CN116410099A - Method for recovering L-alanine from D-aspartic acid mother liquor - Google Patents
Method for recovering L-alanine from D-aspartic acid mother liquor Download PDFInfo
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- CKLJMWTZIZZHCS-UWTATZPHSA-N D-aspartic acid Chemical compound OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 title claims abstract description 150
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 title claims abstract description 71
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 title claims abstract description 71
- 229960003767 alanine Drugs 0.000 title claims abstract description 71
- 239000012452 mother liquor Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000010413 mother solution Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 36
- 229960005261 aspartic acid Drugs 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004587 chromatography analysis Methods 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 229940024606 amino acid Drugs 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012527 feed solution Substances 0.000 claims 2
- 238000004042 decolorization Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 235000003704 aspartic acid Nutrition 0.000 description 5
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 229940000635 beta-alanine Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 108700016171 Aspartate ammonia-lyases Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- GHOKWGTUZJEAQD-UHFFFAOYSA-N Chick antidermatitis factor Natural products OCC(C)(C)C(O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-UHFFFAOYSA-N 0.000 description 1
- 150000008557 D-aspartic acids Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229940055726 pantothenic acid Drugs 0.000 description 1
- 235000019161 pantothenic acid Nutrition 0.000 description 1
- 239000011713 pantothenic acid Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for recovering L-alanine from D-aspartic acid mother liquor. The method comprises the following steps: firstly adding alkali into the D-aspartic acid mother liquor to adjust the pH value of the D-aspartic acid mother liquor to be 6-7; and then the D-aspartic acid mother solution is sequentially subjected to continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment to obtain the L-alanine. Based on the method, the L-alanine with high yield and purity can be recovered from the D-aspartic acid mother liquor.
Description
Technical Field
The invention relates to the field of production of D-aspartic acid, in particular to a method for recovering L-alanine from D-aspartic acid mother liquor.
Background
D-aspartic acid production has been reported in Japanese research and has been recently reported. The reported methods for preparing D-aspartic acid are physical, chemical and biological. Among the physical methods, there are the preferential crystallization method and the chemical method, which are divided into chemical resolution and chemical asymmetric synthesis. Some of the methods have the disadvantages of lengthy synthesis steps and complex process, some chiral auxiliary agents are expensive, some optical purity is low, and no industrial report is seen. Biological methods are also divided into biological resolution and biological asymmetric synthesis. Among them, biological resolution is more studied. Currently, enzymes commonly used for biological resolution are L-aspartic acid alpha decarboxylase, L-aspartic acid beta decarboxylase, aspartase, and the like. Resolution with L-aspartic acid a decarboxylase can stereospecifically remove the alpha carboxyl group of L-aspartic acid to produce beta-alanine and CO 2 And this process does not work for D-aspartic acid. Along with CO 2 The reaction is essentially irreversible, thus allowing high conversion of the product and allowing simultaneous production of two useful products. Wherein beta-alanine is useful in the synthesis of pantothenic acid, derivatives thereof have been used as buffers in electroplating. Because the strain with high activity which can produce the enzyme is directly screened from the nature, the strain is quite idle and difficult to select. However, the method relates to the transformation of the bacteria by genetic engineering, and is still in the primary stage at present, and the enzyme activity is still low.
Thus, at present, the resolution is mostly carried out by using L-aspartic acid beta decarboxylase. The microorganism containing high activity L-aspartic acid beta decarboxylase in nature is more, and the enzyme can specifically catalyze L-aspartic acid to remove beta carboxyl to generate L-alanine. Thus, we can use this enzyme to convert L-aspartic acid in DL-aspartic acid (D-aspartic acid and L-aspartic acid in a mixed form) to L-alanine and obtain the product D-aspartic acid.
However, the DL-aspartic acid (D-aspartic acid and L-aspartic acid exist in a mixed form) is resolved by L-aspartic acid beta decarboxylase, the D-aspartic acid mother liquor after the D-aspartic acid is extracted contains a large amount of L-alanine as a byproduct, and how to fully recycle the L-alanine is turned into wealth, so that the recycling of resources is realized, and the method is the focus of attention of the current industry. At present, when the part of L-alanine is recovered, direct evaporation concentration is often adopted, but the recovery of the L-alanine with high purity is difficult and the yield is not high by evaporation concentration. Therefore, it is necessary to provide a novel recovery treatment method capable of recovering L-alanine having a high purity and a high recovery rate from a D-aspartic acid mother liquor.
Disclosure of Invention
The invention mainly aims to provide a method for recovering L-alanine from D-aspartic acid mother liquor, which aims to solve the problems of low purity and low yield existing in the prior art for recovering L-alanine from waste D-aspartic acid mother liquor.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for recovering L-alanine from a D-aspartic acid mother liquor containing L-alanine, D-aspartic acid, L-aspartic acid and water, the method comprising: firstly, regulating the pH value of the D-aspartic acid mother solution to 6-7; and then the D-aspartic acid mother solution after pH adjustment is sequentially subjected to continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment to obtain the L-alanine.
Further, the D-aspartic acid mother liquor contains 50 to 80wt% of L-alanine, 5 to 25wt% of D-aspartic acid and 5 to 30wt% of L-aspartic acid based on the percentage of the solute.
Further, a base is added to the D-aspartic acid mother liquor to adjust the pH, preferably, the base is one or more of sodium hydroxide, potassium hydroxide or ammonia water with a mass concentration of 25-28%, more preferably, ammonia water with a mass concentration of 25%.
Further, the method for recovering L-alanine from D-aspartic acid mother liquor after anion resin adsorption treatment and before crystallization treatment further comprises: adding a decoloring adsorbent into the feed liquid treated by the anion resin to decolor the feed liquid; preferably, the decolorizing treatment is carried out at 25-80 deg.c for 0.5-2 hr.
Further, the decolorizing adsorbent is one or more of wood powder active carbon and/or decolorizing resin; preferably, the dosage of the decolorized adsorbent is 0.1-2.0% of the weight of the feed liquid after the treatment of the anionic resin; preferably, the decolorizing resin is one or more of ADS-17, HPD-750, AB-8, or D101.
Further, the crystallization treatment adopts a concentrated crystallization mode; preferably, the temperature of concentration crystallization is 50-85 ℃, and the vacuum degree is-0.085 to-0.095 MPa.
Further, in the process of treating the anionic resin, the anionic resin is LX-67, A600MB or PA510, preferably LX-67.
Further, in the continuous chromatographic treatment process, the chromatographic packing is cationic resin; preferably, the cationic resins are D301, D354, D113, more preferably D301.
Further, in the continuous chromatographic treatment process, the liquid inlet flow rate of the D-aspartic acid mother solution is controlled to be 1-5 BV/h, and after the inorganic salt and the amino acid are separated, the continuous chromatography is regenerated by pure water, and the pure water regeneration flow rate is controlled to be 1-5 BV/h.
Further, the treatment temperature in the continuous chromatographic treatment process is 5-60 ℃.
Firstly, the invention adjusts the pH value of the mother liquor to 6-7 by adding alkali into the mother liquor, on the one hand, the solubility of L-alanine can be reduced while the solubility of aspartic acid impurities (such as D-aspartic acid and L-aspartic acid) in the mother liquor is improved, and more aspartic acid impurities (such as D-aspartic acid and L-aspartic acid) in the mother liquor are promoted to be dissolved, so as to provide the following continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment processesA more preferable purification environment for L-alanine. On the other hand, the base may be dissolved with D-aspartic acid and L-aspartic acid (COOH-CH (NH) 3 ) + -CH 2 -COOH) to form the corresponding salt, and further, in the cooperation of the subsequent continuous chromatography and the adsorption treatment of the anion resin, the continuous chromatography can remove some inorganic salt impurities more effectively, so that the anion resin can adsorb and only the salt of D-aspartic acid and the salt of L-aspartic acid in the mixed material more effectively, and a feed liquid containing only L-alanine is obtained. Finally, the feed liquid is subjected to crystallization treatment to obtain the L-alanine with high yield and purity; in addition, in the continuous chromatographic treatment, pure water regeneration is used for replacing the existing acid-base regeneration, so that the treatment capacity of the regenerated waste water is greatly reduced, the separation operation does not need to use alkali and acid raw materials, the cost is saved, the pure water regeneration is better and environment-friendly, and the novel process realizes environment friendliness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a schematic flow chart of the recovery of L-alanine from D-aspartic acid mother liquor in one embodiment of the present invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
Generally, the person skilled in the art uses L-aspartic acid beta decarboxylase to split DL-aspartic acid (D-aspartic acid and L-aspartic acid are present in a mixed form), and in the process of obtaining the product D-aspartic acid, an acid (such as sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, preferably sulfuric acid) is added to the system to adjust the pH of the system to 2.5-3.0, so as to extract the product D-aspartic acid. Thus, the D-aspartic acid mother liquor after extracting the product D-aspartic acid contains L-alanine and D-DThe composition contains, in addition to aspartic acid, L-aspartic acid and water, SO 4 2- (sulfuric acid), cl - (hydrochloric acid), NO 3 2- (nitric acid) or PO 4 2- (phosphoric acid) and the like.
As described in the background section of the present invention, the prior art has problems of low purity and low yield in recovering L-alanine from waste D-aspartic acid mother liquor. In order to solve this problem, the present invention proposes a treatment method for recovering L-alanine from D-aspartic acid mother liquor, as shown in FIG. 1, comprising: firstly adding alkali into the D-aspartic acid mother liquor to adjust the pH value of the D-aspartic acid mother liquor to be 6-7; and then the D-aspartic acid mother solution is sequentially subjected to continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment to obtain the L-alanine.
Firstly, the pH value of the mother liquor is adjusted to be 6-7 by adding alkali into the mother liquor, so that on one hand, the solubility of aspartic acid impurities (such as D-aspartic acid and L-aspartic acid) in the mother liquor can be improved, and meanwhile, the solubility of L-alanine can be reduced, so that more aspartic acid impurities (such as D-aspartic acid and L-aspartic acid) in the mother liquor can be promoted to be dissolved, and a better L-alanine purification environment is provided for the subsequent continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment processes. On the other hand, the base may be dissolved with D-aspartic acid and L-aspartic acid (COOH-CH (NH) 3 ) + -CH 2 -COOH) to form the corresponding salt, and further, in the cooperation of the subsequent continuous chromatography and the adsorption treatment of the anion resin, the continuous chromatography can remove some inorganic salt impurities more effectively, so that the anion resin can adsorb and only the salt of D-aspartic acid and the salt of L-aspartic acid in the mixed material more effectively, and a feed liquid containing only L-alanine is obtained. Finally, the feed liquid is subjected to crystallization treatment to obtain the L-alanine with high yield and purity.
In a preferred embodiment, the D-aspartic acid mother liquor has an L-alanine content of 50 to 80wt%, a D-aspartic acid content of 5 to 25wt% and an L-aspartic acid content of 5 to 30wt% based on the percentage of the solute. Based on the composition of the material, the treatment method provided by the invention has better applicability and higher recovery purity and recovery rate of the L-alanine.
In a preferred embodiment, the base is one or more of sodium hydroxide, potassium hydroxide or ammonia water with a mass concentration of 25-28%. More preferably, the base is aqueous ammonia with a mass concentration of 25%.
In a preferred embodiment, the treatment method further comprises, after the anionic resin treatment and before the crystallization treatment: adding a decoloring adsorbent into the feed liquid treated by the anion resin to decolor the feed liquid; preferably, the decolorizing treatment is carried out at 25-80 deg.c for 0.5-2 hr.
In order to further enhance the decolorizing effect, in a preferred embodiment, the decolorizing adsorbent is wood-based powdered activated carbon and/or decolorizing resin, preferably the decolorizing resin is ADS-17, HPD-750, AB-8 or D101. More preferably, the amount of the decolorizing adsorbent is 0.1-2.0% by weight of the feed liquid. Wherein, the parameters of the decolorized adsorbent are shown in the following table:
| decolorizing resin model | Decolored light transmittance/% | L-alanine retention rate/% |
| ADS-17 | 92.3 | 0.35 |
| HPD-750 | 91.9 | 1.22 |
| AB-8 | 89.8 | 0.32 |
| D101 | 83.1 | 6.89 |
| Wooden powdered active carbon | 99.6 | 0.12 |
In order to recover L-alanine having higher purity and better crystal quality, in a preferred embodiment, the crystallization is performed by concentration crystallization. Preferably, the concentration temperature of the concentrated crystals is 50-85 ℃, and the concentration vacuum degree is-0.085 to-0.095 MPa. In a more preferred embodiment, the feed liquid is placed into a concentration tank for concentration and crystallization treatment (in the process, the crystal form of better L-alanine seed crystal can be supplemented), after the feed liquid is concentrated to 60-70% of crystal, the feed liquid in the concentration tank is slowly cooled to 10-15 ℃ at the cooling rate of about 10 ℃/h, and the L-alanine crystal with higher yield, higher purity and higher crystal form quality can be recovered through filtration. More preferably, the cooling speed in the cooling process can be 8-12 ℃/h, and based on the cooling speed, the stability of a crystallization system can be promoted to be better, so that the crystal form quality of the L-alanine is further improved.
In order to further recover L-alanine in higher yields and purities, in a preferred embodiment, the anionic resin used in the anionic resin treatment is LX-67, A600MB or PA510. More preferably LX-67.
In order to further enhance the treatment effect of the inorganic impurity salt, a better L-alanine purification environment is provided for the subsequent anion resin treatment, so that the purity of the L-alanine is further enhanced, and in a preferred embodiment, the continuous chromatographic instrument model is StarSep-30025, and the resin filler is D301, D354 and D113, and more preferably D301 in the continuous chromatographic treatment process. In a preferred embodiment, in the continuous chromatographic treatment process, the liquid inlet flow rate of the D-aspartic acid mother solution can be controlled to be 1-5 BV/h, and after various inorganic salt components (ammonium radical, sulfate radical and the like) are separated from amino acid components (D-aspartic acid salt, L-alanine and the like), the continuous chromatographic treatment is performed by using pure water for regeneration, and the pure water regeneration flow rate is 1-5 BV/h. Preferably, the continuous chromatographic temperature is 5-60 ℃. Based on the method, the continuous chromatographic treatment process is smoother, the material separation is more thorough, and especially the removal effect on inorganic salt impurities is better, so that the recovery rate and recovery purity of the subsequent L-alanine are further improved.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
In the D-aspartic acid mother solution, the content of L-alanine is 60wt%, the content of D-aspartic acid is 20wt%, the content of L-aspartic acid is 15wt%, and SO 4 2- The content of D-aspartic acid mother liquor is 20g/L, and the pH value of the D-aspartic acid mother liquor is 2.9.
1) Adding 25% ammonia water to the mother liquor of D-aspartic acid to control the pH value of the mother liquor of D-aspartic acid to 6.5, NH 4 + The mass concentration of (C) is 8g/L.
2) The D-aspartic acid mother liquor treated in the step 1) is treated by continuous chromatography, the liquid inlet flow rate of the D-aspartic acid mother liquor is controlled to be 2.0BV/h, various fast salt components such as ammonium radical, sulfate radical and the like are firstly discharged, slow amino acid components are discharged, the separation of salt and amino acid is realized by the continuous chromatography, then the continuous chromatography is regenerated by pure water, and the pure water regeneration flow rate is 1-2BV/h so as to carry out the next round of separation operation; the resin filler is a weakly acidic D301 positive resin; the separation temperature is 5-10 ℃.
The ammonium sulfate is separated and removed within 10 to 20 minutes.
3) And (3) treating the feed liquid treated in the step (2) by LX-67 anionic resin.
4) Adding wood powder active carbon (the dosage is 0.4% of the weight of the feed liquid) into the feed liquid treated in the step 3), and decoloring the feed liquid at 25-60 ℃ for 0.5-2 h.
5) Vacuum concentrating the feed liquid treated in the step 4) at the concentration temperature of 50-85 ℃ and the concentration vacuum degree of-0.095 Mpa until the crystal ratio is 70%; then slowly cooling to 10 ℃ at the speed of 10 ℃/h to obtain the L-alanine crystal.
The yield of L-alanine was 93% and the purity was 99.8%.
Example 2
The only difference from example 1 is that:
in step 3), A600MB was used as the anionic resin.
The yield of L-alanine was 87% and the purity was 99.2%.
Example 3
The only difference from example 1 is that:
in step 3), PA510 is used as the anionic resin.
The yield of L-alanine was 92% and the purity was 98.9%.
Example 4
The only difference from example 1 is that:
in step 5), the concentration vacuum degree is-0.085 MPa.
The yield of L-alanine was 84% and the purity was 99.5%.
Example 5
The only difference from example 1 is that:
in the D-aspartic acid mother liquor, the content of L-alanine is 80wt%, the content of D-aspartic acid is 10wt%, the content of L-aspartic acid is 5wt%, and SO 4 2- The content of D-aspartic acid mother liquor is 20g/L, and the pH value of the D-aspartic acid mother liquor is 2.9.
The yield of L-alanine was 95.3% and the purity was 99.85%.
Example 6
The only difference from example 1 is that:
in the D-aspartic acid mother liquor, the content of L-alanine is 50wt%, the content of D-aspartic acid is 25wt%, the content of L-aspartic acid is 15wt%, and SO 4 2- The content of D-aspartic acid mother liquor is 20g/L, and the pH value of the D-aspartic acid mother liquor is 2.9.
The yield of L-alanine was 92.5% and the purity was 99.4%.
Comparative example 1
The only difference from example 1 is that:
directly concentrating the mother liquor in vacuum at the concentration temperature of 50-85 ℃ and the concentration vacuum degree of-0.095 MPa.
The yield of L-alanine was 79% and the purity was 97.5%.
Comparative example 2
The only difference from example 1 is that:
in step 3): and (3) treating the feed liquid treated in the step (2) through cationic resin D001.
The yield of L-alanine was 74% and the purity was 97%.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recovering L-alanine from a D-aspartic acid mother liquor containing L-alanine, D-aspartic acid, L-aspartic acid, and water, the method comprising:
firstly, regulating the pH value of the D-aspartic acid mother solution to 6-7; and then the D-aspartic acid mother solution after pH adjustment is sequentially subjected to continuous chromatographic treatment, anion resin adsorption treatment and crystallization treatment to obtain the L-alanine.
2. The method for recovering L-alanine from D-aspartic acid mother liquor according to claim 1, wherein the content of L-alanine in the D-aspartic acid mother liquor is 50 to 80% by weight, the content of D-aspartic acid is 5 to 25% by weight, and the content of L-aspartic acid is 5 to 30% by weight, based on the percentage of the solute.
3. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in claim 1 or 2, wherein a base is added to the D-aspartic acid mother liquor to adjust pH; preferably, the alkali is one or more of sodium hydroxide, potassium hydroxide and ammonia water with a mass concentration of 25-28%, more preferably ammonia water with a mass concentration of 25%.
4. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in any one of claims 1 to 3, wherein after the anion resin adsorption treatment and before the crystallization treatment, the method for recovering L-alanine from a D-aspartic acid mother liquor further comprises: a step of adding a decolorization adsorbent to the anion resin-treated feed solution to decolorize the anion resin-treated feed solution;
preferably, the decolorizing treatment is carried out at a temperature of 25-80 ℃ for 0.5-2 hours.
5. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in claim 4, wherein the decolorizing adsorbent is one or more of wood-based powdered activated carbon and/or decolorizing resin;
preferably, the dosage of the decoloring adsorbent is 0.1-2.0% of the weight of the feed liquid after the anionic resin treatment;
preferably, the decolorizing resin is one or more of ADS-17, HPD-750, AB-8, or D101.
6. The method for recovering L-alanine from a mother liquor of D-aspartic acid as claimed in claim 5, wherein the crystallization treatment adopts a concentrated crystallization mode;
preferably, the temperature of the concentrated crystallization is 50-85 ℃, and the vacuum degree is-0.085 to-0.095 MPa.
7. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in any one of claims 1 to 6, wherein the anion resin used in the anion resin treatment is LX-67, A600MB or PA510, preferably LX-67.
8. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in any one of claims 1 to 7, wherein the chromatographic packing is a cationic resin during the continuous chromatographic treatment; preferably, the cationic resins are D301, D354, D113, more preferably D301.
9. The method for recovering L-alanine from a D-aspartic acid mother liquor according to claim 8, wherein in the continuous chromatography treatment process, the liquid inlet flow rate of the D-aspartic acid mother liquor is controlled to be 1-5 BV/h, and after the inorganic salt and the amino acid are separated, the continuous chromatography is regenerated by pure water, and the pure water regeneration flow rate is controlled to be 1-5 BV/h.
10. The method for recovering L-alanine from a D-aspartic acid mother liquor as claimed in claim 9, wherein the process temperature during the continuous chromatography process is 5 to 60 ℃.
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