CN117960160A - Catalyst for low-temperature catalytic ozonation, catalytic filter cloth, preparation method and application - Google Patents
Catalyst for low-temperature catalytic ozonation, catalytic filter cloth, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
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- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 47
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
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- 239000011702 manganese sulphate Substances 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000012752 auxiliary agent Substances 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001276 controlling effect Effects 0.000 abstract 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for low-temperature catalytic ozonation, catalytic filter cloth, a preparation method and application thereof, wherein the preparation of the catalyst for low-temperature catalytic ozonation comprises the steps of V-Ti-based catalyst synthesis, active ingredient impregnation and surface modification, the prepared modified Mo-VTiOx composite catalyst is used for etching the surface of the catalyst by acid, the intermetallic interaction of Mn, V and Ti and the acid etching are utilized for regulating and controlling the surface acidic sites, and polyvalent metal Mn with low temperature and high activity is used as a main active phase, so that the catalytic ozonation performance at low temperature is effectively improved; the modified Mo-VTiOx composite catalyst is combined with the filter cloth by a blending wire drawing method to form catalytic filter cloth with firm combination of the catalyst and the filter cloth, and the catalyst is coated or linked by polytetrafluoroethylene fibers, so that the problem of catalyst loss in the use process is solved, and the recycling rate of the catalytic filter cloth is improved.
Description
Technical Field
The invention relates to the technical field of water pollution remediation, in particular to a catalyst for low-temperature catalytic ozonation, catalytic filter cloth, a preparation method and application thereof.
Background
In recent years, the abuse and residual use of antibiotics has led to the generation of a large number of antibiotic resistance genes, which are classified as emerging pollutants, detectable in both wastewater and waste activated sludge, the transmission of which has been a threat to global public health. Waste activated sludge is a heterogeneous colloidal system in which extracellular polymers come from complex networks with spatial conformations. The network can capture a large amount of water molecules, and solid-liquid separation is difficult to complete only by mechanical pressure, so that the subsequent treatment is challenging and difficult. Thus, national new pollutant remediation action programs place new demands on new pollutant abatement of sludge abatement processes.
The catalytic ozonation technology is one of the advanced oxidation technologies based on ozone, can effectively enhance the water separation and dehydration performances of the sludge, and simultaneously reduce sewage organic matters in the secondary sewage after biological treatment, including natural organic matters, soluble microorganism products and new pollutants. The catalytic efficiency of the catalytic ozonation technology is mainly limited by mass transfer of organic pollutants, effective catalytic area, catalytic activity of the catalyst and the like. Patent 201410454415.6 'a supported ozone catalyst, a preparation method and application' uses active carbon as a carrier, can improve the CODcr removal rate of antibiotic wastewater, but has the problems of active carbon loss, narrow application range of industrial wastewater and the like. The patent CN217459044U 'heterogeneous ozone catalytic oxidation and membrane separation integrated reactor' aims at low efficiency of the traditional solid-liquid separation means, and develops a heterogeneous reactor, but the reactor consists of a primary membrane reaction box, a secondary membrane reaction box, a catalyst layer, a tubular micro-nano membrane and the like, and has large occupied area and needs additional equipment. Therefore, it is necessary to develop a water pollutant catalytic ozonation catalytic material with wide application range, simple use and durable catalytic activity.
Disclosure of Invention
In order to solve at least one of the problems, the invention provides a catalyst for catalyzing ozone oxidation at a low temperature, a catalytic filter cloth, a preparation method and application. The catalytic filter cloth prepared by the method has the advantages that the combination of the catalyst and the filter cloth is tighter, the loss rate of the catalyst in repeated use is low, and the synergistic removal efficiency of sewage organic matters and particulate matters can be ensured.
In order to achieve the above purpose, the invention adopts the following technical means:
the first aspect of the invention provides a preparation method of a catalyst for low-temperature catalytic ozonation, which comprises the following steps:
(1) V-Ti based catalyst synthesis
The volume ratio of N, N-dimethylformamide to water is (10-15): 1 preparing a mixed solution I, and then mixing a vanadium precursor, titanium sulfate and an organic ligand according to a molar ratio (1-2): (2-4): (0.2-1) dissolved in the mixed solution II;
Transferring the mixed solution II to a reaction kettle, reacting for 20-24 hours at 120 ℃, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying the solid particles at 105 ℃ for 6-10 hours, and calcining the solid particles at 500 ℃ for 3-6 hours to obtain the V-Ti-based catalyst;
(2) Active ingredient impregnation
Adding a manganese metal precursor into an aqueous solution of a V-Ti-containing catalyst, stirring at normal temperature for 10-15h, and roasting at 300 ℃ for 3-6h to obtain a Mn-VTiOx composite catalyst;
(3) Surface modification
Adding Mn-VTiOx composite catalyst into acid solution, stirring at normal temperature for 4-8h, washing with water, then adding polytetrafluoroethylene emulsion, then drying at 105 ℃, and finally roasting at 400 ℃ for 3-6h to obtain the catalyst for low-temperature catalytic ozonation: modified Mo-VTiOx composite catalyst.
The manganese metal precursor in the step (2) is one of manganese nitrate, manganese sulfate or manganese acetate; preferably, the manganese metal precursor is manganese nitrate.
The concentration of the manganese metal precursor in the step (2) is 5-10% by weight; preferably, the concentration of the manganese metal precursor is 10% by weight.
The acid solution in the step (3) is one of a silicotungstic acid solution, a phosphotungstic acid solution and a nitric acid solution; preferably, the acid solution is a silicotungstic acid solution.
The concentration of the acid solution in the step (3) is 1 to 5mol/L, preferably the concentration of the acid solution is 1mol/L
The vanadium precursor in the step (1) can be one of vanadium nitrate, ammonium metavanadate, sodium metavanadate and potassium metavanadate; the organic ligand is one of terephthalic acid, 2, 5-dihydroxyterephthalic acid or trimesic acid; the roasting atmosphere in the steps (2) and (3) is nitrogen or air.
The second aspect of the invention provides a preparation method of catalytic filter cloth, wherein the catalytic filter cloth is prepared by combining a modified Mn-VTiOx composite catalyst prepared by the method according to any one of claims 1-6 with filter cloth by adopting a blending wire drawing method, and the steps are as follows: the modified Mn-VTiOx composite catalyst, the auxiliary agent and the polytetrafluoroethylene resin are mixed according to the weight ratio of (0.1-1): (0.1-1): (0.5-2) uniformly mixing, standing at 80 ℃ for 8-24h, promoting the auxiliary agent to be fully mixed with polytetrafluoroethylene resin and catalyst to form a material, and then calendaring the material at 40-80 ℃, longitudinally pulling the material at 200-300 ℃, degreasing at 340-450 ℃, slitting, curling and needling to obtain the catalytic filter cloth.
The auxiliary agent is one of kerosene, liquid paraffin or petroleum ether.
In a third aspect the present invention provides a catalytic filter cloth prepared according to the method of the second aspect.
The catalyst for low-temperature catalytic ozonation prepared by the method in the first aspect and the application of the catalytic filter cloth in the third aspect in preparation of products for removing organic matters and particulate matters in water.
The beneficial effects of the invention are that
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a catalyst for catalyzing ozone oxidation at low temperature, namely Mn-VTiOx catalyst, which is used as a catalytic active component for catalyzing filter cloth, the surface of the catalyst is etched by acid, the surface acidic sites are regulated and controlled by the intermetallic interaction of Mn, V and Ti and the acid etching, the catalytic ozonation performance at low temperature is effectively improved, and polyvalent metal Mn with high activity at low temperature is used as a main active phase.
(1) According to the catalytic filter cloth, the catalyst is combined with the filter cloth by a blending wire drawing method, the catalyst is coated or linked by polytetrafluoroethylene fibers, the problem that the catalyst runs off along with the movement of fluid in the use process is solved, and the characteristics of the filter cloth are utilized to effectively intercept water particles.
(2) When the catalytic filter cloth prepared by the invention is applied, the filter material is replaced on the existing pollution treatment equipment, and new equipment and operation procedures are not required to be modified or added, so that the pollution treatment equipment is effectively reduced, and the cost is reduced.
Drawings
FIG. 1 shows a flow chart for the preparation of a catalytic filter cloth;
FIG. 2 shows a block diagram of a catalytic ozonation apparatus;
Wherein, 1, an oxygen supply tank, 2, a mass flowmeter, 3, an ozone generator, 4, a feeding tank, 5, peristaltic pumps I,6, peristaltic pumps II,7, a catalytic filter cloth filter, 8 and a sampling port.
Detailed Description
The following examples are presented herein to demonstrate preferred embodiments of the present invention. It will be appreciated by those skilled in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, the disclosure of which is incorporated herein by reference as is commonly understood by reference. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the claims.
The invention discloses a preparation method of catalytic filter cloth, which can be used for removing water pollutants and particulate matters, wherein the specific preparation steps of the catalytic filter cloth are as shown in figure 1: the catalyst is prepared through the steps of V-Ti catalyst synthesis, active ingredient impregnation, surface modification and the like, and then the catalyst is combined with the filter cloth by a blending wire drawing method to form the catalytic filter cloth with firm combination of the catalyst and the filter cloth.
In practical application, the prepared filter cloth strengthens mass transfer between the catalyst and the wastewater and ozone by forcing the wastewater to flow through the filter cloth pore canal containing the catalyst, and improves the catalytic performance and the ozone utilization rate.
The composite catalytic filter cloth comprises an oxygen supply tank 1, a mass flowmeter 2, an ozone generator 3 and a feeding tank 4 which are sequentially connected, wherein the feeding tank 4 is connected with a catalytic filter cloth filter 7 through a peristaltic pump I5 and a peristaltic pump II 6, the catalytic filter cloth is arranged in the catalytic filter cloth filter 7, and a sampling port 8 is arranged at the lower end of the catalytic filter cloth filter 7.
The catalytic ozonation device is used for performing performance test in a cross-flow mode by keeping constant pressure of 0.2Mpa, and the test process is as follows:
The catalytic filter cloth to be detected is arranged in a catalytic filter cloth device, 1.2L of sewage before treatment is added into a feeding tank, an oxygen supply tank 1, a mass flowmeter 2 and an ozone generator 3 are opened, ozone is continuously input into the feeding tank 4, 20mg/L of ozone is input, then a peristaltic pump I5 and a peristaltic pump II 6 are utilized to enable water body solution to circularly flow between the feeding tank 4 and a catalytic filter cloth filter 7, the reaction temperature is 80 ℃, the circulation treatment time is 30min, and a sampling port 8 is used for sampling in the test process.
The catalyst content of the catalytic filter cloth is detected by the weight of the filter cloth before and after loading.
The technical scheme of the patent is further described in detail below with reference to the specific embodiments.
Example 1
The specific preparation steps of the catalytic filter cloth of the embodiment are as follows:
(1) V-Ti catalyst synthesis
A) 15:1, preparing a mixed solution of N, N-dimethylformamide and water, and then mixing the mixed solution with the water according to a molar ratio of 1:2:0.2 ammonium metavanadate, titanium sulfate and trimesic acid are dissolved in the mixed solution;
b) Transferring the mixed solution to a reaction kettle, reacting for 24 hours at 120 ℃, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying the solid particles at 105 ℃ for 8 hours, and calcining the solid particles at 500 ℃ for 4 hours to obtain a V-Ti catalyst;
(2) Active ingredient impregnation
Adding 5wt% manganese sulfate into an aqueous solution containing a V-Ti catalyst, stirring at normal temperature for 12 hours, and roasting at 300 ℃ for 4 hours to obtain a Mn-VTiO x composite catalyst;
(3) Surface modification
Adding 2g of Mn-VTiO x composite catalyst into 2mol/L nitric acid solution, stirring at normal temperature for 6h, washing with water, pouring 5wt% polytetrafluoroethylene emulsion, stirring uniformly, drying at 105 ℃, and roasting at 400 ℃ for 4h to obtain a modified Mo-VTiO x composite catalyst;
(4) Blending wire drawing
The weight ratio is 0.2:0.2:1 mixing the modified Mn-VTiO x composite catalyst, liquid paraffin and polytetrafluoroethylene resin, standing for 8-24 hours at 80 ℃ after the liquid paraffin, the polytetrafluoroethylene resin and the catalyst are uniformly mixed, promoting the liquid paraffin to be fully mixed and forming a material, and then sequentially carrying out steps of calendaring at 60 ℃, longitudinal pulling at 260 ℃, degreasing at 400 ℃, slitting, curling, needling and the like on the material to finally prepare the catalytic filter cloth.
Polytetrafluoroethylene catalytic filter cloth prepared by the method: the nonwoven fabric had a catalyst content of 190.6g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 9.8mg/L after treatment and is 72.8%, and the catalyst only runs off 6.4g/m 2 after being recycled for 24 times.
Example 2
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 1, except that the manganese sulfate addition in step (2) was changed to manganese acetate, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 192.2g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 9.0mg/L after treatment and is 75.0%, and the catalyst only runs off 7.2g/m 2 after being recycled for 24 times.
Example 3
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 1, except that the manganese sulfate addition in step (2) was changed to manganese nitrate, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 187.9g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 8.6mg/L after treatment and is 76.1%, and the catalyst only runs off 5.4g/m 2 after being recycled for 24 times.
Example 4
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 3, except that the manganese nitrate addition in step (2) was changed to 7% by weight, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 193.3g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 6.7mg/L after treatment and is 81.4%, and the catalyst only runs off 6.2g/m 2 after being recycled for 24 times.
Example 5
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 3, except that the manganese nitrate addition in step (2) was changed to 10% by weight, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 201.1g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 4.5mg/L after treatment and is 87.5%, and the catalyst only runs off 5.5g/m 2 after being recycled for 24 times.
Example 6
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 3, except that the nitric acid of step (3) was changed to silicotungstic acid, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above method was 202.9g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 2.0mg/L after treatment and 94.4%, and the catalyst only runs off 7.1g/m 2 after being recycled for 24 times.
Example 7
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 3, except that the nitric acid of step (3) was changed to phosphotungstic acid, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above method was 200.2g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 3.7mg/L after treatment and is 89.7%, and the catalyst only runs off 6.6g/m 2 after being recycled for 24 times.
Example 8
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 4, except that the concentration of silicotungstic acid in step (3) was changed to 1mol/L, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 199.7g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 1.6mg/L after treatment and is 95.6%, and the catalyst only runs off 5.7g/m 2 after being recycled for 24 times.
Example 9
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 4, except that the concentration of silicotungstic acid in step (3) was changed to 5mol/L, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 204.1g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 77.5% after treatment and the catalyst is only lost by 6.0g/m 2 after being recycled for 24 times.
Example 10
The procedure for preparing the catalytic filter cloth of this example was similar to that of example 8, except that the polytetrafluoroethylene emulsion of step (3) was changed to 0mol/L, and the catalyst content of the catalytic filter cloth of polytetrafluoroethylene prepared by the above-mentioned method was 182.4g/m 2.
The sewage of a certain urban sewage treatment plant is detected by adopting a catalytic ozonation device, the COD content in the sewage before treatment is 36mg/L, the COD removal rate is 8.9mg/L after treatment and is 75.3%, and the catalyst is lost by 15.0g/m 2 after being recycled for 24 times.
TABLE 1 conditions of urban wastewater treatment plant before and after treatment with catalytic filter materials
Results: by comparing the examples 1-3, it is known that different Mn metal precursors can lead the filter cloth to have different catalytic activities, and lead the COD removal rate to be different, and the steps from big to small are as follows: manganese nitrate (76.1%) > manganese acetate (75.0%) > manganese sulfate (72.8%).
By comparing the embodiments 3-5, the increase of Mn metal content in the filter material can effectively improve the catalytic activity of the catalytic filter cloth, and the COD removal rate is sequentially from large to small: manganese nitrate (87.5%) > manganese acetate (81.4%) > manganese sulfate (76.1%), which is mainly attributable to the low temperature high activity of Mn metal and its high availability to ozone.
By comparing the embodiments 5-7, it can be known that different acids have different etching effects on the catalyst, so as to form different catalytic activities, and the COD removal rate is sequentially from large to small: silicotungstic acid (94.4%) > phosphotungstic acid (89.7%) > nitric acid (87.5%).
By comparing examples 7-9, it is known that the concentration of acid in the acid etching step can influence the acid etching effect, so as to form different catalytic activities, and the COD removal rate is sequentially from large to small: 1mol/L (95.6%) >2mol/L (94.4%) >5mol/L (77.5%). This is attributable to the introduction of acidic sites while the silicotungstic acid forms an active site protective layer on the catalyst surface, but the protective layer formed by the high concentration of silicotungstic acid can block the active sites from contacting with organic contaminants, resulting in a reduction in the catalytic activity of the catalytic filter cloth.
By comparing the embodiment 8 with the embodiment 10, the addition of the polytetrafluoroethylene emulsion can improve the linkage between the catalyst and the polytetrafluoroethylene filter cloth, further relieve the loss phenomenon of the catalytic filter cloth in the use process, and reduce the lost catalyst content from 15g/m 2 to 5.7g/m 2 after the cyclic use.
The present invention is not limited to the above embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art may make some substitutions and modifications to some technical features without departing from the principles of the present invention according to the disclosed technical disclosure, and these substitutions and modifications should also be considered as being within the scope of the present invention.
Claims (10)
1. The preparation method of the catalyst for low-temperature catalytic ozonation is characterized by comprising the following steps of:
(1) V-Ti based catalyst synthesis
The volume ratio of N, N-dimethylformamide to water is (10-15): 1 preparing a mixed solution I, and then mixing a vanadium precursor, titanium sulfate and an organic ligand according to a molar ratio (1-2): (2-4): (0.2-1) dissolved in the mixed solution II;
Transferring the mixed solution II to a reaction kettle, reacting for 20-24 hours at 120 ℃, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying the solid particles at 105 ℃ for 6-10 hours, and calcining the solid particles at 500 ℃ for 3-6 hours to obtain the V-Ti-based catalyst;
(2) Active ingredient impregnation
Adding a manganese metal precursor into an aqueous solution of a V-Ti-containing catalyst, stirring at normal temperature for 10-15h, and roasting at 300 ℃ for 3-6h to obtain a Mn-VTiOx composite catalyst;
(3) Surface modification
Adding Mn-VTiOx composite catalyst into acid solution, stirring at normal temperature for 4-8h, washing with water, then adding polytetrafluoroethylene emulsion, then drying at 105 ℃, and finally roasting at 400 ℃ for 3-6h to obtain the catalyst for low-temperature catalytic ozonation: modified Mo-VTiOx composite catalyst.
2. The method for preparing a catalyst for low-temperature catalytic ozonation according to claim 1, wherein the manganese metal precursor in the step (2) is one of manganese nitrate, manganese sulfate or manganese acetate.
3. The method for preparing a catalyst for low-temperature catalytic ozonation according to claim 2, wherein the concentration of the manganese metal precursor in the step (2) is 5-10% by weight.
4. The method for preparing a catalyst for low-temperature catalytic ozonation according to claim 1, wherein the acid solution in the step (3) is one of a silicotungstic acid solution, a phosphotungstic acid solution and a nitric acid solution.
5. The method for preparing a catalytic filter cloth for low-temperature catalytic ozonation according to claim 4, wherein the concentration of the acid solution in the step (3) is 1-5 mol/L.
6. The method for preparing a catalyst for low-temperature catalytic ozonation according to claim 1, wherein the vanadium precursor in the step (1) is one of vanadium nitrate, ammonium metavanadate, sodium metavanadate and potassium metavanadate; the organic ligand is one of terephthalic acid, 2, 5-dihydroxyterephthalic acid or trimesic acid; the roasting atmosphere in the steps (2) and (3) is nitrogen or air.
7. A method for preparing catalytic filter cloth, which is characterized in that the catalytic filter cloth is prepared by combining a modified Mn-VTiOx composite catalyst prepared by the method according to any one of claims 1-6 with filter cloth by adopting a blending wire drawing method, and the steps are as follows: the modified Mn-VTiOx composite catalyst, the auxiliary agent and the polytetrafluoroethylene resin are mixed according to the weight ratio of (0.1-1): (0.1-1): (0.5-2) uniformly mixing, standing at 80 ℃ for 8-24h, promoting the auxiliary agent to be fully mixed with polytetrafluoroethylene resin and catalyst to form a material, and then calendaring the material at 40-80 ℃, longitudinally pulling the material at 200-300 ℃, degreasing at 340-450 ℃, slitting, curling and needling to obtain the catalytic filter cloth.
8. The method for preparing catalytic filter cloth according to claim 7, wherein the auxiliary agent is one of kerosene, liquid paraffin and petroleum ether.
9. A catalytic filter cloth prepared according to the method of any one of claims 7-8.
10. Use of a catalyst for low temperature catalytic ozonation prepared by the method of any one of claims 1 to 7, and a catalytic filter cloth according to claim 9, for preparing a product for removing organic matter and particulate matter from a body of water.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004004898A1 (en) * | 2002-07-09 | 2004-01-15 | Daihatsu Motor Co., Ltd. | Catalyst for clarifying exhaust gas |
| CN109046371A (en) * | 2018-08-15 | 2018-12-21 | 浙江大学台州研究院 | Efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst and preparation method thereof |
| CN111957320A (en) * | 2020-07-28 | 2020-11-20 | 华南理工大学 | Supported catalyst filter fiber for catalytic degradation of pollutants in water, and preparation and application thereof |
| CN111992232A (en) * | 2020-08-31 | 2020-11-27 | 西华大学 | Supported transition metal carbide and preparation method and application thereof |
| CN113952982A (en) * | 2021-11-05 | 2022-01-21 | 安徽元琛环保科技股份有限公司 | Manganese-based ultralow-temperature denitration catalyst and preparation method thereof |
| KR20220067068A (en) * | 2020-11-17 | 2022-05-24 | 한국과학기술원 | Catalytic composite for catalytic ozone oxidation process and preparation method thereof |
| CN116159556A (en) * | 2022-12-19 | 2023-05-26 | 江苏方洋水务有限公司 | Supported ozone catalyst and preparation method and application thereof |
| CN117643917A (en) * | 2023-11-30 | 2024-03-05 | 浙江大学台州研究院 | Catalytic filter material for cooperatively removing dioxin and particulate matters at low temperature, preparation method and application thereof |
-
2024
- 2024-03-20 CN CN202410321667.5A patent/CN117960160A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004004898A1 (en) * | 2002-07-09 | 2004-01-15 | Daihatsu Motor Co., Ltd. | Catalyst for clarifying exhaust gas |
| CN109046371A (en) * | 2018-08-15 | 2018-12-21 | 浙江大学台州研究院 | Efficient cobaltous tungstate/nitrogen-doped graphene elctro-catalyst and preparation method thereof |
| CN111957320A (en) * | 2020-07-28 | 2020-11-20 | 华南理工大学 | Supported catalyst filter fiber for catalytic degradation of pollutants in water, and preparation and application thereof |
| CN111992232A (en) * | 2020-08-31 | 2020-11-27 | 西华大学 | Supported transition metal carbide and preparation method and application thereof |
| KR20220067068A (en) * | 2020-11-17 | 2022-05-24 | 한국과학기술원 | Catalytic composite for catalytic ozone oxidation process and preparation method thereof |
| CN113952982A (en) * | 2021-11-05 | 2022-01-21 | 安徽元琛环保科技股份有限公司 | Manganese-based ultralow-temperature denitration catalyst and preparation method thereof |
| CN116159556A (en) * | 2022-12-19 | 2023-05-26 | 江苏方洋水务有限公司 | Supported ozone catalyst and preparation method and application thereof |
| CN117643917A (en) * | 2023-11-30 | 2024-03-05 | 浙江大学台州研究院 | Catalytic filter material for cooperatively removing dioxin and particulate matters at low temperature, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 项焱 等: "非均相臭氧催化氧化在难降解有机废水生化尾水深度处理中 的研究及应用", 《净水技术》, vol. 42, no. 1, 25 January 2023 (2023-01-25), pages 40 - 50 * |
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