WO2020134834A1 - Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst - Google Patents

Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst Download PDF

Info

Publication number
WO2020134834A1
WO2020134834A1 PCT/CN2019/121560 CN2019121560W WO2020134834A1 WO 2020134834 A1 WO2020134834 A1 WO 2020134834A1 CN 2019121560 W CN2019121560 W CN 2019121560W WO 2020134834 A1 WO2020134834 A1 WO 2020134834A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
plasma
ppm
removal rate
transition metal
Prior art date
Application number
PCT/CN2019/121560
Other languages
French (fr)
Chinese (zh)
Inventor
黄逸凡
杨环环
高明
白力诚
喻学锋
Original Assignee
中国科学院深圳先进技术研究院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 中国科学院深圳先进技术研究院 filed Critical 中国科学院深圳先进技术研究院
Publication of WO2020134834A1 publication Critical patent/WO2020134834A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
    • 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
    • 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
    • C02F2101/306—Pesticides

Definitions

  • the invention relates to the field of sewage treatment, and more particularly, to a method for synergistically catalyzing and degrading glyphosate wastewater by low-temperature plasma.
  • Glyphosate is a low-toxicity, high-efficiency, and broad-spectrum biocidal herbicide. It has grown rapidly in recent years and has become the world's largest pesticide product in terms of production and usage.
  • the mother liquor wastewater has the characteristics of large discharge, high toxicity, high salt content, high content of refractory compounds, and difficulty in treatment.
  • the organic impurities in the mother liquor mainly include glyphosate, diglyphosate, phosphite, phosphate, glycine, methanol, formaldehyde and other components, and the main components are glyphosate, glycine, phosphate and so on.
  • the treatment of glyphosate wastewater mainly adopts the adsorption method, wet catalytic oxidation method, and chlorine oxidation method.
  • the above methods have achieved good results, but the steps are cumbersome, require a large number of chemical reagents, and the reaction conditions also require high temperature and high pressure. The requirements are higher, and there are certain restrictions in industrial applications.
  • Low-temperature plasma technology is a new and highly efficient environmental protection technology that is commonly used in the treatment of exhaust gas and less used in wastewater treatment.
  • the existing low-temperature plasma technology is used in wastewater treatment methods, and it cannot solve the degradation of glyphosate wastewater.
  • the purpose of the present invention is to provide a method for synergistically catalyzing the degradation of glyphosate wastewater with low-temperature plasma in response to the existing procedures which are cumbersome, require a large amount of chemical reagents, and require high temperature and high pressure.
  • a method for preparing a transition metal alloy catalyst composite includes the following steps:
  • the transition metal salt and the carrier are mixed in a solvent, and after drying, the mixture is calcined in a mixed gas of inert gas and hydrogen at 350-550°C; a transition metal alloy catalyst is obtained;
  • the carrier is at least one selected from activated carbon, azacarbon, alumina, titania, silica, molecular sieve ZMS-5, and rare earth oxide.
  • the rare earth oxide is selected from at least one of CeO 2 and ZrO 2 .
  • the mass of the transition metal compound is 5% to 30% of the carrier; the transition metal compound is at least one selected from the group consisting of iron salts, cobalt salts, copper salts, and nickel salts; anion selected from Cl -, NO 3 - at least one of -, SO 4 2- or C 2 H 3 O 2.
  • the solvent is water.
  • the volume ratio of the inert gas and hydrogen is 93-97: 3-7.
  • the inertness is argon or nitrogen, preferably argon.
  • the firing time is 1 to 5 hours.
  • the transition metal alloy catalyst composite is prepared by the method described in any one of the above.
  • a method for synergistically catalyzing and degrading glyphosate wastewater by low-temperature plasma The above-mentioned transition metal alloy catalyst composite is mixed with glyphosate wastewater, and then subjected to plasma treatment for degradation reaction.
  • the dosage ratio of the transition metal alloy catalyst to glyphosate wastewater is 50-1000 mg: 17-100 mL.
  • the degradation reaction time is 10 minutes to 200 minutes
  • the discharge temperature of the plasma is 20 to 80° C.
  • the plasma discharge power density is 1 to 500 W/cm 3 .
  • the glyphosate wastewater is the waste liquid generated in the glyphosate production workshop, and is referred to as the mother liquid; or it is the hardly degradable brine obtained after the mother liquid undergoes wet catalytic oxidation.
  • the specific operation of the wet catalytic oxidation is to mix the mother liquor with the catalyst, and react at 150 to 260°C and 2 to 8 MPa for 2 to 6 hours.
  • the liquid obtained after the reaction is brine.
  • the catalyst includes the transition metal alloy catalyst composite described above.
  • the TOC value of the mother liquor is 10000-10200 ppm
  • the COD is 59000-61000 ppm
  • the total phosphorus content is 24000-26000 ppm
  • the total nitrogen content is 4500-5500 ppm
  • the NaCl content is 14-19%.
  • the brine NaCl content is 3-8%.
  • the present invention aims at the characteristics of glyphosate wastewater, through the design of the catalyst components, and forms a good synergy with the plasma, to achieve efficient degradation of glyphosate wastewater at normal temperature and pressure, the method of the present invention is novel and unique , Simple and efficient, breaking through the limitation that the existing technology can not degrade glyphosate wastewater, in the treatment of glyphosate wastewater, the treatment process is simple, the time required is short, the efficiency is high, and it has excellent application prospects.
  • the catalyst used in the present invention is easy to prepare and has a low price, does not cause a large economic burden on industrial processing of a large number of organic pollutants, and combined with plasma has a better degradation effect on glyphosate wastewater.
  • the present invention solves the tedious steps of the glyphosate wastewater degradation method in the prior art and requires a large number of chemical reagents, the reaction conditions also require high temperature, high pressure, etc., and proposes a method for the degradation of glyphosate wastewater by low-temperature plasma cooperative catalyst, Greatly improve the removal efficiency of glyphosate wastewater, and has the advantages of continuous, convenient and fast.
  • the reagent raw materials used in the following examples are raw reagent raw materials that are commercially available or commercially available.
  • equipment used in the following embodiments is equipment conventionally used in the art.
  • the glyphosate wastewater selected in the embodiments of the present invention is the mother liquor generated in the glyphosate production workshop and the hardly degradable brine obtained after wet catalytic oxidation.
  • the organic impurities in the mother liquor mainly include glyphosate, diglyphosate, phosphite, phosphate, glycine, methanol, formaldehyde, etc.
  • the main components are glyphosate, glycine, phosphate, etc.; the brine is mainly difficult Degraded phosphorus-containing organic compounds (the composition of the mother liquor produced in the glyphosate production workshop is complex, and it is difficult to detect the specific content of glyphosate, diglyphosate and other components at this stage of the analysis method). After a total organic carbon (TOC) test, the TOC value of the mother liquor was found to be 10063 ppm.
  • the main pollutant composition data of the glyphosate mother liquor are: Chemical Oxygen Demand (COD) is 60,000 ppm, total phosphorus content is 25000 ppm, total nitrogen content is 5000 ppm, and NaCl content is 16%.
  • the brine selected in the embodiments of the present invention is a hard-to-degrade brine obtained after wet catalytic oxidation of the mother liquor.
  • the specific operation of the wet catalytic oxidation is to mix the mother liquor with a catalyst (such as the catalyst described in the following example) at 150- The reaction is carried out at 260°C and 2-8 MPa oxygen for 2 to 6 hours.
  • the liquid obtained after the reaction is brine.
  • the brine is mainly refractory phosphorus-containing organic substances (such as glyphosate, bisphosphonate, and phosphite, etc.), the pH value is about 7, the TOC value is about 200 ppm, the COD is about 1200 ppm, and the total phosphorus content It is 500 ppm, the total nitrogen content is 85 ppm, and the NaCl content is 6%.
  • the brine was added to a catalyst (such as the catalyst described in the following examples) to continue to react at 260°C and 8 MPa of oxygen for 2 hours. The TOC value was still 198 ppm, and the organic phosphorus was not substantially degraded.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-SiO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 96 ppm, the organic phosphorus degradation rate after treatment was 52%, and the COD removal rate reached 24%. The total phosphorus removal rate was 48%, and the total nitrogen removal rate was 53%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-P25 catalyst was weighed to degrade 20 mL of brine, the TOC value was 112 ppm, the organic phosphorus degradation rate after treatment was 44%, and the COD removal rate reached 18%. The phosphorus removal rate was 41%, and the total nitrogen removal rate was 43%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 110 ppm, the degradation rate of organic phosphorus after treatment was 45%, and the COD removal rate reached 19%. The total phosphorus removal rate was 42%, and the total nitrogen removal rate was 43%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-Al 2 O 3 catalyst was weighed to degrade 20 mL of brine, the TOC value was 107 ppm, the organic phosphorus degradation rate after treatment was 47%, and the COD removal rate reached 20 %, the total phosphorus removal rate is 44%, and the total nitrogen removal rate is 48%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-ZMS-5 catalyst was weighed to degrade 20 mL of brine, the TOC value was 100 ppm, the organic phosphorus degradation rate after treatment was 50%, and the COD removal rate reached 22% The total phosphorus removal rate is 48%, and the total nitrogen removal rate is 54%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed to degrade 20 mL of brine, the TOC value was 35 ppm, the organic phosphorus degradation rate after treatment was 83%, and the COD removal rate reached 58%. The phosphorus removal rate is 80%, and the total nitrogen removal rate is 85%.
  • Example 7 Referring to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed, and 20 mL of brine was subjected to a degradation reaction for 10 min, the TOC value was 45 ppm, and the degradation rate of the organic phosphorus after the treatment was 78 %, COD removal rate reached 44%, total phosphorus removal rate was 75%, and total nitrogen removal rate was 80%.
  • Example 7 Referring to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5g of the above FeCu-AC catalyst was weighed to degrade 20mL brine for 50min, the TOC value was 20ppm, and the degradation rate of the organic phosphorus after treatment was 94%. The COD removal rate reached 72%, the total phosphorus removal rate was 92%, and the total nitrogen removal rate was 95%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-NC catalyst was weighed to degrade 20 mL of brine, the TOC value was 68 ppm, the organic phosphorus degradation rate after treatment was 76%, and the COD removal rate reached 30%. The phosphorus removal rate was 63%, and the total nitrogen removal rate was 65%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above Fe-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 124 ppm, the degradation rate of organic phosphorus after the treatment was 38%, and the COD removal rate reached 15%. The total phosphorus removal rate was 35% and the total nitrogen removal rate was 40%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above Cu-CeO 2 catalyst was weighed to degrade 20 mL of brine, with a TOC value of 143 ppm, an organic phosphorus degradation rate of 28% after treatment, and a COD removal rate of 15%. The total phosphorus removal rate was 25%, and the total nitrogen removal rate was 30%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above Co-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 116 ppm, the degradation rate of organic phosphorus after the treatment was 42%, and the COD removal rate reached 18%. The total phosphorus removal rate was 40%, and the total nitrogen removal rate was 43%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above Ni-CeO2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 142 ppm, the degradation rate of organic phosphorus after the treatment was 28%, and the COD removal rate reached 15%. The phosphorus removal rate was 27%, and the total nitrogen removal rate was 32%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCo-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 116 ppm, the degradation rate of organic phosphorus after the treatment was 42%, and the COD removal rate reached 34%. The total phosphorus removal rate was 40%, and the total nitrogen removal rate was 45%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-CeO2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 35 ppm, the organic phosphorus degradation rate after the treatment was 88%, and the COD removal rate reached 55%. The phosphorus removal rate was 84%, and the total nitrogen removal rate was 86%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 44 ppm, the organic phosphorus degradation rate after treatment was 78%, and the COD removal rate reached 36%. The total phosphorus removal rate was 75%, and the total nitrogen removal rate was 80%.
  • Example 1 Referring to the plasma treatment method of Example 1, 0.1 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 30 ppm, the organic phosphorus degradation rate after treatment was 85%, and the COD removal rate reached 40%. The total phosphorus removal rate was 82%, and the total nitrogen removal rate was 82%.
  • Example 21 Referring to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 0.4 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of the mother liquor for 80 min, the TOC value was 1800 ppm, and the degradation rate of the organic phosphorus after the treatment was 82% The COD removal rate reached 31%, the total phosphorus removal rate was 73%, and the total nitrogen removal rate was 77%.
  • Example 7 Referring to the plasma treatment method of Example 7, without adding any catalyst, 15 mL of brine was degraded for 20 minutes, and the TOC value was 197 ppm. After the treatment, there were no obvious signs of removal of organic phosphorus, COD, total phosphorus, and total nitrogen.
  • Example 7 According to the plasma treatment method of Example 7, without adding any catalyst, 15 mL of brine was degraded for 30 minutes, and the TOC value was 193 ppm. After treatment, there was no obvious sign of removal of organic phosphorus, COD, total phosphorus, and total nitrogen.
  • the degradation of 20 mL of the mother liquor was 30 minutes, the TOC value was 12042 ppm, and the plasma alone had no degradation effect on the mother liquor for 30 minutes.
  • Comparative Examples 1-4 From the above Comparative Examples 1-4, it can be seen that the plasma alone has little degradation effect on the high salinity, refractory glyphosate wastewater, and with the synergy of the catalyst, the glyphosate wastewater of unknown composition in just 30 minutes Under the effect of, TOC can be reduced by more than 80%.
  • Comparative Examples 5-6 show that without plasma treatment, only with catalyst treatment, at normal temperature and pressure, even if the catalyst acts on brine or mother liquor for 120 minutes, the organic phosphorus is basically not degraded. From Comparative Examples 1-6, it can be shown that the action of the plasma or catalyst alone and the liquid to be treated cannot degrade the organic phosphorus wastewater.
  • the wet catalytic oxidation method alone has no way to further degrade the phosphorus-containing organic compounds in brine.
  • the plasma and the catalyst in the embodiments of the present invention have a synergistic effect in the treatment of glyphosate wastewater, and without high temperature and high pressure, it can produce a good degradation effect on glyphosate wastewater and efficiently remove TOC , Organic phosphorus, COD, total phosphorus, total nitrogen and other polluting components.
  • the present invention discloses a method for degrading glyphosate wastewater by a low-temperature plasma co-catalyst, which is a non-noble metal alloy catalyst mixed with wastewater to be treated, and then placed under a plasma discharge channel, which is generated by plasma High-energy electrons fully ionize organic molecules, water molecules, oxygen molecules, etc., thereby stimulating higher-energy active particles, synergizing with the catalyst, and efficiently degrading high-salinity refractory glyphosate wastewater.
  • the invention aims at the characteristics of glyphosate wastewater, through the design of the catalyst components, and forms a good synergy with the plasma, to achieve efficient degradation of glyphosate wastewater at normal temperature and pressure, the method of the invention is novel, unique and simple High efficiency, breaking through the limitation that the existing technology cannot degrade glyphosate wastewater, the treatment process of glyphosate wastewater is simple, the time required is short, the efficiency is high, and it has excellent application prospects.
  • the catalyst used in the present invention is easy to prepare itself, has a low price, does not cause a large economic burden on industrial processing of a large amount of organic pollutants, and combined with plasma has a better degradation effect on glyphosate wastewater.
  • the invention solves the problems of the glyphosate wastewater degradation method in the prior art which is cumbersome and requires a large amount of chemical reagents, and the reaction conditions also require high temperature and high pressure.
  • the low-temperature plasma synergistic catalyst method for degrading glyphosate wastewater is greatly improved. It improves the removal efficiency of glyphosate wastewater, and has the advantages of being continuous, convenient and fast.
  • the method of the invention can produce continuous and uniform filament streamer discharge under the condition of lower power, avoid direct contact between the electrode and waste water, prevent the electrode from being corroded by high salinity waste water, and prolong the service life of the electrode.
  • the present invention uses inexpensive and easily available transition metals and carriers as catalysts, which greatly improves the plasma processing efficiency, reduces power consumption costs, and reduces wastewater treatment costs.

Abstract

A method for degrading glyphosate wastewater by synergy of low-temperature plasma and a catalyst. A transition metal alloy catalyst is mixed with wastewater to be treated, and then the mixture is placed in a plasma discharge channel; by means of synergy of high-energy electrons generated by plasma and the catalyst, glyphosate wastewater having high salinity and difficult to degrade is efficiently degraded. The technical deficiencies in the prior art such as complicated steps of a glyphosate wastewater degradation method, the need of a large number of chemical reagents, and requirements for high temperature and high pressure in the reaction conditions can be solved.

Description

一种低温等离子体协同催化降解草甘膦废水的方法Low-temperature plasma cooperative catalytic degradation method for glyphosate wastewater 技术领域Technical field
本发明涉及污水处理领域，更具体地，涉及一种低温等离子体协同催化降解草甘膦废水的方法。The invention relates to the field of sewage treatment, and more particularly, to a method for synergistically catalyzing and degrading glyphosate wastewater by low-temperature plasma.
背景技术Background technique
草甘膦是一种低毒、高效、广谱的灭生性除草剂，近年来增长迅速，现已成为全球产量和用量最大的农药品种。其母液废水具有排放量大、毒性大、含盐量高，难降解化合物含量高、治理难度大等特点。母液中的有机杂质主要包括草甘膦、双甘膦、亚磷酸盐、磷酸盐、甘氨酸、甲醇、甲醛等多种成分，其主要成分是草甘膦、甘氨酸、磷酸盐等。Glyphosate is a low-toxicity, high-efficiency, and broad-spectrum biocidal herbicide. It has grown rapidly in recent years and has become the world's largest pesticide product in terms of production and usage. The mother liquor wastewater has the characteristics of large discharge, high toxicity, high salt content, high content of refractory compounds, and difficulty in treatment. The organic impurities in the mother liquor mainly include glyphosate, diglyphosate, phosphite, phosphate, glycine, methanol, formaldehyde and other components, and the main components are glyphosate, glycine, phosphate and so on.
目前，处理草甘膦废水主要采用吸附法、湿式催化氧化法、氯氧化法，上述方法均取得了良好效果，但是步骤繁琐，且需要大量化学试剂，反应条件也需要高温、高压，这对设备的要求较高，在工业应用方面存在有一定地限制。At present, the treatment of glyphosate wastewater mainly adopts the adsorption method, wet catalytic oxidation method, and chlorine oxidation method. The above methods have achieved good results, but the steps are cumbersome, require a large number of chemical reagents, and the reaction conditions also require high temperature and high pressure. The requirements are higher, and there are certain restrictions in industrial applications.
低温等离子体技术是一种新型高效的环保技术通常应用于废气的处理，较少的用于废水处理。现有的低温等离子体技术用于废水处理的方法中，也不能解决对草甘膦废水的降解。Low-temperature plasma technology is a new and highly efficient environmental protection technology that is commonly used in the treatment of exhaust gas and less used in wastewater treatment. The existing low-temperature plasma technology is used in wastewater treatment methods, and it cannot solve the degradation of glyphosate wastewater.
发明内容Summary of the invention
本发明的目的在于针对现有技术存在步骤繁琐，且需要大量化学试剂，反应条件需要高温、高压等不足，提供一种低温等离子体协同催化降解草甘膦废水的方法。The purpose of the present invention is to provide a method for synergistically catalyzing the degradation of glyphosate wastewater with low-temperature plasma in response to the existing procedures which are cumbersome, require a large amount of chemical reagents, and require high temperature and high pressure.
本发明所采取的技术方案是：The technical solution adopted by the present invention is:
一种过渡金属合金催化剂复合体的制备方法，包括以下步骤：A method for preparing a transition metal alloy catalyst composite includes the following steps:
将过渡金属盐与载体在溶剂中混合，干燥后于惰性气体和氢气的混合气体中在350～550℃条件下焙烧混合物；得过渡金属合金催化剂；The transition metal salt and the carrier are mixed in a solvent, and after drying, the mixture is calcined in a mixed gas of inert gas and hydrogen at 350-550°C; a transition metal alloy catalyst is obtained;
所述载体选自活性炭、氮杂碳、氧化铝、二氧化钛、二氧化硅、分子筛ZMS-5、稀土氧化物中的至少一种。The carrier is at least one selected from activated carbon, azacarbon, alumina, titania, silica, molecular sieve ZMS-5, and rare earth oxide.
优选的，所述稀土氧化物选自CeO 2、ZrO 2中的至少一种。 Preferably, the rare earth oxide is selected from at least one of CeO 2 and ZrO 2 .
优选的，所述过渡金属化合物的质量为载体的5％～30％；所述过渡金属化合物选自铁盐、钴盐、铜盐、镍盐中的至少一种；所述过渡金属化合物中的阴离子选自Cl -、NO 3-、SO 4 2-或C 2H 3O 2 -中的至少一种。 Preferably, the mass of the transition metal compound is 5% to 30% of the carrier; the transition metal compound is at least one selected from the group consisting of iron salts, cobalt salts, copper salts, and nickel salts; anion selected from Cl -, NO 3 - at least one of -, SO 4 2- or C 2 H 3 O 2.
优选的，所述溶剂为水。Preferably, the solvent is water.
优选的，所述惰性气体和氢气的体积比为93～97：3～7。Preferably, the volume ratio of the inert gas and hydrogen is 93-97: 3-7.
优选的，所述惰性为氩气或氮气，优选为氩气。Preferably, the inertness is argon or nitrogen, preferably argon.
优选的，所述焙烧时间为1～5h。Preferably, the firing time is 1 to 5 hours.
上述任一项所述方法制备得到过渡金属合金催化剂复合体。The transition metal alloy catalyst composite is prepared by the method described in any one of the above.
一种低温等离子体协同催化降解草甘膦废水的方法，将上述所述的过渡金属合金催化剂复合体与草甘膦废水混合，再经等离子体处理进行降解反应。A method for synergistically catalyzing and degrading glyphosate wastewater by low-temperature plasma. The above-mentioned transition metal alloy catalyst composite is mixed with glyphosate wastewater, and then subjected to plasma treatment for degradation reaction.
优选的，所述过渡金属合金催化剂与草甘膦废水的用量比为50～1000mg：17～100mL。Preferably, the dosage ratio of the transition metal alloy catalyst to glyphosate wastewater is 50-1000 mg: 17-100 mL.
优选的，所述降解反应时间为10min～200min，所述等离子体的放电温度为20～80℃；等离子体放电功率密度为1～500W/cm 3。 Preferably, the degradation reaction time is 10 minutes to 200 minutes, the discharge temperature of the plasma is 20 to 80° C.; and the plasma discharge power density is 1 to 500 W/cm 3 .
优选的，所述草甘膦废水为草甘膦生产车间产生的废液，记为母液；或者为母液经过湿式催化氧化之后得到的难以降解的卤水。Preferably, the glyphosate wastewater is the waste liquid generated in the glyphosate production workshop, and is referred to as the mother liquid; or it is the hardly degradable brine obtained after the mother liquid undergoes wet catalytic oxidation.
优选的，所述湿式催化氧化的具体操作为将母液与催化剂混合，在150～260℃、2～8MPa条件下反应2～6h，反应之后得到的液体即为卤水。Preferably, the specific operation of the wet catalytic oxidation is to mix the mother liquor with the catalyst, and react at 150 to 260°C and 2 to 8 MPa for 2 to 6 hours. The liquid obtained after the reaction is brine.
优选的，所述催化剂包括上述所述的过渡金属合金催化剂复合体。Preferably, the catalyst includes the transition metal alloy catalyst composite described above.
优选的，所述母液TOC值为10000～10200ppm，COD为59000～61000ppm，总磷含量为24000～26000ppm，总氮含量为4500～5500ppm，NaCl含量为14～19％。Preferably, the TOC value of the mother liquor is 10000-10200 ppm, the COD is 59000-61000 ppm, the total phosphorus content is 24000-26000 ppm, the total nitrogen content is 4500-5500 ppm, and the NaCl content is 14-19%.
优选的，所述卤水NaCl含量为3～8％。Preferably, the brine NaCl content is 3-8%.
本发明的有益效果是：The beneficial effects of the invention are:
1.本发明针对草甘膦废水的特性，通过对催化剂组分的设计，与等离子体之间形成良好的协同作用，实现草甘膦废水在常温常压下进行高效降解，本发明方法新颖独特，简单高效，突破现有技术无法降解草甘膦废水的限制，在处理草甘膦废水方面处理工艺简单、所需时间短、效率高，具有极好的应用前景。1. The present invention aims at the characteristics of glyphosate wastewater, through the design of the catalyst components, and forms a good synergy with the plasma, to achieve efficient degradation of glyphosate wastewater at normal temperature and pressure, the method of the present invention is novel and unique , Simple and efficient, breaking through the limitation that the existing technology can not degrade glyphosate wastewater, in the treatment of glyphosate wastewater, the treatment process is simple, the time required is short, the efficiency is high, and it has excellent application prospects.
2.本发明采用的催化剂本身容易制备，价格低廉，不会给工业处理大量有机污染物造成较大的经济负担，而且结合等离子体对草甘膦废水有较好的降解效果。2. The catalyst used in the present invention is easy to prepare and has a low price, does not cause a large economic burden on industrial processing of a large number of organic pollutants, and combined with plasma has a better degradation effect on glyphosate wastewater.
3.本发明解决了现有技术中草甘膦废水降解方法步骤繁琐且需要大量化学试剂，反应条件也需要高温、高压等不足，提出一种低温等离子体协同催化剂降解草甘膦废水的方法，大大提高了草甘膦废水的去除效率，且具有持续、方便、快速等优点。3. The present invention solves the tedious steps of the glyphosate wastewater degradation method in the prior art and requires a large number of chemical reagents, the reaction conditions also require high temperature, high pressure, etc., and proposes a method for the degradation of glyphosate wastewater by low-temperature plasma cooperative catalyst, Greatly improve the removal efficiency of glyphosate wastewater, and has the advantages of continuous, convenient and fast.
具体实施方式detailed description
下面结合具体实施例进一步说明本发明应用。下述实施例仅用于示例性说明，不能理解为对本发明的限制。除非特别说明，下述实施例中使用的试剂原料为常规市购或商业途径获得的生试剂原料。除非特别说明，下述实施例中使用的设备为本领域常规使用的设备。The application of the present invention will be further described below in conjunction with specific embodiments. The following embodiments are for illustrative purposes only, and cannot be construed as limiting the present invention. Unless otherwise specified, the reagent raw materials used in the following examples are raw reagent raw materials that are commercially available or commercially available. Unless otherwise specified, the equipment used in the following embodiments is equipment conventionally used in the art.
本发明实施例选用的草甘膦废水为草甘膦生产车间产生的母液和经过湿式催化氧化之后得到的难以降解的卤水。母液中的有机杂质主要包括草甘膦、双甘膦、亚磷酸盐、磷酸盐、甘氨酸、甲醇、甲醛等多种成分，其主要成分是草甘膦、甘氨酸、磷酸盐等；卤水中主要为难降解的含磷有机物(草甘膦生产车间产生的母液成分复杂，现阶段分析方法难以检测草甘膦、双甘膦等成分的具体含量)。经过总有机碳(Total Organism Carbon，TOC)测试，发现母液的TOC值为10063ppm。草甘膦母液主要污染物成分数据为：化学需氧量(Chemical Oxygen Demand，COD)为60000ppm，总磷含量为25000ppm，总氮含量为5000ppm，NaCl含量为16％。The glyphosate wastewater selected in the embodiments of the present invention is the mother liquor generated in the glyphosate production workshop and the hardly degradable brine obtained after wet catalytic oxidation. The organic impurities in the mother liquor mainly include glyphosate, diglyphosate, phosphite, phosphate, glycine, methanol, formaldehyde, etc. The main components are glyphosate, glycine, phosphate, etc.; the brine is mainly difficult Degraded phosphorus-containing organic compounds (the composition of the mother liquor produced in the glyphosate production workshop is complex, and it is difficult to detect the specific content of glyphosate, diglyphosate and other components at this stage of the analysis method). After a total organic carbon (TOC) test, the TOC value of the mother liquor was found to be 10063 ppm. The main pollutant composition data of the glyphosate mother liquor are: Chemical Oxygen Demand (COD) is 60,000 ppm, total phosphorus content is 25000 ppm, total nitrogen content is 5000 ppm, and NaCl content is 16%.
本发明实施例选用的卤水为母液经过湿式催化氧化之后得到的难以降解的卤水，所述湿式催化氧化的具体操作为将母液与催化剂(如以下实施例中所述的催化剂)混合，在150-260℃、2-8MPa氧气条件下反应2～6h，反应之后得到的液体即为卤水。本发明实施例卤 水中主要为难降解的含磷有机物(如草甘膦、双甘膦以及亚磷酸盐等)，pH值为约为7，TOC值约为200ppm，COD约为1200ppm，总磷含量为500ppm，总氮含量为85ppm，NaCl含量为6％。将该卤水加入催化剂(如以下实施例中所述的催化剂)继续在260℃、8MPa氧气条件下反应2h，TOC值仍为198ppm，有机磷基本上没有降解。说明既使进一步提高反应温度和压强，延长反应时间，单独使用湿式催化氧化法没有办法使卤水中的含磷有机物进一步降解，使其达到可排放的标准，而且这种高温高压长时间的外得方式对设备的腐蚀性大，反应条件严苛。所以需要另一种方法对卤水做进一步处理，使卤水中难降解含磷有机物达到可排放的标准。The brine selected in the embodiments of the present invention is a hard-to-degrade brine obtained after wet catalytic oxidation of the mother liquor. The specific operation of the wet catalytic oxidation is to mix the mother liquor with a catalyst (such as the catalyst described in the following example) at 150- The reaction is carried out at 260°C and 2-8 MPa oxygen for 2 to 6 hours. The liquid obtained after the reaction is brine. In the embodiment of the present invention, the brine is mainly refractory phosphorus-containing organic substances (such as glyphosate, bisphosphonate, and phosphite, etc.), the pH value is about 7, the TOC value is about 200 ppm, the COD is about 1200 ppm, and the total phosphorus content It is 500 ppm, the total nitrogen content is 85 ppm, and the NaCl content is 6%. The brine was added to a catalyst (such as the catalyst described in the following examples) to continue to react at 260°C and 8 MPa of oxygen for 2 hours. The TOC value was still 198 ppm, and the organic phosphorus was not substantially degraded. It shows that even if the reaction temperature and pressure are further increased and the reaction time is extended, there is no way to use the wet catalytic oxidation method alone to further degrade the phosphorus-containing organic compounds in the brine, so that it can reach the discharge standard. The method is highly corrosive to the equipment and the reaction conditions are severe. Therefore, another method is needed for further treatment of the brine, so that the refractory phosphorus-containing organic matter in the brine can reach the dischargeable standard.
实施例1Example 1
将1.0g ZrO 2、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-ZrO 2。 Dissolve 1.0g ZrO 2 , 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry it and put it in a vacuum tube furnace with 95% inert gas (Ar) protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-ZrO 2 .
称取0.5g上述FeCu-ZrO 2催化剂，20mL卤水充分混合均匀之后置于反应器中，打开等离子体开关，调节放电电压和电流，待放电稳定，产生均匀的紫色丝状流光，持续放电进行降解反应20min，等离子体的放电温度为20-80℃；等离子体放电功率密度为1-500W/cm 3；收集处理过的废水，稀释之后用岛津(SHIMADZU)总有机碳分析仪测定TOC，值为105ppm，处理后有机磷降解率为78％，COD的去除率达到20％，总磷去除率为45％，总氮去除率为50％。 Weigh 0.5g of the above FeCu-ZrO 2 catalyst, 20mL of brine was mixed thoroughly and placed in the reactor, turn on the plasma switch, adjust the discharge voltage and current, wait for the discharge to stabilize, produce a uniform purple filament streamer, continue to discharge for degradation After 20 minutes of reaction, the discharge temperature of the plasma is 20-80℃; the plasma discharge power density is 1-500W/cm 3 ; the treated wastewater is collected, and after dilution, the TOC is measured by Shimadzu (SHIMADZU) total organic carbon analyzer. It is 105ppm, the degradation rate of organic phosphorus after treatment is 78%, the removal rate of COD reaches 20%, the removal rate of total phosphorus is 45%, and the removal rate of total nitrogen is 50%.
实施例2Example 2
将0.5g SiO 2、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-SiO 2。 Dissolve 0.5g SiO 2 , 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and put in a vacuum tube furnace to pass 95% inert gas (Ar) protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-SiO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-SiO 2催化剂，对20mL卤水进行降解，TOC值为96ppm，处理后有机磷降解率为52％，COD的去除率达到24％，总磷去除率为48％，总氮去除率为53％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-SiO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 96 ppm, the organic phosphorus degradation rate after treatment was 52%, and the COD removal rate reached 24%. The total phosphorus removal rate was 48%, and the total nitrogen removal rate was 53%.
实施例3Example 3
将1.0g TiO2(P25)、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-P25。 Dissolve 1.0g TiO2 (P25), 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) Protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-P25.
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-P25催化剂，对20mL卤水进行降解，TOC值为112ppm，处理后有机磷降解率为44％，COD的去除率达到18％，总磷去除率为41％，总氮去除率为43％。Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-P25 catalyst was weighed to degrade 20 mL of brine, the TOC value was 112 ppm, the organic phosphorus degradation rate after treatment was 44%, and the COD removal rate reached 18%. The phosphorus removal rate was 41%, and the total nitrogen removal rate was 43%.
实施例4Example 4
将1.0g CeO2、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-CeO 2。 Dissolve 1.0g CeO2, 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5 % Hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-CeO 2催化剂，对20mL卤水 进行降解，TOC值为110ppm，处理后有机磷降解率为45％，COD的去除率达到19％，总磷去除率为42％，总氮去除率为43％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 110 ppm, the degradation rate of organic phosphorus after treatment was 45%, and the COD removal rate reached 19%. The total phosphorus removal rate was 42%, and the total nitrogen removal rate was 43%.
实施例5Example 5
将1.0g Al2O3、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-CeO 2。 Dissolve 1.0g Al2O3, 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5 % Hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-Al 2O 3催化剂，对20mL卤水进行降解，TOC值为107ppm，处理后有机磷降解率为47％，COD的去除率达到20％，总磷去除率为44％，总氮去除率为48％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-Al 2 O 3 catalyst was weighed to degrade 20 mL of brine, the TOC value was 107 ppm, the organic phosphorus degradation rate after treatment was 47%, and the COD removal rate reached 20 %, the total phosphorus removal rate is 44%, and the total nitrogen removal rate is 48%.
实施例6Example 6
将1.5g ZMS-5、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-ZMS-5。 Dissolve 1.5g ZMS-5, 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection , 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-ZMS-5.
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-ZMS-5催化剂，对20mL卤水进行降解，TOC值为100ppm，处理后有机磷降解率为50％，COD的去除率达到22％，总磷去除率为48％，总氮去除率为54％。Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-ZMS-5 catalyst was weighed to degrade 20 mL of brine, the TOC value was 100 ppm, the organic phosphorus degradation rate after treatment was 50%, and the COD removal rate reached 22% The total phosphorus removal rate is 48%, and the total nitrogen removal rate is 54%.
实施例7Example 7
将0.5g AC(活性炭)、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-AC。 Dissolve 0.5g AC (activated carbon), 1.21g FeCl 3 6H 2 O, 1.34g CuCl 2 in 10mL of water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) Protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-AC.
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水进行降解，TOC值为35ppm，处理后有机磷降解率为83％，COD的去除率达到58％，总磷去除率为80％，总氮去除率为85％。Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed to degrade 20 mL of brine, the TOC value was 35 ppm, the organic phosphorus degradation rate after treatment was 83%, and the COD removal rate reached 58%. The phosphorus removal rate is 80%, and the total nitrogen removal rate is 85%.
实施例8Example 8
参照实施例7的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水进行降解反应10min，TOC值为45ppm，处理后有机磷降解率为78％，COD的去除率达到44％，总磷去除率为75％，总氮去除率为80％。Referring to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed, and 20 mL of brine was subjected to a degradation reaction for 10 min, the TOC value was 45 ppm, and the degradation rate of the organic phosphorus after the treatment was 78 %, COD removal rate reached 44%, total phosphorus removal rate was 75%, and total nitrogen removal rate was 80%.
实施例9Example 9
参照实施例7的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水降解20min，TOC值为37ppm，处理后有机磷降解率为82％，COD的去除率达到56％，总磷去除率为80％，总氮去除率为83％。With reference to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed, and 20 mL of brine was degraded for 20 min, the TOC value was 37 ppm, and the degradation rate of organic phosphorus after the treatment was 82%. The COD removal rate reached 56%, the total phosphorus removal rate was 80%, and the total nitrogen removal rate was 83%.
实施例10Example 10
参照实施例7的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水降解30min，TOC值为31ppm，处理后有机磷降解率为87％，COD的去除率达到63％，总磷去除率为86％，总氮去除率为89％。With reference to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed to degrade 20 mL of brine for 30 min, the TOC value was 31 ppm, and the degradation rate of organic phosphorus after treatment was 87%. The COD removal rate reached 63%, the total phosphorus removal rate was 86%, and the total nitrogen removal rate was 89%.
实施例11Example 11
参照实施例7的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水降解40min，TOC值为24ppm，处理后有机磷降解率为91％，COD的去除率达到69％，总磷去除率为89％，总氮去除率为94％。With reference to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5 g of the above FeCu-AC catalyst was weighed to degrade 20 mL of brine for 40 min, the TOC value was 24 ppm, and the degradation rate of the organic phosphorus after treatment was 91%. The COD removal rate reached 69%, the total phosphorus removal rate was 89%, and the total nitrogen removal rate was 94%.
实施例12Example 12
参照实施例7的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.5g上述FeCu-AC催化剂，对20mL卤水降解50min，TOC值为20ppm，处理后有机磷降解率为94％，COD的去除率达到72％，总磷去除率为92％，总氮去除率为95％。Referring to the preparation method of the alloy catalyst of Example 7 and the plasma treatment method of Example 1, 0.5g of the above FeCu-AC catalyst was weighed to degrade 20mL brine for 50min, the TOC value was 20ppm, and the degradation rate of the organic phosphorus after treatment was 94%. The COD removal rate reached 72%, the total phosphorus removal rate was 92%, and the total nitrogen removal rate was 95%.
实施例13Example 13
将0.5g氮杂碳(NC)、1.21g FeCl 3 6H 2O、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-NC。 Dissolve 0.5g of aza carbon (NC), 1.21g of FeCl 3 6H 2 O, 1.34g of CuCl 2 in 10mL of water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas ( Ar) protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-NC.
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-NC催化剂，对20mL卤水进行降解，TOC值为68ppm，处理后有机磷降解率为76％，COD的去除率达到30％，总磷去除率为63％，总氮去除率为65％。Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-NC catalyst was weighed to degrade 20 mL of brine, the TOC value was 68 ppm, the organic phosphorus degradation rate after treatment was 76%, and the COD removal rate reached 30%. The phosphorus removal rate was 63%, and the total nitrogen removal rate was 65%.
实施例14Example 14
将1.0g CeO 2、1.21g FeCl 3 6H 2O，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为Fe-CeO2。 Dissolve 1.0g CeO 2 and 1.21g FeCl 3 6H 2 O in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5% hydrogen reduction Metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named Fe-CeO2.
参照实施例1的等离子体处理方式，称取0.5g上述Fe-CeO 2催化剂，对20mL卤水进行降解，TOC值为124ppm，处理后有机磷降解率为38％，COD的去除率达到15％，总磷去除率为35％，总氮去除率为40％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above Fe-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 124 ppm, the degradation rate of organic phosphorus after the treatment was 38%, and the COD removal rate reached 15%. The total phosphorus removal rate was 35% and the total nitrogen removal rate was 40%.
实施例15Example 15
将2.0g CeO 2、1.34g CuCl 2，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为Cu-CeO 2。 Dissolve 2.0g CeO 2 and 1.34g CuCl 2 in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5% hydrogen to reduce the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named Cu-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述Cu-CeO 2催化剂，对20mL卤水进行降解，TOC值为143ppm，处理后有机磷降解率为28％，COD的去除率达到15％，总磷去除率为25％，总氮去除率为30％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above Cu-CeO 2 catalyst was weighed to degrade 20 mL of brine, with a TOC value of 143 ppm, an organic phosphorus degradation rate of 28% after treatment, and a COD removal rate of 15%. The total phosphorus removal rate was 25%, and the total nitrogen removal rate was 30%.
实施例16Example 16
将2.0g CeO 2、2.02g CoCl 2 6H 2O，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为Co-CeO 2。 Dissolve 2.0g CeO 2 and 2.02g CoCl 2 6H 2 O in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5% hydrogen reduction Metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named Co-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述Co-CeO 2催化剂，对20mL卤水进行降解，TOC值为116ppm，处理后有机磷降解率为42％，COD的去除率达到18％，总磷去除率为40％，总氮去除率为43％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above Co-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 116 ppm, the degradation rate of organic phosphorus after the treatment was 42%, and the COD removal rate reached 18%. The total phosphorus removal rate was 40%, and the total nitrogen removal rate was 43%.
实施例17Example 17
将2.0g CeO 2、2.06g NiCl 2 6H 2O，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为Ni-CeO 2。 Dissolve 2.0g CeO 2 and 2.06g NiCl 2 6H 2 O in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) protection, 5% hydrogen reduction Metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named Ni-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述Ni-CeO2催化剂，对20mL卤水进行降解，TOC值为142ppm，处理后有机磷降解率为28％，COD的去除率达到15％，总磷去除率为27％，总氮去除率为32％。Referring to the plasma treatment method of Example 1, 0.5 g of the above Ni-CeO2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 142 ppm, the degradation rate of organic phosphorus after the treatment was 28%, and the COD removal rate reached 15%. The phosphorus removal rate was 27%, and the total nitrogen removal rate was 32%.
实施例18Example 18
将2.0g CeO 2、1.81g FeCl 3 6H 2O，1.17g CuCl 2 2H 2O溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCo-CeO 2。 Dissolve 2.0g CeO 2 , 1.81g FeCl 3 6H 2 O, 1.17g CuCl 2 2H 2 O in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) Protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCo-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCo-CeO 2催化剂，对20mL卤水进行降解，TOC值为116ppm，处理后有机磷降解率为42％，COD的去除率达到34％，总磷去除率为40％，总氮去除率为45％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCo-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 116 ppm, the degradation rate of organic phosphorus after the treatment was 42%, and the COD removal rate reached 34%. The total phosphorus removal rate was 40%, and the total nitrogen removal rate was 45%.
实施例19Example 19
将2.0g CeO 2、1.21g FeCl 3 6H 2O，0.67g CuCl 2 2H 2O溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCu-CeO 2。 Dissolve 2.0g CeO 2 , 1.21g FeCl 3 6H 2 O, 0.67g CuCl 2 2H 2 O in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace with 95% inert gas (Ar) Protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCu-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCu-CeO2催化剂，对20mL卤水进行降解，TOC值为35ppm，处理后有机磷降解率为88％，COD的去除率达到55％，总磷去除率为84％，总氮去除率为86％。Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCu-CeO2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 35 ppm, the organic phosphorus degradation rate after the treatment was 88%, and the COD removal rate reached 55%. The phosphorus removal rate was 84%, and the total nitrogen removal rate was 86%.
实施例20Example 20
将2.0g CeO 2、0.61g FeCl 3 6H 2O、1.34g CuCl 2、0.64g CoCl 2 2H 2O，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCuCo-CeO 2。 Dissolve 2.0g CeO 2 , 0.61g FeCl 3 6H 2 O, 1.34g CuCl 2 , 0.64g CoCl 2 2H 2 O, dissolve in 10mL water, stir and mix evenly, immerse overnight, dry and place in a vacuum tube furnace to pass 95 % Inert gas (Ar) protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCuCo-CeO 2 .
参照实施例1的等离子体处理方式，称取0.5g上述FeCuNi-CeO 2催化剂，对20mL卤水进行降解，TOC值为44ppm，处理后有机磷降解率为78％，COD的去除率达到36％，总磷去除率为75％，总氮去除率为80％。 Referring to the plasma treatment method of Example 1, 0.5 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 44 ppm, the organic phosphorus degradation rate after treatment was 78%, and the COD removal rate reached 36%. The total phosphorus removal rate was 75%, and the total nitrogen removal rate was 80%.
实施例21Example 21
将2.0g CeO 2、0.61g FeCl 3 6H 2O、1.34g CuCl 2、1.03g NiCl 2 6H 2O，溶于10mL水中，搅拌混合均匀，浸渍过夜，干燥之后置于真空管式炉中通入95％惰性气体(Ar)保护，5％的氢气还原金属合金。3℃/min的速率升温至400℃，还原4h。冷却至室温取出样品后研磨待用，所制备的催化剂命名为FeCuCo-CeO 2。 Dissolve 2.0g CeO 2 , 0.61g FeCl 3 6H 2 O, 1.34g CuCl 2 , 1.03g NiCl 2 6H 2 O, dissolve in 10mL water, stir and mix evenly, immerse overnight, after drying, place in a vacuum tube furnace and pass 95 % Inert gas (Ar) protection, 5% hydrogen reduces the metal alloy. The temperature was raised to 400°C at a rate of 3°C/min and reduced for 4h. After cooling to room temperature, the sample was taken out and ground for use. The prepared catalyst was named FeCuCo-CeO 2 .
参照实施例1的等离子体处理方式，称取0.1g上述FeCuNi-CeO 2催化剂，对20mL卤水进行降解，TOC值为30ppm，处理后有机磷降解率为85％，COD的去除率达到40％，总磷去除率为82％，总氮去除率为82％。 Referring to the plasma treatment method of Example 1, 0.1 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of brine, the TOC value was 30 ppm, the organic phosphorus degradation rate after treatment was 85%, and the COD removal rate reached 40%. The total phosphorus removal rate was 82%, and the total nitrogen removal rate was 82%.
实施例22Example 22
参照实施例21的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.2g上述FeCuNi-CeO 2催化剂，对20mL卤水降解30min，TOC值为23ppm，处理后有机磷降解率为88％，COD的去除率达到52％，总磷去除率为85％，总氮去除率为86％。 With reference to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 0.2 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of brine for 30 min, the TOC value was 23 ppm, and the organic phosphorus degradation rate after treatment was 88% The COD removal rate reached 52%, the total phosphorus removal rate was 85%, and the total nitrogen removal rate was 86%.
实施例23Example 23
参照实施例21的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.2g上述FeCuNi-CeO 2催化剂，对20mL母液降解30min(由于母液有机磷含量非常高，在短时间内降解率有限，且由于高盐度不适合用生物的方法降解)，TOC值为5314ppm，处理后有机磷降解率为53％，COD的去除率达到10％，总磷去除率为43％，总氮去除率为45％。 With reference to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 0.2 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of the mother liquor for 30 min (due to the very high organic phosphorus content of the mother liquor, the degradation rate in a short time Limited, and due to high salinity is not suitable for biological degradation), TOC value is 5314ppm, organic phosphorus degradation rate after treatment is 53%, COD removal rate reaches 10%, total phosphorus removal rate is 43%, total nitrogen removal The rate is 45%.
实施例24Example 24
参照实施例21的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.2g上述FeCuNi-CeO 2催化剂，对20mL母液降解80min，TOC值为2300ppm，处理后有机磷降解率为77％，COD的去除率达到17％，总磷去除率为65％，总氮去除率为73％。 Referring to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 0.2 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of the mother liquor for 80 min, the TOC value was 2300 ppm, and the degradation rate of the organic phosphorus after treatment was 77% The COD removal rate reached 17%, the total phosphorus removal rate was 65%, and the total nitrogen removal rate was 73%.
实施例25Example 25
参照实施例21的合金催化剂制备方法和实施例1的等离子体处理方式，称取0.4g上述FeCuNi-CeO 2催化剂，对20mL母液降解80min，TOC值为1800ppm，处理后有机磷降解率为82％，COD的去除率达到31％，总磷去除率为73％，总氮去除率为77％。 Referring to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 0.4 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of the mother liquor for 80 min, the TOC value was 1800 ppm, and the degradation rate of the organic phosphorus after the treatment was 82% The COD removal rate reached 31%, the total phosphorus removal rate was 73%, and the total nitrogen removal rate was 77%.
实施例26Example 26
参照实施例21的合金催化剂制备方法和实施例1的等离子体处理方式，称取1.0g上述FeCuNi-CeO 2催化剂，对100mL母液降解150min，TOC值为1000ppm，处理后有机磷降解率为95％，COD的去除率达到70％，总磷去除率为90％，总氮去除率为93％。 Referring to the preparation method of the alloy catalyst of Example 21 and the plasma treatment method of Example 1, 1.0 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 100 mL of the mother liquor for 150 min, the TOC value was 1000 ppm, and the organic phosphorus degradation rate after treatment was 95% The COD removal rate reached 70%, the total phosphorus removal rate was 90%, and the total nitrogen removal rate was 93%.
对照例1Comparative Example 1
参照实施例7的等离子体处理方式，不加任何催化剂，对15mL卤水降解10min，TOC值为216ppm，等离子体单独作用10min基本上没有效果，处理后有机磷、COD、总磷、总氮均没有被明显去除的迹象。Referring to the plasma treatment method of Example 7, without adding any catalyst, the degradation of 15 mL of brine for 10 min, TOC value is 216 ppm, plasma alone for 10 min basically has no effect, after treatment, organic phosphorus, COD, total phosphorus, total nitrogen have no Signs that were clearly removed.
对照例2Comparative Example 2
参照实施例7的等离子体处理方式，不加任何催化剂，对15mL卤水降解20min，TOC值为197ppm，处理后有机磷、COD、总磷、总氮也均没有被明显去除的迹象。Referring to the plasma treatment method of Example 7, without adding any catalyst, 15 mL of brine was degraded for 20 minutes, and the TOC value was 197 ppm. After the treatment, there were no obvious signs of removal of organic phosphorus, COD, total phosphorus, and total nitrogen.
对照例3Comparative Example 3
参照实施例7的等离子体处理方式，不加任何催化剂，对15mL卤水降解30min，TOC值为193ppm，处理后有机磷、COD、总磷、总氮也均没有被明显去除的迹象。According to the plasma treatment method of Example 7, without adding any catalyst, 15 mL of brine was degraded for 30 minutes, and the TOC value was 193 ppm. After treatment, there was no obvious sign of removal of organic phosphorus, COD, total phosphorus, and total nitrogen.
对照例4Comparative Example 4
参照实施例7的等离子体处理方式，不加任何催化剂，对20mL母液降解30min，TOC值为12042ppm，等离子体单独对母液作用30min基本上没有降解效果。Referring to the plasma treatment method of Example 7, without adding any catalyst, the degradation of 20 mL of the mother liquor was 30 minutes, the TOC value was 12042 ppm, and the plasma alone had no degradation effect on the mother liquor for 30 minutes.
对照例5Comparative Example 5
参照实施例7的合金催化剂制备方法，不使用等离子体处理，称取0.2g上述FeCuNi-CeO 2催化剂，对20mL卤水降解120min，TOC值为198ppm，有机磷基本上没有降解。 Referring to the preparation method of the alloy catalyst of Example 7, without using plasma treatment, 0.2 g of the above FeCuNi-CeO 2 catalyst was weighed, and the 20 mL brine was degraded for 120 min, the TOC value was 198 ppm, and the organic phosphorus was not substantially degraded.
对照例6Comparative Example 6
参照实施例7的合金催化剂制备方法，不使用等离子体处理，称取0.2g上述 FeCuNi-CeO 2催化剂，对20mL母液降解120min，TOC值为11000ppm，有机磷基本上没有降解。 Referring to the preparation method of the alloy catalyst of Example 7, without plasma treatment, 0.2 g of the above FeCuNi-CeO 2 catalyst was weighed to degrade 20 mL of the mother liquor for 120 min, the TOC value was 11,000 ppm, and the organic phosphorus was not substantially degraded.
由上述实施例24-26可知，延长等离子体放电时间和提高催化剂的用量可以使母液的降解率提高，在工业上可以通过泵浦将废水循环处理，直至达到可排放的标准。It can be seen from the above Examples 24-26 that prolonging the plasma discharge time and increasing the amount of catalyst can increase the degradation rate of the mother liquor. In the industry, the wastewater can be circulated and treated by pumping until it reaches the dischargeable standard.
由上述对照例1-4可知，单独的等离子体对高盐度、难降解的草甘膦废水几乎不具有降解效果，而有了催化剂的协同，未知组分的草甘膦废水在短短30min的作用下，TOC能够降低80％以上。对照例5-6说明，不用等离子体处理，只用催化剂处理，在常温常压下，即使催化剂对卤水或母液作用120min，有机磷基本上也没有降解。从对照例1-6可以说明单独的等离子体或催化剂与待处理液作用，均不能降解有机磷废水。并且单独使用湿式催化氧化法(高温高压)没有办法使卤水中的含磷有机物进一步降解。结合前面的实施例，说明本发明实施例中等离子体和催化剂在处理草甘膦废水中具有协同作用，且不需高温高压，就能够对草甘膦废水产生很好的降解效果，高效去除TOC、有机磷、COD、总磷、总氮等污染成分。From the above Comparative Examples 1-4, it can be seen that the plasma alone has little degradation effect on the high salinity, refractory glyphosate wastewater, and with the synergy of the catalyst, the glyphosate wastewater of unknown composition in just 30 minutes Under the effect of, TOC can be reduced by more than 80%. Comparative Examples 5-6 show that without plasma treatment, only with catalyst treatment, at normal temperature and pressure, even if the catalyst acts on brine or mother liquor for 120 minutes, the organic phosphorus is basically not degraded. From Comparative Examples 1-6, it can be shown that the action of the plasma or catalyst alone and the liquid to be treated cannot degrade the organic phosphorus wastewater. And the wet catalytic oxidation method alone (high temperature and high pressure) has no way to further degrade the phosphorus-containing organic compounds in brine. Combined with the previous examples, it is shown that the plasma and the catalyst in the embodiments of the present invention have a synergistic effect in the treatment of glyphosate wastewater, and without high temperature and high pressure, it can produce a good degradation effect on glyphosate wastewater and efficiently remove TOC , Organic phosphorus, COD, total phosphorus, total nitrogen and other polluting components.
综上所述，本发明公开了一种低温等离子体协同催化剂降解草甘膦废水的方法，是将非贵金属合金催化剂与待处理废水混合，然后置于等离子体放电通道下，利用等离子体产生的高能电子，充分电离有机物分子、水分子、氧气分子等，从而激发出更高能量的活性粒子，与催化剂协同作用，高效降解高盐度难降解草甘膦废水。In summary, the present invention discloses a method for degrading glyphosate wastewater by a low-temperature plasma co-catalyst, which is a non-noble metal alloy catalyst mixed with wastewater to be treated, and then placed under a plasma discharge channel, which is generated by plasma High-energy electrons fully ionize organic molecules, water molecules, oxygen molecules, etc., thereby stimulating higher-energy active particles, synergizing with the catalyst, and efficiently degrading high-salinity refractory glyphosate wastewater.
本发明针对草甘膦废水的特性，通过对催化剂组分的设计，与等离子体之间形成良好的协同作用，实现草甘膦废水在常温常压下进行高效降解，本发明方法新颖独特，简单高效，突破现有技术无法降解草甘膦废水的限制，在处理草甘膦废水方面处理工艺简单、所需时间短、效率高，具有极好的应用前景。The invention aims at the characteristics of glyphosate wastewater, through the design of the catalyst components, and forms a good synergy with the plasma, to achieve efficient degradation of glyphosate wastewater at normal temperature and pressure, the method of the invention is novel, unique and simple High efficiency, breaking through the limitation that the existing technology cannot degrade glyphosate wastewater, the treatment process of glyphosate wastewater is simple, the time required is short, the efficiency is high, and it has excellent application prospects.
本发明采用的催化剂本身容易制备，价格低廉，不会给工业处理大量有机污染物造成较大的经济负担，而且结合等离子体对草甘膦废水有较好的降解效果。The catalyst used in the present invention is easy to prepare itself, has a low price, does not cause a large economic burden on industrial processing of a large amount of organic pollutants, and combined with plasma has a better degradation effect on glyphosate wastewater.
本发明解决了现有技术中草甘膦废水降解方法步骤繁琐且需要大量化学试剂，反应条件也需要高温、高压等不足，提出一种低温等离子体协同催化剂降解草甘膦废水的方法，大大提高了草甘膦废水的去除效率，且具有持续、方便、快速等优点。The invention solves the problems of the glyphosate wastewater degradation method in the prior art which is cumbersome and requires a large amount of chemical reagents, and the reaction conditions also require high temperature and high pressure. The low-temperature plasma synergistic catalyst method for degrading glyphosate wastewater is greatly improved. It improves the removal efficiency of glyphosate wastewater, and has the advantages of being continuous, convenient and fast.
本发明方法能够在较低功率条件下产生持续均匀的丝状流光放电，避免电极和废水的直接接触，以防电极被高盐度废水腐蚀，延长电极的使用寿命。同时，本发明选用价廉易得的过渡金属和载体作为催化剂，大大提高了等离子体处理效率，减少耗电费用，降低了废水处理成本。The method of the invention can produce continuous and uniform filament streamer discharge under the condition of lower power, avoid direct contact between the electrode and waste water, prevent the electrode from being corroded by high salinity waste water, and prolong the service life of the electrode. At the same time, the present invention uses inexpensive and easily available transition metals and carriers as catalysts, which greatly improves the plasma processing efficiency, reduces power consumption costs, and reduces wastewater treatment costs.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, changes, modifications, substitutions, combinations, etc. that do not deviate from the spirit and principles of the present invention Simplified, all should be equivalent replacement methods, all included in the protection scope of the present invention.

Claims (10)

  1. 一种过渡金属合金催化剂复合体的制备方法，包括以下步骤：A method for preparing a transition metal alloy catalyst composite includes the following steps:
    将过渡金属盐与载体在溶剂中混合，干燥后于惰性气体和氢气的混合气体中在350～550℃条件下焙烧混合物；得过渡金属合金催化剂；The transition metal salt and the carrier are mixed in a solvent, and after drying, the mixture is calcined in a mixed gas of inert gas and hydrogen at 350-550°C; a transition metal alloy catalyst is obtained;
    所述载体选自活性炭、氮杂碳、氧化铝、二氧化钛、二氧化硅、分子筛ZMS-5、稀土氧化物中的至少一种。The carrier is at least one selected from activated carbon, azacarbon, alumina, titania, silica, molecular sieve ZMS-5, and rare earth oxide.
  2. 根据权利要求1所述的方法，其特征在于，所述稀土氧化物选自CeO 2、ZrO 2中的至少一种。 The method according to claim 1, wherein the rare earth oxide is selected from at least one of CeO 2 and ZrO 2 .
  3. 根据权利要求1所述的方法，其特征在于，所述过渡金属化合物的质量为载体的5％～30％；所述过渡金属化合物选自铁盐、钴盐、铜盐、镍盐中的至少一种；所述过渡金属化合物中的阴离子选自Cl -、NO 3-、SO 4 2-或C 2H 3O 2 -中的至少一种。 The method according to claim 1, characterized in that the mass of the transition metal compound is 5% to 30% of the support; the transition metal compound is at least selected from the group consisting of iron salts, cobalt salts, copper salts, and nickel salts one kind; metal compound is selected from the transition anion Cl -, NO 3 - at least one of -, SO 4 2- or C 2 H 3 O 2.
  4. 根据权利要求1所述的方法，其特征在于，所述溶剂为水；所述惰性气体和氢气的体积比为93～97：3～7；所述焙烧时间为1～5h。The method according to claim 1, wherein the solvent is water; the volume ratio of the inert gas and hydrogen is 93 to 97: 3 to 7; and the calcination time is 1 to 5 hours.
  5. 权利要求1～4任一项所述方法制备得到过渡金属合金催化剂复合体。The transition metal alloy catalyst composite is prepared by the method according to any one of claims 1 to 4.
  6. 一种低温等离子体协同催化降解草甘膦废水的方法，其特征在于，将权利要求5所述的过渡金属合金催化剂复合体与草甘膦废水混合，再经等离子体处理进行降解反应。A low-temperature plasma synergistic catalytic degradation method for glyphosate wastewater, characterized in that the transition metal alloy catalyst complex of claim 5 is mixed with glyphosate wastewater, and then subjected to plasma treatment for degradation reaction.
  7. 根据权利要求6所述的方法，其特征在于，所述降解反应时间为10min～200min，所述等离子体的放电温度为20～80℃；等离子体放电功率密度为1～500W/cm 3。 The method according to claim 6, wherein the degradation reaction time is 10 min to 200 min, the discharge temperature of the plasma is 20 to 80°C, and the plasma discharge power density is 1 to 500 W/cm 3 .
  8. 根据权利要求6所述的方法，其特征在于，所述草甘膦废水为草甘膦生产车间产生的废液，记为母液；或者为母液经过湿式催化氧化之后得到的难以降解的卤水。The method according to claim 6, characterized in that the glyphosate wastewater is the waste liquid produced in the glyphosate production workshop, and is referred to as mother liquor; or it is hard-degradable brine obtained after wet catalytic oxidation of the mother liquor.
  9. 根据权利要求8所述的方法，其特征在于，所述湿式催化氧化的具体操作为将母液与催化剂混合，在150～260℃、2～8MPa条件下反应2～6h，反应之后得到的液体即为卤水；所述催化剂包括权利要求5所述的过渡金属合金催化剂复合体。The method according to claim 8, characterized in that the specific operation of the wet catalytic oxidation is to mix the mother liquor with the catalyst and react at 150 to 260°C and 2 to 8 MPa for 2 to 6 hours. The liquid obtained after the reaction is It is brine; the catalyst includes the transition metal alloy catalyst composite body of claim 5.
  10. 根据权利要求8或9所述的方法，其特征在于，所述母液TOC值为10000～10200ppm，COD为59000～61000ppm，总磷含量为24000～26000ppm，总氮含量为4500～5500ppm，NaCl含量为14～19％。The method according to claim 8 or 9, wherein the TOC value of the mother liquor is 10000 to 10200 ppm, the COD is 59000 to 61000 ppm, the total phosphorus content is 24000 to 26000 ppm, the total nitrogen content is 4500 to 5500 ppm, and the NaCl content is 14 to 19%.
PCT/CN2019/121560 2018-12-29 2019-11-28 Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst WO2020134834A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811630589.8A CN109621958B (en) 2018-12-29 2018-12-29 Method for degrading glyphosate wastewater by virtue of low-temperature plasma concerted catalysis
CN201811630589.8 2018-12-29

Publications (1)

Publication Number Publication Date
WO2020134834A1 true WO2020134834A1 (en) 2020-07-02

Family

ID=66079263

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/121560 WO2020134834A1 (en) 2018-12-29 2019-11-28 Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst

Country Status (2)

Country Link
CN (1) CN109621958B (en)
WO (1) WO2020134834A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112264068A (en) * 2020-10-17 2021-01-26 中南大学 Nitrogen and phosphorus co-doped carbon-based CoFe alloy nano material and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114887565B (en) * 2022-04-15 2024-01-12 浙江理工大学 Liquid phase discharge device and application thereof
CN115430442A (en) * 2022-09-30 2022-12-06 西安交通大学 VP-Fe 3 O 4 Catalyst, preparation method and method for degrading medical wastewater by using catalyst in cooperation with underwater bubble plasma

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0323821A1 (en) * 1987-12-31 1989-07-12 Monsanto Company Process for treating glyphosate process waste streams
CN103663667A (en) * 2012-09-19 2014-03-26 中国中化股份有限公司 Catalytic wet oxidation pretreatment method of glyphosate production wastewater
CN105948217A (en) * 2016-05-19 2016-09-21 四川福思达生物技术开发有限责任公司 Method for treating waste water generated in glyphosate production process
CN106277275A (en) * 2016-08-25 2017-01-04 李文汇 The method and device of azithromycin in a kind of degradation water
CN106348420A (en) * 2015-07-16 2017-01-25 中国科学院成都有机化学有限公司 Method for treating glyphosate waste water through wet catalytic oxidation
CN108585336A (en) * 2018-05-23 2018-09-28 上海邵雍环境科技有限公司 The processing method of glyphosate mother solution wet oxidation sequential catalyst wet oxidation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110180423A1 (en) * 2008-02-11 2011-07-28 Wisconsin Alumni Research Foundation Methods for removing contaminants from aqueous solutions using photoelectrocatalytic oxidization
CN101648972B (en) * 2009-09-08 2012-11-21 浙江新安化工集团股份有限公司 Method for recycling glyphosate from glyphosate mother liquid
CN103357413A (en) * 2012-03-26 2013-10-23 江南大学 Method for preparing binary-oxide composite solid acid catalyst and method for treating degradation-resistant organic pollutants by catalyzing oxidization of H2O2
CN103721721B (en) * 2014-01-07 2016-01-20 天津大学 Nanometer Copper cobalt dual-metal catalyst and Synthesis and applications
CN108640165B (en) * 2018-05-15 2020-07-03 武汉中科先进技术研究院有限公司 Metal oxide nano-structure composite material and preparation method thereof
CN108565132B (en) * 2018-05-15 2019-09-27 中国科学院深圳先进技术研究院 A kind of fibrous material and preparation method thereof with metal oxide nanostructure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0323821A1 (en) * 1987-12-31 1989-07-12 Monsanto Company Process for treating glyphosate process waste streams
CN103663667A (en) * 2012-09-19 2014-03-26 中国中化股份有限公司 Catalytic wet oxidation pretreatment method of glyphosate production wastewater
CN106348420A (en) * 2015-07-16 2017-01-25 中国科学院成都有机化学有限公司 Method for treating glyphosate waste water through wet catalytic oxidation
CN105948217A (en) * 2016-05-19 2016-09-21 四川福思达生物技术开发有限责任公司 Method for treating waste water generated in glyphosate production process
CN106277275A (en) * 2016-08-25 2017-01-04 李文汇 The method and device of azithromycin in a kind of degradation water
CN108585336A (en) * 2018-05-23 2018-09-28 上海邵雍环境科技有限公司 The processing method of glyphosate mother solution wet oxidation sequential catalyst wet oxidation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENG , RENYANG ET AL: "Effect of Metal Loadings on Pt-Co/AC Catalyst for Low Temperature Oxygenation of Benzene", ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION, vol. 30, no. 2, 30 April 2014 (2014-04-30), CN, pages 211 - 217, XP009521710, ISSN: 1001-8719, DOI: 10.3969/j.issn.1001-8719.2014.02.004 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112264068A (en) * 2020-10-17 2021-01-26 中南大学 Nitrogen and phosphorus co-doped carbon-based CoFe alloy nano material and preparation method and application thereof

Also Published As

Publication number Publication date
CN109621958B (en) 2020-09-04
CN109621958A (en) 2019-04-16

Similar Documents

Publication Publication Date Title
WO2020134834A1 (en) Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst
CN110585916B (en) Method and device for removing gaseous pollutants through electro-Fenton catalytic oxidation
Mi et al. Enhanced catalytic degradation by using RGO-Ce/WO3 nanosheets modified CF as electro-Fenton cathode: Influence factors, reaction mechanism and pathways
Wang et al. Non-thermal plasma oxidation of Cu (II)-EDTA and simultaneous Cu (II) elimination by chemical precipitation
Ye et al. A novel NH2-MIL-88B (Fe)-modified ceramic membrane for the integration of electro-Fenton and filtration processes: A case study on naproxen degradation
CN104628200B (en) A kind of method utilizing photoelectric combination technical finesse organic wastewater
Mansoori et al. Activated biochar supported iron-copper oxide bimetallic catalyst for degradation of ciprofloxacin via photo-assisted electro-Fenton process: a mild pH condition
Wu et al. Effective degradation of diatrizoate by electro-peroxone process using ferrite/carbon nanotubes based gas diffusion cathode
Chen et al. Preferential removal of 2, 4-dichlorophenoxyacetic acid from contaminated waters using an electrocatalytic ceramic membrane filtration system: Mechanisms and implications
CN105618080A (en) Ozone catalytic oxidation catalyst for treating reverse osmosis concentrated water and preparation method of catalyst
Wang et al. Mechanism for enhancing biodegradability of antibiotic pharmacy wastewater by in-situ generation of H2O2 and radicals over MnOx/nano-G/2-EAQ/AC cathode
Li et al. Activation of peroxymonosulfate by a waste red mud-supported Co3O4 quantum dots under visible light for the degradation of levofloxacin
Bu et al. The degradation of sulfamilamide wastewater by three-dimensional electrocatalytic oxidation system composed of activated carbon bimetallic particle electrode
CN113198546A (en) Quantum dot/peroxide composite material, preparation method and application thereof
Ji et al. In situ H2O2 generation and corresponding pollutant removal applications: a review
CN109876822B (en) Copper-manganese bimetallic ozone catalyst, preparation method and application thereof
Wang et al. Decomplexation of Cu-1-hydroxyethylidene-1, 1-diphosphonic acid by a three-dimensional electrolysis system with activated biochar as particle electrodes
Shi et al. Wood induced preparation of Fe3C decorated biochar for peroxymonosulfate activation towards bisphenol a degradation with low ion leaching
CN110386692B (en) Auxiliary agent wastewater treatment process
Wang et al. Continuous efficient removal and inactivation mechanism of E. coli by bismuth-doped SnO 2/C electrocatalytic membrane
WO2023151437A1 (en) Three-dimensional particle electrode, preparation method therefor, and use thereof
Ren et al. Synergistic and electrocatalytic degradation of antibiotics by silver/protonated polyaniline-titanium-based composite electrodes in a common chamber reactor: Regulatory factors, degradation mechanism, toxicity assessment
CN114044554A (en) Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst
JP3988483B2 (en) Treatment of free chlorine in water
Song et al. Facile synthesis of bimetallic ACF/CC@ FeOCl–Cu composite cathode for efficient degradation of sulfamethoxazole at neutral pH by a flow-through heterogeneous electro-Fenton process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19904161

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19904161

Country of ref document: EP

Kind code of ref document: A1