CN110028136B - Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles - Google Patents
Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles Download PDFInfo
- Publication number
- CN110028136B CN110028136B CN201910379778.0A CN201910379778A CN110028136B CN 110028136 B CN110028136 B CN 110028136B CN 201910379778 A CN201910379778 A CN 201910379778A CN 110028136 B CN110028136 B CN 110028136B
- Authority
- CN
- China
- Prior art keywords
- phts
- ceo
- wastewater
- manganese
- mno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000945 filler Substances 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- 239000002245 particle Substances 0.000 title claims abstract description 35
- 229910003320 CeOx Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 101001038505 Homo sapiens Ly6/PLAUR domain-containing protein 1 Proteins 0.000 title claims abstract 11
- 102100040284 Ly6/PLAUR domain-containing protein 1 Human genes 0.000 title claims abstract 11
- 201000010917 PTEN hamartoma tumor syndrome Diseases 0.000 title claims abstract 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000000703 Cerium Chemical class 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000012876 carrier material Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 229960001841 potassium permanganate Drugs 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004065 wastewater treatment Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000013335 mesoporous material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000010802 sludge Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- WSVIUXVBNODWOP-UHFFFAOYSA-N cerium(3+) trinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WSVIUXVBNODWOP-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910017278 MnxOy Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- -1 manganese oxide compound Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/33—
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
An electrocatalytic three-dimensional MnOx-CeOx/PHTS filler particle wastewater treatment method belongs to the field of preparation of electrocatalytic MnO by using a PHTS mesoporous material as a carrier and manganese salt and cerium salt as precursors through an isometric impregnation method, combined drying and roasting processesx‑CeOxThe PHTS nanometer three-dimensional filler particle method is characterized in that the filler can be directly used for the first-stage and second-stage electro-catalysis organic wastewater treatment, and the COD removal rate in the phenol and other production wastewater treatment reaches more than 85%; the filler solves the defects that the traditional iron-carbon filler is easy to harden in the wastewater treatment process and the sludge is generated and is easy to cause secondary pollution, and is suitable for the treatment of wastewater in the industrial production fields of pharmacy, chemical industry, dye and the like.
Description
Technical Field
The invention relates to the field of water pollution control, in particular to electro-catalytic three-dimensional MnO for industrial wastewater treatmentx-CeOxPreparation of PHTS filler particles and a method for treating wastewater. MnOxRefers to oxides of manganese in various valence states, including +3, +4, + 5; CeO (CeO)xRefers to oxides of cerium including cerium oxide.
Background
Manganese oxide widely exists in nature, has excellent physical properties and chemical properties, and plays an important role in environmental purification. MnxOyBelongs to valence-variable compounds and mainly shows various redox properties. The manganese oxide compounds commonly used in wastewater treatment mainly include: manganese sesquioxide (Mn)2O3) Manganese dioxide (MnO)2) Manganomanganic oxide (Mn)3O4) The reaction mechanism of the manganic ores (MnO) and the manganite (MnOOH) is mainly that a manganese oxide compound is combined with organic matters such as phenol and the like in the wastewater, and the organic matters in the wastewater are removed and weakened through the oxidation action of the lost electrons of a manganese element. However, in the process of treating wastewater, the manganese oxide is easy to cause the reduction of the valence state of the active high-valence manganese, thereby weakening or even losing the capability of continuously treating the organic matter in the wastewater, and the research and development of the high-efficiency active manganese wastewater treatment material has important value.
The ecological environment research center of the Chinese academy of sciences discloses a preparation method of a catalyst (application number 200710121727.5) for efficiently catalyzing organic pollutants in ozone oxidation water, and Mn is prepared by taking mesoporous zirconium as a carrierxO/ZrO2The catalyst is used for catalyzing the ozone decomposition and oxidation of organic pollutants in water, and the mesoporous zirconium selected by the method has high specific surface area to reduce MnxLoss of O species, but lack a detailed description of the preparation and properties of the mesoporous zirconium. Southern chemical catalyst corporation disclosed a manganese compound, its preparation method and its use (application No. 02829370.3), using divalent manganese mixed with alkaline compounds and potassium permanganate to react and precipitate to obtain the characteristic manganese compound, obviously, under alkaline conditions, because different manganese salts theoretically precipitate under different conditions, will make the mixing method to prepare uniform, stable manganese oxide cause difficulty, for the patent discloses for the elimination of environmental pollutants gas application brings uncertainty. Tianjin chemical research and design institute discloses an ozone decomposition catalyst and a preparation method thereof (CN 1785507A). The spraying process is adopted, and the active component which takes manganese oxide as a main active component and adds alkali metal or alkaline earth metal as an auxiliary agent is loaded on a metal or ceramic honeycomb carrier. Studies on overground water etc. (catalytic report, 2010, 31 (9)), MnOx-CeOx catalyst with copper etc. introduced shows good results in phenol wastewater treatment, its high activity is derived from high valence state manganese ions, while cerium oxide provides good oxygen donor. However, in the wastewater treatment process, Cu-MnCeOx is used as a catalyst, molecular oxygen is used as an oxygen source, and the reaction at 120 ℃ and 1.0 MPa is requiredThe treatment amount of the phenol simulated wastewater is only 4 mg/ml, and the method has certain limitation in industrial application.
The invention selects PHTS with high specific surface area and large aperture developed in the early stage of Jiazhiqi as a carrier (Zhaoyun, Jiazhiqi, etc., an aluminum-doped PHTS mesoporous material and application thereof, ZL 201010130036.3), loads MnOx-CeOx active component, and realizes high-efficiency treatment of high-concentration organic wastewater under the conditions of normal pressure, room temperature and low voltage by means of an electrocatalysis device.
Disclosure of Invention
The invention provides low-cost and environment-friendly electro-catalytic three-dimensional MnOx-CeOxThe PHTS filler particle preparation and the method for treating organic wastewater can be particularly used for the treatment process of organic wastewater such as phenol and the like.
Electro-catalytic three-dimensional MnOx-CeOxA process for treating organic sewage by PHTS filler particles features that a certain quantity of organic sewage such as phenol is added to electrocatalysis unit, and three-dimensional MnO is added to electrocatalysis unitx-CeOxThe PHTS filler particles are used for degrading organic matters such as phenol in the wastewater and improving the biodegradability of the wastewater by means of electrocatalysis and combining a three-dimensional catalytic oxidation technology of the filler particles.
Electrocatalytic three-dimensional MnOx-CeOxThe method for treating the wastewater by the PHTS filler particles is characterized by comprising the following steps:
(1) dissolving P123 into a mineral acid aqueous solution, controlling the content of P123 to be 1-l0Wt%, controlling the concentration of mineral acid to be 0.01-1.6M, then adding a silicon source, controlling the molar ratio of silicon to P123 in the silicon source to be 59-65:1, simultaneously adding a doped aluminum source, controlling the aluminum content in the doped aluminum source to be 1% -15% of the mass of silicon, adjusting the reaction temperature to be 25-45 ℃, reacting for 30min-5h, adding toluene, controlling the toluene to be 1% -20% of the mass of P123, continuing to react for 10-48 h, then transferring to a hydrothermal synthesis kettle, controlling the reaction temperature to be 60-130 ℃, reacting for 24-72h, filtering, separating, drying at 70-120 ℃, roasting for 3-15h at 450-600 ℃ to obtain a PHTS carrier material, wherein the specific surface area of the PHTS carrier material is 400-1200cm2Per g, pore volume is 0.4-1.1cm3(ii)/g, pore size is 4-18 nm;
(2) weighing manganese salt, cerium salt and glucose, dispersing into water, wherein the manganese salt is one or any combination of potassium permanganate, manganese acetate and manganese carbonate, and the addition amount of the manganese salt is 5-50% of the weight of the PHTS carrier; the cerium salt is cerium nitrate or cerium sulfate; the addition amount of the cerium salt is 1 to 10 percent of the mass of the PHTS carrier; the adding amount of the glucose is 1 to 25 percent of the mass of the PHTS carrier; soaking the mixture on a PHTS carrier material by an equal volume impregnation method, drying the mixture at 105 ℃ for 3h, and roasting the dried mixture at 400-950 ℃ for 1-3h to obtain MnOx-CeOxPHTS filler particles;
(3) in a wastewater electrolysis device, 100mL of organic wastewater is measured, and 1-50g of MnO is addedx-CeOxThe electrolytic voltage is controlled to be 5-30V, the electrode is a titanium electrode, the length is 20cm, the width is 2cm, the thickness is 0.1cm, and the distance between the electrodes is 2 cm; electrolyzing the organic wastewater at room temperature and normal pressure, wherein the air introduction amount is 10-100ml/min, and the reaction time is 0.5-4 h.
Catalytic three-dimensional MnO in the inventionx-CeOxMethod for treating wastewater by using/PHTS filler particles, characterized in that MnO is usedx-CeOxthe/PHTS filler particles are prepared by impregnating manganese salt, cerium salt and a small amount of glucose dispersion liquid onto PHTS (Plugged Hexagonal structured silica, see ZL 201010130036.3 for preparation details) carrier material by an equal volume impregnation method, drying, and roasting at high temperature to obtain MnOx-CeOxPHTS filler particles.
MnO of the present inventionx-CeOxThe preparation and drying temperature of the PHTS filler particles is 105 ℃, the time duration is 3h, the roasting temperature is 400-950 ℃, preferably 550-850 ℃, and the roasting time is 1-3 h.
Adding a certain amount of MnO in a wastewater electrolysis devicex-CeOxThe electrolytic voltage is controlled to be 5-30V, the electrode is a titanium electrode, the length is 20cm, the width is 2cm, the thickness is 0.1cm, and the electrode distance is 2 cm; electrolyzing at room temperature and normal pressure to treat organic wastewater.
MnOx-CeOxThe addition amount of PHTS filler particles is 1-50g, the air introduction amount is 10-100ml/min, preferably 20-50ml/min, and the reaction time is 0.5h-4h, preferably 1-2 h.
The inventionThe MnOx-CeOxThe salt content of the organic wastewater treated by the electro-catalysis of the PHTS filler particles is 0-10%. The salt includes sodium chloride and sodium sulfate.
The invention can degrade organic waste water such as phenol and the like, and COD in the organic waste waterCr50-50000ppm, COD after wastewater treatmentCrThe removal rate reaches more than 85 percent, and the method can be directly used for the first-stage and second-stage electro-catalysis organic wastewater treatment.
Electrocatalytic three-dimensional MnOx-CeOxThe preparation method of PHTS filler particles and the method for treating organic wastewater comprise the following steps:
1) preparing a PHTS filler particle carrier: dissolving a nonionic surfactant P123 into a hydrochloric acid aqueous solution, controlling the content of P123 to be 1-10 wt% and the concentration of mineral acid to be 0.01-1.6M, then adding tetraethoxysilane, wherein the molar ratio of silicon to P123 is 59-65:1, adjusting the reaction temperature to 25-45 ℃, reacting for 30min-5h, adding a trimethylbenzene mesoporous structure regulator which accounts for 1-20% of the mass of P123, continuing to react for 10-48 h, then transferring to a hydrothermal synthesis kettle, controlling the reaction temperature to 60-130 ℃, reacting for 24-72h, filtering, separating, drying at 70-120 ℃, and roasting at 450-600 ℃ for 3-15h to obtain a white PHTS mesoporous material, wherein the specific surface area of the white PHTS mesoporous material is 400-1200cm2G, pore volume of 0.4-1.1cm3G, the pore diameter is 4-18 nm. The material has unique micropore and mesoporous structure, is beneficial to the transmission of reaction substances in pore channels, and is suitable for being used as a carrier to prepare a load type material.
2) Electrocatalytic three-dimensional MnOx-CeOxPreparation of PHTS filler particles: weighing a certain amount of the PHTS filler particle carrier in the step 1), dispersing one or more of manganese salt, cerium nitrate or cerium sulfate salt and glucose in any combination of potassium permanganate, manganese acetate and manganese carbonate into quantitative water required by the same volume of impregnated filler particle carrier, and then impregnating the PHTS filler particle carrier; the adding amount of the manganese salt is 5-50 percent of the weight of the PHTS carrier, preferably 10-40 percent; the addition amount of the cerium salt is 1-10% of the weight of the PHTS carrier, and preferably 1-5%; the adding amount of the glucose is 1-25% of the weight of the PHTS carrier. Finally, the impregnated filler particles are dried for 3h at 105 ℃ and baked at 400 ℃ and 950 DEG CThe sintering is carried out for 1-3h, preferably for 1-3h at the temperature of 550-850 ℃.
3) Subjecting the electrocatalytic three-dimensional MnO of the step 2)x-CeOxthe/PHTS filler particles are added into 100mL of waste water solution containing phenol and the like, the adding amount is 1-50g, the voltage is controlled to be 5-30V, the air introducing amount is 10-100mL/min, preferably 20-50mL/min, and the reaction time is 0.5h-4h, preferably 1-2 h.
4) And 3) the salt content range in the wastewater solution containing phenol and the like is 0-10%. The salt includes sodium chloride and sodium sulfate.
5) Step 3) the waste water solution containing phenol and the like, the waste water COD thereofCr50-50000ppm, COD after wastewater treatmentCrThe removal rate reaches more than 85 percent, and the method can be directly used for the first-stage and second-stage electro-catalysis organic wastewater treatment.
The method for treating organic wastewater provided by the invention is simple, low in cost, beneficial to industrial popularization and suitable for treating wastewater in the industrial production fields of pharmacy, chemical industry, dyes and the like.
Drawings
FIG. 1 is a structural view of an electrocatalytic device in the present invention.
In the figure, 1, an electrolytic barrel, 2, an air inlet pipe, 3, an overflow pipe, 4, an electrode, 5 and filler particles.
Detailed Description
The following non-limiting examples will further illustrate the present invention, but the contents of the claims of the present invention are not limited to the exemplified embodiments.
As shown in figure 1, the electro-catalytic device comprises an electrolytic barrel 1, wherein the lower part of the electrolytic barrel 1 is provided with a gas inlet 2 pipe, the upper part of the electrolytic barrel 1 is provided with an overflow pipe 3, and an electrode 4 and filler particles 5 are arranged in the electrolytic barrel 1.
The PHTS material is prepared by dissolving 3.0g of nonionic surfactant P123 into 100ml of acid solution, controlling the temperature to be 35 ℃ for dissolution, then adding 6.6g of tetraethoxysilane, continuing to perform heat preservation reaction, adding 50mg of trimethylbenzene, continuing to perform reaction for 22h, then transferring into a 100 ℃ hydrothermal synthesis kettle, aging for 24h, filtering, drying at 80 ℃, and then roasting at 500 ℃ for 6h to obtain white aluminum PHTS.
Electrocatalytic three-dimensional MnOx-CeOxPHTS filler particlesPreparation of seeds: weighing a certain amount of manganese salt, cerium salt and a small amount of glucose, dispersing into water, soaking onto PHTS (Plugged Hexagonal textured Silicas) carrier material by an isometric impregnation method, drying, and roasting at high temperature to obtain MnOx-CeOxPHTS filler particles.
The manganese salt comprises one or more of potassium permanganate, manganese acetate and manganese carbonate in any combination, and the cerium salt comprises cerium nitrate or cerium sulfate.
Example 1
Manganese acetate (11.84 g), cerium nitrate nonahydrate (0.83 g), and glucose (5 g) were dispersed in 16mL of water, and 30g of PHTS was immersed in the mixture, and the mixture was dried at 105 ℃ for 3 hours and calcined at 830 ℃ for 1 hour to prepare MnOx-CeOxPHTS filler particles.
The electrocatalysis apparatus shown in FIG. 1 contains 100ml COD, (10000 ppm phenol waste water containing 2% sodium chloride), 10g MnO was addedx-CeOxThe voltage of the PHTS filler particles is controlled to be 15V, the air inlet amount is 20ml/min, the room temperature and normal pressure reaction time is 2 hours, the COD is reduced to 500ppm, and the degradation rate is 95%.
Example 2
Weighing 2g of potassium permanganate, 9.1g of manganese acetate, 1.05g of cerium nitrate nonahydrate and 6g of glucose, dispersing into 17mL of water, soaking 30g of PHTS, stirring, drying at 105 ℃ for 3h, and roasting at 630 ℃ for 1h to prepare MnOx-CeOxPHTS filler particles.
The electrocatalysis device is filled with 100ml COD, (1500 ppm phenol waste water liquid containing 2.5% sodium sulfate), 10g MnO is addedx-CeOxThe voltage of PHTS filler particles is controlled to be 13V, the air inlet amount is 20ml/min, the room temperature and normal pressure reaction time is 2 hours, the COD is reduced to 100ppm, and the degradation rate is 93.3 percent.
Example 3
Manganese acetate 9.4g, cerium nitrate nonahydrate 0.85g, and glucose 5g were dispersed in 16.3mL of water, and 30g of PHTS was immersed in the solution, followed by stirring, drying at 105 ℃ for 3 hours, and calcining at 730 ℃ for 1 hour to obtain MnOx-CeOxPHTS filler particles.
The electrocatalysis device is filled with 100ml COD (8000 ppm phenol waste water liquid) and 10g MnOx-CeOxPHTS filler particlesControlling the voltage to be 15V, leading in air with the volume of 20ml/min, reacting for 2 hours at room temperature and normal pressure, reducing COD to 700ppm, and having the degradation rate of 91.2%.
In the invention, P123 is a nonionic surfactant.
Claims (1)
1. Electrocatalytic three-dimensional MnOx-CeOxThe method for treating the wastewater by the PHTS filler particles is characterized by comprising the following steps:
(1) dissolving P123 into a mineral acid aqueous solution, controlling the content of P123 to be 1-l0Wt%, controlling the concentration of mineral acid to be 0.01-1.6M, then adding a silicon source, controlling the molar ratio of silicon to P123 in the silicon source to be 59-65:1, simultaneously adding a doped aluminum source, controlling the aluminum content in the doped aluminum source to be 1% -15% of the mass of silicon, adjusting the reaction temperature to be 25-45 ℃, reacting for 30min-5h, adding toluene, controlling the toluene to be 1% -20% of the mass of P123, continuing to react for 10-48 h, then transferring to a hydrothermal synthesis kettle, controlling the reaction temperature to be 60-130 ℃, reacting for 24-72h, filtering, separating, drying at 70-120 ℃, roasting for 3-15h at 450-600 ℃ to obtain a PHTS carrier material, wherein the specific surface area of the PHTS carrier material is 400-1200cm2Per g, pore volume is 0.4-1.1cm3(ii)/g, pore size is 4-18 nm;
(2) weighing manganese salt, cerium salt and glucose, dispersing into water, wherein the manganese salt is one or any combination of potassium permanganate, manganese acetate and manganese carbonate, and the addition amount of the manganese salt is 5-50% of the weight of the PHTS carrier; the cerium salt is cerium nitrate or cerium sulfate; the addition amount of the cerium salt is 1 to 10 percent of the mass of the PHTS carrier; the adding amount of the glucose is 1 to 25 percent of the mass of the PHTS carrier; soaking the mixture on a PHTS carrier material by an equal volume impregnation method, drying the mixture at 105 ℃ for 3h, and roasting the dried mixture at 400-950 ℃ for 1-3h to obtain MnOx-CeOxPHTS filler particles;
(3) in a wastewater electrolysis device, 100mL of organic wastewater is measured, and 1-50g of MnO is addedx-CeOxThe electrolytic voltage is controlled to be 5-30V, the electrode is a titanium electrode, the length is 20cm, the width is 2cm, the thickness is 0.1cm, and the distance between the electrodes is 2 cm; electrolyzing the organic wastewater at room temperature and normal pressure, wherein the air introduction amount is 10-100ml/min, and the reaction time is 0.5-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910379778.0A CN110028136B (en) | 2019-05-08 | 2019-05-08 | Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910379778.0A CN110028136B (en) | 2019-05-08 | 2019-05-08 | Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110028136A CN110028136A (en) | 2019-07-19 |
| CN110028136B true CN110028136B (en) | 2021-07-02 |
Family
ID=67241573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910379778.0A Active CN110028136B (en) | 2019-05-08 | 2019-05-08 | Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110028136B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683272B (en) * | 2021-10-26 | 2022-07-08 | 杭州水处理技术研究开发中心有限公司 | Advanced treatment system and method for polyurethane wastewater |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804994A (en) * | 2010-03-19 | 2010-08-18 | 山西大学 | Aluminum-doped PHTS mesoporous material and application thereof |
| WO2012013220A1 (en) * | 2010-07-27 | 2012-02-02 | Siemens Aktiengesellschaft | Adsorbent for removing arsenic from an aqueous solution |
| CN102923826A (en) * | 2012-11-14 | 2013-02-13 | 东南大学 | Device for compositely catalytic oxidation treatment of organic wastewater and preparation method of catalytic anode |
| CN103318990A (en) * | 2013-07-04 | 2013-09-25 | 哈尔滨工业大学 | Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation |
| CN105481063A (en) * | 2016-01-19 | 2016-04-13 | 武汉大学 | Particle electrode for treatment of refractory organic wastewater and preparation method for particle electrode |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
| CN106881081A (en) * | 2017-03-15 | 2017-06-23 | 武汉工程大学 | A kind of three-dimensional ordered mesoporous manganese-cerium composite oxide catalyst and its preparation method and application |
-
2019
- 2019-05-08 CN CN201910379778.0A patent/CN110028136B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804994A (en) * | 2010-03-19 | 2010-08-18 | 山西大学 | Aluminum-doped PHTS mesoporous material and application thereof |
| WO2012013220A1 (en) * | 2010-07-27 | 2012-02-02 | Siemens Aktiengesellschaft | Adsorbent for removing arsenic from an aqueous solution |
| CN102923826A (en) * | 2012-11-14 | 2013-02-13 | 东南大学 | Device for compositely catalytic oxidation treatment of organic wastewater and preparation method of catalytic anode |
| CN103318990A (en) * | 2013-07-04 | 2013-09-25 | 哈尔滨工业大学 | Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation |
| CN105481063A (en) * | 2016-01-19 | 2016-04-13 | 武汉大学 | Particle electrode for treatment of refractory organic wastewater and preparation method for particle electrode |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
| CN106881081A (en) * | 2017-03-15 | 2017-06-23 | 武汉工程大学 | A kind of three-dimensional ordered mesoporous manganese-cerium composite oxide catalyst and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110028136A (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106517484B (en) | Method for treating organic wastewater by using ferric oxychloride to catalytically activate monopersulfate | |
| WO2017128600A1 (en) | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method therefor | |
| CN101492199B (en) | Method for removing arsenic with platinum doped titanium dioxide photoelectrocatalysis oxidization | |
| CN102923826A (en) | Device for compositely catalytic oxidation treatment of organic wastewater and preparation method of catalytic anode | |
| CN113171779B (en) | Preparation method and application of B-site five-membered high-entropy perovskite catalyst | |
| CN104289250A (en) | Loaded type ozone catalyst and preparation method and application thereof | |
| CN101187646A (en) | Granule electrode possessing photoelectric catalytic function and its uses | |
| CN101590403A (en) | Multifunctional coupling catalyst and preparation method thereof | |
| CN102145293A (en) | Soft magnetic composite photocatalyst and preparation method thereof | |
| CN109621974B (en) | CuMn2O4Method for treating polluted water by ozone catalytic oxidation and removal of pollutants through rGO composite material | |
| CN106512988B (en) | A kind of molecular sieve carried type MnO2- ZnO ozone catalyst and preparation method thereof | |
| CN106955728A (en) | A kind of preparation method of high efficiency load type ozone oxidation catalyst and application | |
| CN113976103B (en) | High-activity visible-light-driven photocatalyst for wastewater treatment and preparation method thereof | |
| CN110028136B (en) | Method for treating wastewater by electrocatalysis three-dimensional MnOx-CeOx/PHTS filler particles | |
| CN113307335B (en) | Method for treating organic wastewater by using heterogeneous Fenton coupling tube type membrane electrode | |
| CN111085113A (en) | Deamination ultrafiltration membrane for oxidative degradation of ammonia nitrogen in non-photoelectric response, preparation method and application of deaminization ultrafiltration membrane in sewage deaminization | |
| CN113856692A (en) | Preparation of perovskite catalyst and method for treating atrazine wastewater by activating persulfate through perovskite catalyst | |
| CN101559995B (en) | Method for preparing particle-catalytic electrode material | |
| CN105642333A (en) | Multifunctional environment purification composite material, and preparation method and application thereof | |
| CN109574193B (en) | Ruthenium ruthenate lanthanide perovskite catalyst and method for degrading carbamazepine by heterogeneous activated peroxymonosulfate | |
| CN110975879A (en) | Metal-doped ceramsite catalyst and preparation method and application thereof | |
| CN107337262B (en) | Method for degrading organic pollutants in water body through oxygen-assisted anodic catalytic oxidation at low voltage | |
| CN110605133A (en) | Nitrogen-doped titanium-carbon composite catalyst and preparation method and application thereof | |
| CN113620388B (en) | Chemical wastewater treatment method based on mesoporous cerium-based catalyst activated persulfate coupled tubular membrane electrode | |
| CN109876816A (en) | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |