Activated carbon material for adsorbing organic gas and preparation method thereof

Abstract

The invention relates to the technical field of activated carbon materials, and discloses an activated carbon material for adsorbing organic gas and a preparation method thereof. The invention comprises the following steps: adding activated carbon powder, epoxidized cardanol, graphene oxide modified quaternized chitosan, bentonite, and nano titanium dioxide into a grinding device, grinding, and obtaining a primary material A; then adding a water-based epoxy resin adhesive and water thereto, stirring, and drying to obtain an activated carbon material for adsorbing organic gas. The chitosan in the silane-modified chitosan contains polar groups such as amino and hydroxyl groups in its structure, which can adsorb organic gas; the graphene therein also has a good adsorption effect on organic gas, while reducing its agglomeration effect; the siloxane and quaternary ammonium salt groups therein also have a good adsorption effect on organic gas. The cardanol in the epoxidized cardanol contains functional groups such as benzene rings, phenolic hydroxyl groups, and long-chain alkanes, which give the cardanol multiple reactivity and can absorb organic gas.

Description

Technical Field

[0001] The invention relates to the technical field of activated carbon materials, in particular to an activated carbon material for adsorbing organic gas and a preparation method thereof. Background Art

[0002] VOCs (volatile organic compounds) are mainly organic volatilization gases in the storage, transportation, loading and unloading of various oil products, chemical products (crude oil, finished oil, benzene series, etc.), production of petrochemical enterprises, and printing and dyeing spraying industry production processes. It is one of the main pollutants of haze and photochemical pollution. Therefore, how to avoid this phenomenon is the key to solving the problem. Bentonite is a clay mineral with montmorillonite as the main component. It has extremely strong hygroscopicity and expansibility. In terms of gas adsorption, it can adsorb or absorb gas molecules of VOCs. It is applied to the present invention to improve its adsorption effect on organic gases. For example, patent CN108704628A discloses a modified activated carbon adsorption material and its preparation method, which effectively improves the microporous adsorption performance of activated carbon, and calcium cyclopentaneate can improve heat resistance and stability, thereby improving the use environment of the finished material, but the adsorption of organic gases needs to be improved. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies in the prior art, the present invention provides an activated carbon material for adsorbing organic gases and a preparation method thereof, which has a good adsorption effect.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: an activated carbon material for adsorbing organic gas, comprising the following components by weight: 50-75 parts by weight of activated carbon powder, 3-6 parts by weight of epoxidized cardanol, 4-6 parts by weight of graphene oxide modified quaternized chitosan, 2-5 parts by weight of bentonite, 1-3 parts by weight of nano titanium dioxide, 0.8-1 parts by weight of water-based epoxy resin adhesive, and 8-10 parts by weight of water.

[0007] Preferably, the preparation method of the graphene oxide modified quaternary ammonium chitosan is:

[0008] (1) ultrasonically dispersing 5-7 parts by weight of graphene oxide into 70-95 parts by weight of thionyl chloride, and after uniform dispersion, heating to react for 1-3 hours, and after the reaction, filtering, washing, and drying to obtain chlorinated graphene;

[0009] (2) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to a reaction kettle, introducing nitrogen protection, and then continuing to add tetramethylammonium hydroxide catalyst, reacting at 65-85° C. for 2-6 hours, cooling and discharging after the reaction to obtain a double-terminal epoxy silicone oil;

[0010] (3) adding 6-8 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 60-90° C., adding 7-12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting for 6-9 hours, washing with anhydrous ethanol after the reaction, drying, dialyzing, and concentrating to obtain quaternized chitosan;

[0011] (4) adding double-terminal epoxy silicone oil and quaternized chitosan to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride ether catalyst thereto, reacting at 75-95° C. for 6-12 hours, filtering after the reaction, washing with deionized water and ethanol in turn, and drying to obtain silane-modified chitosan;

[0012] (5) Add 7-15 parts by weight of chlorinated graphene to ether solvent, stir and disperse, continue to add 5-10 parts by weight of silane-modified chitosan and 0.1-0.2 parts by weight of triethylamine catalyst, react at 60-85° C. for 6-10 hours, and after reaction, wash and dry to obtain graphene oxide-modified quaternary ammonium chitosan.

[0013] Preferably, the reaction temperature in (1) is 75-90°C.

[0014] Preferably, the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst in (2) is 1:1.1-1.3:0.01-0.02.

[0015] Preferably, the reaction temperature in (3) is 70-85°C.

[0016] Preferably, the mass ratio of the double-ended epoxy silicone oil, quaternized chitosan and boron trifluoride etherate catalyst in (4) is 0.6-0.8:1:0.01-0.03.

[0017] Preferably, it is characterized in that the preparation method of the epoxidized cardanol is:

[0018] S1. Add 4-8 parts by weight of cardanol and 2-3 parts by weight of 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stir to dissolve, then continue to add an aqueous sodium hydroxide solution thereto, react at 60-85° C. for 5-8 hours, and after completion, dropwise add dilute hydrochloric acid to neutralize, concentrate to remove the solvent, filter, wash and dry to obtain an intermediate 1; wherein the mass fraction of the aqueous sodium hydroxide solution is 3%;

[0019] S2. Add 3-6 parts by weight of intermediate 1 and 5-12 parts by weight of epichlorohydrin to N,N-dimethylformamide solvent, stir and mix, react at 60-80° C. for 4-6 hours, and then distill under reduced pressure and wash to obtain epoxidized cardanol.

[0020] Preferably, the preparation method of the activated carbon material for adsorbing organic gas is: adding activated carbon powder, epoxidized cardanol, graphene oxide modified quaternized chitosan, bentonite, and nano-titanium dioxide into a grinding device, grinding to 250-350 mesh to obtain a preliminary material A; then continuing to add water-based epoxy resin adhesive and water thereto, stirring for 20-40 minutes, and drying to obtain an activated carbon material for adsorbing organic gas.

[0021] (III) Beneficial technical effects

[0022] The present invention adds activated carbon powder, epoxidized cardanol, graphene oxide modified quaternized chitosan, bentonite and nano titanium dioxide into a grinding device, grinds to obtain a primary material A; then continues to add a water-based epoxy resin adhesive and water, stirs, and dries to obtain an activated carbon material for adsorbing organic gas.

[0023] The chitosan in silane-modified chitosan contains polar groups such as amino and hydroxyl groups in its structure. These groups make chitosan have strong adsorption properties and can adsorb organic gases; the graphene in it also has a good adsorption effect on organic gases, while reducing its agglomeration effect; the siloxane and quaternary ammonium salt groups contained in it also have a good adsorption effect on organic gases. The cardanol in epoxidized cardanol contains functional groups such as benzene rings, phenolic hydroxyl groups and long-chain alkanes. These functional groups give cardanol a variety of reactivity and can absorb organic gases; during the stirring process, the hydroxyl groups in silane-modified chitosan will undergo a ring-opening reaction with the epoxy groups in epoxidized cardanol, and cross-linking will occur between them to form a cross-linked network, making it more effective in adsorbing organic gases. DETAILED DESCRIPTION

[0024] Example 1

[0025] (1) ultrasonically dispersing 5 parts by weight of graphene oxide into 70 parts by weight of thionyl chloride, and after being evenly dispersed, reacting at 75° C. for 1 hour, and after the reaction, filtering, washing, and drying to obtain chlorinated graphene;

[0026] (2) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to a reaction kettle, introducing nitrogen for protection, and then continuing to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1:1.1:0.01, reacting at 65° C. for 2 hours, cooling and discharging after the reaction, to obtain a double-terminal epoxy silicone oil;

[0027] (3) adding 6 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 60° C., adding 7 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it at 70° C. for 6 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0028] (4) adding double-ended epoxy silicone oil and quaternized chitosan to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, quaternized chitosan, and boron trifluoride etherate catalyst is 0.6:1:0.01, reacting at 75° C. for 6 h, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain silane-modified chitosan;

[0029] (5) adding 7 parts by weight of chlorinated graphene to an ether solvent, stirring and dispersing, and then adding 5 parts by weight of silane-modified chitosan and 0.1 parts by weight of triethylamine catalyst, reacting at 60° C. for 6 hours, washing and drying after the reaction, to obtain graphene oxide-modified quaternary ammonium chitosan;

[0030] (6) Add 4 parts by weight of cardanol and 2 parts by weight of 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stir to dissolve, then continue to add an aqueous sodium hydroxide solution, react at 60° C. for 5 hours, and then dropwise add dilute hydrochloric acid to neutralize, concentrate to remove the solvent, filter, wash and dry to obtain an intermediate 1;

[0031] (7) Add 3 parts by weight of intermediate 1 and 5 parts by weight of epichlorohydrin to N,N-dimethylformamide solvent, stir and mix, react at 60° C. for 4 hours, and then perform reduced pressure distillation and washing to obtain epoxidized cardanol;

[0032] (8) Add 50 parts by weight of activated carbon powder, 3 parts by weight of epoxidized cardanol, 4 parts by weight of graphene oxide-modified quaternized chitosan, 2 parts by weight of bentonite, and 1 part by weight of nano-titanium dioxide into a grinding device and grind to 250 mesh to obtain a preliminary material A; then continue to add 0.8 parts by weight of an aqueous epoxy resin adhesive and 8 parts by weight of water, stir for 20 minutes, and dry to obtain an activated carbon material that adsorbs organic gases.

[0033] Example 2

[0034] (1) ultrasonically dispersing 7 parts by weight of graphene oxide into 95 parts by weight of thionyl chloride, and after being evenly dispersed, reacting at 90° C. for 3 hours, and after the reaction, filtering, washing, and drying to obtain chlorinated graphene;

[0035] (2) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to a reaction kettle, introducing nitrogen protection, and then continuing to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1:1.3:0.02, reacting at 85° C. for 6 hours, cooling and discharging after the reaction, and obtaining a double-terminal epoxy silicone oil;

[0036] (3) adding 8 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 90° C., adding 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it at 85° C. for 9 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0037] (4) adding double-ended epoxy silicone oil and quaternized chitosan to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, quaternized chitosan, and boron trifluoride etherate catalyst is 0.8:1:0.03, reacting at 95° C. for 12 h, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain silane-modified chitosan;

[0038] (5) adding 15 parts by weight of chlorinated graphene to an ether solvent, stirring and dispersing, and then adding 10 parts by weight of silane-modified chitosan and 0.2 parts by weight of triethylamine catalyst, reacting at 85° C. for 10 h, washing and drying after the reaction, to obtain graphene oxide-modified quaternary ammonium chitosan;

[0039] (6) Add 8 parts by weight of cardanol and 3 parts by weight of 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stir to dissolve, then continue to add an aqueous sodium hydroxide solution, react at 85° C. for 8 hours, and then dropwise add dilute hydrochloric acid to neutralize, concentrate to remove the solvent, filter, wash and dry to obtain an intermediate 1;

[0040] (7) Add 6 parts by weight of intermediate 1 and 12 parts by weight of epichlorohydrin to N,N-dimethylformamide solvent, stir and mix, react at 80° C. for 6 hours, and then distill under reduced pressure and wash to obtain epoxidized cardanol;

[0041] (8) 75 parts by weight of activated carbon powder, 6 parts by weight of epoxidized cardanol, 6 parts by weight of graphene oxide-modified quaternized chitosan, 5 parts by weight of bentonite, and 3 parts by weight of nano-titanium dioxide were added to a grinding device and ground to 350 mesh to obtain a preliminary material A; then 1 part by weight of an aqueous epoxy resin adhesive and 10 parts by weight of water were added thereto, stirred for 40 minutes, and dried to obtain an activated carbon material for adsorbing organic gases.

[0042] Example 3

[0043] (1) ultrasonically dispersing 6 parts by weight of graphene oxide into 85 parts by weight of thionyl chloride, and after being evenly dispersed, reacting at 82° C. for 23 hours, and after the reaction, filtering, washing, and drying to obtain chlorinated graphene;

[0044] (2) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to a reaction kettle, introducing nitrogen for protection, and then continuing to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1:1.2:0.01, reacting at 75° C. for 4 hours, cooling and discharging after the reaction, to obtain a double-terminal epoxy silicone oil;

[0045] (3) adding 7 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 80° C., adding 10 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it at 82° C. for 8 h, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan;

[0046] (4) adding double-ended epoxy silicone oil and quaternized chitosan to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, quaternized chitosan, and boron trifluoride etherate catalyst is 0.7:1:0.02, reacting at 85° C. for 10 h, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain silane-modified chitosan;

[0047] (5) adding 12 parts by weight of chlorinated graphene to an ether solvent, stirring and dispersing, and then adding 8 parts by weight of silane-modified chitosan and 0.1 parts by weight of triethylamine catalyst, reacting at 75° C. for 8 hours, washing and drying after the reaction, to obtain graphene oxide-modified quaternary ammonium chitosan;

[0048] (6) Add 6 parts by weight of cardanol and 2 parts by weight of 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stir to dissolve, then continue to add an aqueous sodium hydroxide solution, react at 75° C. for 6 hours, and then dropwise add dilute hydrochloric acid to neutralize, concentrate to remove the solvent, filter, wash and dry to obtain an intermediate 1;

[0049] (7) Add 5 parts by weight of intermediate 1 and 8 parts by weight of epichlorohydrin to N,N-dimethylformamide solvent, stir and mix, react at 70° C. for 5 h, and then perform vacuum distillation and washing to obtain epoxidized cardanol;

[0050] (8) Add 65 parts by weight of activated carbon powder, 5 parts by weight of epoxidized cardanol, 4 parts by weight of graphene oxide-modified quaternized chitosan, 5 parts by weight of bentonite, and 2 parts by weight of nano-titanium dioxide into a grinding device and grind to 280 mesh to obtain a preliminary material A; then continue to add 0.9 parts by weight of an aqueous epoxy resin adhesive and 9 parts by weight of water, stir for 30 minutes, and dry to obtain an activated carbon material that adsorbs organic gases.

[0051] Comparative Example 1

[0052] Compared with Example 3, this comparative example does not add epoxidized cardanol.

[0053] Comparative Example 2

[0054] Compared with Example 3, this comparative example does not add graphene oxide to modify the quaternary ammonium chitosan.

[0055] The activated carbon adsorption materials prepared in Examples 1-3 and Comparative Examples 1-2 were tested for formaldehyde and benzene adsorption capacity according to the industry standard LY / T3012-2018 "Activated Carbon for Indoor Air Purification". The test results are shown in Table 1;

[0056] Table 1: Tests for organic gases.

[0057]

[0058] It can be seen from Table 1 that Examples 1-3 of the present invention have better adsorption effects than Comparative Examples 1-2.

[0059] 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. An activated carbon material for adsorbing organic gas, characterized in that: The invention comprises the following components by weight: 50-75 parts by weight of activated carbon powder, 3-6 parts by weight of epoxidized cardanol, 4-6 parts by weight of graphene oxide modified quaternized chitosan, 2-5 parts by weight of bentonite, 1-3 parts by weight of nano titanium dioxide, 0.8-1 parts by weight of water-based epoxy resin adhesive, and 8-10 parts by weight of water; The preparation method of the graphene oxide modified quaternary ammonium chitosan is: (1) ultrasonically dispersing 5-7 parts by weight of graphene oxide into 70-95 parts by weight of thionyl chloride, and after uniform dispersion, heating to react for 1-3 hours, and after the reaction, filtering, washing, and drying to obtain chlorinated graphene; (2) Add octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introduce nitrogen protection, and then continue to add tetramethylammonium hydroxide catalyst, react at 65-85°C for 2-6 hours, cool and discharge after reaction, and obtain double-terminal epoxy silicone oil; (3) adding 6-8 parts by weight of chitosan to dimethyl sulfoxide solvent to dissolve it, heating it in a water bath at 60-90° C., adding 7-12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting for 6-9 hours, washing with anhydrous ethanol after the reaction, drying, dialyzing, and concentrating to obtain quaternized chitosan; (4) adding double-terminal epoxy silicone oil and quaternized chitosan to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride ether catalyst thereto, reacting at 75-95° C. for 6-12 hours, filtering after the reaction, washing with deionized water and ethanol in turn, and drying to obtain silane-modified chitosan; (5) Add 7-15 parts by weight of acylated graphene to ether solvent, stir and disperse, continue to add 5-10 parts by weight of silane-modified chitosan and 0.1-0.2 parts by weight of triethylamine catalyst, react at 60-85° C. for 6-10 hours, and after reaction, wash and dry to obtain graphene oxide-modified quaternary ammonium chitosan.

2. The activated carbon material for adsorbing organic gas according to claim 1, characterized in that: The reaction temperature in (1) is 75-90°C.

3. The activated carbon material for adsorbing organic gas according to claim 1, characterized in that: The mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst in (2) is 1:1.1-1.3:0.01-0.

02.

4. The activated carbon material for adsorbing organic gas according to claim 1, characterized in that: The reaction temperature in (3) is 70-85°C.

5. The activated carbon material for adsorbing organic gas according to claim 1, characterized in that: The mass ratio of the double-terminal epoxy silicone oil, quaternized chitosan and boron trifluoride etherate catalyst in (4) is 0.6-0.8:1:0.01-0.

03.

6. The activated carbon material for adsorbing organic gas according to claim 1, characterized in that: The preparation method of the epoxidized cardanol is: S1. Add 4-8 parts by weight of cardanol and 2-3 parts by weight of 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stir to dissolve, then continue to add an aqueous sodium hydroxide solution thereto, react at 60-85° C. for 5-8 hours, and after completion, dropwise add dilute hydrochloric acid to neutralize, concentrate to remove the solvent, filter, wash and dry to obtain an intermediate 1; S2. Add 3-6 parts by weight of intermediate 1 and 5-12 parts by weight of epichlorohydrin to N,N-dimethylformamide solvent, stir and mix, react at 60-80° C. for 4-6 hours, and then distill under reduced pressure and wash to obtain epoxidized cardanol.

7. A method for preparing an activated carbon material for adsorbing organic gas according to any one of claims 1 to 6, characterized in that: The preparation method of the activated carbon material for adsorbing organic gas is as follows: adding activated carbon powder, epoxidized cardanol, graphene oxide modified quaternized chitosan, bentonite, and nano titanium dioxide into a grinding device, grinding to 250-350 meshes to obtain a preliminary material A; then continuing to add a water-based epoxy resin adhesive and water thereto, stirring for 20-40 minutes, and drying to obtain the activated carbon material for adsorbing organic gas.

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