CN101555243A - Manufacturing method and device of cyclic refined lactic acid dimmer and manufacturing method and device of polylactic acid - Google Patents
Manufacturing method and device of cyclic refined lactic acid dimmer and manufacturing method and device of polylactic acid Download PDFInfo
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- CN101555243A CN101555243A CN 200910134801 CN200910134801A CN101555243A CN 101555243 A CN101555243 A CN 101555243A CN 200910134801 CN200910134801 CN 200910134801 CN 200910134801 A CN200910134801 A CN 200910134801A CN 101555243 A CN101555243 A CN 101555243A
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- lactic acid
- lactide
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- evaporation
- cyclic dimer
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 373
- 239000004310 lactic acid Substances 0.000 title claims abstract description 220
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 218
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 40
- 239000004626 polylactic acid Substances 0.000 title abstract description 3
- 238000009833 condensation Methods 0.000 claims abstract description 120
- 230000005494 condensation Effects 0.000 claims abstract description 120
- 238000007670 refining Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 72
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims description 114
- 230000008020 evaporation Effects 0.000 claims description 112
- -1 poly(lactic acid) Polymers 0.000 claims description 82
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 38
- 239000010408 film Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 24
- 238000009434 installation Methods 0.000 claims description 23
- 238000011144 upstream manufacturing Methods 0.000 claims description 20
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-Lactic acid Natural products C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 229930182843 D-Lactic acid Natural products 0.000 claims description 11
- 229940022769 d- lactic acid Drugs 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 abstract description 194
- 230000008016 vaporization Effects 0.000 abstract 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 29
- 239000012535 impurity Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 241000196324 Embryophyta Species 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- 238000004821 distillation Methods 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 238000012691 depolymerization reaction Methods 0.000 description 11
- 230000004927 fusion Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 3
- MYUGERSVZRUHOX-UHFFFAOYSA-J 2,3-dihydroxybutanedioate;tin(4+) Chemical compound [Sn+4].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O MYUGERSVZRUHOX-UHFFFAOYSA-J 0.000 description 3
- QJDGQRSDUWBFJB-UHFFFAOYSA-N 2-hydroxypropanoic acid;tin Chemical compound [Sn].CC(O)C(O)=O QJDGQRSDUWBFJB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- BEUROAIAWHFZGE-UHFFFAOYSA-N naphthalene-2-carboxylic acid;tin Chemical compound [Sn].C1=CC=CC2=CC(C(=O)O)=CC=C21 BEUROAIAWHFZGE-UHFFFAOYSA-N 0.000 description 3
- 125000005474 octanoate group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 2
- 239000001521 potassium lactate Substances 0.000 description 2
- 235000011085 potassium lactate Nutrition 0.000 description 2
- 229960001304 potassium lactate Drugs 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 2
- NGSFWBMYFKHRBD-UHFFFAOYSA-N sodium;2-hydroxypropanoic acid Chemical compound [Na+].CC(O)C(O)=O NGSFWBMYFKHRBD-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- YLGZRMLFAGSRHM-UHFFFAOYSA-N dodecanoic acid;tin Chemical compound [Sn].CCCCCCCCCCCC(O)=O YLGZRMLFAGSRHM-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
The invention provides manufacturing method and device of cyclic refined lactic acid dimmer and manufacturing method and device of polylactic acid. The manufacturing method of cyclic refined lactic acid is characterized by steps of depolymerising lactate condensation compound obtained by condensing lactic acid to obtain gasiform lactide; condensing the gasiform lactide; dividing condensed lactide into refined lactide of optical-activity lactide containing any one of L-lactide and D-lactide and refined residue except refined lactide; vaporizing lactide in the refined residue to separate the refined residue into lactide and vaporized and separated residue except lactide, wherein the lactide in the vaporizing process is condensed and then is reused in a refining process.
Description
Technical field
The present invention relates to a kind of manufacture method and manufacturing installation of cyclic refined lactic acid dimmer.The invention still further relates to a kind of manufacture method and manufacturing installation of poly(lactic acid).
Background technology
Poly(lactic acid) is the aliphatic polyester that lactic acid is made as raw material.As one of method of synthesizing polylactic acid, comprise and pass through concentrated lactic acid, reduce contained humidity, make its condensation then, generate lactate condensation compound (lactic acid oligomer),, generate lactic acid cyclic dimer (rac-Lactide) by making it carry out a depolymerization to wherein adding catalyzer such as weisspiessglanz, it is refining to utilize crystallization to separate out etc. where necessary, thereby adds the method that catalyzer such as stannous octoate carries out ring-opening polymerization then in rac-Lactide.
In enrichment process, in as monomeric lactic acid, contain about 10～15% moisture (hereinafter referred to as free-water) sometimes as impurity, implement removing of this free-water in order to make it easily the esterification treatment between monomer take place.In this enrichment process, utilize the heating 120～250 ℃ under and utilize the decompression of use vacuum pump etc. to implement removing of moisture in case of necessity.
The condensation operation is in the heating under 120～250 ℃ and utilizes under the reduced pressure atmosphere of vacuum pump etc., preferably utilizes the decompression below the 10Torr to gasify, remove the water that generates owing to the esterification between monomer.Decompression herein is different with the decompression in the enrichment process, is the necessary condition that is used to advance esterification.Utilize this condensation operation, generate lactate condensation compound (below be sometimes referred to as oligomer) from monomer.
The oligomer that generates in the condensation operation is sent to the depolymerization operation, in the heating under 120～250 ℃ and utilize under the reduced pressure atmosphere of vacuum pump etc., preferably under the reduced pressure atmosphere below the 100Torr, by contacting, generate lactic acid cyclic dimer ester (below be sometimes referred to as rac-Lactide) with depolymerization catalyzer such as stannous octoate, ANTIMONY TRIOXIDE SB 203 99.8 PCT.The rac-Lactide that generates mostly is gas usually greatly under the environment of depolymerization operation, after utilizing the cooling condensation recovery, be sent to refining step.
Because lactic acid is the molecule with chirality (chirality), so there is the enantiomorph (enantiomer) that is called as L-lactic acid and D-lactic acid.Therefore, as the rac-Lactide of cyclic dimer L-rac-Lactide as the cyclic dimer of L-lactic acid is arranged, as the D-rac-Lactide of the cyclic dimer of D-lactic acid and as the optically active isomer that is called as Study of Meso-Lactide of the cyclic dimer of L-lactic acid and D-lactic acid.Because at the most lactic acid that exist of occurring in nature is L-lactic acid, so what use mostly in poly(lactic acid) is synthetic is the L-rac-Lactide.In refining step, utilize means such as solvent extraction, recrystallization to separate L-rac-Lactide and D-rac-Lactide and Study of Meso-Lactide.
The manufacture method of the rac-Lactide as poly(lactic acid) in synthetic has been developed various technology.
For example comprise utilizing and distill the method (conventional art 1: for example record in patent documentation 1) that obtains refined lactide from the crude lactide that the depolymerization operation, generates.In the method, utilize fractional distillating tube to be concentrated in the crude lactide that generates in the depolymerization operation, in distillation system (system), supply with continuously as steam then, in the distillation tower in distillation system, be separated into jar overhead product at the bottom of lower boiling overhead product, rac-Lactide and the high boiling point tower.
In addition, also be included in and use distillation tower to be separated in after the crude lactide that generates in the depolymerization operation, make the rac-Lactide fusion-crystallizationization, thereby obtain the method (conventional art 2: for example record in patent documentation 2) of refined lactide.In the method,, take out crude lactide, take out high boiling fractions such as oligomer from the bottom, separate from sidepiece by taking out lactic acid, water etc. from cat head (overhead).Afterwards, making after the crude lactide fusion that sidepiece takes out, by cooling, form few crystallization phases of impurity and the many liquid phases of impurity, fractional crystallization phase and liquid phase by crystallization phases being heated to the fusing point less than rac-Lactide, come fusion to remove impurity then.
And then, comprise that also the gas cooling that purified in the depolymerization operation is contained crude lactide to zero pour, solidifies rac-Lactide, make other impurity liquefaction, the method (conventional art 3: for example record in patent documentation 3) of coming separation and purification.
Patent documentation 1: No. 3258324 communique of patent
Patent documentation 2: the flat 10-504563 communique of special table
Patent documentation 3: the flat 7-505150 communique of special table
In foregoing conventional art 1 and 2, for full dose distillation crude lactide, must need to make a large amount of heat energy of crude lactide fusion evaporation, efficient is low.In addition, thermal process is long owing to use distillation tower, and rac-Lactide generation thermal degradation when and then decomposition or isomerized possibility are big, and yield may reduce.On the other hand, in conventional art 3 since with the isolating impurity of rac-Lactide in contain a lot of rac-Lactides, so yield is low.
Summary of the invention
The present invention proposes just in view of the above problems.The object of the present invention is to provide a kind of device that obtains the method for rac-Lactide effectively and be used for this method.
The inventor etc. concentrate on studies to above-mentioned problem in order to realize described purpose, and the result is so that finish the present invention.Below the present invention is described in detail.
(1) a kind of manufacture method of cyclic refined lactic acid dimmer is characterized in that,
Comprise:
Thereby the lactate condensation compound that the lactic acid condensation is obtained is carried out the depolymerization operation that depolymerization obtains gasiform lactic acid cyclic dimer;
Make the condensation operation of gasiform lactic acid cyclic dimer condensation;
The lactic acid cyclic dimer that has been condensed is separated into the refining step of the refining residue beyond cyclic refined lactic acid dimmer that any kind that contains in L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer and the cyclic refined lactic acid dimmer;
To make with extra care the evaporation separation circuit that residue is separated into lactic acid cyclic dimer and lactic acid cyclic dimer evaporation separating residual thing in addition by making the lactic acid cyclic dimer evacuator body in the refining residue,
Make isolating lactic acid cyclic dimer condensation in the evaporation separation circuit, in refining step, utilize again.
(2) according to (1) described method, it is characterized in that,
The evaporation separation circuit is the operation that makes lactic acid cyclic dimer evacuator body under the state that makes refining residue filming.
(3) according to (2) described method, it is characterized in that,
Use centrifugal-film evaporator to evaporate separation circuit.
(4) according to any described method in (1)～(3), it is characterized in that,
Also comprise:
The enrichment process of concentrated lactic acid; With
Thereby make lactic acid condensation behind the enrichment process obtain the condensation operation of lactate condensation compound,
In the depolymerization operation, use the lactate condensation compound that in the condensation operation, obtains.
(5) according to (4) described method, it is characterized in that,
Evaporation separating residual thing is the material that contains lactate condensation compound, this evaporation separating residual thing is back in the enrichment process and with lactic acid concentrate, utilization again.
(6) according to (4) described method, it is characterized in that,
Evaporation separating residual thing is the material that contains lactate condensation compound, this evaporation separating residual thing is back in the condensation operation and with lactic acid condensation, utilization again.
(7) according to any described method in (1)～(4), it is characterized in that,
Evaporation separating residual thing contains lactate condensation compound, in the depolymerization operation, utilizes this evaporation separating residual thing again.
(8) a kind of manufacture method of poly(lactic acid) is characterized in that,
Comprise:
Utilize any cyclic refined lactic acid dimmer manufacturing process that described method is made cyclic refined lactic acid dimmer in (1)～(7); With
The cyclic refined lactic acid dimmer that utilizes cyclic refined lactic acid dimmer manufacturing process to obtain is carried out the ring-opening polymerization operation that poly(lactic acid) is made in ring-opening polymerization.
(9) a kind of manufacturing installation of cyclic refined lactic acid dimmer is characterized in that,
Possess:
Thereby make the lactate condensation compound depolymerization obtain the depolymerizer of gasiform lactic acid cyclic dimer;
Be configured in the downstream side of depolymerizer, make from the condensing works of the lactic acid cyclic dimer condensation of depolymerizer gas supplied shape;
Be configured in the downstream side of condensing works, will be separated into cyclic refined lactic acid dimmer and cyclic refined lactic acid dimmer refining residue in addition and the refining plant that possesses cyclic refined lactic acid dimmer relief outlet and refining residue relief outlet of discharging that any kind that contains L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer from the lactic acid cyclic dimer that has been condensed that condensing works is supplied with;
Be configured in the refining residue relief outlet downstream side of refining plant, the evaporation tripping device that possesses lactic acid cyclic dimer relief outlet and evaporation separating residual thing relief outlet that will be separated into the evaporation separating residual thing beyond lactic acid cyclic dimer and the lactic acid cyclic dimer by making the lactic acid cyclic dimer evacuator body in this refining residue from the refining residue that refining plant is supplied with and discharge;
Be connected with the lactic acid cyclic dimer relief outlet downstream side of evaporation tripping device and the upstream side of condensing works, supply with the supply road of lactic acid cyclic dimer to condensing works.
(10) a kind of manufacturing installation of cyclic refined lactic acid dimmer is characterized in that,
Possess:
Thereby make the lactate condensation compound depolymerization obtain the depolymerizer of gasiform lactic acid cyclic dimer;
Be configured in the downstream side of depolymerizer, make from the condensing works of the lactic acid cyclic dimer condensation of depolymerizer gas supplied shape;
Be configured in the downstream side of condensing works, will be separated into cyclic refined lactic acid dimmer and cyclic refined lactic acid dimmer refining residue in addition and the refining plant that possesses cyclic refined lactic acid dimmer relief outlet and refining residue relief outlet of discharging that any kind that contains L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer from the lactic acid cyclic dimer that has been condensed that condensing works is supplied with;
Be configured in the refining residue relief outlet downstream side of refining plant, the evaporation tripping device that possesses lactic acid cyclic dimer relief outlet and evaporation separating residual thing relief outlet that will be separated into the evaporation separating residual thing beyond lactic acid cyclic dimer and the lactic acid cyclic dimer by making the lactic acid cyclic dimer evacuator body in this refining residue from the refining residue that refining plant is supplied with and discharge;
Be configured in the lactic acid cyclic dimer relief outlet downstream side of evaporation tripping device, condensation is from second condensing works of the lactic acid cyclic dimer of evaporation tripping device supply;
Be connected with the downstream side of second condensing works and the upstream side of refining plant, supply with the supply road of lactic acid cyclic dimer to refining plant.
(11) according to (9) or (10) described device, it is characterized in that,
The evaporation tripping device is a thin-film evaporator.
(12) according to (11) described device, it is characterized in that,
Thin-film evaporator is a centrifugal-film evaporator.
(13) according to any described device in (9)～(12), it is characterized in that,
Also possess:
The concentrating unit of concentrated lactic acid; With
Be configured in the downstream side of concentrating unit, condensation from concentrating unit supply with concentrate after the condensation device of lactic acid;
Depolymerizer is disposed at the downstream side of condensation device according to the mode from condensation unit feeding lactate condensation compound.
(14) according to (13) described device, it is characterized in that,
Also possess:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of concentrating unit, supply with the supply road of evaporation separating residual thing to concentrating unit.
(15) according to (13) described device, it is characterized in that,
Also possess:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of condensation device, to the supply road of condensation unit feeding evaporation separating residual thing.
(16) according to any described device in (9)～(13), it is characterized in that,
Also possess:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of depolymerizer, supply with the supply road of evaporation separating residual thing to depolymerizer.
(17) a kind of manufacturing installation of poly(lactic acid) is characterized in that,
Possess:
(9)～(16) manufacturing installation of any described cyclic refined lactic acid dimmer in; With
Be configured in the cyclic refined lactic acid dimmer relief outlet downstream side of the refining plant in this manufacturing installation, thereby will carry out the ring-opening polymerization device that poly(lactic acid) is made in ring-opening polymerization from the cyclic refined lactic acid dimmer that refining plant is supplied with.
If utilize method of the present invention, then can separate remaining rac-Lactide in the refining residue that reclaims, utilizes again in lactide refined operation by utilizing evaporation, improve the manufacturing efficient of rac-Lactide.Come the conventional art of refined lactide to compare with the full dose of passing through the distillation crude lactide as above-mentioned conventional art 1, the necessary heat energy of method of the present invention is few, the efficient height.
In the method for the invention, make oligomer in the evaporation separating residual thing of evaporation in the separation circuit be back to the depolymerization operation or situation about more utilizing again in the operation of upstream under, the manufacturing efficient of rac-Lactide further improves.
In the method for the invention, utilize the mechanism that does not follow heating to make with extra care and using thin-film evaporator to evaporate under the situation of separation circuit, because the thermal process of the rac-Lactide of making is few, so can there not be the high-quality rac-Lactide of deterioration with high-level efficiency manufacturing more.
Description of drawings
Fig. 1 is the sketch chart of an embodiment of expression poly(lactic acid) manufacturing installation of the present invention.
Fig. 2 is the mode chart of the structure of the centrifugal-film evaporator that can use in the present invention.Fig. 2 (a) is its side cross-sectional view, and Fig. 2 (b) is its cross-sectional view.
Fig. 3 is the sketch chart of an embodiment of expression poly(lactic acid) manufacturing installation of the present invention.
Among the figure, 1-lactic acid feedway, 2-liquid-feeding pump, 3-lactic acid concentrating unit, 4-liquid-feeding pump, 5-concentrated lactic acid dashpot (buffer tank), the 6-liquid-feeding pump, 7-lactic acid condensation device, 8-liquid-feeding pump, 9-oligomer dashpot, 10-liquid-feeding pump, 11-depolymerizer, the 12-reflux cooler, 13-rac-Lactide condenser (condensing works), 14-liquid-feeding pump, the lactide refined device of 15-, 16-liquid-feeding pump, 17-ring-opening polymerization device, the 18-return channel, 19-water cooler, 20-reliever, the 21-return channel, 22-water cooler, 23-reliever, the 24-condenser, 25-impurity water cooler, 26-reliever, 27-evaporates tripping device, 28-liquid-feeding pump, 29-second reflux cooler, the 30-second rac-Lactide condenser (second condensing works), 31-condenser, 32-impurity water cooler, the 33-reliever, 34-refined lactide relief outlet, 35-makes with extra care the residue relief outlet, 36-rac-Lactide relief outlet, 37-evaporation separating residual thing relief outlet, 38-supplies with the road, 39-supplies with the road, and 40-supplies with the road.
Embodiment
(enrichment process and concentrating unit)
The enrichment process of lactic acid is meant from the dewatered operation of the lactic acid that becomes the raw material that is used for synthesis of lactide from.The best moisture that moisture evaporation is removed contain in the lactic acid by heating as much as possible.Heating is preferably under nitrogen circulation, carry out under 120～150 ℃.
The lactic acid concentrating unit typically possesses the reactor, the heating arrangements (for example thermophore chuck (jacket), heat exchanger) that is used for heating the lactic acid of accommodating at reactor that are used for accommodating lactic acid at least, be used to be stirred in stirring mechanism (for example agitating wing), lactic acid supplying opening, the lactic acid relief outlet of the lactic acid that reactor accommodates.The lactic acid concentrating unit also can further possess return channel.In the lactic acid enrichment process, as gas generation water and lactic acid, and if return channel is set in the lactic acid concentrating unit, then can in return channel, import the gas that contains water and lactic acid, cool off described gas with return channel, a condensation lactic acid returns the lactic acid concentrating unit.
(condensation operation and condensation device)
Thereby lactic acid condensation operation is to make its condensation generate the operation of oligomer by under reduced pressure heating lactic acid.In lactic acid condensation operation, follow condensation, generate moisture.In the present invention, oligomer is the notion that comprises from 2 aggressiveness of lactic acid to the lactic acid polymer of molecular weight about 50,000.Utilize the molecular weight of the oligomer that lactic acid condensation operation of the present invention obtains to calculate and be generally 150～10,000, be preferably 500～5,000 with molecular-weight average.
The lactic acid condensation reaction is usually below the pressure 100Torr, below the preferred 10Torr and then below the preferred 1Torr, usually 120～250 ℃, preferred 160～220 ℃, more preferably 170～200 ℃ of enforcements down.Can be short as much as possible by making heat-up time, suppress the thermolysis of lactic acid and oligomer.
Lactic acid condensation device typically possesses the reactor, the heating arrangements (for example thermophore chuck, heat exchanger) that is used for heating the reaction mixture of accommodating at reactor that are used for accommodating reaction mixture at least, be used to be stirred in stirring mechanism (for example agitating wing), lactic acid supplying opening, the oligomer relief outlet of the reaction mixture that reactor accommodates.Lactic acid condensation device preferably is connected with the reliever of decompression in the reactor.Then, also preferably between lactic acid condensation device and reliever, be situated between at return channel.In the lactic acid condensation reaction, as the rac-Lactide of gas generation moisture, lactic acid, low-molecular-weight oligomer and generation in it decomposes.They move to reliever from the reactor of lactic acid condensation device.Can make these gases enter return channel, from gas, remove lactic acid, low-molecular-weight oligomer, rac-Lactide, it is refluxed in lactic acid condensation device.
About the lactic acid condensation reaction, also can add the catalyzer that is used for the lactic acid condensation reaction where necessary.As catalyzer, known in the past catalyzer be can use, the catalyzer (for example lactic acid tin, tartrate tin, two stannous octoates, two lauric acid tin, two palmitinic acid tin, distearyl acid tin, two oleic acid tin, α-Nai Jiasuan tin, β-naphthoic acid tin, stannous octoate etc.) of organotin system and powder tin etc. for example can be enumerated.
(depolymerization operation and depolymerizer)
The depolymerization operation is thereby that lactate condensation compound is carried out depolymerization, forms the operation that rac-Lactide produces gasiform rac-Lactide.In the present invention, rac-Lactide (lactic acid cyclic dimer) is to instigate 2 molecule lactic acid to slough the cyclic ester that produces behind 2 molecular waters through dehydration reaction.
In depolymerization reaction, also can add the catalyzer that is used for depolymerization reaction where necessary.As catalyzer, can use known in the past catalyzer, for example can use the catalyzer that constitutes by metal of selecting the group that constitutes from periodic law Table I A family, IIIA family, IVA family, IVB family, IIB family and VA family or metallic compound.
As the catalyzer that belongs to IA family, for example can enumerate alkali-metal oxyhydroxide (for example sodium hydroxide, potassium hydroxide, lithium hydroxide etc.), basic metal and faintly acid salt (for example Sodium.alpha.-hydroxypropionate, sodium acetate, yellow soda ash, Sodium octoate, sodium stearate, potassium lactate, potassium acetate, salt of wormwood, potassium octanoate etc.), alkali alcoholate (for example sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.) etc.
As the catalyzer that belongs to IIIA family, for example can enumerate aluminum ethylate, aluminum isopropylate, aluminum oxide, aluminum chloride etc.
As the catalyzer that belongs to IVA family, for example can enumerate the catalyzer (for example lactic acid tin, tartrate tin, two stannous octoates, distearyl acid tin, two oleic acid tin, α-Nai Jiasuan tin, β-naphthoic acid tin, stannous octoate etc.) of organotin system, in addition, can also enumerate powder tin, stannic oxide, tin halides etc.
As the catalyzer that belongs to IIB family, for example can enumerate zinc powder, zinc halide, zinc oxide, organic zinc based compound.
As the catalyzer that belongs to IVB family, for example can enumerate zirconium compounds such as titanium sub-group compound, zirconium iso-propoxide such as tetrapropyl titanic acid ester etc.
Wherein, preferably use antimony based compounds such as tin based compounds such as stannous octoate or ANTIMONY TRIOXIDE SB 203 99.8 PCT.
Relative oligomer, the usage quantity of these catalyzer is 0.01～20 weight %, is preferably 0.05～15 weight %, more preferably about 0.1～10 weight %.
Depolymerizer typically possesses the reactor, the heating arrangements (for example thermophore chuck, heat exchanger) that is used for heating the reaction mixture of accommodating at reactor that are used for accommodating reaction mixture, be used to be stirred in stirring mechanism (for example agitating wing), oligomer supplying opening, rac-Lactide relief outlet, the resistates relief outlet of the reaction mixture that reactor accommodates.In addition, also possess temperature measuring mechanism such as thermometer usually.As reactor, be not particularly limited, can use vertical reactor, horizontal reactor, box reactor etc.As agitating wing, can use paddle wheel (paddle) wing, turbine (turbine) wing, anchor (anchor) wing, two moving (double motion) wing, hurricane band (helical ribbon) wing etc.
The heating of reactor can use that normally used heating arrangements carries out in this technical field.For example, be included in the chuck that the reactor peripheral part is provided with thermophore, by the reactor wall, utilize the method for conducting heat reacting by heating liquid, perhaps, in the interior of rotating shaft of agitating wing, by thermophore, utilize the method for the heating of conducting heat etc., can be used singly or in combination these methods.
Reliever is set in depolymerizer, under the reduced pressure atmosphere below the 100Torr, below the preferred 10Torr,, implements the depolymerization reaction of oligomer usually 120～250 ℃, preferred 120～200 ℃ of heating down by common.Utilize this depolymerization reaction, generate rac-Lactide as gas.
(condensation operation and condensing works)
The condensation operation is by the steam that contains rac-Lactide that generates in depolymerizer, thus the operation that the condensation rac-Lactide reclaims.The gas shape rac-Lactide that generates in the depolymerization operation moves to reliever from the reactor of depolymerizer.Can be by between the reactor of depolymerizer and reliever, being situated between at condensing works, thus the rac-Lactide condensation is reclaimed.
Because the steam that contains rac-Lactide that generates in depolymerizer contains impurity such as lactic acid oligomer mostly, so preferred before the condensation of carrying out rac-Lactide, make the steam that in depolymerizer, generates by being maintained at and the reflux cooling operation of reflux cooler of the suitable temperature of condensation does not take place rac-Lactide as the lactic acid oligomer generation condensation of impurity.Preferably in the reflux cooling operation, make and contain in the operation of the isolating liquid return that contains oligomer of rac-Lactide steam before the depolymerization operation.As the device that oligomer is returned, comprise lactic acid concentrating unit, the concentrated lactic acid dashpot that between lactic acid concentrating unit and lactic acid condensation device, disposes, lactic acid condensation device, the oligomer dashpot that between lactic acid condensation device and depolymerizer, disposes, depolymerizer inlet etc.In the reflux cooling operation, sometimes with contain the isolating oligomer of rac-Lactide steam molecular weight under the effect of depolymerization reaction and diminish.In order to improve the yield of rac-Lactide, preferably make its condensation that molecular weight is improved once more, so thereby the liquid that contains the low-molecular weight oligo thing is back in the lactic acid condensation operation once more by condensation.In addition, reflux according to the molecular weight after separating in order to make oligomer, also can the multistage reflux cooler.In this case, the low-molecular weight oligo thing is got back at least one of lactic acid concentrating unit, concentrated lactic acid dashpot, lactic acid condensation device, made the high molecular oligomer get back at least one of lactic acid condensation device, lactic acid oligomer dashpot, depolymerizer inlet.
For reflux cooler, be preferably the surface condenser that steam and cooling agent are contacted indirectly across metal tube.This is because if rac-Lactide and oligomer directly contact with the cooling agent that contains water, then can take place to decompose and generation acid.This not only can hinder the progress of ring-opening polymerization as acid catalyst, but also may cause the corrosion to materials such as water coolers.As cooling agent, using rac-Lactide and oligomer under the situation as inert cooling agent, be not limited to above-mentionedly, but in this case, must make cooling agent dry fully, thereby reduce wet amount.
In rac-Lactide condensation operation, (preferred by reflux cooler) that will obtain in the depolymerization operation contains in the rac-Lactide steam importing rac-Lactide condensing works, makes the rac-Lactide cooling condensation.The rac-Lactide of condensation of being cooled is fed into refining step.The steam that contains more water vapour that does not have condensation in rac-Lactide condensation operation is entered in another condensing works that more downstream is provided with, condensation lactic acid, low molecular oligomer, rac-Lactide, with the gas delivery that contains water vapour, condensation product is refluxed in the rac-Lactide condensing works.The gas that contains water vapour further is imported into the impurity water cooler, can be condensed, liquefy.The impurity that has been liquefied goes out of use usually.
For the rac-Lactide condensing works, also can adopt device with structure identical with reflux cooler.The rac-Lactide condensing works possesses condenser bodies, rac-Lactide steam supplying opening, rac-Lactide relief outlet, residual vapor relief outlet at least.Be called simply in this manual under the situation in " downstream side of condensing works ", be meant " the rac-Lactide relief outlet downstream side of condensing works ".
(refining step and refining plant)
The rac-Lactide that obtains in the condensation operation is main component using under the situation of L-lactic acid as raw material with the L-rac-Lactide, but contains the D-rac-Lactide that generates because of racemization and Study of Meso-Lactide as by product.In addition, it is more to be mixed in the situation of impurity such as lactic acid oligomer in rac-Lactide.In addition, the rac-Lactide that obtains under the situation of using D-lactic acid as raw material is main component with the D-rac-Lactide, contains L-rac-Lactide and Study of Meso-Lactide as by product.
The depolymerization operation is to separate any one the operation of refined lactide of opticity rac-Lactide (being generally the L-rac-Lactide) of needs that contains as L-rac-Lactide or D-rac-Lactide from the such crude lactide that has been condensed the condensation operation.
As the purified method, be not particularly limited, preferably without the process for purification of the heating of the reason of the deterioration that becomes rac-Lactide.As such process for purification, can use solvent extraction, fusion-crystallizationization etc.For example, in the fusion-crystallization method, the crude lactide that has been melted is cooled at least the zero pour of rac-Lactide, make partly crystallization of melts, form few solid crystal phase of impurity and the many liquid phases of impurity, fractional crystallization phase and liquid phase, make the crystallization phases sweating then, impurity is removed in fusion.Residue after the separation and purification rac-Lactide (refining residue) is used to evaporation separation circuit described later.Refining residue is generally liquid.
Lactide refined device is configured in the downstream side of the rac-Lactide relief outlet of condensing works, typically possesses the reactor, crude lactide supplying opening, refined lactide relief outlet, the refining residue relief outlet that are used to accommodate crude lactide.Lactide refined device also possesses temperature measuring mechanism such as thermometer.
Can be from the refined lactide that the refined lactide relief outlet of lactide refined device is discharged in order to make poly(lactic acid) as the raw material of ring-opening polymerization operation described later.
Refining residue contains more rac-Lactide.Therefore, utilize evaporation separation circuit described later,, make it be back to refining step and utilized in the past and again from refining residue Separation and Recovery rac-Lactide.
(evaporation separation circuit and evaporation tripping device)
The refining residue (being generally liquid) of discharging from the refining residue relief outlet of lactide refined device is transferred to the evaporation tripping device.Thereby the evaporation separation circuit is the operation that the rac-Lactide in the evaporation separation and purification residue reclaims.
The evaporation tripping device is configured in the refining residue relief outlet downstream side of refining plant, typically possesses the vaporizer of evaporation separate lactide, refining residue supplying opening, rac-Lactide relief outlet, evaporation separating residual thing relief outlet at least.The evaporation tripping device also possesses temperature measuring mechanism such as thermometer usually.As the evaporation tripping device, can also can use distillation tower for vertical or horizontal, make refining residue filming but preferably use as the use external force of representative with centrifugal-film evaporator, make under the state of its filming, make the device of rac-Lactide evaporation.By carrying out filming, rise at short notice easily as the temperature of the refining residue of process object, can with the several seconds～finish the evaporation of rac-Lactide tens of seconds.In addition, because liquid film is thin, so the evaporation of rac-Lactide is very fast.The thermal process of process object thing is short like this, so the optically active isomer that generates because of isomerization reaction is reached by being thermal decomposited the less rac-Lactide that reclaims effectively of the impurity that generates.
The rotor that centrifugal-film evaporator typically has the device cover (casing) that has been fixed of the heatable inner-wall surface that comprises cylindric or circular cone tubular and rotates along the axle center of described inner-wall surface in device cover.It is parallel with turning axle and outstanding to the radius of a circle direction that forms by rotation on turning axle that the described wing is configured to tabular component usually.The shape of the wing as other comprises that the tabular component relative rotation axi is disposed at the shape of the spirrillum (screw) on the turning axle obliquely.Centrifugal-film evaporator can be any one of level, vertical, its intermediary angle for the relative ground of turning axle.The centrifugal force that the rotation wing of the refining residue utilization rotation of supplying with in the device cover brings, the inner-wall surface collision to the device cover forms film on this inner-wall surface.The heating of utilization on inner-wall surface promotes the evaporation of film.In the manner, have the rotation that can reduce equipment scale, the spacing width that can utilize the wing and inner room and the wing and control strong points such as thickness of liquid film.With the schematic diagram of centrifugal-film evaporator in Fig. 2.
Centrifugal-film evaporator possesses following advantage.At first, because steam capability is big, so be suitable for the processing of the material of viscosity higher.This is because under the effect of the rotation wing, liquid becomes the film of homogeneous, but also owing to stirred powerfully, so even high-viscosity material also can be obtained bigger heat transfer coefficient.Then, owing to can shorten the residence time, so be suitable for the processing of determination system of thermal unstable material.This is because liquid is by the state processing with film, by the concentration of extremely stipulating with extremely short time concentration, so be suitable for the processing of determination system of thermal unstable material.Then, because can corresponding vacuum-evaporation, so be suitable for the processing of determination system of thermal unstable material or high boiling substance.This is because because the boiling point rising that liquid head (head) causes by the state processing with film, does not take place liquid, can make its evaporation with the boiling point under the vacuum tightness in the system.In addition, also owing to can turn round continuously by non-cohesive incrustation scale (scale), so be suitable for the processing of high-viscosity material or slurries.This be because, liquid is stirred the wing and stirs, heat-transfer surface often is updated to new liquid.In addition, also owing to dispersive drop under the effect of the rotation wing knocks in the centrifugal-film evaporator, thereby the liquid film drop that is pushed back under action of centrifugal force on the rotation wing is absorbed, and becomes drop, disperses and then is discharged from from the evaporation tripping device so can prevent oligomer.
Because centrifugal-film evaporator is compared with device volume, evaporation area is big, so compare with the situation of using distillation tower, can make equipment miniaturization.
In addition, the evaporation tripping device also is equipped with reliever, under the reduced pressure atmosphere below the 100Torr, below the preferred 10Torr, 120～250 ℃, preferred 170～230 ℃ of heating down, implements the evaporation separation of refining residue by common usually.Containing with the lactic acid oligomer in the residue after utilizing this evaporation Separation and Recovery rac-Lactide (evaporation separating residual thing) is the high boiling substance of main component.
(utilization again of rac-Lactide)
After isolating rac-Lactide is condensed in the evaporation separation circuit, in described refining step, be reused.
The condensation of isolating rac-Lactide also can make it be back in the rac-Lactide condensation device that is provided with between above-mentioned depolymerizer and the refining plant to carry out in the evaporation separation circuit.That is, refined lactide manufacturing installation of the present invention also can possess the rac-Lactide relief outlet downstream side of connection evaporation tripping device and the upstream side of condensing works, and supplies with the supply road of rac-Lactide to condensing works.
In addition, the condensation of isolating rac-Lactide also can carried out in the independent second rac-Lactide condensing works that is provided with in addition in the evaporation separation circuit.That is, refined lactide manufacturing installation of the present invention also can further possess the upstream side of second condensing works of the rac-Lactide of the rac-Lactide relief outlet downstream side, condensation that are configured in the evaporation tripping device supplying with from the evaporation tripping device and the downstream side that is connected this second condensing works and refining plant and in addition to the supply road of refining plant supply rac-Lactide.The formation of the formation of second condensing works and the condition of condensation and the condensing works that is provided with between depolymerizer and refining plant and the condition of condensation are identical.Also can between the evaporation tripping device and second condensing works, further dispose the second reflux cooling device.
(utilization again of evaporation separating residual thing)
The evaporation separating residual thing (waste liquid) of discharging from the evaporation separating residual thing relief outlet of evaporation tripping device is back to the depolymerization operation or the operation of upstream side more, but under the situation of judging the raising that can not help the raw material yield owing to contain situation such as more impurity, also can discard.
Particularly, contain under the situation of lactic acid oligomer at evaporation separating residual thing, evaporation residue is back in the lactic acid enrichment process and concentrates, utilize again with lactic acid, evaporation residue is back in the lactic acid condensation operation with lactic acid condensation, utilization again, perhaps to be made evaporation residue be back in the depolymerization operation and directly utilizes in the manufacturing of rac-Lactide again.
(ring-opening polymerization operation and ring-opening polymerization device)
In addition, the invention still further relates to the device that a kind of refined lactide of utilizing above-mentioned refined lactide manufacturing process to obtain by ring-opening polymerization is made the method for poly(lactic acid) and is used for this method.
The refined lactide of discharging from lactide refined device is transferred to the ring-opening polymerization device, utilizes the ring-opening polymerization device to convert poly(lactic acid) to.
In the ring-opening polymerization device, under inert gas atmosphere, 120～250 ℃, preferably heating under 120～200 ℃, implement the ring-opening polymerization of rac-Lactide by usually.Ring-opening polymerization preferably is decompressed to below the 10torr and carries out.Utilize this ring-opening polymerization to generate poly(lactic acid).
Ring-opening polymerization typically possesses the reactor, the heating arrangements (for example thermophore chuck, heat exchanger) that is used for heating the reaction mixture of accommodating at reactor that are used for accommodating reaction mixture, be used to be stirred in stirring mechanism (for example agitating wing), refined lactide supplying opening, the poly(lactic acid) relief outlet of the reaction mixture that reactor accommodates.In addition, the ring-opening polymerization device also possesses temperature measuring mechanism such as thermometer usually.As reactor, be not particularly limited, can use vertical reactor, horizontal reactor, box reactor etc., also can connect and use 2 above reactors.As agitating wing, can use paddle, the turbine wing, the anchor wing, two moving wing, the hurricane band wing etc.
As the heating means of reactor, can use the method for utilization normally used heating arrangements in this technical field.As heating means, for example, be included in the reactor peripheral part chuck of thermophore is set, by the reactor wall, utilize the method for conducting heat reacting by heating liquid, perhaps, by the heat-transfer pipe (coil (coil)) of inside reactor, utilize the method for the heating of conducting heat etc., can be used singly or in combination these methods.
As the catalyzer of ring-opening polymerization, also can use the catalyzer identical where necessary with the catalyzer that is used for depolymerization reaction.As catalyzer, can use known in the past catalyzer, for example can use the catalyzer that constitutes by metal of selecting the group that constitutes from periodic law Table I A family, IIIA family, IVA family, IVB family, IIB family and VA family or metallic compound.
As the catalyzer that belongs to IA family, for example can enumerate alkali-metal oxyhydroxide (for example sodium hydroxide, potassium hydroxide, lithium hydroxide etc.), basic metal and faintly acid salt (for example Sodium.alpha.-hydroxypropionate, sodium acetate, yellow soda ash, Sodium octoate, sodium stearate, potassium lactate, potassium acetate, salt of wormwood, potassium octanoate etc.), alkali alcoholate (for example sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.) etc.
As the catalyzer that belongs to IIIA family, for example can enumerate aluminum ethylate, aluminum isopropylate, aluminum oxide, aluminum chloride etc.
As the catalyzer that belongs to IVA family, for example can enumerate the catalyzer (for example lactic acid tin, tartrate tin, two stannous octoates, distearyl acid tin, two oleic acid tin, α-Nai Jiasuan tin, β-naphthoic acid tin, stannous octoate etc.) of organotin system, in addition, can also enumerate powder tin, stannic oxide, tin halides etc.
As the catalyzer that belongs to IIB family, for example can enumerate zinc powder, zinc halide, zinc oxide, organic zinc based compound.
As the catalyzer that belongs to IVB family, for example can enumerate zirconium compounds such as titanium sub-group compound, zirconium iso-propoxide such as tetrapropyl titanic acid ester etc.
Wherein, preferably use antimony based compounds such as tin based compounds such as stannous octoate or ANTIMONY TRIOXIDE SB 203 99.8 PCT.
Relative rac-Lactide, the usage quantity of these catalyzer is 1～2000ppm, is preferably 5～1500ppm, more preferably about 10～1000ppm.
In ring-opening polymerization,, also can add the polymerization starter that is used for depolymerization reaction as required for adjustment of molecular weight etc.As polymerization starter, can use material with hydroxyl as alcohols such as 1-dodecanol and so on.Wherein, the concentration of polymerization starter is under the situation of 700ppm, and the weight-average molecular weight of poly(lactic acid) is about 200000.
Below, based on the concrete embodiment of description of drawings poly(lactic acid) manufacturing installation of the present invention, but scope of the present invention has more than and is limited to these embodiments.
(concrete embodiment 1)
Be illustrated in to Fig. 1 pattern in the poly(lactic acid) manufacturing installation of the present invention, utilize supply with road 38 and will be supplied in the reflux cooler 12 of upstream side of rac-Lactide condenser 13 and then the embodiment (embodiment 1) that utilizes again from the rac-Lactide that the rac-Lactide relief outlet 36 of evaporation tripping device 27 is discharged.Device shown in Figure 1 begins to dispose successively lactic acid feedway 1, liquid-feeding pump 2, lactic acid concentrating unit 3, liquid-feeding pump 4, concentrated lactic acid dashpot 5, liquid-feeding pump 6, lactic acid condensation device 7, liquid-feeding pump 8, oligomer dashpot 9, liquid-feeding pump 10, depolymerizer 11, reflux cooler 12, rac-Lactide condenser 13, liquid-feeding pump 14, lactide refined device 15, liquid-feeding pump 16, ring-opening polymerization device 17 from the response path upstream side, disposes evaporation tripping device 27 successively from refining residue (waste liquid) relief outlet 35 beginnings of lactide refined device 15.The treatment condition of the device in the use present embodiment as mentioned above.
Supply with lactic acid from lactic acid feedway 1, in lactic acid concentrating unit 3, be heated, and then remove moisture, become concentrated lactic acid.
The gas that contains water and lactic acid that takes place in the lactic acid enrichment process enters return channel 18, and lactic acid is removed from gas, is back to lactic acid concentrating unit 3.
The concentrated lactic acid of making in lactic acid concentrating unit 3 is sent to lactic acid condensation device 7 via concentrated lactic acid dashpot 5.
In lactic acid condensation device 7, carry out the condensation reaction of lactic acid.Make consequential moisture evaporation.The gas of the rac-Lactide that contains moisture, lactic acid, low-molecular-weight oligomer and take place in it decomposes that takes place in the lactic acid condensation reaction moves to reliever 23 from lactic acid condensation device 7.These gases enter return channel 21, and lactic acid, low-molecular-weight oligomer, rac-Lactide are removed from gas, are back to lactic acid condensation device 7.
The oligomer that generates in lactic acid condensation device 7 is sent to depolymerizer 11.
In depolymerizer 11, carry out the depolymerization reaction of oligomer.The gas rac-Lactide that utilizes this reaction to generate is sent to reflux cooler 12.
In reflux cooler 12, by the cooling gas rac-Lactide, the impurity such as oligomer that liquefaction contains in the rac-Lactide are sent to rac-Lactide condenser 13 as the rac-Lactide of gas.With the isolating liquid that contains oligomer of rac-Lactide mostly under the effect of depolymerization reaction the molecular weight of oligomer diminish.The oligomer that preferably the condensation molecular weight is little once more for the yield that improves rac-Lactide improves molecular weight, so be back to lactic acid condensation device 7 with the isolating liquid that contains the low-molecular weight oligo thing of rac-Lactide.
The gas rac-Lactide is cooled in rac-Lactide condenser 13 after the condensation, is sent to lactide refined device 15.Enter condenser 24 with the isolating gas that contains more water vapour of rac-Lactide, lactic acid, low-molecular-weight oligomer, rac-Lactide are removed from gas, are back to rac-Lactide condenser 13.
The steam that is not condensed in condenser 24 enters impurity water cooler 25, in this liquefaction that is condensed.The situation that the impurity that has been liquefied goes out of use usually is more.The gas of condensation in impurity water cooler 25 is not released to outside the system via reliever 26.
Separation and purification purpose rac-Lactide in lactide refined device 15 mainly is L-rac-Lactide and other impurity.Discharge isolating refined lactide lactide refined device 15 from refined lactide relief outlet 34 respectively, discharge refining residue from refining residue relief outlet 35.
The rac-Lactide of discharging from the refined lactide relief outlet 34 of lactide refined device 15 is transferred to ring-opening polymerization device 17.
In ring-opening polymerization device 17, carry out the ring-opening polymerization of rac-Lactide.
In evaporation tripping device 27, separate the rac-Lactide that from the refining residue (waste liquid) that the refining residue relief outlet 35 of lactide refined device 15 is discharged, contains.The gas rac-Lactide that utilizes this reaction to generate is discharged from from the rac-Lactide relief outlet 36 that evaporates tripping device 27, utilizes and supplies with road 38, is sent to the reflux cooler 12 of the upstream side that is positioned at rac-Lactide condenser 13, is reused.The evaporation separating residual thing (waste liquid) that contains oligomer is discharged from from the evaporation separating residual thing relief outlet 37 that evaporates tripping device 27, utilize and supply with road 39, be back to the upstream side of depolymerizer 11, but under the situation of judging the raising that can not help the raw material yield owing to contain more impurity etc., also can discard.
(concrete embodiment 2)
Be illustrated in to Fig. 3 pattern in the poly(lactic acid) manufacturing installation of the present invention, by between evaporation tripping device 27 and refining plant 15, second reflux cooler 29 and the second rac-Lactide condenser 30 being set, make at evaporation tripping device 27 isolating rac-Lactides of discharging by second reflux cooler 29 and the second rac-Lactide condenser 30 from rac-Lactide relief outlet 36, condensation, utilize and supply with road 40, be back to the upstream side of refining plant 15, and then the embodiment that utilizes again.If utilize this embodiment of the present invention, then have the setting that is adapted at evaporating the condensing condition of the rac-Lactide of the composition of isolating rac-Lactide in the tripping device and become easily, the management of the quality of refined lactide and the poly(lactic acid) easy advantage that becomes.
In embodiment shown in Figure 3, the rac-Lactide that has been condensed in the second rac-Lactide condenser 30 is reused through supplying with the upstream side that road 40 is transferred to refining plant 15.Enter condenser 31 with the isolating gas that contains more water vapour of rac-Lactide, lactic acid, low molecular oligomer, rac-Lactide are removed from gas, are back to the second rac-Lactide condenser 30.
The steam that is not condensed in condenser 31 enters impurity water cooler 32, and at this, liquefaction is condensed.The situation that the impurity that has been liquefied goes out of use usually is more., be not released to outside the system by the gas of impurity water cooler 32 condensations process reliever 33.
In Fig. 3, the integrant with symbol identical with Fig. 1 have with based on each integrant identical functions and feature in the above-mentioned embodiment 1 of Fig. 1 explanation.
[embodiment]
Below illustrate in greater detail the present invention in an embodiment, but scope of the present invention is not limited to these embodiment.
[embodiment 1]
Use poly(lactic acid) manufacturing installation shown in Figure 1, carry out the manufacturing of poly(lactic acid).As raw material, in depolymerizer 11, drop into the lactic acid oligomer of number-average molecular weight 630.Being reflected in depolymerizer 11 be decompressed to below the 10torr, carry out under 200 ℃ the temperature.The residence time of the lactic acid oligomer in the depolymerizer 11 is 5 hours, and thickness of liquid film (liquid is dark) is 55cm, and catalyzer (stannous 2-ethylhexoate) concentration is 0.7kg/m
3
Be decompressed to below the 10torr evaporation being reflected in the tripping device 27, carry out under 210 ℃ the temperature.As evaporation tripping device 27, use centrifugal-film evaporator.
At this, the supply flow rate that the residence time of oligomer is defined as the fusion oligomer equates the fusion oligomer hold-up in the fusion oligomer supply flow rate/oligomer depolymerizer 11 in the time of after the thickness of liquid film stabilization with the condensation product flow of the steam of discharging from depolymerizer.
Optically active isomer rate in the depolymerization operation increase to 0.9% (before lactide refined device 15, measuring).
In addition, the painted of its quality of expression that is delivered to the poly(lactic acid) that ring-opening polymerization obtains by the rac-Lactide that will obtain counts 2.5 with the b value, and rac-Lactide when thinking depolymerization and the influence of the pyrolysated of oligomer are little.Being reflected in ring-opening polymerization device 17 be decompressed to below the 10torr, carry out under 200 ℃ the temperature.The concentration of the polymerization starter during ring-opening polymerization is 700ppm.The weight-average molecular weight of the poly(lactic acid) that obtains is about 200000.
From as can be known above, by reclaiming rac-Lactide from the waste liquid from lactide refined device that went out of use in the past, the steady running of the raising of yield and equipment (plant) becomes possibility.Then, the result can obtain the high poly(lactic acid) of quality.
[embodiment 2]
Use poly(lactic acid) manufacturing installation shown in Figure 3, carry out the manufacturing of poly(lactic acid).As raw material, in depolymerizer 11, drop into the lactic acid oligomer of number-average molecular weight 630.Being reflected in depolymerizer 11 be decompressed to below the 10torr, carry out under 200 ℃ the temperature.The residence time of the lactic acid oligomer in the depolymerizer 11 is 5 hours, and thickness of liquid film (liquid is dark) is 55cm, and catalyzer (stannous 2-ethylhexoate) concentration is 0.7kg/m
3
Be decompressed to below the 10torr evaporation being reflected in the tripping device 27, carry out under 210 ℃ the temperature.As evaporation tripping device 27, use centrifugal-film evaporator.
At this, the supply flow rate that the residence time of oligomer is defined as the fusion oligomer equates the fusion oligomer hold-up in the fusion oligomer supply flow rate/oligomer depolymerizer 11 in the time of after the thickness of liquid film stabilization with the condensation product flow of the steam of discharging from depolymerizer.
Optically active isomer rate in the depolymerization operation increase to 0.9% (before lactide refined device 15, measuring).
In addition, the painted of its quality of expression that is delivered to the poly(lactic acid) that ring-opening polymerization obtains by the rac-Lactide that will obtain counts 2.5 with the b value, and rac-Lactide when thinking depolymerization and the influence of the pyrolysated of oligomer are little.Being reflected in ring-opening polymerization device 17 be decompressed to below the 10torr, carry out under 200 ℃ the temperature.The concentration of the polymerization starter during ring-opening polymerization is 700ppm.The weight-average molecular weight of the poly(lactic acid) that obtains is about 200000.
From as can be known above, by reclaiming rac-Lactide from the waste liquid from lactide refined device that went out of use in the past, the raising of yield and the steady running of equipment become possibility.Then, the result can obtain the high poly(lactic acid) of quality.
[comparative example]
Use the lactic acid oligomer of the number-average molecular weight 630 identical with embodiment 1 and 2, after the depolymerization operation, be concentrated in the crude lactide that generates in the depolymerization operation with fractional distillating tube, then as steam, supply to distillation tower, in distillation tower, be separated into jar overhead product at the bottom of lower boiling overhead product, rac-Lactide and the high boiling point tower, utilize the device in the past (device of conventional art 1) that obtains refined lactide, carry out the depolymerization of batch mode.In the method, make and utilize distillation tower and the isolating unreacted oligomer of refined lactide, crude lactide etc. to be back in the depolymerization operation.In the depolymerization time is that 10 hours, initial stage liquid level are that 80cm, initial stage catalyst concn are 5kg/m
3Condition under, implement depolymerization reaction.Depolymerization reaction is being decompressed to below the 10torr, is carrying out under 200 ℃ the temperature.As a result, for the rac-Lactide that generates, the optically active isomer rate in the depolymerization operation increase to 9%.
Be delivered to the painted of poly(lactic acid) that ring-opening polymerization obtains by the rac-Lactide that will obtain and count 4.4 with the b value.Being reflected in the ring-opening polymerization device be decompressed to below the 10torr, carry out under 200 ℃ the temperature.The concentration of the polymerization starter during ring-opening polymerization is 700ppm.
As can be known from these results, if thereby the crude lactide that utilizes the full dose distillation to obtain in the depolymerization operation obtains refined lactide, make the method in the past that is back to the depolymerization operation from the refining residue of distillation tower, then because the thermolysis of lactic acid oligomer, generate impurity, as a result, the quality of poly(lactic acid) reduces.
Claims (17)
1. the manufacture method of a cyclic refined lactic acid dimmer is characterized in that, comprising:
The depolymerization operation, its lactate condensation compound that lactic acid condensation will be obtained carries out depolymerization and obtains gasiform lactic acid cyclic dimer;
The condensation operation, it makes the condensation of gasiform lactic acid cyclic dimer;
Refining step, the lactic acid cyclic dimer that it will be condensed are separated into cyclic refined lactic acid dimmer and the cyclic refined lactic acid dimmer refining residue in addition that any kind that contains in L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer;
The evaporation separation circuit, it will be made with extra care residue by making the lactic acid cyclic dimer evacuator body in the refining residue and be separated into lactic acid cyclic dimer and lactic acid cyclic dimer evaporation separating residual thing in addition,
Wherein, make isolating lactic acid cyclic dimer condensation in the evaporation separation circuit, and in refining step, utilize again.
2. method according to claim 1 is characterized in that,
The evaporation separation circuit is the operation that makes lactic acid cyclic dimer evacuator body under the state that makes refining residue filming.
3. method according to claim 2 is characterized in that,
Use centrifugal-film evaporator to evaporate separation circuit.
4. according to any described method in the claim 1～3, it is characterized in that, also comprise:
The enrichment process of concentrated lactic acid; With
Make the lactic acid condensation behind the enrichment process and obtain the condensation operation of lactate condensation compound,
Wherein, in the depolymerization operation, use the lactate condensation compound that in the condensation operation, obtains.
5. method according to claim 4 is characterized in that,
Evaporation separating residual thing is the material that contains lactate condensation compound, this evaporation separating residual thing is back in the enrichment process and concentrates and utilization again with lactic acid.
6. method according to claim 4 is characterized in that,
Evaporation separating residual thing is the material that contains lactate condensation compound, this evaporation separating residual thing is back in the condensation operation also utilizes with the lactic acid condensation again.
7. according to any described method in the claim 1～4, it is characterized in that,
Contain lactate condensation compound in the evaporation separating residual thing, in the depolymerization operation, utilize this evaporation separating residual thing again.
8. the manufacture method of a poly(lactic acid) is characterized in that, comprising:
The manufacturing process of cyclic refined lactic acid dimmer, it makes cyclic refined lactic acid dimmer by any described method in the claim 1～7; With
The ring-opening polymerization operation, its cyclic refined lactic acid dimmer that will be obtained by the manufacturing process of cyclic refined lactic acid dimmer carries out ring-opening polymerization and makes poly(lactic acid).
9. the manufacturing installation of a cyclic refined lactic acid dimmer is characterized in that, possesses:
Depolymerizer, it makes the lactate condensation compound depolymerization and obtains gasiform lactic acid cyclic dimer;
Condensing works, the downstream side that it is configured in depolymerizer makes the lactic acid cyclic dimer condensation from depolymerizer gas supplied shape;
Refining plant, it is configured in the downstream side of condensing works, to be separated into cyclic refined lactic acid dimmer and refining residue beyond the cyclic refined lactic acid dimmer and discharge that any kind that contains L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer from the lactic acid cyclic dimer that has been condensed that condensing works is supplied with, and have cyclic refined lactic acid dimmer relief outlet and refining residue relief outlet;
The evaporation tripping device, it is configured in the refining residue relief outlet downstream side of refining plant, to be separated into the evaporation separating residual thing beyond lactic acid cyclic dimer and the lactic acid cyclic dimer by making the lactic acid cyclic dimer evacuator body in this refining residue from the refining residue that refining plant is supplied with and discharge, and have lactic acid cyclic dimer relief outlet and evaporation separating residual thing relief outlet;
Supply with the road, it is connected with the lactic acid cyclic dimer relief outlet downstream side of evaporation tripping device and the upstream side of condensing works, and supplies with the lactic acid cyclic dimer to condensing works.
10. the manufacturing installation of a cyclic refined lactic acid dimmer is characterized in that, possesses:
Depolymerizer, it makes the lactate condensation compound depolymerization and obtains gasiform lactic acid cyclic dimer;
Condensing works, the downstream side that it is configured in depolymerizer makes the lactic acid cyclic dimer condensation from depolymerizer gas supplied shape;
Refining plant, it is configured in the downstream side of condensing works, to be separated into cyclic refined lactic acid dimmer and refining residue beyond the cyclic refined lactic acid dimmer and discharge that any kind that contains L-lactic acid cyclic dimer and the D-lactic acid cyclic dimer is an opticity lactic acid cyclic dimer from the lactic acid cyclic dimer that has been condensed that condensing works is supplied with, and have cyclic refined lactic acid dimmer relief outlet and refining residue relief outlet;
The evaporation tripping device, it is configured in the refining residue relief outlet downstream side of refining plant, to be separated into the evaporation separating residual thing beyond lactic acid cyclic dimer and the lactic acid cyclic dimer by making the lactic acid cyclic dimer evacuator body in this refining residue from the refining residue that refining plant is supplied with and discharge, and have lactic acid cyclic dimer relief outlet and evaporation separating residual thing relief outlet;
Second condensing works, the lactic acid cyclic dimer relief outlet downstream side that it is configured in the evaporation tripping device makes the lactic acid cyclic dimer condensation of supplying with from the evaporation tripping device;
Supply with the road, it is connected with the downstream side of second condensing works and the upstream side of refining plant, supplies with the lactic acid cyclic dimer to refining plant.
11. according to claim 9 or 10 described devices, it is characterized in that,
The evaporation tripping device is a thin-film evaporator.
12. device according to claim 11 is characterized in that,
Thin-film evaporator is a centrifugal-film evaporator.
13., it is characterized in that also possessing according to any described device in the claim 9～12:
The concentrating unit of concentrated lactic acid; With
Be configured in the downstream side of concentrating unit, condensation from concentrating unit supply with concentrate after the condensation device of lactic acid,
Wherein, depolymerizer is disposed at the downstream side of condensation device according to the mode from condensation unit feeding lactate condensation compound.
14. device according to claim 13 is characterized in that, also possesses:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of concentrating unit, and supply with the supply road of evaporation separating residual thing to concentrating unit.
15. device according to claim 13 is characterized in that, also possesses:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of condensation device, and evaporate the supply road of separating residual thing to the condensation unit feeding.
16., it is characterized in that also possessing according to any described device in the claim 9～13:
Be connected with the evaporation separating residual thing relief outlet downstream side of evaporation tripping device and the upstream side of depolymerizer, and supply with the supply road of evaporation separating residual thing to depolymerizer.
17. the manufacturing installation of a poly(lactic acid) is characterized in that, possesses:
The manufacturing installation of any described cyclic refined lactic acid dimmer in the claim 9～16; With
Be configured in the cyclic refined lactic acid dimmer relief outlet downstream side of the refining plant in this manufacturing installation, and make the cyclic refined lactic acid dimmer ring-opening polymerization of supplying with from refining plant and make the ring-opening polymerization device of poly(lactic acid).
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| JP2008103580A JP5459974B2 (en) | 2008-04-11 | 2008-04-11 | Method and apparatus for producing purified lactic acid cyclic dimer, and method and apparatus for producing polylactic acid |
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Cited By (8)
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| CN101845038A (en) * | 2010-05-13 | 2010-09-29 | 中国石油天然气集团公司 | Method and device for processing lactide refined raffinate |
| CN110105325A (en) * | 2019-06-20 | 2019-08-09 | 南京大学 | A kind of alkali metal compound catalyzes and synthesizes the process of lactide |
| CN110156745A (en) * | 2019-06-20 | 2019-08-23 | 南京大学 | A kind of process catalyzing and synthesizing lactide |
| CN111153886A (en) * | 2020-01-16 | 2020-05-15 | 南京大学 | Method and device for synthesizing lactide with high yield and rapidness |
| CN112851628A (en) * | 2019-11-26 | 2021-05-28 | 南京华基塔业有限公司 | Reaction system and method for preparing lactide from lactic acid |
| CN113234056A (en) * | 2021-07-12 | 2021-08-10 | 北京朗净汇明生物科技有限公司 | Preparation method and preparation device of crude lactide and prepared crude lactide |
| CN114573797A (en) * | 2022-04-01 | 2022-06-03 | 温州邦鹿化工有限公司 | Continuous polymerization process for producing polylactic acid slices from lactide |
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| JP2012097224A (en) * | 2010-11-04 | 2012-05-24 | Hitachi Plant Technologies Ltd | Manufacturing apparatus for and manufacturing method for polyhydroxycarboxylic acid |
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| US5319107A (en) * | 1990-09-18 | 1994-06-07 | Biopak Technology, Ltd. | Method to produce cyclic esters |
| US5117008A (en) * | 1990-10-23 | 1992-05-26 | E. I. Du Pont De Nemours And Company | Solvent scrubbing recovery of lactide and other dimeric cyclic esters |
| US5236560A (en) * | 1992-03-13 | 1993-08-17 | E. I. Du Pont De Nemours And Company | Solventless dimeric cyclic ester distillation process |
| CA2115472C (en) * | 1993-02-17 | 2002-08-13 | William George O'brien | Melt crystallization purification of lactides |
| US5521278A (en) * | 1994-08-18 | 1996-05-28 | Ecological Chemical Products | Integrated process for the manufacture of lactide |
| JP4075085B2 (en) * | 1996-10-25 | 2008-04-16 | トヨタ自動車株式会社 | Method for producing lactide |
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| CN1176070C (en) * | 2002-12-26 | 2004-11-17 | 浙江大学 | Method of preparing lactide using recovered lactic acid polymer as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845038A (en) * | 2010-05-13 | 2010-09-29 | 中国石油天然气集团公司 | Method and device for processing lactide refined raffinate |
| CN101845038B (en) * | 2010-05-13 | 2014-01-15 | 中国石油天然气集团公司 | Method and device for processing lactide refined raffinate |
| CN110105325A (en) * | 2019-06-20 | 2019-08-09 | 南京大学 | A kind of alkali metal compound catalyzes and synthesizes the process of lactide |
| CN110156745A (en) * | 2019-06-20 | 2019-08-23 | 南京大学 | A kind of process catalyzing and synthesizing lactide |
| WO2020253243A1 (en) * | 2019-06-20 | 2020-12-24 | 南京大学 | Process method for catalyzed synthesis of lactide with alkali metal compound |
| WO2020253244A1 (en) * | 2019-06-20 | 2020-12-24 | 南京大学 | Process for catalytic synthesis of lactide |
| CN112851628A (en) * | 2019-11-26 | 2021-05-28 | 南京华基塔业有限公司 | Reaction system and method for preparing lactide from lactic acid |
| CN111153886A (en) * | 2020-01-16 | 2020-05-15 | 南京大学 | Method and device for synthesizing lactide with high yield and rapidness |
| CN113234056A (en) * | 2021-07-12 | 2021-08-10 | 北京朗净汇明生物科技有限公司 | Preparation method and preparation device of crude lactide and prepared crude lactide |
| CN114573797A (en) * | 2022-04-01 | 2022-06-03 | 温州邦鹿化工有限公司 | Continuous polymerization process for producing polylactic acid slices from lactide |
| WO2023208121A1 (en) * | 2022-04-29 | 2023-11-02 | 爱美客技术发展股份有限公司 | Method of preparing methoxy poly(ethylene glycol)-b-poly(l-lactide) block copolymer |
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| CN101555243B (en) | 2013-08-14 |
| JP2009256210A (en) | 2009-11-05 |
| JP5459974B2 (en) | 2014-04-02 |
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