CN103588639A - PHB material alcoholysis recovery method - Google Patents
PHB material alcoholysis recovery method Download PDFInfo
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- CN103588639A CN103588639A CN201310644048.1A CN201310644048A CN103588639A CN 103588639 A CN103588639 A CN 103588639A CN 201310644048 A CN201310644048 A CN 201310644048A CN 103588639 A CN103588639 A CN 103588639A
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- plasma liquid
- methyl
- sulfonic acid
- hydrogen sulfate
- phb
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 9
- 238000011084 recovery Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 239000002608 ionic liquid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229950004288 tosilate Drugs 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 12
- JNONJXMVMJSMTC-UHFFFAOYSA-N hydron;triethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)CC JNONJXMVMJSMTC-UHFFFAOYSA-N 0.000 abstract 2
- BGEHHDVYQRNMJB-UHFFFAOYSA-N morpholine;sulfuric acid Chemical compound OS([O-])(=O)=O.C1COCC[NH2+]1 BGEHHDVYQRNMJB-UHFFFAOYSA-N 0.000 abstract 2
- ZNCXUFVDFVBRDO-UHFFFAOYSA-N pyridine;sulfuric acid Chemical compound [H+].[O-]S([O-])(=O)=O.C1=CC=[NH+]C=C1 ZNCXUFVDFVBRDO-UHFFFAOYSA-N 0.000 abstract 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 abstract 2
- 230000003628 erosive effect Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 8
- LDLDJEAVRNAEBW-UHFFFAOYSA-N Methyl 3-hydroxybutyrate Chemical class COC(=O)CC(C)O LDLDJEAVRNAEBW-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical class [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- -1 saturated sodium bicarbonate, saturated sodium-chlor Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for chemically depolymerizing PHB materials to generate 3-hydroxy butyric acid alkyl ester to achieve chemical recycling of the PHB materials. The PHB material alcoholysis recovery method is characterized in that 1-methyl-3-(3-sulfonic acid propyl) imidazole hydrogen sulfate salt plasma liquid, N-methyl-N-(3-sulfo propyl) morpholine hydrogen sulfate salt plasma liquid, N-(3-sulfonic acid propyl) pyridine hydrogen sulfate salt plasma liquid, N-(3-sulfonic acid propyl) pyridine p-toluene sulfonate plasma liquid and N-(3-sulfonic acid propyl) triethylamine hydrogen sulfate salt plasma liquid are adopted as catalysts, alcoholysis reactions are carried out under the temperature ranging from 110DEG C to 150DEG C, and after the reactions come to an end, the 3-hydroxy butyric acid alkyl ester is obtained through operation like filtering and distillation, and the recycled plasma liquid can be directly used without being processed, wherein the 1-methyl-3-(3-sulfonic acid propyl) imidazole hydrogen sulfate salt plasma liquid, N-methyl-N-(3-sulfo propyl) morpholine hydrogen sulfate salt plasma liquid, N-(3-sulfonic acid propyl) pyridine hydrogen sulfate salt plasma liquid, N-(3-sulfonic acid propyl) pyridine p-toluene sulfonate plasma liquid and N-(3-sulfonic acid propyl) triethylamine hydrogen sulfate salt plasma liquid can be easily recycled. Compared with the traditional method, the method has the advantages that traditional strong acid in the background art is not needed, and therefore equipment erosion and waste water discharge are obviously improved; because the plasma liquid serves as the catalysts and can be recycled, reaction conditions are improved, and the problem that catalysts in the background art can not be recycled is solved.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate to particularly and a kind ofly take ionic liquid as catalyzer, poly 3-hydroxy butyrate (PHB) material that will give up carries out the novel method that chemical depolymerization reclaims 3-hydroxybutyrate alkyl ester.
Technical background
It is a kind of thermoplastic material of highly crystalline that poly 3-hydroxy butyrate is also poly-beta-hydroxy-butanoic acid ester (being called for short PHB), energy film forming the same as chemosynthesis plastics and wire drawing, physics-chem characteristic is similar to conventional plastic, particularly there is good biocompatibility, biological degradability and in human body the characteristic of natural degradation, it is had broad application prospects at industrial circles such as medical science, agricultural, electronics and food.In recent years, along with take oil, coal, be the day by day exhausted of the main disposable energy, PHB is owing to having the multiple good characteristic of human's demand, so the application of PHB and be worth also increasingly, and its distant view has obtained extensively approving in the world.Along with production and the Growth of Consumption of PHB, the amount of the waste and old PHB of generation is also more and more.Although PHB can degrade under field conditions (factors), because PHB fragility is large, degradation cycle is long, and waste stacks or landfill can take up room, contaminate environment; In addition, its degraded product CO
2and H
2o, because cannot directly carrying out cycling and reutilization, is also the huge wasting of resources.Therefore,, when constantly strengthening the research of PHB material preparation technology, the recycle utilization research of useless PHB is also subject to people's attention day by day.
The chemical recycling of reporting at present is mainly divided into thermolysis and the large class of chemical depolymerization two.Thermal decomposition method, because temperature is higher, is easy to produce side reaction, is difficult to obtain highly purified object product.So compare with thermolysis, chemical depolymerization rule is more effective, and wherein alcoholysis method is one of important chemical depolymerization method, by the method, the PHB alcoholysis of giving up can be generated to corresponding 3-hydroxybutyrate alkyl ester product.At present, alcoholysis method mainly carries out under traditional strong acid exists, such as (Macromolecules, 1995 such as R.Lehrle, 28,4408-4414) reported with 1,2-ethylene dichloride and made solvent, the alcoholysis of sulphuric acid catalysis PHB methyl alcohol, after having reacted, after washing, adopt 1,2-ethylene dichloride repeatedly to extract, saturated sodium-chlor, saturated sodium bicarbonate, saturated sodium-chlor obtains the mixture of 3-hydroxybutyrate methyl esters and methyl alcohol alcoholysis dimer, tripolymer, the tetramer, pentamer.(the Enzyme and Microbial Technology such as Y.Lee, 2000,27:33-36) utilize the alcoholysis reaction (methyl alcohol, ethanol, propyl alcohol) of the vitriol oil (93%-98%) or concentrated hydrochloric acid (38%) catalysis PHB, although can reclaim corresponding 3-hydroxybutyrate alkyl ester, but long reaction time (24h), and product yield is low, adopt a large amount of methylene dichloride to make solvent simultaneously.The shortcoming of these methods is need to apply the strong acid as catalyst of a large amount of tradition, catalyzer can not repeat reuse, equipment corrosion, need neutralization washing and cause wastewater flow rate large.Therefore introducing novel method improves existing technique drawback, and the chemical recycling of realizing useless poly-PHB material is significant.
Summary of the invention
The present invention proposes a kind of novel method of useless PHB being carried out to chemical cycle recovery by alcoholysis reaction.The method adopts the ionic liquid can repeat reuse to make catalyzer, and the PHB that will give up carries out alcoholysis reaction, does not need to use any traditional soda acid on the one hand, in having avoided and water washing process, thereby can significantly improve equipment corrosion, reduce discharge of wastewater; Ionic liquid can repeat reuse on the other hand.
The novel method that the object of this invention is to provide the useless PHB of a kind of alcoholysis, to overcome that a large amount of inorganic acid alkalis of need consumption, equipment corrosion and the environmental pollution that exist in traditional method are serious, catalyzer can not be recycled and the shortcoming such as severe reaction conditions.
Technical scheme of the present invention is achieved in that adopting ionic liquid is catalyzer, and at certain pressure and temperature, the PHB that will give up carries out alcoholysis reaction.After reaction finishes, by air distillation, operate the unreacted raw alcohol of Separation and Recovery and underpressure distillation obtains product 3-hydroxybutyrate alkyl ester, remaining ionic liquid is as catalyzer direct reuse.
Ionic liquid described in the inventive method has following general structure:
Wherein, n=3~4, R
1, R
2, R
3for C
1~C
4alkyl.X is HSO
4, p-CH
3c
6h
4sO
3deng.The most frequently used is 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, N-methyl-N-(3-sulfonic group propyl group) morpholine hydrosulfate, N-(3-sulfonic group propyl group) pyridine hydrosulfate, N-(3-sulfonic group propyl group) pyridine tosilate and N-(3-sulfonic group propyl group) triethylamine hydrosulfate etc.
Due under reaction conditions, the ionic liquid adopting has katalysis, thereby can avoid the use of traditional strong acid, highly basic, has simplified technical process, has reduced discharge of wastewater.Temperature described in the inventive method is generally at 110~150 ℃, and the mass ratio of ionic liquid and useless PHB is generally 0.01~0.5:1, is preferably 0.02~0.2:1.The reaction principle relating in the present invention is as follows:
Wherein, R is C
1~C
4alkyl.
Present method realizes by following steps:
Ionic liquid, alcohol and useless PHB are joined in reactor by a certain percentage, at a certain temperature stirring reaction certain hour.After reaction finishes, by simple distillation, operated and reclaimed unreacted raw alcohol and obtain product 3-hydroxybutyrate alkyl ester by underpressure distillation, remaining ionic liquid is as catalyzer direct reuse.
Present method is compared with traditional method, is characterized in: (1), without the traditional strong acid, the highly basic that adopt in background technology, has significantly improved equipment corrosion and discharge of wastewater problem.(2) owing to adopting ionic liquid as catalyzer, relaxed reaction conditions on the one hand, ionic liquid can be realized repetition reuse on the other hand, has overcome catalyzer in background technology and can not repeat reuse problem.
Specific implementation method
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
Embodiment 1: the useless PHB of 8.0g is put into autoclave, add successively 0.24g1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, 14.92g methyl alcohol, after adding at 110 ℃ stirring reaction 3h, be down to room temperature, reaction solution after filtering, by filtrate Distillation recovery methyl alcohol, through treating processess such as underpressure distillation, obtain product, PHB percent alcoholysis 94.6%, 3-hydroxybutyrate methyl esters yield 88.7%.
Embodiment 2: experiment condition and step are with embodiment 1, just change 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate into N-methyl-N-(3-sulfonic group propyl group) morpholine hydrosulfate, PHB percent alcoholysis 94.0%, 3-hydroxybutyrate methyl esters yield 87.4%.
Embodiment 3: experiment condition and step, with embodiment 1, just change 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate into N-(3-sulfonic group propyl group) pyridine hydrosulfate, PHB percent alcoholysis 94.1%, 3-hydroxybutyrate methyl esters yield 88.3%.
Embodiment 4: experiment condition and step are with embodiment 1, just change 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate into N-(3-sulfonic group propyl group) pyridine tosilate, temperature of reaction changes 140 ℃ into, PHB percent alcoholysis 94.5%, 3-hydroxybutyrate methyl esters yield 88.5%.
Embodiment 5: experiment condition and step, with embodiment 1, just change 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate into N-(3-sulfonic group propyl group) triethylamine hydrosulfate, PHB percent alcoholysis 92.8%, 3-hydroxybutyrate methyl esters yield 86.4%.
Embodiment 6-10: experiment condition and step, with embodiment 1, just change respectively methyl alcohol into ethanol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol, and acquired results is in Table 1.
The reaction result of table 1 embodiment 6-10
Embodiment 11-16: experiment condition and step, with embodiment 1, just change ionic liquid into the ionic liquid reclaiming in embodiment 1, carry out repeating reuse experiment for six times, and reuse the results are shown in Table 2.
The repetition reuse result of table 2 ionic liquid
Comparative example 1: experiment condition and step, with embodiment 1, just change 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate into the vitriol oil, PHB percent alcoholysis 52.1%, 3-hydroxybutyrate methyl esters yield 43.9%.
Claims (4)
1. the novel method of 3-hydroxybutyrate alkyl ester is reclaimed in the alcoholysis of useless poly 3-hydroxy butyrate (being called for short a PHB) material under ionic liquid environment, being about to useless PHB, ionic liquid and corresponding alcohol adds in reactor, at a certain temperature, stirring reaction certain hour, reaction finish after, solids removed by filtration residue, by filtrate through the unreacted raw alcohol of normal pressure Distillation recovery, through underpressure distillation, obtain product 3-hydroxybutyrate alkyl ester, remaining ionic liquid is as catalyzer direct reuse.
2. method according to claim 1, the ionic liquid that wherein adopted has following general structure:
Wherein, n=3~4, R
1, R
2, R
3for C
1~C
4alkyl, X is HSO
4, p-CH
3c
6h
4sO
3, the most frequently used is 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfate, N-methyl-N-(3-sulfonic group propyl group) morpholine hydrosulfate, N-(3-sulfonic group propyl group) pyridine hydrosulfate, N-(3-sulfonic group propyl group) pyridine tosilate and N-(3-sulfonic group propyl group) triethylamine hydrosulfate.
3. method according to claim 1, wherein alcoholysis reaction temperature is 110~150 ℃.
4. method according to claim 1, wherein alcohol used is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
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Cited By (3)
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CN107188802A (en) * | 2017-04-27 | 2017-09-22 | 青岛科技大学 | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type |
CN113416130A (en) * | 2021-06-24 | 2021-09-21 | 东莞理工学院 | Method for preparing R-3-hydroxy methyl butyrate |
CN115043727A (en) * | 2022-08-04 | 2022-09-13 | 东莞理工学院 | Method for preparing 3-bromobutyrate compound and 3-hydroxybutyrate compound by degrading poly-3-hydroxybutyrate |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107188802A (en) * | 2017-04-27 | 2017-09-22 | 青岛科技大学 | Using the method for the ionic liquid-catalyzed butyric ester of alcohol depolymerization 3 of bisgallic acid type |
CN107188802B (en) * | 2017-04-27 | 2020-01-03 | 青岛科技大学 | Method for catalyzing alcohol to depolymerize 3-hydroxybutyrate by using double-acid ionic liquid |
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CN113416130B (en) * | 2021-06-24 | 2022-09-13 | 广东邦固化学科技有限公司 | Method for preparing R-3-hydroxy methyl butyrate |
CN115043727A (en) * | 2022-08-04 | 2022-09-13 | 东莞理工学院 | Method for preparing 3-bromobutyrate compound and 3-hydroxybutyrate compound by degrading poly-3-hydroxybutyrate |
CN115043727B (en) * | 2022-08-04 | 2024-04-26 | 东莞理工学院 | Method for preparing 3-bromobutyrate compounds and 3-hydroxybutyrate compounds by degrading poly (3-hydroxybutyrate) |
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