CN110586161A - Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst - Google Patents
Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst Download PDFInfo
- Publication number
- CN110586161A CN110586161A CN201910896284.XA CN201910896284A CN110586161A CN 110586161 A CN110586161 A CN 110586161A CN 201910896284 A CN201910896284 A CN 201910896284A CN 110586161 A CN110586161 A CN 110586161A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nitrogen
- silicon dioxide
- nonmetal
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 24
- 230000000593 degrading effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000011592 zinc chloride Substances 0.000 claims abstract description 26
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229920000767 polyaniline Polymers 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- 239000002351 wastewater Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/618—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
A preparation method of a nonmetal catalyst for efficiently degrading phenol comprises the following steps: adding 10-40 wt.% of nitrogen precursor, 10-40 wt.% of silicon dioxide and 40-60 wt.% of zinc chloride into 100-500 mml of distilled water according to mass percent, and uniformly stirring and mixing to obtain a suspension solution; heating and stirring the obtained suspension at a set temperature for a set time to obtain a nitrogen precursor, silicon dioxide and zinc chloride solid compound; carrying out pyrolysis reaction on the obtained solid compound at a set temperature for a set time to obtain a carbonized compound; after the obtained product is carbonizedThe compound of (2) is subjected to alkali washing; and centrifuging the solution subjected to alkali washing, and drying in vacuum to obtain the nitrogen-doped hierarchical pore carbon material, namely the target catalyst. The specific surface area of the catalyst is 1000m2More than g. The invention has simple process, easily obtained raw materials and low cost. The prepared catalyst has high efficiency of catalyzing and degrading phenol at normal temperature, does not need to raise the system temperature, and can save energy consumption.
Description
Technical Field
The invention relates to a preparation method of a nonmetal catalyst. In particular to a preparation method of a nonmetal catalyst for efficiently degrading phenol and the catalyst.
Background
In recent years, with the continuous progress of industrialization in China, the discharge of organic wastewater becomes one of the important problems facing nowadays. Among them, phenol-containing wastewater is one of the major solutions in the control of water pollution in our country because of its high toxicity and high pollution as the main wastewater generated in the petrochemical industry. The discharge standard of the primary and secondary waste water can not exceed 0.5mg L, and the phenolic substances are second pollutants which are clearly specified in the Integrated wastewater discharge Standard of China (GB8978-1996)–1The third level standard should not exceed 2.0mg L–1. Therefore, how to reduce the concentration of phenol in an aqueous environment is a very urgent task.
At present, methods for treating organic wastewater mainly comprise an adsorption method, an evaporation concentration method, an activated sludge method and the like, but phenol cannot be completely degraded. Advanced oxidation technologies have attracted increased attention because of their ability to completely degrade contaminants. However, the catalyst of the traditional advanced oxidation technology generally contains metal or metal oxide, and has the defects of toxic metal penetration, high treatment cost, easy generation of secondary pollution and the like to different degrees. Therefore, how to prepare cheap non-metallic materials without secondary pollution for advanced oxidation technology is receiving wide attention.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a nonmetal catalyst for efficiently degrading phenol, which has the advantages of simple process, easily obtained raw materials, low cost and high efficiency of catalyzing and degrading phenol, and the catalyst.
The technical scheme adopted by the invention is as follows: a preparation method of a nonmetal catalyst for efficiently degrading phenol comprises the following steps:
1) adding 10-40 wt.% of nitrogen precursor, 10-40 wt.% of silicon dioxide and 40-60 wt.% of zinc chloride into 100-500 mml of distilled water according to mass percent, and uniformly stirring and mixing to obtain a suspension solution;
2) heating and stirring the obtained suspension at a set temperature for a set time to obtain a nitrogen precursor, silicon dioxide and zinc chloride solid compound;
3) carrying out pyrolysis reaction on the obtained solid compound at a set temperature for a set time to obtain a carbonized compound;
4) performing alkali washing on the obtained carbonized compound;
5) and centrifuging the solution subjected to alkali washing, and drying in vacuum to obtain the nitrogen-doped hierarchical pore carbon material, namely the target catalyst.
The nitrogen precursor in the step 1) is more than one of polyaniline, polyacrylonitrile, urea and melamine.
The mass ratio of the silicon dioxide to the nitrogen-containing precursor in the step 1) is 0.25-4: 1.
the set temperature in the step 2) is 50-90 ℃, and the set time is 5-10 h.
The pyrolysis reaction time in the step 3) is 0.5-4 h, and the reaction temperature is 400-1000 ℃.
The alkali used for alkali washing in the step 4) is one of potassium hydroxide and sodium hydroxide, the concentration is 1-10M, and the alkali washing time is 4-10 h.
The rotating speed of the centrifugation in the step 5) is 8000-15000 rpm, and the drying temperature is 60-150 ℃.
The catalyst prepared by adopting the preparation method of the nonmetal catalyst for efficiently degrading phenol has the specific surface area of 1000m2More than g.
The preparation method of the nonmetal catalyst for efficiently degrading phenol and the catalyst have the advantages of simple process, easily obtained raw materials, low cost and high efficiency of catalyzing and degrading phenol. Can solve the problems of low degradation efficiency, high treatment cost and easy generation of secondary pollution of the metal catalyst in the prior advanced oxidation technology. The catalyst prepared by the method has obvious catalytic effect at normal temperature, does not need to raise the system temperature, and can save energy consumption. The invention has the following beneficial effects:
1. cheap and easily available raw materials are used as the nitrogen-containing precursor, and the preparation method is low in cost and simple and feasible.
2. The nitrogen-doped hierarchical porous carbon material prepared by the method is used as a catalyst, has an obvious catalytic degradation effect on phenol, can be completely degraded within 10min, and is beneficial to further application of carbon nano materials in the field of environment-friendly water treatment.
3. The catalyst prepared by the method does not contain metal, and cannot cause secondary pollution to water.
Drawings
FIG. 1 is an SEM image of a non-metallic catalyst prepared in example 1 of the present invention;
FIG. 2 shows a non-metallic catalyst N prepared in example 1 of the present invention2Adsorption-removal of attached figures;
FIG. 3 is a graph showing the change of the concentration of phenol solution in different periods of time when phenol is degraded by using the nonmetal catalyst prepared by the method of the present invention.
Detailed Description
The following provides a detailed description of the preparation method of the nonmetal catalyst for degrading phenol with high efficiency and the catalyst thereof, which are provided by the invention, with reference to the examples and the accompanying drawings.
The invention relates to a preparation method of a nonmetal catalyst for efficiently degrading phenol, which comprises the following steps:
1) adding 10-40 wt.% of nitrogen precursor, 10-40 wt.% of silicon dioxide and 40-60 wt.% of zinc chloride into 100-500 mml of water solution according to mass percent, and uniformly stirring and mixing to obtain a suspension solution; wherein the content of the first and second substances,
the nitrogen precursor is more than one of polyaniline, polyacrylonitrile, urea and melamine. The mass ratio of the silicon dioxide to the nitrogen-containing precursor is 0.25-4: 1.
2) heating and stirring the obtained suspension at a set temperature for a set time to obtain a nitrogen precursor, silicon dioxide and zinc chloride solid compound; wherein the set temperature is 50-90 ℃, and the set time is 5-10 h.
3) Carrying out pyrolysis reaction on the obtained solid compound at a set temperature for a set time to obtain a carbonized compound; wherein the pyrolysis reaction time is 0.5-4 h, and the reaction temperature is 400-1000 ℃.
4) Performing alkali washing on the obtained carbonized compound; the alkali used for alkali washing is one of potassium hydroxide and sodium hydroxide, the concentration is 1-10M, and the alkali washing time is 4-10 h.
5) And centrifuging the solution subjected to alkali washing, and drying in vacuum to obtain the nitrogen-doped hierarchical pore carbon material, namely the target catalyst. Wherein the rotating speed of the centrifugation is 8000-15000 rpm, and the drying temperature is 60-150 ℃.
The catalyst prepared by the preparation method of the nonmetal catalyst for efficiently degrading phenol has the specific surface area of 1000m2More than g.
Specific examples are given below:
example 1
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.5: 1, adding 0.2g of silicon dioxide, 0.4g of polyacrylonitrile and 0.4g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing at 10000rpm for 10min, and performing vacuum drying at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
The SEM image of the prepared non-metal catalyst is shown in figure 1; prepared non-metal catalyst N2Adsorption-desorption is illustrated in figure 2.
Example 2
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.25: 1, adding 0.1g of silicon dioxide, 0.4g of polyacrylonitrile and 0.5g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 90 ℃ for 5 hours to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 6 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 3
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.33: 1, adding 0.1g of silicon dioxide, 0.3g of polyacrylonitrile and 0.6g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 70 ℃ for 10 hours to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 4
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 1.25: 1, adding 0.25g of silicon dioxide, 0.2g of polyacrylonitrile and 0.55g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 8h to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 5
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.5: 1, adding 0.2g of silicon dioxide, 0.4g of polyacrylonitrile and 0.4g of zinc chloride into 250ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 6
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.5: 1, adding 0.2g of silicon dioxide, 0.4g of polyacrylonitrile and 0.4g of zinc chloride into 500ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 1000 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing at 15000rpm for 10min, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 7
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 4: 1, adding 0.4g of silicon dioxide, 0.1g of polyaniline and 0.5g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyaniline, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 400 ℃ for 2h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 10M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 150 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 8
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.5: 1, adding 0.2g of silicon dioxide, 0.2g of polyaniline, 0.2g of polyacrylonitrile and 0.4g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyaniline, polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 0.5h to obtain a carbonized compound;
(4) performing alkali washing on the carbonized compound for 4 hours by using sodium hydroxide with the concentration of 4M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 60 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
Example 9
(1) According to the mass ratio of silicon dioxide to the nitrogen-containing precursor of 0.5: 1, adding 0.2g of silicon dioxide, 0.2g of polyaniline, 0.2g of polyacrylonitrile and 0.4g of zinc chloride into 100ml of distilled water, and uniformly stirring and mixing to obtain a suspension solution;
(2) heating and stirring the suspension solution at 50 ℃ for 5 hours to obtain a polyaniline, polyacrylonitrile, silicon dioxide and zinc chloride solid compound;
(3) carrying out pyrolysis reaction on the solid compound at 600 ℃ for 4h to obtain a carbonized compound;
(4) performing alkaline washing on the carbonized compound for 10 hours by using potassium hydroxide with the concentration of 1M;
(5) and centrifuging the solution obtained after the alkali washing for 10min at 8000rpm, and drying in vacuum at 75 ℃ to prepare the nitrogen-doped hierarchical porous carbon material, namely the catalyst.
The method also comprises the steps of preparing 100mL of a phenol aqueous solution with the concentration of 200mg/L, adding 5mg of the nitrogen-doped hierarchical porous carbon material prepared in any one of the examples 1-9 as a catalyst, adding 0.1g of Peroxymonosulfate (PMS) as an oxidant, reacting in a water bath at 25 ℃, sampling at intervals, and carrying out quantitative analysis by using a liquid chromatograph. The concentration change of the phenol solution in different periods when the nonmetal catalyst prepared by the method of the invention is used for degrading phenol is shown in figure 3.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the nonmetal catalyst for efficiently degrading phenol is characterized by comprising the following steps of:
1) adding 10-40 wt.% of nitrogen precursor, 10-40 wt.% of silicon dioxide and 40-60 wt.% of zinc chloride into 100-500 mml of distilled water according to mass percent, and uniformly stirring and mixing to obtain a suspension solution;
2) heating and stirring the obtained suspension at a set temperature for a set time to obtain a nitrogen precursor, silicon dioxide and zinc chloride solid compound;
3) carrying out pyrolysis reaction on the obtained solid compound at a set temperature for a set time to obtain a carbonized compound;
4) performing alkali washing on the obtained carbonized compound;
5) and centrifuging the solution subjected to alkali washing, and drying in vacuum to obtain the nitrogen-doped hierarchical pore carbon material, namely the target catalyst.
2. The method for preparing the nonmetal catalyst for degrading the phenol with high efficiency according to claim 1, wherein the nitrogen precursor in the step 1) is more than one of polyaniline, polyacrylonitrile, urea and melamine.
3. The preparation method of the nonmetal catalyst for efficiently degrading phenol according to claim 1, wherein the mass ratio of the silicon dioxide to the nitrogen-containing precursor in the step 1) is 0.25-4: 1.
4. the method for preparing the nonmetal catalyst for degrading phenol efficiently according to claim 1, wherein the set temperature in the step 2) is 50-90 ℃ and the set time is 5-10 hours.
5. The method for preparing the nonmetal catalyst for efficiently degrading phenol according to claim 1, wherein the pyrolysis reaction time in the step 3) is 0.5-4 h, and the reaction temperature is 400-1000 ℃.
6. The preparation method of the nonmetal catalyst for efficiently degrading phenol according to claim 1, wherein the alkali used for alkali washing in the step 4) is one of potassium hydroxide and sodium hydroxide, the concentration of the alkali used is 1-10M, and the alkali washing time is 4-10 h.
7. The method for preparing the nonmetal catalyst for degrading phenol efficiently according to claim 1, wherein the rotation speed of the centrifugation in the step 5) is 8000-15000 rpm, and the drying temperature is 60-150 ℃.
8. A method of using the composition of any one of claims 1 to 7The catalyst prepared by the preparation method of the nonmetal catalyst for degrading phenol is characterized in that the specific surface area of the prepared catalyst is 1000m2More than g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910896284.XA CN110586161A (en) | 2019-09-22 | 2019-09-22 | Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910896284.XA CN110586161A (en) | 2019-09-22 | 2019-09-22 | Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110586161A true CN110586161A (en) | 2019-12-20 |
Family
ID=68862147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910896284.XA Pending CN110586161A (en) | 2019-09-22 | 2019-09-22 | Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110586161A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410471A (en) * | 2021-05-21 | 2021-09-17 | 河南师范大学 | Preparation method of soft and hard template of nitrogen and sulfur double-doped hierarchical pore carbon catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566961A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Metal-free nitrogen-doped functionalized mesoporous carbon catalyst and preparation method and applications thereof |
| CN104353481A (en) * | 2014-10-31 | 2015-02-18 | 中国石油大学(北京) | Nitrogen-doped mesoporous carbon catalyst for wastewater degradation as well as preparation method and application thereof |
| CN105148991A (en) * | 2015-09-14 | 2015-12-16 | 东华大学 | Nitrogen/sulphur/chlorine co-doped multistage hole carbon catalyst and preparation method thereof |
| CN105304913A (en) * | 2015-11-12 | 2016-02-03 | 东华大学 | Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof |
| CN107262032A (en) * | 2017-06-29 | 2017-10-20 | 山东大学 | A kind of catalyst of adsoption catalysis oxidation Synergistic degradation phenol and preparation method and application |
-
2019
- 2019-09-22 CN CN201910896284.XA patent/CN110586161A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566961A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Metal-free nitrogen-doped functionalized mesoporous carbon catalyst and preparation method and applications thereof |
| CN104353481A (en) * | 2014-10-31 | 2015-02-18 | 中国石油大学(北京) | Nitrogen-doped mesoporous carbon catalyst for wastewater degradation as well as preparation method and application thereof |
| CN105148991A (en) * | 2015-09-14 | 2015-12-16 | 东华大学 | Nitrogen/sulphur/chlorine co-doped multistage hole carbon catalyst and preparation method thereof |
| CN105304913A (en) * | 2015-11-12 | 2016-02-03 | 东华大学 | Nitrogen/transition metal-codoped hierarchical-pore carbon oxygen reduction catalyst, and preparation method and application thereof |
| CN107262032A (en) * | 2017-06-29 | 2017-10-20 | 山东大学 | A kind of catalyst of adsoption catalysis oxidation Synergistic degradation phenol and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| WEN ZHANG，等: "Synergy of nitrogen doping and structural defects on hierarchically porous carbons toward catalytic oxidation via a non-radical pathway", 《CARBON》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410471A (en) * | 2021-05-21 | 2021-09-17 | 河南师范大学 | Preparation method of soft and hard template of nitrogen and sulfur double-doped hierarchical pore carbon catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020102333A4 (en) | Method for preparing biochar from phosphoric acid-modified enteromorpha prolifera, and use of biochar in removal of cadmium | |
| CN112516964B (en) | Nitrogen-doped biochar and preparation method and application thereof | |
| CN107744832B (en) | High-molecular-material-modified sludge biochar catalyst, and preparation and application thereof | |
| CN111437825A (en) | Iron-manganese biochar catalyst and application thereof in conditioning sludge dehydration | |
| CN111318254B (en) | Preparation method of high-efficiency regenerated activated carbon | |
| CN110302807B (en) | Preparation method and application of modified zero-valent iron liquid catalyst | |
| CN114229983A (en) | Method for preparing catalytic activated biochar from iron-containing excess sludge and removing antibiotics | |
| CN114177927A (en) | Two-dimensional carbon nitride supported iron monatomic catalyst and preparation method and application thereof | |
| CN114405471B (en) | Aluminum-iron bimetal modified biochar dephosphorizing material and preparation method thereof | |
| CN114057279A (en) | Method for accelerating iron circulation by using hydrothermal carbon to promote catalytic degradation of organic pollutants | |
| CN111320318A (en) | Zero-emission advanced treatment process for RO (reverse osmosis) concentrated water | |
| CN110586161A (en) | Preparation method of nonmetal catalyst for efficiently degrading phenol and catalyst | |
| CN110589822B (en) | Method for preparing activated carbon from plastic waste and application of activated carbon | |
| CN109225187B (en) | Preparation method and application of sludge-based ceramic-based catalyst | |
| CN111592090A (en) | Application method of red mud-based heterogeneous Fenton catalyst for advanced wastewater treatment | |
| CN111068731A (en) | Multielement carbon nitride based non-metallic material, preparation method and application thereof | |
| CN114011436A (en) | Preparation method and application of three-dimensional composite material catalyst | |
| CN109158123A (en) | Using discarded diaper as the method for raw material synthetic non-metallic C catalyst | |
| CN113750966B (en) | Sludge biological adsorption material for defluorination and preparation method thereof | |
| CN108579766B (en) | Preparation method of cadmium sulfide-based composite catalyst capable of treating industrial wastewater | |
| CN115193437B (en) | Catalyst based on solid waste and environmental wastewater recycling and reuse and preparation method and application thereof | |
| CN107586566B (en) | Method for catalyzing coal gasification reaction by using concentrated miscellaneous salt solution | |
| CN113976085B (en) | Preparation method and application of lignin modified titanium carbide oil-water separation material | |
| CN115041166A (en) | Heterogeneous persulfate catalyst and preparation method and application thereof | |
| CN115025796A (en) | Biomass-loaded MOFs-derived composite catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191220 |