CN110526521A - A kind of landfill leachate graphene integrated purification system and technique - Google Patents
A kind of landfill leachate graphene integrated purification system and technique Download PDFInfo
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2103/06—Contaminated groundwater or leachate
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F3/28—Anaerobic digestion processes
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Abstract
The present invention provides a kind of landfill leachate graphene integrated purification systems, including landfill leachate collection and conveying device, it further include having anaerobism groove, Multistage filtering device, multistage graphene purifier, graphene photocatalytic degradation device, multiple purifying slot, multistage graphene bactericidal unit, graphene ceramic water-purification device, the present invention also provides the purification processes of the above-mentioned purification system of application, purified treatment is carried out to landfill leachate using the system, can reach and purify thorough, efficient, low cost and other effects.
Description
Technical field
The present invention relates to waste leachate purification fields, and in particular to a kind of landfill leachate graphene integrated purifying system
System and technique.
Background technique
In general landfill leachate refers to the moisture that rubbish itself contains in refuse landfill, into landfill yard
Sleet water and other moisture, deduct rubbish, overburden layer saturation moisture capacity, and undergo waste layer and overburden layer and formed one
In addition the organic wastewater of kind high concentration also includes the moisture that sanitary fill place leaks out.Consumer waste infiltration liquid refers in particular to live
Refuse landfill, the high concentrated organic wastewater for accumulating place leakage belong to country and forbid strictly in line high pollution waste water.
Existing consumer waste infiltration liquid sewage treatment equipment or technique there is a problem of it is various, after purification water quality without
Method qualified discharge.Such as: conditioning tank adds surface aeration stripping to handle, and low efficiency, time-consuming, residual ammonia pollutes air, and only
Obtain 68% nitrogen nitrogen removal efficiency and (Wang Zongping, Tao Tao, the Yuan Ju newly equal landfill leachate pretreatment-of 76% COD removal rate
Ammonia aeration [J] water supply and drainage, 2001 (6), 15-19);Electrolytic oxidation energy consumption is high, and noble metal catalyst used is expensive,
Plant maintenance also more difficult (Li Ming, Yang Yong, the season experimental study of the catalytic electrolysis to ammonia nitrogen removal in landfill leachate such as the people
[J] Lanzhou Jiaotong University journal, 2007,26 (3): 35-37);UV/O3Method handles the investment of percolate method and operation cost is higher,
It promotes the use of more difficult.Market, which is also called, purifies thorough, efficient, safety, device simplicity, inexpensive consumer waste infiltration liquid
Technology for clarifying and relevant device or device.
Summary of the invention
In order to make up the deficiencies in the prior art, the present invention provides a kind of landfill leachate graphene integration is net
Change system is handled landfill leachate using the system, can be reached and be purified thorough, efficient, low cost and other effects.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of landfill leachate graphene integrated purification system, including landfill leachate is collected and conveying device, also wraps
Include following device:
Anaerobism groove, the anaerobism groove is interior to be equipped with multi-layer porous scaffold, is equipped with ammoxidation biomembrane on the bracket;
Multistage filtering device, the Multistage filtering device is interior to be equipped with multistage graphene enhancing filter screen;
Multistage graphene purifier, every grade of graphene purifier is interior to enhance diatom porcelain material filled with graphene
Material or heavy metal adsorption graphene nanocomposite material or Large ratio surface graphene nano material;
Graphene photocatalytic degradation device, the graphene photocatalytic degradation device is interior to be filled with graphene photocatalytic degradation
Agent;
Multiple purifying slot, the multiple purifying slot is interior to be equipped with ozone generator, graphene nano bactericidal agent and graphite alkylene
Learn oxygen demand scavenger;
Multistage graphene bactericidal unit, every grade of graphene bactericidal unit is interior to be filled with superparamagnetic nanoparticle-oxygen
The group of graphite alkene composite nano materials or the graphene bactericidal agent or following graphene composite material and bactericidal agent
It closes:
Chlorine ball-graphene nanocomposite material, chlorine ball are grafted quaternary ammonium quaternary alkylphosphonium salt solid bactericide, the chloro- 5,5- bis- of the bromo- 3- of 1-
Methyl hydantoin-graphene nanocomposite material, 2,2-Dibromo-3-nitrilopropionamide-graphene nanocomposite material, 1,3- bis-
The bromo- 2- nitro of bromo- 5,5- Dimethyl Hydan-graphene nanocomposite material, 2--styrene-graphene nanocomposite material, two
Benzyl acetate bromide-graphene nanocomposite material, bromination dodecyl dimethyl hexadecyldimethyl benzyl ammonium-graphene nanocomposite material, bromine
The bromo- 2,5- chlorophenesic acid-graphite of nitre propyl alcohol-graphene nanocomposite material, tribromphenol-graphene nanocomposite material, 4-
Alkene nanocomposite, the bromo- 2,4- dicyanobutane-graphene nanocomposite material of 1,2- bis-, α-bromocinnamaldehyde-graphene are received
Bis- (bromoacetic acid) ester-graphene nanocomposite materials of nano composite material, 2- butylene-1,4-diol, the bromo- 2- nitro second of 2,2- bis-
Alcohol-graphene nanocomposite material, N- (the bromo- 2- aminomethyl phenyl of 4-) chloroacetamide-graphene nanocomposite material, 2,2- bis-
Bromo- 3- cyano propionamide-graphene nanocomposite material, solid ternary stable chlorine dioxide-graphene nanocomposite material, height
Ferrite-graphene nanocomposite material, Fluoxastrobin-graphene nanocomposite material, aliette-graphene nano composite wood
Material, height gather iodo- graphene nanocomposite material.Graphene in the bactericidal agent can be graphene, graphene oxide, boron doping
Graphene, nitrogen-doped graphene nanometer sheet, nanobelt, nanotube, nano-cluster, nanofiber, three-dimensional framework material, quantum dot etc.
In any one.
Graphene ceramic water-purification device, graphene ceramic water-purification device are filled with graphene porous ceramic film material.
Further, the ammoxidation biomembrane be autotrophic type, preparation the following steps are included:
S101, prepare bacterium source and ammonia oxidizing bacteria culture medium, the bacterium source is commercially available anaerobic grain sludge, floating containing sludge
Mustiness bacterium, from oxygen type denitrifying bacterium etc.;Ammonia oxidizing bacteria culture medium includes following ingredient: ammonium chloride 1.0g, potassium dihydrogen phosphate
0.7g, bitter salt 0.5g, CALCIUM CHLORIDE DIHYDRATE 0.5g, sodium chloride 10g, sodium bicarbonate 1g, trace element solution 1ml,
Distilled water 999ml.PH 1N sodium hydroxide or 5% sodium carbonate or 1N HCl adjust (being generally adjusted to 8.0), 121 DEG C of sterilizings 20
~30 minutes.
Wherein, trace element solution configuration proportion is as follows: Salzburg vitriol 320mg, cobalt chloride hexahydrate 320mg, and four
Ammonium paramolybdate tetrahydrate 240mg, Zinc vitriol 440mg, EDTA 1000mg, green vitriol 1000mg, sulfuric acid monohydrate
Manganese 870mg, distilled water 100ml.
S102, bacterium source inoculation, the bacterium source is linked by 25% ratio by volume fills the training of 100ml ammonia oxidizing bacteria
It in the 250ml triangular flask for supporting base, shakes 12 days, keeping temperature is 42 DEG C, and revolving speed is controlled in 180/min, detects culture medium therebetween
Middle ammonia nitrogen concentration is such as lower than 10mg/L, is then transferred in fresh culture medium with 25% ratio, finally obtains the bacterium of enrichment
Culture.
S103, bacterial cultures access is had in the 250ml triangular flask of biologic packing material, it is useless that 100ml ammonia nitrogen is added
Water carries out biofilm culture on shaking table;With the increase of biomass on biologic packing material, it is gradually increased the concentration of ammonia nitrogen, operation 20
It, changes a water in every 24 hours, changes water also and be the ammonia nitrogen waste water of special configuration.Microorganism well-grown on filler, falls off
Biomembrane has good settling property, and in the case where influent ammonia nitrogen is 200mg/L, ammonia nitrogen removal rate on the one reaches 50-60
When above, it is believed that the biofilm stage terminates, to obtain autotrophic type ammoxidation biomembrane.
Further, the multistage graphene enhancing filter screen is total to three-level, wherein the first order, the enhancing of second level graphene
Filtering meshes are stacked at the water inlet of the Multistage filtering device, and third level graphene enhances filter screen and is set to the multistage filtering
The water outlet of device, the middle part lower end of the Multistage filtering device are equipped with subsider, the multistage graphene enhancing filter screen
Graphene additive amount is 0.25~5.0%.
The mesh number of first, second and third grade of graphene enhancing filter screen is respectively 10-18,18-35,35-50 mesh, the master of three
Want material in polypropylene, polysulfones, sulfonated polysulfone, polyether sulfone, Kynoar, polytetrafluoroethylene (PTFE), polycarbonate, polyether-ether-ketone
Any one.
Further, the graphene enhancing diatom ceramic material is fired by the raw material of following weight ratio: diatom
Native 46.8%, kaolin 20.1%, feldspar 13.4%, graphene 3.5%, aluminium oxide 4.0%, boron glass 3.4%, talcum powder
3.4%, quartz powder 5.4%;The regenerated fiber cloth or glass fibre cloth bag of graphene enhancing diatom ceramic material 16-70 mesh
It wraps up in.
The heavy metal adsorption graphene nanocomposite material is graphene oxide, hydroxylating graphene, carboxyl graphite
Graphene oxide, the chitosan-modified hydroxylating graphene, acid that alkene, chitosan-modified graphene oxide, glutaraldehyde are coupled
Salt nanotube-graphene oxide, hydroxyapatite-graphene oxide, three acyloxylation stone of N- (trimethoxy silicon propane) ethylenediamine
Black alkene, hydroxyl carbon nano tube-graphene oxide, titanium pillared montmorillonite-graphene oxide, aluminum oxide-graphene oxide,
Aluminium polychloride-graphene oxide, poly- hydroxyl-aluminum pillared vermiculite, poly- hydroxyl-aluminum pillared vermiculite-graphene oxide, 13X type molecule
Sieve, sodium alginate-graphene oxide, EDTA- graphene oxide, polyamidoamine amine dendrimer Bio-sil, polyamide-
It is any in amine type amine dendrimer-graphene oxide, N- (2,3- glycidyl) iminodiacetic acid modified graphene oxide
It is a kind of;The heavy metal adsorption graphene nanocomposite material is wrapped up by the regenerated fiber cloth or glass fabric of 16-70 mesh.
The Large ratio surface graphene nanocomposite material is single-layer graphene nanometer sheet, three-dimensional meso-hole graphene nano material
Material, three-dimensional macropore graphene nano material, graphene aerogel, graphene nano fiber or graphene organic backbone composite Nano
Any one in material.The regenerated fiber cloth or glass fabric of the Large ratio surface graphene nano material 16-70 mesh
Package.
Further, the graphene photocatalytic degradation agent be graphene oxide/titania nanoparticles, graphene/
Titania nanoparticles, graphene oxide/titanium dioxide nano-belts, graphene/titanium dioxide nano-belts, graphene oxide/
Titania nanotube, graphene/titania nanotube, graphene oxide/titanium dioxide nano-rod, graphene/titanium dioxide
Titanium nanometer rods, phosphotungstic acid/graphene oxide, phosphotungstic acid/graphene, tungstic acid/graphene oxide, tungstic acid/graphene,
Zinc oxide/graphene oxide, zinc oxide/graphene, cuprous oxide/graphene, cuprous oxide/graphene oxide, bismuth tungstate/stone
Black alkene, silver orthophosphate/graphene, molybdenum disulfide/graphene, any one or a few in mangano-manganic oxide/graphene oxide.Stone
The regenerated fiber cloth or glass fabric of black alkene photocatalytic degradation agent 16-70 mesh wrap up.
Further, the graphene nano bactericidal agent is silver/graphene oxide, silver/cobalt ferrite/graphene, four oxidations
Three-iron/graphene oxide, yttrium oxide/graphene, bismuth oxychloride/graphene, bismuth oxybromide/graphene oxide, titanium dioxide/oxygen
Graphite alkene, titanium dioxide/silver/graphene oxide, zinc oxide/graphene oxide any one or a few;Graphene nano
The size of sterilizing is between 10-500nm.
The graphene COD scavenger is ferrous sulfate/graphene nanocomposite material, potassium permanganate/graphite
Alkene nanocomposite, potassium bichromate/graphene nanocomposite material, titanium dioxide/graphene nanocomposite, oxidation stone
Black alkene/titania nanoparticles, graphene oxide/titanium dioxide nano-belts, graphene oxide/titania nanotube, stone
Black alkene/titanium dioxide nano-rod, phosphotungstic acid/graphene oxide, tungstic acid/graphene oxide, zinc oxide/graphene oxide are multiple
One of condensation material is a variety of.
Further, in the superparamagnetic nanoparticle-graphene oxide composite nano materials, super-paramagnetism nano grain
The material of son is γ-Fe2O3、Fe3O4、Y2O3、MnZn、CoFe2O4One or more of, partial size is less than 10nm.
Further, regenerated fiber cloth or the glass fabric package of graphene porous ceramic film material 16-70 mesh,
Its preparation process is as follows:
S201, select silicon carbide or boron carbide porous ceramic film material as substrate;
S202, the substrate is sonicated, dichloride copper or cobaltous dichloride solution gradient impregnate, vacuum is done after lifting
It is dry, then by the temperature programming of inert gas atmosphere, obtain the silicon carbide for having metal film to surface or boron carbide porous ceramic film material raw material;
S203, the obtained raw material of step S202 is put into chemical vapor deposition reaction chamber sealing, heated up (with 10 DEG C/min
Heating rate be heated to 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, constant temperature time continues 10 minutes, 30 minutes, 60 points respectively
Clock) afterwards by methane (being passed through 1,5,10,15 ml/min units), adjust hydrogen flowing quantity (adjust hydrogen flowing quantity to 30 milliliters/
Minute, the reaction time is distinguished 30 minutes, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes, 300 minutes) it carries out instead
It answers;
S204, stop being passed through methane after reaction, keep the flow of hydrogen and argon gas constant, cooling down (control drop
Warm rate is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature), obtain graphene porous ceramic film material.
The present invention also provides a kind of technique using above-mentioned landfill leachate graphene integrated purification system, the rubbish
Rubbish percolate successively passes through following processing step after collecting:
S301, the anaerobism groove carry out pre- removal of ammonia and nitrogen processing by ammoxidation biomembrane;
S302, the Multistage filtering device are filtered processing;
S303, the multistage graphene purifier purified treatment;
S304, the graphene photocatalytic degradation device carry out photocatalytic degradation processing;
S305, the multiple purifying slot are sterilized, reduce COD processing;
S306, the multistage graphene bactericidal unit carry out further sterilization treatment;
S307, the graphene ceramic water-purification device are purged contaminant trace species, are then discharged out processing water.
Embodiment as one preferred in step S303, only retains level-one graphene purifier and carries out at purification
Reason, the graphene purifier of remaining grade are interspersed between the graphene bactericidal units at different levels in step S306.
Compared with the existing technology, the present invention has following advantageous effects:
(1) landfill leachate graphene integrated purification system of the present invention, Multistage filtering device can remove infiltration
Residual solids suspended matter in filtrate;The grapheme material added in multistage graphene purifier, can enhance to pollutant
The characteristics such as absorption and antibacterial, further to remove the residual greasy dirt in sewage, solid suspension, organic matter, heavy metal etc.;Graphite
Alkene photocatalytic degradation device can then be degraded the organic pollutants such as residual azo dyes in water body by photocatalytic Degradation;It is more
Weight purification tank can carry out depth sterilizing to water body and reduce remaining COD;Multistage graphene bactericidal unit then can be right
Various harmful bacterias in water body carry out classification and kill, finally, graphene ceramic water-purification device is responsible for remaining trace in purifying water body
Measure pollutant.
(2) landfill leachate graphene integrated purifying technique of the present invention, by being applied to above system,
Classification processing can be carried out to the various pollutants in water body, utmostly to remove the high strength ammonia in house refuse subsequent filtrate
Nitrogen, solid suspension, greasy dirt, surfactant, harmful organic substance, heavy metal, all kinds of pathogenic bacteria, helminth, residual volatile
The pollutants such as gas with foreign flavor, it is ensured that consumer waste infiltration liquid discharge safety realizes the efficient green of urban and rural domestic refuse percolate
Processing.
Detailed description of the invention
Fig. 1 is landfill leachate graphene integrated purification system schematic diagram of the present invention.
Wherein: 1- delivery pipe;2- anaerobism groove;21- multi-layer porous scaffold;22- agitating device;3- delivery pipe;4- multistage mistake
Filter device;41- subsider;5- first order graphene purifier;6- graphene photocatalytic degradation device;7- drainage duct;8-
Multiple purifying slot;81- graphene nano bactericidal agent;82- ozone generator;83- graphene COD scavenger;9- water delivery
Pipe;10- first order graphene bactericidal unit;The second level 11- graphene purifier;The second level 12- graphene bactericidal unit;
13- third level graphene purifier;14- third level graphene bactericidal unit;15- drainpipe;16- graphene ceramic water-purification dress
It sets.
Specific embodiment
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But the present invention can be with
It is different from the other modes of this description much to implement, those skilled in the art can be without violating the connotation of the present invention
Similar popularization is done, therefore the present invention is not limited by the specific embodiments disclosed below.
In the following embodiments, firstly, multistage graphene purifier and multistage graphene bactericidal unit have three-level;Its
It is secondary, it is not connected directly between multistage graphene purifier, between multistage graphene bactericidal unit, but interspersed setting is not
With between equipment.Those skilled in the art can select according to the actual situation less or more rank graphene purifier and
Graphene bactericidal unit, or graphene purifiers at different levels and graphene bactericidal unit any combination at different levels are placed on technique
In process, similar change should all be within protection scope of the present invention.
Embodiment 1
As shown in Figure 1, the percolate in the places such as household refuse landfill sites, house refuse stack-up-yard is received through leachate collection valve
It is conveyed into anaerobism groove 2 (containing aeration opening) after collection by penetrating fluid delivery pipe 1, built-in multi-layer porous scaffold 21 in the anaerobism groove 2,
Aperture is 2mm, is located at 22 top of agitating device.The autotrophic type ammoxidation biomembrane cultivated in advance is pre-placed on bracket 21.
7.5, temperature is 30 DEG C for pH control in anaerobism groove 2, and timely adjustment is anaerobic environment (< 0.5% air saturation), in percolate
Nitrite pollution object can be used as electron acceptor, under the stirring of lower section agitating device 22 realize part nitrification and anaerobism ammonia oxygen
Change reaction, with efficient ammonia nitrogen removal, and aeration excludes N in due course2Equal innocuous gas.
By delivery pipe 3, (bottom is provided with pre-filtering sieve to percolate through pollutants such as the pre- removal of ammonia and nitrogen of anaerobism groove 2, sieve
Several 16 mesh of mesh, to remove most of solid suspension) it is conveyed into the further filtering of Multistage filtering device 4, to remove percolate
Middle residual solids suspended matter.Being equipped with three-level graphene in Multistage filtering device 4 altogether enhances filter screen.
Wherein, first order graphene enhancing filter screen and second level graphene enhancing filter screen are stacked in multistage filtering
The water outlet of Multistage filtering device is then arranged in the water inlet of device, third level graphene enhancing filter screen.Multistage filtering
The middle position lower end of device 4 is provided with residual solids waste sedimentation slot 41 (containing dump valve), is settled with being discharged in filter process
Fraction solids suspended matter.
Further, the mesh number of first order graphene enhancing filter screen is 10 mesh, and second level graphene enhances filter screen
Mesh number is 18 mesh, and the mesh number that third level graphene enhances filter screen is 35 mesh.First, second, third grade of graphene enhancing filtering
Net main material be polycarbonate, graphene addition purpose be in order to enhance the antibacterial activity of filter screen, mechanical strength and
Corrosion resistance, graphene additive amount are 2.5%.
Percolate through 4 filtration treatment of Multistage filtering device enters first order graphene purifier 5 by water (flow) direction.The
The graphene enhancing diatom ceramic material of useful 16 mesh regenerated fiber cloth package is filled inside level-one graphene purifier 5, to remove
Residual greasy dirt, residual solids suspended matter, surfactant and some organic pollutants in decontaminated water etc..Specifically, graphite
Alkene enhancing diatom ceramic material is fired by the raw material of following weight ratio: diatomite 46.8%, kaolin 20.1%, feldspar
13.4%, graphene 3.5%, aluminium oxide 4.0%, boron glass 3.4%, talcum powder 3.4%, quartz powder 5.4%.Graphene
Addition can enhance the characteristics such as absorption, antibacterial to pollutant.
Enter graphene photocatalytic degradation device by water (flow) direction through the purified water body of first order graphene purifier 5
6, to remain the organic pollutants such as azo dyes in water body of further degrading.Filling is useful in graphene photocatalytic degradation device 6
The graphene photocatalytic degradation agent of 16 mesh regenerated fiber cloth package.Graphene photocatalytic degradation agent is preferably graphene oxide/bis-
Titanium dioxide nanoparticle, can remaining REACTIVE Red 195, methyl orange, sieve in catalytic degradation percolate sewage under illumination condition
The residual organic contaminants such as azo dyes and phenol, oxalic acid, organohalogen compounds such as red bright B.Graphene photocatalytic degradation device
In cylinder, material is transparent glass material.
Sewage after photocatalytic degradation is imported into multiple purifying slot 8 by drainage duct 7 (containing valve).Multiple purifying slot
8 size is the equal 0.5m of length and width, and height 0.8m, bottom is equipped with blowdown valve.The purpose of multiple purifying slot 8, which is further to settle, seeps
Solid suspension in filtrate sewage carries out depth sterilizing to water body, and reduces chemical residue oxygen demand.
Then the depth sterilizing of multiple purifying slot 8 applies ozone by adding graphene nano bactericidal agent 81 in water body
Sterilizing (passing through ozone generator 82) is realized.Graphene nano bactericidal agent 81 is preferably silver/graphene oxide, and size exists
Between 20-100nm.Further, synchronous addition graphene COD scavenger 83 is changed in water body with reducing in water body
Learn oxygen demand.Graphene COD scavenger 83 is preferably potassium permanganate/graphene nanocomposite material, with water body of degrading
Middle residual organic matter and COD.
8 lower end of multiple purifying slot is equipped with the adjustable portable agitato of revolving speed, and the non-sedimentation time by stirring disturbance, allows and goes out
Bacterium and COD reducing effect are more thorough.The solid waste that multiple purifying slot 8 generates during sedimentation then periodically passes through
The discharge of solid waste dump valve.
Is transported to by water-supply-pipe 9 (filter screen that lower end is provided with 18 mesh) through the purified water body of multiple purifying slot 8
In level-one graphene bactericidal unit 10.Superparamagnetic nanoparticle-oxidation is filled with inside first order graphene bactericidal unit 10
Graphene composite nano material, except part lingering sneak worm and pathogenic bacteria etc. in decontaminated water.The material of superparamagnetic nanoparticle
Material is preferably γ-Fe2O3, and partial size is less than 10nm.Graphene oxide and partial size have excellent less than the super paramagnetic material of 10nm
Antibacterial activity, formed composite nano materials after, generate superposition sterilization effect, can further kill remaining in percolate sewage
The pathogens such as Escherichia coli, cholera bacteria, shigella dysenteriae, salmonella, Klebsiella pneumoniae, snail fever substance, reach
Further clean-up effect.
Water body after the sterilizing of first order graphene bactericidal unit 10 enters second level graphene water purification cartridge along water (flow) direction
Set 11.The heavy metal adsorption graphene nano of the useful 16 mesh regenerated fiber cloth package of filling in second level graphene purifier 11
Composite material.Heavy metal adsorption graphene nanocomposite material is preferably chitosan-modified graphene oxide, to remove water body
In the heavy metals such as remaining copper, nickel, lead, cadmium, mercury, arsenic, total chromium, Cr VI.
Second level graphene sterilizing dress is flowed into along water (flow) direction through the purified water body of second level graphene purifier 11
It sets in 12.It is compound filled with the chloro- 5,5- Dimethyl Hydan-graphene nano of the bromo- 3- of 1- in second level graphene bactericidal unit 12
Material and bactericidal agent, the graphene in bactericidal agent are graphene oxide.
Percolate sewage after second level graphene bactericidal unit 12 further sterilizing imported into third along water (flow) direction
In grade graphene purifier 13.The big ratio of the useful 16 mesh regenerated fiber cloth package of filling in third level graphene purifier 13
Surface graphene nano material.Large ratio surface graphene nanocomposite material is preferably three-dimensional meso-hole graphene nano material, with
The smell substances such as chlorine residue, the organic pollutants such as polycyclic aromatic hydrocarbon, aldehydes, volatile phenol, biological agent, chemical solution in effective absorption effluent
Heavy metal contaminants such as the residual contaminants such as agent, grease stain, and residual lead, chromium, mercury etc..
Third level graphene sterilizing dress is flowed into along water (flow) direction through the purified water body of third level graphene purifier 13
It sets in 14.Graphene bactericidal agent is filled in third level graphene bactericidal unit 14.Graphene bactericidal agent is preferably silver/ferrous acid
Cobalt/graphene, size is between 10-50nm.
Percolate sewage after third level graphene bactericidal unit 14 further sterilizing is by water (flow) direction through drainpipe 15
It is drained into graphene ceramic water-purification device 16.The useful 16 mesh regenerated fiber cloth of filling or glass in graphene ceramic water-purification device 16
The graphene porous ceramic film material of glass fiber cloth package, can further remove remaining contaminant trace species in water body.Graphene is more
Hole ceramic material preparation process is as follows:
The first step selects commercially available carborundum porous ceramics material as substrate.
Second step, substrate is sonicated, cupric chloride solution gradient are impregnated, are dried in vacuo after lifting, then by lazy
Property gas atmosphere temperature programming, obtains the carborundum porous ceramics material feedstock for having metal film to surface.
Third step, the raw material that second step is obtained are put into chemical vapor deposition reaction chamber sealing, check pyroreaction room gas
Residual gas in pyroreaction room is discharged under protective atmosphere, then carries out temperature programming for close property.With 10 DEG C/min of heating
Speed is heated to 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, and constant temperature time continues 10 minutes, 30 minutes, 60 minutes respectively, later
It is passed through the methane of 1,5,10,15 ml/min units, adjusts hydrogen flowing quantity to 30 ml/mins, the reaction time distinguishes 30 points
Clock, 60 minutes, 150 minutes, 180 minutes, 210 minutes, 240 minutes, 300 minutes.Stop being passed through methane after reaction, keep
The flow of hydrogen and argon gas is constant, and control rate of temperature fall is 10 DEG C/min and drops to 400 DEG C, then naturally cools to room temperature, thus
Obtain graphene porous ceramic film material.
Multistage graphene purifier, multistage graphene bactericidal unit and graphene ceramic water-purification device 16 are column
Shape, material are stainless steel.
Water body after above-mentioned technique deep purifying presses " life rubbish through water-supply-pipe (containing sample tap for sample detection at any time)
Rubbish fills contamination control standard " (GB16889-2008) detection indices, qualified discharge is net after obtaining waste leachate purification
Water.
Embodiment 2
The present embodiment difference from example 1 is that:
1, the aperture of the multi-layer porous scaffold 21 built in anaerobism groove 2 is 3mm, and the pH control in anaerobism groove 2 is 7.6, temperature
It is 28 DEG C.
2, the mesh number of the pre-filtering sieve between anaerobism groove 2 and Multistage filtering device 4 is 12, and first order graphene increases
The mesh number of strong filter net is 12, and the mesh number that second level graphene enhances filter screen is 20, and third level graphene enhances filter screen
Mesh number is 40, and the material of first, second, third grade of graphene enhancing filter screen is polypropylene, and the additive amount of graphene is
2.0%.
3, the glass fabric package of graphene enhancing 20 mesh of diatom ceramic material.
4, the material of graphene photocatalytic degradation device 6 is crystalline ceramics.
5, the size of multiple purifying slot 8 is length and width 0.4m, height 0.5m;Graphene nano bactericidal agent 81 be bismuth oxybromide/
Graphene oxide, size is between 10-30nm;Graphene COD scavenger 83 is ferrous sulfate/graphene nano
Composite material.
6, the mesh number of the filter screen between multiple purifying slot 8 and first order graphene bactericidal unit 10 is 20;The
The material of superparamagnetic nanoparticle in level-one graphene bactericidal unit 10 is Fe3O4, partial size is less than 10nm.
7, the heavy metal adsorption graphene nanocomposite material in second level graphene purifier 11 is hydroxyl graphite
Alkene is wrapped up with the glass fiber cloth of 20 mesh.
8, dibromoacetic acid benzyl ester-graphene nanocomposite material and sterilizing are filled in second level graphene bactericidal unit 12
Agent, the graphene in bactericidal agent are nitrogen-doped graphene nanometer sheet.
9, the Large ratio surface graphene nanocomposite material in third level graphene purifier 13 is graphene aerogel,
It is wrapped up with the glass fabric of 20 mesh.
10, the graphene bactericidal agent in third level graphene bactericidal unit 14 is silver/graphene oxide, and size is in 10-
Between 30nm.
11, in graphene ceramic water-purification device 16, the regenerated fiber cloth or glass of 20 mesh of graphene porous ceramic film material
Fiber cloth package;The substrate of graphene porous ceramic film material is boron carbide porous ceramics, is impregnated using cobaltous dichloride solution gradient,
Obtained raw material is the boron carbide porous ceramic film material that there is metal film on surface.
12, the material of multistage graphene purifier, multistage graphene bactericidal unit and graphene ceramic water-purification device 16
Matter is ceramics.
Remaining device structure is same as Example 1 with process flow, and details are not described herein.
Embodiment 3
The present embodiment difference from example 1 is that:
1, the aperture of the multi-layer porous scaffold built in anaerobism groove 2 is 5mm.
2, the mesh number of the pre-filtering sieve between anaerobism groove 2 and Multistage filtering device 4 is 8, and first order graphene increases
The mesh number of strong filter net is 14, and the mesh number that second level graphene enhances filter screen is 18, and third level graphene enhances filter screen
Mesh number is 40, and the material of first, second, third grade of graphene enhancing filter screen is polyether-ether-ketone, and the additive amount of graphene is
1.5%.
3, the glass fabric package of graphene enhancing 30 mesh of diatom ceramic material.
4, the material of graphene photocatalytic degradation device 6 is crystalline ceramics, and graphene photocatalytic degradation agent is phosphotungstic acid/oxygen
Graphite alkene.
5, the size of multiple purifying slot 8 is length and width 1.0m, height 0.8m;Graphene nano bactericidal agent 81 is yttrium oxide/stone
Black alkene, size is between 50-200nm;Graphene COD scavenger 83 is potassium bichromate/graphene nano composite wood
Material.
6, the mesh number of the filter screen between multiple purifying slot 8 and first order graphene bactericidal unit 10 is 16-50;
The material of superparamagnetic nanoparticle in first order graphene bactericidal unit 10 is CoFe2O4, partial size is less than 10nm.
7, the heavy metal adsorption graphene nanocomposite material in second level graphene purifier 11 is polyamidoamine
Amine dendrimer-graphene oxide is wrapped up with the glass fiber cloth of 30 mesh.
8, chlorine ball-graphene nanocomposite material and bactericidal agent, sterilizing are filled in 12 devices of second level graphene sterilizing
Graphene in agent is graphene.
9, the glass fibers of 20 mesh of Large ratio surface graphene nanocomposite material in third level graphene purifier 13
Wei Bu package.
10, the graphene bactericidal agent in third level graphene bactericidal unit 14 is ferroso-ferric oxide/graphene oxide, ruler
It is very little between 10-30nm.
11, in graphene ceramic water-purification device 16, the regenerated fiber cloth or glass of 30 mesh of graphene porous ceramic film material
Fiber cloth package.
12, the material of multistage graphene purifier, multistage graphene bactericidal unit and graphene ceramic water-purification device 16
Matter is polycarbonate.
Remaining device structure is same as Example 1 with process flow, and details are not described herein.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, although referring to embodiment to this
Invention is described in detail, for those skilled in the art, still can be to recorded in foregoing embodiments
Technical solution modify or equivalent replacement of some of the technical features, but it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of landfill leachate graphene integrated purification system, including landfill leachate is collected and conveying device, feature
It is, further includes:
Anaerobism groove, the anaerobism groove is interior to be equipped with multi-layer porous scaffold, is equipped with ammoxidation biomembrane on the bracket;
Multistage filtering device, the Multistage filtering device is interior to be equipped with multistage graphene enhancing filter screen;
Multistage graphene purifier, in every grade of graphene purifier filled with graphene enhancing diatom ceramic material or
Person's heavy metal adsorption graphene nanocomposite material or Large ratio surface graphene nano material;
Graphene photocatalytic degradation device, the graphene photocatalytic degradation device is interior to be filled with the agent of graphene photocatalytic degradation;
Multiple purifying slot, interior ozone generator, graphene nano bactericidal agent and the graphene chemistry of being equipped with of the multiple purifying slot need
Oxygen amount scavenger;
Multistage graphene bactericidal unit, every grade of graphene bactericidal unit is interior to be filled with superparamagnetic nanoparticle-oxidation stone
Black alkene composite nano materials or the graphene bactericidal agent;
Graphene ceramic water-purification device, graphene ceramic water-purification device are filled with graphene porous ceramic film material.
2. landfill leachate graphene integrated purification system according to claim 1, which is characterized in that the ammoxidation
Biomembrane is autotrophic type, is prepared from the following steps:
S101, prepare bacterium source and ammonia oxidizing bacteria culture medium, the bacterium source is commercially available anaerobic grain sludge;
S102, bacterium source inoculation, the bacterium source is linked into the ammonia oxidizing bacteria culture medium by 25% ratio by volume, vibration
Swing the bacterial cultures being enriched with after heat preservation;
S103, the bacterial cultures is accessed in biologic packing material, ammonia nitrogen waste water is added, biofilm culture is carried out on shaking table, is obtained
To autotrophic type ammoxidation biomembrane.
3. landfill leachate graphene integrated purification system according to claim 2, it is characterised in that:
The multistage graphene enhancing filter screen is total to three-level, wherein the first order, second level graphene enhancing filtering meshes are stacked at
The water inlet of the Multistage filtering device, third level graphene enhance the water outlet that filter screen is set to the Multistage filtering device,
The middle part lower end of the Multistage filtering device is equipped with subsider, and the graphene additive amount of the multistage graphene enhancing filter screen is
0.25~5.0%.
4. landfill leachate graphene integrated purification system according to claim 1-3, which is characterized in that institute
It states graphene enhancing diatom ceramic material to be fired by the raw material of following weight ratio: diatomite 46.8%, kaolin
20.1%, feldspar 13.4%, graphene 3.5%, aluminium oxide 4.0%, boron glass 3.4%, talcum powder 3.4%, quartz powder
5.4%;
The heavy metal adsorption graphene nanocomposite material is graphene oxide, hydroxylating graphene, carboxylated graphene, shell
Graphene oxide, the chitosan-modified hydroxylating graphene, silicate nanometer that graphene oxide, the glutaraldehyde of glycan modification are coupled
Pipe-graphene oxide, hydroxyapatite-graphene oxide, N- (trimethoxy silicon propane) ethylenediamine trigalloyl graphene oxide, hydroxyl
Base carbon nano tube-graphene oxide, titanium pillared montmorillonite-graphene oxide, aluminum oxide-graphene oxide, polymerization chlorine
Change aluminium-graphene oxide, poly- hydroxyl-aluminum pillared vermiculite, poly- hydroxyl-aluminum pillared vermiculite-graphene oxide, 13X type molecular sieve, seaweed
Sour sodium-graphene oxide, EDTA- graphene oxide, polyamidoamine amine dendrimer Bio-sil, polyamidoamine are tree-like
Any one in macromolecular-graphene oxide, N- (2,3- glycidyl) iminodiacetic acid modified graphene oxide;
The Large ratio surface graphene nanocomposite material be single-layer graphene nanometer sheet, three-dimensional meso-hole graphene nano material,
Three-dimensional macropore graphene nano material, graphene aerogel, graphene nano fiber or graphene organic backbone composite Nano material
Any one in material.
5. landfill leachate graphene integrated purification system according to claim 1-3, it is characterised in that: institute
Stating graphene photocatalytic degradation agent is graphene oxide/titania nanoparticles, graphene/titania nanoparticles, oxygen
Graphite alkene/titanium dioxide nano-belts, graphene/titanium dioxide nano-belts, graphene oxide/titania nanotube, graphite
Alkene/titania nanotube, graphene oxide/titanium dioxide nano-rod, graphene/titanium dioxide nano-rod, phosphotungstic acid/oxidation
Graphene, phosphotungstic acid/graphene, tungstic acid/graphene oxide, tungstic acid/graphene, zinc oxide/graphene oxide, oxygen
Change zinc/graphene, cuprous oxide/graphene, cuprous oxide/graphene oxide, bismuth tungstate/graphene, silver orthophosphate/graphene,
Any one or a few in molybdenum disulfide/graphene, mangano-manganic oxide/graphene oxide.
6. landfill leachate graphene integrated purification system according to claim 1-3, it is characterised in that: institute
Stating graphene nano bactericidal agent is silver/graphene oxide, silver/cobalt ferrite/graphene, ferroso-ferric oxide/graphene oxide, oxidation
Yttrium/graphene, bismuth oxychloride/graphene, bismuth oxybromide/graphene oxide, titanium dioxide/graphene oxide, titanium dioxide/
Silver/graphene oxide, zinc oxide/graphene oxide any one or a few;
The graphene COD scavenger is ferrous sulfate/graphene nanocomposite material, potassium permanganate/graphene is received
Nano composite material, potassium bichromate/graphene nanocomposite material, titanium dioxide/graphene nanocomposite, graphite oxide
Alkene/titania nanoparticles, graphene oxide/titanium dioxide nano-belts, graphene oxide/titania nanotube, graphite
Alkene/titanium dioxide nano-rod, phosphotungstic acid/graphene oxide, tungstic acid/graphene oxide, zinc oxide/graphene oxide are compound
One of material is a variety of.
7. landfill leachate graphene integrated purification system according to claim 1-3, it is characterised in that: institute
It states in superparamagnetic nanoparticle-graphene oxide composite nano materials, the material of superparamagnetic nanoparticle is γ-Fe2O3、
Fe3O4、Y2O3、MnZn、CoFe2O4One or more of, partial size is less than 10nm.
8. landfill leachate graphene integrated purification system according to claim 1-3, which is characterized in that institute
The preparation process for stating graphene porous ceramic film material is as follows:
S201, select silicon carbide or boron carbide porous ceramic film material as substrate;
S202, the substrate is sonicated, dichloride copper or cobaltous dichloride solution gradient are impregnated, are dried in vacuo after lifting,
Again by the temperature programming of inert gas atmosphere, the silicon carbide for having metal film to surface or boron carbide porous ceramic film material raw material are obtained;
S203, the obtained raw material of step S202 is put into chemical vapor deposition reaction chamber sealing, by methane after heating, adjusts hydrogen
Throughput is reacted;
S204, stop being passed through methane after reaction, keep the flow of hydrogen and argon gas constant, graphene is obtained after cooling down
Porous ceramic film material.
9. the technique of the application described in any item landfill leachate graphene integrated purification systems of claim 1-8, feature
It is, the landfill leachate successively passes through following processing step after collecting:
S301, the anaerobism groove carry out pre- removal of ammonia and nitrogen processing by ammoxidation biomembrane;
S302, the Multistage filtering device are filtered processing;
S303, the multistage graphene purifier purified treatment;
S304, the graphene photocatalytic degradation device carry out photocatalytic degradation processing;
S305, the multiple purifying slot are sterilized, reduce COD processing;
S306, the multistage graphene bactericidal unit carry out further sterilization treatment;
S307, the graphene ceramic water-purification device are purged contaminant trace species, are then discharged out processing water.
10. landfill leachate graphene integrated purifying technique according to claim 8 or claim 9, it is characterised in that: step
Only retain level-one graphene purifier in S303 and carry out purified treatment, the graphene purifier of remaining grade is interspersed in step
Between the graphene bactericidal units at different levels in S306.
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