Trace additive based on L-valine fermentation waste liquid as well as preparation method and application of trace additive

Abstract

The invention relates to a trace additive based on L-valine fermentation waste liquid and a preparation method and application thereof.The preparation method comprises the following specific steps that 1, the L-valine fermentation waste liquid is subjected to vacuum evaporation and concentration to obtain a concentrated solution, activated carbon is added into the concentrated solution for decoloration treatment, and a compound amino acid decoloration solution is obtained after filtering; 2, carrying out adsorption treatment on the compound amino acid decoloring solution by using modified cation exchange resin to obtain a compound amino acid treatment solution; and 3, mixing the compound amino acid treating fluid with metal salt, adjusting the pH value of the compound amino acid treating fluid, carrying out chelation reaction, separating out an amino acid metal chelate, centrifuging, drying and crushing to obtain the trace additive. According to the method, the pretreated L-valine fermentation waste liquid and the metal ions are subjected to chelation reaction to prepare the amino acid metal chelate which is high in chelation rate and excellent in oxidation resistance, the L-valine fermentation waste liquid is fully utilized, and the dual problems of waste liquid treatment and resource utilization can be solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of metal chelates, and particularly relates to a trace additive based on L-valine fermentation waste liquid and a preparation method and application thereof. BACKGROUND

[0002] The L-valine fermentation waste liquid is a waste liquid generated in the L-valine fermentation process, usually containing incompletely extracted complex amino acids, organic acids, residual sugars and a small amount of inorganic salts and other components. The traditional treatment method is to discharge after neutralization or simply recover, which not only causes resource waste, but also may cause environmental pollution. The existing preparation method of amino acid chelates usually uses a single amino acid after purification to react with a metal salt, which is high in cost and cannot realize resource utilization of the waste liquid.

[0003] Based on the above problems, the present application provides a trace additive based on L-valine fermentation waste liquid and a preparation method and application thereof. SUMMARY

[0004] The present application aims to solve the above problems and provide a trace additive based on L-valine fermentation waste liquid and a preparation method and application thereof.

[0005] The present application achieves the above-mentioned purposes through the following technical solutions: The present application provides a preparation method of a trace additive based on L-valine fermentation waste liquid, and the specific steps are as follows: Step one: the L-valine fermentation waste liquid is concentrated by vacuum evaporation to obtain a concentrated liquid, activated carbon is added to the concentrated liquid for decolorization treatment, and a complex amino acid decolorization liquid is obtained after filtration; Step two: the complex amino acid decolorization liquid is subjected to adsorption treatment by using a modified cation exchange resin to obtain a complex amino acid treatment liquid; The modified cation exchange resin is obtained by soaking the cation exchange resin in a solution containing Fe 3+ after ion exchange reaction by ultrasonic treatment, and then washing with deionized water until neutral. Step three: the complex amino acid treatment liquid is mixed with a metal salt, the pH is adjusted, and a chelation reaction is carried out to obtain a reaction liquid. After the reaction liquid is cooled to room temperature, ethanol is added (the volume ratio of the reaction liquid to ethanol is 1:1) to precipitate the amino acid metal chelate, the product is obtained by centrifugal separation, and the product is washed with deionized water for 3 times, vacuum dried at 50-60 DEG C, crushed and sieved (80 mesh sieve) to obtain a powdery amino acid metal chelate, i.e. the trace additive.

[0006] As a further optimization scheme of the present application, in step one, the solid content of the L-valine fermentation waste liquid after concentration is 15-25%, and the amount of activated carbon is 0.5%-2% of the weight of the concentrated liquid. The decoloring treatment is stirring decoloring at 80-90℃ for 1-2h.

[0007] As a further optimization scheme of the present application, in step two, the flow rate of the adsorption treatment is 1-5BV / h, and the eluent is deionized water.

[0008] As a further optimization scheme of the present application, in step two, the power of the ultrasonic treatment is 180-260w, the time is 20-25min, and the temperature is 30-40℃.

[0009] As a further optimization scheme of the present application, in step two, the solid-liquid ratio of the cation exchange resin to the solution containing Fe 3+ is 30-40g·L -1 , and the Fe 3+ concentration is 0.1-0.4mol·L -1 .

[0010] As a further optimization scheme of the present application, in step three, the metal salt includes at least one of ferrous sulfate, zinc sulfate, copper sulfate, and manganese sulfate; the molar ratio of the metal ion to the complex amino acid is 1:2-3; and the pH is adjusted to 5.0-6.5.

[0011] As a further optimization scheme of the present application, in step three, the chelation reaction is stirring reaction at 45-75℃ for 1-2h.

[0012] The present application also provides a trace additive based on L-valine fermentation waste liquor, which is prepared by the preparation method as described above.

[0013] The present application also provides an application of the trace additive based on L-valine fermentation waste liquor as described above, which can be used as a feed additive, an agricultural micro-fertilizer, and a pharmaceutical intermediate.

[0014] The present application has the following beneficial effects: 1) The present application prepares an amino acid metal chelate with high chelation rate and excellent antioxidant performance by chelation reaction of the pretreated L-valine fermentation waste liquor with metal ions, and fully utilizes the L-valine fermentation waste liquor, so as to solve the dual problems of waste liquor treatment and resource utilization; 2) The present application improves the chelation rate and antioxidant performance of the final amino acid metal chelate to a certain extent by decoloring treatment and adsorption treatment of the L-valine fermentation waste liquor, wherein the modified cation exchange resin used in the adsorption treatment is prepared by ultrasonic treatment and soaking in a solution containing Fe 3+The modified cation exchange resin is prepared by the solution of the synergistic modification, and the trace additive can achieve the effect of higher chelation rate at lower chelation reaction temperature by using the modified cation exchange resin to adsorb the composite amino acid decolorizing solution, so as to reduce the temperature requirement of the chelation reaction, and in the actual production process, the advantages of reducing energy consumption and saving production cost are obtained. DETAILED DESCRIPTION

[0015] It is necessary to point out here that the following detailed description is only used to further illustrate the application, and cannot be understood as limiting the protection scope of the application, and the skilled in the art can make some non-essential improvements and adjustments to the application according to the above application content.

[0016] I. Materials 1. Activated carbon: purchased from Jiangxi Huaiyushan Activated Carbon (Group) Co., Ltd., specific surface area 600-800 m 2 / g; 2. Cation exchange resin: 001x7 type cation exchange resin; 3. Solution containing Fe 3+ : ferric sulfate (Fe2(SO4)3) is dissolved in water to obtain, and the solution containing Zn 2+ , Cu 2+ is respectively copper sulfate (CuSO4) and zinc sulfate (ZnSO4) dissolved in water to obtain; 4. Soluble metal salt: ferrous sulfate (FeSO4·7H2O), zinc sulfate (ZnSO4·7H2O), copper sulfate (CuSO4·5H2O), manganese sulfate (MnSO4·H2O); 5. pH regulator: ammonia water or citric acid; 6. L-valine fermentation waste liquid is the waste liquid generated in the process of producing L-valine fermentation waste liquid by conventional fermentation method, and the composition of the L-valine fermentation waste liquid of the application is shown in Table 1: Table 1 Composition Table ; The method used in the application is the conventional method known by the skilled in the art, and the raw materials and reagents used are commercially available products, unless otherwise specified.

[0017] II. Method 2.1. Preparation of trace additive based on L-valine fermentation waste liquid 2.1.1. Raw material pretreatment (1) The L-valine fermentation waste liquid is concentrated by vacuum evaporation to obtain a concentrated liquid (the volume of the concentrated liquid is 1 / 5-1 / 3, preferably 1 / 3, of the volume of the L-valine fermentation waste liquid), and the solid content in the concentrated liquid is 21%, then activated carbon is added for decolorization treatment, and after filtration, a composite amino acid decolorized liquid is obtained, and the filtration can remove the bacterial protein and pigment; wherein the decolorization treatment is stirring decolorization at 80℃ for 2h, and the amount of activated carbon is 0.5% of the weight of the concentrated liquid; (2) The composite amino acid decolorized liquid is treated by adsorption using modified cation exchange resin (diameter-height ratio of 1:8) to obtain a composite amino acid treated liquid, wherein the flow rate of the adsorption treatment is 1BV / h, the eluent is deionized water, and through the adsorption treatment, Ca 2+ , Mg 2+ and other impurities can be removed; Method for obtaining modified cation exchange resin (Fe 3+ loaded cation exchange resin): A, ultrasonic treatment is performed on the cation exchange resin, the cation exchange resin is immersed in distilled water, the volume ratio of the cation exchange resin to the distilled water is 1:3, the cation exchange resin is treated by ultrasonic waves, the power of the ultrasonic treatment is 180w, the time is 20min, and the temperature is 30℃; B, the cation exchange resin treated by ultrasonic waves is soaked in a solution containing iron ions (Fe 3+ ) for ion exchange reaction, the solid-liquid ratio of the cation exchange resin to the solution containing iron ions is 35g·L -1 , the concentration of iron ions is 0.3mol·L -1 , after the reaction is completed, deionized water is used to wash to neutral, and the modified cation exchange resin is prepared.

[0018] 2.1.2, chelation reaction and post-treatment The composite amino acid treated liquid is mixed with metal salt (FeSO4·7H2O), the molar ratio of metal ions to composite amino acid is 1:2, the pH is adjusted to 5.5, and the reaction liquid is obtained after chelation reaction at 45-75℃ for 1.5h; after the reaction liquid is cooled to room temperature, ethanol is added (the volume ratio of the reaction liquid to ethanol is 1:1) to precipitate the amino acid metal chelate, the product is separated by centrifugation, the product is washed with deionized water for 3 times, vacuum dried at 55℃, crushed and sieved (80 mesh sieve) to obtain a powdery amino acid metal chelate, i.e. trace additive (denoted as S1 group).

[0019] 2.2, adjustment of the preparation method of the trace additive based on L-valine fermentation waste liquid S2 group: based on S1 group, in this group, the decolorization treatment is adjusted, the adjusted decolorization treatment is stirring decolorization at 85°C for 1.5h, the amount of activated carbon is 1% of the weight of L-valine fermentation wastewater; the rest is consistent with S1 group S3 group: based on S1 group, in this group, the decolorization treatment is adjusted, the adjusted decolorization treatment is stirring decolorization at 90°C for 1h, the amount of activated carbon is 2% of the weight of L-valine fermentation wastewater; the rest is consistent with S1 group.

[0020] S4 group: based on S2 group, in this group, the adsorption treatment is adjusted, the flow rate of the adjusted adsorption treatment is 3BV / h, the eluent is deionized water; the rest is consistent with S2 group.

[0021] S5 group: based on S2 group, in this group, the adsorption treatment is adjusted, the flow rate of the adjusted adsorption treatment is 5BV / h, the eluent is deionized water; the rest is consistent with S2 group.

[0022] 2.3, setting of comparative test D1 group: based on S4 group, in this group, the step (1) of raw material pretreatment is adjusted: the L-valine fermentation wastewater is concentrated by vacuum evaporation to obtain a concentrated solution, the solid content in the concentrated solution is 21%; that is, the decolorization treatment is omitted; the rest is consistent with S4 group.

[0023] D2 group: based on S4 group, in this group, the step (2) of raw material pretreatment is omitted; the rest is consistent with S4 group.

[0024] D3 group: based on S4 group, in this group, the step (1) of raw material pretreatment is adjusted: the L-valine fermentation wastewater is concentrated by vacuum evaporation to obtain a concentrated solution, the solid content in the concentrated solution is 21%; that is, the decolorization treatment is omitted; the step (2) of raw material pretreatment is also omitted; the rest is consistent with S4 group.

[0025] D4 group: based on S4 group, in this group, the adsorption treatment of step (2) is replaced by equal mass of cation exchange resin instead of modified cation exchange resin for adsorption treatment of composite amino acid decolorization liquid; the rest is consistent with S4 group.

[0026] D5 group: based on S4 group, in this group, the method of obtaining modified cation exchange resin is adjusted, that is, the modified cation exchange resin only undergoes soaking treatment with a solution containing Fe 3+ ; that is, step A is omitted; the rest is consistent with S4 group.

[0027] D6 group: based on S4 group, in this group, the method for obtaining the modified cation exchange resin is adjusted, that is, the modified cation exchange resin is only subjected to ultrasonic treatment (i.e. step B is omitted); the rest is consistent with S4 group.

[0028] D7 group: based on S4 group, in this group, zinc ions (Zn 2+ ) of the same concentration are used to replace iron ions; the rest is consistent with S4 group.

[0029] D8 group: based on S4 group, in this group, copper ions (Cu 2+ ) of the same concentration are used to replace iron ions; the rest is consistent with S4 group.

[0030] III. Test 3.1, chelation rate test of trace additives The chelation rate of the amino acid metal chelate (trace additive) after 1.5h of chelation reaction at different chelation reaction temperatures (45℃, 55℃, 65℃, 75℃) of the above example groups (S1-5 groups) and the comparison example groups (D1-8 groups) was determined by EDTA complexometric titration, and recorded in Table 2: Table 2: Chelation rate test data record table of trace additives ; Experimental conclusion: from the above table, it can be seen that the trace additives of the example groups (S1-5 groups) can achieve the highest chelation rate at 55℃ during the chelation reaction, among which S4 group is the best, with a chelation rate as high as 95.8%, which can reduce energy consumption in actual production process; Through comparison with the comparison example groups (D1-8 groups), it can be seen that the decolorization treatment and adsorption treatment of L-valine fermentation waste liquid before chelation reaction can improve the chelation rate of the final amino acid metal chelate to a certain extent; Moreover, after ultrasonic treatment, soaking in a solution containing Fe 3+ , both of which can modify the cation exchange resin, and then using the modified cation exchange resin to adsorb the composite amino acid decolorization liquid, can achieve a higher chelation rate at a lower chelation reaction temperature, among which ultrasonic treatment can reduce the chelation reaction temperature, and soaking in a solution containing Fe 3+ has a significant effect on improving the chelation rate.

[0031] 3.2, antioxidant performance test of trace additives The antioxidant performance of the trace additives of the example groups (S1-5 groups) and the comparative example groups (D1-8 groups) was evaluated by using the DPPH free radical scavenging activity determination method, and the DPPH free radical scavenging rates of the trace additives (the concentration of the trace additives used for testing was 15 mg / mL) of the example groups (S1-5 groups) and the comparative example groups (D1-8 groups) were shown in Table 3: Table 3 Test data record table of the antioxidant performance of the trace additives ; Experimental conclusion: from the data in Table 3, it can be known that the trace additive of the S4 group of the present application has good antioxidant capacity, and is the optimal example; it is found by comparison that the modified cation exchange resin prepared by using the present application can significantly improve the antioxidant activity of the trace additive when used for adsorbing and treating the composite amino acid decolorizing solution, and has obvious application advantages when used as a feed additive, an agricultural micro-fertilizer and a pharmaceutical intermediate, such as being able to improve the nutrient absorption efficiency, enhance the antioxidant capacity, improve the crop quality, improve the stability of the medicine in the storage and use process, etc.

[0032] The above-described tests only express several embodiments of the present application, the description is more specific and detailed, but it cannot be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application.

Claims

1. A method for preparing a trace additive based on L-valine fermentation waste liquid, characterized in that: The specific steps are as follows: Step 1: vacuum evaporation is performed on the L-valine fermentation waste liquid to obtain a concentrated solution, activated carbon is added to the concentrated solution for decolorization, and after filtration, a composite amino acid decolorized solution is obtained; Step 2: using a modified cation exchange resin to adsorb the composite amino acid decolorization solution to obtain a composite amino acid treatment solution; Wherein, the modified cation exchange resin is a cation exchange resin which is immersed in a liquid containing Fe after ultrasonic treatment. 3+ The ion exchange reaction is carried out in a solution, and then washed with deionized water until neutrality is obtained; Step 3: Mix the composite amino acid treatment solution with the metal salt, adjust the pH, perform a chelation reaction to obtain a reaction solution, use ethanol to precipitate the amino acid metal chelate, and then obtain a powdered amino acid metal chelate, i.e., a trace additive, after centrifugation, washing with deionized water, vacuum drying, and crushing and sieving.

2. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 1, wherein: In step 1, the solid content of the L-valine fermentation waste liquid after concentration is 15-25%, and the amount of the activated carbon used is 0.5%-2% of the weight of the concentrated liquid; The decolorization treatment is performed by stirring at 80-90° C. for 1-2 hours.

3. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 1, wherein: In step 2, the flow rate of the adsorption treatment is 1-5 BV / h, and the eluent is deionized water.

4. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 2, wherein: In step 2, the power of ultrasonic treatment is 180-260W, the time is 20-25min, and the temperature is 30-40°C.

5. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 1, wherein: In step 2, the cation exchange resin is mixed with Fe 3+ The solid-liquid ratio of the solution is 30-40g·L -1 , Fe 3+ The concentration is 0.1-0.4 mol·L -1 .

6. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 1, wherein: In step three, the metal salt includes at least one of ferrous sulfate, zinc sulfate, copper sulfate, and manganese sulfate; the molar ratio of metal ions to complex amino acids is 1:2-3; and the pH is adjusted to 5.0-6.

5.

7. The method for preparing a trace additive based on L-valine fermentation waste liquid according to claim 1, characterized in that: In step 3, the chelation reaction is carried out by stirring at 45-75° C. for 1-2 hours.

8. A trace additive based on L-valine fermentation waste liquid, characterized in that: The method is prepared according to any one of claims 1 to 7.

9. An application of the trace additive based on L-valine fermentation waste liquid as claimed in claim 8, characterized in that: The trace additive can be used as a feed additive, agricultural micro-fertilizer and pharmaceutical intermediate.