CN117000245A - Preparation and use methods of biochar-supported iron-copper bimetallic catalyst - Google Patents
Preparation and use methods of biochar-supported iron-copper bimetallic catalyst Download PDFInfo
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- CN117000245A CN117000245A CN202310860570.7A CN202310860570A CN117000245A CN 117000245 A CN117000245 A CN 117000245A CN 202310860570 A CN202310860570 A CN 202310860570A CN 117000245 A CN117000245 A CN 117000245A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010802 sludge Substances 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 239000005749 Copper compound Substances 0.000 claims abstract description 8
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a preparation and use method of a biochar-supported iron-copper bimetallic catalyst, which comprises the following preparation steps: fully mixing papermaking black liquor acid-separated matter, fenton sludge, bivalent copper compound and water according to a certain proportion, and drying and crushing the mixture after stirring; and carrying out anaerobic pyrolysis on the crushed sample, carrying out hydrothermal treatment on the pyrolyzed sample and the ethanol-water mixed solution, carrying out vacuum drying on the sample subjected to the hydrothermal treatment, and crushing and drying the sample to obtain the biochar-supported iron-copper bimetallic catalyst. The using method is as follows: the pH value of the wastewater is not required to be regulated, a biochar loaded iron-copper bimetallic catalyst and hydrogen peroxide are added into a reactor to carry out stirring and mixing reaction, and after the reaction is finished, an electromagnet is adopted to separate and recycle the catalyst. The biochar-supported iron-copper bimetallic catalyst prepared by the invention has the advantages of wide working pH range, high stability, high catalytic activity, easy recovery and the like.
Description
Technical Field
The invention belongs to the technical field of heterogeneous Fenton catalyst preparation application and waste resource comprehensive utilization, and particularly provides a preparation and use method of a biochar-supported iron-copper bimetallic catalyst.
Background
Fenton advanced oxidation technology is mainly based on the catalysis of hydrogen peroxide by an iron-based catalyst to generate hydroxyl free radicals with strong oxidability to degrade organic pollutants in water, and has been successfully used for difficult-to-treat wastewater in industries such as dye, pharmacy, papermaking and the like in recent years. Although the conventional Fenton process using ferrous ions as a catalyst has the advantages of quick reaction and convenient operation, the wide application is limited by the problems of narrow working pH range (3-4) and large amount of Fenton sludge.
The ferroferric oxide has an inverse spinel structure, electrons can be effectively transferred between ferrous iron and ferric iron of an octahedral site, so that the interconversion between them is promoted, and thus, the ferroferric oxide nanoparticle has excellent surface activity and good magnetic separation performance. Ferroferric oxide nano-particles are successfully used in the fields of landfill leachate, dye wastewater and the like as heterogeneous catalysts of Fenton reaction. However, the ferroferric oxide nano particles have the problems of easy agglomeration and remarkable reduction of catalytic activity under the medium-high pH condition, so that the catalytic oxidation efficiency is reduced.
Black liquor is a cooking effluent produced during alkaline pulping in the paper industry, and solids typically contain about 2/3 organics (30-40% alkali lignin) and 1/3 inorganics (primarily cooking effluent). Currently, the black liquor is burned with alkali recovery technology to recover heat energy and chemicals. The traditional (homogeneous) Fenton treatment process is the most commonly used advanced treatment process of papermaking wastewater at present, and the process generates a large amount of iron-containing sludge (i.e. Fenton sludge). How to more effectively and resource utilize papermaking industry waste, namely papermaking black liquor and Fenton sludge, is a main environmental problem facing the papermaking industry. However, there are few reports on the preparation of high-performance catalysts from papermaking black liquor and Fenton sludge as main raw materials.
Disclosure of Invention
The invention aims to provide a preparation and use method of a biochar-supported iron-copper bimetallic catalyst. The Fenton heterogeneous catalyst (biochar-supported iron-copper bimetallic catalyst) which takes zero-valent iron as a core and ferroferric oxide as a shell structure and coexists with zero-valent copper in biochar is prepared by using papermaking black liquor acid-out, fenton sludge and bivalent copper-based compounds as raw materials through pyrolysis-hydrothermal treatment, so that the problems that the pH value needs to be regulated, the stability is poor and the black liquor and the Fenton sludge cannot be recycled in the traditional Fenton process are solved, and meanwhile, the efficient utilization way of the black liquor and the Fenton sludge is widened.
The invention is realized by the following technical scheme:
the preparation method of the biochar-supported iron-copper bimetallic catalyst comprises the following preparation steps:
(1) Fully mixing papermaking black liquor acid-separated matter, fenton sludge, bivalent copper compound and water according to a certain proportion, stirring the mixture for 2-6 hours, drying at 105-110 ℃, and then crushing the dried sample to be less than 1mm;
(2) Carrying out anaerobic pyrolysis on the crushed sample for 1-3 hours at 750-900 ℃;
(3) Carrying out hydrothermal treatment on the pyrolyzed sample and the ethanol-water mixed solution;
(4) And (3) carrying out vacuum drying on the sample subjected to the hydrothermal treatment at the temperature of 60 ℃, and crushing the dried sample to obtain the biochar-supported iron-copper bimetallic catalyst.
The ratio of the solid content of the acid analyte in the papermaking black liquor to the mass of iron in Fenton sludge is 1.5-2.5, the ratio of the mass of iron in Fenton sludge to the mass of copper in a bivalent copper compound is 1.5-3, the bivalent copper compound is copper sulfate or copper nitrate, and the addition amount of water ensures that the solid content in the mixture is not higher than 30%. .
The volume ratio of the ethanol to the water in the ethanol-water mixed solution is 4:6-7:3, and the ratio of the mass (g) of the pyrolysis sample to the volume (milliliter) of the ethanol-water mixed solution is 1:50-1:400.
The temperature of the hydrothermal treatment is 180-240 ℃ and the time is 12-24 hours.
The method for using the biochar-supported iron-copper bimetallic catalyst comprises the steps of adding wastewater containing organic pollutants into a reactor, adding the biochar-supported iron-copper bimetallic catalyst and hydrogen peroxide into the reactor for stirring and mixing reaction without adjusting the pH of the wastewater, and separating and recycling the biochar-supported iron-copper bimetallic catalyst by adopting an electromagnet after the reaction is finished.
The ratio of the biochar-supported iron-copper bimetallic catalyst (g) to hydrogen peroxide (mol) is 10:1-200:1.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, papermaking black liquor, fenton sludge and a bivalent copper compound are taken as raw materials, under the conditions defined by the invention, a catalyst of biological carbon loaded with nano zero-valent iron and nano zero-valent copper can be obtained, the surface part of the nano zero-valent iron can be converted into nano ferroferric oxide through further hydrothermal treatment, the nano zero-valent iron is taken as a core, the nano ferroferric oxide is taken as a shell structure, and nano zero-valent copper is coexistent in a Fenton catalyst (biological carbon loaded with iron-copper bimetallic catalyst) of the biological carbon, wherein the biological carbon promotes adsorption of organic pollutants, and the concentration of pollutants near catalytic active sites is improved; under the combined action of biochar, nano zero-valent iron and nano zero-valent copper, the ferric iron of the nano ferroferric oxide is promoted to be converted into ferrous iron in the heterogeneous catalysis process, and the catalytic activity of the nano ferroferric oxide is improved; the nano zero-valent copper has higher catalytic activity in a wide pH range, so that the adsorption-catalytic oxidation performance of the catalyst is improved under the synergistic effect of nano ferroferric oxide, nano zero-valent iron, nano zero-valent copper and biochar.
(2) The biochar and shell-core structure improve the stability of the catalyst and slow down the leaching of metal ions during Fenton oxidation.
(3) In the preparation process, the iron element in Fenton sludge can be converted into paramagnetic ferroferric oxide and zero-valent iron, and a magnetic field (such as an electromagnet) can be used for separating and recovering the biochar-supported iron-copper bimetallic catalyst.
Drawings
FIG. 1 is an X-ray diffraction pattern of a biochar supported iron-copper bimetallic catalyst
FIG. 2 is a transmission electron microscope image of a biochar-supported iron-copper bimetallic catalyst
Detailed Description
The present invention is further described below with reference to specific examples, but it should be noted that these examples are only for illustrating the present invention and not for limiting the scope of the present invention, and various changes or modifications to the present invention should be made by those skilled in the art after reading the detailed description of the present invention.
Example 1:
and (3) regulating the pH value of the papermaking black liquor to 8 by adopting dilute sulfuric acid for acid precipitation, and obtaining an acid precipitate of the papermaking black liquor after dehydration. Fully mixing papermaking black liquor acid-separated matter, fenton sludge, copper nitrate and water according to a certain proportion, stirring for 2 hours, drying at 110 ℃, and then crushing the dried sample to be less than 1mm. Wherein, the ratio of the solid content of the acid-separated matter of the papermaking black liquor to the mass of iron in Fenton sludge is 1.5, the ratio of the mass of iron in Fenton sludge to the mass of copper in copper nitrate is 3, and the addition amount of water ensures that the solid content of the mixture is 20 percent. The crushed sample is subjected to anaerobic pyrolysis for 2 hours at 800 ℃, and the pyrolyzed sample and the ethanol-water mixed solution are subjected to hydrothermal treatment. Wherein the volume ratio of ethanol to water in the ethanol-water mixed solution is 6.5:3.5, the ratio of the mass (g) of the pyrolysis sample to the volume (milliliter) of the ethanol-water mixed solution is 1:300, the temperature of the hydrothermal treatment is 180 ℃, and the time is 24 hours. And (3) carrying out vacuum drying on the sample subjected to the hydrothermal treatment at the temperature of 60 ℃, and crushing the dried sample to obtain the biochar-supported iron-copper bimetallic catalyst. The X-ray diffraction pattern is shown in figure 1. The transmission electron microscope image is shown in fig. 2. The saturation magnetization was 40.5emu/g.
Adding wastewater containing 10mg/L rhodamine B dye into a reactor, adding a biochar-supported iron-copper bimetallic catalyst and hydrogen peroxide into the reactor, stirring and mixing for reaction, and separating and recycling the biochar-supported iron-copper bimetallic catalyst by adopting an electromagnet after the reaction is finished. Wherein the dosage of the biochar-supported iron-copper bimetallic catalyst and hydrogen peroxide is 0.2g/L and 0.001mol/L respectively, namely the ratio of the biochar-supported iron-copper bimetallic catalyst (g) to the hydrogen peroxide (mol) is 200:1. The removal rate of rhodamine B reaches 100%, and the removal rate still reaches 98% after 5 times of recycling. The iron leaching concentration is less than 0.1mg/L, and the copper leaching concentration is less than 0.5mg/L.
Example 2:
and (3) regulating the pH value of the papermaking black liquor to 9 by adopting flue gas for acid precipitation, and obtaining papermaking black liquor acid precipitate after dehydration. Fully mixing papermaking black liquor acid-separated matter, fenton sludge, copper sulfate and water according to a certain proportion, stirring the mixture for 6 hours, drying at 105 ℃, and then crushing the dried sample to be less than 1mm. Wherein, the ratio of the solid content of the acid-separated matter of the papermaking black liquor to the mass of iron in Fenton sludge is 2.5, the ratio of the mass of iron in Fenton sludge to the mass of copper in copper nitrate is 1.5, and the addition amount of water makes the solid content of the mixture be 30 percent. The crushed sample is subjected to anaerobic pyrolysis at 900 ℃ for 1 hour, and the pyrolyzed sample and the ethanol-water mixed solution are subjected to hydrothermal treatment. Wherein the volume ratio of ethanol to water in the ethanol-water mixed solution is 4.5:5.5, the ratio of the mass (g) of the pyrolysis sample to the volume (milliliter) of the ethanol-water mixed solution is 1:70, the temperature of the hydrothermal treatment is 240 ℃, and the time is 12 hours. And (3) carrying out vacuum drying on the sample subjected to the hydrothermal treatment at the temperature of 60 ℃, and crushing the dried sample to obtain the biochar-supported iron-copper bimetallic catalyst. The saturation magnetization was 62.5emu/g.
Papermaking wastewater (effluent of secondary sedimentation tank, COD) Cr =200 mg/L) is added into a reactor, a biochar-supported iron-copper bimetallic catalyst and hydrogen peroxide are added into the reactor for stirring and mixing reaction, and after the reaction is finished, an electromagnet is adopted for separating and recycling the biochar-supported iron-copper bimetallic catalyst. Wherein the dosages of the biochar-supported iron-copper bimetallic catalyst and the hydrogen peroxide are respectively 0.3g/L and 0.012mol/L, namely the ratio of the iron-based heterogeneous catalyst (g) to the persulfate (mol) is 25:1. COD of the treated wastewater Cr The concentration is less than 50mg/L, and COD after 5 times of recycling Cr The concentration is still less than 60mg/L. The iron leaching concentration is less than 0.1mg/L, and the copper leaching concentration is less than 1mg/L.
Claims (6)
1. The preparation method of the biochar-supported iron-copper bimetallic catalyst is characterized by comprising the following preparation steps:
(1) Fully mixing papermaking black liquor acid-separated matter, fenton sludge, bivalent copper compound and water according to a certain proportion, stirring the mixture for 2-6 hours, drying at 105-110 ℃, and then crushing the dried sample to be less than 1mm;
(2) Carrying out anaerobic pyrolysis on the crushed sample for 1-3 hours at 750-900 ℃;
(3) Carrying out hydrothermal treatment on the pyrolyzed sample and the ethanol-water mixed solution;
(4) And (3) carrying out vacuum drying on the sample subjected to the hydrothermal treatment at the temperature of 60 ℃, and crushing the dried sample to obtain the biochar-supported iron-copper bimetallic catalyst.
2. The method for preparing the biochar-supported iron-copper bimetallic catalyst according to claim 1, wherein the ratio of the solid content of the acid-separated matter of the papermaking black liquor to the mass of iron in the Fenton sludge is 1.5-2.5, the ratio of the mass of iron in the Fenton sludge to the mass of copper in the divalent copper compound is 1.5-3, the divalent copper compound is copper sulfate or copper nitrate, and the addition amount of water is such that the solid content in the mixture is not higher than 30%.
3. The method for preparing the biochar-supported iron-copper bimetallic catalyst according to claim 1, wherein the volume ratio of ethanol to water in the ethanol-water mixed solution is 4:6-7:3, and the ratio of the mass (g) of a pyrolysis sample to the volume (milliliter) of the ethanol-water mixed solution is 1:50-1:400.
4. The method for preparing the biochar-supported iron-copper bimetallic catalyst according to claim 1, wherein the hydrothermal treatment is carried out at 180-240 ℃ for 12-24 hours.
5. A method for using the biochar-supported iron-copper bimetallic catalyst according to claims 1-4, wherein the wastewater containing organic pollutants is added into a reactor, the pH of the wastewater is not required to be regulated, the biochar-supported iron-copper bimetallic catalyst and hydrogen peroxide are added into the reactor for stirring and mixing reaction, and an electromagnet is used for separating and recycling the biochar-supported iron-copper bimetallic catalyst after the reaction is finished.
6. The method of using a biochar supported iron-copper bimetallic catalyst according to claim 5, wherein the ratio of biochar supported iron-copper bimetallic catalyst (g) to hydrogen peroxide (mol) is 10:1 to 200:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117446949A (en) * | 2023-11-27 | 2024-01-26 | 苏州安峰环保技术有限公司 | Preparation method and application of silver-modified biochar-loaded nano zero-valent iron material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117446949A (en) * | 2023-11-27 | 2024-01-26 | 苏州安峰环保技术有限公司 | Preparation method and application of silver-modified biochar-loaded nano zero-valent iron material |
| CN117446949B (en) * | 2023-11-27 | 2024-05-24 | 苏州安峰环保技术有限公司 | Preparation method and application of silver-modified biochar-loaded nano zero-valent iron material |
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