CN114433161A - Composite material for efficiently activating monopersulfate and preparation method and application thereof - Google Patents
Composite material for efficiently activating monopersulfate and preparation method and application thereof Download PDFInfo
- Publication number
- CN114433161A CN114433161A CN202111598582.4A CN202111598582A CN114433161A CN 114433161 A CN114433161 A CN 114433161A CN 202111598582 A CN202111598582 A CN 202111598582A CN 114433161 A CN114433161 A CN 114433161A
- Authority
- CN
- China
- Prior art keywords
- monopersulfate
- temperature
- composite material
- organic pollutants
- mixed solution
- 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.)
- Granted
Links
- 230000003213 activating effect Effects 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 239000002689 soil Substances 0.000 claims abstract description 20
- 239000003480 eluent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims description 31
- 230000015556 catabolic process Effects 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012425 OXONE® Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- -1 sulfate radical Chemical class 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002091 nanocage Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- BZTYNSQSZHARAZ-UHFFFAOYSA-N 2,4-dichloro-1-(4-chlorophenyl)benzene Chemical compound C1=CC(Cl)=CC=C1C1=CC=C(Cl)C=C1Cl BZTYNSQSZHARAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000185 dioxinlike effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 230000008684 selective degradation Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
A composite material for efficiently activating monopersulfate and its preparation method and application are disclosed, the effective component is Co-C3N5Materials and polymonosulfates, Co-C3N5The material is prepared by first reacting a mixture of 3 amino-1,calcining 2,4 triazole as precursor to obtain C3N5Then passing through the catalyst with CoCl2·6H2The composite material can efficiently degrade organic pollutants in wastewater. Mainly depends on the transition metal Co to activate the peroxymonosulfate to generate hydroxyl free radicals with strong oxidizing property, thereby rapidly and effectively degrading organic pollutants in a short time. The composite material can quickly activate the peroxymonosulfate, and has the advantages of high treatment efficiency, good stability, wide action range, small environmental interference and the like in the process of degrading organic pollutants. The invention has wide application prospect in the aspect of treating organic pollution wastewater and soil eluent.
Description
Technical Field
The invention belongs to the technical field of organic pollution wastewater treatment, and particularly relates to a composite material for efficiently activating monopersulfate, and a preparation method and application thereof.
Background
With the rapid development of human society and the continuous improvement of living standard. While people produce large quantities of organic compounds to meet the ever-increasing social needs of the human society, they also cause organic pollution and bring ecological risks. Persistent Organic Pollutants (POPs) refer to natural or synthetic Organic Pollutants that are bioaccumulating, long-term residual, not easily decomposed, and highly toxic, can migrate long distances through various environmental media (air, water, biological, etc.), and can pose serious hazards to human health and the environment. POPs have high residue, bioaccumulation, semi-volatility and "triple effect" effects, they can migrate in atmospheric environment for long distances, and frequent exchange occurs on environmental multi-medium and multi-interface, so that POPs widely exist in various environmental media (water, soil, gas, etc.) as well as tissues, organs, animals and plants and human bodies all over the world, and attract wide attention of governments, scientific communities and the public. POPs are resistant to biological degradation, photolysis, chemical decomposition, and the like, and thus can persist in the environment. Wherein the half-life period of the dioxin-like substances in the atmosphere is 8-400 days, 166 days-21.9 years in water and about 17-273 years in soil and sediments; the half-life of polychlorinated biphenyls in the atmosphere is about 3 days to 1.4 years, in water is about 60 days to 27.3 years, in soil and sediments is 2.96 to 38 years, and the half-life of polychlorinated biphenyls in human bodies is about 7 years, so that the development of a method for repairing organic pollutants, which has high efficiency, short repair period, low cost and easy popularization and application, is urgently needed.
Advanced Oxidation Processes (AOPs) are developed in the 80 th century in 20 th century and are a technology for treating refractory organic pollutants. The concept of AOPs has been proposed as a marker for the generation of OH. Compared with other traditional oxidation methods, the advanced oxidation technology has the following characteristics: (1) a large amount of free radicals with strong oxidizability are generated in a reaction system, and the OH oxidation-reduction potential is as high as 2.80V; (2) the reaction speed is high, and the oxidation rate constant of most organic pollutants in the process can reach 106-109M-1s-1(ii) a (3) The application range is wide, and the free radicals with higher oxidation potential can almost oxidize all organic matters until the organic matters are completely decomposed; (4) the reaction conditions are mild, and no special requirements on temperature and pressure are usually required; (5) chain reactions can be induced; (6) can be used in combination with other water treatment technologies as a pretreatment or advanced treatment for other treatment technologies.
Traditional advanced oxidation techniques degrade organic pollutants with hydroxyl radical generation as the primary active group, based on sulfate radical (SO)4 ·-) The advanced oxidation of (2) is a new technology which is developed in recent years and widely applied to the pollution remediation of soil and underground water. Monopersulfates can be activated by heat, ultraviolet light, transition metals, bases, and hydrogen peroxide to produce sulfate radicals (SO)4 ·-) The catalyst has stronger oxidizability, the oxidation-reduction potential of the catalyst is 2.6-3.1V, and pollutants can be indirectly degraded. Compared with the traditional Fenton reagent based on hydroxyl (& OH) to degrade pollutants, SO4 ·-Has many advantages, such as selective degradation targetsThe effect of pollutants on soil organic matters is small; is stable under acidic and neutral conditions, and SO is generated under alkaline conditions4 ·-Can be reacted with H2O or OH-OH is generated by reaction, so that the novel advanced oxidation technology based on sulfate radical has better degradation effect on pollutants in a wider pH range, and the characteristics make the novel advanced oxidation technology based on sulfate radical have wide prospect in the restoration of organic polluted soil and the treatment process of waste water.
The transition metal ions can effectively activate PMS to generate SO4 ·-。Co2+Is the metal ion with the best effect of activating PMS, which is caused by Co in the process of activating PMS2+Is recycled:
Co2++H2O→CoOH++H+
CoOH++HSO5 -→CoO++SO4 ·-+H2O
CoO++2H+→Co3++H2O
Co2++HSO5 -→Co3++SO4 ·-+OH-
Co3++HSO5 -→Co2++SO5 ·-+H+
PMS/Co2+the system is successfully applied to the degradation of naphthol, 2, 4-dichlorophenol (2,4-DCP) and atrazine. Although Co is present2+In small amounts, in Co2+The catalyst still has higher activity when the molar ratio of the catalyst to PMS is 1:1000, but Co2+Has toxicity and can cause secondary pollution. The above disadvantages are overcome if cobalt ions can be immobilised without deactivating them. Therefore, the development of an environmentally friendly, efficient and inexpensive persulfate catalyst is urgently required.
Disclosure of Invention
The technical problem to be solved is as follows: the invention develops a composite material for efficiently activating monopersulfate and a preparation method and application thereof, aiming at the problems of low efficiency, narrow pH application range and the like in the process of treating organic polluted wastewater or soil eluent by using the existing homogeneous metal ion activated monopersulfate; in the aspect of an activating agent, the composite material overcomes the defects of complex preparation steps, high cost, difficult recycling and the like of the activating agent in the prior art; in the aspect of activation performance, the composite material effectively activates peroxymonosulfate to degrade polychlorinated biphenyl organic pollution with higher treatment difficulty.
The technical scheme is as follows: a composite material for efficiently activating monopersulfate contains Co-C as effective component3N5Materials and per-monosulfates, said Co-C3N5The material is prepared by calcining 3 amino-1, 2,4 triazole as precursor to obtain C3N5Then, the reaction solution is reacted with CoCl2·6H2O molten salt calcination to obtain the material.
The calcination procedure was as follows: the initial temperature is 25 ℃, the temperature is increased to 500 ℃ at the heating rate of 5 ℃/min, the temperature is maintained for 180min, then the temperature is reduced, the mixture is taken out, and the ultra-pure water is used for washing until the washing liquid is neutral.
The monopersulfate is at least one of potassium monopersulfate, sodium monopersulfate and ammonium monopersulfate, and the concentration of the monopersulfate is 0.5-3.0 mM.
The preparation method of the composite material for efficiently activating the monopersulfate comprises the following steps: the method comprises the following steps: weighing 5g of 3-amino-1, 2, 4-triazole in a crucible, and calcining in a tubular furnace under a set temperature-rising program, wherein the temperature-rising program comprises the following steps: setting the initial temperature to be 25 ℃, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 180min, and then naturally cooling to obtain a solid; step two: putting the solid obtained in the step one into a mortar for even grinding, washing with ultrapure water, centrifuging until the washing liquid is neutral, and then putting into a freeze dryer for freeze drying for 12h to completely dry to obtain the target solid C3N5(ii) a Step three: 0.5g of C obtained in step two was weighed3N5Placing the powder in a mortar, and adding C3N53% by mass of CoCl2·6H2Fully grinding O and 2.5g KCl in a mortar, transferring the obtained mixture into a crucible, calcining in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 2.5 ℃/min, keeping the temperature for 240min, and taking out after cooling; step four: obtained in the third stepTransferring the solid into a 50mL centrifuge tube, and washing and centrifuging by using ultrapure water until the washing liquid is neutral; step five: putting the washed mixed solution into a freeze dryer for freeze drying for 12 hours to obtain a target product Co-C3N5The freeze-drying pressure is 1.0mbar and the temperature is-40 ℃.
The application of the composite material for efficiently activating the monopersulfate in degrading organic pollutants comprises the following steps: mixing Co-C3N5Adding the mixture into waste water containing organic pollutants to obtain a mixed solution; step two: adding monopersulfate into the mixed solution obtained in the first step to obtain a mixed solution containing a catalyst and an oxidant; step three: and (5) physically and uniformly mixing the mixed solution obtained in the step two for reaction for 5-30 min.
Co-C as described above3N5The amount of (B) was 0.2 g/L.
The organic pollutant is polychlorinated biphenyl 28.
The pH of the reaction system is 3.0-9.0.
The reaction system is suitable for treating organic pollutants in wastewater and soil eluent with the chloride ion concentration of 1-10 mM; or the waste water with the nitrate concentration of 1-10mM neutralizes the organic pollutants in the soil eluent; or the treatment of waste water with bicarbonate concentration below 10mM for neutralizing organic pollutants in soil eluent.
Has the beneficial effects that: (1) the Co-C provided by the invention3N5The method for treating organic polluted wastewater or soil eluent by activating monopersulfate is to load transition metal Co on an inorganic non-metallic material, thereby preparing the environment-friendly efficient activator. Has the following advantages: compared with the prior art of publication No. CN101045573A, which utilizes transition metal ions to activate monopersulfate, the patent overcomes the secondary risk caused by the toxicity of metal ions. The patent application document refers to the calcination of the precursor 3-amino-1, 2, 4-triazole to obtain C3N5Then loading Co to C by molten salt method3N5On the material. Experiments prove that Co is effectively loaded on an inorganic non-metallic material, is stable and not easy to dissolve out, and catalyzes the processOnly the valence state of Co element is changed, Co ion is hardly dissolved out, and Co-C3N5The solid is easy to separate, recycle and reuse, and the problems of secondary pollution and difficult recycling caused by the prior art and the homogeneous or heterogeneous activated monopersulfate reaction process are solved.
(2) The Co-C provided by the invention3N5The method for treating organic polluted wastewater or soil eluent by activating monopersulfate can be prepared from raw materials with lower cost, and has the following advantages: utilizing MnXCo with the prior art publication No. CN2016106838143-XO4Compared with the nano cage activated monopersulfate for treating the wastewater with the anti-epileptic drug pollution, the nano cage activated monopersulfate has the advantages of MnXCo3-XO4The synthesis steps of the nano cage are complex and the obtaining cost is high. And Co-C in the present patent application3N5The preparation steps are simple and easy to implement, the cost of the catalyst is greatly reduced, and the problems of complex synthesis and high cost of the catalyst for heterogeneous activation of monopersulfate in the prior art are solved.
(3) The Co-C provided by the invention3N5The method for treating organic polluted wastewater or soil eluent by activating monopersulfate can quickly react at normal temperature and normal pressure, and has low energy consumption and simple operation. Compared with other catalysts, the catalyst has the characteristics of high free radical generation rate, short reaction time, high pollutant degradation efficiency and the like.
(4) Co-C provided by the invention3N5Method for treating organic polluted wastewater or soil eluent by activating monopersulfate, Co-C3N5The process of activating the monopersulfate to generate free radicals to remove pollutants is carried out on the surface of the activating agent, is less influenced by environmental factors, has wide pH applicability, and can degrade organic pollutants in a wide pH value range (3.0-9.0);
(5) the Co-C provided by the invention3N5The method of activating monopersulfate to treat organic polluted waste water or soil eluent has reaction system suitable for chloride ion, nitrate radical and bicarbonate radical in the concentration of 355-1775mg/L, 620-3100mg/L and 620-3100mg/L separatelyTreatment of organic contaminants in an environmental medium.
(6) The Co-C provided by the invention3N5The method for treating the organic polluted wastewater or the soil eluent by activating the monopersulfate has the advantages of simple operation, low cost, high reaction efficiency, wide application range and economy and feasibility.
Drawings
FIG. 1 shows Co-C prepared in example 13N5Scanning electron microscope images of;
FIG. 2 shows the utilization of Co-C in example 23N5Graph of the efficiency of activated monopersulfate for degrading polychlorinated biphenyl 28(PCB 28);
FIG. 3 shows Co-C in example 33N5The amount of the compound affects the degradation efficiency graph of the polychlorinated biphenyl 28;
FIG. 4 is a graph showing the effect of monopersulfate concentration on the degradation efficiency of polychlorinated biphenyl 28 in example 4;
FIG. 5 is a graph showing the effect of pH on the degradation efficiency of polychlorinated biphenyl 28 in example 5;
FIG. 6 is a graph showing the effect of chloride ions on the degradation efficiency of polychlorinated biphenyl 28 in example 6;
FIG. 7 is a graph showing the effect of nitrate on the degradation efficiency of polychlorinated biphenyl 28 in example 7;
FIG. 8 is a graph of the efficiency of bicarbonate salts affecting the degradation of polychlorinated biphenyl 28 in example 7;
FIG. 9 shows Co-C in example 83N5An efficiency chart of recycling and degrading polychlorinated biphenyl 28.
Detailed Description
The invention is further illustrated by the following examples, which illustrate the salient features and significant improvements of the invention, and which are intended to be illustrative only and are in no way limited to the following examples. The embodiment is preparation and application of a composition for efficiently activating persulfate.
Example 1
The composite material for efficiently activating monopersulfate and the application thereof are completed according to the following steps, wherein the Co-C is3N5Is prepared from 3 amino-1, 2,4 triazole and CoCl2·6H2The raw materials such as O and the like are prepared according to the following steps:
the method comprises the following steps: 5g of 3-amino-1, 2, 4-triazole is weighed into a crucible and placed into a tube furnace to be calcined under a set temperature-rising program. The temperature rising procedure is as follows: setting the initial temperature to 25 ℃, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 180min, and then naturally cooling to obtain a solid.
Step two: putting the solid obtained in the step one into a mortar for even grinding, washing with ultrapure water, centrifuging until the washing liquid is neutral, and then putting into a freeze dryer for freeze drying for 12h to completely dry to obtain the target solid C3N5。
Step three: 0.5g of C obtained in step two was weighed3N5Placing the powder in a mortar, and adding C3N53% by mass of CoCl2·6H2O (in terms of the mass of the transition metal) and 2.5g of KCl were sufficiently ground in a mortar, and the resulting mixture was transferred to a crucible, calcined in a muffle furnace, raised to 550 ℃ at a temperature rise rate of 2.5 ℃/min, and held for 240 min. And taking out after cooling.
Step four: transferring the solid obtained in the third step into a 50mL centrifuge tube, washing with ultrapure water, and centrifuging until the washing solution is neutral.
Step five: putting the washed mixed solution into a freeze dryer for freeze drying for 12h to completely dry the mixed solution to obtain the target solid Co-C3N5. The freeze-drying pressure is 1.0mbar and the temperature is-40 ℃.
Co-C3N5As shown in fig. 1, it can be seen that the approximate size of the particles is on the micron scale.
Example 2
In this example, Co-C was used3N5The method for treating the organic wastewater containing the polychlorinated biphenyl 28 by activating the monopersulfate comprises the following specific steps:
the method comprises the following steps: Co-C obtained in example 13N5Adding the mixture into waste water containing organic pollutants to obtain a mixed solution;
step two: adding monopersulfate into the mixed solution obtained in the first step to obtain a mixed solution containing a catalyst and an oxidant;
step three: physically and uniformly mixing the mixed solution obtained in the step two for reaction for 5-30 min;
step four: separating and detecting the solution obtained in the third step;
the present embodiment employs Co-C3N5Co (I) on the surface can rapidly transfer electrons to activate monopersulfate to generate hydroxyl radicals on the surface of the mineral, so that the aim of rapidly degrading target pollutants is fulfilled, the implementation result is shown in figure 2, and the embodiment is based on Co-C3N5The monopersulfate is activated to generate hydroxyl radicals, the rapid reaction can be realized at normal temperature and normal pressure, the energy consumption is low, and the operation is simple. Compared with other activators, the free radical generation rate is high, and the pollutant degradation efficiency is very high and can reach 90% in the same time.
Example 3
This example is similar to example 2 in steps, but differs therefrom only in that: Co-C in the first step3N5In the present example, Co-C was examined3N5The same as in example 2 was repeated except that the treatment effect on waste water containing 0.5ppm of polychlorinated biphenyl 28 was applied at 0.1g/L, 0.2g/L, 0.5g/L and 1.0 g/L. As a result, as shown in FIG. 3, it can be seen that Co-C3N5At a dose of 0.2g/L, the effect of the treatment of polychlorinated biphenyl 28 was best due to the excess of Co-C3N5The radicals are quenched to inhibit degradation of the contaminants.
Example 4
This example is similar to example 2 in steps, but differs therefrom only in that: the amount of potassium monopersulfate used in the second step was varied, and in this example, the effect of treating wastewater containing 0.5ppm of polychlorinated biphenyl 28 was examined for the amounts of potassium monopersulfate used, namely, 0.5mM, 1mM, 2mM, and 3mM, as in example 2. As shown in FIG. 4, it was revealed that the treatment effect of polychlorinated biphenyl 28 was the best when the amount of potassium monopersulfate was 2mM, because the excessive amount of potassium monopersulfate generated a large amount of radicals, which self-quenched to lower the reaction efficiency.
Example 5
This example is similar to example 2 in steps, but differs therefrom only in that: in the third step, the pH values of the mixed solution obtained in the second step are adjusted to be 3, 5, 7, 9 and 11 respectively; the rest is the same as example 2. As shown in FIG. 6, the results showed that at a pH range of 3 to 11, both showed degradation of polychlorinated biphenyl 28; the degradation efficiency (85-90%) is not very different in the pH value range of 3-9; the efficiency of polychlorinated biphenyl 28 degradation decreased significantly (43%) when the pH increased to 11.
Example 6
This example is similar to example 2 in steps, but differs therefrom only in that: in the second step, chloride ions with the concentration of 1-10mM are added (the source of the chloride ions is to add sodium chloride with corresponding concentration); the rest is the same as example 2. As shown in FIG. 7, the results show that the polychlorinated biphenyl 28 is efficiently degraded in the chloride ion concentration range of 1-10 mM; the degradation efficiency of the polychlorinated biphenyl 28 without chloride ions is 90 percent; the degradation efficiency of the added chloride ion polychlorinated biphenyl 28 with the concentration of 1mM and 10mM is 89 percent and 82 percent respectively; Co-C in the presence of large amounts of chloride ions in the environment3N5The monopersulfate can still be activated to remove the polychlorinated biphenyl 28.
Example 7
This example is similar to example 2 in steps, but differs therefrom only in that: in the second step, nitrate ions with the concentration of 1-10mM are added (the source of the nitrate ions is to add sodium nitrate with the corresponding concentration); the rest is the same as example 2. As shown in FIG. 8, the results show that the polychlorinated biphenyl 28 is efficiently degraded in the nitrate ion concentration range of 1-10 mM; the degradation efficiency of the polychlorinated biphenyl 28 without nitrate ions is 94 percent; the degradation efficiency of the polychlorinated biphenyl 28 after 1 mg/L and 10mg/L of nitrate ions are respectively 88 percent and 80 percent; Co-C in the presence of large amounts of nitrate ions in the environment3N5The monopersulfate can still be activated to remove the polychlorinated biphenyl 28.
Example 8
This example is similar to example 2 in steps, but differs therefrom only in that: in the first step, Co-C added in the second circulation and the third circulation3N5Are respectively a reactionCo-C recovered after primary and after secondary reaction3N5(ii) a The rest is the same as example 2. As shown in FIG. 9, Co-C3N5The degradation rate of the polychlorinated biphenyl 28 in the first use is 94 percent; Co-C3N5The degradation rate of polychlorinated biphenyl 28 in the second use is 93 percent; Co-C3N5The degradation rate of the polychlorinated biphenyl 28 used for the third time is 92 percent, the initial concentration of the polychlorinated biphenyl 28 in the third circulation is 0.5ppm, and the implementation effect shows that Co-C3N5Has certain cycle performance.
Claims (9)
1. The composite material for efficiently activating monopersulfate is characterized in that the effective component is Co-C3N5Materials and per-monosulfates, said Co-C3N5The material is prepared by calcining 3 amino-1, 2,4 triazole as precursor to obtain C3N5Then, the reaction solution is reacted with CoCl2·6H2O molten salt calcination to obtain the material.
2. The composite material for high efficiency activation of monopersulfate according to claim 1, wherein the calcination procedure is: the initial temperature is 25 ℃, the temperature is increased to 500 ℃ at the heating rate of 5 ℃/min, the temperature is maintained for 180min, then the temperature is reduced, the mixture is taken out, and the ultra-pure water is used for washing until the washing liquid is neutral.
3. The composite material for activating monopersulfate with high efficiency according to claim 1, wherein the monopersulfate is at least one of potassium monopersulfate, sodium monopersulfate and ammonium monopersulfate, and the concentration of the monopersulfate is 0.5 to 3.0 mM.
4. The method for preparing the high-efficiency activated monopersulfate composite material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps: the method comprises the following steps: weighing 5g of 3-amino-1, 2, 4-triazole in a crucible, and calcining in a tubular furnace under a set temperature-rising program, wherein the temperature-rising program comprises the following steps: setting initial temperature at 25 deg.C, heating to 500 deg.C at a rate of 5 deg.C/min, maintaining for 180min, and coolingNaturally cooling to obtain a solid; step two: putting the solid obtained in the step one into a mortar for even grinding, washing with ultrapure water, centrifuging until the washing liquid is neutral, and then putting into a freeze dryer for freeze drying for 12h to completely dry to obtain the target solid C3N5(ii) a Step three: 0.5g of C obtained in step two was weighed3N5Placing the powder in a mortar, and adding C3N53% by mass of CoCl2·6H2Fully grinding O and 2.5g KCl in a mortar, transferring the obtained mixture into a crucible, calcining in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 2.5 ℃/min, keeping the temperature for 240min, and taking out after cooling; step four: transferring the solid obtained in the third step into a 50mL centrifuge tube, and washing and centrifuging by using ultrapure water until the washing liquid is neutral; step five: putting the washed mixed solution into a freeze dryer for freeze drying for 12h to obtain a target product Co-C3N5The freeze-drying pressure is 1.0mbar, and the temperature is-40 ℃.
5. The use of a high efficiency activated monopersulfate composite material according to any one of claims 1 to 3 in the degradation of organic pollutants, characterized by the fact that in step one: mixing Co-C3N5Adding the mixture into waste water containing organic pollutants to obtain a mixed solution; step two: adding monopersulfate into the mixed solution obtained in the first step to obtain a mixed solution containing a catalyst and an oxidant; step three: and (5) physically and uniformly mixing the mixed solution obtained in the step two for reaction for 5-30 min.
6. Use according to claim 5, wherein said Co-C is3N5The amount of (B) was 0.2 g/L.
7. Use according to claim 5, characterized in that the organic contaminant is polychlorinated biphenyl 28.
8. The use according to claim 5, wherein the reaction system has a pH of 3.0 to 9.0.
9. The use according to claim 5, wherein the reaction system is suitable for the treatment of organic contaminants in wastewater and soil eluents having a chloride ion concentration of 1 to 10 mM; or the waste water with the nitrate concentration of 1-10mM neutralizes the organic pollutants in the soil eluent; or the treatment of waste water with bicarbonate concentration below 10mM for neutralizing organic pollutants in soil eluent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111598582.4A CN114433161B (en) | 2021-12-24 | 2021-12-24 | Composite material for efficiently activating monopersulfate, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111598582.4A CN114433161B (en) | 2021-12-24 | 2021-12-24 | Composite material for efficiently activating monopersulfate, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114433161A true CN114433161A (en) | 2022-05-06 |
| CN114433161B CN114433161B (en) | 2023-11-28 |
Family
ID=81364519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111598582.4A Active CN114433161B (en) | 2021-12-24 | 2021-12-24 | Composite material for efficiently activating monopersulfate, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114433161B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917947A (en) * | 2022-05-18 | 2022-08-19 | 成都理工大学 | C 3 N 5 /CLDH composite photocatalytic material and preparation method thereof |
| CN115138389A (en) * | 2022-08-12 | 2022-10-04 | 成都工业学院 | Cobalt hydroxide/cobalt oxide/P-doped carbon nitride nanocomposite and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| WO2018033829A1 (en) * | 2016-08-15 | 2018-02-22 | Sabic Global Technologies B.V. | Preparation of nitrogen rich three dimensional mesoporous carbon nitride and its sensing and photocatalytic properties |
| US10377631B1 (en) * | 2018-04-25 | 2019-08-13 | Charles Montross | Catalyst solvents for carbon nitride |
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN111362249A (en) * | 2020-02-24 | 2020-07-03 | 中国科学院深圳先进技术研究院 | Two-dimensional porous nitrogen-doped carbon, preparation method thereof and application thereof in lithium ion battery |
| CN111392845A (en) * | 2020-01-10 | 2020-07-10 | 中国科学院南京土壤研究所 | Composition for degrading organic pollutants as well as preparation method and application thereof |
| CN112023972A (en) * | 2020-09-03 | 2020-12-04 | 上海应用技术大学 | Composite photocatalytic material and preparation method and application thereof |
| CN112958092A (en) * | 2021-02-05 | 2021-06-15 | 暨南大学 | Activated persulfate catalyst and preparation method and application thereof |
| CN113559911A (en) * | 2021-07-30 | 2021-10-29 | 中国科学院生态环境研究中心 | Monoatomic catalyst, preparation method and application thereof |
| CN113600170A (en) * | 2021-07-16 | 2021-11-05 | 西安理工大学 | Transition metal monoatomic active catalyst and preparation method and application thereof |
-
2021
- 2021-12-24 CN CN202111598582.4A patent/CN114433161B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| WO2018033829A1 (en) * | 2016-08-15 | 2018-02-22 | Sabic Global Technologies B.V. | Preparation of nitrogen rich three dimensional mesoporous carbon nitride and its sensing and photocatalytic properties |
| US10377631B1 (en) * | 2018-04-25 | 2019-08-13 | Charles Montross | Catalyst solvents for carbon nitride |
| CN111392845A (en) * | 2020-01-10 | 2020-07-10 | 中国科学院南京土壤研究所 | Composition for degrading organic pollutants as well as preparation method and application thereof |
| CN111362249A (en) * | 2020-02-24 | 2020-07-03 | 中国科学院深圳先进技术研究院 | Two-dimensional porous nitrogen-doped carbon, preparation method thereof and application thereof in lithium ion battery |
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN112023972A (en) * | 2020-09-03 | 2020-12-04 | 上海应用技术大学 | Composite photocatalytic material and preparation method and application thereof |
| CN112958092A (en) * | 2021-02-05 | 2021-06-15 | 暨南大学 | Activated persulfate catalyst and preparation method and application thereof |
| CN113600170A (en) * | 2021-07-16 | 2021-11-05 | 西安理工大学 | Transition metal monoatomic active catalyst and preparation method and application thereof |
| CN113559911A (en) * | 2021-07-30 | 2021-10-29 | 中国科学院生态环境研究中心 | Monoatomic catalyst, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHAOHUA SHEN ET.AL: "Boosting photocatalytic hydrogen production by creating isotype heterojunctions and single-atom active sites in highly-crystallized carbon nitride", vol. 67, pages 2 * |
| 张莉;陈迪钊;张再兴;向德轩;麻常林;杨晓霞;: "介孔石墨相氮化碳吸附材料在环境中的应用", no. 1, pages 223 - 228 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917947A (en) * | 2022-05-18 | 2022-08-19 | 成都理工大学 | C 3 N 5 /CLDH composite photocatalytic material and preparation method thereof |
| CN114917947B (en) * | 2022-05-18 | 2023-10-27 | 成都理工大学 | C (C) 3 N 5 CLDHs composite photocatalytic material and preparation method thereof |
| CN115138389A (en) * | 2022-08-12 | 2022-10-04 | 成都工业学院 | Cobalt hydroxide/cobalt oxide/P-doped carbon nitride nanocomposite and preparation method and application thereof |
| CN115138389B (en) * | 2022-08-12 | 2023-07-18 | 成都工业学院 | Cobalt hydroxide/cobalt oxide/P doped carbon nitride nanocomposite and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114433161B (en) | 2023-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ziembowicz et al. | Limitations and future directions of application of the Fenton-like process in micropollutants degradation in water and wastewater treatment: A critical review | |
| Lu et al. | Application of calcium peroxide in water and soil treatment: a review | |
| Jiang et al. | Recent progress in Fenton/Fenton-like reactions for the removal of antibiotics in aqueous environments | |
| Han et al. | Graphitic nitride-catalyzed advanced oxidation processes (AOPs) for landfill leachate treatment: A mini review | |
| Shih et al. | Mineralization and deflourization of 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) by UV/persulfate oxidation and sequential adsorption | |
| CN109529894A (en) | A kind of application activating persulfate catalyst and its be catalyzed persulfate removal pollutant | |
| CN114433161A (en) | Composite material for efficiently activating monopersulfate and preparation method and application thereof | |
| CN108745396A (en) | A kind of nanometer of confinement Zero-valent Iron@spindle-type porous carbon catalytic oxidation method for treating water | |
| CN1370618A (en) | Oxidizing catalyst and its preparation, regeneration process and usage in treating waste water | |
| CN112194236A (en) | Method for treating salt-containing degradation-resistant wastewater by activating peroxymonosulfate through biochar-copper oxide composite material | |
| CN106045130B (en) | A method of persulfate degradation of organic waste water is catalyzed using Bayan Obo ore | |
| CN106582772A (en) | CoFe<2>O<4>/g-C<3>N<4> magnetic nanomaterial and preparation method therefor | |
| CN108176403B (en) | Co-loaded activated carbon fiber3O4Method for preparing catalytic material | |
| Ma et al. | Phenol removal and biofilm response in coupling of visible-light-driven photocatalysis and biodegradation: Effect of hydrothermal treatment temperature | |
| CN109772402B (en) | Fenton-like reaction catalyst, preparation method, method for degrading organic sewage and application of Fenton-like reaction catalyst | |
| CN114409054B (en) | Water treatment method for removing organic pollutants by activating persulfate and cooperatively controlling halogenated byproducts | |
| CN105967314A (en) | Method for restoring organic matter polluted water body using ferrous oxalate-activated persulfate system | |
| CN110756163A (en) | Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof | |
| CN109987693A (en) | The method that dithionite activate persistent organic pollutants in persulfate processing waste water | |
| CN108640248B (en) | Method for removing estrogen in water by activating peroxymonosulfate based on carbon-based magnetic iron-cobalt bimetallic material | |
| CN111392845A (en) | Composition for degrading organic pollutants as well as preparation method and application thereof | |
| CN105174423A (en) | Coal chemical and biochemical tail-water treatment method | |
| CN106587325A (en) | Method for treating difficult-to-degrade wastewater by non-homogeneously activating peroxymonosulfate through CoxFe1-xP material | |
| CN111153485A (en) | Composition for efficiently activating persulfate and application thereof | |
| CN115245825B (en) | Fenton-like catalyst converted from animal manure and synthesis method and application thereof |
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 |