CN108314894A - A kind of composite material and preparation method and application - Google Patents
A kind of composite material and preparation method and application Download PDFInfo
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- CN108314894A CN108314894A CN201810092331.0A CN201810092331A CN108314894A CN 108314894 A CN108314894 A CN 108314894A CN 201810092331 A CN201810092331 A CN 201810092331A CN 108314894 A CN108314894 A CN 108314894A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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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
- C02F1/722—Oxidation by peroxides
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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Abstract
The present invention relates to a kind of composite material and preparation method and application, in particular to the composite materials of nano-metal-oxide/branched polymer.The nano-metal-oxide/branched polymer composite material is synthesized according to following mass percent, including following components：Branched polymer：10~80%；Molysite：10~30%；Other metal salts：0~40%；Solvent is water, by the way that iron ion and other metal ions in branched polymer solution, to be prepared in the method being co-precipitated in situ.Product of the present invention is mainly in combination with oxidants such as hydrogen peroxide, persulfates, for the high grade oxidation catalytic degradation removal of the organic matters such as Wastewater Dyes, have many advantages, such as that preparation is simple, high catalytic efficiency, catalyst separation facility, service life is long, applicable pH range is wide.
Description
Technical field
The present invention relates to waste water advanced oxidization advanced treating field, especially a kind of nano-metal-oxide/branched polymeric
Object composite material and preparation method and application are primarily adapted for use in the removal of the pollutants such as organic dyestuff in wastewater.
Background technology
Due to its toxicity and not, biodegradable has become the mankind and the ecosystem to the organic wastewater of industrial discharge
Important threat.Textile industry is China's conventional column industry and important people's livelihood industry, but entire textile industry discharge of wastewater
Amount is high, and especially dyeing and finishing industry, waste water annual emissions account for the 80% of textile industry wastewater emission amount, accounts for national industry
The 35% of wastewater emission amount.Contain a large amount of organic matter in waste water from dyestuff, color and luster is deep, and acid-base property is strong, and salt content is high, is always
Problem in wastewater treatment.Fenton methods decompose the potential of organic dyestuff with rapid mineralization as a kind of high-level oxidation technology
And it is concerned.Fenton methods are a kind of advanced oxidation processes, utilize Fe and H2O2Between chain reaction catalysis to generate OH free
Base, and OH free radicals have strong oxidizing property, various toxic and difficult to degrade organic compound can be aoxidized, to reach depollution
The purpose of object.But tradition Fenton systems are hydrogen peroxide and catalyst Fe2+The oxidation system of composition is to utilize Fe2+Homogeneously
It is catalyzed H2O2The hydroxyl radical free radical (HO) for decomposing generation strong oxidizing property acts on organic pollution, and there are the narrow (pH of catalytic pH range
=3-5), be also easy to produce iron cement and Fe under alkaline condition2+The problems such as being difficult to reuse causes homogeneous Fenton systems gradual
Heterogeneous Fenton system is replaced.
But Fe3O4、γ-Fe2O3, the ferriferous oxides such as FeOOH as typical heterogeneous Fenton catalyst, due to from
The reason of body structure and activity, shows lower catalytic efficiency, limits their industrial applications.Mainly pass through tune at present
Control catalyst itself composed structure feature, with other metal composites and catalyst nanoparticles are carried on porous substrate
On improve the activity of iron-based heterogeneous Fenton catalyst.But the catalyst mistake for using the above method excellent in processability
Cheng Zhong generally requires high-temperature calcination, the introducing of hydro-thermal method or even high cost substrates, and it is recycled, activity regulation is difficult,
This makes the possibility smaller of above-mentioned heterogeneous Fenton catalyst industrialization.
Invention content
The present invention proposes a kind of composite material, in particular to nano-metal-oxide/branched polymer composite material, gram
It has taken according to deficiency existing for current heterogeneous Fenton catalyst, and it is applied to the degradation treatment of waste water from dyestuff.
The particular content of the present invention is as follows：
A kind of composite material, including following components (mass percent)：
Branched polymer：10~80%
Molysite：10~30%
Other metal salts：0~40%
Solvent is water,
Wherein, above-mentioned branched polymer is water solubility；Molysite is Fe2+、Fe3+One or two kinds of group of soluble-salt etc.
It closes；Other metal salts are containing Cu2+, Ce3+, Zn2+, Co2+, Ni2+, Mn2+The combination of one or more of soluble-salt.
Preferably, the branched polymer described in above-mentioned composite material is branched polyethylene imine, ultrabranching polyamide, surpasses
In branched polyethylene glycol diacrylate, hyperbranched polyamino acid, superbrnaching end-hydroxy polyethers, Hyperbranched Polymer with Terminal Amido etc.
One or more kinds of combinations.As more preferably selecting, branched polyethylene imine, ultrabranching polyamide, amine-terminated hyperbrancedization polymerization
The modified polymer such as object and related butene dioic acid, succinic acid.
Further, branched polyethylene imine hair molecular weight is 600~25000 dalton, the change of ultrabranching polyamide
It is as follows to learn structure
Further, ultrabranching polyamide is formed by methyl acrylate and diethylenetriamine polycondensation, ultrabranching polyamide
Chemical constitution it is as follows:
Hyperbranched poly glycol diacrylate is by 2,2- (vinyl dioxy) diethylamine and polyethyleneglycol diacrylate
Reaction is prepared, and the chemical constitution of hyperbranched poly glycol diacrylate is as follows:
Hyperbranched polyamino acid is formed by N- (3- aminopropyls) zineb ammonium succinate from polycondensation, hyperbranched polyamino acid
Chemical constitution is as follows:
Superbrnaching end-hydroxy polyethers is obtained through glycidol ring-opening polymerisation, and the chemical constitution of superbrnaching end-hydroxy polyethers is as follows
It is shown:
Hyperbranched Polymer with Terminal Amido is made by divinyl sulfone and N- amido piperazines through polycondensation reaction, and amine-terminated hyperbrancedization is poly-
The chemical constitution for closing object is as follows:
A kind of preparation method of composite material, includes the following steps successively：
(1) certain mass water, soluble branched polymer are added into reaction bulb, until branched polymer is completely dissolved；
(2) molysite and other metallic salts are put into mass ratio into reaction bulb, 2-5h is stirred at room temperature；
(3) liquid that is vigorously stirred in (2) is simultaneously slowly dropped into ammonium hydroxide the pH of solution is adjusted to 9-11；
(4) reaction bulb in (3) is placed in 1~4h under the conditions of 50~70 DEG C of waters bath with thermostatic control；
(5) by the reaction bulb in (4) under the conditions of 70~90 DEG C still aging 1~4h；
(6) reaction system for obtaining (5) is washed 3-5 times through centrifugation, absolute ethyl alcohol, until pH detections are neutral；
(7) by the product in (6) it is vacuum dried after, as nano-metal-oxide/branched polymer composite material.
Preferably, above-mentioned composite material is applied to wastewater treatment, at 0 DEG C~60 DEG C, with hydrogen peroxide or persulfuric acid
Salt is oxidant, under the conditions of pH is 3~7, by nano-metal-oxide/branched polymer composite material and waste water reaction 15~
60min can make the degradation removal rate of the dyestuff in waste water reach 85% or more, show the good catalytic degradation effect to organic dyestuff
Fruit.
Advantageous effect：
The nano-metal-oxide that the present invention prepares/branched polymer composite material is low with manufacturing cost, is catalyzed
It is active high, can within the scope of wider temperature and pH the effectively organic dyestuff in degrading waste water, this to it is novel, efficient it is non-
The exploitation of phase Fenton catalyst, waste water advanced and promotion environment solution have important practical significance.
Specific implementation mode
Specific and detailed introduction is carried out to the present invention below by specific embodiment, so as to more fully understand the present invention,
But following embodiments is not intended to limit the scope of the invention.
Embodiment 1
A kind of nano-metal-oxide/branched polymer composite material, including following components (mass percent)：
Branched polymer：10~80%
Molysite：10~30%
Other metal salts：0~40%
Solvent is water,
Wherein, above-mentioned branched polymer is water solubility；Molysite is Fe2+、Fe3+One or two kinds of group of soluble-salt etc.
It closes；Other metal salts are containing Cu2+, Ce3+, Zn2+, Co2+, Ni2+, Mn2+The combination of one or more of soluble-salt.It is branched
Polymer refers to branched polymer compound, and shape has the 3-d modelling of spherical shape as the macromolecular of dendritic shape.Over-expense
The irregular polymer of height cladodification but structure that fluidized polymer is made of cladodification primitive.Nano-metal-oxide refers to grain
Diameter reaches nano level metal oxide.
It is oxidation with hydrogen peroxide by the nano-metal-oxide/branched polymer composite material when being 7 for 20 DEG C and pH
Agent, nano-metal-oxide/branched polymer composite material are reachable to the degradation rate of the organic dyestuff such as reactive orange within half an hour
85% or more, it shows to the good catalytic degradation ability of organic dyestuff, and after reusing 5 times, catalytic performance is substantially not
Become.
Embodiment 2
A kind of nano-metal-oxide/branched polymer composite material, including following components (mass percent)：
Solvent is water, and branched polyethylene imine molecular weight is 600~25000 dalton, the chemistry knot of ultrabranching polyamide
Structure is as follows
Specific operation process is as follows：
150ml deionized waters are added into reaction bulb, it is complete that 0.75g branched polyethylene imine stirring and dissolvings are then added.
Then sequentially add 0.405g ferric chloride hexahydrates, 0.12g anhydrous cupric sulfates, stirring at normal temperature 4h.Then with vigorous stirring with
Its pH value of solution is adjusted to 11 by ammonium hydroxide, coprecipitation reaction 2h under the conditions of 65 DEG C of waters bath with thermostatic control.Finally stood under the conditions of 85 DEG C
It is aged 1h.Obtained reaction system is washed 3 times through centrifugation, absolute ethyl alcohol repeatedly, until pH neutrality, collects solid.It will
Solid is placed in oven drying and obtains a nanometer CuFe oxides/branched polymer composite material for 24 hours.Dissipating color measurement through dynamic optical should
The grain size of nano-metal-oxide/branched polyethylene imine composite material is 90nm.
The concrete application of the catalyst, at room temperature, the item of catalyst amount 50mg/L, pH=7 and 8wt% hydrogen peroxide
Under part, in 30min or so, the degradation rate to the reactive orange K-G dyestuffs of a concentration of 200mg/L is 87.5%.Recycling catalyst makes
After 5 times, the degradation rate to reactive orange K-G is 85.5%, and degradation property is basically unchanged.
Embodiment 3
A kind of nano-metal-oxide/branched polymer composite material, including following components (mass percent)：
Solvent is water, wherein ultrabranching polyamide is formed by methyl acrylate and diethylenetriamine polycondensation, hyperbranched polyamides
The chemical constitution of amine is as follows:
Specific operation process is as follows：
The deionized water and 1.0g maleic acid modified ultra-branching polyamide of 100ml, stirring are added into reaction bulb
Until polymer is completely dissolved.0.266g ferric chloride hexahydrates, seven chloride hydrate ceriums of 0.037g, at room temperature room temperature is then added
Stir 3h.Then with ammonium hydroxide, by solution, its pH is adjusted to 10.5 with vigorous stirring, is co-precipitated under the conditions of 50 DEG C of waters bath with thermostatic control
React 3h.Finally still aging 2h under the conditions of 75 DEG C.Obtained reaction system is washed 3 times through centrifugation, absolute ethyl alcohol repeatedly,
Until pH is neutrality, solid is collected.Solid is placed in oven drying, and to obtain nano Ce Fe oxides/branched polymer for 24 hours multiple
Condensation material.It is 75nm to dissipate color to measure the grain size of the nano-metal-oxide/modified ultra-branching polyamide compoiste material through dynamic optical.
The concrete application of the catalyst, at room temperature, the item of catalyst amount 50mg/L, pH=5 and 8wt% hydrogen peroxide
Under part, in 20min or so, the degradation rate to the reactive orange K-G dyestuffs of a concentration of 200mg/L is 92.5%.Recycling catalyst makes
After 5 times, the degradation rate to reactive orange K-G is 90.3%, and degradation property is basically unchanged.
Embodiment 4
A kind of nano-metal-oxide/branched polymer composite material includes following components (mass percent)：
Solvent is water, wherein hyperbranched poly glycol diacrylate is by 2,2- (vinyl dioxy) diethylamine and poly- second
Omega-diol diacrylate reaction is prepared, and the chemical constitution of hyperbranched poly glycol diacrylate is as follows:
Specific operation process is as follows：
Deionized water, the 0.8g hyperbranched poly glycol diacrylates of 100ml, 0.283g six are added into reaction bulb
Ferric Chloride Hydrated, 0.102g Nickel dichloride hexahydrates, at room temperature stirring at normal temperature 3h.Then with vigorous stirring with ammonium hydroxide by solution
Its pH is adjusted to 10, coprecipitation reaction 2h under the conditions of 55 DEG C of waters bath with thermostatic control.Finally still aging 4h under the conditions of 70 DEG C.Will
The reaction system arrived is washed 3 times through centrifugation, absolute ethyl alcohol repeatedly, until pH is neutrality, collects solid.Solid is placed in baking oven
It is dry to obtain the oxide/hyperbranched polyethyleneglycol diacrylate composite material of nano-Ni/Fe for 24 hours.Color is dissipated through dynamic optical to measure
The grain size of the nano-metal-oxide/hyperbranched poly glycol diacrylate composite material is 90nm.
The concrete application of the catalyst, at room temperature, catalyst amount 60mg/L, pH=6 and 10wt% sodium peroxydisulfate
Under conditions of, in 25min or so, the degradation rate to the methylene blue dye of a concentration of 200mg/L is 96%.Recycle catalyst
After 5 times, the degradation rate to methylene blue is 92%, and degradation property is basically unchanged.
Embodiment 5
A kind of nano-metal-oxide/branched polymer composite material includes following components (mass percent)：
Solvent is water, and hyperbranched polyamino acid is formed by N- (3- aminopropyls) zineb ammonium succinate from polycondensation, hyperbranched
The chemical constitution of polyaminoacid is as follows:
Specific operation process is as follows：
The deionized water of addition 100ml, 0.7g hyperbranched polyamino acids into reaction bulb, 0.216g ferric chloride hexahydrates,
0.168g zinc chloride, at room temperature stirring at normal temperature 2h.Then with ammonium hydroxide, by solution, its pH is adjusted to 11 with vigorous stirring, 50
Coprecipitation reaction 2h under the conditions of DEG C water bath with thermostatic control.Finally still aging 3h under the conditions of 70 DEG C.Repeatedly by obtained reaction system
It is washed 3 times through centrifugation, absolute ethyl alcohol, until pH is neutrality, collects solid.Solid is placed in oven drying and obtains nanometer for 24 hours
The oxide/hyperbranched polyaminoacid of ZnFe.Dissipating color through dynamic optical, to measure the nano-metal-oxide/hyperbranched polyamino acid compound
The grain size of material is 90nm.
The concrete application of the catalyst, at room temperature, catalyst amount 50mg/L, pH=6 and 8wt% sodium peroxydisulfate
Under the conditions of, in 25min or so, the degradation rate to the methylene blue dye of a concentration of 200mg/L is 94%.Recycling catalyst makes
After 5 times, the degradation rate to methylene blue is 91.3%, and degradation property is basically unchanged.
Embodiment 6
A kind of nano-metal-oxide/branched polymer composite material includes following components (mass percent)：
Solvent is water, and superbrnaching end-hydroxy polyethers is obtained through glycidol ring-opening polymerisation, the change of superbrnaching end-hydroxy polyethers
It is as follows to learn structure:
Specific operation process is as follows：
Deionized water, the ends the 0.4g superbrnaching end-hydroxy polyethers of 100ml, tetra- chloride hydrates of 0.197g are added into reaction bulb
Ferrous iron, 0.136g manganese chlorides, at room temperature stirring at normal temperature 3h.Then with ammonium hydroxide, by solution, its pH is adjusted to 9 with vigorous stirring,
Coprecipitation reaction 1h under the conditions of 70 DEG C of waters bath with thermostatic control.Finally still aging 1h under the conditions of 80 DEG C.The reaction system that will be obtained
It is washed 5 times through centrifugation, absolute ethyl alcohol repeatedly, until pH is neutrality, collects solid.Solid is placed in oven drying to obtain for 24 hours
Nanometer MnFe oxides/branched polymer composite material.Color, which is dissipated, through dynamic optical measures the nano-metal-oxide/terminal hydroxy group over-expense
The grain size for changing polyethers composite material is 70nm.
The concrete application of the catalyst, at room temperature, catalyst amount 50mg/L, pH=6 and 8wt% sodium peroxydisulfate
Under the conditions of, in 25min or so, the degradation rate to the methylene blue dye of a concentration of 200mg/L is 93%.Recycling catalyst makes
After 5 times, the degradation rate to methylene blue is 91.2%, and degradation property is basically unchanged.
Embodiment 7
A kind of nano-metal-oxide/branched polymer composite material includes following components (mass percent)：
Solvent is water, and Hyperbranched Polymer with Terminal Amido is made by divinyl sulfone and N- amido piperazines through polycondensation reaction, holds ammonia
The chemical constitution of base dissaving polymer is as follows:
Specific operation process is as follows：
Deionized water, the 0.5g Hyperbranched Polymer with Terminal Amido of 100ml are added into reaction bulb, until branched polymer is complete
Dissolving；Put into 0.133g ferric chloride hexahydrates in mass ratio into reaction bulb, 0.037g cobalt chloride hexahydrates, room temperature at room temperature
Stir 3h.Then with ammonium hydroxide, by solution, its pH is adjusted to 10 with vigorous stirring, is co-precipitated under the conditions of 55 DEG C of waters bath with thermostatic control anti-
Answer 2h.Finally still aging 4h under the conditions of 70 DEG C.By obtained reaction system repeatedly through centrifugation, absolute ethyl alcohol washing 3 times, directly
It is neutrality to pH, collects solid.Solid is placed in oven drying, and to obtain nano Co Fe oxides/branched polymer for 24 hours compound
Material.It is 80nm to dissipate color to measure the grain size of the nano-metal-oxide/Hyperbranched Polymer with Terminal Amido composite material through dynamic optical.
The concrete application of the catalyst, at room temperature, catalyst amount 50mg/L, pH=6 and 8wt% sodium peroxydisulfate
Under the conditions of, in 25min or so, the degradation rate to the methylene blue dye of a concentration of 200mg/L is 95%.Recycling catalyst makes
After 5 times, the degradation rate to methylene blue is 93.3%, and degradation property is basically unchanged.
The description of the aforementioned specific exemplary embodiment to the present invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining the specific principle of the present invention and its actually answering
With so that those skilled in the art can realize and utilize the present invention a variety of different exemplary implementation schemes and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of composite material, it is characterised in that：Including following components (mass percent)：
Branched polymer：10~80%
Molysite：10~30%
Other metal salts：0~40%
Solvent is water,
Wherein, above-mentioned branched polymer is water solubility；Molysite is Fe2+、Fe3+Soluble-salt in one or two kinds of combination；Its
His metal salt is containing Cu2+, Ce3+, Zn2+, Co2+, Ni2+Or Mn2+The combination of one or more of soluble-salt.
2. composite material according to claim 1, it is characterised in that：Branched polymer is branched polyethylene imine, over-expense
Change polyamide, hyperbranched poly glycol diacrylate, hyperbranched polyamino acid, superbrnaching end-hydroxy polyethers, amine-terminated hyperbranced
One or more of fluidized polymer.
3. composite material according to claim 2, it is characterised in that：Branched polymer is the molecule of branched polyethylene imine
Amount is 600~25000 dalton, and the chemical constitution of ultrabranching polyamide is as follows：
4. composite material according to claim 2, it is characterised in that：Ultrabranching polyamide is by methyl acrylate and divinyl
Triamine polycondensation forms, and the chemical constitution of ultrabranching polyamide is as follows:
5. composite material according to claim 2, it is characterised in that：Hyperbranched poly glycol diacrylate is by 2,2-
(vinyl dioxy) diethylamine is reacted with polyethyleneglycol diacrylate and is prepared, hyperbranched poly glycol diacrylate
Chemical constitution is as follows:
6. composite material according to claim 2, it is characterised in that：Hyperbranched polyamino acid is by N- (3- aminopropyls) Dai Sen
Zinc ammonium succinate is formed from polycondensation, and the chemical constitution of hyperbranched polyamino acid is as follows:
7. composite material according to claim 2, it is characterised in that：Superbrnaching end-hydroxy polyethers is poly- through glycidol open loop
Conjunction obtains, and the chemical constitution of superbrnaching end-hydroxy polyethers is as follows:
8. composite material according to claim 2, it is characterised in that：Hyperbranched Polymer with Terminal Amido is by divinyl sulfone and N-
Amido piperazine is made through polycondensation reaction, and the chemical constitution of Hyperbranched Polymer with Terminal Amido is as follows:
9. the preparation method of composite material according to claim 1, it is characterised in that:Include the following steps successively：
(1) certain mass water, soluble branched polymer are added into reaction bulb, until branched polymer is completely dissolved；
(2) molysite and other metallic salts are put into mass ratio into reaction bulb, 2-5h is stirred at room temperature；
(3) liquid that is vigorously stirred in (2) is simultaneously slowly dropped into ammonium hydroxide the pH of solution is adjusted to 9-11；
(4) reaction bulb in (3) is placed in 1~4h under the conditions of 50~70 DEG C of waters bath with thermostatic control；
(5) by the reaction bulb in (4) under the conditions of 70~90 DEG C still aging 1~4h；
(6) reaction system for obtaining (5) is washed 3-5 times through centrifugation, absolute ethyl alcohol, until pH detections are neutral；
(7) by the product in (6) it is vacuum dried after, as nano-metal-oxide/branched polymer composite material.
10. the application of composite material described in claim 1, it is characterised in that：At 0 DEG C~60 DEG C, with hydrogen peroxide or persulfuric acid
Salt is oxidant, under the conditions of pH is 3~7, by above-mentioned nano-metal-oxide/branched polymer composite material and waste water reaction 15
~60min.
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| CN109455776A (en) * | 2018-11-14 | 2019-03-12 | 陈云 | A kind of sewage scavenging material and preparation method thereof |
| CN109970137A (en) * | 2019-05-10 | 2019-07-05 | 天津工业大学 | A method of the hyperbranched magnetic material rich in functional group removes heavy-metal composite pollution object |
| CN114149109A (en) * | 2021-12-03 | 2022-03-08 | 内蒙古科技大学 | Method for purifying slime water by cerium catalysis |
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