CN113398893A - Preparation method and application of biomass-based polymer modified carbon material - Google Patents

Preparation method and application of biomass-based polymer modified carbon material Download PDF

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CN113398893A
CN113398893A CN202110537473.5A CN202110537473A CN113398893A CN 113398893 A CN113398893 A CN 113398893A CN 202110537473 A CN202110537473 A CN 202110537473A CN 113398893 A CN113398893 A CN 113398893A
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biomass
carbon material
based polymer
modified carbon
room temperature
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CN113398893B (en
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胡勋
孙恺
孙艺凡
邵月文
张丽君
明丛
李庆银
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University of Jinan
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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
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Abstract

The invention relates to the technical field of carbon material preparation, in particular to a preparation method and application of a biomass-based polymer modified carbon material. The carbon material is applied to adsorbing heavy metal ions in water at room temperature. Adding 50mg of biomass-based polymer modified carbon material into 100mg/L aqueous solution of chromium (III) chloride, and after 6 hours at room temperature, adding Cr3+The removal rate of (2) was 99.9%.

Description

Preparation method and application of biomass-based polymer modified carbon material
Technical Field
The invention relates to a preparation method and application of a biomass-based polymer modified carbon material.
Background
The problem of heavy metal pollution of water bodies in China is increasingly serious, and waste water with excessive heavy metal ion content such as chromium, mercury, lead, copper and the like can enter organisms through the water bodies, soil, food chains and the like to be continuously enriched, so that serious harm is caused to human health and social development. The main methods for removing heavy metal ions include adsorption, chemical precipitation, ion exchange, membrane separation, flocculation, etc. Among them, the adsorption method is often used for adsorbing heavy metal ions in water because of its characteristics of low cost and simple operation. For natural adsorption materials, such as zeolite, kaolinite, coal ash, etc., the adsorption capacity cannot be adjusted, the reutilization performance is poor, and the application is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a biomass modified carbon material and application of the biomass modified carbon material in heavy metal ion adsorption.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a biomass-based polymer modified carbon material is characterized by comprising the following steps:
(1) adding 1-5 parts by mass of saccharides into 10-50 parts by mass of alcohols, uniformly stirring at room temperature, putting into a high-pressure reaction kettle, introducing 3-5MPa nitrogen, heating to 220 ℃ at 160-5 MPa for 4-10h, and cooling to room temperature to obtain a soluble polymer solution;
(2) adding 5-10 parts by mass of biomass coke into the polymer solution in the step (1), uniformly stirring at room temperature, heating to 50-80 ℃, stirring in a water bath for 4-8 hours, and evaporating the solvent to dryness to obtain a black solid;
(3) and (3) putting the black solid into a tubular furnace, calcining for 1-4h at the temperature of 210-310 ℃ in a nitrogen atmosphere, and taking out the black solid after cooling to obtain the biomass-based polymer modified carbon material.
The biomass-based polymer modified carbon material is characterized in that the saccharide in the step (1) is one of xylose, glucose, fructose and inulin.
The biomass-based polymer-modified carbon material according to claim 1, wherein the alcohol in step (1) is one of methanol, ethanol and isopropanol.
The biomass-based polymer modified carbon material is characterized in that the preparation method of the biomass coke in the step (2) comprises the following steps: 5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke.
The application of the biomass-based polymer modified carbon material is characterized in that the biomass-based polymer modified carbon material is applied to adsorbing heavy metal ions in water at room temperature. Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+The removal rate was calculated.
The preparation method of the invention has the following advantages and beneficial effects:
the biomass-based polymer modified carbon material developed by the invention has strong ability of adsorbing heavy metal ions because the modification of the carbohydrate-derived polymer introduces more electron-rich groups such as hydroxyl groups on the surface of the carbon.
Drawings
FIG. 1 is the specific surface area and Cd of biomass-based polymer modified carbon materials of examples 1-6 of the present invention2+The removal rate of (3).
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Comparative example 1
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. The specific surface area of the sample was 251.2m when measured by a physical adsorption apparatus2(ii) in terms of/g. Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate was 38.5%.
Example 1
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 5g of xylose into 50 g of ethanol, uniformly stirring at room temperature, then placing into a high-pressure reaction kettle, introducing 5MPa of nitrogen, heating to 220 ℃ for 4h, and cooling to room temperature to obtain a soluble polymer solution. And adding 5g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 80 ℃, stirring in a water bath for 8 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tube furnace, calcining for 2h at 210 ℃ in a nitrogen atmosphere, and taking out the black solid after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the sample was 459.9m when measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate of 89.9%.
Example 2
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 1g of xylose into 20 g of methanol, uniformly stirring at room temperature, then placing into a high-pressure reaction kettle, introducing 3MPa of nitrogen, heating to 160 ℃ for 10 hours, and cooling to room temperature to obtain a soluble polymer solution. And adding 5g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 50 ℃, stirring in a water bath for 4 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tube furnace, calcining for 4h at 310 ℃ in a nitrogen atmosphere, and taking out the black solid after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the sample was 480.5m when measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal was 91.2%.
Example 3
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Will be provided withAdding 2.6g of xylose into 10g of isopropanol, uniformly stirring at room temperature, then placing into a high-pressure reaction kettle, introducing 4MPa of nitrogen, heating to 200 ℃ for 6 hours, and cooling to room temperature to obtain a soluble polymer solution. And adding 10g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 70 ℃, stirring in a water bath for 6 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tubular furnace, calcining for 1h at 260 ℃ in a nitrogen atmosphere, and taking out after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the sample was 519.1m when measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate was 96.7%.
Example 4
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 2.6g of xylose into 10g of ethanol, uniformly stirring at room temperature, then placing into a high-pressure reaction kettle, introducing 4MPa of nitrogen, heating to 200 ℃ for 6 hours, and cooling to room temperature to obtain a soluble polymer solution. And adding 10g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 70 ℃, stirring in a water bath for 6 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tubular furnace, calcining for 1h at 260 ℃ in a nitrogen atmosphere, and taking out after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the sample was 540.3m as measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate was 99.9%.
Example 5
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 2.6g glucose into 10g ethanol, stirring at room temperature, placing into a high pressure reaction kettle, introducing 4MPa nitrogen, heating to 200 deg.C for 6 hr, cooling to room temperature to obtain soluble polymerAnd (4) solution. And adding 10g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 70 ℃, stirring in a water bath for 6 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tubular furnace, calcining for 1h at 260 ℃ in a nitrogen atmosphere, and taking out after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the powder was 508.4m as measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal was 95.4%.
Example 6
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 2.6g of fructose into 10g of ethanol, stirring uniformly at room temperature, then placing into a high-pressure reaction kettle, introducing 4MPa of nitrogen, heating to 200 ℃ for 6 hours, and cooling to room temperature to obtain a soluble polymer solution. And adding 10g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 70 ℃, stirring in a water bath for 6 hours, and evaporating the solvent to dryness to obtain a black solid. And (3) putting the black solid into a tubular furnace, calcining for 1h at 260 ℃ in a nitrogen atmosphere, and taking out after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area is 450.2m by using a physical adsorption instrument2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate was 89.5%.
Example 7
5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke. Adding 2.6g of inulin into 10g of ethanol, stirring uniformly at room temperature, putting into a high-pressure reaction kettle, introducing 4MPa nitrogen, heating to 200 ℃, and cooling to room temperature to obtain a soluble polymer solution. And adding 10g of biomass coke into the polymer solution, uniformly stirring at room temperature, heating to 70 ℃, stirring in a water bath for 6 hours, and evaporating the solvent to dryness to obtain a black solid. Black color will beAnd putting the solid into a tubular furnace, calcining for 1h at 260 ℃ in a nitrogen atmosphere, and taking out after cooling to obtain the biomass-based polymer modified carbon material. The specific surface area of the resulting dispersion was 499.4m when measured by a physical adsorption apparatus2/g；
Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+Calculated removal rate was 94.6%.

Claims (6)

1. A preparation method of a biomass-based polymer modified carbon material is characterized by comprising the following steps:
adding 1-5 parts by mass of saccharides into 10-50 parts by mass of alcohols, uniformly stirring at room temperature, putting into a high-pressure reaction kettle, introducing 3-5MPa nitrogen, heating to 220 ℃ at 160-5 MPa for 4-10h, and cooling to room temperature to obtain a soluble polymer solution;
adding 5-10 parts by mass of biomass coke into the polymer solution in the step (1), uniformly stirring at room temperature, heating to 50-80 ℃, stirring in a water bath for 4-8 hours, and evaporating the solvent to dryness to obtain a black solid;
and (3) putting the black solid into a tubular furnace, calcining for 1-4h at the temperature of 210-310 ℃ in a nitrogen atmosphere, and taking out the black solid after cooling to obtain the biomass-based polymer modified carbon material.
2. The biomass-based polymer-modified carbon material according to claim 1, wherein the saccharide in step (1) is one of xylose, glucose, fructose and inulin.
3. The biomass-based polymer-modified carbon material according to claim 1, wherein the alcohol in step (1) is one of methanol, ethanol and isopropanol.
4. The biomass-based polymer-modified carbon material according to claim 1, wherein the biomass char in the step (2) is prepared by: 5g of sawdust is put into a tube furnace and calcined for 2h at 500 ℃ under the atmosphere of argon, and the solid obtained is the biomass coke.
5. Use of a biomass-based polymer modified carbon material according to claim 1, wherein the carbon material is used for adsorbing heavy metal ions in water at room temperature.
6. Adding 50mg of biomass-based polymer modified carbon material into a chromium (III) chloride aqueous solution with the mass concentration of 100mg/L, stirring at room temperature for 6 hours, and sampling Cr in a test solution3+The removal rate was calculated.
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Publication number Priority date Publication date Assignee Title
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CN102219204A (en) * 2011-03-16 2011-10-19 吉林大学 Preparation method of biomass-based colloidal carbon
CN103801265A (en) * 2014-02-28 2014-05-21 东北林业大学 Method for preparing spherical carbon heavy metal adsorbent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824097A (en) * 2010-03-29 2010-09-08 天津科技大学 Method for producing polyglucose
CN102219204A (en) * 2011-03-16 2011-10-19 吉林大学 Preparation method of biomass-based colloidal carbon
CN102179228A (en) * 2011-04-15 2011-09-14 华东理工大学 Method for preparing carbon adsorbing material used for efficiently removing harmful ions from waste water
CN103801265A (en) * 2014-02-28 2014-05-21 东北林业大学 Method for preparing spherical carbon heavy metal adsorbent

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