CN109835897B - Metal/heteroatom modified distiller's grain-based activated carbon and preparation method thereof - Google Patents
Metal/heteroatom modified distiller's grain-based activated carbon and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a metal/heteroatom modified spirit vinasse-based activated carbon and a preparation method thereof. The method comprises the following steps: (1) crushing the dried distiller's grains to 50-200 meshes, adding 2.5-20% of nitrogen-containing compound and 2-8% of transition metal compound in mass percent into a mortar, grinding and mixing uniformly, carbonizing the mixture at 600-900 ℃ for 1-3 h in a nitrogen atmosphere, soaking the carbonized activated carbon in acid for 5-15 h, filtering, washing and drying; (2) and (3) activating the carbonized activated carbon at the high temperature of 700-900 ℃ for 2-5 h in an activated gas atmosphere to obtain the metal/heteroatom modified distiller's grain-based activated carbon. The method is simple, convenient, quick and easy to operate, is suitable for industrial production, and the prepared modified vinasse-based activated carbon has a large specific surface area and a large pore diameter, is a high-efficiency catalyst and can effectively remove organic pollutants in water by catalytic oxidation.
Description
Technical Field
The invention belongs to the technical field of activated carbon preparation, and particularly relates to metal/heteroatom modified distiller's grain-based activated carbon and a preparation method thereof.
Background
With the rapid development of various industries such as chemical industry, pesticide, medicine, printing and dyeing and the like and the continuous promotion of the town integration process, the problem of organic matter pollution in water is increasingly prominent, and the organic matter pollution has a considerable potential toxic effect on water resources and human health. And the conventional sewage treatment process (activated sludge, elution, coagulation, membrane treatment, adsorption and the like) is difficult to effectively remove pollutants which are high in toxicity and difficult to biochemically degrade in the water body. The Fenton oxidation technology is a common advanced oxidation technology, and can deeply oxidize and degrade organic pollutants in a water body so as to remove the organic pollutants. However, the traditional Fenton technology has the problems of large sludge amount, difficult catalyst recovery and the like, and restricts the application and popularization of the technology. Therefore, more and more researches are being made on the use of activated carbon supported transition metals to make heterogeneous catalysts, to effectively achieve the catalyst recovery problem and to avoid the generation of sludge.
In the existing activated carbon supported transition metal catalyst, the problem that the activated metal is easy to dissolve out still exists, and a method for preparing the high-efficiency stable activated carbon supported transition metal catalyst is lacked. The invention takes vinasse as a biomass resource, adopts a blending mode to calcine the vinasse, transition metal and nitrogen-containing compounds at high temperature, and then utilizes a gas activation mode to obtain the metal/heteroatom modified vinasse-based activated carbon for oxidative degradation of organic pollutants in water. By utilizing the strong interaction between the transition metal and the nitrogen-containing precursor, the stability of the traditional catalyst can be improved, and the resource utilization of the bulk waste vinasse can be realized, thereby achieving two purposes at one stroke.
Disclosure of Invention
Aiming at the problems of organic wastewater treatment and the necessity of resource utilization of the distiller's grains, the invention provides the metal/heteroatom modified distiller's grain-based activated carbon and the preparation method thereof, and the metal/heteroatom modified distiller's grain-based activated carbon is used for catalytic oxidation degradation of organic pollutants in water and can effectively realize the reutilization of the distiller's grains.
The technical scheme adopted by the invention for preparing the metal/heteroatom modified distiller's grain-based activated carbon is as follows:
a preparation method of metal/heteroatom modified distiller's grain-based activated carbon comprises the following steps:
(1) mixing the dried and crushed white spirit vinasse with a nitrogen source and a metal compound, uniformly grinding, carbonizing at 600-900 ℃ for 1-3 h in a protective gas atmosphere, then soaking in acid liquor, filtering and drying to obtain carbonized active carbon;
(2) and (3) putting the carbonized activated carbon into activated gas at 700-900 ℃ for activation for 2-5 h to obtain the modified distiller's grain-based activated carbon.
Further, the grain diameter of the crushed white spirit vinasse in the step (1) is 50-200 meshes.
Furthermore, the weight of the nitrogen source is 2.5-14.5% of the total weight of the mixture.
Further, the nitrogen source in step (1) is dicyandiamide, melamine, ammonium chloride, urea, or the like.
Further, the weight of the metal compound is 2-8% of the total weight of the mixture.
Further, in the step (1), the metal compound is ferric chloride, ferric nitrate, nickel nitrate, cobalt chloride and the like.
Further, the concentration of the acid solution in the step (1) is 1-4 mol/L.
Further, the acid solution is hydrochloric acid or sulfuric acid.
Further, the activating gas in the step (2) is carbon dioxide or water vapor.
The activated carbon prepared by the method.
The invention has the beneficial effects that:
1. the method selects the distiller's grains as raw materials, mixes and grinds the distiller's grains, nitrogen sources (dicyandiamide, melamine, ammonium chloride, urea and the like) and metal compounds (ferric chloride, nickel nitrate, cobalt chloride and the like), and then carbonizes the mixture at high temperature, and then activates the mixture by adopting carbon dioxide or water vapor at high temperature to obtain the metal/heteroatom modified distiller's grain-based activated carbon
2. The specific surface area of the prepared metal/heteroatom modified white spirit vinasse-based activated carbon can reach 240m2More than g, total pore volume of 0.16cm3The pore size is concentrated and distributed at 3-4 nm, so that organic pollutants such as acid red, methyl orange and the like in the water body can be effectively degraded by persulfate oxidation under normal temperature and normal pressure, the removal rate reaches over 60 percent, and the removal rate of organic matters oxidized by persulfate alone is only about 10 percent.
Drawings
FIG. 1 is a representation of the activated carbon prepared in example 1; wherein, FIG. 1a is an aperture detection diagram; FIG. 1b is a graph showing nitrogen adsorption and desorption;
FIG. 2 is a representation of the activated carbon prepared in example 2; wherein, FIG. 2a is an aperture detection diagram; FIG. 2b is a graph showing nitrogen adsorption and desorption;
FIG. 3 is a graph representing the activated carbon prepared in example 3; wherein, FIG. 3a is an aperture detection diagram; FIG. 3b is a graph showing nitrogen adsorption and desorption;
FIG. 4 is a graph showing the tetracycline hydrochloride catalyzed degradation by activated carbon prepared in example 1;
FIG. 5 is a graph of the catalytic degradation of methyl orange by activated carbon prepared in example 2;
FIG. 6 is a graph showing the catalytic degradation of methylene blue by activated carbon prepared in example 3.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
Example 1
A preparation method of metal/heteroatom modified distiller's grain-based activated carbon comprises the following steps:
(1) crushing the dried distiller's grains to 50-100 meshes by using a crusher, then uniformly mixing 10g of distiller's grain powder, 0.3607g of ferric nitrate and 1.45g of melamine, fully grinding in a mortar, then placing the obtained mixture in a tubular furnace, calcining for 1h at 750 ℃ in a nitrogen atmosphere, and carbonizing;
(2) taking out the calcined activated carbon, cooling the calcined activated carbon to room temperature, and soaking the activated carbon in a hydrochloric acid solution with the concentration of 3mol/L for 12 hours;
(3) after soaking, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture at 100 ℃;
(4) and (3) putting the dried activated carbon in a carbon dioxide atmosphere at 800 ℃ for activation for 2 h.
The specific surface area and the pore structure property of the prepared activated carbon are characterized, and the result is shown in a figure 1a and a figure 1 b; wherein, FIG. 1a is a pore size distribution diagram, as can be seen from FIG. 1a, the pore size of the prepared activated carbon is intensively distributed in 3-4 nm, FIG. 1b is a nitrogen adsorption and desorption isotherm, as can be seen from FIG. 1b, at a relative partial pressure P/P0An obvious hysteresis loop exists between 0.4 and 0.9, which indicates that the synthesized doped carbon material is of a mesoporous structure. The specific surface area of the polymer was found to be 295.4m by analysis2(iv)/g, total pore volume 0.183cm3(g) mesoporous volume is 0.145cm3The obtained modified distiller's grains-based activated carbon has large specific surface area and pore volume.
Example 2
A preparation method of metal/heteroatom modified distiller's grain-based activated carbon comprises the following steps:
(1) crushing the dried distiller's grains to 100-200 meshes by using a crusher, then uniformly mixing 10g of distiller's grain powder, 0.3607g of cobalt nitrate and 0.65g of melamine, fully grinding in a mortar, then placing the obtained mixture in a tubular furnace, calcining for 1h at 750 ℃ in a nitrogen atmosphere, and carbonizing;
(2) taking out the calcined activated carbon, cooling the calcined activated carbon to room temperature, and soaking the activated carbon in a hydrochloric acid solution with the concentration of 3mol/L for 12 hours;
(3) after soaking, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture at 100 ℃;
(4) and (3) putting the dried activated carbon in a carbon dioxide atmosphere at 800 ℃ for activation for 2 h.
The specific surface area and the pore structure property of the prepared activated carbon are characterized, and the result is shown in a figure 2a and a figure 2 b; wherein, fig. 2a is a pore size distribution diagram, as can be seen from fig. 2a, the pore size of the prepared activated carbon is intensively distributed in the range of 3-4 nm, fig. 2b is a nitrogen adsorption and desorption isotherm, as can be seen from fig. 2b, an obvious hysteresis loop exists between the relative partial pressure P/P0 of 0.4-0.9, which indicates that the synthesized doped carbon material is of a mesoporous structure. The specific surface area is 248.5m by analysis2(iv)/g, total pore volume 0.169cm3(g) mesoporous volume is 0.123cm3The obtained modified distiller's grains-based activated carbon has large specific surface area and pore volume.
Example 3
A preparation method of metal/heteroatom modified distiller's grain-based activated carbon comprises the following steps:
(1) crushing the dried distiller's grains to 100-200 meshes by using a crusher, then uniformly mixing 10g of distiller's grain powder, 0.3607g of ferric nitrate and 2g of melamine, fully grinding in a mortar, then placing the obtained mixture in a tube furnace, calcining for 1h at 750 ℃ in a nitrogen atmosphere, and carbonizing;
(2) taking out the calcined activated carbon, cooling the calcined activated carbon to room temperature, and soaking the activated carbon in a hydrochloric acid solution with the concentration of 3mol/L for 12 hours;
(3) after soaking, carrying out suction filtration, washing the mixture to be neutral by using deionized water, and drying the mixture at 100 ℃;
(4) and (3) putting the dried activated carbon in a steam atmosphere at 900 ℃ for activation for 2 h.
The specific surface area and the pore structure property of the prepared activated carbon are characterized, and the result is shown in a figure 3a and a figure 3 b; wherein, fig. 3a is a pore size distribution diagram, as can be seen from fig. 3a, the pore size of the prepared activated carbon is intensively distributed at 3-4 nm, fig. 3b is a nitrogen adsorption and desorption isotherm, as can be seen from fig. 3b, an obvious hysteresis loop exists between the relative partial pressure P/P0 of 0.4-0.9, which indicates that the synthesized doped carbon material is of a mesoporous structure. The specific surface area was found to be 271.5m by analysis2(ii)/g, total pore volume 0.161cm3(g) mesoporous volume is 0.135cm3The obtained modified white spirit is shown in the specificationThe vinasse-based activated carbon has large specific surface area and pore volume.
Example 4
Experiments of catalyzing persulfate to degrade organic pollutants are carried out by respectively using the activated carbon prepared in the embodiments 1-3, and the experimental results are shown in the figures 4-6.
As shown in FIG. 4, it can be seen that compared with the oxidation of persulfate alone, the addition of activated carbon in example 1 significantly improves the efficiency of catalyzing sodium persulfate to degrade tetracycline hydrochloride, and the removal rate reaches over 10%, while the removal rate of persulfate alone is only 55%. The degradation experimental conditions were: the temperature is 30 ℃, the concentration of sodium persulfate is 1.2g/L, the addition of active carbon is 0.2g/L, and the initial concentration of tetracycline hydrochloride is 20 mg/L.
As shown in fig. 5, it can be seen that compared with the oxidation of persulfate alone, the addition of activated carbon in example 2 significantly improves the efficiency of catalyzing sodium persulfate to degrade methyl orange, and the removal rate reaches over 90%, while the removal rate of persulfate alone is only 12%. The degradation experimental conditions were: the temperature is 30 ℃, the concentration of sodium persulfate is 1.2g/L, the addition amount of active carbon is 0.2g/L, and the initial concentration of methyl orange is 100 mg/L.
As shown in fig. 6, it can be seen that compared with the oxidation of persulfate alone, the addition of activated carbon in example 3 significantly improves the efficiency of catalyzing sodium persulfate to degrade methylene blue, and the removal rate reaches over 75%, while the removal rate of persulfate alone is only 13%. The degradation experimental conditions were: the temperature is 30 ℃, the concentration of sodium persulfate is 1.2g/L, the addition of active carbon is 0.2g/L, and the initial concentration of methylene blue is 100 mg/L.
Claims (9)
1. A preparation method of metal/heteroatom modified distiller's grain-based activated carbon is characterized by comprising the following steps:
(1) mixing the dried and crushed white spirit vinasse with a nitrogen source and an iron, cobalt or nickel metal compound, uniformly grinding, carbonizing at 600-900 ℃ for 1-3 h in a nitrogen protective gas atmosphere, then soaking in acid liquor, filtering and drying to obtain carbonized active carbon;
the nitrogen source is dicyandiamide, melamine, ammonium chloride or urea;
(2) and (3) putting the carbonized activated carbon into activated gas at 700-900 ℃ for activation for 2-5 h to obtain the modified distiller's grain-based activated carbon.
2. The method for producing a metal/heteroatom-modified distiller's grain-based activated carbon as claimed in claim 1, wherein the grain size of the pulverized distiller's grain in step (1) is 50 to 200 mesh.
3. The method of making a metal/heteroatom-modified distillers' grains-based activated carbon as in claim 1, wherein the weight of the nitrogen source is 2.5-20% of the total weight of the mixture.
4. The method of making a metal/heteroatom-modified distillers' grains-based activated carbon as in claim 1, wherein the weight of the metal compound is 2-8% of the total weight of the mixture.
5. The method for producing a metal/heteroatom-modified distiller's grain-based activated carbon as claimed in claim 1 or 4, wherein the metal compound in the step (1) is ferric chloride, ferric nitrate, nickel nitrate, cobalt nitrate or cobalt chloride.
6. The method for producing a metal/heteroatom-modified distiller's grain-based activated carbon according to claim 1, wherein the concentration of the acid solution in the step (1) is 1 to 4 mol/L.
7. The method for producing a metal/heteroatom-modified distillers' grains-based activated carbon as claimed in claim 6, wherein the acid solution is hydrochloric acid or sulfuric acid.
8. The method for producing a metal/heteroatom-modified distiller's grain-based activated carbon as claimed in claim 1, wherein the activated gas in the step (2) is carbon dioxide or water vapor.
9. Activated carbon produced by the method of any one of claims 1 to 8.
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| CN110627037B (en) * | 2019-06-26 | 2021-07-06 | 陕西科技大学 | Preparation method of nitrogen-doped biomass porous carbon nano electrode material |
| CN110655169A (en) * | 2019-10-17 | 2020-01-07 | 威海中远造船科技有限公司 | Sewage treatment method for enhancing Fenton reaction by adopting activated carbon |
| CN111389368A (en) * | 2020-04-22 | 2020-07-10 | 徐州工程学院 | Preparation method of excess sludge biochar and application of excess sludge biochar in removing tetracycline in water |
| CN114849760B (en) * | 2022-06-08 | 2023-10-17 | 四川轻化工大学 | Catalyst and preparation method and application thereof |
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