WO2012016580A1 - The novel biodegradable polymer process - Google Patents
The novel biodegradable polymer process Download PDFInfo
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- WO2012016580A1 WO2012016580A1 PCT/EP2010/061168 EP2010061168W WO2012016580A1 WO 2012016580 A1 WO2012016580 A1 WO 2012016580A1 EP 2010061168 W EP2010061168 W EP 2010061168W WO 2012016580 A1 WO2012016580 A1 WO 2012016580A1
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- Prior art keywords
- lactate
- lactide
- stage
- reactor
- culture medium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/56—Lactic acid
Definitions
- This invention relates to an advantageous process for making a
- biodegradable polymer on the basis of lactic acid obtained by
- microbiological conversation that can be used for production of packaging materials and biomedical products.
- the invention relates in addition with associated process equipment.
- Lactic acid is derived from culture medium in the form of ammonium lactate and the process is also accompanied by separation of other by-product acids, such as acetic acid.
- the biodegradable polymer process comprises a number of consecutive stages (see Fig. 2). Brief Description of Drawings
- Figure 1 illustrates the biodegradable polymer process flow diagram
- Figure 2 illustrates the installation diagram of the equipment for carrying trough the method according to the present invention.
- Fermentation is conducted in reactor R1.
- a membrane reactor is charged with starch (saccharification needed), molasses or other saccharides originated feedstock and the process is conducted with ammonia solution adding for pH adjustment of the reaction medium to obtain ammonium lactate solution.
- reactor R2 is charged with filtered-off calcium lactate
- butyl lactate solution in butanol is transferred to still R3 of rectification column CM by pump P3.
- butanol is returned to reactor R1 while butyl lactate is transferred to oligomerisation reactor R3.
- Reactor R4 is charged with butyl lactate and a catalyst (SnCI 4 ) to
- HOCH(CH 3 )COOC 4 H 9 HOCH(CH 3 )CO[OCH(CH3)CO]n-iOC 4 H9 +(n-1 )C 4 H 9 OH
- toluene is added to reactor R5 for recrystallisation of raw lactide from it. Lactide precipite is separated from mother solution at filter F2.
- the recrystallised monomer is charged into column CI2 and process temperature is then gradually increased to 90°C at the rate of 5°C per minute. The liquid phase containing impurities is drained from the column. The purified monomer is melted and pumped to polymerisation reactor R6.
- octoate octoate
- polymerisation in the melt is conducted at 180-200°C.
- hot water is supplied to condenser C5
- the reactor pressure is reduced to 2 mm Hg and the unreacted part of the monomer is stripped.
- lactide stripping the melted polymer is drained from the reactor and routed for processing or granulation.
- Example 1 Fermentation [0021] Reactor R1 (reaction space makes 700 litres) is charged with 70 kg of glucose dextrose, saccharose or other sugars derived by hydrolysis or fermentolysis of plant raw materials (e.g. grain, etc.) for autoclaving. Then added nitrate source - 1.5 kg of peptone (yeast extract, etc.). Thereafter, lactic acid bacteria are introduced into the fermentation reactor cooled to 37°C. The cultivation process is conducted at 37°C, pH being strictly controlled at 7.0 by ammonia during 90 min. The fermentation process yield is 75.5 kg of ammonium lactate (which is equivalent to 64 kg of lactic acid).
- Reactor R2 is charged with 500 kg of culture medium containing 150 g/l of ammonium lactate, the mixer is activated and the reactor pressure is reduced to 0.02 MPa. Water supply to condenser C2 is then turned on. The reactor temperature is gradually increased to 80°C so that water removal is ensured. The concentration process lasts until obtaining about 250 kg of distillation product in the reactor receiver.
- butanol Upon stripping at rectification column, butanol is returned to reactor R2 while butyl lactate is transferred to oligomerisation reactor R4. Butyl lactate yield is 77.2 kg (80%).
- Reactor R4 is charged with 77.2 kg of butyl lactate and 0.7 kg of tin
- Reactor R4 is charged with 41.7 kg of oligomer with a polycondensation degree of >8. Hot water is then supplied to jacket of condenser C4. The reactor pressure is reduced to 1 -4 kPa and the products are stripped to reactor R5 at 190°C to 230°C. The yield of depolymerisation products is 41.3 kg (99%).
- reactor R5 Upon depolymerisation, reactor R5 is charged with 40 kg of toluene and heated to 100°C with mixing. Mixing lasts for 20 minutes, whereupon water is supplied to the reactor jacket. The solution is cooled to 30°C with continuous mixing. The formed lactide suspension is transferred to filter F2 by pump P4. The re-crystallised monomer is charged into column CI2 and process temperature is then gradually increased to 90°C at the rate of 5°C per minute. The liquid phase containing impurities is drained from the column. The purified monomer is melted and pumped to polymerisation reactor R6.
- the total yield of purified lactide is 35 kg (lactide yield makes 85%, purity degree being 99.99%).
- Reactor R6 is charged with 35.0 kg of lactide, 0.09 kg of catalyst (tin
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention relates to an advantageous method for making a biodegradable polymer that can be used for production of packaging materials and biomedical products whereas the method comprises the step of fermentation of starch, saccharose and/or similar carbohydrate feedstock for preparing ammonium lactate; thereafter synthesis of lactate ester from calcium lactate derived from culture medium containing ammonium lactate; followed by catalytic polycondensation of lactate ester to form oligomer; and thereafter depolymerisation of oligomer for preparing lactide and catalytic polymerisation of lactide for preparing polylactic acid.
Description
Description
The novel biodegradable polymer process
Technical Field
[0001] This invention relates to an advantageous process for making a
biodegradable polymer on the basis of lactic acid obtained by
microbiological conversation that can be used for production of packaging materials and biomedical products. The invention relates in addition with associated process equipment.
Background Art
[0002] The prior art US patent US 6569989 B (OHARA HITOMI) 19.09.2002 in the field of deriving lactide and polylactic acid from lactic acid obtained by fermentation comprises the following four stages of polymer synthesis:
• synthesis of lactate ester from ammonium lactate;
• catalytic polycondensation of lactate ester to form oligomer;
• depolymerisation of oligomer for preparing lactide;
• polymerisation of lactide for preparing polylactic acid.
[0003] Essential disadvantages of the prior art:
1. Lactic acid is derived from culture medium in the form of ammonium lactate and the process is also accompanied by separation of other by-product acids, such as acetic acid.
2. There is a need for esterification of concentrated culture medium which is accompanied by formation of additional by-products, such as ethyl acetate, and brings about excess consumption of alcohol;
3. There is a need for fine purification of ethyl lactate prior to
oligomerisation stage.
[0004] The mentioned disadvantages can be eliminated by using the developed method (see Fig. 1 ). The selective separation of lactic acid in the form of calcium lactate makes it possible to obtain a higher-purity alkyl lactate at the esterification stage and cut down alcohol consumption. Calcium compounds and butanol formed during esterification are recyclable.
Disclosure of Invention
[0005] The biodegradable polymer process comprises a number of consecutive stages (see Fig. 2).
Brief Description of Drawings
[0006] The novel biodegradable polymer process on the basis of lactic acid
obtained by microbiological conversion and its associated process equipment is described in detail with references to the accompanied drawings where:
[0007] Figure 1. illustrates the biodegradable polymer process flow diagram
according to the present invention, and
[0008] Figure 2. illustrates the installation diagram of the equipment for carrying trough the method according to the present invention.
Best Mode for Carrying Out the Invention
[0009] 1. Fermentation is conducted in reactor R1. For fermentation, a membrane reactor is charged with starch (saccharification needed), molasses or other saccharides originated feedstock and the process is conducted with ammonia solution adding for pH adjustment of the reaction medium to obtain ammonium lactate solution.
HOCH(CH3)COOH + NH3 = HOCH(CH3)COONH4
[0010] 2. Pre-concentration of culture medium to ammonium lactate content in interval of 40 to 60% by vacuum removal of water under heating is accomplished in reactor R2. Then, calcium lactate is separated by adding calcium salts and bringing pH to 6.5-4.0.
2HOCH(CH3)COONH4+ Ca++ = Ca(HOCH(CH3)COO)2 + 2 NH4 +
NH4 + + OH" = NH3 + H2O
[001 1] Calcium lactate precipitation is separated from mother solution at filter F1.
Thereafter, reactor R2 is charged with filtered-off calcium lactate
precipitation, equimolar quantity of strong hydrochloric acid and a 2-fold molar excess of butanol for subsequent boiling of the mixture under reflux (C1 ).
Ca(HOCH(CH3)COO)2 + 2 HCI = CaCI2 + 2 HOCH(CH3)COOH
HOCH(CH3)COOH + C4H9OH = HOCH(CH3)COOC4H9 + H2O
[0012] Upon esterification, the reaction mass is cooled, washed with a small
amount of water and the organic layer is separated. The reflux condenser C1 is cut off, water supply to condenser C2 is turned on and water removal
from the organic layer in the form of water/butanol azeotrope is
accomplished.
[0013] Water layer containing chloride, calcium lactate and butanol is routed to process stage I.
[0014] Upon water removal, butyl lactate solution in butanol is transferred to still R3 of rectification column CM by pump P3. Upon stripping at rectification column, butanol is returned to reactor R1 while butyl lactate is transferred to oligomerisation reactor R3.
[0015] 3. Reactor R4 is charged with butyl lactate and a catalyst (SnCI4) to
conduct oligomerisation with heating up to 180-220°C and butanol stripping.
n HOCH(CH3)COOC4H9 = HOCH(CH3)CO[OCH(CH3)CO]n-iOC4H9 +(n-1 )C4H9OH
[0016] 4. At oligomer polycondensation degree of >8, the reactor pressure is
reduced to 1 -4 kPa, hot water is supplied to jacket of condenser C4 and lactide is stripped to reactor R5.
2HOCH(CH3)CO[OCH(CH3)CO]n-iOC4H9 = (n-1 )[OCH(CH3)CO]2 + 2 HOCH(CH3)COOC4H9
[0017] Upon depolymerisation, toluene is added to reactor R5 for recrystallisation of raw lactide from it. Lactide precipite is separated from mother solution at filter F2. The recrystallised monomer is charged into column CI2 and process temperature is then gradually increased to 90°C at the rate of 5°C per minute. The liquid phase containing impurities is drained from the column. The purified monomer is melted and pumped to polymerisation reactor R6.
[0018] 5. The reactor loaded with monomer melt is charged with catalyst (tin
octoate) and polymerisation in the melt is conducted at 180-200°C. When the reaction is over, hot water is supplied to condenser C5, the reactor pressure is reduced to 2 mm Hg and the unreacted part of the monomer is stripped. Upon lactide stripping, the melted polymer is drained from the reactor and routed for processing or granulation.
[0019] The invention is illustrated bv the following examples.
[0020] Example 1. Fermentation
[0021] Reactor R1 (reaction space makes 700 litres) is charged with 70 kg of glucose dextrose, saccharose or other sugars derived by hydrolysis or fermentolysis of plant raw materials (e.g. grain, etc.) for autoclaving. Then added nitrate source - 1.5 kg of peptone (yeast extract, etc.). Thereafter, lactic acid bacteria are introduced into the fermentation reactor cooled to 37°C. The cultivation process is conducted at 37°C, pH being strictly controlled at 7.0 by ammonia during 90 min. The fermentation process yield is 75.5 kg of ammonium lactate (which is equivalent to 64 kg of lactic acid).
[0022] Example 2. Calcium Lactate Preparation
[0023] Reactor R2 is charged with 500 kg of culture medium containing 150 g/l of ammonium lactate, the mixer is activated and the reactor pressure is reduced to 0.02 MPa. Water supply to condenser C2 is then turned on. The reactor temperature is gradually increased to 80°C so that water removal is ensured. The concentration process lasts until obtaining about 250 kg of distillation product in the reactor receiver.
[0024] Water supply to the reactor jacket is then turned on and the reactor is cooled to 30°C. The reactor pressure is increased to the atmospheric value and the reactor is charged with 180 kg of solution containing 340 g/l of calcium chloride. The formed suspension is transferred to filter F1 by pump P2. The output product amounts to 140 kg of calcium lactate precipitation, water content being about 50% (69.4 kg on a dry basis, 90% yield).
[0025] Example 3. Butyl Lactate Preparation
[0026] The calcium lactate precipitation containing 69.4 kg of basic substance is charged into reactor R2 along with 74.0 kg of strong hydrochloric acid, 20.0 kg of water and 450.0 kg of butanol. Water supply to condenser C1 is then turned on and the mixture is boiled for 2 hours. Then, condenser C1 is cut off, water supply to condenser C2 is turned on and water removal in the form of water/butanol azeotrope takes place for 3 hours.
[0027] Upon esterification, water supply to the reactor jacket is turned on, the reactor is cooled to 30°C and charged with 100.0 kg of water with subsequent mixing for 5 minutes. Upon phase separation, the organic
layer is separated. Water layer containing chloride, calcium lactate and butanol is routed to process stage I.
[0028] Upon separation of water layer, water removal from the organic layer in the form of water/butanol azeotrope is conducted in reactor R2. Upon water removal in the separation vessel, butyl lactate solution in butanol is transferred to still R3 of rectification column CM by pump P3.
[0029] Upon stripping at rectification column, butanol is returned to reactor R2 while butyl lactate is transferred to oligomerisation reactor R4. Butyl lactate yield is 77.2 kg (80%).
[0030] Example 4. Oligomer Preparation
[0031] Reactor R4 is charged with 77.2 kg of butyl lactate and 0.7 kg of tin
chloride (IV). Water supply to condenser C4 is then turned on. The mixer is activated and the reactor temperature is increased to 180°C. The butanol stripping process is conducted with gradual increase of
temperature to 210°C during 10 hours until oligomer polycondensation degree of >8. Oligomer yield is 41.7 kg (99%).
[0032] Example 5. Lactide Preparation
[0033] Reactor R4 is charged with 41.7 kg of oligomer with a polycondensation degree of >8. Hot water is then supplied to jacket of condenser C4. The reactor pressure is reduced to 1 -4 kPa and the products are stripped to reactor R5 at 190°C to 230°C. The yield of depolymerisation products is 41.3 kg (99%).
[0034] Upon depolymerisation, reactor R5 is charged with 40 kg of toluene and heated to 100°C with mixing. Mixing lasts for 20 minutes, whereupon water is supplied to the reactor jacket. The solution is cooled to 30°C with continuous mixing. The formed lactide suspension is transferred to filter F2 by pump P4. The re-crystallised monomer is charged into column CI2 and process temperature is then gradually increased to 90°C at the rate of 5°C per minute. The liquid phase containing impurities is drained from the column. The purified monomer is melted and pumped to polymerisation reactor R6.
[0035] The liquid phase from column CI2 is combined with mother lactide solution in toluene and subjected to concentration under heating and repeated
re-crystallisation from toluene in reactor R5. Thereafter, the re-crystallised monomer is once again charged into column CI2 and purified as described above.
[0036] The total yield of purified lactide is 35 kg (lactide yield makes 85%, purity degree being 99.99%).
[0037] Example 6. Polymer Production
[0038] Reactor R6 is charged with 35.0 kg of lactide, 0.09 kg of catalyst (tin
octoate) and is then heated to 100°C. Upon monomer melting, the mixer is activated and the reaction mass temperature is increased to 180°C. As viscosity grows, the temperature is increased to 200°C during 5 hours. After the reaction is over, hot water is supplied to condenser C5, the reactor pressure is reduced to 2 mm Hg and the nonreacted part of the monomer is stripped. Upon lactide stripping, the polymer melt is drained from the reactor and routed for processing or granulation.
Claims
1. The method of biodegradable polymer process comprising the following
stages:
1 ) fermentation of starch, saccharose and/or similar carbohydrate feedstock for preparing ammonium lactate;
2) synthesis of lactate ester from calcium lactate derived from culture medium containing ammonium lactate;
3) catalytic polycondensation of lactate ester to form oligomer;
4) depolymerisation of oligomer for preparing lactide;
5) catalytic polymerisation of lactide for preparing polylactic acid.
2. A method according to the claim 1 wherein the stage 1 ) comprises the
following steps:
- cultivation of microorganisms for lactic-acid fermentation of culture medium;
- neutralisation of the formed lactic acid by ammonia for preparing ammonium lactate.
3. A method according to the claim 1 wherein the stage 2) comprises the
following steps:
- concentration of culture medium is containing ammonium lactate by heating;
- conversion of ammonium lactate to calcium lactate;
- calcium lactate reaction with alcohol for synthesis of lactate ester.
4. A method according to the claim 3 wherein the stage 2) comprises the
following:
- concentration of culture medium containing ammonium lactate by heating and removal of water;
- separation of calcium lactate from the concentrated culture medium upon introduction of calcium chloride.
5. A method according to the claim 3 wherein comprising reaction of calcium
lactate derived from culture medium with chlorohydric acid and alcohol for obtaining lactate ester and calcium chloride, the latter being returned to lactate preparation stage.
6. A method according to the claim 3 wherein comprising reaction of calcium
lactate derived from culture medium with chlorohydric acid and alcohol, which forms a water/alcohol azeotropic mixture, for obtaining lactate ester and calcium chloride, the latter being returned to the lactate preparation stage.
7. A method according to the claim 3 wherein comprising the following steps:
- reaction of calcium lactate derived from culture medium with chlorohydric acid and alcohol conducted in a reactor with boiling under reflux;
- washing out calcium chloride from the formed reaction mass with water;
- further esterification with removal of water in the form of water/alcohol azeotrope.
8. A method according to the claim 3 wherein conducted in a reactor fitted with an anchor-and-gate mixer, a reflux condenser, an inclined condenser and a separation vessel.
9. A method according to the claim 3 wherein the ester purification process is conducted in a reactor fitted with a re-boiler, a rectification column, a dephlegmator and a reflux separator, the minimum number of the column theoretically perfect plates being 120.
10. A method according to the claim 1 wherein the oligomerisation process
comprising stage 3) polycondensation in boiling lactate ester with stripping of alcohol.
1 1. A method according to the claim 10 wherein in the oligomerisation process the stage 3) is accomplished in a reactor fitted with an anchor-and-gate mixer and an inclined condenser.
12. A method according to the claim 1 wherein the lactide process in stage 4) comprises oligomer depolymerisation for preparing lactide under vacuum heating in a reactor fitted with an anchor-and-gate mixer and an inclined condenser.
13. A method according to the claim 12 wherein the purification of lactide is
prepared as per by crystallisation of the melt in a column with a
length-diameter ratio of 1/3.
14. A method according to the claim 13 wherein in the lactide purification process the separation of impurities is accomplished by heating of the reactor to 90°C at the rate of 5°C/min.
15. A method according to the claim 1 wherein in said method of biodegradable polymer process the stage 5) comprises ring-opening polymerisation of lactide for preparing polylactide.
16. A method according to the claim 1 wherein in said method the biodegradable polymer process in the stage (5) is accomplished in a reactor fitted with an anchor-and-gate mixer and an inclined condenser.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10744898.7A EP2601303A1 (en) | 2010-08-02 | 2010-08-02 | The novel biodegradable polymer process |
| EA201300208A EA201300208A1 (en) | 2010-08-02 | 2010-08-02 | THE PROCESS OF OBTAINING A BIOLDEPENDABLE POLYMER, BASED ON FRICTAL ACID SYNTHESIZED BY MICROBIOLOGICAL METHOD, AND EQUIPMENT FOR ITS OBTAIN |
| PCT/EP2010/061168 WO2012016580A1 (en) | 2010-08-02 | 2010-08-02 | The novel biodegradable polymer process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2010/061168 WO2012016580A1 (en) | 2010-08-02 | 2010-08-02 | The novel biodegradable polymer process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012016580A1 true WO2012016580A1 (en) | 2012-02-09 |
Family
ID=43066614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2010/061168 WO2012016580A1 (en) | 2010-08-02 | 2010-08-02 | The novel biodegradable polymer process |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2601303A1 (en) |
| EA (1) | EA201300208A1 (en) |
| WO (1) | WO2012016580A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400478A (en) * | 2017-08-16 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A method of lactate is directly obtained from lactic fermentation liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004611A1 (en) * | 1997-10-14 | 2002-01-10 | Cargill, Incorporated | Lactic acid processing; methods; arrangements; and, products |
| US20020132967A1 (en) * | 2001-01-31 | 2002-09-19 | Hitomi Ohara | Process for producing lactide and process for producing polylactic acid from fermented lactic acid employed as starting material |
| US20030158360A1 (en) * | 2000-04-20 | 2003-08-21 | Gerking L?Uuml;Der | Method for producing polylactic acid and corresponding device |
-
2010
- 2010-08-02 WO PCT/EP2010/061168 patent/WO2012016580A1/en active Application Filing
- 2010-08-02 EP EP10744898.7A patent/EP2601303A1/en not_active Withdrawn
- 2010-08-02 EA EA201300208A patent/EA201300208A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004611A1 (en) * | 1997-10-14 | 2002-01-10 | Cargill, Incorporated | Lactic acid processing; methods; arrangements; and, products |
| US20030158360A1 (en) * | 2000-04-20 | 2003-08-21 | Gerking L?Uuml;Der | Method for producing polylactic acid and corresponding device |
| US20020132967A1 (en) * | 2001-01-31 | 2002-09-19 | Hitomi Ohara | Process for producing lactide and process for producing polylactic acid from fermented lactic acid employed as starting material |
| US6569989B2 (en) | 2001-01-31 | 2003-05-27 | Toyota Jidosha Kabushiki Kaisha | Process for producing lactide and process for producing polylactic acid from fermented lactic acid employed as starting material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400478A (en) * | 2017-08-16 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A method of lactate is directly obtained from lactic fermentation liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| EA201300208A1 (en) | 2013-08-30 |
| EP2601303A1 (en) | 2013-06-12 |
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