CNG NGH TNG HP HO DU

Ngi son: PGS, TS Trn Cng Khanh

I-GII THIU V CNG NGH TNG HP HO DU
I-1/V tr ca CNTHHD trong h thng sn xut cc hp cht hu c:
CN ch bin NL rn
Nhin liu
rn
Du m Kh t nhin
CN ch bin du, kh
H/C thm H
2
, CO Axtylen H/C no lfin
CNG NGH TNG HP HO DU
Cc hp
cht trung
gian
Cht
HBM,
ty ra
Nhin liu
du nhn
tng hp
Dung mi
Cc
mnme
Cc CN Tng hp hu c CN Cao phn t
Sn TH Si TH
Cao su TH Cht do
Cht mu
Dc phm Nng dc
Cht n
H.1.1-V tr CN THHD trong h thng CN SX cc hp cht hu c


-T nguyn liu than , du m v kh t nhin qua cc qu trnh ch
bin ta c nm loi hp cht ban u l cc hydroccbon thm, H2, CO
v hn hp H2+CO (c gi l kh tng hp"), axtylen, cc loi
hydroccbon no ( mch thng, nhnh, vng ) v cc lfin.
Vi s pht trin mnh ca h thng CN SX cc hp cht hu c
nhim v ca CN THHD phi ch ng sn xut cc hp cht ban u ny,
c bit quan trng l cc lfin, hydro v cc hydroccbon thm.
-Trong hn na th k qua cc cht ban u trn ch yu c sn xut
t du kh, do vy CN tng hp hu c c gi l CN THHD.
-Nh vy, CN THHD i t cc hp cht ban u tng i n gin
sn xut ra hng lot cc hp cht hu c quan trng, c s dng trc tip
nh cht hot ng b mt, ty ra, cc loi du nhn v nhin liu tng hp
cng cc ph gia khng th thiu c cho cc sn phm du m, cng nh
lm hp cht trung gian, lm nguyn liu cho mt lot cc CN sn xut cc
hp cht hu c khc nh sn xut cht do, si tng hp, cao su tng hp,
sn tng hp, cc cht mu, cht n, dc phm, cht bo v thc vt, kch
thch sinh trng ...
a/Cc hp cht trung gian:
*L cc hp cht c hot tnh ho hc cao nh cc hp cht cha halogen,
cha oxy (cc ru, aldhit, xton, axit hu c, cc oxit hu c),cc hp
cht cha nit, lu hunh.... V d:
+1,2 Dicloetan l hp cht trung gian quan trng sn xut vinyl
clorua - mt mnme quan trng, cng nh sn xut etylendiamin, vt liu
cao su chu xng du tiokol.
+Oxit etylen l hp cht trung gian sn xut cc glycol ( MEG,
DEG, TEG...), cc etanolamin (MEA, DEA,TEA...), cht HBM khng
ion...
*L sn phm quan trng ca THHD, c sn lng ln, a dng v chng
loi, c s dng cho nhiu ngnh THHC, trong c bn thn CN THHD
b/Cc mnme, cc ph gia cho cng nghip polyme nh cht n
nh, cht chng oxi ho, cht ho do... vi cc c im: sn lng ln, a
dng v chng loi vi cc vt liu polyme mi, yu cu thun cc
mnme rt cao m bo tnh nng, mu sc ca polyme (thng yu cu
trn 99,9%).
c/Cht HBM v git ra:
*Cu to cht HBM c 2 phn: ght v thch nc, nh vy chng tp
trung b mt phn chia pha vi cc tnh nng qu gi nh gim sc cng b
mt, tng cng thm t b mt, to nh tng, ty ra b mt v do c
ng dng rt rng ri trong cng nghip cng nh trong i sng.
*ng dng trong cng nghip: CN dt nhum (git ty, thm t, to nh),
CN khong sn (dung dch khoan, tuyn khong...), vi hiu ng Rebinder
c dng lm ph gia trong dung dch lm mt ca qu trnh ct gt kim
loi, trong dung dch khoan, cht tr nghin, lm ph gia nh ho cho vt
liu xy dng, trong CN ho cht, cng nghip sn xut polyme, thc phm,
m phm ...
*Cc cht HBM v git ra thng c thi ra mi trng, do vy
gim nhim cn loi d phn hu sinh hc (phn ght nc c cu to
mch thng).
d/Nhin liu v du bi trn tng hp, cc ph gia cho cc sn phm
du m:
*To cc vt liu bi trn tng hp lm vic nhng iu kin khc nghit:
nhit cao trn 300
0
C hay nhit thp di -60
0
C, hay iu kin chu ti
trng ln.
*Sn xut cc nhin liu c bit nh nhin liu phn lc c sc y ln.
*Sn xut cc loi ph gia cho cc sn phm du: ph gia chng oxi ho v
c ch kim loi, ph gia bm dnh b mt, ph gia tng ch s nht, ph
gia ty ra b mt, ph gia chng kch n cho xng nhin liu, ph gia
chng ng c v ph gia tng cng bt chy cho du diezel ...
-Nh vy, CN THHD c vai tr v tr bn l trong h thng sn xut
cc sn phm hu c, l mt giai on bin i su sc ca vt cht nn c
hiu qu kinh t cao, c th ni tim lc cng nghip ho hc ca mi nc
ph thuc vo trnh pht trin ca CN THHD.
I.2-Xu th pht trin ca CN THHD:
a/S dng nhng thnh tu khoa hc k thut lin quan: ho hc cc
hp cht hu c, cc thnh tu v xc tc, v k thut phn ng, v cc qu
trnh v thit b ho hc to nn cc cng ngh mi t ph thi, m rng
ngun nguyn liu ban u...
b/Nng cao cng sut ca thit b, c bit TBP lin quan vi t
ng ho qu trnh.V d sn xut Etylen cng sut thit b tng t 20 nghn
tn/nm ln 250 nghn tn/nm gi thnh gim 4 ln, u t gim 2-3 ln,
nng sut lao ng tng 2,5-3 ln. n nay cng sut ca mt n v sn
xut Etylen thng t 400-500 nghn tn/nm v Etylen tr thnh nguyn
liu r, di do, chim v tr quan trng trong CN THHD.
c/Lin hp sn xut nhm tn dng nguyn liu ban u, ci thin ch
tiu kinh t- k thut ca qu trnh sn xut, to cng ngh sn xut khng
ph thi.
V d sn xut mnme vinyl clorua (VCM):
*Lin hp vi cc cng on sn xut Etylen, in phn NaCl sn xut
clo cng nh vi cng on polyme ho VCM thnh PVC.
*Kt hp qu trnh clo ho vi oxi clo ho Etylen v cng on nhit phn
1,2 dicloetan thnh VCM:
- Clo ho Etylen CH
2
=CH
2
+Cl
2
CH
2
Cl-CH
2
Cl
- Nhit phn 1,2 DCE 2CH
2
Cl-CH
2
Cl 2CH
2
=CHCl +2HCl
- O xiclo ho Etylen CH
2
=CH
2
+2HCl +1/2O
2
CH
2
Cl-CH
2
Cl +H
2
O
Tng cng 2CH
2
=CH
2
+Cl
2
+1/2O
2
2CH
2
=CHCl +H
2
O
*Kt hp qu trnh clo ho etylen vi hi droclo ho a xtylen v cng on
nhit phn 1,2 dicloetan thnh VCM:
- Clo ho Etylen CH
2
=CH
2
+Cl
2
CH
2
Cl-CH
2
Cl
- Nhit phn 1,2 DCE CH
2
Cl-CH
2
Cl CH
2
=CHCl +HCl
- Hidroclo ho Axtylen CH CH +HCl CH
2
=CHCl
Tng cng CH
2
=CH
2
+CHCH +Cl
2
2CH
2
=CHCl

II-SN XUT CC HP CHT BAN U CHO THHD:

II.1/SN XUT CC OLEFIN.
-L nguyn liu quan trng nht ca THHD, c bit l Etylen.
-Chia thnh 2 nhm: *Cc lfin thp C2 - C5
*Cc lfin cao C6 - C18
II.1.1/Sn xut cc O. thp:
Bng 2.1 Mt s tnh cht ca O thp
Hp cht T
S
,
0
C T
ti hn
,
0
C Gii hn n vi kkh,%V
Etylen -103,7 9,9 3 32
Propylen -47,7 91,8 2,2 10
Buten-1 -6,3 146,2 1,6 9,4
Cis Buten-2 13,7 157 1,6 9,4
Trans Buten-2 0,9
1,6 9,4
Iso Buten -7 144,7 1,6 9,4
Cc n-Penten 30 37 1,3 8,8
Cc i-Penten 20,1 38,6 1,3 8,8

-E
=
c T ti hn thp, ch ho lng khi nn v lm lnh nhit thp (
bng NH3 lng hay propan lng ),cc O khc c th ho lng khi nn v lm
lnh bng nc.
-O c Ts thp hn H/C no: E=so vi E(T
S
=-88,6
0
C) c ATs=15
0
C, c th
tch ring bng chng luyn. Vi P=/P kh hn (ATs =5,5
0
C). Vi C4
khng th tch ring tng cu t bng phng php ny.
-Gii hn n di vi khng kh thp: nguy him cao v d to hn hp n
khi c r r.
-Electron t ca lin kt kp c kh nng tng tc mnh vi b mt cht
rn, dung mi c cc nh axton, furfural, axtonitril... Nh dng php
chng trch ly c th tch butadien (Ts = -4,4
0
C) t hn hp H/C C4.
-O thp ch yu c sn xut t kh crcking xc tc v bng cng ngh
crcking cc H/C c mt hi nc gi l crcking hi (steam cracking).
II.1.1.A-Cng ngh cracking hi
a/C s nhit ng:
-So vi cc H/C no nhit to thnh cc O tng theo nhit chm hn, do
vy nhit cao nhit to thnh cc O nh hn cc H/C no v bn hn.
bn tng theo th t sau:
Parafin <Olefin < Diolefin < Alkylbenzen < Benzen < Thm nhiu nhn
Hnh 2.1 trnh by tng quan nhit to thnh ca cc loi H/C vo nhit

H.2.1.1-Nhit to thnh ca mt s hydrocacbon
ph thuc vo nhit
-Trn c s ny c th sn xut O. t cc H/C no nhit tng i
cao, trong sn xut E
=
thng nhit 800 900
0
C v cp nhiu nhit cho
qu trnh ct lin kt C-C v C-H.
b/C ch v ng hc ca phn ng:
-C ch chui gc, phc tp:
*Vi etan
-To gc t do: C
2
H
6
CH
3
* +CH
3
*
CH
3
* +C
2
H
6
CH
4
+C
2
H
5
*
-Pht trin chui:
To E
=
: C
2
H
5
* C
2
H
4
+H*
To H2 v ti sinh gc C
2
H
5
*:
H* +C
2
H
6
H
2
+C
2
H
5
*
-t chui: H* +H* H
2

H* +C
2
H
5
* C
2
H
6

C
2
H
5
* +CH
3
* C
3
H
8

C
2
H
5
* +C
2
H
5
* C
4
H
10
Do vy, ngoi C2 trong hn hp sn phm cn c C1, C3, C4....Vi
nguyn liu u l H/C no mch di hn, nh naphta chng hn, th sn
phm cng phc tp. V d vi C
8
H
18

-To gc t do: n-C
8
H
18
C
6
H
13
* +C
2
H
5
* (1)
E
1
=335 Kj/mol
-Ct | ca gc to E
=
v mt gc khc:
C
6
H
13
* C
4
H
9
* +C
2
H
4
(2)
E
2
=E
1
/3
-Phn ng gia mt phn t vi gc:
C
2
H
5
* +C
8
H
18
C
2
H
6
+C
8
H
17
* (3)
E
3
=E
1
/9
-Phn ng gia hai gc t do:
C
2
H
5
* +C
4
H
9
* C
2
H
4
+C
4
H
10
(4)
E
4
=E
1
/50
Ch : Gc t do khng c kh nng ng phn ho (chuyn H* v
nhm CH3*) v khi ct mch C - C v tr | to sn phm ch yu l E=, do
nguyn liu naphta c thnh phn n-parafin ln th hiu sut E= cng cao.
l c trng ca qu trnh cracking hi vi c ch chui gc.
R-CH2- CH2-CH2* C2H4 +R-CH2*
So snh vi qu trnh cracking xc tc vi s to thnh phn t hot ng l
cacbocation vi kh nng ng phn ho cao trc khi ct | nn ch yu to
O. c mch cacbon t 3 tr ln (t E
=
) v nhiu hp cht izo.
R-CH2-CH2-CH2
+
R-CH2-CH
+
-CH3 CH3-CH=CH2 +R
+

Gc t do cng xc tin phn ng ph trng hp O. to thnh, dn
n to nha v cc lm gim hiu sut sn phm. hn ch phn ng ni
tip ny cn thi gian phn ng ngn v s dng hi nc.
c/K thut cracking hi:
Trn c s c trng v nhit ng hc v ng hc ca phn ng c
th rt ra yu cu v TBP nh sau:
-Nhit cao 800 900
0
C.
-Cp nhiu nhit cho qu trnh.
-Gim p sut ring phn ca O bng cch cho thm hi nc.
-TGL ngn khong trn di 1 giy ph thuc vo nhit phn ng:
c thc hin bng cch a nhanh n nhit phn ng v sau lm
lnh nhanh sn phm (gi l "ti" sn phm) dp tt phn ng chui gc.
C nhng gii php khc nhau nh dng cht mang nhit l cht rn
chu nhit dng lp tnh hay chuyn ng (hnh 2.2) hay kh chy nhit
cao (hnh 2.3), tuy vy hin nay vn s dng l ng cng sut ln v hin
i (hnh 2.4 ).


N
a
p
h
t
a
N
a
p
h
t
a

H.2.1.3-TBP cracking hi ACR (Advanced Cracking Reactor)




S cng ngh cng on nhit phn: Hnh 2.5 trnh by s cng ngh
ca cng on cracking hi.


H.2.1.5-S cng ngh cng on cracking hi
-Tn dng nhit ca l ng:
*Khi l c dng un nng nc mm v nguyn liu (naphta v hi
nc ) trong zn i lu ca l.
*Sn phm ra nhit cao cn lm lnh nhanh xung 400 450
0
C dp
tt cc phn ng ph theo c ch chui gc v to hi nc p sut cao.
nhit cn li trong sn phm dng un nng y thp tch 2 v hm
nng naphta cng nh nc mm.
-Sn phm ca cng on ny l du t(F.O.), xng nhit phn vi
hm lng ln H/C thm v O v kh cha O t C2 n C4, trong ch
yu l etylen. Hn hp kh ny c a qua cng on tchtip theo.
d/Nguyn liu sn xut O:
-Ton th gii dng 50% naphta, 2530% kh etan v propan, 20% gasoil,
ring Nht v Ty u - 80% naphta, M - 50% etan.
-Hiu sut E
=
ph thuc vo nguyn liu nh bng 2.1

Bng 2.1-Hiu sut cc O ph thuc vo nguyn liu, % KL nguyn liu
Sn phm Etan Propan n-Butan Naphta
nng
G.O.
nh
G.O.
nng
Kh t (H
2
+CH
4
) 16,1 30,0 21,4 18,1 11,9 11,8
Etylen 76,2 42,0 36,2 31,2 26,4 24,3
Propylen 2,9 16,2 20,4 14,8 14,2 13,8
Butadien 1,4 3,2 3,0 3,8 3,9 3,7
Cc C4
=
0,6 1,4 12,6 4,2 4,7 4,3
Xng nhit phn 2,8 6,0 4,1 24,2 19,5 17,7
Du FO -- 1,2 2,3 3,7 19,4 24,4

T bng 2.1:
-Etan cho hiu sut E= cao nht, n 76% khi lng nguyn liu.
-Cc nguyn liu nng hiu sut E
=
gim, cc O. C3 v C4 tng , k c
butadien.
-Do c ch chui gc ca phn ng, hiu sut E
=
ph thuc vo thnh
phn ca naphta: n-parafin tng th hiu sut E
=
tng.
-Trong kh sn phm c mt lng nh a xetylen, cn phi x l trc
khi tch ( hidro ho chn lc thnh E
=
).
e/Tch kh cha O ca cracking hi:
-Kh sn phm ca cracking hi l nhng cu t c nhit si thp, thng
dng cng ngh nn n 4 MPa v lm lnh n -100
0
C bng cch bay hi
Etylen lng ( Ts =-103,7
0
C ) c sn trong dy chuyn cng ngh. S
khi ca cng on tch kh cracking hi c trnh by hnh 2.6


H.2.1.6-S khi ca cng on tch kh cracking hi
Qu trnh c tin hnh theo s cng ngh 2.7








H.2.1.7-S cng ngh tch kh cracking hi
g/Tch phn on C4:
-Thnh phn ca phn on C4 ca kh cracking hi bng 2.2
Bng 2.2
Hp cht % khi lng Tsi,
0
C
i-Butan <5 - 11,4
n-Butan <5 -0,5
i-Buten 20 35 -6,9
Buten-1 10 15 -6,3
Buten-2 Trans 4 6 0,9
Buten-2 Cis 3 5 3,7
Butadien-1,3 35 50 -4,4

-Cc hp cht c nhit si gn nhau, c bit butadien c thnh phn cao
v d b polime ho, sau khi tch butadien ta c hn hp C4 giu i-buten
c gi l raffinate-1.
-Tch Butadien:
a/Trch li bng dung dch amiac ng 1: [Cu(NH
3
)
2
]
1+
X
-
.
Butadien to phc nn ho tan vo dung dch ny. Cc buten c ho tan
thp hn t 10 n 50 ln.
iu kin trch li: T = -14
0
C; P =0,30,4 MPa; T l: Dung dch/C4 = 8.
Tin hnh trng thi lng.
iu kin nh: T = 80
0
C; P =0,1 MPa.
b/Chng trch li:
-L qu trnh chng c thm mt cu t th 3 l hp cht c cc v nhit
si cao, butadien vi hai ni i tng tc mnh vi cu t th 3 v b ko
xung y thp chng.
- bay hi tng i ca cc hp cht trong hn hp C4 khi c cu t th
3 c trnh by bng 2.3
Bng 2.3
Hp cht Khng
c cu t
th 3
NMP
N-metyl
pyrroli-
done
Ts,
0
C =
204209
DMF
Dimetyl
formamit
Ts,
0
C =
153
ACN
Aceto-
nitril
Ts,
0
C =
80 82
DMAC
Dimetyl
axetamit
Ts,
0
C =
165169
Furfural


Ts,0C =
162
Butan 1,17 3,66 3,43 3,13 3,13 2,89
1-B= 1,08 2,38 2,17 1,92 2,07 1,78
Trs-2-B= 1,23 1,9 1,76 1,59 1,71 1,20
Cis-2-B= 1,37 1,63 1,56 1,45 1,52 1,26
Butadien 1,00 1,00 1,00 1,00 1,00 1,00
BASF
1968
Zeon
1965- 68
Shell
1956
UC
1956
Philipps
1940
Hnh 2.8 trnh by s cng ngh chng trch lica Shell dng dung mi l
axetonitril.


H.2.1.8-S chng trch li vi axetonitril ca Shell
Thnh phn ca phn on C4 sau khi tch butadien (Raffinate-1) v tch i-
buten (Raffinate-2) nh bng 2.4
Hp cht Raffinate-1,% KL Raffinate-2,% KL
i-Butan 3 6
n-Butan 11 19
1-Buten 25 45
2-Buten 16 30
i-Buten 45 <0,1
Butadien <0,5 -

-Raffinate-1 c hm lng i-buten ln l nguyn liu tt cho sn xut MTBE
do kh nng phn ng cao ch c i-buten tham gia phn ng to ete vi
metanol.

CH
3
OH +CH
2
=C(CH
3
)
2
CH
3
-O-C(CH
3
)
2

y cng l phng php tch i-buten sch t hn hp khi kt hp vi cng
ngh phn hu MTBE thnh metanol v i-buten.
-Mt cng ngh khc tch i-buten t hn hp l phn ng thun nghch vi
nc to TBA:
(CH3)2C=CH2 +H2O (CH3)3C-OH
Vi dung dch H2SO4 4550% 300C i-buten tham gia phn ng nhanh
hn n-buten 1500 ln.
II.1.1.B-Cracking xc tc:
-Hiu sut cc phn on sn phm ca qu trnh cracking xc tc c th a
ra nh bng 2.5
Bng 2.5
Sn phm % KL nguyn liu vo
Phn on C2 4,4
Phn on C3 2,7
Phn on C4 4,9
Phn on C5 5,0
Phn on xng 27,5
Phn on gasoil 43,0
Phn on du nng 8,5
Cc (t khi ti sinh xc tc) 4,0
-Thnh phn cc phn on kh cha O:





Bng 2.6
Phn on C2 Phn on C3 Phn on C4 Phn on C5
H/C %KL
H2 1,3
CH4 29,5
Etan 25,4
Etylen 20,9
Propan 3,5
P= 11,8
Tr 7,6
H/C %KL
C2- 0,4
P 26,9
P= 72,0
C4+ 0,7



H/C %KL
C3- 0,5
n-B 11,0
i-B 33,0
n-B= 37,0
i-B= 18,0
C5+ 0,5

H/C %KL
C4- 2,0
i-Pentan 31,5
n-Pentan 5,5
i-Penten 37,5
n-Penten 22,5
C6+ 1,0


II.1.1.C-Hin nay sn xut O p dng cng ngh cracking su (
DCC ), DCC ch 1c hiu sut propylen cao, DCC ch 2 c hiu sut
i-olefin cao nh bng 2.7
Bng 2.7
Hp cht DCC ch 1 DCC ch 2 FCC thng dng
Etylen 6,1 2,3 0,9
Propylen 20,5 14,3 6,8
Butylen
trong i-C4=
14,3
5,4
16,4
6,1
11,0
3,3
Amylen
trong i-C5=
---
---
9,8
6,5
8,5
4,3

-Gn y c cng ngh sn xut O t kh t nhin qua metanol th dng
cng ngh UOP/Hydro MTO (Methanol to Olefin) theo s hnh 2.9



H.2.1.9-S cng ngh chuyn ho metanol thnh olefin
Phn ng: Metanol Olefin C2 C4 +H
2
O
Xc tc: MTO-100 trn c s ry phn t khng phi zeolit.
Nguyn liu: Metanol th ( c nc ).
chuyn ho cao: X =0,99.
Hiu sut phn ng: 5,204 tn MeOH cho
0,882 tn Etylen
0,882 tn Propylen
0,272 rn Butylen
0,100 tn C5+
0,088 tn kh t ( CH
4
)
2,980 tn cc hp cht khc(nc, cc, CO
2
)
T l Etylen/Propylen thay i t 0,75 n 1,5.
II.1.1.D-Dehidro ho xc tc cc parafin thp C4 v C5
II.1.2-Sn xut cc O cao.
-Quan trng l cc -olefin mch thng: O. C6C9 sn xut cht
ho do; C10C18 sn xut cht HBM v git ra, ph gia cho du bi
trn, du nhn tng hp poly -olefin, ng trng hp vi etylen.
II.1.2.a/Cracking n-parafin cao C22C30
-Phn ng: R
1
-CH
2
-CH
2
-CH
2
-CH
2
-R
2
R
1
-CH=CH
2
+R
2
-CH=CH
2
+H
2

C ch chui gc:
R1-CH2-CH2-CH2-CH2-R2R1-CH2-CH2*+R2-CH2-CH2*
R1-CH2-CH2* R1-CH=CH2 +H*
R2-CH2-CH2*+H* R2-CH=CH2 +H2
-iu kin phn ng:
-Ging cracking hi nhng nhit thp hn, 500600
0
C, c mt hi
nc, cp nhit cho phn ng, lm lnh nhanh sn phm, TBP: l ng.
-Duy tr chuyn ho X thp.
-Nguyn liu vo t hp cht loi naphten v mch nhnh th -olefin
sn phm t tp cht.
-Sn phm l mt hn hp O t C2 n Cn-1(Cn l nguyn liu vo),
nhng c th c 60% sn phm lng, trong c n 90% l -olefin.
Sn phm ph l O c ni i trong mch, cc dien, pa ra fin v thm.
II.1.2.b/Dehidro ho xc tc n-parafin mch di:
-L phn ng xc tc kh-rn, thun nghch, thu nhit ( AH
R
=113
134 Kj/mol), do cn bng ca phn ng ph thuc vo nhit .
-y l phng php cng c dng sn xut O C4-C5, mch di
d dehi dro ho hn: T phn ng 400 - 500
0
C,vi mch ngn: 600 650
0
C.
-Xc tc: Pt/Al
2
O
3
, MoO
3
/Al
2
O
3
hay SiO
2
, lm vic trong mi trng
H
2
( P =0,30,5 MPa, t l H
2
/HC =1/2 ), xc tc mau mt hot tnh do cc
ph b mt nn cn ti sinh bng cch t cc.
-Cc cng ngh:
in hnh l cng ngh PACOL ca UOP vi cng ngh xc tc
chuyn ng lp ri, ngoi ra c mt s cng ngh sn xut olefin thp nh
CATOFIN ca Houdry (xc tc c nh, ti sinh theo chu k), OLEFLEX
ca UOP ( xc tc chuyn ng ), STAR ca Philipps (dng hi nc thay
hidro).
II.1.2.c/Phng php oligome ho etylen:
T tylen thu c lfin mch thng, tylen l ngun nguyn liu
ban u r v di do nh cng ngh cracking hi c thc hin qui m
ln. T P=, B=ch c olefin mch nhnh, kh phn hu sinh hc nn cht
git ra t chng gy nhim mi trng.
A-Cng ngh vi xc tc etyl nhm:
* Phn ng c hai giai on oligome ho v tch mch.
Giai on 1: Oligome ha T =100
0
C, P =10 MPa.
-CH2-CH2-R1
Al(C2H5)3 +3nC2H4 Al {-CH2-CH2-R2
-CH2-CH2-R3
R1, R2, R3 c s nguyn t C chn v khng bng nhau.
Giai on 2: Tch mch T = 300
0
C, P =1MPa.
-CH2-CH2-R1 R1-CH=CH2
Al -CH2-CH2-R2 +3C2H4 Al(C2H5)3 +R2-CH=CH2
-CH2-CH2-R3 R3-CH=CH2
*Cc cng ngh:
+Cng ngh Gulf Oil:
-C hai giai on tin hnh ng thi trong mt TBP iu kin
T =2000C, P =25 MPa.
-Sn phm c mch phn bb t C4 n C30,trong c 91 n 97%
-ole fin mch thng.
-S dng: Cng ty Gulf Oil v Mitsubishi Chemical Industry.
+Cng ngh Ethyl:
-C ba TBP oligome ho, chuyn alkyl v t lng ho nhm kim
sot chiu di mch.
-S cng ngh nh hnh 2.10

H.2.1.10-S khi cng ngh Ethyl ligme ho tylen
1-TBP ligme ho v tch mch nh Gulf Oil
2-Chng tch:
+Phn on C4 a qua 3 chuyn alkyl.
+Phn on C6-C10 c th s dng hay a qua 3 nh phn on C4.
+Phn on C12-C18 em s dng.
3-Chuyn alkyl: lfin C4 chuyn alkyl vi alkyl nhm mch di
AlR'
3
c alkyl nhm AlR
3
mch ngn v -olefin mch di.
4-Chng tch: c -lfin mch di (C12-C18), mch trung bnh
(C6-C10) v alkyl nhm mch ngn AlR
3
chuyn sang 5.
5-TBP ligme ho theo t lng: Cho thm tylen theo t lng
c alkyl nhm mch di AlR'
3
, sau a tr li qua 3 chuyn alkyl
vi lfin C4.
Cng ngh ny trin khai nm 1970 Texas (110.000 tn /nm), cho php
chuyn ho 95% etylen thnh olefin cao, nhng sn phm thu c ch c
63% l -ole fin mch thng, cn li l mch nhnh v ni i bn trong.
B-Cng ngh vi xc tc phc kim loi chuyn tip (Ni, Co, Zr ):
*Tiu biu l cng ngh SHOP (Shell Higher Olefine Process) - l
cng ngh quan trng v hin i nht sn xut -lfin: sn phm c
hm lng lfin mch thng cao (>99%), cc hp cht dien, thm, no ch
c dng vt, hiu sut t 96-97%.
*Cng ngh kt hp 3 phn ng: ligme ho, ng phn ho v
chuyn v (methathesis), nh c th t phn on olfin mong mun.
*S khi c trnh by hnh 2.11
1-Oligome ha:
-Xc tc to thnh ngay trong TBP t mui Ni v ligand to phc L
(L c cng thc chung RR'P-CH
2
-COR'' nh diphenylphosphino axetic axit



H.2.1.11-S khi cng ngh SHOP
Xc tc ho tan trong dung mi c cc etylen glycol hay 1,4 butandiol.
-iu kin phn ng: T= 80 - 1200C; P=7 - 14 MPa.
2-Lng tch: lfin to thnh khng tan trong dung mi c cc, lng
tch sn phm v dung dch xc tc quay li h phn ng ligme ho 1.
3-Chng tch thnh 3 phn on: C4-C10- S dng hoc a xung
ng phn ho 4; C12-C18- S dng; >C18- a xung ng phn ho.
4-ng phn ho: +T=80 - 140
0
C; P=0,3 - 2MPa.
+Pha lng, xc tc MgO.
+Nguyn liu l -O C4-C10, >C14, >C20, 90%
lfin chuyn ni i vo trong.
R-CH=CH
2
R1-CH=CH-R
2

5-Chuyn v: +Xc tc d th Re, Mo.
+ iu kin phn ng nh ng phn ho.
+Phn ng:
R
1
-CH=CH-R
2
+R
3
-CH=CH-R
4

R
1
-CH=CH-R
3
+R
2
-CH=CH-R
4

Phn ng chuyn v c th thc hin gia O mch di vi etylen:
C
10
H
21
-CH=CH-C
10
H
21
+CH
2
=CH
2

2 C
10
H
21
-CH=CH
2

y cng thc hin phn ng ng phn ho t O c ni i bn
trong thnh -olefin.
Nh my u tin theo cng ngh SHOP nm 1977 Lousiana vi
cng sut 200.000 tn /nm.
Sn xut -olefin cc khu vc:
Cng ngh Ty u M Nht
Oligome ho etylen, % 40 93 100
Cracking parafin C22-C30 60 7 ---

II.2-SN XUT HC THM.
*Mt s tnh cht ca HC thng gp
Bng 2.2.1
Hp cht Tsi,
0
C Tnng chy,
0
C Tbc chy,
0
C
Benzen 80,1 +5,5 -14
Toluen 110,6 -9,5 +5
o-Xylen 144 -25,2 +29
m-Xylen 139,1 -47,9 +29
p-Xylen 138,3 +13,3 +29
Etyl benzen 136,2 -95 +15
Cumen 152 -96 +43
Naphtalen 218 +80,3 ---

II.2.1-Ngun nguyn liu ban u:
a-Du cc:
Du cc nh: 10-15l/tn than, c 63% B, 13% T, 8% X.
Du cc nng: 30-38l/tn than, cha naphtalen, antraxen.
hnh dung vai tr ngun nguyn liu ny cho HC thm: HC thm
t than M: 1957 - 77%, 1970 - 10%, 1981 - 7%.
b-Xng cracking hi:
Hiu sut xng 20% t naphta. BTX chim trn 60%.
Xng cracking hi, du cc u c cha HC khng no nn cn x l
H2 trc khi tch.
c-Phn on C6-C9 ca sn phm reforming xc tc:
Cha n 70% HC thm, ngoi ra cn HC pa ra fin, naphten c nhit
si xp x.
p ng nhu cu HC thm cho THHD ngy nay cn thc hin qu
trnh thm ho phn on C6-C9 ca naphta theo cng ngh tng t refor-
ming xc tc.
II.2.2-Phng php tch HC thm:
a-Phng php kt tinh:
-Dng cho benzen khi tch t nguyn liu c hm lng B cao nh
du cc nh, phn on C6 ca xng cracking hi.
-Ph bin hn khi tch p-X t hn hp C8 ( hin nay b cnh tranh bi
phng php hp ph chn lc hin i v hiu qu hn ).
b-Phng php hp ph chn lc:
-Hp ph chn lc HC thm ln b mt cht rn t hn hp, sau
tin hnh nh bng nhit trong dng cht cht nh hp ph. Cui cng chng
tch cht nh hp ph khi sn phm HC thm v phn on HC x l.
-c trng l cng ngh PAREX ca UOP: tch p-X t hn hp cc
ng phn theo cng ngh SORBEX- hp ph v nh lin tc trn lp cht
hp ph tnh nh thay i dng chy bng van quay.
-Cng ngh PAREX c th hnh dung qua s hnh 2.2.1


H.2.2.1-S tch p-Xylen theo cng ngh PAREX
-Cng ngh PAREX ca UOP thng tch hp vi ng phn ho hn
hp xylen IZOMAR nh hnh II.2.2.2

H.2.2.2-Tch hp cng ngh tch p-Xylen vi ng phn ho

c-Chng trch li:
-Thm dung mi c kh nng tng tc vi HC thm v ko hp cht
ny xung y thp, cn cc hp cht khng thm ln nh thp chng, sau
tin hnh tch HC thm v dung mi. Nh vy, dung mi thng c
chn c nhit si cao, tng tc mnh vi electron t ca hp cht thm.
-C nhiu cng ngh chng trch li:
*Distapex ca hng Lurgi dng N-metylpyrrolidone (Ts=202
0
C).
*Morphylane ca Koppers dng N-formylmorpholine (Ts=2440C).
*Tetra ca Union Carbide dng tetraetylenglycol (Ts=3280C).
*Stex ca Toray dng dimetylacetamide (Ts=1610C).
Cng ngh Distapex c trnh by hnh II.2.2.3



H.2.2.3-Cng ngh Distapex chng trch li tch benzen t
phn on C6 ca cracking hi
d-Trch li lng- lng:
-L phng php cong ngh kinh t v ph bin nht, thng kt hp
vi chng trch li.
-Dung mi s dng l cc hp cht c cc, ho tan tt HC thm
nhng khng tan ln vi cc HC parafinic v naphtenic.Ngoi ra dung mi
cn c khi lng ring nng hn nguyn liu c trch li v c nhit
si khc vi HC thm c trch ( khong 30-40
0
C ) d tch chng sau
khi trch.
-Cc cng ngh:
*Cng ngh ca Shell UOP v ARCO dng Sulfolane (d=1,26;
Ts=287
0
C).
*Cng ngh Arosolvan ca Lurgi dng N-metylpyrrolidone + nc
hay etylen glycol (40%)( d=1,005-1,027; Ts=202
0
C ).
*Cng ngh Tetra ca UnionCarbide dng tetraetylen glycol
(d=1,130; Ts=328
0
C).
*Cng ngh Aromex ca Kopper v SNAM Progetti dng N-fo
rmyl morfoline vi 2 n 5% nc (d=1,150; Ts=244
0
C).
*Cng ngh Aromex ca Howe Baker dng diglycolamin vi 7%
nc (d=1,06; Ts=221
0
C).
S cng ngh tch thm bng phng php trch li kt hp vi
chng trch li nh hnh II.2.2.4
T
h

p

t
r

c
h

l
i
T
h

p

c
h

n
g

t
r

c
h

l
i
R

a
R

a
T

c
h

d
u
n
g

m

i
Dung mi+Thm
Dung mi
HC thm
HC tch thm
P
h

n

c
h

a

t
h

m

H.2.2.4-Cng ngh tch thm bng trch li kt hp vi
chng trch li
II.2.3-Cc phng php khc:
p ng nhu cu khc nhau ca cc HC thm cn tin hnh cc
qu trnh sau:
-Alkyl ho benzen bng etylen v propylen sn xut etylbenzen v
cumen.
C6H6 +C2H4 C2H5-C6H5
C6H6 +C3H6 C3H7-C6H5
-ng phn ho hn hp xylen sn xut p-xylen.
o-Xylen m-Xylen p-Xylen
-Hidrodealkyl ho alkylbenzen thnh benzen.
C6H5-CH3 +H2 C6H6 +CH4
-Phn b li gc alkyl
2C6H5-CH3 C6H6 +C6H4(CH3)2

II.3-SN XUT H2 v CO:
Sn xut H2:
-Nhu cu H2 ngy cng tng sn xut phn m v nhiu qu trnh
cng ngh ho du khc:
V d: *Kh lu hunh: cho Xng - 12 m3/m3; Gasoil - 50 m3/m3; Phn
on nng - 100 m3/m3
*Hi dro cracking - 240 700 m3/m3.
*Sn xut metanol - 1600 m3/tn.
*Sn xut NH3 - 2000 m3/tn.
*Sn xut benzen9Hi dro dealkyl ho toluen) - 350 m3/tn.
-Cc ngun H2:
+Kh Reforming xc tc, kh cc, kh cracking hi. Cc kh ny thng ln
vi HC khc, c bit l metan v etan. Thng yu cu thun H2 t 80 -
95% nn kh reforming xc tc l thch hp, vi cc kh khc cn phi x l.
+Chuyn ho cc HC, cc vt liu cha C khc (than , g, sinh khi...)
bng cch phn hu nhit, oxi ho mt phn, chuyn ho vi hi nc.
+Phn hu nc.
-Cc qu trnh tinh ch H2:
a/Hp ph tp cht bng silicagel, than hot tnh, Al2O3 hot tnh,
zeolit. Hiu qu ca vic tinh ch ph thuc vo tp cht ca hn hp.
b/Phng php thm thu: qua mng hu c hay mng kim loi.
c/Lm lnh thm ho lng.
II.3.1-Cng ngh sn xut H
2
t cc vt liu hu c:
Cc cng ngh v cng on x l nh s khi hnh 2.3.1
A-Oxi ho mt phn:
+Phn ng: a/Phn ng chy:
-Vi metan:
CH
4
+3/2O
2
CO +2H
2
O AH
298
=-519,5 Kj/mol
-Vi HC nng:
C
n
H
m
+(2n+m)/4 . O
2
nCO +m/2 . H
2
O
b/Chuyn ho CO:
CO +H
2
O CO
2
+H
2
AH
298
=-41 Kj/mol
*L phn ng thun nghch to nhit, do T thp, H2 cng nhiu.
*H
2
O to thnh t phn ng a/ hay a thm vo.
c/Phn hu do nhit cao:
CH
4
C +2H
2
AH
298
=74,8 Kj/mol
C
n
H
m
nC +m/2 . H
2

y l phn ng ph to mui, khi c mt H
2
O, CO
2
(sn phm ca
phn ng a/ v b/ ) mt phn mui s phn ng:
C +CO
2
2CO
C +H
2
O CO +H
2

+Cng ngh:
*Thng tin hnh on nhit, nhit vo 500-600
0
C.
*T s O
2
/HC rt quan trng:
Khi O
2
/CH
4
<0,5 - to nhiu mui.
O
2
/CH
4
tng: tng nhit phn ng (c th t 1000
0
C
hay cao hn), tng lng hi nc, gim hm lng CH
4
.
*S cng ngh Texaco hnh 2.3.2









H.2.3.1-S sn xut H
2
t nguyn liu cha ccbon

T
B
P

o
x
i

h
o

t

p
h

n
T
h

p

t

c
h

F
u
e
l

O
i
l
T
h

p

r

a

k
h

T
h

p

t

c
h

h

i

n

c

H.2.3.2-Cng ngh Texaco: sn xut H
2
bng oxi ho mt phn

B-Chuyn ho bng hi nc (Reforming hi nc):
+Phn ng: L phn ng o xi ho HC bng hi nc.
a/ C
n
H
m
+1/4(4n-m)H
2
O 1/8(4n+m)CH
4
+1/8(4n-m)CO
2

L phn ng thun nghch to nhit v thc t chuyn ho hon ton
400 - 600
0
C.
b/Sau tin hnh phn ng:
CH
4
+H
2
O CO +3H
2
AH
298
=206,2 Kj/mol.
Cn bng phn ng nh bng II.3.1
Bng II.3.1-Thnh phn % mol ca cc cu t cn bng theo nhit
( P =0,1 MPa ; T l CH
4
/H
2
O =1/1)
T,
0
C CH
4
H
2
O CO H
2

427 42,6 42,6 3,7 11,0
527 30,0 30,0 10,0 30,0
627 14,5 14,4 17,5 52,5
727 5,5 5,5 22,2 66,7
827 1,8 1,8 24,1 72,3
927 0,5 0,5 24,5 74,5

chuyn ho ht CH
4
cn thm O
2
hay khng kh v chuyn ho
tip. sn xut NH
3
a thm khng kh c lng N
2
cn thit cho qu
trnh tng hp NH
3
pha sau.
+Xc tc:
Thng l Ni/Al
2
O
3
hay Ni/Aluminsilicat Ca hay Mg vi cht kch
ng l Kali.
Nhit phn ng 850 - 940
0
C, P =1,5 - 2,5 MPa.
Lu lng ring ca hn hp phn ng (VHSV-Volume Hourly
Space Velocity): Fv/V
R
=1600 - 2000 h
-1
.
+TBP: L ng, s ng n = 500, L ng = 10 - 15 m; D ng = 80 - 150 mm.
Cng on Reforming hi nh hnh II.3.3
Nc mm
Nhin liu
Kh thi
Nc ngng
Kh cha H
2
Hi nc
qu nhit,
Pcao
Kh t
nhin
H
2
Hi nc

H.2.3.3-S cng on chuyn ho bng hi nc.
C-Cng ngh t nhit:
Mt s cng ngh t nhit do kt hp hai qu trnh oxi ho mt phn
to nhit vi reforming hi nc thu nhit. in hnh l cng ngh pht trin
trong nhng nm 50 do hp tc gia SBA (Socit Belge de l'azote) v
Haldor Topsoe, trn nguyn tc trn kh chy vi hi nc v cho vo lp
xc tc c nh trn c s Ni 2 MPa v 950
0
C. Cng ngh ny ch dng
cho cc nguyn liu nh nh kh t nhin, LPG v naphta lin quan n cc
dn sut lu hunh v to cc ca cc nguyn liu nng.
D-Chuyn ho CO:
-Kh thu c t cc cng ngh trn cn cha nhiu CO (bng 2.3.2)
Bng 2.3.2-
Oxi ho mt phn Reforming hi
Cu t
H
2

CO
CO
2

CH
4

N
2

Kh khc
Kh TN Naphta FO THAN
61 51 47 40
35 45 47 35
2-3 2-3 4 21
- - 1 2
0-1 0-1 - 2
2-0 2-0 1 -
Kh TN
55-57
12-15
7-12
-
22-24*
4-2
*Dng khng kh chuyn ho nt CH
4

Phn ng: CO +H
2
O CO
2
+H
2
AH
298
= 41,2 Kj/mol
L phn ng thun nghch, to nhit: cn tin hnh nhit thp, d
hi nc.
250
0
C, t l H
2
O/CO =3 chuyn ho hon ton CO. Tuy vy
nhit thp to nhiu metan v cacbon nn trong cng nghip thc hin hai
giai on chuyn ho:
-Giai on 1: Nhit cao trnh to mui.
Xc tc: 80 -95% oxit st v 5-10% oxit crm.
Nhit : 350 450
0
C.
Gii nhit phn ng bng cch phun nc trc tip vo gia cc lp
xc tc on nhit.
-Giai on 2: Nhit thp chuyn ho hon ton CO ( 0,05 0,1V ).
Xc tc: Oxit ng ( 15-30%), oxit km ( 30%) trn Al
2
O
3

Nhit : 200 250
0
C
E-Tinh ch H
2
:
Yu cu thun H
2
trn 97%, CO <1%.
Kh CO
2
bng hp th vi dung dch kim, alkanolamin.
KhCO: -Hp th bng dung dch ng 1.
-Mtan ho: CO +H
2
CH
4
+H
2
O
Xc tc: Ni/Al
2
O
3
c kch ng vi Cr
2
O
3

Nhit : 300
0
C.
Nng CO < 20 ppm.
Sn xut CO:
-CO c s dng ring l hay dng hn hp vi H
2
(kh tng hp).
-CO c trong cc kh thi cng nghip: kh l cao, kh cc, kh ca
qu trnh sn xut mui than, kh ca sn xut nhm, kh ca sn xut t
n): thu hi v tch.
-Ging H
2
, CO c sn xut t vt liu cha cacbon bng reforming
hi v oxi ho mt phn.
-Cc phng php tch:
Hp th v nh vi dung dch ng 1.
Lm lnh ho lng nhit thp (Ts = -191
0
C) vi hai cng ngh:
ngng t mt phn v ti bng CH
4
lng.

II.4-SN XUT CC HC NO:
-Chia thnh P. thp: C1 C5 v cao: >C5.
-P. c trong cc phn on ca du m: tch v chuyn ho gia
chng theo yu cu.
A- Cc P. C1 C5 c T si khc nhau ln tch bng php
chng (bng 2.4.1)
Bng 2.4.1
Hp cht T si,0C T ti hn,0C Gii hn n,%V
Metan -161,6 -82,6 5 - 15
Etan -88,6 32 2,9- 15
Propan -41,2 96,8 2,1 - 9,5
n-Butan -0,5 152 1,8 - 9,1
i-Butan -11,7 134 1,8 - 8,4
Pentan 36,1 - 1,3 - 7,6
i-Pentan 27,8 - 1,3 - 7,6

-Cc iso c nhit si thp so vi mch thng tng ng, c th tch
bng php chng, nhng hin nay c phng php tch bng hp ph chn
lc trn zeolit 5A hiu qu hn, phng php ny cng c dng tch p.
mch di trong pha lng nn c gii thiu phn sau.
- sn xut cc hp cht cu to iso tin hnh qu trnh ng phn
ho kt hp vi cng on tch nh hnh 2.4.1


H.2.4.1-Sn xut i-Butan kt hp cng ngh PH v tch
B-Sn xut cc p. cao
-Gi tr l cc p. mch thng C10 n C40.
-Thnh phn HC trong cc phn on tu tng m. Trong cc phn
on du ho, du diezen, du nhn c th cha n 30% n-p. Trong qu
trnh sn xut cc sn phm ny thng tch n-p gim nhit ng c
ca DO v du nhn cng nh tng ch s nht ca sn phm ny.
-Do nhit si ca cc n-p gn nhau thng sn xut v s dng
theo tng phn on.
-Phng php tch:
1/Lm lnh kt tinh:
-Cc n-p c nhit nng chy cao hn ccHC khc.
-Cc giai on cng ngh nh hnh 2.4.2
-Dng dung mi gim nht cho cc phn on nng. Dung mi
thng l hn hp xton va HC thm, propan lng c s dng lm dung
mi ng thi l cht lm lnh (T si = -42,1
0
C).


H.2.4.2-S tch n-parafin bng phng php kt tinh
2/Phng php cacbamit:
-Da vo tnh cht n-p to phc rn vi ur nhit thp v phn
hu tr li n-p v ur nhit 80 - 100
0
C.
-Phn ng:
RH +nCO(NH
2
)
2
RH.nCO(NH
2
)
2
.
-Phc rn c thnh phn 8 phn t r cho mt nguyn t C.
-Vi phn on HC nng thm dung mi (nh CH
2
Cl
2
) gim
nht.
-S tch n-p dng ur hnh 2.4.3

H.2.4.3-S tch n-parafin dng cht to phc ur
3/Phng php hp ph chn lc:
-Parafin mch thng c ng knh ng hc nh hn i-p v cc HC
khc nn c th chui vo l xp v hp ph chn lc trn zeolit CaA(zeolit
5A).Cc n-p vi chiu di mch khc nhau u c kch thc ng hc theo
chiu ngang nh nhau v c th tin hnh tch n-p bng hp ph chn lc
i vi cc hn hp HC pha kh cng nh pha lng. Kch thc l xp ca
mt s zeolit v ng knh ng hc ca mt s cht c trnh by hnh
2.4.4

H.2.4.4-Quan h gia kch thc hiu dng ca l xp mt s loi
zeolit v ng knh ng hc phn t ca mt s hp cht.
-C th tin hnh qu trnh tch vi cng ngh gin on theo tng
chu k hp ph v nh. Hin nay c cng ngh lin tc vi cc lp zeolit 5A
c nh ca UOP vi thng hiu MOLEX, tng t cng ngh PAREX
nh hnh 2.2.1.

III-CC QU TRNH OXI HO.
-L cc qu trnh quan trng ca THHD: Sn xut nhiu sn phm c
gi tr nh cc ru, cc aldehit, cc xeton, cc axit hu c, cc oxit, cc
monome ....Tc nhn oxi ho l khng kh v oxi k thut r v sn.
-Phn ng oxi ho c hiu ng nhit cao, c bit i vi cc qu
trnh pha kh cn ch cc bin php gii nhit.
-Mt phn ng ph cn lu l phn ng oxi ho hon ton thnh
CO
2
v nc: lun lun xy ra song song v ni tip vi cc sn phm chnh
ca qu trnh oxi ho khng hon ton, lm gim ng k hiu sut ca mt
cng ngh sn xut. Ngoi ra, hiu ng nhit ca phn ng ph ny rt ln,
gy thm kh khn cho vic duy tr nhit thch hp cho phn ng.
-Cc loi phn ng: Oxi ho theo c ch ng li,chui gc trong pha
kh v pha lng, oxi ho d th trn xc tc rn, oxi ho vi xc tc phc.

III.1-Oxi ho theo c ch chui gc bng o xi phn t:
-Ph bin, lin quan n qu trnh t o xi ho cc hp cht hu c, cc
sn phm du, cc hp cht polime... trong mi trng c o xi ca bu kh
quyn.
III.1.1-C ch phn ng: Chui gc phn nhnh, t phn t O2(0=0) s
thun li hn v mt nng lng khi t ng li ch mt lin kt thnh gc
t do *O-O*.
-Giai on khi mo: To gc t do, thng vi s tham gia ca O2.
RH +O
2
R* +*O-O-H ( 1 )
RH +O
2
+HR R* +H-O-O-H +R* ( 2 )
R-R' +hv R +R' ( 3 )
-Pht trin chui: To hp cht hidropeoxit(H/P) v hon nguyn gc.
R* +O
2
R-O-O* ( 4 )
R-O-O* +RH R-O-O-H +R* ( 5 )
Phn ng 4 v 5 c quay vng vi s tham gia ca RH v O
2
, dn n tch t
hp cht trung gian khng bn l cc H/P.
-Phn nhnh: Phn hu cc H/P thnh cc gc t do mi v do tng
nhanh vn tc oxi ho.
R-O-O-H R-O* +*O-H ( 6 )
R-O-O-H +H-O-O-R R-O-O* +H2O +R-O* ( 7 )
R-O-O-H +H-O-R' R-O* +H
2
O +R'-O* ( 8 )
Phn ng 6 trong pha kh, phn ng 7 v 8 trong pha lng do c lin
kt hidro.
-t chui: Do kt hp cc gc
R* +R* R-R ( 9 )
R-O* +R* R-O-R ( 10 )
R-O-O* +R-O- O* R-O-O-R +O
2
( 11 )
R-O-O* +R* R-O-O-R ( 12 )
*H/P l sn phm phn t u tin ca qu trnh oxi ho. Ph thuc
vo nguyn liu ban u ta c H/P bc 1,2,3.
V d: Vi nguyn liu etylbenzen c H/P bc 2, vi cumen c
H/P bc 3
*H/P l hp cht khng bn, phn hu thnh gc theo 6,7,8. bn
theo th t sau:
H/P bc 3 > H/P bc 2 > H/P bc 1.
H/P bc 3 bn, c bit khi nhm O-O-H nh vo nguyn t C
cnh nhn thm hay ni i, c th c lp c nh (CH3)
3
C-O-O-H,
C6H5-C(CH3)
2
-O-O-H.
*S tch t H/P trong hn hp phn ng n mt nng no bt
u tng nhanh vn tc oxi ho theo hm m nh hnh 3.1.1. T khi bt u
n thi im gi l giai on cm ng ca qu trnh oxi ho.

H.3.1-c trng ng hc phn ng oxi ho theo c ch chui gc
III.1.2-Phn hu H/P to ru v hp cht ccbonyl:
-To ru:
t lin kt yu O-O nh cc phn ng 6,7,8 to gc RO*.
Do tn cng ca gc alkyl R*
R-O-O-H +R* R-O* +R-O-H
R-O* +RH R-O-H +R*
-To hp cht ccbonyl: t lin kt C-H ti nguyn t C c nhm
O-O-H do tn cng ca gc *O-H, sau t lin kt O-O.
-To aldehit: T H/P bc 1
R-CH
2
-O-O-H +*O-H H
2
O +R-C*H-O-O-H
R-C*H-O-O-H R-CHO +*O-H
-To xton: T H/P bc 2
R
2
CH-O-O-H +*O-H H2O +R
2
C*-O-O-H
R
2
C*-O-O-H R
2
CO +*O-H
nhit cao, pha kh, phn ng phc tp hn, c th t lin kt
C-C.
III.1.3-Oxi ho ru, aldehit v xton to thnh:
-Oxi ho ru bc 2: t lin kt C-H nguyn t C c nhm O-H
to gc oxi-alkyl, sau o phn ng vi O
2
to gc oxi-peoxit v to thnh
oxi-H/P, hp cht ny phn hu thnh xton v H
2
O
2
.
R
2
CH-O-H +R
2
C(OH)-O-O* R
2
C*-O-H +R
2
C(OH)-O-O-H
R
2
C*-O-H +O
2
R
2
C(OH)-O-O*
R
2
C(OH)-O-O-H R
2
C=O +H-O-O-H
Trn c s ny hin nay H2O2 c sn xut ch yu bng qu trnh oxi ho
qua tc cht hu c nh ru izopropylic v anthraquinol.
Vi izopropylic ta c phn ng;
CH3-CH(OH)-CH
3
+O
2
(CH
3
)
2
C=O +H
2
O
2

(CH
3
)
2
C=O +H
2
CH
3
-CH(OH)-CH
3

-Oxi ho aldehit: t lin kt C-H ti nhm -CHO to gc axyl, sau
phn ng vi O
2
thnh gc axyl-peoxit v chuyn ho thnh peaxit.
R-CH=O +R-CO-O-O* R-CO-O-O-H +R -C*=O
R-C*=O +O
2
R-CO-O-O*
Peaxit t phn hu c tham gia ca lin kt hidro thnh gc axyloxi v
axylpeoxit v thnh axit.
R-CO-O-O-H +R-CO-O-O-H R-CO-O* +H
2
O +R-CO-O-O*
R-CO-O* +R-CHO R-CO-O-H +R-C*=O
Hoc tng tc vi aldehit ban u
R-CO-O-O-H +R-CHO R-CO-O-O-CH(OH)-R 2R-CO-O-H
Cc gc axyl v axyloxi c th phn hu ra CO v CO
2
, nht l khi
nhit cao
R-C*=O R* +CO
R-CO-O* R* +CO
2

-Oxi ho xton:
-Xton bn hn ru v aldehit.
-t lin kt C-H ti v tr so vi nhm C=O thnh gc -
xetoalkyl,sau phn ng vi O
2
thnh -xetopeoxit v tip theo thnh
-xetohidropeoxit
R-CH
2
-CO-R' +R-CH(-O-O*)-CO-R' R-C*H-CO-R'
+R-CH(-O-O-H)-CO-R'
R-C*H-CO-R' +O
2
R-CH(-O-O*)-CO-R'
Tip theo -xetoH/P chuyn thnh axit t mch C-C theo c ch ion
v c ch gc
C ch ion:
R-CH(-O-O-H)-CO-R' +H+ R-CH(-O-O
+
H2)-CO-R'
R-CH(-O-O+H2)-CO-R' R-CH(-O
+
)-CO-R' +H2O
R-CH(-O+)-CO-R' R-CHO +R'-C
+
=O
R'-C+=O +H
2
O R'-CO-O-H +H
+

R-CHO +1/2O
2
R-CO-O-H
C ch gc:
R-CH(-O-O-H)-CO-R' +R'-C*=O R-CH(-O*)-CO-R' +R'-CO-O-H
R-CH(-O*)-CO-R' R-CHO +R'-C*=O
Sau , aldehit phn ng vi oxi thnh axit R-CO-O-H theo c ch
bit, cn axyl quay v phn ng vi -xetoH/P theo phn ng trc v
to thnh axit R'-CO-O-H.
Song song vi phn ng chnh trn, t xton c th thnh ru
xton, dixeton do oxi ho nhm CH
2
v tr khc , sau d chng tip tc b
oxi ho thnh oxi axit, xto axit, axit hai chc...
T ru xton to oxi axit:
R-CH(OH)-(CH2)
n
-CO-R' +1,5O
2
R-CH(OH)-(CH2)
n-1
-CO-O-H
+R'-CO-O-H
T dixeton to xto axit:
R-CO-(CH
2
)
n
-CO-R' +1,5O
2
R-CO-(CH
2
)
n-1
-CO-O-H
+R'-CO-O-H
T xeto axit to axit hai chc:
R-CO-(CH
2
)
n-1
-CO-O-H +1,5O
2
R-CO-O-H
+H-O-CO-(CH
2
)
n-2
-CO-O-H
III.2-Sn xut phnol.
-Cng thc: C6H5OH ; d
4
20
=1,072 ; T
n/c
=41
0
C ; T
s
=182
0
C.
-Ph ng dng ca phnol rt rng, l nguyn liu quan trng sn
xut nha phnol, nha epoxi (qua bisphnol A), nha polyamit (qua
caprolactam) lm cht kt dnh, sn, cht do, si tng hp v nhiu qu
trnh tng hp hu c ng lu khc nh sn xut cht mu, nng dc,
dc phm,cht ho do, cht hot ng b mt ... Nhng ng dng ch yu
3 vng a l c trnh by bng

Cc s dng chnh, % KL Ty u M Nht
Nha phnol fomalhit
Nha polyamit (caprolactam)
Nha epoxi (Biphnol A)
34
17
21
35
16
24
47
5
26

-Cc cng ngh sn xut phnol c trnh by bng

Cc cng ngh sn xut, %KL Ty u M Nht
T benzen qua benzen sulfoaxit
T cumen qua cumen hidropeoxit
T toluen qua axit benzoic
Cc cng ngh khc (cc ho than ,
t benzen qua clobenzen ...)

82
17
1

97
2
1
2
97

1

Nh vy, cng ngh ch yu sn xut phnol hin nay l oxi ho
cumen.
a/Cng ngh oxi ho cumen:
-c trng ca phn ng:
C hai giai on phn ng: oxi ho cumen thnh hidrpeoxit (HP) v
chuyn ho HP thnh phnol c mt xc tc axit c tin hnh ring
bit theo cc phn ng nh sau:
C
6
H
5
CH(CH
3
)
2
+O
2
C
6
H
5
C-O-OH(CH
3
)
2

AH
298
=112 kj/mol.

C
6
H
5
C-O-OH(CH
3
)
2
H
+
C
6
H
5
OH + CH
3
-CO-CH
3

AH
298
=253 kj/mol.
+Phn ng chnh v ph ca giai on oxi ho:


C
6
H
5
CH(CH
3
)
2
C
6
H
5
C(CH
3
)
2
OO*
C
6
H
5
C(CH
3
)
2
OOH
C
6
H
5
C*(CH
3
)
2
O
2
C
6
H
5
COCH
3
+ CH
3
O*
+R*
C
6
H
5
C(CH
3
)
2
OH +C
6
H
5
C(CH
3
)
2
O*
+RH
C
6
H
5
C(CH
3
)
2
OH + R*
CH
3
OH
HCOOH
Atophenon
Dimetyl phenyl cacbinol

+Phn ng chnh v ph ca qu trnh oxi ho tin hnh theo c ch
chui gc, pha lng, khng dng xc tc. Yu cu nguyn liu ban u, nht
l cumen tun hon, khng cha cc hp cht c kh nng bt gc nh
phnol, styren, cc hp cht c lu hunh v nit ... lm chm qu trnh oxi
ho. Phn ng ph l chuyn ho tip cumen HP hay gc cumen peoxit
thnh dimtyl phnyl ccbinol, axtophnon v mt s hp cht khc.
hn ch phn ng ph mt mt duy tr chuyn ho thp (X =20 25 %)
gim nng HP v gc HP trong hn hp phn ng v gim dn nhit
phn ng theo mc tch t HP trong sn phm (ngha l gim nhit
phn ng theo tng ca X), mt khc TBP cn c TGL ca pha lng
ng u trnh chuyn ho tip HP to thnh theo c ch chui gc trong
mi trng ca qu trnh oxi ho.
+Qu trnh oxi ho cumen l d th kh-lng xy ra trong phm vi
ng hc 100 - 130
0
C ( TGL ca pha lng khong t 2 - 3 h t
chuyn ho X ca cumen nh trn ) nn c tin hnh trong TBP loi si
bt l loi thit b c m hnh dng chy gn vi KLT (bt kh i ln ko
theo cht lng v to s khuy trn mnh trong thit b). phn b TGL
ca pha lng ng u cn dng 3 - 5 thp si bt ni tip nh hnh 3.2. S
dng h thit b ni tip cn gip cho vic ch nhit trong tng thit b
khc nhau, gim dn khi X tng nh trn.
+Phn ng to nhit, gii nhit bng cch bm tun hon hn hp
phn ng qua thit b trao i nhit hay dng v bc ngoi.
+Phn ng chnh v ph ca qu trnh chuyn ho HP thnh phnol v
axton:



H.3.2-S cng ngh sn xut phnol t cumen.
1-TBP oxi ho cumen thnh hidropeoxit. 2-Thp chng chn khng
tch cumen. 3-Thng phn ng c khuy phn hu HP cumen thnh
phnol v axton. 4-Thit b phn hu hon ton HP cumen. 5-Tch
H
2
SO
4
dnh anionit. 6-Thp tch axton. 7-Thp tch cumen v -
mtyl styren. 8-Thp tch phnol. 9-Thit b thu hi phnol t cn.
10-Thng hp ph cumen t kh thi.




III.3-Sn xut axit axtic: Tsi =117,9
0
C; Tnng chy = 16,66
0
C
-Tuy c nhit si cao hn nc gn 20
0
C nhng rt kh chng tch
nc t dung dch long v thnh phn pha hi trong cn bng hi-lng t
khc vi pha lng. Do vy, nng nng axit axetic t dung dch long
thng dng phng php trch li vi dung mi etyl axetat, butyl axetat, izo-
propyl ete hay c th chng ng ph d th vi cc dung mi trn.
-Sn xut v s dng nh bng 3.3.1
Bng 3.3.1
S dng, % KL Ty u M Nht
SX anhydric axetic 8 6 4
SX axetat xenlul 12 10 18
SX este 16 12 9
SX monoclo axtic 9 2 5
SX axit terephtalic 6 10 11
SX vinyl axetat 37 52 27
Dt, nhum, khc 12 8 26
Sn xut, % KL
T axetaldehit 45 20 52
T butan v naphta 16 17 6
T metanol 34 62 42
T nguyn liu khc 5 1 -

III.3.1-Phng php oxi ho axtaldehit:
-C hai cng ngh: Sn xut AcOH vi xc tc mui Co v sx ng
thi AcOH v (Ac)
2
O vi xc tc hn hp mui Co v Cu.
a/SX AcOH:
-Phn ng:
CH
3
-CHO +1/2O
2
CH
3
-CO-O-H AH
298
=265 Kj/mol
-C ch phn ng :
CH
3
-CH=O +CH
3
-CO-O-O* CH
3
-CO-O-O-H +CH
3
-C*=O
CH
3
-C*=O +O
2
CH
3
-CO-O-O*
Chuyn ho tip axit peaxetic vi axetaldehit:
CH
3
-CO-O-O-H +CH
3
-CH=O CH
3
-CO-O-O-CH(OH)-CH
3


CH
3
-CO-O-O-CH(OH)-CH
3
2CH
3
-CO-O-H v
CH
3
-CO-O-O-CH(OH)-CH
3
CH
3
-CO-O-H +CH
3
-O-CH=O.
Ngoi ra t gc axtyl peoxit chuyn ho thnh gc axtyloxi v
thnh mtanol, fomaldhit, axit fomic:
2CH
3
-CO-O-O* CH
3
-CO-O-O-O-O-CO-CH
3
2CH
3
-CO-O*+O
2

2CH
3
-CO-O* 2CH
3
* +2CO
2

2CH
3
* +2O
2
2CH
3
-O-O*
2CH
3
-O-O* 2CH
3
-O* +O
2

CH
3
OH +CH
2
=O +O
2

-Vai tr ca xc tc:
+Xc tin tng tc peaxit vi axtaldehit.
+Gim gc axtyl peoxi v do gim phn ng ph nh phn ng:
CH
3
-CO-O-O* +Co
2+
CH
3
-CO-O-O
-
+Co
3+

-iu kin phn ng:
Cht oxi ho Khng kh Oxi k thut
Nhit , 0C 55 65 70 80
p sut, MPa 0,5 1 0,15 0,3
-Sn phm ph ch yu l fomaldhit, axit fomic, mtyl v tyl axtat,
axton v CO
2
.
S cng ngh hnh 3.3
K
h

n
g

k
h

H.3.3-S cng ngh oxi ho axetaldehit thnh axit axetic
bng khng kh.
1-Thp x l khng kh. 2- TBP oxi ho. 3-Thp ra kh thi
4-Thit b phn hu axit peaxtic. 5-Thp chng axtaldehit.
6-Thp tch mtyl axtat. 7-Thp chng ng ph tch nc v tinh
ch axit axtic. 8-Thp chng ng ph tch tyl axtat trong nc.
b/Sn xut ng thi axit axtic v anhydric axtic (T
si
=139,6
0
C):
-Xc tc l hn hp mui Co hay Mn v Cu vi t l Co (Mn) : Cu =
1 : ( 1 3 ).
-Cht oxi ho ngho oxi hn khng kh - hn hp nit vi 7 9% th
tch oxi - tng nng gc axtyl CH
3
-C*=O. T c phn ng:
CH
3
-C*=O +Cu
2+
(CH
3
-CO-O

)
2
CH
3
-C
+
=O +Cu
1+
(CH
3
-CO-O

)
+CH
3
-CO-O

CH
3
-C
+
=O +CH
3
-CO-O

(CH
3
-C=O-)
2
O.
-iu kin phn ng: T = 60 80
0
C; P =0,4 1 MPa.
-Sn phm c t l AcOH / (Ac)
2
O =( 3 5 ) / ( 7 5 )
-Tch nc bng chng ng ph vi Etyl axtat.
-S cng ngh hnh 3.4

T
B
P

o
x
i

h
o

p

t
h

a
x
e
t
a
l
d
e
h
i
t
C
h

n
g

a
x
e
t
a
l
d
e
h
i
t
C
h

n
g

n
g

p
h

C
h

n
g
E
t
y
l

a
x
e
t
a
t
C
h

n
g

a
x
e
t
a
l
d
e
h
i
t
C
h

n
g

A
x
i
t

a
x
e
t
i
c
T
i
n
h

c
h

A
n
h
y
d
r
i
c

a
x
e
t
i
c
A
n
h
y
d
r
i
c

a
x
e
t
i
c
N

c
A
x
e
t
a
l
d
e
h
i
t

H.3.4-Sn xut ng thi axit v anhydric axtic bng
oxi ho axtaldehit
III.3.2-Sn xut AcOH t mtanol v CO:
-y l cng ngh mi, tc pht trin nhanh do hiu qu kinh t
cao.
-Phn ng:
CH
3
OH +CO CH
3
-CO-O-H AH
298
=138,6 Kj/mol
-Xc tc: Phc Co v Rh, hot ho bng it.
*Vi xc tc phc Co, hot ho bng HI tin hnh 250
0
C v
p sut 70 MPa. a vo cng nghip nm 1960 do cng ty BASF, c s
u tin cng sut 3600 tn/nm, sau ln 10.000 tn /nm-1964, 35.000
tn /nm- 1970, 45.000 tn- 1981. Cng theo cng ngh ny M sn xut
45.000 t/n- 1966, 64.000t/n - 1981.
*Vi xc tc phc Rh, hot ho bng HI do hng Monsanto
pht hin nm 1968. Xc tc c hot tnh v chn lc cao hn nhiu. Qu
trnh c th thc hin p sut kh quyn, tuy nhin trong cng nghip tin
hnh 180
0
C v 3 MPa. Hiu sut t 99% theo metanol, 90% theo CO.
a vo cng nghip nm 1970 vi 135.000 t/n, 1975 a ln 180.000 t/n.
-S cng ngh nh hnh 3.3.3



H.3.5-S cng ngh sn xut axit axetic t metanol v CO.
1-TB ch to phc xc tc. 2-TB trao i ion x l xc tc lm
vic. 3-Thng cha xc tc. 4-TB ch to mtyl ioua. 5-Thng cha mtyl
ioua. 6-TBP ccbonyl ho. 7-Thp hp th mtyl ioua bng mtanol.
8-Thp tch kh. 9-Thp chng ly phn on giu axit axtic. 10-Thp
chng ng ph tch nc. 11-Thp tch nc. 12-Thp tn thu axit axtic t
phn on nng. 13-Thp tinh ch axit axtic.

III.4-Sn xut axit trphtalic(ATP):
-L nguyn liu sn xut polytylen trphtalat (PET) bng phn
ng a t vi tylen glycol:
HO-CH
2
-CH
2
-[O-CO-C
6
H
4
-CO-O-CH
2
-CH
2
]
n
-OH
Nha PET dng sn xut si polyeste (7080%), ngoi ra dng
lm phim, ng.
- tinh khit ca monome rt quan trng di vi cht lng ca si,
do vy qu trnh tinh ch sn phm cn c ch trong cng ngh sn
xut v song song vi ATP ngi ta sn xut c este ca n l dimetyl
terephtalat (DMTP) d tinh ch: ATP khng nng chy, thng hoa
300
0
C, cn DMTP c T
nng chy
=141
0
C, T
si
=284
0
C, ho tan trong te v
mtanol nng, nh vy c th tinh ch bng kt tinh hay chng ct chn
khng.
-Phng php sn xut ch yu l oxi ho p-xylen (c tch bng
cng ngh lin tc hp ph chn lc PAREX).
III.4.1-Oxi ho p-X bng HNO
3
:
C
6
H
4
(CH
3
)
2
+4HNO
3
C
6
H
4
(COOH)
2
+4H
2
O +4NO
AH
298
=750 Kj/mol
-KP: 165
0
C, 1 MPa, pha lng d th TBP loi thng c khuy.
-ATP to thnh khng tan,tch bng li tm v chuyn thnh DMTP
150
0
C, XT l H
2
SO
4
, v chuyn qua giai on tinh ch.
-Hiu sut tng cng t 90%.
-Cn thu hi NO v ti sinh HNO
3
m bo v kinh t v mi trng:
NO +1/2O
2
NO
2
.
4NO
2
+O
2
+2H
2
O 4HNO
3
.
-y l cng ngh c ca Du Pont, BASF: ln hp cht nit kh tinh
ch, dng sn xut t 1970.
III.4.2-Oxi ho p-xylen thnh DMTP
-Oxi ho nhm etyl th nht to thnh axit p-toluic d, nhm CH
3
th
2 kh oxi ho hn. Khi este ho nhm -CO-O-H th nht th qu trnh oxi
ho tip theo d hn. Hn na, DMTP d tinh ch nh ni trn.
-C 4 phn ng ln lt nh sau
1/Oxi ho p-X thnh axit p-toluic:
C
6
H
4
(CH
3
)
2
+3/2O
2
CH
3
-C
6
H
4
-CO-O-H +H
2
O
AH
298
=690 Kj/mol
C ch chui gc, xc tc l naphtenat Co,Mn.
2/Este ho axit p-toluic vi mtanol thnh p-mtyl toluat:
CH
3
-C
6
H
4
-CO-O-H +CH
3
OH CH
3
-C
6
H
4
-CO-O-CH
3
+H
2
O
AH
298
=30 Kj/mol
Phn ng thun nghch, d metanol v tch nc phn ng n
cng, xc tc axit.
3/Oxi ho nhm mtyl cn li thnh mtyl trphtalat:
CH
3
-C
6
H
4
-CO-O-CH
3
+3/2O
2
H-O-CO-C
6
H
4
-CO-CH
3
+H
2
O
AH
298
=675 Kj/mol
4/Este ho thnh DMTP:
H-O-CO-C
6
H
4
-CO-O-CH
3
+CH
3
OH CH
3
-O-CO-C
6
H
4
-CO-O-CH
3

+H
2
O
AH
298
=30 Kj/mol
Trong sn xut thc hin p 1 v 3 trong 1 TBP oxi ho, v p 2 v
4 trong mt TBP este ho.
-TBP oxi ho:
+H d th kh-lng thp si bt. Dng h thp ni tip m bo
ng lc hc ca TB cao, gii nhit qua thnh bng ng xon hay bm tun
hon qua thit b trao i nhit.
+KP: 150 180
0
C, 0,6 1 MPa, XT: naptenat Co.
+Nguyn liu vo: Hn hp p-X v p-mtyl toluat.
+TBP l thp si bt ni tip.
-TBP este ho:
+KP: 250
0
C, 2,5 MPa, XT: p-toluen sunfoaxit.
+TB thng c khuy ni tip c tch nc bng cch bay hi.



H.3.6- S cng ngh sn xut imtyl Trphtalat (DMTP).
1-Chun b xc tc oxi ho. 2-TBP oxi ho. 3-H TB thu hi p-Xylen
trong kh thi. 4-TBP este ho. 5-Chun b xc tc este ho. 6-Thp tch
mtanol. 7-Thp tinh ch mtanol. 8-Thp tch DMTP. 9-Thp tinh ch
DMTP. 10-Ho tan DMTP. 11-Kt tinh ln 1. 12-Li tm. 13-Ra tinh th.
14-Ho tan DMTP. 15-Kt tinh ln 2. 16-Nng chy DMTP. 17-Thp chng
tinh ch DMTP.
III.4.3-Oxi ho p-Xylen thnh ATP theo cng ngh Amoco:
-Trn c s xc tc mi cha Br-: axetat Co +NaBr, dung mi l axit
axetic, c th oxi ho c hai nhm metyl:
C
6
H
4
(CH
3
)
2
+3O
2
C
6
H
4
(CO-O-H)
2
+2H
2
O
AH
298
=1360 Kj/mol
-KP: 195 205
0
C, 2 3 MPa, hn hp phn ng: 100 phn
AcOH, 15 phn p-Xylen, 2 phn xc tc ( t l Br/Co = 2/1).
- chuyn ho p-X trn 95%, hiu sut 90 92%, thun ATP t
99,5%.



H.3.8-S cng ngh sn xut ATP bng cch oxi ho trc tip
p-X theo cng ngh Amoco.
1-TB iu ch xc tc. 2-H TBP si bt ni tip. 3-TB kt tinh.
4-Lc li tm. 5-TB sy kh. 6-Thp hp th. 7-Thp chng tch nc.
8-Thp chng tch axit axtic. 9-TB ra ATP. 10,11-TB ho tan ATP
nhit cao. 12-TB hidro ho. 13-Lc xc tc. 14-TB kt tinh.

III.5-Oxi ho trn xc tc rn.
III.5.1-Sn xut Fomaldehit:
-TS =19
0
C, l cht kh.
-Ho tan tt vo nc, phn ng to thnh oxi mtylen glycol:
nCH
2
O +H
2
O HO(CH
2
O)
n
H
n t 1 10 ph thuc vo nng CH
2
O.
Nh c th vn chuyn, s dng fommalhit dng dung
dch 35 55% CH
2
O, c gi l dung dch Fomalin, cng nh tch mtanol
cha chuyn ho t dung dch Fomalin trong cng ngh sn xut.
-ng dng ca Fomalhit:




S dng Fomaldhit, % Ty u M Nht
Nha nhit rn
Trong : Mlamin - Fomalhit
Phnol - Fomalhit
Ur - Fomalhit
61
6
9
46
58
4
22
32
46
6
9
31
Pentaerythritol [ C(CH
2
OH)
4
] 8 7 8
Nha polyaxtal 6 8 19
Urotropin (hexamtylentetramin) 3 5 5
Butaniol [ HO(CH
2
)
4
OH ] 5 11 -
Cc ng dng khc 17 11 22

-Fomaldehit c sn xut t mtanol bng qu trnh oxi-dehidro ho
trn xc tc bc v oxi ho trn xc tc oxit Fe-Mo.
-y l cc qu trnh pha hi nn cn trnh to hn hp n metanol -
khng kh c thnh phn t 6 n 40% th tch metanol.
a/Cng ngh xc tc bc:
+Nhit phn ng: 650 - 720
0
C.
+Tin hnh qu trnh trn gii hn n, hn hp phn ng cha
khong 45% th tch mtanol, do thiu oxi cho phn ng oxi ho nn c
thm phn ng chnh dhidro ho mtanol
CH
3
OH +1/2O
2
CH
2
O +H
2
O ( 1 ) AH
298
= 156 kJ /mol
CH
3
OH CH
2
O +H
2
( 2 ) AH
298
=+85 kJ /mol
Phn ng (2) thun nghch, thu nhit. Cn bng ph thuc nhit :
400
0
C - X
CB
=50%; 500
0
C - X
CB
=90%; 600
0
C - X
CB
=99%
Tng nhit phn ng ca qu trnh l to nhit, qu trnh nm phm
vi khuch tn ngoi, on nhit v t nhit, iu chnh nhit phn ng
bng cch pha thm hi nc vo hn hp phn ng.
Thnh phn ca kh thi sau thp hp th cha 15 20% th tch
hidro, c t thu hi nhit trc khi thi.
+Phn ng ph: CH
2
O CO +H
2
( nhit cao, xt st)
CH
3
OH +H
2
CH
4
+H
2
O
CH
2
O +O
2
HCOOH
CH
2
O +O
2
CO
2
+H
2
O
T thnh phn ca kh thi sau thp hp th c th tnh c chn
lc v hiu sut ca qu trnh. Ngay sau lp xc tc cn lm lnh nhanh hn
hp phn ng trnh phn hu fomalhit.
+Thit b phn ng vi lp xc tc mng (khong 30 - 50mm) gm
Ag tinh th hay Ag trn cht mang l xp ln t trn li ng, cng b
phn t in mi phn ng khi m my v lm lnh ng chm t st
ngay sau lp xc tc nh hnh

+C hai cng ngh sn xut:
Cng ngh 650
0
C, X
MeOH
=85%, chng thu hi mtanol cha
chuyn ho t dung dch fomalin sau thp hp th.
Cng ngh 720
0
C ca BASF, X
MeOH
=98- 99%, khng phi chng
thu hi mtanol.
S cng ngh vi xc tc Ag tin hnh nhit cao 720
0
C ca
BASF

Nc mm
Khng kh
Nc mm
Hi nc
Formalin
50% CH
2
O
Metanol
Hi nc
1
2
3
5
6
7 7
Khng
kh
4
Kim thi
(+Natri Fomat)
Dung dch kim

H.3.5.2-S cng ngh oxi ho metanol thnh formaldehit
trn xc tc Ag 720
0
C
1-Lc bi khng kh. 2-TB to hn hp hi metanol-khng kh.
3-TBP. 4-TB lm lnh ng chm. 5-Thp hp th formaldehit
6-L t kh thi. 7-Thit b trao i anion kh axit fomic.
b/Cng ngh xc tc oxit Fe-Mo:
+Xc tc Fe
2
O
3
- MoO
3
vi t l mol tng ng 1/1,5.
+Nhit phn ng: 290 - 310
0
C.
+Lm vic di gii hn n ( hn hp khong 6% th tch mtanol ),
d oxi nn ch c phn ng oxi ho (1) to nhiu nhit l phn ng chnh.
Do nng mtanol thp dn n th tch hn hp phn ng rt ln (4-5 ln
so vi xc tc bc) nn cn tun hon kh thi ngho oxi sau thp hp th
c th a nng mtanol ln m khng to thnh hn hp n, nh
gim c kch thc thit b, ng ng, cng sut my nn kh ... cng
nh cn tin hnh trao i nhit gia dng nng v dng lnh ca hn hp
phn ng.
+Xc tc lp tnh, TBP dng ng chm ( hnh 4.22 ), ng knh
ng tng i nh c 20 - 25 mm.

H
1-TBP ng chm. 2-Thp hp th fomalhit. 3-TB x l kh thi
4-TB trao i anion kh axit fomic.

III.5.2-Sn xut oxit etylen (OE):
a/Tnh cht v ng dng:
-T
S
=10,8
0
C, tn tr v vn chuyn dng lng di p sut nit.
-Ho tan tt vo nc v khi c xc tc axit v nhit s phn ng
to etylen glycol:

CH
2
-CH
2
+ H
2
O
HOCH
2
- CH
2
OH
O

-Gii hn n vi khng kh: 2,6 80% th tch OE.
-Kh nng phn ng cao, l hp cht trung gian quan trng.



S dng,% Ty u M Nht
Sn xut Etanolamin 10 8 6
Sn xut Etylen Glycol 45 61 58
Sn xut Ete Glycolic 11 6 6
Sn xut cht HBM khng ion 21 12 21
Cc ng dng khc 13 13 9
b/Cng ngh sn xut:
-Ch yu hin nay l oxi ho Etylen bng oxi trn xc tc Ag.
-Phn ng:
Chnh:

O
CH
2
-CH
2
CH
2
=CH
2
+ 1/2O
2
0
298
H =105 kJ /mol
Ph:
CH
2
=CH
2
+3O
2
2CO
2
+2H
2
O

0
298
H =1330 kJ /mol

O
CH
2
-CH
2
+ 5/
2
O
2
2CO
2
+ H
2
O


0
298
H =1225 kJ /mol
Hiu sut OE trong sn xut cng nghip thng khong 70% do vy
nhit phn ng c 500 kJ /mol Etylen chuyn ho. y l phn ng to nhit
cao v chn lc nhy vi s thay i nhit nn TBP dng loi ng
chm vi ng knh ng kh b, c 20 25 mm.
-Xc tc: Ag/cht mang c xp thp.
+Cu t hot tnh l Ag.
+Cht kch ng, tng chn lc:
Mui Ba, Ca, x phng Na,Li.
Hp cht clo hu c: Dicloetan, Diclopropan. Cc cht
ny cho ng thi vo hn hp phn ng vi hm lng 10 ppm.
+Cht mang: Dn nhit tt, b mt b c 0,1 0,2 m
2
/g.
Thng dng -Al2O3 (Shell), silic ccbua (Scientific Design, Montecatini),
vt liu silicat, ferrosilic (Dyanamit Nobel).
+Rt nhiu patent v xc tc Ag/cht mang lin quan n
phng php ch to xc tc, cht kch ng, cht mang, xp, b mt
ring, dn nhit ca xc tc.
-iu kin cng ngh:
+Nhit : T
p
=260 290
0
C. L thng s quan trng sau xc
tc v nhit tng th chn lc gim mnh.
+p sut: Khng nh hng n qu trnh phn ng. Trong
cng nghip thng tin hnh 1 3 MPa tng cng trao i nhit,
gim th tch thit b, d tch OE (hp th vo nc, lm lnh ho lng).
. +Nguyn liu:
Etylen c hm lng 95 98%, sch tp cht axtylen, cc olfin
khc v hp cht lu hunh.
Cht oxi ho: khng kh v oxi k thut. Thng dng oxi k thut
trnh tn tht Etylen trong kh thi.
Gii hn n E-KK l 3 28,6% th tch Etylen
+Cc cng ngh:
Cng ngh Shell (H. ): Dng Oxi k thut c thun trn 95%,
Etylen c th cha n 10% th tch CH
4
, tin hnh trn gii hn n, d
Etylen v tun hon li sau khi kh CO
2
.

H. . -Cng ngh Shell sn xut OE
1-TBP ng chm. 2-Thp hp th OE bng nc. 3-Thp nh OE.
4-Thp tch kh. 5-Thp tch OE. 6-Thp tinh ch OE. 7-Thng cha nc
hp th. 8-Thp hp th b sung. 9-Thp hp th CO
2
. 10-Thp nh CO
2
.
11-TB tch nc.
Cng ngh Scientific Design (H. ): Dng khng kh, lm vic di
gii hn n vi t l th tich KK/E =10/1, hai TBP ni tip chuyn ho
nt Etylen sau khi hp th OE. Hn hp kh sau TBP th nht cha 2%
OE, 2-3% E=(XE =25 30%, S =70%), sau khi hp th OE tun hon li
khong 60%, kh cn li thm khng kh v a vo TBP th 2. y duy
tr chuyn ho cao X =75-80% vi chn lc S =50%. Hiu sut tng
cng t 60 - 65%.




H. . -Cng ngh Scientific Design sn xut OE.
1-TBP th nht. 2-Thp hp th. 3-TBP th 2. 4-Thp hp th.
5-Thp nh hp th OE. 6-Thp tch OE. 7,8-Thp tinh ch OE. 9-TB tch
kh-lng. 10-Thp tch kh thi.
III.5.3-Sn xut Etylen Glycol (EG).
T
NC
= ,T
S
=197
0
C.
ng dng:
Lnh vc ng dng, % Ty u M Nht
Cht chng ng lnh 33 47 13
Si Polyeste 48 36 64
Nha Polyeste khng no, nha alkyt,
cc ng dng khc.
19 17 23
Sn xut: Phng php cng nghip ch yu l t OE.
+Phn ng:

O
CH
2
-CH
2
+ H
2
O
HOCH
2
-CH
2
OH
0
298
H =75 kJ /mol
Sn phm ph l DEG [HO(CH
2
-CH
2
O)
2
H] v
TEG [ HO(CH
2
-CH
2
O)
3
H]
sn xut MEG dng t l OE/H2O =1/20 25, khi hn hp
phn ng c thnh phn 88,5% MEG, 10,5% DEG v 0,5% TEG.
+iu kin cng ngh:
Phn ng ng th pha lng, on nhit.
T
vo
=150
0
C, T
ra
=210
0
C.
Thi gian phn ng: 45 60 ph. Khng dng xc tc.
+Cng ngh:
Sau phn ng c c trong h 4 TB ni tip, TB sau dng hi th ca
TB trc. Tip theo chng chn khng tch nc v cc glycol.


H. . -Cng ngh sn xut Etylen Glycol.
1-TB trn. 2-TBP pha lng, on nhit. 3-H thng c c. 4-Thp
tch nc. 5-Thp tch MEG. 6-Thp tch DEG. 7-Thp tch TEG.
III.5.4-Sn xut Anhyric Maleic (AM) v Anhyric Phtalic (AP).
A-Sn xut AM:
- T
N/C
=53
0
C; TS =202
0
C.
-c s dng t 50% (M, Nht) n 90% (Ty u) cho sn xut
nha polieste khng no l polyme mch thng dng lng, ng rn vi
monome vinyl khc nh styren c mt cht khi mo thnh polyme mch
khng gian.

nHO-RO-H +
H[ORO-C-CH=CH-C-]
n
OH
CH
CH C
O
C
O
O

-c sn xut bng oxi ho Benzen, n-Butan v n-Buten pha hi
trn xc tc rn.
Nguyn liu ban u, % Ty u M Nht
T Benzen 74 - 65
T n-Butan 20 100 14
T n-Buten - - 21
Sn phm ph ca sn xut AP 6 - -

a/T Benzen:
+Phn ng:
Chnh:


CH
CH C
O
C
O
O
+ 4O2
+ CO
2
+ CO + 2H
2
O


0
298
H =1470 kJ /mol
Ph:

+ 6O
2
3CO
2
+ 3CO + 3H
2
O

0
298
H =2320 kJ /mol
Nhit phn ng (chnh v ph) rt ln, cn tn dng to hi nc.
+iu kin cng ngh:
T
P
=350-400
0
C; P =0,1-0,2 MPa.
Xc tc V
2
O
5
+MoO
3
/Al
2
O
3
vi cht n nh P
2
O
5
.
Gii hn n Benzen-KK l 1,4 7,1% TT. Tin hnh 1,2-1,3% BZ.
TBP dng ng chm, gii nhit bng mui nng chy. TGL =0,1s.
chuyn ho X =95%, chn lc S =67%.


H. . -Cng ngh sn xut AM t Benzen.
1-TBP dng ng chm trao i nhit vi mui nng chy. 2-Ni hi
3-TB tch lng-kh 60
0
C. 4-Thp hp th AM bng nc. 5-TB bay hi
chn khng (30-60 kPa) mng mng. 6-TB thu hi AM trong cn. 7,8-Thp
chng chn khng tinh ch AM (10-20 kPa).
b/T n-Butan:
Sn xut 50% AM. Gi n-Butan r hn Benzen.
+Phn ng:
Chnh:

CH
CH C
O
C
O
O
CH
3
-CH
2
-CH
2
-CH
3
+ 7/2O
2
+4H
2
O


0
298
H =1240 kJ /mol
Ph:
CH
3
-CH
2
-CH
2
-CH
3
+11/2O
2
2CO
2
+2CO +5H
2
O

0
298
H =2090kJ /mol
+iu kin phn ng:
iu kin lm vic ging vi cng ngh sn xut t Benzen. D dng
chuyn h TB t BZ qua nguyn liu ny.
Xc tc trn c s oxit P,V v Fe/cht mang Al2O3,SiO2.
Mt khc bit ng lu : lng nc to thnh vi nguyn liu ny
ln hn (gp i) nn hn ch nhit lm lnh tch AM, lm lnh trn
im sng ca hi nc v ch tch c 25-30%, sau hp th bng
dung mi ibutyl hexahidrophtalat, nh hp th AM v tinh ch AM trong
hai thp chng chn khng.



H. . -Cng ngh sn xut AM t n-Butan.
1-TBP ng chm. 2-Ni hi. 3-TBtch kh-lng. 4-Thp hp th
AM bng dung mi hu c. 5-Thp nh AM. 6,7-Thp chng chn khng
tinh ch AM. 8-Bc hi chn khng mng mng ti sinh dung mi.
B-Sn xut AP:
T
NC
=131
0
C, T
S
=284,5
0
C.
ng dng v cc phng php sn xut:

ng dng, % Ty u M Nht
Sn xut nha Alkyd 16 19 14
Sn xut cht ho do Phtalat 63 51 63
Sn xut nha Polyeste khng no 19 25 15
Cc ng dng khc 2 5 8
Phng php sn xut, %
T Naphtalen 8 15 29
T o-Xylen 92 85 71
+Phn ng:
Chnh:
T Naphtalen:

C
O
C
O
O
+4,5O
2
+2CO
2
+ 2H
2
O


0
298
H =1790 kJ /mol
T o-Xylen:

C
O
C
O
O
+ 3H
2
O
CH
3
CH
3
+3O
2


0
298
H =1108 kJ /mol
Ph:
Vi Naphtalen:

CH
CH C
O
C
O
O
C
10
H
8
+ 12O
2
+6CO
2
+ 3H
2
O


C
10
H
8
+12O
2
10CO
2
+4H
2
O
0
298
H =5050 kJ /mol
Vi o-Xylen cng c 2 phn ng ph trn, khi oxi ho hon ton to
nhit 4380 kJ /mol.
Do vy nhit phn ng thc t khi chuyn ho mt mol nguyn liu:
Vi Naphtalen, hiu sut 80-85%: 2100 - 2500 kJ /mol.
Vi o-Xylen, hiu sut 77-79%: 1300 - 1800 kJ /mol.
+iu kin phn ng: Ging nhau cho c hai nguyn liu.
Xc tc trn c s V
2
O
5
c thm ph gia tng chn lc.
Gii hn n di ca o-Xylen vi khng kh l 1,7% mol (70-80g/m
3
)
ca Naphtalen l 0,9% mol (44g/m
3
).Tin hnh qu trnh di gii hn n,
t l mol KK/HC thng t 60 - 120.
T
P
=350-430
0
C. Cng nghip dng 2 loi TBP:
-Loi ng chm: Dng cht trao i nhit l mui nng chy
(53%KNO
3
+40% NaNO
2
+7% NaNO
3
- l hn hp tcti c T
NC
=150
0
C,
chu nhit n 550
0
C).
-Loi tng si: Vi loi TBP ny c th nng cao nng HC m
khng s to hn hp n do hin tng khuy trn mnh trong lp si c
nhiu kh tr v hi nc. Ngoi ra cng do hin tng khuy trn mnh ca
lp si d dng gii nhit phn ng v dng tc nhn mang nhit l nc.
Tuy vy, hiu sut AP thp hn khi dng lp xc tc c nh.
+Cng ngh:
Tch sn phm bng cch lm lnh gin on trong hai TB theo chu
k: Lm lnh kt tinh AP v nng chy ho lng AP.
Tinh ch AP:
-Gia nhit n 230 - 300
0
C trong 10 - 24 gi trong TB thng c khuy
c lm lnh hi lu bay hi v phn hu cc tp cht nh Naphtoquinon,
o-Tolualhit, Phtalid. Trong giai on ny c th thm NaOH, H
2
SO
4
,
H
3
BO
3
.
-Cui cng chng chn khng.

H. . -Cng ngh sn xut AP t o-Xylen.
1-TBP ng chm. 2-Ni hi. 3-TB lm lnh kt tinh v nng chy
AP. 4-Thp hp th. 5,6-TB x l AP bng nhit . 7,8-Thp chng tinh
ch AP.
Ht chn khng
Nc thi
Nc
Kh thi
(i t)
Hi nc
Hi nc
Nc mm
Khng kh
Naphtal en
S.P.
nng
Nc
Hi
Anhydric Phtal ic
1
3
4
5
6
Chn khng
2
2

H. . -Cng ngh sn xut AP t Naphtalen.
1-TBP tng si. 2-Ni hi. 3-TB kt tinh v nng chy AP. 4-Thp
hp th. 5-TB x l AP bng nhit . 6-Chng chn khng tinh ch AP.

IV-Cc qu trnh clo ho.
IV.1-c trng ca qu trnh clo ho:
+Mc ch:
-Sn xut cc monome cha clo: vinyl clorua, cloropren.
-Sn xut cc hp cht trung gian: CH
3
Cl, icloetan, Clobenzen.
-Sn xut dung mi cha Clo, cht ho do.
+C ch phn ng: Qu trnh clo ho cc hp cht hu c thng tin
hnh theo hai c ch: C ch chui gc v c ch ion to phc t.
a/C ch chui gc:
Phn ng:
-Clo ho cc HC no: Th hidro v to HCl.
CH
4
+Cl
2
CH
3
Cl +HCl
RH +Cl
2
RCl +HCl
-Clo ho cng vo nhn thm:
C
6
H
6
+3Cl
2
C
6
H
6
Cl
6
-Th v cng Clo vo lfin pha kh, xu th tng loi phn ng ph
thuc vo nhit :
CH
2
=CH-CH
3
+Cl
2
CH
2
=CH-CH
2
Cl +HCl ( >300
0
C)
CH
2
=CH-CH
3
+Cl
2
CH
2
Cl-CHCl-CH
3
( <200
0
C)
Cc giai on:
+To gc t do: Lin kt Cl-Cl (239 kJ /mol) yu hn lin kt C-C
(345 kJ /mol) v C-H (365 kJ /mol) b t to gc Cl*.
Do nhit cao (phn ng pha kh):

Cl
2
Cl* + Cl*
t
0

Do phn ng vi HC, c bit vi lfin, c th tin hnh c pha kh
v lng: RH +Cl
2
R* +Cl* +HCl
CH
2
=CH
2
+Cl
2
CH
2
Cl- C*H
2
+Cl*
Do hp ph mt lng t hv:

Cl
2
Cl* + Cl*
hn

T nng lng lin kt ca Cl-Cl c th tnh c bc sng ca nh
sng c nng lng lm t lin kt ny:
E =N.hv =239 (kJ /mol).
N =6,02486 . 10
23
(S Avogadro).
h =6,626 . 10
34
(J .s).
v =C/ . Trong C =2,998 . 10
10
(cm/s) =2,998 . 1018(A
0
/s).
v =E/N.h =239 . 10
3
/6,02486 . 10
23
. 6,626 . 10
34
=
5,9868 . 10
14
(s
1
).
= C/v =2,998 . 1018 (A
0
/s)/5,9868 . 1014(s
1
) =5000 (A
0
).
Do c mt cht khi mo (to gc t do):
.Peroxit benzoil: (C
6
H
5
COO)
2
2C
6
H
5
* +2CO
2
.
.Azodiizobutylnitril:

NC-C-N N-C-CN
CH
3
CH
3
CH
3
CH
3
NC-C*
CH
3
CH
3
+ N
2

V cc g t do ny s tng tc vi phn t clo thnh Cl*.
+Pht trin chui:
Vi HC no:
Cl* +RH R* +HCl
R* +Cl2 Cl* +RCl
Vi lfin: Theo phn ng cng:

Cl* + C=C CCl -C*


CCl -C*
+ Cl
2
Cl* + CCl - CCl

+t chui:
Do kt hp cc gc t do to thnh phn t.
Do hp ph gc t do ln thnh thit b.
Do kt hp vi cc hp cht bt gc (lu hunh v cc hp cht cha
lu hunh, cc hp cht phnol, vi phn t oxi). c bit phn t oxi c
trong Clo in gii, nn tin hnh qu trnh Clo ho theo phn ng chui
gc cn dng Clo bc hi t Clo lng.
Cng ngh


V.1-Sn xut 1,2 icloetan (1,2 CE):
-C hai phng php cng nghip sx 1,2 CE: Clo ho v oxiclo ho
etylen. Phng php sau nhm tn dng HCl to thnh nhng qu trnh clo
ho theo phn ng th, cng nh qu trnh phn hu nhit 1,2CE sn
xut vinyl clorua.
a/Qu trnh Clo ha Etylen:
+Phn ng:
CH
2
=CH
2
+Cl
2
CH
2
Cl - CH
2
Cl AH
298
=220 Kj/mol
Kh Kh Lng ( T
s
=85
0
C)
Thc t l phn ng kh-lng: sc etylen v clo vo 1,2CE lng ho
tan FeCl
3
0,5% vi vai tr xc tc. Phn ng xy ra trong pha lng vi vn
tc cao ngay nhit thng. Nh vy, qu trnh c c trng d th kh-
lng, to nhiu nhit, tin hnh nhit thp c nhit si ca pha lng.
nhit hi cao ( 80 - 100
0
C ) phn ng ph clo ho tip thnh tricloetan
c c tng cng, v vy cng ngh c tin hnh clo ho nhit thp
v gii nhit phn ng bng nc.
+ n nay phn ng ph theo c ch chui gc b hn ch bng
cch dng xc tc FeCl
3
v clo c cha oxi, nn c th tin hnh nhit
cao hn v s dng nhit phn ng ( kh ln) tch sn phm dng hi
khng b ln vi xc tc.
+ Cng ngh tin b nht dng TBP dng CD, kt hp vi thp
chng, tn dng nhit phn ng tinh ch CE khng ch t thit b clo
ho m t cc b phn khc ca h thng lin hp, v d t cng on oxiclo
ho hay cng on nhit phn CE v tch VC.
+Hnh 5.1 trnh by h thng TBP kt hp thp chng luyn tinh
ch CE.

H.5.1.H TBP tng hp 1,2 CE nhit cao, tn dng nhit
phn ng tinh ch sn phm.

S cng ngh vi TBP dng thp si bt, tin hnh nhit
xp x nhit si ca CE v gii nhit phn ng bng cch bay hi sn
phm phn ng, c trnh by hnh 5.2.



H.5.2-S cng ngh sn xut 1,2 icloetan t Clo v Etylen.
1-TBP Clo ho Etylen. 2-Lng tch . 3-Lm lnh trc tip tch CE
4-Ra bng nc 5-Phn li lng-lng. 6-Chng ng ph tch CE.
7-Chng ng ph kh nc. 8-Chng 1,2 CE.9-Chng thu hi CE
b/Qu trnh oxiclo ho Etylen:
-Phn ng:
C
2
H
4
+2HCl +1/2O
2
CH
2
Cl-CH
2
Cl +H
2
O
AH
298
=295 Kj/mol
-Xc tc CuCl2/ cht mang,Tp = 200 300
0
C.
-L qu trnh pha kh to nhiu nhit.
-C ch cho thy xc tc l cht chuyn Clo:
C
2
H
4
+2CuCl
2
C
2
H
4
Cl
2
+Cu
2
Cl
2

Cu
2
Cl
2
+2HCl +1/2O
2
2CuCl
2
+H
2
O
-p dng trong cng nghip t 1960, khi bt u sn xut vinyl clorua
t Etylen.
-TBP: Dng 2 loi ng chm v tng si.
S cng ngh oxiclo ho vi hai loi TBP trnh by hnh 5.3
v 5.4.


H.5 3- Sn xut CE bng oxiclo ho etylen dng TBP
dng ng chm.
1-H TBP dng ng chm. 2-TB lm lnh trc tip v trung ho
HCl. 3-TB phn ly kh-lng. 4-TB sy kh. 5-TBP clo ho etylen.
6,7-TB phn ly tch CE. 8-TB phn lyCE-nc. 9-Thp chng
ng ph tch CE trong nc. 10-Thp chng ng ph tch nc
lm khan CE. 11,12-H thp tinh ch CE.



H.5.4 -Sn xut CE bng oxiclo ho etylen dng TBP
dng tng si.
1-TBP dng lp si. 2-TB phn ly tch XT. 3,4-Thp lm lnh trc
tip v trung ho HCl. 5-Thp hp th CE bng alkylbenzen. 6-Thp
nh CE. 7-Thng phn li CE-nc. 8-Thp chng ng ph tch
CE. 9-Thp chng ng ph lm khan CE. 10,11-H thng thp
tinh ch CE.
V.2-Sn xut vinyl clorua: CH
2
=CHCl, T
s
=13,4
0
C
-L monome quan trng, sn lng ln.
-C 2 cng ngh sn xut: t axetylen v t 1,2 DCE.
a/Cng ngh hidroclo ho axetylen:
-Phn ng:
CHCH +HCl CH
2
=CHCl AH
298
=100 Kj/mol
-Xc tc HgCl
2
10% /than hot tnh, xc tc gim hot tnh do bay hi
HgCl
2
khi b mt than nn, thi gian lm vic ca xc tc t 3 n 6 thng,
T
p
=130 170
0
C, p sut ch thng tr lc trong h thng, d nh HCl,
t l HCl/C
2
H
2
=1,1/1.
-Phn ng ph to thnh 1,1DCE, nhng ch 1-2%:
CH
2
=CHCl +HCl CH
3
-CHCl
2

-TBP: ng chm, ng knh ng D = 50 mm, c th gii nhit
phn ng bng du tun hon hay bng cch bay hi nc di p sut 0,5
1 MPa, T
max
khng c vt qu 200
0
C v HgCl
2
bay hi lm gim nhanh
hot tnh xc tc. Trong qu trnh lm vic T
max
chuyn dch theo dng kh
v pha cui ng v thng hoa HgCl
2
.
-Cng ngh sn xut nh hnh 5.3

H.5.5-S cng ngh sn xut vinyl clorua t axetylen.
1-TB trn. 2-TBP hidroclo ho axetylen. 3-Thp ra HCl bng nc.
4-Thp ra kim. 5-Thng phn li lng-lng-kh. 6-Thp chng ng ph
tch nc. 7-Thp hp th axetylen. 8-Thp nh axetylen. 9-Thp chng.

b/Cng ngh crcking 1,2DCE:
-Phn ng:
CH2Cl-CH2Cl CH2=CHCl +HCl AH298=70 Kj/mol
C ch chui gc nhit cao:
Khi u to gc:
CH2Cl-CH2Cl CH2Cl-C*H2 +Cl*
Tip tc chui:
Cl* +CH2Cl-CH2Cl CH2Cl-C*HCl +HCl
CH2Cl-C*HCl CH2=CHCl +Cl*
-KP:
+Tp = 500 550
0
C. P =2 3 MPa . Dng p sut ny
gim kch thc thit b pha kh, tng h s trao i nhit, d tch sn phm
vinyl clorua ( lm lnh ngng t bng nc ).
+Thi gian lu 10 20 giy, X =50 60% trnh phn ng
ph to cc do polime ho VCM tip theo.
+Hiu sut t 95 99%
-TBP: L ng, lm lnh nhanh bng ti trc tip vi CE tun
hon.
-Trong sn phm nhit phn ngoi VCM cn CE cha chuyn ho
v mt lot cc hp cht khc nh axetylen, vinyl axetylen, 1,3 butadien,
2 clo1,3 butadien, benzen, clobenzen v cc dn sut clo khc ca cc hp
cht C1,C2,nha v cc.

H.5.6 -Sn xut VCM t icloetan
1-TBP dng l ng. 2-TB lm lnh trc tip. 3-Thp tch HCl.
4-Thp tch CVM. 5,6-Tinh ch VCM. 7,8,9-Tinh ch CE cha
chuyn ho.
-Do qu trnh sn xut VCM t icloetan tch ra HCl nn thng lin
hp sn xut 1,2 CE bng clo ho v oxiclo ho vi crcking CE thnh
VCM nh phn 1 ni. S khi tch hp cc sx trn nh hnh . .


H.5.7-Tch hp sn xut 1,2 Dicloean v Vinyl clorua monome.