CN108996669A - A kind of polyethylene-graphene composite biological packing and preparation method thereof - Google Patents
A kind of polyethylene-graphene composite biological packing and preparation method thereof Download PDFInfo
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- CN108996669A CN108996669A CN201810894016.XA CN201810894016A CN108996669A CN 108996669 A CN108996669 A CN 108996669A CN 201810894016 A CN201810894016 A CN 201810894016A CN 108996669 A CN108996669 A CN 108996669A
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- Prior art keywords
- polyethylene
- graphene
- composite biological
- biological packing
- graphene composite
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Classifications
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/106—Carbonaceous materials
-
- 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
- C02F3/02—Aerobic processes
- C02F3/08—Aerobic processes using moving contact bodies
-
- 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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
First graphene aerogel microballoon is made through spraying, cooling, filtering, dry, thermal reduction in graphene oxide by a kind of preparation method of polyethylene-graphene composite biological packing；Polyethylene is dissolved by heating in dimethylbenzene again；Then the xylene solution of polyethylene and graphene aerogel microballoon are uniformly mixed under negative pressure and smash graphene aerogel microballoon；Polyethylene-graphene composite material is then obtained by heating volatilization dimethylbenzene；Composite material Freezing smashing is finally obtained into pellet, then the pellet is added in the screw extruder with membrana oralis, blending extrusion, cutting obtain polyethylene-graphene composite biological packing finished product.Present invention improves the surface roughness of existing polyethylene carrier and specific surface areas, increase porosity, improve surface hydrophilicity, final optimization pass application effect.
Description
Technical field
The present invention relates to organic polymers and composite material of inorganic matter field, and in particular to a kind of polyethylene-graphene is multiple
Close biologic packing material and preparation method thereof.
Background technique
Graphene is a kind of carbonaceous green wood as SP2 hydbridized carbon atoms bi-dimensional cellular shape lattice structure made of tightly packed
Material, thickness can be single layer or several layers of.2004, (Novoselov K S, the Geim A such as British scientist Geim and Novoselov
2004,306 (5696): K, Morozov S V et al.Science 666~669) theoretically confirm graphene monocrystalline
In the presence of, and using adhesive tape removing high starch breeding method be made can really self-existent two-dimensional graphene lamella, so far
Start the upsurge of graphene scientific research and engineer application.Compared with carbon nanotube (CNTs), graphene has superior property
Can, such as room temperature carrier mobility~10000cm2/Vs of graphene, theoretical specific surface area~2630m2/ g, it is seen that light is saturating
Rate~97.7%, Young's modulus~1TPa are crossed, the coefficient of heat conduction is 3000-5000W/ (mK).The side of graphene is prepared at present
Method is numerous, has vapor deposition, epitaxial growth method, mechanical glass method, oxidation-reduction method etc., wherein oxidation-reduction method is to make on a large scale
Standby graphene most efficient method (Huang X, Qi X, Boey F, Zhang H.Chem Soc Rev, 2012,41 (2): 666
~686).Graphene combines the structure feature of carbon nanotube conducting and clay layer, to develop high-performance, multifunctional polymer
Nanocomposite provides new direction, and many graphene/polymer composites are produced and study in recent years.
The relevant report about polyethylene/graphene composite material is mainly used for anti-static composite material, tubing, heat at present
Quick electric resistor composite etc..Such as a kind of ultra-high molecular weight polyethylene/graphite alkene disclosed in 103450537 B of patent No. CN is anti-
Ultra-high molecular weight polyethylene will be placed in high-speed mixer with graphene powder and stir by the preparation method of electrostatic composite material,
Obtain ultra-high molecular weight polyethylene/graphite alkene composite particles；By ultra-high molecular weight polyethylene/graphite alkene composite particles 180~
5~10min is preheated at 240 DEG C, then hot pressing 30min under the conditions of mutually synthermal, 10MPa, obtain ultra-high molecular weight polyethylene/
Grapheme material.This method is not related to solvent, is prepared by Electrostatic Absorption, then hot-forming, antistatic compound needed for preparation
Material.
For pure polyethylene biologic packing material, the hole configurations of the adjustable filler of addition of graphene improves its table
Surface roughness and specific surface area improve the mechanical property of filler, increase its porosity, assign surface charge, improve its surface parent
It is aqueous, shorten the biofilm time, be conducive to microorganism growth, can be used for improving sewage treating efficiency.Currently, being based on polyethylene/stone
There is not been reported for the related data of biologic packing material of MBBR technique for black alkene composite material.
Summary of the invention
The object of the present invention is to provide a kind of polyethylene-graphene composite biological packings and preparation method thereof, improve existing
The surface roughness and specific surface area of polyethylene carrier increase porosity, improve surface hydrophilicity, finally increase its application effect
Fruit.
The technical solution adopted by the present invention is that:
A kind of polyethylene-graphene composite biological packing, the polyethylene and 0.3- for being 594-599.7 parts including parts by weight
6 parts of graphene.
A kind of polyethylene-graphene composite biological packing, the polyethylene and 0.3- for being 594-599.7 parts including parts by weight
6 parts of graphene aerogel microballoon.
Further, the graphene of 0.1-50g is added in every kilogram of polyethylene.
Further, the density of the composite biological packing is 0.95-1.05g/cm3, it is porous shape, porosity is
75%-90%, hole count 4-70.
Further, the weight accumulation of the composite biological packing is 50-250kg/m3, specific surface area be greater than be equal to
800m2/m3, shrinking percentage is less than or equal to 0.2%.
Further, the polyethylene be high density polyethylene (HDPE), low density polyethylene (LDPE) or linear low density polyethylene it
One, in addition, the polyethylene can also be replaced by one of polyurethane, polypropylene, polyvinyl chloride.
Further, the diameter of the graphene is 0.5-20 μm, with a thickness of 0.5-10nm, specific surface area 20-
800m2/g。
A method of preparing polyethylene-graphene composite biological packing, comprising the following steps:
Step 1: graphene oxide is prepared into 6mg/mL aqueous solution, ultrasonic disperse is uniform；
Step 2: graphene oxide aqueous dispersions are atomized into graphene oxide drop microballoon using spray-on process, and cold
But receiving liquid collection is carried out in bath；
Step 3: the graphene oxide ice microballoon in two receiving liquid of filtration step obtains graphene oxide after freeze-drying
Aerogel microball；
Step 4: it is micro- that the graphite oxide aerogel microballoon of step 3 by thermal reduction is obtained into graphene aerogel
Ball；
Step 5: 594-599.7 parts of polyethylene are dissolved in dimethylbenzene under conditions of 100-150 DEG C；
Step 6: by the xylene solution of polyethylene and 0.3-6 parts of graphene aerogel microballoons in the negative of 0.1-200mbar
Pressure is uniformly mixed；
Step 7: the graphene aerogel microballoon in the mixed liquor of step 6 is smashed using ultrasonic disperse；
Step 8: the mixed liquor of step 7 is placed on 120oIt is heated in baking oven, volatilization dimethylbenzene obtains polyethylene-graphite
Alkene composite material；
Step 9: the polyethylene in step 8-graphene composite material Freezing smashing is obtained into pellet, then the pellet is added
Enter into the screw extruder with membrana oralis, blending extrusion, cutting obtain polyethylene-graphene composite biological packing finished product.
Beneficial effects of the present invention:
Graphene is made graphene aerogel microballoon first and mixed again with polyethylene by the present invention, utilizes the porous of microballoon
Property, it solves the problems, such as graphene dispersion, so that being filled between two layers of graphene by polyethylene, avoids asking for graphene aggregation
Topic, increases effectively the specific surface area of final filler, improves the mechanical property of filler, increases its porosity, assigns surface electricity
Lotus, improves its surface hydrophilicity, shortens the biofilm time, is conducive to microorganism growth and is greatly improved when being used for sewage treatment
Treatment effeciency.Preparation method of the present invention is simple, the easily operated control of technique, and environmental protection, low energy consumption.
Detailed description of the invention
Fig. 1 is the biologic packing material outside drawing prepared by the present invention with porous structure.
Specific embodiment
The present invention is described in further detail below with reference to embodiment.
Embodiment 1
(1) prepare graphite oxide: natural graphite is prepared as graphite oxide through Brodie oxidizing process.
(2) prepare graphene oxide aqueous dispersions: at room temperature, by 3g Brodie oxidizing process preparation graphite oxide and
The mixing of 400mL deionized water, is placed in ultrasonic washing instrument, and 200W ultrasonic disperse is stirred overnight after twenty minutes, and it is equal to obtain dispersion
The even graphene oxide aqueous dispersions in dark-brown 7.5mg/mL.
(3) trash ice is placed in the good open Dewar bottle of heat preservation, sodium chloride powder is added, stir evenly to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with ethyl acetate is put into trash ice/sodium chloride cooling bath as receiving liquid.Meanwhile it will match
The graphene oxide aqueous dispersions of the 7.5mg/mL made are fitted into the syringe on electrostatic atomizer, adjust syringe nozzle
Height is allowed to after being separated by suitable distance with receiving liquid, and adjusting voltage is 15KV, is started spraying and is quickly cooled down in receiving liquid
Drop microballoon.
(4) ethyl acetate receiving liquid is quickly filtered with sieve and obtains brownish black graphene oxide ice microballoon, and it is dry to be transferred to freezing
In dry machine, under the conditions of vacuum degree 20Pa, -50 DEG C of temperature, drying obtains brown oxidation graphene aerogel microballoon for 24 hours.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas protection by 5 DEG C/min
Heating rate be warming up to 800 degrees Celsius and keep obtaining black light graphite alkene aerogel microball in 5 hours.Average grain diameter is
247 μm, density 5.0kg/m3。
(6) 597g high density polyethylene (HDPE) is dissolved in 10L xylene solution under the conditions of 150 DEG C.
(7) by the polyethylene solution in graphene aerogel microballoon obtained in step 5 and step 6 1mbar negative pressure
Lower to be uniformly mixed, 200W ultrasonic disperse 30 minutes, then 80 DEG C of heating in vacuum for 24 hours, obtained the compound block-shaped material of polyethylene-graphene
Material.
(8) the compound blocky material use refrigerator pulverizer of polyethylene-graphene in step 7 is granulated.
(9) polyethylene in step 9-graphene oxide particle is added in the screw extruder with specific membrana oralis,
Blending extrusion, cutting obtain polyethylene-graphene oxide composite biological packing finished product, and the density of the material is 0.989g/cm3,
Porosity is 85%, weight accumulation 130kg/m3, specific surface area 900m2/m3, shrinking percentage is less than 1%.
Embodiment 2
(1) prepare graphite oxide: natural graphite is prepared as graphite oxide through Brodie oxidizing process.
(2) prepare graphene oxide aqueous dispersions: at room temperature, by 6g Brodie oxidizing process preparation graphite oxide and
The mixing of 1000mL deionized water, is placed in ultrasonic washing instrument, and 200W ultrasonic disperse is stirred overnight after twenty minutes, and it is equal to obtain dispersion
The even graphene oxide aqueous dispersions in dark-brown 6mg/mL.
(3) trash ice is placed in the good open Dewar bottle of heat preservation, sodium chloride powder is added, stir evenly to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with ethyl acetate is put into trash ice/sodium chloride cooling bath as receiving liquid.Meanwhile it will match
The graphene oxide aqueous dispersions of the 6mg/mL made are fitted into the syringe on electrostatic atomizer, and it is high to adjust syringe nozzle
Degree is allowed to after being separated by suitable distance with receiving liquid, and adjusting voltage is 15KV, is started spraying and is quickly cooled down liquid in receiving liquid
Drip microballoon.
(4) ethyl acetate receiving liquid is quickly filtered with sieve and obtains brownish black graphene oxide ice microballoon, and it is dry to be transferred to freezing
In dry machine, under the conditions of vacuum degree 20Pa, -50 DEG C of temperature, drying obtains brown oxidation graphene aerogel microballoon for 24 hours.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas protection by 5 DEG C/min
Heating rate be warming up to 800 degrees Celsius and keep obtaining black light graphite alkene aerogel microball in 5 hours.Average grain diameter is
320 μm, density 5.2kg/m3。
(6) 594g linear low density polyethylene is dissolved in 10L xylene solution under the conditions of 120 DEG C.
(7) by the polyethylene solution in graphene aerogel microballoon obtained in step 5 and step 6 in the negative of 0.1mbar
Pressure is uniformly mixed, and 200W ultrasonic disperse 30 minutes, then 80 DEG C of heating in vacuum for 24 hours, obtained the compound bulk of polyethylene-graphene
Material.
(8) the compound blocky material use refrigerator pulverizer of polyethylene-graphene in step 7 is granulated.
(9) polyethylene in step 8-graphene oxide particle is added in the screw extruder with specific membrana oralis,
Blending extrusion, cutting obtain polyethylene-graphene oxide composite biological packing finished product, and the density of the material is 1.023g/cm3,
Porosity is 78%, weight accumulation 115kg/m3, specific surface area 1100m2/m3, shrinking percentage is less than 0.5%.
Claims (8)
1. a kind of polyethylene-graphene composite biological packing, which is characterized in that including parts by weight be 594-599.7 part gather
Ethylene and 0.3-6 parts of graphene.
2. a kind of polyethylene-graphene composite biological packing, which is characterized in that including parts by weight be 594-599.7 part gather
Ethylene and 0.3-6 parts of graphene aerogel microballoon.
3. a kind of polyethylene-graphene composite biological packing as described in claim 1, which is characterized in that every kilogram of polyethylene
The middle graphene that 0.1-50g is added.
4. a kind of polyethylene-graphene composite biological packing as described in claim 1, which is characterized in that the compound bio
The density of filler is 0.95-1.05g/cm3, it is porous shape, porosity 75%-90%, hole count 4-70.
5. a kind of polyethylene-graphene composite biological packing as described in claim 1, which is characterized in that the compound bio
The weight accumulation of filler is 50-250kg/m3, specific surface area, which is greater than, is equal to 800m2/m3, shrinking percentage is less than or equal to 0.2%.
6. a kind of polyethylene-graphene composite biological packing as described in claim 1, which is characterized in that the polyethylene
For one of high density polyethylene (HDPE), low density polyethylene (LDPE) or linear low density polyethylene, in addition, the polyethylene can also be replaced by
One of polyurethane, polypropylene, polyvinyl chloride.
7. a kind of polyethylene-graphene composite biological packing as described in claim 1, which is characterized in that the graphene
Diameter be 0.5-20 μm, with a thickness of 0.5-10nm, specific surface area 20-800m2/g。
8. a kind of prepare polyethylene-graphene composite biological packing method, which comprises the following steps:
Step 1: graphene oxide is prepared into 6mg/mL aqueous solution, ultrasonic disperse is uniform；
Step 2: graphene oxide aqueous dispersions are atomized into graphene oxide drop microballoon using spray-on process, and in cooling bath
Middle progress receiving liquid collection；
Step 3: the graphene oxide ice microballoon in two receiving liquid of filtration step obtains graphene oxide airsetting after freeze-drying
Glue microballoon；
Step 4: the graphite oxide aerogel microballoon of step 3 is obtained into graphene aerogel microballoon by thermal reduction；
Step 5: 594-599.7 parts of polyethylene are dissolved in dimethylbenzene under conditions of 100-150 DEG C；
Step 6: by the xylene solution of polyethylene and 0.3-6 parts of graphene aerogel microballoons under the negative pressure of 0.1-200mbar
It is uniformly mixed；
Step 7: the graphene aerogel microballoon in the mixed liquor of step 6 is smashed using ultrasonic disperse；
Step 8: the mixed liquor of step 7 being placed in 120 ° of baking ovens and is heated, and it is multiple that volatilization dimethylbenzene obtains polyethylene-graphene
Condensation material；
Step 9: the polyethylene in step 8-graphene composite material Freezing smashing is obtained into pellet, then the pellet is added to
In screw extruder with membrana oralis, blending extrusion, cutting obtain polyethylene-graphene composite biological packing finished product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110104910A (en) * | 2019-06-21 | 2019-08-09 | 安吉国千环境科技有限公司 | A kind of sewage disposal technology method based on MBBR technique |
| CN111849051A (en) * | 2020-06-22 | 2020-10-30 | 北交源生态环境科技(北京)有限公司 | Graphene MBBR (moving bed biofilm reactor) suspension carrier filler and preparation method thereof |
| CN113999445A (en) * | 2021-10-20 | 2022-02-01 | 国网电力科学研究院有限公司 | Graphene/polyethylene composite material and preparation method thereof |
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Application publication date: 20181214 |