CN107684907A - A kind of noble metal catalyst for CWO industrial wastewater, preparation method and applications - Google Patents

A kind of noble metal catalyst for CWO industrial wastewater, preparation method and applications Download PDF

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Publication number
CN107684907A
CN107684907A CN201710881665.1A CN201710881665A CN107684907A CN 107684907 A CN107684907 A CN 107684907A CN 201710881665 A CN201710881665 A CN 201710881665A CN 107684907 A CN107684907 A CN 107684907A
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noble metal
preparation
metal catalyst
carrier
catalyst
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CN107684907B (en
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陶海祥
江海云
郑搏英
吴小亮
赵瑞强
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Zhejiang Qicai Eco Technology Co Ltd
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Zhejiang Qicai Eco Technology Co Ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a kind of noble metal catalyst for CWO industrial wastewater and its preparation method and application, belong to environment functional material and technical field of waste water processing, wherein catalyst is made up of carrier loaded active component, and the carrier is CeO2And TiO2Mixture, one or two or more kinds of compositions of the active component in noble metal Ru, Rh, Pt, Pd.Preparation method comprises the following steps：1. prepared by carrier：Ceria powder, titanium dioxide powder and pore creating material are mixed, after ball mill ball milling, add binding agent and water kneading together, then through extrusion, drying, roasting and be made；2. load active component：Above-mentioned carrier is dried, loaded noble metal catalyst is made in roasting reduction after activity component impregnation liquid dipping.The method for preparing catalyst is simple, it is cheap, can industrialize, and can apply to catalytic wet oxidation technology processing actual industrial waste water.

Description

A kind of noble metal catalyst for CWO industrial wastewater, preparation method And its application
Technical field
The present invention relates to environment functional material and technical field of waste water processing, is used for CWO in particular to one kind The noble metal catalyst of industrial wastewater, preparation method and applications.
Background technology
Wet oxidation process (Wet Air Oxidation, abbreviation WAO) is one kind weight to grow up from the 1950s Poisonous and harmful, high concentrated organic wastewater the effective treating method of degraded wanted, initially by the U.S. F. J. Zimmermann in It is proposed, and achieve multinomial patent within 1958, therefore also referred to as Annemarie Zimmermann method.Refer specifically in high temperature (150 ~ 350 DEG C) and high pressure Under the conditions of (0.5~20 MPa), using the oxygen in air as oxidant, by the organic matter in sewage and containing N, S harmful substance oxygen CO is resolved into change2、N2、SO4 2-And H2The innocuous substances such as O, it is finally reached the purpose of purification sewage.
Traditional Wet Oxidation Process needs higher temperature and pressure and relatively long reaction time, especially right It is difficult to oxidized organic compound in some, reaction condition requires more harsh.Therefore, since the 1970s, ground Study carefully staff development catalytic wet oxidation technology (Catalytic Wet Air Oxidation, abbreviation CWAO), i.e., to conventional wet Catalyst is added in formula oxidation reaction system, can not only reduce reaction temperature and pressure, and improve reaction efficiency.Due to Catalytic wet air oxidation have reaction condition is relatively mild, treatment effeciency is high, reaction speed is fast, device is small, it is applied widely, can The advantages such as Resource recovery and secondary pollution are low, therefore have a good application prospect.
The core of catalytic wet oxidation technology is catalyst, including homogeneous catalyst and heterogeneous catalyst.Homogeneous catalyst The advantages that active high, reaction speed is fast, but because catalyst is soluble in water, it is necessary to carry out subsequent treatment, avoid catalyst stream Become estranged secondary pollution；The advantages that heterogeneous catalyst is active high, easily separated, stability is good, turns into wet oxidizing catalyst Study hotspot.Wherein noble metal catalyst has good catalytic activity and higher stability, but has that cost is higher to ask Topic；The transition metal oxides such as metallic copper, iron equally have preferable catalytic activity, but more serious catalysis in the reaction be present Agent active component dissolution phenomenon, makes catalyst activity reduction, and cause secondary pollution problem.At present, numerous researcher's exploitations Go out a series of good heterogeneous catalysis wet oxidizing catalyst of catalytic performances, but it is often expensive, greatly hinder the skill Application of the art in actual industrial wastewater treatment.
Because the industrial condition of CWO reaction is very harsh, catalyst is substantially immersed in high temperature, height always In the waste water of pressure, and because the intermediate product of CWO reaction is small carboxylic acid molecules, its stronger acidity is also to be permitted What more common catalyst active components and carrier can not be born.In fact, in catalytic wet oxidation catalyst research direction, pole Most of research work is all concentrated in noble metal catalyst system.
In addition, the stability of catalyst is similarly dependent on the stability of carrier, the choosing of wet oxidation heterogeneous catalysis agent carrier Select and equally seem particularly significant.In common carrier, one pack system TiO2Mouldability is bad, not easy-formation, and the carrier after shaping Intensity and specific surface area are relatively low；Under wet oxidation harsh conditions, the TiO as carrier2In the presence of the possibility that crystalline phase change occurs Property, cause catalyst to crush and ftracture, influence the stability of catalyst performance.
Application publication number discloses a kind of heterogeneous catalysis wet oxidation for the A of CN 103521222 Chinese invention patent and urged Agent and preparation method thereof, cerium salt, zirconates, titanium salt mixed solution and ammoniacal liquor are co-precipitated generation gelatinous mass, taken out by vacuum Filter, washing, drying and roasting are prepared for TiO2-ZrO2-CeO2Carrier, and use infusion process by noble-metal-supported in above-mentioned TiO2- ZrO2-CeO2On carrier, finished catalyst is obtained after fired, reduction.
Application publication number is that the A of CN 104148048 Chinese invention patent discloses a kind of wet oxidizing catalyst carrier Preparation method, use with a kind of, dilute in nano titanium oxide, titanium salt (titanium tetrachloride, titanyl sulfate and butyl titanate) At least one of earth metal salt lanthanum nitrate, cerous nitrate, praseodymium nitrate and neodymium nitrate are raw material, after mixing by a certain percentage, are added dropwise Ammoniacal liquor obtains white depositions, and the titanic oxide shaping carrier containing rare earth element is made through suction filtration, extrusion, drying, roasting.The preparation Ingredient requirement used in method is high, and the specific surface area of the titanium dioxide such as used is 20~300 m2/ g, crystal particle diameter be 5~ 100 nm, and carrier preparation technology route is longer.
Application publication number is that the A of CN 103157517 Chinese invention patent discloses a kind of corrosion-resistant, high temperature resistant, high-strength Degree, the catalytic wet oxidation catalyst of bigger serface, to aoxidize titanium stabilized zirconium oxide as carrier, load high activity and be not easy Noble metal Ru, Pt of loss, prepare excellent catalytic wet oxidation catalyst.It is compound that titanium zirconium is obtained using sol-gel process White gum thing, filtered, washing, with extrusion after shaping assistant kneading, titanium zirconium complex carrier is obtained after roasting, and by normal Pressure incipient impregnation or vacuum equi-volume impregnating are prepared for carried noble metal/TiZrO2Catalyst.
Up to the present, the process route of most of published wet oxidizing catalyst preparation method is complicated, is unfavorable for Industrialized production.
The content of the invention
Present invention aim to provide a kind of noble metal catalyst for CWO industrial wastewater, and carry For its preparation method, its application field is introduced, makes catalyst that there is high stability and high catalytic performance, carrier has specific surface area Greatly, the advantages that intensity height, good moldability, stability are good, cheap, preparation method is simple, it is cheap, can industrialize, be applied to Catalytic wet oxidation technology handles actual industrial waste water.
To achieve the above object, a kind of precious metal catalyst for CWO industrial wastewater designed by the present invention Agent, it is made up of carrier loaded active component；
Wherein, the carrier is CeO2And TiO2Mixture, wherein CeO2Content be 2 ~ 70 wt%, TiO2Content for 30 ~ 98wt%；
One or two or more kinds of compositions of the active component in noble metal Ru, Rh, Pt, Pd, the active component Load capacity in the catalyst is 0.2 ~ 5 wt%.
A kind of preparation method of noble metal catalyst, comprises the following steps：
1. prepared by carrier：Ceria powder, titanium dioxide powder and pore creating material are mixed, after ball mill ball milling, add binding agent With water together kneading, then through extrusion, drying, roasting and carrier is made；
2. load active component：Above-mentioned carrier is dried, support type is made in roasting reduction after activity component impregnation liquid dipping Noble metal catalyst.
As the preferred of above-mentioned technical proposal, step 1. described in pore creating material be polyethylene glycol, sesbania powder, starch, first One kind or any several composition in base cellulose, carboxymethyl cellulose, activated carbon.
As the preferred of above-mentioned technical proposal, step 1. described in binding agent be Ludox, citric acid, nitric acid, natural gum, One or more of compositions in methylcellulose, paraffin.
As the preferred of above-mentioned technical proposal, step 1. in Ball-milling Time be 0.5 ~ 12 hour.
As the preferred of above-mentioned technical proposal, step 1. in drying temperature be 30 ~ 90 DEG C, drying time is 12 ~ 120 small When；Sintering temperature is 450 ~ 650 DEG C, and roasting time is 2 ~ 12 hours, and calcination atmosphere is air atmosphere.
As the preferred of above-mentioned technical proposal, step 1. described in the addition of pore creating material be ceria powder and titanium dioxide The 1.5% ~ 3% of titanium valve gross mass, the addition of the binding agent for ceria powder and titanium dioxide powder gross mass 0.5% ~ 30%。
As the preferred of above-mentioned technical proposal, step 2. described in carrier incipient impregnation RuCl3、PdCl2、RhCl3Or H2PtCl6Solution, the load capacity of active component in the catalyst are 0.2 ~ 5 wt%.
As the preferred of above-mentioned technical proposal, step 2. in drying temperature be 80 ~ 120 DEG C, drying time is 8 ~ 24 small When；Sintering temperature is 300 ~ 450 DEG C, and roasting time is 2 ~ 6 hours, and calcination atmosphere is hydrogen and nitrogen mixture atmosphere or single hydrogen Gas atmosphere.
A kind of technique of CWO processing industrial wastewater, intermittent reaction condition are：The unrestricted model of catalyst amount Enclose, reaction temperature is 180 ~ 280 DEG C, and reaction pressure is 3 ~ 8 MPa, and the reaction time is 0.5 ~ 4 hour；
Successive reaction condition is：Reaction temperature is 180 ~ 280 DEG C, and reaction pressure is 3 ~ 8 MPa, and air speed is 0.25 ~ 2 h-1。
The carried noble metal CeO of the present invention2-TiO2Catalyst is applied to processing high-concentration hardly-degradable organic industrial sewage （COD=15000~60000 mg/L）, the temperature and pressure of wet oxidation is advantageously reduced, and treatment effeciency can be improved.
The present invention uses common ceria and titania powder as raw material, after adding pore creating material, passes through ball mill Sufficient ball milling, and the extruded moulding in the presence of binding agent are carried out to powder stock, prepares high surface area, high stable, resistance to The resistant to elevated temperatures catalyst carrier of burn into, using noble metal Ru, Pd, Pt, Rh that high activity not easily runs off as active component, prepare Go out the wet oxidation Heterogeneous Noble Metals Catalysts with high activity, high stability.
The present invention compared with prior art, has advantages below and beneficial effect：
（1）The present invention uses raw material cheap and easy to get in carrier preparation process, and catalyst preparation cost is low.
（2）Catalyst preparation process route of the present invention is simple, easy industrialized production；
（3）Because introducing pore creating material when carrier is molded, catalyst has high-specific surface area, the spy of active component good dispersion Point.
Brief description of the drawings
Fig. 1 is the TOC clearance variation diagrams of CWO simulated wastewater containing triethylamine described in embodiment 7.
Fig. 2 is the TOC clearance variation diagrams of CWO waste water in dye production described in embodiment 8.
Fig. 3 is the TOC clearance variation diagrams of CWO waste water in dye production described in embodiment 9.
Fig. 4 is the TOC clearance variation diagrams of CWO waste water in dye production described in embodiment 10.
Fig. 5 is the TOC clearance variation diagrams of CWO waste water in dye production described in embodiment 11.
Fig. 6 is the TOC clearance variation diagrams of CWO waste water in dye production described in embodiment 12.
Embodiment
With reference to specific embodiment, the present invention is described in further detail：
Table 1 is the content of material proportioning of catalyst described in 1 ~ embodiment of embodiment 6
Table 2 is the carrier preparation technology parameter of catalyst described in 1 ~ embodiment of embodiment 6
Table 3 is the active component load process parameter of catalyst described in 1 ~ embodiment of embodiment 6
The content of material proportioning of catalyst described in the 1 ~ embodiment of embodiment 6 of table 1
The carrier preparation technology parameter of catalyst described in the 1 ~ embodiment of embodiment 6 of table 2
The active component load process parameter of catalyst described in the 1 ~ embodiment of embodiment 6 of table 3
Embodiment 7：
Simulated wastewater application test：The mg/L of TOC=5300 triethylamine simulated wastewater is prepared, wastewater pH=5 ~ 6 is adjusted with acid, takes A certain amount of loaded noble metal catalyst is 5 MPa in fixed bed reaction pipe, being passed through air to gross pressure, heats and maintains For temperature at 220 DEG C, reaction velocity is 1 h in reaction tube-1, in course of reaction, useless water and air continues into certain proportion Reaction system, the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 are shown in Fig. 1.
Embodiment 8：
Actual industrial wastewater application is tested：Take certain dyestuff company industrial production wastewater, the mg/L of COD=35800, TOC=14600 Mg/L, it in fixed bed reaction pipe, being passed through air to gross pressure is 5 MPa to take a certain amount of loaded noble metal catalyst, is added For temperature at 220 DEG C, reaction velocity is 1 h in heat and maintenance reaction pipe-1, in course of reaction, give up water and air in certain proportion Reaction system is continued into, the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 is shown in Fig. 2.
Embodiment 9：
Actual industrial wastewater application is tested：Take certain dyestuff company industrial production wastewater, the mg/L of COD=27600, TOC=10500 Mg/L, it in fixed bed reaction pipe, being passed through air to gross pressure is 3 MPa to take a certain amount of loaded noble metal catalyst, is added For temperature at 180 DEG C, reaction velocity is 2 h in heat and maintenance reaction pipe-1, in course of reaction, give up water and air in certain proportion Reaction system is continued into, the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 is shown in Fig. 3.
Embodiment 10：
Actual industrial wastewater application is tested：Take certain dyestuff company industrial production wastewater, the mg/L of COD=58200, TOC=21800 Mg/L, it in fixed bed reaction pipe, being passed through air to gross pressure is 8 MPa to take a certain amount of loaded noble metal catalyst, is added For temperature at 280 DEG C, reaction velocity is 0.5 h in heat and maintenance reaction pipe-1, in course of reaction, the water and air that gives up is with certain ratio Example continues into reaction system, and the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 is shown in Fig. 4.
Embodiment 11：
Actual industrial wastewater application is tested：Certain a certain amount of dyestuff company industrial production wastewater is taken in autoclave, COD= The mg/L of 28300 mg/L, TOC=12700, and a certain amount of loaded noble metal catalyst is added in autoclave, it is passed through Air to gross pressure is 3 MPa, heats and for temperature at 180 DEG C, the reaction time be 2 h in maintenance reaction pipe, in course of reaction, sky Gas continues into reaction system with certain flow, and the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 is shown in Fig. 5.
Embodiment 12：
Actual industrial wastewater application is tested：Certain a certain amount of dyestuff company industrial production wastewater is taken in autoclave, COD= The mg/L of 43100 mg/L, TOC=15700, and a certain amount of loaded noble metal catalyst is added in autoclave, it is passed through Air to gross pressure is 6 MPa, heats and for temperature at 250 DEG C, the reaction time be 2 h in maintenance reaction pipe, in course of reaction, sky Gas continues into reaction system with certain flow, and the processing concrete outcome using catalyst described in 1 ~ embodiment of embodiment 6 is shown in Fig. 6.

Claims (10)

  1. A kind of 1. noble metal catalyst for CWO industrial wastewater, it is characterised in that：
    It is made up of carrier loaded active component；
    Wherein, the carrier is CeO2And TiO2Mixture, wherein CeO2Content be 2 ~ 70 wt%, TiO2Content for 30 ~ 98wt%；
    One or two or more kinds of compositions of the active component in noble metal Ru, Rh, Pt, Pd, the active component Load capacity in the catalyst is 0.2 ~ 5 wt%.
  2. 2. the preparation method of the noble metal catalyst described in a kind of claim 1, it is characterised in that comprise the following steps：
    1. prepared by carrier：Ceria powder, titanium dioxide powder and pore creating material are mixed, after ball mill ball milling, add binding agent With water together kneading, then through extrusion, drying, roasting and carrier is made；
    2. load active component：Above-mentioned carrier is dried, support type is made in roasting reduction after activity component impregnation liquid dipping Noble metal catalyst.
  3. 3. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 1. described in pore-creating Agent is polyethylene glycol, sesbania powder, starch, methylcellulose, carboxymethyl cellulose, one kind in activated carbon or any several group Compound.
  4. 4. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 1. described in bonding Agent is one or more of compositions in Ludox, citric acid, nitric acid, natural gum, methylcellulose, paraffin.
  5. 5. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 1. in Ball-milling Time For 0.5 ~ 12 hour.
  6. 6. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 1. in drying temperature For 30 ~ 90 DEG C, drying time is 12 ~ 120 hours；Sintering temperature is 450 ~ 650 DEG C, and roasting time is 2 ~ 12 hours, is calcined gas Atmosphere is air atmosphere.
  7. 7. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 1. described in pore creating material Addition be the 1.5% ~ 3% of ceria powder and titanium dioxide powder gross mass, the addition of the binding agent is ceria The 0.5% ~ 30% of powder and titanium dioxide powder gross mass.
  8. 8. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 2. described in carrier Incipient impregnation RuCl3、PdCl2、RhCl3Or H2PtCl6Solution, the load capacity of active component in the catalyst are 0.2 ~ 5 wt%.
  9. 9. the preparation method of noble metal catalyst according to claim 2, it is characterised in that：Step 2. in drying temperature For 80 ~ 120 DEG C, drying time is 8 ~ 24 hours；Sintering temperature is 300 ~ 450 DEG C, and roasting time is 2 ~ 6 hours, calcination atmosphere For hydrogen and nitrogen mixture atmosphere or single hydrogen atmosphere.
  10. 10. a kind of technique of CWO processing industrial wastewater, using the catalyst described in claim 1, its feature exists In：
    Intermittent reaction condition is：Catalyst amount unlimited range, reaction temperature are 180 ~ 280 DEG C, and reaction pressure is 3 ~ 8 MPa, reaction time are 0.5 ~ 4 hour；
    Successive reaction condition is：Reaction temperature is 180 ~ 280 DEG C, and reaction pressure is 3 ~ 8 MPa, and air speed is 0.25 ~ 2 h-1。
CN201710881665.1A 2017-09-26 2017-09-26 Noble metal catalyst for catalyzing wet oxidation of industrial wastewater, preparation method and application thereof Active CN107684907B (en)

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CN112624299A (en) * 2019-09-24 2021-04-09 中国石油化工股份有限公司 Method for treating phosphorus-containing organic wastewater
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CN111558297A (en) * 2020-05-12 2020-08-21 山东交通学院 Method for reducing exhaust emission of engine
CN112607905A (en) * 2020-12-14 2021-04-06 浙江奇彩环境科技股份有限公司 Method for removing total nitrogen in organic nitrogen wastewater
CN115475616A (en) * 2021-06-16 2022-12-16 中国石油化工股份有限公司 Wet oxidation catalyst and preparation method and application thereof
CN115475616B (en) * 2021-06-16 2024-03-26 中国石油化工股份有限公司 Wet oxidation catalyst and preparation method and application thereof
CN114105279A (en) * 2021-12-06 2022-03-01 浙江工业大学台州研究院 Method for catalytic treatment of industrial wastewater based on heterogeneous catalyst

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