CN104383958A - Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof - Google Patents
Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof Download PDFInfo
- Publication number
- CN104383958A CN104383958A CN201410572458.4A CN201410572458A CN104383958A CN 104383958 A CN104383958 A CN 104383958A CN 201410572458 A CN201410572458 A CN 201410572458A CN 104383958 A CN104383958 A CN 104383958A
- Authority
- CN
- China
- Prior art keywords
- oxidation catalyst
- preparation
- fenton oxidation
- sio
- heterogeneous
- 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
Abstract
The invention discloses a heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof. Prussian blue is used as iron sources, the Prussian blue is deposited on an amino-functional SiO2 mesoporous film with vertical hole passages in an automatic assembly manner, the Prussian blue is fixed through the physical absorption and the interaction force between the positive and negative charges, the bonding is firm, and the loosing is avoided; the prepared catalyst is the film catalyst, the specific surface area is large, the utilization efficiency of active components is high, the catalytic efficiency is high, and compared with the powdery and granular catalysts, the separation and the recovery are easy. Because the catalyst is provided with the mesoporous passages which are vertically distributed, the internal diffusion resistance is little, and many organic matters are suitable for being treated; at the same time, the Prussian blue loaded by the catalyst contains various states of iron, so that the Prussian blue has a cooperating function; in addition, the preparation method disclosed by the invention is simple in technology and wild in condition, so that the preparation method is suitable for popularization and application.
Description
Technical field
The present invention relates to field of catalyst preparation, be specifically related to a kind of heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof.
Background technology
Fenton (Fenton) reagent refers to the oxidation system that hydrogen peroxide and ferrous ion form.In containing the acid solution of ferrous ion, add hydrogen peroxide, hydrogen peroxide produces active hydroxyl radical free radical (OH) under the catalytic action of ferrous ion.Compare with other oxidant, hydroxyl radical free radical has higher standard oxidation reduction electrode potential, and this is the theoretical foundation that Fenton reagent has compared with strong oxidizing property.At present, Fenton reagent oxidizing process, as a kind of advanced oxidation processes, is widely used in the process containing hardly degraded organic substance industrial wastewaters such as phenols, arylamine class, pesticide and nuke rubbish.The specific embodiment of the method waste water is adjusted to acid; Under room temperature, stirring condition, the hydrogen peroxide needed according to Fenton reagent oxidation reaction and the ratio requirement of ferrous ion material amount, once add solvable ferrous salt, after ferrous salt dissolves completely, hydrogen peroxide is added, control the reaction time, until the oxidized decomposition of hardly degraded organic substance in waste water; Complete the solution of reaction also in acid, be adjusted to alkalescence, the ferrous ion now in solution, iron ion can be separated out with precipitation of hydroxide form; After filtration, filtrate can reuse or discharge, and filter cake is waste residue, need process further, dispose.Due to adopt be the ferrous salt of solubility as catalyst, therefore, also this oxidizing process is called homogeneous phase Fenton reagent oxidizing process.
Due to homogeneous phase Fenton reagent oxidizing process there is such as secondary pollution, the shortcoming such as soluble ferrite cannot reuse, so Fenton reagent oxidizing process develops from homogeneous method to multi-phases process just gradually, as CN102659235 discloses a kind of multiphase Fenton catalytic oxidation technologies using FeOCl to be source of iron, during for the treatment of waste water from dyestuff, percent of decolourization reaches 99%; The preparation method of the heterogeneous Fenton oxidation catalyst of a kind of activated carbon supported ferrous sulfate disclosed in CN102626627, acid-treated active carbon is joined in copperas solution, make ferrous ion immobilized on the activated carbon as heterogeneous Fenton oxidation catalyst, for the treatment of phenol wastewater, clearance reaches 90.73%; It is Prussian blue that CN102962063 discloses one immobilization on the carriers such as molecular sieve, kaolin, building waste, prepare the method for light fenton catalyst, degradable organic pollutant malachite green, rhodamine B and methyl orange under visible light illumination, percent of decolourization all can reach 95%.Said method, for the shortcoming overcoming homogeneous phase Fenton reagent, serves positive effect in Promote Technology.Such as, but also there are some defects, in use Metal ion release is slow for FeOCl, and catalytic efficiency is low; The porous materials such as active carbon, molecular sieve, kaolin, by physical absorption load iron ion, along with access times increase, iron ion runs off and causes clearance to decline rapidly; Powdered or pellet type catalyst, reclaimed by filtering-depositing, process is comparatively loaded down with trivial details.
Therefore, research and develop the oxidation catalyst in a kind of novel Fenton-like system, solve and use the secondary pollution problem that homogeneous phase Fenton reagent medicament runs off and iron containing sludge brings in the past; And the problem that existing heterogeneous Fenton oxidation catalyst iron ion easily runs off, treatment effeciency is low and catalyst not easily reclaims, become instantly popular research direction.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of heterogeneous ultraviolet-Fenton oxidation catalyst newly, solve and use the secondary pollution problem that homogeneous phase Fenton reagent medicament runs off and iron containing sludge brings in the past, and the problem that existing heterogeneous Fenton oxidation catalyst iron ion easily runs off, treatment effeciency is low and catalyst not easily reclaims; Meanwhile, a kind of preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst is newly set up.
The present invention's adopted technical scheme that solves the problem is:
A preparation method for heterogeneous ultraviolet-Fenton oxidation catalyst, comprises the following steps:
Step 1: with double type surfactant for template, with 3-aminopropyl trimethoxysilane (APS) for helping structure directing agent, and add silicon source, adopt sol-gel process (sol-gel), there is in substrate material surface preparation the SiO of vertical channel structure
2mesopore film (VC SiO
2mesopore film);
Step 2: will there is the SiO of vertical channel structure
2mesopore film is placed in ethanol/monoethanolamine mixed solution and dissolves removal template, exposes the amino group introduced by 3-aminopropyl trimethoxysilane in vertical channel simultaneously, realizes VC SiO
2the amino functional of mesopore film;
Step 3: with Prussian blue (PB) for source of iron is at the SiO with vertical channel structure
2mesopore film carries out Prussian blue LBL self-assembly, obtains PB/VC SiO
2mesopore film is heterogeneous ultraviolet-Fenton oxidation catalyst.
The surfactant of double type described in step 1 is preferably dodecyl disodium glutamate, myristyl disodium glutamate, cetyl disodium glutamate or octadecyl disodium glutamate.
The source of silicon described in step 1 is preferably ethyl orthosilicate (TEOS), and described base material is preferably sheet glass or silicon wafer.
Preferably, in step 1, the molar ratio range in template, APS, silicon source is 1:1-3:1-40, most preferably is template: APS: silicon source=1:2:3.
Further, the concrete operations of sol-gel process described in step 1 are: by template water heating for dissolving, then room temperature is cooled to, add ethanol, stir, add 3-aminopropyl trimethoxysilane and silicon source simultaneously, basement material when solution shows slightly milky, leave standstill a period of time, take out base material, ultrasonic cleaning post-drying in ethanol.
In above-mentioned concrete steps, preferably use heating water bath to dissolve template, the temperature of described water-bath is preferably 80 DEG C; The concentration range forming template solution is preferably 2-5mg/mL, and the best is 2.5mg/mL; The amount adding ethanol is preferably water alcohol volume ratio 1:1-1.5, and the best is 1:1.35; Time of repose is preferably 30-180min, and the best is 90min.
Preferably, the ethanol of ethanol in step 2/monoethanolamine mixed solution and the volume ratio of monoethanolamine are 1:5.
Further, the concrete operations of step 2 are: will have the SiO of vertical channel structure
2mesopore film is placed in ethanol/monoethanolamine mixed solution and adds hot reflux 3-36 hour, and the best is 24 hours; Then also dry with alcohol flushing, be preferably 2 hours drying time.
Further, the concrete operations of step 3 are: will have the SiO of vertical channel structure
2mesopore film is alternately placed in K
4fe (CN)
6solution and FeCl
3soak in solution, 30-90s/ time (the best is 60s/ time), 10-30 time (the best is 20 times), then rinsing, drying.
Preferably, K in above-mentioned concrete steps
4fe (CN)
6the concentration of solution is 5-30mM, and the best is 10mM; FeCl
3the concentration of solution is 5-30mM, and the best is 10mM.
Present invention also offers the heterogeneous ultraviolet-Fenton oxidation catalyst using above-mentioned method to prepare.
Catalyst prepared by the present invention can be applicable to sewage disposal, especially decolorization of dye effluent, other nitric wastewaters of degrading; The heterogeneous Fenton reagent oxidizing process that the catalyst using the present invention to prepare carries out and biochemical process coupling, can be used as the pre-treatment step of waste water difficult for biological degradation; The heterogeneous Fenton reagent oxidizing process that the catalyst using the present invention to prepare carries out also can be used as the one of deep oxidation method, process high concentration, toxic, hardly degraded organic substance.As wastewater treatment bactericide, that the inventive method is prepared secures the Prussian blue SiO with vertical channel structure
2mesopore film is deposited directly to uviol lamp surface, is aided with H
2o
2, in ultraviolet sterilization process, strengthen bactericidal effect further, improve effluent quality.
In other respects, the organic molecules such as catalyst prepared by the present invention all right degradation of formaldehyde, methyl alcohol, ethanol, air in clean room, in car.
The SiO with vertical channel of the present invention
2mesoporous material can be used as catalyst carrier for the preparation of other loaded catalysts.
Amination of the present invention has vertical channel SiO
2mesoporous material can make the transition as functionalization material and prepare other functionalization materials.
The preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst of the present invention has following beneficial effect:
1. the heterogeneous Fenton oxidation catalyst prepared of the present invention, is source of iron with Prussian blue, is Prussian bluely deposited on the amino functional SiO with vertical channel in self assembly mode
2on mesopore film, realize Prussian blue immobilization by physical absorption and positive and negative charge interaction force, in conjunction with firm, anti-current is lost;
2. the catalyst prepared by is film catalyst, and specific area is large, and active component utilization ratio is high, and catalytic efficiency is high, compared with Powdered, pellet type catalyst, easily separated, easily reclaim;
3. the catalyst prepared by has the mesopore orbit of vertical distribution, and inside diffusional resistance is little, and the organism kinds being suitable for processing is many;
4. the catalyst cupport prepared by Prussian blue, comprises the iron of variform, has synergy;
5. preparation method's technique is simple, mild condition.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the SiO with vertical channel prepared by the embodiment of the present invention 1
2the scanning electron microscope (SEM) photograph of mesopore film;
Fig. 2 is the SiO with vertical channel prepared by the embodiment of the present invention 1
2the transmission electron microscope picture of mesopore film;
Fig. 3 is the SiO with vertical channel prepared by the embodiment of the present invention 1
2scanning electron microscope (SEM) photograph after mesopore film LBL self-assembly is Prussian blue;
Fig. 4 is the SiO with vertical channel prepared by the embodiment of the present invention 1
2mesopore film removes infrared total reflection ATR spectrogram before and after template;
Fig. 5 is the SiO with vertical channel prepared by the embodiment of the present invention 1
2infrared spectrogram after mesopore film LBL self-assembly is Prussian blue.
Detailed description of the invention
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The aqueous solution 32mL of preparation 2.5mg/mL dodecyl disodium glutamate, adds 0.48mL 0.1MHCl, 80 DEG C of stirring in water bath 30 minutes; After being cooled to room temperature, by water: ethanol contend adds ethanol than for 1:1.35, stir 30 minutes, be that 1:2.3:2.67 adds 3-aminopropyl trimethoxysilane and ethyl orthosilicate by dodecyl disodium glutamate, 3-aminopropyl trimethoxysilane, ethyl orthosilicate mol ratio, 30 DEG C are stirred 30min; Treat that solution colour shows slightly milky white, insert the sheet glass through EtOH Sonicate cleaning, room temperature leaves standstill 2 hours, and take out sheet glass, ultrasonic 10 minutes in ethanol, 80 DEG C of oven dry, obtained the SiO with vertical channel
2mesopore film.The mesoporous SiO of vertical channel will be deposited
2ethanol/monoethanolamine volume ratio put into by the sheet glass of film is the mixed solution of 1:5,80 DEG C of backflow 24h, alcohol flushing, mesoporous SiO
2removal is dissolved in the inner formword agent of film normal duct, and 80 DEG C of dryings 2 hours, obtain amido modified vertical channel SiO
2mesopore film.By amido modified vertical channel SiO
2mesopore film immerses 10mM K
4fe (CN)
660s in the aqueous solution, with deionized water rinsing, then immerses 10mM FeCl
360s in the aqueous solution, uses deionized water rinsing.Repeat 20 times, 80 DEG C of oven dry, obtaining load has Prussian blue vertical channel SiO
2mesopore film, as Fenton reagent oxidation catalyst, with H
2o
2form heterogeneous Fenton reagent together.
Figure 1 shows that the SiO with vertical channel prepared by the present embodiment
2the scanning electron microscope (SEM) photograph of mesopore film, Fig. 2 is its transmission electron microscope picture, Fig. 3 show its deposition Prussian blue after surface sweeping Electronic Speculum figure (20 times circulation).We also measure to obtain and remove infrared total reflection ATR spectrogram (about Fig. 4,3000nm are chain alkyl characteristic peak, and about 1600nm is carbonyl characteristic peak) before and after template.Fig. 5 display be deposition Prussian blue after infrared spectrogram (about 680nm is Prussian blue characteristic peak).
Embodiment 2-4
With embodiment 1, change Template Types, water is prepared with ethanol contend ratio, template, 3-aminopropyl trimethoxysilane, the mutual mol ratio of ethyl orthosilicate (i.e. template/APS/TEOS), obtaining load equally has Prussian blue vertical channel SiO
2mesopore film, as Fenton oxidation catalyst, with H
2o
2form heterogeneous Fenton reagent together.The membrane material surface ratio that embodiment 3 and embodiment 4 obtain is more coarse.Particular content is as shown in table 1:
Table 1
Embodiment 5
Configure 10 μMs of rhodamine B aqueous solution, adjust ph, to 3.5, is got 5ml and is joined in the beaker of parcel tinfoil, be placed in camera bellows, and the load of putting into 1cm × 1cm embodiment 1 preparation has Prussian blue vertical channel SiO
2the sheet glass of mesopore film, adds 1mM H
2o
2, open uviol lamp prolonged exposure solution 40 minutes, percent of decolourization is 99%.Reuse 6 times continuously, percent of decolourization all reaches 99%.Preserved by sheet glass and reuse after 7 days, 30 days in deionized water again, percent of decolourization still can reach 99%.
From above embodiment, the method technique that the present invention prepares heterogeneous Fenton oxidation catalyst is simple, and mild condition is source of iron with Prussian blue, is Prussian bluely deposited on the amino functional SiO with vertical channel in self assembly mode
2on mesopore film, realize Prussian blue immobilization by physical absorption and positive and negative charge interaction force, in conjunction with firm, anti-current is lost; Prepared catalyst is film catalyst, and specific area is large, and active component utilization ratio is high, and catalytic efficiency is high, compared with Powdered, pellet type catalyst, easily separated, easily reclaim; Simultaneously because catalyst has the mesopore orbit of vertical distribution, inside diffusional resistance is little, and the organism kinds being suitable for processing is many; In addition, catalyst cupport Prussian blue, comprises the iron of variform, has synergy.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a preparation method for heterogeneous ultraviolet-Fenton oxidation catalyst, is characterized in that, comprise the following steps:
Step 1: with double type surfactant for template, with 3-aminopropyl trimethoxysilane for helping structure directing agent, and adds silicon source, adopts sol-gel process, has the SiO of vertical channel structure in substrate material surface preparation
2mesopore film, i.e. VC SiO
2mesopore film;
Step 2: will there is the SiO of vertical channel structure
2mesopore film is placed in ethanol/monoethanolamine mixed solution and dissolves removal template, exposes the amino group introduced by 3-aminopropyl trimethoxysilane in vertical channel simultaneously, realizes VC SiO
2the amino functional of mesopore film;
Step 3: be that source of iron is at the SiO with vertical channel structure with Prussian blue
2mesopore film carries out Prussian blue LBL self-assembly, obtains PB/VC SiO
2mesopore film is heterogeneous ultraviolet-Fenton oxidation catalyst.
2. the preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst as claimed in claim 1, it is characterized in that, the surfactant of double type described in step 1 is preferably dodecyl disodium glutamate, myristyl disodium glutamate, cetyl disodium glutamate or octadecyl disodium glutamate.
3. the preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst as claimed in claim 1, is characterized in that, the source of silicon described in step 1 is ethyl orthosilicate, and described base material is sheet glass or silicon wafer.
4. the preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst as claimed in claim 1, is characterized in that, the molar ratio range in template described in step 1, described 3-aminopropyl trimethoxysilane, described silicon source is 1:1-3:1-40.
5. the preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst as claimed in claim 1, is characterized in that, the ethanol of ethanol described in step 2/monoethanolamine mixed solution and the volume ratio of monoethanolamine are 1:5.
6. the preparation method of the heterogeneous ultraviolet-Fenton oxidation catalyst as described in claim 1 or 5, is characterized in that, the concrete operations of step 2 are the SiO by having vertical channel structure
2mesopore film is placed in ethanol/monoethanolamine mixed solution and adds hot reflux 3-36 hour, then also dry with alcohol flushing.
7. the preparation method of heterogeneous ultraviolet-Fenton oxidation catalyst as claimed in claim 1, is characterized in that, the concrete operations of step 3 are: will have the SiO of vertical channel structure
2mesopore film is alternately placed in K
4fe (CN)
6solution and FeCl
3soak in solution, 30-90s/ time, 10-30 time, then rinsing, drying.
8. heterogeneous ultraviolet-Fenton oxidation catalyst prepared by the preparation method of the heterogeneous ultraviolet-Fenton oxidation catalyst as described in claim 1-5,7 any one.
9. the heterogeneous ultraviolet-application of Fenton oxidation catalyst in sewage disposal prepared by the preparation method of the heterogeneous ultraviolet-Fenton oxidation catalyst as described in claim 1-5,7 any one.
10. the heterogeneous ultraviolet-application of Fenton oxidation catalyst in purifying air prepared by the preparation method of the heterogeneous ultraviolet-Fenton oxidation catalyst as described in claim 1-5,7 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410572458.4A CN104383958B (en) | 2014-10-23 | 2014-10-23 | Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410572458.4A CN104383958B (en) | 2014-10-23 | 2014-10-23 | Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104383958A true CN104383958A (en) | 2015-03-04 |
| CN104383958B CN104383958B (en) | 2017-02-15 |
Family
ID=52601969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410572458.4A Active CN104383958B (en) | 2014-10-23 | 2014-10-23 | Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104383958B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108671901A (en) * | 2018-05-25 | 2018-10-19 | 北京师范大学 | A kind of water body removes the preparation method and application of caesium surface modified membrane |
| CN112138549A (en) * | 2020-09-24 | 2020-12-29 | 常州大学 | Composite fiber membrane for purifying Cs in water and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62161542A (en) * | 1986-01-10 | 1987-07-17 | Seiko Epson Corp | Ink jet recording apparatus |
| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
-
2014
- 2014-10-23 CN CN201410572458.4A patent/CN104383958B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62161542A (en) * | 1986-01-10 | 1987-07-17 | Seiko Epson Corp | Ink jet recording apparatus |
| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
Non-Patent Citations (1)
| Title |
|---|
| AURELIE GOUX等: "Prussian Blue electrodeposition within an oriented mesoporous silica film: preliminary observations", 《J. MATER. SCI.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108671901A (en) * | 2018-05-25 | 2018-10-19 | 北京师范大学 | A kind of water body removes the preparation method and application of caesium surface modified membrane |
| CN108671901B (en) * | 2018-05-25 | 2020-10-02 | 北京师范大学 | Preparation method and application of surface modified membrane for removing cesium in water body |
| CN112138549A (en) * | 2020-09-24 | 2020-12-29 | 常州大学 | Composite fiber membrane for purifying Cs in water and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104383958B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sharma et al. | Adsorptional-photocatalytic removal of fast sulphon black dye by using chitin-cl-poly (itaconic acid-co-acrylamide)/zirconium tungstate nanocomposite hydrogel | |
| Amaly et al. | Synergistic adsorption‑photocatalytic degradation of tetracycline by microcrystalline cellulose composite aerogel dopped with montmorillonite hosted methylene blue | |
| CN103553273B (en) | Integrated treatment method for wastewater by using photocatalytic coupling microbiological method | |
| CN110479224A (en) | Cobalt/nitrogen carbon nanomaterial derived from a kind of organic metal framework and its preparation method and application | |
| CN108212158B (en) | Fenton catalyst and preparation method and application thereof | |
| Jawad et al. | Fabrication, optimization and application of an immobilized layer-by-layer TiO 2/Chitosan system for the removal of phenol and its intermediates under 45-W fluorescent lamp | |
| CN112156662B (en) | Self-cleaning electrostatic spinning nanofiber filter membrane, preparation method and application | |
| CN109261213A (en) | A kind of preparation method and application of bismuth oxyiodide/titanium-based metal organic framework composite material | |
| CN103846099B (en) | A kind of support type polyoxometallate and preparation method thereof | |
| CN105036292A (en) | Method for degrading rhodamine B dye wastewater by catalyzing Oxone with magnetic cobalt catalyst | |
| CN108751335A (en) | A kind of method of antibiotic in light-Fenton-like system concerted catalysis oxidative degradation water environment | |
| CN104383958A (en) | Heterogeneous ultraviolet-Fenton oxidation catalyst and preparation and application thereof | |
| CN104445571B (en) | A kind of ultraviolet-aided heterogeneous Fenton oxidation sewage water treatment method | |
| CN108722344A (en) | It is a kind of to load nano zero-valence iron-copper bi-metal molecular sieve, preparation method and its application of dephosphorization | |
| CN110902804A (en) | Method for removing pollutants in wastewater by utilizing thermally-assisted benzoquinone wastewater to catalyze persulfate | |
| CN110182888A (en) | A kind of photocatalytic reaction device and technique handling rose red b high-salt wastewater | |
| CN110368990A (en) | A kind of preparation method and applications of Cu system polyoxometallate-functional graphene oxide nano material | |
| CN107117683A (en) | A kind of MOFs of Co containing In under visible light in catalytic degradation water body Antibiotics of Low Concentration method | |
| CN111533210A (en) | Method for treating dye wastewater by using UV (ultraviolet) to heat and activate persulfate | |
| CN106430714A (en) | Method for deep treatment of pesticide wastewater | |
| CN113354060B (en) | Method for realizing efficient degradation of environmental pollutants by using red phosphorus in ferric iron/persulfate system | |
| CN113354059B (en) | Method for promoting ferric iron/hydrogen peroxide system to degrade environmental pollutants by using amorphous red phosphorus | |
| CN108358429A (en) | A kind of method of anaerobically digested sludge dehydration | |
| CN103111321B (en) | A kind of preparation method of ironloading molecular sieves type class fenton catalyst and application thereof | |
| CN101597093B (en) | Method for removing phosphate in sewage by photo-catalytic reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |