Preparation process of high-adsorbability carbon black

Abstract

The invention relates to the technical field of carbon black, in particular to a preparation process of high-adsorbability carbon black, which comprises the following steps: performing pore-forming treatment on carbon black to obtain a porous carbon black material, then treating the porous carbon black material with a first mixed amino acid solution to obtain a carbon black material loaded with a first mixed amino acid adsorption layer, and drying the carbon black material to obtain the high-adsorbability carbon black. And treating the carbon black material with a second mixed amino acid solution to obtain a carbon black material loaded with a second mixed amino acid adsorption layer, and treating the carbon black material loaded with mixed amino acids with laccase and tyrosinase. The carbon black product obtained by the preparation process has high adsorbability, and is used for treating metal ions in wastewater, so that the removal rate of the metal ions is greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon black, and particularly to a preparation process of highly adsorbent carbon black. Background Art

[0002] Carbon black is an amorphous carbon with various properties such as dispersion, adsorption, and conductivity. According to its various properties, it is widely used in many fields such as the environmental protection field, the chemical industry field, food and medicine, etc. Among them, in the environmental protection field, carbon black is often used to adsorb heavy metal ions in wastewater; however, the existing carbon black products have poor adsorption performance, resulting in a low clearance rate of heavy metal ions in wastewater; therefore, in view of the above problems, it is necessary to develop a preparation process of highly adsorbent carbon black. Summary of the Invention

[0003] The technical problem to be solved by the present invention is: aiming at the deficiencies of the prior art, to provide a preparation process of highly adsorbent carbon black, and by using this preparation process, carbon black products with high adsorption performance can be obtained, greatly improving the clearance rate of heavy metal ions in wastewater.

[0004] To solve the above technical problem, the technical solution of the present invention is: A preparation process of highly adsorbent carbon black, the preparation process includes the following steps: (1) Take carbon black and potassium hydroxide, stir and mix them evenly and then grind, and reserve the obtained mixed material; (2) Take the mixed material in step (1), carry out carbonization treatment under nitrogen protection, and then carry out cooling, washing, and drying to obtain a porous carbon black material for standby; (3) Take the porous carbon black material in step (2), add the first mixed amino acid solution, heat, ultrasonically disperse, then carry out magnetic stirring and drying to obtain a carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), add the second mixed amino acid solution, heat, ultrasonically disperse, then carry out magnetic stirring and drying to obtain a carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), add a buffer solution, control the temperature and pH of the reaction system, first add laccase for reaction, then add tyrosinase to continue the reaction, and after enzyme inactivation, centrifugation, washing, and drying, a highly adsorbent carbon black product can be obtained.

[0005] As an improved technical solution, the carbon black and the potassium hydroxide in step (1) are mixed in a mass ratio of 1:1 - 3, and the particle size of the ground mixed material is 40 - 60 μm.

[0006] As an improved technical solution, during the carbonization treatment of the mixed material in step (2), the temperature is first raised to 600 - 700 °C at a rate of 5 - 10 °C / min, and then continued to be raised to 700 - 850 °C at a rate of 3 - 5 °C / min, followed by heat preservation for 1.5 - 2.5 h, and the nitrogen flow rate during the entire carbonization treatment is 50 - 100 mL / min.

[0007] As an improved technical solution, after the carbonization treatment in step (2), the material is cooled to 15 - 25 °C, and during washing, pickling is first used, followed by water washing.

[0008] As an improved technical solution, in step (3), the first mixed amino acid solution is a mixture of hydroxyproline, pyroglutamic acid, and purified water in a mass - volume ratio of 1 - 2 mg:1 - 3 mg:6 - 8 ml; the porous carbon black material and the first mixed amino acid solution are mixed in a mass ratio of 1 mg:0.71 - 1.28 mg.

[0009] As an improved technical solution, in step (3), it is heated to 70 - 90 °C and ultrasonically dispersed at a power of 500 - 600 w for 20 - 40 min.

[0010] As an improved technical solution, in step (4), the second mixed amino acid solution is a mixture of histidine, tyrosine, and purified water in a mass - volume ratio of 0.5 - 2.5 mg:1 - 2 mg:5 - 9 ml; the carbon black material loaded with the first mixed amino acid adsorption layer and the second mixed amino acid solution are mixed in a mass ratio of 1 mg:0.65 - 2.1 mg; it is heated to 85 - 105 °C and ultrasonically dispersed at a power of 600 - 700 w for 30 - 40 min.

[0011] As an improved technical solution, in step (5), the carbon black material loaded with the second mixed amino acid adsorption layer, laccase, and tyrosinase are mixed in a mass ratio of 1 mg:0.1 - 0.2 mg:0.2 - 0.3 mg, and the carbon black material loaded with the second mixed amino acid adsorption layer and the buffer solution are mixed in a mass - volume ratio of 1 mg:10 - 30 ml.

[0012] As an improved technical solution, in step (5), the buffer solution is a citric acid - phosphate buffer with a pH of 5 - 6, and the pH of the reaction system is controlled to be 5.5 - 6, the temperature is controlled to be 27 - 35 °C, and the reaction time is 2 - 4 h.

[0013] After adopting the above - mentioned technical solution, the beneficial effects of the present invention are: The present invention first performs pore-forming treatment on carbon black to obtain porous carbon black material (this treatment can increase the specific surface area of the carbon black material and enhance the adsorption of metal ions), and then treats it with the first mixed amino acid solution to obtain carbon black material loaded with the first mixed amino acid adsorption layer (hydroxyproline and pyroglutamic acid form the first adsorption layer on the porous carbon black after carbonization. These two amino acids contain carboxyl and hydroxyl groups, which can provide metal ion coordination sites). Then, it is further treated with the second mixed amino acid solution to obtain carbon black material loaded with the second mixed amino acid adsorption layer (the imidazole group of histidine and the phenolic hydroxyl group of tyrosine can further enhance the chelating ability of metal ions). Then, it is treated with laccase and tyrosinase on the carbon black material loaded with mixed amino acids (the phenolic hydroxyl group of tyrosine is oxidized to form quinone, which then undergoes non-enzymatic cross-linking with adjacent amino / thiol groups, ensuring the stability of the amino acid adsorption layer). Furthermore, a carbon black product with high adsorption performance can be obtained, which is used for the treatment of metal ions in wastewater, greatly improving the removal rate of metal ions. Detailed implementation mode

[0014] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Example 1

[0015] A preparation process of high-adsorption carbon black includes the following steps: (1) Take 50 mg of carbon black, add potassium hydroxide according to the mass ratio of 1:1, stir and mix evenly, and then grind to obtain 100 mg of mixed material with a particle size of 40 μm for standby; (2) Take 100 mg of the mixed material in step (1), and perform carbonization treatment under nitrogen protection (the specific carbonization treatment operation is: first heat up to 600 °C at a rate of 5 °C / min, and then continue to heat up to 700 °C at a rate of 3 °C / min, keep the temperature for 1.5 h, and the nitrogen flow rate during the whole carbonization treatment is 50 mL / min), then cool to 15 °C, wash (using acid washing and then water washing), and dry to obtain 43.2 mg of porous carbon black material for standby; (3) Take 43.2 mg of the porous carbon black material in step (2), add the first mixed amino acid solution (hydroxyproline, pyroglutamic acid and purified water are mixed according to the mass-volume ratio of 1 mg:1 mg:6 ml) according to the mass ratio of 1:0.8, heat to 70 °C, ultrasonically disperse for 20 min at a power of 500 w, magnetically stir for 2 h, and then dry to obtain 46.98 mg of carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take 46.98 mg of the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), and add the second mixed amino acid solution (histidine, tyrosine, and purified water mixed in a mass-volume ratio of 0.5 mg: 1 mg: 5 ml) according to a mass ratio of 1:0.65. Heat to 85 °C, ultrasonically disperse for 30 min at a power of 600 w, magnetically stir for 2 h, and then dry to obtain 48.8 mg of the carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take 48.8 mg of the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), and add a buffer solution (citric acid-phosphate buffer solution with pH 5) according to a mass-volume ratio of 1:10 (mg / ml). Control the temperature of the reaction system to 27 °C and the pH to 5.5. First, add laccase and react for 1 h, then add tyrosinase and continue to react for 1 h (it should be noted that the carbon black material loaded with the second mixed amino acid adsorption layer, laccase (purchased from the manufacturer, enzyme activity is 50 - 150 U / mg), and tyrosinase (purchased from the manufacturer, enzyme activity is 100 - 1000 U / mg) are added according to a mass ratio of 1 mg: 0.1 mg: 0.2 mg). Heat to 85 °C to inactivate the enzyme, centrifuge, wash (wash the solid phase collected by centrifugation with the above buffer solution), and dry to obtain a highly adsorbent carbon black product. Example 2

[0016] A preparation process of highly adsorbent carbon black, comprising the following steps: (1) Take 50 mg of carbon black, add potassium hydroxide according to a mass ratio of 1:1.5, stir and mix evenly, and then grind to obtain 125 mg of the mixed material with a particle size of 45 μm for standby; (2) Take 125 mg of the mixed material in step (1), and carry out carbonization treatment under nitrogen protection (the specific carbonization treatment operation is: first heat to 620 °C at a rate of 6 °C / min, and then continue to heat to 750 °C at a rate of 3.5 °C / min, hold for 1.8 h, and the nitrogen flow rate during the whole carbonization treatment is 65 mL / min). Then cool to 18 °C, wash (first use acid washing, and then use water washing), and dry to obtain 44.3 mg of the porous carbon black material for standby; (3) Take 44.3 mg of the porous carbon black material in step (2), and add the first mixed amino acid solution (hydroxyproline, pyroglutamic acid, and purified water mixed in a mass-volume ratio of 1.2 mg: 1.5 mg: 6 ml) according to a mass ratio of 1:0.71. Heat to 75 °C, ultrasonically disperse for 25 min at a power of 520 w, magnetically stir for 2.5 h, and then dry to obtain 48.69 mg of the carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take 48.69 mg of the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), and add the second mixed amino acid solution (histidine, tyrosine and purified water are mixed according to the mass-volume ratio of 0.8 mg: 1.3 mg: 6 ml) according to the mass ratio of 1:1.02 (mg / ml). Heat to 90 °C, ultrasonically disperse at a power of 620 w for 32 min, magnetically stir for 2.5 h, and then dry to obtain 52.6 mg of the carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take 52.6 mg of the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), and add the buffer solution (citric acid-phosphate buffer solution with pH 5.3) according to the mass-volume ratio of 1:15 (mg / ml). Control the temperature of the reaction system to 30 °C and the pH to 5.8. First, add laccase and react for 1 h, then add tyrosinase and continue to react for 1.5 h (it should be noted that the carbon black material loaded with the second mixed amino acid adsorption layer, laccase, and tyrosinase are added according to the mass ratio of 1 mg: 0.12 mg: 0.23 mg). Heat to 85 °C to inactivate the enzyme, centrifuge, wash (wash the solid phase collected by centrifugation with the above buffer solution), and dry to obtain a highly adsorbent carbon black product. Example 3

[0017] A preparation process of highly adsorbent carbon black, comprising the following steps: (1) Take 50 mg of carbon black, add potassium hydroxide according to the mass ratio of 1:2.5, stir and mix evenly, and then grind to obtain 175 mg of the mixed material with a particle size of 50 μm for standby; (2) Take 175 mg of the mixed material in step (1), and carry out carbonization treatment under nitrogen protection (the specific carbonization treatment operation is: first heat up to 680 °C at a rate of 7 °C / min, and then continue to heat up to 820 °C at a rate of 4 °C / min, keep warm for 2 h, and the nitrogen flow rate during the whole carbonization treatment is 75 mL / min). Then cool to 20 °C, wash (first use acid washing, and then use water washing), and dry to obtain 46.8 mg of the porous carbon black material for standby; (3) Take 46.8 mg of the porous carbon black material in step (2), and add the first mixed amino acid solution (hydroxyproline, pyroglutamic acid and purified water are mixed according to the mass-volume ratio of 1.5 mg: 2.5 mg: 7 ml) according to the mass ratio of 1:1.1. Heat to 85 °C, ultrasonically disperse at a power of 580 w for 35 min, magnetically stir for 3.5 h, and then dry to obtain 58.03 mg of the carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take 58.03 mg of the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), and add the second mixed amino acid solution (histidine, tyrosine and purified water are mixed in a mass-volume ratio of 1 mg: 1.5 mg: 8 ml) according to a mass ratio of 1:2.1. Heat to 100 °C, ultrasonically disperse at a power of 680 w for 35 min, magnetically stir for 3.5 h, and then dry to obtain 65.29 mg of the carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take 65.29 mg of the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), and add the buffer solution (citric acid-phosphate buffer solution with pH 5.5) according to a mass-volume ratio of 1:25 (mg / ml). Control the temperature of the reaction system to be 32 °C and the pH to be 6. First, add laccase and react for 1.5 h, then add tyrosinase and continue to react for 2 h (it should be noted that the carbon black material loaded with the second mixed amino acid adsorption layer, laccase, and tyrosinase are added according to a mass ratio of 1 mg: 0.15 mg: 0.25 mg). Heat to 85 °C to inactivate the enzyme, centrifuge, wash (wash the solid phase collected by centrifugation with the above buffer solution), and dry to obtain a highly adsorbent carbon black product. Example 4

[0018] A preparation process of highly adsorbent carbon black, comprising the following steps: (1) Take 50 mg of carbon black, add potassium hydroxide according to a mass ratio of 1:2, stir and mix evenly, and then grind to obtain 150 mg of a mixed material with a particle size of 55 μm for standby; (2) Take 150 mg of the mixed material in step (1), and carry out carbonization treatment under nitrogen protection (the specific carbonization treatment operation is: first heat to 650 °C at a rate of 8 °C / min, and then continue to heat to 800 °C at a rate of 4.5 °C / min, and keep warm for 2.3 h, and the nitrogen flow rate during the whole carbonization treatment is 85 mL / min). Then cool to 22 °C, wash (use acid washing first, and then use water washing), and dry to obtain 45.1 mg of porous carbon black material for standby; (3) Take 45.1 mg of the porous carbon black material in step (2), and add the first mixed amino acid solution (hydroxyproline, pyroglutamic acid and purified water are mixed in a mass-volume ratio of 1.8 mg: 2.25 mg: 7.5 ml) according to a mass ratio of 1:1.28. Heat to 80 °C, ultrasonically disperse at a power of 550 w for 30 min, magnetically stir for 3 h, and then dry to obtain 55.23 mg of the carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take 55.23 mg of the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), and add the second mixed amino acid solution (histidine, tyrosine and purified water are mixed in a mass-volume ratio of 1.2 mg: 1.5 mg: 7 ml) according to a mass ratio of 1:1.62. Heat to 95 °C, ultrasonically disperse at a power of 650 w for 35 min, magnetically stir for 3 h, and then dry to obtain 62.2 mg of the carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take 62.2 mg of the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), and add buffer solution (citric acid-phosphate buffer solution with pH 5.8) according to a mass-volume ratio of 1:20 (mg / ml). Control the temperature of the reaction system to be 35 °C and the pH to be 5.8. First add laccase and react for 1.8 h, then add tyrosinase and continue to react for 1.2 h (it should be noted that the carbon black material loaded with the second mixed amino acid adsorption layer, laccase, and tyrosinase are added according to a mass ratio of 1 mg: 0.18 mg: 0.27 mg). Heat to 85 °C to inactivate the enzyme, centrifuge, wash (wash the solid phase collected by centrifugation with the above buffer solution), and dry to obtain a highly adsorbent carbon black product. Example 5

[0019] A preparation process of highly adsorbent carbon black, comprising the following steps: (1) Take 50 mg of carbon black, add potassium hydroxide according to a mass ratio of 1:3, stir and mix evenly, and then grind to obtain 200 mg of a mixed material with a particle size of 60 μm for standby; (2) Take 200 mg of the mixed material in step (1), and carry out carbonization treatment under nitrogen protection (the specific carbonization treatment operation is: first heat up to 700 °C at a rate of 10 °C / min, and then continue to heat up to 850 °C at a rate of 5 °C / min, and keep warm for 2.5 h, and the nitrogen flow rate during the whole carbonization treatment is 100 mL / min), then cool to 25 °C, wash (using acid washing and then water washing), and dry to obtain 42.8 mg of porous carbon black material for standby; (3) Take 42.8 mg of the porous carbon black material in step (2), and add the first mixed amino acid solution (hydroxyproline, pyroglutamic acid and purified water are mixed in a mass-volume ratio of 2.5 mg: 2 mg: 8 ml) according to a mass ratio of 1:1.25. Heat to 90 °C, ultrasonically disperse at a power of 600 w for 40 min, magnetically stir for 4 h, and then dry to obtain 53.39 mg of the carbon black material loaded with the first mixed amino acid adsorption layer for standby; (4) Take 53.39 mg of the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), and add the second mixed amino acid solution (histidine, tyrosine and purified water are mixed according to the mass-volume ratio of 2.5 mg: 2 mg: 9 ml) according to the mass ratio of 1:1.35. Heat to 105 °C, ultrasonically disperse at a power of 700 w for 40 min, magnetically stir for 4 h, and then dry to obtain 58.44 mg of the carbon black material loaded with the second mixed amino acid adsorption layer for standby; (5) Take 58.44 mg of the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), and add buffer solution (citric acid-phosphate buffer solution with pH 6.0) according to the mass-volume ratio of 1:30 (mg / ml). Control the temperature of the reaction system to 35 °C and the pH to 6. First add laccase and react for 2 h, then add tyrosinase and continue to react for 2 h (it should be noted that the carbon black material loaded with the second mixed amino acid adsorption layer, laccase, and tyrosinase are added according to the mass ratio of 1 mg: 0.2 mg: 0.3 mg). Heat to 85 °C to inactivate the enzyme, centrifuge, wash (wash the solid phase collected by centrifugation with the above buffer solution), and dry to obtain the highly adsorbent carbon black product.

[0020] To better prove that the carbon black obtained by the process method of the present invention has good adsorption properties, taking Example 3 as a reference, 12 comparative examples are given. The carbon blacks prepared in Examples 1-5 and Comparative Examples 1-12 are subjected to heavy metal ion adsorption tests. The specific test results are shown in Table 1, and the specific tests are as follows: Cu 2+ Adsorption test: Weigh 0.3 g of the highly adsorbent carbon black products prepared in Examples 1-5 and the comparative examples respectively, add them to 100 mL of the Cu 2+ solution with an initial concentration of 100 mg / L, and use a constant temperature oscillator to oscillate and adsorb at a rotation speed of 250 r / min for a certain time. Then take the filtrate and use ICP to measure the remaining Cu 2+ concentration in the solution. Calculate the removal rate according to the following formula: Removal rate (%) = (C0 - C e ) / C0 × 100, where C e is the Cu 2+ concentration (mg / L) in the final solution; C0 is the initial Cu 2+ concentration (mg / L) in the solution.

[0021] Fe 3+ Adsorption test: Weigh 0.3 g of the highly adsorbent carbon black products prepared in Examples 1-5 and the comparative examples respectively, add them to 100 mL of the Fe 3+ solution with an initial concentration of 100 mg / L, and use a constant temperature oscillator to oscillate and adsorb at a rotation speed of 250 r / min for a certain time. Then take the filtrate and use ICP to measure the remaining Fe3+ Concentration, the removal rate is calculated according to the following formula: Removal rate (%) = (C0 - C e ) / C0 × 100, where C e is the concentration of Fe in the final solution (mg / L); C0 is the initial concentration of Fe in the solution 3+ (mg / L). 3+

[0022] Cr 3+ Adsorption test: Weigh 0.3 g of the highly adsorbent carbon black products prepared in Examples 1-5 and the comparative example respectively, and add them to 100 mL of a Cr solution with an initial concentration of 100 mg / L 3+ . After constant-temperature oscillating adsorption at a rotation speed of 250 r / min for a certain period of time, take the filtrate, and use ICP to measure the remaining Cr concentration in the solution 3+ . The removal rate is calculated according to the following formula: Removal rate (%) = (C0 - C e ) / C0 × 100, where C e is the concentration of Cr in the final solution (mg / L); C0 is the initial concentration of Cr in the solution 3+ (mg / L). 3+

[0023] Hg 2+ Adsorption test: Weigh 0.3 g of the highly adsorbent carbon black products prepared in Examples 1-5 and the comparative example respectively, and add them to 100 mL of a Hg solution with an initial concentration of 100 mg / L 2+ . After constant-temperature oscillating adsorption at a rotation speed of 250 r / min for a certain period of time, take the filtrate, and use ICP to measure the remaining Cd concentration in the solution 2+ . The removal rate is calculated according to the following formula: Removal rate (%) = (C0 - C e ) / C0 × 100, where C e is the concentration of Hg in the final solution (mg / L); C0 is the initial concentration of Hg in the solution 2+ (mg / L). 2+

[0024] Comparative Example 1 Different from Example 3, the carbon black was not pore-formed, and the other operations were the same.

[0025] Comparative Example 2 Different from Example 3, in step (3), it was heated to 65 °C, and the other operations were the same.

[0026] Comparative Example 3 Different from Example 3, in step (3), it was heated to 95 °C, and the other operations were the same.

[0027] Comparative Example 4 ​​​Different from Example 3, step (3) is missing, and the remaining operations are the same.

[0028] Comparative Example 5 Different from Example 3, in step (4), it is heated to 80 °C, and the remaining operations are the same.

[0029] Comparative Example 6 Different from Example 3, in step (4), it is heated to 110 °C, and the remaining operations are the same.

[0030] Comparative Example 7 Different from Example 3, in step (4), glycine is used instead of histidine in the second mixed amino acid solution, and the remaining operations are the same.

[0031] Comparative Example 8 Different from Example 3, the carbon black material after being wrapped with the first and second mixed amino acids is not treated with laccase and tyrosinase, and the remaining operations are the same.

[0032] Comparative Example 9 Different from Example 3, the specific carbonization treatment operation of the mixed material in step (2) is: directly heating to 820 °C, and the remaining operations are the same.

[0033] Comparative Example 10 Different from Example 3, the specific carbonization treatment operation of the mixed material in step (2) is: first heating to 680 °C at a rate of 7 °C / min, and then continuing to heat to 880 °C at a rate of 4 °C / min, and the remaining operations are the same.

[0034] Comparative Example 11 Different from Example 3, the carbon black and potassium hydroxide in step (1) are mixed in a mass ratio of 1:4, and the remaining operations are the same.

[0035] Comparative Example 12 Different from Example 3, the carbon black in step (1) is subjected to pore-forming treatment with nitric acid, and the remaining operations are the same.

[0036]

[0037] It can be found from the data in Table 1 that the comprehensive comparison of the investigation results of the adsorption performance of metal ions by the carbon black products prepared by the process method of Example 3 of the present invention is better than that of other examples and comparative examples.

[0038] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation process of highly adsorbent carbon black, characterized in that, The preparation process includes the following steps: (1) Take carbon black and potassium hydroxide, stir and mix them evenly and then grind them. Keep the obtained mixed material for later use; (2) Take the mixed material in step (1), carry out carbonization treatment under nitrogen protection, then cool, wash and dry it. Keep the obtained porous carbon black material for later use; (3) Take the porous carbon black material in step (2), add the first mixed amino acid solution, heat and ultrasonically disperse it, then carry out magnetic stirring and drying. Keep the carbon black material loaded with the first mixed amino acid adsorption layer for later use; (4) Take the carbon black material loaded with the first mixed amino acid adsorption layer in step (3), add the second mixed amino acid solution, heat and ultrasonically disperse it, then carry out magnetic stirring and drying. Keep the carbon black material loaded with the second mixed amino acid adsorption layer for later use; (5) Take the carbon black material loaded with the second mixed amino acid adsorption layer in step (4), add a buffer solution, control the temperature and pH of the reaction system, first add laccase for reaction, then add tyrosinase to continue the reaction, and obtain a highly adsorbent carbon black product after enzyme inactivation, centrifugation, washing and drying.

2. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (1), the carbon black and the potassium hydroxide are mixed in a mass ratio of 1:1 - 3, and the particle size of the ground mixed material is 40 - 60 μm.

3. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (2), when carrying out the carbonization treatment on the mixed material, first heat it to 600 - 700 °C at a rate of 5 - 10 °C / min, then continue to heat it to 700 - 850 °C at a rate of 3 - 5 °C / min, keep it warm for 1.5 - 2.5 h, and the flow rate of nitrogen during the whole carbonization treatment is 50 - 100 mL / min.

4. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, After the carbonization treatment in step (2), cool the material to 15 - 25 °C, and first carry out acid washing and then water washing during washing.

5. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (3), the first mixed amino acid solution is a mixture of hydroxyproline, pyroglutamic acid and purified water in a mass - volume ratio of 1 - 2 mg:1 - 3 mg:6 - 8 ml; the porous carbon black material and the first mixed amino acid solution are mixed in a mass ratio of 1 mg:0.71 - 1.28 mg.

6. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (3), heat it to 70 - 90 °C and ultrasonically disperse it for 20 - 40 min at a power of 500 - 600 w.

7. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (4), the second mixed amino acid solution is a mixture of histidine, tyrosine and purified water in a mass - volume ratio of 0.5 - 2.5 mg:1 - 2 mg:5 - 9 ml; the carbon black material loaded with the first mixed amino acid adsorption layer and the second mixed amino acid solution are mixed in a mass ratio of 1 mg:0.65 - 2.1 mg; heat it to 85 - 105 °C and ultrasonically disperse it for 30 - 40 min at a power of 600 - 700 w.

8. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, In step (5), the carbon black material loaded with the second mixed amino acid adsorption layer, laccase and tyrosinase are mixed in a mass ratio of 1 mg:0.1 - 0.2 mg:0.2 - 0.3 mg, and the carbon black material loaded with the second mixed amino acid adsorption layer and the buffer solution are mixed in a mass - volume ratio of 1 mg:10 - 30 ml.

9. The preparation process of a highly adsorbent carbon black according to claim 1, characterized in that, The buffer solution described in step (5) is a citric acid-phosphate buffer solution with a pH of 5-6.0, and the pH of the reaction system is controlled to be 5.5-6, the temperature is controlled to be 27-35 °C, and the reaction time is 2-4 h.

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