CN103977800B - The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst - Google Patents
The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst Download PDFInfo
- Publication number
- CN103977800B CN103977800B CN201410208704.8A CN201410208704A CN103977800B CN 103977800 B CN103977800 B CN 103977800B CN 201410208704 A CN201410208704 A CN 201410208704A CN 103977800 B CN103977800 B CN 103977800B
- Authority
- CN
- China
- Prior art keywords
- feooh
- shell structure
- nuclear shell
- structure nano
- synthetic method
- 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.)
- Expired - Fee Related
Links
Abstract
The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst, it relates to the synthetic method of nuclear shell structure nano magnetic FeOOH.The present invention will solve the problem that hydroxyl oxidize iron catalyst difficulty reclaims, easily causes secondary pollution and be difficult to apply in Practical Project.The inventive method: one, prepare iron salt solutions, add auxiliary agent; Two, tetraethoxysilane is added; Three, solid formation B is immersed in ferric salt solution; Four, obtained nuclear shell structure nano magnetic FeOOH.It is large that the nano-core-shell structure magnetic FeOOH that the present invention obtains has specific area, magnetic property is good easily separated, catalytic activity is high, prepare simple advantage, and the core-shell structure magnetic FeOOH that the present invention obtains can promote that ozone decomposed generates hydroxyl radical free radical, increase generating rate and the quantity of free radical in water body.The present invention is used for the synthesis of nuclear shell structure nano magnetic FeOOH ozone catalyst.
Description
Technical field
The present invention relates to the synthetic method of nuclear shell structure nano magnetic FeOOH, belong to Advanced Treatment of Drinking Water field.
Background technology
With the raising of industrial fast development and human substance life horizontal, organic pollutants kind is tending towards variation.Some difficult degradation hazardous contaminants, although concentration is low, harm is large, removal is difficult, and conventional processes can not remove these poisonous and harmful micropollutants effectively, directly threatens urban water supply water quality safety.At water treatment field nano-metal-oxide catalytic ozonation because of the feature such as its efficient oxidation performance, catalyst preparing be simple, become current research focus.FeOOH is extensively present in nature, has stable chemical property, higher specific area and trickle grain structure, its rich surface hydroxyl group, and surface hydroxyl is considered to catalysis ozone and decomposes the active sites improving oxidation usefulness.Early-stage Study finds that FeOOH shows very strong catalytic activity to micro-hardly degraded organic substance in removal water, but in reaction system, hydroxyl oxidize iron catalyst is difficult to reclaim, easily cause secondary pollution, limits its large-scale promotion application in actual water treatment.Magnetic Nano material has that specific area is large, surface-active is high and the feature such as fast reaction under magnetic fields, is widely used in bioengineering, field of medicaments, also represents broad prospect of application at environmental area.Therefore, preparation has the magnetic hydroxyl oxidize iron catalyst that high-efficiency catalytic activity easily reclaims and has practical significance on this basis.
Summary of the invention
The object of the invention is the problem reclaiming, easily cause secondary pollution and be difficult to apply in Practical Project to solve hydroxyl oxidize iron catalyst difficulty, the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst is provided.
The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst of the present invention, is realized by following steps:
One, preparing iron ion molar concentration is the iron salt solutions of 0.5mol/L ~ 2mol/L, and then add auxiliary agent, the molar concentration making auxiliary agent is 0.01mol/L ~ 0.03mol/L, obtains mixed liquor A;
Two, be under the condition of 20 DEG C ~ 30 DEG C in temperature, the mixed liquor A obtained by the aqueous slkali titration step one that molar concentration is 0.5mol/L ~ 2mol/L is 9 ~ 12 to the pH value of mixed liquor A, obtain suspension, after leaving standstill 10min ~ 30min, under nitrogen protection condition, in 40 DEG C ~ 80 DEG C activation 6h ~ 12h, then ultrasonic disperse 10min ~ 20min, add the tetraethoxysilane that molar concentration is 0.1mol/L ~ 0.5mol/L again, the condition lower magnetic force being 120r/min ~ 300r/min in rotating speed stirs 6h ~ 12h, invariable by washed with de-ionized water 2 ~ 3 times pH value to cleaning fluid after suction filtration solid formation, roasting 2h ~ 3h under 60 DEG C ~ 550 DEG C conditions, obtain solid formation B,
Three, solid formation B step 2 obtained is 1g:(1 ~ 2 according to quality and volume ratio) to immerse molar concentration be in the ferric salt solution of 0.5mol/L ~ 2mol/L for the ratio of mL, then dry at 40 DEG C ~ 60 DEG C, obtain solid C;
Four, it is in the aqueous slkali of 0.5mol/L ~ 2mol/L that solid C step 3 obtained immerses molar concentration, obtain suspension, the pH value regulating suspension is 9 ~ 12, after stirring 30min ~ 120min, at 40 DEG C ~ 80 DEG C, activates 24h ~ 48h, then suction filtration solid formation, first use washes of absolute alcohol 1 ~ 2 time, then use washed with de-ionized water 3 ~ 5 times, invariable to cleaning fluid pH value, dry under 40 DEG C ~ 100 DEG C conditions, obtain nuclear shell structure nano magnetic FeOOH.
Beneficial effect of the present invention:
The present invention prepares core-shell structure magnetic FeOOH, improves Nano ferric hydroxide Separation of Solid and Liquid performance, and exploiting economy practicality, safely and effectively catalytic ozonation technology, provide a kind of synthetic method of new catalyst.
It is large that the nano-core-shell structure magnetic FeOOH that the present invention obtains has specific area, magnetic property is good easily separated, catalytic activity is high, prepare simple advantage, and the core-shell structure magnetic FeOOH that the present invention obtains can promote that ozone decomposed generates hydroxyl radical free radical, increase generating rate and the quantity of free radical in water body.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the core-shell structure magnetic FeOOH that embodiment one is synthesized;
Fig. 2 is the room temperature hysteresis curve of the core-shell structure magnetic FeOOH that embodiment one is synthesized;
Fig. 3 removes Effectiveness Comparison experimental result picture, and wherein zero represent core-shell magnetic FeOOH catalytic ozonation clearance, represents independent ozonisation clearance, and △ represents core-shell magnetic FeOOH adsorb organic compound clearance;
Fig. 4 is that strengthening hydroxyl radical free radical generates result figure, and wherein A represents the decomposition of core-shell magnetic FeOOH catalysis ozone and generates hydroxyl free rheobase, and B represents ozone selfdecomposition and generates hydroxyl free rheobase.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the synthetic method of present embodiment nuclear shell structure nano magnetic FeOOH ozone catalyst, carry out according to the following steps:
One, preparing iron ion molar concentration is the iron salt solutions of 0.5mol/L ~ 2mol/L, and then add auxiliary agent, the molar concentration making auxiliary agent is 0.01mol/L ~ 0.03mol/L, obtains mixed liquor A;
Two, be under the condition of 20 DEG C ~ 30 DEG C in temperature, the mixed liquor A obtained by the aqueous slkali titration step one that molar concentration is 0.5mol/L ~ 2mol/L is 9 ~ 12 to the pH value of mixed liquor A, obtain suspension, after leaving standstill 10min ~ 30min, under nitrogen protection condition, in 40 DEG C ~ 80 DEG C activation 6h ~ 12h, then ultrasonic disperse 10min ~ 20min, add the tetraethoxysilane that molar concentration is 0.1mol/L ~ 0.5mol/L again, the condition lower magnetic force being 120r/min ~ 300r/min in rotating speed stirs 6h ~ 12h, invariable by washed with de-ionized water 2 ~ 3 times pH value to cleaning fluid after suction filtration solid formation, roasting 2h ~ 3h under 60 DEG C ~ 550 DEG C conditions, obtain solid formation B,
Three, solid formation B step 2 obtained is 1g:(1 ~ 2 according to quality and volume ratio) to immerse molar concentration be in the ferric salt solution of 0.5mol/L ~ 2mol/L for the ratio of mL, then dry at 40 DEG C ~ 60 DEG C, obtain solid C;
Four, it is in the aqueous slkali of 0.5mol/L ~ 2mol/L that solid C step 3 obtained immerses molar concentration, obtain suspension, the pH value regulating suspension is 9 ~ 12, after stirring 30min ~ 120min, at 40 DEG C ~ 80 DEG C, activates 24h ~ 48h, then suction filtration solid formation, first use washes of absolute alcohol 1 ~ 2 time, then use washed with de-ionized water 3 ~ 5 times, invariable to cleaning fluid pH value, dry under 40 DEG C ~ 100 DEG C conditions, obtain nuclear shell structure nano magnetic FeOOH.
The beneficial effect of present embodiment:
It is large that the nano-core-shell structure magnetic FeOOH that present embodiment obtains has specific area, magnetic property is good easily separated, catalytic activity is high, prepare simple advantage, and the core-shell structure magnetic FeOOH that present embodiment obtains can promote that ozone decomposed generates hydroxyl radical free radical, increase generating rate and the quantity of free radical in water body.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: the iron salt solutions described in step one is the mixed solution of divalent iron salt solution or divalent iron salt and trivalent iron salt, and in the mixed solution of wherein divalent iron salt and trivalent iron salt, the mol ratio of ferrous ion and ferric ion is 1:(2 ~ 3.5).Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike: described divalent iron salt is frerrous chloride or ferrous sulfate, and trivalent iron salt is ferric nitrate, ferric sulfate or iron chloride.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the auxiliary agent described in step one is urea or EDTA.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: the preparation iron ion molar concentration described in step one is the iron salt solutions of 0.5mol/L, then adds auxiliary agent, makes the molar concentration of auxiliary agent be 0.01mol/L.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: the aqueous slkali described in step 2 is potassium hydroxide, NaOH or ammoniacal liquor.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: the roasting 3h under 60 DEG C of conditions described in step 2, obtains solid formation B.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: the trivalent iron salt described in step 3 is ferric nitrate, ferric sulfate or iron chloride.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike: it is in the ferric salt solution of 0.5mol/L that solid formation B step 2 obtained described in step 3 immerses molar concentration according to the ratio that quality and volume ratio are 1g:1.5mL.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike: after the stirring 60min described in step 4, at 40 DEG C, activate 48h.Other is identical with one of detailed description of the invention one to nine.
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment one:
The synthetic method of the present embodiment nuclear shell structure nano magnetic FeOOH ozone catalyst, carry out according to the following steps:
One, preparing molar concentration is the iron salt solutions of 0.5mol/L, wherein Fe
2+and Fe
3+mol ratio be 1:2, then add urea, the molar concentration making urea is 0.01mol/L, obtains mixed liquor A;
Two, under 20 DEG C of conditions, be the aqueous slkali titration A of 0.5mol/L by molar concentration be 12 to solution ph, obtain suspension, after leaving standstill 30min, under the nitrogen atmosphere of 0.5mL/min encloses, in 40 DEG C of activation 6h, ultrasonic disperse 10min, add the tetraethoxysilane that molar concentration is 0.1mol/L again, the condition lower magnetic force stirring 8h being 120r/min in rotating speed makes its complete hydrolysis, suction filtration solid formation washed with de-ionized water 2 times, invariable to cleaning fluid pH value, roasting 3h under 60 DEG C of conditions, obtains solid formation B;
Three, it is in the iron nitrate solution of 0.5mol/L that solid formation B step 2 obtained immerses molar concentration according to the ratio that quality and volume ratio are 1g:1.5mL, then dries at 60 DEG C, obtains solid C;
Four, it is in the sodium hydroxide solution of 1mol/L that solid C step 3 obtained immerses molar concentration, obtain suspension, the pH value regulating suspension is 12, after stirring 60min, at 40 DEG C, activates 48h, then suction filtration solid formation, first use washes of absolute alcohol 1 time, then use washed with de-ionized water 3 times, constant to cleaning fluid pH value, dry under 60 DEG C of conditions, obtain nuclear shell structure nano magnetic FeOOH.
Contrast experiment:
Remove the organic pollution parachloronitrobenzene of same concentrations in water respectively, one group adds ozone separately, and ozone dosage is 1.0mg/L; Another group adds the core-shell structure magnetic FeOOH of ozone and embodiment one synthesis, and ozone dosage is 1.0mg/L, and magnetic FeOOH dosage is 100mg/L; In two groups of water, the removal effect of parachloronitrobenzene as shown in Figure 3.Compared with independent ozone oxidation parachloronitrobenzene clearance, O3 catalytic oxidation clearance (reaction 20min) improves nearly 30 percentage points, and magnetic FeOOH absorption parachloronitrobenzene clearance is very little, negligible to the contribution of catalytic elimination rate less than 3 percentage points.Experimental data illustrates that the active stiff stability of core-shell structure magnetic FeOOH catalytic elimination pollutant is high.Under this experiment condition, add core-shell structure magnetic nanoneedle iron ore and the utilization rate of ozone can be made to improve nearly 20 ~ 30 percentage points.
Magnetic FeOOH decomposes the catalyst generating hydroxyl radical free radical as catalysis ozone active strong for having catalytic elimination organic pollution in test, and self stability is high, is easy to recycle, and does not produce the advantages such as secondary pollution.This invention is preparation technology simply, easily synthesize, with low cost, can be applied in engineering of water treatment on a large scale.
Claims (8)
1. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst, is characterized in that it comprises the following steps:
One, preparing iron ion molar concentration is the iron salt solutions of 0.5mol/L ~ 2mol/L, and then add auxiliary agent, the molar concentration making auxiliary agent is 0.01mol/L ~ 0.03mol/L, obtains mixed liquor A;
Two, be under the condition of 20 DEG C ~ 30 DEG C in temperature, the mixed liquor A obtained by the aqueous slkali titration step one that molar concentration is 0.5mol/L ~ 2mol/L is 9 ~ 12 to the pH value of mixed liquor A, obtain suspension, after leaving standstill 10min ~ 30min, under nitrogen protection condition, in 40 DEG C ~ 80 DEG C activation 6h ~ 12h, then ultrasonic disperse 10min ~ 20min, add the tetraethoxysilane that molar concentration is 0.1mol/L ~ 0.5mol/L again, the condition lower magnetic force being 120r/min ~ 300r/min in rotating speed stirs 6h ~ 12h, invariable by washed with de-ionized water 2 ~ 3 times pH value to cleaning fluid after suction filtration solid formation, roasting 2h ~ 3h under 60 DEG C ~ 550 DEG C conditions, obtain solid formation B,
Three, solid formation B step 2 obtained is 1g:(1 ~ 2 according to quality and volume ratio) to immerse molar concentration be in the ferric salt solution of 0.5mol/L ~ 2mol/L for the ratio of mL, then dry at 40 DEG C ~ 60 DEG C, obtain solid C;
Four, it is in the aqueous slkali of 0.5mol/L ~ 2mol/L that solid C step 3 obtained immerses molar concentration, obtain suspension, the pH value regulating suspension is 9 ~ 12, after stirring 30min ~ 120min, at 40 DEG C ~ 80 DEG C, activates 24h ~ 48h, then suction filtration solid formation, first use washes of absolute alcohol 1 ~ 2 time, then use washed with de-ionized water 3 ~ 5 times, invariable to cleaning fluid pH value, dry under 40 DEG C ~ 100 DEG C conditions, obtain nuclear shell structure nano magnetic FeOOH;
Five, the iron salt solutions described in step one is the mixed solution of divalent iron salt solution or divalent iron salt and trivalent iron salt, and in the mixed solution of wherein divalent iron salt and trivalent iron salt, the mol ratio of ferrous ion and ferric ion is 1:(2 ~ 3.5); Wherein divalent iron salt is frerrous chloride or ferrous sulfate, and trivalent iron salt is ferric nitrate, ferric sulfate or iron chloride.
2. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, is characterized in that the auxiliary agent described in step one is urea or EDTA.
3. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, it is characterized in that the preparation iron ion molar concentration described in step one is the iron salt solutions of 0.5mol/L, then add auxiliary agent, make the molar concentration of auxiliary agent be 0.01mol/L.
4. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, is characterized in that the aqueous slkali described in step 2 is potassium hydroxide, NaOH or ammoniacal liquor.
5. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, is characterized in that the roasting 3h under 60 DEG C of conditions described in step 2, obtains solid formation B.
6. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, is characterized in that the trivalent iron salt described in step 3 is ferric nitrate, ferric sulfate or iron chloride.
7. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, it is characterized in that solid formation B step 2 obtained described in step 3 immerses molar concentration according to the ratio that quality and volume ratio are 1g:1.5mL is in the ferric salt solution of 0.5mol/L.
8. the synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst according to claim 1, after it is characterized in that the stirring 60min described in step 4, activates 48h at 40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208704.8A CN103977800B (en) | 2014-05-16 | 2014-05-16 | The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208704.8A CN103977800B (en) | 2014-05-16 | 2014-05-16 | The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103977800A CN103977800A (en) | 2014-08-13 |
| CN103977800B true CN103977800B (en) | 2016-01-20 |
Family
ID=51270111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410208704.8A Expired - Fee Related CN103977800B (en) | 2014-05-16 | 2014-05-16 | The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103977800B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349904A (en) * | 2017-08-29 | 2017-11-17 | 苏州北控环保科技有限公司 | The preparation of magnetic carbon nano-fiber composite material and its application in river regulation |
| CN108126686B (en) * | 2017-12-27 | 2019-12-03 | 苏州大学 | Core-shell catalyst and preparation method thereof and the application in catalytic ozonation |
| CN108314087B (en) * | 2018-03-12 | 2019-11-08 | 清华大学 | A kind of preparation method and applications of the super particle of unformed FeOOH |
| CN114772702B (en) * | 2022-03-28 | 2023-10-24 | 上海电力大学 | Method for removing iohexol in water by catalyzing ozone through oxidation-reduction medium reinforced ferric oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711426A (en) * | 1970-02-26 | 1973-01-16 | Topsoe H | Process for preparing a chromium-promoted iron oxide catalyst |
| CN101143733A (en) * | 2007-08-28 | 2008-03-19 | 武汉大学 | Method for preparing magnetic ferric oxide nano particles |
| CN103420429A (en) * | 2013-07-26 | 2013-12-04 | 重庆绿色智能技术研究院 | Preparation method of nano magnetic iron oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57124404A (en) * | 1981-01-26 | 1982-08-03 | Toda Kogyo Corp | Manufacture of magnetic iron oxide powder |
-
2014
- 2014-05-16 CN CN201410208704.8A patent/CN103977800B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711426A (en) * | 1970-02-26 | 1973-01-16 | Topsoe H | Process for preparing a chromium-promoted iron oxide catalyst |
| CN101143733A (en) * | 2007-08-28 | 2008-03-19 | 武汉大学 | Method for preparing magnetic ferric oxide nano particles |
| CN103420429A (en) * | 2013-07-26 | 2013-12-04 | 重庆绿色智能技术研究院 | Preparation method of nano magnetic iron oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103977800A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Photocatalysis activation of peroxodisulfate over the supported Fe3O4 catalyst derived from MIL-88A (Fe) for efficient tetracycline hydrochloride degradation | |
| Deng et al. | Facile fabrication of mediator-free Z-scheme photocatalyst of phosphorous-doped ultrathin graphitic carbon nitride nanosheets and bismuth vanadate composites with enhanced tetracycline degradation under visible light | |
| CN111790422B (en) | Graphitized nitrogen-complexed Fe (III) -Fe0Catalyst, and synthesis method and application thereof | |
| CN108855164A (en) | A kind of carbon cloth load MoS2/Ag3PO4The preparation method of composite photocatalyst material | |
| CN103977800B (en) | The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst | |
| CN104190472B (en) | A kind of new and effective multiphase Fenton catalyst Fe 3O4@EDTA preparation and application | |
| CN104069860B (en) | The preparation of magnetic nano copper ferrum oxyhydroxide and the application in O3 catalytic oxidation depollution thereof | |
| CN103816903B (en) | The synthetic method of iron-base magnetic nanoneedle iron ore | |
| CN111167482A (en) | MoS2/CuFe2O4Catalyst, preparation method and application thereof | |
| CN107252685A (en) | A kind of hydroxyl aminated compounds functional magnetic graphene oxide catalysis material and its preparation method and application | |
| CN109650484A (en) | A kind of waste water treating agent and preparation method thereof | |
| Tang et al. | A novel S-scheme heterojunction in spent battery-derived ZnFe2O4/g-C3N4 photocatalyst for enhancing peroxymonosulfate activation and visible light degradation of organic pollutant | |
| CN105032375A (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| CN108083347B (en) | Preparation of cobalt ion induced flower-like cobalt manganese oxide and product and application thereof | |
| CN105566400A (en) | Heterogeneous cobalt metal-organic skeleton and preparation and application to wastewater treatment field | |
| CN102659126A (en) | Preparation method and application of iron-manganese composite silicate | |
| CN106964333B (en) | Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone | |
| CN105642298B (en) | The graphene-supported nano Ce of reproducibility0/Fe0Composite material and its preparation method and application | |
| Gao et al. | Co3O4@ Fe3O4/cellulose blend membranes for efficient degradation of perfluorooctanoic acid in the visible light-driven photo-Fenton system | |
| CN109499563A (en) | A kind of preparation method of zinc oxide-active carbon composite catalyst | |
| CN108722445B (en) | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application | |
| CN109985616A (en) | A kind of catalyst and preparation method thereof of photocatalytic degradation organic wastewater | |
| CN110342628A (en) | A kind of processing method that copper waste water is complexed | |
| CN101798092A (en) | Polyferro-silicate, preparation method thereof and applications thereof in water treatment | |
| CN102114420A (en) | Method for preparing zinc silicate catalyst |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20180516 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |