Modified activated carbon adsorbent and preparation method thereof

Abstract

The invention relates to the technical field of adsorbent modification, and discloses a modified activated carbon adsorbent and a preparation method thereof.The modified activated carbon adsorbent is obtained by putting coconut shell activated carbon, coal activated carbon, wooden activated carbon, bentonite, coal tar and modified cardanol into a high-temperature and high-pressure reactor to react. A quaternary ammonium salt group in the modified activated carbon adsorbent removes heavy metal ions in sewage through complexation, and an intermediate 1 is subjected to amidation reaction, so that the substitution degree of quaternary ammonium salt is improved, and the heavy metal ions are more effectively removed; carbonyl and nitrogen atoms in the structure of an amido bond formed by amidation are coordinated with heavy metal ions to form a stable complex, so that the heavy metal ions in the sewage are removed; the anacardol contained in the adsorbent has a long chain, so that the adsorption site of heavy metal ions in sewage is improved, and the long chains are mutually wound to form net laying and sweeping, so that the heavy metal ions are removed.

Description

Technical Field

[0001] The invention relates to the technical field of adsorbent modification, in particular to a modified activated carbon adsorbent and a preparation method thereof. Background Art

[0002] With the progress of society, industrial and mining enterprises are developing rapidly, and various chemicals are being developed and utilized for this purpose, which is also accompanied by sewage discharge, which contains a large amount of heavy metal ions, and brings a lot of toxic and harmful substances to the living environment, thereby affecting human health. Therefore, how to avoid this phenomenon is the key to solving the problem. Activated carbon is an environmentally friendly material. It is made by activating carbon-containing materials such as wood, coal, and fruit shells under high temperature and hypoxia conditions. Activated carbon adsorption is a water treatment method that utilizes the physical adsorption, chemical adsorption, oxidation, catalytic oxidation and reduction properties of activated carbon to remove pollutants in water. In addition, activated carbon adsorbent can also adjust environmental conditions to reduce the generation of harmful substances, and its application in the present invention improves its adsorption and decontamination capabilities. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a modified activated carbon adsorbent and a preparation method thereof, which has strong adsorption capacity and saves costs.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a modified activated carbon adsorbent, comprising the following components by weight: 350-450 parts by weight of coconut shell activated carbon, 350-450 parts by weight of coal activated carbon, 350-450 parts by weight of wood activated carbon, 60-100 parts by weight of bentonite, 30-50 parts by weight of coal tar, and 10-15 parts by weight of modified cardanol.

[0007] Preferably, the modified cardanol comprises the following steps:

[0008] (1) adding 8-15 parts by weight of N-methyliminodiacetic acid and 6-12 parts by weight of 1-chlorooctadecane to a reactor containing acetonitrile solvent, reacting at 85-95° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0009] (2) Add intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stir evenly, heat to 110-125° C., then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, reflux for 20-32 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0010] (3) dissolving cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, adding potassium carbonate thereto, stirring and dispersing, heating to 45-60° C., reflux reaction for 10-18 hours, cooling to room temperature after the reaction, filtering, evaporating the solvent from the filtrate, adding deionized water thereto, extracting with ethyl acetate, and drying the organic phase to obtain intermediate 3;

[0011] (4) Add intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stir and dissolve, continue to add p-toluenesulfonic acid catalyst, react at 65-80° C. for 4-7 hours, and then distill under reduced pressure, filter and dry to obtain modified cardanol.

[0012] Preferably, the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane in (1) is 1:1.2-1.4.

[0013] Preferably, the mass ratio of the intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine in (2) is 1.2-1.5:1:0.01-0.03:0.01-0.02.

[0014] Preferably, the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol and potassium carbonate in (3) is 1.6-2.2:1:0.02-0.03.

[0015] Preferably, the mass ratio of intermediate 3, intermediate 2 and p-toluenesulfonic acid catalyst in (4) is 1:0.8-1.2:0.03-0.04.

[0016] Preferably, the preparation method of the modified activated carbon adsorbent is: placing coconut shell activated carbon, coal-based activated carbon, wood activated carbon, bentonite, coal tar, and modified cardanol in a high temperature and high pressure reactor, reacting for 15-30 minutes, to obtain the modified activated carbon adsorbent.

[0017] (III) Beneficial technical effects

[0018] The invention provides a modified activated carbon adsorbent by placing coconut shell activated carbon, coal-based activated carbon, wood activated carbon, bentonite, coal tar and modified cardanol in a high-temperature and high-pressure reactor for reaction.

[0019] N-methyliminodiacetic acid and 1-chlorooctadecane are subjected to quaternization reaction to obtain intermediate 1, which is then subjected to amidation reaction with 2,2'-(ethylenedioxy)bis(ethylamine) to obtain intermediate 2. Cardanol and 2,2'-dibromo-4,4'-biphenol are subjected to substitution reaction to generate a large number of hydroxyl groups to obtain intermediate 3. Intermediate 3 and intermediate 2 are subjected to esterification reaction to increase the substitution degree of cardanol and obtain modified cardanol.

[0020] The quaternary ammonium salt groups in the modified activated carbon adsorbent remove heavy metal ions in sewage through complexation, and the intermediate 1 increases the degree of substitution of the quaternary ammonium salt through amidation reaction, making it more effective in removing heavy metal ions; the amide bond formed by the amidation reaction, the carbonyl group and nitrogen atom in its structure coordinate with the heavy metal ions to form a stable complex, thereby removing heavy metal ions in sewage; the cardanol contained therein has a longer chain, which increases the adsorption sites for heavy metal ions in sewage, and the long chains are entangled with each other to form a "net-spreading and rolling sweeping" to remove heavy metal ions. DETAILED DESCRIPTION

[0021] Example 1

[0022] (1) adding 8 parts by weight of N-methyliminodiacetic acid and 6 parts by weight of 1-chlorooctadecane to a reactor filled with acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane is 1:1.2, reacting at 85° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0023] (2) adding intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stirring evenly, heating to 110° C., and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine is 1.2:1:0.01:0.01, reflux reaction for 20 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0024] (3) dissolving cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, and then adding potassium carbonate thereto, wherein the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol to potassium carbonate is 1.6:1:0.02, stirring and dispersing, heating to 45° C., reflux reaction for 10 h, after the reaction is completed, cooling to room temperature, filtering, evaporating the solvent from the filtrate, adding deionized water thereto, extracting with ethyl acetate, and drying the organic phase to obtain intermediate 3;

[0025] (4) adding intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stirring and dissolving, continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 3, intermediate 2, and p-toluenesulfonic acid catalyst is 1:0.8:0.03, reacting at 65° C. for 4 h, and then distilling under reduced pressure, filtering and drying to obtain modified cardanol;

[0026] (5) 350 parts by weight of coconut shell activated carbon, 350 parts by weight of coal activated carbon, 350 parts by weight of wood activated carbon, 60 parts by weight of bentonite, 30 parts by weight of coal tar, and 10 parts by weight of modified cardanol were placed in a high temperature and high pressure reactor and reacted for 15 minutes to obtain a modified activated carbon adsorbent.

[0027] Example 2

[0028] (1) adding 15 parts by weight of N-methyliminodiacetic acid and 12 parts by weight of 1-chlorooctadecane to a reactor filled with acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane is 1:1.4, reacting at 95° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0029] (2) Add intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stir evenly, heat to 125° C., and then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine is 1.5:1:0.03:0.02, reflux for 32 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0030] (3) dissolving cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, and then adding potassium carbonate thereto, wherein the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol to potassium carbonate is 2.2:1:0.03, stirring and dispersing, heating to 60° C., reflux reaction for 18 h, after the reaction is completed, cooling to room temperature, filtering, evaporating the solvent from the filtrate, adding deionized water thereto, extracting with ethyl acetate, and drying the organic phase to obtain intermediate 3;

[0031] (4) adding intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stirring and dissolving, continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 3, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1.2:0.04, reacting at 80° C. for 7 h, and then distilling under reduced pressure, filtering and drying to obtain modified cardanol;

[0032] (5) 450 parts by weight of coconut shell activated carbon, 450 parts by weight of coal activated carbon, 450 parts by weight of wood activated carbon, 100 parts by weight of bentonite, 50 parts by weight of coal tar, and 15 parts by weight of modified cardanol were placed in a high temperature and high pressure reactor and reacted for 30 minutes to obtain a modified activated carbon adsorbent.

[0033] Example 3

[0034] (1) adding 11 parts by weight of N-methyliminodiacetic acid and 9 parts by weight of 1-chlorooctadecane to a reactor filled with acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane is 1:1.3, reacting at 90° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0035] (2) adding intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stirring evenly, heating to 117° C., and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine is 1.3:1:0.02:0.015, reflux reaction for 26 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0036] (3) Dissolve cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, and then add potassium carbonate thereto, wherein the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol and potassium carbonate is 1.9:1:0.025, stir and disperse, heat to 50° C., reflux for 14 h, and after the reaction is completed, cool to room temperature, filter, evaporate the solvent from the filtrate, add deionized water, extract with ethyl acetate, and dry the organic phase to obtain intermediate 3;

[0037] (4) adding intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 3, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1:0.035, reacting at 72° C. for 5 h, and then distilling under reduced pressure, filtering and drying to obtain modified cardanol;

[0038] (5) 400 parts by weight of coconut shell activated carbon, 400 parts by weight of coal activated carbon, 400 parts by weight of wood activated carbon, 80 parts by weight of bentonite, 40 parts by weight of coal tar, and 12 parts by weight of modified cardanol were placed in a high temperature and high pressure reactor and reacted for 22 minutes to obtain a modified activated carbon adsorbent.

[0039] Example 4

[0040] (1) adding 8 parts by weight of N-methyliminodiacetic acid and 6 parts by weight of 1-chlorooctadecane to a reactor filled with acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane is 1:1.2, reacting at 85° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0041] (2) adding intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stirring evenly, heating to 110° C., and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine is 1.2:1:0.01:0.01, reflux reaction for 20 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0042] (3) dissolving cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, and then adding potassium carbonate thereto, wherein the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol to potassium carbonate is 2.2:1:0.03, stirring and dispersing, heating to 60° C., reflux reaction for 18 h, after the reaction is completed, cooling to room temperature, filtering, evaporating the solvent from the filtrate, adding deionized water thereto, extracting with ethyl acetate, and drying the organic phase to obtain intermediate 3;

[0043] (4) adding intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stirring and dissolving, continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 3, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1.2:0.04, reacting at 80° C. for 7 h, and then distilling under reduced pressure, filtering and drying to obtain modified cardanol;

[0044] (5) 400 parts by weight of coconut shell activated carbon, 400 parts by weight of coal activated carbon, 400 parts by weight of wood activated carbon, 80 parts by weight of bentonite, 40 parts by weight of coal tar, and 12 parts by weight of modified cardanol were placed in a high temperature and high pressure reactor and reacted for 22 minutes to obtain a modified activated carbon adsorbent.

[0045] Example 5

[0046] (1) adding 15 parts by weight of N-methyliminodiacetic acid and 12 parts by weight of 1-chlorooctadecane to a reactor filled with acetonitrile solvent, wherein the mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane is 1:1.4, reacting at 95° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1;

[0047] (2) Add intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stir evenly, heat to 125° C., and then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, wherein the mass ratio of intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine is 1.5:1:0.03:0.02, reflux for 32 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2;

[0048] (3) Dissolve cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, and then add potassium carbonate thereto, wherein the mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenol and potassium carbonate is 1.9:1:0.025, stir and disperse, heat to 50° C., reflux for 14 h, and after the reaction is completed, cool to room temperature, filter, evaporate the solvent from the filtrate, add deionized water, extract with ethyl acetate, and dry the organic phase to obtain intermediate 3;

[0049] (4) adding intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of intermediate 3, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1:0.035, reacting at 72° C. for 5 h, and then distilling under reduced pressure, filtering and drying to obtain modified cardanol;

[0050] (5) 350 parts by weight of coconut shell activated carbon, 350 parts by weight of coal activated carbon, 350 parts by weight of wood activated carbon, 60 parts by weight of bentonite, 30 parts by weight of coal tar, and 10 parts by weight of modified cardanol were placed in a high temperature and high pressure reactor and reacted for 15 minutes to obtain a modified activated carbon adsorbent.

[0051] Comparative Example 1

[0052] The difference between this comparative example and Example 5 is that no modified activated carbon is added.

[0053] Take 200mL of wastewater into a beaker. 2+和 Pb 2+ The initial concentration of the wastewater was 100 mg / L. The wastewater adsorbent was added to the wastewater, and the wastewater was ultrasonically dispersed for 5 minutes and then placed on a shaker for 12 hours. The supernatant was taken and the Cd content in the supernatant was determined by ICP. 2+ and Pb 2 + The concentration after adsorption, the removal rate of heavy metal ions w = (initial concentration-concentration after adsorption) / initial concentration, the test results are shown in Table 1.

[0054] Table 1: Heavy metal ion removal rate test.

[0055] project <![CDATA[Cd 2+ Removal rate (%)]]> <![CDATA[Pb 2+ Removal rate (%)]]> Example 1 87.1 86.5 Example 2 92.5 91.8 Example 3 89.7 90.4 Example 4 77.5 89.5 Example 5 89.5 90.2 Comparative Example 1 53.1 51.4

[0056] It can be seen from Table 1 that Examples 1-5 of the present invention have better removal effects on heavy metal ions than Comparative Example 1, indicating that the flocculation effect is better.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A modified activated carbon adsorbent, characterized in that: The invention comprises the following components by weight: 350-450 parts by weight of coconut shell activated carbon, 350-450 parts by weight of coal activated carbon, 350-450 parts by weight of wood activated carbon, 60-100 parts by weight of bentonite, 30-50 parts by weight of coal tar and 10-15 parts by weight of modified cardanol.

2. The modified activated carbon adsorbent according to claim 1, characterized in that The modified cardanol comprises the following steps: (1) adding 8-15 parts by weight of N-methyliminodiacetic acid and 6-12 parts by weight of 1-chlorooctadecane to a reactor containing acetonitrile solvent, reacting at 85-95° C., cooling after the reaction, concentrating under reduced pressure, washing with petroleum ether, and recrystallizing with ethanol to obtain intermediate 1; (2) Add intermediate 1 and 2,2'-(ethylenedioxy)bis(ethylamine) to N,N-dimethylformamide solvent, stir evenly, heat to 110-125° C., then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 4-dimethylaminopyridine, reflux for 20-32 hours, cool after completion, precipitate, filter and wash to obtain intermediate 2; (3) dissolving cardanol and 2,2'-dibromo-4,4'-biphenol in a flask filled with acetone solvent, adding potassium carbonate thereto, stirring and dispersing, heating to 45-60° C., reflux reaction for 10-18 hours, cooling to room temperature after the reaction, filtering, evaporating the solvent from the filtrate, adding deionized water thereto, extracting with ethyl acetate, and drying the organic phase to obtain intermediate 3; (4) Add intermediate 3 and intermediate 2 to N,N-dimethylformamide solvent, stir and dissolve, continue to add p-toluenesulfonic acid catalyst, react at 65-80° C. for 4-7 hours, and then distill under reduced pressure, filter and dry to obtain modified cardanol.

3. The modified activated carbon adsorbent according to claim 1, characterized in that: The mass ratio of N-methyliminodiacetic acid to 1-chlorooctadecane in (1) is 1:1.2-1.

4.

4. The modified activated carbon adsorbent according to claim 1, characterized in that The mass ratio of the intermediate 1, 2,2'-(ethylenedioxy)bis(ethylamine), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 4-dimethylaminopyridine in (2) is 1.2-1.5:1:0.01-0.03:0.01-0.

02.

5. The modified activated carbon adsorbent according to claim 1, characterized in that: The mass ratio of cardanol, 2,2'-dibromo-4,4'-biphenylene glycol and potassium carbonate in (3) is 1.6-2.2:1:0.02-0.

03.

6. The modified activated carbon adsorbent according to claim 1, characterized in that: The mass ratio of intermediate 3, intermediate 2 and p-toluenesulfonic acid catalyst in (4) is 1:0.8-1.2:0.03-0.

04.

7. A method for preparing the modified activated carbon adsorbent according to any one of claims 1 to 6, characterized in that: The preparation method of the modified activated carbon adsorbent is as follows: coconut shell activated carbon, coal-based activated carbon, wood activated carbon, bentonite, coal tar, and modified cardanol are placed in a high-temperature and high-pressure reactor, reacting for 15-30 minutes to obtain the modified activated carbon adsorbent.