CN100999744A - Process of mfg. lactic acid or poly lactic acid by industry and agriculture waste or by-products containing sugar - Google Patents
Process of mfg. lactic acid or poly lactic acid by industry and agriculture waste or by-products containing sugar Download PDFInfo
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- CN100999744A CN100999744A CN 200610130554 CN200610130554A CN100999744A CN 100999744 A CN100999744 A CN 100999744A CN 200610130554 CN200610130554 CN 200610130554 CN 200610130554 A CN200610130554 A CN 200610130554A CN 100999744 A CN100999744 A CN 100999744A
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Abstract
The present invention provides one simple process of producing lactic acid and polylactic acid with sugar containing industrial and agricultural waste or side product in low cost and high yield. The process includes the steps of pre-treating sugar containing industrial and agricultural waste or side product, fermentation of the treated matter, ultrafiltering to obtain clear liquid, acidification to prepare lactic acid, dewatering lactic acid and pre-polymerizing, crystallizing the pre-polymer to purify, and polymerizing reaction to obtain polylactic acid.
Description
Technical field
The invention belongs to material and make the field, relate to the manufacture method of a kind of organism and superpolymer, particularly make the method for lactic acid and poly(lactic acid) with sacchariferous agriculture and industry waste or by product.
Background technology
Lactic acid is a kind of very useful organism, is widely used in fields such as food, medicine, chemical industry.Along with the enhancing of the reach of science and environmental consciousness, the developing of lactic acid is used and to be subjected to people more and more and to pay attention to, and is especially manufacturing with the lactic acid development aspect a kind of complete eco-friendly macromolecular material-poly(lactic acid).
Poly(lactic acid) is a kind of macromolecular material of nontoxic, fully biodegradable, has excellent biological compatibility, and its eventual degradation product is water and carbonic acid gas, and intermediate product-lactic acid is that normal sugar can not assembled at vitals for hydrolysis products in the human body.Wrapping material, agricultural film etc. can be widely used as, biotechnology and medical science field of medicaments can be widely used in again, as: the solid support material of fracture fixation material, operating sutures, tissue engineering bracket material, agents alleviate etc.
At present, the production method of lectic acid that is occurred nearly all is to adopt the higher crop products of starch content, as: rice, Chinese sorghum, potato or the like are as raw material, by gelatinization, saccharification, inoculation, fermentation, neutralization, acidolysis, concentrate, operations such as crystallization, precipitation make lactic acid, and produce dissimilar lactic acid with the inoculation of different bacillus, and as: D type lactic acid or L type lactic acid.Chinese patent prospectus (number of patent application: CN87101404.1, CN87107162A, CN200410041622.5, CN200310118919.2, CN02136165.5, CN200510057160.0) described production method of lectic acid all belongs to the method that the high starch material of employing is a raw material manufacturing lactic acid.The deficiency of this type of disclosed lactic acid manufacture method is to adopt main food crop, as: rice, corn etc. are as the manufacturing raw material of lactic acid, but the lactic acid extraction transformation efficiency is but not too high.
The poly(lactic acid) producer rule that is occurred mostly adopts lactic acid (mostly being L type lactic acid) from starchiness as raw material, through acid by dehydrating lactic technology, precondensation, crystallization treatment, made poly(lactic acid) by the pulverizing of crystallization oligopolymer, solid state polymerization or synthetic melt phase polycondensation.This class poly(lactic acid) manufacture method is at U.S. Pat 5247059, Japanese Patent JP59-96123, world patent WO98/212611 and Chinese patent prospectus (number of patent application: CN03115321.6, CN200410017211.2, CN200410017212.7, CN200410067337.8 has in CN200410041426.6) and describes in detail.
Chinese patent prospectus CN200410066456.4 discloses a kind of poly(lactic acid) preparation method, promptly adopt lactic acid to be the most initial raw material, the low-molecular-weight poly(lactic acid) prepolymer of preparation, crystallisate carry out solid state polymerization or chain extension polycondensation more earlier, the middle need pulverized the sealing preservation with prepolymer or crystallisate, and so just having caused poly(lactic acid) is not to make from the lactic acid continuous one-step.
German patent DE 10020898.3, U.S. Pat 6326458 and Japanese Patent JP56-14688 disclose from flour, corn and cereal starch and have made lactic acid, hand over fat to prepare high molecular weight polylactic acid by ring-opening polymerization with its dimer third then.The disclosed poly(lactic acid) preparation method's of this class shortcoming is that preparation cost is too high, and its practical application is severely limited.
Summary of the invention
One of purpose of the present invention is to provide the method for making lactic acid and poly(lactic acid) with sacchariferous agriculture and industry waste or by product, to avoid adopting precious staple food crop, as: rice, corn, flour etc. are as the most initial starting material of lactic acid and poly(lactic acid), the by product that makes full use of agriculture and industry waste and low value is made high value added product, reduces environmental pollution to help, turns waste into wealth.
The method of another object of the present invention is to provide that technology is simple, the cost of goods manifactured sacchariferous agriculture and industry waste of usefulness very cheap, that ratio defective product is higher or by product being made lactic acid and poly(lactic acid).
The method that sacchariferous agriculture and industry waste of the usefulness that the present invention relates to or by product are made lactic acid and poly(lactic acid) is directly to produce poly(lactic acid) or its middle product-lactic acid from the determined starting material of the present invention, and its process is a successive, also can be intermittently.
The determined starting material of the present invention contain and are higher than 25% (w/w) fermentable sugars: the tankage of crop stalk, bagasse, Semen Maydis grit, decayed fruit thing, beet, beet pulp, sugaring/food/cheese industry, fruit juice, syrup, molasses, sweet sorghum, farm crop, natural biological, contain sugared thing, arbitrarily two or more adulterant in them, two or more mixing solutions or single liquefaction things arbitrarily in them.
The method that sacchariferous agriculture and industry waste of related usefulness or by product are made lactic acid and poly(lactic acid) comprises the steps:
1) sacchariferous agriculture and industry waste or by product pre-treatment:
Comprise the impurity elimination thing, soak and/or the dilution of sugar water with diluted acid, diluted alkaline;
2) pretreated system fermentation:
Yeast extract paste and/or cereal immersion liquid quasi-growth promoter, enzyme thing are added through the pre-treatment system, the microbial bacteria family of inoculating lactic acid mushroom, in the fermentation culture temperature is to ferment under 36-45 ℃, anaerobism or the little oxygen condition, and 5.0--6.5 is regulated and maintained to the pH value of fermented liquid with the neutralizing agent that comprises basic metal, carbonate, sodium hydroxide, potassium hydroxide and/or ammoniacal liquor in the fermenting process;
3) acidifying is by the fermentation clear liquid of ultrafiltration:
With one or more acidifying fermentation clear liquids in the mineral acid, make its pH value below 3.6, preferable at 2.0--2.9, mineral acid comprises sulfuric acid, hydrochloric acid; Preferably, fermentation clear liquid is passed through a ultrafiltration again before by acidifying;
4) obtain lactic acid:
Make by the acidifying system and pass through one deck nano level filter membrane, reverse osmosis membrane and/or electrodialysis at least, carry out ultrapurification, make lactic acid, the filter opening footpath of the nano level filter membrane that is used to purify is less than 200 nanometers, and is preferable less than 100 nanometers;
5) acid by dehydrating lactic pre-polymerization:
The system top temperature is 235 ℃ in the process, vacuum tightness is 7MPa-0.001MPa in the device, progressively heat up, carry out the metal catalyst, weight-average molecular weight of preceding or middle adding 0.01--5% (w/w) less than 10 in process, in 000 acid, alcohol or the lipid organism/organic oligomer one or more, system is stirred all the time;
6) adopt solvent method or vacuum crystallization device to carry out the prepolymer crystallization purifying: Tc is 55--185 ℃ in the process, and vacuum tightness is 10MPa--0.01MPa;
7) adopt twin screw extruder or polymerizing reactor to carry out polyreaction and make poly(lactic acid), temperature is an envrionment temperature in the process--230 ℃, vacuum tightness are 10MPa--0.001MPa, and the reaction system comprises one or more in stablizer, catalyzer, food nutrition additive, chainextender, weighting agent, properties-correcting agent, processing aid, tinting material or other polymkeric substance.
The inventor finds, do not pursuing high purity too and/or too under the situation of high molecular weight polylactic acid, can omit this step of prepolymer crystallization purifying.
The lactic acid that sacchariferous agriculture and industry waste of the usefulness that the present invention relates to or by product produce can be L type lactic acid, also can be D type lactic acid, depends on the kind of inoculating bacillus.Can be by producing dissimilar lactic acid with different bacillus inoculations, for example: make L type lactic acid by inoculating with lactobacillus (Lactobacillus), or by using De Shi milk-acid bacteria (Lactobacillus delbrueckii) inoculation manufacturing D type lactic acid.
The poly(lactic acid) that sacchariferous agriculture and industry waste of the usefulness that the present invention relates to or by product produce can be a poly (l-lactic acid), also can be poly-D-lactic acid, or their mixture, depends primarily on type, polyreaction system component and the kind of lactic acid.Can be by making poly (l-lactic acid) with L type lactic acid, with the poly-D-lactic acid of D type lactic acid manufacturing, or with the L of suitable proportion, D type lactic acid component polymerization manufacturing their macromolecule mixture, mixture or multipolymer etc.
Description of drawings
Accompanying drawing is a process flow diagram of making lactic acid and poly(lactic acid) with sacchariferous agriculture and industry waste or by product.
Embodiment
Further specify the present invention below by embodiment, but the present invention is not limited in these embodiment declared ranges.
Embodiment 1:
With reference to accompanying drawing: with sacchariferous agriculture and industry waste or by product, as bagasse (or the sweet sorghum straw after crushed), impurity elimination, as impurity elimination skin etc., with diluted acid and/or diluted alkaline immersion treatment (immersion treatment: handled 20--100 minute between 110--130 ℃ with diluted acid earlier, use diluted alkaline (1--6% (V/V)) between 110--160 ℃, to handle 10--100 minute again).Growth stimulant such as cereal immersion liquid, yeast extract paste and/or the nitrogen pledge of 1.5--5.5% (w/w) are added pretreated solution.
Then, they are inserted fermentation unit (not shown), add enzyme, as cellulase, inoculating lactobacillus under anaerobism or little oxygen condition (2-8% (w/w)) ferments, enzymic hydrolysis is carried out simultaneously with fermentation between yeast phase, and 5.0-6.5 is regulated and maintained to the pH value of system with the neutralizing agent that comprises basic metal, carbonate, sodium hydroxide, potassium hydroxide and/or ammoniacal liquor.Leavening temperature maintains 35-45 ℃, and ultra-filtration membrane (not shown) ultrafiltration that the system after having fermented installs the exit by fermentation produces fermentation clear liquid.Celliferous residue, the fermented liquid of removing the lactic acid that fermentation produces return in the fermentation unit.Fermentation unit can be common, conventional fermentation unit, is preferably and is built-in with the fermentation unit of one deck ultra-filtration membrane at least.
With in the mineral acid one or more, as sulfuric acid, hydrochloric acid, the fermentation clear liquid that acidifying is filtered makes its pH value below 3.6, and is preferable at 2.0-2.9.Preferably, fermentation clear liquid is passed through a ultrafiltration again before by acidifying.Acidified system is by one deck nano level filter membrane, reverse osmosis membrane and/or electrodialysis (not shown) at least, by super purification, the filter opening footpath of the nano level filter membrane that is used for purifying first is less than 100 nanometers, preferable less than 50 nanometers, the filter opening of the nano level film that is used for purifying subsequently footpath is smaller or equal to the filter opening footpath of preceding once used nano level film.Be lactic acid by the product that obtains after the ultrapurification, its purity is greater than 90%.
Gained lactic acid is inserted same device (not shown) dewater and pre-polymerization, its dehydration pre-polymerization condition is for progressively to be warming up to 230 ℃ from room temperature (envrionment temperature).The dehydration pre-polymerization time is 5-48 hour.Metal catalyst or organic oligomer can be during the course, are that (processed has been carried out after 3 hours at least) adds system after the system temperature reaches 120 ℃ preferably, also can be when dehydration-processing begins or before add system, more excellent is to adopt the former.
The lactic acid oligomer that is obtained can by such as: ethanol, ethyl acetic acid, toluene class organic solvent carry out purifying crystal after filtration, used mother liquor can be used repeatedly to avoid waste in the process, also can carry out purifying crystal by adopting vacuum crystallization device, its Tc is 55-185 ℃, and the time is between 1-12 hour.
Enter twin screw extruder experience 0.5-40 minute melt phase polycondensation, aqueous vapor devolatilization and metering by the system (the employing vacuum crystallization device is then direct by the system of crystallization and purification) after dehydration, drying with the organic solvent crystallization and purification and extrude, poly(lactic acid) is made in cooling immediately; Or enter polymerizing reactor, as reactor or reactor, stir down, carry out 10-48 hour, temperature is that envrionment temperature-230 ℃, vacuum tightness are the polyreaction of 10MPa-0.001MPa, reaction product makes poly(lactic acid) through precipitate and separate, drying.
Twin screw extruder or polymerizing reactor have at least one vacuum orifice and corresponding vacuum extractor.
The system that participates in polyreaction can not comprise catalyzer, but for quickening polyreaction and/or making reaction thoroughly, preferably in polymerization process, add 0.01-5% (w/w) metal catalyst, weight-average molecular weight and go into system less than in 10,000 acid, alcohol or the lipid organism/organic oligomer one or more.According to the product performance needs, also can add in stablizer, catalyzer, food nutrition additive, chainextender, weighting agent, properties-correcting agent, processing aid, tinting material or other polymkeric substance one or more at the polyreaction system.
Embodiment 2:
With reference to accompanying drawing: with sacchariferous agriculture and industry waste or by product, as: liquid state contains sugared thing, sugaring raffinate, syrup etc., can adopt to comprise that conventional centrifugation technique etc. removes suspending sundries, and being diluted with water to wherein then, fermentable sugars concentration is 6-12% (w/w).
Growth stimulant such as cereal immersion liquid, yeast extract paste and/or the nitrogen pledge of 1.5-5.5% (w/w) are added pretreated solution, then, they are inserted fermentation unit, add enzyme, as: cellulase, inoculating lactobacillus ferments under anaerobism or little oxygen condition, and enzymic hydrolysis is carried out simultaneously with fermentation between yeast phase, and 5.0-6.5 is regulated and maintained to the pH value of system with the neutralizing agent that comprises basic metal, carbonate, sodium hydroxide, potassium hydroxide and/or ammoniacal liquor.Leavening temperature maintains 35-45 ℃, and ultra-filtration membrane (not shown) ultrafiltration that the system after having fermented installs the exit by fermentation produces fermentation clear liquid.Celliferous residue, the fermented liquid of removing the lactic acid that fermentation produces return in the fermentation unit.Fermentation unit can be common, conventional fermentation unit, is preferably and is built-in with the fermentation unit of one deck ultra-filtration membrane at least.With in the mineral acid one or more, as sulfuric acid, hydrochloric acid, the fermentation clear liquid that acidifying is filtered makes its pH value below 3.6, and is preferable at 2.0-2.9.Preferably, fermentation clear liquid is passed through a ultrafiltration again before by acidifying.Acidified system is by one deck nano level filter membrane, reverse osmosis membrane and/or electrodialysis (not shown) at least, by super purification, the filter opening footpath of the nano level filter membrane that is used for purifying first is less than 100 nanometers, preferable less than 50 nanometers, the filter opening of the nano level film that is used for purifying subsequently footpath is smaller or equal to the filter opening footpath of preceding once used nano level film.Be lactic acid by the product that obtains after the ultrapurification, its purity is greater than 90%.Gained lactic acid is inserted same device (not shown) dewater and pre-polymerization, its dehydration pre-polymerization condition is for progressively to be warming up to 230 ℃ from room temperature (envrionment temperature).The dehydration pre-polymerization time is 5-48 hour.Metal catalyst or organic oligomer can be during the course, are that (processed has been carried out after 3 hours at least) adds system after the system temperature reaches 120 ℃ preferably, also can be when processed begins or before add system, more excellent is to adopt the former.The lactic acid oligomer that is obtained can by such as: ethanol, ethyl acetic acid, toluene class organic solvent carry out purifying crystal after filtration, used mother liquor can be used repeatedly to avoid waste in the process, also can carry out purifying crystal by adopting vacuum crystallization device, its Tc is 55-185 ℃, and the time is between 1-12 hour.(adopt in the vacuum crystallization device after dehydration, drying by system with the organic solvent purifying crystal, then direct by the system of purifying crystal) enter twin screw extruder experience 0.5-40 minute melt phase polycondensation, aqueous vapor devolatilization and metering and extrude, poly(lactic acid) is made in cooling immediately; Or enter polymerizing reactor, and as reactor or reactor, stir down, carry out 10-48 hour polyreaction, reaction product makes poly(lactic acid) through precipitate and separate, drying.
Twin screw extruder or polymerizing reactor have at least one vacuum orifice and corresponding vacuum extractor.The system that participates in polyreaction can not comprise catalyzer, but for quickening polyreaction and/or making reaction thoroughly, preferably in polyreaction, add 0.01-5% (w/w) metal catalyst, weight-average molecular weight and go into system less than in 10,000 acid, alcohol or the lipid organism/organic oligomer one or more.According to the product performance needs, also can add in stablizer, catalyzer, food nutrition additive, chainextender, weighting agent, properties-correcting agent, processing aid, tinting material or other polymkeric substance one or more at the polyreaction system.
Embodiment 3 (embodiment 1):
4 liters of molasses, 25 grams per liter capes immersion liquid and 10 grams per liter yeast extract pastes are inserted in 10 liters of bio-reactors, after regulating initial sugar-containing concentration to 72 grams per liter of system, insert 400 milliliters of lactobacilluss of cultivating through one day, fermentation under anaerobic, leavening temperature is 43 ℃, carries out under stirring, and continues 48 hours, the pH value of fermentation system is regulated with ammoniacal liquor and is maintained 5.9, and the output of gained crystalline lactic acid is 63 grams per liters.
Embodiment 4 (embodiment 2):
4 liters of fermentation clear liquid through ultrafiltration are inserted a bottom to be had in the container of one deck separation nano membrane, the filter opening footpath of film is less than 50 nanometers, add hydrochloric acid and make the fermentation clear liquid acidifying, the pH value of system is reduced to 2.2-2.3 in the process, under 18bar pressure, initial flow rate is to carry out nanofiltration under 58 liters/square metre hours, gets the lactic acid of 60.4 grams per liters.Extraction yield is 96%.
Embodiment 5 (embodiment 3):
Contain 45.3% (w/w) lactic acid solution with 4 kilograms and insert in one 20 liters the dehydration polymerizer, slowly be warming up to the tin protochloride (Sncl that 140 ℃ (after about 5 hours) add 0.1% (w/w) from room temperature (envrionment temperature)
2).The pre-collecting process of whole dehydration is about 18 hours, and behind the adding catalyzer, the system temperature maintenance is at 180-220 ℃, in the process, vacuum tightness progressively is increased to 0.05MPa, and mixing speed is 250-150 rev/min, the result makes 1.52 kilograms of lactic acid prepolymer, and its GPC gel chromatography detection molecules amount is 56,900.
Embodiment 6 (embodiment 4):
The product (80 gram) of embodiment 3 is inserted in 300 milliliters of vacuum-pumping reactors, add 0.3% (w/w) zinc chloride catalyzer, progressively heat to 180 ℃, vacuum tightness is to 0.09MPa, stir reaction down 5 hours, after reaction finishes, with the chloroform dissolving and use the ethanol sedimentation purified product, make poly(lactic acid) after the vacuum-drying under the normal temperature.Its GPC gel chromatography detection molecules amount is 201400.
Embodiment 7 (embodiment 5):
With 0.4% (w/w) zinc chloride, 5% (w/w) diphenylmethanediisocyanate, 2% (w/w) polyvinyl alcohol and 1.5 kilograms of lactic acid prepolymer uniform mixing, add screw slenderness ratio and be 45 parallel dual-screw extruding machine (German JP industrial technology equipment company limited), this forcing machine fuselage has a vacuum orifice that connects vacuum extractor, the working vacuum degree is that vacuum tightness is to 0.004MPa, reinforced oral region barrel zone temperature is an envrionment temperature, other is respectively distinguished barrel zone temperature and is separately positioned between 130 ℃-190 ℃, head temperature is 160 ℃, screw speed is 100 rev/mins, weight-average molecular weight is 192400 poly(lactic acid).
Claims (9)
1. make the method for lactic acid and poly(lactic acid) with sacchariferous agriculture and industry waste or by product, it is characterized in that this method comprises the steps:
1) sacchariferous agriculture and industry waste or by product pre-treatment:
Comprise the impurity elimination thing, soak and/or the dilution of sugar water with diluted acid, diluted alkaline;
2) pretreated system fermentation:
Yeast extract paste and/or cereal immersion liquid quasi-growth promoter, enzyme thing are added through the pre-treatment system, the microbial bacteria family of inoculating lactic acid mushroom, in the fermentation culture temperature is to ferment under 36-45 ℃, anaerobism or the little oxygen condition, with one or more neutralizing agents 5.0-6.5 is regulated and maintained to the pH value of fermented liquid in the fermenting process;
3) acidifying is by the fermentation clear liquid of ultrafiltration:
With one or more acidifying fermentation clear liquids in the mineral acid, make its pH value below 3.6, preferable at 2.0-2.9;
4) obtain lactic acid:
Make by the acidifying system and pass through one deck nano level filter membrane, reverse osmosis membrane and/or electrodialysis at least, carry out ultrapurification, make lactic acid;
5) acid by dehydrating lactic pre-polymerization:
The system top temperature is 235 ℃ in the process, vacuum tightness is 7MPa-0.001MPa in the device, progressively heat up, carry out the metal catalyst, weight-average molecular weight of preceding or middle adding 0.01-5% (w/w) less than 10 in process, in 000 acid, alcohol or the lipid organism/organic oligomer one or more, system is stirred all the time in the process;
6) prepolymer crystallization purifying;
7) make poly(lactic acid) through polyreaction.
2. the sacchariferous agriculture and industry waste of usefulness according to claim 1 or by product are made the method for lactic acid and poly(lactic acid), and it is characterized in that: described sacchariferous agriculture and industry waste or by product contain and be higher than 25% (w/w) fermentable sugars: the tankage of crop stalk, bagasse, Semen Maydis grit, decayed fruit thing, beet, beet pulp, sugaring/food/cheese industry, fruit juice, syrup, molasses, sweet sorghum, farm crop, natural biological, contain sugared thing, two or more arbitrarily adulterant in them, two or more mixing solutions or single liquefaction things arbitrarily in them.
3. sacchariferous agriculture and industry waste of usefulness according to claim 1 or by product are made the method for lactic acid and poly(lactic acid), and it is characterized in that: described neutralizing agent comprises basic metal, carbonate, sodium hydroxide, potassium hydroxide, ammoniacal liquor.
4. sacchariferous agriculture and industry waste of usefulness according to claim 1 or by product are made the method for lactic acid and poly(lactic acid), and it is characterized in that: described mineral acid comprises sulfuric acid, hydrochloric acid.
5. sacchariferous agriculture and industry waste of usefulness according to claim 1 or by product are made the method for lactic acid and poly(lactic acid), it is characterized in that: described prepolymer crystallization purifying adopts solvent method or vacuum crystallization device.
6. sacchariferous agriculture and industry waste of usefulness according to claim 5 or by product are made the method for lactic acid and poly(lactic acid), and it is characterized in that: the solvent that described solvent method adopted comprises one or more in ethanol, ethyl acetic acid, the toluene.
7. sacchariferous agriculture and industry waste of usefulness according to claim 5 or by product are made the method for lactic acid and poly(lactic acid), it is characterized in that: the Tc that described employing vacuum crystallization device carries out the prepolymer crystallization purifying is 55-185 ℃, and vacuum tightness is 10MPa-0.01MPa.
8. sacchariferous agriculture and industry waste of usefulness according to claim 1 or by product are made the method for lactic acid and poly(lactic acid), it is characterized in that: described polyreaction is in twin screw extruder that possesses at least one vacuum orifice and corresponding vacuum extractor or polymerizing reactor, and working temperature is that envrionment temperature-230 ℃, vacuum degree control are carried out under the condition of 10MPa-0.001MPa.
9. sacchariferous agriculture and industry waste of usefulness according to claim 8 or by product are made the method for lactic acid and poly(lactic acid), and it is characterized in that: described polyreaction system comprises one or more in stablizer, catalyzer, food nutrition additive, chainextender, weighting agent, properties-correcting agent, processing aid, tinting material or other polymkeric substance.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973642A (en) * | 2010-11-16 | 2011-02-16 | 宜兴汇洋环保科技有限公司 | Method for preparing sustained-release carbon material by using low molecular weight polylactic acid |
| CN104814545A (en) * | 2015-04-22 | 2015-08-05 | 湖州环球手套有限公司 | Corn glove based on 3D printing and preparation method of corn glove |
| CN110437060A (en) * | 2019-07-26 | 2019-11-12 | 刘秀丽 | The method of lactic acid is recycled in a kind of production of phytic acid |
| CN115156284A (en) * | 2022-05-24 | 2022-10-11 | 清华大学 | Method for repairing oil-containing saline-alkali soil based on marginal halophytic energy plant sweet sorghum |
-
2006
- 2006-12-25 CN CN 200610130554 patent/CN100999744A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973642A (en) * | 2010-11-16 | 2011-02-16 | 宜兴汇洋环保科技有限公司 | Method for preparing sustained-release carbon material by using low molecular weight polylactic acid |
| CN101973642B (en) * | 2010-11-16 | 2012-08-29 | 宜兴汇洋环保科技有限公司 | Method for preparing sustained-release carbon material by using low molecular weight polylactic acid |
| CN104814545A (en) * | 2015-04-22 | 2015-08-05 | 湖州环球手套有限公司 | Corn glove based on 3D printing and preparation method of corn glove |
| CN110437060A (en) * | 2019-07-26 | 2019-11-12 | 刘秀丽 | The method of lactic acid is recycled in a kind of production of phytic acid |
| CN115156284A (en) * | 2022-05-24 | 2022-10-11 | 清华大学 | Method for repairing oil-containing saline-alkali soil based on marginal halophytic energy plant sweet sorghum |
| CN115156284B (en) * | 2022-05-24 | 2024-01-19 | 清华大学 | Method for repairing oily saline-alkali soil by utilizing marginal salinized energy plant sweet sorghum |
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