San Xuat VA Tu C2H4

Thiet ke phan xng san xuat VA
t C2H4
MUC LUC
Trang
Phan I : M au.
2
Phan II: Tong quan ly thuyet
............................................3
A Gii thieu nguyen lieu va san pham
I Gii thieu ve nguyen lieu
etylen...................................................3
1 Tnh chat vat ly..
3
2 Tnh chat hoa hoc..
3
3 Phng phap ieu che
etylen...............................................4
IIGii thieu ve nguyen lieu axt acetic
1 Tnh chat vat ly.

4
5
3 Cac phng phap san xuat axt
acetic..................................................6
III Gii thieu ve san pham vinyl acetat
1 Tnh chat vat ly..

10
11
3 Tnh hnh san xuat va ng dung
.....................................................13
B Cac cong nghe tong hp vinyl acetat

I Qua trnh tong hp VA t C2H4 va
CH3COOH.................................................... 15
1 Tien hanh trong pha long..

16
2 Tien hanh trong pha hi
17
IIQua trnh tong hp VA t C2H2 va

CH3COOH.................................................... 23
1 Tien hanh trong pha long..

23
2 Tien hanh trong pha hi....
23
-1-

t C2H4
III Cac phng phap khac.
28
1 Phan ng cua anhydric acetic va
acetaldehit...................................................28
2 Cacbonyl hoa cua metyl acetat...
28
3 Nhiet phan etylen glycol diacetat...
29
IV anh gia u nhc iem cua cac qua trnh
1 u iem. .29
2 Nhc iem..29
3 Ket luan... 29
Phan III : Tnh toan
A. Tnh can bang vat chat

.................................................. 30
B. Tnh can bang nhiet lng..
40
Phan IV: ket luan.

47
Tai lieu tham khao.... . .49
-2-

t C2H4
Phan I
M au
Cong nghe che bien dau mo c xem nh bat
au ra i vao nam 1859, khi ma Edwin Drake(My)khai
c dau tho. Luc bay gi lng dau tho khai thac
c con rat t, ch mot vai nghn lt/ngay va ch phuc
vu cho muc ch thap sang. Nhng ch mot nam sau o,
khong ch rieng My ma ca cac nc khac ngi
ta cung a tm thay dau. T o san lng dau khai
thac tang len rat nhanh, va ng dung trong nhieu lnh
vc ac biet la cong nghiep che bien kh va cong
nghiep tong hp cac hp chat hu c.
Ngay nay, khi cac nganh cong nghiep ac biet la
cong nghiep tong hp cac hp chat hu c phat trien
th dau mo tr thanh nguon nguyen lieu so mot cho
cong nghiep tong hp hu c.
Mot trong nhng qua trnh quan trong o la qua
trnh tong hp hu c : Vinyl hoa. Qua trnh nay tong hp
nen cac hp chat hu c trung gian phuc vu thiet thc
trong i song va ky thuat. Nh qua trnh nay ngi ta
co the tong hp ra vinyl acetat t acetylen , etylen va axt
acetic trong pha long va pha kh, trong o, qua trnh tong
hp vinyl acetat t acetylen va axt acetic la mot trong
nhng phng phap cho hieu suat cao, nhng hien nay xu
hng cac hang san xuat chu yeu i t etylen va axt
acetic thay cho acetylen va axt acetic, v etylen de tong hp,
t nguon nguyen lieu rat re tien va hieu suat thu
c cung tng oi cao.
Vinyl acetat la mot trong nhng monome quan trong
trong cong nghiep tong hp chat deo va si tong hp.
Ngoai ra vinyl acetat con c ng dung trong san xuat
sn, keo dan co o ben cao, ben vi hoa chat va cac
chat oxi hoa. Trung hp vinyl acetat ta thu c polyvinyl
acetat, mot polyme co gia tr trong cong nghiep sn keo
dan.
Ngay nay, vi nhu cau ngay cang nhieu ve chat deo
va si tong hp th cong nghiep san xuat VA tren the
gii ngay cang phat trien, ong thi c nhieu nha
khoa hoc quan tam, nghien cu nham nang cao hieu
qua kinh te. ong thi nhu cau con ngi oi hoi san
pham ngay cang cao nen nghanh san xuat ngay cang
phat trien e ap ng nhu cau o. V vay, cong
-3-

t C2H4
nghiep san xuat Vinyl acetat Viet Nam noi rieng va
tren the gii noi chung ngay cang phat trien.
-4-

t C2H4
Phan II
Tong quan ly thuyet

A Gii thieu nguyen lieu va san pham:
I Gii thieu ve nguyen lieu etylen :
1Tnh chat vat ly:
Etylen la mot chat kh, nhiet o nong chay la
-169,40c, nhiet o soi la -103,90c, ty trong d204 =0,566.
2Tnh chat hoa hoc:

Etylen la mot hydrocacbon khong no nen co nhng
phan ng quan trong nh cong , trung hp , oxi hoa
2.1Phan ng cong
a. Cong H2:
CH2=CH2 + H2 Pd CH3-CH3
b.Cong vi Br2:
Ni
CH2=CH2 + H2
CH2Br-CH2Br
Theo c che electronphi :
(Pt)
+
Br : Br
> Br + BrBr+
+ CH2=CH2 > BrCH2-CH+2 >
CH2- CH2
Br
Br
CH2- CH2
Br
Br2
CH2-CH2
Br
OH - CH2OH-CH2Br
c.Cong halogen(HX):
CH2=CH2 + HCl Peroxit CH3CH2Cl
C che:
HCl
>
H+
+ Cl*
Cl*
+ CH2=CH2 > CH *2CH2Cl
CH *2CH2Cl
+ H* > CH3-CH2Cl
d. Cong hp vi HClO:
R-CH=CH2
+ HClO > R-CHOH-CH2Cl
CH2=CH2
+ HClO > CH2OH-CH2Cl
2.1 Phan ng oxi hoa:
Tuy thuoc vao ieu kien khac ma san pham oxi
hoa cua anken (C2H4) cung khac nhau.
a. Tao thanh 1,2 diencol :
-5-

t C2H4
R-CH=CH-R
CH2=CH2
2K2MnO4.
+ 2OH-
+ KMnO4
>
R - CH-CH-R
OH OH
+ KOH > CH2-CH2 +
OH
OH
b.Tao hon hp andehit , xeton :

R2C=CHR + KMnO4 H+
R2C=O
+
R CHO
2.3 Phan ng tong hp oxo cua andehit:
CH2=CH2
+
CO + H2
t0/Co
CH3-CH2CHO
2.4 Phan ng polime hoa :
T C2H4 ta trung hp thu c cac polime, nhng
polime nay co gia tr rat cao trong i song va ky
thuat nh : nha , vai si tong hp
nCH2=CH2
> (-CH2-CH2-)n
3. Phng phap ieu che :
Co rat nhieu cach ieu che C 2H4 t cac nguon
nguyen lieu re tien the long va the hi.
a. Bang phng phap tach H2O ra khoi ancol:
CH3CH2OH
> CH2=CH2
+ H 2O
Phng phap nay thu c C2H4 vi hieu suat rat thap,
ngoai ra con ieu che bang axt oxalac.
CH3CH2OH + H2C2O4 > HO- C- C- OC2H5 > CH2=CH2
+H2C2O4
O O
the hi cho ancol 3000c 3500c ta dung xuc tac Al2O3

CH3CH2OH
> CH2=CH2
+ H 2O
b. Bang phng phap tach HX t dan xuat mono
halogen :
CH3-CH2Cl ru/kiem ac
CH2=CH2
+ HCl
c. Bang phng phap tach HX t dan xuat ihalogen:
Br-CH2 CH2-Br + Zn
> CH2=CH2 + ZnBr2
d. Bang phng phap tach CO2 khoi axt khong no :
to
CH2=CH COOH
> CH2=CH2 + CO2
II. Gii thieu ve nguyen lieu axt acetic:
1. Tnh chat vat ly:
Axt acetic la chat long khong mau, co mui giam,
axt acetic khan nong chay 16,6 0c, nhiet o soi la
-6-

t C2H4
118,10c ap suat P=101,3 Kpa, co ty trong la 1,05g/cm 3.
Sc cang be mat khi tiep xuc vi khong kh 20 0c la
23,5dyn/cm2. Nhiet o ti han la 321,6 0c, ap suat ti
han la 57,2atm, ty trong ti han la 0,351g/cm 3. Nhiet
chay tao thanh CO2 va H2O la 209,4Kcal/mol 200c.Nhiet
nong chay la 44,7Cal/g 16,58 0c, nhiet hoa hi 118,3 0c
la 96,8Cal/g.
Axt acetic tan vo han trong nc, la dung moi tan tot
trong nhieu chat hu c, vo c (P,S), la hon hp rat on
nh, hi cua axt khong b phan huy 4000c.
Cac tap chat thng co trong axit acetic la nc va
anhyrc acetic, axt acetic ong ran co tnh hut am manh.
S co mat cua nc nong o nho hn 0,1% the tch
lam giam nhiet o nong chay cua axt acetic(0,2 0c).
Axt acetic la chat oc, de lam hong niem mac
mat, co the lam bong da.
Ta co the anh gia o tinh khiet cua axt acetic qua
nhiet.
Nhiet o ong ac cua dung dch CH3COOH
% Axt acetic
99,5
99
98,5
98
97
Nhiet o ong
ac
16,6
15,65
14,8
14,0
13,25
Ty trong cua CH3COOH phu thuoc vao nong o cua

no c cho trong bang sau:
-7-

t C2H4
D420
0,9982
1,0055
1,0125
1,0195
1,0263
1,0325
1,0384
1,0438
1,0488
1,0534
1,0574
Ty trong cua CH3COOH 200c

% trong
D420
% trong
lng
lng
0
1,0611
55
5
1,0642
60
10
1,066
65
15
1,0685
70
20
1,0696
75
25
1,0700
80
30
1,0689
85
35
1,0661
90
40
1,0605
95
45
1,0492
100
50
Ty trong cua axt acetic at cc ai la 1,0696 khi nong

o axt la 79%. Ap suat cua axt acetc thay oi theo
nhiet o nh sau:
Nhiet
Ap suat hi
(mmg)
Nhiet o
Ap
suat
C
0
3,5
90
(mmg)
292,7
10
6,4
100
417,0
20
11,8
110
582,0
30
20,4
120
794,0
40
34,2
130
1067,0
50
56,3
140
1404,0
60
88,3
150
1847,0
70
137,0
160
2461,1
80
202,3
170
2860,0
2. Tnh chat hoa hoc :
-8-

t C2H4
Phan t axt acetc co hieu ng lien hp gia cac
ien t phan cc cua oxi vi cacbon trong nhom
cacbonyl va hieu ng la H+ rat de tach ra. Nhom
cacbonyl phan cc manh, no la trung tam phan ng ln,
nguyen t hidro trong goc CH 3 tng oi linh hoat co the
thay the bang cac halogen.
a. Tnh axt:
2CH3COOH
+ 2 Na
> 2CH 3COONa
+
H2
b. Este hoa:
H+
CH3COOH
+ C2H5OH
CH3COOC2H5
+ H 2O
c. Tao halogenuaxt:
O
CH3COOH
+ PCl5
CH3 C
+POCl3
+ HCl
Cl
d. Tao thanh amit axt :
O
O
CH3COOH
+ NH3
CH3C ONH4 -HOH CH3
C NH2
Axetiamit
e. Phan ng ecacbonyl hoa :
CH3COOH
MnO4 CH3COCH3 + H2O
+ CO2
f. Tao thanh anhyric acetic :

CH3COOH
xt P2O5 (CH3CO)2O
+ H 2O
g. Phan ng the halogen vao goc hydrocacbon :
CH3COOH
+ Cl2
9001000c
CH3COOCl
HCl
Axt acetc co rat nhieu ng dung trong cong nghiep
tong hp hu c, tao cac polyme co gia tr trong cong
nghiep nh :
acetat xenlulo, monovinyl acetat , monoclo
acetat, este, dung moi cho san xuat ATP, det, nhuom,
phat trien nhieu nc tren the gii:
S dung %
Sanxuat(Ac
)
Acetatxenlulo
Tay Au
8
12
16
-9-
My
6
10
12
Nhat
4
18
9

t C2H4
Este(EA,BA,A
A)
Monoclo
acetic
Dung
moi
cho
san
xuat ATP
Vinylacetat
Det ,nhuom
Cac
san
xuat khac
9
6
2
10
5
11
37
52
3
5
27
12
26
3. Phng phap ieu che axt acetic:

Co rat nhieu phng phap san xuat AcOH, trc
ay, ngi ta ieu che AcOH bang nhieu phng phap
rat thu cong nh: len men giam, chng kho go, nhng
vi yeu cau s dung AcOH ngay cang ln nh hien nay.
Ngoai hai phng phap tren con s dung cac phng
phap quan trong khac.
Mc san xuat, tieu thu c bieu th theo bang sau:
San xuat %
Tay
Au
45
16
5
34
955
1,245
My
Nhat
Acetanldehit
20
52
Butan va naphta
17
6
Etanol
/
/
Methnol
62
12
San
1.200
330
pham(103t/nam)
1,450
540
Kha nang san
xuat(103t/nam)
960
1,175
330
Mc tieu
thu(103t/n)
San lng acid acetic tren the gii vao 1984: 4,4.10 6
t/nam
vao 1986:4,6.106 t/nam
Qua trnh cacbonyl hoa metanol la cong nghiep tng
oi mi va pho bien trong cac nam, v nguon nguyen
lieu doi dao va re tien.
Nam 1913, hang Basf a mo ta qua trnh san xuat
AcOH t metanol va CO nhiet o va ap suat cao:
CH3OH + CO
CH3COOH
H = - 138,6 KJ
- 10 -

t C2H4
Do ieu kien nhiet o va ap suat khac nghiet
cung vi s co mat cua chat an mon manh a ngan
chan viec thng mai hoa qua trnh nay vao 1941.
en nam 1968 hang Mansato cong bo kham pha
mi . Xuc tac Rh vi hoat tnh va o chon loc rat cao
cho phan ng Cacbonyl hoa MeOH thanh AcOH, ngay ap
suat thng vi hieu suat chuyen hoa la 99% oi vi
MeOH va 90% vi CO.
Qua trnh co s dung c a vao thc te nam
1970 tai Taxas My. Nang suat bc au la
135.000t/nam, sau o m rong vi nang suat la
180.000t/nam t nam 1975.
Hai cong nghe cua qua trnh san xuat AcOH bang
cacbonyl hoa methnol:
1. Qua trnh BASF:
Toc o phan ng phu thuoc vao hieu suat hi
rieng phan cua CO va nong o MeOH . Hieu suat
chuyen hoa AcOH at 90% oi vi MeOH va 70% oi vi
CO.
C che phan ng:
Co2(CO)8
+ H2O + CO
Co(CO) 4H
+
CO2
(1)
CH3OH
(2)
+ HI
CH3I
Co(CO)4H
+ H 2O
H+
[Co(CO) 4]-
(3)
(4)
(6)
[Co(CO)4]CH3Co(CO)4
(5)
O
CH3 C-Co(CO)3
O
CH3 C Co (CO)4
[Co(CO)4]- (7)
CH3P
CH3Co(CO)4
I-
O
CH3- C Co(CO)3
O
+
CO
+ HI
CH 3
C Co (CO)4
CH 3COP +
- 11 -
H+

t C2H4
(8)
CH3COP
+ H 2O
CH3COOH
HI
Phan ng co the c xem la qua trnh chuyen

hoa CO bang hi nc nhiet o 250 0c , ap suat 65. 106
Pa , xuc tac la cacbonuyl coban.
San pham cua qua trnh BASF la : CH 3CHO , CH4 ,
C2H5OH , CO2 khoang 3,5% mat mat di dang CH4, 4,5%
dang san pham phu long , 2% dang kh thai , khoang
10% CO nguyen lieu bien oi thanh CO2 , theo c che sau:
CO
H 2O
CO 2
H2
(9)
2. Qua trnh Mansanto :
Nhiet o phan ng la 2000c, ap suat 3,5.106 Pa.
Xuc tac : cac kim loai qu hiem nh Pd , Rh
So vi qua trnh BASF th qua trnh nay tien hanh ieu kien
em du hn, san pham phu sinh ra khong ang ke, he thong
thiet b phan ng n gian hn.
Ben canh hai qua trnh tren con co qua trnh sau :
Oxi hoa trc tiep cac hydrocacbon no :
Nguyen lieu chu yeu la i t n- Butan, phan ng xay ra nh
sau :
CH3CH2CH2CH3
+ O2
2CH3COOH H0298=
-985kj/mol
Qua trnh oxi hoa Acetaldehit
C che phan ng:
Qua trnh oxi hoa acetaldehit xay ra theo c che chuoi
goc t do. Trong o, san pham trung gian la axit peraxetic.
O
O
CH3 C
O2
CH3 C OO
O
CH 3 O
CH3C
O
+
O2
O
CH3 O
-OOH
CH3 C- OOH
CH3
CH3-C
OH
C
CH3-C
- 12 -
CH 3- O- C- H
OH
C+
+ CH3-O

t C2H4
O O
O
CH3-C-O-
O-
CH3
+
OH
C+
O
2 CH3- C - OOH
HO
O
CH3- C OOH
O
+ CH3-C-H
CH3-C
CH3
OH
O O
C
H
Axt paraxetic phan ng vi axetanldehyt tao thanh

AcOH. Axetandehit manoperaxetat(AMP). AMP phan huy
thanh AcOH.
III. Gii thieu ve san pham Vinyl acetat:
1.Tnh chat vat ly cua VA:
Vinyl acetat goi tat VA, cong thc phan t CH 2=CHOCOCH3, khoi lng phan t:86,09 , la chat long chay
c ,khi chay co mui ac trng nhe, khong mau, nhiet
o soi t0s=72,70c , ty trong 200c, d420=0,935g/ml, iem
nong chay -100,20c, o nht la 0,4mPAS ap suat hi
200c la 12Kpa va 42,6 Kpa, he so gian n the tch la
0,0014K.
Nhiet o bat chay :3850c
Gii han no tren /di trong khong kh :
13,42,3% the tch
Nhiet dung rieng :1,926Kj/kg
- 13 -

t C2H4
Nhiet hoa hi la :379,3Kj/kg 72,7 0c
Nhiet chay la
: 2082 Kj/mol
Ch so khuc xa n020 = 1,3956

Nhiet cua qua trnh trung hp la 1035,8Kj/kg
Nc trong Vinyl acetat chiem 0,9%trong lng 200c ,
Vinyl acetat
trong nc chiem 2,3% trong lng 20 0c.
Hon hp ang ph vi nc soi 66 0c/100Kpa, nc

chiem 7,3% trong lng.
Hon hp ang ph cua vinyl acetat co thanh phan
va tnh chat :
Nc co nhiet o ang ph
: 66,0 0c, chiem
92,7% khoi lng VA

MeOH co nhiet o ang ph: 58,90c, chiem
63,4%khoi lng VA
2-propanol(CH3-CH-CH3)
: 70,80c, chiem 77,6%khoi
lng VA
OH
Xyclohexan(C6H12) nhiet o ang ph 67,40c,

chiem 61,3% khoi lng VA
Heptan (C7H16) nhiet o ang ph 72,00c, chiem

83,5% khoi lng VA.
2. Tnh chat hoa hoc cua vinyl acetat :

Phan t vinyl acetat (VA) : CH2=CHO-COCH3, ta thay
co lien ket oi , nen mang ay u cac tnh chat hoa
hoc cua hp chat hydrocacbon khong no :
Phan ng cong
Phan ng trung hp
- 14 -

t C2H4
Phan ng oxi hoa
a. Phan ng cong :
Cong vi brom:
CH2=CH
+ Br2
Br- CH2- CH-Br
OCOCH3
OCOCH3
Cong vi halogen(HX : HBr, HCl):

CH2=CH
HBr
peroxit
CH3- CH-
Br
OCOCH3
OCOCH3
Cong ROH :
CH2=CH-
ROH
H+
CH3CHO + CH3COOR
OCOCH3
Cong hp chat xianua :
CH2=CH
+ CH3-CH-CN
OH-
CH3-CH-CN +
CH3CHO
OCOCH3
OH
OCOCH3
Cong hp vi andehit nit, cloua nitronyl:

CH2=CH
+ O=N-O-N=O
CH2- CH-
OCOCH3
OCOCH3
CH2=CH
NO2 N=O
+ Cl-N=O
CH2- CH-
OCOCH3
OCOCH3
Cl
Cong hp vi axt:
OCOCH3
- 15 -
N=O

t C2H4
CH2=CH
+CH3COOH H+
CH3CH
OCOCH3
OCOCH3
Cong vi C6H5OH
OH
CH2=CH
OH
H+
CH=CH2
OCOCH3
+ CH3CHO
Cong vi
andehit formic:
CH2=CH
HCHO
H+,H3PO4
CH2=CH-CHO
CH3COOH
OCOCH3
b. Phan ng trung hp, ong trung hp:
n CH2=CH
-CH 2- CH-
OCOCH3
OCOCH 3 n
ong trung hp gia VA va VC ta c mot loai

chat deo Vinylic. Vinylic dung lam man mong , sn. Vat
lieu tam ngam.
Phan ng:
-CH2-CH-
-CH2- CH-
-CH2-CH-
CH2-CH- n
OCOCH3
Cl
OCOCH3
Cl
c. Phan ng oxi hoa :
CH2=CH
+2KMnO4+2KOH
CH2-CH-
OCOCH3+ 2K2MnO4
OCOCH3
OH
- 16 -
OH

t C2H4
d. Phan ng thuy phan cua PVA:
-CH2-CH-
H+
-CH2-CH-
nCH3COOH
OCOCH3
nH2O
OH
Khi thuy phan PVA vi s co mat cua xuc tac H +

ta c polyvinyl ancol, ay la mot polimer co gia tr va
quan trong.
- 17 -

t C2H4
3. Tnh hnh san xuat va ng dung:
Vinyl acetat:CH2=CHOCOCH3 la
a.ng dung cua VA:
mot trong nhng monomer rat quan trong, khi trung hp

tao thanh poly vinyl acetat:
-CH2-CH-
OCOCH3
Polimer nay c s dung e san xuat sn , cac
chat ket dnh, vecni, s dung trong cong nghiep det,
giay, lam vai gia da..va cho cac qua trnh san xuat
polyvinyl alcol, polyvinylbutyren, polyvinyl acetat co tnh dnh
tot va c ng dung trong san xuat chat deo, keo
dan,. Khi thuy phan polyvinyl acetat ta thu c mot
polimer khac la polyvinyl ancol:
-CH2-CH-
OH
Polyvinyl ancol c s dung lam chat nhu hoa va
tang o nht cho cac dung dch nc.
Copolime vinyl acetat c ng dung e san xuat
nha, vai
Tnh hnh s dung vinyl acetat cac nc:
- 18 -

t C2H4
S dung %
Etylen-vinyl
Tay Au
4
My
7
Nhat
11
acetat
60
58
16
Poly vinyl acetat
17
21
71
Poly vinyl alcol
Poly vinyl butyral
11
Copolymevinylclo
rua
khac
b. Tnh hnh san xuat VA:
Vinyl monome c phat hien ra trong qua trnh trung hp

va ac biet la kha nang tao hp chat polime. T o,
ngi ta tong hp bang phng phap trc tiep va sm
nhat t acetylen. Tuy nhien, acetylen la nguon nguyen
lieu rat at, ngay nay, trong cong nghiep hoa hoc no
c thay the bang etylen va propylen.
Do tnh kinh te cua nguon nguyen lieu ma ngay nay
trong cong nghiep san xuat vinyl acetat t metyl acetat hay
i metyl ete vi CO va H2 ang c nghien cu va hoan
thien, cong nghe va phat trien v nguon nguyen lieu
nay rat doi dao va re tien.
Tnh hnh san xuat vinyl acetat vao 1984 cac nc
- 19 -

t C2H4
San xuat
%
Acetylen
Etylen
Tay Au
My
Nhat
43
57
/
100
19
81
San lng vinyl acetat tang rat nhanh, vao nam 1985
tren the gii co 106tan/nam, vao nam 1984 at 2,7
106tan/nam. en nam 1986 san lng vinyl acetat
mot nc tren the gii nh sau:
My
Canada
Chau My La Tinh
Tay Au
ong Au
Chau Phi
Trung ong
Nhat
Chau A va
ong A
1,15.106tan/nam
0,05.106tan/nam
0,09.106tan/nam
0,56.106Tan/nam
> 0,16.106Tan/nam
/
/
6
0,58.10 tan/nam
>0,15. 106tan/nam
B Cac cong nghe tong hp vinyl acetat:

Cho en nay, co rat nhieu phng phap tong hp VA
t cac nguon nguyen lieu khac nhau, mot so phng
phap chu yeu sau :
Tong hp vinyl acetat t C2H2 va CH3COOH

trong pha long va pha kh.
Tong hp vinyl acetat t C2H4 va CH3COOH

trong pha long va pha hi kh.
Tong hp vinyl acetat i t acetat hay di metyl

ete vi CO va H2 trong pha long co mat cua xuc tac
ong the nh muoi cua Rh hay cac kim loai qui Pt ta thu
c Etyliden diacetat. Sau o, thuy phan ta thu c Vinyl
acetat va CH3COOH.
Nhn chung, cung vi s phap trien cua cong nghe
va nhu cau kinh te cao, nen ngay nay qua trnh tong hp
Vinyl acetat trong pha long t c s dung en, v chung
gay an mon thiet b va cong nghe, chu yeu la s
- 20 -

t C2H4
dung trong pha kh, ac biet la s thay the nguyen lieu
acetylen(C2H2) bang nguyen lieu re tien, de tong hp la
C2H4(etylen).
I. Qua trnh tong hp vinyl acetat t etylen va axit acetic:
Do tnh kinh te cua nguon nguyen lieu ma tren the
gii a va ang co xu hng tm ra nhng phng phap
san xuat vinyl acetat co hieu qua tng ng vi phng
phap san xuat VA t C2H2 va CH3COOH, nhng lai s dung
nguon nguyen lieu re tien, de san xuat. Mot trong
nhng phng phap mi c s dung gan ay trong
tong hp Vinyl acetat la i t nguyen lieu etylen(C 2H4).
Thay v i t nguyen lieu C 2H2 at tien. Qua trnh tiet
kiem c hn 20% gia thanh san xuat. Phng phap
nay a vao qua trnh oxi hoa etylen vi s co mat
cua CH3COOH va xuc tac Pd2+(muoi Pd2+)
Phng phap nay tien hanh trong pha long vi cong
nghe Bayer/Hoechst, USI
Hien nay, cong nghe san xuat chu yeu la pha hi
v pha long gay an mon thiet b nen t s e tong hp
VA.
1. Cong nghe tong hp vinyl acetat t C2H4 va CH3COOH
trong pha long:
Qua trnh tong hp vinylacetat t etylen(C2H4) c
phat minh bi cac hang Hoechst(c), ICI(Anh), Nippon
Gosei(Nhat) va c cac hang ICI ap dung vao san
xuat vi qui mo ln Anh va My trong vai nam gan
ay vi san lng la 45,36 trieu kg/nam.
Phng phap nay chu yeu la san xuat acetaldehit
bang cach oxy hoa etylen bang oxy trong thiet b oxy
hoa, hoac e san xuat aceton t propylen.
Phan ng chnh trong qua trnh tong hp vinyl acetat
xay ra :
a. San xuat acetaldehit:
CH2=CH2
+ PdCl2 + H2O
CH3-CHO + Pd +
2HCl
b. Oxi hoa paladi(Pd) bang muoi CuCl2:
Pd
+ CuCl2
PdCl2 + 2CuCl
2CuCl
Suy ra :
+ HCl +
O2
CuCl2
O
- 21 -
+ H 2O

t C2H4
CH2=CH2
+ CH3- C - O - H
+PdCl 2 CH2=CH-O-C-CH3 +
2HCl + Pd
Cac ac tnh va thong so cua qua trnh:
S bien oi axt acetic thu c 20 30%; 23% oi
vi etylen. Hieu suat at c 7080% oi vi etylen,
thanh phan oxy va kh etylen(C2H4) nam trong gii han
cho phep: 94,5% oi vi C2H4 va 5,5% oi vi oxy.
Cac phan ng tien hanh nhiet o 110 1300c,
va apn suat la 3.106Pa.
Oxy ong vai tro tac nhan trc tiep trong dung dch
xuc tac, v e ngan chan nhanh muoi CuCl 2 gay ra do
thieu oxy trong moi trng phan ng.
Dung dch xuc tac chiem 3050 mg/l muoi Pd2+. ac
biet hp chat nong o cao hn se thch hp cho trnh ime
hoa cua etylen thanh buten(C 4H8). Muoi ong (Cu2+) cha
36g/l, ac biet can s tham gia cua muoi clorua e lam
xuc tac hoat manh. San pham tao thanh axt acetic,
ong oxalat, este, axt formic va CO 2. Qua trnh xay ra lam
hi nc cua lo phan ng c lam lanh va ngng tu
xay ra:
a. S phan bo kh c tuan hoan tr lai sau khi
lam lanh va thu hoi CO2
b. Trong pha long : s tach va tuan hoan lai
CH3COOH, qua thap phan bo thu san pham nhe va
actaldehit, qua thap loc bang hi nc, thu c vinyl acetat
tinh khiet.
Acetaldehit c tach ra t san pham nhe bang
thap loc, sau o, oxi hoa acetaldehit thu c acid acetic
vi xuc tac Mangan acetat.
Cac thiet b dung trong qua trnh tong hp nay
phai c lam bang Titan(Ti), nha tham composit, s
e tranh s an mon do trong san pham cua phan ng
co HCl tao thanh.
Xu hng hien nay, e tong hp vinyl acetat trong pha
long bi cac hang Hoechst, ICIkhong dung en v :
Gay an mon thiet b phan ng.
Vat lieu e che tao thiet b chong an mon
rat at.
Do o, chi ph cho toan bo qua trnh san xuat cao
hn khoang 50% so vi qua trnh tong hp vinyl acetat t
- 22 -

t C2H4
acetylen va axt acetic trong pha hi t etylen va CH 3COOH
vi oxi.
Cho nen, hien nay cac hang Hoechst-Bayerchu yeu
tong hp VA t etylen va axt acetic trong pha hi, thay cho
acetylen va acid acetic.
2.Cong nghe tong hp VA t C 2H4 va CH3COOH cua hang
Hoechst- Bayer trong pha hi:
Hang Hoechst-Bayer la hai tap oan cong nghiep
ln tren the gii co rat nhieu cong trnh nghien cu
va phat minh cong nghe trong cong nghe hoa hoc.
S o cong nghe tong hp VA t C 2H4 va CH3COOH
trong pha hi.
Cac thong so cong nghe:
Xuc tac cua qua trnh la Paladi hay muoi Pd 2+ va
muoi kim loai chiem t
1en 3% trong lng, ket hp vi cac kim loai khac nh
Platium(Pt) (hang USI chemicals), Cadimi va vang(Au)(hang
Bayer/Hoechst),cung nh Bi,Ba,Fe va kim loai tr khac.
Acetat cua kim loai kiem nh : Na, Ktren chat mang
la -oxt nhom, cac dang cau truc cua axt silic, hoac
than hoat tnh.
Lng xuc tac can dung tnh theo lng san pham
VA la 200g/lt gi. Thi gian hoat ong toi acua xuc
tac la bon thang.
Nhiet o phan ng t 1601800c.
Ap suat lam viec t 0,50,8.106Pa.
Thanh phan hon hp a vao phan ng 15%

mol CH3COOH ;
- 23 -

t C2H4
50%C2H4, 29% kh tr (CO2); long oxi toi a la 6%. The tch
cua kh tr va kh N 2 c ieu khien theo lng kh d
(10%) no phu thuoc vao o tinh khiet a vao.
Hieu cua qua trnh pha hi 8890% oi vi etylen, 98% oi
vi axt acetic.
Day chuyen cong nghe :
1 :Thiet b boc hi CH3COOH;

2 :Thiet b phan ng;
3 :Thiet b un nong s bo;
4 : Thiet b trao oi nhiet ngc dong;
5 : Thap hap thu
6 : Thap loc kh bang hi nc;
7 : May nen tuan hoan
8 : Thap hap thu kh CO2
9 : Thap tai sinh
10: Thap chng cat s bo;
11: Thiet b tach long /kh
12: Thap tach nc
13: Thap tach san pham nhe cuoi cung
14: Thap tach san pham nang cuoi cung
15: Bm
16: Thap chng cat phan nhe;
Nguyen l hoat ong:
Qua trnh phan ng xay ra nh sau :

O
CH2=CH2
+ CH3- C -O H + O2
H2O
H0298=-180kj/mol
- 24 -
CH 2=CH-O-C-CH3 +

t C2H4
Qua trnh phan ng xay ra dang thiet b loai
thap, thng dung hai tac nhan phan ng song song
nhau. Axt acetic nguyen chat va axt tuan hoan a vao
cung vi etylen(C2H4) trong thiet b boc hi (1), nhiet o
trong thap (1) la 140 0c va ap suat 1.10 6Pa, c gia nhiet
en nhiet o 1600c. hon hp ra khoi nh thap qua thiet
b un nong (3), ra khoi thiet b nay hon hp c tron
vi oxy mot lng nhat nh. Lng oxi nay c xac
nh bi gii han t boc chay cua hon hp C 2H4 va O2.
ra khoi thiet b boc hi (1) ay thap, mot phan qua
thiet b tach c a tr lai ay thap, mot phan nh
bm (15) bm san pham nang ra ngoai.
Hon hp ra khoi nh thap (1) tron vi oxy a
vao thap phan ng (2). Hon hp kh ra khoi thiet b
phan ng tren nh thap nhiet o 1600c va ap suat
0,7.106 Pa, c lam lanh trong thiet b trao oi nhiet
ngc dong(4) vi tac nhan lam lanh la hon hp kh
etylen kh tuan hoan. Hon hp kh nay se c am len
ong thi co s ngng tu khong hoan toan cua axt
acetic. Hon hp qua thiet b un nong (3) va chuyen vao
thap hap thu(5) ong thi cung vi dong dung dch
tuan hoan axt acetic. Tai ay, vinyl acetat tho c tao
thanh
(CH2=CH-O-C-CH3)
O
Kh ra khoi thap (5) nh thap mot phan kh c lam
sach a thai ra ngoai, mot phan c nen lai qua may
nen(7). Kh ra khoi may nen c a vao thap hap thu
- 25 -

t C2H4
kh CO2(8), e ngan chan s tch tu trong qua trnh tong
hp, dung thuoc th K2CO3 e hap thu kh CO2. ra khoi
ay thap (8) c a sang thap tai sinh (9) e tai sinh
lai thuoc th, ra khoi thap kh CO 2, phan ay thap co
mot phan c chuyen tr lai ay thap, mot phan
lam dung moi a vao thap(8),ra khoi nh thap (8) la
kh etylen(C2H4), kh nay c tuan hoan lai lam nguyen
lieu ban au a vao thap(1). VA va nc ra khoi ay
thap (5) va (6) c bm(15) bm ve cung vi chat c
che chuyen sang thap tach s bo(10). Dung dch tach ra
ay thap la 9798% axt acetic, mot phan a tr lai
ay thap, mot phan c tuan hoan ve lam nguyen
lieu cho vao thap (1). Thanh phan ra khoi nh thap qua
bo ngng tu vao thiet b tach long/kh(11), c phan ra
lam hai thap khac nhau(moi thap gom 25a), mot vao
thap chng cat phan nhe (16), ra khoi ay thap mot
phan qua bo ngng tu un nong a lai ay thap, mot
phan nh bm (15)bm thai ra ngoai lng nc thai
khong can thiet. Hai vao thap tach nc(12) cua Vinyl
acetat, a so phan cat c lay t thap tach phan
nhe(16) e lam giau lng VA, phan khong ngng tu (C 2H4
va O2), sau khi nen lai c a sang phan oan phan ng
va hon hp khong ong soi VA/H 2O(t0s=660c, trong o
nc chiem 7,3%trong lng ). Chung c bat au
bang hai cot khac nhau. Pha tach xay ra trong thiet b
tach (11) : hai phan ba pha hu c c hoi lu cho vao
thap chng cat th ba, va pha nc c a vao thap
chng cat phan nhe(16). Toan bo phan thu hoi cha
- 26 -

t C2H4
mot so hp chat hu c (1000 en 2000ppm). Hi nc ra
khoi ay thap tach(12), ket hp cung chat c che cho
vao thap tach san pham nang sau cung(thap nay
gom 100 en 120 a). VA thu c ap ng yeu cau VA
thng pham. Thap tach cuoi cung nay c thiet ke
e thu hoi etyl acetat trong san pham nang va thap
tach(13) cung thiet ke e thu hoi lai c metyl acetat
va acetaldehit trong so thanh phan nhe Vinyl acetat thu
hoi va tinh che c yeu cau trong qua trnh xay ra co
s tham gia cua chat c che, chung dang hon hp kh
O2 va CO2. Toan bo thiet b cua phan xng c che
tao bang thep hp kim chat lng cao(ty le Cr/Ni=18/8).
S o day chuyen cong nghe
- 27 -

t C2H4
- 28 -

t C2H4
II. Qua trnh tong hp vinyl acetat t C2H2 va CH3COOH :
Qua trnh tong hp nay c bat au phat trien
trong pha long vao nam 1912. Nhng cong nghe chnh la
pha hi va c ng dung bi hang Wacker (vao nam
1930), en nam 1960 phng phap tong hp nay van
con ton tai khap ni tren the gii, chu yeu la Tay
au.
Phan ng cua qua trnh san xuat VA la phan ng
toa nhiet.
CH CH
+ CH3COOH
CH2=CH-O-C-CH3
H0298=
-118kj/mol
O
1. Qua trnh tong hp Vinyl acetat t C 2H2 va CH3COOH
trong pha long :
Qua trnh nay xay ra nhiet thap t 60800c va
ap suat thap 0,10,2. 106 Pa.
Yeu cau lp xuc tac hoat ong manh nh muoi
cua kim loai thuy ngan(Hg2+) dang cac dang nh :
oxt , photphat, sufat cua thuy ngan, chung nam
dang huyen phu trong acid(axt acetic) chiem 15% e han
che s tao thanh etyliden diacetat, nhiet o on nh
60800c. lng acetylen con lai trong xuc tac huyen phu
co the b giam, hoac mat mat. Tuy nhien, trong trng
hp nay khong the thieu viec s dung chat c che
polime nh : HF,BF3trong ieu kien nay, hieu suat Vinyl
acetat thu c hn 90%.
2. Qua trnh tong hp Vinyl acetat t C 2H2 va CH3COOH
trong pha hi:
- 29 -

t C2H4
Phan ng xay ra trong pha hi nhiet o 1802100c,
ap suat kh quyen. Xuc tac cho phan ng acetat kem
tren chat mang la than hoat tnh. S o qua trnh tong
hp gom ba bc sau:
a. s hoat hoa cua kem acetat tren chat mang than
hoat tnh tong hp nen VA.
b. s hap phu hoa hoc tren lp xuc tac bien oi
thanh VA.
c. phan ng cua axt acetic va hap phu acetylen.
C che cua phan ng bao gom cac giai oan hap
phu hoa hoc acetylen tao thanh phc , vi ion kem, sau
o, la s tan cong cua phan t acetylen a c hoat
hoa bang ion acetat va cuoi cung la tac dung vi acetic
:
+CHCH
Zn2+(OAc)2+AcOH Zn2+(OAc)-2
Zn2+(OAc)-2
Zn2+OAc-
HCCH
[CH=CHOAc]
+ CH2=CHOAc.
Vinyl acetat co kha nang ket hp tiep tuc vi AcOH tao

thanh etyliden diacetat. Do vay, se xuat hien mot he
phan ng song song noi tiep :
+ HOAc
CHCH
CH2=CHOAc
+HOAc
CH3-CH(OAc)2
Giai oan au xay ra vi van toc ln hn nhieu so vi

giai oan th hai, tuy nhien, van can phai co mot lng
d C2H2 so vi AcOH e han che toi a s tao thanh
etyliden- diacetat. Mot phan phu khac cua qua trnh la
acetaldehit, tao bi s thuy phan acetylen.
- 30 -

t C2H4
Ngoai ra, con co mot lng acton sinh ra do qua trnh
ceton hoa axt :
CH3-COOH
CH3-CO-CH3 + CO2
+ H2 O
Tuy nhien, con xay ra s trung hp cua mot so

chat trong he phan ng, ket qua la tao thanh cac hp
chat nha. e tranh s phat trien manh cua cac phan
ng phu va e tang nang suat cua thiet b phan ng
can o chuyen hoa axt acetic mc o va phai
(60%) khi o hieu suat vinyl acetat se at 95 98% tnh theo
AcOH va 92 95% tnh theo axetylen.
San
pham chnh la acetandelhit (>1phan tram),aceton,
crotoanldehit, etylidenacetat, methyl vinyl ketonva lng

hydrocacbon khong no.
Trong san xuat cong nghiep, t le mol gia axetylen
va axit acetic t 3,5:1 en 5:1. Xuc tac c chuan b
bang cach tam acetat kem len than hoat tnh, sau o
say kho. Xuc tac chuan b bang phng phap nay
cha 30% acetat kem va co hoat tnh cao, nhiet o
1701800c. Sau mot thi gian hoat ong hoat tnh cua no
se giam dan do mot lng nha bam tren be mat. V
vay, can phai nang nhiet o t t len 210220oc.
Qua trnh phan ng c thc hien ap suat kh
quyen, trong thiet b dang ong chum va lam lanh bang
nc ngng tu, vi lp xuc tac long gia (FCC).
S o cong nghe c bieu dien tren hnh sau:
1.Thiet b bay hi :
7. Thiet b tinh che
2.Thiet b phan ng :
8.
pham nhe
- 31 -
Thap
tach
san

t C2H4
3.Thiet b trao oi nhiet ngc chieu
9. Thiet b cha
vinyl acetat sach

4. Thiet b lam lanh
10.Thap tach san
pham trung gian

5. Thiet b un nong
11.Thiet b cha axt
acetic sach
6. Thiet b nen kh
12. Bm
Nguyen l hoat ong :

Lng acetylen(C2H2), axt acetic tinh khiet va tuan
hoan c a vao thiet b boc hi(1), ap suat 0,3.
106Pa,va nhiet o 70800c, ra khoi thiet b nay ay
thap, mot phan c un nong va a tr lai ay thap
bi thiet b un nong(5), mot phan san pham nang a
ra ngoai qua bm(12), hon hp kh ra khoi nh thap c
gia nhiet qua thiet b trao oi nhiet ngc chieu(3), sau
o c un nong bi thiet b (5) ra khoi thiet b nhiet
o 1701900c. Hon hp kh nay c a en thiet b
phan ng(2), qua trnh nay dien ra vi lp xuc tac co
nh hay long gia. Xuc tac gom than hoat tnh, c tam
2030% kem acetat. He thong lp xuc tac nay c
cha trong ong co ng knh 5cm va chieu cao ong
3,54m, vong tuan hoan kn cua chat long lam lanh, thu
hoi c em un nong len nhiet o 200 0c. Trong xuc
tac long gia phan ng xay ra tao cuon chm xuong
dang vo nh hnh. Qua trnh xay ra lien tuc trong thiet b
phan ng e tai sinh xuc tac. Lng acetylen thu c
se c tuan hoan tr lai sau khi ra khoi thiet b. Hon
hp kh hi nc ra khoi thiet b phan ng c lam lanh
bi thiet b trao oi nhiet (3), phan ln c ngng tu
- 32 -

t C2H4
trong thap tinh che(7),vi chat long lanh. Qua trnh thu
c bang cach s dung chnh san pham ngng tu axt
acetic. Hau het kh con lai chu yeu la acetylen, c
tuan hoan tr lai vao thiet b(1), mot t le khong
ang ke c lam sach e ngan s tao nguyen to tr
trong qua trnh tong hp.
Lng ngng tu c lam lanh trong tng cot, nhng
phan nhe c tach au tien trong thap tach(8) thap
nay gom 35 a bao gom kh acetylen, acetanldehit, aceton,
propinolandelhit, acrolin trang thai long. Ra khoi thiet
b nay ket hp cung vi chat c che vao thap(9), ra
khoi nh thap(9), thap nay gom 50 en 60 a, tach
thu c vinyl acetat thng pham, san pham ra khoi ay
thap, mot phan a tr lai thap(9), mot phan a vao
thap tach san pham trung gian(10), ra khoi nh thap thu
c divinyl acetylen,crotonandelhit. San pham tach ra khoi
ay thap, chuyen vao thiet b(11), nh thap(11) tach
ra axt acetic, lng nay c tuan hoan tr lai lam
nguyen lieu cho vao thap (1). Ra khoi ay thap tach ra
san pham nang.
e ngan chan qua trnh polime hoa vinyl acetat trong
suot qua trnh chng cat, oi hoi qua trnh nay can co
mat cua chat c che (hydroquinon, dimethylamin, ) toan
bo thiet b phan ng c che tao bang thep hp kim,
thanh phan gom Cr chiem t 1520%, Ni chiem t
1015%.
S o cong nghe bieu dien theo hnh sau :
- 33 -

t C2H4
- 34 -

t C2H4
III. Cac phng phap khac:
Trong so cac phng phap e tong hp vinyl acetat
khac nhau th co mot so phng phap c ng dung
rat pho bien trong ky thuat va cong nghe.
1. Phan ng cua anhydrit acetic va acetanldehit :
Phan ng nay xay ra nhiet o tren 300 0c vi
xuc tac la axt, san pham tao thanh etyliden diacetat, sau
o, lai phan huy thanh vinyl acetat va axt acetic.
Phan ng :
O
CH3-CHO
(CH3-CO)2O
CH3CH(O- C -CH3)2
O
O
CH3-CH(O-C-CH3)2
CH3-COOH
+ CH2=CH-O-
C-CH3
Phng phap nay c tong hp vao 1953 Pampa,
Texas, cong nghe cua hang Celanese, cong suat at
20.000 tan/nam. Cho en nay cac hang nay khong con
tong hp t phng phap nay na.
2. Phng phap cacbonyl hoa cua metyl acetat :
Phng phap nay c tien hanh bi hang Halcon,
qua trnh tong hp da tren viec s dung cac kh e
san xuat ra metanol, metyl acetat va anhydrit acetic, sau o,
ket hp vi etyliden acetat. San pham tao thanh chung
lai phan huy ra thanh VA va axt acetic va axt tao thanh
tham gia vao qua trnh este hoa vi metanol.
Qua trnh xay ra :
O
4CO
+
5H2
CH 2=CH- O - CCH3 + 2H2O
cacbonyl hoa cua metyl acetat la phng phap chu yeu
e tong hp VA(hieu suat thu c 85%), c che phan
ng la
O
CH3-C-O-CH3
(CH3-CO)2O
O
+ CO
(CH3-CO)2O
O
CH3-C-O-CH3 + CO + H2
CH3-CH(O-C-CH3)2 + CH3COOH
- 35 -

t C2H4
Phng phap nay tien hanh trong pha long nhiet o
la 1301600c va ap suat 47.106Pa.
Xuc tac s dung : cac kim loai qu nh : Pd, Rh,
metyl iodic va nhom amin hay photphin(PH3).
Anhydric acetic c tao thanh ong vai tro nh hp
chat trung gian, s bien oi trc tiep tao ra san pham
etyliden diacetat va lam tang ty le CO trong qua trnh
tong hp kh.
CH3COOH sinh ra tham gia vao qua trnh este hoa vi
CH3OH :
CH3COOH
+ CH3OH
CH3COOCH3
+
H2O
Nh vay, thc chat cua qua trnh tong hp vinyl
acetat t methnol va kh tong hp.
Nhc iem cua qua trnh la co rat nhieu san
pham va kho tach ra khoi san pham VA nen qua trnh
nay t c s dung.
3. Nhiet phan etylen glycol diacetat : c thc hien bi
hang Halcon
Nhiet o xay ra 5005500c, hieu suat at c
8587%
Phan ng xay ra:
O
O
O
CH3-C-O-CH2-CH2-O-C-CH3
CH 2=CH-O-C-CH3 +
CH3COOH
Etylen glycol diacetat c tao thanh bi acetoxylat hoa
cua etylen nhiet o 4000c va ap suat 3.106 Pa.
Xuc tac cho qua trnh : O2, Te, Br2...
3CH2=CH2 + 5CH3COOH
CH3-C-O-CH2CH2-O-C-CH3
+
O
HO-CH2-CH2-O-C-CH3 + 2H2O
IV. anh gia u nhc iem cua cac qua trnh tong hp
VA :
1. u iem :
Phng phap tong hp vinyl acetat trong pha hi at
hieu suat chuyen hoa cao, xuc tac re tien hn cac
xuc tac khac, t an mon thiet b phan ng.
2. Nhc iem :
Tien hanh nhiet o cao hn cac phng

phap khac
- 36 -

t C2H4
San pham hi vinyl acetat rat oc, VA rat de

trung hp, tao thanh PVA. V the, khong nen gi VA qua
24 gi ma khong co chat on nh. Chat on nh
thng la diphenyl amin(0,010,02%)hay hydroquinol.
Sau khi c VA nen cha trong cac thung nhom,
sat hoac thep e van chuyen hay co the a ngay sang
phan xng khac.
3. Ket luan :
Qua cac phng phap san xuat vinyl acetat a trnh
bay tren ta thay cong nghe tong hp VA ngay cang
phat trien va hoan thien hn. Trong o, phng phap
tong hp vinyl acetat t acetylen va axt acetic trong pha hi
at o chuyen hoa cao hn ca. Nhng do tnh kinh te t
nguon nguyen lieu nen phng phap nay t c s
dung, thay vao o la i t etylen va axt acetic, v nguon
nguyen lieu nay re tien hn so vi acetylen.
Hien nay, hai tap cong nghiep ln nh : Hoechst
Bayer a ap dung phng phap tong hp nay, hieu suat
thu c 8890% oi vi etylen; 98% oi vi axt acetic.
- 37 -

t C2H4
Phan 3
Tnh toan
A. Tnh can bang vat chat :
Tnh toan phan xng san xuat VA vi nang suat
day chuyen 50.000 tan/nam
Thanh phan nguyen lieu nh sau :
C2H4 ky
O2 ky thuat
CH3COOH ky
thuat
thuat
(% khoi lng)
(% the tch)
(%khoi lng)
C2H 4
O2
98%
CH3COOH
98%
92%
N2
2%
Tap chat
CH4
2%
5%
C3H 6
3%
o chuyen hoa tnh theo C2H4 95%, ton that 2%
Ap dung cong thc tnh e qui oi nong o cua C 2H4
ky thuat ra nong o % khoi lng
ai =
Mi Xi
Mi Xi
Trong o :
Xi : phan kmol cua cac cau t
Mi : khoi lng cua cac cau t
Coi cac chat kh ieu kien tieu chuan nen ta co
phan mol cua cac chat kh t le vi phan the tch cua
cac chat kh o. Do o ta co :
XC
2H 4
= 0,92kmol / kmol
X CH = 0, 05kmol / kmol
4
X C H = 0, 03kmol / kmol
3 6
MC
2H4
= 28kg / kmol
M CH = 16kg / kmol
4
M C H = 42kg / kmol
3 6
Thay cac gia tr vao cong thc tren ta co phan khoi

lng cac chat la :
- 38 -

t C2H4
28.0,92
= 0,9260
28.0,92 + 16.0, 05 + 42.0, 03
16.0, 05
aCH 4 =
= 0, 02876
28.0,92 + 16.0, 05 + 42.0, 03
42.0, 03
aC3 H 6 =
= 0, 04529
28.0,92 + 16.0, 05 + 42.0, 03
aC2 H 4 =
Vay : ta co bang so lieu sau :

C2H4 ky thuat
O2 ky thuat
(% khoi lng)
(% khoi lng)
CH3COOH ky
thuat
(% khoi lng)
CH3COOH
98
Tap chat
2
C2H 4
O2
0,9260
98
CH4
N2 va kh tr
0,02876
khac
2
C3H 6
0,04529
Mc o chuyen hoa : 95% trong o 92% C2H4
thanh VA, 7,5% tao thanh CO2 va 0,5% tao thanh etyl,
metyl acetat, acetaldehit, ton that 2%
Day chuyen hoat ong lien tuc 24/24 gi trong
ngay. Day chuyen ch ngng hoat ong khi cac thiet b
en ky kiem tra bao quan va sa cha, nh ta biet
trong mot nam co 365 ngay, ta chon day chuyen hoat
ong la 340 ngay, con 25 ngay danh cho viec kiem tra
sa cha,bao quan va thay the cac chi tiet b hong
hoc.
Nang suat cua phan xng trong 1 gi la:
50.000.000
= 6127, 451kg / h
340.24
Nang suat cua qua trnh chnh la lng san pham

tinh khiet ra khoi thap chng luyen i vao thung cha
san pham va bang 6127,451kg/h.
Do hieu suat cua he thong thap chng luyen la
96% nen lng VA i vao he thong chng luyen :
6127, 451.100
= 6382, 761kg / h
96
ay la lng vat chat i ra khoi thiet b ngng tu, do

hieu suat cua thiet ngng tu la 98% nen lng vat chat
i vao thap ngng tu la:
- 39 -

t C2H4
6382, 761.100
= 6513, 021kg / h
98
Gia s khi lng VA i vao he thong ngng tu va qua he

thong chng luyen e tr thanh lng san pham VA
cuoi cung th b mat mat la 2% nen lng VA thc te
vao thiet b ngng tu la:
6513, 021.100
= 6645,9402kg / h
98
vay lng VA i ra khoi thiet b phan ng la:

6645,9402kg/h
I. Tnh can bang vat chat cho thiet b phan ng:
1. Lng vat chat i vao thiet b phan ng:
Lng vat chat i vao thiet b phan ng bao gom :
C2H4, CH3COOH ,O2 va tap chat(CH4, C3H6, cac tap chat do
CH3COOH mang vao).
Cac phan ng xay ra :
(1) C2H4 + 0,5O2 + CH3COOH
CH2=CH
+ H 2O
H298=-180kj/mol
OCOCH3
2CO2
(2) C2H4 + 3O2

H298=-135kj/mol
(3) CH2=CH2 +
H298=-244kj/mol
(4) CH2=CH2
O2
O2
+ 2H2O
CH3CHO
+ CH3COOH
CH3-CH2
+ O2
OCOCH3
a. Tnh lng C2H4 tinh khiet can a vao cho mot lan
phan ng :
Goi x(kg/h) la lng C2H4 tinh khiet a phan ng e
tao thanh VA vi o chuyen hoa 95% va CO2
Theo phan ng (1)
(1) C2H4 + 0,5O2 + CH3COOH
CH2=CH
+ H 2O
H298=-180kj/mol
28kg/h
100%)
xkg/h
OCOCH3
86kg/h
(hieu suat
6645,94kg/h(hieu suat 95%)
- 40 -

t C2H4
V C2H4 a vao ch co 92% la chuyen hoa VA(vi o
chuyen hoa la 95%),con 7,5% CO2 va 0,5%etyl acetat,
acetandelhit
Do o, x ay chnh la 92% lng C 2H4 tinh khiet
c :
X=
28.6645,94
= 2163, 794kg / h
86
ay chnh la 92% lng C2H4 trong tong so C2H4 chuyen

hoa thanh VA va CO2, etyl acetat, acetandehit
Do o, lng C2H4 tinh khiet cho toan bo chuyen hoa
la :
2163, 794.100
= 2351,950kg / h
92
Lng C2H4 con lai 7,5% chuyen hoa thanh CO 2

2351,95.7,5% = 176,3963kg/h
Lng C2H4 con lai 0,5% chuyen hoa thanh etyl acetat,
acetanldehit
2351,95.0,5%=11,7598kg/h
Hieu suat chuyen hoa cua C2H4 can cho mot lan
phan ng :
2351,95.100
= 2475, 737 kg / h
95
Lng C2H4 con lai khong tham gia chuyen hoa tao VA
va CO2 va etyl acetat, acetaldehit :
2475,737 - 2351,95 = 123,787kg/h
b. Tnh lng CH3COOH, O2 can phan ng vi C 2H4 e
tao thanh VA, CO2, etyl acetat, acetanldehit :
(1) C2H4 + 0,5O2 + CH3COOH
CH2=CH
+ H 2O
H298=-180kj/mol
OCOCH3
C 28kg C2H4/h phan ng vi 16kg O2/ h phan ng vi
60kgCH3COOH/h
2163,794kgC2H4/h phan ng vi ykgO 2/h phan ng vi
zkgCH3COOH/h
vay :
16.2163, 794
= 1236, 4537kg / h
28
60.2163, 794
z=
= 4636, 701kg / h
28
y=
Tnh lng O2 can phan ng vi C2H4 e tao thanh

san pham phu CO2
- 41 -

t C2H4
(2) C2H4 + 3O2
2CO2
+ 2H2O
H298=-135kj/mol
c 28kgC2H4/h phan ng vi 96kgO2/h tao thanh
88kgCO2/h
Thc te 176,3963kgC2H4/h phan ng vi mkgO 2/h tao
thanh nkgCO2/h
Lng oxi can phan ng:
96.176,3963
= 604, 7873kg / h
28
m=
Lng CO2 tao thanh :

n=
88.176,3963
= 554,388kg / h
28
Tnh lng CH3COOH,O2 can phan ng vi C2H4 e tao

thanh etyl acetat va acetandelhit :
(3) CH2=CH2 +
1/2O2
CH3CHO
H298=244kj/mol
c 28kgC2H4/h phan ng vi 16kgO2/h tao thanh
44kgCH3CHO/h
11,7598kg/h
gkgO2/h tao thanh
hkgCH3CHO/h
Lng oxi can phan ng:
g=
11, 7598.16
= 6, 71989kg / h
28
Lng acetandelhit :
h=
(4) CH2=CH2
44.11, 7598
= 18, 4797 kg / h
28
O2
+ CH3COOH
CH3-CH2
+ O2
OCOCH3
C 28kgC2H4/h phan ng vi 32kgO2/h vi 60kg axt/h tao
thanh 88kg etyl acetat/h
11,7598kgC2H4/h phan ng vi k kgO2/h tao thanh l kg
axt/h tao j kg axt/h
Lng O2 can phan ng :
k=
32.11, 7598
= 13, 44kg / h
28
Lng CH3COOH can phan ng:
- 42 -

t C2H4
l=
60.11, 7598
= 25,1996kg / h
28
Lng etyl acetat tao thanh :

j=
11, 7598.88
= 36,96kg / h
28
Vay : tong lng CH3COOH, O2 can cho tao thanh Vinyl

acetat, CO2, etyl acetat, acetandelhit :
y + z + m + g + k + l = 1236,4537 + 4636,701 +
604,7873 + 6,72 + 13,44 + 25,20 = 6523,302 kg/h.
Tong lng CH3COOH can cho tao thanh VA va etyl
acetat :
z+ l
= 4636,701 + 25,2 = 4661,901 kg/h.
Tong lng O2 can cho tao thanh VA va acetanldehit
etyl acetat :
Y + m + g + k = 1236,4537 +604,7873 + 6,72 +
13,44 = 1861,4017 kg/h
Do s chuyen hoa cua CH 3COOH la 98% nen lng
CH3COOH tinh khiet thc te la:
4661,901.100
4757, 042
= 4757, 042kg / h =
= 79, 27 kmol / h
98
60
Dos chuyen hoa cua O2 la 98% nen lng O2 tinh khiet

thc te la:
1861, 4017.100
1899,3894
= 1899,3894kg / h =
= 59,3559kmol / h
98
32
Lng CH3COOH con lai khong tham gia chuyen hoa tao
VA, etyl acetat:
4757,042 4661,901 = 95,141kg/h
Lng O2 con lai khong tham gia chuyen hoa thanh VA,
CO2, acetanldehit, etyl acetat :
1899,3894 1861,4017 = 37,9877 kg/h
Lng O2 can a vao v ta co 98% O 2 tinh khiet va 2% N2
va tap chat khac nen lng axt ky thuat la:
1899,3894.100
= 1938,1524kg / h
98
Lng CH3COOH can a vao v co 98% CH 3COOH tinh khiet

va 2% tap chat, nen lng axt ky thuat la :
4757, 042.100
= 4854,12kg / h
98
c. Tnh lng C2H4 can cho toan bo qua trnh trong gi

phan ng:
- 43 -

t C2H4
Trong thc te san xuat e hieu suat cua qua trnh
c cao nhat th ty le so mol C 2H4/O2 va C2H4/CH3COOH
la 2:1
Do o, lng C2H4 theo ty le la:
2. 59,36
= 118,72 kmol/h = 118,72 . 28
=
3324,16 kg/h
2. 79,27
= 158,54 kmol/h = 158,54 . 28
=
4439,68 kg/h
Lng C2H4 can cho lan phan ng la 2163,79 kg/h. Do o,
So vong co the phan ng cua C2H4 vi O2 la :
3324,16
= 1,54 vong
2163, 79
so vong co the phan ng cua C 2H4 vi CH3COOH

la :
4439, 68
= 2, 05 vong
2163, 79
Vay : so vong co the phan ng cua toan bo lng

C2H4 la:
1,54 + 2,05 = 3,59 vong
Lng C2H4 ton that trong toan bo qua trnh la 2% tng
ng vi :
2.3324,16 2.4439, 68
+
= 155, 28kg / h
100
100
Do o, lng C2H4 b mat mat sau mot lan phan ng

la :
155, 28
= 43, 25kg / h
3,59
Lng C2H4 tinh khiet can a vao trong mot gi :

3324,16 + 4439,68 + 43,25 = 7850,343kg/h
Ta biet lng C2H4 chiem 92,6% khoi lng C2H4 ky thuat
c a vao thiet b phan ng.
Suy ra ta co:
Lng C2H4 ky thuat can a vao thiet b phan ng la:
- 44 -

t C2H4
7807, 093.100
= 8430,986kg / h
92, 6
Vay: tong lng C2H4 ky thuat can cho toan bo qua

trnh trong 1 gi la : 8430,986kg/h.
d. Tnh lng tap chat do nguyen lieu mang vao :
1. Do C2H4 mang vao:
Lng CH4 :
2,876.8430,986
= 242, 48kg / h
100
Lng C3H6 :
4,529.8430,986
= 381,84kg / h
100
2. Do O2 mang vao:
Trong lng O2 ky thuat mang vao co 2% N2 va cac kh tr
khac, nen suy ra tap chat do O2 mang vao :
mO2 =
1938,1524.2
= 38, 763kg / h
100
3. Do CH3COOH mang vao :

Trong lng CH3COOH ky thuat mang vao co 2% tap chat
nen suy ra tap chat do CH3COOH mang vao :
mCH3COOH =
4854,12.2
= 97, 08kg / h
100
Vay: tong lng tap chat do nguyen lieu mang vao :

M tapchat = mCH 4 + mC3H 6 + mtapchatO2 + mCH 3COOH
= 242, 48 + 381,84 + 38, 763 + 97, 08 = 760,163kg / h
2. Lng vat chat i ra khoi thiet b phan ng:

Theo so lieu tnh toan phan tren ta co:
Lng san pham VA i ra
: 6645,94 kg/h;
Lng san pham phu CO2 tao thanh
: 554,388
kg/h;
Lng san pham phu acetandelhit tao thanh :
18,48
kg/h;
- 45 -

t C2H4
Lng san pham phu etyl acetat tao thanh
: 36,96
kg/h;
Lng axt acetic i ra
: 95,14
kg/h;
Lng O2 i ra
: 37,99
kg/h;
Ta biet lng tap chat i ra bang lng tap chat mang
vao nen ta co :
Lng tap chat cua axt acetic ky thuat la
: 97,08
kg/h;
Lng tap chat cua O2 ky thuat la
: 38,76
kg/h;
Lng tap chat cua C2H4 ky thuat
:
242,48
+ 381,84
= 624,32
kg/h;
Bang so lieu can bang tai thiet b phan ng:
Cau t
C2H 4
O2
CH3COOH
CH4
C3H 6
Tap chat do
CH3COOH
mang vao
Tap chat do
O2 mang vao
Tong vao
Khoi lng
(kg/h)
7850,343
604,79
4757,042
242,48
381,84
97,08
38,76
13836,335
Cau t
VA
CO2
Acetandelhit
Etylacetat
C2H 4
CH4
C3H 6
Tap chat
CH3COOH
Tap chat O2
O2
CH3COOH
Tong ra
Khoi lng
(kg/h)
6645,94
554,388
18,48
36,96
5686,549
242,48
381,84
97,08
38,76
37,99
95,14
13835,607
II. Tnh can bang vat chat cho he thong ngng tu:
Tnh lng vat chat i vao thiet b ngng tu:
Ta biet lng vat chatn i vao he thong ngng tu chnh
la lng vat chat i ra khoi thiet b phan ng. Do o, ta
co lng vat chat i vao he thong ngng tu :
- 46 -

t C2H4
Bang so lieu ve lng vat chat i vao thiet b ngng tu :
Cau t
VA
CO2
Acetandehit
Etyl acetat
C2H4 tinh khiet con d
O2 tinh khiet con d
CH3COOH tinh khiet con d
CH4
C3H 6
Tap chat O2
Tap chat CH3COOH
Khoi lng(kg/h)
6645,94
554,388
18,48
36,96
123,79
37,99
95,14
242,48
381,84
38,76
97,08
Lng vat chat i ra he thong ngng tu :

Khi vao he thong ngng tu th cac cau t sau b ngng tu
o la : VA, Acetanldehit, CO 2, con lai CH3COOH tinh khiet
C2H4, CH4, C3H6, O2, Etyl acetat th khong b ngng tu.
Do hieu suat cua he thong ngng tu la 98% nen ta
co:
Lng VA ngng tu va i vao be cha :
98.6645,94
= 6513, 02kg / h
100
Suy ra, lng VA khong b ngng tu va c a ti thiet

b tach :
6645,94 - 6513,02 = 132,92 kg/h;
Lng acetanldehit c ngng tu va i vao be cha :
98.18, 48
= 18,11kg / h;
100
Suy ra, lng acetandehit khong ngng tu va c a ti

thiet b tach :
18,48 - 18,11 = 0,37 kg/h;
Lng CO2 c ngng tu va i vao be cha
- 47 -

t C2H4
98.554,388
= 534,3kg / h;
100
Suy ra, lng CO2 khong b ngng tu va a ti thiet b

tach :
544,388 - 534,3 = 11,1 kg/h;
Bang so lieu can bang vat chat cho he thong ngng tu
Lng vat chat vao
Lng vat chat ra
Cau t
Khoilng(kg
Cau t
Khoilng(kg
/h)
/h)
VA
6645,94
VA
6513,02
CO2
554,388
CO2 ngng tu
534,3
Acetanldehit
18,48
Acetanldehit
18,11
Etyl acetat
36,96
ngng tu
O2(tinh
76,7
Etyl acetat
36,96
khiet va
CH3COOH(tinh
192,2
tap chat )
192,22
khiet va tap
CH3COOH(ti
chat )
132,9
nh khiet
VA khong
va tap
5686,549
ngng tu va
chat )
242,48
c a ti
11,1
C2H 4
381,84
thiet b tach
CH4
CO2 khong
0,37
C3H 6
ngng tu
Acetanldehit
5686,549
khong ngng
76,7
tu
C2H 4
242,48
O2(tinh khiet
381,84
13835,607
va tap chat)
13835,607
CH4
Tong vao
C3H 6
Tong ra
Tai thiet b tach kh cac cau t Vinyl acetat khong
ngng tu, acetanldehit khong ngng tu, CO2khong ngng, CH4,
C3H6, O2, etyl acetat se c tach ra thu c C 2H4 tinh
khiet , se c tach ra tren nh thap. Mot phan c
nen lai qua may nen, sau o a vao thap hap thu kh
CO2. Ra khoi thap c C2H4 tinh khiet va lng C2H4 nay
tuan hoan tr lai tron vi thap chng s bo.
III. Tnh can bang vat chat cho thap chng s bo:
1. Tnh can bang vat chat vao thap chng:
- 48 -

t C2H4
Bang can bang vat chat i vao thap chng s bo:
Cau t
Khoi lng(kg/h)
Vinyl acetat
6513,02
CO2
554,388
CH3COOH(tinh khiet va tap
192,22
chat)
76,7
O2(tinh khiet va tap chat)
2. Lng vat chat ra khoi thap :
Thap chng cat dung e tach CH3COOH(tinh khiet va tap
chat),ta se thu c CH3COOH (tinh khiet va tap chat)
ay thap, con hon hp VA va H2O ra khoi nh thap
c lam lanh a vao thiet b lang tach long/kh. Nhng
do hieu suat cua thap chng la 97% nen lng
CH3COOH(tinh khiet va tap chat) c tach ra :
192, 22.97
= 186, 45kg / h
100
Lng CH3COOH(tinh khiet va tap chat) se c tuan

hoan tr lai thiet b tron vi CH3COOH ban au.
Suy ra, lng CH3COOH(tinh khiet va tap chat) con lai trong
hon hp va i sang thiet b tach:
192,22 - 186,45 = 5,8 kg/h;
Bang can bang vat chat thap chng cat :
Lng vat chat vao
Lng vat chat ra
cau t
VA
CO2
CH3COOH(ti
nh
khiet
va
tap
chat)
O2(tinh
khiet
va
tap chat)
Khoi
lng(kg/h)
6513,02
554,388
192,22
76,7
7336,328
Tong vao
Cau t
Khoi
lng(kg/h)
VA
6513,02
CO2
554,388
CH3COOH(tinh
186,45
khiet
va
tap
chat
c
tach
5,8
ra)
CH3COOH
(tinh khiet i
76.7
sang thiet b
tach)
7336,328
O2(tinh khiet
va
tap
chat)
Tong ra
- 49 -

t C2H4
B. Can bang nhiet lng
Tnh can bang nhiet lng tai thiet b phan ng,
vi cac thong so sau:
Hon hp nguyen lieu au sau khi qua thiet b truyen
nhiet so(4), c gia nhiet bi nhiet cua hon hp kh
san pham len en 1600c. Do o, nhiet cua hon hp
au i vao thiet b phan ng chnh (2) la 160 0c.
Nhiet do cua hon hp san pham i ra khoi thiet b
phan ng chnh (2) la 1800c
Hon hp nguyen lieu au vao gom cac cau t:
C2H4 tinh khiet, CH4, C3H6, O2 tinh khiet va tap chat va
axt acetic tinh khiet va tap chat.
Hon hp san pham au ra gom co cac cau t sau
:
San pham chnh VA, san pham phu CO2, acetanldehit, etyl
acetat, C2H4 tinh khiet con d, CH3COOH tinh khiet con d
va tap chat, O2 tinh khiet con d va tap chat N2 va cac
kh tr khac, tap chat CH4 , C3H6.
Do cac phan ng xay ra trong thiet b phan ng
eu toa nhiet tng oi ln, nen ta can khong che
c nhiet o trong o e phan ng tao thanh san
pham chnh at hieu qua cao nhat. V vay, ta chon tac
nhan khong che nhiet o la dau tai nhiet, vi cac
thong so sau:
Nhiet o au vao cua dau la : 1100c
Nhiet o au ra cua dau la
: 1600c
Nhiet dung rieng cua dau la [I-192]
Tai au vao 1100c la Cp = 0,53 kcal/kg.o;
Tai au ra 1600c la Cp = 0,58 kcal/kg.o;
Khoi lng rieng cua dau la = 900kg/m3;
1. Tnh lng nhiet dung cua cac cau t:
a. Tnh nhiet dung cua cac cau t i vao thiet b phan
ng:
S dung toan o [I-197]
Nhiet dung rieng cua C2H4 1600c Cp = 0,52
kcal/kg.o;
Nhiet dung rieng cua CH4 1600c Cp = 0,593
kcal/kg.o;
Nhiet dung rieng cua O2 1600c
Cp = 0,24
kcal/kg.ol;
- 50 -

t C2H4
oi vi CH3COOH va tap chat cua no, do lng
tap chat chiem lng khong ang ke va co tnh chat
hoa ly gan giong vi CH3COOH. Do o, khi tnh toan ta
coi nh tnh toan chung cho CH3COOH dung cong thc thc
nghiem sau :
CP = a0 + a1T + a2T2
[I-153]
Vi : a0, a1, a2 : cac he so cua phng trnh c tra
theo bang
T
: nhiet o(K);
Chat
He so cua phng
khoang nhiet o
trnh
T(K)
3
6
CH3COOH
a0
a1.10
a2.10
300700
5,2
46,16
-18,35
Thay cac he so vao phng trnh ta co nhiet dung
rieng cua CH3COOH 1600c(T = 433K);
C pCH COOH = 5, 2 +
3
46,16.433 18,35
+
.4332 = 21, 75kcal / mol 0 = 0,3625kcal / kg 0
3
6
10
10
oi vi C3H6, do ay la mot hp chat hoa hoc

nen viec kiem tra trc tiep gia tr nhiet dung rieng la
kho khan. Bi vay, ta co the tnh theo cong thc thc
nghiem sau :
M.C = n1C1 + n2.C2 + n3C3 +
[I-152];
Trong o:
M
: khoi lng mol cua hp chat ,
(kg/kmol);
C
: nhiet dung rieng cua hp chat hoa
hoc(J/kg.o);
n1, n2, n3 : so nguyen t cua cac nguyen to trong
hp chat ;
C1,C2,C3
: la nhiet dung rieng nguyen t cua cac
nguyen to tng ng trong hp chat
(J/kg nguyen
t.o);
Bang nhiet dung nguyen t cua cac nguyen to
[I-152]
Nguyen to
C
H
O
Nhiet dung
11700
18000
25100
nguyen
t(J/kg
nguyen
t.o)
T o ta co:
- 51 -

t C2H4
M C3H 6 .C pC H = nC .cC + nH .cH
3 6
vi
M C3H 6 = 42kg / kmol ;
nC
cC
nH
cH
Suy ra :
=3
= 11700
=6
= 18000
C pC H =
3 6
;
;
;
;
3.11700 + 6.1800
3407,143
= 3407,143( J / kg 0 ) =
= 0,814kcal / kg 0 ;
42
4,1868.103
b. Tnh nhiet dung rieng cua cac cau t i ra thiet b

phan ng 1800c:
Nhiet dung rieng cua VA trang thai tai ap suat
kh quyen (P=1atm), va nhiet o 1800c la CP = 0,352
kcal/kg.o;
Nhiet dung rieng cua kh CO2 la
CP = 0,24
kcal/kg.o;
oi vi acetanldehit(CH3CHO): nhiet dung rieng cua
CH3CHO c tnh theo cong thc thc nghiem :[I-152];
Suy ra :
CPCH CHO =
3
2.11700 + 4.25100
= 2738, 64 J / kg 0 = 0, 654kcal / kg 0 ;
44
oi vi etyl acetat(CH3CH2OCOCH3): nhiet dung rieng

cua etyl acetat c tnh theo cong thc thc nghiem : [I152];
Tng t suy ra :
CPetylacetat =
4.11700 + 8.18000 + 2.25100

= 2738, 64 J / kg 0 = 0, 654kcal / kg 0 ;
88
S dung toan o tra bang [I- 197] ta co:

0
Nhiet dung rieng cua C2H4 1800c : CP = 0,54kcal / kg ;
C2 H 4
Nhiet dung rieng cua CH4 180 c CP

0
CH 4
= 0, 60kcal / kg 0 ;
0
Nhiet dung rieng cua O2 1800c: CP = 0, 24kcal / kg ;
O2
Nhiet dung rieng cua C3H6 180 c CP = 0,814kcal / kg ;

oi vi CH3COOH va tap chat cua no, tng t nh
phan tch tren, ta dung cong thc thc nghiem va bang
so lieu [I-153];
Thay cac he so vao phng trnh, ta co nhiet dung rieng
cua axt acetic 1800c (T=453K);
0
C3H 6
- 52 -

t C2H4
CPCH COOH = 5, 2 +
3
46,16.453 18,35
+
.4532 = 22,34kcal / kmol 0 = 0,372kcal / kg 0 ;
3
6
10
10
Bang nhiet dung rieng cua cac cau t cac nhiet o

khac nhau
au vao tai nhiet o
au ra tai nhiet o 1800c
0
160 c
Cau t
Nhiet dung
Cau t
Nhiet dung
rieng
rieng
CP(kcal/kg.o
CP(kcal/kg.o
)
)
C2H4tinh
0,52
C2H4tinh
0,54
khiet
0,363
khiet
0,372
CH3COOH
CH3COOH
ky
ky
thuat(ca
thuat(ca
lng tinh
0,24
lng tinh
0,24
khiet va
khiet va
0,593
tap chat)
tap chat)
0,814
O2ky
0,593
O2 ky
0,24
thuat(tinh
0,814
thuat
0,654
khiet va
CH4
0,654
tap chat)
C3H 6
0,352
CH4
CO2
C3H 6
acetanldehit
etyl acetat
VA
- 53 -

t C2H4
3. Tnh nhiet lng au vao cua thiet b phan ng:
Nhiet lng au vao cua thiet b phan ng la
tong nhiet lng cua hon hp nguyen lieu au mang
vao, nhiet lng do cac phan ng xay ra trong thiet b
phan ng tao ra va nhiet lng do dau tai nhiet mang
vao :
Qvao
= Qhon hp kh + Qcac phan ng
+ QDau tai nhiet
a. Nhiet lng do hon hp kh mang vao :
Qh khi = QC H + QCH COOH + QO + QCH + QC H kcal / h ;
Nhiet lng tng cau t c tnh theo cong thc
sau:
Q i = G i C i ti
(kcal/h)
[I];
Trong o:
Gi : khoi lng cua cau t th i
(kg/h);
CPi : nhiet dung rieng cua cau t th i(kcal/kg.o)
Ti : nhiet o cua cau t th i
(k);
Ap dung cong thc tren cho tng cau t ta co:
2
QC2 H 4 = 7850,343.0,52.160 = 653148,52kcal / h ;
QCH 4 = 242, 48.0,59.160 = 22890,112kcal / h;

QC3 H 6 = 381,84.0,814.160 = 49730,841kcal / h;
oi vi CH3COOH va O2 nh a gia thiet phan tren

va viec tnh toan cho tap chat cua axt acetic, O 2 coi nh
la tnh toan chung cho CH3COOH, O2 nen ta at:
QCH 3COOH = 4757, 042.0,3625.160 = 275908, 43kcal / h;
QO2 = 604, 79.0, 24.160 = 23223,936kcal / h;
Do o:
Qhon hp kh = 653148,52 + 22890,112 + 49730,84 + 275908,43
+ 23223,936
= 1024901,8 kcal/h;
Vay:
QHon hp kh = 1024901,8 kcal/h;
b. Nhiet lng do cac phan ng tao ra trong thiet b phan
ng:
Nhiet lng do phan ng chnh tao ra :
(1) C2H4 + 0,5O2 + CH3COOH
CH2=CH + H2O H298=42,96kcal/mol
OCOCH3
ay la phan ng toa nhiet vi H298=-42,96kcal/mol, theo
phan ng th khi tao thanh 1 mol VA(hay 86gVA ) th lng
nhiet toa ra la 42,96 kcal/mol.
- 54 -

t C2H4
Do o, khi tao thanh 6645,94 kg/h, tng ng vi
6645,94.1000 = 6645940(gVA/g) th lng nhiet toa ra la :
Vay:
6645940.42,96
= 3319878,8kcal / h;
86
lng nhiet do phan ng chnh toa ra la:

Qphan ng chnh = 3319878,8kcal/h;
c.Nhiet lng do phan ng phu tao ra la:
Cac phan ng phu tao thanh mot lng qua nho
metyl acetat, glycol mono diacetat, etyl acetat do o, nhiet
lng do phan ng phu nay toa ra cung rat be co the
bo qua. Do o, nhiet lng duy nhat do phan ng phu
tao ra ay co the coi la phan ng phu tao thanh CO 2,
CH3CHO theo phan ng sau:
(2) C2H4 + 3O2
2CO2
+ 2H2O
H298=32,22kcal/mol
ay la phan ng thu nhiet vi H298=32,22kcal/mol, theo
phan ng th khi tao thanh 2mol CO2(88gCO2) th thu vao
mot lng la 32,22kcal/mol. Do o,khi tao thanh
554,388kg/h, tng ng vi 554,388.1000 = 554388gCO 2/h th
thu vao mot lng nhiet la:
554388.32, 22
= 202981, 6kcal / h;
88
Vay: lng nhiet do phan phu thu vao la:

QPhan ng phu = -202981,6kcal/h;
(3) CH2=CH2 +
O2
CH3CHO
H298=58,23kj/mol
ay la phan ng thu nhiet vi H298=58,23kj/mol, theo
phna ng th khi tao thanh 1mol CH3CHO(44gCH3CHO) th thu
vao 1 lng la 18,48 kg/h,tng ng vi 18480gCH 3CHO/h
th thu c mot lng nhiet :
18480.58, 23
= 24456, 6kcal / h;
44
Vay : lng nhiet do phan ng phu thu vao la:

QPhan ng phu acetanldehit = - 24456,6kcal/h;
Ta co nhiet lng do cac phan ng tao ra trong thiet b
phan ng la:
QCac phan ng = QPhan ng chnh + QPhan ng phu
= 3319878,8 - 202981,6 - 24456,6
= 3092440,6kcal/h;
- 55 -

t C2H4
d. Nhiet lng do dau tai nhiet mang vao thiet b phan
ng la:
Dau tai nhiet dung e khong che nhiet o trong
thiet b phan ng, trc khi vao thiet b phan ng
c nang len nhiet o 110 0c nen lng nhiet do dau
mang vao la:
QDau mang vao
= mDau. CP dau vao . tdau vao (kcal/h);
= mDau 0,53 . 110
(kcal/h);
= 58,3 . mDau
(kcal/h);
Vay: tong nhiet lng au vao cua thiet b phan
ng:
QVao
= Q Hon hp kh + QCac phan ng + QDau vao
(kcal/h);
= 1024901,8 + 3092440,6 + Q Dau mang vao
= 4117342,4 + Q Dau mang vao
(kcal/h);
(kcal/h);
4. Tnh nhiet lng au ra cua thiet b phan ng
Nhiet lng au ra cua thiet b phan ng la
tong nhiet lng cua hon hp kh san pham mang ra,
nhiet lng do mat mat ra moi trng xung quanh va
nhiet lng do dau khong che nhiet o mang ra:
QRa
= QHon hp kh san pham + QMat mat + QDau
ra
a. Nhiet lng do hon hp kh san pham mang ra:
Qhonhopkhisanpham = QVA + QCO2 + QC2 H 4 + QCH3CHO + QCH 3COOH + QO2 + QCH 4 + QC3 H 6 (kcal / h);
Tng t nh tren ta ap dung cong thc [I] e tnh

nhiet lng cua tng cau t:
QVA = 6645,94.0,352.180 = 421086, 74kcal / h;
QCO2 = 554,388.0, 24.180 = 23949,561kcal / h;
QC2 H 4 = 5686,549.0,54.180 = 552732.55kcal / h;
QCH 3CHO = 18, 48.0, 654.180 = 2175, 466kcal / h;
QCH 3COOH = 192, 22.0,372.180 = 12871, 051kcal / h;
QO2 = 76, 7.0, 24.180 = 3313, 44kcal / h;
QCH 4 = 242, 48.0, 6.180 = 26187,84kcal / h;
QC3 H6 = 381,84.0,814.180 = 55947,196kcal / h;
Do o, ta co:
- 56 -

t C2H4
QHon hp kh san pham = 421086,74 + 23949,56 + 552732,55 +
2175,466 + 12871,051 + 3313,44 + 26187,84 + 55947,196 =
1098263,6 kcal/h;
Vay: QHon hp kh san pham = 1098263,6 kcal/h;
b. Nhiet lng do mat mat ra moi trng xung quanh:
Nhiet lng do mat mat trong thiet b phan ng ra
moi trng xung quanh do toa nhiet hoac do truyen nhiet
thng co gia tr bang 5% tong nhiet lng cua au
vao thiet b phan ng. Do o ta co:
QMat mat = 5%(4117342,4 + QDau mang vao)(kcal/h);
= 0,05.4117342,4 + 0,05. Q Dau mang vao(kcal/h);
= 205867,12 + 0,05.Q Dau mang vao (kcal/h);
c. Nhiet lng do dau tai nhiet mang ra:
Dau tai nhiet i ra khoi thiet b phan ng co nhiet o
la 1600c do o nhiet lng do dau tai nhiet mang ra la:
QDau mang ra = mDau. CP Dau ra . tDau ra (kcal/h);
= mDau.0,58 . 160
(kcal/h);
= 92,8. mDau
(kcal/h);
Vay: tong nhiet lng au ra cua thiet b phan ng
la:
QRa = QHon hp kh san pham + QMat mat + QDau mang ra
= 1098263,6 + 205867,12 + 0,05.Q Dau mang vao + QDau
mang ra (kcal/h);
= 1304130,7 + 0,05. Q Dau mang vao + QDau mang ra
(kcal/h);
Tnh lng dau tai nhiet can a vao e khong che
nhiet o trong thiet b phan ng la:
T phng trnh can bang nhiet lng :
QVao = Qra
Ta co:
4117342,4 + QDau mang vao = 1304130,7 + 0,05. QDau mang
vao + QDau mang ra
2813211,7 =QDau mang ra 0,95QDau mang vao
2813211,7 = 92,8.mDau - 0,95.58,3.mDau
- 57 -

t C2H4
2813211,7 = 37,415.mDau
Suy ra :
mDau
= 75189,407kg/h;
Vay lng dau lu chuyen ben ngoai cac ong trong
thiet b phan ng e khong che nhiet o thiet b
phan ng la mDau = 75189,407 kg/h;
T o ta tnh c:
-Nhiet lng do dau tai nhiet mang vao la:
QDau mang vao = 58,3 . 75189,407 = 4383542,4(kcal/h);
- Nhiet lng do dau tai nhiet mang ra la:
QDau mang ra = 92,8. 75189,407 = 6977576,9(kcal/h);
-Nhiet lng b mat mat ra moi trng xung quanh :
QMat mat
= 205867,12 + 0,05.4383542,4 = 425044,24
(kcal/h);
- 58 -

t C2H4
Bang can bang nhiet lng cua thiet b phan ng
Nhiet lng au vao
Nhiet lng au ra (kcal/h)
(kcal/h)
QHon hp kh(C2H4,
1024901 QHon hp kh san
1098263,6
O2,CH3COOH(tinh
,8
pham(VA, CO2,
khiet va tap
CH3CHO, C2H4d,
chat),CH4, C3H6)
CH3COOH, O2(tinh
khiet va tap
chat), CH4, C3H6)
QCac phan ng(phan 3092440 QMat mat
425044,24
ng chnh va
,6
phan ng phu)
QDau mang vao
4383542 QDau mang ra
6977576,9
,4
tong nhiet
8500884 tong nhiet
8500884,7
lng au vao
,8
lng au ra
QVao
QRa
- 59 -

t C2H4
Phan IV
Ket luan
Sau hn bon tuan c giao nhiem vu thiet ke mot
phan xng san xuat Vinyl acetat vi nang suat 50.000
tan/nam, en nay em a hoan thanh ung thi gian quy
nh. Noi dung cong viec bao gom :
-Trnh bay tong quan ly thuyet ve VA va a ra cac
phng phap tong hp VA t acetylen, etylen va axt acetic
trong cac pha.
-Tnh toan can bang vat chat, can bang nhiet
lng trong thiet b phan ng
-Hai ban ve day chuyen san xuat kho A4.
-Mot ban ve day chuyen san xuat VA t etylen va
axt acetic kho A0.
-Ban o an nay a giup em van dung nhng kien
thc chuyen nganh a c hoc va hoan thien hn ve
kha nang tnh toan. ay chnh la nhng kien thc het
sc quy bau giup em trong qua trnh hoc tap va cong
tac sau nay.
Ha
ngay.thang.nam 2004
noi,
Sinh vien thc hien
Nguyen Thai Hue
- 60 -

t C2H4
Tai lieu tham khao

1. Tap the tac gia ai Hoc Bach Khoa Ha Noi - So
tay qua trnh va thiet b cong nghe hoa chat Tap
1,2 Nha xuat ban khoa hoc va ky thuat, Ha Noi
1992, 2000
2. Phan Minh Tan Tong hp hu c hoa dau Tap 1.
3. Trng ai Hoc Bach Khoa Ha Noi Tong hp hu
c c ban Tap 2- 1986
4. Vng nh Nhan So tay tom tat ky s hoa chat
1961.
5. Nguyen Minh Chau ai Hoc Qui Nhn - Hoa hoc hu
c 1986.
6. Ullmans Encyclopedia of industrial chemistry Vol A1
1996
9. Petrochemical processes
- Tap 2
1989.
- 61 -

San Xuat VA Tu C2H4

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San Xuat VA Tu C2H4

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Thiet ke phan xng san xuat VA

IIGii thieu ve nguyen lieu axt acetic

1 Tnh chat vat ly.

III Gii thieu ve san pham vinyl acetat

1 Tnh chat vat ly..

B Cac cong nghe tong hp vinyl acetat

1 Tien hanh trong pha long..

IIQua trnh tong hp VA t C2H2 va

1 Tien hanh trong pha long..

Thiet ke phan xng san xuat VA

IV anh gia u nhc iem cua cac qua trnh

A. Tnh can bang vat chat

Phan IV: ket luan.

Tai lieu tham khao.... . .49

Thiet ke phan xng san xuat VA

Thiet ke phan xng san xuat VA

Thiet ke phan xng san xuat VA

Tong quan ly thuyet

2Tnh chat hoa hoc:

Thiet ke phan xng san xuat VA

b.Tao hon hp andehit , xeton :

the hi cho ancol 3000c 3500c ta dung xuc tac Al2O3

Thiet ke phan xng san xuat VA

Ty trong cua CH3COOH phu thuoc vao nong o cua

Thiet ke phan xng san xuat VA

Ty trong cua CH3COOH 200c

Ty trong cua axt acetic at cc ai la 1,0696 khi nong

2. Tnh chat hoa hoc :

Thiet ke phan xng san xuat VA

f. Tao thanh anhyric acetic :

Thiet ke phan xng san xuat VA

3. Phng phap ieu che axt acetic:

Thiet ke phan xng san xuat VA

Thiet ke phan xng san xuat VA

Phan ng co the c xem la qua trnh chuyen

Thiet ke phan xng san xuat VA

Axt paraxetic phan ng vi axetanldehyt tao thanh

Thiet ke phan xng san xuat VA

Ch so khuc xa n020 = 1,3956

trong nc chiem 2,3% trong lng 20 0c.

Hon hp ang ph vi nc soi 66 0c/100Kpa, nc

: 66,0 0c, chiem

92,7% khoi lng VA

: 70,80c, chiem 77,6%khoi

Xyclohexan(C6H12) nhiet o ang ph 67,40c,

Heptan (C7H16) nhiet o ang ph 72,00c, chiem

2. Tnh chat hoa hoc cua vinyl acetat :

Thiet ke phan xng san xuat VA

Br- CH2- CH-Br

Cong vi halogen(HX : HBr, HCl):

Cong hp vi andehit nit, cloua nitronyl:

Thiet ke phan xng san xuat VA

ong trung hp gia VA va VC ta c mot loai

Thiet ke phan xng san xuat VA

Khi thuy phan PVA vi s co mat cua xuc tac H +

Thiet ke phan xng san xuat VA

a.ng dung cua VA:

mot trong nhng monomer rat quan trong, khi trung hp

Thiet ke phan xng san xuat VA

Poly vinyl acetat

Poly vinyl alcol

Poly vinyl butyral

b. Tnh hnh san xuat VA: