TEPZZ¥Z8Z_87B_T

(19)

(11) EP 3 080 187 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C08G 63/08 (2006.01) C08G 63/78 (2006.01)
06.09.2017 Bulletin 2017/36
(86) International application number:
(21) Application number: 14809056.6 PCT/EP2014/077076

(22) Date of filing: 09.12.2014 (87) International publication number:

WO 2015/086613 (18.06.2015 Gazette 2015/24)

(54) IMPROVED PROCESS FOR PRODUCING POLYLACTIDE

VERBESSERTES VERFAHREN ZUR HERSTELLUNG VON POLYLACTID
PROCESSUS AMÉLIORÉ POUR LA PRODUCTION DE POLYLACTIDE

(84) Designated Contracting States: • COSZACH, Philippe

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB B-7760 Escanaffles (BE)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • FERON, Marie-Astrid
PL PT RO RS SE SI SK SM TR B-7050 Erbisoeul (BE)
• DELRUE, Arnaud
(30) Priority: 10.12.2013 EP 13196404 B-7160 Piéton (BE)

(43) Date of publication of application: (74) Representative: Pronovem

19.10.2016 Bulletin 2016/42 Office Van Malderen
Avenue Josse Goffin 158
(73) Proprietor: Futerro S.A. 1082 Bruxelles (BE)
7760 Escanaffles (BE)
(56) References cited:
(72) Inventors: EP-A1- 2 607 399 US-A1- 2006 014 975
• PENU, Christian
F-59880 Saint Saulve (FR)
EP 3 080 187 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 3 080 187 B1

Description

[0001] The present invention relates to a process for the production of polylactide (PLA).
[0002] Particularly, the present invention relates to an improved process where the goal is to recover a maximum of
5 useful matters in order to recycle without loss and so significantly improving the global yield of the production process
of PLA when starting from lactic acid.

Background

10 [0003] Mainly two types of process have been described for the production of PLA; the first one consists in a direct
polycondensation of lactic acid, as described for instance in JP patent 733861; such type of process is limited by the
use of a solvent and the difficulty of removing water out of the reaction medium.
[0004] It is well known that in a second type of usual process for producing PLA starting from lactic acid, a significant
loss of products, including lactic acid, lactide, oligomers of lactic acid and similar, occurs at each step of the global
15 polymerization process; such steps may be summarized as follows: (i) oligomerization of lactic acids into oligomers, (ii)
cyclization of the oligomers into lactide species, (iii) purification of lactide to obtain a suitable grade to start the last step
which is the polymerization by ring opening of the purified lactide. Of course after this last step a devolatilization shall
take place to recover the non-converted lactide. US2006/14975 discloses a process for production of purified lactide
starting from an aqueous solution of lactic acid, including evaporation of water with formation of oligomers, depolymer-
20 ization to give lactide, condensation and then crystallization of the crude lactide product to give purified lactide.
[0005] EP2607399 discloses a process for producing a high molar mass polylactic acid, which comprises the following
steps: a) polycondensation, b) conversion of the polylactic acid of low molar mass obtained in step a) to a lactide, c)
separation of the volatile fractions, d) recrystallization of the lactide, e) polymerization of the recrystallized lactide pro-
ducing a high molar mass polylactic acid, f) devolatilization and g) recovery of the final polylactic acid product with a
25 high degree of purity.
[0006] Depending of the various processes for the production of PLA, it may be said that a lot of matters are lost all
along the achievement of the process, so decreasing considerably the overall yield of said process. Indeed, if we take
as a reference, a theoretical process without any recycling, the overall yield is as low as about 50% (molar).
It was therefore envisioned in the past to control certain partial recycling of streams issued from the step of evaporation
30 of water from the starting lactic acid aqueous solution, from the step of oligomerization and from the step of the cyclization
reaction; with such recycling operations, the overall yield has reached values as high as 75% (molar); however, even
with those efforts which have been made and described to recover and finally recycle such type of lost product, this is
not yet satisfactory to conduct an industrial process.
[0007] Therefore, there is a need for a process which enables not only to drastically reduce such loss of products, but
35 mainly to incorporate in a global process the implementation of the recovery of the lost products and a process to convert
such products to the starting monomer or its derivatives.
[0008] Therefore, the object of the present invention is to provide a process for the production of PLA wherein the
recovery of the oligomers of lactic acid, lactide, and catalytic residues as well are implemented in order to treat and
convert them into the starting monomer or its derivatives.
40 [0009] Another object is to recover the residues at each step of the process.
[0010] A further object is to treat the residues of lactic acid oligomers.
[0011] Another object is to implement the recovery and the recycle of the streams of lactic acid and water.
[0012] Another object is to provide a trans-esterification process to convert the oligomers residues with an alcohol.
[0013] Finally the process of the invention should also provide for treating the formed lactate compounds by hydrolysis
45 in order to recover the alcohol and the lactic acid or its derivatives.
[0014] At least one of these objectives is met by the process of the invention.

Detailed description

50 [0015] The process of the present invention is also described in view of the accompanying drawings where Figure 1
is representing the global flow sheet of a process for the production of PLA with the recovery steps and conversion steps
to the starting monomer.

DESCRIPTION OF THE GLOBAL PROCESS

55
[0016] The present invention provides an integrated process for the production of polylactide (PLA) comprising the
steps of:

2
 EP 3 080 187 B1

(1) Water evaporation from the lactic acid aqueous solution starting stream;
(2) Oligomerization of lactic acid and recycle of reaction water and unconverted lactic acid;
(3) Cyclization of the lactic acid oligomers and production of crude lactide and recycle of unreacted monomers,
catalytic residues and heavy products;
5 (4) Purification of the crude lactide and recycle of lactic acid, water, heavy components, catalytic residues and
impurities;
(5) Ring opening polymerization of the purified lactide and production of PLA;
(6) Purification of the PLA by devolatilization and recycle of non-reacted lactide; wherein

10 - recycle of step (2) comprises water, which is purged, and lactic acid which is recycled to reactor (20);
- recycle of step (3) is sent to trans-esterification reactor (80);
- recycle of step (4) comprising (i) the light components, is sent to reactor (20) the other part to the hydrolysis
reactor (90), and (ii) the heavy components stream is sent to trans-esterification reactor (80);
- recycle of step (6) is sent partially to step (4) and the rest is sent to trans-esterification reactor (80).
15
[0017] The first step of the process to produce PLA consists in the removal of water from the starting aqueous solution
of lactic acid (from 50 to 100% concentration) and the second step consists in the oligomerization of the lactic acid
monomers into oligomers of low viscosity and molecular weight, generally comprised between 400 and 5,000 Dalton,
in presence or not of a catalyst like for example a tin based catalyst. Typical temperature and pressure range for these
20 two steps are respectively 100°C to 200°C and 5 mbara to 500 mbara. The molecular weight was measured by chro-
matography by gel permeation compared to standard polystyrene in chloroform at 30°C.
From these first and second steps, the process of the invention provides for the recovery of water, non-reacted lactic
acid, oligomers of lactic acid.
The Applicant has noted that the residues of water and lactic acid are relatively pure, and therefore may be directly
25 recycled to the evaporation step or the oligomerization step.
The Applicant has found that such a recycling of lactic acid could represent up to 5-15% by weight of the incoming lactic
acid stream.
[0018] The oligomers coming from the step of oligomerization are then sent to the cyclization step which consists of
treating the oligomers in a cyclization reactor, in the presence of a usual catalyst for such reaction like a tin based
30 catalyst. From this third step, and besides the obtained crude lactide stream which will be sent to the purification, it is
necessary to recover the unreacted oligomers, the non volatile impurities, the high boiling point lactic acid oligomers,
the low molecular weight polylactic acid, having a molecular weight comprised between 2,000 and 8,000 Dalton, as well
as the heavy residues and the catalytic residues which all form the cyclization residues. Typical temperature and pressure
range for this step are respectively 200°C to 320°C and 5 mbara to 80 mbara.
35 These cyclization residues are sent back to the oligomerization step. However it is important to note that in order to
avoid dramatic accumulation of catalytic residues in the system as well as degradation by-products, a purge is absolutely
needed, which also contribute to the elimination of impurities giving rise to unwanted color. The products of the purge
are then sent to the trans-esterification reactor (80).
[0019] During the fourth step, which is the purification of the crude lactide stream which may comprise different types
40 of purification units like distillation means, crystallization means and analogs, it is recovered a light components stream
containing lactic acid and water which is divided into two sub-streams, the first, representing from 10 to 100% by weight
of the light components stream, is sent to the hydrolysis reactor (90) while the second, representing from 0 to 90% by
weight of the light components stream, is recycled to reactor (20), while a bottom stream, containing heavy oligomers,
lactide and impurities constituting stream will be recycled to the trans-esterification reactor (80).
45 [0020] The purified lactide is finally sent to the step of polymerization by ring opening to form PLA, having a molecular
weight comprised between 10,000 and 200,000 Dalton.
This polymerization step is followed by a devolatilization step to purify the obtained PLA and to recover unreacted
monomers and diluents as well as impurities.
[0021] The Applicants have now found that by operating the improved process of the invention, which comprises the
50 steps of the water evaporation, oligomerization, crude lactide production, purification of the crude lactide, polymerization
of the purified lactide by ring opening (ROP), devolatilization and the recovery of PLA, the improvement consists in:

(i) recovery water and lactic acid in steps evaporation, oligomerization, cyclization and purification, and sent them
back to step of evaporation and/or oligomerization,
55 (ii) recovery of oligomers of lactic acid, lactide, catalytic residues of steps cyclization, purification, and devolatilization
and sent them back to a trans-esterification reactor, where a trans-esterification reaction shall take place, and finally
(iii) send the so formed alkyl lactate to a hydrolysis step to recover the starting monomer.

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 EP 3 080 187 B1

[0022] According to the process of the present invention, the trans-esterification reaction may be operated in accord-
ance with known processes and under usual conditions; such a reaction may be achieved in one or more than one
reactors at a temperature comprised between 80 and 200°C and at a pressure comprised between the atmospheric
pressure and 10-50 bara and in the presence of a catalyst.
5 [0023] According to one embodiment of the process of the present invention, the recycle stream from cyclization (noted
step(3)) and the heavy components recycled from lactide purification (noted step(4)) and the part of stream coming from
devolatilization (noted step(6)) are collected and sent to the trans-esterification reactor (80) where the trans-esterification
reaction is conducted in one or more than one continuous stirred reactors working at a temperature ranging between
80 and 200°C, preferably between 100 and 180°C and at pressure ranging between 1 and 20 bara, preferably between
10 2 and 15 bara, and finally the recovery of a stream comprising alkyl lactate which is sent to the hydrolysis reactor (90).
[0024] Generally the catalyst is at least partially supplied with the flow recovered from the cyclization step coming from
the production of crude lactide stream.
With the trans-esterification reaction an alkyl lactate is formed and recovered which is further sent to a hydrolysis step
to finally recover the starting monomer.
15 [0025] Before being sent to the hydrolysis reaction, the crude alkyl lactate exiting the reactor (80) is first purified in
order to separate the lactate molecules from the heavier molecules. With this purification step, it is generally expected
to recover substantially 80 to 100% of the lactate molecules, based on the fed lactate molecules. Usually, to achieve
such a separation, the mixture coming out of the trans-esterification reactor (80) is first sent to a distillation step operated
under pressure of 0.01 to 4 bara preferably between 0.1 to 1 bara and at a temperature comprised between 40 to 180°C,
20 preferably between 60 to 150°C, said distillation step comprising one or more than one distillation columns or equivalent
apparatus, where it is recovered at one side, the light components like lactate molecules which are then sent to the
hydrolysis and on the other side the heavy components such as the catalytic residues, oligomers and the unreacted
products, which are partially recycled to reactor (80) for trans-esterification and the rest is purged and optionally treated
for example by filtration or decantation to separate the catalytic residues from the oligomers. These catalytic residues
25 can be sent back to trans-esterification and/or oligomerization and/or cyclization reactors as such or with an additional
treatment (e.g. drying).
The hydrolysis reactor (noted 90) is receiving, after distillation, the stream from the trans-esterification reactor as well
as the part of light components coming from the purification of lactide and which is directly sent to the hydrolysis reactor.
The hydrolysis reactor is then operated in accordance with the usual process to achieve such reaction and in accordance
30 with usual conditions.
The hydrolysis reaction may be summerized as follows:

Alkyle lactate + water → lactic acid + alcohol.

35 [0026] According to one embodiment of the present invention, this type of reaction is achieved either in batch or
continuously, and the reactor for such reaction may be realized generally in a reactive distillation column, a plug flow
reactor or a continuous stirred reactor system operated at a temperature comprised between 70 and 180°C, preferably
90 to 150°C and at a pressure comprised from 0.01 and 10 bara, preferably between atmospheric pressure and 3 bara.
The alcohol, which is most often an aliphatic alcohol having from 1 to 12 carbon atoms might be withdrawn from the
40 reaction medium in order to increase reaction efficiency. The hydrolysis reaction may be conducted in the presence of
a catalyst, which may be lactic acid itself.
The finally recovered lactic acid may be further concentrated and then recycled to the oligomerization reaction, or to the
upstage lactic acid production step.
[0027] The process of the invention has the unexpected advantage that it can recover all the residues which are
45 mentioned like water, lactic acid oligomers and lactide, that cannot be done in the previous processes, and therefore,
the process of the invention enables to reach very weak amount of lost products.
[0028] The overall process for producing PLA and taking into account the steps of the present invention to drastically
reduce the loss of products while recovering a maximum and recycling the products like water, lactic acid, oligomers,
catalytic residues at the different steps may be described in view of Figure 1 which represent a flow sheet of the process.
50 An aqueous solution of lactic acid is subjected to water elimination through evaporation. The eliminated water recovered
from reactor (20) which contains some lactic acid is then recycled to reactor (20), while the main flow coming out from
reactor (20) is sent to the oligomerization reaction in reactor (30). During said oligomerization reaction, some water,
lactic acid, which has not oligomerized are withdrawn from reactor (30) and after separation of the water, which is simply
purged, the remaining lactic acid is recycled to reactor (20).
55 [0029] The main flow coming out from reactor (30) is sent to the cyclization reactor (40) for the production of a crude
lactide stream. From reactor (40), a flow is withdrawn containing the unreacted oligomers, catalytic residues and heavier
products, said flow being sent to the trans-esterification reactor (80).
[0030] The crude lactide stream resulting from cyclization is then sent to purification of lactide and which is represented

4
 EP 3 080 187 B1

by reactors (50), comprising any well known apparatus used for such purification and comprising at least distillation
and/or melt crystallization means.
[0031] From purification step, represented by reactor (50), the light components lactic acid and water are recovered
and recycled to reactor (20), while part of it, which may be up to 100%, is sent to the hydrolysis reactor (90) where lactic
5 acid can act as catalyst of the hydrolysis reaction. Depending on lactic acid concentration in this stream and hydrolysis
process efficiency, the minimum content of the light components stream to be sent to the hydrolysis reactor evolves
between a few to several tens of percents.On the other hand the heavier components, the impurities and catalytic
residues withdrawn from purification step, represented by (50), are recovered and recycled to the trans-esterification
reactor (80).
10 [0032] The purified lactide is then sent to ring opening polymerization in reactor (60) and the obtained PLA is purified
in a devolatilization reactor (70).
From the devolatilization reactor (70) it is recovered and recycled the non reacted lactide which is withdrawn and recycled
partially to lactide purification or directly to the trans-esterification unit (80).
[0033] The process of the invention is further described by the following examples which are in no way limitative of
15 the scope of the invention.

Examples

Example 1
20
[0034] We started with 6,000Kg of an 88% aqueous solution of lactic acid.
[0035] This solution was subjected to water elimination by heating at a temperature of 100°C and under reduced
pressure of 250 mbara.
Water recovered was purged and the lactic acid recovered was recycled to reactor (20).
25 [0036] The concentrated lactic acid (100%) is sent to reactor (30) for oligomerization, which is operated at temperature
of 160°C and at a reduced pressure of 250 and down to 80 mbara, to produce oligomers of lactic acid having a molecular
weight of about 950 Dalton (comprised between 900 and 1,000 Dalton.).
[0037] From reactor (30) water is withdrawn and purged, while unreacted lactic acid is recovered and recycled to
reactor (20).
30 The oligomers formed in reactor (30) were then sent to the cyclization step in reactor (40).
[0038] The cyclization of the oligomers of lactic acid was achieved in the presence of Sn octanoate as catalyst, at a
temperature of 250°C and pressure of 10 mbara and enabled to produce a crude lactide stream.
[0039] From reactor (40), the unreacted oligomers, the catalytic residues as well as the heavier components were
withdrawn and the withdrawn flow was sent to the trans-esterification reactor (80).
35 [0040] The crude lactide stream coming out from reactor (40) was sent to the purification step of the crude lactide.
Said purification comprises, in the present example, melt crystallization means (50), from which the heavy components
withdrawn from melt-crystallization means (50) were recovered and sent to the trans-esterification reactor (80).
[0041] The obtained lactide was then subjected to ring opening polymerization in reactor (60) at a temperature of
185°C during 30 minutes in the presence of Sn octanoate and the obtained PLA is purified in a devolatilization reactor
40 (70) from which the non-reacted lactide was removed and recycled to lactide purification. In case of presence of catalytic
or other impurities, devolatilization stream can be sent to trans-esterification reactor (80).
[0042] We finally recovered PLA with an overall molar yield of 96%.

Example 2
45
[0043] By way of comparison a process has been conducted with the recycling as described in the prior art, meaning
at the evaporation step, at the oligomerization and cyclization steps. The overall molar yield obtained in said comparative
process was of 78%.

50
Claims

1. An integrated process for the production of polylactide (PLA) comprising the steps of:

55 (1) Water evaporation from the lactic acid aqueous solution starting stream;
(2) Oligomerization of lactic acid and recycle of reaction water and unconverted lactic acid;
(3) Cyclization of the lactic acid oligomers and production of crude lactide and recycle of unreacted monomers,
catalytic residues and heavy products;

5
 EP 3 080 187 B1

(4) Purification of the crude lactide and recycle of lactic acid, water, heavy components, catalytic residues and
impurities;
(5) Ring opening polymerization of the purified lactide and production of PLA;
(6) Purification of the PLA by devolatilization and recycle of non-reacted lactide;
5
wherein

- recycle of step (2) comprises water, which is purged, and lactic acid which is recycled to reactor (20);
- recycle of step (3) is sent to trans-esterification reactor (80);
10 - recycle of step (4) comprising (i) the light components stream, is sent to reactor (20) and/or to the hydrolysis
reactor (90), and (ii) the heavy components stream is sent to trans-esterification reactor (80);
- recycle of step (6) is sent partially to step (4) and the rest is sent to trans-esterification reactor (80).

2. Integrated process according to claim 1 wherein the recycles of step (3), the heavy components recycled from step
15 (4) and the recycles of step (6) are collected and sent to trans-esterification reactor (80) to be subject to trans-
esterification reaction under a pressure comprised between 1 and 20 bara and preferably 2 and 15 bara and at a
temperature comprised between 80 and 200°C, preferably between 100 and 180°C, and finally the recovery of a
stream comprising alkyl lactate which is sent to the hydrolysis reactor (90).

20 3. Integrated process according to claim 1 wherein the light components stream, containing lactic acid and water issued
from step (4) is divided into two sub-streams, the first, representing from 10 to 100% by weight of the light components
stream, is sent to the hydrolysis reactor (90) while the second, representing from 0 to 90% by weight of the light
components stream, is recycled to reactor (20).

25 4. Integrated process according to claims 1 and 2, wherein the heavy components recycled from step (4) and the
stream of alkyl lactate recovered from trans-esterification reactor (80) are collected and sent to the hydrolysis reactor
(90), to be subject to hydrolysis reaction under a pressure comprised between 0.01 and 10 bara, preferably between
1 and 3 bara, at a temperature comprised between 70 and 180°C, preferably between 90 and 150°C to recover
lactic acid or its derivatives.
30
5. Integrated process according to claim 4 wherein the stream of alkyl lactate exiting the reactor (80) is separated into
two streams through distillation means in order to recover, the first stream containing the light components (lactate,
alcohol and the like) to be sent to the reactor (90) and the second stream containing the heavy components (catalytic
residues, oligomers and the like) to be recycled to reactor (80) or purged, said distillation means being operated
35 under a pressure comprised between 0.01 bara and 4 bara, preferably between 0.1 and 1 bara, at a temperature
comprised between 40 and 180°C, preferably between 60 to 150°C.

6. Integrated process according to claim 5 wherein the catalytic residues contained in the purged heavy components
are optionally separated and treated before being sent back to trans-esterification reactor (80), and/or oligomerization
40 reactor (30), and /or cyclization reactor (40).

Patentansprüche

45 1. Integriertes Verfahren zum Herstellen von Polylactid (PLA), das die Schritte umfasst:

(1) Verdampfen von Wasser aus dem Ausgangsstrom wässriger Milchsäurelösung;

(2) Oligomerisieren von Milchsäure und Rückführen von Reaktionswasser und nicht umgewandelter Milchsäure;
(3) Cyclisieren der Milchsäureoligomere und Herstellen von rohem Lactid und Rückführen von nicht reagierten
50 Monomeren, katalytischen Resten und schweren Produkten;
(4) Reinigen des rohen Lactids und Rückführen von Milchsäure, Wasser, schweren Komponenten, katalytischen
Resten und Verunreinigungen;
(5) Ringöffnungspolymerisation des gereinigten Lactids und Herstellen von PLA;
(6) Reinigen des PLA durch Entgasen und Rückführen von nicht reagiertem Lactid;
55
wobei:

- die Rückführung von Schritt (2) Wasser, das gesäubert wird, und Milchsäure, das zum Reaktor (20) rückgeführt

6
 EP 3 080 187 B1

wird, umfasst;
- die Rückführung von Schritt (3) zum Umesterungsreaktor (80) gesendet wird
- die Rückführung von Schritt (4), die (i) den Strom leichter Komponenten umfasst, zum Reaktor (20) und/oder
zum Hydrolysereaktor (90) gesendet wird, und (ii) den Strom schwerer Komponenten umfasst, zum Umeste-
5 rungsreaktor (80) gesendet wird;
- die Rückführung von Schritt (6) teilweise zu Schritt (4) gesendet wird und der Rest zum Umesterungsreaktor
(80) gesendet wird.

2. Integriertes Verfahren nach Anspruch 1, wobei die Rückführungen von Schritt (3), die schweren Komponenten, die
10 aus Schritt (4) rückgeführt wurden, und die Rückführungen von Schritt (6) gesammelt und zum Umesterungsreaktor
(80) gesendet werden, um einer Umesterungsreaktion unter einem Druck zwischen 1 und 20 bar absolut und
vorzugsweise zwischen 2 und 15 bar absolut und bei einer Temperatur zwischen 80 und 200 °C, vorzugsweise
zwischen 100 und 180 °C, unterzogen zu werden, und schließlich Gewinnen eines Stroms, der Alkyllactat umfasst,
der zum Hydrolysereaktor (90) gesendet wird.
15
3. Integriertes Verfahren nach Anspruch 1, wobei der Strom leichter Komponenten, der Milchsäure und Wasser enthält
und aus Schritt (4) ausgegeben wird, in zwei Teilströme geteilt wird, wobei der erste, der 10 bis 100 Gew.-% des
Stroms leichter Komponenten darstellt, an den Hydrolysereaktor (90) gesendet wird, während der zweite, der 0 bis
90 Gew.-% des Stroms leichter Komponenten darstellt, zum Reaktor (20) rückgeführt wird.
20
4. Integriertes Verfahren nach Anspruch 1 und 2, wobei die schweren Komponenten, die aus Schritt (4) rückgeführt
werden, und der Strom von Alkyllactat, der aus dem Umesterungsreaktor (80) gewonnen wurde, gesammelt und
an den Hydrolysereaktor (90) gesendet werden, um einer Hydrolysereaktion unter einem Druck zwischen 0,01 und
10 bar absolut, vorzugsweise zwischen 1 und 3 bar absolut, bei einer Temperatur zwischen 70 und 180 °C, vor-
25 zugsweise zwischen 90 und 150 °C, unterzogen zu werden, so dass Milchsäure oder Derivate davon gewonnen
werden.

5. Integriertes Verfahren nach Anspruch 4, wobei der Strom von Alkyllactat, der aus dem Reaktor (80) austritt, durch
ein Destillationsmittel in zwei Ströme getrennt wird, um den ersten Strom zu gewinnen, der die leichten Komponenten
30 (Lactat, Alkohol und dergleichen) enthält, die zum Reaktor (90) zu senden sind, und den zweiten Strom zu gewinnen,
der die schweren Komponenten (katalytische Reste, Oligomere und dergleichen) enthält, die zum Reaktor (80)
rückzuführen oder zu säubern sind, wobei das Destillationsmittel unter einem Druck zwischen 0,01 bar absolut und
4 bar absolut, vorzugsweise zwischen 0,1 und 1 bar absolut, bei einer Temperatur zwischen 40 und 180 °C, vor-
zugsweise zwischen 60 und 150 °C, betrieben wird.
35
6. Integriertes Verfahren nach Anspruch 5, wobei die katalytischen Reste, die in den gesäuberten schweren Kompo-
nenten enthalten sind, optional getrennt und behandelt werden, bevor sie zurück zum Umesterungsreaktor (80)
und/oder Oligomerisationsreaktor (30) und/oder Cyclisierungsreaktor (40) gesendet werden.

40
Revendications

1. Procédé intégré de production de polylactide (PLA) comprenant les étapes suivantes :

45 (1) Évaporation de l’eau à partir du courant de départ constitué d’une solution aqueuse d’acide lactique ;
(2) Oligomérisation de l’acide lactique et recyclage de l’eau réactionnelle et de l’acide lactique non converti ;
(3) Cyclisation des oligomères d’acide lactique et production de lactide brut et recyclage des monomères n’ayant
pas réagi, des résidus catalytiques et des produits lourds ;
(4) Purification du lactide brut et recyclage de l’acide lactique, de l’eau, des composants lourds, des résidus
50 catalytiques et des impuretés ;
(5) Polymérisation par ouverture de cycle du lactide purifié et production de PLA ;
(6) Purification du PLA par dévolatilisation et recyclage du lactide n’ayant pas réagi ;

dans lequel
55
- le produit de recyclage de l’étape (2) comprend de l’eau, qui est purgée, et de l’acide lactique qui est recyclé
vers le réacteur (20) ; ;
- le produit de recyclage de l’étape (3) est envoyé vers le réacteur de trans-estérification (80) ;

7
 EP 3 080 187 B1

- le produit de recyclage de l’étape (4) comprenant (i) le courant de composants légers est envoyé vers le
réacteur (20) et/ou vers le réacteur d’hydrolyse (90), et (ii) le courant de composants lourds est envoyé vers le
réacteur de trans-estérification (80) ;
- le produit de recyclage de l’étape (6) est envoyé partiellement vers l’étape (4) et le reste est envoyé vers le
5 réacteur de trans-estérification (80).

2. Procédé intégré selon la revendication 1 dans lequel les produits de recyclage de l’étape (3), les composants lourds
recyclés à partir de l’étape (4) et les produits de recyclage de l’étape (6) sont collectés et envoyés vers le réacteur
de trans-estérification (80) pour être soumis à une réaction de trans-estérification sous une pression comprise entre
10 1 et 20 bara et de préférence entre 2 et 15 bara et à une température comprise entre 80 et 200 °C, de préférence
entre 100 et 180 °C, et pour finir la récupération d’un courant comprenant du lactate d’alkyle qui est envoyé vers le
réacteur d’hydrolyse (90).

3. Procédé intégré selon la revendication 1 dans lequel le courant de composants légers, contenant de l’acide lactique
15 et de l’eau provenant de l’étape (4), est divisé en deux sous-courants, le premier, représentant de 10 à 100 % en
poids du courant de composants légers, est envoyé vers le réacteur d’hydrolyse (90) tandis que le second, repré-
sentant de 0 à 90 % en poids du courant de composants légers, est recyclé vers le réacteur (20).

4. Procédé intégré selon les revendications 1 et 2, dans lequel les composants lourds recyclés à partir de l’étape (4)
20 et le courant de lactate d’alkyle récupéré à partir du réacteur de trans-estérification (80) sont collectés et envoyés
vers le réacteur d’hydrolyse (90), pour être soumis à une réaction d’hydrolyse sous une pression comprise entre
0,01 et 10 bara, de préférence entre 1 et 3 bara, à une température comprise entre 70 et 180 °C, de préférence
entre 90 et 150 °C, pour récupérer l’acide lactique ou ses dérivés.

25 5. Procédé intégré selon la revendication 4 dans lequel le courant de lactate d’alkyle quittant le réacteur (80) est séparé
en deux courants par des moyens de distillation afin de récupérer le premier courant contenant les composants
légers (lactate, alcool et autres) à envoyer vers le réacteur (90) et le second courant contenant les composants
lourds (résidus catalytiques, oligomères et autres) à recycler vers le réacteur (80) ou à purger, lesdits moyens de
distillation étant utilisés sous une pression comprise entre 0,01 bara et 4 bara, de préférence entre 0,1 et 1 bara, à
30 une température comprise entre 40 et 180 °C, de préférence entre 60 à 150 °C.

6. Procédé intégré selon la revendication 5 dans lequel les résidus catalytiques contenus dans les composants lourds
purgés sont facultativement séparés et traités avant d’être renvoyés vers le réacteur de trans-estérification (80)
et/ou le réacteur d’oligomérisation (30) et/ou le réacteur de cyclisation (40).
35

40

45

50

55

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EP 3 080 187 B1

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 EP 3 080 187 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• JP 733861 A [0003] • EP 2607399 A [0005]

• US 200614975 B [0004]

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