CN109621958A - A kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water - Google Patents
A kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water Download PDFInfo
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- CN109621958A CN109621958A CN201811630589.8A CN201811630589A CN109621958A CN 109621958 A CN109621958 A CN 109621958A CN 201811630589 A CN201811630589 A CN 201811630589A CN 109621958 A CN109621958 A CN 109621958A
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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
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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
- B01J23/70—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
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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
- B01J23/70—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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
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- 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
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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
- 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
Abstract
The invention discloses a kind of methods of low-temperature plasma synergistic catalytic degradation glyphosate waste water, non-noble metal alloys catalysts are mixed with waste water to be processed, it is subsequently placed under plasma discharge channels, the high energy electron and catalyst generated using plasma is acted synergistically, the high salinity of efficient degradation glyphosate waste water difficult to degrade, it solves glyphosate waste water biodegrading process complex steps in the prior art and needs a large amount of chemical reagent, reaction condition is also required to the technical deficiencies such as high temperature, high pressure.
Description
Technical field
The present invention relates to sewage treatment fields, sweet more particularly, to a kind of low-temperature plasma synergistic catalytic degradation grass
The method of phosphine waste water.
Background technique
Glyphosate is a kind of less toxic, efficient, wide spectrum steriland herbicide, and rapid development, has become the whole world in recent years
Yield and the maximum pesticide species of dosage.Its mother liquor waste water is with discharge amount is big, toxicity is big, salt content is high, compound difficult to degrade
The features such as content is high, difficulty of governance is big.Organic impurities in mother liquor mainly includes glyphosate, pmida, phosphite, phosphoric acid
The Multiple components such as salt, glycine, methanol, formaldehyde, main component are glyphosate, glycine, phosphate etc..
Currently, processing glyphosate waste water mainly uses absorption method, Wet Catalytic Oxidation Method, oxychloride method, the above method is equal
It achieves good result, but complex steps, and needs a large amount of chemical reagent, reaction condition is also required to high temperature, high pressure, this is to setting
Standby is more demanding, and there are definitely limit in terms of industrial application.
Lower temperature plasma technology is the processing that the new and effective environmental protection technology of one kind is usually applied to exhaust gas, less use
In wastewater treatment.Existing lower temperature plasma technology is for that can not solve to glyphosate waste water in the method for wastewater treatment
Degradation.
Summary of the invention
It is an object of the invention to be directed to the prior art, there are complex steps, and need a large amount of chemical reagent, reaction condition
The deficiencies of needing high temperature, high pressure provides a kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water.
The technical solution used in the present invention is:
A kind of preparation method of transition metal alloy catalyst composite, comprising the following steps:
Transition metal salt is mixed in a solvent with carrier, it is dry after in the mixed gas of inert gas and hydrogen
Baking mixes under the conditions of 350~550 DEG C；Obtain transition metal alloy catalyst；
The carrier is selected from active carbon, azepine carbon, aluminium oxide, titanium dioxide, silica, molecular sieve ZMS-5, rare earth oxygen
At least one of compound.
Preferably, the rare earth oxide is selected from CeO2、ZrO2At least one of.
Preferably, the quality of the transistion metal compound is the 5%~30% of carrier；The transistion metal compound choosing
From at least one of molysite, cobalt salt, mantoquita, nickel salt；Anion in the transistion metal compound is selected from Cl-、NO3-、
SO4 2-Or C2H3O2 -At least one of.
Preferably, the solvent is water.
Preferably, the volume ratio of the inert gas and hydrogen is 93~97:3~7.
Preferably, the inertia is argon gas or nitrogen, preferably argon gas.
Preferably, the calcining time is 1~5h.
Transition metal alloy catalyst composite is prepared in any of the above-described the method.
A kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water, by transition metal alloy described above
Catalyst composite is mixed with glyphosate waste water, then plasma-treated carry out degradation reaction.
Preferably, the amount ratio of the transition metal alloy catalyst and glyphosate waste water be 50~1000mg:17~
100mL。
Preferably, the degradation reaction time is 10min~200min, and the discharge temp of the plasma is 20~80
℃；Plasma discharge power density is 1~500W/cm3。
Preferably, the glyphosate waste water is the waste liquid that glyphosate production workshop generates, and is denoted as mother liquor；Or it is passed through for mother liquor
Cross the brine for being difficult to degrade obtained after catalytic wet oxidation.
Preferably, the concrete operations of the catalytic wet oxidation are to mix mother liquor with catalyst, in 150~260 DEG C, 2
2~6h is reacted under the conditions of~8MPa, the liquid obtained after reaction is brine.
Preferably, the catalyst includes transition metal alloy catalyst composite described above.
Preferably, the mother liquor TOC value is 10000~10200ppm, and COD is 59000~61000ppm, and total phosphorus content is
24000~26000ppm, total nitrogen content are 4500~5500ppm, and NaCl content is 14~19%.
Preferably, the brine NaCl content is 3~8%.
The beneficial effects of the present invention are:
1. the present invention is directed to the characteristic of glyphosate waste water, by the design to catalytic component, the shape between plasma
At good synergistic effect, realize that glyphosate waste water carries out efficient degradation, the method for the present invention novel and unique, letter at normal temperatures and pressures
It is single efficiently, break through the prior art can not degradation of glyphosate waste water limitation, in terms of handle glyphosate waste water treatment process simply,
Required time is short, high-efficient, has fabulous application prospect.
2. catalyst that the present invention uses itself is easy preparation, cheap, a large amount of organic contaminations of industrial treatment will not be given
Object causes biggish financial burden, and binding plasma has preferable degradation effect to glyphosate waste water.
3. the present invention solves glyphosate waste water biodegrading process complex steps in the prior art and needs a large amount of chemical reagent,
Reaction condition is also required to the deficiencies of high temperature, high pressure, proposes a kind of low-temperature plasma synergistic catalyst degradation glyphosate waste water
Method, substantially increases the removal efficiency of glyphosate waste water, and has many advantages, such as persistently, easily and fast.
Specific embodiment
Present invention application is further illustrated combined with specific embodiments below.Following embodiments only for illustration, no
It can be interpreted as limitation of the present invention.Unless stated otherwise, reagent raw material used in following embodiments is regular market purchase or quotient
The life reagent raw material that industry approach obtains.Unless stated otherwise, equipment used in following embodiments is commonly used in the art
Equipment.
The glyphosate waste water that the embodiment of the present invention is selected is for the mother liquor of glyphosate production workshop generation and by catalytic wet
The brine for being difficult to degrade obtained after oxidation.Organic impurities in mother liquor mainly include glyphosate, pmida, phosphite,
The Multiple components such as phosphate, glycine, methanol, formaldehyde, main component are glyphosate, glycine, phosphate etc.；It is main in brine
It to be that (mother liquor composition that glyphosate production workshop generates is complicated, and analysis method is difficult to examine at this stage for phosphorus-containing matter difficult to degrade
Survey the concrete content of the ingredients such as glyphosate, pmida).It is tested by total organic carbon (Total Organism Carbon, TOC),
It was found that the TOC value of mother liquor is 10063ppm.Glyphosate mother solution major pollutants compositional data are as follows: COD (Chemical
Oxygen Demand, COD) it is 60000ppm, total phosphorus content 25000ppm, total nitrogen content 5000ppm, NaCl content is
16%.
The brine that the embodiment of the present invention is selected is the brine for being difficult to degrade that mother liquor obtains later by catalytic wet oxidation,
The concrete operations of the catalytic wet oxidation are to mix mother liquor with catalyst (catalyst as will be illustrated in the example below),
150-260 DEG C, 2~6h is reacted under 2-8MPa Oxygen Condition, the liquid obtained after reaction is brine.Halogen of the embodiment of the present invention
It is mainly phosphorus-containing matter (such as glyphosate, pmida and phosphite) difficult to degrade in water, pH value is about 7, TOC value
About 200ppm, COD are about 1200ppm, and total phosphorus content 500ppm, total nitrogen content 85ppm, NaCl content is 6%.It should
Brine is added catalyst (catalyst as will be illustrated in the example below) continuation and reacts 2h under 260 DEG C, 8MPa Oxygen Condition,
TOC value is still 198ppm, organic phosphorus to there is no degradation.Illustrate both to make to further increase reaction temperature and pressure, extend anti-
Between seasonable, Wet Catalytic Oxidation Method is used alone and has no idea to make the phosphorus-containing matter in brine further to degrade, reaches
The standard that can be discharged, and this high temperature and pressure is outer that mode is big to the corrosivity of equipment for a long time, and reaction condition is harsh.Institute
To need another method to be further processed brine, phosphorus-containing matter difficult to degrade in brine is made to reach the standard that can be discharged.
Embodiment 1
By 1.0g ZrO2、1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, soaks
Stain is stayed overnight, and being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-ZrO2。
Weigh the above-mentioned FeCu-ZrO of 0.5g2Catalyst, 20mL brine be sufficiently mixed it is uniform be placed in reactor, open
Plasma shutter adjusts discharge voltage and electric current, stabilization to be discharged, generates uniform purple filiform streamer, continuous discharge into
Row degradation reaction 20min, the discharge temp of plasma are 20-80 DEG C；Plasma discharge power density is 1-500W/cm3；
Processed waste water is collected, measures TOC with Shimadzu (SHIMADZU) total organic carbon analyzer after dilution, is worth for 105ppm, place
The removal rate that organic phosphorus degrading rate is 78%, COD after reason reaches 20%, and total tp removal rate is 45%, nitrogen removal rate 50%.
Embodiment 2
By 0.5g SiO2、1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, soaks
Stain is stayed overnight, and being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-SiO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCu-SiO of 0.5g is weighed2Catalyst, to 20mL brine
It degrades, TOC value is 96ppm, and organic phosphorus degrading rate is that the removal rate of 52%, COD reaches 24% after processing, total tp removal rate
It is 48%, nitrogen removal rate 53%.
Embodiment 3
By 1.0g TiO2 (P25), 1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is stirred
Even, steeped overnight, being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing gold
Belong to alloy.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, it is prepared
Catalyst is named as FeCu-P25.
Referring to embodiment 1 corona treatment mode, weigh the above-mentioned FeCu-P25 catalyst of 0.5g, to 20mL brine into
Row degradation, TOC value are 112ppm, and organic phosphorus degrading rate is that the removal rate of 44%, COD reaches 18% after processing, total tp removal rate
It is 41%, nitrogen removal rate 43%.
Embodiment 4
By 1.0g CeO2,1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, soaks
Stain is stayed overnight, and being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCu-CeO of 0.5g is weighed2Catalyst, to 20mL brine
It degrades, TOC value is 110ppm, and organic phosphorus degrading rate is that the removal rate of 45%, COD reaches 19% after processing, total phosphorus ligands
Rate is 42%, nitrogen removal rate 43%.
Embodiment 5
By 1.0g Al2O3,1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, soaks
Stain is stayed overnight, and being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCu-Al of 0.5g is weighed2O3Catalyst, to 20mL brine
It degrades, TOC value is 107ppm, and organic phosphorus degrading rate is that the removal rate of 47%, COD reaches 20% after processing, total phosphorus ligands
Rate is 44%, nitrogen removal rate 48%.
Embodiment 6
By 1.5g ZMS-5,1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, soaks
Stain is stayed overnight, and being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-ZMS-5.
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCu-ZMS-5 catalyst of 0.5g is weighed, to 20mL brine
It degrades, TOC value is 100ppm, and organic phosphorus degrading rate is that the removal rate of 50%, COD reaches 22% after processing, total phosphorus ligands
Rate is 48%, nitrogen removal rate 54%.
Embodiment 7
By 0.5g AC (active carbon), 1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is stirred
Even, steeped overnight, being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing gold
Belong to alloy.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, it is prepared
Catalyst is named as FeCu-AC.
Referring to embodiment 1 corona treatment mode, weigh the above-mentioned FeCu-AC catalyst of 0.5g, to 20mL brine into
Row degradation, TOC value are 35ppm, and organic phosphorus degrading rate is that the removal rate of 83%, COD reaches 58% after processing, and total tp removal rate is
80%, nitrogen removal rate 85%.
Embodiment 8
Referring to the alloy catalyst preparation method of embodiment 7 and the corona treatment mode of embodiment 1, weigh on 0.5g
FeCu-AC catalyst is stated, degradation reaction 10min is carried out to 20mL brine, TOC value is 45ppm, and organic phosphorus degrading rate is after processing
The removal rate of 78%, COD reach 44%, and total tp removal rate is 75%, nitrogen removal rate 80%.
Embodiment 9
Referring to the alloy catalyst preparation method of embodiment 7 and the corona treatment mode of embodiment 1, weigh on 0.5g
FeCu-AC catalyst is stated, to 20mL brine degradation 20min, TOC value is 37ppm, and organic phosphorus degrading rate is 82%, COD after processing
Removal rate reach 56%, total tp removal rate is 80%, nitrogen removal rate 83%.
Embodiment 10
Referring to the alloy catalyst preparation method of embodiment 7 and the corona treatment mode of embodiment 1, weigh on 0.5g
FeCu-AC catalyst is stated, to 20mL brine degradation 30min, TOC value is 31ppm, and organic phosphorus degrading rate is 87%, COD after processing
Removal rate reach 63%, total tp removal rate is 86%, nitrogen removal rate 89%.
Embodiment 11
Referring to the alloy catalyst preparation method of embodiment 7 and the corona treatment mode of embodiment 1, weigh on 0.5g
FeCu-AC catalyst is stated, to 20mL brine degradation 40min, TOC value is 24ppm, and organic phosphorus degrading rate is 91%, COD after processing
Removal rate reach 69%, total tp removal rate is 89%, nitrogen removal rate 94%.
Embodiment 12
Referring to the alloy catalyst preparation method of embodiment 7 and the corona treatment mode of embodiment 1, weigh on 0.5g
FeCu-AC catalyst is stated, to 20mL brine degradation 50min, TOC value is 20ppm, and organic phosphorus degrading rate is 94%, COD after processing
Removal rate reach 72%, total tp removal rate is 92%, nitrogen removal rate 95%.
Embodiment 13
By 0.5g azepine carbon (NC), 1.21g FeCl3 6H2O、1.34g CuCl2, it is dissolved in 10mL water, is stirred
Even, steeped overnight, being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing gold
Belong to alloy.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, it is prepared
Catalyst is named as FeCu-NC.
Referring to embodiment 1 corona treatment mode, weigh the above-mentioned FeCu-NC catalyst of 0.5g, to 20mL brine into
Row degradation, TOC value are 68ppm, and organic phosphorus degrading rate is that the removal rate of 76%, COD reaches 30% after processing, and total tp removal rate is
63%, nitrogen removal rate 65%.
Embodiment 14
By 1.0g CeO2、1.21g FeCl3 6H2O is dissolved in 10mL water, is uniformly mixed, steeped overnight, drying
It is placed in vacuum tube furnace and is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing metal alloy.The speed of 3 DEG C/min
Rate is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, prepared catalyst is named as Fe-
CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned Fe-CeO of 0.5g is weighed2Catalyst, to 20mL brine into
Row degradation, TOC value are 124ppm, and organic phosphorus degrading rate is that the removal rate of 38%, COD reaches 15% after processing, total tp removal rate
It is 35%, nitrogen removal rate 40%.
Embodiment 15
By 2.0g CeO2、1.34g CuCl2, it is dissolved in 10mL water, is uniformly mixed, steeped overnight, the postposition of drying
95% inert gas (Ar) protection, 5% hydrogen reducing metal alloy are passed through in vacuum tube furnace.The rate liter of 3 DEG C/min
Temperature restores 4h to 400 DEG C.It is cooled to room temperature after taking out sample and grinds for use, prepared catalyst is named as Cu-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned Cu-CeO of 0.5g is weighed2Catalyst, to 20mL brine into
Row degradation, TOC value are 143ppm, and organic phosphorus degrading rate is that the removal rate of 28%, COD reaches 15% after processing, total tp removal rate
It is 25%, nitrogen removal rate 30%.
Embodiment 16
By 2.0g CeO2、2.02g CoCl2 6H2O is dissolved in 10mL water, is uniformly mixed, steeped overnight, drying
It is placed in vacuum tube furnace and is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing metal alloy.The speed of 3 DEG C/min
Rate is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, prepared catalyst is named as Co-
CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned Co-CeO of 0.5g is weighed2Catalyst, to 20mL brine into
Row degradation, TOC value are 116ppm, and organic phosphorus degrading rate is that the removal rate of 42%, COD reaches 18% after processing, total tp removal rate
It is 40%, nitrogen removal rate 43%.
Embodiment 17
By 2.0g CeO2、2.06g NiCl2 6H2O is dissolved in 10mL water, is uniformly mixed, steeped overnight, drying
It is placed in vacuum tube furnace and is passed through 95% inert gas (Ar) protection, 5% hydrogen reducing metal alloy.The speed of 3 DEG C/min
Rate is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds for use, prepared catalyst is named as Ni-
CeO2。
Referring to embodiment 1 corona treatment mode, weigh the above-mentioned Ni-CeO2 catalyst of 0.5g, to 20mL brine into
Row degradation, TOC value are 142ppm, and organic phosphorus degrading rate is that the removal rate of 28%, COD reaches 15% after processing, total tp removal rate
It is 27%, nitrogen removal rate 32%.
Embodiment 18
By 2.0g CeO2、1.81g FeCl3 6H2O, 1.17g CuCl2 2H2O is dissolved in 10mL water, is uniformly mixed,
Steeped overnight, being placed in vacuum tube furnace for drying are passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCo-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCo-CeO of 0.5g is weighed2Catalyst, to 20mL brine
It degrades, TOC value is 116ppm, and organic phosphorus degrading rate is that the removal rate of 42%, COD reaches 34% after processing, total phosphorus ligands
Rate is 40%, nitrogen removal rate 45%.
Embodiment 19
By 2.0g CeO2、1.21g FeCl3 6H2O, 0.67g CuCl2 2H2O is dissolved in 10mL water, is uniformly mixed,
Steeped overnight, being placed in vacuum tube furnace for drying are passed through 95% inert gas (Ar) protection, and 5% hydrogen reducing metal closes
Gold.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.It is cooled to room temperature after taking out sample and grinds stand-by, prepared catalysis
Agent is named as FeCu-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCu-CeO2 catalyst of 0.5g is weighed, to 20mL brine
It degrades, TOC value is 35ppm, and organic phosphorus degrading rate is that the removal rate of 88%, COD reaches 55% after processing, total tp removal rate
It is 84%, nitrogen removal rate 86%.
Embodiment 20
By 2.0g CeO2、0.61g FeCl3 6H2O、1.34g CuCl2、0.64g CoCl2 2H2O is dissolved in 10mL water,
It being uniformly mixed, steeped overnight, being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, 5%
Hydrogen reducing metal alloy.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.Be cooled to room temperature take out sample after grinding to
With prepared catalyst is named as FeCuCo-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCuNi-CeO of 0.5g is weighed2Catalyst, to 20mL halogen
Water is degraded, and TOC value is 44ppm, and organic phosphorus degrading rate is that the removal rate of 78%, COD reaches 36% after processing, total phosphorus ligands
Rate is 75%, nitrogen removal rate 80%.
Embodiment 21
By 2.0g CeO2、0.61g FeCl3 6H2O、1.34g CuCl2、1.03g NiCl2 6H2O is dissolved in 10mL water,
It being uniformly mixed, steeped overnight, being placed in vacuum tube furnace for drying is passed through 95% inert gas (Ar) protection, 5%
Hydrogen reducing metal alloy.The rate of 3 DEG C/min is warming up to 400 DEG C, restores 4h.Be cooled to room temperature take out sample after grinding to
With prepared catalyst is named as FeCuCo-CeO2。
Referring to the corona treatment mode of embodiment 1, the above-mentioned FeCuNi-CeO of 0.1g is weighed2Catalyst, to 20mL halogen
Water is degraded, and TOC value is 30ppm, and organic phosphorus degrading rate is that the removal rate of 85%, COD reaches 40% after processing, total phosphorus ligands
Rate is 82%, nitrogen removal rate 82%.
Embodiment 22
Referring to the alloy catalyst preparation method of embodiment 21 and the corona treatment mode of embodiment 1,0.2g is weighed
Above-mentioned FeCuNi-CeO2Catalyst, to 20mL brine degradation 30min, TOC value is 23ppm, and organic phosphorus degrading rate is after processing
The removal rate of 88%, COD reach 52%, and total tp removal rate is 85%, nitrogen removal rate 86%.
Embodiment 23
Referring to the alloy catalyst preparation method of embodiment 21 and the corona treatment mode of embodiment 1,0.2g is weighed
Above-mentioned FeCuNi-CeO2Catalyst, (since mother liquor organic phosphorous content is very high, in a short time to 20mL mother liquor degradation 30min
Degradation rate is limited, and since the method for the unsuitable biology of high salinity is degraded), TOC value is 5314ppm, organic phosphorus drop after processing
Solution rate is that the removal rate of 53%, COD reaches 10%, and total tp removal rate is 43%, nitrogen removal rate 45%.
Embodiment 24
Referring to the alloy catalyst preparation method of embodiment 21 and the corona treatment mode of embodiment 1,0.2g is weighed
Above-mentioned FeCuNi-CeO2Catalyst, to 20mL mother liquor degradation 80min, TOC value is 2300ppm, and organic phosphorus degrading rate is after processing
The removal rate of 77%, COD reach 17%, and total tp removal rate is 65%, nitrogen removal rate 73%.
Embodiment 25
Referring to the alloy catalyst preparation method of embodiment 21 and the corona treatment mode of embodiment 1,0.4g is weighed
Above-mentioned FeCuNi-CeO2Catalyst, to 20mL mother liquor degradation 80min, TOC value is 1800ppm, and organic phosphorus degrading rate is after processing
The removal rate of 82%, COD reach 31%, and total tp removal rate is 73%, nitrogen removal rate 77%.
Embodiment 26
Referring to the alloy catalyst preparation method of embodiment 21 and the corona treatment mode of embodiment 1,1.0g is weighed
Above-mentioned FeCuNi-CeO2Catalyst, to 100mL mother liquor degradation 150min, TOC value is 1000ppm, organic phosphorus degrading rate after processing
Reach 70% for the removal rate of 95%, COD, total tp removal rate is 90%, nitrogen removal rate 93%.
Reference examples 1
Referring to the corona treatment mode of embodiment 7, any catalyst is not added, to the degradation of 15mL brine 10min, TOC
Value is 216ppm, and plasma independent role 10min there is no effect, and organic phosphorus after processing, COD, total phosphorus, total nitrogen do not have
There is the sign obviously removed.
Reference examples 2
Referring to the corona treatment mode of embodiment 7, any catalyst is not added, to the degradation of 15mL brine 20min, TOC
Value is 197ppm, the sign that organic phosphorus after processing, COD, total phosphorus, total nitrogen are not obviously removed yet.
Reference examples 3
Referring to the corona treatment mode of embodiment 7, any catalyst is not added, to the degradation of 15mL brine 30min, TOC
Value is 193ppm, the sign that organic phosphorus after processing, COD, total phosphorus, total nitrogen are not obviously removed yet.
Reference examples 4
Referring to the corona treatment mode of embodiment 7, any catalyst is not added, to the degradation of 20mL mother liquor 30min, TOC
Value is 12042ppm, and plasma individually there is no degradation effect to mother liquor effect 30min.
Reference examples 5
Referring to the alloy catalyst preparation method of embodiment 7, corona treatment is not used, it is above-mentioned to weigh 0.2g
FeCuNi-CeO2Catalyst, to 20mL brine degradation 120min, TOC value is 198ppm, organic phosphorus to there is no degradation.
Reference examples 6
Referring to the alloy catalyst preparation method of embodiment 7, corona treatment is not used, it is above-mentioned to weigh 0.2g
FeCuNi-CeO2Catalyst, to 20mL mother liquor degradation 120min, TOC value is 11000ppm, organic phosphorus to there is no degradation.
By above-described embodiment 24-26 it is found that mother can be made by extending the dosage of plasma discharge time and raising catalyst
The degradation rate of liquid improves, industrially can be by pumping by waste water circular treatment, until reaching the standard that can be discharged.
By above-mentioned reference examples 1-4 it is found that individually plasma hardly has high salinity, glyphosate waste water difficult to degrade
There is degradation effect, and have the collaboration of catalyst, for the glyphosate waste water of unknown component under the action of short 30min, TOC can
Reduce by 80% or more.Reference examples 5-6 explanation does not have to corona treatment, only uses catalyst treatment, at normal temperatures and pressures, even if
Catalyst acts on 120min to brine or mother liquor, organic phosphorus also not degrade substantially.It can illustrate individually from reference examples 1-6
Plasma or catalyst and liquid to be processed act on, and are unable to degrading organic phosphor waste water.And catalytic wet oxidation is used alone
Method (high temperature and pressure) has no idea to make the phosphorus-containing matter in brine further to degrade.In conjunction with the embodiment of front, illustrate this hair
Bright embodiment plasma and catalyst have synergistic effect in processing glyphosate waste water, and are not required to high temperature and pressure, energy
It is enough that good degradation effect is generated to glyphosate waste water, efficiently remove the pollutant components such as TOC, organic phosphorus, COD, total phosphorus, total nitrogen.
In conclusion the invention discloses a kind of method of low-temperature plasma synergistic catalyst degradation glyphosate waste water,
It is to mix non-noble metal alloys catalysts with waste water to be processed, is subsequently placed under plasma discharge channels, utilizes plasma
The high energy electron that body generates, is adequately ionized organic molecule, hydrone, oxygen molecule etc., to inspire the work of higher energy
Property particle, with catalyst act synergistically, the high salinity of efficient degradation glyphosate waste water difficult to degrade.
The present invention is formed between plasma for the characteristic of glyphosate waste water by the design to catalytic component
Good synergistic effect realizes that glyphosate waste water carries out efficient degradation at normal temperatures and pressures, the method for the present invention novel and unique, simply
Efficiently, break through the prior art can not degradation of glyphosate waste water limitation, in terms of handle glyphosate waste water treatment process simply, institute
It takes time short, high-efficient, there is fabulous application prospect.
Catalyst that the present invention uses itself is easy preparation, cheap, will not give a large amount of organic pollutants of industrial treatment
Biggish financial burden is caused, and binding plasma has preferable degradation effect to glyphosate waste water.
The present invention solves glyphosate waste water biodegrading process complex steps in the prior art and needs a large amount of chemical reagent, instead
The deficiencies of answering condition to be also required to high temperature, high pressure proposes a kind of side of low-temperature plasma synergistic catalyst degradation glyphosate waste water
Method, substantially increases the removal efficiency of glyphosate waste water, and has many advantages, such as persistently, easily and fast.
The method of the present invention can generate the Filamentous streamer-discahrge of continuous uniform under the conditions of lower-wattage, avoid electrode and give up
The direct contact of water, is corroded to prevent electrode by high salinity waste water, extends the service life of electrode.Meanwhile present invention selection is inexpensive
The transition metal and carrier being easy to get substantially increase plasma processing efficiency as catalyst, reduce power consumption expense, reduce
Cost for wastewater treatment.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of transition metal alloy catalyst composite, comprising the following steps:
Transition metal salt is mixed in a solvent with carrier, it is dry after in the mixed gas of inert gas and hydrogen 350~
Baking mixes under the conditions of 550 DEG C；Obtain transition metal alloy catalyst；
The carrier is selected from active carbon, azepine carbon, aluminium oxide, titanium dioxide, silica, molecular sieve ZMS-5, rare earth oxide
At least one of.
2. the method according to claim 1, wherein the rare earth oxide is selected from CeO2、ZrO2In at least one
Kind.
3. the method according to claim 1, wherein the quality of the transistion metal compound is the 5% of carrier
~30%；The transistion metal compound is selected from least one of molysite, cobalt salt, mantoquita, nickel salt；The transition metal compound
Anion in object is selected from Cl-、NO3-、SO4 2-Or C2H3O2 -At least one of.
4. the method according to claim 1, wherein the solvent is water；The body of the inert gas and hydrogen
Product is than being 93~97:3~7；The calcining time is 1~5h.
5. transition metal alloy catalyst composite is prepared in any one of Claims 1 to 4 the method.
6. a kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water, which is characterized in that will be described in claim 5
Transition metal alloy catalyst composite mixed with glyphosate waste water, then plasma-treated carry out degradation reaction.
7. according to the method described in claim 6, it is characterized in that, the degradation reaction time be 10min~200min, it is described
The discharge temp of plasma is 20~80 DEG C；Plasma discharge power density is 1~500W/cm3。
8. according to the method described in claim 6, it is characterized in that, the glyphosate waste water is what glyphosate production workshop generated
Waste liquid is denoted as mother liquor；Or the brine for being difficult to degrade obtained later for mother liquor by catalytic wet oxidation.
9. according to the method described in claim 8, it is characterized in that, the concrete operations of the catalytic wet oxidation be by mother liquor with
2~6h is reacted in catalyst mixing under the conditions of 150~260 DEG C, 2~8MPa, and the liquid obtained after reaction is brine；Institute
Stating catalyst includes transition metal alloy catalyst composite described in claim 5.
10. method according to claim 8 or claim 9, which is characterized in that the mother liquor TOC value is 10000~10200ppm,
COD is 59000~61000ppm, and total phosphorus content is 24000~26000ppm, and total nitrogen content is 4500~5500ppm, and NaCl contains
Amount is 14~19%.
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| PCT/CN2019/121560 WO2020134834A1 (en) | 2018-12-29 | 2019-11-28 | Method for degrading glyphosate wastewater by synergy of low-temperature plasma and catalyst |
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| 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 |
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| 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 |
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