CN109731547B - Modified activated carbon for efficient adsorption and dearomatization and preparation method thereof - Google Patents
Modified activated carbon for efficient adsorption and dearomatization and preparation method thereof Download PDFInfo
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- CN109731547B CN109731547B CN201910085132.1A CN201910085132A CN109731547B CN 109731547 B CN109731547 B CN 109731547B CN 201910085132 A CN201910085132 A CN 201910085132A CN 109731547 B CN109731547 B CN 109731547B
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Abstract
The invention discloses a modified activated carbon for efficient adsorption and dearomatization and application thereof, belonging to the field of activated carbon preparation. The modified activated carbon capable of efficiently and selectively adsorbing aromatic amino acid is obtained by performing synergistic treatment on the activated carbon by nitric acid and sulfuric acid, filtering and drying. The activated carbon has good application in preparing high F value oligopeptide (branched chain amino acid/aromatic amino acid is more than 20), can greatly reduce the adsorption loss of the activated carbon to the branched chain amino acid, and can obtain high F value oligopeptide products. The method has the advantages of simple operation, mild treatment process and high modification efficiency.
Description
Technical Field
The invention relates to modified activated carbon for efficient adsorption and dearomatization and a preparation method thereof, belonging to the field of activated carbon preparation.
Background
Activated carbon is a good adsorbent, and is widely applied to many fields of industrial production due to the developed void structure and the huge specific surface area. Since most commercial activated carbons do not meet the practical application, they need to be modified in different ways for different studies. The modification method comprises chemical modification and physical modification. The physical modification is to improve the adsorption capacity and adsorption performance of the activated carbon by changing the pore structure and specific surface area of the activated carbon, and mainly comprises high-temperature calcination, cremation and the like. The chemical modification means that the surface functional group of the activated carbon is changed to meet the selective adsorption of a specific substance, and mainly comprises acid-base modification, oxidation modification and the like.
Disclosure of Invention
The invention aims to obtain activated carbon capable of selectively adsorbing aromatic amino acid by utilizing chemical modification, so that a high-F-value oligopeptide product is efficiently prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
it is a first object of the present invention to provide a method for preparing modified activated carbon using HNO3Solution and H2SO4Modifying the activated carbon by the solution; the modification is carried out by respectively using HNO with the concentration of 3-10 mol/L3Solution and H with the concentration of 0.1-1 mol/L2SO4The solution is prepared according to the solid-liquid ratio of 1: soaking the activated carbon for 10-20 h at a ratio of 5-10, cleaning and drying.
In an embodiment of the present invention, the method specifically includes:
(1) to 3-10 mol/L of HNO3The ratio of 1: 5-1: adding granular activated carbon into the mixture with a solid-liquid ratio (g/mL) of 7, soaking for 10-20 h, and then washing with deionized water until the pH value is 5.0-6.0;
(2) using 0.1-1 mol/L H2SO4The solution is prepared by mixing the following components in percentage by weight: 5-1: and (3) soaking the activated carbon treated in the step (1) for 10-20 hours at a solid-to-liquid ratio (g/mL), then washing with deionized water until the pH value is 5.0-6.0, and putting into a 105 ℃ drying oven for drying.
The second purpose of the invention is to provide modified activated carbon prepared by the method.
The third purpose of the invention is to provide the application of the modified activated carbon as an adsorbent in the fields of food and biology.
In one embodiment of the present invention, the application is to prepare high F value oligopeptide, specifically: and adding 90-120 g/L of the enzymolysis liquid to the maize yellow powder enzymolysis liquid to obtain the modified activated carbon.
In one embodiment of the present invention, the corn gluten enzymatic hydrolysate is prepared as follows:
(1) taking corn gluten meal as a raw material, adding natto protease according to the ratio of 5000-7000U/g of the corn gluten meal, carrying out enzymolysis for 4-6 hours at the temperature of 50-55 ℃ and under the condition of pH of 8.0-10.0, inactivating enzyme, and filtering to obtain soluble protein;
(2) adding flavourzyme into the soluble oligopeptide liquid obtained in the step (1) by 20000-25000U/g soluble protein, and carrying out enzymolysis for 4 hours at 40-55 ℃ and pH 6.5-7.5 to obtain an enzymolysis liquid obtained after two steps of enzymolysis;
(3) centrifuging the enzymatic hydrolysate prepared in the step (2) at 8000r/min for 10min to obtain an enzymatic supernatant;
(4) mixing the raw materials in a ratio of 1: 10-1: 15 (g/mL), adding modified activated carbon into the enzymolysis supernatant obtained in the step (3), and adsorbing for 1.5-2.5 h at the temperature of 40-55 ℃ and under the condition of pH of 2.0-3.0;
(5) and (4) centrifuging the oligopeptide liquid adsorbed in the step (4), wherein the supernatant is the high F value oligopeptide.
In one embodiment of the invention, the Bacillus natto (Bacillus natto) is Bacillus natto (Bacillus natto) CICC10023, which is purchased from China center for culture and management of industrial microorganisms.
In one embodiment of the invention, the natto protease is prepared by the following steps: inoculating bacillus natto in a fermentation medium, fermenting for 4-6 hours at 37 ℃ and pH of 9.0, centrifuging and removing thalli to obtain a natto protease liquid.
In one embodiment of the invention, the fermentation medium comprises: 8-10 g/L of glucose, 15-20 g/L of fish meal peptone, 1-2 g/L of calcium chloride and 1-2 g/L of magnesium sulfate.
Has the advantages that: the invention provides an active carbon modification method, which reduces the specific surface area and the total pore volume of active carbon by means of nitric acid-sulfuric acid synergistic modification, but can achieve the effect of improving the selective adsorption of aromatic amino acid by the active carbon, and can reduce the adsorption loss of branched chain amino acid, compared with the method that the retention rate of the branched chain amino acid is increased from 45% to 80% before modification, the adsorption selectivity of the active carbon is greatly improved, and the preparation of high F value oligopeptide is facilitated.
Drawings
FIG. 1 shows HNO concentrations3The modification effect of the solution on the activated carbon.
FIG. 2 shows H at different concentrations2SO4The modification effect of the solution on the activated carbon.
FIG. 3 shows the effect of HCl solutions of different concentrations on the modification of activated carbon.
FIG. 4 is an electron micrograph of activated carbon before and after modification and changes in pore volume; a is unmodified activated carbon; b is modified active carbon.
FIG. 5 shows the adsorption and dearomatization effects of modified activated carbon at different pH values.
FIG. 6 shows the adsorption and dearomatization effects of modified activated carbon at different carbon-to-liquid ratios.
FIG. 7 shows the adsorption and dearomatization effects of modified activated carbon at different temperatures.
FIG. 8 shows the adsorption and dearomatization effects of modified activated carbon at different adsorption times.
FIG. 9 shows adsorption effects before and after modification of activated carbon; a is unmodified activated carbon; b is modified active carbon.
Detailed Description
Oligopeptide adsorption loss rate: not only the oligopeptides at the tail ends of aromatic amino acids are removed, but also the oligopeptides with branched amino acid groups are partially adsorbed in the adsorption process of activated carbon, so that a great deal of oligopeptides are lost. The oligopeptide loss rate is shown in the following formula:
and (3) amino acid component detection: centrifuging the adsorption solution at 10000r/min for 10min, taking out the supernatant, and detecting amino acid components by using high-efficiency solution relative to the supernatant by adopting an OPA derivation method.
Example 1
And preparing a free amino acid mixed solution containing leucine, isoleucine, valine, phenylalanine and tyrosine with the concentration of 5mmol/L respectively.
Preparing modified activated carbon: to HNO with the concentration of 3, 4, 5, 6, 8 and 10mol/L respectively3The ratio of 1: 5(g/mL) of carbon liquid, adding granular activated carbon, soaking for 20h, then washing with deionized water until the pH value is 5.0-6.0, and putting into a 105 ℃ oven for drying to obtain the modified activated carbon.
The active carbon prepared under the conditions is added into the amino acid mixed solution by 100g/L, the mixture is adsorbed for 2 hours under the conditions of pH 2.0-3.0 and temperature 55 ℃, and the branched chain retention rate and the aromatic amino acid removal rate are measured, and the result shows that (as shown in figure 1), the active carbon is modified by 3-5 mol/L nitric acid solution, so that the branched chain retention rate can reach 75-80%, and the aromatic amino acid removal rate can reach 97-99%.
Example 2
The specific implementation manner is the same as that of example 1, except that H with the concentration of 0.05, 0.1, 0.5, 1, 5 and 10mol/L is used2SO4Solution replacement of HNO3And (3) solution.
The results of measuring the branched chain retention rate and the aromatic amino acid removal rate of the solution after the modified activated carbon treatment show that (as shown in figure 2), the concentration of H is 0.1-10 mol/L2SO4The solution modified activated carbon can ensure that the retention rate of the branched chain reaches 70-75 percent and the removal rate of the aromatic amino acid reaches 97-98 percent.
Example 3
The specific implementation manner is the same as example 1, except that HCl solutions with concentrations of 0.05, 0.1, 0.5, 1, 5 and 10mol/L are used to replace HNO3And (3) solution.
The results of the determination of the branch chain retention rate and the aromatic amino acid removal rate of the solution after the modified activated carbon treatment show that (as shown in fig. 3), the HCl solution with the concentration of 1mol/L has relatively good effect of modifying the activated carbon, and can enable the branch chain retention rate to reach 58% and the aromatic amino acid removal rate to reach 99%.
Example 4
Firstly, mixing 1: soaking the activated carbon in 5mol/L nitric acid for 20h at a carbon liquid ratio of 5(g/ml), washing with deionized water until the pH value is 5.0-6.0, and then mixing the activated carbon with a water solution in a ratio of 1: soaking the activated carbon in 0.1mol/L nitric acid for 20 hours at a carbon liquid ratio of 5(g/ml), washing with deionized water until the pH value is 5.0-6.0, and drying in a drying oven at 105 ℃ to obtain the modified activated carbon.
The characterization of the activated carbon before and after modification was determined, and as can be seen from the scanning electron microscope results (as shown in fig. 4), the surface of the activated carbon before modification had a large number of micropores, while the number of micropores decreased after modification, which may be due to collapse of micropores after acid modification. Meanwhile, as can be seen from the results of the measurement by the full-automatic specific surface area analyzer (see table 1), the number of micropores is reduced after the modification of the activated carbon, which is consistent with the results of the scanning electron microscope. Therefore, after the active carbon is modified, the total adsorption amount is reduced due to the collapse of micropores, so that the adsorption loss rate is reduced in the process of adsorbing the enzymolysis liquid, and the product yield is improved.
TABLE 1
Example 5
(1) Carrying out enzymolysis on the maize yellow powder by using natto protease (enzyme concentration is 200U/ml) obtained by fermenting bacillus natto at the temperature of 37 ℃ and the pH value of 9.0 for 48 hours according to the adding amount of 5000U/g maize yellow powder, carrying out enzymolysis for 6 hours at the temperature of 55 ℃ and the pH value of 9.0, finally putting the obtained product into boiling water for inactivating enzyme for 10 minutes, and filtering to obtain soluble protein;
(2) carrying out enzymolysis on the soluble oligopeptide liquid in the step (1) by using flavourzyme, adding the flavourzyme at 20000U/g, and carrying out enzymolysis for 4 hours at 50 ℃ under the condition of pH 7.0 to obtain enzymolysis liquid after two-step enzymolysis;
(3) centrifuging the enzymatic hydrolysate prepared in the step (2) at 8000r/min for 10min to obtain an enzymatic supernatant;
(4) preparing 5mol/L HNO3Solution, at a ratio of 1: 5, adding granular activated carbon in a solid-liquid ratio, soaking for 20 hours, and then cleaning with deionized water until the pH value is 5.0-6.0 for later use;
(5) 0.1mol/L of H is used2SO4Solution, at a ratio of 1: 5, soaking the activated carbon in the step (4) for 20 hours in a solid-to-liquid ratio, then cleaning the activated carbon with deionized water until the pH value is 5.0-6.0, and finally drying the activated carbon in a 105 ℃ drying oven for later use;
(6) and (3) adsorbing and dearomatizing the enzymolysis liquid in the step (3) by using modified activated carbon, wherein the ratio of the enzymolysis liquid to the enzymolysis liquid in the adsorption process is 1: adding modified activated carbon into the mixture according to the carbon-to-liquid ratio (g/L) of 10, and adsorbing the mixture for 1.5 to 2.5 hours at the temperature of 55 ℃ and under the condition of pH of 2.5 to 3.5;
(7) and (4) centrifuging the oligopeptide liquid adsorbed in the step (6) to obtain a supernatant, wherein the F value of the supernatant is 23-24.
Example 6
The procedure is as in example 5, except that the activated carbon used is modified with HCl only, the modified activated carbon is prepared as in example 3, and the HCl concentration is 1 mol/L.
The results show that the ratio of 1: adding modified activated carbon into the mixture at a carbon-to-liquid ratio (g/L) of 10 to obtain a supernatant, wherein the F value of the supernatant is 13-15.
Example 7
The procedure is as in example 5, except that the activated carbon used is not modified.
The results show that the ratio of 1: adding modified activated carbon into the mixture with a carbon-to-liquid ratio (g/L) of 10 to obtain a supernatant, wherein the F value of the supernatant is 9-11.
Example 8
The embodiment is the same as embodiment 5 except that the pH of adsorption is controlled to 2 to 7.
The result shows (as shown in FIG. 5), when the pH is 2, the F value of the obtained supernatant can reach 11; after a pH of more than 3, the F value of the supernatant is less than 10.5.
Example 9
The embodiment is the same as example 5 except that the ratio of the activated carbon to the enzymolysis solution (in g: mL) is adjusted to 1: 10. 1: 15. 1: 20. 1: 30.
the results show (as in fig. 6), the char-to-liquid ratio is 1: 10-1: when 15 hours, the F value of the obtained supernatant can reach more than 11; the carbon-liquid ratio is less than 1: after 10, the supernatant F value was less than 10.5.
Example 10
The embodiment was the same as example 5 except that the adsorption temperatures were adjusted to 25, 30, 40, 50 and 60 ℃.
The result shows (as figure 7), the temperature is 30 ℃, the supernatant fluid F value can reach 12.2; the temperature is adjusted to be above 40 ℃, and the F value of the supernatant is lower than 11.
Example 11
The embodiment is the same as example 5 except that the adsorption time is adjusted to 0.5, 1, 2 and 3 hours, respectively.
The result shows (as shown in FIG. 8), when the adsorption time is 1-2 h, the F value of the obtained supernatant can reach 9-10.5; when the adsorption time is less than 1h or more than 2h, the F value of the supernatant is less than 9.
Example 12
The specific embodiment is the same as example 5, except that the adsorption dearomatization treatment is performed with modified activated carbon and unmodified activated carbon, respectively.
The F values and the adsorption loss rates under different adsorption times are measured, and the results show (as shown in figure 9) that the selective adsorption effect of the modified activated carbon on the aromatic amino acid is obviously improved, the F value of the adsorption solution is improved from 11.5 to 24, and meanwhile, the loss rate of oligopeptides in the enzymolysis solution is also reduced, and is reduced from 65% to 45%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The application of the modified activated carbon in selectively adsorbing aromatic amino acid as an adsorbent in the fields of food and biology is characterized in that the modified activated carbon uses HNO3Solution and H2SO4Modifying the activated carbon by the solution; the modification method comprises the following steps:
(1) to 3-10 mol/L of HNO3The ratio of 1: adding granular activated carbon into the mixture according to the solid-liquid ratio of 5-7, soaking for 10-20 h, and then cleaning until the pH value is 5.0-6.0;
(2) using 0.1-1 mol/L H2SO4The solution is prepared by mixing the following components in percentage by weight: soaking the activated carbon treated in the step (1) for 10-20 hours at a solid-to-liquid ratio of 5-7, then cleaning until the pH value is 5.0-6.0, and drying; the unit of the solid-to-liquid ratio in the step (1) and the step (2) is g/mL.
2. A preparation method of high F value oligopeptide is characterized in that 90-120 g/L of modified activated carbon prepared by the modification method in claim 1 is added into a maize yellow powder enzymolysis liquid; the corn gluten enzymatic hydrolysate is a solution containing oligopeptides obtained by enzymolysis of natto protease and flavourzyme.
3. The method according to claim 2, wherein the natto protease is obtained by fermentation with bacillus natto; the bacillus natto is bacillus natto CICC 10023.
4. A method for adsorbing aromatic amino acids, which comprises adsorbing the aromatic amino acids with the modified activated carbon prepared by the modification method of claim 1 or with an adsorbent comprising the modified activated carbon of claim 1.
5. Use of a method according to claim 2 or 3 for the preparation of a high F oligopeptide or for the preparation of a product comprising a high F oligopeptide.
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| JP2010501320A (en) * | 2006-08-23 | 2010-01-21 | カーボン ソリューションズ インコーポレイテッド | Acid impregnated activated carbon and method for forming and using the same |
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