CN109912001B - Persulfate activator and preparation method and application thereof - Google Patents
Persulfate activator and preparation method and application thereof Download PDFInfo
- Publication number
- CN109912001B CN109912001B CN201711327201.2A CN201711327201A CN109912001B CN 109912001 B CN109912001 B CN 109912001B CN 201711327201 A CN201711327201 A CN 201711327201A CN 109912001 B CN109912001 B CN 109912001B
- Authority
- CN
- China
- Prior art keywords
- persulfate
- activator
- tetracycline
- nickel
- degradation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a persulfate activator, a preparation method and application thereof, wherein the persulfate activator is NixFe3‑ xO4Wherein x is 0.2 to 0.8. The preparation method comprises the following steps: and calcining the slurry obtained by mixing the nickel source, the iron source, the polyvinyl alcohol and the water to obtain the persulfate activator. The persulfate activator is used for activating persulfate to oxidize and degrade tetracycline, so that the defects that in the prior art, the application pH range of the wastewater for removing antibiotics is narrow, the removal efficiency is low and the like in the process of activating persulfate can be overcome, and the persulfate activator also has the advantages of stable catalytic performance, good activation effect, strong corrosion resistance, environmental friendliness, recyclability and the like.
Description
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a persulfate activator as well as a preparation method and application thereof.
Background
The advanced oxidation technology is a novel technology which is newly developed in recent years and is used for treating refractory organic pollutants, has the advantages of short period, quick response, low cost, good treatment effect and the like, and becomes a hotspot and frontier of the research in the field of domestic and foreign medical wastewater treatment. Especially, compared with the traditional advanced oxidation technology such as Fenton method, the persulfate-activated advanced oxidation technology has the advantages of strong stability, good solubility, wide applicable pH range, long service life of generated sulfate radical and the like, and is more favorable for degrading high-concentration organic pollutants.
Under the condition of normal temperature, the persulfate is relatively stable, and can generate sulfate radicals and hydroxyl radicals with strong oxidizing property after being activated by heating, chelating or non-chelating transition metal ions, light, alkali, activated carbon and other activation modes, so that target pollutants can be efficiently and quickly removed. The thermal persulfate activation technology has high energy consumption, the optical persulfate activation technology is harsh to operating conditions, the alkali persulfate activation technology can cause overhigh pH value in water, and the utilization rate of the activated carbon persulfate activation technology to activated carbon is not high. Compared with other activation modes, the transition metal ion activation has low requirements on equipment, low energy consumption and simple and convenient operation, the ferrous ion in the transition metal ions is widely used for activating the persulfate at present, but certain disadvantages exist in the ferrous ion activation, the ferrous ion is stable, an acidic condition is needed, the requirement on pH is high, and the ferrous ion can compete with pollutants for sulfate radicals when excessive, so that the oxidation capability of the persulfate is limited. Therefore, there is a need to develop a technology for stably and efficiently removing contaminants from medical wastewater.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of narrow pH application range, low removal efficiency and the like of the prior art for removing the antibiotic wastewater by using the ferrous salt activated persulfate, providing a persulfate activator which has stable catalytic performance, good activation effect, strong corrosion resistance, environmental protection and can be recycled, correspondingly providing a preparation method of the persulfate activator which has simple process, low cost and environmental protection, and correspondingly providing the application of the persulfate activator in the oxidative degradation of tetracycline by using the persulfate, and having the advantages of wide pH application range, high degradation efficiency, convenient operation and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a persulfate activator which is NixFe3-xO4Wherein x is 0.2 to 0.8.
The persulfate activator as described above, preferably, the NixFe3-xO4Is Ni0.2Fe2.8O4、Ni0.4Fe2.6O4、Ni0.6Fe2.4O4、Ni0.8Fe2.2O4One or more of (a).
As a general inventive concept, the present invention also provides a method for preparing the persulfate activator described above, comprising the steps of:
mixing and grinding a nickel source, an iron source and polyvinyl alcohol, adding water, uniformly mixing, and calcining the obtained slurry to obtain the persulfate activator.
In the preparation method of the persulfate activator, preferably, the molar ratio of nickel in the nickel source to iron in the iron source is 0.2-0.8: 2.2-2.8.
In the preparation method of the persulfate activator, preferably, the nickel source is one or more of nickel nitrate, nickel sulfate and nickel acetate, and the iron source is one or more of ferric nitrate, ferric sulfate and ferric chloride.
In the preparation method of the persulfate activator, preferably, the dosage of the polyvinyl alcohol is 0.5-1.5 of the total mass of the nickel source and the iron source.
In the preparation method of the persulfate activator, preferably, the calcining temperature is 400-600 ℃ and the calcining time is 20-40 min.
As a general inventive concept, the invention also provides the application of the persulfate activator or the persulfate activator prepared by the preparation method in oxidative degradation of tetracycline by persulfate, which is characterized in that the persulfate activator is used for activating persulfate so as to accelerate degradation of tetracycline by persulfate.
The above application, preferably, comprises the following steps: and adding the persulfate activator into tetracycline wastewater with the pH value of 3-9, stirring under a dark condition for adsorption reaction, and after adsorption balance is achieved, adding persulfate for activation reaction and degradation reaction to complete degradation of tetracycline.
In the application, preferably, the concentration of the tetracycline in the tetracycline waste water is 10-50 mg/L; the addition amount of the persulfate activator is 100-500 mg/L; the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the addition amount of the persulfate is 5.0-180.0 mu M.
The persulfate activator of the invention is NixFe3-xO4(x is 0.2-0.8), the persulfate is activated, and the principle that the persulfate can accelerate the degradation of tetracycline is as follows: in the oxidation reaction system, Ni2+And Fe2+Is NixFe3-xO4Main activation center of (2), Ni2+And Fe2+The persulfate can be converted into a sulfate radical having a strong oxidizing property, and at the same time, the sulfate radical can be further converted into a hydroxyl radical. The sulfate radicals and the sulfate radicals are mutually excited to form mutual excitation chain reaction of the radicals, so that a system with stronger oxidizing capability is formed, and the degradation efficiency of pollutants is improved. In addition, during the reaction, the persulfate can react with water to generate HSO5 -. By and HSO5 -Reaction of Ni3+With Fe3+Is reduced to Ni2+And Fe2+And continuously plays a role in the activation of persulfate, further improves the generation amount of free radicals, and realizes the full degradation of antibiotic wastewater. In addition to activation, Fe2+In promoting Ni2+Plays a great role in the restoration of active centers. By Fe2+And Ni3+Can react with Ni3+Is changed back to Ni2+. Due to Ni2+The activation performance of the catalyst is better than that of Fe2+Thus, the restoration of this activity is extremely important for the whole persulfate activation process, greatly improving the activation performance of the activator.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts NixFe3-xO4And (x is 0.2-0.8), compared with a single ferrous activated persulfate method and a Fenton oxidation method, the nickel ferrite activated persulfate technology improves the generation amount of free radicals, improves the utilization rate of an oxidant, and can still ensure a higher removal rate of pollutants in a wider pH range. NiO-Fe with same mole number of iron and nickel2O3In contrast, NixFe3-xO4In addition to providing activation of Ni and Fe, there is also an interaction between the two ions Ni and Fe. By Fe2+And Ni3+Promoting the action of Ni2+The activation effect is recovered, the generation of free radicals is promoted, and the persulfate activation effect and the tetracycline wastewater degradation effect are further improved.
2. The invention prepares Ni by adjusting the atomic ratio of a nickel source and an iron source and adopting a one-step calcination methodxFe3-xO4(x is 0.2-0.8), has the advantages of simple preparation process, easy control, easily obtained raw materials, low cost, less energy consumption, short time consumption and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization.
3. The invention adopts NixFe3-xO4The method for activating persulfate so as to degrade tetracycline in wastewater has the advantages of good activation effect, high oxidation rate, high treatment efficiency, wide application range and the like, and is simple in realization process, low in cost, low in investment and operation cost, green, environment-friendly, easy to popularize and capable of realizing effective degradation of antibiotic wastewater. And the persulfate activator has the advantages of stable catalytic performance, strong corrosion resistance and the like in the using process. Taking tetracycline dye wastewater as an example, after four times of recycling, the persulfate activator still shows high-efficiency activation performance, and the degradation efficiency is still as high as 55% after four times of recycling. Therefore, the persulfate activator disclosed by the invention is a novel catalyst activator with good stability, corrosion resistance and high efficiency, and has a good practical application prospect.
Drawings
FIG. 1 is a graph comparing the time-degradation efficiency of the persulfate activators of example 3 of the present invention and comparative example 1 when activating persulfate to degrade tetracycline waste water.
FIG. 2 shows different amounts of Ni0.6Fe2.4O4A corresponding time-degradation efficiency relation graph when the activated persulfate degrades the tetracycline wastewater.
FIG. 3 is a graph showing the relationship between time and degradation efficiency corresponding to degradation of tetracycline waste water by the same amount of activator added and different amounts of sodium persulfate added.
FIG. 4 shows different reaction pH values for Ni0.6Fe2.4O4A corresponding time-degradation efficiency relation graph when the activated persulfate degrades the tetracycline wastewater.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1:
one persulfate activator of the invention is Ni0.2Fe2.8O4The preparation method comprises the following steps:
(1) 0.2g of nickel nitrate, 1.8g of ferric nitrate and 2.0g of polyvinyl alcohol are weighed and ground in an agate mortar, wherein the molar ratio of nickel in the nickel nitrate to iron in the ferric nitrate is 0.2: 2.8, and the mass ratio of the polyvinyl alcohol to the sum of the nickel nitrate and the ferric nitrate is 1: 1.
(2) Placing the mixture obtained after the uniform grinding in the step (1) into a crucible, pouring 15ml of deionized water, placing the mixture into a muffle furnace for calcining after the uniform mixing, controlling the heating rate of the muffle furnace to be 10 ℃/min, keeping the temperature at 500 ℃ for 30min, and cooling and grinding the calcined product to obtain the Ni of the embodiment0.2Fe2.8O4A persulfate activator.
Example 2:
one persulfate activator of the invention is Ni0.4Fe2.6O4The preparation method comprises the following steps:
the process for preparing the persulfate activator of this example is substantially the same as that of example 1, except that: in the step (1), the molar ratio of nickel in the nickel nitrate to iron in the iron nitrate is 0.4: 2.6, and Ni of the embodiment is obtained after preparation04Fe2.6O4A persulfate activator.
Example 3:
one persulfate activator of the invention is Ni0.6Fe2.4O4The preparation method comprises the following steps:
the process for preparing the persulfate activator of this example is substantially the same as that of example 1, except that: in the step (1), nickel and ferric nitrate in the nickel nitrateThe molar ratio of iron in (1) is 0.6: 2.4, and Ni of this example is obtained after preparation0.6Fe2.4O4A persulfate activator.
Comparative example 1:
NiO-Fe of this comparative example2O3Persulfate activator, 0.5g NiO, 3.8g Fe2O3Uniformly mixing to obtain NiO-Fe of the comparative example2O3A catalyst.
Example 4:
one persulfate activator of the invention is Ni0.8Fe2.2O4The preparation method comprises the following steps:
the process for preparing the persulfate activator of this example is substantially the same as that of example 1, except that: in the step (1), the molar ratio of nickel in the nickel nitrate to iron in the iron nitrate is 0.8: 2.2, and Ni of the embodiment is obtained after preparation0.8Fe2.2O4A persulfate activator.
Example 5:
comparative study of the use of the persulfate activators of example 3 and comparative example 1 for the oxidative degradation of tetracycline by activating persulfate, comprising the following steps:
three groups of tetracycline waste water with the concentration of 20mg/L, the volume of 100mL and the pH value of 7 are prepared, and 30mg of Ni of example 3 is correspondingly added in two groups0.6Fe2.4O4Persulfate activator, NiO-Fe of comparative example 12O3And (3) a persulfate activator is stirred for one hour under the dark condition for adsorption balance, and then 52.5 mu M of sodium persulfate is added into the three groups respectively, so that the tetracycline wastewater is degraded after the reaction is completed.
Determination of degradation efficiency: and (4) respectively sucking 4mL of reaction solution from each reaction solution every 5min, centrifuging for 5min at 7000rpm, sucking supernatant and detecting on an ultraviolet-visible spectrophotometer instrument. FIG. 1 is a graph comparing the time-degradation efficiency of the persulfate activators activated persulfate to degrade tetracycline wastewater according to example 3 of the present invention and comparative example 1, wherein C represents tetracycline after degradationConcentration of (C)0Indicates the initial concentration of tetracycline. The degradation effect after 35 minutes is shown in table 1.
TABLE 1Ni0.6Fe2.4O4、NiO-Fe2O3Influence on the degradation of tetracycline wastewater by activated persulfate
| Activating agent | Blank space | Ni0.6Fe2.4O4 | NiO+Fe2O3 |
| Degradation Rate (%) | 8 | 69 | 53 |
In this example, Ni of the present invention is compared0.6Fe2.4O4Persulfate activator and NiO-Fe with same mole number of iron and nickel2O3The degradation effect of the persulfate activator on the tetracycline wastewater degraded by activated persulfate can be seen from figure 1 and table 1, and NiO-Fe2O3In contrast, Ni0.6Fe2.4O4The catalyst greatly improves the activation effect of persulfate, effectively promotes sodium persulfate to generate sulfate radicals and hydroxyl radicals to oxidize and degrade tetracycline, and obviously improves the degradation effect of tetracycline wastewater.
Example 6:
the application comparison research of the persulfate activator of the invention with different addition amounts in the process of activating persulfate to carry out oxidative degradation on tetracycline comprises the following steps:
200mg/L, 250mg/L, 300mg/L, 350mg/L and 400mg/L of Ni of example 3 are correspondingly added into five tetracycline wastewater with the concentration of 20mg/L, the volume of 100mL and the pH value of 70.6Fe2.4O4Stirring for one hour under dark condition, respectively adding 52.5 mu M sodium persulfate after adsorption balance, and finishing degradation of tetracycline wastewater after complete reaction.
FIG. 2 shows different amounts of Ni0.6Fe2.4O4A corresponding time-degradation efficiency relation graph when the activated persulfate degrades the tetracycline wastewater. The degradation effect after 35 minutes is shown in table 2.
TABLE 2 different addition amounts of Ni0.6Fe2.4O4Influence on the degradation of tetracycline wastewater by activated persulfate
| Concentration of activating agent (mg/L) | 200 | 250 | 300 | 350 | 400 |
| Degradation Rate (%) | 53 | 62 | 69 | 73 | 74 |
As can be seen from FIG. 2 and Table 2, the degradation rate of tetracycline increases significantly as the catalyst concentration increases from 200mg/L to 350mg/L, probably because as the catalyst concentration increases, the active sites available to the catalyst for activating persulfate increase, resulting in more activation of sodium persulfate to sulfate radicals and hydroxyl radicals, which promotes degradation of tetracycline. And 350mg/L and 400mg/L of Ni0.6Fe2.4O4At this concentration, the tetracycline degradation rate hardly changed, indicating that 350mg/L of Ni was present0.6Fe2.4O452.5. mu.M of sodium persulfate had been sufficiently deactivated.
Example 7:
the comparative study on the degradation of tetracycline wastewater by the same addition amount of persulfate activator and different addition amounts of sodium persulfate comprises the following steps:
adding 350mg/L of Ni into five tetracycline wastewater with the concentration of 20mg/L, the volume of 100mL and the pH value of 7 respectively0.6Fe2.4O4And (3) stirring the catalyst for one hour under a dark condition until the adsorption is balanced, correspondingly adding 10.5 mu M, 21.0 mu M, 31.5 mu M, 42.0 mu M and 52.5 mu M of sodium persulfate, and finishing the degradation of the tetracycline wastewater after the reaction is completed.
FIG. 3 is a graph showing the relationship between time and degradation efficiency corresponding to degradation of tetracycline waste water by the same amount of activator added and different amounts of sodium persulfate added. The degradation effect after 35 minutes is shown in table 3.
TABLE 3 results of the effect of different amounts of sodium persulfate added on the degradation of tetracycline waste water
| Sodium persulfate concentration (. mu.M) | 10.5 | 21.0 | 31.5 | 42.0 | 52.5 |
| Degradation Rate (%) | 55 | 58 | 68 | 75 | 73 |
As shown in FIG. 3 and Table 3, as the concentration of sodium persulfate increased, the sulfate radical and hydroxyl radical, which are the activation products of sodium persulfate, increased, resulting in a gradually increasing degradation rate of tetracycline. Whereas, when the sodium persulfate concentration exceeded 42.0. mu.M, the tetracycline degradation rate decreased slightly, probably due to self-scavenging of sulfate radicals and reaction with sodium persulfate, so that 42.0. mu.M was the optimum sodium persulfate concentration.
Example 8:
the research on the influence of different pH values on the degradation of tetracycline wastewater by activating persulfate through the persulfate activator comprises the following steps:
ni with the concentration of 350mg/L is respectively added into four tetracycline waste waters with the concentration of 20mg/L, the volume of 100mL and the pH values of 3, 5, 7 and 9 respectively0.6Fe2.4O4Stirring for one hour under dark condition, adding sodium persulfate with the concentration of 42.0 mu M after adsorption balance, and finishing degradation of tetracycline wastewater after complete reaction.
FIG. 4 shows different reaction pH values for Ni0.6Fe2.4O4A corresponding time-degradation efficiency relation graph when the activated persulfate degrades the tetracycline wastewater. The degradation effect after 35 minutes is shown in table 4.
TABLE 4 results of the influence of different pH values on the degradation of tetracycline waste water by activated persulfate
| |
3 | 5 | 7 | 9 |
| Degradation Rate (%) | 55 | 63 | 75 | 28 |
From the results in Table 4, it is clear that Ni0.6Fe2.4O4The catalyst is more suitable for exerting the activation performance in a neutral tetracycline waste water environment. Acidic condition to Ni0.6Fe2.4O4The catalytic activity of the catalyst is slightly inhibited, and at the same time Ni0.6Fe2.4O4The catalyst is not suitable for strong alkaline conditions which can cause Ni0.6Fe2.4O4The catalyst loses most of its catalytic activity.
In conclusion, the persulfate activator disclosed by the invention has the advantages of excellent activation performance, easiness in recovery, better stability, low price and the like, and therefore, the persulfate activator has better application prospect in tetracycline wastewater treatment.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (3)
1. The application of a persulfate activator in oxidative degradation of tetracycline by persulfate, wherein the persulfate activator is used for activating persulfate so as to accelerate degradation of tetracycline by persulfate, comprises the following steps: adding the persulfate activator into tetracycline wastewater with the pH value of 5-7, stirring under a dark condition for adsorption reaction, and after adsorption balance is achieved, adding persulfate for activation reaction and degradation reaction to complete degradation of tetracycline; the concentration of the tetracycline is 10-50 mg/L; the addition amount of the persulfate activator is 300-500 mg/L; the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the addition amount of the persulfate is 31.5-52.5 mu M;
the persulfate activator is Ni0.6Fe2.4O4(ii) a The preparation method of the persulfate activator comprises the following steps: mixing a nickel source, an iron source and polyvinyl alcohol, grinding, adding water, uniformly mixing, and calcining the obtained slurry to obtain a persulfate activator; the molar ratio of nickel in the nickel source to iron in the iron source is 1: 4; the calcining temperature is 400-600 ℃, and the calcining time is 20-40 min.
2. The use of claim 1, wherein the nickel source is one or more of nickel nitrate, nickel sulfate and nickel acetate and the iron source is one or more of ferric nitrate, ferric sulfate and ferric chloride.
3. The use according to claim 2, wherein the polyvinyl alcohol is used in an amount of 0.5 to 1.5% by mass based on the total mass of the nickel source and the iron source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711327201.2A CN109912001B (en) | 2017-12-13 | 2017-12-13 | Persulfate activator and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711327201.2A CN109912001B (en) | 2017-12-13 | 2017-12-13 | Persulfate activator and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912001A CN109912001A (en) | 2019-06-21 |
| CN109912001B true CN109912001B (en) | 2021-06-25 |
Family
ID=66958580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711327201.2A Active CN109912001B (en) | 2017-12-13 | 2017-12-13 | Persulfate activator and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912001B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923786A (en) * | 2012-11-29 | 2013-02-13 | 江苏技术师范学院 | Method for preparing nano ferrate in fused salt manner |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5053273A (en) * | 1988-10-11 | 1991-10-01 | Mihama Corporation | Magnetic powder coated with a copolymer of polyoxyethylene allyl methyl diether and maleic anhydride |
| CN102151567B (en) * | 2011-02-25 | 2012-08-29 | 哈尔滨工业大学 | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone |
| CN104528876B (en) * | 2015-01-13 | 2016-06-29 | 重庆工业职业技术学院 | High concentration basic organic wastewater ultrasonically catalyzing processing method |
| CN106140173A (en) * | 2015-04-14 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of ferrite/metal oxide materials and its preparation method and application |
| CN105198067A (en) * | 2015-09-30 | 2015-12-30 | 中山大学 | Method for treating water by using zero-valent iron-nickel bi-metal activated persulfate |
-
2017
- 2017-12-13 CN CN201711327201.2A patent/CN109912001B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923786A (en) * | 2012-11-29 | 2013-02-13 | 江苏技术师范学院 | Method for preparing nano ferrate in fused salt manner |
| CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912001A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109908910B (en) | Persulfate composite activator and preparation method and application thereof | |
| CN102259993B (en) | Water treatment method utilizing complex-ferrous-activated persulfate oxidation | |
| CN103896388B (en) | A kind of method utilizing the heterogeneous organic wastewater treatment through persulfate activation of dual catalyst | |
| CN109896598B (en) | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water | |
| CN107311291A (en) | The method of sulfite oxidation degraded organic pollutants is combined using heterogeneous iron-based material under aeration condition | |
| CN105347618A (en) | Biological denitrogenation system for waste water containing high ammonia nitrogen | |
| CN102060379B (en) | Application of immobilized quinone compound in accelerating denitrification process of microorganism | |
| CN103787537B (en) | A kind for the treatment of process of sewage and application thereof | |
| CN110548512B (en) | Preparation method and application of magnetic iron oxide | |
| CN103420480B (en) | A kind of anaerobism molysite biological denitrification process | |
| CN111592090A (en) | Application method of red mud-based heterogeneous Fenton catalyst for advanced wastewater treatment | |
| CN102515329A (en) | Polymeric ferric sulfate and production method thereof | |
| CN110586126A (en) | Catalyst and method for sewage treatment at normal temperature and normal pressure | |
| CN103708651B (en) | A kind for the treatment of process of high chlor-alkali used water difficult to degradate | |
| CN114380384A (en) | Method for purifying water by activating peroxymonosulfate with ferric salt and polyphenol compounds | |
| CN108178370B (en) | Method for breaking nickel-containing complex by persulfate and catalytic ceramsite participating in advanced oxidation | |
| CN109912001B (en) | Persulfate activator and preparation method and application thereof | |
| CN108640249A (en) | A method of sillenite bismuth ferrite catalysis persulfate is modified based on boron, neodymium and goes to remain incretion interferent in water removal | |
| CN111099739B (en) | Method for rapidly recovering activity of anaerobic ammonium oxidation bacteria | |
| CN114011436A (en) | Preparation method and application of three-dimensional composite material catalyst | |
| CN102863071B (en) | Advanced treatment method for decolorizing yeast wastewater | |
| CN103739035A (en) | Rapid microwave treatment method of dye wastewater | |
| CN104529078A (en) | Refuse landfill leachate treatment method | |
| CN110759457A (en) | Method for removing organic pollutants in water based on perovskite oxide | |
| CN105600923A (en) | Biological denitrification method of high ammonia-nitrogen wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |