CN115709057B - 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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- CN115709057B CN115709057B CN202211291824.XA CN202211291824A CN115709057B CN 115709057 B CN115709057 B CN 115709057B CN 202211291824 A CN202211291824 A CN 202211291824A CN 115709057 B CN115709057 B CN 115709057B
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 230000003647 oxidation Effects 0.000 title claims abstract description 99
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 59
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 46
- 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 35
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 35
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 28
- 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 23
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 23
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000005470 impregnation Methods 0.000 claims description 21
- 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 16
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 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
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000012876 carrier material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 44
- 239000011259 mixed solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [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
- 239000002253 acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
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- 239000000654 additive Substances 0.000 description 1
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 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
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 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
- 238000005245 sintering Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to the technical field of wastewater treatment, and in particular 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 roasting the powder, wherein the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10:1:1. 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 active components, and through reasonable use of various raw materials and modification operation, the ozone oxidation efficiency of the catalyst is effectively ensured, the problem that the existing ozone oxidation catalyst based on montmorillonite carrier cannot ensure mechanical strength and improve the ozone oxidation efficiency is solved, and the ozone oxidation catalyst 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
Along with the continuous development of society, people's knowledge of environmental protection is also increasing. The industrial wastewater is used as wastewater, sewage and waste liquid generated in the industrial production process, has the characteristics of large volume, difficult treatment and the like, and especially the industrial wastewater discharged by petrochemical enterprises, coal chemical industry or coking enterprises, acid-base industry, pharmaceutical industry, dye industry and the like, if the industrial wastewater cannot be effectively treated, the industrial wastewater can cause great harm to the environment and seriously affect the health and safety of human beings.
At present, the main treatment method of industrial wastewater is as follows: 1. chemical treatment; 2. a biological treatment method; 3. physical treatment; 4. a physical and chemical comprehensive treatment method. The ozone oxidation treatment is used as 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 quick reaction, small dosage, easy on-site preparation, convenient operation, no secondary pollution and the like, so that the method is widely applied. The ozone oxidation catalyst is of various kinds, for example, tao Tulei, activated carbon type, activated alumina type catalyst and the like.
However, the above technical solutions have the following disadvantages in practical use: most of ozone oxidation catalysts in the prior art have the problem that the mechanical strength cannot be ensured and the ozone oxidation efficiency is improved, and for the working environment in which ozone is required to be introduced for ozone oxidation, the continuously-blown ozone can impact the catalyst, so that the loss of the catalyst is easy to occur, and the ozone oxidation efficiency cannot be effectively ensured.
Disclosure of Invention
The invention aims to provide an ozone oxidation catalyst for industrial wastewater treatment, which solves the problems that most of the existing ozone oxidation catalysts for industrial wastewater treatment provided in the background art have low mechanical strength and ozone oxidation efficiency cannot be effectively ensured for a working environment requiring ozone to be introduced for ozone oxidation.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
an ozone oxidation catalyst for industrial wastewater treatment is prepared by taking powder as a carrier, soaking in excessive metal nitrate solution and roasting; wherein the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10:1:1.
Another object of the embodiment of the present invention is to provide a method for preparing an ozone oxidation catalyst for industrial wastewater treatment, which includes the following steps:
1) Weighing powder as a carrier, and adding the powder into excessive metal nitrate solution for impregnation to obtain an impregnating material;
2) And (3) carrying out heat treatment on the impregnating material and roasting 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 faces advanced oxidation chain scission technology, particularly ozone oxidation technology and the like, which are carried out when the biodegradability of wastewater of petrochemical enterprises or coal chemical industry or coking enterprises is not high. The ozone oxidation catalyst can be used for carrying out ozone oxidation on wastewater of petrochemical enterprises or coal chemical industry or coking enterprises, so that the ozone oxidation efficiency is effectively improved.
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, immersing the powder in excessive metal nitrate solution and roasting the powder, wherein the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10:1:1. 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 active components, and through reasonable use of various raw materials and modification operation, the ozone oxidation efficiency of the catalyst is effectively ensured, the problem that most of the ozone oxidation catalysts based on montmorillonite carriers in the prior art cannot ensure mechanical strength and improve the ozone oxidation efficiency at the same time is solved, and the ozone oxidation catalyst has wide market prospect.
Drawings
Fig. 1 is a graph showing the results of TOC removal rate detection 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 drawings and the specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the embodiments of the invention. These are all within the scope of embodiments of the present invention.
In the embodiment of the invention, an 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 taking powder as a carrier, soaking in excessive metal nitrate solution and roasting; wherein the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10:1:1.
As another preferred embodiment of the invention, the preparation method of the powder comprises the steps of weighing montmorillonite, palygorskite and spodumene according to the proportion to prepare powder, carrying out ultrasonic treatment under an acidic condition, filtering, washing with water, adding tetrabutyl titanate ethanol solution to uniformly mix, washing, drying, heating to 400-500 ℃ in a hydrogen atmosphere, preserving heat for 1-6 hours, and grinding to obtain the powder.
Preferably, the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to a certain weight ratio of 8:1:1.
As another preferred embodiment of the present invention, the tetrabutyl titanate ethanol solution has a concentration of 1 to 10% by weight and is added at 0.1 times the weight of the solid obtained by filtration.
As another preferred embodiment of the invention, when tetrabutyl titanate ethanol solution is added for uniform mixing, the method is a pre-dipping process, provided that: the time is 4 hours, the temperature is 30 ℃, and the pressure is 0.15MPa.
As another preferred embodiment of the invention, the metal nitrate solution is prepared by adding powder to the metal nitrate solution exceeding the volume of the powder by an excessive impregnation method, and standing for 24 hours, specifically, adding 2 milliliters of the metal nitrate solution to 1 gram of powder.
As another preferred embodiment of the invention, the metal nitrate solution contains magnesium nitrate and cobalt nitrate, and the mol ratio of the magnesium nitrate to the cobalt nitrate is 1mol:5-15 mmol.
As another preferred embodiment of the invention, the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 10mmol of cobalt nitrate in deionized water to uniformly disperse to prepare 1L of solution. In practical application, a small amount of beta-amino-I Ding Chunxiang is required to be added, so that the metal nitrate can be mixed with water, can be used as an additive, has the functions of a dispersing agent and pH adjustment, and can effectively ensure the impregnation effect of the metal nitrate solution in the process of standing for 24 hours.
As another preferred embodiment of the invention, the ultrasonic treatment is ultrasonic vibration 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 is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to a certain ratio of 8:1:1; the preparation method of the powder comprises the steps of weighing montmorillonite, palygorskite and spodumene according to a proportion, mixing and ball milling the materials to obtain powder, carrying out ultrasonic treatment under an acidic condition (specifically, carrying out ultrasonic vibration under the condition that the ultrasonic power is 30kHz and the temperature is 70 ℃ to generate cavitation effect, at the moment, carrying out acid etching and ultrasonic vibration to enable the powder materials such as the layered stacked montmorillonite to be peeled into two-dimensional sheets to be dispersed and uniformly mixed), obtaining 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 water after being not dried, so that 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, thereby effectively improving the oxidation effect, ensuring the catalytic activity of an ozone oxidation catalyst for industrial wastewater treatment), carrying out uniform mixing, reacting at the temperature of 75 ℃ for 3h, washing, drying, heating under the hydrogen atmosphere to avoid the two-dimensional sheet materials formed before sintering together, and carrying out grinding for 4 hours at the temperature, thus obtaining the powder.
As another preferred embodiment of the present invention, the powder is a powdery material of 100-800 mesh by ball milling.
As another preferred embodiment of the present invention, the system is made acidic under acidic conditions using sulfuric acid, boric acid, hydrochloric acid, silicic acid, etc., preferably by mixing the powder with 1-5% by weight of an aqueous sulfuric acid solution according to 1 g: mixing at a ratio of 200-500 ml.
As another preferable embodiment of the invention, the water washing to neutrality is to wash the solid obtained by filtering the mixed solution with pure water for more than 3 times until the pH of the washing solution is between 7 and 8.
In the embodiment of the invention, the active components are loaded by adopting the carrier material prepared by taking montmorillonite, palygorskite and spodumene as base materials, so that compared with a single carrier directly adopting calcined montmorillonite, the specific surface area can be increased to increase the catalytic effect and ensure the mechanical strength, and the prepared ozone oxidation catalyst for industrial wastewater treatment can be better suitable for the running conditions for industrial wastewater treatment. Solves the problems that most of ozone oxidation catalysts in the prior art, especially those based on montmorillonite carriers, cannot ensure mechanical strength and improve ozone oxidation efficiency.
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 impregnating material;
2) And (3) carrying out heat treatment on the impregnating material and roasting to obtain the ozone oxidation catalyst for industrial wastewater treatment.
In another preferred embodiment of the invention, in the preparation method of the ozone oxidation catalyst for industrial wastewater treatment, the roasting is to heat-treat the impregnated material obtained after impregnation, then heat-raise the temperature to 450 ℃ at a heating rate of 1-10 ℃/min, and roast the impregnated material at a constant temperature for 2-8 hours to obtain the ozone oxidation catalyst for industrial wastewater treatment.
As another preferred embodiment of the invention, the preparation method of the ozone oxidation catalyst for industrial wastewater treatment further comprises the steps of taking the impregnated material obtained after impregnation as a catalyst precursor before roasting, firstly drying the catalyst precursor in a baking oven at 120 ℃ for 2 hours, then placing the catalyst precursor in a closed system, and carrying out constant temperature treatment at 90 ℃ for 24 hours, namely the operation of heat treatment.
It should be noted that, the preparation is simple and convenient by adopting the impregnation method, and compared with the blending method and the like, the method has higher feasibility in process and has no obvious disadvantage in catalytic performance.
As another preferred embodiment of the 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 excessive metal nitrate solution for impregnation to obtain an impregnating material;
2) And taking the impregnated material obtained after impregnation as a catalyst precursor, firstly drying the catalyst precursor in a baking oven at 120 ℃ for 2 hours, then placing the catalyst precursor in a closed system, carrying out constant temperature treatment at 90 ℃ for 24 hours, then heating to 450 ℃ at a heating rate of 1-10 ℃/min, carrying out constant temperature 2-8 hours for roasting, and sieving a primary product to ensure that the particle size is 2-10 mm, thereby finally obtaining the ozone oxidation catalyst for industrial wastewater treatment.
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 especially suitable for an industrial wastewater advanced oxidation technology, and mainly faces to an advanced oxidation chain scission process, especially an ozone oxidation process and the like, which are carried out when the biodegradability of wastewater of petrochemical enterprises or coal chemical industry or coking enterprises is not high. The existing ozone oxidation catalyst for industrial wastewater treatment has the problems that the mechanical strength is low, the ozone oxidation efficiency cannot be effectively ensured for the working environment in which ozone is required to be introduced for ozone oxidation, and the embodiment of the invention can effectively improve the ozone oxidation efficiency by adopting the ozone oxidation catalyst to carry out ozone oxidation on wastewater of petrochemical enterprises or coal chemical industry or coking enterprises, meanwhile, especially for the ozone oxidation catalyst in the prior art, when montmorillonite is directly used as a carrier, the problem that the mechanical strength is easy to be reduced after active components are loaded is mostly existed, and for the working environment in which ozone is required to be introduced for ozone oxidation, the continuously-blown ozone can impact the catalyst, the catalyst is easy to be lost, the ozone oxidation efficiency cannot be effectively ensured.
The technical effects of the ozone oxidation catalyst for industrial wastewater treatment according to the embodiments of the present invention will be further described below by way of specific examples.
Example 1
An ozone oxidation catalyst for industrial wastewater treatment, the preparation method specifically comprises the following steps:
1) Montmorillonite, palygorskite and spodumene are taken as base materials, weighed according to the weight ratio of 5:1:1, mixed and ball-milled to prepare powder (100 meshes), and the powder is mixed with 1% wt sulfuric acid aqueous solution according to 1 g under acidic conditions: 200 ml of mixed solution 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 ℃ so as to generate cavitation effect, at the moment, acidic etching and ultrasonic oscillation can cause powder materials such as montmorillonite stacked in layers to be peeled into two-dimensional sheets to be dispersed and uniformly mixed), mixed solution is obtained, then the mixed solution is filtered and washed to be neutral, tetrabutyl titanate ethanol solution is added (the washed material contains a small amount of water after being not dried, the tetrabutyl titanate in the tetrabutyl titanate ethanol solution is hydrolyzed to form titanic acid, the titanic acid is loaded on the washed material as an auxiliary oxidant, the oxidation effect can be effectively improved, the catalytic activity of an ozone oxidation catalyst for industrial wastewater treatment is ensured), the mixed solution is uniformly (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 75 ℃, the mixed solution is washed, dried, and the two-dimensional sheet materials formed before being heated under the atmosphere (the heating under the atmosphere can be prevented from being caused to be sintered together) are heated to 400 ℃ for 1 hour, and the mixed solution is ground, so that the powder materials are obtained; wherein the tetrabutyl titanate ethanol solution concentration is 1wt% and is added according to 0.1 time of the weight of the solid obtained by filtering.
2) Weighing powder as a carrier by adopting an excessive impregnation method, and adding the powder into excessive metal nitrate solution for impregnation for 24 hours to obtain an impregnating material; wherein, the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 5mmol of cobalt nitrate in deionized water for uniform dispersion to prepare 1L solution (a small amount of beta-amino isobutanol perfume is added for dispersion), and specifically, 1 g of powder is added with 2 ml of metal nitrate solution.
3) And taking the impregnated material obtained after impregnation as a catalyst precursor, firstly drying in a baking oven at 120 ℃ for 2 hours, then placing in a closed system, carrying out constant temperature treatment at 90 ℃ for 24 hours, then heating to 450 ℃ at a heating rate of 1 ℃/min, carrying out constant temperature 2 hours for roasting, and sieving a primary product to ensure that the particle size is 2mm, thereby finally obtaining the ozone oxidation catalyst for industrial wastewater treatment.
Example 2
An ozone oxidation catalyst for industrial wastewater treatment, the preparation method specifically comprises the following steps:
1) Montmorillonite, palygorskite and spodumene are taken as base materials, weighed according to the weight ratio of 10:1:1, mixed and ball-milled to prepare powder (800 meshes), and the powder is mixed with 5% wt sulfuric acid aqueous solution according to 1 g under acidic conditions: mixing at a ratio of 500 ml), performing ultrasonic treatment (specifically, performing ultrasonic oscillation for 4 hours under the conditions of ultrasonic power of 40kHz and temperature of 90 ℃ to generate cavitation effect) to obtain mixed solution, filtering the mixed solution, washing the mixed solution to be neutral, adding tetrabutyl titanate ethanol solution to uniformly mix (the time is 4 hours, the temperature is 30 ℃ and the pressure is 0.15 MPa), reacting at 75 ℃ for 3 hours, washing, drying, heating to 500 ℃ under hydrogen atmosphere, preserving heat for 6 hours, and grinding to obtain the powder; wherein the tetrabutyl titanate ethanol solution concentration is 10wt% and is added according to 0.1 time of the weight of the solid obtained by filtering.
2) Weighing powder as a carrier by adopting an excessive impregnation method, and adding the powder into excessive metal nitrate solution for impregnation for 24 hours to obtain an impregnating material; wherein, the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 15mmol of cobalt nitrate in deionized water to uniformly disperse to prepare 1L of solution, and specifically, adding 2 ml of metal nitrate solution into 1 g of powder.
3) And taking the impregnated material obtained after impregnation as a catalyst precursor, firstly drying in a baking oven at 120 ℃ for 2 hours, then placing in a closed system, carrying out constant temperature treatment at 90 ℃ for 24 hours, then heating to 450 ℃ at a heating rate of 10 ℃/min, carrying out constant temperature 8 hours for roasting, and sieving a primary product to ensure that the particle size is 10mm, thereby finally obtaining the ozone oxidation catalyst for industrial wastewater treatment.
Example 3
An ozone oxidation catalyst for industrial wastewater treatment, the preparation method specifically comprises 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 to obtain powder (400 meshes), then carrying out ultrasonic treatment (specifically ultrasonic oscillation for 4 hours under the conditions of ultrasonic power of 30kHz and temperature of 70 ℃ in an acidic condition (mixing the powder with 2%wt sulfuric acid aqueous solution according to the proportion of 1 g: 350 ml)) to obtain a mixed solution, then filtering and washing the mixed solution to be neutral, adding tetrabutyl titanate ethanol solution to uniformly mix (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 hydrogen atmosphere, preserving heat for 4 hours, and grinding to obtain the powder; wherein the tetrabutyl titanate ethanol solution concentration is 2wt% and is added according to 0.1 time of the weight of the solid obtained by filtering.
2) Weighing powder as a carrier by adopting an excessive impregnation method, and adding the powder into excessive metal nitrate solution for impregnation for 24 hours to obtain an impregnating material; wherein, the metal nitrate solution is prepared by dissolving 1mol of magnesium nitrate and 10mmol of cobalt nitrate in deionized water to uniformly disperse to prepare 1L of solution, and specifically, adding 2 ml of metal nitrate solution into 1 g of powder.
3) And taking the impregnated material obtained after impregnation as a catalyst precursor, firstly drying in a baking oven at 120 ℃ for 2 hours, then placing in a closed system, carrying out constant temperature treatment at 90 ℃ for 24 hours, then heating to 450 ℃ at a heating rate of 2 ℃/min, carrying out constant temperature for 4 hours for roasting, and sieving a primary product to ensure that the particle size is 5mm, thereby finally obtaining the ozone oxidation catalyst for industrial wastewater treatment.
Example 4
The procedure of example 3 was repeated except that the temperature was increased to 450℃at a rate of 5℃per minute and the temperature was kept constant for 6 hours for calcination, as compared with example 3.
Example 5
The procedure of example 3 was repeated except that the temperature was increased to 450℃at a heating rate of 8℃per minute and the temperature was kept constant for 2 hours for calcination, as compared with example 3.
Example 6
The procedure of example 3 was repeated except that the temperature was increased to 450℃at a rate of 9℃per minute and the temperature was kept constant for 5 hours for calcination, as compared with example 3.
Example 7
In comparison with example 3, the procedure was the same as in example 3 except that montmorillonite, palygorskite and spodumene were weighed in a weight ratio of 6:1:1.
Example 8
In comparison with example 3, the procedure was the same as in example 3 except that montmorillonite, palygorskite and spodumene were weighed in a weight ratio of 7:1:1.
Example 9
In comparison with example 3, the procedure was the same as in example 3 except that montmorillonite, palygorskite and spodumene were weighed in a weight ratio of 9:1:1.
Example 10
In comparison with example 4, the procedure was the same as in example 4 except that hydrogen was replaced with nitrogen.
Example 11
In comparison with example 4, the procedure was as in example 4 except that argon was used instead of hydrogen.
Example 12
In comparison with example 4, the procedure was the same as in example 4 except that helium was used instead of hydrogen.
Comparative example 1
An ozone oxidation catalyst for industrial wastewater treatment was the same as in example 3 except that the powder was prepared based on montmorillonite alone, and the total amount of the powder was the same as in example 3, as compared with example 3.
Comparative example 2
Existing commercial montmorillonite support products.
Comparative example 3
Existing commercial iron oxide (the carrier is alumina) ozone oxidation catalyst products.
Performance testing
The catalysts prepared by the methods of examples 1-12 were tested for performance. Specifically, the mechanical strength was measured, and the measurement results are shown in Table 1. According to detection, the catalyst prepared by the method in the examples 1-12 is larger than 100N, has good mechanical properties, and particularly the ozone oxidation catalyst for industrial wastewater treatment in the example 3 has good mechanical properties, so that the mechanical property index of the commercial iron oxide (carrier alumina) ozone oxidation catalyst in the market is achieved, therefore, when the ozone oxidation catalyst in the prior art is directly used as a carrier, most of the problems of easy reduction of mechanical strength occur after active components are loaded, and the powder prepared by the method of acid treatment, ultrasonic treatment and the like by using montmorillonite, palygorskite, spodumene and the like as raw materials has good mechanical strength, is suitable for the working environment requiring ozone oxidation, reduces the loss of the catalyst caused by continuously blown ozone, and effectively ensures the ozone oxidation efficiency.
Table 1 mechanical strength test results table
Next, the treatment of industrial wastewater was simulated by using a m-cresol solution as a model, and a specific method was to use 225 mL of a 100ppm m-cresol solution under a sealed environment as an industrial wastewater model, to detect catalytic performance by adding 1 g of the catalyst prepared in example 3 and samples in comparative examples 1 to 3, and to continuously introduce 160mL/min of ozone at a concentration of 50ppm for reaction for 35 minutes, to sample, to analyze TOC values of water, and to compare the TOC values before and after to obtain TOC removal rate, thereby simulating and verifying the catalytic ozonation performance of the ozonation catalyst of the present invention.
The results of TOC removal test are shown in Table 2, and the TOC values are analyzed specifically, wherein the TOC of the water is 80mg/L, and the TOC removal rate of the produced water is good and is generally below 40 mg/L. Meanwhile, the results of specific TOC removal rates are shown in Table 2, with the product of comparative example 3 as a control.
Table 2 TOC removal rate 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 ozone oxidation catalyst for industrial wastewater treatment provided by the embodiment of the invention can effectively ensure the removal rate of TOC, is better than the catalytic performance of the commercial products, and can be seen from the previous results that the mechanical strength of the treated material is ensured. Meanwhile, the catalyst prepared by directly adopting montmorillonite for loading is as shown in comparative example 2, and the catalyst has lower catalytic performance, because the specific surface area cannot be effectively expanded after loading, the phenomenon of mechanical strength reduction is easy to occur after active components are loaded, and reaming is not generated after reasonable treatment, so that the catalyst is impacted by continuously blown ozone in the working environment in which ozone oxidation is required to be performed, the catalyst loss is easy to occur, and the ozone oxidation efficiency cannot be effectively ensured.
Specific surface areas were measured using a high-precision specific surface area tester model 3H-2000BET-A, manufactured by Bei Shide company, and specific surface areas were measured for the products of example 3 and comparative examples 1-2, and the specific results are shown in Table 3.
TABLE 3 specific surface area measurement results Table
| Project | 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 invention, the powder materials such as the layered stacked montmorillonite are peeled into two-dimensional sheets by adopting acid etching and ultrasonic vibration to finish dispersion and uniform mixing, compared with the single direct use of a montmorillonite carrier, the specific surface area can be increased to increase the catalytic effect, the mechanical strength is ensured, the prepared ozone oxidation catalyst for industrial wastewater treatment is suitable for the working environment requiring ozone oxidation, the loss of the catalyst caused by continuously blowing ozone is reduced, and the ozone oxidation efficiency is effectively ensured.
While the preferred embodiments of the present invention have been described in detail, the present embodiments are not limited to the above embodiments, and various changes may be made without departing from the spirit of the present embodiments within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the embodiments of the present invention.
Claims (8)
1. The ozone oxidation catalyst for industrial wastewater treatment is characterized by being prepared by taking powder as a carrier, soaking in excessive metal nitrate solution and roasting; wherein, the powder is prepared by taking montmorillonite, palygorskite and spodumene as base materials according to the weight ratio of 5-10:1:1;
the metal nitrate solution contains magnesium nitrate and cobalt nitrate, and the molar ratio of the magnesium nitrate to the cobalt nitrate is 1mol:5-15mmol;
the preparation method of the powder comprises the steps of weighing montmorillonite, palygorskite and spodumene according to the proportion to prepare powder, carrying out ultrasonic treatment under an acidic condition, filtering, washing with water, adding tetrabutyl titanate ethanol solution to uniformly mix, washing, drying, heating to 400-500 ℃ under a hydrogen atmosphere, preserving heat for 1-6 hours, and grinding to obtain the powder.
2. The ozone oxidation catalyst for industrial wastewater treatment according to claim 1, wherein the tetrabutyl titanate ethanol solution concentration is 1-10wt%.
3. The ozone oxidation catalyst for industrial wastewater treatment according to claim 1, wherein the ultrasonic treatment is ultrasonic vibration under the conditions that ultrasonic power is 20-40kHz and temperature is 60-90 ℃.
4. The ozone oxidation catalyst for industrial wastewater treatment according to claim 1, wherein the weight ratio of montmorillonite, palygorskite, spodumene in the powder is 8:1:1.
5. The ozone oxidation catalyst for industrial wastewater treatment according to claim 1, wherein the produced powder is a powdery material ground into 100-800 mesh by ball milling.
6. A method for preparing an ozone oxidation catalyst for industrial wastewater treatment according to any one of claims 1 to 5, comprising the steps of:
1) Weighing powder as a carrier, and adding the powder into excessive metal nitrate solution for impregnation to obtain an impregnating material;
2) And (3) carrying out heat treatment on the impregnating material and roasting to obtain the ozone oxidation catalyst for industrial wastewater treatment.
7. The method for producing an ozone oxidation catalyst for industrial wastewater treatment according to claim 6, wherein in the method for producing an ozone oxidation catalyst for industrial wastewater treatment, the calcination is performed by heating the impregnated material obtained after the impregnation to 450 ℃ at a heating rate of 1 to 10 ℃/min and then calcining at a constant temperature for 2 to 8 hours.
8. The method for producing an ozone oxidation catalyst for industrial wastewater treatment according to claim 6, wherein in the method for producing an ozone oxidation catalyst for industrial wastewater treatment, the heat treatment is that the impregnated material obtained after impregnation is baked as a catalyst precursor in an oven at 120 ℃ for 2 hours before baking, then placed in a closed system, and subjected to constant temperature treatment at 90 ℃ for 24 hours.
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