l H2). Dng lng ra t thp tch ph c v o 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 gi i on, v cui cng Two-Stage HDS/
HDA tc l cng ngh gm 2 phn ng l HDS v HD nhng trong cng 2 gi i
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

Single-Stage
HDS/ HAD

Utral-Deep HDS

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

22

II. C ng ngh C H dro

C -HDS ca CDTech

Hnh 5: C ng ngh CDH dro

CD-HDS ca CDTech

C 21 phn xng CDHydro/CD-HDS ng vn h nh x xng FCC

v hn 12 phn xng ngx dng. Vitng cngsut t c 1.3 triu
thng/ng y. Bn qu n cng ngh thuc v CDTech (Catalytic Distillation
Technologies).
C ng ngh b o g 2 qu trnh CDH dro 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 h m 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 to nb phn xng FCC bt u vi phn tch naphtha nh
trong thp CDH dro. Lu hunh mercaptan phn ng vilng diolefin d
sn xut cc hp cht lu hunh nng hn, cc dio efin cn i mt phn bo ha
o efin bng phn ng vi h dro.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
23

khi u hunh i tp trung pha di ni

qu trnh HDS.

cc iu kin

c cao ca

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 s u x
l t ch tiu cht ng s cho php pha ch xng du p ng cc quy nh
hin h nh h trong tng i.
Xc tc chng ct v c bn oi b s tch t bnxc tc do oi b cc
tin cc nng t khu vc xc tc, trc khi cc c th hnh th nh 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

24

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/cm2 v nhit t 320400oC 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 v o thp chng tch nhm loi b H2S v NH3. Kh
Off-Gas(ch yu l H2) c i ra bng dung dch in, s u cng vi
dng sn ph thp chng c v o thit bi phn ng HDA th h i, ni
m cc hp cht ro tic c bo ha bi H2trn xc tc.Phn ng n cng
thc hin ti p sut 2060 kg/cm2nhng ti nhit 260-300oC. Sn phm ra
c lm mt bng kh ng kh s u v o 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.

25

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 h drotre ter sn xut diesel vi tng h
Aromatic nh hn 5

ng

khi ng. Trong qu trnh hu nh to n b ng u

hunh b loi b hon ton, t trng ca sn ph

c ci thin ng thi lm

tng ch s xet n 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 SiO2v -Al2O3khng 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 45-50oC, tc th tch c o hn, v p sut cho qu trnh gim

xung.
Nguyn liu sau khi qua cc thit b tr o i nhit, trn vi kh t thp
tch ph v c gia nhit n nhit cn thit trong t trc khi v o
thit b phn ng HDS. Dng sn ph

i r tip tc c v o phn ng

HDA vi 2 dng i ngc chiu. Sau phn ng sn ph

26

c i chng

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 H2) 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 c ng 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.
Ngo i 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 N phth ,
27

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

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 H2 sch v kh tun hon, sau khi gia nhit c v o thit b phn ng.
Do cc phn ng c H drotre ting t nhit rt

nh nn ngi t thng chi

xc tc th nh nhiu tng khc nh u ( c th iu chnh nhit s u

v c th b xung th

i tng,

dng H2 nu cn thit), hoc c nhiu thit b ni tip

nhau.
Trn cc tng xc tc thng c cc tng Cer

ic 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 s ng tng xc tc khc.
Dng sn ph

s u 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 H2 ch phn ng,

H2S, NH3, 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 c o c th lm sch H2S, NH3 ra khi dng kh, trc khi c
tun hon quay tr li thit b phn ng.
Dng sn ph
H2S, NH3, v

c i v o

t thp tch, c th tch trit cc kh

t s kh nh khc r khi sn ph

28

cui cng.

CHNG 3: CU TO THIT B HDS

I.Thp dc trc
Cu to:
Thp hnh tr, c ng knh kh ng c nh D= 2-3 , chiu c o H=10-20m.
Ngu n khi, v d
10-20

90-100

, c ch to t cc p thp c chiu d

it nng di p c c o i vs nh u. Cc p bn ngo i

thng, thp bn trong

t
thp

thp inox.c ch to bng cc vt iu t bit c

kh nng chu c p sut c o ~ 40 t.Bn ngo i c p cch nhit bng Cer

hoc b tong phun c b d

t 150-200

ic

.C b phn phn phi hi

bo ngu n 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

hidro.
Thp phn ng dc trc
theo c ng sut. V thp

thp hnh tr, cu to in khi. ng knh th

bng thp c rbon c ch to bng cch

i
it

nng cc p thp vo nhau, p trong cng l p thp khng g, chu

nhit cao ( p thp dy 10-15mm). Bn ngo i c p cch nhit d
200

v thng

p t bng bt ng phun. Trong thp ch xc tc,

ph trn v ph di p xc tc
dng kh, p

s n

s xc tc kh ng b

ng theo

c cc kch thc khc nh u, gn xc tc c kch thc

to hn, v nh dn.

29

Hot ng:
Trong thit b phn ng dc trc, khi kh ngu n iu nng chu n ng
qua p xc tc dc theo hng trc thp phn ng, khi qu xc tc s c s
chu n h v h hc x r , dng kh s u khi i r khi p xc tc c
ra ngoi.
c im:
+ R tin, cu to n gin
+ Khi tng c ng sut th ng knh v chiu c o thit b tng

tng ng

xc tc nn dng cho thp dc trc c c ng sut nh ( ng knh t 2-3m, cao

t 8 n 20m)
+ Lng xc tc dng nhiu hn. OK
+ Thi gi n phn ng d i hn
+ Tr c n
30

II.Thp xuyn tm
Cu to:
Cc th ng s thp nh thit b dc trc, nhng

bo khi kh ngu n iu

chu n ng qu xc tc theo hng bn knh th

Thit b phn ng xu n t

cng c cu trc hnh tr, v cng c p t

bng bt ng phun. Nhng to chu n ng hng t

ngi t b tr ph trong thit b

c dng hi kh,

t cc h i v hnh tr bng thp c c

th nh, gi h i p v c cc ch xc tc.
C ng dn ngu n iu v o v ng trung t

dng sn ph

cn c cc ng xc tc v o v r khi cc h i v.

31

r , ngo i r

Hot ng:
Hn hp hi kh i t ng tip iu s qu cc th nh cc h i v, qu p xc
tc theo phng vu ng gc vi trc c

ri i v o ng trung t

v i r

ngoi.
c im:
+ Cu to phc tp, t tin.
+ Khi tng c ng sut th tng chiu c o thp nn kh ng 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 gi n 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

dc trc kh ng cn c s dng n v c th

thit b phn ng

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 refor ing, b n u th nh phn ngu n iu d phn ng s

phn ng nh nh nn cn t xc tc t c th dng thp phn ng oi xu n t ,
c ng v s u ngu n iu c ng kh phn ng cn nhiu xc tc hn, thi gi n
phn ng d i hn th t c th chn thit b dc trc hoc thit b xu n t

kch

thc n hn.
Thit b dng xu n t

vn u vit hn c v n gi

nhit cc b khi xc tc, g

t hot tnh xc tc.

32

c hin tng qu

III.Thit b tng s i ( Ebu

ted-Bed Reactor )

S cng ngh

Cu to thit b

33

Dng ngu n iu v kh h dro i t di n ( h drogen nd feed) sc v o p

xc tc x r qu trnh phn ng h drodesunfu h .S u dng sn ph
n trn thit b phn ng ri c thu go
b

tun ho n b

v o thit b go

sn ph

ri c

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.

34

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
ng nh nc ngo i qu tng th
cng gp i cht kh khn song nh

hiu bit v k nng. Vic lm vic nhm

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.

35

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 Th nh 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)

36