Cng ngh lc du

TS. Nguyn Thanh Sn

1
CC QU TRNH CHUYN HA DI TC DNG CA NHIT
QU TRNH GIM NHT CC PHN ON CN
lm tng gi tr ca cc phn on cn, cc qu trnh chuyn ho bng nhit c
thay th bng mt qu trnh cracking mm nhm lm gim nht ca cc phn on cn nng
c th s dng chng lm cht t (c cht lng nh sn phm thng mi). y l qu trnh
gim nht. Nguyn liu ca qu trnh ny l :
- Cn ca qu trnh chng ct kh quyn vn hnh ch sn xut ti a xng v gazole,
nhng vn m bo cc c tnh v nht v n nh ca cn.
- Cn ca qu trnh chng ct chn khng vn hnh vi mc ch lm gim n mc ti a
nht sn xut du t cng nghip.
I. C s ca qu trnh :
I.1. Nguyn liu :
Mt cch n gin c th xem cn l mt h keo c to thnh t mt pha phn tn l
cc mixen cha cc asphaltne v cc maltne a nhn thm c khi lng phn t ln v mt
pha lin tc l cc maltne khc.
Cc asphaltne l cc phn t phc tp c khi lng phn t ln hn 1000, c nhiu
nhn thm, c cha nhiu nhnh mch thng, cc d nguyn t (S,N,O) v cc kim loi nng
(Ni,V).
Cc maltne c khi lng phn t thp hn asphaltne. Chng c to thnh t cc
phn t hydrocacbon (HC) parafin, naphten v thm. Chng cng cha cc d nguyn t v cc
kim loi nng nhng vi hm lng thp hn.
I.2. Phn ng b gy mch :
Trong qu trnh gim nht, cc maltne b b gy mch to thnh cc phn t nh hn,
trong khi lng asphaltne tng ln do phn ng vng ho v ngng t cc nhn thm.
Cc phn ng b gy mch phn t v c ch ca cc phn ng ny i vi cc HC nh
v cc phn on nh (qu trnh cracking hi sn xut ethylne, propylne, butadine,
benzene) c nghin cu rt nhiu. Trong trng hp cc cu t ca du nng, nh hng
ca nhit ln phn ng b gy mch phn t cha c bit r. Tuy nhin ngi ta c th
nhn dng mt vi phn ng sau :
Cng ngh lc du
TS. Nguyn Thanh Sn
2
- B gy lin kt C-C ca cc HC mch thng trong cc paraffine (to thnh olfine) v
trong cc alkylaromatique (phn ng alkyl ho). y l cc phn ng s cp.
- Oligome ho v vng ho to thnh cc naphtne t cc hp cht olfine to thnh t
phn ng s cp.
- Ngng t cc phn t mch vng to thnh polyaromatique.
Ngoi ra cn c cc phn ng xy ra vi cc d nguyn t trong asphaltne :
- to H
2
S, thiophne, mercaptan
- to phenol
I.3.C ch v ng hc cc phn ng :
Cc phn ng b gy mch phn t nu trn l cc phn ng dy chuyn xy ra theo c
ch gc. Trn quan im ng hc phn ng, ngi ta c th din t vn tc cc phn ng theo
phng trnh bc mt nh sau :
( )

= =
RT
E
x k
dt
dx
V exp 1 hay
x
t k

=
1
1
ln '
vi x l phn khi lng nguyn liu b chuyn ho.
Nng lng hot ho (E) thay i theo bn cht v thnh phn ca nguyn liu.

Nguyn liu E (kJ/mol)
Cn chng ct kh quyn
Cn chng ct chn khng
Cn chng ct chn khng tch asphalte
315
230
150

Cc phn ng to thnh asphaltne v to cc c nng lng hot ho t 250 380
kJ/mol. Nng lng hot ho ny cng ln khi nhit tng ln.

II. Cc thng s ca qu trnh :
II.1 Cc thng s vn hnh :
Cng ngh lc du
TS. Nguyn Thanh Sn
3
II.1.1 Nhit khi ra khi l (t
s
) :
Mc d cc phn ng xy ra trong vng nhit tng trong cc ng truyn nhit trong l
t nhng nhit sau khi ra khi l vn c xem nh mt thng s vn hnh, nhit ny
nm trong khong 430 490C tu thuc vo loi nguyn liu v cng ngh. Nu trong s
cng ngh, sau l t c lp t mt bung lm ngui (chambre de maturation soaker) m
trong cc phn ng c th tip din, trong trng hp ny nhit sau khi ra khi l c th
chn theo chuyn ho mong mun : tng nhit ny ln 6 -7C s lm tng chuyn ho
ln 1% nhng n b gii hn trn do s kt ta cc asphaltne trong cn gim nht.
II.1.2 Lu lng nguyn liu :
Khi tng lu lng nguyn liu s lm gim thi gian lu trong thit b phn ng nhng
ng thi cng lm bin i ch chy trong cc ng truyn nhit v trong bung lm ngui.
Khi lu lng tng ln 10%, nu mun gi nguyn chuyn ho c th tng nhit sau khi ra
khi l (t
s
) ln 3C b tr hiu ng do tng lu lng.
II.1.3 p sut :
Trong s cng ngh khng c bung lm ngui, p sut ch cn vi bars l trnh
hin tng ho hi ca nguyn liu. Trong s c bung lm ngui, p sut c chn sao cho
cc sn phm mong mun phi trng thi hi v thot nhanh khi vng phn ng, trong khi cc
sn phm nng lm ngui trng thi lng. Trong thc t tu thuc vo loi nguyn liu m
chn p sut ph hp, vi cn nng (rsidu court) th p sut vo khong 5-8 bars v cn nh
(rsidu long) th p sut vo khong 10 12 bars.
II.1.4 Phun hi nc vo trong ng cp nhit:
Phun hi nc vo trong ng cp nhit ci thin s truyn nhit trong cc ng. Qu
trnh ny s lm gim chuyn ho, b tr chuyn ho b gim c th tng nhit ca
l.
II.2 Hiu sut v c tnh ca cc sn phm:
Trong qu trnh gim nht, ngi ta thu c 4 sn phm: phn on kh (C
4
-
), xng
(C
5
165C), gasoil (165 350C) v cn (350C
+
). Hiu sut ca cc sn phm ny cng nh
c tnh ca chng ph thuc vo bn cht ca nguyn liu v chuyn ho thu c trong cc
iu kin vn hnh thch hp.


Cng ngh lc du
TS. Nguyn Thanh Sn
4
Bng 1 : Hiu sut in hnh
Ch vn hnh Mt giai on, khng hi
lu, khng lm ngui
Hai giai on (*), c hi
lu, khng lm ngui
Loi nguyn liu
d
4
15

V
50

Hiu sut (% kl)
C1 C4
Xng (C5 165C)
Gazole (165 350C)
Cn 350C +
chuyn ho (%)
Rsidu court
1,010
42,0

1,9
4,1
11,7
82,3
6,0
Rsidu long
0,978
34,6

3,6
7,8
25,8
62,8
11,4
(*) Gim nht v cracking nhit DSV

Bng 2 : Hiu sut so vi chuyn ho
Sn phm Hiu sut/ chuyn ho
C
4
-

Xng
Gazole
H
2
S
0,32
0,68
2,3
0,01 ca % S trong nguyn liu (*)
(*) Gi tr trung bnh ph thuc vo bn cht ca S trong nguyn liu

II.2.1 chuyn ho :
chuyn ha c nh ngha bng tng lng kh (H
2
S, C
4
-
) v xng so vi lng
nguyn liu ca qu trnh. Ngi ta xc nh gi tr ny khi xem xt n 3 yu t :
Cng ngh lc du
TS. Nguyn Thanh Sn
5
- Bn cht v c tnh ca nguyn liu
- Cc c trng ca qu trnh (l t c km theo bung lm ngui hay khng)
- Cc sn phm mong mun nhn c
Cc yu t ny khng c lp vi nhau ; vi mt loi nguyn liu cho, ngi ta phi
vn hnh qu trnh sao cho cc sn phm thu c trong iu kin ti u (lng cc to thnh
trong l thp, thi gian dng bo dng phi ngn, cn gim nht phi c n nh cao).
Trong thc t, trong cc phn xng gim nht, chuyn ha (ph thuc theo ngun
gc nguyn liu) thay i t 6 n 7 %. Trong trng hp mun sn xut lng gazole cc i,
chuyn ha c th t n 10 12%.

Loi du th chuyn ha (% kl) so vi nguyn liu
Arabe nng
Iran nng
Koweit
Nigeria
Brent
Sarin (paraffinique)
Souedieh (asphaltnique)
6,0
6,5
7,0
7,0
7,0
4,0
5,5

Hnh 1 : Quan h gia chuyn ha v n nh ca sn phm


Cng ngh lc du
TS. Nguyn Thanh Sn
6
II.2.2 Cht lng sn phm
- Phn on kh (C
4
-
) cha cc kh tr (CO, CO
2
, N
2
), H
2
S to thnh t qu trnh chuyn
ha nguyn liu v cc hydrocacbon t C
1
n C
4
. Hm lng S trong phn on ny cao
hn trong nguyn liu t 2-5 ln. H
2
S phi c loi b bng qu trnh x l bng amine
trc khi a i s dng nh LPG hay kh t. Phn on HC cha cc lng bng nhau
cc HC khng no (thylne, propylne, butnes) v cc ng ng bo ha ca chng.
- Xng (C
5
165C) l loi nhin liu c cht lng thp : ch s octane thp, hm lng
olfin cao ( 45%), hm lng S ln (0,2 0,5 ln hm lng S trong nguyn liu), n c
cha cc hp cht ca nit. Trong xng ny cng c cha cc diolfin (thng qua ch s
anhydride malique, I
AM
= 10). Khi s dng xng ny lm nguyn liu cho qu trnh
reforming xc tc cn phi x l bng hydro.
- Gazole (165 350C) c ch s cetane thp (<= 50), n cha t 2 3% lu hunh
(0,4 0,8 ln hm lng S trong nguyn liu). Mu ca n (xc nh theo ASTM) thay
i rt nhanh do s oxy ha bng khng kh. Hm lng olfin trong gazole ny rt cao
(ch s Brm khong 25). Khi hm lng S ca gazole ny thp th n c th c s
dng nh l cht pha long cho du nng lm gim nht. Khi hm lng S cao th
n phi c x l trong phn xng HDS ci thin ch s Cetane, n nh v mu
ca n. Khi n c th c s dng nh l mt thnh phn phi trn gazole thng
phm.
- Cn (350C +) l mt loi du t c nht c ci thin so vi nguyn liu. Tuy
nhin t n tiu chun ca sn phm thng phm cn phi b sung mt lng
gazole pha long. lm c iu ny cn phi hiu r quy tc phi trn gia du t
v cht pha long. Ngi ta nh ngha ch s trn ln V theo cng thc sau :
) 85 , 0 log( log 5 , 33 ) ( + + =
t t
t A V
Trong :
- t : nhit khi xc nh
- A : hng s ph thuc vo nhit (A
50
= 19,2 ; A
100
= 26,4)
-
t
: nht nhit t (mm
2
.s)
i lng V
t
c tnh cng theo khi lng v n cho php tnh ton nht ca hn hp
fuel-gazole. Ngi ta cng c th xc nh c lng gazole pha long cn thit thu c
mt fuel t tiu chun thng mi.
Cng ngh lc du
TS. Nguyn Thanh Sn
7
Tiu chun cht lng ch yu ca loi du ny l n nh, bi v n cha mt lng
asphaltne trng thi huyn ph. Nh vy gazole pha long phi c hm lng HC thm cao
(LCO, phn on chit HC) c kh nng phn tn cc asphaltne.
II. 3 Cng ngh ca qu trnh gim nht :
II.3.1 S cng ngh :
Nguyn liu sau khi un nng s b c a vo mt l ng nng nhit ln n nhit
cracking. Sau khi ra ra khi l cc phn ng cracking b ngng li do b lm lnh bi dng
gazole hay cn c nhit thp. Hn hp hydrocacbon sau khi i qua mt thit b tch dng
cyclon c a n thit b tch phn on thu c cc sn phm C
4
-
, xng v gazole (m
mt phn trong c dng lm lnh) v cn gim nht.

Hnh 2 : S cng ngh c trng ca qu trnh gim nht
Trong mt vi trng hp, hn hp sau khi ra khi l c a n mt bung lm lnh.
Mc ch ca bung ny l ko di thi gian lu (thi gian phn ng) v cho php vn hnh
l nhit thp hn khong 30C.
Nu chng ta mong mun thu c lng gazole cc i, chng ta c th kt hp mt
qu trnh gim nht v mt qu trnh cracking nhit ca phn ct nng t thp chng phn on
nh m t trong hnh sau
Cng ngh lc du
TS. Nguyn Thanh Sn
8

Hnh 3 : S cng ngh gim nht c b tr mt bung lm lnh (soaker drum)

Hnh 4 : S cng ngh ci tin ca phn xng gim nht thu c lng gazole cc i

II.3.2 Cc thit b c trng :
II.3.2.1 L t :
Vai tr ca n l nng nhit ca nguyn liu n nhit phn ng v duy tr nhit
ny thi gian kh di thu c chuyn ha mong mun.
Cng ngh lc du
TS. Nguyn Thanh Sn
9
Cc loi l khc nhau :
- Loi l trong s truyn nhit c thc hin ch do s i lu hoc ch do s bc x
hay kt hp c hai phng thc truyn nhit trn.
- L c nhiu phng bc x ni tip nhau
- L c cu to t cc ng thng ng v ng nm ngang
- L dng nhin liu kh hoc du t
Tuy nhin cc loi l ny phi tun th mt vi yu cu m bo vn hnh tt :
- Dng nhit trung bnh phi t 22 30 kW/m
2
; trong mi trng hp dng nhit cc b
khng c vt qu 60 70 kW/m
2
hu qu s gia tng s ng cc gy hi cho s vn
hnh ca l (tng tn tht p sut (tr lc), tng nhit thnh ng).
- Cc ng phi chu c nhit 650 C. Thng thng ngi ta chn loi vt liu thp
hp kim (9 Cr 0,5 Mo).
- Cc thit b phun hi nc hoc condensat phi c lp t trong vng ni m s bay
hi ca cc HC l thp tng s chy xoy ca dng lu th nhm lm gim s ng
cc. T l phun hi nc so vi nguyn liu vo khong 0,5 %.
- Cc thit b tch cc l khng th thiu. Chng bao gm mt thit b phun hn hp khng
kh/hi nc cho php tch cc trong l nhit khong 550C.

Hnh 5 : L cp nhit ca phn xng gim nht
II. 3.2.2 Bung lm lnh :
l mt bnh t ngay sau l t cho php tng thi gian lu ca nguyn liu v vn
hnh nhit trong l thp hn. Trong thit b ny cc phn ng cracking xy ra khong 40
60%. Cc phn ng ny l phn ng thu nhit, nhit ra thp hn nhit vo 10 20C.
Cng ngh lc du
TS. Nguyn Thanh Sn
10
Nhit ra ca l (C) Thi gian lu (pht)
410
440
455
470
500
32
8
4
2
0,5
C bung lm lnh
C bung lm lnh
C bung lm lnh
Khng c bung lm lnh
Khng c bung lm lnh

Bung lm lnh l mt thit b phn ng vi dng lu th chy t di ln trn, c th
tch vo khong 15 m
3
/1000 t/ngy vi t l gia chiu cao v ng knh t 5 8. Cc kch
thc ny tng ng vi mt thi gian lu l t 15 20 pht.
Nh vo thit b ny ngi ta thu c cc li ch sau :
- Gim s tiu th nhin liu 15 % do nhit ra khi l h t 20 n 30C ;
- Tng khong thi gian gia hai ln tch cc do vn tc ca s ng cc trong l gim t
3 4 ln.
- tuyn chn cao hn do s chnh lch v nng lng hot ha ca s to thnh cc cu
t nh (250 kJ/mol) v cc cu t nng hn (230 kJ/mol). V vy s tham gia ca gazole
vo s hnh thnh xng v kh s thp hn khi trong s c bung lm lnh. Kt qu l
s chuyn ha cc phn on nng s cao hn.
- Gim gi thnh ca l v thit b gia nhit, t dn n gim u t ban u t 10
15%.
Nhng kt qu nghin cu gn y v bung lm lnh cho thy khi lp t cc a l
nhm lm ng nht ha thi gian lu ca cc phn khc nhau trong nguyn liu s lm tng
chuyn ha.
II.3.2.3 Thit b tch dng cyclon :
Chc nng ca loi thit b ny l phn tch cc sn phm ca phn ng thnh 2 pha lng
v kh m khng lm gim nhit . Qu trnh tch xy ra phn trn ca thit b, dng lu th
i vo thit b theo phng tip tuyn m bo phn tch tt 2 pha kh / lng. Pha lng chy dc
theo thnh thit b v tp trung phn di. Mt phn cht lng b lm lnh do trao i nhit vi
nguyn liu v c s dng nh l cht lm lnh cho phn di ca thit b.
Cng ngh lc du
TS. Nguyn Thanh Sn
11
QU TRNH CC HA
Qu trnh chuyn ha cc phn on nng di tc dng ca nhit c pht trin trn
c s 2 cng ngh khc nhau :
- Cng ngh th nht c gi l cc ha tr (cokfaction retarde delayed coking), y
l qu trnh phn hy nhit c thc hin trong mt thit b phn ng rng trong cc
to thnh trong phn ng s lng ng, cc sn phn phm nh s thot ra i v cc thit
b x l. Cng ngh ny hin nay c s dng rt nhiu trong cng nghip. Nhiu cng
ty hot ng trong lnh vc du kh (Foster Wheeler, Conoco, Lummus) c nhiu b
quyt cng ngh xy dng, lp t v vn hnh loi cng ngh ny.
- Cng ngh th hai l cng ngh Flexicoking, c pht trin bi Exxon Research and
Engineering Co. Trong cng ngh ny, s chuyn ha cc hydrocacbon xy ra trong mt
lp tng si to thnh t cc ht cc, mt phn lp ht ny c trch ra mt cch lin
tc.
I. Qu trnh cc ha tr :
Cng ngh ny c s dng rng ri trong cng nghip lc du. M, n c s dng
rng ri, mc ch ch yu l chuyn ha cc cn nng thnh cc sn phm trng (LPG, xng),
cc c s dng nh l mt cht t. Chu u, n c s dng sn xut mt lng cc
ch cung cp cho cng nghip sn xut nhm, sn xut cc in cc in phn bauxite.
Qu trnh cc ha tr l mt qu trnh rt linh hot, n c th x l nhiu loi nguyn liu khc
nhau v sn xut cc loi cc c cht lng khc nhau theo nhu cu ca th trng.
Tn gi cc ha tr xut pht t nguyn nhn l trc khi vo thit b cc ha nguyn liu
c un nng trong l cp nhit ln n nhit cao hn nhit to cc, nhng vn tc ca
nguyn liu i trong ng truyn nhit rt ln (thi gian lu gim n ti thiu) v phn ng cc
ha xy ra trong thit b to cc thay v trong ng truyn nhit.
I.1 Nguyn liu :
Cc phn xng cc ha tr c th x l cc loi nguyn liu cn nng nh :
- Cn qu trnh chng ct chn khng
- Cn ca qu trnh cracking xc tc (decant oil hoc slurry)
- Cn ca qu trnh gim nht hoc goudron ca cracking xc tc
- Asphalte hay phn trch ca du nht
Cng ngh lc du
TS. Nguyn Thanh Sn
12
Hiu sut v cht lng ca cc sn phm ph thuc vo 4 c trng : hm lng cacbon
Conradson v lu hunh, hm lng kim loi, im phn on TBP.
I.1.1 Hm lng cacbon cn (CCR):
mt iu kin cng ngh xc nh, hm lng cacbon cn cng cao, hiu sut thu hi
cc cng cao. Thng thng, mc tiu l thu cc i cc phn on trung bnh v sn xut ti
thiu cc, v th khi hm lng cacbon cn cng ln th mc tiu ny cng kh t c. Trc
y, cc gi tr CCR thng nh hn 10% (nguyn liu l cn chng ct kh quyn - RAT), ngy
nay ngi ta s dng cc loi cn nng hn t cc loi du th nng nn CCR c th ln n
20% thm ch 30%.
I.1.2 Hm lng lu hunh
Lu hunh trong cn thng c khuynh hng tp trung trong cc v phn chng nng.
Cng nh CCR, ngun gc ca nguyn liu c nh hng n hm lng lu hunh, v do
nh hng n hm lng S trong cc.
I.1.3 Hm lng kim loi
Hm lng cc kim loi, ch yu l Ni v V, c khuynh hng ngy cng cao trong nguyn liu.
Trong qu trnh cc ha, lng kim loi ny s nm li hu ht trong cc, hm lng c th n
1000 ppm.
I.1.4 im phn on TBP
im phn on TBP ca cn chng ct chn khng l khong 550C, nhng n c th
thay i theo ngun gc ca du th v vn hnh ca phn xng chng ct chn khng. im
phn on TBP c lin quan n CCR, hm lng S v hm lng kim loi. N nh hng n
hiu sut v cht lng cc sn phm ca phn xng cc ha.
I.2 C s qu trnh :
I.2.1 Cc phn ng ha hc
C ch chnh xc ca cc phn ng cc ha kh phc tp, nn vic m t cc phn ng v
qu trnh chuyn ha trong thit b phn ng rt kh khn. Ngi ta c th nh danh hai c ch
ch yu cng tn ti xy ra vi nhiu loi nguyn liu v 3 giai on ring bit v ni tip nhau
trong cc thit b phn ng.
C ch th nht da vo cc phn ng tch nhm alkyl (dsalkylation) - kt ta t cc
hp cht c khi lng phn t ln, cc asphaltne v hp cht nha.
C ch th hai da vo cc phn ng ngng t cc hp cht polyaromatic.
Cng ngh lc du
TS. Nguyn Thanh Sn
13
Ba giai on c th nh danh trong qu trnh l :
- Bay hi tng phn v cracking s b trong khi nng nhit ln n nhit ca thit b
phn ng
- Cracking pha hi khi n i qua thit b phn ng
- Cracking lin tip v trng hp pha lng lu li trong thit b phn ng cho n khi n
chuyn ha thnh cc.
Cc phn ng ny u l phn ng thu nhit v lm gim nhit trong thit b phn ng khong
50C.
I.2.2 iu kin vn hnh :
Ba thng s vn hnh quyt nh n hiu sut ca qu trnh v cht lng sn phm l :
nhit , p sut v t l hi lu phn sn phm cn nng sau thit b phn ng.
a/ Nhit :
Nhit cc ha (485 505C) c tc ng trc tip n hm lng cc cht d chy
(VCM volatil combustible matter) trong cc. nhit cao, phn ln nguyn liu s b bay
hi ti vng tip liu ca thit b phn ng v gp phn lm gim to thnh cc. p sut v t
s hi lu khng i, hiu sut thu cc gim khi tng nhit . Nhng, nhit qu cao, cc
to thnh s rt cng v rt kh tch bng ct thy lc. nhit qu thp, cc to thnh s rt
mm vi hm lng VCM cao.
b/ p sut :
nhit v t s hi lu khng i, khi p sut tng s duy tr cc hydrocacbon pha
lng trong thit b phn ng v do s lm tng hiu sut thu cc v kh. Khi mc tiu chnh
ca phn xng cc ha l ci thin chuyn ha ca nh my lc du th cn gim n mc
thp nht hiu sut thu cc v tng ti a hiu sut thu cc trung gian. Trong trng hp ny r
rng l phi vn hnh qu trnh p sut cng thp cng tt. nh hng ca p sut n hiu
sut cc sn phm c gii thiu trong bng sau.
p sut cc ha (bar) 1,0 3,0
Kh + C4 (% kl)
C5 195C naphta (% kl)
195C
+
distillat (% kl)
Cc (% kl)
9,1
12,5
51,2
27,2
9,9
15,0
44,9
30,2
Cng ngh lc du
TS. Nguyn Thanh Sn
14
c/ T s hi lu :
T s hi lu cng c nh hng tng t nh nh hng ca p sut n s phn b cc
sn phm. T s hi lu cng cao, hiu sut thu cc v kh cng cao. Thc t, t s hi lu s
khng ch im cui ca phn ct nng, t s ny cng cao th lng sn phm nng hi lu v
thit b phn ng cc ha, ti n s b chuyn ha thnh cc v kh. Khi mun thu ti a sn
phm lng th phi gim t s hi lu. Tuy nhin, khi gim t s hi lu, cht lng ca phn ct
nng s t l nghch vi hiu sut thu phn on ny nh ch ra trong bng :
p sut (bar)
T s hi lu (%)
1,7
15
1,0
5
Hiu sut (% kl)
c trng ca distillat
D
4
20

CCR (%kl)
25,7

0,936
0,35
35,2

0,957
0,8

I.3 Sn phm :
I.3.1 Kh :
Gm hai phn : mt phn l C1 C2, c s dng lm kh t trong phn xng cc
ha hoc a i lm kh t trong nh my lc du (sau khi ra bng amine- ethanol amine),
mt phn khc l C3-C4. Sau khi tch lu hunh (ra bng amine v loi b cc mercaptans
bng Merox) do c cha nhiu olfin, chng c th c s dng lm nguyn liu cho qu trnh
alkyl ha hoc polyme ha.
I.3.2 Naphta :
Naphta nh sau khi loi b mercaptans hoc tch loi lu hunh bng hydro, s c a
i phi trn xng.
Naphta nng, sau khi kh lu hunh, c s dng lm nguyn liu cho reforming xc
tc, hoc a i phi trn xng do c hm lng olfine cao.
I.3.3 Phn ct :
Phn ct nh cn phi c x l bng hydro n nh mu trc khi a i phi trn
trong sn phm gazole.
Cng ngh lc du
TS. Nguyn Thanh Sn
15
Phn ct nng thng c s dng lm nguyn liu cho qu trnh FCC, bng cch phi
trn vi cc sn phm ca qu trnh chng ct trc tip. N c th c s dng lm nguyn liu
cho qu trnh hydrocracking tng hiu sut thu xng, krosne v gazole.
I.3.4 Cc
Cc thu c t qu trnh cc ha tr c th c trng mt cch n gin theo hnh dng
c trng bn ngoi : cc xp (sponge coke), cc hnh kim (needle coke), cc dng vin (shot
coke).
Cc xp c dng tng ming hnh dng khng ng nht, xp ln. Loi ny thng
lm cht t, mt vi loi c hm lng lu hunh v kim loi thp c th c s dng lm
anode trong sn xut nhm.
Cc hnh kim l loi cc c cht lng tt nht ca qu trnh cc ha tr. N c dng
hnh kim v c cu trc tinh th di rt nh. Do n c CTE v in tr b nn n c th c
dng lm in cc trong sn xut thp.
Cc dng vin l sn phm khng mong mun c hnh dng vin nh, n thng c
phi trn vi cc xp s dng lm nhin liu trong thit b sn xut hi nc (cogenerator).
Ty thuc vo mc ch s dng m cc thu c t du m c th c phn loi thnh hai
hng : Fuel grade coke bao gm cc xp v cc vin v cc c bit (specialty coke) bao gm
cc lm anode, cc kim v mt vi loi cc c ngun gc khc.
* Fuel grade coke bao gm phn ln lng cc thu c t cc ha tr. Cc c trng
ca loi cc ny cho trong bng sau :
Bng 2. c trng ca Fuel Grade Coke
Heat content 13000 ~ 15000 BTU/lb
Volatile Combustible Matter (VCM) ~ 10%
Sulfur > 2.5 wt %
Ash 0.1 ~ 0.3 wt%
HGI (Hardgrove Index) ~ 100
Vanadium >200 ~ 400 ppm

M, loi fuel grade coke dc s dng trong hai lnh vc chnh : cc nh my in v
l nung xi mng s dng t chy hn hp cc v than .
Cng ngh lc du
TS. Nguyn Thanh Sn
16
u im ca cc khi s dng lm nhin liu trong cc qu trnh ny l : cc c BTU cao
hn than (10500 ~ 13000 BTU/lb i vi than en mm), v hm lng tro thp (hu ht cc
loi than u c hm lng tro l 10%).
Mt tr ngi ln khi t chy loi cc ny l n c hm lng thp cc cht bay hi
(VCM), so vi 20~40% i vi than en mm. Hm lng VCM thp s dn n mt s hu qu
: trc ht m bo qu trnh chy n nh th phi phi hp cc vi than s dng nh
l ngun nhin liu. iu ny cng s gii hn lng cc trong hn hp. Ni chung, nhin liu
cho ni hi c th s dng n 20% coke trong hn hp; i vi l nung chm c th dng n
50% coke trong hn hp. Hu qu khc l cc phi c nghin mn (normally pass 90% 200
mesh compared to 65~80 % of coal).
Specialty coke
Loi cc ny cn phi c nung nhit cao (2000 ~ 2300F) loi b m, cc
cht hu c d bay hi v tng t trng thc.
*Anodes coke thng c s dng ch to anode trong in phn nhm. Cng
nghip sn xut nhm l ni s dng nhiu nht loi cc ny. Khi s dng sponge coke lm
anode, cn phi ch n cc vn sau :
- Hm lng Vanadium v nickel s nh hng rt ln n l luyn nhm, v chng ng
vai tr nh l cht xc tc oxy ha anode trong qu trnh in phn lm tng s tiu th anode.
- Natri c trong cc cng xc tc cho qu trnh oxy ha anode.
- T trng v kch thc ca cc l cc thng s vt l nh hng n cu trc ca anode
do s nh hng n tnh cht c hc.
in phn nhm l mt qu trnh tiu th anode (cacbon). Phn ng ha hc c th c
biu din nh sau :
2Al
2
O
3
+ 3C > 4 Al + 3 CO
2

Hin nay ngi ta s dng hai loi anode: Prebaked anode v Soderberg anode.
Lng anode tiu th tiu th i vi cc loi anode :
- Prebake anodes 0.44 kg/kg nhm
- Soderberg anodes 0.50kg/kg nhm.
Mt vi c trng ca cc anode c trnh by trong bng 3.

Cng ngh lc du
TS. Nguyn Thanh Sn
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Bng 3 : c trng ca Anodes Coke
Green Calcined
VCM, wt%, Dry Basis 8-10 0.3
Sulfur, wt% 3.0 Max. 3.0 Max.
Ni ppm 0.3 Max. 0.3 Max.
V ppm 200 Max. 200 Max.
HGI 80
VBD g/cm3 0.78 Min.
Real Density g/cm3 2.06 Min.
Granulometry +4 mesh
-28 mesh
40%
10%

Cc hnh kim (Needle coke) l loi cc thu c t qu trnh cc ha tr. Hin nay ch
cn mt s t nh my sn xut loi cc cht lng cao ny. C nhiu cng trnh nghin cu v
qu trnh hnh thnh cc hnh kim, la chn nguyn liu v chun b nguyn liu. Trong cc qu
trnh cng nghip, iu quan trng cn phi tnh n khi mong mun sn xut cc hnh kim cht
lng cao l la chn nguyn liu ph hp. Thng thng cc loi nguyn liu sau thng c
xem xt :
- Slurry oil c hm lng lu hunh thp ca qu trnh FCC (decanted oil)
- Nha ng chuyn ha t gasoil bng qu trnh craking nhit.
- Decanted oil kh lu hunh.
- Coal Tar Pitch
Tt c cc nguyn liu phi c API thp, hm lng lu hunh v kim loi thp, hm
lng asphalten v thm ha (aromaticity) cao.
Qu trnh sn xut cc kim trong cng ngh cc ha tr s rt khc bit vi qu trnh sn
xut cc lm nhin liu v cc lm anode. Mc tiu trong cng ngh ny l thu c ti a cc
kim c cht lng cao, cc sn phm lng l sn phm ph. t c mc tiu cn p
dng nhit cao v p sut cao, t s hi lu ln. Ni chung, nhit ca qu trnh cao hn
Cng ngh lc du
TS. Nguyn Thanh Sn
18
khong 50F so vi qu trnh sn xut cc dng lm nhin liu v p sut cao hn 50 90 psig,
t s hi lu nm trong khong 60 % - 100%.
Bng 5: Cc c trng ca cc hnh kim (Needle Coke)
Green Calcined Graphite Artifact
VCM, wt%,Dry Basis 5-7
Sulfur, wt% 0.5 Max. 0.5 Max.
Ash wt% 0.1 Max. 0.1 Max.
Real Density g/cm3 2.10-2.14
CTE, x10-7/C 2.5 (30-125C)
in tr, Ohm-in,x10-6 320
Flexural Strength, psi 2500
Granulometry @ -1.0 mm 25% Max.

I.4 S cng ngh :
Nguyn liu ban u c a vo y ca thp chng phn on. Ti y n c trn
ln vi dng sn phm ra t nh ca hai thp to cc. Trong thp chng phn on qu trnh
phn tch s xy ra. nh thp ta thu c dng sn phm nh. Dng sn phm ny sau khi
c ngng t s c cho qua bnh tch. Khi kh s c tch ra pha trn v lng ly ra
pha di l Unstabilized Naphta. Mt phn lng ny s c hi lu tr li thp chng phn
on. phn thn ca thp chng phn on ngi ta cng thu c sn phm trung bnh. Dng
sn phm ny sau khi qua thit b Stripper tch phn nh hi lu tr li thp chng th thu
c Gas Oil.
Dng sn phm y ca thp chng phn on c dn qua mt l t nng nng nhit
ln n 770 K ri c a vo hai thp luyn cc t pha di.
Trong hai thp luyn cc, qu trnh cc ho v ct tch cc din ra. p sut lm vic trong hai
thp luyn cc khong 2 bar. Khi qu trnh kt thc sn phm cc c ly ra y ca hai thit
b luyn cc, cn phn sn phm nh ca qu trnh cc ho c nhit 710 K c ly ra nh
hai thp luyn cc s c dn vo thp chung phn on trn chung vi dng nguyn liu
ban u.

Cng ngh lc du
TS. Nguyn Thanh Sn
19

Hnh 1 : S cng ngh ca qu trnh cc ha tr
Ngoi h thng cc ha tr truyn thng th hin nay Cng ty Foste Wheeler USA ci tin v
thit k h thng cc ha tr SYDEC vi nng sut v cht lng sn phm cao hn.
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