CHNG 1.

C S L THUYT
1.1. Gii thiu vDimethyl terephthalate
Dimethylterephthalate (DMT) l mt este ca axit terephthalicv methanol. DMT l
mt thnh phn chnh c s dng trong sn xut polyester v nha cng nghip.
1.1.1. Tnh cht l ho ca Dimethyl terephthalate( DMT)
- Cng thc cu to:

- Cng thc phn t: C
6
H
4
(CO
2
CH
3
)
2
.
- Tn theo h thng l: dimethyl 1,4-benzenedicarboxylate ( hoc terephthalic axit
ester dimethyl ).
a. Tnh cht vt l
Bng 1: Thng s c trng ca Dimethyl terephthalate[1]
Khi lng phn t M = 194,18 g/mol
ha tan 1.2 g/cm
3

Nhit nng chy t
nc
= 142 ( 288 )
Nhit si t
s
= 288 ( 550 )
axit pK
a
= - 7,21
kim pK
b
= - 6,60
Mt hi ( so vi khng kh) 1,04
p sut hi 1.15 mmHg (93)
Ngoi cc thng s vt l nu ra bng 1 trn th Dimethyl terephthalate cn c mt
vi tnh cht c trng nh sau:
- DMT l mt hp cht hu c mu trng, khng mi, tn ti dng cht rn kt
tinh dng tinh khit bt thng nhit phng.
- DMTc tnh n nh cao nhng r chy n.
- DMT nng chy s gy bng nng cho da khi tip xc.
- tan ca DMT trong cc dung mi thng thng ( nc, ether..) nhng d tan
trong ethanol nng.
b. Tnh cht ha hc
Dimethyl terephthalate l mt cht hu c c y tnh cht ca mt este c gc
hydrocacbon v gc axit nn c kh nng tham gia tt c cc phn ng in hnh ca mt
este nh:
- DMT xy ra phn ng vi axit gii phng nhit cng vi ru v axit. Axit oxy
ha mnh c th gy ra mt phn ng mnh m l ta nhit t chy cc sn
phm phn ng. Nhit cng c to ra bi s tng tc ca este vi cc gii php kim.
- Tham gia phn ng x phng ha
- Trn este DMT vi cc kim loi kim v hirua to ra hydro d chy.
- DMT l cht ha hc nhy cm vi nhit, d tan chy khi phn ng vi nc do
nhit .
- DMT khng tng thch vi cht oxi ha mnh, axit mnh v baz mnh.
Di y l mt s phn ng in hnh ca DMT vi cc cht:
- Phn ng ca DMT vi Ethylene Glycol to Bis-(2-hydroxyethyl)terephthalate
150-200:
O
C O CH
3
Dimethyl terephthalate
O
C O CH
3
+ CH
2
HO CH
2
OH
Ethylene glycol
C O
C O CH
3
O
O
CH
2
CH
2
OH
CH
2
HO CH
2
+ OH 2 CH
3
Bis-(2-hydroxyethyl) terephthalate
Methanol

- Phn ng ca DMT vi EG to ra hn hp hai sn phm ng dng trong ngnh
cng nghip dt may, tng hp t si tiu dng v cng nghip:
CH
2
HO CH
2
OH O C OCH
3
+ OC O
DMT
EG
-CH
3
OH
H
3
C
O C OCH
3
OC O CH
2
HO CH
2
HET
O C O OC O CH
2
HO CH
2
CH
2
CH
2
OH
BHET

- Phn ng vi hn hp (butanol v 2-metyl-1-propanol) vi xc tc hi lu th
c hn hp cc sn phm v methanol:

- Phn ng vi 1,4-butanediol(BDO) to thnh Bishydroylbutyl Terephthalate
(BDO este) v methanol
O
O H
3
C
O
O CH
3
HO
+
(CH
2
)
4
OH
O
O
O
O
(CH
2
)
4
OH
OH(CH
2
)
4
Dimethyl terephthalate
Methanol
1,4-butanediol(BDO)
CH
3
OH
Bishydroxylbutyl terephthalate
(BDO este)
+

- Phn ng ca DMT vi 1,3-propanediol to thnh Polytrimethylene Terephthalate
(PTT):
C
6
H
4
(COOCH
3
)
2
+ HO(CH
2
)
3
OH [O
2
CC
6
H
4
CO
2
(CH
2
)
3
)]
n
+ 2 CH
3
OH
- Phn ng ca DMT vi 2-Ethyl hexanol to thnh Dioctyl Terephthalate (DOTP)
cho ng dng ha do PVC:
C
6
H
4
(CO)
2
(OCH
3
)
2
+ 2 C
8
H
17
OH C
6
H
4
(CO
2
C
8
H
17
)
2
+ CH
3
OH
1.1.2. ng dng ca hp cht
- DMT c s dng trong sn xut polyester, bao gm Polyethylene Terephthalate
(PET) v Polytrimethylene Terephthalate (PTT) vi vai tr l benzene thay th vi cc
nhm carboxymethyl (CO
2
CH
3
) ti cc v tr 1 v 4 vDimethyl Terephthalate d bay hi
v l cht trung gian trong mt s chu trnh hi lu ca PET, v d nh t chai nha.
- Hydro ha DMT thnh cc diol cyclohexanedimethanol l mt monomer hu ch.
- DMTl mt nguyn liu c s dng trong sn xut phi orthophthalate do s
dng ru khc nhau.Ngoi ra, DMT c s dng trong vic sn xut cc Polybutylene
Terephthalate, mt nha nhit do k thut Polymer.
- Cc dn xut ca DMT cng tm thy s dng rng ri trong men dy polyester v
cch in vecni, polyester khng bo ha v lp ph polyester, cht kt dnh nng chy
nha alky khng, ph gia cho m bi trn c bit v nguyn liu ngnh dt nhum.
1.2. C s l thuyt ca qu trnh sn xut Dimethyl Terephthalate (DMT)
1.2.1. Cc phng php sn xut Dimethyl Terephthalate
a. Sn xut Dimethyl Terephthalatet nguyn liu p-xylen
Khi qut qu trnh tng hp DMT t ngun nguyn liu p-xylen theo phng trnh
phn ng sau:
[O
2
]
CH
3
CH
3
CH
3
OH/Co
O
2
CH
3
OH
C
C
TA
OH O
OH
O
C
C
OCH
3
O
OCH
3
O
DMT

Cc qu trnh phn ng din ra trong qu trnh tng hp ny c m t bi
Katzschmann thng qua cc giai on sau :
- Qu trnh oxy ha khng kh ca p-xylen to thnh axit p-toluic:
C
6
H
4
-(CH
3
)
2
+

CH
3
-C
6
H
4
-COOH + H
2
O ;

= - 690 kJ/mol
- Este ha ca axit p-toluic bi methanol to thnh p-methyl toluate:
CH
3
-C
6
H
4
-COOH + CH
3
OH CH
3
-C
6
H
4
-COCH
3
+ H
2
O ;

= - 30 kJ/mol
- Qu trnh oxy ha ca cc nhm methyl cn li sinh ra axit methyl terephthalate:
CH
3
-C
6
H
4
-COCH
3
+

HOOC-C
6
H
4
-COO-CH
3
+ H
2
O;

= - 675kJ/mol
- Este ha axit methyl terephthalate n dimethyl terephthalate:
HOOC-C
6
H
4
-COO-CH
3
+ CH
3
OH H
3
C-OOC-C
6
H
4
-COO-CH
3
+ H
2
O;

= - 675kJ/mol
Theo phng php sn xut ny th hiu sut thu c Dimethyl Terephthalate
(DMT) thp v c s mt mt nguyn liu tng giai on phn ng, ng thi qu trnh
ny tiu hao nhit nhiu cho qu trnh cc oxi ha v ester ha. Xc tc cho qu trnh sn
xut ny l Co/Mn kim loi nn kh nng ti sinh xc tc km v cn nhiu thit b ph
tr cho qu trnh. Vic thu hi sn phm cng din ra phc tp v cn nhiu cng on
nn nh hng n yu t kinh t cao.
b. Sn xut Dimethyl Terephthalatet phn ng ester ha ca axit terephthalic v
methanol
Dimethyl Terephthalate (DMT) c sn xut t qu trnh ester ha ca axit
terephthalic v methanol di xc tc l dung dch H
2
SO
4
theo phng trnh tng hp
sau:
COOH
COOH
2 CH
3
OH
H
2
SO
4
COOCH
3
COOCH
3
2 H
2
O

Phng php sn xut ny s dng ngun nguyn liu trc tip sn c trn th trng,
qu trnh sn xut din ra n gin t thit b phn ng nn d kim sot hot ng ca
cc thit b. Cng vi hiu sut thu Dimethyl Terephthalate (DMT) t gi tr cao v
c th tn dng ngun methanol hi lu cho phn ng tng hp DMT.
1.3. Ngun nguyn liu cho qu trnh tng hp Dimethyl Terephthalate theo
phng php este ha
T vic so snh cc phng php sn xut DMT trn, nhm chng ti la chn
phng php mt giai on l qu trnh sn xut DMT trc tip t axit terephthalic v
methanol di xc tc l dung dch H
2
SO
4
.
1.3.1. Axit terephthalic
Axit terephthalic l cht mu trng c mi hi chua, thng thng dng tinh th
hoc bt, c th gy kch ng mt, da v ng h hp. Nhit nng chy ca axit
terephthalic cao l v n c kh nng to lin kt hydro gia 2 phn t, mt phn na l
do axit terephthalic (para-phthalic axit) c cu trc i xng nn mng li tinh th c
cu trc chc ch hn. Axit terephthalic km tan trong nc v ru, ha tan trong
nc l 0.0017g/100ml nc ( 25oC).
Axit terephthalic l mt axit a chc, tnh axit yu ( so vi cc axit v c mnh nh
H
2
SO
4
, HCl, HNO
3
) nhng c tnh axit mnh hn cc hp cht hu c c cha nhm
OH.
c ngun axit terephthalic cho qu trnh ny th ngi ta i t qu trnh oxy ha
nitric ca p-xylen iu kin 165 v 1.10
6
Pa theo phng trnh:
C
6
H
4
-(CH
3
)
2
+ HNO
3
C
6
H
4
-(COOH)
2
+ 4HNO
2
+ 4NO;

= 750 kJ/mol
1.3.2. Methanol
- Methanol l mt hp cht hu c trng thi lng, khng mu, c mi ancol nh
c trng, d bay hi, d chy nhit thng.
- nhit phng, n l mt cht lng phn cc, v c s dng nh mt cht
chng ng, dung mi, nhin liu, v nh l mt cht lm bin tnh cho ethanol.
Ngun methanol trong cng nghip c sn xut ch yu bi qu trnh tng hp
hydrocacbon .
1.3.3. Axit sunfuric
Axit sunfuric l mt axit v c mnh, mu trng tn tai dng lng vi nhiu dng
nng khc nhau, c kh nng ha tan v hn trong nc v ta nhiu nhit vi bt k
t l no. Axit sunfuric c ng dng rng ri trong ngnh cng nghip ha cht. Ngoi
ra axit sunfuric cn ng vai tr l cht xc tc cho cc phn ngeste ha vi vai tr kh
nc tng hiu sut ca qu trnh v trnh gy cc phn ng ph khng mong mun
xy ra.
1.4. C s ca phn ng este ha to DMT
1.4.1. C ch ca phn ng to thnh DMT
Xt phng trnh phn ng to thnh DMT t ngun nguyn liu l axit terephthalic
v methanol:
COOH
COOH
2 CH
3
OH
H
2
SO
4
COOCH
3
COOCH
3
2 H
2
O

Phn ng thuc phn ng thay th - phn ngeste ha di xc tc axit, xy ra theo
c ch phn ng nh sau: u tin H
+
tn cng vo nhm cacbonyl, din ra qu trnh
proton ha to thnh cation trung gian. Sau oxi ca methanol tn cng vo cation, km
theo s proton ha v tch nc. C ch phn ng ny din ra nh cc c ch ca phn
ng este ha hp cht hu c khc.
H
+
ca xc tc H2SO4 tn cng vo gc cacbony ca axit terephthalate din ra qu
trnh proton ha to thnh cation trung gian, sau nhm hydroxyl v chc CH
3
ca ru
methanol tn cng vo cation OH
+
mi hnh thnh v C ca nhm cacbonyl ca axit
terephthalate. Sau chuyn v H
+
(proton ha) tch nc v to thnh Dimethyl
Terephthalate theo c ch sau:
C
OH
O
OH
O
C
+
2 H
+
C
OH
+
HO
OH
OH
+
C
HOR
'
..
C
OH
O
OH
C
HO
R'
H
+
O
OH
R'
H
+
C
OH
R'O
OH
C
H
2
O
+
OR'
OH
2
+
R'O
OR'
OR'
H
2
O
C
OH
OH
C
+
+
+
C
O
R'O
O
C
+H
3
O
2
+

Phn ng este ha xy ra mt lot o ngc phn ng phn ng cn bng l phn
ng kim sot este ha v phn ng kim sot qu trnh thy phn ca este.
Ru s dng nhn nc este ha hnh thnh nhm hydroxyl c ngun gc t cc
axit cacboxylic v ru hydro. Nhng este ha ca axit cacboxylic vi ru l mt ru
alkoxy. Phn ng este ha, ru nh mt tc nhn nucleophin tn cng vo nhm
cacbonyl di dng i in t, i nhn carboxyl ng vai tr hin din ca mt axit
Protonic.
1.4.2. Cc yu t nh hng n phn ng este ha to DMT
- Phn ng to DMT l thun nghch ta nhiu nhit vi

= - 675kJ/mol. Khi
nhit tng th hiu sut phn ng tng, nhng thng th thc hin phn ng nhit
si ca metanol trnh trng hp metanol bay hi qu nhiu lm gim hiu sut
phn ng, cng nh tn nng lng lm lnh v hn ch phn ng ph xy ra (do nhit
cao).
- Nu thi gian qu ngn th lng nguyn liu phn ng cn t, hiu sut thp.Tuy
nhin nu thi gian phn ng qu lu th to ra nhiu sn phm ph v tn nhiu chi ph.
Thi gian phn ng ph hp th cn phi kho st v n cn ph thuc vo loi nguyn
liu, xc tc v c nhit phn ng.
- Cc loi xc tc vi hot tnh khc nhau nn lng xc tc cn dng cng khc
nhau.Ngoi ra lng xc tc cn ph thuc vo nguyn liu.thng th xc tc cng
nhiu s cho hiu sut phn ng cng cao. Nu khng c s hin din ca mt axit, cc
phn ng este ha gia axit vi ru xy ra rt kh khn. La chn xc tc cho qu trnh
este ha to DMT l axit H
2
SO
4
c nng v c s hnh thnh hydrat ha:
H
2
SO
4
+ H
2
O H
3
O
+
+ HSO
4
-

HSO
4
-
+ H
2
O H
3
O
+
+ SO
4
2

Do s hyrat ha ca axt sulfuric l phn ng thun xt theo nhit ng lc
hc (H = 880 kJ/mol), axt sulfuric l mt cht hp th nc rt tt v to ra H
+
tham
gia tn cng vo nhm cacbony ca axit terephthalic to iu kin tt cho phn ng este
hoa din ra cn bng.
- Theo l thuyt t l axit terephthalic/methanol l 1/2 v m bo s hnh thnh
DMT theo nguyn tc phn ng este ha v vi lng va methanol nh vy trnh
cc phn ng ph trong qu trnh tng hp DMT xy ra. l cc phn ng to mi
trng khng tt cho qu trnh tng hp DMT:
CH
3
OH + H
2
SO
4

CH
3
HSO
4
+ H
2
O
CH
3
HSO
4
+ H
2
SO
4

(CH
3
)
2
O + H
2
SO
4

- Phng php thu hi Dimethyl Terephthalate (DMT): trong qu trnh sn xut
Dimethyl Terephthalate (DMT) theo phng php este ha th ngoi DMT ra cn c cha
ch yu phn hi methanol. thu c DMT nguyn cht ngi ta s dng phng
php chng ct thu methanol hi lu cho qu trnh ester ha. ng thi lng sn
phm l DMT th thu c s c em kt tinh thu c DMT tinh khit. Xc tc
ca qu trnh tng hp DMT thu hi c s c em x l bng cch dng loi baz
thch hp trung ha v em ng dng cho cc qu trnh sn xut ha hc khc.
1.5. Cc quy trnh cng ngh sn xut Dimethyl Terephthalate
1.5.1. Cng ngh n gin s dng p lc
T este ha axit terephthalic vi methanol sn xut Dimethyl Terephthalate theo
phng php cn bng p lc c s dng xc tc axit sulfuric, nhit phn ng 65-100
, thi gian phn ng 10-16h. Phng php ny lng methanol c tiu th vi s
lng ln, nng lc sn xut thp. Nhng khi tng p lc phn ng este ha khong 0.39
0.49MPa th thi gian phn ng c th c rt ngn xung cn 1-2h, gim tht thot
methanol so vi phng php cn bng p lc. Trong nhng nm gn y, phn ng este
ha sn xut Dimethyl Terephthalate lng thng p sut cao, nhit phn ng l
250-300 , p lc ca 2-2.5MPa, c cht xc tc l thic, km, hp cht antimony thu
Dimethyl Terephthalate nng sut ln n 96-98% hoc cao hn.
1.5.2. Cng ngh Witton - Hegelishi (Witten-Hercules)
Mt cch khc sn xut Dimethyl Terephthalate l thng qua vic sn xut DMT
theo phng php sn xut ca Witton - Hegelishi (Witten-Hercules), trong s dng
p- xylen cho qu trnh oxy ha, vi qu trnh oxy ha u tin ca este carboxyl trnh
xy ra qu trnh oxy ha xut hin tip theo ca phn ng ph. n gin ha qu trnh
ny, c th c kt hp trong mt qu trnh oxy ha hai bc ca l phn ng oxy ha,
ng thi c kt hp trong qu trnh este ha hai bc este ha l phn ng. Sn phm
ca p-xylen v methyl benzoat lu trong mt l phn ng thp ng thi cc phn ng
oxy ha, nhit phn ng 140-170 , p sut 0.4-0.7MPa, c xc tc mui Coban hay
Coban kim loi v mui mangan, khng kh lin tc b oxy ha cho qu trnh sn xut
methyl benzoat v monomethyl terephthalate. Sn phm oxy ha ti 200-280 , 2-2.5
MPa vi mt lng d ca methanol trong cc phn ng este ha. T trn cng ca l
phn ng sn phm chng ct este ha ca methanol, chng ct ti ch sau khi s dng;
este ha l phn ng t pha di ra khi este th, tch bng cch chng ct ca methyl
benzoat (ti ch cc l phn ng oxy ha) v Dimethyl Terephthalic. DMT th s
c ha tan vi dimethyl terephthalate c ha tan trong methanol, v kt tinh kt
tinh, tch ly tm, v dimethyl terephthalate kt qu hn na tinh ch bng chng ct, v
d, sn phm cp cht x, tinh khit 99,9%. Tiu hao nguyn liu c nh: p-xylene
630kg / tn, 440kg methanol / tn.
1.5.3. Cng ngh GT-DMT GTC[2]
Cng ngh GT-DMT GTC l mt lot cc ci tin quy trnh sn xut dimethyl
terephthalate. Cng ngh gm qu trnh oxy ha, chng ct, este ha, kt tinh, v x l
nc thi v tiu th nng lng thp hn, tng cng nng lc v ci thin nng
sut. Nhiu d n nhm ci thin sn xut DMT t paraxylene v nguyn liu methanol
c kt qu trong cc chng trnh x l hiu qu cho quy trnh sn xut ny.
Phng php ph bin sn xut DMT t p-xylen v methanoltheo cng ngh CNG
bao gm bn bc chnh: qu trnh oxy ha, este ha, chng ct, v kt tinh. Mt hn
hp ca PX v p-methyl toluate b oxy ha vi khng kh trong s hin din ca mt cht
xc tc kim loi nng ( coban/mangan). Tt c cc cht hu c hu ch c thu hi t
cc offgas v ti ch vo h thng. Hn hp axit t qu trnh oxy ha l este ha vi
methanol to ra mt hn hp ca cc este. Hn hp este th c chng ct loi b
tt c cc ni hi nng v d lng sn xut; este nh hn c ti ch phn qu trnh
oxy ha. DMT liu sau c gi n phn kt tinh loi b DMT ng phn, axit
cn li v aldehyde thm. Lc ny to ra DMT p ng thng s k thut trn th gii th
trng v c a thch trong mt s ng dng polyester. Cc sn phm c thu hi
bn hoc t cho gi tr nhin liu v vt liu trung gian c th s dng c ti ch.




Hnh 1: S quy trnh Cng nghGT-DMT GTC
CHNG 2.THIT D CHUN SN UT
2.1. La chn phng php sn xut Dimethyl Terephthalate (DMT)
T vic so snh cc phng php sn xut DMT trn, nhm chng ti la chn
phng php mt giai on l qu trnh sn xut DMT trc tip t axit terephthalic v
methanol di xc tc l dung dch H2SO4 c nng.Phng php ny th t phc tp
hn cc phng php cn li v cc thit b phn ng v ngun nguyn liu sn c ph
hp vi ngun cung cp hoaschaats cat h trng trong nc. Phng php ny hot
ng iu kin nhit , p sut n gin vi nng sut n nh v thu c sn phm
l DMT vi hiu sut thu hi cao.
2.2. y dng quy trnh sn xut Dimethyl terephthalate
T nhng nh gi tng quan v c s ha l, ngun nguyn liu v tnh kh quan ca
phng php sn xut DMT t phng php este ha trc tip gia axit terephthalic v
methanol di xc tc H
2
SO
4
c nng th quy trnh cng ngh sn xut c thit k
theo tng sau:






Hnh 2: S trn n t
t trtt ng
ng t tn c trtc
Methanol
Methanol
Xc tc
H
2
SO
4

Axit terephthalic
PHN NG TCH
X L CN V THU HI XC TC
KT TINH
SN PHM
SN PHM
Qu trnh sn xut Dimethyl terephthalate bng phng php este ha methanol v
acid terephthalic tri qua cc giai on: phn ng, tch, thu hi sn phm v x l cn,
thu hi xc tc.
- Phn ng: thc hin qu trnh este haeste ha methanol v acid terephthalic c s
tham gia ca xc tc H
2
SO
4
.
- Tch sn phm: phn dung dch DMT sau phn ng cn ln methanol, xc tc s
c a qua h thng cc thit b tch thu hi methanol hi lu li cho qu trnh sn
xut, phn cn v xc tc s c a vo h thng cc thit b x l.
- Sau khi qua h thng cc thit b tch th sn phm l DMT dng dung dch s
c a qua thit b kt tinh thu DMT dng tinh khit v d em bo qun lm
ngun nguyn liu cho cc qu trnh sn xut khc.
2.3. Cc thit b trong s cng ngh sn xut DMT
2.3.1. Thit b phn ng
Xy ra qu trnh bin i ha hc t ngun nguyn liu ban du di tc dng ca cc
qu trnh tuyn nhit, truyn khi di s iu chnh nhit , p sut ph hp vi c ch
ca phn ng din ra t nng sut v hiu sut cao nht. c nhiu laoij thit b phn
ng ph hp cho tng loi phn ng din ra nh phn ng este ha, oxi ha, nhit phn
hyCc thit b phn ng ph bin nh thit b phn ng lin tc c cnh khuy, thit
b phn ng lm vic gin on v thit b phn ng bn lin tc.

Hnh 3: Cc dng thit b phn ng
2.3.2. Thit b trao i nhit
Thit b trao i nhit gip gia nhit cho dng nguyn liu trc khi a vo h thng
cc thit b chuyn ha khc nhau to iu kin nhit thun li cho qu trnh
chuyn ha din ra nh chuyn ha to sn phm, dng cho thp chng, v cc giai on
khc nhau trong quy trnh sn xut
C nhiu loi thit b gia nhit khc nhau nh thit b gia nhit dng ng chum, thit
b gia nhit dng tm, thit b gia nhit hi nc Reboiler

a. Thit b gia nhit dng tm b. Thit b gia nhit Reboiler
Hnh 4: Mt s dng thit b gia nhit
2.3.3. Thit b chng ct
Chng ct l qu trnh dng nhit tch mt hn hp lng ra thnh cc cu t ring
bit da vo bay hi khc nhau ca cc cu t trong hn hp cng mt nhit
.Chng ct da trn nhit si khc nhau ca cc cht lng tham gia.
C nhiu phng php chng ct khc nhau nh: chng ct phn on, chng ct li
cuns dng cc thit b chng khc nhau nh thp chng mm xuyn l, thp chng
a. Thp chng mm chp, thp mTrong qu trnh sn xut DMT s dng thp
chng li cun thu hi sn phm DMT v lng methanol dung hi lu cho qu trnh
este ha.
2.3.4. Thit b tch
Thit b tch gip tch ring cc sn phm khc nhau thu hi li dng sn phm
mong mun v a hi lu cho qu trnh sn xut. c nhiu loi thit b tch khc nhau
nh thit b tachs2 pha, tch 3 pha S dng thit b tch trong qu trnh sn xut DMT
tch Methanol hi lu cho qu trnh este hoa din ra v tch loi b xc tc d trong
qu trnh em x l v thu hi.
2.3.5. Thit b ph tr
Cc loi thit b ph tr khc nh bm, van, dng diu chnh lu lng cc
dng nguyn liu v sn phm vo ra cho qu trnh sn xut. Vic s dng h thng cc
thit b ph tr ny gip kim sot c ch lm vic ca cc thit b trong quy trnh
sn sut din ra an ton hn v tit kim ngun nguyn liu hn.
Thit b kt tinh kt tinh thu DMT dng tinh th d lu tr sn phm lm
nguyn liu cho qu trnh sn xut khc v ng gi hay vn chuyn thun tin d dng
hn.
2.4. Thit s cng ngh sn xut DMT
S thit k quy trnh sn xut DMT theo hnh 5:
Nguyn liu ban u l axit terephthalic v methanol t h thng b cha (9) cng
xc tc axit sufuaric cho vo c a vo thp phn ng lin tc c cnh khuy (1). Ti
y xy ra phn ng este ha gia axit terephthalic v methanol di tc dng ca xc
tc H
2
SO
4
to ra Dimethyl terephthalate. Hn hp sau phn ng gm lng d axit
terephthalic, hi methanol, xc tc d nh thp phn ng v sn phm Dimethyl
terephthalate v methanol lng y thp phn ng. Hn hp nh thp c a qua
thit b trao i nhit ri qua thit b tch thu hi ngun nguyn liu (axit terephthalic,
methanol, xc tc). Ngun axit terephthalic thu hi t thp tch (4)c hi lu li cho
thp phn ng (1).Sn phm y thp (methanoldng lng v DMT) i qua thit b gia
nhit s b ri a vo h thng chng ct (2), (3) vi s gia nhit y thp nh thit b
gia nhit hi nc reboiler. Ti thp chng (2) phn hi methanol c thu hi nh
thp sau qua thp tch (5) thu hi methanol hi lu cho ngun nguyn liu sn xut
DMT thp phn ng v phn nc thi cha xc tc c a ra ngoi x l v thu
hi sau ngun sn phm y thp c gia nhit s b ri qua bm a vo thp
chng (3).Ti thp chng (3) phn sn phm DMT c thu hi nh thp sau qua
thp tch nc (6) v i qua thit b kt tinh thu c DMT dng tinh th ri a vo
b cha sn phm (10), cng vi phn thi gm cc hp cht cn v nc thi c
a vo b cha thu hi v x l.

















CHNG III: TNH TON
2.1. Tnh cn bng vt cht
2.1.1. Tnh thi gian cho mt m sn xut
Trnh t cc bc din ra trong qu trnh phn ng nh sau:
Qu trnh Thi gian (pht)
- Np liu 30
- Gia nhit cho thit b phn ng 60
- Phn ng chnh 360
- Thi gian tho liu 30
=> Tng thi gian 480 (8 gi)

B tr mt ngy lm vic 3 ca, thi gian mi ca l: 24 :3 = 8 gi
Nh vy, mi ngy ta sn xut c 3 m sn phm, vi thi gian ca mi m
sn phm l 8 gi.
2.1.2. Nng sut ca mi m sn phm
S ngy lm vic thc t trong mt nm l 330 ngy.
Nng sut ca thit b phn ng l 200000 tn/ nm, do , nng sut ca mt
ngy lm vic ca thit b phn ng l:

= 606.06 tn/ngy
Nng sut tnh theo mi gi sn xut l :

tn/ h
S gi lm vic ca mt nm l: 24330 = 7920 gi


Thi gian ca mi m sn phm l 8 gi, vy s m sn phm ca thit b phn ng
trong mt nm l:

m
Nng sut ca 1 m sn phm trong 1 nm l:

tn/m
2.1.3. Tnh cn bng vt cht cho thit b phn ng
Nng sut ca thit b phn ng trong 1 thng sn xut l:

tn/ thng
Cc s liu sau c tnh ton cho 1 thng sn xut.
Nguyn liu u vo c xc nh nh sau:

Vy:
Do hao ht nguyn liu u vo l 2% nn:
- Lng p-xylen u vo ca qu trnh l:
16 666.67 205 : 0.98 = 3 486 395.255 tn/thng
- Lng metanol u vo ca qu trnh l:
16 666.67 120 : 0.98= 2 040 816.74 tn/thng
- Lng oxi trong khng kh u vo ca qu trnh l:
16 666.67 300 21% :0.98 = 1 071 428.786 tn/thng
- Lng Nito trong khng kh u vo ca qu trnh l:
16 666.67 300 79% = 4 030 613. 051 tn/thng
* Phn ng tng qut ca qu trnh sn xut DMT l:
C
6
H
4
(CH
3
)
2
+ 3 O
2
+ 2 CH
3
OH H
3
C OOC C
6
H
4
COO CH
3
+ 4
H
2
O
Do hiu sut ca qu trnh l 87%, chuyn ha t 95%, hao ht nguyn liu 2%
nn lng p-xylen cn cho qu trnh l:

- Lng metanol cn cho qu trnh l:

- Lng oxi cn cho qu trnh l:

- Lng nc hnh thnh trong qu trnh phn ng:

Vy:
- Lng p-xylen khng tham gia vo qu trnh phn ng (cn li sau phn ng):
3 486 395.255 - = 3 475 544.86 tn/thng
- Lng metanol khng tham gia vo qu trnh phn ng l:
2 040 816.74 = 2 034 164.24 tn/thng
- Lng oxi khng tham gia vo qu trnh phn ng l:
1 071 428.786 1 061 602 tn/thng
T nhng s liu trn, ta c bng cn bng vt cht ca qu trnh cho mt thng sn
xut:

S
TT
Tn cht u vo (tn/thng) u ra (tn/thng)
Lng
vo
Phn
ng
Lng ra
1. p-xylen 3 486 395.255 3 475 544.86
2. metanol 2 040 816.74 2 034 164.24
3. oxi 1 071 428.786 1 061 602
4. Nito 4 030 613. 051 0 4 030 613. 051
5. DMT 0 0 16 666.67
6. H
2
O 0 0
7. Tng 10 629 243.83 10 24 776.4

2.1.4. Tnh chi ph nguyn liu cho 1 thng sn xut
Chi ph nguyn liu cho 1 thng sn xut c tnh theo bng sau(gi mua
nguyn liu c tnh ti thi im thng 1/ 2013):
Cht Khi lng
(tn/thng)
n gi
(USD/tn)
Chi ph (USD/thng)
(Khi lng n
gi)
p-xylen 3 486 395.255 1655 5.77 10
9

metanol 2 040 816.74 435 0.8877 10
9

Tng chi ph 6.6577 10
9


2.2. Tnh cn bng nhit lng cho thit b este ha
Cc phn ng chnh xy ra trong thit b este ha:
Giai on este ha axit p-toluic bng methanol thnh p-metyl toluate

(CH
3
)C
6
H
4
COOH + CH
3
OH CH
3
C
6
H
4
COO CH
3
+ H
2
O
H
o
298
= -30 kJ/mol
Giai on este ha thnh dimetyl terephtalat
HOOC-C
6
H
4
-COO-CH
3
+ CH
3
OH H
3
C-OOC-C
6
H
4
-COO-CH
3
+ H
2
O
H
o
298
= -30 kJ/mol

Ta c cn bng nhit nh sau:
Tng lng nhit dng vo =Tng lng nhit dng ra
Hay: Q
1
+Q
2
+Q
3
=Q
4
+Q
5
+Q
6
(*)
Trong :
- Q
1
: Lng nhit do hn hp nguyn liu mang vo (kJ/h)
- Q
2
: Lng nhit do nc ti nhit mang vo (kJ/h)
- Q
3
: Lng nhit do cc phn ng ta ra (kJ/h)
- Q
4
: Lng nhit do cc sn phm mang ra (kJ/h)
- Q
5
: Lng nhit do nc ti nhit mang ra (kJ/h)
- Q
6
: Lng nhit mt mt ra mi trng (kJ/h)
1. Tnh lng nhit do hn hp nguyn liu mang vo (Q
1
)
Hn hp nguyn liu u vo thit b phn ng c nhit 160
0
C (433 K)
Nguyn liu vo thit b este ha chnh l sn phm ca qu trnh oxi ha theo cc
phn ng sau:
Giai on oxi ha bng khng kh p-xylen thnh axit p-toluic

C
6
H
4
-(CH
3
)
2
+ 3/2 O
2
(CH
3
)C
6
H
4
COOH + H
2
O (1)

Giai on este ha axit p-toluic bng methanol thnh p-metyl toluate

(CH
3
)C
6
H
4
COOH + CH
3
OH CH
3
C
6
H
4
COO CH
3
+ H
2
O (2)

Giai on oxy ha nhm metyl cn li thnh metyl terephtalat

CH
3
C
6
H
4
COO CH
3
+ 3/2 O
2
HOOC-C
6
H
4
-COO-CH
3
+ H
2
O (3)

Giai on este ha thnh dimetyl terephtalat

HOOC-C
6
H
4
-COO-CH
3
+ CH
3
OH H
3
C-OOC-C
6
H
4
-COO-CH
3
+ H
2
O (4)

Theo phng trnh phn ng ta c, s mol ca axit p-toluic, m etyl terephtalat to
thnh phn ng (1), (3) bng s mol ca DMT to thnh phn ng (4).
=> n
p-toluic
= n
metyl terephtalat
= n
DMT
=

10
6
mol

Lng p-toluic vo thit b este ha l: 10
6
136 =11 683.76 tn
Lng metyl terephtalat vo thit b este ha l: 10
6

180 = 15 463.8 tn
S mol metanol nguyn liu =

212.13 10
6
mol
* Nhit dung ring ca cc cht ha hc c tnh theo cng thc:
M.c = n
1
c
1
+ n
2
c
2
+ n
3
c
3
+ . (I.41, s tay tp 1)
Trong M l khi lng mol ca hp cht, c l nhit dung ring ca hp cht ha
hc (J/kg.), n
1
, n
2
,n
3
l s nguyn t ca cc nguyn t trong hp cht; c
1
, c
2
,c
3
,.l
nhit dung nguyn t ca cc nguyn t tng ng, J/kg nguyn t.
Tra bng I.141 ta c:
Tra bng I.141 ta c:
- Nhit dung ring ca axit p-toluic l:
136 . c = 11700 8 + 18000 8 + 225100 => c
p-toluic
= 2116.8 J/kg.
- Nhit dung ring ca metanol l:
32. c = 11700 + 4 18000 + 25100 => c
toluen
= 3400 J/kg.
- Nhit dung ring ca metyl terephatalat l:
180 . c = 9 11700 + 8 18000 + 4 25100 => c
metyl terephatalat
= 1942.8 J/kg.
Ta c bng sau:
N
guyn
liu
Khi lng
(tn/thng)
Mol x
i
(Ph
n mol)
Cp
(J/k
g.)
p-
toluic
11 683.76 10
6

0.223
7
211
6.8
M
etanol


212.13
10
6

0.552
6
340
0
Metyl
terephtalat
15
463.8
10
6

0.223
7
194
2.8
Tng 33935.86 383.95
10
6

1
Nhit dung ring ca hn hp nguyn liu vo thit b phn ng c tnh theo
cng thc sau:
C
P ng.liu
= C
p
i
x
i
(J/kg.)
= 0.22372116.8+ 0.55263400+ 0.22371942.8
= 2786.97 J/kg.
Vy lng nhit do hn hp nguyn liu mang vo l:
Q
1
= G
ng.liu
C
P ng.liu
T
ng.liu
=

2786.97

433 K
= 6.2 10
10
J/h = 6.2 10
7
kJ/h
2. Tnh lng nhit do nc ti nhit mang vo(Q
2
)

Q
2
= G
nc
C
Pnc
T
nc

Trong :
- G
nc
: khi lng nc ti nhit i vo, kg/h
- Q
2
: lng nhit do nc ti nhit mang vo, kJ/h
- T
nc
: nhit nc ti nhit mang vo,
o
C
- C
P(nc)
: nhit dung ring ca nc ti nhit, kJ/kg

.k
Tra bng I.147 (s tay qu trnh v thit b cng ngh ha cht tp 1) ta c:
C
p nc
= 0.99892 kcal/kg. = 4.1868 10
3
0.99892 = 4182.28 J/kg. 25
0
C
=> Q
2
= G
nc
4182.28 25 = 104.557 G
nc
kJ/h
3. Tnh lng nhit do cc phn ng ta ra (Q
3
):

(CH
3
)C
6
H
4
COOH + CH
3
OH CH
3
C
6
H
4
COO CH
3
+ H
2
O (1)
H
o
298
= -30 kJ/mol
HOOC-C
6
H
4
-COO-CH
3
+ CH
3
OH H
3
C-OOC-C
6
H
4
-COO-CH
3
+ H
2
O (2)
H
o
298
= -30 kJ/mol
Q
3
= n
p-toluic
H
o
298(1)
+ n
DMT
H
o
298(2)


Q
3
= 10
6
mol 30 kJ/mol + 10
6
mol 30 kJ/mol
=> Q
3
= 5154.6 10
6
kJ/thng = 7.81 10
6
kJ/h
4. Tnh lng nhit do cc sn phm mang ra(Q
4
)
Hn hp sn phm u ra c nhit l 220
o
C (493K)
Ta c nhit dung ring ca cc cht 220
0
C nh sau:
Sn phm
Khi lng
Tn/thng
Mol
(10
6
mol)
x
i
(Phn
mol)
Cp(J/kg.)
DMT 16666.67
85.91 0.33 2048.45
H
2
O 3092.76
171.82 0.67

4506.25
Tng 19759.43
257.73 1

- Nhit dung ring ca DMT :
194 c
DMT
= 11700 10+1800010+251004 => c
DMT
= 2048.45 J/kg.
- Tra bng I.147 (s tay qu trnh v thit b cng ngh ha cht tp 1) ta c:
C
p nc
= 1.00763 kcal/kg. = 4.1868 10
3
1.00763 =4506.25 J/kg.
Nhit dung ring ca hn hp sn phm l:
C
P
(sn phm)

= C
p
i
x
i
(J/kg.)
= 0.33 2048.45+0.674506.25
= 3695.176 J/kg.
Vy: Nhit lng do dng sn phm mang ra l:
Q
4
= G
sp
C
P(sp)
T
sp
(kJ/h) =

493 K
= 5.02 10
10
J/h = 5.02 10
7
kJ/h
5.Nhit lng do nc ti nhit mang ra(Q
5
)
Q
5
= G
nc
C
Pnc
T
nc

Trong :
- G
nc
: khi lng nc ti nhit i ra, kg/h
- Q
2
: lng nhit do nc ti nhit mang ra, kJ/h
- T
nc
: nhit nc ti nhit ra,
o
C
- C
P(nc)
: nhit dung ring ca nc ti nhit, kJ/kg

.k
Nhit dung ring ca nc 45
0
C l :
C
p nc
= 0.9989 kcal/kg. = 0.9989 4.1868 10
3
J/kg. = 4182.2 J/kg.
=> Q
5
= G
nc
4182.2 45 =188.199 G
nc
kJ/h
6. Nhit lng do mt mt(Q
6
).
Do coi mt mt nhit cho mi trng l 5% nhit u vo nn:
Q
6
=0,05(Q
1
+Q
2
+Q
3
)
=> Q
6
= 0.05 (6.2 10
7
+ 104.557 G
nc
+ 7.81 10
6
) = 0.349 10
7
+ 5.228 G
nc
Thay cc gi tr Q
1
, Q
2
, Q
3
, Q
4
,Q
5
, Q
6
vo biu thc (*) ta c:
Q
1
+Q
2
+Q
3
=Q
4
+Q
5
+Q
6
6.2 10
7
+ 104.557 G
nc
+ 7.81 10
6
=5.02 10
7
+188.199 G
nc
+0.34910
7
+5.228
G
nc
6.981 10
7
+ 104.557 G
nc
= 5.369 10
7
+ 193.427 G
nc

G
nc
= 181 388.55 kg/h
Vy lng nc ti nhit cn dng cho qu trnh l 155 958. 14 kg/h hay
119 716.443 tn/thng










Kt lun

Sau khi hon thnh n, em :
- Tm hiu c cu to, tnh cht ca acrylonitril
- Cc ng dng quan trng ca acrylonitri
- Hiu v nh gi cc cng ngh sn xut acrylonitril trong cng
nghip
- Tnh ton cn bng nhit v cn bng vt cht trong thit b phn
ng