XC TC NH MY M PH M

GVHD: TS. NGUYN HU LNG

i Hc Bch Khoa TP. H Ch Minh

Khoa CN Ha & Thc Phm
Nghnh K Thut Ha Du

MN: XC TC CNG NGHIP TRONG CH BIN DU KH

TI : XC TC TRONG NH MY M
PH M

GVHD : TS. Nguyn Hu Lng

HVTH : Nguyn nh Phc
MSHV : 10400160
Lp

: KTHD-CH2010

Thng 12 nm 2010
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Mc Lc
1

Lch s hnh thnh v pht trin: ............................................................................... 1

Nguyn liu sn xut v sn phm nh my: ............................................................. 1

2.1

Nguyn liu sn xut: ........................................................................................ 1

2.2

Sn phm: .......................................................................................................... 2

Qui trnh cng ngh: ................................................................................................. 4

3.1

Phn xng Ammoniac: .................................................................................... 4

3.1.1

Kh lu hunh:........................................................................................... 4

3.1.2

Cng on Steam Reforming: ..................................................................... 6

3.1.3

Chuyn ha CO: ....................................................................................... 10

3.1.4

Cng on tch CO2: ................................................................................ 11

3.1.5

Cng on mtan ha: .............................................................................. 14

3.1.6

Cng on tng hp NH3: ......................................................................... 16

3.2

Phn xng sn xut Urea: .............................................................................. 18

3.2.1

B phn nn CO2: ..................................................................................... 18

3.2.2

B phn tng hp Urea v thu hi NH3, CO2 p sut cao: ...................... 19

3.2.3

Lm sch Urea v thu hi NH3, CO2 trung v thp p: ........................... 19

3.2.4

C c Urea: ............................................................................................. 21

3.2.5

To ht Urea: ............................................................................................ 22

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XC TC TRONG NH MY M PH M
1 Lch s hnh thnh v pht trin:
- Nh my m Ph m t ti khu cng nghip Ph M 1, huyn Tn Thnh, tnh B
Ra- Vng Tu l nh my phn bn ln v hin i u tin ca Tng cng ty du kh Vit
Nam.
- Nh my c vn u t 370 triu USD, c xy dng trn din tch 63 hecta, s dng
cng ngh ca hng Haldor Topsoe (an Mch) sn xut Ammoniac v cng ngh ca
hng Snamprogetti (Italy) sn xut Urea (cng sut 740.000 tn/nm). y l cng ngh
vi dy chuyn khp kn u vo l kh thin nhin, u ra l Urea v Ammoniac lng. Chu
trnh cng ngh khp kn cng vi vic t to in nng v hi nc gip nh my hon
ton ch ng trong sn xut k c khi li in quc gia c s c hoc khng in
cung cp.
- Nh my c khnh thnh v i vo hat ng vo ngy 22/9/2004.

2 Nguyn liu sn xut v sn phm nh my:

2.1 Nguyn liu sn xut:
Hot ng ca phn xng Amnic c m t trong lc di y:

Hi trung p
Kh thin nhin
Ammonia

Nc kh khong

Ccbon ixt
Khng kh
in

PHN XNG
AMNIC
Condensate t tuc-bin
Condensate cng ngh

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Hot ng ca phn xng Ur c m t trong lc di y:

Hi thp p

Ammonia

Urea
PHN XNG UREA

Kh ccbon ixit

Condensate t hi

in
Condensate t qu trnh

Nguyn liu chnh ca nh my l kh ng hnh Bch H, ngoi ra c th s dng

kh thin nhin t bn trng Nam Cn Sn v cc b khc thuc lc a pha Nam. Lng
kh tiu th cho nh my khong 53.000 54.000 NM3/h (khong 450 triu m3/nm). Kh
thin nhin l hn hp cc Cacbua Hydro nh, ch yu l Metane (CH4). Kh thin nhin c
th khai thc t m kh hoc c tch ra t kh ng hnh ti cc m du.

Nit: Nguyn liu tng hp NH3 v c ly t khng kh.

Hydro:c to ra nh phn ng Reforming kh thin nhin bng hi nc, l
nguyn liu tng hp NH3.
CO2:l nguyn liu tng hp Urea, c iu ch t cng on Reforming kh
thin nhin.

2.2 Sn phm:
Sn phm ph-Ammoniac:
Ammonia tng hp c ch yu sn xut Urea. Lng cn d c a v bn
cha.
Cng sut 1350 tn Ammonia/ngy (tng ng khong 422.598 tn/nm).
NH3 (%wt)

99.8 min.

H2O (%wt)

0.2 max.

Oil (ppm wt) 5 max.

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Ammonia l cht kh c cng thc phn t NH3, ha lng iu kin p sut thng v
nhit thp (khong 320C) hoc iu kin nhit thng v p sut cao (khong 15
bar), c mi khai c trng.
Sn phm chnh - Urea:
Cng sut:

2200 tn/ngy.

C ht: 1.4 2.8 mm: >95%.

Hm lng N2:> 46.3%.
m: < 0.4%.
Hm lng biuret:

< 1%

Urea l hp cht ha hc c cng thc phn t CO(NH2)2, nhit thng Urea

khng mu, mi v, ho tan trong nc, nhit nng chy khong 1350C, t trng khong
1,3230. Urea thy phn chm to thnh Cacbamt Amn sau phn hy thnh NH3 v
CO2, y l c s s dng Urea lm phn bn. Trong cng nghip Urea c tng hp
t NH3 lng v CO2 kh iu kin nhit v p sut cao.

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Qui trnh cng ngh:

3.1 Phn xng Ammoniac:

3.1.1 Kh lu hunh:

Phn ln kh thin nhin nguyn liu c cha mt lng nh lu hunh tn ti dng

hp cht.
Xc tc dng cho cng ngh reforming bng hi nc th rt nhy cm vi hp cht
cha lu hunh, bi v chng s gy mt hot tnh hoc l nhim c xc tc. Do cc

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hp cht lu hunh phi c kh b trc khi i vo cng on Reforming. iu ny

c thc hin trong cng on kh lu hunh ca phn xng NH3.
Trong qu trnh kh lu hunh, cc hp cht lu hunh hu c c chuyn ha thnh
H2S bng xc tc hydro ha. Sau H2S c hp ph bng ZnO. Thnh phn lu hunh
vo reformer t cc ngun (kh nguyn liu, kh tun hon, hi nc) phi nh hn 0.05
phn triu khi lng.
Cng on kh lu hunh bao gm thit b hydro ha, 10-R-2001 v hai thit b hp
ph sulphur 10-R-2002A/B.
Xc tc cho 10-R-2001 l coban/molypden oxit v cht hp ph trong 10-R-2002A/B l
oxit km.

Qu trnh hydro ho ti thit b 10-R-2001:

Dng kh thin nhin cng dng kh hydro quay v t my nn 10-K-4031 i vo thit
b hydro ho 10-R-2001 nhit 4000C. Ti 10-R-2001, di nhit v xc tc cobaltmolybdenum oxit (TK-250), xy ra phn ng hydro ho:
RSH + H2
COS + H2

RH + H2S

CO + H2S

Ngoi cc phn ng hydro ho trn, xc tc TK-250 cn xc tin phn ng hydro ho

cc hp cht hydro cacbon khng no thnh cc hp cht hydro cacbon no v phn ng
chuyn ho cc hp cht Nit hu c thnh Ammonia v cc hp cht hydrocacbon no.
Trong sut qu trnh vn hnh, cc hp cht CO, CO2 trong kh nguyn liu cn c
hn ch n mc ti thiu. Nu c cc hp cht ny trong ngun kh nguyn liu s xy ra
cc phn ng gy nh hng n hm lng cc hp cht lu hunh ra khi thp hp th
lu hunh nh sau:
CO2 + H2

CO + H2O

CO2 + H2S

COS + H20

Trong trng hp hm lng cc hp cht CO cao s xy ra phn ng cc ho hnh

thnh lp mui cacbon bm trn b mt xc tc lm gim hat tnh ca xc tc

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2 CO

C + CO2

Qu trnh hp th lu hunh ti thit b 10-R-2002A/B:

Dng kh thin nhin sau khi hydro ho c a vo thit b hp th lu hunh 10-R2002A/B.
Hai thit b hp th ny ging ht nhau v c lp ni tip nhau. Thit b 10-R-2002B
ng vai tr h tr trong trng hp trong dng kh ra t 10-R-2002A cn lu hunh hoc
trong trng hp thay xc tc 10-R-2002A. Mi thit b c 3 tng xc tc cha 3 loi xc
tc HTZ. Nhit vn hnh bnh thng khong 4000C. Oxit km phn ng vi cc hydro
sulphide v carbonyl sulphide theo phn ng sau:
ZnO + H2S

ZnS + H2O

ZnO + COS

ZnS + CO2

ZnO khng phn ng oxy hoc hydro bt k nhit no. Trong qu trnh vn hnh
khng c hi nc lt vo 10-R-2002A/B, ZnO s b hydrate ho v khng th ti to
thnh ZnO trong thit b phn ng ti sinh.

3.1.2 Cng on Steam Reforming:

Qu trnh reforming hi nc c th c din t bi cc phn ng sau y:

CnHm + H2O
CH4 + 2H2O

CO + H2O

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Cn-1Hm-2 + CO + 2H2 Q

(1)

CO + 3H2 Q (2)
CO2 + H2 + Q (3)

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Phn ng (1) miu t c ch phn ng reforming hydrocacbon bc cao s chuyn ha

tng bc xung thnh nhng hydrocacbon bc thp, v cui cng thnh phn t metan, v
c chuyn ho nh trong phn ng (2). i vi hydrocacbon bc cao phn ng bt u
xy ra 500 0C v i vi metan 600 0C.
Nhit pht ra t phn ng (3) rt nh trong khi nhit cn cho phn ng (1) v phn ng
(2) l rt ln.
Phn ng xy ra theo hai bc, reforming s cp 10-H-2001 v reforming th cp 10R-2003.
Nhit cn thit cho phn ng trong hai thit b reforming c cp theo hai cch khc
nhau. Trong reformer s cp, nhit cn thit cho phn ng c cung cp di dng gin
tip t l t; trong reformer th cp, nhit c cung cp trc tip t qu trnh t ca kh
cng ngh vi khng kh. S chuyn ho trong reforming s cp s c iu chnh sao
cho khng kh s cp nhit cho reforming th cp m bo yu cu t l H2/N2= 3/1.
iu ny cn phi khng ch lng metan nh l kh tr trong kh tng hp mc cng
thp cng tt.
Hm lng metan trong kh cng ngh c khng ch bng hng s cn bng ca
phn ng (2) , gim khi tng nhit , tng hi nc v gim p sut.
Trc khi vo refomer s cp H-2001, hn hp hi nc v kh t nhin c hm
nng ln khong 535oC trong b hm 10-E-2001 nm trong b phn kh thi ca reforming
s cp. Sau c a vo cc ng thng ng cha xc tc.Cc ng xc tc c t
trong bung t reforming s cp, m bc x nhit c truyn t cc bc t n
thnh ng.
m bo chy hon ton kh nhin liu, cc bc t s vn hnh vi lng khng
kh tha khong 10% tng ng vi 2% th tch 02 trong kh thi.
Hydrocacbon trong kh nguyn liu vo reforming s cp c chuyn ho thnh hydro
v cabon oxit.
Khi vn hnh trng hp 1 vi HRU (thit b thu hi hydro) lm vic v s dng kh
thi c x l nh l kh nhin liu cho reforming, kh cng ngh ra khi reforming
nhit khong 7800C v hm lng metan khong 15% mol tnh theo kh kh.
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Khi vn hnh trng hp 2 vi HRU (thit b thu hi hydro) khng lm vic v s

dng kh thi khng c x l nh l kh nhin liu cho reforming, kh cng ngh ra khi
reforming nhit khong 8000C v hm lng metan khong 13% mol tnh theo kh
kh.
Trong khong khng gian trng pha trn ca reformer th cp ngi ta lp bc t 10J-2001, ti khng kh trn mt phn vo kh cng ngh. y xy ra ch yu l phn
ng chy lm nhit tng ln. T khong khng ny, kh cng ngh i qua lp xc tc
pha di, m phn ng reforming xy ra hon ton v lm ngui hn hp kh. Nhit
hn hp kh ra khi reformer th cp khong 958 oC v hm lng metan khong 0.6%
mol tnh theo kh kh.
Kh ra khi reformer th cp cha khong 13,5% mol CO v 7,5% mol CO2, chnh v
vy, s c nguy c hnh thnh cacbon theo phn ng Boudouard nh sau:
2CO CO2 + C (mui than)
Trong khi vn hnh reforming s cp cacbon c th hnh thnh mt phn pha ngoi v
pha trong xc tc. Cacbon nm pha ngoi ht xc tc s lm tng tn tht p sut trong
lp xc tc v pha trong ht xc tc s lm gim hot tnh v bn c hc ca xc tc.
t l hi nc v cacbon thp, vic hnh thnh cacbon c th xy ra v kt qu l
cacbon lng t, c bit l trong ht xc tc.Nu xc tc khng c hon nguyn trn
vn hoc mt phn b oxy ha, cacbon cng c th hnh thnh.

Reformer s cp:
Reformer s cp c tng cng 180 ng xc tc reformer c lp t trong hai bung
bc x nhit. Phn trn ca cc ng reformer c np xc tc loi RK-211 v RK-201,
trong khi phn y ca cc ng xc tc c np bng xc tc R-67-7H.
Cht xc tc bn trong khng kh n nhit 80 0C. Nu tip xc vi khng kh ti
nhit cao hn, n s b oxy ho, nhng nhit s khng nh hng g n xc tc.
Hn hp hi nc v kh thin nhin nhit khong 535 0C i vo nh ca cc ng
thng ng thng qua ng gp phn phi pha trn. Hn hp kh i ra khi ng nhit
khong 783 0C v i vo ng gom pha di.

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Cc ng xc tc trong bung t c t bng 480 bc t c sp xp 6 hng thng

ng trong mi bung nhm d dng kim sot profile nhit dc theo chiu di ca
ng xc tc. Bng cch ny s ti u ho vic x dng cc ng xc tc t tin. Khi thi i
ln v ra gn vi nh bung bc x nhit. Nhit khi i ra khong 1027 0C. Hn hp
kh t nhin v kh nh ra t cng on tch CO2 c t chung vi kh thi x l t
chu trnh tng hp NH3 trong cc bc t reforming s cp.

Reformer th cp:
Reformer th cp c np bi xc tc RKS-2-7H. Lp xc tc nm trn hai lp ca
cc ht nhm vi kch c khc nhau v li nhm c t trn nh ca lp xc tc gi
cht xc tc khi rung ng v bo v cht xc tc khi tip xc trc tip vi ngn la.
Trong reformer th cp qu trnh t kh cng ngh vi khng kh khin cho nhit
kh ln n 1100-1200oC trong phn trn ca reformer th cp. Do phn ng reforming vi
metan hp th nhit, nhit gim khi kh i xung di qua lp xc tc v ra nhit
khong 958 0C.
Cht xc tc bt u b phn r trong khong nhit t 1400-1500 0C.
Cht xc tc c hot ho khng c php tip xc vi khng kh ti nhit ln
hn 100 0C. V nhit to ra do phn ng oxy ho khng c gii phng khi bnh reformer
th cp, n c th dn n tnh trng qu nhit v ph hy cht xc tc.

Thu hi nhit tha:

Nhit tha ca khi thi t bung bc x nhit trong reformer s cp v ca kh cng
ngh i ra t reformer th cp c dng hm nng cc dng cng ngh khc nhau v
to ra hi nc siu cao p.

Thu hi nhit tha khi thi:

B gom khi thi t hai bung bc x nhit i vo cng on thu hi nhit tha khi
thi, ti y nhit tha khi thi c s dng :
-

Hm nng hn hp kh t nhin/hi nc trc khi i vo reformer s cp.

Hm nng khng kh cng ngh cho reformer th cp 10-R-2003.

Qu nhit cho hi nc cao p.

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Hm nng hn hp kh t nhin/hydro tun hon trc khi i vo hydroho/ hp

ph sulphur 10-R-2001.

Hm nng nc cp ni hi ca cng on thu hi nhit tha cng ngh.

Ti u ra nhit khi thi gim xung khong 162 oC.

Cng on thu hi nhit tha khi thi c ni vi ng khi thng qua qut khi 10K-2001. N ht khi ra mi trng thng qua ng khi reforming 10-SK-2001.

Thu hi nhit tha cng ngh:

Kh cng ngh ri cng on reforming i vo l hi nhit tha 10-E-2008 v b qu
nhit hi nc 10-E-2009.
Hi nc bo ho p sut 118 barg c sinh ra trong 10-E-2008. Trong 10-E-2009
hi nc c qu nhit t 324 ln 376 oC.
Kh cng ngh c lm ngui n 360 0C trong b qu nhit 10-E-2009 trc khi i
vo chuyn ho CO nhit cao 10-R-2004.

3.1.3 Chuyn ha CO:

Cacbon monoxit trong kh cng ngh ri khi cng on reforming c chuyn ho

thnh cacbon dioxit v hydro theo phn ng chuyn ho CO trong 10-R-2004 v 10-R2005:
CO + H2O CO2 + H2 + Q

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Cn bng ca phn ng chuyn ho chuyn v pha to thnh nhiu CO2 hn khi

nhit thp v c nhiu hi nc hn; tuy nhin tc phn ng do s tng nu
nhit cao hn. Nhit ti u cho phn ng chuyn ho ph thuc vo hot tnh ca
cht xc tc v thnh phn ca kh.
Do chuyn ho CO c hnh thnh qua hai bc va m bo tc ca phn
ng v hiu sut chuyn ho CO cao:

Bc th nht thc hin trong thit b chuyn ho CO nhit cao 10-R-2004,

c lp t xc tc SK-201-2 kim loi crom tng cng bng oxit st.

Bc th hai c thc hin trong thit b chuyn ho CO nhit thp, ti y

c np hai loi xc tc khc nhau. Lp trn nh l xc tc crome LSK, lng xc tc

ln hn l LK-821-2 bao gm oxt ng km crm hoc nhm v n c hot tnh cao hn.

Thu hi nhit tha:

Gia hai thit b chuyn ho CO, kh cng ngh c lm ngui bng chui cc trao i
nhit: Thit b cn bng nhit 10-E-2011, b qu nhit hi nc 10-E-2010 v b hm nng
nc l hi s mt 10-E-2012. Kh cng ngh c lm ngui bng chui cc trao i
nhit n nhit u vo thit b chuyn ha CO nhit thp l 190 oC.
Sau thit b chuyn ha CO nhit thp, kh cng ngh c lm ngui bng b hm
nng nc l hi s hai 10-E-2013, ni un tripper 10-E-3002 trc khi i vo cng on
tch CO2.

3.1.4 Cng on tch CO2:

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H thng tch CO2 c da trn qu trnh MDEA hot ho hai cp (cng ngh ca
BASF). Dung mi c dng cho qu trnh hp th CO2 l MDEA 03. H thng cng ngh
chnh bao gm mt thp hp th CO2 hai cp, mt thp gii hp CO2 v hai bnh tch flash.
Dng CO2 b tch khi kh cng ngh bi s hp th vo trong dung dch MDEA cha
40% MDEA. ng vai tr nh mt cht hot ho qu trnh hp th, dung dch MDEA cha
ng 3% khi lng cht piperazine, cht ny gip tng tc truyn khi ca CO2 t pha
kh sang pha lng. Phn cn li ca dung dch l nc. Phn ng tng th xy ra trong qu
trnh hp th CO2 c miu t bi cc phn ng di y:
R3N + H2O + CO2 R3NH+ + HCO32R2NH + CO2 R2NH2+ + R2N-COOPhn ng u l phn ng cho amine bc ba (v d MDEA). Phn ng th hai l phn
ng cho amine bc hai (v d piperazine).
Kh ri khi cng on chuyn ho CO c hm lng CO2 khong 8,2% mol (kh kh).
Do s c mt ca hi nc, kh ny cng cha mt lng nhit ng k c th thu hi
c, ch yu l nhit ngng t. Lng nhit ny c thu hi bi b gia nhit nc ni
hi s 2 (10-E-2013), ni un thp gii hp CO2 (10-E-3002) v b gia nhit nc mm
(10-E-3005). Sau kh nc ngng t qu trnh c tch ra khi dng kh trong bnh tch
kh cui cng 10-V-3004, kh ny i vo thp hp th CO2 ti nhit khong 75oC.
Trong thp hp th CO2 (10-T-3002), CO2 c tch ra khi dng kh bng hp th
ngc dng trong hai cp. Trong phn di ca thp hp th, dung dch bn thun ti sinh
c dng hp th phn ln CO2. Trong phn trn ca thp ny, dung dch thun ti sinh
c dng tch CO2 cn li. Ti u ra ca thp hp th, hm lng CO2 trong kh
gim xung thp hn 500 phn triu (kh kh).
Cc dung dch i vo thp hp th ti nhit 50oC (dung dch thun) v 73oC (dung
dch bn thun) v c gia nhit n khong 82oC bi cc phn ng hp th to nhit.
Dung dch giu CO2 ri khi thp hp th CO2 c gim p thng qua tuc bin thu lc
10-HT-3001, tuc bin ny ko mt trong nhng bm dung dch bn thun (bm 10-P-3001
A), do vy, gim mc tiu th nng lng ca qu trnh mt cch ng k. Tch ti sinh
dung dch giu CO2 c thc hin trong hai cp t c tinh khit cao ca sn

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phm CO2. Trong bnh tch cao p 10-V-3002, hu ht cc thnh phn kh tr ho tan
c gii phng ti p sut khong 5,5 barg. Dung dch giu CO2 tip tc n bnh tch
thp p 10-V-3001, ni m hu ht CO2 c gii phng khi dung dch ti p sut 0,27
barg.
CO2 thot ra khi bnh tch thp p cha y hi nc bo ho ti nhit khong
72oC. Hn hp ny c lm ngui n 45oC trong b lm lnh kh tch thp p 10-E3006, v nc ngng t c tch ra khi CO2 thnh phm trong bnh K.O. (10-V-3003).
CO2 thnh phm ri khi 10-V-3003 c xut n phn xng ur p sut 0,18 barg.
Dung dch t y ca bnh tch thp p c chia thnh hai dng. Phn ln dung dch
c bm dung dch bn thun 10-P-3001 a ti phn di ca thp hp th. Phn cn li
c chuyn n thp gii hp kh CO2 bng bm chia dng 10-P-3003A/B. Trc khi
i vo nh thp gii hp, dung dch bn thun c gia nhit bng dung dch thun n t
y thp gii hp nh trao i nhit 10-E-3001.
Trong thp gii hp, CO2 c kh bng nhit, nhit cho yu cu ny c to ra trong
ni un thp gii hp nh vo kh nng cng ngh.
Dng CO2 bo ho hi nc ra khi nh thp gii hp khong 90 oC s i qua
bnh tch thp p. Hi nc ngng t s lm tng nhit trong bnh tch thp p, kt qu
l bnh tch thp p lm vic tt hn.
Trc khi c bm n nh thp hp th bng bm dung dch thun 10-P-3002A/B,
dung dch thun t y ca thp gii hp c lm ngui n 50 oC nh trao i nhit 10E-3001, b hm nng nc mm 10-E-3004 v b lm ngui dung dch thun 10-E-3003.
Kh nh ra t bnh tch cao p c a n h thng kh nhin liu reforming.

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3.1.5 Cng on mtan ha:

Bc tinh ch kh cui cng trc khi vo thp tng hp l metan ho, mt qu trnh
m cc loi CO d s c chuyn ho thnh Metan CH4 do Metan ng vai tr nh mt
kh tr trong chu trnh tng hp amnic trong khi cc hp cht cha oxy nh l cacbon
oxit (CO v CO2) l cc k c hi i vi cht xc tc ca phn ng tng hp amnic.
Qu trnh metan ho xy ra trong bnh metan ho 10-R-3001, v cc phn ng lin quan
l nhng phn ng ngc ca phn ng reforming:
CO + 3H2

CH4 + H2O + Q

CO2 + 4H2

CH4 + 2H2O + Q

Ngoi hot tnh ca cht xc tc c tnh cht quyt nh n cc phn ng mtan ha

cn c nhit , p sut v hm lng hi nc trong kh cng ngh. Nhit thp, p sut
cao v hm lng hi nc thp gip cho cn bng ho hc ca phn ng chuyn v pha
metan ho.
Trong khong nhit c gi l 280-450oC; tuy nhin, cc iu kin cn bng l
hon ton c li n mc hot tnh xc tc trn thc t ch l mt nhn t xc nh hiu
sut ca qu trnh metan ho. Hot tnh ca cht xc tc tng khi tng nhit , nhng tui
th ca cht xc tc li gim i.
Nhit u vo ca bnh metan ho 10-R-3001 c thit k l 300 oC ti lc khi
ng. Kh ra khi thit b metan ho thng thng cha b hn 10 ppm CO+CO2, nhit
tng qua lp xc tc thng thng nm trong khong 20oC. Phn ng metan ho bt u
nhit khong 210 oC, nhng m bo hiu qu hm lng CO v CO2 thp trong kh
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tng hp, nhit vn hnh nn trong khong 250-340 oC tu thuc vo hot tnh xc tc
v thnh phn kh cng ngh.
Nhit pht nhit tng ln l 74 0C/%mol CO v 60 0C/%mol CO2.
Kh cng ngh i vo cng on metan ho c m t nh sau:

Kh cng ngh t thp hp th CO2 (10-T-3002) c gia nhit n nhit ny khi

chng i qua b trao i nhit kh-kh 10-E-3011 v b cn bng nhit (10-E-2011).

Trong vn hnh bnh thng, nhit tng qua lp xc tc cn nm trong khong

20oC, tng ng vi nhit u ra khong 320oC. B trao i nhit kh-kh 10-E-3011

lm lnh kh c tinh lc n khong 74oC. Kh sau c dn n b lm lnh cui
cng 10-E-3021 v b tch kh cui cng 10-V-3011, ni m nc ngng t c tch ra
khi kh cng ngh.

T thit b tch kh cui cng kh nguyn liu cho tng hp amonic c a n

my nn kh tng hp.

Kh sau khi tinh ch cha N2, H2 vi mt t l kh tr nh Ar v CH4 khong 1,3%

mol. T l thch hp ca H2 v N2 s ph thuc vo vic b thu hi hydro (HRU) c lm

vic hay khng. Nu HRU khng c a vo vn hnh, t l l gn 3:1. Nu HRU c
a vo vn hnh, t l c iu chnh sao cho t l H2:N2 trong kh tng hp sau khi thm
hydro thu hi c s l 3:1.
Bnh metan ho 10-R-3001 c mt lp xc tc loi PK-7R. Cht xc tc PK-7R l loi
xc tc niken cha khong 27% niken, xc tc niken trn cht mang ceramic.
Bi v phn ng c thc hin nhit thp hn rt nhiu so vi xy ra trong
reformer, nn xc tc phi rt hot tnh nhit thp, tri li c tnh xc tc nhit
cao hn l khng quan trng lm.
Phn ng metan ho bt u ti nhit di 280 oC v gy ra s gia tng nhit
trong lp xc tc. S gia tng nhit tng ph thuc vo hm lng CO v CO2 trong kh
cng ngh. Cht xc tc metan ho khng c php tip xc vi nhit ln hn 420oC
trong mt khong thi gian di.Cht xc tc khng c php tip xc vi hi nc ngng
t, v iu ny c th gy nn s phn r.

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3.1.6 Cng on tng hp NH3:

Qu trnh tng hp amnic xy ra theo phn ng di y:

3/2 H2 + N2

NH3 + 11 kcal/mol NH3 to thnh

Phn ng tng hp NH3 i km theo l pht nhit v gim s mol. Nng amonic
iu kin cn bng tng khi nhit gim v p sut tng. Bn cnh iu kin cn bng,
ng hc ca vic hnh thnh amonic cng rt quan trng. Tc phn ng hnh thnh
NH3 ph thuc vo hai yu t i lp nhau:

Tc phn ng tng khi tng nhit .

Khi gim nhit v tng p sut, cn bng s chuyn v hng hnh thnh
amonic.

M t cng ngh:
Qu trnh tng hp amnic xy ra trong thp tng hp amnic (10-R-5001) theo phn
ng di y:
3H2 + N2 2NH3 + Q
y l phn ng thun nghch v ch mt phn hydro v nit c chuyn ho thnh
Ammonia khi kh tng hp i qua lp xc tc. Trong 10-R-5001, khong 25% nit v
hydro c chuyn ho thnh amnic. Phn khng chuyn ho c cn li s c ti
tun hon n thp tng hp sau mt qu trnh tch amnic thnh phm di dng lng.
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Chu trnh tng hp amnic c thit k vi mt p sut ti a l 152 barg. p sut

vn hnh bnh thng s l 137 barg trong thp tng hp amnic, ph thuc vo ph ti v
hot tnh ca cht xc tc. Khi ph ti gim, p sut chu trnh tng hp s gim theo.
Nhit vn hnh bnh thng s l trong khong t 360 - 485oC i vi lp xc tc
th nht v t 370 - 445oC i vi lp xc tc th hai trong bnh 10-R-5001. Sau khi kh
tng hp i qua 10-R-5001, kh i ra c lm lnh xung nhit ti hu ht
Ammonia c ngng t.
Mt lng nhit ng k gii phng trong phn ng tng hp Ammonia c s dng
sn xut hi nc siu p trong ni hi nhit tha 10-E-5001 v gia nhit nc l hi
p sut cao trong 10-E-5002.
Kh tng hp tinh khit cha mt lng nh tp cht, ch yu l cc kh tr Ar v CH4.
Mt dng phng khng lin tc t chu trnh tng hp l cn thit trnh s tch t ca
nhng kh tr ny trong chu trnh tng hp.

Quy trnh tng hp:

Kh tng hp c tinh ch t cng an metan ho c phi trn vi dng khi H2
thu hi t cm thu hi Hydro 10-PK-5001 t t l H2/ N2 = 3/1, sau em nn n
khong 132 barg trc khi n c a vo trong chu trnh tng hp.
Dng kh sau c lm lnh v tch loi nc trc khi tun hon li my nn kh
10-4031. Dng kh i ra t my nn p sut 138barg c gia nhit ln 2540C trc khi
vo thp tng hp 10-R-5001. Trong 10-R-5001, qu trnh tng hp Ammoniac din ra trn
nn xc tc KM1R hoc KM1.
Hn hp ra khi thit b 10-R-5001 c lm lng xung -50C. Dng NH3 lng s c
tch ra khi dng nguyn liu ti bnh tch 10-V-5001 v a sang bnh gim p 10-V5002. Dng Ammoniac lng t y bnh 10-V-5002 c trn vi dung dch NH3 99% t
thit b thu hi Ammoniac, sau mt phn c dn sang phn xng Urea, phn cn li
gim p v bm v bn cha 40-TK-5001 c kh nng cha t 20.000 n 25000 tn NH3.
Dng kh i ra t bnh tch kh 10-V-5014 c a vo ht thng thu hi NH3.Kh
thot ra t h thng c a vo h thng thu hi Hydro 10-PK-5002. Phn kh giu H2
c hi lu v my nn kh tng hp 10-K-4031 lm kh nguyn liu tng hp NH3.

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Phn kh c hm lng H2 thp c a v trn vi dng kh nguyn liu vo thp 10-H2001.

3.2 Phn xng sn xut Urea:

Hot ng ca phn xng Urea c tm tt qua s sau:

Tng hp v thu
hi Urea p sut cao

Lm sch v thu
hi Urea p sut
trung bnh v thp
X l condensate t
qu trnh cng ngh

C c chn khng

To ht
Condensate t qu trnh
(a ti B phn x l
Condensate dng li cho
ni hi tn dng nhit d)

3.2.1 B phn nn CO2:

Kh CO2 c ly t Phn xng Ammonia iu kin nhit l 45oC v p sut l
0,18 bar sau c nn ti p sut 157 bar bng my nn ly tm bn cp, mi cp c
trang b thm thit b lm lnh v thit b tch nc.

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3.2.2 B phn tng hp Urea v thu hi NH3, CO2 p sut cao:

Urea c tng hp t Ammonia lng v kh ccbon ixit. Trong thit b phn ng
Urea, 20-R-1001, Ammonia v CO2 phn ng to thnh ccbamat amn, trong mt
phn s thu phn to thnh Urea v nc.
Cc phn ng nh sau:
2 NH3 + CO2
NH2COONH4

NH2COONH4

NH2CONH2

+ H2O

Trong iu kin tng hp (nhit khong 188 - 190 oC, p sut khong

152 -

157 bar), phn ng u tin xy ra nhanh chng v hon ton, phn ng th hai xy ra
chm v quyt nh tc phn ng.
Ammonia n chu trnh tng hp c bm n p sut khong 220 bar. Trc khi vo
thit b phn ng, Ammonia c gia nhit v c s dng lm cht lng y trong thit
b phun dung dch ccbamat, ti y dung dch ccbamat thu hi c nng ln n p sut
tng hp. Hn hp Ammonia lng v ccbamat c a vo t y thit b phn ng
Urea, ni m n phn ng vi ccbon ixit c nn.
Sn phm phn ng ra khi thit b phn ng chy vo phn trn ca thp tch 20-E1001, lm vic p sut 147 bar, ti y xy ra s phn hu ccbamat. Cc kh ra khi nh
ca thp tch ch yu bao gm Ammonia v ccbon ixit c ngng t v a tr li
thit b phn ng Urea.

3.2.3 Lm sch Urea v thu hi NH3, CO2 trung v thp p:

Qu trnh lm sch Urea v thu hi cc kh khng ngng xy ra trong hai giai on p
sut gim nh sau:

Giai on th nht 19,5 bar.

Giai on th hai 4 bar.

Cc thit b trao i nhit trong qu trnh lm sch Urea c gi l cc thit b phn

hy bi v trong cc thit b ny xy ra s phn hy ccbamat d.
i.Giai on lm sch v thu hi th nht 19,5 bar:

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Dung dch, vi hm lng CO2 cn li thp, ri y thp tch 20-E-1001 c gin n

n p sut 19,5 bar v vo phn trn thp phn hy trung p. Thit b ny c chia thnh
3 phn chnh:
+ Thit b tch nh 20-V-1002, ti y cc kh c tch ra trc khi dung dch
i vo chm ng.
+ Thit b phn hy dng mng ri trong ng 20-E-1002 A/B, ti y ccbamat b
phn hy.
+ Bn cha dung dch ur 20-Z-1002 ni dung dch Ur lm sch ln u (t
60-63% khi lng) c tp trung.
Kh giu NH3 v CO2 ri nh thp tch 20-V-1002 c hp th mt phn bi dung
dch nc ccbamat n t b phn thu hi p sut 4 bar. Pha hn hp sau c a
n thit b ngng t trung p 20-E-1006 ni CO2 c hp th hu nh hon ton v nhit
ngng t/phn ng c hp th bi nc lm mt. Dng pha hn hp t 20-E-1006 chy
vo y thit b hp thu trung p 20-T-1001. Dng Ammonia v kh tr bo ha vi mt
thnh phn rt nh CO2 (20-100 phn triu), ra khi nh ca b phn tinh ct c ngng
t mt phn.
Dng kh khng ngng, c cha kh NH3 bo ho c a ti thp hp th v thu hi
Ammonia 20-T-1005. Ti y, dng Ammonia lng n t Phn xng Ammonia s hp
th mt phn kh NH3 trong kh tr. Lng Ammonia cn li trong dng kh tr ri nh
ca 20-T-1005 s c hp th gn nh trit bng nc ngng t ti thp hp th 20-T1003. Kh tr thi ra khi nh thp 20-T-1003 c hm lng NH3 khng ng k. Dng
dung dch NH3-H2O ra khi y thp 20-T-1003 c bm hi lu li thit b hp th trung
p 20-T-1001. Dng dung dch ccbamt ra khi y thit b 20-T-1001 c bm hi lu
n b phn thu hi tng hp Urea.
ii.Giai on lm sch v thu hi th hai 4,0 bar:
Dung dch vi hm lng CO2 cn li rt thp ri y thit b phn hy trung p c
gin n n p sut 4 bar g v i vo phn trn ca thit b phn hy thp p. Thit b ny
c chia thnh ba phn chnh:

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+ Thit b tch nh 20-V-1003, ti y cc kh c tch ra trc khi dung dch

i vo chm ng.
+ Thit b phn hy dng mng ri trong ng 20-E-1003, ti y ccbamat b phn
hy.
+ Bn cha dung dch Urea 20-Z-1003 ni dung dch Urea lm sch ln th hai
(t nng 69-71% khi lng) c tp trung.
Kh NH3 v CO2 ri nh thit b 20-V-1003 c lm mt ngng t bng nc lm
mt, sau c thu hi trit ti thit b hp th 20-T-1004 bng nc ngng t. Kh tr
thi khi nh thit b 20-T-1004 c hm lng NH3 khng ng k. Dung dch ngng t
cha NH3 v CO2 c bm hi lu tr li y ca thit b hp th trung p 20-T-1001 ca
giai on lm sch v thu hi th nht.

3.2.4 C c Urea:
Dung dch Urea ri y thit b phn hy thp p c gin n n p sut

0,33 bar

v i vo phn trn ca thit b c c s b chn khng. Thit b ny c chia thnh ba

phn chnh:
+ Thit b tch nh 20-V-1004 ni m cc kh i c tch ra trc khi dung dch
vo chm ng. Hi c tch bng h thng chn khng th nht 20-PK-1003.
+ Thit b c c dng mng ri 20-E-1004 ni mt lng nh ccbamat c
phn hy v nc bay hi.
+ Thit b cha cht lng y 20-Z-1004 ni dung dch Ur (84-87% khi
lng) c tp trung.
Dung dch Urea ri bn cha c c s b chn khng 20-Z-1004 c a n y
thit b c c chn khng th nht 20-E-1014 hot ng p sut 0,33 bar. Pha hn hp ra
khi 20-E-1014: hi mt ln na c tch bi h thng chn khng th nht 20-PK-1003,
trong khi dung dch Urea nng chy (95% khi lng) nh trng lc chy vo y thit b
c c chn khng th hai 20-E-1015 hot ng p sut 0,03 bar. Tip , pha hn hp ra
khi 20-E-1015: hi c tch bi h thng chn khng th hai 20-PK-1004 trong khi
dung dch Urea nng chy (99,75% khi lng) c a n b phn to ht.

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3.2.5 To ht Urea:
Urea nng chy t cng on c c c a ti vi phun to ht, t y nhng git
Urea nng chy ri dc theo thp to ht 20-Z-1008, ha rn khi tip xc vi dng khng
kh lnh ngc chiu. Mt t l rt nh Ammonia (vi phn triu) cn li trong Urea nng
chy sau khi c c: dung dch axt sulphric vi nng 98% c phun vo Urea nng
chy, theo cch ny H2SO4 phn ng vi NH3 to ra sulphat amn trn ln v ha rn vi
sn phm Urea. Ht Urea c tp trung gia ca chn thp to ht bng thit b co
quay, thng qua mt phu hnh nn, ri vo bng ti ca thp to ht. Tip , mt tm
chn c s dng nhm loi b Urea b kt tng v c x ra trc tip, sau ha tan
trong bn cha Urea kn ngm v a tr li cc thp tch Urea. Cui cng, sn phm Urea
c a ti bng ti sn phm.

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Bng tm tc xc tc v ha cht chnh trong nh my

Qu trnh

K hiu

Tui th

Thnh phn(%kl)

(nm)
Al2O3:75 - 78
Hydro ha

TK-250

>5

MoO3:12 - 18
CoO: 2 - 5

Hp ph
lu

HTZ-3

ZnO:99-100

hunh
Ni:12 15
NiO: 0 3
RK-211

3-5

MgO: 25 30
Al2O3:60 65
K2O , CaO: 1 - 4

Reforming
s cp

NiO: 15 20
RK-201

3-5

MgO: 20 25
Al2O3:55 60
K2O , CaO: 1 - 4
NiO: 15 20

R-67-7H

3-5

MgO: 20 25
Al2O3:55 60
Ni:7 13

RSK-2-

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7H

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>5

MgO: 25 30

Reforming

Al2O3:60 70

th cp

Ni:2 6
RSK-2P

>5

MgO: 22 35
Al2O3:65 75
Fe2O3:80 90

Chuyn ha
CO

SK-201-2

Nhit cao

Cr2O3: 8 13
CuO: 1 2
Cr2O3: 40 - 50

LSK

Chuyn ha

CuO: 15 - 20

CO
Nhit thp

ZnO: 25 - 35

ZnO: 25 - 35
LK-821-2

Al2O3: 5 - 15
CuO: 44 - 55
CuCO3: 2 - 5
NiO: 1 - 5

Mtan ha

PK-7R

10

Ni: 25 - 30
Al2O3: 60 - 70

KM-1

>10

Tng hp NH3

Fe3O4 : 91 95
K2O, Al2O3,CaO, SiO2: 5 - 9

KM1R

>10

Fe, FeO : 89 93
K2O, Al2O3,CaO, SiO2:7-11

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