CN111068739B - Preparation method and application of copper ferrite/zeolite spinel composite material - Google Patents
Preparation method and application of copper ferrite/zeolite spinel composite material Download PDFInfo
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- CN111068739B CN111068739B CN201911422653.8A CN201911422653A CN111068739B CN 111068739 B CN111068739 B CN 111068739B CN 201911422653 A CN201911422653 A CN 201911422653A CN 111068739 B CN111068739 B CN 111068739B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 104
- 239000010949 copper Substances 0.000 title claims abstract description 104
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 103
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 100
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010457 zeolite Substances 0.000 title claims abstract description 100
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 57
- 239000011029 spinel Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 39
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 36
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 16
- 229960004543 anhydrous citric acid Drugs 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910021538 borax Inorganic materials 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000004328 sodium tetraborate Substances 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 210000004324 lymphatic system Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
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- Magnetic Ceramics (AREA)
Abstract
A preparation method and application of a copper ferrite/zeolite spinel composite material relate to the technical field of water treatment. The invention provides a preparation method and application of a copper ferrite/zeolite spinel composite material, and the prepared catalyst is practical, convenient and efficient, and can effectively catalyze ozone oxidation to degrade organic pollutants atrazine in water. The method comprises the following steps: adding copper nitrate and ferric nitrate into absolute ethyl alcohol, stirring, then adding anhydrous citric acid, and stirring again to obtain a copper ferrite sol-state mixed solution; adding natural zeolite powder into the copper ferrite sol-state mixed solution, continuously stirring until the copper ferrite sol-state mixed solution is evaporated to dryness, then grinding, calcining at high temperature, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material. The invention can obtain the preparation method and the application of the copper ferrite/zeolite spinel composite material.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method and application of a copper ferrite/zeolite spinel composite material.
Background
The traditional advanced oxidation technology takes OH as a main active substance to degrade pollutants. OH has strong oxidizability and nonselectivity, so that the OH can quickly react with organic matters, and the oxidation rate constant is mostly 108M-1 s-1～1010M-1s-1. The heterogeneous catalytic ozonation process is one of advanced oxidation technologies, and mainly promotes the decomposition of ozone into OH, so that the removal effect of organic matters is improved. The heterogeneous catalysis ozone oxidation process does not need to add complex chemical agents into a reaction system, the solid catalyst added into the reaction device is easy to recycle, and meanwhile, the heterogeneous catalysis ozone oxidation process has the characteristics of simplicity in operation and operation, convenience in maintenance and the like, so that the heterogeneous catalysis ozone oxidation process has a good application prospect in the actual water treatment process.
Atrazine (Atrazine, ATZ), also known as Atrazine, is a triazine herbicide, widely used in the control and prevention of weeds in corn, orchards and farmlands, and becomes one of the most widely used and important herbicides in the world at present due to its excellent herbicidal efficacy, low cost and ready availability. China is a big agricultural country, and the production and use of pesticides all live in the top of the world, which accounts for about one tenth of the total world production. From the beginning of the 80 th of the last century, atrazine is used in China, and the application range is still expanded continuously in recent years. Research shows that 20-70% of the applied pesticide can be remained in soil for a long time, and the atrazine has soil leaching property and is easy to permeate into a water-containing layer through rainfall or surface water leaching to generate biological enrichment so as to cause water environment pollution. When a human body is exposed in atrazine for a long time, the immune system, the lymphatic system, the reproductive system and the endocrine system are affected, possibly malformation, organism mutation induction and the like are generated, and the health of the human body is seriously harmed. Therefore, it is important to develop an effective treatment technique to remove atrazine from water.
The degrading and removing of atrazine mainly comprises the following three methods: physical adsorption, chemical oxidation and biodegradation, but the above methods have the problems of high general cost, slow experimental process and incomplete atrazine degradation. The adsorption method is difficult to prepare the economic and effective adsorbent, and has the problem of analysis; the oxidation method is adopted, the operation and treatment cost of the process is high, and the popularization of the process is limited to a certain extent; there are concerns about whether secondary pollution will occur or not, whether substances harmful to humans will be released by microorganisms, and the like, by utilizing microbial degradation.
Disclosure of Invention
The invention provides a preparation method and application of a copper ferrite/zeolite spinel composite material, and the prepared catalyst is practical, convenient and efficient, and can effectively catalyze ozone oxidation to degrade organic pollutants atrazine in water.
The preparation method of the copper ferrite/zeolite spinel composite material comprises the following steps:
firstly, adding copper nitrate and ferric nitrate into absolute ethyl alcohol at the temperature of 90-100 ℃, uniformly stirring, then adding anhydrous citric acid, and uniformly stirring to obtain a copper ferrite sol-state mixed solution, wherein the molar ratio of the copper nitrate to the ferric nitrate is 1:2, the ratio of the total amount of the copper nitrate and the ferric nitrate to the volume of the absolute ethyl alcohol is 11.49mmol (100 mL-120 mL), and the ratio of the volume of the absolute ethyl alcohol to the amount of the anhydrous citric acid is (100 mL-120 mL):7.66 mmol;
adding natural zeolite powder into the copper ferrite sol-state mixed solution at the speed of 10-20 mg/s under the temperature condition of 90-100 ℃, continuously stirring until the copper ferrite sol-state mixed solution is evaporated to dryness, then grinding, heating to 400 ℃, calcining for 8 hours under the temperature condition of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-state mixed solution is 1 (1-5).
The invention has the beneficial effects that:
compared with a single ozone system, a single natural zeolite catalytic ozone system and a single copper ferrite catalytic ozone system, the copper ferrite/zeolite spinel composite material greatly improves the efficiency of degrading atrazine by ozone, the degradation rate of atrazine is improved by about 30% within 40 minutes, when the mass ratio of copper ferrite to natural zeolite powder is 1:1, the prepared copper ferrite/zeolite spinel composite material catalyzes ozone to oxidize and degrade atrazine in water, and the degradation is completed within 120 min; the copper ferrite/zeolite spinel composite material prepared by the invention has stable performance, and only 0.05 mg/L-0.09 mg/L of metal ions are dissolved out in the water solution after reaction.
The copper ferrite/zeolite spinel composite material prepared by the method is simple in preparation method, low in raw material price, strong in magnetism, easy to recover and reusable.
The invention can obtain the preparation method and the application of the copper ferrite/zeolite spinel composite material.
Drawings
FIG. 1 is a graph showing the comparison of the efficiency of atrazine removal in the reactor 1# to 6# in the comparative experiment, C0Is the initial concentration of atrazine, CtThe concentration of atrazine at any time t; ■ stand for a single ozone system, ● for a single natural zeolite catalyzed ozone system, a-up for a single copper ferrite catalyzed ozone system, a-x for the copper ferrite/zeolite spinel composite catalyzed ozone system prepared in example three, a-x for the copper ferrite/zeolite spinel composite catalyzed ozone system prepared in example two,
the copper ferrite/zeolite spinel composite material prepared in the first representative example catalyzes an ozone system;
FIG. 2 is a graph showing the removal efficiency of atrazine in water within 0-120 min for the copper ferrite/zeolite spinel composite material prepared in the first embodiment, C0Is the initial concentration of atrazine, Ct■ represents the catalytic ozone system of the copper ferrite/zeolite spinel composite material prepared in the first embodiment, which is the concentration of atrazine at any time t.
Detailed Description
The first embodiment is as follows: the preparation method of the copper ferrite/zeolite spinel composite material of the embodiment is completed according to the following steps:
firstly, adding copper nitrate and ferric nitrate into absolute ethyl alcohol at the temperature of 90-100 ℃, uniformly stirring, then adding anhydrous citric acid, and uniformly stirring to obtain a copper ferrite sol-state mixed solution, wherein the molar ratio of the copper nitrate to the ferric nitrate is 1:2, the ratio of the total amount of the copper nitrate and the ferric nitrate to the volume of the absolute ethyl alcohol is 11.49mmol (100 mL-120 mL), and the ratio of the volume of the absolute ethyl alcohol to the amount of the anhydrous citric acid is (100 mL-120 mL):7.66 mmol;
adding natural zeolite powder into the copper ferrite sol-state mixed solution at the speed of 10-20 mg/s under the temperature condition of 90-100 ℃, continuously stirring until the copper ferrite sol-state mixed solution is evaporated to dryness, then grinding, heating to 400 ℃, calcining for 8 hours under the temperature condition of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-state mixed solution is 1 (1-5).
The beneficial effects of the embodiment are as follows:
compared with a single ozone system, a single natural zeolite catalytic ozone system and a single copper ferrite catalytic ozone system, the copper ferrite/zeolite spinel composite material greatly improves the efficiency of degrading atrazine by ozone, the degradation rate of atrazine is improved by about 30% within 40 minutes, when the mass ratio of copper ferrite to natural zeolite powder is 1:1, the prepared copper ferrite/zeolite spinel composite material catalyzes ozone to oxidize and degrade atrazine in water, and the complete degradation is achieved within 120 min; the copper ferrite/zeolite spinel composite material prepared by the embodiment has stable performance, and only 0.05 mg/L-0.09 mg/L of metal ions are dissolved out in the water solution after reaction.
The copper ferrite/zeolite spinel composite material prepared by the embodiment has the advantages of simple preparation method, low price of raw materials, strong magnetism, easiness in recovery and reusability.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: adding copper nitrate and ferric nitrate into absolute ethyl alcohol at the temperature of 90-100 ℃ in the first step, and uniformly stirring at the stirring speed of 120-180 r/min.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the first or second differences from the present embodiment are as follows: adding anhydrous citric acid in the step one, and uniformly stirring at a stirring speed of 120-180 r/min to obtain the copper ferrite sol-state mixed solution.
The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: and step two, adding the natural zeolite powder into the copper ferrite sol-state mixed solution at the speed of 10-20 mg/s under the temperature condition of 90-100 ℃, and continuously stirring at the stirring speed of 120-180 r/min until the copper ferrite sol-state mixed solution is evaporated to dryness.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the natural zeolite powder in the second step is prepared by the following steps: taking natural zeolite with consistent particle size, crushing the natural zeolite by a high-speed crusher, and then sequentially washing the natural zeolite by pure water and 0.1mol/L hydrochloric acid to obtain the natural zeolite powder.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and in the second step, the temperature is increased to 400 ℃ at the heating rate of 3 ℃/min, and the calcination is carried out for 8 hours at the temperature of 400 ℃.
The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the particle size of the copper ferrite spinel loaded on the copper ferrite/zeolite spinel composite material in the second step is 2-30 microns.
The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: and in the second step, the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-gel mixed solution is 1: 1.
The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the application of the copper ferrite/zeolite spinel composite material is characterized in that the copper ferrite/zeolite spinel composite material is used as a catalyst and is used for catalyzing ozone oxidation to degrade atrazine in water.
The detailed implementation mode is ten: the ninth embodiment differs from the ninth embodiment in that: when the copper ferrite/zeolite spinel composite material is used as a catalyst, the addition amount is 0.05 g/L-1.0 g/L.
The other steps are the same as in the ninth embodiment.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the copper ferrite/zeolite spinel composite material comprises the following steps:
firstly, placing 120mL of absolute ethyl alcohol in a water bath, adding 3.83mmol of copper nitrate and 7.66mmol of ferric nitrate into 120mL of absolute ethyl alcohol at the temperature of 95 ℃, uniformly stirring at the stirring speed of 180r/min, then adding 7.66mmol of absolute citric acid, and uniformly stirring at the stirring speed of 180r/min to obtain copper ferrite sol-state mixed solution;
adding natural zeolite powder into the copper ferrite sol-phase mixed solution at the speed of 10mg/s under the temperature condition of 95 ℃, continuously stirring at the stirring speed of 180r/min until the copper ferrite sol-phase mixed solution is dried by distillation, then grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 8 hours at the temperature of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the particle size of the copper ferrite spinel loaded on the copper ferrite/zeolite spinel composite material is 2-30 mu m, and the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-phase mixed solution is 1: 1.
The natural zeolite powder in the second step is prepared by the following steps: taking natural zeolite with consistent particle size, crushing the natural zeolite by a high-speed crusher, and then sequentially washing the natural zeolite by pure water and 0.1mol/L hydrochloric acid to obtain the natural zeolite powder.
Example two: the preparation method of the copper ferrite/zeolite spinel composite material comprises the following steps:
firstly, placing 120mL of absolute ethyl alcohol in a water bath, adding 3.83mmol of copper nitrate and 7.66mmol of ferric nitrate into 120mL of absolute ethyl alcohol at the temperature of 95 ℃, uniformly stirring at the stirring speed of 180r/min, then adding 7.66mmol of absolute citric acid, and uniformly stirring at the stirring speed of 180r/min to obtain copper ferrite sol-state mixed solution;
adding natural zeolite powder into the copper ferrite sol-phase mixed solution at the speed of 10mg/s under the temperature condition of 95 ℃, continuously stirring at the stirring speed of 180r/min until the copper ferrite sol-phase mixed solution is dried by distillation, then grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 8 hours at the temperature of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the particle size of the copper ferrite spinel loaded on the copper ferrite/zeolite spinel composite material is 2-30 mu m, and the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-phase mixed solution is 1: 2.
The natural zeolite powder in the second step is prepared by the following steps: taking natural zeolite with consistent particle size, crushing the natural zeolite by a high-speed crusher, and then sequentially washing the natural zeolite by pure water and 0.1mol/L hydrochloric acid to obtain the natural zeolite powder.
Example three: the preparation method of the copper ferrite/zeolite spinel composite material comprises the following steps:
firstly, placing 120mL of absolute ethyl alcohol in a water bath, adding 3.83mmol of copper nitrate and 7.66mmol of ferric nitrate into 120mL of absolute ethyl alcohol at the temperature of 95 ℃, uniformly stirring at the stirring speed of 180r/min, then adding 7.66mmol of absolute citric acid, and uniformly stirring at the stirring speed of 180r/min to obtain copper ferrite sol-state mixed solution;
adding natural zeolite powder into the copper ferrite sol-phase mixed solution at the speed of 10mg/s under the temperature condition of 95 ℃, continuously stirring at the stirring speed of 180r/min until the copper ferrite sol-phase mixed solution is dried by distillation, then grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 8 hours at the temperature of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the particle size of the copper ferrite spinel loaded on the copper ferrite/zeolite spinel composite material is 2-30 mu m, and the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-phase mixed solution is 1: 5.
The natural zeolite powder in the second step is prepared by the following steps: taking natural zeolite with consistent particle size, crushing the natural zeolite by a high-speed crusher, and then sequentially washing the natural zeolite by pure water and 0.1mol/L hydrochloric acid to obtain the natural zeolite powder.
And (3) comparison test:
six 500mL reactors (1# -6 #) were selected at 20 ℃:
adding ultrapure water and 10mmol/L, PH of 7 borax buffer solution into a reactor No. 1, adding the copper ferrite/zeolite spinel composite material prepared in the first embodiment at a ratio of 0.20g/L, finally adding 2 mu mol/L atrazine, introducing ozone, timing the reaction at the moment, and taking points at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.
In a No. 2 reactor, ultrapure water and 10mmol/L, PH borax buffer solution of 7 are added, then the copper ferrite/zeolite spinel composite material prepared in the second example is added according to the proportion of 0.20g/L, finally 2 mu mol/L atrazine is added, at the moment of introducing ozone, the reaction is started, and points are taken at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.
Adding ultrapure water and 10mmol/L, PH of 7 borax buffer solution into a 3# reactor, adding the copper ferrite/zeolite spinel composite material prepared in the third embodiment at the ratio of 0.20g/L, finally adding 2 mu mol/L atrazine, introducing ozone, timing the reaction at the moment, and taking points at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.
Adding ultrapure water and 10mmol/L, PH of 7 borax buffer solution into a No. 4 reactor, adding a natural zeolite catalyst in a ratio of 0.20g/L, adding 2 mu mol/L atrazine, introducing ozone, starting reaction timing at the moment, and respectively taking points at 0min, 2min, 5min, 10min, 20min, 30min and 40 min.
Adding ultrapure water and 10mmol/L, PH of 7 borax buffer solution into a No. 5 reactor, adding a copper ferrite catalyst according to the proportion of 0.20g/L, adding 2 mu mol/L atrazine, introducing ozone, starting the reaction at the moment, and respectively taking points at 0min, 2min, 5min, 10min, 20min, 30min and 40 min.
Adding ultrapure water and 10mmol/L, PH borax buffer solution of 7 in a No. 6 reactor, adding 2 mu mol/L atrazine, introducing ozone, timing reaction, and taking points at 0min, 2min, 5min, 10min, 20min, 30min and 40 min.
FIG. 1 is a graph showing the comparison of the efficiency of atrazine removal in the reactor 1# to 6# in the comparative experiment; as shown in fig. 1, compared with a single ozone system, a single natural zeolite catalytic ozone system and a single copper ferrite catalytic ozone system, the copper ferrite/zeolite spinel composite materials prepared in the first to third embodiments show very high catalytic activity, the atrazine removal rate in water is improved by about 30% compared with the effect of ozone alone within 40 minutes of reaction time, and the copper ferrite/zeolite spinel composite materials have high chemical stability, only the dissolution of trace copper and iron ions in the water solution after the reaction is detected, and can be applied to the field of actual water treatment. The copper ferrite/zeolite catalyst has no obvious adsorption effect; ozone oxidation is used alone, and only a small amount of atrazine can be degraded; therefore, the copper ferrite/zeolite spinel composite materials prepared in the first to third embodiments are simple to manufacture, low in cost, simple to operate and high in catalytic efficiency.
FIG. 2 is a graph showing the removal efficiency of atrazine in water within 0-120 min for the copper ferrite/zeolite spinel composite material prepared in the first embodiment; as shown in FIG. 2, the copper ferrite/zeolite spinel composite material prepared in the first example completely degrades atrazine in water at 120 min.
Claims (1)
1. The preparation method of the copper ferrite/zeolite spinel composite material is characterized by comprising the following steps:
firstly, adding copper nitrate and ferric nitrate into absolute ethyl alcohol at the temperature of 90-100 ℃, uniformly stirring at the stirring speed of 120-180 r/min, then adding absolute citric acid, and uniformly stirring at the stirring speed of 120-180 r/min to obtain copper ferrite sol-state mixed solution, wherein the molar ratio of the copper nitrate to the ferric nitrate is 1:2, the ratio of the total amount of the copper nitrate and the ferric nitrate to the volume of the absolute ethyl alcohol is 11.49mmol (100-120 mL), and the ratio of the volume of the absolute ethyl alcohol to the amount of the absolute citric acid is (100-120 mL):7.66 mmol;
adding natural zeolite powder into the copper ferrite sol-state mixed solution at the temperature of 90-100 ℃, continuously stirring at the stirring speed of 120-180 r/min until the copper ferrite sol-state mixed solution is dried by distillation, then grinding, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 8h at the temperature of 400 ℃, finally air-cooling to room temperature, and grinding to obtain the copper ferrite/zeolite spinel composite material, wherein the particle size of the copper ferrite spinel loaded on the copper ferrite/zeolite spinel composite material is 2-30 mu m; the mass ratio of the copper ferrite to the natural zeolite powder in the copper ferrite sol-gel mixed solution is 1:1, the copper ferrite/zeolite spinel composite material is used as a catalyst and is used for catalyzing ozone oxidation to degrade atrazine in water, and the addition amount of the copper ferrite/zeolite spinel composite material is 0.20 g/L; the natural zeolite powder is prepared by the following steps: taking natural zeolite with consistent particle size, crushing the natural zeolite by a high-speed crusher, and then sequentially washing the natural zeolite by pure water and 0.1mol/L hydrochloric acid to obtain the natural zeolite powder.
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