CN117583013A - Ozone oxidation catalyst for wastewater treatment and preparation method thereof - Google Patents
Ozone oxidation catalyst for wastewater treatment and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 44
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 19
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000011777 magnesium Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000006385 ozonation reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229960001680 ibuprofen Drugs 0.000 description 5
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010327 methods by industry Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003052 fractional factorial design Methods 0.000 description 1
- 239000010921 garden waste Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- IUBSYMUCCVWXPE-UHFFFAOYSA-N metoprolol Chemical compound COCCC1=CC=C(OCC(O)CNC(C)C)C=C1 IUBSYMUCCVWXPE-UHFFFAOYSA-N 0.000 description 1
- 229960002237 metoprolol Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010918 textile wastewater Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to an ozone oxidation catalyst for advanced treatment of high-salt organic wastewater and a preparation method thereof. After the surface of the metal oxide carrier is modified by the carbon nitride substance, the Mg-based double-site ozone catalyst prepared by the invention has MgO metal sites and N/C nonmetallic sites, forms double-site synergistic catalysis, has high catalytic efficiency and high stability, and can remarkably reduce the treatment cost of an ozone method compared with the traditional single-metal oxide catalyst. The catalyst prepared by the method has high catalytic efficiency and high stability, the removal efficiency reaches 72%, and the catalyst can be recycled.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an ozone oxidation catalyst for advanced treatment of high-salt organic wastewater and a preparation method thereof.
Background
The high-salt organic wastewater treatment is an important component part, and the high-salt organic wastewater is derived from industrial production processes such as petrochemical industry, textile printing and dyeing and the like. The high-salt refractory organic wastewater contains a large amount of soluble inorganic salts such as Cl besides refractory organic pollutants such as polychlorinated biphenyl, polycyclic aromatic hydrocarbon, dye, pesticide, antibiotics and the like - 、Na + 、SO 4 2- 、Ca 2+ Etc. The method has the characteristics of complex water quality, large pH change, high toxicity, large harm, inhibition on microbial activity, large wastewater volume, high salt content, high toxicity, difficult degradation and the like, belongs to the industrial wastewater with three-cause toxicity difficult to treat, seriously threatens the safety of water environment, and has important environmental protection value and social significance in advanced treatment. Although the high-salt organic wastewater is difficult to treat, under the drive of policies, the trend of realizing zero emission of the advanced treatment of the high-salt organic wastewater is obviously evident.
The heterogeneous ozone catalytic oxidation technology has the advantages of strong oxidizing property, simple operation, easy recovery of catalyst, small occupied area and the like, and becomes one of the effective modes of advanced wastewater treatment. The process can effectively catalyze ozone to generate free radicals to mineralize refractory organic matters, and simultaneously overcomes the problems of difficult recovery of the catalyst, easy secondary pollution and the like caused by homogeneous catalysis. The reaction process mainly comprises the steps of adsorbing ozone molecules through active sites on the surface of a catalyst, decomposing the ozone molecules into active free radicals such as hydroxyl free radicals or superoxide free radicals with stronger oxidability, and reacting the active free radicals with organic pollutants adsorbed on the surface of the catalyst or in a water body, so that mineralization of the organic pollutants is realized. Therefore, the key of the heterogeneous ozone catalytic oxidation process is a high-efficiency catalyst, and extensive researchers at home and abroad have conducted extensive research on the catalyst. The heterogeneous ozone oxidation catalysts commonly used at present are various, and mainly comprise a single-metal or multi-metal oxide catalyst containing Fe, mn, ce, zn, ti and the like, a carbon-based nonmetal catalyst containing N, F and the like, and a catalyst such as a Metal Organic Framework (MOF) and the like.
Metal oxideThe catalyst has the most wide application due to the advantages of low cost, simple synthesis and the like, but the traditional transition metal oxide catalyst is usually MnO at present 2 、Fe 2 O 3 The catalyst with the transition metal oxide as an active center usually generates multiple valence state circulation conversion in the ozone catalytic oxidation process, and electrons can be provided for conversion of ozone into free radicals, so that generation of active oxygen species is promoted, and therefore, the transition metal oxide shows better ozone catalytic oxidation activity. Metal active component loss is a major problem with metal oxide catalysts. Fe which will have magnetic properties such as Ahmadi 3 O 4 The catalyst of PAC@Fe3O4 is designed and synthesized on a carbon carrier (PAC), and the catalytic performance (AHMADI M, KAKAVANDI B, JAAFARZADH N, et al, catalytic ozonation of high saline petrochemical wastewater using PAC@FeIIFe2IIIO4: optimization, mechanisms and biodegradability studies [ J ] of the catalyst in the ozone oxidation treatment of high-salinity petrochemical wastewater (about 362-400 mg/L)].Separation and Purification Technology,2017,177:293-303.)。PAC@Fe 3 O 4 After the catalyst catalyzes ozone oxidation for 120min, the removal rate of COD and TOC can reach 75.3% and 50.3%, and the catalyst has good ozone catalytic oxidation performance, but the removal efficiency of COD and TOC is respectively reduced to 58.3% and 41.1% after repeated use of the catalyst, which is mainly due to the loss of Fe components of surface active sites, and the leaching concentration of Fe is between 0.05 and 0.2mg/L in the period of 5 times of cyclic use. Similarly, he et al explored alpha-MnO 2 、β-MnO 2 And gamma-MnO 2 MnO of three different crystalline phases 2 alpha-MnO was found when the catalyst was affected by the oxidative degradation properties of Ibuprofen (IBU) 2 Contains the most abundant oxygen vacancies, has the highest removal performance for IBU and has the degradation efficiency of 99 percent. But at alpha-MnO 2 The leaching of manganese ions is a critical issue in catalytic ozonation, there is no significant leaching during the first four runs, while in the fifth run, mn 2+ Leaching was increased to 0.1mg/L, while IBU removal efficiency was increased from 5 runs>99.51% drops to 89%, further indicating that leaching of Mn active ingredient isThe main cause of the deterioration of the catalyst performance (HEY, WANG L J, CHEN Z, et al catalytic ozonation for metoprolol and ibuprofen removal over different MnO) 2 nanocrystals:efficiency,transformation and mechanism[J].Science ofthe Total Environment,2021,785:147328.)。
The magnesium oxide is cheap and easy to obtain, and Mg ions are basically pollution-free to water environment, contain alkaline sites and can be used as a green and efficient metal active component. Currently researchers have generally carried MgO directly on carriers such as AC, al 2 O 3 Preparing Mg-based ozone oxidation catalyst on the surface. For example, zhou et al (Zhou L, zhang S, li Z, et al efficiency degradation ofphenol in aqueous solution by catalytic ozonation over MgO/AC [ J)]Journal of Water Process Engineering,2020, 36:101168.) MgO is used as a metal active component, AC is used as a carrier, an MgO/AC catalyst is prepared by an isovolumetric impregnation method, ozone is mainly converted into active free radicals such as hydroxyl free radicals through the action of MgO to realize the oxidative degradation of organic pollutants, and the COD removal rate can reach more than 80% after the reaction of phenol simulated wastewater (210 mg/L) for 120 min. Shen et al (Zhou L, zhang S, li Z, et al efficiency degradation ofphenol in aqueous solution by catalytic ozonation over MgO/AC [ J)]Journal of Water Process Engineering,2020, 36:101168.) the MgO/ceramic honeycomb (MgO/CH) composite material is prepared by using honeycomb ceramics as a carrier through an excessive impregnation method, and is used for removing acetic acid in water, and the removal rate of the acetic acid can reach 81.6% within 30 min. However, it is notable that the activity of MgO catalyst is significantly reduced in multiple recycles (Zhou L, zhang S, li Z, et al Effectent degradation ofphenol in aqueous solution by catalytic ozonation over MgO/AC [ J)]Journal ofWater Process Engineering,2020, 36:101168.) and MgO catalysts are currently used for simulating wastewater systems, conventional MgO catalysts have poor degradation due to the presence of large amounts of inorganic salt ions and refractory organics in the actual wastewater (Bagheri M, roshanaei G, asgari G, et al application of carbon-supported nano-magnesium oxide for catalytic ozonation of real textile wastewater: fractional factorial design and optimization [ J].Desalination Water Treat,2020,175:79-89.). Therefore, the stability and catalytic activity of Mg-based catalysts are required to be further improved.
In summary, the conventional transition metal oxide catalysts, such as the single metal oxide or the double metal oxide catalysts containing Mn, fe, etc., exhibit good ozone catalytic oxidation performance, but there is still a need to solve the problems of secondary pollution and activity degradation caused by easy leaching as the metal active component playing the role of the main ozone catalytic oxidation. Therefore, there is a strong need to develop an ozone oxidation catalyst which is green, efficient and has good stability.
Disclosure of Invention
After the surface of the metal oxide carrier is modified by the carbon nitride substance, the Mg-based double-site ozone catalyst prepared by the invention has MgO metal sites and N/C nonmetallic sites, forms double-site synergistic catalysis, has high catalytic efficiency and high stability, and can remarkably reduce the treatment cost of an ozone method compared with the traditional single-metal oxide catalyst.
In a first aspect, the invention provides an ozone oxidation catalyst for wastewater treatment, the catalyst comprising a support, a non-metallic active component and a metallic active component, wherein the non-metallic active component is covalently modified with the surface of the support, the surface-modified support is obtained by anchoring and dragging metal ions in the metallic active component through amino or hydroxyl groups, wherein the metallic active component and the non-metallic active component form a two-site synergistic catalysis, and the surface area of the catalyst is 140-150m 2 Per gram, pore volume of 0.4-0.5cm 3 /g。
Further, the carrier is a metal oxide, preferably aluminum oxide; the nonmetallic active ingredient is selected from carbon nitride substances such as dopamine or dopamine hydrochloride; the metal active component is a metal oxide, preferably magnesium oxide.
Further, the covalent modification of the nonmetallic active ingredient and the carrier surface means: the nonmetallic active component is used as a modifier and is coated and polymerized on the surface of the carrier.
In a second aspect, the present invention provides a method for preparing the ozone oxidation catalyst according to the first aspect, comprising the steps of:
s1, removing organic impurities on a carrier pore channel and the surface of the carrier to obtain a pretreated carrier;
s2, adding a nonmetallic active component into the pretreated carrier to obtain a carrier with a modified surface;
s3, contacting the modified carrier with a metal active component to obtain a catalyst precursor;
s4, drying and roasting the catalyst precursor to obtain the ozone oxidation catalyst.
Further, in step S1, organic impurities on the pore channels and the surface of the carrier are removed by washing, drying and roasting, wherein the roasting temperature is 300-400 ℃, and the roasting time is 2-5 hours.
Further, in step S2, the mass ratio of the added nonmetallic active ingredient to the carrier is 0.5-1.5: 10 to 30 percent.
Further, in step S3, the concentration of the additive metal active component is 0.05 to 0.5mol/L.
Further, in step S4, the baking is performed under an inert gas atmosphere, the baking temperature is 600-1000 ℃, and the baking time is 1-5 hours.
In a third aspect, the present invention provides the use of an ozone oxidation catalyst as described in the first aspect in the deep treatment of high salt organic wastewater.
Further, the high salt organic wastewater includes, but is not limited to, chemical industrial park wastewater, reverse osmosis concentrate, and/or petrochemical wastewater.
In some embodiments of the invention, the reaction conditions for the ozone oxidation treatment are: COD of the wastewater: 100-110mg/L, TDS:5150-5200mg/L, pH=8+ -1, ozone flow rate of 0.03L/min, catalyst loading of 100-500g/L, reaction time of 0-120min, and ozone concentration of 6-30mg/L.
The beneficial effects are that:
1. the ozone oxidation catalyst prepared by the method has high catalytic efficiency and high stability, the removal efficiency reaches 72%, and the catalyst can be recycled.
2. By the conditions under different conditions, the optimal conditions for treating the high-salt organic wastewater are determined.
3. The alumina used by the catalyst carrier has higher specific surface area and larger pore volume, has good adsorption capacity, enriches pollutants on the surface of the catalyst, and can obviously assist in the catalytic oxidation reaction.
Drawings
FIG. 1 catalyst preparation flow;
figure 2 catalyst effect comparison.
Detailed Description
The term "TDS" (Total dissolved solids ), also known as total dissolved solids, as used herein is measured in milligrams per liter (mg/L), which indicates how much milligrams of dissolved solids are dissolved in 1 liter of water. The higher the TDS value, the more dissolved substances contained in the water. Total dissolved solids refers to the total amount of all solutes in water, including both inorganic and organic content. The conductivity value is generally used to approximate the salt content of the solution, and in general, the higher the conductivity, the higher the TDS. Thus, TDS also reflects the salt level in the wastewater.
The term "advanced wastewater treatment" as used herein generally refers to a treatment of secondary effluent after biochemical treatment or the like by further treating the remaining organic matter by a technique such as advanced oxidation or the like.
The term "water" as used herein refers to deionized water, distilled water or ultrapure water unless otherwise specified.
In order that the invention may be readily understood, a detailed description of the invention will be provided below with reference to the accompanying drawings and examples. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
The invention is further illustrated by the following figures and examples. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, are commercially available.
In the following examples, COD measurement was performed using a DR5000 ultraviolet spectrophotometer (american hashing company) after digestion on a hash DRB200 digestion instrument (american hashing company) using a hash COD reagent. TDS determination was performed using a DDSJ-319L conductivity meter (Shanghai Lei Ci instruments Co., ltd.). The COD removal rate was calculated according to the following formula:
COD removal rate = (COD raw-after COD oxidation)/COD raw x 100%
Example 1 ozone oxidation catalyst article 1 and performance measurement
The preparation flow of the ozone oxidation catalyst is shown in figure 1.
Alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 2 hours, and removing organic impurities on pore channels and surfaces to obtain a pretreated carrier;
(2) Placing the pretreated carrier in a 25mmol/L Tri-HCl buffer solution, fully stirring for 2 hours, adding 0.3mol dopamine hydrochloride into a conical flask, oscillating for 8 hours at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 9 hours at 60 ℃ in a vacuum drying oven to obtain the carrier with the modified surface;
(3) Placing the modified carrier on a carrier containing Mg 2+ Mg in the solution of (2) 2+ The concentration is between 0.2mol/L, and after the full oscillation is carried out for 10 hours, the mixture is stood and aged for 15 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 5 hours at 800 ℃ to obtain a Mg-based double-site catalyst sample.
Reaction conditions: chemical industry garden waste water COD:100-110mg/L, TDS:5150-5200mg/L, pH=8+ -1, ozone flow rate of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, and ozone concentration of 6-30mg/L.
Experimental results show that when the ozone concentration is 18Mg/L, the COD removal rate of the Mg-based double-site catalyst is the highest and is 68%.
Example 2 ozone oxidation catalyst article 2 and performance measurements
Alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 2 hours, and removing organic impurities on pore channels and surfaces to obtain a pretreated carrier;
(2) Placing the pretreated carrier in a 25mmol/L Tri-HCl buffer solution, fully stirring for 2 hours, adding 0.3mol dopamine hydrochloride into a conical flask, oscillating for 8 hours at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 9 hours at 60 ℃ in a vacuum drying oven to obtain the carrier with the modified surface;
(3) Placing the modified carrier on a carrier containing Mg 2+ Mg in the solution of (2) 2+ The concentration is between 0.2mol/L, and after the full oscillation is carried out for 10 hours, the mixture is stood and aged for 15 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 5 hours at 800 ℃ to obtain a Mg-based double-site catalyst sample.
Reaction conditions: petrochemical wastewater reverse osmosis concentrated water, chemical industrial park wastewater COD:100-110mg/L, TDS:5150-5200mg/L, pH=8+ -1, ozone flow rate of 0.03L/min, catalyst loading of 100-500g/L, reaction time of 60min, and ozone concentration of 18mg/L.
Experimental results show that when the adding amount of the catalyst is 100-500g/L, the COD removal rate is increased along with the increase of the adding amount of the catalyst, and the main reason is that after the adding amount of the catalyst is increased, the active site is increased, and the contact time with ozone molecules is longer, so that the adsorption conversion of ozone is facilitated. When the adding amount of the catalyst is 100g/L, the COD removal rate is lower, and the reason is that besides few active sites, the stay time of the ozone in the catalyst layer is shorter, so that the decomposition and conversion of the ozone are not facilitated. Therefore, the addition amount is 500g/L, and the COD removal rate is 68%.
Example 3 ozone oxidation catalyst article 3 and performance measurements
Alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 2 hours, and removing organic impurities on pore channels and surfaces to obtain a pretreated carrier;
(2) Placing the pretreated carrier in a 25mmol/L Tri-HCl buffer solution, fully stirring for 2 hours, adding 0.3mol dopamine hydrochloride into a conical flask, oscillating for 8 hours at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 9 hours at 60 ℃ in a vacuum drying oven to obtain the carrier with the modified surface;
(3) Placing the modified carrier on a carrier containing Mg 2+ Mg in the solution of (2) 2+ The concentration is between 0.2mol/L, and after the full oscillation is carried out for 10 hours, the mixture is stood and aged for 15 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 5 hours at 800 ℃ to obtain a Mg-based double-site catalyst sample.
Reaction conditions: petrochemical wastewater reverse osmosis concentrated water, chemical industrial park wastewater COD:100-110mg/L, TDS:5150-5200mg/L, pH=3-11, ozone flow rate of 0.03L/min, catalyst loading of 500g/L, reaction time of 60min and ozone concentration of 18mg/L.
Experimental results show that the pH has a larger influence on the COD removal rate, the COD removal rate gradually rises along with the rise of the pH value, and the results show that the alkaline environment is favorable for the conversion of ozone into active free radicals. The original pH value of the wastewater is about 7, which is beneficial to the ozone catalytic process, so that the pH regulator is not added, the ozone catalytic reaction is carried out under the original pH value, and the COD removal rate is 60%.
Example 4 ozone oxidation catalyst article 4 and performance measurements
Alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 2 hours, and removing organic impurities on pore channels and surfaces to obtain a pretreated carrier;
(2) Placing the pretreated carrier in a 25mmol/L Tri-HCl buffer solution, fully stirring for 2 hours, adding 0.3mol dopamine hydrochloride into a conical flask, oscillating for 8 hours at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 9 hours at 60 ℃ in a vacuum drying oven to obtain the carrier with the modified surface;
(3) Placing the modified carrier on a carrier containing Mg 2+ Mg in the solution of (2) 2+ The concentration is between 0.2mol/L, and after the full oscillation is carried out for 10 hours, the mixture is stood and aged for 15 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 5 hours at 800 ℃ to obtain a Mg-based double-site catalyst sample.
Reaction conditions: petrochemical wastewater reverse osmosis concentrated water, chemical industrial park wastewater COD:100-110mg/L, TDS:5150-5200mg/L, pH=8+ -1, ozone flow rate of 0.03L/min, catalyst loading of 500g/L, reaction time of 0-120min, and ozone concentration of 18mg/L.
Experimental results show that the oxidation reaction time has a large influence on the COD removal rate, the COD removal rate gradually rises along with the increase of the oxidation reaction time, and when the oxidation time is 120min, the COD removal rate is 72%.
Example 5 an ozone oxidation catalyst article 5 and performance measurements
Alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 2 hours, and removing organic impurities on pore channels and surfaces to obtain a pretreated carrier;
(2) Placing the pretreated carrier in a 25mmol/L Tri-HCl buffer solution, fully stirring for 2 hours, adding 0.3mol dopamine hydrochloride into a conical flask, oscillating for 8 hours at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 9 hours at 60 ℃ in a vacuum drying oven to obtain the carrier with the modified surface;
(3) Placing the modified carrier on a carrier containing Mg 2+ Mg in the solution of (2) 2+ The concentration is between 0.2mol/L, and after the full oscillation is carried out for 10 hours, the mixture is stood and aged for 15 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 5 hours at 800 ℃ to obtain a Mg-based double-site catalyst sample.
Reaction conditions: petrochemical wastewater reverse osmosis concentrated water, chemical industrial park wastewater COD:100-110mg/L, TDS:5150-5200mg/L, pH=8+ -1, ozone flow rate of 0.03L/min, catalyst loading of 500g/L, reaction time of 60min, and ozone concentration of 18mg/L.
For the wastewater of chemical industry park, the method is compared with the conventional MgO/Al 2 O 3 In comparison with Al 2 O 3 The removal rate of the PDA-MgO catalyst COD is improved by 13% (see figure 2), the performance is good, the stability and the activity are good, and the catalyst can be reused.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. An ozone oxidation catalyst for wastewater treatment comprises a carrier, a non-metallic active component and a metallic active component, wherein the non-metallic active component and the surface of the carrier are subjected to covalent modification to obtain surface repairAnchoring and traction are carried out on metal ions in the metal active component by amino or hydroxyl on the decorated carrier, wherein the metal active component and the non-metal active component form a double-site synergistic catalysis effect, and the surface area of the catalyst is 140-150m 2 Per gram, pore volume of 0.4-0.5cm 3 /g。
2. The ozone oxidation catalyst for wastewater treatment according to claim 1, wherein the carrier is a metal oxide; the nonmetallic active component is selected from carbon nitride substances; the metal active component is a metal oxide.
3. The ozone oxidation catalyst for wastewater treatment according to claim 2, wherein the metal oxide is selected from the group consisting of aluminum oxide; the nonmetallic active ingredient is selected from carbon nitride substances such as dopamine or dopamine hydrochloride; the metal active component is selected from magnesium oxide.
4. The ozone oxidation catalyst for wastewater treatment according to claim 1, wherein the covalent modification of the nonmetallic active ingredient with the surface of the carrier means: the nonmetallic active component is used as a modifier and is coated and polymerized on the surface of the carrier.
5. A method of preparing the ozone oxidation catalyst according to claim 1, the method comprising the steps of:
s1, removing organic impurities on a carrier pore channel and the surface of the carrier to obtain a pretreated carrier;
s2, adding a nonmetallic active component into the pretreated carrier to obtain a carrier with a modified surface;
s3, contacting the modified carrier with a metal active component to obtain a catalyst precursor;
s4, drying and roasting the catalyst precursor to obtain the ozone oxidation catalyst.
6. The method for preparing an ozone oxidation catalyst according to claim 5, wherein in step S1, organic impurities on the support channels and surfaces are removed by washing, drying and roasting, wherein the roasting temperature is 300-400 ℃, and the roasting time is 2-5 hours.
7. The method for preparing an ozone oxidation catalyst according to claim 5, wherein in step S2, the mass ratio of the added nonmetallic active ingredient to the carrier is 0.5 to 1.5:10 to 30 percent.
8. The method for preparing an ozone oxidation catalyst according to claim 5, wherein in step S3, the concentration of the additive metal active component is 0.05 to 0.5mol/L.
9. The method for producing an ozone oxidation catalyst according to claim 5, wherein in step S4, the calcination is performed under an inert gas atmosphere at a temperature of 600 to 1000 ℃ for a time of 1 to 5 hours.
10. Use of the ozone oxidation catalyst according to any one of claims 1-4 for the deep treatment of high-salt organic wastewater.
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