CN115181041A - Method for generating sulfone compound by catalytic oxidation of sulfoxide compound - Google Patents
Method for generating sulfone compound by catalytic oxidation of sulfoxide compound Download PDFInfo
- Publication number
- CN115181041A CN115181041A CN202210909552.9A CN202210909552A CN115181041A CN 115181041 A CN115181041 A CN 115181041A CN 202210909552 A CN202210909552 A CN 202210909552A CN 115181041 A CN115181041 A CN 115181041A
- Authority
- CN
- China
- Prior art keywords
- iron
- chlorite
- compounds
- sulfoxide
- catalytic
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds, and belongs to the technical field of catalytic production of chemicals by environmental functions. The method comprises the steps of adding a sulfoxide compound into an iron-based catalytic chlorite system under an acidic condition, and carrying out ultrasonic treatment to obtain the sulfone compound. The method utilizes chlorite as an oxidant, an iron-based material as a catalyst, utilizes the iron-based material to catalyze the chlorite to generate high-valence iron oxide species, adopts a new catalytic oxidation system, utilizes an oxygen atom transfer reaction, can directionally oxidize sulfoxide compounds into sulfone compounds, has few byproducts, is simple and safe to construct the system, and realizes waste utilization.
Description
Technical Field
The invention relates to a method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds, belonging to the technical field of catalytic production of chemicals by environmental functions.
Background
The sulfone compound is a compound containing sulfonyl group and R 1 -SO 2 -R 2 The organic compound is characterized by being widely applied to natural products and drug molecules, is an important medical intermediate, and has more value. With the simplest being Dimethylsulfone (DMSO) 2 ) For example, it is an organic sulfide, which can be used as high-temperature solvent and raw material for organic synthesis in industry; the composition of human body protein can be maintained medically; in addition, some sulfone compounds are used as medicines, have an antibacterial action mechanism similar to that of sulfanilamide, have a strong direct inhibition effect on the leprosy, and can be used for treating various skin diseases besides leprosy.
At present, the synthesis of sulfone compounds mainly comes from the oxidation of sulfoxide compounds or thioether, and the oxidant is generally peroxide, ozone, oxygen and the like, but the above methods are generally harsh in conditions and complicated in post-treatment, and inevitably generate a large amount of byproducts which are difficult to treat, and the environment is hard to bear due to mass production. Therefore, how to orient the conversion to avoid the generation of byproducts is the key to the synthesis of the sulfone compound; in addition, "waste utilization" and "green catalysis" are important guiding ideas in production development. Therefore, it is important to provide a method for synthesizing sulfone compounds, which is free of byproducts, efficient, environment-friendly and economical in steps.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds, which comprises the steps of catalyzing the protonation of chlorite by using a byproduct chlorite treated by chlorine dioxide as an oxidant and an iron-based material as a catalyst, and directionally oxidizing the sulfoxide compounds to the sulfone compounds.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds, which comprises the steps of adding the sulfoxide compounds into an iron-based catalytic chlorite system under an acidic condition, and carrying out ultrasonic treatment to obtain the sulfone compounds.
Further, hydrogen ions are introduced to adjust the pH value to be 3-7, so that the sulfoxide compound is added into the iron-based catalytic chlorite system to be in acidic protection in the reaction process of the water phase.
Further, the source of hydrogen ions is sulfuric acid.
Further, to avoid waste of hydrogen ions, it is preferable to adjust the pH to 4 to 5.
Further, the pH of the acidic conditions is determined by the iron-based catalytic chlorite system.
Further, the preparation method of the iron-based catalytic chlorite system comprises the following steps: chlorite is added to water, the pH is adjusted to acidic conditions, and an iron-based material is added as a catalyst.
Further, the dosage of the iron-based material in the iron-based catalytic chlorite system is 20mg/L, and the iron-based material is zero-valent iron and comprises foam zero-valent iron, sponge iron, scrap iron or an iron-carbon-based catalyst.
Further, the specific preparation method of the iron-carbon-based catalyst comprises the following steps: dissolving 2g of ferric chloride hexahydrate, 2.5g of urea and 2.5g of glucose in 30mL of deionized water, carrying out hydrothermal treatment at 180 ℃ for 18h, and then placing the product in a tubular furnace for carrying out thermal treatment at 800 ℃ for 1h to obtain the product.
Further, zero-valent iron is preferable in order to avoid waste of the iron-based material and ensure ion precipitation.
Further, the concentration of chlorite in the iron-based catalytic chlorite system is (1-6) mM.
Further, to provide an oxidation source, the chlorite salt is preferably sodium chlorite.
Further, the molar ratio of the sulfoxide compound to the chlorite in the iron-based catalytic chlorite system is (0.3-3): (1-6).
Furthermore, the ultrasonic frequency of ultrasonic treatment is more than or equal to 28kHz, the ultrasonic intensity is more than or equal to 30W/L, and in order to enhance liquid phase mass transfer, prevent and control iron-based surface passivation and improve reaction efficiency.
Further, the time of the ultrasonic treatment is 20-60 min.
The invention discloses the following technical effects:
under the action of acidity, the zero-valent iron is utilized to release ionic iron, the ionic iron is sequentially converted into ferrous iron and ferric iron after being released, the conversion process is included, and finally the ferric iron is catalyzed to catalyze chlorite to be decomposed to generate high-valent iron oxidized species and chlorine dioxide, and the high-valent iron oxidized species serving as an intermediate active species can act on sulfoxides to generate an oriented catalytic oxidation reaction of oxygen atom transfer to generate sulfones. Therefore, the method takes the chlorite as an oxidant, takes the iron-based material as a catalyst, utilizes the iron-based catalysis chlorite to generate high-valence iron oxide species, adopts a new catalytic oxidation system, utilizes oxygen atom transfer reaction, can directionally oxidize the sulfoxide compound into the sulfone compound, and has few byproducts.
The method for generating the sulfone compound by catalytic oxidation of the sulfoxide compound has the advantages that the construction of a catalytic system is simple and safe, and the waste utilization is realized by using the chlorite which is a byproduct of chlorine dioxide treatment as an oxidant.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a diagram of the reaction process of PMSO directional oxidation to PMSO2 in example 1 of the present invention;
FIG. 2 shows example 1 (US/CI/H) + /Fe 0 ) And comparative example 1 (US/CI/H) + ) Wherein (a) is example 1 and (b) is comparative example 1;
FIG. 3 is a total ion flow diagram of PMSO, the compound used in example 1;
FIG. 4 is a mass spectrum corresponding to PMSO which is the compound used in example 1;
FIG. 5 shows PMSO, a compound prepared in example 1 2 The total ion flow map of (a);
FIG. 6 preparation of example 1The resulting compound PMSO 2 The corresponding mass spectrum.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The invention provides a method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds, which comprises the steps of adding the sulfoxide compounds into an iron-based catalytic chlorite system under an acidic condition, and carrying out ultrasonic treatment to obtain the sulfone compounds.
Further, hydrogen ions are introduced to adjust the reaction system to an acidic condition, wherein the pH value is more than 3 and less than 7, so that the sulfoxide compound is added into the iron-based catalytic chlorite system to be subjected to acidic protection in the reaction process in the water phase.
Further, the hydrogen ion source is sulfuric acid, and the concentration of the sulfuric acid solution used in the embodiment of the invention is 1mol/L.
Further, to avoid waste of hydrogen ions, it is preferable that the acidic condition is pH =4 to 5.
Further, the pH level of the acidic conditions is determined by the iron-based catalytic chlorite system.
Further, the preparation method of the iron-based catalytic chlorite system comprises the following steps: chlorite is added to water, the pH is adjusted to acidic conditions, and an iron-based material is added as a catalyst.
Further, the dosage of the iron-based material in the iron-based catalytic chlorite system is 20mg/L, and the iron-based material is zero-valent iron and comprises foam zero-valent iron, sponge iron, scrap iron or an iron-carbon-based catalyst.
Further, the specific preparation method of the iron-carbon-based catalyst comprises the following steps: dissolving 2g of ferric chloride hexahydrate, 2.5g of urea and 2.5g of glucose in 30mL of deionized water, carrying out hydrothermal treatment at 180 ℃ for 18h, and then placing the product in a tubular furnace for carrying out thermal treatment at 800 ℃ for 1h to obtain the product.
Further, zero-valent iron is preferable in order to avoid waste of the iron-based material and ensure ion precipitation.
Further, the concentration of chlorite in the iron-based catalytic chlorite system is (1-6) mM.
Further, to provide an oxidation source, the chlorite salt is preferably sodium chlorite.
Further, the molar ratio of the sulfoxide compound to the chlorite salt in the iron-based catalytic chlorite salt system is (0.3-3): (1-6).
Furthermore, the ultrasonic frequency of ultrasonic treatment is more than or equal to 28kHz, the ultrasonic intensity is more than or equal to 30W/L, ultrasonic is used as physical field drive, and in order to enhance liquid phase mass transfer, prevent and control iron-based surface passivation and improve reaction efficiency.
Further, the time of the ultrasonic treatment is 20-60 min.
The raw materials used in the examples of the present invention are commercially available.
The technical solution of the present invention is further illustrated by the following examples.
Example 1
A method for catalyzing the directional oxidation of methyl phenyl sulfoxide (PMSO) to generate methyl phenyl sulfone (PMSO 2):
adding 3mM sodium chlorite into 250mL of water, adjusting the pH value to 4.5 by using a sulfuric acid solution, then adding foamed zero-valent iron to enable the adding amount of the foamed zero-valent iron to be 20mg/L, then adding 0.3mM PMSO, and carrying out ultrasonic treatment for 30min at the ultrasonic frequency of 28kHz and the ultrasonic intensity of 30W/L, thus obtaining PMSO2 through directional oxidation.
The reaction process diagram of the PMSO directional oxidation to PMSO2 in the embodiment 1 of the invention is shown in figure 1.
Example 2
Catalyzing methyl phenyl sulfoxide (PMSO) to generate methyl phenyl sulfone (PMSO) through directional oxidation 2 ) The method of (1):
adding 3mM sodium chlorite into 250mL of water, adjusting the pH value to 4 by using sulfuric acid solution, then adding sponge iron to ensure that the addition amount of the sponge iron is 200mg/L, then adding 0.3mM PMSO, and carrying out ultrasonic treatment for 60min under the ultrasonic frequency of 28kHz and the ultrasonic intensity of 30W/L, thus directionally oxidizing to generate PMSO 2 。
Example 3
Catalyzing methyl phenyl sulfoxide (PMSO) to generate methyl phenyl sulfone (PMSO) through directional oxidation 2 ) The method comprises the following steps:
adding 3mM sodium chlorite into 250mL of water, adjusting the pH value to 4 by using sulfuric acid solution, then adding scrap iron to ensure that the adding amount of the scrap iron is 100mg/L, then adding 0.3mM PMSO, and carrying out ultrasonic treatment for 60min under the ultrasonic frequency of 28kHz and the ultrasonic intensity of 30W/L, thus obtaining the PMSO by directional oxidation 2 。
Example 4
Catalyzing methyl phenyl sulfoxide (PMSO) to generate methyl phenyl sulfone (PMSO) through directional oxidation 2 ) The method comprises the following steps:
preparation of a ferric carbon-based catalyst: dissolving 2g of ferric chloride hexahydrate, 2.5g of urea and 2.5g of glucose in 30mL of deionized water, carrying out hydrothermal treatment at 180 ℃ for 18h, and then placing the product in a tubular furnace for carrying out thermal treatment at 800 ℃ for 1h to obtain the product.
Adding 2mM sodium chlorite into 250mL of water, adjusting the pH value to 5 by using sulfuric acid solution, then adding an iron-carbon-based catalyst to ensure that the adding amount of the iron-carbon-based catalyst is 20mg/L, then adding 3mM PMSO, and carrying out ultrasonic treatment for 20min under the ultrasonic frequency of 28kHz and the ultrasonic intensity of 30W/L, thus obtaining PMSO by directional oxidation 2 。
Comparative example 1
The only difference from example 1 is that no foam zero-valent iron was added.
Gas chromatography-mass spectrometry combined test
Examples 1 to 4 are substantially all zero-valent iron, so that the performance test of example 1 was performed alone, and in the process of ultrasonic treatment of example 1 and comparative example 1, respectively, example 1 was performed by measuring 15mL of reaction sample at 5 th, 15 th, 25 th min, etc., and then mixing, and comparative example 1 was performed by measuring 45mL of reaction sample after accumulating reaction for 30min, and then the test was performed by gas chromatography-mass spectrometry, and example 1 (US/CI/H) + /Fe 0 ) And comparative example 1 (US/CI/H) + ) The total ion flow diagram of (a) is example 1, (b) is comparative example 1, and fig. 3 is the total ion flow diagram of PMSO, the compound used in example 1; FIG. 4 is a mass spectrum corresponding to PMSO, the compound used in example 1; FIG. 5 shows PMSO, a compound prepared in example 1 2 The total ion flow map of (a); FIG. 6 shows PMSO, a compound prepared in example 1 2 The corresponding mass spectrum. As can be seen from FIGS. 2 to 6, PMSO 2 Generated in (m/z 156, 141, 125, 94, 77) and almost free of by-product peaks, PMSO and PMSO in the total ion flow diagram 2 The peak intensity is obvious, and in comparative example 1, although almost no by-product is generated, PMSO 2 The relative production amount is far lower than that of the example 1, no by-product is generated in the reaction within 30min in the example 1, and the pure product is always kept in the comparative example1 little PMSO even if 30min is accumulated 2 The production, and more particularly the usefulness of example 1, illustrates that the process provided in example 1 can be used to direct conversion to PMSO 2 。
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. A method for generating sulfone compounds by catalytic oxidation of sulfoxide compounds is characterized in that the sulfoxide compounds are added into an iron-based catalytic chlorite system under an acidic condition, and ultrasonic treatment is carried out to obtain the sulfone compounds.
2. The method for catalytically oxidizing sulfoxides to sulfones compounds of claim 1, wherein the acidic condition is 3 < pH < 7.
3. The method for catalytically oxidizing sulfoxides to sulfones compounds according to claim 1, wherein the iron-based catalytic chlorite system is prepared by the following method: chlorite is added to water, the pH is adjusted to acidic conditions and an iron-based material is added as a catalyst.
4. The method for catalytically oxidizing sulfoxides to sulfones compounds according to claim 3, wherein the iron-based material in the iron-based catalytic chlorite system is used in an amount of 20mg/L and is zero-valent iron.
5. The method of claim 3, wherein the concentration of chlorite in the iron-based catalytic chlorite system is (1-6) mM.
6. The method for catalytically oxidizing sulfoxides to sulfones compounds of claim 1, wherein the molar ratio of sulfoxides to chlorite in the iron-based catalytic chlorite system is (0.3-3): (1-6).
7. The method for catalytically oxidizing sulfoxide compounds to generate sulfone compounds according to claim 1, wherein the ultrasonic frequency of the ultrasonic treatment is not less than 28kHz, and the ultrasonic intensity is not less than 30W/L.
8. The method for catalyzing and oxidizing sulfoxide compounds to generate sulfone compounds as claimed in claim 1, wherein the time of ultrasonic treatment is 20-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210909552.9A CN115181041B (en) | 2022-07-29 | 2022-07-29 | Method for generating sulfone compound by catalytic oxidation of sulfoxide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210909552.9A CN115181041B (en) | 2022-07-29 | 2022-07-29 | Method for generating sulfone compound by catalytic oxidation of sulfoxide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115181041A true CN115181041A (en) | 2022-10-14 |
| CN115181041B CN115181041B (en) | 2023-06-09 |
Family
ID=83520335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210909552.9A Active CN115181041B (en) | 2022-07-29 | 2022-07-29 | Method for generating sulfone compound by catalytic oxidation of sulfoxide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181041B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248795A (en) * | 1977-02-10 | 1981-02-03 | Union Carbide Corporation | Preparation of organic sulfone compounds |
| EP1334956A2 (en) * | 2002-02-07 | 2003-08-13 | Sumitomo Chemical Company, Limited | Method for preparing sulfone or sulfoxide compound |
| JP2010208988A (en) * | 2009-03-10 | 2010-09-24 | Dnp Fine Chemicals Fukushima Co Ltd | Method of producing sulfoxide compound |
| CN102249959A (en) * | 2011-05-19 | 2011-11-23 | 浙江工业大学 | Method for preparing sulfoxide through catalytic oxidation |
| JP2017052730A (en) * | 2015-09-10 | 2017-03-16 | 日本軽金属株式会社 | Method for producing sulfone compound |
| CN113801044A (en) * | 2020-06-12 | 2021-12-17 | 沈阳中化农药化工研发有限公司 | Method for synthesizing sulfone compound by oxidizing sulfoxide compound |
-
2022
- 2022-07-29 CN CN202210909552.9A patent/CN115181041B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4248795A (en) * | 1977-02-10 | 1981-02-03 | Union Carbide Corporation | Preparation of organic sulfone compounds |
| EP1334956A2 (en) * | 2002-02-07 | 2003-08-13 | Sumitomo Chemical Company, Limited | Method for preparing sulfone or sulfoxide compound |
| JP2010208988A (en) * | 2009-03-10 | 2010-09-24 | Dnp Fine Chemicals Fukushima Co Ltd | Method of producing sulfoxide compound |
| CN102249959A (en) * | 2011-05-19 | 2011-11-23 | 浙江工业大学 | Method for preparing sulfoxide through catalytic oxidation |
| JP2017052730A (en) * | 2015-09-10 | 2017-03-16 | 日本軽金属株式会社 | Method for producing sulfone compound |
| CN113801044A (en) * | 2020-06-12 | 2021-12-17 | 沈阳中化农药化工研发有限公司 | Method for synthesizing sulfone compound by oxidizing sulfoxide compound |
Non-Patent Citations (1)
| Title |
|---|
| YANG ZONG ET AL.: "Unraveling the Overlooked Involvement of High-Valent Cobalt-Oxo Species Generated from the Cobalt(II)-Activated Peroxymonosulfate Process", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》, vol. 54, pages 16231 - 16239 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115181041B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110624569A (en) | MoS doped with metal ions2Method for degrading PPCPs by activating monopersulfate | |
| CN102633349B (en) | Method for treating track non-degradable organisms in water by aid of heterogenous sulfate radical oxidation | |
| CN103224256B (en) | Polymerization ferric sulfate water treatment agent and preparation method thereof | |
| CN111203236B (en) | Preparation method and application of cobalt disulfide/carbon fiber composite material | |
| CN103663666A (en) | Method for carrying out cooperative oxidation treatment on organic wastewater by potassium permanganate and potassium hydrogen persulfate | |
| CN108435231A (en) | A kind of TiO2/ CN23 photochemical catalysts and the preparation method and application thereof | |
| Xiao et al. | Graphitic carbon nitride for photocatalytic degradation of sulfamethazine in aqueous solution under simulated sunlight irradiation | |
| CN106397329A (en) | Synthesis technology of allantoin | |
| CN113731448A (en) | Homogeneous Fenton cocatalyst, and preparation method and application thereof | |
| Sun et al. | Bulk-to-nano regulation of layered metal oxide gears H2O2 activation pathway for its stoichiometric utilization in selective oxidation reaction | |
| You et al. | Hematite/selenium disulfide hybrid catalyst for enhanced Fe (III)/Fe (II) redox cycling in advanced oxidation processes | |
| CN106673171A (en) | Method for promoting peroxymonosulfate to generate sulfate radicals for degrading organic matters | |
| CN115181041A (en) | Method for generating sulfone compound by catalytic oxidation of sulfoxide compound | |
| Yin et al. | Facet-dependent reactivity of α-Fe2O3 nanosheet on reactive oxygen species generation in Fenton-like process | |
| CN112723493B (en) | Cobaltosic oxide/magnesium oxide-titanium composite electrode, preparation method and application thereof, and treatment method of ammonia nitrogen-containing wastewater | |
| Zhu et al. | Selective oxidation of aniline contaminants via a hydrogen-abstraction pathway by Bi2· 15WO6 under visible light and alkaline conditions | |
| CN108484366B (en) | Method for preparing hydroquinone by hydroxylation of phenol under visible light catalysis | |
| CN106830272A (en) | A kind of utilization wall erosion thing catalysis persulfate controls the method for treating water of halogenated disinfection by-products | |
| CN107055739A (en) | A kind of method of Taste and odor compounds in magnetic nanoparticle activation persulfate degradation water | |
| CN113797924A (en) | Single-atom carbon-doped magnesium-manganese binary oxide and preparation method and application thereof | |
| JP2003040805A (en) | Method for photo-decomposing organofluorine compound | |
| CN117964088A (en) | By monoclinic phase W18O49Method for promoting Fenton-like degradation of acetaminophen in water body | |
| CN105772037B (en) | A kind of ultraviolet catalytic removes material of bromate and preparation method thereof in water removal | |
| CN105600910B (en) | A kind of method for treating water for being catalyzed peroxide and producing singlet oxygen depollution | |
| CN103055846B (en) | Method for preparing tungstate with visible-light photocatalytic activity by microwave hydrothermal process |
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 |