CN115709057A - Ozone oxidation catalyst for industrial wastewater treatment and preparation method thereof - Google Patents
Ozone oxidation catalyst for industrial wastewater treatment and preparation method thereof Download PDFInfo
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- CN115709057A CN115709057A CN202211291824.XA CN202211291824A CN115709057A CN 115709057 A CN115709057 A CN 115709057A CN 202211291824 A CN202211291824 A CN 202211291824A CN 115709057 A CN115709057 A CN 115709057A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 230000003647 oxidation Effects 0.000 title claims abstract description 89
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 59
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 53
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 34
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 27
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 22
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 20
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
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- 238000001914 filtration Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
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- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000006385 ozonation reaction Methods 0.000 claims description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 3
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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Abstract
The invention relates to the technical field of wastewater treatment, and particularly discloses an ozone oxidation catalyst for industrial wastewater treatment and a preparation method thereof, wherein the ozone oxidation catalyst comprises the following raw materials: montmorillonite, palygorskite, spodumene, metal nitrate solutions; wherein the ozone oxidation catalyst is prepared by taking powder as a carrier, soaking the powder in excessive metal nitrate solution and then roasting, and the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10: 1. The ozone oxidation catalyst provided by the embodiment of the invention adopts the carrier material prepared by taking montmorillonite, palygorskite and spodumene as base materials to load the active component, effectively ensures the ozone oxidation efficiency of the catalyst by reasonably using various raw materials and modification operation, solves the problem that the existing ozone oxidation catalyst based on the montmorillonite carrier cannot ensure the mechanical strength and simultaneously improves the ozone oxidation efficiency, and has wide market prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an ozone oxidation catalyst for industrial wastewater treatment and a preparation method thereof.
Background
With the continuous development of society, people have an increasing awareness of environmental protection. The industrial wastewater as wastewater, sewage and waste liquid generated in the industrial production process has the characteristics of large volume, difficult treatment and the like, and particularly, the industrial wastewater discharged from petrochemical enterprises, coal chemical or coking enterprises, acid-base industries, pharmaceutical industries, dye industries and the like can cause great harm to the environment if not effectively treated, thereby seriously affecting the health and safety of human beings.
At present, the main treatment method of industrial wastewater is as follows: 1. chemical treatment; 2. biological treatment; 3. a physical treatment method; 4. physical and chemical comprehensive treatment method. The ozone oxidation treatment is a treatment method for oxidizing organic matters or inorganic matters in industrial wastewater by using ozone as a strong oxidant so as to achieve the purposes of disinfection, oxidation or decoloration, and has the advantages of fast reaction, small using amount, easy local preparation, convenient operation, no secondary pollution and the like, so that the ozone oxidation treatment is widely applied. There are many kinds of catalysts for ozone oxidation, for example, clay-based, activated carbon-based, activated alumina-based catalysts, and the like.
However, the above technical solutions have the following disadvantages in practical use: the ozone oxidation catalyst among the prior art mostly has the problem that can't guarantee improvement ozone oxidation efficiency when mechanical strength, to needing to let in ozone and carrying out ozone oxidation's operational environment, the ozone that constantly drums into can cause the impact to the catalyst, easily leads to appearing the loss of catalyst, and ozone oxidation efficiency can't obtain effective assurance.
Disclosure of Invention
The present invention provides an ozone oxidation catalyst for industrial wastewater treatment, so as to solve the problems that most existing ozone oxidation catalysts for industrial wastewater treatment in the background art have low mechanical strength, and ozone oxidation efficiency cannot be effectively guaranteed for a working environment in which ozone needs to be introduced for ozone oxidation.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an ozone oxidation catalyst for industrial wastewater treatment is prepared by using powder as a carrier, soaking the carrier in excessive metal nitrate solution and then roasting the impregnated carrier; wherein the powder material is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10: 1.
Another object of an embodiment of the present invention is to provide a method for preparing an ozone oxidation catalyst for industrial wastewater treatment, including the steps of:
1) Weighing powder as a carrier, and adding the powder into excessive metal nitrate solution for impregnation to obtain an impregnation material;
2) And roasting the impregnated material after heat treatment to obtain the ozone oxidation catalyst for industrial wastewater treatment.
Furthermore, the ozone oxidation catalyst for industrial wastewater treatment is suitable for the advanced oxidation technology of industrial wastewater, and mainly aims at advanced oxidation chain scission processes, particularly ozone oxidation processes and the like, which are performed in petrochemical enterprises, coal chemical industries or coking enterprises and are not high in wastewater biodegradability. Through ozone oxidation catalyst can carry out ozone oxidation with the waste water of petrochemical enterprise or coal chemical industry or coking enterprise, has effectively improved ozone oxidation efficiency.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the ozone oxidation catalyst for industrial wastewater treatment provided by the embodiment of the invention is prepared by taking powder as a carrier, soaking the powder in excessive metal nitrate solution and then roasting, wherein the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10: 1. The ozone oxidation catalyst provided by the embodiment of the invention adopts the carrier material prepared by taking montmorillonite, palygorskite and spodumene as the base material to load the active component, effectively ensures the ozone oxidation efficiency of the catalyst by reasonably using various raw materials and modification operation, solves the problem that most of ozone oxidation catalysts based on montmorillonite carriers in the prior art cannot ensure the mechanical strength and simultaneously improve the ozone oxidation efficiency, and has wide market prospect.
Drawings
FIG. 1 is a table showing the results of the TOC removal rate measurements of an ozone oxidation catalyst for industrial wastewater treatment according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments. The following examples will assist those skilled in the art in further understanding the embodiments of the present invention, but are not intended to limit the embodiments of the present invention in any way. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the embodiments of the present invention. These are all within the scope of the embodiments of the present invention.
In the embodiment of the invention, the ozone oxidation catalyst for industrial wastewater treatment comprises the following raw materials: montmorillonite, palygorskite, spodumene, metal nitrate solutions; specifically, the ozone oxidation catalyst for industrial wastewater treatment is prepared by soaking powder serving as a carrier in an excessive metal nitrate solution and then roasting the soaked powder; wherein the powder material is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10: 1.
As another preferable embodiment of the invention, the preparation method of the powder material comprises the steps of weighing montmorillonite, palygorskite and spodumene according to the proportion to prepare powder, carrying out ultrasonic treatment under acidic conditions, filtering, washing, adding tetrabutyl titanate ethanol solution, mixing uniformly, washing, drying, heating to 400-500 ℃ under hydrogen atmosphere, keeping the temperature for 1-6 hours, and grinding to obtain the powder material.
Preferably, the powder material is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to a certain weight ratio of 8: 1.
As another preferable example of the embodiment of the present invention, the tetrabutyl titanate ethanol solution is added at a concentration of 1 to 10% by weight in an amount of 0.1 times the weight of the solid obtained by filtration.
As another preferred embodiment of the present invention, when the tetrabutyl titanate ethanol solution is added to be mixed uniformly, it is actually a pre-dipping process, provided that: the time is 4h, the temperature is 30 ℃, and the pressure is 0.15MPa.
As another preferred embodiment of the present invention, the metal nitrate solution is prepared by adding the powder material to the metal nitrate solution exceeding the volume of the powder material by an excess impregnation method, and standing for 24 hours, specifically, 2 ml of the metal nitrate solution is usually added to 1 g of the powder material.
As another preferred embodiment of the present invention, the metal nitrate solution contains magnesium nitrate and cobalt nitrate, and the molar ratio of the magnesium nitrate to the cobalt nitrate is 1 mol: 5-15mmol.
As another preferred embodiment of the present invention, the metal nitrate solution is obtained by dissolving 1mol of magnesium nitrate and 10mmol of cobalt nitrate in deionized water, and uniformly dispersing to prepare 1L of solution. In practical application, a small amount of beta-aminoisobutanol aroma is required to be added, the beta-aminoisobutanol aroma can be mixed with water and used as an additive, the dispersant and the pH adjusting function are achieved, and the impregnation effect of the metal nitrate solution in the process of standing for 24 hours can be effectively guaranteed.
As another preferred embodiment of the present invention, the ultrasonic treatment is ultrasonic oscillation for 4 hours under the conditions that the ultrasonic power is 20-40kHz and the temperature is 60-90 ℃.
As another preferred embodiment of the invention, the powder material is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to a certain ratio of 8: 1; the preparation method of the powder comprises the steps of weighing montmorillonite, palygorskite and spodumene according to a proportion, mixing and ball-milling the mixture to obtain powder, carrying out ultrasonic treatment under an acidic condition (specifically, carrying out ultrasonic oscillation under the conditions that the ultrasonic power is 30kHz and the temperature is 70 ℃ to generate a cavitation effect, peeling the powder such as montmorillonite stacked in a layered mode into two-dimensional sheets by the acidic etching and the ultrasonic oscillation, completing dispersion and uniform mixing to obtain a mixed solution, filtering and washing the mixed solution to be neutral, adding a tetrabutyl titanate ethanol solution (the washed material contains a small amount of moisture without drying), hydrolyzing tetrabutyl titanate in the tetrabutyl titanate ethanol solution to form titanic acid, loading the tetrabutyl titanate ethanol solution on the washed material as an auxiliary oxidant, effectively improving the oxidation effect, ensuring the catalytic activity of an ozone oxidation catalyst for industrial wastewater treatment), uniformly mixing, reacting for 3 hours at 75 ℃, washing, drying, heating the mixed material in a hydrogen atmosphere (the condition that the two-dimensional sheets formed before are sintered together due to heating in an air atmosphere is avoided), and carrying out heat preservation for 4 hours to obtain the powder.
As another preferred embodiment of the present invention, the powder is a powdery material ground into 100-800 mesh by ball milling.
As another preferred embodiment of the present invention, the system is made acidic by using sulfuric acid, boric acid, hydrochloric acid, silicic acid, etc. under the acidic condition, preferably, the powder is mixed with 1-5% by weight of sulfuric acid aqueous solution according to 1 g: mixing at a ratio of 200-500 ml.
In another preferred embodiment of the present invention, the washing with water to neutrality is to wash the solid obtained by filtering the mixed solution with pure water for 3 times or more until the pH of the washing solution is between 7 and 8.
In the embodiment of the invention, the active component is loaded by adopting the carrier material prepared by taking montmorillonite, palygorskite and spodumene as base materials, compared with the method of directly adopting a calcined montmorillonite carrier alone, the method can improve the specific surface area to increase the catalytic effect and ensure the mechanical strength, and the prepared ozone oxidation catalyst for industrial wastewater treatment can better adapt to the operation condition for industrial wastewater treatment. Solves the problem that the ozone oxidation catalyst in the prior art, especially the ozone oxidation catalyst based on the montmorillonite carrier mostly has the problem that the mechanical strength can not be ensured and the ozone oxidation efficiency can not be improved.
The embodiment of the invention also provides a preparation method of the ozone oxidation catalyst for industrial wastewater treatment, which specifically comprises the following steps:
1) Weighing powder as a carrier, and adding the powder into excessive metal nitrate solution for impregnation to obtain an impregnation material;
2) And roasting the impregnated material after heat treatment to obtain the ozone oxidation catalyst for industrial wastewater treatment.
In another preferred embodiment of the present invention, in the preparation method of the ozone oxidation catalyst for industrial wastewater treatment, the calcination is to heat treat the impregnated material obtained after impregnation, then raise the temperature to 450 ℃ at a temperature raising rate of 1-10 ℃/min, and perform calcination at a constant temperature for 2-8h to obtain the ozone oxidation catalyst for industrial wastewater treatment.
As another preferred embodiment of the present invention, in the preparation method of the ozone oxidation catalyst for industrial wastewater treatment, the method further comprises the steps of drying the impregnated material obtained after impregnation as a catalyst precursor in an oven at 120 ℃ for 2 hours before calcination, placing the catalyst precursor in a closed system, and performing constant temperature treatment at 90 ℃ for 24 hours, that is, the heat treatment operation.
It should be noted that, the preparation of the embodiment of the present invention is performed by using an impregnation method, which is simple and convenient, and compared with a blend type, the preparation method has higher process feasibility and no obvious disadvantage in catalytic performance.
As another preferred embodiment of the present invention, the preparation method of the ozone oxidation catalyst for industrial wastewater treatment comprises the following steps:
1) Weighing powder as a carrier, and adding the powder into an excessive metal nitrate solution for impregnation to obtain an impregnation material;
2) And (3) drying the impregnated material as a catalyst precursor in a 120 ℃ oven for 2h, placing the catalyst precursor in a closed system, carrying out constant temperature treatment at 90 ℃ for 24h, heating to 450 ℃ at a heating rate of 1-10 ℃/min, carrying out constant temperature roasting for 2-8h, sieving a primary product to obtain the ozone oxidation catalyst for treating industrial wastewater, wherein the particle size of the primary product is 2-10 mm, and finally obtaining the ozone oxidation catalyst for treating industrial wastewater.
The ozone oxidation catalyst for industrial wastewater treatment provided by the embodiment of the invention can be effectively applied to a water treatment process, is particularly suitable for an advanced oxidation technology of industrial wastewater, and is mainly used for an advanced oxidation chain scission process, particularly an ozone oxidation process and the like, which are performed in the face of low biodegradability of wastewater of petrochemical enterprises, coal chemical industries or coking enterprises. The ozone oxidation catalyst for industrial wastewater treatment in the prior art is mostly low in mechanical strength, and the ozone oxidation efficiency cannot be effectively guaranteed in a working environment in which ozone needs to be introduced for ozone oxidation.
The technical effects of the ozone oxidation catalyst for industrial wastewater treatment according to the embodiment of the present invention will be further described below by referring to specific examples.
Example 1
An ozone oxidation catalyst for industrial wastewater treatment is prepared by the following steps:
1) Montmorillonite, palygorskite and spodumene are taken as base materials and weighed according to the weight ratio of 5: 1, mixed and ball-milled into powder (100 meshes), and then under the acidic condition (the powder and 1 percent of sulfuric acid aqueous solution are mixed according to the weight ratio of 1 g: 200 ml of the mixture) is subjected to ultrasonic treatment (specifically, ultrasonic oscillation is carried out for 4 hours under the conditions that the ultrasonic power is 20kHz and the temperature is 60 ℃ to generate a cavitation effect, powder materials such as montmorillonite stacked in a layered manner can be peeled into two-dimensional sheets by acid etching and ultrasonic oscillation at the time, the two-dimensional sheets are dispersed and mixed uniformly) to obtain a mixed solution, then the mixed solution is filtered and washed to be neutral, tetrabutyl titanate ethanol solution (the washed material can contain a small amount of moisture without being dried, tetrabutyl titanate in the tetrabutyl titanate ethanol solution is hydrolyzed to form titanic acid, and the titanic acid is loaded on the washed material as an auxiliary oxidant, so that the oxidation effect can be effectively improved, the catalytic activity of an ozone oxidation catalyst for industrial wastewater treatment is ensured) and mixed uniformly (the time is 4 hours, the temperature is 30 ℃, the pressure is 0.15 MPa), the mixed solution is reacted for 3 hours at 75 ℃, washed, dried and heated to 400 ℃ for 1 hour under a hydrogen atmosphere (the condition that the two-dimensional sheets formed before can be sintered together under heating in an air atmosphere are avoided), and ground to obtain the powder materials; wherein the tetrabutyl titanate ethanol solution has a concentration of 1wt% and is added in an amount of 0.1 times the weight of the solid obtained by filtration.
2) Weighing powder as a carrier by adopting an excess impregnation method, and adding the powder into excess metal nitrate solution for impregnation for 24 hours to obtain an impregnated material; wherein, the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 5mmol of cobalt nitrate in deionized water, uniformly dispersing to prepare 1L of solution (adding a small amount of beta-aminoisobutanol aroma for dispersion), and specifically adding 2 mL of metal nitrate solution into 1 g of powder.
3) And (3) drying the impregnated material as a catalyst precursor in a 120 ℃ oven for 2h, placing the catalyst precursor in a closed system, carrying out constant temperature treatment at 90 ℃ for 24h, heating to 450 ℃ at a heating rate of 1 ℃/min, carrying out constant temperature roasting for 2h, sieving a primary product to obtain the ozone oxidation catalyst for treating industrial wastewater, wherein the particle size of the primary product is 2 mm.
Example 2
An ozone oxidation catalyst for industrial wastewater treatment is prepared by the following steps:
1) Montmorillonite, palygorskite and spodumene are taken as base materials and weighed according to the weight ratio of 10: 1, mixed and ball-milled into powder (800 meshes), and then the powder is mixed with 5 percent of aqueous sulfuric acid solution under the acidic condition (the weight of the powder is calculated according to the proportion of 1 g: 500 ml of the mixture is mixed) and ultrasonic treatment is carried out (specifically, ultrasonic oscillation is carried out for 4 hours under the conditions that the ultrasonic power is 40kHz and the temperature is 90 ℃ so as to generate cavitation effect), so as to obtain mixed solution, then the mixed solution is filtered and washed to be neutral, tetrabutyl titanate ethanol solution is added to be uniformly mixed (the time is 4 hours, the temperature is 30 ℃, and the pressure is 0.15 MPa), the mixed solution is reacted for 3 hours at the temperature of 75 ℃, washed, dried, heated to 500 ℃ under the hydrogen atmosphere, kept warm for 6 hours, and ground, so as to obtain the powder material; wherein the tetrabutyl titanate ethanol solution has a concentration of 10wt% and is added in an amount of 0.1 times the weight of the solid obtained by filtration.
2) Weighing powder as a carrier by adopting an excess impregnation method, and adding the powder into excess metal nitrate solution for impregnation for 24 hours to obtain an impregnated material; the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 15mmol of cobalt nitrate in deionized water, uniformly dispersing to prepare 1L of solution, and specifically adding 2 ml of metal nitrate solution into 1 g of powder.
3) And (3) drying the impregnated material as a catalyst precursor in a 120 ℃ oven for 2h, placing the catalyst precursor in a closed system, carrying out constant temperature treatment at 90 ℃ for 24h, heating to 450 ℃ at a heating rate of 10 ℃/min, carrying out constant temperature roasting for 8h, sieving a primary product until the particle size is 10mm, and finally obtaining the ozone oxidation catalyst for treating industrial wastewater.
Example 3
An ozone oxidation catalyst for industrial wastewater treatment is prepared by the following steps:
1) Montmorillonite, palygorskite and spodumene are taken as base materials according to the weight ratio of 8:1:1, mixing and ball-milling the mixture to prepare powder (400 meshes), carrying out ultrasonic treatment (specifically, carrying out ultrasonic oscillation for 4 hours under the conditions that the ultrasonic power is 30kHz and the temperature is 70 ℃) under an acidic condition (mixing the powder and 2wt% of sulfuric acid aqueous solution according to the proportion of 1 g to 350 ml), obtaining a mixed solution, then filtering and washing the mixed solution to be neutral, adding tetrabutyl titanate ethanol solution, uniformly mixing (the time is 4 hours, the temperature is 30 ℃, and the pressure is 0.15 MPa), reacting for 3 hours at 75 ℃, washing, drying, heating to 450 ℃ under a hydrogen atmosphere, preserving heat for 4 hours, and grinding to obtain the powder; wherein the tetrabutyl titanate ethanol solution has a concentration of 2wt% and is added in an amount of 0.1 times the weight of the solid obtained by filtration.
2) Weighing powder as a carrier by adopting an excess impregnation method, and adding the powder into an excess metal nitrate solution for impregnation for 24 hours to obtain an impregnated material; the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 10mmol of cobalt nitrate in deionized water, uniformly dispersing to prepare 1L of solution, and specifically adding 2 ml of metal nitrate solution into 1 g of powder.
3) And (3) drying the impregnated material as a catalyst precursor in a 120 ℃ oven for 2h, placing the catalyst precursor in a closed system, carrying out constant temperature treatment at 90 ℃ for 24h, heating to 450 ℃ at a heating rate of 2 ℃/min, carrying out constant temperature roasting for 4h, sieving a primary product to obtain the ozone oxidation catalyst for treating industrial wastewater, wherein the particle size of the primary product is 5mm, and finally obtaining the ozone oxidation catalyst for treating industrial wastewater.
Example 4
The same procedure as in example 3 was repeated, except that the temperature was raised to 450 ℃ at a rate of 5 ℃/min and the temperature was maintained for 6 hours, as compared with example 3.
Example 5
The same procedure as in example 3 was repeated, except that the temperature was raised to 450 ℃ at a temperature raising rate of 8 ℃/min and the temperature was maintained for 2 hours, as compared with example 3.
Example 6
The same procedure as in example 3 was repeated, except that the temperature was raised to 450 ℃ at a temperature raising rate of 9 ℃/min and the temperature was maintained for 5 hours, as compared with example 3.
Example 7
The procedure was repeated as in example 3 except that montmorillonite, palygorskite and spodumene were weighed at a weight ratio of 6: 1 as compared with example 3.
Example 8
The procedure of example 3 was repeated, except that montmorillonite, palygorskite and spodumene were weighed at a weight ratio of 7: 1, as compared with example 3.
Example 9
The procedure of example 3 was repeated, except that montmorillonite, palygorskite and spodumene were weighed at a weight ratio of 9: 1, as compared with example 3.
Example 10
Same as example 4 except that hydrogen was replaced with nitrogen as compared with example 4.
Example 11
The same as example 4 except that the hydrogen gas was replaced with argon gas as compared with example 4.
Example 12
The same as example 4 except that the hydrogen gas was replaced with helium gas, as compared with example 4.
Comparative example 1
An ozone oxidation catalyst for industrial wastewater treatment was the same as example 3 except that the powder was prepared based on montmorillonite alone and the total amount of the powder in this example was the same as that in example 3, as compared with example 3.
Comparative example 2
The existing commercial montmorillonite carrier product.
Comparative example 3
There are commercially available commercial iron oxide (carrier is alumina) ozonation catalyst products.
Performance test
The catalysts prepared by the methods in examples 1-12 were tested for performance. Specifically, the mechanical strength was measured, and the results are shown in Table 1. Tests show that the catalysts prepared by the methods in examples 1-12 are all larger than 100N, and have good mechanical properties, especially the ozone oxidation catalyst for industrial wastewater treatment in example 3 has good mechanical properties, and reaches the mechanical property index of commercial iron oxide (carrier alumina) ozone oxidation catalysts sold in the market, so that for the ozone oxidation catalyst in the prior art, when montmorillonite is directly used as a carrier, most of the ozone oxidation catalysts have the problem that the mechanical strength is easily reduced after active components are loaded.
TABLE 1 table of mechanical strength test results
In the following, a metacresol solution is used as a model to simulate the treatment of industrial wastewater, and a specific method is to use 225 mL of 100ppm metacresol solution in a sealed environment as an industrial wastewater model, respectively add the catalyst prepared by the method in example 3 and the samples in comparative examples 1-3 to detect the catalytic performance, wherein the adding amount of the catalyst is 1 g, simultaneously, 160mL/min of ozone with the concentration of 50ppm is continuously introduced to react for 35 minutes, then the samples are taken, the TOC value of water is analyzed, and the TOC removal rate can be obtained by comparing the previous TOC value with the next TOC value, so that the catalytic ozone oxidation performance of the ozone oxidation catalyst in the invention is simulated and verified.
The results of the TOC removal rate test are shown in table 2, specifically, the TOC values are analyzed, the TOC of the inlet water is 80mg/L, and the produced water has good TOC removal rate, generally below 40 mg/L. Meanwhile, the specific TOC removal results are shown in Table 2 with the product of comparative example 3 as a control.
TABLE 2 TOC removal test results Table
| Group of | TOC removal Rate |
| Example 3 | 63.5％ |
| Comparative example 1 | 55.3％ |
| Comparative example 2 | 13.2％ |
| Comparative example 3 | 33.5％ |
The data in table 2 are plotted to obtain fig. 1, and it can be seen from the data in fig. 1 that the removal rate of TOC can be effectively ensured by using the ozone oxidation catalyst for industrial wastewater treatment provided by the embodiment of the present invention, which is superior to the catalytic performance of the commercial products, and the mechanical strength of the treated material can be ensured according to the results. Meanwhile, as shown in comparative example 2, the catalyst prepared by directly loading montmorillonite has lower catalytic performance, because the specific surface area after loading cannot be effectively expanded, and meanwhile, the phenomenon of reduction of mechanical strength is easy to occur after loading active components, and no pore expansion is generated through reasonable treatment, therefore, for the working environment in which ozone needs to be introduced for ozone oxidation, the catalyst is impacted by continuously blown ozone, the loss of the catalyst is easy to cause, and the ozone oxidation efficiency cannot be effectively ensured.
Specific surface areas of the products of example 3 and comparative examples 1 to 2 were measured by a high-precision specific surface area measuring instrument of Bechard corporation, model 3H-2000BET-A, and the specific results are shown in Table 3.
TABLE 3 table of specific surface area measurement results
| Item | Specific surface area m 2 /g |
| Example 3 | 205 |
| Comparative example 1 | 189 |
| Comparative example 2 | 105 |
As can be seen from the data in table 3, in the embodiment of the present invention, the powder materials such as the layered stacked montmorillonite can be peeled into two-dimensional sheets by using the acid etching and the ultrasonic vibration, so as to complete the dispersion and the uniform mixing, compared with the method of directly using a montmorillonite carrier alone, the method can improve the specific surface area to increase the catalytic effect and simultaneously ensure the mechanical strength, and the prepared ozone oxidation catalyst for the industrial wastewater treatment is suitable for the working environment in which ozone needs to be introduced for ozone oxidation, thereby reducing the loss of the catalyst caused by the continuously blown ozone, and effectively ensuring the ozone oxidation efficiency.
While the preferred embodiments of the present invention have been described in detail, the embodiments of the present invention are not limited to the above embodiments, and various changes can be made without departing from the spirit of the embodiments of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the embodiments of the present invention are still within the scope of the embodiments of the present invention as thus claimed.
Claims (10)
1. An ozone oxidation catalyst for industrial wastewater treatment is characterized in that the ozone oxidation catalyst for industrial wastewater treatment is prepared by taking powder as a carrier, soaking the carrier in excessive metal nitrate solution and then roasting the impregnated carrier; wherein the powder material is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10: 1.
2. The ozonation catalyst for industrial wastewater treatment according to claim 1, wherein the powder is prepared by weighing montmorillonite, palygorskite, and spodumene according to a proportion to prepare powder, performing ultrasonic treatment under an acidic condition, filtering, washing with water, adding tetrabutyl titanate ethanol solution, mixing uniformly, heating to 400-500 ℃ under a hydrogen atmosphere after washing and drying, keeping the temperature for 1-6 hours, and grinding to obtain the powder.
3. The ozonation catalyst for industrial wastewater treatment according to claim 2, wherein the tetrabutyl titanate ethanol solution concentration is 1 to 10wt%.
4. The ozonation catalyst for industrial wastewater treatment according to claim 2, wherein the metal nitrate solution contains magnesium nitrate and cobalt nitrate, and a molar ratio of the magnesium nitrate to the cobalt nitrate is 1 mol: 5 to 15mmol.
5. The ozonation catalyst for industrial wastewater treatment according to claim 2, wherein the ultrasonic treatment is ultrasonic oscillation under the conditions of an ultrasonic power of 20 to 40kHz and a temperature of 60 to 90 ℃.
6. The ozonation catalyst for industrial wastewater treatment according to claim 2, wherein the weight ratio of montmorillonite, palygorskite, and spodumene in the powder is 8: 1.
7. The ozonation catalyst for industrial wastewater treatment according to claim 2, wherein the powdering is a powdery material ground into 100 to 800 mesh by ball milling.
8. A method for preparing the ozone oxidation catalyst for industrial wastewater treatment according to any one of claims 1 to 7, comprising the steps of:
1) Weighing powder as a carrier, and adding the powder into an excessive metal nitrate solution for impregnation to obtain an impregnation material;
2) And roasting the impregnated material after heat treatment to obtain the ozone oxidation catalyst for industrial wastewater treatment.
9. The method of claim 8, wherein the step of calcining comprises heating the impregnated material to 450 ℃ at a heating rate of 1-10 ℃/min after heat treatment, and calcining at a constant temperature for 2-8 hours to obtain the ozone oxidation catalyst for industrial wastewater treatment.
10. The method of claim 8, wherein the heat treatment is carried out by baking the impregnated material obtained after impregnation as a catalyst precursor in an oven at 120 ℃ for 2h before calcination, placing the catalyst precursor in a closed system, and carrying out constant temperature treatment at 90 ℃ for 24h.
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