CN113209940B - Porous activated carbon composite material and preparation method thereof - Google Patents

Porous activated carbon composite material and preparation method thereof Download PDF

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Publication number
CN113209940B
CN113209940B CN202110680886.9A CN202110680886A CN113209940B CN 113209940 B CN113209940 B CN 113209940B CN 202110680886 A CN202110680886 A CN 202110680886A CN 113209940 B CN113209940 B CN 113209940B
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activated carbon
permanganate
cyclodextrin
stirring
deionized water
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CN113209940A (en
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冯向华
王金凤
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Jiangsu Qianhuihe Environmental Protection Recycling Co ltd
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Jiangsu Qianhuihe Environmental Protection Recycling Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

Abstract

The invention relates to the technical field of adsorption materials, in particular to a porous activated carbon composite material and a preparation method thereof. The porous activated carbon composite material is prepared by the following steps: (1) dissolving permanganate and cerium salt into deionized water, then adding activated carbon, and stirring and mixing for 10-20 min to obtain a mixed solution; (2) and (2) adding cyclodextrin and oxalate into the mixed solution in the step (1), stirring and reacting for 10-16 h at the temperature of 60-70 ℃, filtering, washing filter residues with deionized water, and drying at the temperature of 40-50 ℃ to obtain the cyclodextrin-oxalate composite material. According to the invention, the beta-cyclodextrin is added to complex permanganate and cerium salt into a large net structure and wrap active carbon molecules, so that the cerium salt can be exposed on the surfaces of the active carbon molecules, thereby improving the oxygen storage capacity and better improving the formaldehyde oxidation reaction rate of manganese oxide.

Description

Porous activated carbon composite material and preparation method thereof
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a porous activated carbon composite material and a preparation method thereof.
Background
Formaldehyde (HCHO) is a common volatile organic compound in indoor air and seriously harms human health, so that the method has very important research significance on removal and treatment of formaldehyde pollution in the indoor air. The main component used for the filter screen of the air purifier is activated carbon, formaldehyde is removed mainly by adsorption to a pure activated carbon filter material, the service life is limited by adsorption saturation, and once the activated carbon reaches the adsorption saturation, toxic substances can be generated to harm human health. Research shows that the formaldehyde can be completely converted into nontoxic and harmless CO by catalytic oxidation technology 2 And H 2 And O, the process can be realized at normal temperature without additional energy input, and has important significance for prolonging the service life of the filter screen, so that the formaldehyde catalytic oxidation technology is widely concerned by various social circles.
At present, researches on the treatment of formaldehyde by an adsorption method are more and more at home and abroad, common adsorbents comprise activated carbon, diatomite and the like, and although the existing adsorbent has large adsorption capacity, the existing adsorbent has high price, short service life and high operation cost, so that the search for the adsorbent with more excellent adsorption performance and low price is the direction of continuous research in the field.
Based on the situation, the invention provides a porous activated carbon composite material and a preparation method thereof, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a porous activated carbon composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides a porous activated carbon composite, which is prepared by a method comprising the steps of:
(1) dissolving permanganate and cerium salt into deionized water, adding activated carbon, and stirring and mixing for 10-20 min to obtain a mixed solution, wherein the mass ratio of the permanganate to the cerium salt is m Mn ：m Ce 4-6, and the mass ratio of the activated carbon to the permanganate is 8-12;
(2) adding cyclodextrin and oxalate into the mixed solution obtained in the step (1), stirring and reacting for 10-16 h at the temperature of 60-70 ℃, filtering, washing filter residues with deionized water, and drying at the temperature of 40-50 ℃ to obtain the product, wherein the mass ratio of the oxalate to the permanganate is 1-2, and the mass ratio of the cyclodextrin to the permanganate is 3-4.
Preferably, the cyclodextrin is one or the combination of more than two of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Preferably, the cyclodextrin is beta-cyclodextrin, including one or a combination of two or more of sulfobutyl-beta-cyclodextrin, trimethyl-beta-cyclodextrin, 2-hydroxyethyl-beta-cyclodextrin and 2-hydroxypropyl-beta-cyclodextrin.
Preferably, the cyclodextrin is 2-hydroxyethyl- β -cyclodextrin.
Preferably, the permanganate is one or two of potassium permanganate and sodium permanganate.
Preferably, the cerium salt is one or a combination of more than two of cerium acetate, cerium nitrate, cerium sulfate and cerium chloride.
Preferably, the activated carbon is one or a combination of more than two of nutshell, coal or wood granular activated carbon.
Preferably, the oxalate is one or a combination of two or more of sodium oxalate, potassium oxalate, ammonium oxalate and ferric oxalate.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the beta-cyclodextrin is added to complex permanganate and cerium salt into a large net structure and wrap active carbon molecules, so that the cerium salt can be exposed on the surfaces of the active carbon molecules, thereby improving the oxygen storage capacity and better improving the formaldehyde oxidation reaction rate of manganese oxide.
2. The raw materials of the invention are sufficient in China and proper in price, so that the large-scale production of the invention is not limited by too high cost; meanwhile, the preparation method is simple, the total production cost is low, and the industrial large-scale production is facilitated.
Detailed Description
Example 1
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 10min to obtain a mixed solution;
(2) and (2) adding 2-hydroxyethyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at the temperature of 60 ℃, filtering, washing filter residues with deionized water, and drying at the temperature of 40 ℃ to obtain the product.
Example 2
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding 2-hydroxyethyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 10 hours at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the product.
Example 3
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding 2-hydroxyethyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the product.
Comparative example 1
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding alpha-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the alpha-cyclodextrin potassium oxalate-containing water-soluble organic silicon dioxide.
Comparative example 2
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding gamma-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the compound.
Comparative example 3
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding sulfobutyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the product.
Comparative example4
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding trimethyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16 hours at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the sodium oxalate-beta-cyclodextrin solid solution.
Comparative example 5
The specific raw materials were weighed as in table 1, and the preparation steps were as follows:
(1) dissolving potassium permanganate and cerium nitrate into deionized water, then adding coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding 2-hydroxypropyl-beta-cyclodextrin and potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the compound.
TABLE 1
Kind of material Potassium permanganate Cerium nitrate Activated carbon Oxalic acid potassium salt Cyclodextrin Deionized water
Example 1 2g 1g 24g 4g 8g 100ml
Example 2 2g 0.75g 20g 3g 6g 100ml
Example 3 2g 0.5g 16g 2g 6g 100ml
Comparative example 1 2g 0.5g 16g 2g 6g 100ml
Comparative example 2 2g 0.5g 16g 2g 6g 100ml
Comparative example 3 2g 0.5g 16g 2g 6g 100ml
Comparative example 4 2g 0.5g 16g 2g 6g 100ml
Comparative example 5 2g 0.5g 16g 2g 6g 100ml
Example 4 Formaldehyde removal test
And (3) adopting an online dynamic detection system to evaluate the formaldehyde removal efficiency of the activated carbon composite materials prepared in the embodiments and the comparative examples. The initial concentration of the test formaldehyde is 100ppm, and the total flow of the test gas is 500m 3 H is used as the reference value. The test results are shown in Table 2.
Table 2 formaldehyde removal test
Original formaldehyde concentration Formaldehyde concentration after 120min Conversion of Formaldehyde
Example 1 100ppm 4ppm 96％
Example 2 100ppm 6ppm 94％
Example 3 100ppm 5ppm 95％
Comparative example 1 100ppm 18ppm 82％
Comparative example 2 100ppm 21ppm 79％
Comparative example 3 100ppm 14ppm 86％
Comparative example 4 100ppm 16ppm 84％
Comparative example 5 100ppm 10ppm 90％
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (5)

1. A preparation method of a porous activated carbon composite material is characterized in that the porous activated carbon composite material is prepared by the following steps:
(1) dissolving permanganate and cerium salt into deionized water, adding activated carbon, and stirring and mixing for 10-20 min to obtain a mixed solution, wherein the mass ratio of the permanganate to the cerium salt is m Mn ：m Ce 4-6, and the mass ratio of the activated carbon to the permanganate is 8-12;
(2) adding 2-hydroxyethyl-beta-cyclodextrin and oxalate into the mixed solution obtained in the step (1), stirring and reacting for 10-16 h at the temperature of 60-70 ℃, filtering, washing filter residues with deionized water, and drying at the temperature of 40-50 ℃ to obtain the product, wherein the mass ratio of the oxalate to the permanganate is 1-2, and the mass ratio of the 2-hydroxyethyl-beta-cyclodextrin to the permanganate is 3-4.
2. The method according to claim 1, wherein the permanganate is one or both of potassium permanganate and sodium permanganate.
3. The method according to claim 1, wherein the cerium salt is one or a combination of two or more of cerium acetate, cerium nitrate, cerium sulfate and cerium chloride.
4. The method according to claim 1, wherein the activated carbon is one or a combination of two or more of husk, coal, and wood-based granular activated carbon.
5. A method as claimed in claim 1 wherein the porous activated carbon composite is produced by the method comprising the steps of:
(1) dissolving 2g of potassium permanganate and 0.5g of cerous nitrate into 100ml of deionized water, then adding 16g of coconut shell activated carbon, and stirring and mixing for 20min to obtain a mixed solution;
(2) and (2) adding 6g of 2-hydroxyethyl-beta-cyclodextrin and 2g of potassium oxalate into the mixed solution in the step (1), stirring and reacting for 16h at 70 ℃, filtering, washing filter residues with deionized water, and drying at 50 ℃ to obtain the compound.
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Citations (8)

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CN103877945A (en) * 2014-04-08 2014-06-25 云南省玉溪市溶剂厂有限公司 Preparation method of biological binary composite adsorbent in glycerol triacetate refinement process
CN107961663A (en) * 2017-11-20 2018-04-27 广州市奥因环保科技有限公司 Formaldehyde eliminating smell agent
CN108686648A (en) * 2018-04-13 2018-10-23 浙江清华长三角研究院 A kind of preparation method and application of carried active carbon ozone catalyst
CN109304144A (en) * 2018-12-08 2019-02-05 广州绿美环保科技有限公司 A kind of reagent removing formaldehyde and compound smell
CN109304145A (en) * 2018-12-08 2019-02-05 广州绿美环保科技有限公司 A kind of reagent removing formaldehyde
CN109331605A (en) * 2018-11-20 2019-02-15 成都新柯力化工科技有限公司 A kind of lignin-base removes air formaldehyde material and preparation method
CN111569864A (en) * 2020-05-27 2020-08-25 珠海格力电器股份有限公司 Activated carbon composite material for catalytic purification of formaldehyde and preparation method thereof
CN111686701A (en) * 2020-06-17 2020-09-22 李伟 Carboxymethyl chitosan-cyclodextrin-activated carbon composite material and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11345615B2 (en) * 2019-11-13 2022-05-31 King Fahd University Of Petroleum And Minerals Activated carbon-iron/cerium oxide nanocomposite suitable for dye removal

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103877945A (en) * 2014-04-08 2014-06-25 云南省玉溪市溶剂厂有限公司 Preparation method of biological binary composite adsorbent in glycerol triacetate refinement process
CN107961663A (en) * 2017-11-20 2018-04-27 广州市奥因环保科技有限公司 Formaldehyde eliminating smell agent
CN108686648A (en) * 2018-04-13 2018-10-23 浙江清华长三角研究院 A kind of preparation method and application of carried active carbon ozone catalyst
CN109331605A (en) * 2018-11-20 2019-02-15 成都新柯力化工科技有限公司 A kind of lignin-base removes air formaldehyde material and preparation method
CN109304144A (en) * 2018-12-08 2019-02-05 广州绿美环保科技有限公司 A kind of reagent removing formaldehyde and compound smell
CN109304145A (en) * 2018-12-08 2019-02-05 广州绿美环保科技有限公司 A kind of reagent removing formaldehyde
CN111569864A (en) * 2020-05-27 2020-08-25 珠海格力电器股份有限公司 Activated carbon composite material for catalytic purification of formaldehyde and preparation method thereof
CN111686701A (en) * 2020-06-17 2020-09-22 李伟 Carboxymethyl chitosan-cyclodextrin-activated carbon composite material and application thereof

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