WO2020134834A1 - 一种低温等离子体协同催化降解草甘膦废水的方法 - Google Patents

一种低温等离子体协同催化降解草甘膦废水的方法 Download PDF

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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
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catalyst
plasma
ppm
removal rate
transition metal
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French (fr)
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黄逸凡
杨环环
高明
白力诚
喻学锋
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Shenzhen Institute of Advanced Technology of CAS
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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
    • B01J23/70—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.

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Abstract

一种低温等离子体协同催化降解草甘膦废水的方法，将过渡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与催化剂协同作用，高效降解高盐度难降解草甘膦废水，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，反应条件需要高温、高压等技术不足。

Description

一种低温等离子体协同催化降解草甘膦废水的方法 技术领域
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。
背景技术
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。
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。
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。
发明内容
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。
本发明所采取的技术方案是：
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：
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；
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。
优选的，所述稀土氧化物选自CeO 2、ZrO 2中的至少一种。
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。
优选的，所述溶剂为水。
优选的，所述惰性气体和氢气的体积比为93～97：3～7。
优选的，所述惰性为氩气或氮气，优选为氩气。
优选的，所述焙烧时间为1～5h。
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。
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。
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。
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。
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。
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。
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。
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％。
优选的，所述卤水NaCl含量为3～8％。
本发明的有益效果是：
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。
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。
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。
具体实施方式
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。
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％。
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。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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％。
实施例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％。
实施例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％。
实施例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％。
实施例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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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。
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％。
实施例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％。
实施例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％。
实施例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％。
实施例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％。
实施例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％。
对照例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。
对照例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。
对照例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。
对照例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。
对照例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。
对照例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。
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。
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。
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。
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。
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。
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。
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。
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。

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：
    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；
    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。
  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。
  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。
  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。
  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。
  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。
  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。
  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。
  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。
  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％。
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