CN111057732A - Desalination process in glutamine dipeptide production - Google Patents
Desalination process in glutamine dipeptide production Download PDFInfo
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- CN111057732A CN111057732A CN201911383093.XA CN201911383093A CN111057732A CN 111057732 A CN111057732 A CN 111057732A CN 201911383093 A CN201911383093 A CN 201911383093A CN 111057732 A CN111057732 A CN 111057732A
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- 108010016626 Dipeptides Proteins 0.000 title claims abstract description 43
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 17
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims abstract description 71
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims abstract description 58
- 229960003767 alanine Drugs 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 38
- 229930182816 L-glutamine Natural products 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- -1 L-alanine ester Chemical class 0.000 claims abstract description 20
- 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
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 13
- 102000057234 Acyl transferases Human genes 0.000 claims abstract description 11
- 108700016155 Acyl transferases Proteins 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011033 desalting Methods 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-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- 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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- Proteomics, Peptides & Aminoacids (AREA)
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Abstract
The invention relates to a desalination process in the production of glutamine dipeptide, which comprises the following steps: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium base 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 a mixed solution of L-glutamine and acyltransferase to react to obtain the glutamine dipeptide. Through reasonable configuration of raw materials and process parameters for preparing the glutamine dipeptide, the salt is efficiently recovered in the preparation process of the glutamine dipeptide, so that the treatment pressure of subsequent wastewater is reduced, and simultaneously, the alcohol used in the process is recycled, so that the efficient 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 glutamine dipeptide.
Background
At present, the preparation method of glutamine dipeptide is mainly 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, great influence of three wastes on the environment and the like in the preparation process, and further has the defects of long synthesis route, long production period, great environmental pollution, strict process conditions and high cost. The enzyme catalysis technology can avoid the problems and obtain high-quality glutamine dipeptide simply and conveniently, the enzyme method technology generally adopts L-alanine ester hydrochloride and L-glutamine which are converted into the glutamine dipeptide in one step by acyltransferase in aqueous solution under a certain pH value, but a large amount of high-salt waste water is easily generated in the preparation process, which affects the environment and causes burden to factories.
CN105274174A discloses a method for preparing glutamine dipeptide 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 glutamine dipeptide, and the provided production method of glutamine dipeptide has the advantages of low raw material price, short enzyme conversion time, simple and convenient operation, low production cost and the like, and has better industrial application value. But in the process, a large amount of chloride is generated and enters a wastewater system, and the burden is brought to the wastewater treatment. On the other hand, due to the industrialized production of glutamine dipeptide, the pressure of high-salt wastewater is high, the environmental-friendly treatment cost is high, 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 production of glutamine dipeptide is restricted.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a desalting process in the production of glutamine dipeptide, which can remove salt in a system in the preparation process of glutamine dipeptide in the form of solid sulfate and simultaneously recycle alcohol used in the process, thereby realizing efficient green preparation of glutamine dipeptide.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a desalination process in the production of glutamine dipeptide, which comprises the following steps: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium base 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 a mixed solution of L-glutamine and acyltransferase to react to obtain the glutamine dipeptide.
According to the invention, through reasonable configuration of raw materials and process parameters for preparing the glutamine dipeptide, the salt in the preparation process of the glutamine dipeptide is efficiently recovered, so that the treatment pressure of subsequent wastewater is reduced, and simultaneously, the alcohol used in the process is recycled, so that the efficient green preparation of the glutamine dipeptide is realized.
In a preferred embodiment of the present invention, the mixing ratio g/mL of L-alanine to alcohol is 1 (2-10), and examples thereof include 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 and 1:10, but are not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the sulfuric acid has a mass concentration of 70 wt% or more, for example, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 100 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable; when the mass concentration of the sulfuric acid exceeds 100%, the sulfuric acid is fuming sulfuric acid.
The amount of the sulfuric acid added is preferably 0.1 to 1 time the molar amount of L-alanine, and may be, for example, 0.1 time, 0.2 time, 0.3 time, 0.4 time, 0.5 time, 0.6 time, 0.7 time, 0.8 time, 0.9 time or 1 time, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the alcohol includes 1 or at least 2 of methanol, ethanol, propanol or isopropanol, and examples thereof include a combination of methanol and ethanol, a combination of ethanol and propanol, a combination of propanol and isopropanol, and a combination of isopropanol and methanol, but are not limited to the above-mentioned combinations, and other combinations not listed in this range are also applicable.
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, for example, 55 ℃, 57 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃, 85 ℃, 88 ℃ or 90 ℃ or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the catalytic reaction is 20 to 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 is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the end point of the pH of the conditioning solution is until the solution is neutral.
In a preferred embodiment of the present invention, the temperature of the mixed solution is 5 to 15 ℃, and may be, 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 ℃ or 15 ℃, but is not limited to the recited values, and other values not recited in the range are also 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, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the mass of water in the mixed solution is 10 to 20 times of the mass of L-glutamine, and for example, it may be 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, or 20 times, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, the reaction is carried out at a pH of 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, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the reaction time is 15 to 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, but is not limited to the listed values, and other values not listed in the range are also applicable.
As a preferred embodiment of the present invention, the desalination process comprises: mixing L-alanine and alcohol, adding sulfuric acid, performing catalytic reaction at 55-90 deg.C for 20-120min, adding calcium salt and/or calcium base to adjust solution to neutrality, 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 deg.C, maintaining the solution temperature at pH 7-10, and reacting for 15-150min to obtain glutamine dipeptide; the mixing proportion 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 70 wt%; the adding mass of the sulfuric acid is 0.1-1 time of the molar weight 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 L-glutamine.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the desalination process provided by the invention can separate salt generated in the preparation process of glutamine dipeptide from a reaction system in a solid form, and recycle the salt in a by-product form, so that the cost of wastewater treatment is reduced, and the salt removal rate is as high as 97.4%.
(2) By adopting the desalting process provided by the invention, the alcohol in the preparation process can be recovered, the recycling of the alcohol is realized, and the efficient and green preparation of the glutamine dipeptide is further realized.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a desalination process in the production of glutamine dipeptide, which comprises the following steps: mixing L-alanine and methanol, adding 70% concentrated sulfuric acid, performing catalytic reaction at 65 deg.C for 60min, adding calcium carbonate to adjust solution to neutrality, 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 at the pH value of 9 for reaction for 30min to obtain glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1: 4; the adding mass of the sulfuric acid is 0.1 time of the molar weight 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 L-glutamine.
In this example, the salt removal rate was 96.8%, and the methanol recovery rate was 94.9%.
Example 2
The embodiment provides a desalination process in the production of glutamine dipeptide, which comprises the following steps: mixing L-alanine and propanol, adding oleum at 90 deg.C for catalytic reaction for 105min, adding calcium bicarbonate to adjust solution to neutrality, 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 maintain the temperature of the solution unchanged at the pH of 9.5 for reaction for 60min to obtain glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1: 10; the adding mass of the sulfuric acid is 1 time of the molar weight 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 L-glutamine.
In this example, the salt removal rate was 96.6%, and the recovery rate of propanol was 91.3%.
Example 3
The present embodiment provides a desalination process in the production of glutamine dipeptide, comprising: mixing L-alanine and ethanol, adding 90% concentrated sulfuric acid, performing catalytic reaction at 55 deg.C for 120min, adding calcium hydroxide to adjust 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 maintain the temperature of the solution constant at pH 8 for reaction for 15min to obtain glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1: 2; the adding mass of the sulfuric acid is 0.7 time of the molar weight 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.
In this example, the salt removal rate was 97.3%, and the ethanol recovery rate was 97.8%.
Example 4
The present embodiment provides a desalination process in the production of glutamine dipeptide, comprising: mixing L-alanine and isopropanol, adding 80% concentrated sulfuric acid, performing catalytic reaction at 80 deg.C for 20min, adding calcium carbonate to adjust solution to neutrality, 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 maintain the temperature of the solution at pH 7.5 for reaction for 150min to obtain glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1: 7.5; the adding mass of the sulfuric acid is 0.5 time of the molar weight 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 L-glutamine.
In this example, the salt removal rate was 96.5%, and the recovery rate of isopropyl alcohol was 96.6%.
Example 5
The present embodiment provides a desalination process in the production of glutamine dipeptide, comprising: mixing L-alanine and ethanol, adding oleum at 73 deg.C for catalytic reaction for 80min, adding calcium hydroxide to adjust solution to neutrality, 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 maintain the temperature of the solution constant at the pH of 8.5 for 40min to obtain glutamine dipeptide;
the mixing ratio g/mL of the L-alanine and the alcohol is 1: 6; the adding mass of the sulfuric acid is 0.3 time of the molar weight 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.
In this example, the salt removal rate was 97.4%, and the ethanol recovery rate was 97.8%.
From the results of the above examples, it can be seen that the process provided by the present invention can achieve efficient recovery and utilization of salts and alcohols in the glutamine dipeptide production process. Further, the treatment pressure of subsequent wastewater is reduced, and the efficient green preparation of the glutamine dipeptide is realized.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A desalination process in the production of glutamine dipeptide, comprising: mixing L-alanine and alcohol, adding sulfuric acid for catalytic reaction, adding calcium salt and/or calcium base 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 a mixed solution of L-glutamine and acyltransferase to react to obtain the glutamine dipeptide.
2. The desalination process of claim 1, wherein the mixing ratio g/mL of L-alanine and alcohol is 1 (2-10).
3. The desalination process of claim 1 or 2, wherein the mass concentration of the sulfuric acid is at least 70 wt%;
preferably, the adding mass of the sulfuric acid is 0.1 to 1 time of the molar weight of the L-alanine.
4. The desalination process of any one of claims 1-3, wherein the alcohol comprises a combination of 1 or at least 2 of methanol, ethanol, propanol, or isopropanol.
5. The method of any one of claims 1 to 4, wherein the calcium salt comprises calcium carbonate and/or calcium bicarbonate;
preferably, the calcium base comprises calcium hydroxide.
6. The method of any one of claims 1 to 5, wherein the temperature of the catalytic reaction is 55 to 90 ℃;
preferably, the time of the catalytic reaction is 20-120 min;
preferably, the end point of the pH of the conditioning solution is until the solution is neutral.
7. The method of any one of claims 1 to 6, wherein the temperature of the mixed solution is 5 to 15 ℃;
preferably, the molar ratio of the L-glutamine to the L-alanine is 1 (1-2);
preferably, the mass of water in the mixed solution is 10-20 times of the mass of L-glutamine.
8. The method of any one of claims 1 to 7, wherein the reaction has a pH of from 7 to 10.
9. The process according to any one of claims 1 to 8, wherein the reaction time is from 15 to 150 min.
10. The method of any one of claims 1-9, wherein the desalination process comprises: mixing L-alanine and alcohol, adding sulfuric acid, performing catalytic reaction at 55-90 deg.C for 20-120min, adding calcium salt and/or calcium base to adjust solution to neutrality, 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 deg.C, maintaining the solution temperature at pH 7-10, and reacting for 15-150min to obtain glutamine dipeptide; the mixing proportion 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 70 wt%; the adding mass of the sulfuric acid is 0.1-1 time of the molar weight 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 L-glutamine.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 马养民等: "杂环氨基酸酯的合成与表征" * |
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