CN103058346B - Wastewater treatment method - Google Patents
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- CN103058346B CN103058346B CN201110317181.7A CN201110317181A CN103058346B CN 103058346 B CN103058346 B CN 103058346B CN 201110317181 A CN201110317181 A CN 201110317181A CN 103058346 B CN103058346 B CN 103058346B
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Abstract
The invention provides a wastewater treatment method. Specifically, the method includes: under the effect of a magnetic field, suspending magnetic catalyst particles in wastewater, and conducting a mixing treatment on the wastewater, the magnetic catalyst and an oxidant so as to make the B/C of the treated wastewater larger than equal to 0.3. The wastewater treatment method provided by the invention make the magnetic catalyst particles suspended in the wastewater in the presence of an external magnetic field, and performs catalytic oxidation treatment on the wastewater. With the method, the wastewater treatment effect can be improved significantly, the wastewater treatment effect is stable, and the biodegradability of wastewater can be effectively enhanced.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste water.
Background technology
For a long time, the processing of the organic wastewater with difficult degradation thereby in environment is the difficult point in water technology always, is also the important problem of puzzlement countries in the world environment circle.
In recent years, the research of catalyzed oxidation technical finesse organic wastewater with difficult degradation thereby has obtained significant progress.The mechanism of catalyzed oxidation technology is to be combined with oxygenant with catalyzer, produces active extremely strong free radical (as hydroxyl radical free radical) in reaction; By the adduction between free radical and organic compound, replacement, transfer transport, scission of link etc., make the macromole hardly degraded organic substance oxidative degradation in water body become to be easy to biodegradable small-molecule substance again, be even directly degraded into CO
2and H
2o, approaches permineralization.Form catalyzed oxidation technology by catalyzer in reaction is divided into again homogeneous catalysis oxidation and two kinds of heterogeneous catalytic oxidations.Heterogeneous catalytic oxidation technology is simple to operate owing to having, adaptation pH value a wider range, more carrys out approximately to have obtained everybody attention without frequent more catalyst changeout etc.
For example: CN201077792Y discloses a kind of ozone heterogenous catalysis oxygenize water treating device, this treatment unit comprises ozone generation system, mixing wastewater with air system, heterogeneous catalytic oxidation post; Heterogeneous catalytic oxidation post is airtight cavity, lower end is provided with mixing wastewater with air layer, waste water jet orifice gos deep in mixing wastewater with air layer, mixing wastewater with air layer upper end is provided with support water distribution board, heterogeneous catalytic oxidation packing layer, water outlet filter plate, effluent weir and closure fange successively, is provided with exhaust port above closure fange.This device adopts Venturi tube to absorb ozone and ensures air water high-speed mixing, then increases the solubleness of ozone in waste water by waste water jet orifice, ensures the efficient treatment effect of ozone.This apparatus structure is simple, and can improve the oxidation efficiency of ozone, effectively reduces working cost.But, the still not ideal enough height of processing efficiency that adopts this device to carry out wastewater treatment, and the replacing of catalyzer trouble.
CN1872730A discloses a kind of technique of coking wastewater deep treatment, this technology utilization solid catalyst and the secondary oxidizer that does not produce secondary pollution carry out advanced treatment to coking chemical waste water, the preparation method of described solid catalyst be by taking out after support of the catalyst aluminium sesquioxide steeping fluid cupric nitrate dipping, dry, roasting is for subsequent use; Coking chemical waste water, after equalizing tank homogeneous, is carried out to catalytic oxidation with sump pump in the water-in fastener driving device on catalyzer adsorption column top, purify after up to standard and discharged by catalyzer adsorption column water outlet, water outlet bottom is susceptor; Homogeneous pH value of sewage water is 3-7, oxygenant H
2o
2dosage 0.1-0.5ml/100ml waste water, reaction times 45-90 minute.
But, the shortcoming such as prior art remains at treatment effect not high, catalyst change trouble, thus be necessary to develop more effectively, method is processed waste water more easily.
Summary of the invention
The treatment effect that the object of the invention is to the waste water that overcomes prior art is not good, treatment effect is unstable, and the defect of the replacing of catalyzer trouble and a kind of can be effectively also stable waste water be processed is provided, and can effectively improve the method for the biodegradability of waste water.
To achieve these goals, the invention provides a kind for the treatment of process of waste water, wherein, the method is included under the effect in magnetic field, magnetic tool granules of catalyst is suspended in waste water, and waste water and the magnetic catalyzer of tool and oxygenant are carried out to combination treatment, the B/C that makes waste water after treatment is >=0.3.
The present inventor finds, under the effect of externally-applied magnetic field, the magnetic granules of catalyst of tool is suspended in waste water, and make waste water and the magnetic catalyzer of tool and oxygenant carry out combination treatment, and waste water is carried out to catalytic oxidation treatment, can significantly improve the treatment effect of waste water, also be, treatment effect to waste water is better, more stable, and can effectively improve the biodegradability of waste water; Moreover described method can avoid catalyst change trouble and the granules of catalyst can be with problems such as water outlet losses well, and method is more simple.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below will be elaborated to the specific embodiment of the present invention.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the treatment process of described waste water is included under the effect in magnetic field, magnetic tool granules of catalyst is suspended in waste water, and waste water and the magnetic catalyzer of tool and oxygenant are carried out to combination treatment, the B/C that makes waste water after treatment is >=0.3.
According to the present invention, under the effect in magnetic field, magnetic tool granules of catalyst is suspended in waste water, make waste water carry out catalyzed oxidation with oxygenant and catalyzer, waste water is carried out in the process of catalyzed oxidation, the size in described magnetic field can ensure to make the magnetic granules of catalyst of tool to be suspended in waste water, and it is fully contacted with waste water, as long as and the B/C that the condition of described combination treatment can ensure to make processed waste water for >=0.3(, improve the value of the B/C of waste water).
According to the present invention, the selectable range of the magneticstrength in described magnetic field is wider, as long as can make the magnetic granules of catalyst of tool be suspended in waste water, under preferable case, described magneticstrength can be 10-2000 oersted, and more preferably, in situation, described magneticstrength is 100-1000 oersted.In the present invention, described magnetic field can be various magnetic field, the magnetic field producing as electromagnetic field and/or magneticsubstance etc.The producing method in described magnetic field can adopt and well known to a person skilled in the art that ordinary method produces magnetic field.For example, can be wound around conspicuous nurse hertz coil at the outer wall of reactor, make itself and reactor coaxial, and in coil, pass into certain electric current, so that even, stable externally-applied magnetic field to be provided.Wherein, the spacing between the winding number of turns, the coil of coil and the size that passes into the electric current in coil can suitably be adjusted, as long as guarantee to make the magneticstrength that produces to be enough to meet, the magnetic granules of catalyst of tool are suspended in waste water.
According to the present invention, the particle diameter of the magnetic granules of catalyst of described tool can suspend in water and fully contact with waste water as long as can meet, under preferable case, the particle diameter of the magnetic granules of catalyst of described tool can be 0.1-2000 micron, more preferably in situation, the particle diameter of the magnetic granules of catalyst of described tool is 2-1000 micron, and further, under preferable case, the particle diameter of the magnetic granules of catalyst of described tool is 50-300 micron.The selectable range of the kind of the magnetic catalyzer of described tool is wider, thereby and can be for various tools are magnetic and can play the oxidation generation oxidisability stronger free radical of catalytic oxidant to waste water, as the catalyzer of hydroxyl radical free radical.Under preferable case, at least one in the magnetic catalyzer chosen from Fe of described tool, cobalt, nickel, their insoluble hydroxide of metal and their insoluble metal salt; Or at least one in chosen from Fe, cobalt, nickel, their metal oxide, their insoluble hydroxide of metal and their insoluble metal salt and at least one the mixture being selected from manganese, copper, zinc, titanium, silver, aluminium, their metal oxide, their insoluble hydroxide of metal and their insoluble metal salt.Wherein, insoluble hydroxide of metal recited above solubleness in water at a normal atmosphere, 20 DEG C is less than 0.1g/100cm
3; Insoluble metal salt recited above solubleness in water at a normal atmosphere, 20 DEG C is less than 0.1g/100cm
3; Specifically, described insoluble hydroxide of metal can be selected from ferrous hydroxide, ironic hydroxide, aluminium hydroxide and manganous hydroxide (Mn (OH)
2) in one or more; Described insoluble metal salt can be selected from one or more in Iron sulfuret, iron protocarbonate, cupric sulfide, cuprous sulfide, cobaltinitrite, nickelous carbonate, manganous carbonate, zinc carbonate, zinc sulphide and silver chloride.In addition, the magnetic granules of catalyst of described tool can be commercially available, or also can adopt the method for well known to a person skilled in the art to prepare.
In the present invention, described oxygenant can be oxidized the impurity such as the organism in water, and therefore, the oxygenizement of described oxygenant can be decomposed into larger molecular organics the biodegradability of small organic molecule raising waste water.Wherein, the magnetic granules of catalyst of described tool can be under the effect in magnetic field, and further catalytic oxidant produces the stronger free radical of oxidisability, and for example, hydroxyl radical free radical, thereby oxidation that can more effective accelerating oxidation agent, further improve the biodegradability of waste water.
According to the present invention, described oxygenant can be the conventional various oxygenants that the organism in water etc. can be oxidized in this area, under preferable case, described oxygenant can be selected from one or more in hydrogen peroxide (mass percent concentration of hydrogen peroxide can be 27.5%-50% conventionally), ozone, persulphate, hypochlorite, dioxide peroxide and chlorine, more preferably hydrogen peroxide.
According to the present invention, as long as the consumption of the method for described combination treatment, condition and oxygenant and the magnetic catalyzer of tool can meet B/C >=0.3 that makes the waste water after treatment obtaining.Therefore, the selectable range of the amount of described oxygenant and the magnetic catalyzer of tool is wider, and can suitably regulate according to the COD value of waste water, as long as can play the abundant oxygenolysis of the impurity such as bacterium and organism and oily substance making in waste water, and meet the requirement of the B/C of processed waste water.Under preferable case, in described oxygenant and waste water, organic mass ratio is 0.01-10:1; More preferably in situation, in described oxygenant and waste water, organic mass ratio is 0.1-5:1, and under most preferred case, in described oxygenant and waste water, organic mass ratio is 0.1-2:1.
In order to be more beneficial to the abundant contact reacts of waste water and oxygenant and the magnetic granules of catalyst of tool, and considering cost and effect, under preferable case, the method of described combination treatment comprises: under the effect of externally-applied magnetic field, by waste water and the continuous magnetic granules of catalyst contact reacts of tool with suspending of oxygenant.The described catalytic time is not particularly limited, as long as can fully make the magnetic granules of catalyst of waste water and tool contact the requirement the catalytic organism in waste water is oxidized to the B/C value that meets waste water.Wherein, can suitably select according to the difference of the water quality of pending waste water the consumption of the magnetic granules of catalyst of tool and oxygenant; The selectable range of the residence time of described waste water is wider, also can carry out suitable adjusting according to the big or small difference of the consumption of the water quality of waste water, the magnetic granules of catalyst of tool and oxygenant and device, under preferable case, the residence time (reaction times in reactor) of described waste water can be 2-600 minute, further under preferable case, the residence time of described waste water is 5-300 minute, more preferably 10-180 minute.In hour the residence time be equivalent to the inverse of liquid hourly space velocity (volume of the magnetic granules of catalyst of unit volume tool processing waste water per hour), therefore, the liquid hourly space velocity that is equivalent to described waste water can be 0.1-50h
-1, more preferably 0.5-10h
-1, most preferably be 2-8h
-1.In addition, the magnetic catalyzer of described tool can account for the 40-95% of reactor volume conventionally; Under preferable case, the magnetic catalyzer of described tool accounts for the 60-85% of reactor volume.
In the present invention, in described waste water, organic quality can represent with the chemical oxygen demand (COD) of waste water (COD), COD refers under certain conditions, while adopting certain strong oxidizer to process water sample, the oxidant content consuming, it is an index that represents that reducing substances in water (being mainly organism) is how many.Can be understood as so, the waste water that is 1mg/L corresponding to COD value, the consumption of oxygenant is 0.01-10mg, is preferably 0.1-5mg, more preferably 0.1-2mg.
According to the preferred embodiment of one of the present invention, the mode that makes the magnetic catalyzer of waste water and tool and oxygenant carry out combination treatment is: under the effect of externally-applied magnetic field, magnetic tool granules of catalyst is suspended in in reactor, (described reactor is made up of the good material of magnetic permeability, for example, stainless material), pending waste water and oxygenant are passed into from reactor bottom to (waste water and oxygenant can pass into respectively, also after can mixing, pass into), gradually with the magnetic granules of catalyst contact reacts of tool suspending, and from the top of reactor, waste water after treatment is discharged.
According to the present invention, the condition of described combination treatment generally also comprises temperature, pressure and time, and the present invention is all not particularly limited temperature, pressure and the time to combination treatment, for example, described treatment temp can be normal temperature conventionally, for example, and 0-99 DEG C, pressure can be 0-0.03MPa conventionally, is preferably normal pressure (0-0.01MPa).As long as the treatment time can ensure to make the B/C value of waste water to reach requirement.
According to the present invention, in order to make the treatment effect of waste water better, the pH value of the waste water of described pending processing can be 1-9, more preferably 2-7 conventionally.The method of described adjusting waste water ph can be the method for this area routine, for example, adds acid or alkali to regulate, and the concentration of acid or alkali and consumption can be adjusted according to actual needs, as long as ensure the pH value of waste water to be adjusted to 1-9, is preferably 2-7.
According to the present invention, described waste water can be various waste water, for example, printing and dyeing class waste water, paper waste, pharmacy waste water and petrochemical industry waste water etc., under normal circumstances, the B/C of the described waste water of described waste water is < 0.3mg/L, for example, for more unmanageable waste water, its B/C can be 0-0.25mg/L; The COD value of described pending waste water is generally and is greater than 60mg/L, and for example, COD value can be 200-1000mg/L.
The present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
To be further described in detail embodiments of the invention below.
In following embodiment, the measuring method of the COD of waste water is dichromate titration (GB11914-89), and the measuring method of the BOD of waste water is dilution inoculation method (GB/T7488-1987).
The volume for cylindrical reactor, reactor of the magnetically stabilized bed reactor adopting in following embodiment is 2L, and the material of reactor adopts 316L stainless steel, has 5 coils in reactor outside, the number of turn 350 circles of each coil, and the spacing of coil is 30mm.
Embodiment 1
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
The waste water of the present embodiment processing is the high-concentration waste water of certain refinery.
The pH value of above-mentioned pending waste water is adjusted to 6 with aqueous sulfuric acid (mass percent concentration is 98%), described waste water and oxidant hydrogen peroxide (mass percent concentration is 30%) (hydrogen peroxide consumption is 400mg/L) are stablized to reactor bottom from the magnetic of ferriferrous oxide particles (particle diameter is 120 microns) is housed introduces that (reactor, the loadings of ferriferrous oxide particles is reactor volume 65% continuously, the residence time of waste water is 20 minutes), pass into electric current to being wrapped in the coil of described reactor periphery, the magneticstrength that makes additional electromagnetic field is 300 oersteds, described ferriferrous oxide particles is suspended in waste water, and waste water after treatment is drawn from described reactor head, obtain waste water after treatment.Waste water quality index before and after processing is as shown in table 1.
Comparative example 1
This comparative example is for illustrating the reference method of wastewater treatment.
Process waste water according to the method for embodiment 1, different, do not pass into electric current (there is no additional electromagnetic field) to reactor, directly waste water and described oxygenant are passed in the reactor that ferriferrous oxide particles is housed.Waste water quality index before and after processing is as shown in table 1.
Table 1
| Waste water quality index | COD（mg/L） | BOD（mg/L） | B/C |
| Before processing | 860 | 23 | 0.03 |
| Comparative example 1 | 480 | 28 | 0.06 |
| Embodiment 1 | 108 | 33 | 0.31 |
From the results shown in Table 1, method of the present invention can significantly improve the ratio of the B/C of processed waste water, adopt the B/C of method of the present invention waste water after treatment to reach 0.31, and the B/C of comparative example 1 is only 0.06, the biodegradability that processed waste water is described significantly improves, and treatment effect is stable, in addition, the COD value of processed waste water also significantly reduces.
Embodiment 2
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
The waste water of the present embodiment processing is certain chemical plant wastewater.
The magnetic granules of catalyst preparation method of tool who adopts in the present embodiment is as follows: after the titanium dioxide (diameier is 2-10 micron) of the cupric oxide (diameier is 2-10 micron) of 70 % by weight iron powders (diameier is 2-10 micron), 25 % by weight and 5 % by weight is mixed, within 2 hours, obtaining particle diameter at 500 DEG C of sintering is the granules of catalyst of 150 microns.
The pH value of above-mentioned pending waste water is adjusted to 6 with aqueous sulfuric acid (mass percent concentration is 98%), described waste water and oxidant hydrogen peroxide (mass percent concentration is 30%) (hydrogen peroxide consumption is 400mg/L) are introduced continuously from the bottom of the described magnetically stabilized bed reactor that above-mentioned granules of catalyst is housed to (granules of catalyst loadings is reactor volume 70%, the residence time of waste water is 15 minutes), pass into electric current to being wrapped in the coil of described reactor periphery, the magneticstrength that makes additional electromagnetic field is 500 oersteds, described granules of catalyst is suspended in waste water, and waste water after treatment is drawn from described reactor head, obtain waste water after treatment.Waste water quality index before and after processing is as shown in table 2.
Comparative example 2
This comparative example is for illustrating the reference method of wastewater treatment.
Process waste water according to the method for embodiment 1, different, do not pass into electric current (there is no additional electromagnetic field) to reactor, directly waste water and described oxygenant are passed in the reactor that granules of catalyst described in embodiment 2 is housed.Waste water quality index before and after processing is as shown in table 2.
Table 2
| Waste water quality index | COD（mg/L） | BOD（mg/L） | B/C |
| Before processing | 780 | 15 | 0.02 |
| Comparative example 2 | 360 | 24 | 0.07 |
| Embodiment 2 | 86 | 28 | 0.33 |
From the results shown in Table 2, method of the present invention can significantly improve the ratio of the B/C of processed waste water, adopt the B/C of method of the present invention waste water after treatment to reach 0.33, and the B/C of comparative example 1 is only 0.07, the biodegradability that processed waste water is described significantly improves, and treatment effect is stable, in addition, the COD value of processed waste water also significantly reduces.
Embodiment 3
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different, the magneticstrength of additional electromagnetic field is 800 oersteds; The COD value of processed waste water is 98mg/L, and BOD value is 33mg/L, and B/C is 0.34.
Embodiment 4
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different, the loadings of the magnetic granules of catalyst of tool is reactor volume 75%.The COD value of processed waste water is 100mg/L, and BOD value is 33mg/L, and B/C is 0.33.
Embodiment 5
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different, the residence time of waste water is 50 minutes.The COD value of processed waste water is 105mg/L, and BOD value is 35mg/L, and B/C is 0.33.
Embodiment 6
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different, adopt Sodium Persulfate as oxygenant, oxygenant dosage is 1200mg/L, and the COD value of processed waste water is 112mg/L, and BOD value is 36mg/L, and B/C is 0.32.
Embodiment 7
The present embodiment is for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different, the magnetic granules of catalyst preparation method of tool who adopts in the present embodiment is as follows: after the ironic hydroxide powder (diameier is 5-10 micron) of the nickel oxide (diameier is 5-10 micron) of the cobalt oxide powder of 40 % by weight (diameier is 5-10 micron), 35 % by weight and 25 % by weight is mixed, within 2 hours, obtaining particle diameter at 550 DEG C of sintering is the granules of catalyst of 200 microns.The residence time of waste water is 180 minutes, and the COD value of processed waste water is 85mg/L, and BOD value is 35mg/L, and B/C is 0.41.
BOD/COD accounts for whole organic shares than biodegradable organism in value representation waste water, and the biodegradable degree of this waste water.Can find out from the result of embodiment 1 to embodiment 7, adopt method of the present invention can significantly improve the ratio of the B/C of processed waste water, thereby can illustrate, adopt the biodegradability of method of the present invention waste water after treatment to be significantly improved, and the treatment effect of waste water be more stable.
Claims (2)
1. the treatment process of a waste water, it is characterized in that, the method is included under the effect in magnetic field, magnetic tool granules of catalyst is suspended in waste water, and waste water and the magnetic catalyzer of tool and oxygenant are carried out to combination treatment, the B/C that makes waste water after treatment is >=0.3, and the magneticstrength in described magnetic field is 100-1000 oersted;
Wherein, the particle diameter of the magnetic catalyzer of described tool is 50-300 micron;
Wherein, the condition of described combination treatment comprises: in oxygenant and waste water, organic mass ratio is 0.1-5:1;
Wherein, the method for described combination treatment comprises: waste water and oxygenant are passed into magnetically stabilized bed reactor and contact with the magnetic granules of catalyst of tool suspending continuously, the residence time of described waste water is 10-180 minute;
Wherein, the magnetic catalyzer of described tool accounts for the 40-95% of reactor volume;
Wherein, at least one in the magnetic catalyzer chosen from Fe of described tool, cobalt, nickel, their metal oxide, their insoluble hydroxide of metal and their insoluble metal salt; Or at least one in chosen from Fe, cobalt, nickel, their metal oxide, their insoluble hydroxide of metal and their insoluble metal salt and at least one the mixture being selected from manganese, copper, zinc, titanium, silver, aluminium, their metal oxide, their insoluble hydroxide of metal and their insoluble metal salt;
Wherein, described oxygenant is selected from one or more in hydrogen peroxide, ozone, persulphate, hypochlorite, dioxide peroxide and chlorine;
Wherein, the pH value of the waste water of pending processing is 6-9.
2. method according to claim 1, wherein, the magnetic catalyzer of described tool is that the particle diameter that obtains for 2 hours at 550 DEG C of sintering after the ironic hydroxide powder of the nickel oxide of the cobalt oxide powder of 40 % by weight, 35 % by weight and 25 % by weight is mixed is the granules of catalyst of 200 microns.
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| CN103449562A (en) * | 2013-09-03 | 2013-12-18 | 辽宁科技大学 | Method and device for photocatalytic degradation of organic pollutants in wastewater |
| CN103896388B (en) * | 2014-03-26 | 2016-07-06 | 华南理工大学 | A kind of method utilizing the heterogeneous organic wastewater treatment through persulfate activation of dual catalyst |
| CN103936135B (en) * | 2014-05-07 | 2015-10-28 | 东华大学 | A kind of method of marmatite catalysis hydrogen peroxide oxidation process trade effluent |
| CN104743654A (en) * | 2015-04-17 | 2015-07-01 | 南开大学 | Method for efficient treatment of organic wastewater by virtue of pre-magnetized FeO/H2O2 system |
| CN104876306A (en) * | 2015-05-11 | 2015-09-02 | 河海大学 | Method for treating sewage employing magnetic field |
| CN105253983A (en) * | 2015-09-30 | 2016-01-20 | 中山大学 | Water treatment method of zero-valent iron-copper bi-metal activated persulfate |
| CN105731629A (en) * | 2016-02-19 | 2016-07-06 | 博天环境集团股份有限公司 | Catalytic oxidation treatment method of reverse-osmosis strong brine |
| CN109081420A (en) * | 2018-08-06 | 2018-12-25 | 河北科技大学 | A kind of method of ozone cooperative persulfate catalytic oxidation treatment waste water |
| CN109592773A (en) * | 2018-12-12 | 2019-04-09 | 天津大学 | A method of degradation water body glyphosate |
| CN114477600A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for treating phosphorus-containing wastewater |
| CN112979039A (en) * | 2021-02-24 | 2021-06-18 | 北京启元汇通水务科技股份有限公司 | Industrial wastewater deep oxidation treatment system and treatment method |
| CN115677088A (en) * | 2022-10-08 | 2023-02-03 | 广东邦普循环科技有限公司 | Treatment method of phosphorus removal resin regeneration waste liquid |
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