n mn hc

GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 1

LI M U
Vinyl clorua u tin c sn xut vo nm 1835 bi Justus Volt Liebig v sinh vin
ca ng l Henry. H thu c n bng vic thc hin clorua kp etylen theo phng
php ca Hydroxit kali trong etanol.
Vo nm 1912, mt nh bc hc c l Frans, lm vic cho Griesheim-Elektron
c cp bng sang ch v mt phng php sn xut vinyl clorua t axetylen v
hidroclorua s dng thy ngn II clorua nh mt cht xc tc. Phng php ny c
s dng rng ri trong nhng nm 1930 n 1940.
ng dng ca n ngy cng c s dng rng ri. Do ngnh cng nghip v vt
liu polime cng c pht trin. Vinyl clorua c cng thc ha hc l: CH
2
=CHCl.
cho ngnh cng nghip ny tn ti v pht trin hn cn phi nghin cu v sn
xut ra ngun nguyn liu cn cung cp cho n l rt quan trng, cho nn vic iu ch
Vinyl clorua to ra mt bc chuyn ln trong cng nghip ha cht.
Vinyl clorua ng dng trong cng nghip ch yu c dng lm monomer trong qu
trnh polime ha tng hp thnh polivinylclorua (PVC), khong 95% tng hp
vinylclorua dng tng hp PVC v cc polime khc. PVC l cht do c nhiu tnh
cht m ta mong mun nh n nh ha hc cao, t b n mn (t b ph hy bi cc
axit mnh nh H
2
SO
4
, HCl), c kh nng co gin v bn tng i ln, cch in
tt khng thm nc, khng b ph hy khi tip xc vi nc v c mt s tnh nng
u vit khc. Do c nhng tnh nng u vit nh vy nn PVC c dng sn xut
cc loi ng dn cc cht ha hc, lm vt liu lt bn trong cc thit b ha hc lm
vic nhit thp thay th thp khng r v cc hp cht t tin. Nha PVC cn
c s dng trong nhiu ngnh cng nghip khc nh: cng nghip in (sn xut
cc loi dy bc), trong xy dng, trong ngnh sn xut da nhn to Do mang nhiu
c tnh tt nh vy nn nhu cu s dng nha PVC ca nhiu ngnh cng nghip tng
ln mt cch nhanh chng ko theo l s pht trin v cng nghip tng hp PVC.
Cng ngh sn xut VC cng c nhiu pht trin. Hin nay c nhiu cng ngh
sn xut VC t nhng ngun nguyn liu khc nhau hoc t mt ngun nguyn liu c
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 2

th c nhiu cng ngh khc nhau. Vn t ra l phi tm xem cng ngh no l ph
hp nht m bo xy dng mt phn xng sn xut VC t c c v cht
lng cng nh s lng sn phm. C nh th mi thu c hiu qu kinh t cao
nht.


















n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 3


Phn I : TNG QUAN
CHNG 1 : TNH CHT CA NGUYN LIU V SN PHM
1.1. Tnh cht ca nguyn liu:
1.1.1. Tnh cht ca axetylen:
Axetylen c tm quan trng to ln nht trong s cc hidrocacbon cha mt lin kt
ba. l cht kh khng mu, khng mi, khng c, d bt chy.Tuy nhin trong
thc t axetylen c mi ti do s c mt ca cc tp cht. N c kh nng ha tan
trong axeton, etanol, nc v rt nhiu dung mi phn cc. Khi chy, axetylen to
ngn la nng v c mui. y l mt hp cht khng bn, c th phn hy n khi
p sut ring phn ca n trong hn hp vt qu 0,14 MPa. Trong s tt c cc
hidrocacbon, axetylen l hp cht c hnh thnh t phn ng thu nhit ln nht.
Sau y l mt s thng s k thut ca axetylen.
Trng lng ring (0
o
C, P = 760 mmHg): d = 1,17kg/m
3
.
Khi lng phn t: 26,04 vC.
Nhit nng chy: -80,85
o
C .
Nhit chuyn tinh th: -140,15
o
C.
Gii hn n trong khng kh: di(2,5% th tch), trn(81,5% th tch).
T trng hi (khng kh = 1): 0,91.
Nhit ngng t: -83,8
o
C.
Nhit thng hoa: 21,59 Kj/mol.
Nhit dung ring phn t: Cp = 0,402 kJ/kg.
1.1.1.1. Tnh cht vt l:
Axetylen l hidrocacbon khng no, c lin kt ba trong phn t do kh nng
hot ng ha hc cao. Lin kt ba phn t axetylen to thnh do lin kt o v .
Khi tham gia cc phn ng ha hc, lin kt ba trong phn t b ph v to
thnh lin kt i hoc cc hp cht bo ha. Axetylen c kh nng tham gia phn
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 4

ng th, cng, oxi ha, trng hp. V vy t axetylen c th tng hp cc sn
phm khc nhau c th ng dng trong cng nghip v i sng.
1.1.1.2. Tnh cht ha hc:
a. Phn ng th:
Nguyn t hidro ca axetylen th hin tnh axit c kh nng tham gia phn
ng th vi kim loi kim: Cu, Ag, Ni, Co, Zn to thnh axetylenit kim loi
rt d n.

2 2 2 2 2
2Me C H Me C H + +
( Me l kim loi kim)

2
2
Na
HC CH NaC CNa H
+
+


2
2
Cu
HC CH Cu C C Cu H
+
+

Axetylen tc dng vi amit ca kim loi kim v kim th trong ammoniac
lng:

2 3
HC CH MeNH MeC CH NH + +

b. Phn ng cng hp:
Cng vi hydro xc tc Pd p sut 1at v 250- 300
o
C.

2 2 2
, 41, 7 / .
Pd
HC CH H CH CH H Kcal mol + = A =

Cng hydro vi xc tc Ni v nhit :
2 3 3
2
o
Ni
t
HC CH H CH CH +
Phn ng cng vi nc khi c xc tc HgSO4 75
o
C 100
o
C to ra
axetadehyt:
2 3
, 38,8 /
Hg
HC CH H O CH CHO H kcal mol
+
+ A =
Cn khi c oxit km v oxit st 360
o
C 480
o
C, axetylen tc dng vi hi nc to
thnh axeton:

2 3 3 2 2
2 3 2
ZnO
HC CH H O CH COCH CO H + + +

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 5

Axetylen tc dng vi ru 160 180
o
C, p sut P = 420 at v c KOH to thnh
Vinylete:

2
OR
KOH
HC CH ROH CH CH + =

Axetylen tc dng vi mercaptan c xc tc to ra Vinyltroete:

2
HC CH RSH CH CH SH + =

Axetylen tc dng vi CO v H
2
(cacbonyl ha) vi xc tc l Ni(CO)
4
to ra axit
acrylic:

2 2
OO HC CH CO H O CH CH C H + + =

Cng vi mui halogen to hp cht c ng phn cis, trans:

Cng vi halogen:

2
2 2 2
Br
HC CH Br CHBr CHBr CHBr CHBr
+
+ =

Ngoi ra axetylen cn phn ng cng vi nhiu axit v c v hu c to thnh cc
vinyl c gi tr trong cng nghip.
Cng vi HCl, phn ng trong pha hi 150180
o
C c xc tc HgCl
2
than hot tnh,
cn trong pha lng dng xc tc CuCl
2
thu c VC:

2
HC CH HCl CH CH Cl + =

Cng vi H
2
SO
4
to thnh Vinylsunfua:

2 4 2 3
HC CH H SO CH CH O SO H + =

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 6

nhit 80
O
C c CuCl
2
v NH
4
Cl lm xc tc, axetylen tc dng vi HCN to thnh
acrylonitrin:
2
HC CH HCN CH CH CN + =

Tc dng vi axit axtic 180200
o
C pha hi l xc tc axetat Zn trn than hot
tnh hoc Cd trn than hot tnh hoc Hg trn than hot tnh to thnh Vinylaxetat:

3 2 3
OCO HC CH CH COOH CH CH CH + =

Axetylen tc dng vi ru:

2
HC CH ROH RO HC CH + =

Axetylen tc dng vi axit amin:

2 2
HC CH RCO NH RCO NH CH CH + =

c. Phn ng trng hp ca axetylen:
Phn ng dime ha trong mi trng HCl to thnh vinylaxetylen:

,80
2
2
o
xt C
CH CH H C CH C CH =
nhit 600
o
C trn than hot tnh axetylen trng hp to thnh benzen:

6 6
3CH CH C H

1.1.2. Cc phng php iu ch axetylen:
Trong cng nghip axetylen ch yu c sn xut theo hai hng chnh l: t
than v kh t nhin, kh ng hnh. Nc ta do iu kin sn c than , kh t
nhin, kh ng hnh nn c th p dng c c hai phng php trn.
1.1.2.1. Sn xut axetylen t than -Qu trnh cacbua canxi:
Theo phng php ny, vi (oxyt canxi) s b kh bi cacbon (than cc hoc
antraxit) trong l in nhit 22002300
o
C. Phn ng xy ra nh sau:

2 298
3 465 /
o
CaO C CaC CO H kJ mol + + A =

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 7

Cacbua canxi hnh thnh tip tc c phn hy thnh axetylen:

2 2 2 2 2 298
2 ( ) , 139 /
o
CaC H O C H Ca OH H kJ mol + + A =

Qu trnh hp nc ca CaC
2
trong cc thit b cn c gi l qu trnh ti
sinh axetylen. Theo nguyn tc ca s thot nhit, n chia ra lm hai loi:
+ Thit b ti sinh loi t: l loi thit b m nhit ca phn ng c gii phng bng
nc d un nng ln 50-60
o
C. N ch yu c s dng sn xut axetylen ha
tan. Chng gm cc h thng th cacbua canxi vo nc (h cacbua canxi nc),
phun nc vo cacbua canxi (h nc cacbua canxi) v tip xc (nhng ngp cacbua
canxi trong nc).
+ Thit b ti sinh loi kh: l loi thit b trong nhit phn ng c ly ra do mt
khi lng nc d nh s ha hi ca n. Ca(OH)
2
thu c dng kh (vi ti) v
n c s dng ch bin vt liu xy dng.
Cacbon s dng trong qu trnh ny c th l cc hoc nguyn liu s dng thng c
ln cc tp cht nh MgO, hp cht S, P, Al, Fe do xy ra cc phn ng.

2
3 MgO C MgC CO + +


3 4 2 3 2
( ) 8 8 Ca PO C Ca P CO + +

Cc tp cht ny kh tch ra khi hn hp phn ng, ch c th tch ra mt phn.
Chnh v vy m axetylen lun c ln mt lng hp cht nh: PH
3
, NH
3
, SiH
2
,
CH
4
, H
2
, CO
2
, CO. Lng tp cht ny khng c li cho vic s dng axetylen
iu ch VC. Do axetylen to ra phi tri qua giai on lm sch c th dng
anhydrite cromic trn t nung hoc dng nc javen lm sch. Sau
axetylen thnh phn c ra bng kim trung ha axit v sy kh bng H
2
SO
4

hoc CaCl
2
.
T metan:

400 600
4 2 2 2
2 3
o
C
Ni
CH C H H

+
Oxi ha Metan:


1500
4 2 2 2 2 2
4 2 2 4
o
C
CH O C H CO H + + +
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 8

Axetylen sn xut theo phng php cacbuacanxi chi ph nng lng in tiu tn
v vn u t ln. V th ngy nay axetylen ch yu c sn xut bng nhit
phn hydrocacbon, qu trnh xy ra mt giai on cho php tng hp axetylen vi
vn u t v chi ph nng lng t hn. Axetylen sn xut c sch hn nhng
c nng long.
1.1.2.2. Sn xut axetylen t kh thin nhin v kh ng hnh:
Trc chin tranh th gii th hai, sn xut axetylen ngi ta ch yu dng
nguyn liu CaC
2
. Trong thi gian gn y, cc nh nghin cu ch bt u
nghin cu trong cc phng th nghim vi mc ch xc nh iu kin bin
i ca hydrocacbon paraffin thnh axetylen. Trong khi qu trnh cracking
nhit v nhit phn hydrocacbon sn xut olefin pht trin trong cng
nghip. Nh tch ly c kinh nghim c v l thuyt ln thc t ca cng
nghip nhit phn, cho php pht trin v thit k cc thit b u tin sn
xut axetylen t CH
4
v nhng paraffin khc bng cch nhit phn nhit
cao theo phn ng thun nghch sau:

4 2 2 2 298
2 3 , 87, 97 /
o
CH C H H H kcal kg + A =


2 6 2 2 2
2 C H C H H +

Cc phn ng ny u l cc phn ng thu nhit v phn ng tng th tch, cn
bng ca chng ch dch chuyn v pha phi khi nhit khong 100300
o
C.
Trong thc t vi mc ch tng vn tc phn ng cn nhit ln hn
1501600
o
C i vi CH
4
v 1200
o
C i vi hydrocacbon lng, khi nhit phn parafin,
phn ng to thnh axetylen c c ch chui gc, trong chui chuyn ha CH
4
v
C
2
H
6
c th c trnh by nh sau:
Trong kh thu c, ngoi nhng paraffin v olefin phn t thp cn mt lng
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 9

khng ln benzene, nhm axetylen-metyaxetylen (CH
3
-CH
2
-CH3)... Ch bin
axetylen bng phng php ny tng i phc tp do xy ra cc phn ng ph
ch yu l phn hy C
2
H
2
thnh C v H
2
. Phn ng ny mnh lit 1000
o
C v t
tc ln 12001600
o
C ngha l khi t nhit yu cu c c C
2
H
2
. Kt
qu axetylen to thnh b phn hy thnh H
2
v C (mui than).

2
3
4 2 2 2
2 2
H
CH C H C H

+

Ngoi ra trong qu trnh cn xy ra nhng phn ng khng mong mun cng to
thnh C v H
2
nh phn ng:

2
2
2
2 4 2 4 2
2 6 2
4
2 2 2
2 3
H
CH C H
C H C H C H
C H C H

+
+
+

Cng nh cc trng hp khc, vic iu chnh hiu sut sn phm trung gian c
th t c nh s gim mc chuyn ha hydrocacbon ban u bng cch rt
ngn thi gian phn ng. Hiu sut axetylen cao nht khi s cc ha xy ra vi
mc chuyn ha hydrocacbon ban u l 150
o
C v thi gian lu trong vng
phn ng l 0,01 giy.
- C ch ca qu trnh:
Khi ch bin nhit hydrocacbon kh hay phn on du, chng ta hiu phn no
c cu bin i nhit ca hydrocacbon khc nhau trong nguyn liu nhng iu
kin nhit va phi (700 800
o
C), trong phn ng to thnh C
2
H
2
li tin
hnh nhit cao (trn 1000
o
C) v c cu cng cha c nghin cu c th,
v th cha c mt l thuyt thng nht v s to thnh C
2
H
2
khi phn hy nhit
hydrocacbon trong khong 1100 1500
o
C. Tuy nhin nhng nghin cu cho
php gi thuyt i n s thay i c cu cracking khi chuyn ha nhit
cao lm chm cc phn ng pht trin mch theo c cu gc t do v lm tng
tc ca qu trnh phn hy kh cu trc phn t. Cc phn ng bc hai to
thnh cc sn phm ngng t v to cc xy ra trong khong 900 1000
o
C,
song nhit cao li quan st thy phn ng phn hy to thnh hydro, mui,
cacbon t nng n 1500 1700
o
C ( cc sn phm c to ra nhanh chng
tch khi mi trng phn ng ) thy rng cc sn phm bc mt ca s bin
i l Etan. iu ph hp vi c cu c gii thch bi c cu Kasale nh
sau:
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 10


4 2 2
2 4 2 6
2 6 2 4 2
2 4 2 2 2
2 2 2
[ ]
[ ]
2
CH CH H
CH CH C H
C H C H H
C H C H H
C H C H
+
+
+
+
+

Tm li, nc ta do c cc m kh vi tr lng ln v thnh phn ca kh thu
c hu ht l paraffin nn hiu sut chuyn ha cao. V vy vic pht trin
sn xut axetylen t kh thin nhin v kh ng hnh c trin vng rt ln.
1.1.2.3. So snh hai phng php sn xut Axetylen:
Qu trnh sn xut Axetylen t hydrocacbon l qu trnh xy ra theo mt giai
on, cn vn u t v nng lng t hn nhng axetylen thu c long cn
c h thng tch v lm lnh phc tp. Cn i vi qu trnh sn xut axetylen
t cacbua canxi th chi ph nng lng ln ( cho vic thu c CaC
2
) v vn
u t cho sn xut ln, vic vn chuyn khng tin, iu kin lm vic
nh my rt nng nhc. Tuy nhin qu trnh ny c u im ln l axetylen
thu c m c c sch cao ( 99,9% ) , c th dng cho bt c qu trnh
tng hp no. Ngoi ra nguyn liu s dng cho qu trnh da trn ngun
nguyn liu than rt di do v rt ph hp vi iu kin ca nc ta.
Chnh v vy sn xut axetylen t than , vi l hng chnh cung cp
nguyn liu cho VC.
1.2. Tnh cht ca axit HCl:
1.2.1. Tnh cht vt l:
Hydro clorua l mt cht kh khng mu, mi hc gy kch thch nim mc, rt
c. Trong khng kh m, HCl kt hp vi hi nc to khi, HCl tan mnh trong
nc, n dng khan khng n mn kim loi, l mt kh bn nhit ch b phn hy
nh nhit trn 1500
o
C.
T trng d = 1,35g/cm
3
.
Trng lng phn t: M = 35,5 kg/kmol.
Nng ln nht ca dung dch HCl l: 35%.
1.2.2. Tnh cht ha hc:
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 11

HCl l mt axit v hu c in hnh. Khi ha tan trong nc n in ly hon ton:

2
3 HCl H O H O Cl
+
+ +

- Tc dng vi kim v kim loi:


2
2 2
2
HCl NaOH NaCl H O
HCl Zn ZnCl H
+ +
+ +

- Tc dng vi mui:

3 2 2 2
2 CaCO HCl CaCl H O CO + + +

- Ngoi ra HCl cn phn ng c vi nhiu hp cht hu c.

2
2 2 3 2
HCl CH CH CH CH Cl
HCl CH CH CH CH Cl
+ =
+ =

1.2.3. Cc phng php sn xut axit HCl:
- Tronh phng th nghim:
T NaCl rn v dung dch H
2
SO
4
c:

200
2 4 4
200
2 4 2
2 4 2
o
o
t C
t C
NaCl H SO NaHSO HCl
NaCl H SO Na SO HCl
s
>
+ +
+ +

- Trong cng nghip:
Ngi ta tin hnh tng hp HCl t nguyn liu ban u l H
2
v Cl
2
:

2 2

2
o
t C
nh s ng
H Cl HCl

+


1.3. Tnh cht ca sn phm VC:
1.3.1. Tnh cht vt l:
VC c cng cng thc phn t C
2
H
3
Cl.
Cc tn gi: Vinyl clorua, Cloruaetylen, Etylen monoclorua, VC, VCM,
Cloroeten, Monocloroeten, Monocloroetylen,
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 12

iu kin nhit v p sut thng VC l cht kh khng mu, c mi
ete nh. VC rt d bt la, c im bc chy thp do d to hn hp n
vi oxi khng kh. N t tan trong nc, ch yu tan trong cc dung mi
hu c nh: axeton, ru etylic, hydrocacbon thm N c tnh gy m
nh ete, tuy nhin c hi ca n khng cao bng CCl
4
.
+ Trng lng phn t: M = 62,5 kg/kmol.
+ Nhit ng rn: -153,7
o
C.
+ Nhit ngng t: -13,9
o
C nn rt kh ha lng.
+ Nhit ti hn: 142
o
C
+ Nhit bc chy: 415
o
C
+ Nhit nng chy: -153,8
o
C
+ Nhit bc hi 25
o
C: 78,5 Kcal/kg
+ Trng lng ring: 0,969 g/cm
3

+ Nhit to thnh: -83 8 Kcal/kg
+ Nhit trng hp:-366 5 Kcal/kg
+ Nhit dung ring ca VC lng 25
o
C: 0,83 Kcal/kg.
+ Nhit dung ring ca VC hi 25
o
C: Cp = 0,207 Kcal/kg.
+ H s khc x ca VC lng: n
o
= 1,83.
+ T trng d
20
4
: 0,9834.
1.3.2. Tnh cht ha hc:
- VC c cng thc ha hc: CH
2
=CHCl.
- Cng thc cu to ca VC:

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 13

Do c cha lin kt i v nguyn t clo linh ng (Cl c m in ln) nn cc
phn ng ha hc ca VC l phn ng ca lin kt i v phn ng ca nguyn t
clo linh ng.
VC khng tan trong nc, tan trong cc dung mi hu c nh axeton, ru etylic,
hydrocacbon thm, hydrocacbon mch thng.
Trong phn t VC c mt lin kt ni i v mt nguyn t clo linh ng, do
phn ng ha hc ch yu l phn ng kt hp hoc phn ng ca nguyn t clo
trong phn t VC.
Sau y ta xem xt cc phn ng m VC c kh nng tham gia:
1.3.2.1. Phn ng ni i:
Phn ng cng hp:
Tc dng vi halogen cho ta 1,2 dicloetan iu kin nhit 140150
o
C v
c chiu sang xc tc l SbCl
3
.
Khi c xc tc AlCl
3
, FeCl
3
th VC phn ng vi HCl.

2 2 2
CH CHCl HCl CH Cl CH Cl = + =

Vi H
2
:

2 2 3 2
CH CHCl H CH CH Cl = +

Phn ng oxi ha VC nhit 50150
o
C c mt HCl d dng to ra
monoxetandehit:

2 2 2
1
2
CH CHCl O Cl CH CHO = +
Do phn t c cha ni i nn VC c th tham gia phn ng trng hp to
PVC, mt sn phm quan trng.

1.3.2.2. Phn ng ca nguyn t Clo:
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 14

Thy phn:
Khi un nng vi kim, HCl b tch ra khi VC cho ta axetylen.

2 2
2
NaOH
CH CHCl CH CH NaCl H O
+
= + +

Tc dng vi ancolat hoc phenolat cho ta este VC:

2 2
OR CH CHCl RONa CH CH NaCl = + = +

To hp cht c kim:

2 2
CH CHCl Mg CH CH Mg Cl = + =

VC trong iu kin khng c khng kh 450
o
C c th phn hy to thnh axetylen v
HCl, do phn ng dime ha axetylen c th phn ng tip tc to ra mt lng nh 2-
Clo-1,3-butandien. Cn trong iu kin c khng kh VC b oxi ha hon ton to
thnh CO
2
v HCl.
1.4. ng dng ca VC
1.4.1. Trng hp ca vinylclorua (VC) to poly vinylclorua (PVC):
Phng trnh phn ng:

Poly vinylclorua (PVC) l mt cht do mang nhiu tnh cht tt nh: c n
nh ha hc cao, t b n mn bi axit (H
2
SO
4
, HCl), c kh nng co gin,
bn tng i ln, c tnh cch in, khng thm nc v khng b ph hy khi
gp nc nhng li d nhum. Do c nhiu c tnh tt nn PVC c s dng
sn xut cc loi ng dn, bn cha cc cht ha hc. Lm vt liu lt trong cc
thit b ha hc lm vic nhit thp, trng mi trng n mn thay th
thp khng g v hp kim.
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 15

Trong cng nghip in, nha PVC c s dng lm v cch in, cc dng
c cho v tuyn in. Trong xy dng, nha PVC c s dng ch to tm
lp nh, lt sn tng cch m, cc dng c gia nh, ng dn nc sinh hot v
cc loi bao ti ng , o ma
1.4.2. ng trng hp vi cc monome khc:
VC cn c kh nng tham gia ng trng hp mt s monomer khc nh: vinyl
axetat (VA), acryl nitril to thnh cc polyme c gi tr cao. Ngoi ra VC cn
dng sn xut mt s loi si tng hp c tnh cht tt v sn xut mt s
loi sn chu n mn.
1.5. nh hng ca VC ti sc khe con ngi v mi trng:
1.5.1. i vi sc khe con ngi:
Cng nhn trong cc khu cng nghip s dng hoc sn xut VC c nhng ri
ro khi tip xc vi n. Ngi s dng c th b nh hng VC qua khng kh
trong cc sn phm v trong qu trnh s dng sn phm, trong cc cht thi
cha VC hoc qu trnh clo ha khc. VC xm nhp vo c th con ngi qua
khng kh v ngun nc bn m con ngi s dng.
Khi ht phi mt lng ln VC d dn n hn m, nh hng c quan h hp,
to ra s bin i ln trong c th v dn ti t vong. mc thp, dn ti
triu chng nhc u, hoa mt chng mt. nh hng trong thi gian di c th
l nguyn nhn gy bt lc, ri lon tim mch v nhng vn khc nh hng
ti s sng. Vin nghin cu ung th th gii phn loi VC nh l mt cht
gy ung th ngi, d trn c s biu hin bnh c ngi v ng vt.
1.5.2. i vi mi trng:
VC xm nhp vo khng kh trong sut qu trnh sn xut v s dng. trong
khng kh n s ph v cc lin kt ha hc khc nh formyl clorua v
formaldehyl trong hai ti ba ngy. Mc d hu ht VC lan ta trong khng kh,
khi pht ra t t n cng s bc hi hoc ngm vo trong nc cc mch nc
ngm. N s nhanh chng bc hi nu lng hi nc tip xc vi n t. trn b
mt nc n c th khng b vi khun phn hy v tn ti trong nhiu thng ti
nhiu nm.
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 16

1.5.3. Bo qun VC:
Trc y, VC c bo qun v vn chuyn vi s c mt ca mt lng nh
phenol c ch phn ng polyme ha. Ngy nay VC c sn xut vi tinh
khit cao v khng cn cht c ch, trong bo qun ng thi do c lm sch
nc VC khng gy n mn c th c bo qun trong cc thng thp cacbon
thng.













CHNG 2: CC CNG NGH SN XUT VI NYL CLORUA
Cc qu trnh chnh trong cng nghip sn xut VC bao gm:
- Sn xut VC t EDC.
- Sn xut VC bng cc qu trnh lin hp.
- Sn xut VC t axetylen.
2.1. Sn xut VC bng phng php cracking EDC:
2.1.1. C s ca phng php:
Qu trnh c tin hnh da trn phn ng phn hy thu nhit sau:

2 2 2 298
, 70 /
o
CH Cl CH Cl CH CHCl HCl H kJ mol = + A = +

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 17

Phn ng bt u xy ra 300
o
C, p sut kh quyn, nhng phn ng t c tc
cao 400500
o
C.
Qu trnh nhit phn l qu trnh phn ng xy ra theo c ch chui gc gm 3 giai
on: Khi mo, pht trin mch v t mch.
a. Khi mo:

2 2 2 2
* * ClCH CH Cl ClCH CH Cl +

b. Pht trin mch:

2 2 2
2 2
* *
* *
Cl ClCH CH Cl ClCH CHCl HCl
ClCH CHCl CH CHCl Cl
+ +
= +

c. t mch:

2 2 2
* * Cl ClCH CH CH CHCl HCl + = +

Qu trnh to nhiu sn phm ph l sn phm ca qu trnh polyclo ha, sn phm
ca qu trnh phn hy, cc V vy cn s dng cc cht xc tin nh: clo, brom,
iot, tetraclocacbon hoc oxy to thun li cho phn ng chuyn ha chnh.
Cc qu trnh trong cng nghip c tin hnh 500550
o
C, p sut 2,53MPa,
khng s dng xc tc. Mt s h xc tc (than hot tnh, mui clo kim loi) c th
c s dng gim nhit phn ng, tuy nhin thi gian sng ca xc tc thp v
kh khn v mt cng ngh lm cho qu trnh cracking EDC c xc tc khng c
ng dng rng ri trong cng nghip.

2.1.2. S dy chuyn cng ngh sn xut VC t EDC:
Thuyt minh s dy chuyn:
1 : Thit b phn ng.
2 : Thp ti.
3 : Thit b lc.
4 : Thp tch HCl.
5 : Thp lm sch VC th.
6 : Thp tinh ch VC.
7 : Thp tch phn on nh.
8 : Thp tch phn on nng.
9 : Thp thu hi EDC.
10 : Thit b gia nhit bc hi.
11 : Thit b nhng t.
12 : Thit b lng tch.
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 18


Hnh 2.1 S dy chuyn cng ngh sn xut VC t EDC.
S

y

c
h
u
y

n

c

n
g

n
g
h

n

x
u

t





























v
c


t

e
d
c



































2
1
3
4
5
v
c
n
a
o
h
6
n
a
o
h
7
8
9
S

n

p
h

m

n
h

n

p
h

m

n

n
g
E
D
C
e
d
c

t
u

n

h
o

n
1
0
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1 1
3
1
3
1
3
1
3
1
1
1
4
1
4
1
5
1
5
1
5
1
5
1
3
1
3
1
3
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 19

EDC nguyn liu v EDC tun hon c a qua thit b gia nhit v bc hi ti
nhit cn thit(khong 215
o
C), sau c a vo thit b dng l ng. Ti
vng i lu, nguyn liu c gia nhit ti nhit phn ng, phn ng thc s
xy ra trong vng bc x. Sn phm kh thu c u ra ca thit b phn ng l
ng c nhit 500
o
C c ti trnh cc phn ng ph xy ra ni tip nhau
bng cch a qua thp ti tip xc vi dng sn phm c lm lnh xung
50
o
C chy ngc chiu. Kh sn phm s c lm lnh xung 200
o
C. Qu trnh
lm lnh b sung tip theo s lm ngng t hu ht nguyn liu EDC cha phn
ng, mt phn c dng lm cht ti nhit trong thp ti. Phn cn li cng vi
kh khng ngng s c a qua thp chng ct tch sn phm ph HCl. Ti y
HCl s c tch ra khi hn hp dng kh khng ngng phn nh thp. Phn
y ca thp tch HCl c a sang thp chng ct lm sch VC th. Ti thp
ny sn phm VC s nm trong phn nh nh thp v tip tc c a sang thp
tinh ch lm sch VC. Ti thp tinh ch lm sch VC hm lng HCl c gim
t 500 xung 10ppm v phn sn phm ly ra t y thp c trung ho vi
NaOH. Phn nh thp s c hi lu tr li thp tch HCl.
Phn y thp lm sch VC th c a qua h thng thu hi EDC v tun hon
quay tr li thit b phn ng. Qu trnh ny bao gm cc thit b sau:
- Tch phn on nh lm nhim v tch phn sn phm nh (1 thp).
- Tch phn on nng trong 2 thp: phn ln EDC thu c thp th nht lm
vic p sut kh quyn, phn EDC cn li trong sn phm nng c thu thp
th hai lm vic trong chn khng.
2.1.3. u nhc im ca phng php :
u im ca phng php ny l tn dng c phn EDC khng phn ng v
tun hon n tr li thit b phn ng. ng thi tn dng c phn HCl. Tuy
nhin phng php ny c nhc im l c hiu sut chuyn ha thp.
2.2. Sn xut VC bng cc qu trnh lin hp:
2.2.1. Lin hp clo ha etylen, tch HCl v hydro ha axetylen:
Qu trnh da trn cc phn ng:
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 20


2 4 2 2 2
2 2 2
(1)
(2)
C H Cl CH Cl CH Cl
CH Cl CH Cl CH CHCl HCl
+
= +

HCl t phn ng (2) c th c dng cho phn ng hydroclo ha axetylen:

2 2 2
(3) C H HCl CH CHCl + =

Phn ng tng cng:

2 2 2 4 2 2
2 C H C H Cl CH CHCl + + =

S qu trnh:
- Vi ngun nguyn liu u l hn hp ca axetylen v etylen vi t l mol 1:1.















Hnh 2.2 - S qu trnh sn xut VC bng phng php lin hp clo ha
etylen, tch HCl v hydro ha C
2
H
2
(axetylen v etylen dng hn hp).

- Vi ngun nguyn liu u l axetylen v etylen vi t l mol 1:1.







Tch VC
Hydroclo ho
Clo ho Cracking
EDC
HCl
Clo
Hn hp
axetylen v
etylen vi
t l 1/1
Clo ho Cracking
Tch VC
Hydroclo ho
EDC
Axetylen
Etylen
HCl
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 21





Hnh 2.3 S qu trnh sn xut VC bng phng php lin hp clo ha
etylen, tch HCl v hydro ha C
2
H
2
(axetylen v etylen dng ring bit).

2.2.2. Lin hp clo ha, oxy clo ha etylen v cracking EDC
Qu trnh da trn cc phn ng sau:

2 4 2 2 2
2 2 2
2 4 2 2 2
(1)
2 2 2 (2)
1
2 2 (3)
2
C H Cl CH Cl CH Cl
CH Cl CH Cl CH CHCl HCl
C H HCl O CH CHCl H O
+
= +
+ + = +

Phn ng tng cng:

2 4 2 2 2 2
1
2 2
2
C H Cl O CH CHCl H O + + = +
u im ca qu trnh: tiu tn t nng lng (do tn dng c nhit ca cc
phn ng ta nhit), s dng c HCl to thnh v khng dng C
2
H
2
do vy
chi ph r hn.
S qu trnh:







Hnh 2.4 S qu trnh sn xut VC bng phng php lin hp clo ha, oxy
clo ha etylen v cracking EDC.
2.3. Sn xut VC t axetylen:
Clo ha
EDC
EDC
HCl
Oxiclo ho
Crackink
Tch VC
Clo
Etylen
Oxy VC
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 22

Nguyn liu iu ch VC theo phng php ny l C
2
H
2
v HCl.
Qu trnh thc hin da trn phn ng:

2
CH CH HCl CH CHCl + =


p sut thng v khng c xc tc phn ng trn khng xy ra. Khi khng dng
xc tc phi tin hnh phn ng iu kin p sut cao. Tuy nhin p sut cao th li
to ra nhiu sn phm ph nh: diclo etan, phn ng trng hp ca VC to thnh V
vy trnh to sn phm ph v gim khc nghit ca phn ng ngi ta phi
dng xc tc.
sn xut VC theo phng php ny ngi ta c th tin hnh qu trnh trong pha
lng hoc pha kh.
2.3.1. Tin hnh qu trnh trong pha lng:
2.3.1.1. C s ca phng php:
Khi tin hnh qu trnh ny trong pha lng ngi ta tin hnh thi C
2
H
2
v
HCl qua dung dch xc tc c thnh phn: Cu
2
Cl
2
23% khi lng, NH
4
Cl
16% khi lng, c thm CaCl
2
ha tan trong axit HCl 1215% nhit
5060
o
C. Cng c th dng xc tc HgCl
2
trong axit HCl v duy tr nhit
90
o
C. Tuy nhin xc tc ng c xu hng lm tng phn ng ph: trng hp
axetylen thnh vinyl axetylen.

2
2CH CH CH C CH CH =

y l phn ng khng mong mun, v vy ngn nga phn ng ph ngi
ta phi dng HCl ha tan mui ng.
C nhiu quan im v vai tr ca xc tc mui ng v mui thy ngn. Mt
s quan im cho rng mui thy ngn, mui ng tc dng vi axetylen to thnh
hp cht trung gian. Hp cht trung gian ny b phn hy di tc ng ca HCl
hon nguyn xc tc v cho ta sn phm Vinyl clorua.

2
2 2
CH CH HgCl ClCH CH HgCl
ClCH CH HgCl HCl CH CHCl HgCl
+ =
= + = +

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 23

Quan im khc li cho rng mui ng, mui thy ngn tc dng vi axetylen to
phc cht.
2.3.1.2. u nhc im ca phng php:
u im ca phng php ny l qu trnh tin hnh iu kin nhit thp,
t tn nng lng, chnh v vy m thit b phn ng ch to n gin hn. Tuy
nhin, n c nhc im l hiu sut chuyn ha sn phm thp, trong qu
trnh to ra cc sn phm ph khng mong mun, v vy m n s gy kh
khn cho vic phn tch sn phm trong qu trnh tinh ch thu vinyl clorua
tinh khit. Mt khc HCl dng lng gy n mn thit b.
2.3.2. Tin hnh qu trnh trong pha kh:
2.3.2.1. C s ca phng php:
Khc vi phng php trong pha lng, phng php ny xc tc s dng
cho phn ng l HgCl
2
/C* (hoc graphit, silicat), nhit 100170
o
C, p
sut 0,3.10
6
Pa. Trong mui thy ngn HgCl
2
c mang trn cht mang l
than hot tnh. Tuy nhin do mui thy ngn c nn ngi ta c xu hng
thay th mui thy ngn bng cc mui ca cc kim loi khc (BaCl
2
,
CdCl
2
). Qu trnh c m t bng phn ng:

2
/ *
2
HgCl C
CH CH HCl CH CHCl + =

Sn phm ph ca qu trnh thng l axetandehit to thnh do phn ng ca
axetylen vi vt nc c trong nguyn liu v 1,1-dicloetan theo phn ng sau:

2 3 2
CH CHCl HCl CH CHCl = +

2.3.2.2. Cc yu t nh hng n hiu sut chuyn ha ca qu trnh:
a. nh hng ca xc tc:
Khi nng HgCl
2
trn than hot tnh tng th hiu sut chuyn ha
axetylen thnh vinyl clorua tng.
Bng 2.5: nh hng ca nng xc tc ti hiu sut chuyn ha.
HgCl2/C* (%) Hiu sut chuyn ha ( % )
5 69,6
10 86,7
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 24

20 92,3
40 95,4
60 96,8

Theo nh bng trn th ta thy c chuyn ha tng khi nng
HgCl
2
tng. Qua trnh c chuyn ha tng nhanh khi nng HgCl
2

tng t 5 n 10% v sau tng chm. Khi nng HgCl
2
ln hn
20% th chuyn ha vn tng chm nhng ng thi khi qu
trnh ta rt nhiu nhit (nhit ca phn ng). Lm cho xc tc b t
nng cc b dn n HgCl
2
b thng hoa, ng thi axetylen trng hp
bao ph trn b mt lm cho xc tc mt hot tnh nhanh chng. V
vy trn thc t, trong cng nghip ngi ta dng xc tc HgCl
2
10%
ngm trn than hot tnh.
b. nh hng ca nguyn liu:
Nguyn liu trc khi a vo thit b phn ng c th cha nhng tp
cht c hi cho qu trnh nh:
- Lm ng c xc tc:
Khi trong thnh phn ca nguyn liu c cha cc tp cht nh: H
2
S,
PH
3
Th nhng cht ny s tc dng vi xc tc lm gim hot tnh
ca xc tc.

2 2
3 2 3 2
2
2 3 6
H S HgCl HgS HCl
H P HgCl Hg P HCl
+ +
+ +

loi b nhng tp cht gy ng c xc tc ny th hi ca axetylen
trc khi i vo thit b phn ng phi i qua thp cha dung dch K
2
SO
4
( ti y xy
ra phn ng oxy ha kh nhm loi b H
2
S v H
3
P ).

2 2 2 7 2 4 2 2 3
3 2 2 7 3 4 2 2 3
H S K Cr O K SO H Cr O
H P K Cr O K PO H Cr O
+ +
+ +

- Lm tng phn ng ph:
Nu trong thnh phn kh nguyn liu c cha clo s xy ra phn ng
ca axetylen vi clo to sn phm ph l tetracloetan.
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 25


2 2 2 2 2 4
2 C H Cl C H Cl +

Do HgCl
2
cng chnh l xc tc cho phn ng ca axetylen vi nc, v
vy nu trong nguyn liu ban u c cha nhiu hi nc th s lm cho phn ng
ph ny xy ra. Kt qu sinh ra sn phm ph l axetandehit.

2
2 3
HgCl
CH CH H O CH CHO +

Chnh v nhng yu t nguyn liu trn s lm gim hiu sut chuyn ha ca
qu trnh, ng thi sn phm thu c c nhiu sn phm ph, dn n tn km trong
vic phn tch thu c VC tinh khit. Yu cu t ra i vi kh nguyn liu trc
khi a vo thit b phn ng phi c qua cng on x l t nhng tiu chun
cho php. C th i vi nguyn liu kh C
2
H
2
v HCl y phi t tiu chun:
+ Kh C
2
H
2
phi c nng phn trm ln hn 99%; nc nh hn 0,03%;
khng c cht gy ng c xc tc nh: H
2
S, H
3
P
+ Kh HCl phi c nng ln hn 99%; nc nh hn 0,03%; khng c oxi,
clo
c. nh hng ca thnh phn nguyn liu:
m bo cho C
2
H
2
phn ng ht phi cho d HCl. Trong thc t
ngi ta thng khng ch t s C
2
H
2
/HCl = 1/1,1 mol. T s
C2H2/HCl c nh hng trc tip n hiu sut chuyn ha th hin:
Bng 2.6: nh hng ca thnh phn nguyn liu ti hiu sut
chuyn ha.

T l C
2
H
2
/HCl Hiu sut chuyn ha (%)
1/1,09 91,05
1/1,1 96,95
1/1,2 97,75

Qua bng trn ta thy khi HCl d cng nhiu th hiu sut chuyn ha
C2H2 thnh VC cng cao. Tuy nhin khi li xy ra nhng phn ng
ph khng mong mun.
V d:
2 2 3 2
2 C H HCl CH CHCl +

n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 26

Chnh v vy m ngi ta thng khng ch t l C
2
H
2
/HCl = 1/1,1 v
kh tun hon.
d. nh hng ca vn tc th tch:
Vn tc th tch cng nh hng nhiu ti hiu sut chuyn ha ca
qu trnh.




Bng 2.7: nh hng ca vn tc th tch ti hiu sut chuyn ha.
Vn tc th tch (m
3
/m
3
xc tc
gi)
Hiu sut chuyn ha
125 93,66
100 94,55
75 96,06
50 97,40
25 97,46

Nh vy hiu sut chuyn ha s t l nghch vi vn tc th tch. Tc l hiu
sut chuyn ha cng cao khi vn tc nguyn liu cng thp. iu ny c th gii thch
bi quan h gia thi gian lu ca nguyn liu v hiu sut chuyn ha ca qu trnh:
khi thi gian tip xc ca nguyn liu phn ng vi xc tc cng lu th phn ng cng
xy ra trit . Trong khi vn tc li t l thun vi thi gian lu. Chnh v th
c c hiu sut chuyn ha cng cao th phi cho nguyn liu vo vi vn tc cng
nh. Tuy nhin khi a nguyn liu vo vi vn tc qu b th li nh hng ti cng
sut ca dy chuyn sn xut ( lm gim cng sut ). V vy m vic khng ch v
iu chnh vn tc th tch mt gii hn thch hp c chuyn ha cao, ng
thi li m bo cng sut ca dy chuyn l rt quan trng.
e. nh hng ca nhit , p sut:
Nhit thch hp ca phn ng duy tr 160180
o
C. Khi xc tc
gim hot tnh th c th tng nhit ln n 200
o
C. Tuy nhin cn
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 27

phi ch n hai nhit quan trng l: 275
o
C HgCl
2
b phn hy
v 300
o
C n b thng hoa lm xc tc b mt hot tnh, ng thi
gy ra hao ht xc tc. Lm gim hiu sut chuyn ha, chnh v vy
m phi khng ch nhit ca phn ng mt cch hp l s gp phn
tng hiu qu lm vic ca dy chuyn.
2.3.2.3. S dy chuyn cng ngh sn xut VC trong pha kh:
Thuyt minh s dy chuyn:
- X l nguyn liu:
Nguyn liu axetylen sau khi qua h thng my nn ti p sut cao c cho
i qua h thng thp sy gm hai thp (1) v (2), nhm tch ti a lng hi
nc ln trong kh. Tc nhn sy c dng trong qu trnh l dung dch
H
2
SO
4
c. Kh axetylen c bm t di ln i qua lp dung dch H
2
SO
4

c c bm t trn xung, do c tnh ho nc ca H
2
SO
4
c nn kh
C
2
H
2
s c sy ti yu cu cn thit. Kh axetylen sau khi c sy i ra
t nh thp (2) c kt hp vi dng axetylen tun hon cng dng kh HCl
i vo thit b trn (4). Trong qu trnh ny s dng lng HCl d 10%.
- Phn ng:
Hn hp kh t thit b trn (4) c a qua thit b gia nhit n 110
o
C. Sau
c a vo nh ca thit b phn ng ng chm (5). Ti thit b phn
ng (5) cc phn ng ca qu trnh xy ra, ng thi nhit ca phn ng
c tch bi dng cht ti nhit i bn ngoi ng phn ng v qua thit b
trao i nhit t bn ngoi.
- X l kh sn phm:
Hn hp kh i ra khi thit b phn ng c a qua h thng tch HCl d
gm hai thp (6) v (7). Ti thp (6) hn hp sn phm c ra bi nc. Do
axit HCl tan tt trong nc nn ti y phn ln HCl c tch ra y thp
di dng dung dch. Phn kh khng b hp th qua nh thp (6) c a
qua thp (7), ti y phn HCl cn li s c loi b ht bi dung dch
NaOH. Phn kh khng b hp th t nh thp (7) c nn ti 0,7 MPa v
lm lnh, phn ln s ngng t. Nc s dc tch ra hon ton t thit b
n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 28

lng (8) c thnh phn ch yu l axetylen d c a qua h thng thu hi
axetylen gm hai thp (10) v (11). Thp (10) l thp hp th axetylen vi vai
tr tch sn phm nh khng b hp th. Thp (11) l thp nh hp th
axetylen tun hon li thit b phn ng. Phn sn phm y ca thp chng
ct nh c cha phn ln l VC c a sang thp tch VC. y l mt thp
chng ct nhit thp 0,4 0,5 MPa. Sn phm VC thu c nh thp
v phn sn phm nng thu c y thp chng ct.
2.3.2.4. u nhc im ca phng php:
















n mn hc
GVHD: Th Dim Thy

SVTH: Trn Thanh L Trang 29