CN116899604A - Preparation method of nickel-containing waste residue derived metal-nitrogen doped carbon catalyst - Google Patents
Preparation method of nickel-containing waste residue derived metal-nitrogen doped carbon catalyst Download PDFInfo
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- CN116899604A CN116899604A CN202310654838.1A CN202310654838A CN116899604A CN 116899604 A CN116899604 A CN 116899604A CN 202310654838 A CN202310654838 A CN 202310654838A CN 116899604 A CN116899604 A CN 116899604A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000010453 quartz Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 9
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 9
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004377 microelectronic Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000003381 stabilizer Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
The invention relates to a preparation method of a metal-nitrogen doped carbon catalyst derived from nickel-containing waste residues, which comprises the steps of firstly dissolving nickel-containing waste residues with a mixed solution of acid and hydrogen peroxide, filtering to obtain a solution, secondly adding coffee residues into the obtained solution, regulating the pH value of the solution to be alkaline with dopamine hydrochloride, stirring, heating and evaporating the solution to dryness to obtain a solid, finally placing the obtained solid into a quartz boat, placing the quartz boat into a tube furnace, and carbonizing at a high temperature under the condition of ammonia/nitrogen mixed gas to obtain the metal-nitrogen doped carbon catalyst. The catalyst prepared by the invention can be directly used for removing organic pollutants in wastewater, the introduction of nitrogen atoms and metal ions can improve the catalytic activity of the carbon material, and the existence of the metal ions can obviously improve the stability and the recyclability of the carbon material; the prepared catalyst is used in the wastewater treatment process, and valuable metals in nickel slag are fully recovered.
Description
Technical Field
The invention relates to the technical field of nickel solid waste residue recycling, in particular to a preparation method and application of a metal-nitrogen doped carbon catalyst derived from nickel solid waste residue.
Background
With the continuous development of the microelectronic industry in China, the demand of nitrogen trifluoride gas is increasing. Nitrogen trifluoride is of great importance in the microelectronics industry as an excellent plasma etching gas. Electrolytic processes are the most common method for preparing nitrogen trifluoride. However, during the preparation process, a great amount of nickel-containing waste residues are generated in the electrolytic tank, and whether the nickel-containing waste residues can be properly treated or not is relevant to the future development of the microelectronics industry.
The nickel-containing waste slag contains metallic iron and nickel, and the partial metal has high utilization value. The existing treatment mode of the nickel-containing waste slag mainly comprises the step of recycling metals in the nickel-containing waste slag in a precipitation mode and the like to obtain other chemicals. The purity of the chemicals prepared by this method is difficult to be ensured, and thus there is a difficulty in further utilization.
With the continuous development of industry, the problems of scarcity and pollution of water resources in China are more serious. Therefore, there is an urgent need to find efficient and thorough water treatment techniques. Advanced oxidation technology has gained widespread attention as a novel water treatment technology. Carbon materials are catalysts commonly used in advanced oxidation techniques, but have poor stability and require further improvement in activity. Research shows that the introduction of nonmetallic elements and metal ions in the carbon material can obviously improve the activity and stability of the carbon material. Biomass is an important source of carbon materials, and coffee grounds are common biomass materials in life of people, and have larger specific surface area after carbonization.
Disclosure of Invention
In view of the above, the invention provides a recycling method of nickel-containing waste residues generated in the process of preparing nitrogen trifluoride gas by an electrolytic method, and the prepared catalyst is used in the wastewater treatment process to solve the recycling problem of the nickel-containing waste residues generated in the process of preparing nitrogen trifluoride gas by the electrolytic method.
In order to solve the technical problems, the invention is realized as follows:
the preparation method of the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue is characterized in that the target catalyst can be obtained after pickling, polymerization and carbonization, and comprises the following steps:
step 1: dissolving nickel slag in mixed solution of acid and hydrogen peroxide, stirring, and filtering to remove insoluble substances to obtain filtrate;
step 2: adding coffee grounds into the filtrate obtained in the step 1, stirring, adding dopamine hydrochloride, adding alkali to adjust the pH of the solution to be alkaline, and stirring for polymerization;
step 3: evaporating the solution obtained in the step 2 in a heating jacket to obtain a solid;
step 4: and (3) in the carbonization process, placing the solid obtained in the step (3) into a quartz boat, and placing the quartz boat into a tube furnace, and carbonizing at high temperature under the condition of ammonia/nitrogen mixed gas to obtain the target catalyst.
Further, in the step 1, the acid is sulfuric acid solution with the concentration of 1-2M; the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 30%, wherein the volume ratio of the hydrogen peroxide solution with the mass fraction of 30% to the sulfuric acid solution with the concentration of 1-2M is 1:23-1:5.
Further, in the step 1, the solid-to-liquid ratio g of the nickel slag to the mixed solution is as follows: mL is 1: 3-1: 6, the dissolution temperature is 20-60 ℃, and the stirring time is 0.5-2 h.
Further, the filtrate obtained in the step 1 is diluted 10 times to obtain a diluent for the step 2, and the addition amount of the coffee grounds is 1/12-5/12 of the mass of the nickel grounds; the alkali is sodium hydroxide solution with the concentration of 1M.
Further, in the step 2, the solid-to-liquid ratio g of dopamine hydrochloride to filtrate: mL is 1: 30-1:120; adding alkali to adjust the pH of the solution to 10.
Further, in the step 2, the polymerization reaction time is 12-30 hours, and the polymerization reaction temperature is 25-35 ℃.
Further, the heating temperature of the heating sleeve in the step 3 is 90 ℃.
Further, in the step 4, the flow rate of the ammonia gas/nitrogen gas mixture is 100-500 sccm, and the volume ratio of the ammonia gas to the nitrogen gas is 1:10 to 1:5.
further, the carbonization temperature in the step 4 is 700-900 ℃ and the carbonization time is 1-3 h.
Further, the catalyst obtained by the preparation method is used for activating sodium persulfate to degrade bisphenol A.
The beneficial effects are that:
(1) The coffee grounds are selected as carbon sources, so that the coffee grounds are low in price and wide in source; dopamine is selected as a metal ion stabilizer, high temperature and high pressure are not needed in the polymerization process, and the operation is simple;
(2) The invention combines valuable metal iron and nickel in the nickel-containing waste slag with common carbon-based catalysts, thereby realizing the efficient utilization of metals in solid waste, greatly improving the activity and stability of the carbon-based catalysts and solving the problem of poor stability of the carbon-based catalysts;
(3) The invention prepares the metal-nitrogen doped carbon catalyst in the solid waste treatment process, and the catalyst is also applied to the water treatment process. In consideration of the problems of rapid industrial development, more organic pollutants in water, scarcity of water resources and the like in China at present, the catalyst not only efficiently recovers metals in solid waste, but also realizes environmental treatment, and has higher economic benefit and environmental benefit.
(4) The catalyst prepared by the invention can be directly used for removing organic pollutants in wastewater, the introduction of nitrogen atoms and metal ions can improve the catalytic activity of the carbon material, and the existence of the metal ions can obviously improve the stability and the recyclability of the carbon material; the prepared catalyst is used in the wastewater treatment process, and valuable metals in nickel slag are fully recovered.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the intended purpose of the present invention, the following detailed description will explain specific embodiments, features and effects according to the present invention in conjunction with the preferred embodiments.
Example 1
And (3) dissolving 20g of solid nickel-containing waste residues generated in the process of preparing high-purity nitrogen trifluoride gas by an electrolytic method in 60mL of mixed solution of dilute sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 2M, the adding amount is 50mL, the mass fraction of hydrogen peroxide is 30%, the adding amount is 10mL, stirring is carried out at 40 ℃ until the solid nickel-containing waste residues are completely dissolved, and filtering the solution to obtain filtrate. Diluting 5mL of filtrate with distilled water to 50mL to obtain a diluent, adding coffee grounds with the mass of 1/12 of that of nickel residues into the diluent, fully stirring, adding 2g of dopamine hydrochloride, then dropwise adding sodium hydroxide solution to pH of 10, and stirring at 30 ℃ for polymerization for 12h. The solution after the polymerization reaction was evaporated to dryness in a heating mantle at 90 ℃. The mass ratio of the solid after being evaporated to dryness to sodium nitrate is 3:1, and thoroughly grinding and mixing. The mixed solids were placed in a quartz boat and placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under an ammonia/nitrogen mixture, and carbonized at that temperature for 3 hours. Wherein the total flow of the gas is 200sccm, and the volume ratio of ammonia gas to nitrogen gas is 1:10. and cooling the tubular furnace to 25 ℃, and taking out the target catalyst for degrading bisphenol A which is an organic pollutant in water.
The degradation conditions in this example were: the target contaminant was 100ml20 ppm bisphenol A. The catalyst addition was 10mg. The oxidant is sodium persulfate solid with purity of more than 99.5 percent, and the addition amount is 0.1g. The removal rate of the pollutants after 2 hours of reaction at 25 ℃ is 92%.
Example 2
And (3) dissolving 20g of solid nickel-containing waste residue and nickel-containing waste residue generated in the process of preparing high-purity nitrogen trifluoride gas by an electrolytic method in 120mL of mixed solution of dilute sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 1M, the addition amount is 115mL, the mass fraction of hydrogen peroxide is 30%, the addition amount is 5mL, stirring at 60 ℃ until the solution is completely dissolved, and filtering the solution to obtain filtrate. Diluting 5mL of filtrate with distilled water to 50mL to obtain a diluent, adding coffee grounds with the mass of 5/24 of that of nickel residues into the diluent, fully stirring, adding 2g of dopamine hydrochloride, then dropwise adding sodium hydroxide solution to pH of 10, and stirring at 30 ℃ for polymerization for 12h. The solution after the polymerization reaction was evaporated to dryness in a heating mantle at 90 ℃. The mass ratio of the solid after being evaporated to dryness to sodium nitrate is 3:1, and thoroughly grinding and mixing. The mixed solids were placed in a quartz boat and placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under an ammonia/nitrogen mixture, and carbonized at that temperature for 3 hours. Wherein the total gas flow is 300sccm, and the volume ratio of ammonia gas to nitrogen gas is 1:8. and cooling the tubular furnace to 25 ℃, and taking out the target catalyst for degrading bisphenol A which is an organic pollutant in water.
The degradation conditions in this example were: the target contaminant was 100ml20 ppm bisphenol A. The catalyst addition was 10mg. The oxidant is sodium persulfate solid with purity of more than 99.5 percent, and the addition amount is 0.1g. The removal rate of the pollutants after 2 hours of reaction at 25 ℃ is 94%.
Example 3
And (3) dissolving 20g of solid nickel-containing waste residue and nickel-containing waste residue generated in the process of preparing high-purity nitrogen trifluoride gas by an electrolytic method in 120mL of mixed solution of dilute sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 1M, the adding amount is 113mL, the mass fraction of hydrogen peroxide is 30%, the adding amount is 7mL, stirring is carried out at 25 ℃ until the solution is completely dissolved, and filtering the solution to obtain filtrate. Diluting 5mL of filtrate with distilled water to 50mL to obtain a diluent, adding coffee grounds with the mass of 5/24 of that of nickel residues into the diluent, fully stirring, adding 1g of dopamine hydrochloride, then dropwise adding sodium hydroxide solution to pH of 10, and stirring at 25 ℃ for polymerization for 24h. The solution after the polymerization reaction was evaporated to dryness in a heating mantle at 90 ℃. The mass ratio of the solid after being evaporated to dryness to sodium nitrate is 3:1, and thoroughly grinding and mixing. The mixed solids were placed in a quartz boat and placed in a tube furnace, heated to 900 ℃ at a heating rate of 5 ℃/min under an ammonia/nitrogen mixture, and carbonized at that temperature for 1h. Wherein the total gas flow is 400sccm, and the volume ratio of ammonia gas to nitrogen gas is 1:5. and cooling the tubular furnace to 25 ℃, and taking out the target catalyst for degrading bisphenol A which is an organic pollutant in water.
The degradation conditions in this example were: the target contaminant was 100ml20 ppm bisphenol A. The catalyst addition was 10mg. The oxidant is sodium persulfate solid with purity of more than 99.5 percent, and the addition amount is 0.1g. The removal rate of the pollutants after 2 hours of reaction at 25 ℃ is 98 percent.
Example 4
And (3) dissolving 20g of solid nickel-containing waste residue and nickel-containing waste residue generated in the process of preparing high-purity nitrogen trifluoride gas by an electrolytic method in 120mL of mixed solution of dilute sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 1M, the adding amount is 113mL, the mass fraction of hydrogen peroxide is 30%, the adding amount is 7mL, stirring is carried out at 25 ℃ until the solution is completely dissolved, and filtering the solution to obtain filtrate. Diluting 5mL of filtrate with distilled water to 50mL to obtain a diluent, adding coffee grounds with the mass of 1/6 of that of nickel residues into the diluent, fully stirring, adding 2g of dopamine hydrochloride, then dropwise adding sodium hydroxide solution to pH of 10, and stirring at 30 ℃ for polymerization reaction for 30h. The solution after the polymerization reaction was evaporated to dryness in a heating mantle at 90 ℃. The mass ratio of the solid after being evaporated to dryness to sodium nitrate is 3:1, and thoroughly grinding and mixing. The mixed solids were placed in a quartz boat and placed in a tube furnace, heated to 800 ℃ at a heating rate of 5 ℃/min under an ammonia/nitrogen mixture, and carbonized at that temperature for 3 hours. Wherein the total gas flow is 500sccm, and the volume ratio of ammonia gas to nitrogen gas is 1:5. and cooling the tubular furnace to 25 ℃, and taking out the target catalyst for degrading bisphenol A which is an organic pollutant in water.
The degradation conditions in this example were: the target contaminant was 100ml20 ppm bisphenol A. The catalyst addition was 10mg. The oxidant is sodium persulfate solid with purity of more than 99.5 percent, and the addition amount is 0.1g. The removal rate of the pollutants after 2 hours of reaction at 25 ℃ is 99 percent.
Example 5
And (3) dissolving 20g of solid nickel-containing waste residues generated in the process of preparing high-purity nitrogen trifluoride gas by an electrolytic method in 120mL of mixed solution of dilute sulfuric acid and hydrogen peroxide, wherein the concentration of sulfuric acid is 1M, the adding amount is 113mL, the mass fraction of hydrogen peroxide is 30%, the adding amount is 7mL, stirring is carried out at 25 ℃ until the solid nickel-containing waste residues are completely dissolved, and filtering the solution to obtain filtrate. Diluting 5mL of filtrate with distilled water to 50mL to obtain a diluent, adding coffee grounds with the mass of 5/24 of that of nickel residues into the diluent, fully stirring, adding 2g of dopamine hydrochloride, then dropwise adding sodium hydroxide solution to pH of 10, and stirring at 30 ℃ for polymerization reaction for 30h. The solution after the polymerization reaction was evaporated to dryness in a heating mantle at 90 ℃. The mass ratio of the solid after being evaporated to dryness to sodium nitrate is 3:1, and thoroughly grinding and mixing. The mixed solids were placed in a quartz boat and placed in a tube furnace, heated to 800 ℃ at a heating rate of 5 ℃/min under an ammonia/nitrogen mixture, and carbonized at that temperature for 2 hours. Wherein the total gas flow is 500sccm, and the volume ratio of ammonia gas to nitrogen gas is 1:5. and cooling the tubular furnace to 25 ℃, and taking out the target catalyst for degrading bisphenol A which is an organic pollutant in water.
The degradation conditions in this example were: the target contaminant was 100ml20 ppm bisphenol A. The catalyst addition was 10mg. The oxidant is sodium persulfate solid with purity of more than 99.5 percent, and the addition amount is 0.1g. The removal rate of the pollutants after 2 hours of reaction at 25 ℃ is 100 percent.
In view of the above embodiments, the technical solution provided by the present invention can well realize recycling of nickel-containing waste residues. The target catalyst prepared by utilizing the metal ions in the nickel-containing solid waste residue can realize the efficient removal of organic pollutants.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue is characterized in that the target catalyst can be obtained after pickling, polymerization and carbonization, and comprises the following steps:
step 1: dissolving nickel slag in mixed solution of acid and hydrogen peroxide, stirring, and filtering to remove insoluble substances to obtain filtrate;
step 2: adding coffee grounds into the filtrate obtained in the step 1, stirring, adding dopamine hydrochloride, adding alkali to adjust the pH of the solution to be alkaline, and stirring for polymerization;
step 3: evaporating the solution obtained in the step 2 in a heating jacket to obtain a solid;
step 4: and (3) in the carbonization process, placing the solid obtained in the step (3) into a quartz boat, and placing the quartz boat into a tube furnace, and carbonizing at high temperature under the condition of ammonia/nitrogen mixed gas to obtain the target catalyst.
2. The method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the acid in the step 1 is sulfuric acid solution with the concentration of 1-2M; the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 30%, wherein the volume ratio of the hydrogen peroxide solution with the mass fraction of 30% to the sulfuric acid solution with the concentration of 1-2M is 1:23-1:5.
3. The method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the solid-to-liquid ratio g of the nickel residue to the mixed solution in the step 1 is as follows: mL is 1: 3-1: 6, the dissolution temperature is 20-60 ℃, and the stirring time is 0.5-2 h.
4. The method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the filtrate obtained in the step 1 is diluted 10 times to obtain a diluent for the step 2, and the addition amount of the coffee grounds is 1/12-5/12 of the mass of the nickel residues; the alkali is sodium hydroxide solution with the concentration of 1M.
5. The method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the solid-to-liquid ratio g of dopamine hydrochloride to filtrate in the step 2 is as follows: mL is 1: 30-1:120; adding alkali to adjust the pH of the solution to 10.
6. The method for preparing a metal-nitrogen doped carbon catalyst derived from nickel-containing waste residue according to claim 1, wherein the polymerization time in the step 2 is 12-30 h, and the polymerization temperature is 25-35 ℃.
7. The method for preparing a metal-nitrogen doped carbon catalyst derived from nickel-containing waste residue according to claim 1, wherein the heating temperature of the heating sleeve in the step 3 is 90 ℃.
8. The method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the flow rate of the ammonia/nitrogen mixed gas in the step 4 is 100-500 sccm, and the volume ratio of the ammonia to the nitrogen is 1:10 to 1:5.
9. the method for preparing the metal-nitrogen doped carbon catalyst derived from the nickel-containing waste residue according to claim 1, wherein the carbonization temperature in the step 4 is 700-900 ℃ and the carbonization time is 1-3 h.
10. A catalyst obtainable by the process of any one of claims 1 to 9 for the activation of sodium persulfate to degrade bisphenol a.
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