(12) United States Patent

Reimann
(54) PROCESS AND APPARATUS FOR
PRODUCING POLYETHYLENE
TEREPHTHALATE
(75) Inventor: Randolf Reimann, Alzenau (DE)
(73) Assignee: Zimmer AG, Frankfurt am Main (DE)
( *) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days.
(21) Appl. No.: 10/477,796
(22) PCT Filed: Apr. 30, 2002
(86) PCTNo.: PCT/EP02/04740
371 (c)(l),
(2), ( 4) Date: Apr. 23, 2004
(87) PCT Pub. No.: W002/096531
PCT Pub. Date: Dec. 5, 2002
(65) Prior Publication Data
US 2004/0171789 A1 Sep. 2, 2004
(30) Foreign Application Priority Data
May 25, 2001 (DE) ......................................... 101 25 678
(51) Int. Cl? ................................................ C08G 63/00
(52) U.S. Cl. ......................... 528/196; 526/65; 528/271;
528/272; 528/274; 528/483
(58) Field of Search ............................ 526!65; 528/271,
528/272, 274, 483
111111 1111111111111111111111111111111111111111111111111111111111111
US006864345B2
(10) Patent No.: US 6,864,345 B2
Mar.8,2005 (45) Date of Patent:
(56) References Cited
U.S. PATENT DOCUMENTS
3,109,834 A 11/1963 Seiner eta!.
3,469,618 A * 9/1969 Siclari eta!. .............. 159/48.2
3,545,520 A * 12/1970 Siclari et a!. .............. 159/4.04
4,146,729 A 3/1979 Shiffler eta!.
4,758,650 A 7/1988 Schulz
5,059,288 A 10/1991 Curry
5,236,558 A 8/1993 Buyalos et a!.
5,434,239 A * 7/1995 Bhatia ........................ 528/274
5,451,300 A 9/1995 Matros et a!.
5,562,834 A 10/1996 Bremer eta!.
OTHER PUBLICATIONS
John Brown Deutsche Engineering, PET Resin Technology
and Products, South Asia, Polyester & PET 96, Nov. 20 and
21, 1996, Mumbai, Indai.
* cited by examiner
Primary Examiner-Terressa Boykin
(74) Attorney, Agent, or Firm-Norris McLaughlin &
Marcus PA
(57) ABSTRACT
In a process of producing polyethylene terephthalate by
esterification of terephthalic acid with ethylene glycol and
polycondensation, the vapors formed are rectified, the liquid
phase is recirculated to the process, and the lower-boiling
components are condensed. To obtain an almost completely
stripped condensate, condensate is circulated and stripped
the same with air, and the exhaust air is subjected to a
catalytic oxidation.
8 Claims, 1 Drawing Sheet
U.S. Patent
Mar.8,2005
US 6,864,345 B2
22
16 17
10
12
9
7
FIGURE 1
US 6,864,345 B2
1
PROCESS AND APPARATUS FOR
PRODUCING POLYETHYLENE
TEREPHTHALATE
2
subject to considerable variations as a result of changing
concentrations of the organic components in the vapor
condensate. A buffer function does not exist. An improve-
ment of the recovery of ethylene glycol is only possible in
This is a 371 of PCT/EP02/104740 filed Apr. 30, 2002.
This invention relates to a process and an apparatus for
the continuous production of polyethylene terephthalate
(PET), wherein pure terephthalic acid is esterified with
ethylene glycol, then prepolycondensated and subsequently
polycondensated, the vapors formed being rectified, the
liquid phase substantially consisting of ethylene glycol
being recirculated to the production process, and the vapor
phase containing the lower-boiling components water,
acetaldehyde, 2-methyl-1,3-dioxolane, 1,4-dioxane and pos-
sibly acetic acid being condensed.
5 the case of the process of producing PET, in which the
stripped prepurified vapor condensate is subjected to a triple
reverse osmosis. But since sticky, oily masses frequently
occur in the vapor condensate, a blocking of the membranes
of the reverse osmosis takes place after some time, as is
10 assumed. Moreover, the combustion of the exhaust air of the
stripper in the heat transfer furnace provides a direct cou-
pling of the process of producing PET with the heat transfer
furnace, so that malfunctions occurring in the process have
a direct influence on the operation of the heat transfer
BACKGROUND OF THE INVENTION
15 furnace, and malfunctions in the heat transfer furnace have
a direct influence on the production of PET.
For the continuous production of PET, terephthalic acid is
used as raw material. The essential process steps include the
preparation of the raw materials, the esterification, the
20
prepolycondensation and the polycondensation. In detail,
terephthalic acid is mixed with ethylene glycol and a catalyst
to obtain a paste and is then supplied to the esterification.
Esterification is effected at atmospheric pressure by remov-
ing water. Prepolycondensation is effected under a vacuum.
25
Polycondensation is performed at an elevated temperature
and under an increased vacuum. The vapors containing
water, acetaldehyde, 2-methyl-1,3-dioxolane, 1,4-dioxane
and-in dependence on the catalyst used-acetic acid,
which are formed in this process, are rectified, the ethylene
30
glycol obtained as bottom product is recirculated to the
esterification stage, and the lower-boiling components are
discharged as top product and condensed. Due to the lower-
boiling 2-methyl-1,3-dioxolane, which is formed in the
production of PET from acetaldehyde and ethylene glycol
35
by removing water, relatively large amounts of ethylene
glycol are discharged indirectly in the top product. In the
presence of an excess of water, the 2-methyl-1,3-dioxolane
is again decomposed in dependence on the temperature, the
pH-value and the reaction time to obtain the starting com-
40
ponents acetaldehyde and ethylene glycol.
In the production of PET, an aliquot of the vapor con-
densate is usually recirculated to the rectification, and the
excess aliquot is stripped once by means of air, the major
part of the lower-boiling components being converted to the
45
gas phase. The vapor condensate prepurified in this way is
discharged for further treatment.
The exhaust air streams obtained during the production of
PET are supplied to the air blower for stripping the excess
vapor condensate. The exhaust air of the stripping process,
50
which is laden with lower-boiling components, is supplied to
a heat transfer furnace for thermal combustion.
According to a lecture of John Brown Deutsche
Engineering, PET Resin Technology and Products, South
Asia, Polyester & PET 96, Nov. 20 and 21, 1996, Mumbai, 55
India, the entire vapor condensate is stripped once with inert
gas when producing polyethylene terephthalate. By means
SUMMARY OF THE INVENTION
It is the object to develop the above-described process of
producing PET such that the initial loading with organic
components of the condensate formed during the rectifica-
tion of the vapors is stripped to a residual loading and the
condensate can thus easily be charged to a biological waste
water treatment. Furthermore, there should be achieved a
distinct reduction of the losses of ethylene glycol.
The solution of this object consists in that the vapor
condensate is circulated and stripped at the same time and
part of the stripped condensate is discharged. By circulating
the vapor condensate, the range of variation of the concen-
tration of the organic components of the vapor condensate is
reduced considerably and thus evened out in the exhaust air
of the stripper.
DETAILED DESCRIPTION
With a dwell time of the circulating vapor condensate in
the stripping column of about 60 min, the 2-methyl-1,3-
dioxolane is decomposed almost completely into its starting
substances acetaldehyde and ethylene glycol, and thus eth-
ylene glycol is recovered. Stripping the vapor condensate is
expediently effected at temperatures of 45 to 70 C.
In accordance with the particular aspect of the process of
the invention, the exhaust air of the stripping process, which
has a high loading of organic components, is oxidized
catalytically and then discharged to the atmosphere. More-
over it is also possible to catalytically oxidize exhaust air
streams, which are loaded with organic ingredients as a
result of the process of producing PET, along with the
exhaust air of the stripping process. The advantages of the
catalytic oxidation of the organically loaded exhaust air
streams consist in extremely short exhaust air supply lines,
in relatively low operating temperatures and in the mainte-
nance of the usually prescribed emission limit values.
The apparatus for the catalytic oxidation of the exhaust air
streams comprises a heat exchanger, in which the exhaust air
having a temperature of 45 to 70 C. is heated to a tem-
perature of 280 to 320 C., and a reactor including a catalyst,
in which reactor the organic components contained in the
exhaust air are oxidized for more than 99% to obtain carbon
of a three-stage reverse osmosis, a water/ethylene glycol
mixture as concentrate and water as permeate are then
produced from the prepurified vapor condensate. The con-
centrate is recirculated to the process of producing PET, and
the permeate is used as demineralized water. The exhaust air
60
dioxide and water.
of the stripper and the exhaust air of the condensers of the
process columns are combined and by means of a blower
supplied to the heat transfer furnace for thermal combustion. 65
It is disadvantageous that in the above-described pro-
cesses the composition of the exhaust air of the stripper is
BRIEF DESCRIPTION OF THE DRAWINGS
The process in accordance with the invention is repre-
sented in the drawing by way of example as a flow diagram
and will subsequently be explained in detail.
Through line (1), the vapor condensate of the stripping
column (3) having a plurality of packed beds (2), which has
US 6,864,345 B2
3
been withdrawn at the head of a rectification column not
represented here, is supplied to the upper part of said
stripping column. For expelling the dissolved organic com-
ponents contained in the vapor condensate, stripping air is
blown into the lower part of the stripping column (3) through 5
line (4) by means of the blower (5) and guided countercur-
rently with respect to the vapor condensate. The stripped
vapor condensate is withdrawn at the bottom of the stripping
column (3) and again charged to the upper part of the
stripping column (3) through line (6) by means of the liquid 10
pump (7). By means of the heat exchanger (8) disposed in
line ( 6), the temperature of the circulating stripped vapor
condensate is adjusted to the desired value. An aliquot of the
stripped vapor condensate is withdrawn from line (6)
through line (9) and supplied to the rectification column as 15
reflux. Furthermore, excess stripped vapor condensate is
discharged from line (6) through line (10) and upon flowing
through the cooler (11) supplied to a further treatment.
Smaller exhaust air streams obtained in the plant for pro-
ducing polyethylene terephthalate are combined and through 20
line (12) added to the stripping air flowing in line ( 4). The
exhaust air streams of vacuum pumps and of the condenser
of the rectification column are sucked in by means of the
blower (13) and through line (14) combined with the exhaust
air of the stripping column flowing in line (15). This exhaust 25
air containing organic components and having a temperature
of about 60 C. is supplied to a heat exchanger (18) by
adding fresh air blown in through line (16) by means of the
blower (17) and is heated to a temperature of about 300 C.
Upon flowing through a start-up heater (19), the laden 30
exhaust air is supplied to the oxidation plant (20), in which
the organic components contained in the exhaust air are
oxidized for more than 99% to obtain carbon dioxide and
water. Through line (21), the purified exhaust air having an
average temperature of 500 C. leaves the oxidation plant 35
(20), flows through the heat exchanger (18), in which the
temperature is reduced to about 250 C., and is discharged
to the atmosphere through the chimney (22). The purified
exhaust air only contains trace amounts of organic ingredi-

EMBODIMENT
In the production of 300 t PET/day, 5.75 m
3
/h vapor
condensate from the rectification column are charged to the 45
stripping column (3) through line (1) with a temperature of
93 C. The vapor condensate comprises:
1.88 kgih
0.63 kgih
4
-continued
methyl dioxolane, and
ethylene glycol.
The total exhaust air stream, comprising
1813.00 kgih
276.00 kgih
32.50 kgih
1.25 kgih
1.25 kgih
air
water
acetaldehyde
1,4-dioxane
acetic acid
flows through line (15) and the oxidation plant (20) to the
chimney (22). The exhaust air discharged to the atmosphere
only contains 5 mg/Nm
3
organic carbon (TA
mg/Nm
3
), 1 mg/Nm
3
carbon monoxide (TA
mg/Nm
3
) and 2 mg/Nm
3
nitrogen oxides (TA
mg/Nm
3
), so that the emissions contained in the exhaust air
clearly lie far below the specified emission limit values of
the TA air. TA air means "Technische Anleitung zur Rein-
haltung der Luft'' (technical instructions for the prevention
of air pollution) and constitutes an administrative regulation
of the "Bundesimmissionsschutzgesetz" (Federal Immission
Protection Act) in the version of Feb. 27, 1986, which
contains emission and immission limit values.
2.25 m
3
!h of the stripped vapor condensate flowing out at
the bottom of the stripping column (3) are discharged from
the plant for producing PET through line (10), and 3.22 m
3
!h
are supplied as reflux to the rectification column through line
(9). The stripped vapor condensate still contains
0.1 gil
n.n.
3.5 gil
0.3 gil
0.7 gil
acetaldehyde
methyl dioxolane
ethylene glycol
1,4-dioxane
acetic acid
The stripped vapor condensate can be processed in a
biological processing plant and only has a negligeable toxic
effect.
What is claimed is:
1. A process for the continuous production of polyethyl-
ene terephthalate, in which terephthalic acid is esterified
with ethylene glycol, thereafter prepolycondensated and
subsequently polycondensated, the vapors formed being
rectified, the liquid phase substantially consisting of ethyl-
5.0 gil
1.8 gil
4.0 gil
0.4 gil
0.8 gil
acetaldehyde
methyl dioxolane
ethylene glycol
1,4-dioxane
acetic acid, rest water
50 ene glycol being recirculated to the production process, and
the vapor phase containing the lower-boiling components
acetaldehyde, 2-methyl-1,3-dioxolane, 1,4-dioxane and
which also may contain acetic acid being condensed,
wherein the vapor condensate is circulated, stripped with air,
55 and an aliquot of the stripped vapor condensate is dis-
charged.
The exhaust air having a temperature of 64 C., which
flows out of the stripping column (3) charged with 1813 kg/h
fresh air through line ( 4), is combined with the exhaust air
stream having a temperature of 53 C., which originates
60
from other sources and is sucked in through line (14), and
which contains
2. The process as claimed in claim 1, wherein an aliquot
of the stripped vapor condensate is supplied as reflux to the
rectification.
3. The process as claimed in claim 1, wherein the dwell
time of the vapor condensate in the stripper is about 60 min.
4. The process as claimed in claim 1, wherein the vapor
condensate is stripped at temperatures of 45 to 70 C.
50.00 kgih
2.50 kgih
nitrogen
acetaldehyde
5. The process as claimed in claim 1, wherein the exhaust
65 air of the stripping process, which is laden with the lower-
boiling components, including acetaldehyde, is subjected to
a catalytic oxidation.
US 6,864,345 B2
5
6. The process as claimed in claim 1, wherein process
exhaust air laden with organic components, including acetal-
dehyde and 2-methyl-1,3-dioxalane, is combined with the
exhaust air of the stripping process.
7. The process as claimed in claim 1, wherein the reflux
of the stripping process is guided cocurrently with respect to
the inflow of the vapor condensate.
6
8. An apparatus for performing the process as claimed in
any of claims 1 to 7, wherein a heat exchanger, through
which the laden exhaust air of the stripping process can flow,
and a reactor including a catalyst for the catalytic oxidation
s of the exhaust air laden with organic components.
* * * * *