CN111057732B - Desalination process in production of proglutin - Google Patents
Desalination process in production of proglutin Download PDFInfo
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- CN111057732B CN111057732B CN201911383093.XA CN201911383093A CN111057732B CN 111057732 B CN111057732 B CN 111057732B CN 201911383093 A CN201911383093 A CN 201911383093A CN 111057732 B CN111057732 B CN 111057732B
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- 238000010612 desalination reaction Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims abstract description 60
- 229960003767 alanine Drugs 0.000 claims abstract description 60
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 39
- 108010016626 Dipeptides Proteins 0.000 claims abstract description 29
- 229930182816 L-glutamine Natural products 0.000 claims abstract description 29
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- -1 L-alanine ester Chemical class 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 102000057234 Acyl transferases Human genes 0.000 claims abstract description 10
- 108700016155 Acyl transferases Proteins 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 238000002360 preparation method Methods 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011033 desalting Methods 0.000 description 12
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960003857 proglumide Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/02—Preparation of peptides or proteins having a known sequence of two or more amino acids, e.g. glutathione
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
- C07K5/06—Dipeptides
- C07K5/06008—Dipeptides with the first amino acid being neutral
- C07K5/06017—Dipeptides with the first amino acid being neutral and aliphatic
- C07K5/06026—Dipeptides with the first amino acid being neutral and aliphatic the side chain containing 0 or 1 carbon atom, i.e. Gly or Ala
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Zoology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
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Abstract
The invention relates to a desalination process in the production of a glutamine dipeptide, which comprises the following steps: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium alkali to adjust the pH value of the solution, and then carrying out solid-liquid separation to obtain solid salt and filtrate; wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into the mixed solution of L-glutamine and acyltransferase for reaction to obtain the proglutide. Through reasonable configuration of raw materials and technological parameters for preparing the glutamine dipeptide, efficient recovery of salt in the preparation process of the glutamine dipeptide is realized, so that the treatment pressure of subsequent wastewater is reduced, and meanwhile, alcohol used in the process is recycled, so that efficient and green preparation of the glutamine dipeptide is realized.
Description
Technical Field
The invention relates to the field of glutamine dipeptide, in particular to a desalination process in the production of the glutamine dipeptide.
Background
At present, the preparation method of the proglumide mainly comprises a chemical synthesis method and a biological enzyme catalysis method, but the chemical synthesis method has the problems of more reaction steps, expensive reagents, complex production process, difficult product separation, great harm to human bodies in the synthesis process, serious influence of great three wastes on the environment and the like in the preparation process, and further, the chemical synthesis method has the defects of long synthesis route, long production period, great environmental pollution, strict process conditions and high cost. The problem can be avoided by utilizing an enzyme catalysis technology, and the high-quality glutamine dipeptide can be simply obtained, and the enzyme method technology generally adopts hydrochloride of L-alanine ester and L-glutamine to be converted into the glutamine dipeptide in one step through acylase in water solution under a certain pH value, but a large amount of high-salt wastewater is easy to generate in the preparation process, the environment is influenced, and meanwhile, the factory is also burdened.
CN105274174a discloses a method for preparing the proglutide by biological enzyme conversion, which has the advantages of short production time, simple process control, high material reaction rate and low cost. CN106834394a discloses a preparation method of the glutamine dipeptide, and the preparation method of the glutamine dipeptide has the advantages of low raw material price, short enzyme conversion time, simple operation, low production cost and the like, and has good industrial application value. However, a large amount of chloride salt is generated in the process and enters the wastewater system, so that the wastewater treatment is burdened. On the other hand, because of the industrialized production of the glutamine dipeptide, the pressure for producing high-salt wastewater is high, the environmental-friendly treatment cost is high, and no matched environmental-friendly treatment facility is provided, or the environmental-friendly treatment capacity is not matched with the produced wastewater, so that the industrialized mass production of the glutamine dipeptide is restricted.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a desalination process in the production of the glutamine dipeptide, by the process provided by the invention, salt in a system can be removed in the form of solid sulfate in the preparation process of the glutamine dipeptide, and meanwhile, alcohol used in the process is recycled, so that the efficient green preparation of the glutamine dipeptide is realized.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a desalination process in the production of a glutamine dipeptide, which comprises the following steps: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium alkali to adjust the pH value of the solution, and then carrying out solid-liquid separation to obtain solid salt and filtrate;
wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into the mixed solution of L-glutamine and acyltransferase for reaction to obtain the proglutide.
According to the invention, through reasonable configuration of raw materials and technological parameters for preparing the glutamine dipeptide, efficient recovery of salt in the process of preparing the glutamine dipeptide is realized, so that the treatment pressure of subsequent wastewater is reduced, and meanwhile, alcohol used in the process is recycled, so that efficient and green preparation of the glutamine dipeptide is realized.
As a preferable technical scheme of the invention, the mixing ratio g/mL of the L-alanine and the alcohol is 1 (2-10), for example, the L-alanine and the alcohol can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5 or 1:10, and the like, but the L-alanine and the alcohol are not limited to the listed values, and other non-listed values in the range are applicable.
As a preferable embodiment of the present invention, the sulfuric acid may have a mass concentration of 70wt% or more, for example, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt% or 100wt%, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable; fuming sulfuric acid is used when the mass concentration of sulfuric acid exceeds 100%.
The sulfuric acid is preferably added in an amount of 0.1 to 1 times the molar amount of L-alanine, and may be, for example, 0.1 times, 0.2 times, 0.3 times, 0.4 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times, or 1 times, but is not limited to the recited values, and other values not recited in the range are equally applicable.
As a preferred embodiment of the present invention, the alcohol includes 1 or at least 2 of methanol, ethanol, propanol or isopropanol, and may be, for example, a combination of methanol and ethanol, a combination of ethanol and propanol, a combination of propanol and isopropanol or a combination of isopropanol and methanol, etc., but is not limited to the recited combinations, and other non-recited combinations are equally applicable within the scope.
As a preferred embodiment of the present invention, the calcium salt comprises calcium carbonate and/or calcium bicarbonate.
Preferably, the calcium base comprises calcium hydroxide.
In a preferred embodiment of the present invention, the temperature of the catalytic reaction is 55 to 90℃and may be 55℃57℃60℃62℃65℃68℃70℃73℃75℃78℃80℃83℃85℃88℃90℃or the like, but the present invention is not limited to the values recited and other values not recited in the above range are equally applicable.
Preferably, the time of the catalytic reaction is 20-120min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min or 120min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the end point of the pH adjustment of the solution is to neutral.
In a preferred embodiment of the present invention, the temperature of the mixed solution is 5 to 15 ℃, for example, 5 ℃, 5.5 ℃, 6 ℃, 6.5 ℃, 7 ℃, 7.5 ℃, 8 ℃, 8.5 ℃, 9 ℃, 9.5 ℃, 10 ℃, 10.5 ℃, 11 ℃, 11.5 ℃, 12 ℃, 12.5 ℃, 13 ℃, 13.5 ℃, 14, 14.5 ℃, 15 ℃, etc., but the mixed solution is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the molar ratio of L-glutamine to L-alanine is 1 (1-2), and may be, for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the mass of water in the mixed solution is 10 to 20 times the mass of L-glutamine, and may be, for example, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, or 20 times, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferred embodiment of the present invention, the pH of the reaction may be 7 to 10, for example, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9 or 10, etc., but not limited to the values recited, and other values not recited in the range are equally applicable.
In a preferred embodiment of the present invention, the reaction time is 15-150min, for example, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min, 120min, 125min, 130min, 135min, 140min, 145min or 150min, etc., but the present invention is not limited to the above values, and other values not listed in the above range are equally applicable.
As a preferred technical solution of the present invention, the desalination process includes: mixing L-alanine with alcohol, adding sulfuric acid, performing catalytic reaction at 55-90 ℃ for 20-120min, adding calcium salt and/or calcium alkali to adjust the solution to be neutral, and performing solid-liquid separation to obtain solid salt and filtrate;
wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 5-15 ℃ and keeping the solution temperature unchanged for reaction for 15-150min at the pH value of 7-10 to obtain the proglutide; the mixing ratio g/mL of the L-alanine and the alcohol is 1 (2-10); the mass concentration of the sulfuric acid is more than or equal to 70wt%; the addition mass of the sulfuric acid is 0.1-1 times of the molar quantity of the L-alanine; the alcohol comprises 1 or a combination of at least 2 of methanol, ethanol, propanol, or isopropanol; the calcium salt comprises calcium carbonate and/or calcium bicarbonate; the calcium base comprises calcium hydroxide; the mol ratio of the L-glutamine to the L-alanine is 1 (1-2); the mass of water in the mixed solution is 10-20 times of that of the L-glutamine.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The desalting process provided by the invention can separate the salt generated in the preparation process of the glutamine dipeptide from a reaction system in a solid form, and recover and recycle the salt in a byproduct form, thereby reducing the cost of wastewater treatment and ensuring that the salt removal rate is up to 97.4%.
(2) Through the desalting process provided by the invention, the alcohol in the preparation process can be recovered, so that the recovery and utilization of the alcohol are realized, and the efficient green preparation of the glutamine dipeptide is further realized.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The present embodiment provides a desalting process in production of a glutamine dipeptide, the desalting process comprising: mixing L-alanine and methanol, adding 70% concentrated sulfuric acid, performing catalytic reaction at 65 ℃ for 60min, adding calcium carbonate to regulate the solution to be neutral, and performing solid-liquid separation to obtain calcium salt and filtrate;
wherein, the filtrate is concentrated to obtain methanol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 13 ℃ and keeping the solution temperature unchanged for reaction for 30min at the pH value of 9 to obtain the proglutide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1:4; the addition mass of the sulfuric acid is 0.1 time of the molar quantity of the L-alanine; the molar ratio of the L-glutamine to the L-alanine is 1:2; the mass of water in the mixed solution is 10 times of that of the L-glutamine.
The salt removal rate in this example was 96.8%, and the methanol recovery rate was 94.9%.
Example 2
The present embodiment provides a desalting process in production of a glutamine dipeptide, the desalting process comprising: mixing L-alanine and propanol, adding fuming sulfuric acid to perform catalytic reaction at 90 ℃ for 105min, adding calcium bicarbonate to adjust the solution to be neutral, and performing solid-liquid separation to obtain calcium salt and filtrate;
wherein, the filtrate is concentrated to obtain propanol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 15 ℃ to react for 60 minutes at the pH value of 9.5 while maintaining the solution temperature unchanged, so as to obtain the proglutide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1:10; the addition mass of the sulfuric acid is 1 time of the molar quantity of the L-alanine; the molar ratio of the L-glutamine to the L-alanine is 1:1; the mass of water in the mixed solution is 13 times of that of the L-glutamine.
The salt removal rate in this example was 96.6% and the propanol recovery rate was 91.3%.
Example 3
The present embodiment provides a desalting process in production of a glutamine dipeptide, the desalting process comprising: mixing L-alanine and ethanol, adding 90% concentrated sulfuric acid, performing catalytic reaction at 55deg.C for 120min, adding calcium hydroxide to adjust the solution to neutrality, and performing solid-liquid separation to obtain calcium salt and filtrate;
wherein, the filtrate is concentrated to obtain ethanol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 5 ℃ to react for 15min at the pH of 8 while maintaining the solution temperature unchanged, so as to obtain the proglutide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1:2; the addition mass of the sulfuric acid is 0.7 times of the molar quantity of the L-alanine; the molar ratio of the L-glutamine to the L-alanine is 1:1.7; the mass of water in the mixed solution is 20 times of that of the L-glutamine.
The salt removal rate in this example was 97.3%, and the ethanol recovery rate was 97.8%.
Example 4
The present embodiment provides a desalting process in production of a glutamine dipeptide, the desalting process comprising: mixing L-alanine and isopropanol, adding 80% concentrated sulfuric acid, performing catalytic reaction at 80 ℃ for 20min, adding calcium carbonate to regulate the solution to be neutral, and performing solid-liquid separation to obtain calcium salt and filtrate;
wherein, the filtrate is concentrated to obtain isopropanol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 7.5 ℃ to react for 150 minutes at the pH of 7.5 while maintaining the solution temperature unchanged, so as to obtain the proglutide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1:7.5; the addition mass of the sulfuric acid is 0.5 time of the molar quantity of the L-alanine; the molar ratio of the L-glutamine to the L-alanine is 1:1.5; the mass of water in the mixed solution is 15 times of that of the L-glutamine.
The salt removal rate in this example was 96.5%, and the recovery rate of isopropyl alcohol was 96.6%.
Example 5
The present embodiment provides a desalting process in production of a glutamine dipeptide, the desalting process comprising: mixing L-alanine and ethanol, adding fuming sulfuric acid, performing catalytic reaction at 73 ℃ for 80min, adding calcium hydroxide to adjust the solution to be neutral, and performing solid-liquid separation to obtain solid salt and filtrate;
wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 10 ℃ to react for 40min at the pH of 8.5 while maintaining the solution temperature unchanged, so as to obtain the proglutide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1:6; the addition mass of the sulfuric acid is 0.3 times of the molar quantity of the L-alanine; the molar ratio of the L-glutamine to the L-alanine is 1:1.2; the mass of water in the mixed solution is 18 times of that of L-glutamine.
The salt removal rate in this example was 97.4%, and the ethanol recovery rate was 97.8%.
As can be seen from the results of the examples, the process provided by the invention can realize efficient recovery and utilization of salt and alcohol in the preparation process of the glutamine dipeptide. Further, the treatment pressure of the subsequent wastewater is reduced, and the efficient green preparation of the proglutadin is realized.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A desalination process in the production of a glutamine dipeptide, the desalination process comprising: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium alkali to adjust the pH value of the solution, and then carrying out solid-liquid separation to obtain solid salt and filtrate; the mass concentration of the sulfuric acid is more than or equal to 70wt%; the calcium salt comprises calcium carbonate and/or calcium bicarbonate; the calcium base comprises calcium hydroxide; the end point of the pH value of the regulating solution is that the solution is neutral;
wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase for a reaction process to obtain a glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1 (2-10);
the alcohol is 1 or a combination of at least 2 of methanol, ethanol, propanol or isopropanol.
2. The desalination process as defined in claim 1, wherein the sulfuric acid is added in an amount of 0.1 to 1 times the molar amount of L-alanine.
3. The desalination process of claim 1, wherein the catalytic reaction temperature is 55-90 ℃.
4. The desalination process of claim 1, wherein the catalytic reaction time is 20-120min.
5. The desalination process of claim 1, wherein the temperature of the mixed solution is 5-15 ℃.
6. The desalination process of claim 1, wherein the molar ratio of L-glutamine to L-alanine is 1 (1-2).
7. The desalination process of claim 1, wherein the mass of water in the mixed solution is 10-20 times the mass of L-glutamine.
8. The desalination process of claim 1, wherein the reaction process has a pH of 7-10.
9. The desalination process of claim 1, wherein the reaction process is for a period of 15-150 minutes.
10. The desalination process of any one of claims 1-9, wherein the desalination process comprises: mixing L-alanine with alcohol, adding sulfuric acid, performing catalytic reaction at 55-90 ℃ for 20-120min, adding calcium salt and/or calcium alkali to adjust the solution to be neutral, and performing solid-liquid separation to obtain solid salt and filtrate;
wherein, the filtrate is concentrated to obtain alcohol and free L-alanine ester; adding the free L-alanine ester into a mixed solution of L-glutamine and acyltransferase at 5-15 ℃ and keeping the solution temperature unchanged for reaction for 15-150min at the pH value of 7-10 to obtain the proglutide; the mixing ratio g/mL of the L-alanine and the alcohol is 1 (2-10); the mass concentration of the sulfuric acid is more than or equal to 70wt%; the addition mass of the sulfuric acid is 0.1-1 times of the molar quantity of the L-alanine; the alcohol is 1 or a combination of at least 2 of methanol, ethanol, propanol or isopropanol; the calcium salt comprises calcium carbonate and/or calcium bicarbonate; the calcium base comprises calcium hydroxide; the mol ratio of the L-glutamine to the L-alanine is 1 (1-2); the mass of water in the mixed solution is 10-20 times of that of the L-glutamine.
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| CN201911383093.XA CN111057732B (en) | 2019-12-27 | 2019-12-27 | Desalination process in production of proglutin |
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| CN101560190A (en) * | 2009-06-01 | 2009-10-21 | 北京赛科药业有限责任公司 | Method for researching and controlling impurity E in valsartan |
| CN105274174A (en) * | 2015-11-30 | 2016-01-27 | 精晶药业股份有限公司 | Method for preparing alanyl-glutamine dipeptide through biological enzyme conversion |
| CN106316869A (en) * | 2016-08-18 | 2017-01-11 | 精晶药业股份有限公司 | Synthesis method of beta-alanine methyl ester salt product |
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| CN101560190A (en) * | 2009-06-01 | 2009-10-21 | 北京赛科药业有限责任公司 | Method for researching and controlling impurity E in valsartan |
| CN105274174A (en) * | 2015-11-30 | 2016-01-27 | 精晶药业股份有限公司 | Method for preparing alanyl-glutamine dipeptide through biological enzyme conversion |
| CN106316869A (en) * | 2016-08-18 | 2017-01-11 | 精晶药业股份有限公司 | Synthesis method of beta-alanine methyl ester salt product |
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