CN109107542B - Preparation method of composite adsorption phosphorus removal agent and phosphorus removal method - Google Patents
Preparation method of composite adsorption phosphorus removal agent and phosphorus removal method Download PDFInfo
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Abstract
The invention discloses a preparation method and a phosphorus removal method of a composite adsorption phosphorus removal agent, wherein high-molecular polyamidine, hydrous zirconium oxide and a graphene oxide nano material are combined to prepare the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent, the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent has a large amount of positive charges, the advantages of the polyamidine, the hydrous zirconium oxide and the graphene oxide are effectively integrated, and the adsorption performance and the practical application value are improved. The graphene oxide/hydrous zirconium oxide/polyamidine is a novel high-molecular nano composite material. Meanwhile, the preparation process is simple and convenient and the cost is lower.
Description
Technical Field
The invention relates to the technical field of preparation of nanometer functional materials, high polymer materials and environmental materials, in particular to a preparation method of a composite adsorption phosphorus removal agent and a phosphorus removal method.
Background
With the increasing development and utilization activities of human beings on environmental resources, a large amount of domestic sewage and industrial wastewater containing nitrogen and phosphorus nutrient substances are discharged into rivers and lakes, so that the load of the nutrient substances in the water body is increased, the self-purification capacity of the water body is exceeded, and the direct result is water eutrophication. The direct consequence of water eutrophication is that algae plants grow excessively and consume a large amount of oxygen in the water, so that aquatic organisms such as fishes and shellfishes die due to oxygen deficiency; eutrophication deteriorates the water quality of the water source, and increases the difficulty and cost of water treatment; eutrophication deteriorates the water body's sense and lowers the aesthetic value of the water body. Therefore, the removal of excessive phosphorus elements in the water body has great significance for reducing water eutrophication, lightening the treatment burden of a water plant and improving the water environment.
The commonly used treatment methods include chemical precipitation, biological methods, ion exchange methods, membrane separation methods, adsorption methods, and the like. The chemical method is to generate insoluble precipitate by adding a chemical precipitator and phosphate in wastewater, but if the chemical precipitator is operated for a long time, the addition of the chemical precipitator can cause the pH value to rise, so that scale sheets are formed, and a certain amount of sludge can be generated. The biological method treats phosphorus by using the principle that microorganisms take in phosphorus in an aerobic state and release phosphorus in an anaerobic state in the presence of organic matters. The biological method has good treatment effect, but has strict treatment conditions and higher cost. The ion exchange method is a method of removing phosphate anions by replacing phosphate anions on an exchanger by using strongly basic anion exchange resin to perform exchange reaction with the phosphate anions in wastewater. However, the ion exchange resin has high price and high running cost. The membrane technology has high dephosphorization efficiency, but has high cost and technical requirements. The adsorption method is concerned by the advantages of simple process, convenient operation and the like. In the research of the adsorption method, the search for a new adsorbent is the key point for developing a new dephosphorization process.
Disclosure of Invention
The invention provides a preparation method of a composite adsorption phosphorus removal agent and a phosphorus removal method, and aims to solve the problems of cost and effect of phosphorus removal.
In a first aspect, the invention provides a preparation method of a composite adsorption phosphorus removal agent, which comprises the following steps:
(1) and ultrasonically dispersing graphene oxide in ultrapure water for 2 hours to obtain a graphene oxide dispersion liquid.
(2) ZrOCl2·8H2Dissolving O in ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly adding hydrazine hydrate, stirring at 70-110 deg.C for 2-5h(ii) a And after cooling to room temperature, washing with ultrapure water to be neutral, and carrying out vacuum freeze drying for 2 days for later use to obtain the graphene oxide/hydrated zirconium oxide.
(3) Adding N-vinylformamide and acrylonitrile into a round-bottom flask, placing the round-bottom flask in a constant-temperature water bath at 40-60 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water, continuously introducing the nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution under the condition of continuously introducing the nitrogen, continuously introducing the nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3-7h to prepare an intermediate polymer, and drying in vacuum to constant weight.
(4) Adding the prepared graphene oxide/hydrous zirconium oxide and the intermediate polymer into hydrochloric acid, placing the mixture in an oil bath at the temperature of 80-120 ℃, continuously stirring and reacting for 3-7h, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at the temperature of 40 ℃ to obtain the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent.
Optionally, the preparation method of the composite adsorption phosphorus removal agent comprises the following steps:
(1) and ultrasonically dispersing 0.1-0.5g of graphene oxide in 200mL of ultrapure water for 2h to obtain a graphene oxide dispersion liquid.
(2) 15-30g of ZrOCl2·8H2Dissolving O in 200mL of ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly dropwise adding 2-4mL of hydrazine hydrate, and stirring for 2-5h at 70-110 ℃; and after cooling to room temperature, washing with ultrapure water to be neutral, and carrying out vacuum freeze drying for 2 days for later use to obtain the graphene oxide/hydrated zirconium oxide.
(3) Mixing the components in a molar ratio of (0.5-2): adding N-vinylformamide and acrylonitrile of 1 into a round-bottom flask to form a mixed solution, placing the round-bottom flask into a constant-temperature water bath at 40-60 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with the volume 4-8 times that of the mixed solution, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyramidine hydrochloride solution with the mass 0.2-0.5% that of the mixed solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3-7h to prepare an intermediate polymer, and drying in vacuum to constant weight.
(4) Weighing 0.1-0.5g of the graphene oxide/hydrated zirconia, mixing the graphene oxide/hydrated zirconia with the intermediate polymer, adding 0.5-1.5 times of the molar equivalent of the mixed solution and 1-4 times of ultrapure water of the mixed solution, placing the mixture in an oil bath at 80-120 ℃, continuously stirring for reaction for 3-7h, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at 40 ℃ to obtain the graphene oxide/hydrated zirconia/polyamidine composite adsorption dephosphorizing agent.
On the other hand, the invention also provides a phosphorus removal method of the composite adsorption phosphorus removal agent, which comprises the following steps: weighing 0.1-1g of the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent, adding the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent into 1-15mg/L of phosphorus-containing solution, fully and uniformly mixing, oscillating in a constant-temperature water bath for 12h, after adsorption balance is achieved, performing centrifugal filtration, measuring the phosphorus concentration of filtrate by adopting a molybdenum blue colorimetric method, and calculating the adsorption quantity.
The invention has the following beneficial effects:
according to the invention, high-molecular polyamidine and hydrous zirconia are combined with a graphene oxide nano material, the polyamidine contains a large amount of positive charges, the surface of graphene oxide is rich in negative functional groups such as hydroxyl and carboxyl, the graphene oxide and the hydrous zirconia are self-assembled together through hydrogen bonds and electrostatic attraction to prepare the graphene oxide/hydrous zirconia/polyamidine composite adsorption phosphorus removing agent, the graphene oxide/hydrous zirconia/polyamidine composite adsorption phosphorus removing agent has a large amount of positive charges on one hand and can adsorb phosphate radicals with negative valence in water through electrostatic action, on the other hand, the hydrous oxide of metal zirconium has a good adsorption effect on phosphorus in water, and the synergistic effect of the large specific surface area of graphene oxide is combined to obtain a good phosphorus removing effect. The advantages of the polyamidine, the hydrous zirconia and the graphene oxide are effectively integrated, and the adsorption performance and the practical application value are improved. The graphene oxide/hydrous zirconium oxide/polyamidine is a novel high-molecular nano composite material. Meanwhile, the preparation process is simple and convenient and the cost is lower.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Detailed Description
The invention provides a preparation method of a composite adsorption phosphorus removal agent and a phosphorus removal method, and aims to solve the problems of cost and effect of phosphorus removal. The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the composite adsorption phosphorus removal agent provided by the embodiment 1 comprises the following steps:
(1) and ultrasonically dispersing 0.1g of graphene oxide in 200mL of ultrapure water for 2h to obtain a graphene oxide dispersion liquid.
(2) 15g of ZrOCl2After 8H2O was dissolved in 200mL of ultrapure water, slowly added to the graphene oxide dispersion, stirred at 50 ℃ for 2H, adjusted to pH 10 with NaOH; slowly dropwise adding 2mL of hydrazine hydrate, and stirring for 2h at 70 ℃; and after cooling to room temperature, washing with ultrapure water to be neutral, and carrying out vacuum freeze drying for 2 days for later use to obtain the graphene oxide/hydrated zirconium oxide.
(3) Mixing the components in a molar ratio of 0.5: adding 1N-vinylformamide and acrylonitrile into a round-bottom flask to form a mixed solution, placing the round-bottom flask in a constant-temperature water bath at 40 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with 4 times of the volume of the mixed solution, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution with 0.2% of the mass of the mixed solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3h to prepare an intermediate polymer, and drying in vacuum to constant weight.
(4) Weighing 0.1g of graphene oxide/zirconium oxide hydrate, mixing with the intermediate polymer, adding 0.5 time of concentrated hydrochloric acid of the molar equivalent of the mixed solution and 1 time of ultrapure water of the mixed solution, placing in an oil bath at 80 ℃, continuously stirring for reaction for 3 hours, cooling the obtained product, slowly pouring into an acetone solution, separating out a solid product, placing the solid product in a vacuum drying oven, and performing vacuum drying at 40 ℃ to obtain the graphene oxide/zirconium oxide hydrate/polyamidine composite adsorption dephosphorizing agent.
Example 2
The preparation method of another composite adsorption phosphorus removal agent provided in this embodiment 2 includes the following steps:
(1) and ultrasonically dispersing 0.3g of graphene oxide in 200mL of ultrapure water for 2h to obtain a graphene oxide dispersion liquid.
(2) 20g of ZrOCl2·8H2Dissolving O in 200mL of ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly dropwise adding 3mL of hydrazine hydrate, and stirring for 3.5h at 90 ℃; and after cooling to room temperature, washing with ultrapure water to be neutral, and carrying out vacuum freeze drying for 2 days for later use to obtain the graphene oxide/hydrated zirconium oxide.
(3) Mixing a mixture of 1: adding 1N-vinylformamide and acrylonitrile into a round-bottom flask to form a mixed solution, placing the round-bottom flask in a 50 ℃ constant-temperature water bath, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with 6 times of the volume of the mixed solution, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution with 0.35% of the mass of the mixed solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 5h to obtain an intermediate polymer, and drying in vacuum to constant weight.
(4) Weighing 0.3g of graphene oxide/zirconium oxide hydrate, mixing with the intermediate polymer, adding 1 time of concentrated hydrochloric acid of the molar equivalent of the mixed solution and 2 times of ultrapure water of the mixed solution, placing the mixture in an oil bath at 100 ℃, continuously stirring for reaction for 5 hours, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at 40 ℃ to obtain the graphene oxide/zirconium oxide hydrate/polyamidine composite adsorption dephosphorizing agent.
Example 3
The preparation method of another composite adsorption phosphorus removing agent provided in this embodiment 3 includes the following steps:
(1) and ultrasonically dispersing 0.5g of graphene oxide in 200mL of ultrapure water for 2h to obtain a graphene oxide dispersion liquid.
(2) 30g of ZrOCl2·8H2Dissolving O in 200mL of ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly dropwise adding 4mL of hydrazine hydrate, and stirring for 5h at 110 ℃; and after cooling to room temperature, washing with ultrapure water to be neutral, and carrying out vacuum freeze drying for 2 days for later use to obtain the graphene oxide/hydrated zirconium oxide.
(3) Mixing the components in a molar ratio of 2: adding 1N-vinylformamide and acrylonitrile into a round-bottom flask to form a mixed solution, placing the round-bottom flask in a constant-temperature water bath at 60 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with the volume 8 times that of the mixed solution, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution with the mass 0.5% times that of the mixed solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 7h to obtain an intermediate polymer, and drying in vacuum to constant weight.
(4) Weighing 0.5g of graphene oxide/zirconium oxide hydrate, mixing with the intermediate polymer, adding 1.5 times of concentrated hydrochloric acid in molar equivalent of the mixed solution and 4 times of ultrapure water in the mixed solution mass, placing in an oil bath at 120 ℃, continuously stirring for reaction for 7 hours, cooling the obtained product, slowly pouring into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at 40 ℃ to obtain the graphene oxide/zirconium oxide hydrate/polyamidine composite adsorption phosphorus removal agent.
Comparative example 1
The preparation method of the phosphorus removal agent provided by the comparative example 1 comprises the following steps:
(1) 0.1g of graphene oxide and 15g of ZrOCl2·8H2And O, mixing, dispersing in ultrapure water, and performing vacuum freeze drying for 2 days for later use to prepare the graphene oxide/hydrous zirconium oxide.
(2) Mixing the components in a molar ratio of 0.5: adding 1N-vinylformamide and acrylonitrile into a round-bottom flask to form a mixed solution, placing the round-bottom flask in a constant-temperature water bath at 40 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with 4 times of the volume of the mixed solution, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution with 0.2% of the mass of the mixed solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3h to prepare an intermediate polymer, and drying in vacuum to constant weight.
(3) Adding concentrated hydrochloric acid with the molar equivalent of 0.5 time of the mixed solution and ultrapure water with the mass of 1 time of the mixed solution into the intermediate polymer, placing the intermediate polymer in an oil bath at 80 ℃, continuously stirring and reacting for 3 hours, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying to obtain the solid polyamidine.
(4) Dispersing 0.1g of graphene oxide/hydrous zirconium oxide into 20mL of ultrapure water, performing ultrasonic homogenization, preparing 0.3 wt% of polyamidine solution from the solid polyamidine, pouring the solution into the graphene oxide/hydrous zirconium oxide, stirring for 24 hours, pouring the solution into a hydrophobic glass ware, and performing vacuum drying at 40 ℃ to obtain the phosphorus removal agent.
The invention also provides a phosphorus removal method, which comprises the following steps: 0.1-1g of the phosphorus removal agent provided by the above examples and comparative examples is weighed and added into 1-15mg/L phosphorus-containing solution, the mixture is fully mixed and then is subjected to constant temperature water bath oscillation for 12 hours, after adsorption balance is achieved, centrifugal filtration is carried out, the concentration of phosphorus in filtrate is measured by adopting a molybdenum blue colorimetric method, and the adsorption capacity is calculated.
In order to compare the phosphorus removal effect, 1g of the phosphorus removal agent provided in the above examples and comparative examples is weighed and added into the same phosphorus-containing solution (10mg/L), the mixture is fully mixed and then is subjected to constant temperature water bath oscillation for 12 hours, after adsorption balance is achieved, centrifugal filtration is carried out, and the phosphorus concentration of the filtrate is measured by a molybdenum blue colorimetric method. The phosphorus removal effect is compared as follows:
comparison table of phosphorus removal effect of phosphorus removal agent provided by each example and comparative example
| Class of phosphorus removal agent | Phosphorus content (mg/L) in the dephosphorized solution |
| Example 1 | 0.25 |
| Example 2 | 0.32 |
| Example 3 | 0.23 |
| Comparative example 1 | 2.41 |
From the results of example 1 and comparative example 1 in the above table, the phosphorus removal effect of the phosphorus removal agent obtained by simply mixing solid polyamidine, hydrous zirconia and graphene oxide is far inferior to that of the phosphorus removal agent obtained by combining polymeric polyamidine, hydrous zirconia and graphene oxide nano-material by a one-pot stepwise addition method to obtain a graphene oxide/hydrous zirconia/polyamidine composite adsorption phosphorus removal agent. This indicates that the phosphorus removal effect of the phosphorus removal agent cannot be guaranteed by simple mixing.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (3)
1. A preparation method of a composite adsorption phosphorus removing agent is characterized by comprising the following steps:
(1) ultrasonically dispersing graphene oxide in ultrapure water for 2 hours to obtain a graphene oxide dispersion liquid;
(2) ZrOCl2·8H2Dissolving O in ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly adding hydrazine hydrate, and stirring at 70-110 ℃ for 2-5 h; after cooling to room temperature, washing with ultrapure water to neutrality, and carrying out vacuum freeze drying for 2 days for later use to obtain graphene oxide/hydrous zirconium oxide;
(3) adding N-vinylformamide and acrylonitrile into a round-bottom flask, placing the round-bottom flask in a constant-temperature water bath at 40-60 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water, continuously introducing nitrogen for 20min, slowly dropwise adding azodiisobutyl amidine hydrochloride solution under the condition of continuously introducing nitrogen, continuously introducing nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3-7h to prepare an intermediate polymer, and drying in vacuum to constant weight;
(4) adding the prepared graphene oxide/hydrous zirconium oxide and the intermediate polymer into hydrochloric acid, placing the mixture in an oil bath at the temperature of 80-120 ℃, continuously stirring and reacting for 3-7h, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at the temperature of 40 ℃ to obtain the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent.
2. The preparation method of the composite adsorption phosphorus removal agent as claimed in claim 1, comprising the following steps:
(1) ultrasonically dispersing 0.1-0.5g of graphene oxide in 200mL of ultrapure water for 2h to obtain a graphene oxide dispersion liquid;
(2) 15-30g of ZrOCl2·8H2Dissolving O in 200mL of ultrapure water, slowly adding the dissolved O into the graphene oxide dispersion liquid, stirring the mixture at 50 ℃ for 2 hours, and adjusting the pH value to 10 by using NaOH; slowly dropwise adding 2-4mL of hydrazine hydrate, and stirring for 2-5h at 70-110 ℃; after cooling to room temperature, washing with ultrapure water to neutrality, and carrying out vacuum freeze drying for 2 days for later use to obtain graphene oxide/hydrous zirconium oxide;
(3) mixing the components in a molar ratio of (0.5-2): 1, adding N-vinylformamide and acrylonitrile into a round-bottom flask to form a mixed solution, placing the round-bottom flask in a constant-temperature water bath at 40-60 ℃, introducing high-purity nitrogen to remove oxygen for 15min, adding ultrapure water with the volume 4-8 times that of the mixed solution, continuously introducing the nitrogen for 20min, slowly dropwise adding azodiisobutyramidine hydrochloride solution with the mass 0.2-0.5% that of the mixed solution under the condition of continuously introducing the nitrogen, continuously introducing the nitrogen for 5min after dropwise adding is finished, then reacting in the water bath for 3-7h to prepare an intermediate polymer, and drying in vacuum to constant weight;
(4) weighing 0.1-0.5g of the graphene oxide/hydrated zirconia, mixing the graphene oxide/hydrated zirconia with the intermediate polymer, adding 0.5-1.5 times of the molar equivalent of the mixed solution and 1-4 times of ultrapure water of the mixed solution, placing the mixture in an oil bath at 80-120 ℃, continuously stirring for reaction for 3-7h, cooling the obtained product, slowly pouring the cooled product into an acetone solution, separating out a solid product, and placing the solid product in a vacuum drying oven for vacuum drying at 40 ℃ to obtain the graphene oxide/hydrated zirconia/polyamidine composite adsorption dephosphorizing agent.
3. A phosphorus removal method of the composite adsorption phosphorus removal agent prepared by the preparation method of any one of claims 1-2, which is characterized by comprising the following steps: weighing 0.1-1g of the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent, adding the graphene oxide/hydrous zirconium oxide/polyamidine composite adsorption phosphorus removal agent into 1-15mg/L of phosphorus-containing solution, fully and uniformly mixing, oscillating in a constant-temperature water bath for 12h, after adsorption balance is achieved, performing centrifugal filtration, measuring the phosphorus concentration of filtrate by adopting a molybdenum blue colorimetric method, and calculating the adsorption quantity.
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| CN103861559A (en) * | 2014-03-12 | 2014-06-18 | 陕西科技大学 | Zirconia-modified graphene and method for removing fluorine ions in water |
| CN105032348A (en) * | 2015-07-07 | 2015-11-11 | 中国科学院水生生物研究所 | Reduced graphene oxide/nano zirconium dioxide composite adsorption phosphorous removing agent and preparation method thereof |
| CN106000297A (en) * | 2016-05-10 | 2016-10-12 | 郑州大学 | Graphene loaded zirconium oxide composite material, preparing method thereof, and application thereof as desulfurizer adsorbent |
| CN107262064A (en) * | 2017-07-26 | 2017-10-20 | 浙江大学 | A kind of preparation method of daiamid grafted graphene oxide cladded type biological micromolecule adsorbent |
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