CN111153401A - Hydrothermal-stepped dual activation preparation method of hierarchical porous active carbon gas adsorption material - Google Patents

Hydrothermal-stepped dual activation preparation method of hierarchical porous active carbon gas adsorption material Download PDF

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CN111153401A
CN111153401A CN201911370981.8A CN201911370981A CN111153401A CN 111153401 A CN111153401 A CN 111153401A CN 201911370981 A CN201911370981 A CN 201911370981A CN 111153401 A CN111153401 A CN 111153401A
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activated carbon
hydrothermal
gas adsorption
follows
hierarchical porous
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孙靖
孟祥奎
崔锦江
赵儒仕
冷冰
臧志刚
马瑶
姜琛昱
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Jinan Guoke Medical Engineering Technology Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation

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Abstract

The invention discloses a hydrothermal-stepped dual activation preparation method of a hierarchical porous activated carbon gas adsorption material. The specific process steps are as follows: fully mixing acid solutions with different volumes with the activated carbon raw material, then carrying out hydrothermal reaction under different conditions to obtain an activated carbon precursor, and then carrying out stepped dual activation reaction on the activated carbon precursor to obtain the hierarchical porous activated carbon gas adsorption material. The graded porous activated carbon material of the invention shows excellent gas adsorption performance when used for gas adsorption. The preparation method has the advantages of novelty, simple operation, low preparation cost, high product purity and the like.

Description

Hydrothermal-stepped dual activation preparation method of hierarchical porous active carbon gas adsorption material
Technical Field
The invention relates to a preparation method of a gas adsorption material, in particular to a preparation method of a hierarchical porous activated carbon gas adsorption material; belongs to the field of nanometer material.
Background
Adsorption is a common method for purifying gaseous pollutants, and is a method for separating one or more components in a gas or liquid mixture by gathering or condensing the components on the surface of the gas or liquid mixture by using a porous solid adsorbent, wherein a common adsorption material is porous activated carbon. The activated carbon as a typical adsorption material has the characteristics of high specific surface area, stable physical and chemical stability, good environmental compatibility, abundant raw material sources and the like, and compared with an MOF material, the activated carbon has good pore size distribution, so that the activated carbon is considered to be one of gas adsorption materials with great prospects. However, the controllability of the pore size distribution of the existing activated carbon material is low, the preparation process is complex, and the application of the activated carbon material in gas adsorption of complex components is seriously hindered.
In order to improve the pore size distribution of the activated carbon material, researchers have paid extensive attention to further improving the adsorption performance of the activated carbon material. At present, researchers at home and abroad have obtained porous activated carbon materials by various preparation methods (physical activation method, chemical activation method, physical-chemical activation method and the like), but most of the activated carbon materials prepared by the preparation methods still have the problems of uncontrollable pore size distribution and relatively low specific surface area. Li et al (nanomaterials,2019,9(2): 266) synthesize N-doped porous activated carbon material by KOH activation method using waste wool as raw materialExcellent performance in separating impurities from methane gas. Estevez et al (Industrial)&Engineering Chemistry Research,2018,57(4): 1262-1268) adopts sucrose as a carbon source and adopts a template method to synthesize the hierarchical porous carbon material, and the material shows good CO2Gas capture capability. Although the currently prepared activated carbon material has a high specific surface area, the pore size distribution of the activated carbon material is not reasonable for different gas molecules, so the activated carbon material has less application in the aspect of multi-component gas adsorption. The research of the binary adsorption capacity of the activated carbon by Cao Li et al finds that: the adsorption capacity of the organic matter in the binary system is reduced to different degrees compared with the single-component adsorption capacity under the same condition. Therefore, different pore size distributions of the activated carbon material are required for different components, different gas molecules.
Although activated carbon materials have been widely used in the adsorption field, their use in respiratory gases has been rarely reported. Therefore, the skilled person is dedicated to develop a hydrothermal-stepwise dual activation preparation method of a stone-graded porous activated carbon material, so as to obtain activated carbon materials with different pore size distributions, which can effectively adsorb interfering components in respiratory gas with complex components. The method has important scientific research significance and clinical application value.
Disclosure of Invention
The invention aims to overcome the defects of the existing pore size control and provide a simple and novel preparation method of the graded porous activated carbon material. When the activated carbon material prepared by the method is used as a breathing gas adsorption material, the removal capability of interference components in the breathing gas is greatly improved, and the problem that the interference components are difficult to remove in the breathing gas detection process is solved.
In order to achieve the aim, the invention provides a hydrothermal-stepped dual activation preparation method of a hierarchical porous activated carbon gas adsorption material. The technical solution of the invention is as follows: : fully mixing acid solutions with different volumes with the activated carbon raw material, then carrying out hydrothermal reaction under different conditions to obtain an activated carbon precursor, and then carrying out stepped dual activation reaction on the activated carbon precursor to obtain the hierarchical porous activated carbon gas adsorption material.
The preparation method of the hierarchical porous activated carbon material comprises the following specific steps:
(1) fully mixing acid solutions with different volume fractions with an active carbon raw material, and then carrying out hydrothermal reaction to obtain an active carbon precursor, wherein the hydrothermal reaction conditions are as follows: hydrothermal temperature: 120-200 ℃, hydrothermal time: 2-20 h;
(2) activating the obtained activated carbon precursor by a step-type double activation method, wherein the step-type double activation condition is as follows: a step temperature is: 100 ℃ and 600 ℃, the reaction time is as follows: 0.5-3 h; the second gradient temperature is 400-.
In the concrete implementation of the invention, the acid solution adopted in the hydrothermal reaction process is concentrated sulfuric acid, and the optimal condition of the hydrothermal reaction is reaction at 180 ℃ for 5.5 h.
In the preferred embodiment of the present invention, the preferred step-wise dual activation is a one-step reaction at 400 ℃ for 2 h; the reaction is carried out for 2h at 800 ℃ in two steps.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the invention only needs to carry out step-type double activation after hydrothermal reaction to obtain the activated carbon material, does not need other redox atmosphere, reagent and complex experimental device, has easily controlled conditions, simple process and low cost, and solves the difficult problems of complex conventional preparation process and uncontrollable aperture distribution.
(2) The hierarchical porous activated carbon material prepared by the method adopts agricultural wastes as a carbon source, has rich sources, effectively utilizes the original pore-size structure of the biomass raw material, improves the added value of the agricultural wastes, and solves the problem of environmental pollution caused by waste incineration to a great extent.
(3) The hierarchical porous activated carbon material prepared by the invention has the advantages of higher specific surface area, controllable pore size distribution structure and stable physicochemical property, and can effectively remove interference components in the respiratory gas detection process with complex components.
The conception, specific material structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the objects, features and effects of the present invention.
Drawings
FIG. 1 is an SEM image of a graded porous activated carbon material prepared in example 1 of the present invention;
FIG. 2 is a TEM image of a graded porous activated carbon material prepared in example 1 of the present invention (FIG. 2 is a transmission electron micrograph of a graded porous activated carbon adsorbent material);
FIG. 3 is a pore size distribution curve of a graded porous activated carbon material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the acetone detection result of the respiratory gas after the graded porous activated carbon material prepared in example 1 of the present invention adsorbs interfering components;
Detailed Description
The following examples are given for the detailed embodiments and specific procedures, but the scope of the present invention is not limited to the specific examples listed below.
Example 1
Firstly, respectively weighing 2mg of active carbon raw material (corncob powder) and 1.5ml of concentrated sulfuric acid, mixing the two raw materials, and stirring for 30min to ensure that the two raw materials are in full contact reaction; transferring the reacted substances into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal conditions are as follows: reacting for 5.5h at 180 ℃; and washing, centrifuging and drying the reactant after the hydrothermal reaction is finished. Then, putting the dried product into a tubular furnace to carry out stepped dual activation reaction, wherein the reaction conditions are as follows: a step temperature is: at 400 ℃, the reaction time is as follows: 2 h; the temperature of the two steps is 800 ℃, and the reaction time is 2 h. And finally, washing, centrifuging and drying the product after high-temperature activation, wherein the drying conditions are as follows: drying at 80 ℃ for 12h to obtain the graded porous active carbon adsorption material.
The SEM image of the obtained hierarchical porous activated carbon adsorbent is shown in fig. 1, and it can be seen from fig. 1 that the prepared hierarchical porous activated carbon adsorbent has a developed pore structure. FIG. 2 is a transmission electron microscope image of the prepared hierarchical porous activated carbon adsorbent material, in which a large number of worm-like structures are clearly seen on the prepared material, which illustrates that the microporous structure is developed; furthermore, from the TEM images we can see a distinct lattice fringe, indicating that it has a good graphitized structure. FIG. 3 is a graph showing the pore size distribution of the prepared hierarchical porous activated carbon adsorbent, and it can be seen that the material has a good hierarchical porous structure. FIG. 4 is a graph showing the measured acetone content in the respiratory gas after the respiratory gas is pretreated by the prepared hierarchical porous activated carbon adsorbing material. The breathing gas treated by the material can effectively remove the interference gas such as moisture and the like in the breathing gas, and the detection result can be accurate to ppm.
Example 2
Firstly, respectively weighing 2mg of active carbon raw material (corncob powder) and 0ml of concentrated sulfuric acid, mixing the two raw materials, and stirring for 30min to ensure that the raw materials are in full contact reaction; transferring the reacted substances into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal conditions are as follows: reacting for 2 hours at 120 ℃; and washing, centrifuging and drying the reactant after the hydrothermal reaction is finished. Then, putting the dried product into a tubular furnace to carry out stepped dual activation reaction, wherein the reaction conditions are as follows: a step temperature is: the reaction time is as follows at 200 ℃: 1 h; the temperature of the two steps is 600 ℃, and the reaction time is 2 h. And finally, washing, centrifuging and drying the product after high-temperature activation, wherein the drying conditions are as follows: drying for 12h at 100 ℃ to obtain the graded porous active carbon adsorption material.
Example 3
Firstly, respectively weighing 2mg of active carbon raw material (corncob powder) and 6ml of concentrated sulfuric acid, mixing the two raw materials, and stirring for 30min to ensure that the raw materials are in full contact reaction; transferring the reacted substances into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal conditions are as follows: reacting for 10 hours at 180 ℃; and washing, centrifuging and drying the reactant after the hydrothermal reaction is finished. Then, putting the dried product into a tubular furnace to carry out stepped dual activation reaction, wherein the reaction conditions are as follows: a step temperature is: the reaction time is as follows at 600 ℃: 2 h; the temperature of the two steps is 1000 ℃, and the reaction time is 2 h. And finally, washing, centrifuging and drying the product after high-temperature activation, wherein the drying conditions are as follows: drying for 24h at 60 ℃ to obtain the graded porous active carbon adsorption material.

Claims (6)

1. A hydrothermal-stepped dual activation preparation method of a hierarchical porous activated carbon gas adsorption material is characterized by comprising the following specific steps:
(1) fully mixing acid solutions with different volume fractions with the raw material of the activated carbon, and then carrying out hydrothermal reaction to obtain an activated carbon precursor;
(2) and (3) activating the obtained activated carbon precursor by a stepped dual activation method to prepare the hierarchical porous activated carbon gas adsorption material.
2. The method according to claim 1, wherein the acid solution used in step (1) is concentrated sulfuric acid, concentrated hydrochloric acid, or concentrated nitric acid.
3. The method according to claim 1, wherein the volume fraction of the acid solution in the step (1) is 0 to 6 ml.
4. The method according to claim 1, wherein the hydrothermal reaction in step (1) is carried out under the following conditions: hydrothermal temperature: 120-200 ℃, hydrothermal time: 2-20 h.
5. The method of claim 1, wherein the step-wise dual activation in step (2) is performed under the following conditions: a step temperature is: 100 ℃ and 600 ℃, the reaction time is as follows: 0.5-3 h; the second gradient temperature is 400-.
6. The method according to claim 2, wherein the washing and drying conditions after the activated carbon material is activated in the step (2) are as follows: washing reagent: dilute hydrochloric acid, deionized water and absolute ethyl alcohol; the drying temperature is as follows: 60-120 ℃; the drying time is as follows: 8-24 h.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101700489A (en) * 2009-12-14 2010-05-05 康明 Method for preparing coal-based activated carbon for water treatment
CN104724703A (en) * 2015-03-20 2015-06-24 福州大学 Method for preparing adsorptive activated carbon from Musaceae plants
CN106809834A (en) * 2017-04-13 2017-06-09 合肥工业大学 A kind of method that vacuum freeze drying prepares activated carbon from activated sludge
CN108516548A (en) * 2018-03-06 2018-09-11 合肥工业大学 A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition
KR101966229B1 (en) * 2017-11-06 2019-04-05 한국에너지기술연구원 Method for preparation of hierarchically porous nitrogen-doped carbon derived from biomass
CN110523379A (en) * 2019-09-25 2019-12-03 东北农业大学 A kind of low cost preparation method of porous charcoal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101700489A (en) * 2009-12-14 2010-05-05 康明 Method for preparing coal-based activated carbon for water treatment
CN104724703A (en) * 2015-03-20 2015-06-24 福州大学 Method for preparing adsorptive activated carbon from Musaceae plants
CN106809834A (en) * 2017-04-13 2017-06-09 合肥工业大学 A kind of method that vacuum freeze drying prepares activated carbon from activated sludge
KR101966229B1 (en) * 2017-11-06 2019-04-05 한국에너지기술연구원 Method for preparation of hierarchically porous nitrogen-doped carbon derived from biomass
CN108516548A (en) * 2018-03-06 2018-09-11 合肥工业大学 A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition
CN110523379A (en) * 2019-09-25 2019-12-03 东北农业大学 A kind of low cost preparation method of porous charcoal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘玉荣: "《碳材料在超级电容器中的应用》", 31 January 2013, 国防工业出版社 *
贾瑛等: "《轻质碳材料的应用》", 30 November 2013, 国防工业出版社 *

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