CN105753138B - Three-dimensional fusion sediment biofilm packing, preparation method and applications - Google Patents
Three-dimensional fusion sediment biofilm packing, preparation method and applications Download PDFInfo
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- CN105753138B CN105753138B CN201610222088.0A CN201610222088A CN105753138B CN 105753138 B CN105753138 B CN 105753138B CN 201610222088 A CN201610222088 A CN 201610222088A CN 105753138 B CN105753138 B CN 105753138B
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- 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
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Abstract
The invention proposes three-dimensional fusion sediment biofilm packings, preparation method and applications.This method comprises: (1) uses polypropylene, by 3D printing, porous matrix is formed；(2) mixture of nanoparticles is used, by 3D printing, slow release layer is formed in the side wall of the porous matrix and upper surface, to obtain slow release layer-porous matrix complex；(3) heat treatment and treatment with ultraviolet light are carried out, successively to the slow release layer-porous matrix complex to obtain the biofilm packing.Trace nutrient necessary to microorganism grows can be provided in the way of sustained release in use by the biofilm packing of this method preparation, and then the Biofilm Colonization speed, biofilm amount and water treatment efficiency of the filler can be improved.
Description
Technical field
The present invention relates to Material Fields, specifically, the present invention relates to three-dimensional fusion sediment biofilm packings, preparation method
And its application.More particularly it relates to which a kind of method for preparing biofilm packing, biofilm packing and the biomembrane are filled out
Expect the purposes in sewage treatment.
Background technique
China is the country of a serious water shortage, and shortage of water resources is got worse, and per capita water resource is only world average
1/4.And with China's expanding economy, industrial water resources consumption is huge, and wastewater discharge is also larger, therefore improves industry
The recovery utilization rate of waste water is for solving the problems, such as that water scarcity is of great significance.Industrial Wastewater Treatment generallys use life at present
Object contact oxidation method loads a certain number of fillers in cesspool, utilize the biomembrane being adsorbed on filler and sufficiently confession
Oxidation operation in waste water is decomposed by biological oxidation, reaches purification purpose, this method is being weaved by the oxygen answered
It is widely used in the processing of the waste water such as printing and dyeing, petrochemical industry, medicine.
However, current biofilm packing and biofilm packing preparation method still has much room for improvement.
Summary of the invention
The application is to be made based on inventor to the discovery of following facts and problem and understanding:
Current biofilm packing has that the biofilm speed of biomembrane and extension modulus are undesirable, and filler makes
With the service life, shorter and filler service life is difficult to control accurately.Inventor passes through further investigation and many experiments discovery, this
It is that sustainable growth is difficult to due to the quantity of microbiologic population, the speed of bacteria metabolism cannot maintain higher level and make
At.And microorganism is not able to maintain continued propagation and high-caliber metabolism, is micro- due to lacking in sewage treatment system
Caused by the biological necessary micronutrient element of metabolism.Although this problem can be suitable micro- by adding into waste water
Amount nutrient is eased, however this mode disposably launched can not be accurately according to microorganism growing state to micro-
Amount nutrient is controlled in real time, and when micronutrient element is depleted, it is difficult to accomplish to be replenished in time, therefore very
Microorganism is grown the difficult missing for really solving micronutrient element and the negative effect of rate of metabolism.
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, the present invention mentions
A kind of suspended biological film filler and preparation method thereof with nutrient slow-release function out.This method utilizes 3D printing technique,
Biofilm packing of different shapes can be prepared, the Biofilm Colonization speed of filler, biofilm amount and water treatment efficiency are improved, and
And it can accurately control filler service life.Three-dimensional fast shaping prints (Three Dimensional Printing, 3DP) again
Referred to as 3D printing is one kind of rapid shaping technique, it is one kind based on digital model file, with powdery metal or
Plastics etc. can bonding material, construct the technology of object by layer-by-layer printing.Its biggest advantage is that can by material into
Row successively it is compound, therefore can the shape feature to the object constructed accurately regulated and controled.
In one aspect of the invention, the invention proposes a kind of methods for preparing biofilm packing.It is according to the present invention
Embodiment, by 3D printing, forms porous matrix this method comprises: (1) uses polypropylene；(2) it is mixed using nano particle
Object forms slow release layer in the side wall of the porous matrix and upper surface, to obtain the porous base of slow release layer-by 3D printing
Composite；(3) heat treatment and treatment with ultraviolet light are carried out, successively to the slow release layer-porous matrix complex to obtain
The biofilm packing.It is necessary that it can be sustained microorganism growth institute in use using biofilm packing prepared by this method
Trace nutrient, and then the Biofilm Colonization speed, biofilm amount and water treatment efficiency of the filler can be improved.
According to an embodiment of the invention, the specific surface area of the porous matrix is 260-300m2/m3.Thereby, it is possible to effective
Ground increases biomembrane and hangs modulus, and then improves water treatment efficiency.
According to an embodiment of the invention, the density of the biofilm packing is 0.9~1g/cm3.The biomembrane is filled out as a result,
Material can be suspended on sewage, carry out sewage treatment as floating stuffing.It can directly be launched when using as a result, without fixation,
And easy to be filmed, filler are not easy to plug.
According to an embodiment of the invention, the slow release layer with a thickness of 1~3mm, and the slow release layer has and is no more than 5%
Surface thickness deviation.Thus, it is possible to accurately control the service life of the biofilm packing.
According to an embodiment of the invention, the mixture of nanoparticles includes polypropylene, polyethylene glycol, maleic anhydride, resists
Oxidant, degradable polymer and metal oxide nanoparticles, wherein the molecular weight of the polyethylene glycol be 200~
600；The degradable polymer includes being selected from polylactic acid, polylactide-polyglycolic acid copolymer, polytrimethylene carbonate extremely
It is one of few；The metal oxide nanoparticles include being selected from least one of zinc oxide, sodium molybdate, cobalt chloride, the metal
The partial size of oxide nano particles is 20-100nm；The antioxidant includes being selected from antioxidant 1010, antioxidant 1076
And at least one of antioxidant 1135.Degradable polymer can the biofilm packing in use gradually drop
Solution, and then can achieve the effect that metal oxide nanoparticles are sustained into environment, so as to long-term, steadily Xiang Weisheng
Object provides metallic element necessary to it grows.
According to an embodiment of the invention, in the mixture of nanoparticles, the 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).Thereby, it is possible to effectively form the slow release layer by 3D printing, and can have with utility
The slow release layer of the mixture of nanoparticles preparation of aforementioned proportion will not make the global density of biofilm packing excessive and cannot suspend
On the liquid level of sewage.
According to an embodiment of the invention, in step (2), the mixture of nanoparticles is through the following steps that obtain:
The polypropylene, polyethylene glycol, maleic anhydride and metal oxide nanoparticles are dried in (2-1) respectively,
In, the condition of the drying process is carried out to the polypropylene, polyethylene glycol and maleic anhydride are as follows: 90 degrees Celsius of temperature, when
Between 2 hours；To the withering condition of the nano particle are as follows: 280 degrees Celsius of temperature, time 2 h；And (2-2)
By Jing Guo the drying process the polypropylene, polyethylene glycol, maleic anhydride and metal oxide nanoparticles with it is described
Antioxidant and the degradable polymer are mixed and stirred for, to form the mixture of nanoparticles.Thus, it is possible to mention
Usury carries out the efficiency and effect of 3D printing with mixture of nanoparticles.
According to an embodiment of the invention, in step (3), the condition of the heat treatment are as follows: temperature is 50-80 degrees Celsius,
Handling the time is 20-30 minutes；The condition of the treatment with ultraviolet light are as follows: ultraviolet lamp power density is 150W/cm2, light application time
It is 20~50 seconds.Thereby, it is possible to improve the thermal stability of the biofilm packing and hydrophilicity.
In another aspect of this invention, the invention proposes a kind of biofilm packing, the biofilm packing is by preceding
The preparation of method described in face.The biofilm packing can be sustained micro- necessary to microorganism growth in use as a result,
Nutriment is measured, and then the Biofilm Colonization speed, biofilm amount and water treatment efficiency of the filler can be improved.
In still another aspect of the invention, the invention proposes a kind of biofilm packings.According to an embodiment of the invention, the life
Object film filler includes: polypropylene porous matrix；And mixture of nanoparticles slow release layer, the mixture of nanoparticles slow release layer
Be arranged on side wall and the upper surface of the polypropylene porous matrix, the mixture of nanoparticles slow release layer with a thickness of 1
~3mm, and the mixture of nanoparticles slow release layer has the surface thickness deviation no more than 5%, wherein the nano particle
Mixture includes polypropylene, polyethylene glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nano
Grain, the polypropylene, polyethylene glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nanoparticles
Mass ratio is 74.41:3.68:1.16:18.4:2.32:(0.97-1.93), the molecular weight of the polyethylene glycol is 200~600；
The degradable polymer include selected from polylactic acid, polylactide-polyglycolic acid copolymer, polytrimethylene carbonate at least it
One；The metal oxide nanoparticles include being selected from least one of zinc oxide, sodium molybdate, cobalt chloride, the metal oxidation
The partial size of object nano particle is 20-100nm；The antioxidant include selected from antioxidant 1010, antioxidant 1076 and
At least one of antioxidant 1135.It is necessary can be sustained microorganism growth institute in use for the biofilm packing as a result,
Trace nutrient, and then the Biofilm Colonization speed, biofilm amount and water treatment efficiency of the filler can be improved, and should
The service life of biofilm packing can accurately be controlled by adjusting the thickness of slow release layer.
According to an embodiment of the invention, the biofilm packing is floating stuffing.The biofilm packing has complete vertical as a result,
Body structure, large specific surface area, when use, can directly launch, and without fixation, and easy to be filmed, filler are not easy to plug.
According to an embodiment of the invention, the density of the biofilm packing is 0.9~1g/cm3.Thus, it is possible to improve this
The suspension effect of biofilm packing.
According to an embodiment of the invention, the biofilm packing is formed by 3D printing.Thus, it is possible to easily right
The shape and specific surface area of the biofilm packing porous matrix are regulated and controled, and can accurately control the thickness of slow release layer
Degree.
In still another aspect of the invention, the use the invention proposes mentioned-above biofilm packing in sewage treatment
On the way.Thus, it is possible to improve the efficiency and effect of sewage treatment using the feature of previously described biofilm packing.
Detailed description of the invention
Fig. 1 shows biofilm packing structural schematic diagram 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.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings.Below with reference to
The embodiment of attached drawing description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the invention proposes a kind of methods for preparing biofilm packing.It is according to the present invention
Embodiment, the biofilm packing using this method preparation have metallic element slow-release function, and the preparation method technical process is simple,
Material is easy to get, at low cost, and the period is short.Specifically, this method comprises:
S100: porous matrix is formed
According to an embodiment of the invention, in this step, using polypropylene, forming porous matrix by 3D printing.Specifically
It ground in this step can be by the relevant parameter in setting 3D printing step, for example, by according to CAD mathematical model software
The parameters such as thickness, shape, the printing precision of porous matrix are designed, realize the matrix for being formed using polypropylene and there is porous structure.
The specific surface area of the porous matrix is 260-300m2/m3.When the specific surface area of porous matrix is too small, hung on the matrix
The limited area of film, therefore it is attached to the limited amount of microbial flora on matrix, to be extremely difficult to preferable water process effect
Fruit；And when the specific surface area of porous matrix is excessive, biofilm packing volume under the same conditions, will cause the sky in hole
Between it is too small, be unfavorable for the biofilm and growth of microorganism.Inventor has found by many experiments, when the specific surface area of porous matrix
When in above range, there is preferable biofilm effect.Polypropylene material is the common material of biofilm packing, has structure letter
Singly, the advantages that porosity is high, light, intensity is high, antiseptic property is good, aging is biological easy to fall off.Polypropylene material is used as a result,
Porous matrix is formed, the matrix of superior performance can be provided for the biofilm packing.It should be noted that in this step, it is more
The parameters such as concrete shape, the thickness of hole matrix are not particularly limited, and those skilled in the art can select to fit according to the actual situation
When shape and thickness.For example, according to an embodiment of the invention, porous matrix 100 can be porous for honeycomb type with reference to Fig. 4
Matrix, and then the mechanical strength of porous matrix can be improved while improving matrix specific surface area.In addition, the honeycomb of rule
Shape structure is also beneficial to form the slow release layer of structure-controllable in subsequent step.
S200: slow release layer is formed
According to an embodiment of the invention, in this step, by 3D printing, using mixture of nanoparticles in porous matrix
Side wall and upper surface formed slow release layer, to form slow release layer-porous matrix complex.Specifically, the thickness of slow release layer
It can be 1~3mm, and slow release layer has the surface thickness deviation no more than 5%.For example, 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: referring to Fig. 3,200 surface highest of slow release layer
The thickness Hmax that point has subtracts the thickness Hmin that minimum point has, the ratio with average thickness.Above-mentioned average thickness is Hmax
With the average value of Hmin.Thus, it is possible to the slow release layer of a layer thickness uniform, controllable is formed on the surface of porous matrix exposure, into
And the content of the middle nutritional ingredient of the biofilm packing can be accurately controlled, in turn by accurately controlling the thickness of slow release layer
The accurate control to the service life of the biofilm packing may be implemented.For example, with reference to Fig. 1 and Fig. 2, it in this step, can
To be formed uniformly slow release layer 200 on the upper surface of porous matrix 100 and side wall, in practical applications, to make micro- life
Object is attached in the hole of porous matrix 100, and is micro- by the slow release layer 200 on the upper surface of porous matrix 100 and side wall
Biology, which provides, grows necessary nutritional ingredient.
Specifically, according to an embodiment of the invention, above-mentioned mixture of nanoparticles includes polypropylene, polyethylene glycol, Malaysia
Acid anhydrides, antioxidant, degradable polymer and metal oxide nanoparticles.It should be noted that in this step, passing through
The fusing point of polymer of the melt molding temperature contained in mixture of nanoparticles or more is set, and it is heavy by three-dimensional melting to realize
Product molding forms slow release layer.The melt molding temperature can according to specific polymer contained in mixture of nanoparticles come into
Row setting, if the melt molding temperature more than the fusing point of polymer, and the degradable polymerization at a temperature of melt molding
Object does not thermally decompose.In addition, the molecular weight of polyethylene glycol can be 200~600, will pass through 3D printing technique realization
The preparation of slow release layer.Inventor has found by many experiments, when the molecular weight of polyethylene glycol is too low, due to the strand of material
Too short, intermolecular force is smaller, it is difficult to be formed by 3D printing；And when the molecular weight of polyethylene glycol is excessive, then be easy by
It is excessive in molecular weight, the whole viscosity enhancing of mixture of nanoparticles is caused, and then be easy blocking spray head, it is also difficult to realize that 3D is beaten
It is printed as type.When polyethylene glycol molecular weight within the above range, for example, the molecular weight of polyethylene glycol be 400 when, can relatively smoothly
Ground is formed by 3D printing technique.Degradable polymer includes being selected from polylactic acid, polylactide-polyglycolic acid copolymer, poly- Sanya
At least one of methyl carbonic, metal oxide nanoparticles include selected from zinc oxide, sodium molybdate, cobalt chloride at least it
One, and metal oxide nanoparticles can have the partial size of 20-100nm, and antioxidant may include selected from antioxidant
1010, at least one of antioxidant 1076 and antioxidant 1135.Polypropylene, polyethylene glycol and maleic anhydride can be
Slow release layer provides stable chemical performance, light weight and the ontology for not discharging harmful substance, and antioxidant, which can be improved, utilizes 3D
Mixture of nanoparticles is formed the effect of slow release layer by printing technique, and metal oxide nanoparticles can provide for microorganism
Co, Zn etc. grow required metallic element.Contain polylactic acid, polylactide-polyglycolic acid copolymer and polytrimethylene carbonic acid
The degradable polymer of ester can the biofilm packing gradually degrade in use, and degradation rate is moderate, Jin Erke
To achieve the effect that be sustained metal oxide nanoparticles into environment, so as to for a long time, steadily provide it to microorganism
Metallic element necessary to growing.
It is polypropylene, polyethylene glycol, maleic anhydride, anti-oxidant according to an embodiment of the invention, in mixture of nanoparticles
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 has above-mentioned quality ratio, preferably 3D printing can be obtained
Effect can guarantee that the mixture of nanoparticles has and be suitable for while the slow release layer for guaranteeing to be formed has its basic function
The parameters such as the viscosity of 3D printing will not both be difficult to printing shaping solidification, will not be made due to excessively sticky or too fast solidification
At blocking 3D printing equipment.Thereby, it is possible to effectively form slow release layer by 3D printing, and can have with utility above-mentioned
The slow release layer of the mixture of nanoparticles preparation of ratio will not make the global density of biofilm packing excessive and cannot be suspended in dirt
On the liquid level of water.
According to an embodiment of the invention, by the shape to porous matrix and to various composition in mixture of nanoparticles
The regulation of content can have 0.9~1g/cm using biofilm packing prepared by this method3Density.The biomembrane as a result,
Filler can be suspended on sewage, carry out sewage treatment as floating stuffing.This can directly be launched in actual use as a result,
Biofilm packing, without fixation, and easy to be filmed, filler are not easy to plug.
In addition, being formed to further increase the performance of the biofilm packing using method provided by the invention preparation
Before slow release layer, it can further include:
Place is dried to polypropylene, polyethylene glycol, maleic anhydride and metal oxide nanoparticles in (2-1) respectively
Reason.
In this step, the condition for carrying out the drying process to polypropylene, polyethylene glycol and maleic anhydride can be with are as follows:
90 degrees Celsius of temperature, time 2 h.It can be with to the withering condition of nano particle are as follows: 280 degrees Celsius of temperature, the time 2
Hour.Thus, it is possible to the moisture before carrying out 3D printing, in mixture of nanoparticles of going out in advance.
(2-2) receives the polypropylene, polyethylene glycol, maleic anhydride and the metal oxide Jing Guo the drying process
Rice grain is mixed and stirred for antioxidant and degradable polymer, to form the mixture of nanoparticles.
According to an embodiment of the invention, in this step, said mixture can be placed in high-speed mixer and be stirred
It mixes, to be uniformly mixed the mentioned component in mixture.For example, according to one embodiment of present invention, mixing time can be with
It is 10 minutes.
S300: heat treatment and treatment with ultraviolet light
According to an embodiment of the invention, in order to further increase the thermal stability of the biofilm packing, it can be to slow release layer-
Porous matrix complex is heat-treated.According to an embodiment of the invention, can be first with secondary water to slow release layer-porous matrix
Complex is cleaned, to remove slow release layer-porous matrix complex surfaces attachment nano particle, polymer and dust etc.
Then impurity is heat-treated slow release layer-porous matrix complex, to improve the thermal stability of complex.Specifically, root
According to the embodiment of the present invention, the condition of heat treatment can be with are as follows: temperature is 50~80 degrees Celsius, and the processing time is 20-30 minutes.It needs
It is noted that the purpose of above-mentioned heat treatment is to improve slow release layer-porous matrix complex thermal stability, therefore it is heat-treated
Temperature cannot be excessively high, to prevent, polymer in complex from occurring softening or polylactic acid thermally decomposes.
In addition, in order to improve the hydrophilicity of biofilm packing according to an embodiment of the present invention, implementation according to the present invention
Example can carry out treatment with ultraviolet light to slow release layer-porous matrix complex after the heat treatment.By the biomembrane of above-mentioned processing
Filler is cleaned to remove surface residual impurity with secondary water.According to an embodiment of the invention, to slow release layer-porous matrix
It is to improve polyacrylic surface hydrophilic performance, cement properties and specific surface area that complex, which carries out treatment with ultraviolet light,.In air
Under the conditions of ultraviolet light in atmosphere, the molecule of polypropylene surface can in environment oxygen and water react, oxidation life
At oxide groups such as hydroxyl, carboxyls, so as to improve the hydrophilicity of biofilm packing, be conducive to the effect for improving sewage treatment
Fruit.In addition, energy provided by ultraviolet light can also form tiny hole in slow release layer-porous matrix complex surfaces
Hole, so as to further increase the specific surface area of the biofilm packing.According to an embodiment of the invention, the item for the treatment of with ultraviolet light
Part can be with are as follows: uses microwave-excitation ultraviolet lamp, 100~180W/cm of power density2, the illumination reaction time 20~50 seconds.As a result,
Good thermal stability, the biofilm packing with hydrophilicity and large specific surface area can be obtained.
It should be noted that in the present invention, 3D printing can be realized by existing 3D printer.3D printing it is specific
Parameter, such as CAD mathematical model, printing precision etc., those skilled in the art can be according to the strains of microorganism in practical application
Type, the concrete condition of sewage to be treated are designed, to pass through the shape to porous matrix according to above-mentioned actual conditions
Shape, thickness, specific surface area and slow release layer thickness be adjusted, realize better biofilm effect and wastewater treatment efficiency.
For example, according to one embodiment of present invention, can use double spray head three-dimensional melting rapidform machines and carry out 3D printing, polypropylene
The spray head that the slow release layer that the porous matrix and mixture of nanoparticles of formation are formed passes through respectively in double spray heads is beaten
It is printed as type: first according to the filler shape of CAD mathematical model software design, polypropylene being carried out by melting by a spray head and is sunk
Product forms porous matrix；Then according to parameters such as designed slow release layer thickness, shape and printing precision, double spray heads are utilized
Another spray head in three-dimensional melting rapidform machine deposits slow release layer in the inside of porous matrix and upper surface.As a result, may be used
Easily to realize the preparation of the biofilm packing with slow-release function by 3D printing technique.
In conclusion using the above method prepare biofilm packing have the advantages that following characteristics and:
(1) using three-dimensional fused glass pellet printing preparation, there is ion slow-release function, can effectively control metal ion
The thickness and the uniformity of slow release layer, to accurately control the service life of filler.
(2) this method can fast and efficiently prepare biofilm packing, and low in cost.
(3) the biofilm packing application field using this method preparation is extensive, can be directed to different water quality, and design can be sustained
The biofilm packing of variety classes nutrient ions.
In another aspect of this invention, the invention proposes a kind of biofilm packings.According to an embodiment of the invention, the life
Object film filler is prepared using previously described method.Therefore, which has previously described method preparation
The whole features and advantage of biofilm packing, details are not described herein.
In still another aspect of the invention, the invention proposes a kind of biofilm packings.According to an embodiment of the invention, with reference to
Fig. 1 and Fig. 2, the biofilm packing include: polypropylene porous matrix 100 and mixture of nanoparticles slow release layer 200.By
This, can in actual use, by mixture of nanoparticles slow release layer 200 by way of sustained release, and releasing microbe is raw
Micronutrient element necessary to long, and then the Biofilm Colonization speed, biofilm amount and water of the biofilm packing can be improved
Treatment effeciency, and can accurately control filler service life.
Specifically, according to an embodiment of the invention, mixture of nanoparticles slow release layer 200 is arranged in polypropylene porous matrix
On 100 side wall and upper surface, mixture of nanoparticles slow release layer 200 with a thickness of 1~3mm, and mixture of nanoparticles
Slow release layer 200 has the surface thickness deviation no more than 5%.For example, mixture of nanoparticles slow release layer 200 can have about
The thickness of 2mm.About detailed description has been carried out before the definition of thickness deviation, details are not described herein.Wherein, nanometer
Grain mixture includes polypropylene, polyethylene glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nano
Particle, the matter of polypropylene, polyethylene glycol, maleic anhydride, antioxidant, degradable polymer and metal oxide nanoparticles
Measuring ratio can be 74.41:3.68:1.16:18.4:2.32:(0.97-1.93), the molecular weight of polyethylene glycol can be 200~
600；Degradable polymer include selected from polylactic acid, polylactide-polyglycolic acid copolymer, polytrimethylene carbonate at least it
One；Metal oxide nanoparticles include being selected from least one of zinc oxide, sodium molybdate, cobalt chloride, metal oxide nano
The partial size of grain can be 20-100nm；Antioxidant includes being selected from antioxidant 1010, antioxidant 1076 and antioxidant
At least one of 1135.Inventor has found by many experiments, when the molecular weight of polyethylene glycol is too low, due to the molecule of material
Chain is too short, and intermolecular force is smaller, and mixture of nanoparticles slow release layer 200 is difficult to form；And work as the molecular weight of polyethylene glycol
When excessive, then it is easy to cause the whole viscosity enhancing of mixture of nanoparticles since molecular weight is excessive, mixture of nanoparticles is slow
Layer 200 is released also to be difficult to form.When polyethylene glycol molecular weight be 200~600, for example, molecular weight be 400 when, can be more convenient
Ground makes to be sustained formable layer.Polypropylene, polyethylene glycol and maleic anhydride can be 200 offer of mixture of nanoparticles slow release layer
Stable performance, light weight and the ontology for not discharging harmful substance are learned, antioxidant can be improved said mixture and form sustained release
The effect of layer, metal oxide nanoparticles can provide metallic element necessary to it grows for microorganism.Degradable polymerization
Object can the biofilm packing in use gradually degrade, and then can achieve and be sustained metal oxide into environment and receive
The effect of rice grain, so as to provide metallic element necessary to it grows to microorganism for a long time, steadily.
According to an embodiment of the invention, the biofilm packing is floating stuffing.The biofilm packing has complete three-dimensional as a result,
Structure, large specific surface area, when use, can directly launch, and without fixation, and easy to be filmed, filler are not easy to plug.
According to an embodiment of the invention, the density of biofilm packing is 0.9~1g/cm3.Thus, it is possible to improve the biology
The suspension effect of film filler.
According to an embodiment of the invention, the biofilm packing can be formed by 3D printing.Thus, it is possible to easily to this
The shape and specific surface area of biofilm packing porous matrix are regulated and controled, and can accurately control the thickness of slow release layer.
Had about the specific method for preparing biofilm packing using 3D printing technique and using biofilm packing prepared by 3D printing
Some features and advantage, before detailed description has been carried out, details are not described herein.
In still another aspect of the invention, the answering in sewage treatment the invention proposes previously described biofilm packing
With.Thus, it is possible to improve the efficiency and effect of sewage treatment using the feature and advantage of previously described biomembrane.
Below by specific embodiment, the present invention will be described, it will be appreciated to those of skill in the art that below
The purpose that is merely to illustrate that of specific embodiment, without limiting the scope of the invention in any way.In addition, below
Embodiment in, unless stated otherwise, used material and facility is commercially available.If in embodiment below
In, specific treatment conditions and processing method are not expressly recited, then can use condition as known in the art and side
Method is handled.
Embodiment 1
Biology is carried out using bis- spray head three-dimensional meltings rapid shaping (3D printing) machine (EcubMaker) of FANTASY Pro to fill out
The preparation of material.It is arranged 210 degrees Celsius of temperature at more void column shape filler shapes according to CAD mathematical model software design first.Pass through
Polypropylene is carried out fusion sediment by one spray head, forms porous matrix.
Further according to designed 2mm slow release layer thickness, using another spray head in FANTASY Pro molding machine porous
The inside of matrix and upper surface deposit mixture of nanoparticles slow release layer.220 degrees Celsius of temperature setting, mixture of nanoparticles
Including polypropylene, polyethylene glycol, maleic anhydride, antioxidant 1010, polylactic acid and Zinc oxide nanoparticle, mass ratio is
74.41:3.68:1.16:18.4:2.32:0.97.Obtained packing density is 0.92g/cm3。
Biologic packing material is heat-treated again, condition are as follows: temperature is 80 degrees Celsius, and the processing time is 25 minutes.It is finally right
Biologic packing material carries out ultraviolet light post-processing, using microwave-excitation ultraviolet lamp, power density 150W/cm2, the illumination reaction time 50
Second.
Embodiment 2
Wastewater treatment is carried out using the biofilm packing prepared in embodiment 1.Target processing waste water is that knitted fabric printing and dyeing are useless
Water, wherein pH value of waste water is 10, and coloration is 250 times, and BOD value is 220mg/L, COD value 800mg/L, suspended matter 200mg/L.
Activated sludge is derived from certain sewage treatment plant, carries out culture domestication, can very stable processing dyeing waste water, by activated sludge
System is added in waste water for biofilm packing and novel micro metallic element slow-release suspension biofilm packing respectively with commonly, is given up
MLSS is 4000mg/L, sludge loading 0.2kgCOD/kgMLSSd, media-filling rate 40%, using uninterrupted sky in water
Air compressor aeration operation keeps dissolved oxygen 2.8g/L or so with stirring.After persistently handling three days, filled out containing common suspension
It is 30% that COD removal rate, which is 60%, BOD removal rate, in material cesspool；It is outstanding that three-dimensional fusion sediment is sustained containing minor metallic element
It is 75% that COD removal rate, which is 85%, BOD removal rate, in the cesspool of pelagic organism film filler.
Embodiment 3
Wastewater treatment is carried out using the biofilm packing prepared in embodiment 1.It is pure cotton dyeing waste water that target, which handles waste water,
Wherein pH value of waste water is 10, and coloration is 300 times, and BOD value is 380mg/L, COD value 1700mg/L, suspended matter 350mg/L.It is living
Property sludge is derived from certain sewage treatment plant, carries out culture domestication, can very stable processing dyeing waste water, by activated sludge system
System is added in waste water for biofilm packing and novel micro metallic element slow-release suspension biofilm packing respectively with commonly, waste water
Middle MLSS is 7000mg/L, sludge loading 0.2kgCOD/kgMLSSd, media-filling rate 30%, using uninterrupted air
Compressor aeration operation keeps dissolved oxygen 2.5g/L or so with stirring.After persistently handling three days, contain common floating stuffing
It is 40% that COD removal rate, which is 60%, BOD removal rate, in cesspool；Contain minor metallic element slow-release suspension biofilm packing
It is 80% that COD removal rate, which is 90%, BOD removal rate, in cesspool
It can be seen that biofilm packing provided by the invention is handled with good sewage treatment.
In the description of the present invention, it is to be understood that, term " width ", " thickness ", "upper", "lower", "inner", "outside" etc.
The orientation or positional relationship of instruction is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of the description present invention and letter
Change description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with specific orientation construct and
Operation, therefore be not considered as limiting the invention.
In the present invention unless specifically defined or limited otherwise, fisrt feature in the second feature " on " or " down " can be with
It is that the first and second features directly contact or the first and second features pass through intermediary mediate contact.Moreover, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature be directly above or diagonally above the second feature, or be merely representative of
First feature horizontal height is higher than second feature.Fisrt feature can be under the second feature " below ", " below " and " below "
One feature is directly under or diagonally below the second feature, or is merely representative of first feature horizontal height less than second feature.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (12)
1. a kind of method for preparing biofilm packing characterized by comprising
(1) polypropylene is used, by 3D printing, forms porous matrix；
(2) mixture of nanoparticles is used, by 3D printing, forms sustained release in the side wall of the porous matrix and upper surface
Layer, to obtain slow release layer-porous matrix complex, the mixture of nanoparticles includes polypropylene, polyethylene glycol, maleic acid
Acid anhydride, antioxidant, polylactic acid and Zinc oxide nanoparticle, in the mixture of nanoparticles, the polypropylene, poly- second two
Alcohol, maleic anhydride, antioxidant, polylactic acid and Zinc oxide nanoparticle mass ratio be 74.41:3.68:1.16:18.4:
2.32:0.97, wherein the molecular weight of the polyethylene glycol is 200~600；The partial size of the Zinc oxide nanoparticle is 20-
100nm；
(3) heat treatment and treatment with ultraviolet light are carried out, successively to the slow release layer-porous matrix complex to obtain the life
Object film filler.
2. the method according to claim 1, wherein the specific surface area of the porous matrix is 260-300m2/m3。
3. the method according to claim 1, wherein the density of the biofilm packing is 0.92g/cm3。
4. the method according to claim 1, wherein the slow release layer with a thickness of 1~3mm, and the sustained release
Layer has the surface thickness deviation no more than 5%.
5. the method according to claim 1, wherein
The antioxidant includes selected from least one of antioxidant 1010, antioxidant 1076 and antioxidant 1135.
6. the method according to claim 1, wherein the mixture of nanoparticles is through the following steps that obtain
:
(2-1) carries out the polypropylene, the polyethylene glycol, the maleic anhydride and the Zinc oxide nanoparticle respectively
It is dried,
Wherein, the condition of the drying process is carried out to the polypropylene, the polyethylene glycol and the maleic anhydride are as follows: temperature
90 degrees Celsius of degree, time 2 h；To the withering condition of the Zinc oxide nanoparticle are as follows: 280 degrees Celsius of temperature,
Time 2 h；And
(2-2) is by the polypropylene, the polyethylene glycol, the maleic anhydride and the oxidation Jing Guo the drying process
Zinc nanoparticles are mixed and stirred for the antioxidant and the polylactic acid, to form the mixture of nanoparticles.
7. the method according to claim 1, wherein in step (3), the condition of the heat treatment are as follows: temperature
It is 50~80 degrees Celsius, the processing time is 20-30 minutes；
The condition of the treatment with ultraviolet light are as follows: ultraviolet lamp power density is 150W/cm2, light application time is 20~50 seconds.
8. a kind of biofilm packing, which is characterized in that the biofilm packing is described in any item by claim 1~7
Method preparation.
9. a kind of biofilm packing characterized by comprising
Polypropylene porous matrix；And
The side of the polypropylene porous matrix is arranged in mixture of nanoparticles slow release layer, the mixture of nanoparticles slow release layer
On wall and upper surface, the mixture of nanoparticles slow release layer with a thickness of 1~3mm, and the mixture of nanoparticles is slow
Releasing layer has the surface thickness deviation for being no more than 5%, and the biofilm packing is formed by 3D printing,
Wherein, the mixture of nanoparticles includes polypropylene, polyethylene glycol, maleic anhydride, antioxidant, polylactic acid and oxygen
Change zinc nanoparticles, the polypropylene, polyethylene glycol, maleic anhydride, antioxidant, polylactic acid and Zinc oxide nanoparticle
Mass ratio is 74.41:3.68:1.16:18.4:2.32:0.97；
The molecular weight of the polyethylene glycol is 200~600；
The partial size of the Zinc oxide nanoparticle is 20-100nm；
The antioxidant includes selected from least one of antioxidant 1010, antioxidant 1076 and antioxidant 1135.
10. biofilm packing according to claim 9, which is characterized in that the biofilm packing is floating stuffing.
11. biofilm packing according to claim 10, which is characterized in that the density of the biofilm packing is 0.92g/
cm3。
12. purposes of the described in any item biofilm packings of claim 8~11 in sewage treatment.
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