CN105753138A - Three-dimensional fused and deposited biological film filler as well as preparation method and application thereof - Google Patents
Three-dimensional fused and deposited biological film filler as well as preparation method and application thereof Download PDFInfo
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- CN105753138A CN105753138A CN201610222088.0A CN201610222088A CN105753138A CN 105753138 A CN105753138 A CN 105753138A CN 201610222088 A CN201610222088 A CN 201610222088A CN 105753138 A CN105753138 A CN 105753138A
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- nanoparticles
- release layer
- antioxidant
- slow release
- porous matrix
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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
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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
- C02F3/104—Granular carriers
-
- 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
-
- 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
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
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- 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
The invention discloses a three-dimensional fused and deposited biological film filler as well as a preparation method and application thereof. The method comprises the following steps: (1) adopting polypropylene to form a porous matrix through 3D printing; (2) adopting a nano particle mixture to form sustained release layers on the side wall and upper surface of the porous matrix through 3D printing so as to obtain a sustained release layer-porous matrix composite; and (3) carrying out thermal treatment and ultraviolet-light treatment on the sustained release layer-porous matrix composite in sequence to obtain the biological film filler. The biological film filler prepared by the method can provide trace nutrient substances needed for microbial growth in a sustained release manner during use, so that the biological film growing speed, growing amount and water treatment efficiency of the filler can be improved.
Description
Technical field
The present invention relates to Material Field, specifically, the present invention relates to three-dimensional fusion sediment biofilm packing, preparation method and
Its application.Fill out more particularly it relates to an prepare the method for biofilm packing, biofilm packing and this biomembrane
Material purposes in sewage disposal.
Background technology
China is the country of a serious water shortage, and shortage of water resources is day by day serious, and water resource is only the 1/4 of world average per capita.
And along with China's expanding economy, industry water resource consumption is huge, wastewater discharge is the biggest, therefore improves industrial wastewater
Recovery utilization rate for solve water scarcity problem significant.Industrial Wastewater Treatment generally uses biology to connect at present
Touch oxidizing process, in cesspool, i.e. load a number of filler, utilize absorption biomembrane on filler and ample supply
Oxygen, by biological oxidation, decomposes the oxidation operation in waste water, reaches to purify purpose, and the method is in weaving print
The process of the waste water such as dye, petrochemical industry, medicine is widely used.
But, current biofilm packing and biofilm packing preparation method still have much room for improvement.
Summary of the invention
The application is to make following facts and the discovery of problem and understanding based on inventor:
, there is biomembranous biofilm speed and hang the situation that modulus is undesirable, the use longevity of filler in current biofilm packing
Order and be difficult to accurately control shorter and filler service life.Inventor through further investigation and great many of experiments find, this be by
Quantity in microbiologic population is difficult to sustainable growth, and the speed of bacteria metabolism can not maintain what higher level caused.
And microorganism can not keep continued propagation and high-caliber metabolism, it is new owing to sewage disposal system lacking microorganism
The necessary micronutrient element of old metabolism causes.Although this problem can be by adding appropriate micronutrient in waste water
Element is eased, however the mode of this disposable input can not exactly according to growth of microorganism situation to micronutrient
Element carries out real-time control, and when micronutrient element is depleted, it is difficult to accomplish to supplement in time, be therefore difficult to true
Just solving the disappearance of micronutrient element for growth of microorganism and the negative effect of rate of metabolism.
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the present invention proposes one
Plant suspended biological film filler with nutrient slow-release function and preparation method thereof.The method utilizes 3D printing technique, can
Prepare difform biofilm packing, improve the Biofilm Colonization speed of filler, biofilm amount and water treatment efficiency, and
And can accurately control filler service life.Three-dimensional fast shaping prints (Three Dimensional Printing, 3DP) again
Being referred to as 3D to print, be the one of rapid shaping technique, it is a kind of based on mathematical model file, uses powdered gold
Belong to or plastics etc. can bonding material, by the way of successively printing, carry out the technology of constructed object.The advantage of its maximum is can be by material
Material is successively combined, and therefore can regulate and control the shape facility of the object constructed accurately.
In one aspect of the invention, the present invention proposes a kind of method preparing biofilm packing.Enforcement according to the present invention
Example, the method includes: (1) uses polypropylene, is printed by 3D, forms porous matrix；(2) nano-particle is used to mix
Compound, is printed by 3D, and sidewall and upper surface at described porous matrix form slow release layer, in order to acquisition slow release layer-many
Hole substrate complex；(3) described slow release layer-porous matrix complex is carried out heat treatment and treatment with ultraviolet light successively, in order to
Obtain described biofilm packing.Utilize the biofilm packing prepared by the method can in use slow release growth of microorganism institute
Necessary trace nutrient, and then the Biofilm Colonization speed of this filler, biofilm amount and water treatment efficiency can be improved.
According to embodiments of the invention, the specific surface area of described porous matrix is 260-300m2/m3.Thereby, it is possible to effectively
Increase biomembrane and hang modulus, and then improve water treatment efficiency.
According to embodiments of the invention, the density of described biofilm packing is 0.9～1g/cm3.Thus, this biofilm packing can
To be suspended on sewage, carry out sewage disposal as floating stuffing.Thus, can directly throw in during use, need not fix,
And easy to be filmed, filler is not easily blocked.
According to embodiments of the invention, the thickness of described slow release layer is 1～3mm, and described slow release layer has less than 5%
Surface thickness deviation.Thus, it is possible to accurately control the service life of this biofilm packing.
According to embodiments of the invention, described mixture of nanoparticles includes polypropylene, Polyethylene Glycol, maleic anhydride, antioxygen
Agent, degradable polymer and metal oxide nanoparticles, wherein, the molecular weight of described Polyethylene Glycol is 200～600；
Described degradable polymer include selected from polylactic acid, PLGA, PTMC at least it
One；Described metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobaltous chloride at least one, described metal oxygen
The particle diameter of compound nano-particle is 20-100nm；Described antioxidant includes selected from antioxidant 1010, antioxidant 1076
At least one and antioxidant 1135.Degradable polymer can the most progressively the dropping of this biofilm packing
Solve, and then the effect of slow release metal oxide nanoparticles in environment can be reached such that it is able to for a long time, stably to micro-
The necessary metallic element of its growth of biological offer.
According to embodiments of the invention, in described mixture of nanoparticles, described polypropylene, Polyethylene Glycol, maleic anhydride,
The mass ratio of antioxidant, degradable polymer and metal oxide nanoparticles is 74.41:3.68:1.16:18.4:
2.32:(0.97-1.93).Form described slow release layer thereby, it is possible to effectively printed by 3D, and can ensure that utilization
There is slow release layer prepared by the mixture of nanoparticles of aforementioned proportion the global density of biofilm packing will not be made excessive and can not hang
Float on the liquid level of sewage.
According to embodiments of the invention, in step (2), described mixture of nanoparticles through the following steps that obtain: (2-1)
Described polypropylene, Polyethylene Glycol, maleic anhydride and metal oxide nanoparticles are dried respectively process, wherein,
The condition that described polypropylene, Polyethylene Glycol and maleic anhydride carry out described dried is: temperature 90 degrees Celsius, time
2 hours；Condition withering to described nano-particle is: temperature 280 degrees Celsius, time 2 h；And (2-2)
By described polypropylene, Polyethylene Glycol, maleic anhydride and the metal oxide nanoparticles through described dried with described
Antioxidant and described degradable polymer are mixed and stirred for, in order to form described mixture of nanoparticles.Thus, it is possible to
Improve efficiency and the effect utilizing mixture of nanoparticles to carry out 3D printing.
According to embodiments of the invention, in step (3), the condition of described heat treatment is: temperature is 50-80 degree Celsius,
The process time is 20-30 minute；The condition of described treatment with ultraviolet light is: uviol lamp power density is 150W/cm2, during illumination
Between be 20～50 seconds.Thereby, it is possible to improve heat stability and the hydrophilicity of this biofilm packing.
In another aspect of this invention, the present invention proposes a kind of biofilm packing, and described biofilm packing is by above institute
Prepared by the method stated.Thus, this biofilm packing can in use trace battalion necessary to slow release growth of microorganism
Support material, and then the Biofilm Colonization speed of this filler, biofilm amount and water treatment efficiency can be improved.
In still another aspect of the invention, the present invention proposes a kind of biofilm packing.According to embodiments of the invention, this biology
Film filler includes: polypropylene porous matrix；And mixture of nanoparticles slow release layer, described mixture of nanoparticles slow release layer
Being arranged on sidewall and the upper surface of described polypropylene porous matrix, the thickness of described mixture of nanoparticles slow release layer is
1～3mm, and described mixture of nanoparticles slow release layer has the surface thickness deviation less than 5%, wherein, described nanometer
Grain mixture includes that polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable polymer and metal-oxide are received
Rice grain, described polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable polymer and metal-oxide are received
The mass ratio of rice grain is 74.41:3.68:1.16:18.4:2.32:(0.97-1.93), the molecular weight of described Polyethylene Glycol is
200～600；Described degradable polymer includes selected from polylactic acid, PLGA, polytrimethylene carbonic acid
At least one ester；Described metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobaltous chloride at least one,
The particle diameter of described metal oxide nanoparticles is 20-100nm；Described antioxidant includes selected from antioxidant 1010, resists
At least one oxidant 1076 and antioxidant 1135.Thus, this biofilm packing can in use slow release
Trace nutrient necessary to growth of microorganism, so can improve the Biofilm Colonization speed of this filler, biofilm amount and
Water treatment efficiency, and accurately can be controlled by the thickness of regulation slow release layer the service life of this biofilm packing.
According to embodiments of the invention, described biofilm packing is floating stuffing.Thus, this biofilm packing has full solid
Structure, specific surface area is big, can directly throw in, need not fix during use, and easy to be filmed, and filler is not easily blocked.
According to embodiments of the invention, the density of described biofilm packing is 0.9～1g/cm3.Thus, it is possible to improve this biology
The suspension effect of film filler.
According to embodiments of the invention, described biofilm packing is printed by 3D and is formed.Thus, it is possible to easily to this
Shape and the specific surface area of biofilm packing porous matrix regulate and control, and can accurately control the thickness of slow release layer.
In still another aspect of the invention, the present invention proposes foregoing biofilm packing purposes in sewage disposal.By
This, it is possible to use the feature of previously described biofilm packing, improves efficiency and the effect of sewage disposal.
Accompanying drawing explanation
Fig. 1 shows biofilm packing structural representation according to an embodiment of the invention；
Fig. 2 shows biofilm packing structure top view in accordance with another embodiment of the present invention；
Fig. 3 shows slow release layer thickness schematic diagram according to an embodiment of the invention；And
Fig. 4 shows biofilm packing part-structure top view according to an embodiment of the invention.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings.Below with reference to accompanying drawing
The embodiment described is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of method preparing biofilm packing.Enforcement according to the present invention
Example, the biofilm packing utilizing the method to prepare has metallic element slow-release function, and this preparation method technical process is simple, material
Material is easy to get, low cost, and the cycle is short.Specifically, the method includes:
S100: form porous matrix
According to embodiments of the invention, in this step, use polypropylene, printed by 3D and form porous matrix.Specifically,
In this step, can be by arranging the relevant parameter in 3D printing step, such as, by soft according to CAD mathematical model
The parameters such as part the design thickness of porous matrix, shape, printing precision, it is achieved utilize polypropylene to form the base with loose structure
Body.The specific surface area of this porous matrix is 260-300m2/m3.When the specific surface area of porous matrix is too small, on this matrix
Carry out the limited area of biofilm, be therefore attached to the limited amount of microorganism species on matrix, thus be extremely difficult to preferable water
Treatment effect；And when the specific surface area of porous matrix is excessive, under conditions of the volume of biofilm packing is identical, can cause
Space in hole is too small, is unfavorable for biofilm and the growth of microorganism.Inventor finds through great many of experiments, works as porous matrix
Specific surface area when being in above-mentioned scope, there is preferable biofilm effect.Polypropylene material is the material that biofilm packing is conventional,
Have that simple in construction, porosity height, light weight, intensity is high, antiseptic property biology good, old and feeble is prone to advantages such as coming off.Thus,
Use polypropylene material to form porous matrix, can be the matrix of this biofilm packing offer superior performance.It should be noted that
In this step, the parameter such as the concrete shape of porous matrix, thickness is not particularly limited, and those skilled in the art can basis
Practical situation selects suitable shape and thickness.Such as, according to embodiments of the invention, with reference to Fig. 4, porous matrix 100
Can be honeycomb type porous matrix, and then the mechanical strength of porous matrix while improving matrix specific surface area, can be improved.
Additionally, the alveolate texture of rule is also beneficial in subsequent step be formed the slow release layer of structure-controllable.
S200: form slow release layer
According to embodiments of the invention, in this step, printed by 3D, utilize mixture of nanoparticles at porous matrix
Sidewall and upper surface form slow release layer, in order to form slow release layer-porous matrix complex.Specifically, the thickness of slow release layer can
Think 1～3mm, and slow release layer has the surface thickness deviation less than 5%.Such as, the thickness of slow release layer can be about 2mm.
It should be noted that in the present invention, term " thickness deviation " is defined as follows: with reference to Fig. 3, and slow release layer 200 surface is
The thickness Hmax that high point has deducts the thickness Hmin that minimum point has, with the ratio of average thickness.Above-mentioned average thickness is
The meansigma methods of Hmax Yu Hmin.Thus, it is possible to form the slow of a layer thickness uniform, controllable on the surface that porous matrix exposes
Release layer, and then the containing of Middle nutrition composition of this biofilm packing by accurately controlling the thickness of slow release layer, can be accurately controlled
Amount, and then the accurate control in the service life to this biofilm packing can be realized.Such as, reference Fig. 1 and Fig. 2,
In this step, slow release layer 200 can be formed uniformly on the upper surface of porous matrix 100 and sidewall, in order in reality
In application, microorganism is made to be attached in the hole of porous matrix 100, and by the upper surface of porous matrix 100 and sidewall
Slow release layer 200 be that microorganism provides growth necessary nutritional labeling.
Specifically, according to embodiments of the invention, above-mentioned mixture of nanoparticles includes polypropylene, Polyethylene Glycol, maleic acid
Acid anhydride, antioxidant, degradable polymer and metal oxide nanoparticles.It should be noted that in this step, logical
Cross and more than the fusing point of melt molding temperature polymer contained in mixture of nanoparticles is set, it is achieved melted by three-dimensional
Deposition modeling forms slow release layer.This melt molding temperature can be come according to concrete polymer contained in mixture of nanoparticles
It is set, as long as this melt molding temperature is more than the fusing point of polymer, and degradable poly at a temperature of this melt molding
Compound does not thermally decomposes.Additionally, the molecular weight of Polyethylene Glycol can be 200～600, in order to by 3D printing technique
Realize the preparation of slow release layer.Inventor finds through great many of experiments, when the molecular weight of Polyethylene Glycol is too low, due to material
Strand is too short, and intermolecular force is less, it is difficult to by 3D printing shaping；And when the molecular weight of Polyethylene Glycol is excessive,
Then easily excessive due to molecular weight, cause the overall viscosity of mixture of nanoparticles to strengthen, and then easily block shower nozzle, also difficult
To realize 3D printing shaping.When Polyethylene Glycol molecular weight within the above range, such as, the molecular weight of Polyethylene Glycol is 400
Time, it is possible to relatively it is smoothly through 3D printing technique molding.Degradable polymer includes selected from polylactic acid, polylactic acid-PVOH
Acid copolymer, PTMC at least one, metal oxide nanoparticles include selected from zinc oxide, sodium molybdate,
At least one cobaltous chloride, and metal oxide nanoparticles can have the particle diameter of 20-100nm, and antioxidant can wrap
Include selected from antioxidant 1010, antioxidant 1076 and antioxidant 1135 at least one.Polypropylene, Polyethylene Glycol
And maleic anhydride can be that slow release layer provides stable chemical performance, light weight and do not discharges the body of harmful substance, antioxygen
Agent can improve the effect utilizing 3D printing technique that mixture of nanoparticles is formed slow release layer, metal oxide nano
Grain can be that microorganism provides Co, Zn etc. to grow required metallic element.Containing polylactic acid, polylactic acid-polyglycolic acid copolymerization
The degradable polymer of thing and PTMC can the most progressively the degrading of this biofilm packing, and
Degradation rate is moderate, and then can reach the effect of slow release metal oxide nanoparticles in environment such that it is able to long-term,
Stably provide its growth necessary metallic element to microorganism.
According to embodiments of the invention, in mixture of nanoparticles, polypropylene, Polyethylene Glycol, maleic anhydride, antioxidation
The mass ratio of agent, degradable polymer and metal oxide nanoparticles can be 74.41:3.68:1.16:18.4:2.32:
(0.97-1.93).When the mentioned component in mixture of nanoparticles have above-mentioned quality than time, it is possible to obtain preferably 3D and beat
Print effect, while ensureing that the slow release layer formed has its basic function, it is possible to ensure that this mixture of nanoparticles has suitable
In parameters such as the viscosity that 3D prints, printing shaping solidification both will not be difficult to, also will not be due to excessively thickness or too fast solidification
And the 3D printing device that results in blockage.Form slow release layer thereby, it is possible to effectively printed by 3D, and can ensure that utilization
There is slow release layer prepared by the mixture of nanoparticles of aforementioned proportion the global density of biofilm packing will not be made excessive and can not hang
Float on the liquid level of sewage.
According to embodiments of the invention, by the shape to porous matrix and to component contents various in mixture of nanoparticles
Regulation and control, the biofilm packing utilizing the method to prepare can have 0.9～1g/cm3Density.Thus, this biofilm packing
Can be suspended on sewage, carry out sewage disposal as floating stuffing.Thus, this life can directly be thrown in when actually used
Thing film filler, need not fix, and easy to be filmed, and filler is not easily blocked.
Additionally, for the performance improving biofilm packing prepared by the method utilizing the present invention to provide further, forming slow release
Before Ceng, it is also possible to farther include:
(2-1) polypropylene, Polyethylene Glycol, maleic anhydride and metal oxide nanoparticles are dried process respectively.
In this step, the condition that polypropylene, Polyethylene Glycol and maleic anhydride carry out described dried can be: temperature
Spend 90 degrees Celsius, time 2 h.Condition withering to nano-particle can be: temperature 280 degrees Celsius, time
Between 2 hours.Thus, it is possible to before carrying out 3D printing, go out the moisture in mixture of nanoparticles in advance.
(2-2) by described polypropylene, Polyethylene Glycol, maleic anhydride and the metal oxide nano through described dried
Granule is mixed and stirred for antioxidant and degradable polymer, in order to form described mixture of nanoparticles.
According to embodiments of the invention, in this step, said mixture can be placed in homogenizer and be stirred,
To make the mentioned component mix homogeneously in mixture.Such as, according to one embodiment of present invention, mixing time can be
10 minutes.
S300: heat treatment and treatment with ultraviolet light
According to embodiments of the invention, in order to improve the heat stability of this biofilm packing further, can be to slow release layer-porous
Substrate complex carries out heat treatment.According to embodiments of the invention, can first with secondary water, slow release layer-porous matrix be combined
Body is carried out, in order to remove the impurity such as slow release layer-porous matrix complex surfaces attachment nano-particle, polymer and dust,
Then slow release layer-porous matrix complex is carried out heat treatment, in order to improve the heat stability of complex.Specifically, according to this
Inventive embodiment, the condition of heat treatment can be: temperature is 50～80 degrees Celsius, and the process time is 20-30 minute.Need
It is noted that the purpose of above-mentioned heat treatment is to improve the heat stability of slow release layer-porous matrix complex, therefore heat treatment
Temperature can not be too high, soften to prevent polymer in complex from occurring or polylactic acid thermally decompose.
Additionally, for the hydrophilicity improving biofilm packing according to embodiments of the present invention, according to embodiments of the invention,
After the heat treatment slow release layer-porous matrix complex can be carried out treatment with ultraviolet light.Biofilm packing through above-mentioned process
It is carried out with secondary water to remove surface residual impurity.According to embodiments of the invention, slow release layer-porous matrix is combined
It is to improve polyacrylic surface hydrophilic performance, cement properties and specific surface area that body carries out treatment with ultraviolet light.At air atmosphere
In ultraviolet light irradiate under the conditions of, the molecule of polypropylene surface can react with the oxygen in environment and water, oxidation generation hydroxyl
The oxide group such as base, carboxyl, such that it is able to improve the hydrophilicity of biofilm packing, is conducive to improving the effect of sewage disposal.
Additionally, ultraviolet light irradiates the energy provided can also form tiny hole in slow release layer-porous matrix complex surfaces, from
And the specific surface area of this biofilm packing can be improved further.According to embodiments of the invention, the condition for the treatment of with ultraviolet light can
Think: use microwave-excitation uviol lamp, power density 100～180W/cm2, illumination reaction time 20～50 seconds.Thus,
Good thermal stability can be obtained, there is the biofilm packing of hydrophilicity and large specific surface area.
It should be noted that in the present invention, 3D is printed and can be realized by existing 3D printer.It is concrete that 3D prints
Parameter, such as CAD mathematical model, printing precision etc., those skilled in the art can be according to the bacterium of microorganism in reality application
Type, the concrete condition of need sewage to be processed are designed, in order to according to above-mentioned practical situation, by porous matrix
The thickness of shape, thickness, specific surface area and slow release layer be adjusted, it is achieved preferably biofilm effect and sewage disposal
Effect.Such as, according to one embodiment of present invention, it is possible to use double shower nozzle three-dimensionals melt rapidform machine and carry out 3D and beat
Print, porous matrix and the slow release layer of mixture of nanoparticles formation that polypropylene is formed pass through a spray in double shower nozzles respectively
Head carries out printing shaping: first according to the filler shape of CAD mathematical model software design, entered by polypropylene by a shower nozzle
Row fusion sediment, forms porous matrix；Subsequently according to parameters such as slow release layer thickness, shape and the printing precision designed,
Another shower nozzle utilizing double shower nozzle three-dimensional to melt in rapidform machine deposits slow release in the inner side of porous matrix and upper surface
Layer.Thus, it is possible to realized the preparation of this biofilm packing with slow-release function easily by 3D printing technique.
In sum, the biofilm packing utilizing said method to prepare has following characteristics and an advantage:
(1) use three-dimensional fused glass pellet to print preparation, there is ion slow-release function, it is possible to effectively control metal ion and delay
Release thickness and the uniformity of layer, thus accurately control the service life of filler.
(2) this method can prepare biofilm packing fast and efficiently, and with low cost.
(3) utilize biofilm packing application prepared by this method extensive, can for different water quality, design can slow release not
Biofilm packing with kind nutrient ions.
In another aspect of this invention, the present invention proposes a kind of biofilm packing.According to embodiments of the invention, this biology
Film filler utilizes previously described method to prepare.Therefore, this biofilm packing possesses life prepared by previously described method
Whole features of thing film filler and advantage, do not repeat them here.
In still another aspect of the invention, the present invention proposes a kind of biofilm packing.According to embodiments of the invention, with reference to Fig. 1
And Fig. 2, this biofilm packing includes: polypropylene porous matrix 100 and mixture of nanoparticles slow release layer 200.Thus,
Can in actual use, by mixture of nanoparticles slow release layer 200 by the way of slow release, releasing microbe grows
Necessary micronutrient element, and then can improve at the Biofilm Colonization speed of this biofilm packing, biofilm amount and water
Reason efficiency, and can accurately control filler service life.
Specifically, according to embodiments of the invention, mixture of nanoparticles slow release layer 200 is arranged on polypropylene porous matrix 100
Sidewall and upper surface on, the thickness of mixture of nanoparticles slow release layer 200 is 1～3mm, and mixture of nanoparticles delay
Release layer 200 and there is the surface thickness deviation less than 5%.Such as, mixture of nanoparticles slow release layer 200 can have about
The thickness of 2mm.Definition about thickness deviation is previously detailed description, does not repeats them here.Wherein, receive
Rice grain mixture includes polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable polymer and burning
Thing nano-particle, polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable polymer and metal-oxide are received
The mass ratio of rice grain can be 74.41:3.68:1.16:18.4:2.32:(0.97-1.93), the molecular weight of Polyethylene Glycol can
Think 200～600；Degradable polymer includes selected from polylactic acid, PLGA, polytrimethylene carbonic acid
At least one ester；Metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobaltous chloride at least one, metal
The particle diameter of oxide nano particles can be 20-100nm；Antioxidant includes selected from antioxidant 1010, antioxidant 1076
At least one and antioxidant 1135.Inventor finds through great many of experiments, when the molecular weight of Polyethylene Glycol is too low,
Owing to the strand of material is too short, intermolecular force is less, and mixture of nanoparticles slow release layer 200 is difficult to molding；And work as
When the molecular weight of Polyethylene Glycol is excessive, then easily excessive due to molecular weight, cause the overall viscosity of mixture of nanoparticles to strengthen,
Mixture of nanoparticles slow release layer 200 is also difficult to molding.When the molecular weight of Polyethylene Glycol is 200～600, such as, molecular weight
When being 400, can more easily make slow release layer molding.Polypropylene, Polyethylene Glycol and maleic anhydride can be nano-particle
Mixture slow release layer 200 provides stable chemical performance, light weight and does not discharge the body of harmful substance, and antioxidant can
Improving said mixture and form the effect of slow release layer, metal oxide nanoparticles can provide its growth required for microorganism
Metallic element.Degradable polymer can the most progressively the degrading of this biofilm packing, and then can reach to
The effect of slow release metal oxide nanoparticles in environment such that it is able to provide its growth to be musted for a long time, stably to microorganism
The metallic element of palpus.
According to embodiments of the invention, this biofilm packing is floating stuffing.Thus, this biofilm packing has complete three-dimensional knot
Structure, specific surface area is big, can directly throw in, need not fix during use, and easy to be filmed, and filler is not easily blocked.
According to embodiments of the invention, the density of biofilm packing is 0.9～1g/cm3.Fill out thus, it is possible to improve this biomembrane
The suspension effect of material.
According to embodiments of the invention, this biofilm packing can be printed by 3D and be formed.Thus, it is possible to it is raw to this easily
Shape and the specific surface area of thing film filler porous matrix regulate and control, and can accurately control the thickness of slow release layer.Close
Prepare the concrete grammar of biofilm packing in utilizing 3D printing technique and utilize the biofilm packing of 3D printing preparation to be had
Feature and advantage, be previously detailed description, do not repeat them here.
In still another aspect of the invention, the present invention proposes the application in sewage disposal of the previously described biofilm packing.By
This, it is possible to use previously described biomembranous feature and advantage, improve efficiency and the effect of sewage disposal.
Below by specific embodiment, the present invention will be described, it will be appreciated to those of skill in the art that following tool
The purpose that the embodiment of body is merely to illustrate that, and limit the scope of the present invention never in any form.It addition, following
In embodiment, unless stated otherwise, the material and facility used is all commercially available.If in embodiment below,
Concrete treatment conditions and processing method are not expressly recited, then condition as known in the art and method can be used to enter
Row processes.
Embodiment 1
Utilize the double shower nozzle three-dimensional of FANTASY Pro to melt rapid shaping (3D printing) machine (EcubMaker) to carry out biology and fill out
The preparation of material.First become many void columns shape filler shape according to CAD mathematical model software design, temperature 210 degrees Celsius is set.
By a shower nozzle, polypropylene is carried out fusion sediment, form porous matrix.
Further according to the 2mm slow release layer thickness designed, utilize another shower nozzle in FANTASY Pro forming machine in porous
The inner side of matrix and upper surface deposition mixture of nanoparticles slow release layer.Temperature arranges 220 degrees Celsius, and nano-particle mixes
Thing includes polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant 1010, polylactic acid and Zinc oxide nanoparticle, its matter
Amount ratio is 74.41:3.68:1.16:18.4:2.32:0.97.The packing density obtained is 0.92g/cm3。
Again biologic packing material being carried out heat treatment, condition is: temperature is 80 degrees Celsius, and the process time is 25 minutes.The most right
Biologic packing material carries out ultraviolet light post processing, uses microwave-excitation uviol lamp, power density 150W/cm2, the illumination reaction time
50 seconds.
Embodiment 2
The biofilm packing of preparation in embodiment 1 is used to carry out waste water process.It is knitted fabric dyeing waste water that target processes waste water,
Wherein pH value of waste water is 10, and colourity is 250 times, and BOD value is 220mg/L, and COD value is 800mg/L, float
200mg/L.Activated sludge takes from certain sewage treatment plant, carries out cultivating domestication so that it is process dyeing waste water that can be the most stable,
By activated Sludge System respectively be commonly added to for biofilm packing and novel micro metallic element slow-release suspension biofilm packing
In waste water, in waste water, MLSS is 4000mg/L, and sludge loading is 0.2kgCOD/kgMLSS d, and media-filling rate is 40%,
Use uninterrupted air compressor aeration to run, with stirring, keep dissolved oxygen about 2.8g/L.After persistently processing three days,
Being 60% containing COD clearance in common floating stuffing cesspool, BOD clearance is 30%；Containing minor metallic element
In the cesspool of slow release three-dimensional fusion sediment suspended biological film filler, COD clearance is 85%, and BOD clearance is 75%.
Embodiment 3
The biofilm packing of preparation in embodiment 1 is used to carry out waste water process.It is textile dyeing waste water that target processes waste water, its
Middle pH value of waste water is 10, and colourity is 300 times, and BOD value is 380mg/L, and COD value is 1700mg/L, float
350mg/L.Activated sludge takes from certain sewage treatment plant, carries out cultivating domestication so that it is process dyeing waste water that can be the most stable,
By activated Sludge System respectively be commonly added to for biofilm packing and novel micro metallic element slow-release suspension biofilm packing
In waste water, in waste water, MLSS is 7000mg/L, and sludge loading is 0.2kgCOD/kgMLSS d, and media-filling rate is 30%,
Use uninterrupted air compressor aeration to run, with stirring, keep dissolved oxygen about 2.5g/L.After persistently processing three days,
Being 60% containing COD clearance in common floating stuffing cesspool, BOD clearance is 40%；Containing minor metallic element
In the cesspool of slow-release suspension biofilm packing, COD clearance is 90%, and BOD clearance is 80%
As can be seen here, the biofilm packing that the present invention provides has good sewage disposal and processes.
In describing the invention, it is to be understood that term " width ", " thickness ", " on ", D score, " interior ", " outward " etc.
Orientation or the position relationship of instruction are based on orientation shown in the drawings or position relationship, are for only for ease of the description present invention and Jian
Change describe rather than instruction or the hint device of indication or element must have specific orientation, with specific azimuth configuration and
Operation, is therefore not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be
First and second features directly contact, or the first and second features are by intermediary mediate contact.And, first is special
Levy second feature " on ", " top " and " above " but fisrt feature directly over second feature or oblique upper, or only
Only represent that fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below "
Can be fisrt feature immediately below second feature or obliquely downward, or be merely representative of fisrt feature level height less than second
Feature.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " concrete example ",
Or specific features, structure, material or the feature bag that the description of " some examples " etc. means to combine this embodiment or example describes
It is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term necessarily
It is directed to identical embodiment or example.And, the specific features of description, structure, material or feature can be arbitrary
Individual or multiple embodiment or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be combined by art personnel
And combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is exemplary,
Being not considered as limiting the invention, those of ordinary skill in the art within the scope of the invention can be to above-described embodiment
It is changed, revises, replaces and modification.
Claims (14)
1. the method preparing biofilm packing, it is characterised in that including:
(1) use polypropylene, printed by 3D, form porous matrix；
(2) using mixture of nanoparticles, printed by 3D, sidewall and upper surface at described porous matrix are formed slow
Release layer, in order to obtain slow release layer-porous matrix complex；
(3) described slow release layer-porous matrix complex is carried out heat treatment and treatment with ultraviolet light successively, in order to obtain described
Biofilm packing.
Method the most according to claim 1, it is characterised in that the specific surface area of described porous matrix is 260-300
m2/m3。
Method the most according to claim 1, it is characterised in that the density of described biofilm packing is 0.9～1g/cm3。
Method the most according to claim 1, it is characterised in that the thickness of described slow release layer is 1～3mm, and described
Slow release layer has the surface thickness deviation less than 5%.
Method the most according to claim 1, it is characterised in that described mixture of nanoparticles includes polypropylene, poly-second
Glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nanoparticles,
Wherein, the molecular weight of described Polyethylene Glycol is 200～600；
Described degradable polymer includes selected from polylactic acid, PLGA, PTMC extremely
One of few；
Described metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobaltous chloride at least one, described metal oxygen
The particle diameter of compound nano-particle is 20-100nm；
Described antioxidant include selected from antioxidant 1010, antioxidant 1076 and antioxidant 1135 at least one.
Method the most according to claim 5, it is characterised in that in described mixture of nanoparticles, described polypropylene,
The mass ratio of Polyethylene Glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nanoparticles is 74.41:
3.68:1.16:18.4:2.32:(0.97-1.93)。
Method the most according to claim 5, it is characterised in that described mixture of nanoparticles is through the following steps that obtain
:
(2-1) described polypropylene, Polyethylene Glycol, maleic anhydride and metal oxide nanoparticles are dried place respectively
Reason,
Wherein, the condition that described polypropylene, Polyethylene Glycol and maleic anhydride carry out described dried is: temperature 90 is taken the photograph
Family name's degree, time 2 h；Condition withering to described nano-particle is: temperature 280 degrees Celsius, the time 2 is little
Time；And
(2-2) by described polypropylene, Polyethylene Glycol, maleic anhydride and the metal oxide nano through described dried
Granule is mixed and stirred for described antioxidant and described degradable polymer, in order to form described mixture of nanoparticles.
Method the most according to claim 1, it is characterised in that in step (3), the condition of described heat treatment is:
Temperature is 50～80 degrees Celsius, and the process time is 20-30 minute；
The condition of described treatment with ultraviolet light is: uviol lamp power density is 150W/cm2, light application time is 20～50 seconds.
9. a biofilm packing, it is characterised in that described biofilm packing is by described in any one of claim 1～8
Prepared by method.
10. a biofilm packing, it is characterised in that including:
Polypropylene porous matrix；And
Mixture of nanoparticles slow release layer, described mixture of nanoparticles slow release layer is arranged on the side of described polypropylene porous matrix
On wall and upper surface, the thickness of described mixture of nanoparticles slow release layer is 1～3mm, and described mixture of nanoparticles is delayed
Release layer and there is the surface thickness deviation less than 5%,
Wherein, described mixture of nanoparticles includes polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable poly
Compound and metal oxide nanoparticles, described polypropylene, Polyethylene Glycol, maleic anhydride, antioxidant, degradable poly
The mass ratio of compound and metal oxide nanoparticles is 74.41:3.68:1.16:18.4:2.32:(0.97-1.93)；
The molecular weight of described Polyethylene Glycol is 200～600；
Described degradable polymer includes selected from polylactic acid, PLGA, PTMC extremely
One of few；
Described metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobaltous chloride at least one, described metal oxygen
The particle diameter of compound nano-particle is 20-100nm；
Described antioxidant include selected from antioxidant 1010, antioxidant 1076 and antioxidant 1135 at least one.
11. biofilm packings according to claim 10, it is characterised in that described biofilm packing is floating stuffing.
12. biofilm packings according to claim 11, it is characterised in that the density of described biofilm packing is
0.9～1g/cm3。
13. biofilm packings according to claim 10, it is characterised in that described biofilm packing is to be beaten by 3D
Impression becomes.
The biofilm packing described in 14. any one of claim 9～13 purposes in sewage disposal.
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| CN109499505A (en) * | 2018-11-28 | 2019-03-22 | 中广核达胜加速器技术有限公司 | A kind of preparation method of radiation modification polyethylene carrier |
| CN112852588A (en) * | 2021-01-23 | 2021-05-28 | 重庆大学 | Light-guiding three-dimensional porous biological membrane substrate reactor and method for culturing microalgae biological membrane |
| CN114590886A (en) * | 2022-02-21 | 2022-06-07 | 中国科学院合肥物质科学研究院 | Self-degradable biological film filler and preparation method and application thereof |
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| CN104773818A (en) * | 2015-04-23 | 2015-07-15 | 宜兴盛溢基业环保科技有限公司 | Suspended biological film filler of composite trace metal ions and preparation method of suspended biological film filler |
| CN205035140U (en) * | 2015-07-21 | 2016-02-17 | 宜兴盛溢基业环保科技有限公司 | Compound micro - metal ion's little biofilm filler of hollow post suspension |
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| CN104773818A (en) * | 2015-04-23 | 2015-07-15 | 宜兴盛溢基业环保科技有限公司 | Suspended biological film filler of composite trace metal ions and preparation method of suspended biological film filler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109499505A (en) * | 2018-11-28 | 2019-03-22 | 中广核达胜加速器技术有限公司 | A kind of preparation method of radiation modification polyethylene carrier |
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| CN112852588A (en) * | 2021-01-23 | 2021-05-28 | 重庆大学 | Light-guiding three-dimensional porous biological membrane substrate reactor and method for culturing microalgae biological membrane |
| CN114590886A (en) * | 2022-02-21 | 2022-06-07 | 中国科学院合肥物质科学研究院 | Self-degradable biological film filler and preparation method and application thereof |
| CN114590886B (en) * | 2022-02-21 | 2023-09-05 | 中国科学院合肥物质科学研究院 | Self-degrading biological film filler and preparation method and application thereof |
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