CN111187178B - Preparation method of glutamine crystals - Google Patents
Preparation method of glutamine crystals Download PDFInfo
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- CN111187178B CN111187178B CN202010031486.0A CN202010031486A CN111187178B CN 111187178 B CN111187178 B CN 111187178B CN 202010031486 A CN202010031486 A CN 202010031486A CN 111187178 B CN111187178 B CN 111187178B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- 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
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
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Abstract
The invention relates to the field of amino acid preparation, in particular to a preparation method of glutamine crystals. The invention obtains refined glutamine clear liquid through extraction treatment of glutamine fermentation liquor. The pH value of the refined clear liquid is regulated. Adding crystallization auxiliary into the refined solution, and starting evaporation concentration. After concentration, glutamine seeds were added. And continuing to evaporate and crystallize until a certain concentration is reached, and ending the evaporation. And cooling, pre-crystallizing, separating and drying the concentrated solution obtained by evaporation and crystallization to obtain a finished glutamine product and refined mother solution. The crystallization method can improve the crystallization effect of the L-glutamine, and is beneficial to improving the bulk density of the glutamine finished product, thereby improving the refining yield and the product quality.
Description
Technical Field
The invention relates to the field of amino acid preparation, in particular to a preparation method of glutamine crystals.
Background
L-glutamine, the name 2-amino-5-carboxyvaleramide. Glutamine is one of basic amino acids of synthetic proteins, is about more than half of free amino acids of human bodies, is the most abundant amino acid in the body, and is one of the most important amino acids known at present. Glutamine can be used as an effective medicament for treating gastric ulcer, chronic gastritis, neurasthenia, memory disorder left after cerebral hemorrhage, mental development of children with mental deficiency, epileptic seizure, etc.; can also be used as the precursor of other synthetic drugs; and has great relieving effects on motion syndrome and fatigue recovery after high intensity labor or exercise, immune system reconstruction, side effects of chemotherapy and radiotherapy reduction, brain function maintenance and the like.
The current production methods of glutamine mainly comprise chemical synthesis methods, enzyme methods and fermentation methods. The existing chemical synthesis methods all adopt concentrated sulfuric acid as a necessary catalyst, and have the advantages of harsh reaction conditions, more reaction steps and low yield. The chemical reagents used in the chemical synthesis method have residues with different degrees in the product, and glutamine is often used as a medicine or functional food, so that the chemical reagents have high requirements on purity, and the use of a large amount of chemical reagents can cause environmental pollution, so that the quality and the application range of the product are limited. The enzymatic synthesis of glutamine is mainly carried out by NH 3 Adenosine Triphosphate (ATP) and glutamic acid are used as raw materials to produce glutamine by the catalysis of synthase. Compared with chemical synthesis, the enzymatic synthesis reaction steps are relatively simple. However, ATP is necessary, and ATP is expensive, which makes industrial use difficult. Meanwhile, the enzyme reaction substrate NH4+ and the byproduct Adenosine Diphosphate (ADP) obviously inhibit the generation of glutamine, and the reaction yield is low. Therefore, the enzymatic synthesis of glutamine cannot meet the requirement of large-scale industrial production.
The fermentation method is the most commonly used glutamine production method at present, has the advantages of wide raw material sources, low production cost, controllable product quality, single product and the like, and is suitable for large-scale industrial production. Wherein, the separation and extraction of glutamine from fermentation broth is an important step in the production of glutamine by fermentation method, which directly affects the production efficiency of glutamine products.
The quality problems of the L-glutamine products in production, such as small grain size, uneven grain size distribution and small density of the crystallized products, are caused by the fact that the crystal liquid of the L-glutamine is not easy to separate, the storage occupied area is large, and the granulation and the constant volume encapsulation are difficult. Has great influence on the selling price of the product. The crystallization process in the production process is a key step for limiting the quality of the product.
In the current industrial production, no effective improvement means is provided for the concentration and crystallization process of glutamine, so that the finished glutamine product has poor crystal habit, low bulk density and poor product quality. Therefore, it is of great practical importance to provide a process for crystallization of glutamine.
Disclosure of Invention
In view of this, the present invention provides a process for producing glutamine crystals. The glutamine obtained by the method has large and uniform crystal form, the bulk density is not less than 0.65g/ml, the refining yield is not less than 85%, and the product purity can reach 99.5%.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of glutamine crystals, which comprises the following steps:
step 1: pretreating glutamine fermentation liquor to obtain glutamine refined liquor;
step 2: regulating the pH value of the glutamine refined solution, and obtaining an evaporation solution after first evaporation in the presence of a crystallization auxiliary agent;
step 3: mixing the evaporation liquid with glutamine seed crystal, and performing second evaporation to obtain concentrated solution;
step 4: cooling the concentrated solution for pre-crystallization, centrifuging, collecting crystals and drying;
the pH value is 5.5-8.5;
the temperature of the first evaporation and the second evaporation is 35-50 ℃, and the vacuum degree is minus 0.090 to minus 0.099Mpa.
In some embodiments of the invention, the concentration of glutamine in the evaporation liquid in step 2 is 55 to 90g/L.
In some embodiments of the invention, the mass to volume ratio of the glutamine seed crystal to the evaporation liquid in step 3 is (0.8 to 2.0) in g/L: (1.0-2.0).
In some embodiments of the invention, the glutamine fermentation broth described in step 1 has a glutamine concentration of 85 to 110g/L.
In some specific embodiments of the present invention, the concentration of glutamine in the glutamine refining liquid in step 1 is 30-50 g/L, and the light transmittance is not less than 95%.
In some embodiments of the invention, the concentration of glutamine in the concentrate in step 3 is 350 to 500g/L.
In some embodiments of the present invention, the concentration of the crystallization aid in step 2 is +.2 g/L, and the crystallization aid comprises one or more of a fatty acid glyceride, a sucrose ester, a fatty acid sorbitan, a polysorbate, an alkyl glucoside, and a fatty alcohol ester.
In some embodiments of the present invention, the cooling pre-crystallization in step 4 is gradient cooling, the cooling speed is 5-10 ℃/h, and the cut-off temperature of the cooling pre-crystallization is 5-15 ℃.
In some embodiments of the invention, the centrifugation in step 4 is performed at a speed of 1000 to 3000rpm and the centrifugation is performed for a period of 20 to 60 minutes.
In some embodiments of the invention, the temperature of the drying in step 4 is 40 to 60 ℃ and the drying time is 360 to 600 minutes.
In some embodiments of the present invention, water is added to decrystallize the seed crystals in step 3 during the second evaporation process if self-seeding occurs, such that the final concentration is 350 to 500g/L glutamine.
In some embodiments of the invention, the pretreatment method of the glutamine fermentation broth in step 1 comprises: membrane separation, crude product concentration, ion exchange, decolorization and other common extraction methods.
In some embodiments of the present invention, the agent for adjusting pH in step 2 may be one or more of ammonia, sodium hydroxide, potassium hydroxide, and sodium carbonate.
In some embodiments of the present invention, the supernatant obtained after centrifugation in step 4 is also a mother liquor, which may be used as a glutamic acid fermentation broth in the subsequent process of step 1.
In the secondary nucleation process of glutamine, a solution added with a trace crystallization auxiliary agent forms a large amount of secondary nucleation at first, however, the secondary nucleation fine particles are immediately adsorbed on the surface of a seed crystal or are quickly agglomerated to form a macroporous polymer, so that the number of the secondary nucleation fine particles is reduced, the growth of crystals is promoted, and the concentration is stabilized in a metastable zone by adjusting the pH of the feed liquid, so that the occurrence of powder from the crystals can be further reduced, and the bulk density of glutamine is improved.
The invention utilizes the following steps: 1. the glutamine fermentation liquor is extracted to obtain refined glutamine clear liquid. 2. The pH value of the refined clear liquid is regulated. 3. The refined liquid is led into a crystallization evaporator, and crystallization auxiliary agent with a certain concentration is added, and evaporation concentration is started. 4. And (3) adding glutamine seed crystals when concentrating to a certain concentration. 5. And continuing to evaporate and crystallize until a certain concentration is reached, and ending the evaporation. 6. And cooling, pre-crystallizing, separating and drying the concentrated solution obtained by evaporation and crystallization to obtain a finished glutamine product and refined mother solution. The crystallization method can improve the crystallization effect of the L-glutamine, and is beneficial to improving the bulk density of the glutamine finished product, thereby improving the refining yield and the product quality.
The invention discloses a method for improving the crystallization effect of glutamine, the glutamine obtained by the method has large and uniform crystal form, the bulk density is not less than 0.65g/ml, the refining yield is not less than 85%, and the product purity can reach 99.5%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows crystals prepared in comparative examples;
FIG. 2 shows the crystals produced in example 1;
fig. 3 shows a process for preparing the crystals of the present invention.
Detailed Description
The invention discloses a preparation method of glutamine crystals, and a person skilled in the art can properly improve the technological parameters by referring to the content of the description. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
The invention aims to provide a method for improving the crystallization effect of glutamine, which aims to improve the refining yield of glutamine and the bulk density and the product quality of a finished glutamine product.
In order to achieve the above object, the present invention provides the following technical solutions:
a process for improving the crystallizing effect of glutamine includes such steps as extracting the fermented glutamine liquid to obtain refined glutamine liquid, regulating pH value, adding crystallizing assistant, evaporating to a certain concentration, and adding crystal seeds. And continuing to evaporate and crystallize until the final concentration is reached, ending the evaporation, and cooling, pre-crystallizing, separating and drying the concentrated solution obtained by the evaporation and crystallization to obtain a glutamyl finished product and a refined mother solution.
The L-glutamine refined clear liquid is obtained by extracting glutamine fermentation liquor, and the extraction method mainly comprises extraction procedures such as ceramic membrane, ion exchange, concentration crystallization, decolorization, nanofiltration and the like, and mainly aims to remove impurities such as residual sugar, protein, thalli, pigment, inorganic salt and the like in the fermentation liquor, wherein the content of the glutamine in the obtained refined clear liquid is 30-50 g/L, the light transmittance is not less than 95%, and the residual sugar is not more than 1g/L. The refined clear liquid of the glutamine is regulated to pH5.0-8.5 by ammonia water or sodium hydroxide, and crystallization auxiliary agent within 2.0g/L is added into the evaporator bottom material. And (3) starting heating to concentrate and crystallize until the concentration of the glutamyl reaches 55-90g/L, adding seed crystals, wherein the number of the seed crystals is 0.4-1.2% of the volume of the base material, continuously evaporating and concentrating, and if the phenomenon of self-nucleation occurs in the process, adding water to eliminate, concentrating to 300-500g/L, and ending the concentration and crystallization. The concentrated solution is subjected to gradient cooling, the cooling speed is 5-10 ℃/h, the cut-off temperature is 5-15 ℃, the cooled concentrated solution is separated, dried and crushed to obtain a glutamine finished product and refined mother solution, and the refined mother solution can be used in an extraction procedure.
In the steps, the main purpose of regulating the pH of the refined clear liquid is to change the width of an intermediate stable region in the process of glutamine crystallization, reduce the phenomenon of spontaneous nucleation in the process of crystallization, improve the uniformity of crystals and achieve the effect of improving glutamine crystallization; the crystallization auxiliary agent is added into the bottom material in the crystallization process, so that the surface tension of the material is reduced, crystals are easier to grow, the granularity of the crystals is increased, and finally the purpose of improving the crystallization effect is achieved; the crystal seeds are added in the crystallization process, water is added in the concentration crystallization process to eliminate crystals, and the main purposes are to avoid spontaneous nucleation, eliminate spontaneous nucleation, improve the granularity and uniformity of crystals and achieve the purpose of improving the crystallization effect of glutamyl.
The invention has the following advantages:
the glutamyl crystal obtained by the invention has large granularity and good uniformity, as shown in the figure, the original process crystal is tiny, the majority is about 1 mu m, and the density is 0.55-0.60 g/mL. The crystal of the invention is thick and strong, most of the crystals are about 5 mu m, and the bulk density of the finished glutamine products can reach more than 0.65 g/mL.
The raw materials and reagents used in the preparation method of the glutamine crystals provided by the invention can be purchased from the market.
The invention is further illustrated by the following examples:
example 1: the method for improving the crystallization effect of the glutamine
And (3) preprocessing the glutamine workshop fermentation liquor (the concentration of glutamine in the glutamine fermentation liquor is 85 g/L) to obtain refined clear liquid 10L, wherein the content of glutamine is 40g/L.5L was used for the experimental group and 5L was used for the control group.
Experiment
Taking 5L of refined clear liquid, regulating the pH value of the refined clear liquid to 5.5 by using sodium hydroxide, diluting to the content of 30g/L, taking 1L of clear liquid, adding 1g of sucrose ester into the clear liquid while evaporating (the temperature is 50 ℃, the vacuum degree is minus 0.090 Mpa), adding 29g of seed crystal (the mass volume ratio of the glutamine seed crystal to the evaporated concentrated solution is 0.8:1.0) when concentrating to 55g/L, continuing evaporating (the temperature is 50 ℃, the vacuum degree is minus 0.090 Mpa) for crystallization, adding 200ml of water for decrystallization (the final concentration is 350 g/L) when spontaneous nucleation occurs, and concentrating to 10 times and placing into a tank. Cooling the crystallization liquid in gradient, cooling to 5 ℃ per hour, centrifuging by using a bag type centrifuge (the rotating speed is 1000-rpm, the time is 20 min), separating and drying (the temperature is 40 ℃ and the time is 360 min) to obtain 170g of dry finished product, and the primary yield is 85%.
Control
Taking 5L of refined clear liquid, taking 1L of clear liquid as a bottom material, adding 29g of seed crystal while evaporating, continuously evaporating and crystallizing when concentrating 2 times, adding 200ml of water when spontaneous nucleation occurs, crystallizing, controlling the process to be the same as the control group and the experimental group, concentrating 7 times and placing in a tank. The crystallization liquid is cooled down to 10 ℃ rapidly and separated by a bag type centrifuge, 162g of dry finished product is obtained after separation and drying, and the primary yield is 81 percent
The detailed results are shown in Table 1.
Example 2: the method for improving the crystallization effect of the glutamine
And (3) preprocessing the glutamine workshop fermentation liquor (the concentration of glutamine in the glutamine fermentation liquor is 100 g/L) to obtain 300L refined clear liquid, wherein the content of glutamine is 45g/L.150L for the experimental group and 150L for the control group.
Experiment
Taking 150L of refined clear liquid, regulating pH of nanofiltration solution to 8.0 by ammonia water, taking 20L of clear liquid, adding 20g of sucrose ester as a base material, evaporating (the temperature is 45 ℃, the vacuum degree is-0.092 Mpa) while feeding, adding 340g of seed crystal (the mass-volume ratio of the glutamine seed crystal to the evaporated concentrated solution is 0.8:2.0) when concentrating to 80g/L, continuing evaporating (the temperature is 45 ℃, the vacuum degree is-0.092 Mpa) for crystallization, adding water to eliminate crystals when spontaneous nucleation occurs (the final concentration is 450 g/L), and concentrating to 400 g/L. Cooling the crystallization liquid in a gradient way, cooling to 8 ℃ per hour, separating (the rotation speed is 2000rpm, the time is 40 min), separating and drying (the temperature is 50 ℃ and the time is 500 min), and obtaining 5.75kg of dry finished product, wherein the primary yield is 85.2%.
Control
Taking 150L of refined clear liquid, taking 20L of clear liquid as a bottom material, adding 340g of seed crystal while evaporating, continuously evaporating and crystallizing when 80g/L is concentrated, adding water to eliminate crystals when spontaneous nucleation occurs, controlling the process to be the same as that of an experimental group, concentrating to 400g/L, and placing in a tank. The crystallization liquid is quickly cooled to 8 ℃ for separation, and 5.58kg of dry finished product is obtained after separation and drying, and the primary yield is 82.6%.
The detailed results are shown in Table 1.
Example 3: the method for improving the crystallization effect of the glutamine
And (3) preprocessing the glutamine workshop fermentation liquor (the concentration of glutamine in the glutamine fermentation liquor is 115 g/L) to obtain refined clear liquor 260L, wherein the glutamine content is 30g/L.130L for the experimental group and 130L for the control group.
Experiment
Taking 130L of refined clear liquid, regulating pH7.5 of nanofiltration solution by ammonia water, taking 20L of clear liquid, adding 10g of sucrose ester as a base material, adding dropwise while evaporating (the temperature is 47 ℃ and the vacuum degree is-0.091 Mpa), adding 920g of seed crystal (the mass-volume ratio of the glutamine seed crystal to the evaporated concentrated solution is 2.0:1.0) when concentrating to 85g/L, continuing evaporating (the temperature is 47 ℃ and the vacuum degree is-0.091 Mpa) for crystallization, adding water to eliminate crystals when spontaneous nucleation occurs (the final concentration is 470g/L of glutamine), and concentrating to 450g/L and placing in a tank. Cooling the crystallization liquid in gradient, cooling to 5 ℃ per hour, separating (the rotation speed is 2500rpm, the time is 50 min), separating and drying (the temperature is 55 ℃ and the time is 400 min), and obtaining 3.48kg of dry finished product, wherein the primary yield is 87%.
Control
Taking 130L of refined clear liquid, adding 20L of clear liquid as a bottom material while evaporating, adding 920g of seed crystal when concentrating 85g/L, continuously evaporating and crystallizing, adding water when spontaneous nucleation occurs, removing crystals, controlling the process to be the same as that of the control group and the experimental group, concentrating to 450g/L, and placing in a tank. The crystallization liquid is quickly cooled to 5 ℃ for separation, and 3.2kg of dry finished product is obtained after separation and drying, and the primary yield is 80%.
The detailed results are shown in Table 1.
Example 4: the method for improving the crystallization effect of the glutamine
Pretreatment of a glutamine workshop fermentation broth (the concentration of glutamine in the glutamine fermentation broth is 110 g/L) to obtain refined clear liquid 100m 3 The glutamyl content is 50g/L.50m 3 For experimental group, 50m 3 For the control group.
Experiment
Taking 50m 3 Refining clear liquid, regulating pH of nanofiltration solution to 8.5 with ammonia water, and collecting 20m 3 Adding 20kg sucrose ester into the clear solution as base material, evaporating (temperature 35 deg.C, vacuum degree-0.099 Mpa) while feeding, concentrating to 90g/L110kg of seed crystal (the mass-volume ratio of the glutamine seed crystal to the evaporated concentrated solution is 2.0:2.0), continuing to evaporate (the temperature is 35 ℃ and the vacuum degree is-0.099 Mpa) for crystallization, adding water to eliminate crystals when spontaneous nucleation occurs (the final concentration is 500g/L of glutamine), and concentrating to 500g/L, and placing in a tank. Cooling the crystallization liquid in gradient, cooling to 15 ℃ per hour, separating (rotating speed is 3000rpm, time is 60 min), separating and drying (temperature is 60 ℃ and time is 600 min), and obtaining 2150kg of dry finished product with a primary yield of 86%.
Control
Taking 50m 3 Refining the clear solution with 20m 3 Adding 110kg seed crystal when concentrating 90g/L, evaporating and crystallizing, adding water and crystallizing when spontaneous nucleation occurs, controlling the process to be identical to that of the experimental group, concentrating to 500g/L, and placing in a tank. And (3) rapidly cooling the crystallization liquid to 15 ℃ for separation, and obtaining 2050kg of a dry finished product after separation and drying, wherein the primary yield is 82%.
The detailed results are shown in Table 1.
Effect example
Table 1 comparison of yield, product content, and Density of experimental and control groups
As shown in Table 1, the P values of the three indexes of content, yield and density are all less than 0.01, the experimental group and the control group have extremely remarkable differences, the P value of the purity index is more than 0.01 and less than 0.05, and the experimental group and the control group have remarkable differences. The invention obtains unexpected remarkable effect by improving the quality of crystallization, and remarkably improves the quality, density, yield and purity of the finished product.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A process for producing a glutamine crystals, comprising the steps of:
step 1: pretreating glutamine fermentation liquor to obtain glutamine refined liquor;
step 2: regulating the pH value of the glutamine refined solution, and obtaining an evaporation solution after first evaporation in the presence of a crystallization auxiliary agent; the crystallization aid is one or more than two of fatty acid glyceride, sucrose ester, fatty acid sorbitan, polysorbate, alkyl glucoside and fatty alcohol ester;
step 3: mixing the evaporation liquid with glutamine seed crystal, and performing second evaporation to obtain concentrated solution;
step 4: cooling the concentrated solution for pre-crystallization, centrifuging, collecting crystals and drying;
the pH value is 5.5-8.5, and the reagent for regulating the pH value is one or more of ammonia water, sodium hydroxide, potassium hydroxide and sodium carbonate;
the temperature of the first evaporation and the second evaporation is 35-50 ℃, and the vacuum degree is-0.090 to-0.099 Mpa.
2. The method according to claim 1, wherein the concentration of glutamine in the evaporation liquid in the step 2 is 55 to 90g/L.
3. The method according to claim 1 or 2, wherein the mass-to-volume ratio of the glutamine seed crystal to the evaporation liquid in step 3 is (0.8 to 2.0) in g/L: (1.0-2.0).
4. The method according to claim 1 or 2, wherein the concentration of glutamine in the glutamine fermentation broth in step 1 is 85 to 110g/L.
5. The preparation method according to claim 1 or 2, wherein the concentration of glutamine in the glutamine refining liquid in step 1 is 30-50 g/L, and the light transmittance is not less than 95%.
6. The method according to claim 1 or 2, wherein the concentration of glutamine in the concentrated solution in step 3 is 350 to 500g/L.
7. The process according to claim 1 or 2, wherein the concentration of the crystallization aid in step 2 is +.2 g/L.
8. The preparation method according to claim 1 or 2, wherein in the step 4, the cooling pre-crystallization is gradient cooling, the cooling speed is 5-10 ℃/h, and the cut-off temperature of the cooling pre-crystallization is 5-15 ℃.
9. The method according to claim 1 or 2, wherein the rotational speed of the centrifugation in step 4 is 1000 to 3000rpm, and the centrifugation time is 20 to 60 minutes.
10. The method according to claim 1 or 2, wherein the drying temperature in step 4 is 40 to 60 ℃, and the drying time is 360 to 600 minutes.
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