TM Hiu CNG

NGH SN XUT
POLYETYLEN
TEREPHTALAT

TI U LU N

GIO VIN HNG DN: Th.S NGUYN TH LINH

SINH VIN THC HIN: NHM 5

Tm hiu cng ngh sn xut polyetylen terephtalat

m ____1_______

Tiu lun

Tm hiu cng ngh sn xut polyetylen

terephtalat

Gio vin hng dn:

Th.S Nguyn Th Linh

Sinh vin thc hin: Nhm 5

L c Hong
Nguyn Vn Hon
Nguyn Mnh Hng
Nguyn Th Hng
Trn Gia Khnh
Lng nh Khnh

Nhm 5

Lp Lc Ha du K52

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Tm hiu cng ngh sn xut polyetylen terephtalat

MC LC

M U........................................................................................................................3
CHNG 1. TNG QUAN.........................................................................................4

I.

TNH CHT CHUNG CA POLYRTYLEN TEREPHTALAT........................4

II. CC NG DNG CA PET.................................................................................5

CHNG 2. NGUYN LIU V CC PHNG PHP SN XUT PET........6

I.

CC PHNG PHP TNG HP PET.............................................................6

II. NGUYN LIU CHO QU TRNH TNG HP PET......................................10

III. CNG NGH TNG HP MONOMER.............................................................13

III.1 Cng ngh sn xut TPA.......................................................................................13

III.1.1. Cng ngh oxi ha ca hng Amoco............................................................13
III.1.2. Cng ngh ca hng Eastman......................................................................16

III. 2. Cng ngh sn xut DTM...................................................................................18

111.2.1........................................................................................................................... Cng ngh ca hng Witten

19

111.2.2........................................................................................................................... Cng ngh ca hng H&G

21

IV. CNG NGH TRNG HP PET.........................................................................23

IV. 1. IPT (Cng ngh thc hin theo Invista) Quy trnh NG3TM........................25
IV. 2. Cng ngh Lurgi Zimmer DHI.......................................................................26
IV. 3. Cng ngh Buhler (Ti ch PET)...................................................................27

V. NH GI CNG NGH......................................................................................29
V. 1. nh gi cng ngh sn xut monome..........................................................29
IV.2. nh gi cng ngh trng hp PET..........................................................30
KT LUN....................................................................................................................31
TI LIU THAM KHO............................................................................................32
M U
Ngy nay, cng vi s pht trin ca x hi, nhng ngun nguyn liu thinnhin khng p ng cc nhu cu
ngy cng cao ca con ngi c v s lng ln cht lng. iu ny thi thc cc nh khoa hc nghin cu v pht trin
cc loi vt liu dt mi p ng yu cu ca con ngi, v vy m cc loi vt liu nhn to v tng hp bt u ra i v
pht trin nhanh chng. Ch trong mt khong thi gian khng lu, cc loi vt liu ny mang li li ch to ln cho con
ngi bi s a dng v chng loi cng nh cht lng.
Nhm 5

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Tm hiu cng ngh sn xut polyetylen terephtalat

Mt trong nhng vt liu tng hp c ng gp quan trng hn c l polyester,vi nhng tnh nng u vit, n dn
thay th cc cc vt liu trong i sng hng ngy, t nhng dng trong gia nh cho n nhng chi tit ca tu v tr, thm
ch c th lm mt s b phn gi ca c th con ngi.
Polyetylen terephtalat (PET) l mt loi polyester c ng dng ch yu sn xut nha v x si, ngoi ra cn c
th ch to c film v cc nylon c bit do cc thuc tnh ca PET d dng iu chnh trong qu trnh sn xut. N l mt
polymer nhit do c th ti ch c, thn thin vi mi trng v l s la chn s mt tha mn cc nhu cu khc nhau trn
th gii cho mt la chn xanh hn v sinh thi hn.
Mc tiu ti ny l tho lun v cc ngun nguyn liu tng hp nn sn phm PET, cc phng php sn xut
cng nh cc dy chuyn cng ngh v ang c ng dng trn th gii, phn ny c trnh by bng s dng v
thuyt minh s cng ngh. Cui cng l nhng nhn xt, nh gi chung c rt ra.

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Tm hiu cng ngh sn xut polyetylen terephtalat

i Cng thc phn t: (C8Hio04)n i Cng thc

cu to:

CHNG 1. TNG QUAN

I. TNH CHT CHUNG CA POLYRTYLEN TEREPHTALAT.
Ty thuc vo qu trnh tng hp v nhit , polyethylen terephtalatcth tn ti c hai dng v nh hnh trong sutv
bn kt tinh. Vt liu bn kt tinh c th xut hin trong sut (kch thc ht <500 nm) hoc c v trng (ht kch
thc ln n mt vi micron) tu thuc vo cu trc tinh th ca n v kch thc ht.
I PET c cng cao, bn, do dai tt ngay c nhit thp v kh nng chng ro tt. PET c li th l c tnh
cht in cch in tt v kh nng chng n mn cao vi nhiu cht ha hc khc nhau.
Mt trong nhng c im quan trng nht ca PET l ch s nht - Intrinsic Viscosity. Ch s nht ca vt liu
ph thuc vo di ca mch polymer. Mch cng di, cc vt liu cng cng hn, v do IV cng cao. Chiu di
mch trung bnh ca mt l c th ca nha c th c kim sot trong qu trnh polyme ha.Ch s nht ca PET
i vi mt s vt liu:
0.60 dL/g: si
0.65 dL/g: mng
0.76 ^ 0.84 dL/g: chai
0.85 dL/g: dy thng
-1- PET c tnh ht m, ngha l n t nhin hp th nc t mi trng xung quanh n. Do n cn c sy trc
khi a vo cc cng on sn xut tip theo. Nhit v thi gian sy bng khng kh thng thng nh sau: o 140oC
khong 12 gi
o 145oC khong 6,5 gi
o 160oC khong 4 gi
Thi gian sy khng c ngn hn 4 gi. iu ny l do cc vt liu kh trong t hn 4 gi s i hi phi c nhit
trn 160oC. Tip xc vi nhit cao nh vy s lm phn hy lp ngoi ca vt liu trc khi bn trong n kh hon
ton.

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Tm hiu cng ngh sn xut polyetylen terephtalat

Bng 1. Cc tnh cht chung ca PET

Tnh cht vt l
Gi tr Tnh cht nhit
1.3-1.4 im chp chy
3
Khi lng ring (g/cm )
o
Kh nng duy tr ngn la T dp tt Nhit lm vic di ( C)
Gii hn oxi cho php
Ch s khc x
Kh nng chng tia cc
tm
Cn bng nc hp th
nht T=75oC
Tnh cht c hc
H s ma st
Tnh cng

bn chng va p
(J/m)
H s Poisson
Modun ko
bn ko

II.

21%
Nhit lm vic trn (oC)
1.58-1.64 Nhit dung ring (J/kg.K)
Tt
dn nhit (W/m.K) 23oC
<0.7%

S chnh lch nhit

1.8MPa (oC)
600
S chnh lch nhit
mPa.s 0.45MPa r
Gi tr H s gin n nhit (x106 -1
K )
0.2-0.4 Tnh cht ha hc
M94-101 Bn axit
13-35

Gi tr
Trn 200oC
-60 n -40
115-170
1200-1350
0.15-0.4
80
115
20-80
nh gi
Tt vi hu
ht axit
thng
Tt

Bn ru, xeton, halogen, du

m
0.37-0.44 Bn kim
c bit km
nhit cao
Bn
hydrocacbon
aromatic
Kh tt
2-4
80

CC NG DNG CA PET

Tm quan trng ca PET xut pht t thc t l n c s dng rng ri trong nhiu sn
phm.PET c th c
to thnh cc
v
chai
hoc cc hp ng, bn v
chu c va p mnh. Chng c s dng bao ngoi cho cc sn phm c th ung hoc n c nh nc ngt, nc
khong, nc tri cy, thc n tr em, b u phng, du gim, du v gim.
PET c th ko thnh mng mng thng c bao bc vi nhm lm hot gim tnh dn t, lm cho n tnh phn chiu
v chn sng. PET hoc Dacron cng c th c s dng rng ri nh mt lp vt liu cch nhit ph phn ngoi ca trm v
tr quc t (ISS). Ngoi ra, chng cn c s dng cho cc sn phm lin quan n ha cht khc, chng hn nh m phm,
dc phm v cht ty ra gia dng.
Di y l s
polyeylen terephtalat:

khi th hin tm quan trng v cc ng dng ph bin ca

Nhm 5

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TPA/DMT

AIE
PETG

furnishing
Ho I I I

clothing
Textile

Food
containers

Tm hiu cng ngh sn xutEngineering

polyetylen terephtalat
resins

Flexible
Packaging

PET resins
Fibers
Film
and specialities
Beverage
containers

Rigid
packaging

Video &
audio film

Hnh 1. ng dng ph bin ca PET

CHNG 2. NGUYN LIU V CC PHNG PHP SN XUT PET

I. CC PHNG PHP TNG HP PET

I.1. Phn ng gia axit Terephtalic vi Etylen glycol.

Gia axit terephtalic v ethylene glycol l phn ng pha lng. tan ca axit terephtalic trong glycol si p sut
thng rt thp nn nng cao kh nng ha tan phn ng cn c tin hnh p sut 4.10 5 Pa (4 atm), nhit t 240 260oC. y l phn ng t xc tc, tuy nhin mt s axit mnh hoc ester ca axit titanic c thm vo hn hp phn ng
nh l xc tc cho phn ng ester ha. T l mol cc tc cht cho phn ng ester ha trc tip l etylen glycol:axit terephtalic
vo khong 1:1 - 1,3:1. Polyester sn xut bng phng php ester ha trc tip c khi lng phn t cao hn hn so vi
polyester sn xut bng con ng trao i ester (transesterification)

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Tm hiu cng ngh sn xut polyetylen terephtalat

Phn ng ester ha lun lun i km phn ng ete ha, nht l trong mi trng axit. Trong sn xut polyester mt t
kim mnh nh NaOH c thm vo hn hp phn ng hnh thnh h m vi mc ch lm gim tc phn ng ete
ha. Nu phn ng khng tin hnh trong h m lng ete sinh ra lm cho phn t polymer c cu trc khng ng nht.
iu ny lm gim kh nng c l ca si ng thi lm nhit nng chy gim xung di mc c th chp nhn c v
khng th kimsot c. Nu tin hnh phn ng ester ha nhit cao hn mt cht vo khong 280 - 290 oC, tc phn
ng ester ha c kh nng t n ngng. Lc ny phn t polymer khng cn p ng c cc yu cu sn xut si do s
phn b khi lng phn t qu a dng.

Mt sn phm khc ca phn ng ester ha l nc. thc y phn ng t n hiu sut cao nht, nc c chng
ct tch ra khi hn hp phn ng. Cui phn ng ester ha, mui photphat hay photphit c cho vo nhm n nh
polymer. N gip polymer kh tan trong mi trng kim hn so vi nhng polymer khng c cc cht ny. Giai on tip
theo trong qu trnh polymer ha tng t nhau cho c phn ng ester ha trc tip ln phn ng trao i ester. Mt lng xc
tc c thm vo trn ln vi cc obligomer mch thng, glycol d c tch ra bng chng ct hn hp sau phn ng. Nhit
c nng ln khong 280 - 290oC trong khi p sut c gim nhanh v di 25Pa trnh to bt do glycol ha hi, cho
ti lc thu c polyester c khi lng phn t mong mun. Trong qu trnh ngng t ester antimon trioxit to phc vi ester
ca acid titanic ln trong polyester gy ra nhng m c mu khi chng kt hp antimon trioxit. Tuy nhin, hiu ng ny
khng ng k khi c mt P3+ hoc P5+.
Phn ng gm 2 giai on
Giai on 1 : Hn hp PTA v EG c gia nhit, phn ng trng ngng xy ra to BHET ( bis-(hydroxyletyl)terephtalat) v
cc oligome c phn t lng thp.

Temperature
Giai on 2: Phn ng trng ngng tip tc xy ra to PET. Sau phn ng, EG cn d, PET c dng lng chy nht. Nu lm
(BHET
)

+
x
lnh ngay trong nc s to thnh PET v nh hnh.

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2.1.Polyme
Xc tc,ha,
p sut
220oC
thp
HO285oC
C O // w

Oligome
O
COCH
(x=2-5)
2CH2O H x

II

O
COCH2CH2O H

II

Polyetylen
terephtalat (n=130-150)
Tm hiu cng ngh sn xut polyetylen
terephtalat
M=25000

Xc tc thng dng l antimony trioxit, mui ca titan, gecmani, coban, mangan, magie v km. Xc tc s dng vi nng
thch hp lm tng vn tc phn ng.

Cng nh phn ng ester ha, phn ng a t polymer cng l mt phn ng thun nghch. Do vy, trong giai on a t
phi tch glycol mt cch trit . Song song vi phn ng a t polymer, nhit ny cn din ra qu trnh nhit phn
polyester lm gim khi lng phn t. Phn ng ny hnh thnh cc nhm cacboxyl (-COOH) v vinyl ester u mch, sau
cc nhm vinyl ester ny s nhanh chng chuyn thnh cc nhm andehyt.

Trong iu kin p sut thp v tc chng ct ln cc hp cht andehyt nhanh chng tch ra khi hn hp phn ng.
Nhng nu qu trnh din ra p sut cao hoc thi gian chng ct ko di, nhng nhm andehyt ny s to ra nhng nhm
mang mu ln trong phn t polyester. Cui phn ng a t polymer, mt lng t 0,5-2% diphenyl ester hoc diphenyl
terephtalat c cho vo thit b a t kt ni cc obligomer thnh polymer theo phn ng:
Bng cch ny c th gim bt thi gian phn ng a t polymer so vi phng php tip tc chng ct loi glycol. Do
vy y l bin php lm gim nh hng ca cc phn ng ph sinh ra cc hp cht c mu m vn p ng yu cu lm
OC

CO

vwvw

O
2
+
*~C
O
CH2CH2OH
'

O
~wC OCH2CH:

O
C OCH2CH:

O
O C M M f ' + 2
OH

gim cc obligomer.
lm mt cc nhm carboxy u mch, ngi ta cng c th cho vo hn hp mt lng etylen oxit.
I.2. Phn ng trao i este gia Dimetyl Terephtalat (DMT) v EG
Phn ng iu ch DMT t TPA v Metanol

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Tm hiu cng ngh sn xut polyetylen terephtalat

Diinetyl Tel ephtalat (DMT)

< '41
r
Phn ng trans este ha gia DMT v EG, methanol l mt trong cc sn phm.
Dimetyl Teiephhilt (DMT)
trng
Ti
PET
p
H

HO

c
HO

2 H20o

c c o co

CH CH
I.3.
bis(2 h\ croxyetyi )
terephtaiat

CH

oc o c' 'H'cH

OH O
H

(BHET
)

Phn ng ny xy ra nhanh v hiu sut cao. Tuy nhin do

axit clorua t nn phng php nn phng php ny
khng c s dng trong cng nghip.
Phn ng gia Terephtaloyl diclorid v Etylen glycol

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Tm hiu cng ngh sn xut polyetylen terephtalat

II. NGUYN LIU CHO QU TRNH TNG HP PET

Sn xut PET ch yu chia thnh hai giai on. Giai on u l PTA sn xut bng cch s dng p-xylen lm nguyn liu
vi s c mt ca axit lm dung mi, giai on hai l phn ng gia PTA v MEG hnh thnh nn PET. Do cc nguyn liu
sn xut PET l p-xylen v MEG.

II.1. Nguyn liu p-xylen

P-xylen l mt hydrocacbon thm, gm mt vng benzen v hai nhm th metyl th vo hai t cacbon hai v tr 1 v 4
vng thm. P-xylen c ng phn l o-xylen v m-xylen.
Tnh cht ha l:
Cng thc phn t: C8H10
Cng thc ha hc:

Trng lng phn t: 106,17 vC

im si: 137-140oC
T trng: 0,86

Nhit nng chy: 13,3oC

Nhit si: 138,4oC

Cht lng khng mu, khng tan trong nc, tan trong ancol, ete, v cc dung mi hu c.
ng dng:
P- xylen c mt s ng dng nh cht lm tng tr s octan ca xng, lm dung mi trong sn, phm mu, dung mi
trong nghin cu thuc...P-xylen c s dng ch yu sn xut axit terephtalic, mt hp cht quan trng tng hp nha
PET.

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Tm hiu cng ngh sn xut polyetylen terephtalat

- Ngun thu P-xylen:

II.2. Nguyn liu MEG
4- Tnh cht ha l:

Dehydro, Oligome
v Dehydro vng
ha

Kh du m ha
lng (C3, C4)

Mono ethylene glycol / MEG l cht lng c nhit si cao, bay hi thp, c th trn ln vi nc. N c dng lm
dung mi v l nguyn liu ban u cho nhiu qu trnh tng hp
-

Tn ho hc : 1,2 - Ethanediol, Ethylene Glycol

Cng thc ho hc :HOCH2-CH2OH

Cng thc phn t :C2H6O2

Nhit si : 196-1990C

Nhit ng c : -12.30C
- Mono ethylene glycol / MEG l cht lng trong sut, tc bay hi thp, ht m, nhit si cao, c mi nh. N c
th trn ln vi nc, alcohol, polyhydric alcohols, glycol ether, acetone, cyclohexanone. Tan trong du ng vt, du thc
vt v cc dn xut du m, khng tan hoc tan hn ch trong esters, hydrocacbon thm, hydrocacbon bo.
-

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Tm hiu cng ngh sn xut polyetylen terephtalat

4- ng dng:
Mono ethylene glycol / MEG c cc tnh cht nh : lm gim nhit ng nh h nc, kh nng ht m, bn ho
hc, kh nng phn ng vi Ethylene oxide v cc acid khc. V th n c dng nhiu trong cc ng dng :
s Cht trung gian sn xut nha s Cht chng ng v c ch n mn s
Cht gi m
s Dung mi ha tan thuc nhum
4- Ngun thu MEG
Thy phn etylen oxit
Clohydrin ha etylen, thy phn bng dung dch kim hydro cacbonat
Axetoxyl ha etylen, thy phn thu c MEG
Oxi ha etylen c s dng xc tc
Phn ng tng hp gia CO v H2

III. CNG NGH TNG HP MONOMER

TPA v DMT l hai monomer c s dng trng hp nn PET. Di y
l mt vi s v m t cng ngh.
III.1 Cng ngh sn xut TPA
TPA c sn xut bng cch oxy ha p -xylen. Hai cng ngh sn xut TPA c cp l:
> Cng ngh oxi ha ca hng Amoco
> Cng ngh oxi ha nhiu bc ca h ng Eastman

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Tm hiu cng ngh sn xut polyetylen terephtalat

P-xylen l nguyn liu cho hu ht cc qu trnh sn xut TPA trong s dng axit axetic lm dung mi phn ng. Khng
kh c nn cung cp oxy cho phn ng v c a vo vi lng d gim thiu s hnh thnh cc sn phm ph, t
c chuyn ha p-xylen cao.
TPA c sn xut bng phn ng lp xc tc pha lng. Phn ng ta nhit cao, gii phng 2.10 5 kJ/kg p-xylen, nhit ta
ra ny c tn dng un si axit axetic ng thi tn nhit cho phn ng. Qu trnh oxy ha cc nhm metyl xy ra theo ba
giai on. Hai sn phm trung gian c hnh thnh trong phn ng l axit p-toluic v axit 4-formylbenzoic v cui cng TPA
c to th nh.
III.
1.1. Cng ngh oxi ha ca hng Amoco.
COOH

p-Xylene

p-Toluic acid

4-Formylbenzoic acid

COOH
Terephthalic
acid

TPA tr thnh sn phm thng mi ca Cng ty Ha cht Amoco nm 1965. Cng ngh ca Amoco c thm mt cm
thit b tinh ch TPA th nhm thu c sn phm c tinh khit cn thit sn xut PET. Cng ngh ny c s dng
ph bin trn th gii.

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Tm hiu cng ngh sn xut polyetylen terephtalat

M t nh hnh v, nguyn liu i qua l phn ng oxi ha m ti phn ng oxi ha xy ra. Hu ht cc TPA kt ta,
do chng c ha tan thp trong dung mi. Hi t nh l phn ng c ngng t trong thit b trao i nhit, v c hi
luquay tr li l phn ng. Hi nc, c to ra do qu trnh ngng t , c tn dng nh l ngun un nng cho cc b
phn khc trong qu trnh. Kh ngho oxi trong bnh ngng c a ti thp ra loi b hu ht cc kh khng ngng.
L phn ng vn hnh iu kin nhit l 175-225 oC v 1500-3000 kPa, thi gian lu khong 2,5 gi. L phn ng
c ch to titan trnh s n mn mnh ca brom v axit axetic. Cht xc c s dng trong l phn ng oxy ha l kim
loi nng a ha tr, ch yu l coban v mangan, ngoi ra cn c brom l ngun ti to gc t do. H thng cht xc tc ha
tan coban-mangan-brom l trung tm ca qu trnh. Qu trnh oxy ha cc nhm metyl ca p-xylen gn nh hon ton vi tn
tht xylen nh. Cc mui khc ca coban v mangan cng c th c s dng v ngun cung cp brom c th l HBr, NaBr
hoc tetrabrometan.
Dng ra t l phn ng c a ti thit b kt tinh lm vic p sut thp hn p sut thit b phn ng. TPA c kt
tinh v lm lnh sn sng cho cc qu trnh x l tip theo lm vic iu kin gn vi iu kin mi trng. Dng TPA
kt tinh v lm lnh c chuyn ti thit b ly tm loi b nc, sau l ti thp lm kh bng dng khng kh nng
loi b hi m c mt trong sn phm. Tinh th TPA thu c t thp lm kh t tinh khit 99%. Sau n c vn
chuyn ti b cha v c a qua bc tinh ch sn phm.

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Tm hiu cng ngh sn xutpolyetylen terephtalat

Lp Lc Ha du K52
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Tm hiu cng ngh sn xut polyetylen terephtalat

Nc hnh thnh v mt s sn phm phu khng mong mun phi c loi b khi
dung mi axit axetic. Dng lng ra t my li tm c lm sch trong thp thp thu hi
dung mi tinh ch axit axetic. Sn phm nh ca thp thu hi dung mi l axit axetic
c lm sch v b sung thm lng axit axetic mi c tun hon li thp phn
ng, sn phm y thp thu hi dung mi c thu hi v ti sinh cht xc tc.
Cng ngh Amoco gm c cm thit b lm sch t c tinh khit yu cu
trc khi a vo qu trnh qu trnh polyme ha. Trong TPA th c tp cht cht chnh
l axit 4-formylbenzoic (trn 500ppm), ngoi ra cn c tp cht mu, lng d cht xc
tc kim loi v brom.
Cc tinh th c ha tan bi dng nc nng thc hin trong thit b c cnh
khuy. Dng ny c a ti l phn ng hydro ha chn lc. Dng hydro a t vo
thit b, tan trong hn hp dung mi nguyn liu. Ti y, axit 4-formyl benzoic b
hydro ha vi cht xc tc l Pd mang trn cht mang C, lng axit p-toluic c gim
xung trong di 25ppm. Cc tp cht c mu cng c hydro ha thnh sn phm
khng mu. Cht xc tc c chn lc cao m bo tn hao TPA thnh sn phm axit
cacboxylic v vng no nh hn 1%.
Sau phn ng, hn hp c chuyn ti cm thit b kt tinh, p sut thit b gim
dn. Cng vi s h nhit , cc tinh th TPA hnh thnh. Axit p-toluic ha tan v cc
tp cht khc cn li trong dung dch. Sau khi kt tinh, tinh th TPA c a ti thit b
ly tm loi nc v thit b sy kh loi m cho dng sn phm TPA dng bt.
III.1.2.

Cng ngh ca hng Eastman.

Qu trnh ny c chng minh rng rt ph hp cho sn xut PET dng si v

dng chai m khng b gii hn bi tnh cht c bit no. Nh hnh v, p-xyeln l
nguyn liu cho qu trnh, khng kh l tc nhn oxi ha v axit axetic l dung mi.
Phn ng xy ra di tc dng ca cht xc tc Co2+, Mn2+ v brom.
T l lng dung mi v hydrocacbon trong l phn ng l khong 3-5. Cht xc tc
thng chim 0,1-0,2% trng lng dung mi s dng. Nhit v p sut bn trong l
phn ng l 185-204oC v 1200-1750 kPa. Thi gian lu nh hn 1 gi chuyn ha
hon ton v hiu sut qu trnh t c khong 98,3%. Thm vo , nng lng sinh
ra t qu trnh ny c th t ti 10000kW.
B ra axit c dng nh b cha axit axetic cung cp lng axit thiu ht trong
dng nguyn liu vo, lng axit ny c a ti b cha cht oxi ha hi lu v b
lc trc khi vo thit b phn ng oxi ha. B lc c tc dng iu chnh nng axit
v cht xc tc. Cht xc tc, axit axetic v p-xylen c a ng thi ti thit b oxi
ha. Dung dch axit yu t cha cht oxi ha hi lu c bm phun vo nh thp oxi
ha ngn cn s hnh thnh cht rn. Thit b phn ng l dng tng si.

Nhm 5

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Page 16

Tm hiu cng ngh sn xutpolyetylen terephtalat

Hnh 3. Quy trnh cng ngh ca hng Eastman

Nhm 5

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K52

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Tm hiu cng ngh sn xutpolyetylen terephtalat

Thit b ly tm c dng tch tp cht t axit terephtalic th cng dng dung mi ngho thu c t thp loi nc. Dng ngho ny bao gm hn hp sn
phm nh ca thp oxi ha (nc, axit axetic v nito) v dung mi. Cc tp cht khng ha tan trong dung mi ny c loi b ti thit b ly tm. Sau CTA
(crude terephthalic acid) c tinh ch thnh EPTA (Eastman purified terephthlic acid) c thc hin hai thp oxi ha. Qu trnh oxi ha ny i hi phi tng
nhit tng chuyn ha ca CTA. TPA vi hm lng khng tinh khit thp thu c t qu trnh ny. Cui cng, TPA c a ti thit b kt tinh, c
chuyn ha thnh ETPA. ETPA c tch nhanh bnh chn khng v dung dch c thu hi v b cha cht oxi ha hi lu. Cui cng ETPA c a ti thit
b lc quay chn khng v thit b sy kh thu c sn phm cui cng.
Dng ra t thit b ly tm c a ti bnh tch nhanh dng thi (overflow flash drum) thu hi cht xc tc v lc x l loi tp cht ha tan v khng
ha tan v c cn CTA. Tp cht khng tan v cn CTA u c t chy trong thit b tng si ho c b chn lp trong bi rc thi cng nghip. Xc tc c hi
lu n b lc.
Dng hi ca nh thp loi nc c a vo thp bnh ngng. Kh tch ra c a n thit b ti sinh ti sinh oxi ha nhit hoc thp ra. Nc thi t b
nh ngng c a ti h thng x l nc.
III.2.

Cng ngh sn xut DTM

DTM l hp cht trung gian quan trng trong qu trnh sn xut PET c sn xut thng qua phn ng oxy este ha p-xylen.
COOH
ChLOH

COOCH
CH3OH

COOH
P-Xylene

p-Toluc acd

COOCH
Methyl
p-toluate

COOCH3
Dimethyl
terephthalate

COOH

COOH

H-,
0

COOCH
Mononmethyl
terephthalate

hL
O

COOCH3
Monomethyl

COOH
Terephthalic acid

terephthalate

u tin p-xylen b oxi ha bi oxi khng kh to ra axit p-toluic trong mt l phn

ng oxi ha. Sau axit p-toluic b este ha bi metanol to ra metyl p-toluic trong thit
b este ha. Metyl p-toluat c tch ra v c a li l phn ng oxi ha to thnh
mono metyl terephalat (MMT), sau li tin hnh phn ng este ha to DMT v a
i tinh ch. Cui cng DMT em i thy phn, qu trnh ny tri qua hai giai

Tm hiu cng ngh sn xutpolyetylen terephtalat

on, giai on u DMT b thy phn thu c MMT, sau MMT cng b thy phn to axit terephtalat cung cp cho qu trnh trng hp PET.
C nhiu cng ngh sn xut DMT thng qua qu trnh oxi-este ha. Sau y l mt s m t cng ngh sn xut DMT ca cc hng:
> Chemische Werke Witten Hercules
> Sulzer Chemtech H&G Hegmanns

III.2.1. Cng ngh ca hng Witten

Ba vng phn ng ng ch trong cng ngh ny l vng phn ng oxi ha, vng este ha, v vng tinh ch sn phm.
Phn ng oxi ha xy ra trong hai l phn ng mi tip nhau. Cht xc tc (Coban napthtalat) v p-xylen hi lu v metyl p-toluat c a vo thit b phn
ng vn hnh 140-170oC v 400-700 kPa. Thit b phn ng kt hp bin i axit toluic v metyl hydro terephtalat thnh este tng ng. Cht xc tc (toluen
sulfonic acid) c pha long bi metanol trc khi a vo thit b este ha vn hnh 200-250oC.
Dng ra t thit b phn ng este ha c a ti mt dy thit b chng ct. thp chng ct u tin sn phm nh thu c metanol v hn hp nc v
sau hn hp ny c ti thp loi nc, sn phm y l c a ti thp chng ct phn on este p sut chn khng. Metyl p-toluat v p-xylen d ra khi
nh thp ny v c quay tr li thit b phn ng oxi ha.
Dng ra bao gm terephtalat th, li c chng ct p sut chn khng loi b nhng thnh phn nng, sau dng sn phm ra khi thp c a ti
thit b kt tinh p sut chn khng s dng metanol lm dung mi. Tip theo dng sn phm li c kt tinh ln th hai hoc tip xc ngc dng vi metanol
lm sch hon ton.
DMT sau c a ti thit b tch ly tm v bnh khuy melting loi metanol d, v li c chng ct chn khng. Cui cng thu c sn phm DMT
tinh khit vi hiu sut 87%.

Tm hiu cng ngh sn xut polyetylen terephtalat

T
m
hi
u
c
ng
ng
h
s
n
xu
t
po
ly
et
yl
en
te
re
ph
tal

Nhm 5

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Tm hiu cng ngh sn xut polyetylen terephtalat

III.2.2.

Cng ngh ca hng H&G

Cng ngh ny c mt s im ni bt sau: hiu sut chuyn ha p-xylen cao, tht

thot nguyn liu t, tn dng nhit v nng lng ca qu trnh tng hiu sut.
Cng ngh ny thay i v tr np liu, h thng phn phi kh, v h thng iu
chnh sa i c c chuyn ha cao vi s hnh thnh sn phm ph l t nht.
Thc t, s ci tin quan trng nht trong qu trnh ny l vng tinh ch sn phm.
Ngoi ra H&G pht trin h thng chng ct bng cch tin hnh chng ct chn
khng s dng cu trc m bn trong.
Thay i cng ngh kt tinh sang dng kt tinh tan chy hn l kt tinh huyn ph c
tc dng lm gim chi ph u t v vn hnh. Kt tinh tan chy l tnh nng gip ci
thin c qu trnh bng cch loi b c bn l lng, cc my ly tm, bnh khuy v
cc b phn chuyn ng khc. B qua c vng ti ch metanol v nng lng cn
thit cho n. Kt qu l chuyn ha DMT vi tinh khit khng gii hn.
Sn xut DMT thng qu cc qu trnh thy phn cng c pht trin bi H& G
Hegmanns/Sulzer.Thy phn c thc hin 260-280C v 4500-5500 kPa.Este
metyl c thy phn,kt qu pha hi l hn hp metanol/H2O c a i ti ch
metanol.Metanol c ti sinh thu hi trn nh l phn ng este ha trong khi nc
quay tr li phn ng thy phn. Pha lng t l phn ng c a n mt dy thit b
kt tinh thu PTA,sau ly tm v sy kh c sn phm cui cng.
TPA thu c thng qua phn ng thy phn DMT c tinh khit cao.4cacbonbenzaldehyt v axit p-toluic c th c hi cho mt s qu trnh khc,c hai u
c th h xung mc ti thiu mt cch d dng.

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Tm hiu cng ngh sn xutpolyetylen terephtalat

Page 22

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Tm hiu cng ngh sn xut polyetylen terephtalat

Hnh 6. Quy trnh thy phn DMT ca hng H&G

IV. CNG NGH TRNG HP PET.

PET c th c sn xut t EG vi DMT hoc TPA. Nguyn liu ban u i hi tinh khit cao. Trong c hai trng
hp, bc u tin ca phn ng l s hnh thnh BHET nh mt tin polymer. Sau l phn ng trng hp (vi vic loi b
EG) hnh thnh nn PET. BHET cng c th c sn xut bi phn ng ca TPA vi ethylene oxide (ethoxylation) nhng
phng php ny khng ph bin.

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Tm hiu cng ngh sn xut polyetylen terephtalat

Este ha trc tip ca TPA v EG ban u khng c a chung v nhng kh khn trong vic tinh ch ca TPA do n c
ha tan thp v im nng ch y cao. Tuy nhin, vi nhng ci tin trong cng ngh, phng php este ha trc tip t
c tm quan trng. Hu ht cc nh my hin nay s dng TPA v n c nhng u im sau:
> Chi ph sn xut TPA thp hn so vi DMT
> Khi lng phn t ca TPA thp hn so vi DMT dn n chi ph tn cha thp hn
> C th s dng c nc thay v methanol lm tc nhn ngng t
> Khng yu cu xc tc cho qu trnh ester ha.
> PET c thu c vi cht lng cao do c hm lng thp nhm carboxyl cui mch v nhm diglycol lin kt.
Mc trng hp (th hin trng lng phn t polymer) l m t hm ca cc iu kin ca phn ng trng hp, n nh
hng ng k n cc thuc tnh ca nhato thnh. Khi chiu di phn t polymer tng ln, c hai trng lng phn t v
nht ca khi lng phn ng cng tng ln, do ch s nht thng c s dng nh cng c o trng lng phn t
polymer. Khi ngi ta mong mun khi lng phn t rt cao, nh l trng hp nha PET loi chai, s trng hp c th c
thc hin trong nhiu giai on, vi iu kin phn ng khc nhau c s dng trong tng giai on.

Khi bt u vi nguyn liu TPA, bc u tin trong chui trng hp l phn ng este ha ca 1 mol axit vi 2 mol ca
glycol. Nc c gii phng ra trong qu trnh. Bc t ph chnh trong cng ngh phn ng ny c lin quan n p sut
lm vic cao hn p sut kh quyn v nhit lm vic ln hn nhit im si ca glycol, t c thi gian phn ng
ngn hn. Nhit phn ng t 258oC n khong 263oC v nc ca phn ng c loi b khi h thng thng qua mt
thit b hi lu. Cng nghip vn hnh nhit cao v p sut cao hn p sut kh quyn hin nay gn nh ph dng (ph
bin).
Bc th hai trong chui phn ng trng hp l phn ng trng hp BHET v gii phng ca EG tun hon. Nhit
phn ng phi trn nhit nng chy ca polymer 260-265oC v di nhit m ti qu trnh phn hy xy ra nhanh
300oC, do nhit t 275oC v 290oC thch hp thc hin phn ng trng hp. Trong trng hp nhit cao, cn thit
gi polymer trong mt trng thi tan chy, v nht cao c th gy ra s bin cht ca polymer do cn b sung thm
triphenylphosphite l cht n nh thch hp.
Vic loi b hi glycol ( chn khng) khin cn bng dch chuyn v pha to sn phm ngng t. p sut ring phn
ca glycol trn polymer tan chy phi c gim xung cn di 6 mmHg.
Bi tc khuch tn ca sn phm ph EG trong polymer tan chy l tc gii hn gn cui ca phn ng, EG phi
c tch ra nh l mt cch nhanh nht c th. Phn ng trng hpc thc hin chn khng cao v bng cch khuy
Nhm 5

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Tm hiu cng ngh sn xut polyetylen terephtalat

trn dng tan chy mt cch lin tc

tng s tip xc b mt. Thi gian
ca phn ng l t nht hai gi
290oC, ph thuc vo loi l phn
ng s dng.

Nhiu cht xc tc c pht

trin c hiu qu trong phn ng
trng hp cng nh trong phn ng
este ha trc tip hoc phn ng
transeste ha. Trong s ny, cc hp
cht antimon (Sb), chng hn nh
trioxide hoc triaxetat, c dng
ph bin nht.
Cc quy trnh sau y s dng cc
l phn ng khc nhau v mt vi
Hnh 7. Cng ngh theo Invista
trong s chng ph thuc vo pha tan
chy, mt vi ci khc ph thuc vo trng thi rn. S trng hp pha tan chy l thng cho nht vo khong 0,60-0,65.
Polymer sau c chuyn i cc ht rn, kt tinh v trng hp trng thi rn nng cao ch s nht v trng lng
phn t hn na.
IV.1. IPT (Cng ngh thc hin theo Invista) Quy trnh NG3TM
Invista (trc y l DuPont) pht minh ra qu trnh NG3TM sn xut PET trong EG v TPA c np vo thit b
este ha sau , sn phm c este ha c trn vi EG v cht xc tc trong thit b phn ng dng hnh ng. Dng sn
phm l phn ng hnh ng li c np vo thp phn ng c thit k tng mc trng hp bng cch s dng mt
chu trnh khp kn, h thng tun hon nit cho php loi b cc h thng chn khng. Kt qutin polyme t c ch s
nht l 0,2 c a ti mt rotoformer (thit b quay c c l p dng cho pha tan chy) v cui cng sn phm ny c
dn ti thit b trng hp trng thi rn sn xut vin c ch s nht cao.
Nitrogen

Nh cp trn, NG3TM sn xutsn phm trung gianc ch s nht thp v sau c thc hin trng hp
trng thi rn hn trng thi tan chy to thnh ra sn phm trung gian c nht cao hn(thng khong 0,6-0,65). Cc
tnh nng mi ca cng ngh ny l s hnh thnh cc vin ngm(pastilles), m t hnh thc ca ht polymer rn c th c
trng hp tip trong thit b trng hp trng thi rn thng thng. Cc vin ngm c hnh thnh t polymer phn t thp
(mc trng hp t 20-30; ch s nht 0,23-0,28), v c mt cu trc tinh th duy nht iu ph gip cho qu trnh ch
bin tip theo.

IV. 2. Cng ngh Lurgi Zimmer DHI

Cng ngh DHI l qu trnh sn xut PET da trn cc phn ng este ha/ transeste ha ca TPA / DMT tinh khit vi EG.
Nh trong hnh, nguyn liu s dng l TPA tinh khit, TPA c trn ln vi EG v ch t xc tc thm vo, sau hn hp
c a vo thit b este ha. Dng vt cht c tch ra tthit b phn ng este ha / transeste ha c chuyn vo mt
thp thu hi nguyn liu u.
Cc sn phm t thit b este ha c a ti thit b phn ng tin trng hp, y phn ng c thc hin di p
sut chn khng. Chn khng c to ra bi mt h thng trong qu trnh sn xut EG. Sn phm ca thit b phn ng tin
trng hp c chuyn qua thit b phn ng cu i cng.

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Tm hiu cng ngh sn xut polyetylen terephtalat

Hnh 8. Cng ngh hng Lurgi Zimmer DHI

Phn ng trng hp xy ra p sut chn khng v nhit cao trong l phn ng trng hp pha rn. Polyester tan chy
thu c t l phn ng c x l trong mt h thng kt ht tch hp vi mt b phn kt tinh sn phm do cung cp cc
ht c ng u cao, khng bi. Nhng ht ny li c a qua thng qua m t phn xng dealhydization lm gim
nng axetandehyt.

IV. 3. Cng ngh Buhler (Ti ch PET)

Ngy nay, cc chai PET ch yu c ti ch cho cc ng dng k thut. V d nh hp ng thc phm, tuy nhin, cht
lng ca vt liu ti ch, c bit v phng din thm m , him khi tha mn yu cu. Cng ngh Buhler t chai n chai
x l chai sau khi s dng thnh mnh PET c ra sch bin i chng thnh loi vin chai.
Cng ngh ny g m bn giai on tiu biu cho sn xut PET lo i chai: kt tinh, , trng hp pha rn, v lm mt. Dng
nguyn liu khng kt dnh t qu trnh trng hp phn t lng thp c kt tinh b ng cch un nng trong tng si khng
kh ho c nito lm dng kh thi, nhit phi nh hn 185oC ngn chn qu trnh oxi ha.

Nhm 5

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Tm hiu cng ngh sn xut polyetylen terephtalat

Hnh 9. Cng ngh Buhler

Qu trnh c thc hin nng cao im chy ca tinh th ln gi tr cao hn, sau trng hp trng hp trng thi rn
nhm ngn chn qu trnh thiu kt. Lo i vm gia nhit trc c dng trong qu trnh tn dng b mt tip xc vi dng
nito nng tng nhit tinh th ln 210-220 oC. Tinh th sau c a vo thp trng hp trng thi rn, mc
trng hp tng ln, vin to thnh c lm lnh v tn cha.

Nhm 5

Lp Lc Ha du K52

Page 27

V. NH GI CNG NGH.
V.

1. nh gi cng ngh sn xut monome.

Di y l bng so snh u nhc im ca cc cng ngh:
WITTEN
H&G
Cng ngh sn
xut DMT
Hiu sut qu trnh tng i
cao (87%)
s Hiu sut phn ng p-xylen
cao
S tinh khit tng i cao
s Tht thot nguyn liu t s Tn
u im
dng nhit v nng lng ca
S Tiu tn t nhit lng
qu trnh s Gim thiu s thit b
trong qu trnh
s Gim s hnh thnh cc sn
phm ph
Tiu th nhiu in nng do s
s u t vo chi ph c nh ln
dng nhiu bm, my ly tm
Nhc im

Cng ngh sn
xut PTA
u im

Nhc im

AMOCO
s Hiu sut qu trnh cao
s Sn phm c tinh
khit cao.

s Tiu tn nhiu in
nng
s Cn nhiu thit b trong
cng ngh

EASTMAN
s tinh khit tng i cao.
Hiu sut phn ng
cao(98,3%)
S Sthit b t hn s Tn dng
nng lng t qu trnh

s S dng nhiu h thng b

cha, tn din tch hn s S thit
b trao i nhit nhiu

cng ngh giai on trc, s dng DMT l monome cho qu trnh trng hp PET,
cng ngh Witten c s dng. Tuy nhin, nhng ci tin trong cng ngh ca H&G
lm cho cng ngh ny c s dng rng ri hn.
Gn y, p dng cng ngh s dng monome l PTA nhiu hn, do nhng u im
ca PTA hn hn DMT nh trnh by phn trn. Cng ngh Amoco c s dng

ph bin nht t trc n nay. Cng ngh Eastman cng c u th ring em li hiu
qu cao, cng ngh ny c th tr thnh mt xu th mi.

IV. 2. nh gi cng ngh trng hp PET

Cng ngh

IPT Invista

Buhler

Lurgi Zimmer DHI

5
Thit b este ha
L phn ng ng
Thp phn ng
Rotoreformer
SSP

5
Thit b este ha
Tintrng hp
Kt tinh

SSP

6
Thit b este ha
Tintrng hp
SSP
S to ht
Kt tinh
Loi nc

ln hn 0,6

ln hn 0,6

0.86

Pha

Tan chy - SSP

Tan chy - SSP

Tan chy

Tn dng

N2 tun hon

Khng SSP

Cc bc

Chs nht

Mc d mt phn ln ca cc nh my trn ton th gii s dng SSP. C th nhn

thy rng cc cng ngh mi loi b c SSP s tt hn. Xu hng mi trong ngnh
cng nghip ny ang tm cch loi b cc SSP nh Lurgi Zimmer DHI.

KT LUN

Trn th gii cng nh Vit Nam, ngnh cng nghip Nha d cn non trso vi cc ngnh cng nghip lu i khc nh
c kh, in - in t, hocht, dt may v.v. nhng c s pht trin mnh m trong nhng nm gny. Ngnh Nha
vang tr thnh mt trong nhng ngnh cng nghip mi nhn trong k hoch pht trin kinh t.

Khi mt cng ngh mi ra i, lun c s ci tin, v u vit hn cng ngh trc nhm nhiu mc ch khc nhau nh
thu c hiu sut cao, sn phm c tinh khit hn, hay gim
trnh

sn

xut.

chi ph

vn hnh, tng li

nhun t

qu

iu

i hi cc k s cng ngh lun phi tm ti, i mi, ti u cc quy trnh ang c. Cn i vi cc nh u t, phi cp nhp
cc cng ngh hin i trn th gii, da trn nhiu yu t: nguyn liu, th trng, chi ph u t... la chn mt cng ngh
ph hp nht.

Trong bi tiu lun ny, nhm c nhng tm hiu v nha PET, mt loi vt liu rt thng dng ngy nay, v cc cng
ngh sn xut PET trong c cc phn ng tng hp, cht xc tc, cc quy trnh v iu kin vn hnh. V s b, nhm c
ci nhn tng th, nh gi c cc cng ngh sn xut PET.
TI LIU THAM KHO
1. Alain Chauvel, Gilles Lefebvre, Petrolchemical Processes technical and economic characteristics. Volume 2, 1989
2.

Th.S Nguyn Th Linh, Bi ging Cng ngh ha du v Ch bin polyme, lu hnh ni b.

3. Trn Quc Sn, ng Vn Liu, Nguyn Vn Tng , Gio trnh c s ha hc hu c (tp 3), Nxb i hc S Phm,
2007.

4. J.M.Iwasyk, J.A.Rakestraw, K.W.Leffew, ""Process for Polymerization of PolyesterOligmers" USP 5,811,496. Sep.
22,1998
5. John Scheirs, Timothy E. Long, Modern Polyesters: Chemistry and Technology ofPolyesters and Copolyesters,
Wily, Great Britain, 2003
6. http://www. sriconsulting. com
7. http://www.icis.com/v2/chemicals/
8. http://www.insidethebottle.org/
9. http://www.Echem-eg.com/
10. http://www.encyclopedia.com/doc/1G1-18592160.html