CN1289459C - Process for purifying an organic acid - Google Patents
Process for purifying an organic acid Download PDFInfo
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- CN1289459C CN1289459C CN02826698.6A CN02826698A CN1289459C CN 1289459 C CN1289459 C CN 1289459C CN 02826698 A CN02826698 A CN 02826698A CN 1289459 C CN1289459 C CN 1289459C
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
A process is disclosed for purifying an aqueous feed stream (10) comtaining a product organic acid and a strong contaminant such as another organic acid. The molar concentration of the organic acid in the feed stream (10) is at least 20 times greater than that of the contaminant. The feed stream (10) is contacted with an immiscible basic extractant (18) that has a greater affinity for the contaminant and which complexes with the contaminant and some of the organic acid. The complexed extractant is separated from the aqueous stream (10), so as to produce a first effluent stream (20) comprising product organic acid. The complexed extractant is contacted with a displacing acid, for which the extractant has a greater affinity than contaminant or extractant. As a result, a second effluent stream (28) comprising organic acid and a third effluent stream (30) are produced.
Description
Background technology
The present invention relates generally to the method for producing organic acid such as lactic acid.
Lactic acid has various commercial purposes, for example in foodstuff production, medicine, plastics, weaving and in various chemical technologies as parent material.In addition, it also is used for the production poly(lactic acid)---a kind of degradable plastics.
Though can prepare organic acid by chemosynthesis, general relatively more cheap by fermentative production.Clump institute is known, can be by utilizing the fermentation lactic acid producing in next life such as Lactobacillus delbrueckii microorganism.Ferment and contain not sugar fermentation, carbohydrate, amino acid, protein and salt in the resulting meat soup, also contain organic acid such as lactic acid.Usually, organic acid reclaims from fermenting broth, and is further purified before use.The purifying organic acid that reclaims from the meat soup that ferments can contain small amount of impurities, as strong acid or compound that some is unknown.Partial impurities may cause undesirable color and luster, perhaps may disturb the organic acid downstream processing.For example the lactic acid of commerciality sale generally contains small amount of impurities, as pyruvic acid, acetate and oxalic acid.Even the amount that these impurity exist is less relatively, but for for the polymkeric substance of lactic acid-producing, still has negative impact.For example when lactic acid is aggregated production poly(lactic acid) (PLA), even the existence of small amount of acetone acid can cause that also polymkeric substance has undesirable yellow.Yet it is difficult being further purified the lactic acid that only contains the small portion pyruvic acid in first kind of situation.
Therefore, the improved method of needs---particularly lactic acid---for being used for producing and reclaiming relative purified organic acid.
Summary of the invention
One aspect of the present invention is the method for a kind of purifying water-containing material logistics, and described water-containing material logistics contains required product organic acid and at least a strong pollutent.In certain embodiments, the water-containing material logistics can comprise fermenting broth or obtain (no matter any acid of mentioning is required product or pollutent, all should understand the form that described some or all acid all can salt and exist) herein by fermenting broth.Product organic acid volumetric molar concentration can be bigger 10 times than the concentration of strong pollutent at least in the feed stream, and more preferably the product organic acid is at least 20 with the ratio of the volumetric molar concentration of strong pollutent.In certain embodiments, the product organic acid is at least 90 with the ratio of the volumetric molar concentration of strong pollutent, and in certain embodiments, its value is at least 500, and in some other embodiment, its value is at least 1000.The water-containing material logistics is contacted with the first unmixing basic extractant, described extraction agent under existing processing condition (comprising the combination of existing acid, solvent etc.) to strong pollutent with respect to product organic acid selectivity greater than 3.Described selectivity---will below further definition---is preferably greater than 15, more preferably greater than about 25, most preferably greater than about 100.Preferably, described selectivity is greater than the ratio of product organic acid in the raw material with strong pollutent.
The contact procedure of the water-containing material logistics and the first unmixing basic extractant is preferably carried out in abundant balance or near equilibrium stage, and utilizes the first unmixing basic extractant (as solid amine ion-exchanger or liquid amine extraction agent) of capacity to remove most of strong pollutent.In certain embodiments, the first unmixing basic extractant before had been used to handle the solution (for example it is to be recovered utilization) that contains product organic acid and at least a weak pollutent.
The result is, most strong pollutents and less than the product organic acid and the first unmixing basic extractant complexing of about 33wt%." majority " herein refers to the material that surpasses 50% weight, and in the case, described material refers to the strong pollutent of existence.That is to say, surpass the strong pollutent and the extraction agent complexing of 50% weight in the raw material.The first unmixing basic extractant after the complexing separates with aqueous stream, discharges logistics thereby produce first, and it contains the product organic acid, and the product organic acid is bigger than water-containing material logistics with the ratio of strong pollutent.The first unmixing basic extractant of complexing contacts with displacement acid.With respect to strong pollutent or product organic acid, the first unmixing basic extractant has bigger affinity for displacement acid, and therefore, after for some time, product organic acid and strong pollutent are cemented out from the first unmixing basic extractant of complexing.This just produces second the 3rd discharge logistics of discharging logistics and containing most of strong pollutent that contains most of product organic acid (promptly dissolving or being suspended in more than about 50% weight of solid in the logistics is the product organic acid).
Preferably, product organic acid total amount is about 90% weight of product organic acid in the feed stream at least in the first discharge logistics and the second discharge logistics.More preferably, the product organic acid at least about 98% weight is reclaimed in these fluids.
In the multiple embodiments of this method, comprise organic acid, its pK in the strong pollutent
AlValue is than product organic acid pK
AlBe worth low.If required product organic acid is a lactic acid, then strong pollutent preferably has the pK less than about 3.46
AlValue.Some is specifically related to in the embodiment of solid ion-exchange resin as basic extractant in the present invention, and strong pollutent is selected from pyruvic acid, oxalic acid, citraconic acid, citric acid and their mixture.
In other embodiments, strong pollutent can be (as higher pK than the more weak acid of required organic acid product
Al), but may have stronger hydrophobic and/or hydrogen bonded characteristic than product.With respect to interested organic acid, strong pollutent can be removed by the unmixing basic extractant selectivity that contains solvent or solvent mixture, such as being to contain 1M trilaurylamine (Tridodecylamine and 1M dodecanol and being the amine mixt of thinner with the dodecane.
When the unmixing basic extractant contains solvent mixture, interested organic acid preferably have to a certain degree hydrophobicity or strong hydrogen bonded characteristic, and strong pollutent must be (1) with interested acid have similar hydrogen bonded and/or hydrophobic property, and compare the lower pK of interested acid
Al(acid low pK
AlMaterial), or (2) have enough strong hydrogen bonded and/or hydrophobic property, although so that strong pollutent has higher relative pK
Al, it still can be removed.
Therefore, if strong pollutent has lower pK than organic acid product
Al, solid ion-exchange resin can be used as the extraction agent of removing strong pollutent.If the organic acid that for example needs to reclaim is a lactic acid, then can comprise HCl, H with the strong pollutent that the method that the present invention relates to ion exchange resin is removed
2SO
4, pyruvic acid and oxalic acid and other.Yet acetate and butyric acid do not have than the significantly lower pK of lactic acid
Al, thereby they are not easy to be removed by ion exchange resin.But, for the organic acid product, have low pK
AlOr the strong pollutent of high hydrophobicity/hydrogen bonded characteristic can remove by using extraction agent, and wherein said extraction agent is solvent or solvent mixture.For example pyruvic acid, H
2SO
4With butyric acid can the application of the invention the amine solvent extraction agent and from the water-containing material logistics that contains lactic acid, remove.Though the first unmixing basic extractant can adopt various forms, preferably a kind of weak-base ion-exchange resin.Preferably, weak property ion exchange resin contains the tertiary amine part.An advantage of this method multiple embodiments is the ability that is further purified the logistics that contains very low per-cent impurity.For example in one embodiment, the volumetric molar concentration of pollutent is big at least 20 times by force in the molar concentration rate feed stream of product organic acid---such as lactic acid---in the feed stream, and selectivity is greater than about 25 simultaneously.In another embodiment, the volumetric molar concentration of pollutent is big at least 300 times by force in the molar concentration rate feed stream of product organic acid---such as lactic acid---in the feed stream, and selectivity is greater than about 500 simultaneously.
In a kind of embodiment of this method, feed stream, first discharges logistics and second ejecta stream further contains weak pollutent.For example when the product organic acid was lactic acid, weak pollutent can be pK
AlOrganic acid greater than about 4.26 is such as being propionic acid, butyric acid, propanedioic acid, acetate, vinylformic acid, succsinic acid or their mixture.For acid with a plurality of acidic groups such as succsinic acid, have only ionized first group and pK
AlRelevant.For the acid of having only an acidic group, pK
AlWith pKa be of equal value.In this case, thus described method comprises the steps: that further discharging logistics and second with first discharges logistics and mix and form the logistics of mix products organic acid, contacts the logistics of mix products organic acid then with the second unmixing basic extractant.The most of product organic acid and the second unmixing basic extractant complexing.Preferably, the product acid of at least 90% weight is by complexing, and more preferably at least 95%.The second unmixing basic extractant of complexing can separate with logistics then, discharges logistics thereby produce the 4th, and it contains major part and is present in weak pollutent in the logistics of combination product organic acid.Preferably, the second unmixing basic extractant contains weak or strong basic ion exchange resin.
Selectively, the embodiment of this method can comprise further that discharging logistics with the 4th contacts with the 3rd unmixing basic extractant, with respect to weak pollutent, described the 3rd unmixing basic extractant has bigger affinity to the product organic acid, therefore, major part is present in the 4th product organic acid and the 3rd unmixing basic extractant complexing of discharging in the logistics.Then, the 3rd unmixing basic extractant of complexing can separate with logistics, discharges logistics thereby produce the 5th, and it contains major part and is present in weak pollutent in the logistics of mix products organic acid.Then, second unmixing basic extractant of complexing and the 3rd unmixing basic extractant of complexing can contact with one or more displacement acid, thus in one or more additional discharge logistics substitution product organic acid therefrom.
In another variant of this method, the 3rd discharges logistics contacts with additional unmixing basic extractant, and with respect to the product organic acid, described extraction agent has bigger affinity for strong pollutent.The result is that major part is present in the 3rd strong pollutent and the complexing of additional unmixing basic extractant of discharging in the logistics.The additional unmixing basic extractant of complexing separates with residual stream, thereby produces additional discharge logistics, and it contains major part and is present in the 3rd product organic acid of discharging in the logistics.
A particularly preferred embodiment according to the invention is the method for purified lactic acid.This embodiment relates to provides a kind of water-containing material logistics, and it contains lactic acid (being defined as any salt that comprises it herein) and at least a strong pollutent acid, and described strong pollutent acid has the PK less than about 3.46
AlThe volumetric molar concentration of the strong pollutent acid of the molar concentration rate of lactic acid is big at least 20 times in the feed stream.The water-containing material logistics is contacted with first alkaline ion exchanger, for lactic acid, described first alkaline ion exchanger has bigger affinity for strong pollutent acid, therefore, and most of strong pollutent acid and the part lactic acid and the first alkaline ion exchanger complexing.First ion-exchanger of complexing separates with aqueous stream, produces first and discharges logistics, and it contains lactic acid, and the water-containing material logistics frequently of lactic acid and strong pollutent acid is bigger.First alkaline ion exchanger of complexing contacts with displacement acid, such as HCl, H
2SO
4Or H
3PO
4, for strong pollutent acid or lactic acid, first alkaline ion exchanger has bigger affinity for displacement acid.Lactic acid and strong pollutent acid cement out from first alkaline ion exchanger of complexing after for some time, produce the second discharge logistics that contains most of lactic acid and contain the 3rd of most of strong pollutent acid to discharge logistics.
In the part embodiment of this method, strong pollutent acid is selected from pyruvic acid, oxalic acid, citraconic acid, citric acid and their mixture.In some embodiment of this method, the volumetric molar concentration of pollutent acid is big at least 100 times by force in the molar concentration rate feed stream of lactic acid in the feed stream, and selectivity is greater than about 250.In certain embodiments, described ratio is 300 at least, and selectivity is greater than about 500.
Preferably, first alkaline ion exchanger is bigger at least 10 times than its affinity for pyruvic acid for the affinity of displacement acid.
Preferably, first discharge logistics and second and discharge the ratio of lactic acid and strong pollutent in the logistics all greater than 300.More preferably, in them the ratio of lactic acid mole number and strong pollutent mole number all greater than about 1000.In the part embodiment of this method, the lactic acid of at least 90% weight in the feed stream---more preferably 98% weight---is discharged logistics and second first and is discharged in the logistics and reclaimed.
In a kind of specific embodiments of this method, in the water-containing material logistics, with respect to every molar lactic acid, it contains and is no more than about 0.15 mole of positively charged ion, and described positively charged ion is selected from Ca, Mg, Na, Fe, Zn, Zr and Li; With respect to every molar lactic acid, it contains and is no more than about 0.05 mole of negatively charged ion, and described negatively charged ion is selected from Cl, SO
4, PO
4And NO
3With respect to every molar lactic acid, it contains and is no more than about 0.03 mole of strong acid pollutent, and described strong acid pollutent is selected from pyruvic acid, oxalic acid, citraconic acid and citric acid; With respect to every molar lactic acid, it contains and is no more than about 0.02 mole of weak acid pollutent, and described weak acid pollutent is selected from propionic acid, butyric acid, propanedioic acid and succsinic acid.
Another aspect of the present invention is a kind of method of purified lactic acid, and it relates to provides a kind of moisture fermenting broth that contains lactic acid (being defined as any salt that comprises it herein) and pyruvic acid (also being defined as any salt that comprises it herein).In moisture fermenting broth, the volumetric molar concentration of the molar concentration rate pyruvic acid of lactic acid is big at least 20 times.Thereby from meat soup, remove cell and form the water-containing material logistics.Can use any method well known in the art to remove cell (as centrifugal or filter and other).The water-containing material logistics contacts with the medium that is used for the complexing pyruvic acid, and for lactic acid, described medium has bigger affinity for pyruvic acid, thereby most pyruvic acid and part lactic acid have formed complex compound with it.Complex compound separates with aqueous stream, discharges logistics thereby produce first, and it contains lactic acid, and the water-containing material logistics frequently of lactic acid and pyruvic acid is bigger.Complex compound contacts with the medium that is used for therefrom replacing lactic acid and pyruvic acid, contains the 3rd discharge logistics that second of most of lactic acid is discharged logistics and contained most of pyruvic acid thereby produce.
In certain embodiments, the first unmixing basic extractant is the solid alkaline extraction agent, and the water-containing material logistics contacts in bed of packings with the first unmixing basic extractant.Preferably, in relating to the embodiment of bed of packings, the ratio in the second discharge logistics between the volumetric molar concentration of product organic acid volumetric molar concentration and strong pollutent is in about 10% selectivity.
In other embodiments, the first unmixing basic extractant is liquid basified extraction agent, and the water-containing material logistics is contacted with the first unmixing basic extractant.Preferably, the ratio of product organic acid and strong pollutent is in about 10% selectivity.
In addition, water-containing material logistics in certain embodiments contains multiple strong pollutent, and at least a strong pollutent is displacement acid.
Some embodiment relates to a kind of method that relates to the water-containing material logistics, and described water-containing material logistics contains required product organic acid, at least a strong pollutent and weak pollutent.First discharges logistics also contains weak pollutent, and flow through at least single extraction or the rectifying (using method well known in the art) of first ejecta is handled, thereby produce at least two cuts, and the product organic acid cut of purifying, it contains the product organic acid in the feed stream of being present in of the 90%-99.5% weight of having an appointment, with weak pollutent cut, it contains product organic acid and weak pollutent.The ratio of product organic acid volumetric molar concentration and weak pollutent volumetric molar concentration is less than the ratio of product organic acid volumetric molar concentration in the feed stream and weak pollutent volumetric molar concentration in the weak pollutent cut.Weak pollutent cut is contacted with the 3rd unmixing basic extractant, with respect to weak pollutent, described the 3rd unmixing basic extractant for product organic acid selectivity greater than about 3, most of product organic acid and less than about 33% weak pollutent and the 3rd unmixing basic extractant complexing.The 3rd unmixing basic extractant of complexing separates with aqueous stream, thereby produces the discharge logistics that contains weak pollutent.Contain in the discharge logistics of weak pollutent, weak pollutent is bigger than water-containing material logistics with product organic acid ratio.The 3rd unmixing basic extractant of complexing contacts with displacement acid, and with respect to product organic acid or weak pollutent, the 3rd unmixing basic extractant has bigger affinity for displacement acid.Thereby displacement acid exists with enough amounts product organic acid and weak pollutent are cemented out over time from the 3rd unmixing basic extractant of complexing, discharge logistics and contain the logistics of most of product organic acid product organic acid thereby produce the weak pollutent that contains most of weak pollutent.Preferably, the product organic acid cut of purifying contains the product organic acid in the feed stream of being present in of 95% weight-99.5% weight of having an appointment.
Some embodiment relates to a kind of purifying organic acid method, and it comprises provides a kind of water-containing material logistics that contains product organic acid and at least a strong pollutent.The volumetric molar concentration of the strong pollutent of product organic acid molar concentration rate is big at least 20 times.The water-containing material logistics contacts with the first unmixing basic extractant, with respect to the product organic acid, the described first unmixing basic extractant for the selectivity of strong pollutent greater than about 3.Most of strong pollutent and less than the product organic acid and the first unmixing basic extractant complexing of about 33wt%.The first unmixing basic extractant of complexing separates with aqueous stream, discharges logistics thereby produce first, and it contains the product organic acid, and the product organic acid is bigger with the water-containing material logistics frequently of strong pollutent.The first unmixing basic extractant of complexing is through at least a following processing: (1) changes temperature, and (2) change solvent strength, or (3) change displacer concentration.This processing causes for some time after product organic acid and strong pollutent to be displaced from the first unmixing basic extractant of complexing, discharges logistics thereby produce to contain most of product organic acid second discharge logistics and contain the 3rd of most of strong pollutent.Change solvent strength and can use method well known in the art and realize, be present in solvent in the water-containing material logistics as evaporation.In addition, can obtain required product or the selectivity release of impurity from the first unmixing basic extractant of complexing by applied in any combination temperature change, solvent change and/or displacement acid or alkali concn.Displacer as indicated above can be displacement acid or displacement-alkali.Alkali such as NaOH can be used as displacer, by means commonly known in the art the material that displaces are handled then, thereby are reclaimed required product organic acid.
Part lactic acid purification process can relate to being derived from and contains the raw-material fermentation of water lactic acid, and the described water lactic acid starting material that contain make it be suitable as the raw material of main solvent extraction through pre-treatment.This fermentation pre-treatment that comes from moisture lactic raw material can comprise after filtration and careful separate solid and optional through membrane filtration and the macromolecular substance of separate dissolved.Further, available cationite decationize, and remove negatively charged ion with conventional solid anionite or the identical amido extraction agent (as amine, toughener and thinner) that is used for lactic acid master extraction.When using when limiting the quantity of with respect to the raw material of decationized Y sieve, its alternative extraction mineral acid stronger than lactic acid.The step of back is commonly referred to pre-extraction.Have now found that by implementing pre-extraction, wherein use to be specifically designed to this purpose and the composition different with the composition that is applicable to main extraction is extraction agent, just as among the present invention, overall lactic acid recovery is effective.Therefore, embodiment preferred comprises twice solvent extraction (as pre-extraction and main extraction) of order, and each application specific is at the amido extraction agent of its function.The rich extraction agent that the poor extraction agent that uses in the pre-extraction stages uses than main extraction stages has significantly lower amine concentration and lower toughener/amine mol ratio.
The extraction agent (poor extraction agent) that adds initial aqueous lactic raw material and the special selection of stage for this reason in pre-extraction stages.The mineral acid and the organic acid that have precedence over the lactic acid extraction are injected in the aqueous stream, and lactic acid remains in second aqueous stream and (discharges logistics as first) simultaneously, and described second aqueous stream enters main extraction stages.Main extraction stages is used the special extraction agent (rich extraction agent) that differs widely with poor extraction agent.After stripping, aqueous stream, obtain pure lactic acid from main extraction stages, simultaneously impurity is injected side-stream.
Twice solvent extraction has its unique solvent compositions at every turn, and this method structure has additional advantage, and it provides the selection of using the auxiliary separation method of non-solvent to be further purified.When---it is compared with main flow be little and usually also contain the impurity of less amount---, common in this case spendable rectifying or simulated moving bed chromatography method become feasible thereby when being used to contain the lactic acid logistics.Minor flows---generally be that the internal recycling logistics can all or part ofly turn to auxiliary separation method, and despumation and reclaim lactic acid in second time polymers stream.
Certain embodiments of the present invention relate to a kind of method of purified lactic acid.The water-containing material logistics that contains free lactic acid and at least a pollutent contacts with lean solution body extraction agent, and most of pollutent is in pre-extraction stages and the complexing of lean solution body extraction agent.For instance, the water-containing material logistics can be a fermenting broth.In the lean solution body extraction agent, with respect to every kilogram of lean solution body extraction agent, it contains less than about 0.75 mole of amine; With respect to every mole of amine, it contains the 0-0.5 mole toughener of having an appointment; And thinner.The lean solution body extraction agent of complexing separates with the water-containing material logistics at pretreatment stage, discharges logistics thereby produce first, and it contains free lactic acid, and free lactic acid is bigger than the water-containing material logistics of not complexing with the ratio of pollutent.Discharge logistics with first then and contact most of free lactic acid and the complexing of liquid-rich extraction agent in the first discharge logistics with liquid-rich extraction agent in the main extraction stages.The liquid-rich extraction agent contain with lean solution body extraction agent in identical amine, toughener and thinner, yet, in the liquid-rich extraction agent, every kilogram of liquid-rich extraction agent with respect to main extraction stages, its molar weight that contains amine is bigger than the molar weight of amine in every kilogram of lean solution body of pretreatment stage extraction agent, and higher than in the lean solution body extraction agent of the ratio of toughener molar weight and amine molar weight in the liquid-rich extraction agent.Lifting capacity should make first to discharge the ratio of logistics middle reaches molar weight of amine in the molar weight of lactic acid and liquid-rich extraction agent less than about 1.1.This method selectively further comprises strips to the complex compound water that contains lactic acid and liquid-rich extraction agent, thereby produces the logistics of aqueous product lactic acid.
Brief description of the drawings
Fig. 1 is the process flow sheet of one embodiment of this invention.
Fig. 2 is the process flow sheet of another embodiment of the present invention, but it comprises the implementation step except that step shown in Figure 1.
Fig. 3 is the process flow sheet of another embodiment of the present invention, but it comprises the implementation step except that step shown in Figure 1.
Fig. 4 is the process flow sheet of one embodiment of this invention.
The description of illustrative embodiment
Method of the present invention can be used for reclaiming and the various organic acids of purifying.This method is particularly suitable for reclaiming monocarboxylic acid, dicarboxylic acid or the tricarboxylic acid that has 2-8 carbon atom with purifying.Preferably, described organic acid is hydroxy organic acid (the perhaps mixture of two or more this kind acid).Hydroxy organic acid can be α, β, δ, γ or ε alcohol acid.Described organic acid most preferably is a lactic acid.
Method of the present invention can reclaim the organic acid of purifying from fermenting broth.Yet this method also is suitable for the organic acid in other source of purifying, as commercial lactic acid." 88% lactic acid " and " commercial lactic acid " refers to general commercially available lactic acid, and it is actually the mixture of monomer lactic acid, linear two poly(lactic acid) or lactyllactic acid, short chain lactic acid oligomer, water, small content of cyclic two poly(lactic acid) or rac-Lactide and small amount of impurities.When commercial lactic acid during by the dilution of a large amount of water, the slowly hydrolysis or be transformed into the lactic acid of morphon of dipolymer and oligopolymer.When water is diluted to 50wt% concentration with spissated lactic acid, initial dipolymer that exists and oligopolymer will be hydrolyzed into gradually and a kind ofly mainly be monomer lactic acid but still contain two poly(lactic acid) of the 3-4wt% that has an appointment and the mixture of trace higher oligomer.
What Fig. 1 represented is the embodiment that is used for reclaiming from fermenting broth the method for lactic acid.Seed culture medium 10 is fed in the fermentor tank 12 that contains fermentation media.The moisture meat soup that fermentation produces and contains required organic acid---being lactic acid herein under the situation---.[any organic acid of mentioning comprises in the claims in this patent, all should understand part or all of described acid and all can exist with the form of salt.In brief, any acid that herein relates to includes arbitrary form (free acid or salt) or both mixtures.] described meat soup also contains one or more strong pollutents, is pyruvic acid in the case, and unfermentable sugar and other impurity.In part embodiment of the present invention, the ratio between the volumetric molar concentration of the volumetric molar concentration of required product acid (as lactic acid) and strong impurity (as pyruvic acid) is greater than about 300.In certain embodiments, the ratio between the volumetric molar concentration of the volumetric molar concentration of required product acid (as lactic acid) and strong impurity (as pyruvic acid) is greater than about 500, and in certain embodiments, it is greater than 1000.
" the strong pollutent " that use refers to chemical substance herein, and such as organic acid, with respect to interested product, the unmixing basic extractant of selected use has selectivity or affinity more than at least 3 times to it.
For the embodiment of the present invention of wherein using the solid unmixing basic extractant that contains anionite-exchange resin, the strong pollutent that will remove from the logistics of organic acid water-containing material can have the pK lower than the organic acid that will reclaim from feed stream
AlValue.
For the embodiment of the present invention that wherein relates to the liquid unmixing basic extractant that contains solvent, strong pollutent has lower pK for (a) than the organic acid that will reclaim from feed stream
AlValue, perhaps (b) compares with interested organic acid, and strong pollutent has similar or higher pK
AlValue, but described strong pollutent is more hydrophobic or has more hydrogen bonded groups or both have both at the same time.
For example exchange under the situation of extraction agent oxalic acid (pK at solid ion
a=1.27) and pyruvic acid (pK
a=2.48) at lactic acid (pK
a=3.86) in the solution be strong pollutent.Other example that can be present in the strong pollutent in the lactic raw material logistics comprises citraconic acid, citric acid and other pK
AlValue is less than about 3.46 organic acid.Can not exchange the weak pollutent that extraction agent removes by solid ion and can comprise nonacid material such as glucose and weak acid such as acetate, succsinic acid and butyric acid.
For the liquid amido extraction agent that is used for reclaiming lactic acid under 20-30 ℃ from solution, strong pollutent can comprise as above-mentioned strong acid and hydrophobicity weak acid.The hydrophobicity faintly acid example that can remove by liquid unmixing extraction agent is aromatic acid such as phenylformic acid and other a little less than butanic acid, isopropylformic acid and the ring-type.
In the part embodiment of this method, raw material can contain one or more strong pollutents with unknown chemical constitution.For example the lactic acid sold of some merchant contains the pollutent of unknown chemical constitution, and it has the apparent pK less than about 3.46
AlValue.Use the present invention, the concentration that the feed stream that contains this kind lactic acid can be purified to the part types of unknown pollutants is lower.Meat soup 14 is drawn from fermentor tank 12.Cell in the meat soup can be separated, for example by filtering or centrifugation, and is used as waste streams 16 and removes.Selectively, can be further purified meat soup by removing reinforcing yin essence ion and/or positively charged ion.Reinforcing yin essence ion such as chlorion, sulfate ion, phosphate anion and nitrate ion can be removed by selectivity with highly selective from contain organic acid neutrality or acid pH logistics.The strong cation that can be removed comprises Ca, Mg, K, Na, Fe, Zn, Zr and Li positively charged ion.For example fermenting broth and cationite (as strongly acidic cation exchanger), anionite (as weak base anion exchanger) or both can be contacted in proper order.
In step 18, meat soup 14 is contacted with the first unmixing basic extractant then.Preferably, use adverse current to finish this operation.In numerous selections, can use mixer-settler.This extraction agent is that " immiscible " is because its discord meat soup mixes, but extraction agent can yes or no liquid.For example extraction agent can contain amine compound, and described amine compound has the ability with one or more existing organic acid complexings.Particularly, this first extraction agent should be greater than its affinity for required product (lactic acid) for the affinity of strong pollutent (pyruvic acid)." affinity " of Shi Yonging refers under existing processing condition the trend with other material such as lactic acid or pyruvic acid complexing herein, and existing processing condition comprise the particular combinations of existing acid, solvent and other composition.The affinity that equates refers to when the solution with 50% lactic acid and 50% pyruvic acid contacts, described extraction agent will with two kinds of sour complexings of equivalent.Because lactic acid is higher usually with the ratio of pyruvic acid in the material solution of the present invention, therefore, extraction agent should be much larger than its affinity for lactic acid for the affinity of pollutent (pyruvic acid).Preferably, extraction agent is bigger at least 20 times than its affinity for lactic acid for the affinity of pyruvic acid.
The amine liquid extractant can comprise primary, the second month in a season or tertiary amine.In certain embodiments, amine is that the total number of carbon atoms is the alkylamine of about 4-36.Particular instance comprises n-Butyl Amine 99, tri-n-butylamine, octylame, tri-n-octyl amine, didecylamine, lauryl amine and three (lauryl amine) (being also referred to as trilaurylamine (Tridodecylamine) and other.Described amine should with water-containing material solution unmixing, thereby can form two phases.Liquid extractant of the present invention also can be chosen wantonly and comprise thinner and toughener.The component that thinner can be used as alkaline unmixing extraction agent reduces its viscosity, or increases extraction agent and do not need the selectivity of material for other, and other reason.Suitable diluent comprises for example pure or blended aromatics or aliphatic hydrocrbon, such as being dimethylbenzene, toluene, decane, dodecane, kerosene and their mixture." toughener " refers to a kind of chemical substance that can strengthen alkaline unmixing extraction agent performance.Toughener can add strong basicity unmixing extraction agent: strong pollutent complexing or unmixing extraction agent: organic acid complexing and/or help to dissolve complex compound.The example of suitable toughener comprises the polar material that is selected from alcohol, ketone, diketone, lipid acid, muriate and other material known in this field, and described alcohol comprises alkanol and glycol.
Preferably, the amine liquid extractant of the present invention's use contains the single homogeneous three kinds of compositions of formation: amine, toughener and thinner.In a kind of embodiment preferred, amine can be aliphatic secondary amine or the preferred tertiary amine that has about 20 carbon atoms at least, thereby guarantees water-insoluble; Thinner can be neutral liquid such as hydrocarbon, be used to the liquid organic phase that forms under extraction agent and the actual process condition that viscosity is provided; Toughener can be an organic compound, and it has polarity but comes down to neutral, thereby it can not influence acid-base reaction, and this is for being crucial with amine extractant extraction acid.Preferably, toughener is alkanol such as octanol; Ester such as butylacetate; Or can strengthen the ketone of its base strength with amine reaction.
As selection, first basic extractant can comprise deacidite.As previously mentioned, described ion exchange resin should be bigger than its affinity for required product for the affinity of strong pollutent.Suitable ion exchange resin comprises pyrimidine resin, imidazoles resin and tertiary amine resins and other.A special example is Ionac A365 (Sybron Chemicals, Birmingham, New Jersey).Also can use strong basicity and weak base type ion exchanger.Preferably, the consumption of first extraction agent enough produces a total complexing capacity in this method, and it is than bigger with the required amount of existing whole pyruvic acid or other strong pollutent complexing in theory.Like this, although part lactic acid also by complexing, can be reached maximization by the pyruvic acid cut of complexing.
First basic extractant---it has bigger affinity for pyruvic acid for lactic acid---forms complex compound with the most of pyruvic acid that is present in the meat soup.Because relatively large lactic acid concn in the meat soup, extraction agent also form the part complex compound with lactic acid, although its affinity for lactic acid is lower.Therefore,, produce first and discharge logistics 20, wherein the ratio of lactic acid and pyruvic acid higher than in original meat soup 14 along with most of pyruvic acid is removed.
Then, by sour displacement step 24, first basic extractant can be separated with lactic acid with most of pyruvic acid of complexing.To contain the logistics 26 of replacing aqueous acid and contact with first extraction agent, this moment first extraction agent still with pyruvic acid and lactic acid complexing, described displacement acid is as HCl, H
3PO
4, oxalic acid, H
2SO
4Or trifluoroacetic acid.Preferably, displacement acid has-2 to 1.8 pK approximately
aDisplacement acid also can be present in the mixture with other organic acid and material, such as HCl, H
2SO
4, oxalic acid and acetate mixture.Preferably, the concentration of displacement acid is about 1-40%, for H
2SO
42-5% more preferably, 20-30% more preferably for the mixtures that contain different acid.Under the situation of different acid mixtures, has only pK in this mixture
aAcid for-2 to 1.8 is just as displacement acid.
Since extraction agent (being ion-exchanger) for the affinity of displacement acid than it for lactic acid or the affinity of pyruvic acid is bigger, therefore, back two kinds of acid cement out from the complexing site.Because extraction agent is lower than its affinity for other two kinds of acid for the affinity of lactic acid, therefore, lactic acid tends at first be displaced, and removes as the second discharge logistics 28 that is rich in lactic acid.This logistics that is rich in lactic acid can be chosen wantonly with the first discharge logistics 20 and mix, thereby forms blended lactic acid product stream.Preferably, this logistics contains at least about 98% weight and is present in lactic acid in the raw material, and contained pyruvic acid and oxalic acid are more preferably less than about 10ppm, most preferably less than about 2ppm all less than about 20ppm.
After most of lactic acid had been displaced, pyruvic acid began to be replaced in a large number.Therefore produce and be rich in the 3rd of pyruvic acid and discharge logistics 30, it can choose in addition purifying wantonly needing to be used for the method for this specific acid.
The logistics 32 that is produced contains first extraction agent, described extraction agent this moment and the sour complexing of displacement.This logistics 32 is handled through alkali reclaim step 34, during contain the alkali such as the 5%NaOH aqueous solution logistics 36 contact with first extraction agent of complexing.Alkali displaces displacement acid from extraction agent, thereby produces regenerated first extractant stream 38, and it can be recycled 42 and use to step 18.This operation also produces the logistics 40 that contains regenerating acid, but its optional recycle is used to logistics 26.
Also can use the method for other first extraction agent of regenerating.
What Fig. 2 represented is alternative downstream processing step, and when this method original raw material contained weak pollutent and strong pollutent, it was very suitable.
The term of Shi Yonging " weak pollutent " has relation with the embodiment of the present invention that relates to the solid amine extraction agent herein, refers to than the organic acid that will reclaim to have bigger pK
AlThe compound of value.
Refer to a kind of compound at the term " weak pollutent " that uses at the situation of liquid amine mixture, it has bigger pK than the organic acid that will reclaim
AlValue, and general neither highly hydrophobic, again be not inclined to the liquid amine mixture in various compositions form strong hydrogen bond.
For example for solid-based amine, PK
AlValue is that 4.76 acetate can be as weak pollutent in containing the feed stream of lactic acid.Other is present in lactic raw material logistics, the especially example of the weak pollutent from the logistics that fermenting broth obtains usually and comprises propionic acid, butyric acid, acetate, propanedioic acid, succsinic acid and other pK
AlValue is greater than about 4.26 organic acid.
For example for for the liquid extractant of the mixture that contains unmixing amine, pK
AlValue is that 4.76 acetate can be as weak pollutent in containing the feed stream of lactic acid.Yet in the case, for lactic acid, butyric acid is because its hydrophobicity rather than weak pollutent in typical solvent.
In Fig. 2, thereby logistics 28 mixing formation blended lactic acid products streams 50 are discharged in the first discharge logistics 20 and second.This mix products stream contacts with the second unmixing basic extractant in step 52 then.The second unmixing basic extractant can be weak-base ion-exchange resin such as the Amberlite IR 35 that for example contains the tertiary amine part.Preferred second extraction agent for the affinity of lactic acid greater than its affinity for acetate.In addition, the amount that exists of extraction agent should be enough and all the lactic acid complexings basically that exist in the logistics.Therefore, the main and lactic acid formation complex compound of second extraction agent, and on much lower degree, form complex compound with acetate.This complex compound separates with residual liquid, becomes the part of logistics 56, discharges logistics 54 thereby leave the 4th.
The 4th discharges logistics 54 contacts with the 3rd unmixing basic extractant, and described extraction agent is deacidite preferably.Appropriate resin comprises Amberlite IR 35.Preferred this 3rd extraction agent is bigger than its affinity for pyruvic acid for the affinity of lactic acid.Therefore, the 4th discharges most of lactic acid and the ion-exchanger complexing in the logistics, and complex compound is removed in logistics 70.The 5th discharge logistics 68 that is rich in weak pollutent is produced.
What Fig. 3 represented is that another organizes selectable step except that step shown in Figure 1.(molar lactic acid: mole of acetone acid) greater than about 300 the time, this variant of this method is particularly useful when the ratio of lactic acid in the original raw material and pyruvic acid.In this variant of this method, the 3rd discharge logistics 30 that is rich in pyruvic acid contacts with additional unmixing basic extractant in step 80.With respect to lactic acid, this extraction agent has bigger affinity for pyruvic acid, and preferably ion exchange resin such as Amberlite IR-35.Therefore, the main and pyruvic acid complexing of extraction agent, these complex compounds are removed in logistics 84.The additional discharge logistics 82 that is rich in lactic acid is produced, therefrom recyclable lactic acid.
Then, the logistics 84 that contains the main complex compound with pyruvic acid of ion-exchanger is replaced sour logistics 85 and is contacted with containing in step 86, and described logistics 85 is as the 4%HCl aqueous solution.Extraction agent is bigger than its affinity for pyruvic acid for the affinity of displacement acid, thereby along with the former and the extraction agent complexing latter are displaced.Pyruvic acid is removed in discharging logistics 88, simultaneously, contain the logistics 90 of replacing acid complex and enter regeneration step 92, during handle with 94 pairs of complex compounds of alkali logistics.The result obtains the regenerating resin logistics 98 that can recycle in the method and contains the also discharge logistics 96 of application capable of circulation of displacement acid.
Above-mentioned this method embodiment has obtained highly selective, thereby is very effective remove pollutent from organic acid soln or suspension, even originally described organic acid soln or suspension are pure relatively.The ability that this selectivity is removed the impurity that exists with lower concentration is a major advantage of multiple embodiments of the present invention.This moment, used " selectivity " referred under processing condition, the concentration that comprises required product acid, pollutent, solvent and other composition that contacts with extraction agent, described composition can exist in a plurality of liquid phases, at this moment apparent the or effective selectivity of described extraction agent.Owing to contiguity constraint and other reason, selectivity (S) usually is slightly less than theoretical selectivity.Described theoretical selectivity can be expressed as following formula:
The amount of mentioning in the formula can be any quantified measures, such as being the area, mole, gram at gas-chromatography peak or HPLC peak and other.Selectivity should be greater than about 1, preferably much larger than 1.Preferably, when required product was lactic acid, selectivity was at least about 10.Preferably, selectivity is theory optionally 80% at least.More preferably, selectivity is at least the optionally about 90%-95% of theory, most preferably is at least theory optionally about 99%.
Preferably, in the feed stream ratio of organic acid volumetric molar concentration and strong pollutent volumetric molar concentration at least about the selectivity that equals strong pollutent.If feed stream contains lactic acid, the ratio of preferred M lactic acid and M pyruvic acid (strong pollutent) is greater than about 18.In the part embodiment of this method, the ratio (the strong pollutent of M organic acid: M) of organic acid and strong pollutent is greater than the selectivity (S) for strong pollutent, and less than this square (S optionally
2).And in other embodiment of this method, this ratio in the raw material even greater than S
2
Certain embodiments of the present invention relate to the method for purified lactic acid.This method comprises provides a kind of water-containing material logistics 100 that contains free lactic acid and at least a pollutent.In certain embodiments, at least a pollutent is selected from toxilic acid, propanedioic acid, fumaric acid, oxalic acid, citric acid, citraconic acid, pyruvic acid, 2-alpha-ketobutyric acid, 2-hydroxybutyric acid, acetate, 2-hydroxy-3-methyl butyric acid, 4-hydroxyl-phenylpyruvic acid, phenylpyruvic acid, 4-hydroxyl-phenyl-lactic acid, phenyl-lactic acid and their mixture.Water-containing material logistics 100 can be any logistics known in the field.Water-containing material logistics 100 can be fermenting broth or the fluid that obtains after to the meat soup partial purification with approach well known.The pollutent of water-containing material logistics 100 comprises pK
AlLess than about 3.46 (pK of lactic acid for example
a) acid.In certain embodiments, pollutent can be selected from pyruvic acid, oxalic acid, citraconic acid, citric acid and their mixture.
Water-containing material logistics 100 can prepare with second method, and it comprises that providing a kind of contains lactic acid, at least a pollutent and solid aqueous stream raw material, and filters described aqueous stream raw material and remove major part (as greater than about 50%) solid.In certain embodiments, the aqueous stream raw material can contain dissolved molecule (such as fermention medium, protein, carbohydrate, VITAMIN, lipotropy pigment precursor or organic acid and other), second method comprises carries out membrane filtration to the aqueous stream raw material after filtering, thereby removes most of dissolved molecule.The aqueous stream raw material can contain positively charged ion (such as Ca, Na, K, Mg, Fe, Zn, Zr and Li and other), the second method of preparation water-containing material logistics 100 can comprise the aqueous stream raw material after filtering is contacted with cationite, thereby remove most of positively charged ion.In 102 (pre-extraction stages), water-containing material logistics 100 contacts with lean solution body extraction agent 104.Lean solution body extraction agent 104 can be regenerated with approach well known, and in subsequent technique cycle applications.
In the lean solution body extraction agent 104, with respect to every kilogram of lean solution body extraction agent, it contains less than about 0.75 mole of amine; With respect to every mole of amine, it contains the 0-0.5 mole toughener of having an appointment; And contain thinner.Amine can be for example second month in a season or tert-aliphatic amine.Preferably, described amine has 20-36 carbon atom altogether, but can comprise the amine extractant with more carbon atoms well known in the art.In certain embodiments, lean solution body extraction agent comprises tertiary amine, contains the 0.2-0.5 mole amine of having an appointment in every kilogram of lean solution body extraction agent.Toughener can be that well known in the art those can interact to strengthen its alkaline toughener with amine extractant.Toughener can be selected from known tougheners such as alkanol, glycol, ester, diester, ketone and diketone.Preferably, described toughener is C
3-C
12Monohydric primary alcohol.In certain embodiments, contain the 0.1-0.25 mole toughener of having an appointment with respect to every mole of amine in the lean solution body extraction agent 104.Thinner can be selected from aromatic hydrocarbon and aliphatic hydrocrbon.Preferably, thinner is selected from dodecane, decane, dimethylbenzene, toluene, kerosene and their mixture.Contacting between water-containing material logistics 100 and the lean solution body extraction agent 104 102 causes most of pollutent and the complexing of lean solution body extraction agent.
The lean solution body extraction agent of complexing separates with the water-containing material logistics, and produces first and discharge logistics 106, and it contains free lactic acid, and the ratio of free lactic acid and pollutent bigger than in the complexing water-containing material logistics 100 not.Lean solution body extraction agent with method regeneration complexing well known in the art.In certain embodiments, part lactic acid can with the complexing of lean solution body extraction agent, and when regenerating extracting agent, for example through behind the auxiliary lock out operation 118, lactic acid can be recycled 126.
The lifting capacity of discharging logistics 106 at liquid-rich extraction agent 110 first should make first to discharge ratio between the mole number of amine in the mole number of free lactic acid in the logistics 106 and the liquid-rich extraction agent 110 less than about 1.1, is more preferably less than about 0.95.
This method can comprise further that water strips 108 to the complex compound that contains lactic acid and liquid-rich extraction agent, thereby produces aqueous product lactic acid logistics 112.Strip and preferably carrying out under the following temperature: the temperature of discharging the logistics contact procedure than liquid-rich extraction agent and first is high about below 20 ℃.More preferably, reextraction is preferably carried out under following temperature: high more about below 15 ℃ than the temperature that liquid-rich extraction agent and first is discharged in the logistics contact procedure.Have now found that, at approximate uniform temp or do not have to extract under the visibly different temperature and strip, can significantly improve the purity level of the lactic acid that obtains with solvent extraction method.Use drop in the defined compositing range the amido extraction agent and in defined lactic acid load level, use, can realize this purity beneficial effect well.
The methods that Fig. 4 is described to have two main extractions 102 and 108 have following advantage: provide selection for implement solvent-free operation on less side- stream 126 and 116, described to operate in big logistics may be invalid as using on 100,102,106,108 and 112.Therefore, 118 and 124 can be that rectifying or simulation moving-bed (SMB) operate and other.Compare with 112 with big logistics 100,102,106,108, this side- stream 126 and 116 contains the more impurity of close limit usually.This little logistics can be an internal recycle stream as 126 and 116, and it partly or entirely is diverted auxiliary separation the (as rectifying, chromatography and other).Can be discharged into 128 and 122 from this auxiliary isolating impurity, and can become the part of master's waste streams 120 of the present invention.
But Fig. 1-4 has described some particular combinations of applying step, but those skilled in the art will recognize that implementing method of the present invention has multiple.For example this method can be undertaken by intermittence, continuous or semi-continuous mode.
From following embodiment, can further understand embodiments more of the present invention.
Embodiment 1. is with respect to excessive lactic acid, and resin IRA-35 is for the selectivity of pyruvic acid.
Table 1
| Material solution | Balance liquid | Resin | K d | Selectivity | |
| Concentration mol/L | |||||
| Pyruvic acid | 0.005 | 0.001 | 0.024 | 26.9115 | 14.69 |
| Lactic acid | 0.503 | 0.386 | 0.706 | 1.832 | |
| The lactic acid dipolymer | 0.006 | 0.003 | 0.019 | 6.715 | 3.67 |
Prepare the 3ml aqueous solution of raw material that contains lactic acid and pyruvic acid as described in Table 1.Described raw material is 45.3 grams per liter lactic acid and 440 mg/litre pyruvic acid, and it represents typical fermenting broth logistics.In the experiment of single step intermittent balance, it is contacted with weak anion resin IRA-35 down at 20 ℃.Observe, for lactic acid, its selectivity for pyruvic acid is 14.69.In this single step batch experiment, have 81.8% pyruvic acid and from solution, transfer on the ion exchange resin, and have only 23.4% lactic acid to be transferred.
Embodiment 2. uses filled column (multistage) contactor by Continuous Flow purifying to be carried out in the lactic raw material logistics that contains trace pyruvic acid and oxalic acid.
Prepare 3 kinds of material solutions and simulate the fermenting broth that contains lactic acid.First material solution (FS1) is by following preparation: with the pyruvic acid (Aldrich) of the L-lactic acid (Pfansteihl) of 272.7g 88%, 2.572g 95%, the oxalic acid of 20.868g 10%w/v (LabChem, Inc.) and deionized water be mixed to 4 liters of volumes.Similarly, second material solution (FS2) is pressed following preparation: the L-lactic acid of 270.4g88%, the pyruvic acid of 2.424g 95%, oxalic acid and the capacity deionized water of 20.756g 10%w/v are mixed the solution that forms 4 liters of volumes.The 3rd material solution (FS3) is pressed following preparation: the L-lactic acid of 272.7g 88%, the pyruvic acid of 2.4g 95%, oxalic acid and the capacity deionized water of 20.7g 10%w/v are mixed the solution that forms 4 liters of volumes.
(Sybron Chemicals, Inc.)---a kind of alkaline unmixing extraction agent---fills the 40ml pillar with Ionac A-365 weak base anion-exchange resin.Ionac A-365 has porous polypropylene acid esters gel beads structure, specifically contains the vinylformic acid Vinylstyrene with polyamines functional group.Be filled in resin in the pillar with the deionized water wash of several times of bed volume.Packed column is removed lid, and place and be used for the upper reaches feed stream on the ring stand.
Use Eldex B-100-S-4 stainless steel reciprocation pump to adjust the speed that water, material solution and treat fluid enter pillar.Material solution, water and treat fluid flow through pillar under about 19 ℃ of-21 ℃ of temperature.Respectively lactic raw material FS1 and each 4 liters of FS2, FS32.5 liter are being passed through pillar above pumping successively in 52 hours time.Solution is fed to the pillar bottom in succession, and collects elutriant at the pillar top.Elutriant cut from material solution is collected by following order: 6 * 30ml, 2 * 120ml, 29 * 240ml, 1 * 40ml, 8 * 240ml and 9 * 30ml.Successively handle pillar, thereby also collect the acid elutriant cut of 4 * 40ml, 2 * 40ml deionized water wash cut, 4 * 40ml corrodibility (as alkalescence) elutriant cut and 2 * 40 deionized water wash cuts with acidic solution and basic solution.
Successively the elutriant cut of selecting is analyzed undilutedly by HPLC.Inject at the flow of each HPLC elutriant cut with 100 μ l in service with per minute 1.4ml.All analyses are all carried out under 19 ℃-21 ℃ room temperature.Moving phase contains 10% acetonitrile and 0.085%H in deionized water
3PO
4The HPLC post is that the long 300mm of being, diameter are the Jordi organic acid post of 7.8mm.Use UV test set (210nm) to detect the compound that wash-out goes out from the HPLC post.Measure the pH value of some elutriant cut.
After collecting above-mentioned cut, be used for the sample that half flow of aforementioned cut is collected two 30ml according to approximate, whether there is any kinetic limitation thereby measure.Based on following data, obviously there is not kinetic effect.
After feed stream flows through, pillar is regenerated.With the deionized water of 2 times of bed volume, the 1N HCl of 4 times of bed volume pillar is washed, then wash with the deionized water of 2 times of bed volume again.Then, wash with the 1N NaOH of 4 times of bed volume, the deionized water with 2 times of bed volume washs again.Flow and the available following chemical formula of the regeneration of pillar of material solution are described:
Raw material is handled: R
3N → R
3N: lactic acid → R
3N: pyruvic acid-R
3N: oxalic acid
Regeneration (1):
Regeneration (2):
A plurality of new peaks have appearred in bronsted lowry acids and bases bronsted lowry elutriant cut and water lotion afterwards.Wherein the part peak may be because the reaction between middle mutually pyruvic acid of resin and the oxalic acid.
Originally resin is with R
3The form of N exists.After material solution was fed in the pillar, unmixing basic extractant and all were present in the sour complexing in the feed stream.Along with the more raw materials solution feed to pillar, cemented out by pyruvic acid with the lactic acid of unmixing basic extractant complexing.Along with the more raw materials solution feed to pillar, cemented out by oxalic acid with the pyruvic acid of unmixing basic extractant complexing.The HPLC trace analysis that the elutriant sample that terminal collection obtains to the stream of material solution on pillar carries out shows that oxalic acid is still almost all absorbed by the unmixing basic extractant when end of run.When pyruvic acid in the elutriant sample reach grams per liter concentration in the raw material 5% the time, penetrate (pyruvic acid is cemented out from the unmixing basic extractant) that pyruvic acid may take place.From the HPLC data, this takes place when 192 times of bed volume.
Other data of being collected by operational process are summarized in the following table.
Table 2
The HPLC trace sample peak area of material solution
| FS1 | FS2 | FS3 | |
| Oxalic acid | 1614 | 1576 | 1614 |
| Pyruvic acid | 1462 | 1251 | 1292 |
| Lactic acid | 9503 | 7921 | 8285 |
| The lactic acid dipolymer | 3240 | 3544 | 3693 |
| The lactic acid trimer | 685 | 911 | 866 |
Table 3
The relative pK of related acid
aValue
| Acid | pK a |
| HCL | -2 |
| Oxalic acid | 1.27 |
| Pyruvic acid | 2.48 |
| Formic acid | 3.75 |
| Lactic acid | 3.86 |
| Acetate | 4.76 |
Table 4
The comparison of elutriant sample and its raw material
| FS1 | Elutriant cut (the postrun FS1 of upper prop) | |
| Oxalic acid | 512 | 0 |
| Pyruvic acid | 639 | 2 |
| Lactic acid | 44199 | 47288 |
| The lactic acid dipolymer | 15070 | 14179 |
| The lactic acid trimer | 3188 | 2676 |
About 2ppm of pyruvic acid content or 0.002 grams per liter in the corresponding ejecta of pyruvic acid area.
The impurity of several unknown chemical constitutions that occur in the HPLC trace analysis of material solution and elutriant cut may be from the resin impurity of the residual monomer of production of resins and be present in the impurity of the chemical that is used for preparing material solution.
Table 5
Bed lifting capacity based on the breakthrough point place of the theoretical bed capacity of 3.5meq/ml
| Material | Method | The mmol/ml resin |
| Oxalic acid | From analytical data | 1.09 |
| Pyruvic acid | From analytical data | 1.27 |
| Lactic acid, lactic acid dipolymer and lactic acid trimer | From theoretical bed capacity | 1.14 |
Embodiment 3. is from the batch process of the top distillate of lactic acid azeotropic distillation.
By azeotropic distillation and other step the fermenting broth that contains lactic acid is carried out prepurification.Described product contains the pyruvic acid of 19ppm and the lactic acid of 260.9g/L.In simple intermittent balance absorbs, be that the weak base anion-exchange resin Sybron Ionac A-365 of OH-form handles with about 1.2ml with this material of 4.5ml.About 38% lactic acid is removed.Clearly, about 90% pyruvic acid is removed, and pyruvic acid is less than 2ppm in the remaining product.According to estimates, the selectivity with respect to the lactic acid pyruvic acid is 14.73.
Observe in addition, by this processing, during 7.27 minutes elution times, a kind of unknown acid " strong impurity " is removed 99% in this specific HPLC stratographic analysis scheme, and selectivity is about 54.
In following table, based on specific refractory power data (not providing), estimated under 210 nano wave lengths chromatogram response factor for unknown peak, its response factor that shows described material is bigger 4 times than pyruvic acid.
Table 6
| Concentration mol/L | Material solution | Balance liquid | Resin | Kd | Selectivity | The % clearance |
| Peak 7.27 | 12.57×10 -4 | 0.13×10 -4 | 52.47×10 -4 | 401.21 | 176.51 | 99％ |
| Pyruvic acid | 0.22×10 -4 | 0.02×10 -4 | 0.73×10 -4 | 33.49 | 14.73 | 90％ |
| Lactic acid | 2899.92×10 -4 | 1805.11×10 -4 | 4102.98×10 -4 | 2.27 | 38％ | |
| The lactic acid dipolymer | 91.26×10 -4 | 0.55×10 -4 | 178.90×10 -4 | 4.11 | 1.81 | 52％ |
Embodiment 4. is from the continuous processing of the top distillate of lactic acid azeotropic distillation.
By azeotropic distillation and other step the fermenting broth that contains lactic acid is carried out prepurification.
But described product do not contain detection level pyruvic acid, 743g/L lactic acid and estimate at the unknown peak of 7.27 minutes 0.22 grams per liter.
In continuous post contact mode, with about 2.4ml the weak base anion-exchange resin Sybron Ionac A-365 processing of OH-form with this material of 10.0ml.
About 15% lactic acid is removed.Clearly, 98% unknown strong impurity is removed, thereby produces the lactic acid product of this strong impurity less than 4ppm.
This embodiment has illustrated that the present invention is for the effect of removing the not clear strong impurity of precise characteristics.
The continuous processing of embodiment 5. low pH fermenting broths.
The lactic fermentation meat soup (every kind of volume is about 5.5 liters) of two kinds of low pH of preparation also mixes.With SAC (highly acidic cation exchange) resin (＞0.1 mole of resin/molar lactic acid) and WBA (weakly-basic anion exchange) resin (～0.03 mole of resin/molar lactic acid) low pH meat soup is handled.The SAC resin is filled in two 37mm * 450mm pillar, and each is 480ml, and operation successively also successively is filled in the WBA resin in two 15mm * 300mm pillar, and each is 53ml.
After the processing, find that product has low-down pyruvic acid content, it is lower than what find in the lactic acid sample that is provided by ADM and Pfanstiehl.
Table 7
Except that lactic acid was represented with g/l, other all concentration were represented with ppm
| Acid | Impurity | Raw material | Ejecta 1 | Ejecta 2 | Get rid of thing 3 | Ejecta 4 |
| Lactic acid | Product | 60.76g/l | 40.28g/l | 62.64g/l | 63.16g/l | 62.92g/l |
| Pyruvic acid | By force | 270 | ＜20 | ＜20 | ＜20 | ＜20 |
| HCL | By force | 117 | ＜20 | ＜20 | ＜20 | ＜20 |
| H 2SO 4 | By force | 125 | ＜20 | ＜20 | ＜20 | ＜20 |
| H 3PO 4 | By force | 690 | ＜20 | ＜20 | ＜20 | ＜20 |
| Oxysuccinic acid | A little less than | 32 | 19 | 39 | 26 | 23 |
| Acetate | A little less than | 15 | ＜10 | 12 | 14 | 15 |
| Succsinic acid | A little less than | 48 | ＜20 | 41 | 33 | 30 |
From table data as can be seen, inorganic and organic acid can be a strong impurity, can both effectively be removed, although high lactic acid content is arranged.Use 1.4BV/ hour flow for SAC, use 6BV/ hour flow for WBA.
The continuous processing of 6.11 liters of fermenting broths of embodiment
The resin that uses among the regeneration embodiment 5, and with new a collection of fermented material re-treatment.The typical discharge logistics cut collected of being in operation contains the pyruvic acid of 62.8 grams per liter lactic acid and 12.4ppm.
The continuous processing of 7.11 liters of fermenting broths of embodiment
The resin that uses among the regeneration embodiment 6, and with new a collection of fermented material re-treatment.Collect two cuts.After the ion exchange treatment, each cut arrives about 28%w/w lactic acid by evaporation concentration.Before the evaporation, concentration sees Table 8.
Table 8
| The concentration grams per liter | Raw material | Cut |
| Pyruvic acid | 0.145 | 0.005 |
| Lactic acid | 62.000 | 62.000 |
| Oxysuccinic acid peak 9.00 | 0.130 | 0.030 |
As can be seen, pyruvic acid content is reduced to 0.5 mg/litre from 145 mg/litre.Under the situation of having only a small amount of lactic acid loss, reached the nearly 300 times remarkable decline of pyruvic acid content.
Resin anion(R.A) is regenerated, and finds that 0.64% and pyruvic acid of lactic acid total raw material quality are adsorbed to ion exchange resin.In this case, strong acid H
2SO
4And H
3PO
4Be present in the raw material, simultaneously also as displacement acid.
Available additional displacement acid comes regenerating resin, and is better than the pyruvic acid selectivity and replaces additional lactic acid.
Anionite-exchange resin is regenerated, and finds that the ratio of M lactic acid and M pyruvic acid is 19.34 in the resin.It is believed that this is because the resin choice limit.Can not surpass this load.
Embodiment 8. is used for the comparison of the liquid unmixing amine and the solid amine ion-exchanger of serial strong impurity
The acid mixture solution of listed sour impurity in preparation 52.78g/L lactic acid and the various tables of 0.2-0.3g/L.
Come the acid mixture of balance 8ml equal portions with 1.0ml Sybron Ionac A-365 weak anion resin, and measure its selectivity with respect to lactic acid.
Come the acid mixture of each 5ml equal portions of balance respectively with 5ml extraction agent Y, described extraction agent Y is made up of 1.0 moles of trilaurylamine (Tridodecylamines and 1.0 moles of dodecanols, and with dodecane as thinner.
Table 9
| Material | With respect to lactic acid, Ionac A-365 is to the selectivity of impurity | With respect to lactic acid, extraction agent Y is to the selectivity of impurity |
| Pyruvic acid | 20.99 | |
| L MALIC ACID | 198.8 | 3.32 |
| Formic acid | 4.01 | 3.06 |
| Acetate | 0.169 | 0.42 |
| Propionic acid | 0.101 | 1.42 |
| Butanic acid | 0.100 | 5.74 |
| Isopropylformic acid | 0.072 | 6.53 |
Embodiment 9. usefulness displacement acid displacement back U38 strongly basic anionic resin selectivity is removed strong impurity
Preparation Amberlite IRA-93 strongly basic anionic resin in the 62ml pillar, and make it be regenerated as hydroxide form.With the excessive dense lactic fermentation meat soup of plastic resin treatment, described fermenting broth was handled with positively charged ion and weak anion resin in advance.
Use 1N H
2SO
4Resin is replaced.Collect 5 cuts.Preceding two cuts that obtained contain a large amount of weak impurity, acetate and formic acid and lactic acid.The cut of back contains a large amount of pyruvic acid and part lactic acid.
Different pyruvic acid content are to removing the estimation with the influence of displacement efficiency in embodiment 10. raw materials
The lactic acid mole number is 117: 1 with the ratio of pyruvic acid mole number in the material solution.After the processing of amine unmixing basic extractant, product had suitable ratio 486: 1.Therefore, remove pyruvic acid by selectivity, lactic acid has obtained purifying.Extraction agent contains 5.6% mole of lactic acid that is present in the raw material, and this has reduced yield.
Usually, more multistep suddenly or longer extraction sequence can obviously not improve this situation.This is because had low-down pyruvic acid foreign matter content in the raw material, and with respect to lactic acid, amine has only 18 times limited selectivity for pyruvic acid.
Suppose that the value that every kind of material enters the partition ratio of amine phase is a constant.This is reasonably, because concentration can obviously not change in extraction process.The partition ratio of supposing every kind of material is independently, and this also is reasonably, loads because amine is just a small amount of in the case.Under underload, the amine extractant complex compound can be subjected to pyruvic acid and 1: 1 complex compound of amine to form control.The energy of these complex compounds and distribution and sour pK
aRoughly relevant.The amine of usefulness can not be highly reinforcing herein.For example, suppose that pyruvic acid enters the K of amine phase
dBe the ratio between the pyruvic acid mol value of the pyruvic acid mol value of acid unhindered amina phase and the free water of acidity.The partition ratio of pyruvic acid is assumed to 5.0, and lactic acid then is 0.278, thereby selectivity is 18.0.
Table 10
The influence of pyruvic acid material concentration when using identical lactic acid concn (0.66M)
| Initial pyruvic acid concentration in the raw material | 1000 | 500 | 300 | 100 | ppm |
| Required unmixing basic extractant volume | 10.66 | 10.57 | 10.53 | 10.49 | Rise |
| The bed volume of handling | 93.84 | 94.64 | 94.96 | 95.29 | Rise |
| Lactic acid loss during extraction | 3.9％ | 4.7％ | 5.1％ | 5.4％ | |
| M pyruvic acid and M lactic acid than Y pyruvic acid on the ion-exchange bed | 30.5％ | 15.4％ | 9.2％ | 3.1％ |
Owing in the ion-exchange a plurality of steps are arranged, effective pyruvic acid content is low-down in the liquid effluent after second bed volume.In the practice, observe the pyruvic acid content of 2ppm.Suppose that bed is 18: 1 with respect to lactic acid to the selectivity of pyruvic acid, then at the i.e. ion load cut Y on the bed wherein of all following situations
Pyruvic acidDuring greater than about 100/18=5.56%w/w, can lactic acid be separated with pyruvic acid at regeneration period.If lifting capacity is worth less than this, needs that then this liquid effluent is carried out follow-up additional ions exchange and handle.Above-mentioned example at be the situation of the whole desorptions of all substances on ion-exchanger, and not with the liquid effluent fractionation, this is an ideal.
Embodiment 11. repeats the estimation of embodiment 10, but changes lactic acid concn
Table 11 has and changes the lactic acid concn influence in the raw material of identical pyruvic acid concentration
| Initial pyruvic acid concentration in the raw material | 500 | 500 | 500 | ppm |
| Required unmixing basic extractant volume | 10.57 | 12.79 | 15.96 | Rise |
| The bed volume of handling | 94.64 | 78.19 | 62.64 | Rise |
| Lactic acid loss during extraction | 4.74％ | 4.88％ | 5.02％ | |
| The Y pyruvic acid | 15.4％ | 12.7％ | 10.2％ | |
| Initial lactic acid concn in the raw material | 0.66 | 0.80 | 1.00 | mol/L |
For given pyruvic acid content, when lactic acid concn increased, lactic acid fractionation load in bed descended.This makes acquisition independent lactic acid and pyruvic acid cut more difficult.
Above-mentioned description to particular of the present invention is not the exhaustive of the various possibility of the present invention embodiment.Those skilled in the art will appreciate that the change that can make for described particular also will fall within the scope of the present invention.
Claims (20)
1. the method for a purified lactic acid comprises:
A kind of water-containing material logistics that contains free lactic acid and at least a pollutent is provided;
The water-containing material logistics is contacted with lean solution body extraction agent, in the described lean solution body extraction agent, with respect to every kilogram of lean solution body extraction agent, it contains less than about 0.75 mole of amine, with respect to every mole of amine, it contains the 0-0.5 mole toughener of having an appointment, and contains thinner, thus most of pollutent and the complexing of lean solution body extraction agent;
The lean solution body extraction agent of complexing is separated with the water-containing material logistics, discharge logistics thereby produce first, it contains free lactic acid, and the ratio of free lactic acid and pollutent bigger than in the water-containing material logistics that does not contact; With
Discharging logistics with first contacts with the liquid-rich extraction agent, thereby make the first most of free lactic acid and the complexing of liquid-rich extraction agent of discharging in the logistics, wherein the liquid-rich extraction agent contain with lean solution body extraction agent in identical amine, toughener and thinner, and in the liquid-rich extraction agent, the molar weight of the amine that contains with respect to every kilogram of liquid-rich extraction agent is bigger than the molar weight of amine in every kilogram of lean solution body extraction agent, and the ratio of toughener molar weight and amine molar weight higher than in the lean solution body extraction agent in the liquid-rich extraction agent, and lifting capacity should make first to discharge the ratio of logistics middle reaches molar weight of amine in the molar weight of lactic acid and liquid-rich extraction agent less than about 1.1, wherein said toughener is for strengthening the chemical substance of alkaline unmixing extraction agent performance, for being selected from alcohol, ketone, diketone, lipid acid and muriatic polar material, wherein said alcohol is selected from alkanol and glycol.
2. the process of claim 1 wherein that pollutent is pK
aAcid less than about 3.46.
3. the method for claim 2, wherein pollutent is selected from pyruvic acid, oxalic acid, toxilic acid, propanedioic acid, fumaric acid, 2-alpha-ketobutyric acid, 2-hydroxybutyric acid, acetate, 2-hydroxy-3-methyl butyric acid, 4-hydroxyl-phenylpyruvic acid, phenylpyruvic acid, 4-hydroxyl-phenyl-lactic acid, phenyl-lactic acid, citraconic acid, citric acid and their mixture.
4. the process of claim 1 wherein that amine is the second month in a season or tert-aliphatic amine.
5. the method for claim 4, wherein amine contains 20-36 carbon atom.
6. the process of claim 1 wherein that lean solution body extraction agent contains tertiary amine, and with respect to every kilogram of lean solution body extraction agent, it contains the described amine of 0.2-0.5 mole of having an appointment.
7. the process of claim 1 wherein that with respect to every mole of amine lean solution body extraction agent contains the 0.1-0.25 mole toughener of having an appointment.
8. the process of claim 1 wherein that lifting capacity should make first to discharge ratio between the mole number of logistics middle reaches amine in the mole number of lactic acid and liquid-rich extraction agent less than about 0.95.
9. the process of claim 1 wherein that toughener is selected from alkanol, ester, diester, glycol, ketone and diketone.
10. the process of claim 1 wherein that toughener is C
3-C
12The monohydroxy primary alkanol.
11. the process of claim 1 wherein that the water-containing material logistics is a fermenting broth.
12. the process of claim 1 wherein that thinner is selected from aromatic hydrocarbon and aliphatic hydrocrbon.
13. the process of claim 1 wherein that thinner is selected from dodecane, decane, dimethylbenzene, toluene, kerosene and their mixture.
14. the method for claim 1, it comprises that further water strips to the complex compound that contains lactic acid and liquid-rich extraction agent, thereby produces the logistics of aqueous product lactic acid.
15. the method for claim 14 is wherein stripped and is carried out under following temperature: high more about below 20 ℃ than the temperature that liquid-rich extraction agent and first is discharged in the logistics contact procedure.
16. the method for claim 15 is wherein stripped and is carried out under following temperature: high more about below 15 ℃ than the temperature that liquid-rich extraction agent and first is discharged in the logistics contact procedure.
17. the process of claim 1 wherein that the water-containing material logistics prepares with second method, it comprises that providing a kind of contains lactic acid, at least a pollutent and the logistics of solid water-containing material, and filters described water-containing material logistics to remove most of solid.
18. the method for claim 17, wherein the water-containing material logistics further contains the dissolved molecule, and second method further comprises membrane filtration is carried out in the water-containing material logistics after filtering, thereby removes most of dissolved molecule.
19. the method for claim 17, wherein the water-containing material logistics further contains positively charged ion, and second method further comprises the water-containing material logistics after filtering is contacted with cationite, thereby removes most of positively charged ion.
20. the method for claim 17, wherein the water-containing material logistics is a fermenting broth.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/037,664 | 2002-01-03 | ||
| US10/037,664 US6641734B2 (en) | 2002-01-03 | 2002-01-03 | Process for purifying an organic acid |
| US10/295,970 | 2002-11-15 | ||
| US10/295,970 US6942803B2 (en) | 2002-01-03 | 2002-11-15 | Process for purifying an organic acid |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101485679A Division CN1982282A (en) | 2002-01-03 | 2002-12-11 | Process for puriying an organic acid |
| CNA200610148565XA Division CN1982280A (en) | 2002-01-03 | 2002-12-11 | Process for puriying an organic acid |
| CNA2006101485664A Division CN1982281A (en) | 2002-01-03 | 2002-12-11 | Process for puriying an organic acid |
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| CN1289459C true CN1289459C (en) | 2006-12-13 |
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| CN02826698.6A Expired - Fee Related CN1289459C (en) | 2002-01-03 | 2002-12-11 | Process for purifying an organic acid |
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|---|---|
| EP (1) | EP1470099A4 (en) |
| CN (1) | CN1289459C (en) |
| AU (1) | AU2002362143A1 (en) |
| BR (1) | BR0215459A (en) |
| CA (1) | CA2470978A1 (en) |
| WO (1) | WO2003059863A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643191A (en) * | 2012-03-28 | 2012-08-22 | 河南金丹乳酸科技股份有限公司 | Heavy phase lactic acid processing technology |
| CN102659563A (en) * | 2012-03-06 | 2012-09-12 | 河南金丹乳酸科技股份有限公司 | Organic extraction phase for extracting lactic acid from heavy phase lactic acid |
| CN102701950A (en) * | 2012-05-30 | 2012-10-03 | 河南金丹乳酸科技股份有限公司 | Method for continuously producing lactate by utilizing heavy phase lactic acid |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9879289B2 (en) * | 2009-06-05 | 2018-01-30 | Evonik Degussa Gmbh | Method for the preparation of 2-keto carboxylic acid |
| JP5890905B2 (en) * | 2012-07-23 | 2016-03-22 | 旭硝子株式会社 | Method for producing organic acid |
| CN103494850B (en) * | 2013-07-24 | 2015-07-15 | 成都中医药大学 | Process for extracting and purifying total organic acid of aralia cordata |
| CN108947066A (en) * | 2018-07-13 | 2018-12-07 | 宁波永顺精细化工有限公司 | The recovery method of carboxylic acid and barium salt in carboxylic acid barium waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2568095A (en) * | 1949-04-29 | 1951-09-18 | Standard Oil Co | Recovery of organic acids with an amine solvent |
| US4076948A (en) * | 1968-10-10 | 1978-02-28 | El Paso Products Company | Process for treatment of adipic acid mother liquor |
| IL39710A (en) * | 1972-06-19 | 1975-04-25 | Imi Inst For Res & Dev | Recovery of acids from aqueous solutions by solvent extraction |
| IL57024A (en) * | 1979-04-09 | 1982-03-31 | Yissum Appl Eng Syst | Process for the separation of a strong mineral acid from an aqueous solution |
| US5068419A (en) * | 1986-12-18 | 1991-11-26 | Uop | Separation of an organic acid from a fermentation broth with an anionic polymeric adsorbent |
| US5786185A (en) * | 1991-09-13 | 1998-07-28 | Reilly Industries, Inc. | Process for producing and recovering lactic acid |
| US6111137A (en) * | 1996-12-20 | 2000-08-29 | Mitsui Chemicals, Inc. | Purification process of lactic acid |
| US5986133A (en) * | 1997-06-30 | 1999-11-16 | The Texas A&M University System | Recovery of fermentation salts from dilute aqueous solutions |
| US6509179B1 (en) * | 2000-10-12 | 2003-01-21 | Barbara I. Veldhuis-Stribos | Continuous process for preparing lactic acid |
-
2002
- 2002-12-11 EP EP02797276A patent/EP1470099A4/en not_active Withdrawn
- 2002-12-11 CN CN02826698.6A patent/CN1289459C/en not_active Expired - Fee Related
- 2002-12-11 BR BR0215459-5A patent/BR0215459A/en not_active IP Right Cessation
- 2002-12-11 CA CA002470978A patent/CA2470978A1/en not_active Abandoned
- 2002-12-11 WO PCT/US2002/039620 patent/WO2003059863A1/en not_active Application Discontinuation
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659563A (en) * | 2012-03-06 | 2012-09-12 | 河南金丹乳酸科技股份有限公司 | Organic extraction phase for extracting lactic acid from heavy phase lactic acid |
| CN102659563B (en) * | 2012-03-06 | 2014-09-17 | 河南金丹乳酸科技股份有限公司 | Organic extraction phase for extracting lactic acid from heavy phase lactic acid |
| CN102643191A (en) * | 2012-03-28 | 2012-08-22 | 河南金丹乳酸科技股份有限公司 | Heavy phase lactic acid processing technology |
| CN102643191B (en) * | 2012-03-28 | 2014-08-06 | 河南金丹乳酸科技股份有限公司 | Heavy phase lactic acid processing technology |
| CN102701950A (en) * | 2012-05-30 | 2012-10-03 | 河南金丹乳酸科技股份有限公司 | Method for continuously producing lactate by utilizing heavy phase lactic acid |
| CN102701950B (en) * | 2012-05-30 | 2014-08-06 | 河南金丹乳酸科技股份有限公司 | Method for continuously producing lactate by utilizing heavy phase lactic acid |
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| Publication number | Publication date |
|---|---|
| EP1470099A4 (en) | 2006-04-12 |
| WO2003059863A1 (en) | 2003-07-24 |
| CA2470978A1 (en) | 2003-07-24 |
| EP1470099A1 (en) | 2004-10-27 |
| AU2002362143A1 (en) | 2003-07-30 |
| BR0215459A (en) | 2005-04-05 |
| CN1612851A (en) | 2005-05-04 |
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