CN111729642A - Preparation method of novel graphene oxide/gelatin composite filler - Google Patents
Preparation method of novel graphene oxide/gelatin composite filler Download PDFInfo
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- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- 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
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- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides a preparation method of a novel graphene oxide/gelatin composite filler, which comprises the following steps: sequentially and respectively cleaning polypropylene, polyethylene, polyvinyl chloride or polyester filler with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner to remove pollutants and impurities on the surface, and naturally airing for later use; placing polyethylene filler in HNO3And H2SO4Heating the mixed solution in water bath until reaction, washing and drying; preparing graphene oxide/gelatin dispersion liquid; and soaking the polyethylene filler in a glutaraldehyde solution, then soaking in a graphene oxide/gelatin solution, taking out, washing and drying to obtain the graphene/gelatin composite material. The invention uses the dipping method to mix the oxidized stoneThe graphene/gelatin is loaded on the surface of the filler, so that the specific surface area and the biocompatibility of the filler can be improved, a large amount of organic matters can be adsorbed, and the graphene/gelatin composite filler has the characteristics of strong oxidation capacity and strong impact resistance, so that the adsorption effect on microorganisms is enhanced, and the purification purpose is achieved.
Description
Technical Field
The invention belongs to the field of composite filler; in particular to a preparation method of a novel graphene oxide/gelatin composite filler.
Background
The traditional sewage purification treatment technology is divided into an activated sludge method and a biomembrane method. The biomembrane method is characterized in that a group consisting of microorganisms and micro-animals such as protozoa and metazoan is attached to the surface of a filler carrier which is attached and grown on the surface of the filler carrier with a large specific surface area, and a biomembrane shape connected by colloid is presented. When the sewage is continuously contacted with the biological membrane in a flowing or aerating way, organic pollutants and dissolved oxygen in the sewage are taken as nutrient substances and are oxidized and degraded by microorganisms on the biological membrane, so that organic matters, nitrogen, phosphorus and the like are removed. While the organic matters in the sewage are continuously removed, the microorganisms continuously metabolize, and the aged and fallen biological membrane is taken away with the purified sewage and separated in a sedimentation tank.
The filler is used as a carrier of the biological membrane, and the performance of the filler directly influences the sewage treatment effect. At present, the common biological filler in the market is mainly prepared by injection molding of high polymer such as polypropylene, polyethylene, polyvinyl chloride or polyester and the like serving as raw materials into various shapes. In practical application, people find that the plastic fillers have poor hydrophilicity and biological affinity and poor oxygen mass transfer performance, so that the plastic fillers have defects in the aspects of film forming speed, film forming amount and compactness of the film and the fillers, and if the plastic fillers are subjected to appropriate hydrophilic and biological affinity modification, the mass transfer, film forming and water treatment performance of the fillers can be expected to be improved.
The existing filler for adsorbing the microbial biomass completely depends on the microbial concentration in the sewage, and generally only can play the role of a simple carrier. In some industrial wastewater, the concentration of microorganisms is low, the propagation and growth speed of the microorganisms is slow, and the effect of sewage treatment is severely limited. In addition, the filler is not electrified, the affinity of the surface of the filler and microorganisms is limited only by the adsorption effect of negative charges on the surfaces of the microorganisms, the adsorption and deposition speed of a biological film is slow, and the speed and the effect of sewage purification can be limited.
The gelatin protein is an active substance obtained by partial hydrolysis of collagen, is a natural high molecular organic polymer, has a structure similar to that of biological tissues, and therefore has good biocompatibility. The gelatin is used as a carrier to provide more physical attachment points for microorganisms, which is beneficial to the growth of the microorganisms, accelerates the film formation speed and improves the water treatment efficiency. In recent years, graphene is also receiving more and more attention as a new nano material, due to the unique two-dimensional layered crystal structure and high anisotropy of the graphene-based two-dimensional nano material, the layered structure has good controllability, the performance of the material can be regulated and controlled by methods such as dimension increasing and decreasing, intercalation, functional modification and the like, and the two-dimensional layered nano material has a large specific surface area and is rich in a conjugated structure and functional group addition sites. Graphene oxide has similar physicochemical properties, contains a large number of hydrophilic functional groups such as hydroxyl, carboxyl, epoxy and the like on the surface, has very good dispersibility in aqueous solution, is considered to be a chemical substance which most probably forms molecular-level dispersion, is not easy to agglomerate and precipitate, is easier to modify, can react with organic polymer gelatin, and is more stable and uniformly dispersed, so that the graphene oxide and the gelatin can be combined to prepare the nanocomposite for the field of filler coating.
Disclosure of Invention
The invention provides a preparation method of a novel graphene oxide/gelatin composite filler, wherein the novel filler prepared by the method is loaded with a graphene oxide/gelatin composite layer on the surface of the filler by an impregnation method. The graphene oxide material is uniformly and stably dispersed in the gelatin solution, and the graphene oxide/gelatin protein is introduced into the polymer matrix by utilizing the cross-linking property of glutaraldehyde, so that the purpose of hydrophilic and hydrophilic modification of the surface of the polyethylene filler is achieved, and the novel graphene oxide/gelatin composite filler is finally obtained.
The invention is realized by the following technical scheme: the invention relates to a preparation method of a novel graphene oxide/gelatin composite filler, which comprises the following steps:
step one, sequentially and respectively cleaning polypropylene, polyethylene, polyvinyl chloride or polyester filler with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner to remove pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the polyethylene filler treated in the step one into a mixed solution of HNO3 and H2SO4, heating in a water bath until reaction, taking out, washing and drying;
dispersing graphene oxide into a gelatin solution to prepare a graphene oxide/gelatin dispersion solution;
and step four, soaking the polyethylene filler in a glutaraldehyde solution, taking out the polyethylene filler, then soaking the polyethylene filler in a graphene oxide/gelatin solution, taking out the polyethylene filler, washing and drying the polyethylene filler to obtain the novel graphene oxide/gelatin composite filler.
Preferably, in the step one, the cleaning time is 15 min.
Preferably, in the second step, the ratio of the polyethylene filler to the mixed solution of HNO3 and H2SO4 is 1: 1-1: 25.
preferably, in the second step, the reaction temperature is 30-90 ℃.
Preferably, in the second step, the reaction time is 2-8 h.
Preferably, in the third step, the amount of the graphene oxide is 0.5-10g, and the sheet diameter is 0.5-5 μm.
Preferably, in the third step, the volume of the gelatin solution is 500ml, and the mass concentration is 0.5-2 g/L.
Preferably, in the third step, the temperature of the glutaraldehyde solution is 37 ℃, and the mass percentage content is 2-10%.
Preferably, in the fourth step, the soaking time in the glutaraldehyde solution is 12-48 h.
Preferably, in the fourth step, the soaking time in the graphene oxide/gelatin solution is 2-8h, and the temperature is 37 ℃.
The method of the invention has the following advantages:
the invention aims at the defects that the filler adsorption microorganism amount in the prior art is completely dependent on the microorganism concentration in the sewage, the affinity of the filler surface and the microorganism is limited, and the adsorption and deposition speed of a biological film is slow. According to the invention, the graphene oxide/gelatin is loaded on the surface of the filler by using an impregnation method, so that the specific surface area and the biocompatibility of the filler can be improved, a large amount of organic matters can be adsorbed, and the graphene oxide/gelatin composite material has the characteristics of strong oxidation capacity and strong impact resistance, so that the adsorption effect on microorganisms is enhanced, and the purpose of purification is achieved.
Drawings
FIG. 1 is a graph comparing biomass of a common filler with that of the No. 1 composite filler prepared in the example 1 in the same running time;
FIG. 2 is a graph comparing the biomass of a conventional filler with the biomass of the 2# composite filler prepared in example 2 during the same period of operation;
FIG. 3 is a graph comparing the biomass of a conventional filler with the biomass of a 3-component filler prepared in example 3 during the same period of operation;
FIG. 4 is a comparison of biomass of conventional filler with that of No. 4 composite filler prepared in example 4 during the same period of operation.
Detailed Description
The present invention will be described in detail with reference to specific examples. It should be noted that the following examples are only illustrative of the present invention, but the scope of the present invention is not limited to the following examples.
The following examples to which the invention relates were prepared as follows:
step one, sequentially and respectively cleaning polypropylene, polyethylene, polyvinyl chloride or polyester filler with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner to remove pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the polyethylene filler treated in the step one in HNO3And H2SO4Heating the mixed solution in water bath until reaction, taking out, washing and drying;
dispersing graphene oxide into a gelatin solution to prepare a graphene oxide/gelatin dispersion solution;
and step four, soaking the polyethylene filler in a glutaraldehyde solution, taking out the polyethylene filler, then soaking the polyethylene filler in a graphene oxide/gelatin solution, taking out the polyethylene filler, washing and drying the polyethylene filler to obtain the novel graphene oxide/gelatin composite filler.
Example 1
This example adoptscylindrical polyethylene plastic with the diameter of 35mm × 20mm is used as experimental filler, and the specific surface area of the filler is 500m2/m3Density 0.96g/cm3And the porosity is 97.5%.
Step one, sequentially washing a polyethylene filler to be treated by acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 15min, removing pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the obtained treated polyethylene filler in HNO with the mass ratio of 1:183And H2SO4Heating the mixed solution in a water bath to the reaction temperature of 80 ℃, reacting for 4 hours, and then taking out, washing and drying;
step three, taking 0.5g of graphene oxide (with the sheet diameter of 1 mu m) to disperse into 500ml of 1g/L gelatin solution to prepare graphene oxide/gelatin dispersion liquid;
and step four, soaking the polyethylene filler subjected to surface liquid phase oxidation treatment under the water bath condition in a 5% glutaraldehyde solution, taking out the polyethylene filler after 24 hours, soaking the polyethylene filler in a graphene oxide/gelatin dispersion liquid at 37 ℃, taking out the polyethylene filler after 4 hours, washing and drying to obtain the # 1 novel graphene oxide/gelatin composite filler.
The common filler is compared with the 1# composite filler obtained in the example (the biomass of the common filler is compared with the biomass of the 1# composite filler in the same running time): respectively putting an equivalent common filler and a 1# composite filler with a filling ratio of 20% into 2 MBBR reactors, adding activated sludge and simulated domestic sewage which are obtained from a sewage plant into the reactors, taking out the fillers after the aeration operation is carried out for a period of time, and measuring the biomass of the graphene oxide/gelatin composite filler to be higher than that of the common filler by adopting a gravimetric method, as shown in figure 1.
Example 2
in the experiment, cylindrical polypropylene plastic with the diameter of phi 25mm and × 10mm is used as an experiment filler, and the specific surface area of the filler is 680m2/m3Density of 0.98g/cm3And the porosity is 95%.
Step one, sequentially washing a polypropylene filler to be treated with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 15min, removing pollutants and impurities on the surface, and naturally airing for later use;
secondly, placing the obtained treated polypropylene filler in HNO with the mass ratio of 1:183And H2SO4Heating the mixed solution in a water bath to the reaction temperature of 80 ℃, reacting for 4 hours, and then taking out, washing and drying;
step three, taking 0.5g of graphene oxide (with the sheet diameter of 1 mu m) to disperse into 500ml of 1g/L gelatin solution to prepare graphene oxide/gelatin dispersion liquid;
and step four, soaking the polypropylene filler subjected to surface liquid phase oxidation treatment under the water bath condition in a 5% glutaraldehyde solution, taking out the polypropylene filler after 24 hours, soaking the polypropylene filler in a graphene oxide/gelatin dispersion solution, taking out the polypropylene filler after 4 hours, washing and drying the polypropylene filler to obtain the 2# novel graphene oxide/gelatin composite filler.
The common filler is compared with the 2# composite filler obtained in the embodiment (the biomass of the common filler is compared with the biomass of the 2# composite filler in the same running time): respectively putting an equivalent common filler and an equivalent 2# composite filler with a filling ratio of 20% into 2 MBBR reactors, then adding activated sludge and simulated domestic sewage which are obtained from a sewage plant into the reactors, taking out the fillers after the aeration operation is carried out for a period of time, and measuring the biomass of the graphene oxide/gelatin composite filler to be higher than that of the common filler by adopting a gravimetric method, as shown in figure 2.
Example 3
the experiment adopts phi 35mm phi × 20mm cylindrical polyethylene plastic as experiment filler, and the specific surface area of the filler is 500m2/m3Density 0.96g/cm3And the porosity is 97.5%.
Step one, sequentially washing a polyethylene filler to be treated by acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 15min, removing pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the obtained treated polyethylene filler in HNO with the mass ratio of 1:183And H2SO4Heating the mixed solution in a water bath to the reaction temperature of 80 ℃, reacting for 4 hours, and then taking out, washing and drying;
step three, dispersing 2.5g of graphene oxide (with the sheet diameter of 1 mu m) into 500ml of 1g/L gelatin solution to prepare graphene oxide/gelatin dispersion liquid;
and step four, soaking the polyethylene filler subjected to surface liquid phase oxidation treatment under the water bath condition in a 5% glutaraldehyde solution, taking out the polyethylene filler after 24 hours, soaking the polyethylene filler in a graphene oxide/gelatin dispersion solution, taking out the polyethylene filler after 4 hours, washing and drying to obtain the 3# novel graphene oxide/gelatin composite filler.
The common filler is compared with the 3# composite filler obtained in the embodiment (the biomass of the common filler is compared with the biomass of the 3# composite filler in the same running time): respectively putting an equivalent common filler and an equivalent 3# composite filler with a filling ratio of 20% into 2 MBBR reactors, then adding activated sludge and simulated domestic sewage which are obtained from a sewage plant into the reactors, taking out the fillers after the aeration operation is carried out for a period of time, and measuring the biomass of the graphene oxide/gelatin composite filler to be higher than that of the common filler by adopting a gravimetric method, as shown in figure 3.
Example 4
the experiment adopts phi 35mm phi × 20mm cylindrical polyethylene plastic as experiment filler, and the specific surface area of the filler is 500m2/m3Density 0.96g/cm3, porosity 97.5%.
Step one, sequentially washing a polyethylene filler to be treated by acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 15min, removing pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the obtained treated polyethylene filler in HNO with the mass ratio of 1:183And H2SO4Heating the mixed solution in a water bath to the reaction temperature of 80 ℃, reacting for 4 hours, and then taking out, washing and drying;
step three, taking 0.5g of graphene oxide (with the sheet diameter of 1 mu m) to disperse into 500ml of 1g/L gelatin solution to prepare graphene oxide/gelatin dispersion liquid;
and step four, soaking the polyethylene filler subjected to surface liquid phase oxidation treatment under the water bath condition in a 5% glutaraldehyde solution, taking out the polyethylene filler after 36 hours, soaking the polyethylene filler in a graphene oxide/gelatin dispersion solution, taking out the polyethylene filler after 4 hours, washing and drying to obtain the 4# novel graphene oxide/gelatin composite filler.
Comparing the common filler with the 4# composite filler obtained in the embodiment (comparing the biomass of the common filler with the biomass of the 4# composite filler in the same running time): the method comprises the steps of putting 20% of common filler and 4# composite filler in equal amount into 2 MBBR reactors, adding activated sludge and simulated domestic sewage which are obtained from a sewage plant into the reactors, taking out the filler after aeration operation for a period of time, and measuring the biomass of the graphene oxide/gelatin composite filler to be higher than that of the common filler by adopting a gravimetric method, as shown in figure 4.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a novel graphene oxide/gelatin composite filler is characterized by comprising the following steps:
step one, sequentially and respectively cleaning polypropylene, polyethylene, polyvinyl chloride or polyester filler with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner to remove pollutants and impurities on the surface, and naturally airing for later use;
step two, placing the polyethylene filler treated in the step one in HNO3And H2SO4Heating the mixed solution in water bath until reaction, taking out, washing and drying;
dispersing graphene oxide into a gelatin solution to prepare a graphene oxide/gelatin dispersion solution;
and step four, soaking the polyethylene filler in a glutaraldehyde solution, taking out the polyethylene filler, then soaking the polyethylene filler in a graphene oxide/gelatin solution, taking out the polyethylene filler, washing and drying the polyethylene filler to obtain the novel graphene oxide/gelatin composite filler.
2. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the first step, the cleaning time is 15 min.
3. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the second step, the polyethylene filler and HNO are mixed3And H2SO4The ratio of the amount of the mixed liquid is 1: 1-1: 25.
4. the method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the second step, the reaction temperature is 30-90 ℃.
5. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the second step, the reaction time is 2-8 h.
6. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the third step, the taking amount of the graphene oxide is 0.5-10g, and the sheet diameter of the graphene oxide is 0.5-5 μm.
7. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the third step, the volume of the gelatin solution is 500ml, and the mass concentration is 0.5-2 g/L.
8. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the third step, the temperature of the glutaraldehyde solution is 37 ℃, and the mass percentage content is 2-10%.
9. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the fourth step, the soaking time in the glutaraldehyde solution is 12-48 h.
10. The method for preparing the novel graphene oxide/gelatin composite filler according to claim 1, wherein in the fourth step, the soaking time in the graphene oxide/gelatin solution is 2-8h, and the temperature is 37 ℃.
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