CN106186271A - Activated carbon coppe ferrite composite, its preparation method and photocatalysis denitrogenation purposes - Google Patents
Activated carbon coppe ferrite composite, its preparation method and photocatalysis denitrogenation purposes Download PDFInfo
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- CN106186271A CN106186271A CN201610632620.6A CN201610632620A CN106186271A CN 106186271 A CN106186271 A CN 106186271A CN 201610632620 A CN201610632620 A CN 201610632620A CN 106186271 A CN106186271 A CN 106186271A
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- activated carbon
- coppe ferrite
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- 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
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses activated carbon coppe ferrite composite, its preparation method and photocatalysis denitrogenation purposes.Described activated carbon coppe ferrite composite includes that activated carbon and coppe ferrite, wherein said coppe ferrite are spinel structure, and described coppe ferrite has Fd3m space group structure.In the activated carbon coppe ferrite composite that the present invention provides, not only activated carbon can be by the ammonia nitrogen in the absorption property adsorbed water body of self, coordinate bond can also be formed with ammonia nitrogen by the unoccupied orbital of transition metal, thus realize the economic benefits and social benefits to water body ammonia nitrogen and adsorb, and then on the basis of enrichment ammonia nitrogen optionally photocatalytic degradation ammonia nitrogen, realize the intelligent optical catalysis denitrogenation of polluted-water, and the preparation method of described activated carbon coppe ferrite composite is simple, and condition is easily-controllable, and cheaper starting materials is easy to get.
Description
Technical field
The present invention relates to a kind of composite, particularly to a kind of activated carbon-coppe ferrite composite and optionally
Application in photocatalysis denitrogenation, belongs to photocatalysis technology field.
Background technology
Taihu Lake cyanophyceae contamination accident in 2007 causes the whole nation highest attention to ammonia and nitrogen pollution, and ammonia nitrogen processing method is divided into life
Thing method, Physical and chemical method.At present, the ammonia nitrogen (< 100mg/L) of low concentration can pass through nitrification-denitrification technique denitrogenation, nitre
Change effect is divided into ammoxidation and nitrite-oxidizing, and the nitrate of formation becomes gas by denitrification and discharges and reach denitrification effect.
But under the conditions of high ammonia nitrogen heavily contaminated, owing to antibacterial is very sensitive to factors such as weather, temperature, Organic substance, dissolved oxygen, the party
Method cost is high, and the input that management is safeguarded is high, it is therefore desirable to develop new denitrification process.
Along with the development of science and technology, research worker is explored and is utilized semi-conducting material (predominantly TiO2) as photocatalyst
Carry out degradation of ammonia nitrogen, but these research work are exploitation solar energy purification environment has made positive trial, but photocatalytic degradation
Ammonia nitrogen shortage selectivity, and TiO2Only with the ultraviolet light in solar energy, it is impossible to utilize its visible ray, therefore solar energy
Utilization rate is the highest.
Accordingly, it would be desirable to the highest selective photocatalyst of exploitation, in order to quick, stable, lasting, inexpensively, cleanly in fact
The target of existing denitrogenation.
Summary of the invention
It is an object of the invention to provide a kind of activated carbon-coppe ferrite composite, its preparation method and photocatalysis denitrogenation
Purposes, to overcome deficiency of the prior art.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
Embodiments providing activated carbon-coppe ferrite composite, it includes activated carbon and coppe ferrite, described ferrous acid
Copper is distributed in surface and/or the hole of described activated carbon, and wherein said coppe ferrite is spinel structure, and described coppe ferrite
There is Fd3m space group structure.
The embodiment of the present invention additionally provides the preparation method of described activated carbon-coppe ferrite composite.
The embodiment of the present invention additionally provides described activated carbon-coppe ferrite composite purposes in photocatalysis denitrogenation.
Compared with prior art, the invention have the advantages that
(1) in the activated carbon provided-coppe ferrite composite, activated carbon is permissible not only by the absorption property of self
Ammonia nitrogen in adsorbed water body, it is also possible to make activated carbon with ammonia nitrogen weak binding by chemical bond thus realize the economic benefits and social benefits suction of water body ammonia nitrogen
Attached, thus realize the efficient removal of ammonia nitrogen in water body, and then, described activated carbon-coppe ferrite composite can also be by water body ammonia
Nitrogen direct oxidation is nitrogen, will not produce secondary pollution, and when described catalyst is continuing with after photocatalysis denitrogenation 5-10 time,
For the removal efficiency of ammonia nitrogen still more than 95%.
(2) preparation method of the activated carbon provided-coppe ferrite composite is simple, and condition is easily-controllable, and cheaper starting materials is easy to get.
Accompanying drawing explanation
Fig. 1 is the photocatalysis of the activated carbon-coppe ferrite composite catalyst degradation of ammonia nitrogen prepared in the embodiment of the present invention 1
Degradation curve figure；
Fig. 2 be in comparative example 1 of the present invention in the case of ammonia nitrogen and rhodamine B exist simultaneously activated carbon-coppe ferrite composite wood
Expect the photocatalytic degradation curve chart of optionally degradation of ammonia nitrogen；
Fig. 3 be in comparative example 2 of the present invention in the case of ammonia nitrogen and methyl orange exist simultaneously activated carbon-coppe ferrite composite
The optionally photocatalytic degradation curve chart of degradation of ammonia nitrogen；
Fig. 4 is the nitric efficiency that the activated carbon-coppe ferrite composite prepared in the embodiment of the present invention 1 reuses 8 times
Graph of relation with the denitrogenation time.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, the concrete reality to the present invention below in conjunction with the accompanying drawings
The mode of executing is described in detail.The example of these preferred implementations is illustrated in the accompanying drawings.Shown in accompanying drawing and according to
The embodiments of the present invention that accompanying drawing describes are merely exemplary, and the present invention is not limited to these embodiments.
Here, also, it should be noted in order to avoid having obscured the present invention because of unnecessary details, the most only
Show and according to the closely-related structure of the solution of the present invention and/or process step, and eliminate little with relation of the present invention
Other details.
Embodiments providing a kind of activated carbon-coppe ferrite composite, it includes activated carbon and coppe ferrite, described
Coppe ferrite is distributed in surface and/or the hole of described activated carbon, and wherein said coppe ferrite is spinel structure, and described ferrum
Acid copper has Fd3m space group structure.
Further, in described coppe ferrite crystal, oxonium ion is distributed by face-centred cubic structure, 4 adjacent oxonium ions
The line of centres can obtain tetrahedral structure and/or adjacent 8 oxonium ions are connected as octahedral structure, and copper ion occupies tetrahedral
Gap, iron ion occupies octahedral gap.
Further, in described composite, the mass percentage content of coppe ferrite is 90-100%, the quality of activated carbon
Degree is 0%-10%.
The embodiment of the present invention additionally provides described activated carbon-coppe ferrite composite purposes in photocatalysis denitrogenation.
Further, described purposes includes: being added by activated carbon-coppe ferrite composite may be containing the water body of ammonia nitrogen
And form mixed system, and make the ammonia nitrogen in activated carbon-abundant adsorbed water body of coppe ferrite composite, then with radiation of visible light shape
The mixed system become, makes the ammonia nitrogen in water body be degraded to N2Gas, it is achieved the removing of ammonia nitrogen in water body.
More preferred, regulate described mixed system in alkalescence, then with mixed system described in radiation of visible light, it is achieved water
The removing of ammonia nitrogen in body.
It is more highly preferred to, by described mixed system to pH value more than 9, preferably greater than 10.5, then with described in radiation of visible light
Mixed system, it is achieved the removing of ammonia nitrogen in water body.
The embodiment of the present invention additionally provides the preparation method of described activated carbon-coppe ferrite composite and includes: by solubility
Mantoquita, soluble ferric iron salt are dissolved in solvent with activated carbon mixs homogeneously, and regulating obtained mixed solution afterwards is alkalescence, then by institute
State mixed solution under the conditions of 150-200 DEG C, react 6-10h, prepare described activated carbon-coppe ferrite composite.
Further, described soluble copper salt is 1:1-3 with the mol ratio of soluble ferric iron salt.
More preferred, described soluble copper salt includes Cu (NO3)2·6H2O, but it is not limited to this.
More preferred, described soluble ferric iron salt includes Fe (NO3)3·9H2O, but it is not limited to this.
More preferred, described alkaline solution includes NaOH solution, but is not limited to this.
Further, described mixed solution is placed in reaction 8-10h under conditions of temperature is 180-200 DEG C, spends afterwards
Ionized water washs, and is dried in being then placed on the vacuum drying oven that temperature is 40-80 DEG C, i.e. prepares described activated carbon-ferrum
Acid carbon/carbon-copper composite material.
Activated carbon-coppe ferrite composite that the present invention provides includes activated carbon and coppe ferrite, and wherein activated carbon can lead to
Crossing the ammonia nitrogen in the absorption property adsorbed water body of self, coppe ferrite forms coordinate bond by the unoccupied orbital of transition metal with ammonia nitrogen,
Thus realize the economic benefits and social benefits efficient absorption to water body ammonia nitrogen, and then optionally ammonia nitrogen photocatalysis is dropped on the basis of enrichment ammonia nitrogen
Solve as nitrogen, it is achieved the intelligent optical catalysis denitrogenation of polluted-water, and secondary pollution will not be produced.
Below in conjunction with drawings and Examples the technical solution of the present invention is further explained explanation.
Embodiment 1
(1) coppe ferrite (CuFe2O4) synthesis: 1:2 precise Cu (NO in molar ratio3)2·6H2O(4.0400g,
0.01mol)、Fe(NO3)3·9H2O (4.8480g, 0.012mol) is dissolved separately in 10ml deionized water, precise NaOH
(1.9200g, 0.048mol) is dissolved in 10ml deionized water.NaOH is slowly added dropwise mixed under the conditions of magnetic agitation
Close in solution, then be washed with deionized in beaker the NaOH of residual and add in mixed solution.Continuing stirring 20min makes it mix
Closing uniformly, now overall solution volume is about about 50ml.Then mixed solution is added in the hydrothermal reaction kettle of 100ml, use
Debris in deionized water rinse beaker, and add in reactor, the cumulative volume controlled in reactor is about 60ml, then
React 8h under conditions of reactor is placed in 180 DEG C, after cooling, take out and stand, be washed with deionized 3-4 time, then will
It is dried 24h in being placed in the vacuum drying oven of 60 DEG C, obtains sample CuFe2O4。
(2) synthesis of activated carbon-coppe ferrite composite: 1:2 precise Cu (NO in molar ratio3)2·6H2O
(1.2080g,0.005mol)、Fe(NO3)3·9H2O (4.0400g, 0.01mol)) it is dissolved separately in 10ml deionized water, then claim
Take activated carbon (0.048g, CuFe2O4The 4% of quality) ultrasonic dissolution is in 10ml deionized water, by front under magnetic agitation effect
Both are slowly added in Actidose, stir 30min mix homogeneously.Precise NaOH (1.6000g, 0.04mol) dissolves
In 10ml deionized water.Under the conditions of magnetic agitation, NaOH is slowly added dropwise in mixed solution, then uses deionized water
Wash the NaOH of residual in beaker and add in mixed solution.Continue stirring 20min and make its mix homogeneously, now overall solution volume
It is about about 50ml.Then mixed solution is added in the hydrothermal reaction kettle of 100ml, residual with in deionized water rinse beaker
Staying liquid, and add in reactor, the cumulative volume controlled in reactor is about 60ml, and then reactor is placed in the bar of 180 DEG C
React 8h under part, after cooling, take out and stand, be washed with deionized 3-4 time, be then placed on the vacuum drying oven of 60 DEG C
Interior dry 24h, obtains sample activity charcoal-coppe ferrite composite.
The preparation of nessler reagent: accurately weigh 16gNaOH, is dissolved in 40ml water, is sufficiently cooled to room temperature.Weigh 10g HgI2
Mixed dissolution ultrasonic with 7g KI is in 40ml water.Then this mixed solution is slowly injected into NaOH under constant agitation molten
In liquid, dilute and be settled to 100ml, seal and be stored in 100ml volumetric flask.Ammonia nitrogen is as follows with the color mechanism of nessler reagent:
NH4 ++2[HgI4]2-(Yellow)+4HO-→HgO·Hg(NH2)I(Brown)+7I-+3H2O(1)
The preparation of screening agent: accurately weigh 50g sodium potassium tartrate tetrahydrate and be dissolved in 100ml in water, heated and boiled, it is cooled to room
Temperature, adds water and is settled to 100ml, seals and is stored in 100ml volumetric flask.
By reagent colorimetric method, the absorption intensity of ammonia nitrogen can be recorded at wavelength 388nm, thus analyze the dense of ammonia nitrogen
Degree change carrys out Study of Catalyst degradation of ammonia nitrogen optimum condition.
The degraded of ammonia nitrogen: use 50mL beaker is as the reaction unit of photocatalytic degradation ammonia nitrogen, under room temperature (25 DEG C ± 2 DEG C)
Carrying out catalysis degeneration experiment, beaker wall of cup masking foil surrounds to avoid stray light emission.Cover on reactor with filter plate
End, allows visible ray λ > 400nm pass through.Loading the ammonia nitrogen solution of 50ml in reactor, concentration is 100mg/L, uses Na2CO3-
NaHCO3(0.1mol/L) regulate the pH value of reactant liquor as buffer solution, the activated carbon-coppe ferrite adding about 0.1g is combined
Material carries out catalysis degeneration experiment.Reactant liquor is about 10cm with the vertical dimension of light source.The mensuration of ammonia-nitrogen content in course of reaction
Use reagent colorimetric method.Ultraviolet-uisible spectrophotometer is utilized to measure ammonia nitrogen solution under nessler reagent develops the color at wavelength
The trap of 388nm, follows the tracks of ammonia nitrogen with this, sees Fig. 1, and through the degraded of 8h, the degradation rate of ammonia nitrogen reaches 95%, 8 circulations
After degradation of ammonia nitrogen, ammonia nitrogen removal frank, still more than 90%, sees Fig. 4.
Comparative example 1
Other reactions steps and condition are the most same as in Example 1, and difference is:
The experiment of photocatalysis to selectively degradation of ammonia nitrogen is simultaneously introduced in reactor ammonia nitrogen solution and the rhodamine B of 50ml
(wherein, the concentration of ammonia nitrogen is 100mg/L, and the concentration of rhodamine B is 100mg/L), utilizes ultraviolet-uisible spectrophotometer to measure
The trap of solution, sees Fig. 2, and through the degraded of 8 hours, the degradation rate of rhodamine B was only 20%, and in system, residual concentration is still
More than 80mg/L, and the degradation rate of ammonia nitrogen is more than 93%.
Comparative example 2
Other reactions steps and condition are the most same as in Example 1, and difference is:
The experiment of photocatalysis to selectively degradation of ammonia nitrogen is simultaneously introduced in reactor ammonia nitrogen solution and methyl orange (its of 50ml
In, the concentration of ammonia nitrogen is 100mg/L, and the concentration of methyl orange is 100mg/L), utilize ultraviolet-uisible spectrophotometer to measure solution
Trap, see Fig. 3, the degradation rate through the degradation process rhodamine B of 8 hours is only 15%, and in system, residual concentration is still
More than 85mg/L, and the degradation rate of ammonia nitrogen is more than 94%.
Should be appreciated that above-described embodiment is only technology design and the feature of the explanation present invention, its object is to allow and be familiar with this
The personage of item technology will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All
The equivalence change made according to spirit of the invention or modification, all should contain within protection scope of the present invention.
Claims (10)
1. activated carbon-coppe ferrite composite purposes in photocatalysis denitrogenation, described activated carbon-coppe ferrite composite includes
Activated carbon and coppe ferrite, described coppe ferrite is distributed in surface and/or the hole of described activated carbon, and wherein said coppe ferrite is point
Spar type structure, and described coppe ferrite has Fd3m space group structure.
Purposes the most according to claim 1, it is characterised in that: in described coppe ferrite crystal, oxonium ion is to tie by face-centered cubic
Structure distribution, 4 adjacent oxonium ion lines of centres can obtain tetrahedral structure and/or adjacent 8 oxonium ions are connected as octahedral
Body structure, copper ion occupies tetrahedral gap, and iron ion occupies octahedral gap；And/or, ferrous acid in described composite
The mass percent of copper is 90-100%, and the mass percent of activated carbon is 0%-10%.
Purposes the most according to claim 1, it is characterised in that including: being added by activated carbon-coppe ferrite composite may
Water body containing ammonia nitrogen also forms mixed system, and make the ammonia nitrogen in activated carbon-abundant adsorbed water body of coppe ferrite composite, then
The mixed system formed with radiation of visible light, makes the ammonia nitrogen in water body be degraded to N2Gas, it is achieved the removing of ammonia nitrogen in water body.
Purposes the most according to claim 3, it is characterised in that including: regulate described mixed system in alkalescence, then with can
See that light irradiates described mixed system, it is achieved the removing of ammonia nitrogen in water body.
Purposes the most according to claim 3, it is characterised in that including: by described mixed system to pH value more than 9, the most greatly
In 10.5, then with mixed system described in radiation of visible light, it is achieved the removing of ammonia nitrogen in water body.
6. activated carbon-coppe ferrite composite, it is characterised in that: described activated carbon-coppe ferrite composite includes activity
Charcoal and coppe ferrite, described coppe ferrite is distributed in surface and/or the hole of described activated carbon, and wherein said coppe ferrite is spinelle
Type structure, and described coppe ferrite has Fd3m space group structure.
Activated carbon the most according to claim 6-coppe ferrite composite, it is characterised in that: oxygen in described coppe ferrite crystal
Ion is distributed by face-centred cubic structure, and 4 adjacent oxonium ion lines of centres can obtain tetrahedral structure and/or adjacent 8
Individual oxonium ion is connected as octahedral structure, and copper ion occupies tetrahedral gap, and iron ion occupies octahedral gap；And/or,
In described composite, the mass percent of coppe ferrite is 90-100%, and the mass percent of activated carbon is 0%-10%.
8. the preparation method of activated carbon-coppe ferrite composite, it is characterised in that including: by soluble copper salt, solubility
Iron salt is dissolved in solvent with activated carbon mixs homogeneously, and it is alkaline for regulating obtained mixed solution afterwards, then by mixed solution in
React 6-10h under the conditions of 150-200 DEG C, prepare described activated carbon-coppe ferrite composite.
The preparation method of activated carbon the most according to claim 8-coppe ferrite composite, it is characterised in that: described solvable
Property mantoquita and soluble ferric iron salt mol ratio be 1:1-3；And/or, described soluble copper salt includes Cu (NO3)2·6H2O；With/
Or, described soluble ferric iron salt includes Fe (NO3)3·9H2O；And/or, described alkaline solution includes NaOH solution.
The preparation method of activated carbon the most according to claim 8-coppe ferrite composite, it is characterised in that including: by institute
State mixed solution and be placed in reaction 8-10h under conditions of temperature is 180-200 DEG C, be washed with deionized afterwards, then put
It is dried in the vacuum drying oven that temperature is 40-80 DEG C, i.e. prepares described activated carbon-coppe ferrite composite.
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| CN107413296A (en) * | 2017-07-21 | 2017-12-01 | 浙江省农业科学院 | A kind of charcoal ferrojacobsite composite for being used to adsorb heavy metal antimony cadmium |
| CN110523415A (en) * | 2019-09-03 | 2019-12-03 | 浙江天地环保科技有限公司 | Copper and iron layered double hydroxide, copper and iron layered double hydroxide/C-base composte material and its preparation method and application |
| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
| CN111229161A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Using CuFeO2Method for adsorbing oxytetracycline by/BC composite magnetic material |
| CN111841487A (en) * | 2020-06-22 | 2020-10-30 | 安徽创能环保材料有限公司 | Preparation process and application of modified fly ash composite material |
| CN112774630A (en) * | 2021-01-11 | 2021-05-11 | 陈章平 | Preparation method of activated carbon adsorbent for regenerating and adsorbing methyl orange |
| CN113101931A (en) * | 2021-03-22 | 2021-07-13 | 宝璟科技(深圳)有限公司 | Preparation method and application of modified carbon-coated copper nanoparticles carried by cupronickel |
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| CN107413296A (en) * | 2017-07-21 | 2017-12-01 | 浙江省农业科学院 | A kind of charcoal ferrojacobsite composite for being used to adsorb heavy metal antimony cadmium |
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| CN110523415A (en) * | 2019-09-03 | 2019-12-03 | 浙江天地环保科技有限公司 | Copper and iron layered double hydroxide, copper and iron layered double hydroxide/C-base composte material and its preparation method and application |
| CN110523415B (en) * | 2019-09-03 | 2022-07-19 | 浙江天地环保科技股份有限公司 | Copper-iron layered double hydroxide, copper-iron layered double hydroxide/carbon-based composite material, and preparation method and application thereof |
| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
| CN111229161A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Using CuFeO2Method for adsorbing oxytetracycline by/BC composite magnetic material |
| CN111841487A (en) * | 2020-06-22 | 2020-10-30 | 安徽创能环保材料有限公司 | Preparation process and application of modified fly ash composite material |
| CN112774630A (en) * | 2021-01-11 | 2021-05-11 | 陈章平 | Preparation method of activated carbon adsorbent for regenerating and adsorbing methyl orange |
| CN113101931A (en) * | 2021-03-22 | 2021-07-13 | 宝璟科技(深圳)有限公司 | Preparation method and application of modified carbon-coated copper nanoparticles carried by cupronickel |
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