CN115254176A - Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof - Google Patents
Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof Download PDFInfo
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- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 120
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 112
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 28
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
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- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
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- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 19
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- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
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- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- 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
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- 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
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- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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Abstract
The invention discloses a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite, and a preparation method and application thereof. The preparation method comprises the following steps: mixing and stirring (3-mercaptopropyl) methyldimethoxysilane and a nitrate solution to obtain a solution A; slowly adding a sodium hydroxide solution into the solution A to obtain a solution B; mixing the solution B with a sodium silicate solution, heating in a water bath, and stirring until the solution B is clear to obtain a solution C; continuously condensing, refluxing, heating and stirring the solution C in an oil bath until the solution is brown to obtain a solution D; mixing the solution D with a sodium metaaluminate solution, continuously stirring, and standing until an off-white gel is formed; transferring the gel into a high-pressure reaction kettle for reaction; after the reaction is finished, cooling to room temperature, washing with ethanol and pure water until the pH is 7, and drying in vacuum to obtain the catalyst. The nano zeolite coated heavy metal cluster catalyst is efficient and stable, and can be applied to catalytic wet oxidation treatment of high-concentration alkaline residue wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental catalytic materials, and particularly relates to a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite, and a preparation method and application thereof.
Background
Catalytic wet oxidation is an important and widely applied method in advanced oxidation technology, and organic matters and ammonia in wastewater are respectively oxidized and decomposed into CO by air oxidation under the conditions of certain temperature, pressure and catalyst action2、H2O and N2And the like, thereby achieving the effect of purifying the wastewater. The catalytic wet oxidation method uses a high-efficiency, stable and appropriate catalyst in the wet oxidation reaction process, so that the oxidation reaction can be completed under a milder condition in a shorter time, thereby reducing the reaction temperature and pressure, improving the oxidative decomposition capacity and shortening the time required by the reaction. Meanwhile, the corrosion to equipment can be reduced, and the running cost is reduced. The catalytic wet oxidation technology is an effective method for widely treating high-concentration industrial wastewater, and is rapidly developed at home and abroad. In the catalytic wet oxidation technology, the selection of the catalyst is the core of the technology. The preparation of the catalyst with high efficiency, stability and proper price is a key factor for the application and popularization of the catalytic wet oxidation technology. However, most of the existing environmental or chemical catalytic materials have the problems of high cost, large preparation difficulty, unobvious pollutant treatment effect and the like, so the cost is highThe preparation of efficient, stable catalysts has long been the focus of research personnel in the development of catalytic wet oxidation technology.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides a nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst, a preparation method and application thereof.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite comprises the following steps:
step 4, continuously condensing, refluxing, heating and stirring the solution C in an oil bath until the solution is brown to obtain a solution D;
step 6, transferring the grey-white gel to a high-pressure reaction kettle for reaction;
and 7, cooling to room temperature after the reaction is finished, washing with ethanol and pure water until the pH value of a washing liquid is 7, and drying in vacuum at 75 ℃ to obtain the catalyst.
The improvement is that the nitrate solution in the step 1 is a cerium nitrate solution, a silver nitrate solution or a zirconium nitrate solution, and the concentration is 0.1mol/L-0.5mol/L; the concentration of the (3-mercaptopropyl) methyldimethoxysilane in the solution A is 0.12-0.19mol/L.
The improvement is that the concentration of the sodium hydroxide solution in the step 2 is 1.5mol/L-3.5mol/L, and the volume ratio of the sodium hydroxide solution to the solution A is 1.
The improvement is that the concentration of the sodium silicate solution in the step 3 is 6.1-7.6mol/L, and the volume ratio of the sodium silicate solution to the solution B is 1:2.
the improvement is that in the step 4, the heating temperature of the oil bath condensation reflux is 105-120 ℃, and the heating time is 1-2h.
The improvement is that in the step 5, the concentration of the sodium metaaluminate solution is 5.2-7.5mol/L, the standing time is 7-10h, and the volume ratio of the sodium metaaluminate solution to the solution D is 1.
The improvement is that the reaction temperature of the high-pressure reaction kettle in the step 6 is 180-220 ℃, and the reaction time is 10-12h.
The nano zeolite coated heavy metal cluster catalytic material prepared by any one of the preparation methods.
The application of any one of the nano zeolite-coated heavy metal cluster catalytic materials in the treatment of high-concentration organic wastewater, wherein the COD concentration of the high-concentration organic wastewater is 145000-155000mg/L of high-concentration alkaline residue wastewater in the petrochemical industry.
As an improvement, the temperature of the catalytic wet oxidation reaction in the application is 160-200 ℃, the reaction time is 0.5-3.0h, and the adding amount of the catalyst is 0.50-1.80g added in each liter of waste water.
Has the advantages that:
compared with the prior art, the nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and the preparation method and application thereof have the advantages that the prepared catalyst is nano-scale, efficient and stable, and can be applied to catalytic wet oxidation treatment of alkaline residue wastewater with COD concentration as high as 150000 mg/L. The novel high-efficiency nano zeolite-coated heavy metal cluster catalytic wet oxidation catalyst material disclosed by the invention can be widely applied to treatment of other high-concentration chemical organic wastewater, pharmaceutical wastewater and the like.
Drawings
FIG. 1 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 1;
FIG. 2 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 1;
FIG. 3 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 3;
FIG. 4 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 3;
FIG. 5 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 5;
FIG. 6 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 5
FIG. 7 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 7
FIG. 8 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 7;
FIG. 9 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 9
FIG. 10 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 9;
FIG. 11 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 11;
FIG. 12 shows the results of catalytic wet oxidation under different conditions for the catalyst samples synthesized in example 11;
FIG. 13 shows the SEM results of samples of the catalyst synthesized in example 1;
FIG. 14 shows SEM results of samples of the catalyst synthesized in example 3;
FIG. 15 shows the SEM results of a sample of the catalyst synthesized in example 5.
FIG. 16 shows the SEM results of a sample of the catalyst synthesized in example 7;
FIG. 17 shows SEM results of samples of the catalyst synthesized in example 9;
FIG. 18 shows SEM results of samples of the catalyst synthesized in example 11;
FIG. 19 is a flow chart of the manufacturing process and application of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite comprises the following steps:
1) Mixing and stirring (3-mercaptopropyl) methyldimethoxysilane and 0.16mol/L cerium nitrate solution for 45 minutes to obtain solution A, wherein the concentration of the (3-mercaptopropyl) methyldimethoxysilane in the solution A is 0.12mol/L;
2) Slowly adding 1.5mol/L of sodium hydroxide solution into the solution A to obtain solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1;
3) Mixing the solution B with 6.1mol/L sodium silicate solution, heating and stirring the mixture in water bath at 60 ℃ until the mixture is clear, thus obtaining a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1;
4) Continuously condensing, refluxing, heating and stirring the solution C in an oil bath kettle at 105 ℃ for 1.5 hours until the solution is brown to obtain a solution D;
5) Mixing the solution D with 5.5mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 7h to form offwhite gel; wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1;
6) Transferring the grey white gel into a high-pressure reaction kettle, and reacting for 10 hours at 180 ℃;
7) After the reaction is finished, cooling to room temperature, washing with ethanol and pure water until the pH value of the washing liquid is 7, and drying in vacuum at 75 ℃ to obtain the catalyst.
The catalyst prepared in the embodiment is applied to the treatment of high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet rotary stirring reaction kettle), and the specific procedures are as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, the high-pressure reaction kettle is sealed, and a certain oxygen partial pressure is maintained. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was taken with a disposable syringe, filtered with filter paper, and analyzed for residual Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) concentration in the sample.
The initial COD concentration of the caustic sludge wastewater is 153609mg/L, and the TOC concentration is 148943mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from fig. 1, the removal rate of wet oxidation was significantly improved after the addition of the catalyst. If the reaction temperature is 160 ℃ and the reaction time is 2.5h, the removal rate of COD and TOC of the organic wastewater by the wet oxidation device without the catalyst is 30.35 percent and 27.41 percent respectively. When 0.5g/L of catalyst is added under similar conditions, the removal rate of COD of the alkaline residue wastewater by catalytic wet oxidation is improved to 60.29%, and the removal rate of TOC is 57.38%, which is improved by about 30% compared with the removal rate of a wet oxidation system. When the amount of the catalyst is further increased to 1.5g/L, the removal rate of COD and TOC of the wastewater by catalytic wet oxidation under similar reaction conditions is increased by about 38 percent compared with the wet oxidation system rate. This indicates that increasing the amount of catalyst is effective in promoting the removal of wastewater contaminants by the catalytic wet oxidation system.
Example 2
The catalyst prepared in the embodiment 1 is applied to the treatment of high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet rotary stirring reaction kettle), and the specific procedures are as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, the high-pressure reaction kettle is sealed, and a certain oxygen partial pressure is maintained. And heating the reaction kettle to a set reaction temperature, and carrying out a catalytic wet oxidation experiment on the alkali residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the reaction product to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. Then opening the reaction kettle, taking partial supernatant with a disposable syringe, and filteringThe paper was filtered and the samples were analyzed for residual Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) concentration. The initial COD concentration of the caustic sludge wastewater is 153609mg/L, and the TOC concentration is 148943mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As seen from fig. 2, the reaction temperature has a large influence on the catalytic wet oxidation, and the higher the reaction temperature is, the more significant the pollutant removal effect is. If the reaction temperature is 175 ℃, the reaction time is 2.5 hours, and the adding amount of the catalyst is 1.5g/L, the removal rate of COD of the organic wastewater by the catalytic wet oxidation system is 87.23 percent, the removal rate of TOC is 85.59 percent, and the removal rate of COD and TOC is improved by about 18 percent compared with the removal rate of COD and TOC when the reaction temperature is 160 ℃ under similar conditions. The reaction temperature is continuously increased to 195 ℃, and the removal rates of the catalytic wet oxidation system to the COD and the TOC of the wastewater are respectively as high as 95.43 percent and 93.25 percent.
Example 3
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst wrapped by nano zeolite comprises the following steps:
1) (3-mercaptopropyl) methyldimethoxysilane was mixed with a cerium nitrate solution having a concentration of 0.24mol/L and stirred for 45 minutes to obtain a solution A in which the concentration of (3-mercaptopropyl) methyldimethoxysilane in the solution A was 0.14mol/L.
2) Slowly adding 2.4mol/L of sodium hydroxide solution into the solution A to obtain a solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1.
3) And mixing the solution B with 6.5mol/L sodium silicate solution, heating in a water bath at 60 ℃, and stirring until the solution is clear to obtain a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1.
4) And continuously carrying out condensation reflux heating and stirring on the solution C in an oil bath kettle at the temperature of 115 ℃ for 1.5h until the solution is brown to obtain a solution D.
5) Mixing the solution D with 5.9mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 8h until an off-white gel is formed, wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1.
6) The off-white gel was transferred to an autoclave and reacted at 185 ℃ for 11h.
7) After the reaction is finished, cooling to room temperature, washing by using ethanol and pure water until the pH value of a washing liquid is 7, and drying in vacuum at 75 ℃ to obtain a catalyst product.
The catalyst prepared in the embodiment is used for treating caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet type rotary stirring reaction kettle), and the specific procedures are as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was taken with a disposable syringe, filtered with filter paper, and analyzed for residual Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) concentration in the sample. The initial COD concentration of the caustic sludge wastewater is 146083mg/L, and the TOC concentration is 132865mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As seen in fig. 3, the catalytic wet oxidation system has a higher removal efficiency of wastewater than the wet oxidation system. After the catalyst is added, the catalytic removal effect of the wastewater is obviously improved. The reaction temperature is 165 ℃, the reaction time is 2.5h, the removal rate of COD of the wastewater by the wet oxidation device without the catalyst is 32.78%, and the removal rate of TOC is 30.53%. When 0.6g/L of catalyst is added, the removal rate of COD and TOC in the wastewater by catalytic wet oxidation under similar conditions is respectively 64.80 percent and 61.63 percent, which is improved by more than 30 percent compared with the removal rate of pollutants in a wet oxidation system, and shows that the catalyst can effectively improve the degradation rate of the alkaline residue wastewater to the pollutants.
Example 4
The alkaline residue wastewater is treated in a catalytic wet oxidation device (GCF permanent magnet rotary stirring reaction kettle) by using the catalyst prepared in the example 3, and the specific procedure is as follows:
1500mL of alkaline residue wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed to keep a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the reaction product to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. Then the reaction kettle is opened, a part of supernatant is taken by a disposable syringe, and is filtered by filter paper, and the residual Chemical Oxygen Demand (COD) and the concentration of Total Organic Carbon (TOC) in the sample are analyzed. The initial COD concentration of the caustic sludge wastewater is 146083mg/L, and the TOC concentration is 132865mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from fig. 4, increasing the amount of catalyst and the reaction temperature both promote the removal rate of pollutants by catalytic wet oxidation. Such as: the reaction temperature is 165 ℃, the reaction time is 2.5 hours, the adding amount of the catalyst is 1.3g/L, the removal rate of the catalytic wet oxidation system to the COD and the TOC of the wastewater is respectively improved to 74.90 percent and 72.62 percent, and the degradation rate of the system pollutants is improved by 10 percent compared with the system pollutants of which the catalyst is 0.6g/L under the similar conditions. In addition, when the reaction temperature is increased to 185 ℃, the adding amount of the catalyst is 1.3g/L, and the reaction time is 2.5h, the removal rate of the catalytic wet oxidation system to the COD and the TOC of the wastewater is further increased to 91.46 percent and 88.35 percent respectively.
Example 5
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite comprises the following steps:
1) (3-mercaptopropyl) methyldimethoxysilane was mixed with a silver nitrate solution having a concentration of 0.25mol/L and stirred for 45 minutes to obtain a solution A in which the concentration of (3-mercaptopropyl) methyldimethoxysilane in the solution A was 0.16mol/L.
2) Slowly adding 2.2mol/L of sodium hydroxide solution into the solution A to obtain a solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1.
3) And mixing the solution B with 6.9mol/L sodium silicate solution, heating in a water bath (60 ℃) and stirring until the solution B is clear to obtain a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1.
4) Solution C was heated under reflux in an oil bath at 105 ℃ for 1.6h to brown to give solution D.
5) Mixing the solution D with 5.9mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 7h until an off-white gel is formed, wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1.
6) Transferring the grey white gel into a high-pressure reaction kettle, and reacting for 11h at 190 ℃.
7) After the reaction is finished, cooling to room temperature, washing with ethanol and pure water until the pH value of the washing liquid is 7, and drying in vacuum at 75 ℃ to obtain the catalyst product.
The catalyst prepared in the embodiment is used for treating high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet type rotary stirring reaction kettle), and the specific procedures are as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and carrying out a catalytic wet oxidation experiment on the alkali residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the reaction product to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened and a portion of the supernatant was taken with a disposable syringe and filtered through filter paper to analyze the residual COD and TOC concentrations in the sample. The initial COD concentration of the caustic sludge wastewater is 148721mg/L, and the TOC concentration is 135761mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from FIG. 5, the addition of the catalyst can greatly increase the removal rate of the pollutants in the wastewater by wet oxidation. If the reaction temperature is 170 ℃ and the reaction time is 2.5h, the removal rate of COD and TOC of the organic wastewater by the wet oxidation system is 36.53 percent and 33.65 percent respectively. When 0.5g/L of catalyst is added, the removal rate of pollutants in the wastewater by the catalytic wet oxidation system is increased to a great extent, and the removal rates of COD and TOC under similar conditions are respectively increased to 65.21 percent and 63.01 percent.
Example 6
The catalyst prepared in example 5 is used for treating high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet rotary stirring reaction kettle), and the specific procedure is as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, the high-pressure reaction kettle is sealed, and a certain oxygen partial pressure is maintained. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was removed with a disposable syringe, filtered through filter paper, and analyzed for residual COD and TOC concentrations in the sample. The initial COD concentration of the caustic sludge wastewater is 148721mg/L, and the TOC concentration is 135761mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from fig. 6, increasing the amount of the catalyst and increasing the reaction temperature can significantly increase the removal rate of the pollutants in the catalytic wet oxidation wastewater. Such as: when the amount of the catalyst is 1.5g/L, the reaction temperature is 170 ℃, the reaction time is 2.5h, the removal rate of the catalytic wet oxidation system to COD and TOC of the wastewater is 81.49 percent and 78.49 percent respectively, the removal rate of the pollutants of the system is improved by about 15 percent compared with the removal rate of the pollutants of the system under the similar condition with 0.5g/L of the catalyst, and the removal rate of the pollutants of the system is improved by 45 percent compared with the removal rate of the pollutants of the wet oxidation system without the catalyst. When the reaction temperature is increased to 200 ℃, the reaction time is 2.5h, the catalyst amount is 1.5g/L, the removal rate of COD by the catalytic wet oxidation system is up to 98.89%, and the removal rate of TOC is 96.58%.
Example 7
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst wrapped by nano zeolite comprises the following steps:
1) (3-mercaptopropyl) methyldimethoxysilane was mixed with a silver nitrate solution having a concentration of 0.33mol/L and stirred for 45 minutes to obtain a solution A in which the concentration of (3-mercaptopropyl) methyldimethoxysilane in the solution A was 0.17mol/L.
2) And slowly adding 2.4mol/L of sodium hydroxide solution into the solution A to obtain a solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1.
3) And mixing the solution B with 7.1mol/L sodium silicate solution, heating in a water bath (60 ℃) and stirring until the solution B is clear to obtain a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1.
4) Solution C was heated under reflux in an oil bath at 108 deg.C for 1.7h to brown to give solution D.
5) Mixing the solution D with 6.4mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 8.5h until an off-white gel is formed, wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1.
6) Transferring the off-white gel into an autoclave, and reacting for 12 hours at 210 ℃.
7) After the reaction is finished, cooling to room temperature, washing with ethanol and pure water until the pH value of the washing liquid is 7, and drying in vacuum at 75 ℃ to obtain the catalyst product.
The catalyst prepared in the embodiment is used for treating high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet type rotary stirring reaction kettle), and the specific procedures are as follows:
adding 1500mL of alkaline residue wastewater into a 2.0L permanent magnet type rotary stirring reaction kettle, and adding a certain amount of catalystMixing the agents, sealing the high-pressure reaction kettle and keeping a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and carrying out a catalytic wet oxidation experiment on the alkali residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. Then the reaction kettle is opened, a part of supernatant is taken by a disposable syringe, and is filtered by filter paper, and the residual COD and TOC concentration in the sample are analyzed. The initial COD concentration of the wastewater was 150134mg/L, and the TOC concentration was 138266mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As seen in fig. 7, the catalytic wet oxidation system with the added catalyst can significantly promote the removal of wastewater pollutants. The reaction temperature is 175 ℃, the reaction time is 2.5 hours, and the removal rate of COD and TOC of the catalytic wet oxidation system added with 0.7g/L of catalyst is improved by about 30 percent compared with the removal rate of COD and TOC of the wet oxidation system.
Example 8
The catalyst prepared in this example 7 was used to treat high-concentration caustic sludge wastewater in a catalytic wet oxidation unit (GCF permanent magnet rotary stirred tank reactor), and the specific procedure was as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, the high-pressure reaction kettle is sealed, and a certain oxygen partial pressure is maintained. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened and a portion of the supernatant was taken with a disposable syringe and filtered through filter paper to analyze the residual COD and TOC concentrations in the sample. The initial COD concentration of the wastewater was 150134mg/L, and the TOC concentration was 138266mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from fig. 8, increasing the amount of the catalyst, extending the reaction time, and increasing the reaction temperature can improve the pollutant degradation efficiency to some extent. The reaction temperature is 190 ℃, the reaction time is 2.5h, and the removal rate of pollutants by a catalytic wet oxidation system added with 1.4g/L of catalyst is more than 90%.
Example 9
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst coated by nano zeolite comprises the following steps:
1) (3-mercaptopropyl) methyldimethoxysilane was mixed with a zirconium nitrate solution having a concentration of 0.36mol/L and stirred for 45 minutes to obtain a solution A in which the concentration of (3-mercaptopropyl) methyldimethoxysilane in the solution A was 0.18mol/L.
2) Slowly adding 3.2mol/L of sodium hydroxide solution into the solution A to obtain a solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1.
3) And mixing the solution B with 7.3mol/L sodium silicate solution, heating in a water bath (60 ℃) and stirring until the solution B is clear to obtain a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1.
4) The solution C was heated under continuous condensing reflux in an oil bath at 110 deg.C for 1.8h with stirring until the solution was brown to give solution D.
5) Mixing the solution D with 6.6mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 8.5h until an off-white gel is formed, wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1.
6) Transferring the grey white gel into a high-pressure reaction kettle, and reacting for 12h at the temperature of 200 ℃.
7) After the reaction is finished, cooling to room temperature, washing with ethanol and pure water until the pH value of the washing liquid is 7, and drying in vacuum at 75 ℃ to obtain the catalyst product.
The catalyst prepared in the embodiment is used for treating caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet type rotary stirring reaction kettle), and specificallyThe procedure is as follows: 1500mL of high-concentration caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was removed with a disposable syringe, filtered through filter paper, and analyzed for residual COD and TOC concentrations in the sample. The initial COD concentration of the wastewater was 152705mg/L and the TOC concentration was 140071mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from fig. 9, the addition of the catalyst greatly improves the removal rate of the wet oxidation. In addition, the extension of the reaction time can also increase the effect of wastewater removal. The reaction temperature is 180 ℃, the reaction time is 3.0h, and the removal rate of pollutants by the catalytic wet oxidation system is improved by 28 percent when the catalyst amount is 0.6g/L compared with the wet oxidation system without the catalyst.
Example 10
The catalyst prepared in this example 9 was used to treat caustic sludge wastewater in a catalytic wet oxidation unit (GCF permanent magnet rotary stirred tank reactor), and the specific procedure was as follows:
1500mL of high-concentration caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. Then opening the reaction kettle, and taking out part of the reaction kettle by using a disposable syringeThe supernatant was filtered through filter paper and analyzed for residual COD and TOC concentrations in the samples. The initial COD concentration of the wastewater was 152705mg/L and the TOC concentration was 140071mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As can be seen from FIG. 10, the increase of the amount of the catalyst and the increase of the reaction temperature can improve the removal rate of the pollutants in the wastewater. When the reaction temperature is 195 ℃, the reaction time is 3.0h and the catalyst amount is 1.8g/L, the removal rates of the organic wastewater COD and TOC by the catalytic wet oxidation system are respectively up to 96.73 percent and 94.50 percent.
Example 11
A preparation method of a heavy metal cluster catalytic wet oxidation catalyst wrapped by nano zeolite comprises the following steps:
1) (3-mercaptopropyl) methyldimethoxysilane was mixed with a zirconium nitrate solution having a concentration of 0.50mol/L and stirred for 45 minutes to obtain a solution A in which the concentration of (3-mercaptopropyl) methyldimethoxysilane in the solution A was 0.19mol/L.
2) Slowly adding 3.4mol/L of sodium hydroxide solution into the solution A to obtain a solution B, wherein the volume ratio of the sodium hydroxide solution to the solution A is 1.
3) And mixing the solution B with 7.6mol/L sodium silicate solution, heating in a water bath (at 60 ℃), and stirring until the solution B is clear, so as to obtain a solution C, wherein the volume ratio of the sodium silicate solution to the solution B is 1.
4) The solution C was heated and stirred in an oil bath kettle at 120 ℃ under continuous condensing reflux for 2.0h until the solution was brown to give solution D.
5) And mixing the solution D with 7.1mol/L sodium metaaluminate solution, continuously stirring for 2h at room temperature, and standing for 8.5h until an off-white gel is formed, wherein the volume ratio of the sodium metaaluminate solution to the solution D is 1.
6) The off-white gel is transferred to an autoclave and reacted for 11h at 215 ℃.
7) After the reaction is finished, cooling to room temperature, washing by using ethanol and pure water until the pH value of a washing liquid is 7, and drying in vacuum at 75 ℃ to obtain a catalyst product.
The catalyst prepared in the embodiment is used for treating high-concentration caustic sludge wastewater in a catalytic wet oxidation device (GCF permanent magnet rotary stirring reaction kettle), and the specific procedures are as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring. And cooling the catalyst to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was removed with a disposable syringe, filtered through filter paper, and analyzed for residual COD and TOC concentrations in the sample. The initial COD concentration of the wastewater was 154851mg/L and the TOC concentration was 149624mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
Fig. 11 shows that the removal effect of the catalytic wet oxidation system on the pollutants is significantly increased compared to the wet oxidation system. The catalyst amount is 0.8g/L, and when the reaction temperature is 185 ℃, the removal rate of the waste water by catalytic wet oxidation for 3.0h is about 33 percent higher than that of wet oxidation.
Example 12
The catalyst prepared in this example 11 was used to treat high-concentration caustic sludge wastewater in a catalytic wet oxidation unit (GCF permanent magnet rotary stirred tank reactor), and the specific procedure was as follows:
1500mL of caustic sludge wastewater is added into a 2.0L permanent magnet type rotary stirring reaction kettle, a certain amount of catalyst is added for mixing, and the high-pressure reaction kettle is sealed and kept at a certain oxygen partial pressure. And heating the reaction kettle to a set reaction temperature, and then carrying out a catalytic wet oxidation experiment on the alkaline residue wastewater. In the experimental process, a mechanical stirrer is adopted for stirring, and circulating water is utilized to protect electronic equipment for controlling temperature and non-reaction machinery for stirring.And cooling the reaction product to room temperature by using cooling water after the catalytic wet oxidation experiment is finished. The reaction vessel was then opened, a portion of the supernatant was removed with a disposable syringe, filtered through filter paper, and analyzed for residual COD and TOC concentrations in the sample. The initial COD concentration of the wastewater was 154851mg/L and the TOC concentration was 149624mg/L. COD removal rate = (COD)Before reaction-CODAfter the reaction)÷CODBefore reactionX 100%, TOC removal rate = (TOC)Before reaction-TOCAfter the reaction)÷TOCBefore reaction×100%。
As seen in fig. 12, increasing the reaction temperature increased the removal rate of wastewater contaminants. Meanwhile, comparing the experimental results of fig. 11, increasing the amount of the catalyst can also improve the pollutant removal effect. The reaction temperature is 200 ℃, the reaction time is 3.0h, and when the catalyst amount is 1.8g/L, the removal rates of COD and TOC in the wastewater of the catalytic wet oxidation system are respectively 98.86 percent and 96.67 percent.
As can be seen from fig. 13 to 19, the properties of the catalyst are different according to the preparation process of the method for preparing a nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to the present invention. Fig. 13 shows that the catalysts obtained in example 1 and example 2 exhibit a mixture of nano-bulk and rod-like structures. Fig. 14 shows that the catalysts obtained in example 3 and example 4 still show the mixing of nano-block and rod structures, but agglomeration occurs in a part of the area. Fig. 15 shows that the catalysts obtained in example 5 and example 6 have a nanorod structure, and agglomeration occurs in a partial region. The catalysts obtained in examples 7 to 12 shown in fig. 16 to 18 exhibit good nanorod structures without agglomeration.
The nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst is applied to the treatment of high-concentration alkaline residue wastewater in the petrochemical industry, has stable catalytic effect, has a pollutant removal rate of over 95 percent, can effectively reduce the concentration of pollutants in the wastewater, and reduces the pollution and harm to the environment.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a heavy metal cluster catalytic wet oxidation catalyst wrapped by nano zeolite is characterized by comprising the following steps:
step 1, mixing (3-mercaptopropyl) methyldimethoxysilane and a nitrate solution, and stirring for 45-60 minutes to obtain a solution A;
step 2, slowly adding a sodium hydroxide solution into the solution A to obtain a solution B;
step 3, mixing the solution B with a sodium silicate solution, and heating in a water bath to be clear while stirring at the temperature of 60-70 ℃ to obtain a solution C;
step 4, continuously condensing, refluxing, heating and stirring the solution C in an oil bath until the solution is brown to obtain a solution D;
step 5, mixing the solution D with a sodium metaaluminate solution, continuously stirring for 2-3h at room temperature, and standing until an off-white gel is formed;
step 6, transferring the grey-white gel to a high-pressure reaction kettle for reaction;
and 7, cooling to room temperature after the reaction is finished, washing with ethanol and pure water until the pH value of a washing solution is 7, and drying in vacuum at 75 ℃ to obtain the catalyst.
2. The preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein the nitrate solution in step 1 is a cerium nitrate solution, a silver nitrate solution, or a zirconium nitrate solution, and the concentration of the nitrate solution is 0.1mol/L to 0.5mol/L; the concentration of the (3-mercaptopropyl) methyldimethoxysilane in the solution A is 0.12-0.19mol/L.
3. The preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein the concentration of the sodium hydroxide solution in the step 2 is 1.5mol/L-3.5mol/L, and the volume ratio of the sodium hydroxide solution to the solution A is 1.
4. The preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein in the step 3, the concentration of the sodium silicate solution is 6.1-7.6mol/L, and the volume ratio of the sodium silicate solution to the solution B is 1:2.
5. the preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein in the step 4, the oil bath condensation reflux heating temperature is 105-120 ℃, and the heating time is 1-2h.
6. The preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein in the step 5, the concentration of the sodium metaaluminate solution is 5.2-7.5mol/L, the standing time is 7-10h, and the volume ratio of the sodium metaaluminate solution to the solution D is 1.
7. The preparation method of the nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst according to claim 1, wherein the reaction temperature of the high-pressure reaction kettle in the step 6 is 180-220 ℃, and the reaction time is 10-12h.
8. The nano zeolite coated heavy metal cluster catalytic material prepared by the method of any one of claims 1 to 7.
9. The application of the nano zeolite coated heavy metal cluster catalytic material prepared according to claim 1 or claim 8 in treating high-concentration organic wastewater, wherein the COD concentration of the high-concentration organic wastewater is 145000-155000mg/L high-concentration alkaline residue wastewater in the petrochemical industry.
10. The use according to claim 9, wherein the temperature of the catalytic wet oxidation reaction in the use is 160-200 ℃, the reaction time is 0.5-3.0h, and the adding amount of the catalyst is 0.50-1.80g per liter of wastewater.
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