CN117960160B - 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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- CN117960160B CN117960160B CN202410321667.5A CN202410321667A CN117960160B CN 117960160 B CN117960160 B CN 117960160B CN 202410321667 A CN202410321667 A CN 202410321667A CN 117960160 B CN117960160 B CN 117960160B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000004744 fabric Substances 0.000 title claims abstract description 74
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 45
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 238000005491 wire drawing Methods 0.000 claims abstract description 6
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- 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
- 239000002245 particle Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 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
- 238000005406 washing Methods 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
- 229940057995 liquid paraffin Drugs 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
- 238000005530 etching Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 description 34
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
- 230000002572 peristaltic effect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (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 Mn-VTiOx composite catalyst is used for etching the surface of the catalyst by using acid, the intermetallic interaction of Mn, V and Ti and the regulation and control of acid etching on the surface acidic sites are utilized, 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 Mn-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) dissolving in the mixed solution I to obtain a mixed solution II;
Transferring the mixed solution II to a reaction kettle, reacting at 120 ℃ for 20-24 h, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying at 105 ℃ for 6-10 h, and calcining at 500 ℃ for 3-6 h to obtain the V-Ti-based catalyst;
(2) Active ingredient impregnation
Adding a manganese metal precursor into an aqueous solution containing a V-Ti-based catalyst, stirring at normal temperature for 10-15 h, and roasting at 300 ℃ for 3-6 h to obtain a Mn-VTiOx composite catalyst;
(3) Surface modification
Adding Mn-VTiOx composite catalyst into acid solution, stirring at normal temperature for 4-8 h, washing with water, then adding polytetrafluoroethylene emulsion, then drying at 105 ℃, and finally roasting at 400 ℃ for 3-6 h to obtain the catalyst for low-temperature catalytic ozonation: modified Mn-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 1-5 mol/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 8-24 h, 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 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-based 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 performs performance test in a cross-flow mode by maintaining a constant pressure of 0.2 Mpa, and the test process is as follows:
The catalytic filter cloth to be detected is arranged in a catalytic filter cloth device, sewage 1.2L 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, the ozone is input by 20 mg/L, 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 the 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 based 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 at 120 ℃ for 24h, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying at 105 ℃ for 8h, and calcining at 500 ℃ for 4h to obtain a V-Ti-based catalyst;
(2) Active ingredient impregnation
Adding 5wt% manganese sulfate into an aqueous solution containing a V-Ti-based catalyst, stirring at normal temperature for 12h ℃, and roasting at 300 ℃ for 4h to obtain a Mn-VTiO x composite catalyst;
(3) Surface modification
Adding 2 g Mn-VTiO x composite catalyst into 2 mol/L nitric acid solution, stirring at normal temperature for 6 h to wash with water, pouring 5wt% polytetrafluoroethylene emulsion, stirring uniformly, drying at 105 ℃, and roasting at 400 ℃ for 4h to obtain modified Mn-VTiOx 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 at 80 ℃ for 8-24 h after the mixture is uniform, promoting the liquid paraffin, the polytetrafluoroethylene resin and the catalyst to be fully mixed and form a material, and then sequentially carrying out steps of calendaring at 60 ℃, longitudinal drawing 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 190.6 g/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 72.8%, and the catalyst is only lost 6.4 g/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 192.2 g/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 7.2 g/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 187.9 g/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 5.4 g/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 193.3 g/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 is only lost 6.2 g/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 201.1 g/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 is only lost by 5.5 g/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 202.9 g/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 7.1 g/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 200.2 g/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 6.6 g/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 silicotungstic acid concentration in step (3) was changed to 1 mol/L, and the catalyst content of the polytetrafluoroethylene catalytic filter cloth prepared by the above-mentioned method was 199.7 g/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 95.6%, and the catalyst only runs off 5.7 g/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 silicotungstic acid concentration 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 204.1 g/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 8.1mg/L after treatment and 77.5%, and the catalyst is only lost 6.0 g/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 0 mol/L, and the catalyst content of the catalytic filter cloth of polytetrafluoroethylene prepared by the above-mentioned method was 182.4 g/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 15.0 g/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%) >2 mol/L (94.4%) >5 mol/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 15 g/m 2 to 5.7 g/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 (8)
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) dissolving in the mixed solution I to obtain a mixed solution II;
Transferring the mixed solution II to a reaction kettle, reacting at 120 ℃ for 20-24 h, taking out solid particles after the reaction is finished, washing the solid particles with ethanol and water in turn, drying at 105 ℃ for 6-10 h, and calcining at 500 ℃ for 3-6 h to obtain the V-Ti-based catalyst;
(2) Active ingredient impregnation
Adding a manganese metal precursor into an aqueous solution containing a V-Ti-based catalyst, stirring at normal temperature for 10-15 h, and roasting at 300 ℃ for 3-6 h to obtain a Mn-VTiOx composite catalyst;
(3) Surface modification
Adding Mn-VTiOx composite catalyst into acid solution, stirring at normal temperature for 4-8 h, washing with water, then adding polytetrafluoroethylene emulsion, then drying at 105 ℃, and finally roasting at 400 ℃ for 3-6 h to obtain the catalyst for low-temperature catalytic ozonation: modified Mn-VTiOx composite catalyst;
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;
The acid solution in the step (3) is one of a silicotungstic acid solution, a phosphotungstic acid solution and a nitric acid solution.
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 concentration of the acid solution in the step (3) is 1-5 mol/L.
5. 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 1-4 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 8-24 h, 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 at 200-300 ℃, degreasing at 340-450 ℃, slitting, curling and needling to obtain the catalytic filter cloth.
6. The method for preparing catalytic filter cloth according to claim 5, wherein the auxiliary agent is one of kerosene, liquid paraffin and petroleum ether.
7. A catalytic filter cloth prepared according to the method of any one of claims 5-6.
8. The use of a catalyst for low-temperature catalytic ozonation prepared by the method of any one of claims 1 to 4, and a catalytic filter cloth according to claim 7 for preparing a product for removing organic matters and particulate matters in water.
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