CN107324490B - Porous polymer material and preparation method and application thereof - Google Patents

Porous polymer material and preparation method and application thereof Download PDF

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CN107324490B
CN107324490B CN201710545118.6A CN201710545118A CN107324490B CN 107324490 B CN107324490 B CN 107324490B CN 201710545118 A CN201710545118 A CN 201710545118A CN 107324490 B CN107324490 B CN 107324490B
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continuous phase
porous material
phase
dispersed phase
putting
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CN107324490A (en
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汪汉奇
陆冲
李勇锋
马雪华
张俊超
张宇
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SHANGHAI QIYU BIOTECHNOLOGY Co.,Ltd.
East China University of Science and Technology
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Shanghai Qiyu Biotechnology Co ltd
East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2806—Anaerobic processes using solid supports for microorganisms
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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 provides a porous polymer material and a preparation method and application thereof. The porous material includes: the porous material comprises a dispersed phase A, a middle part B and a continuous phase C, wherein A, B and C are all polymer materials, the dispersed phase A is distributed in the continuous phase C in a form of tiny particles through the combination of the middle part B, the dispersed phase A is distributed in the continuous phase C in a form of tiny particles through the bonding effect of the middle part B, the aperture ratio of the porous material is 10-85%, the closed pore ratio is 0-10%, and the specific surface area is 50-900 m 2/g. The invention also provides a preparation method of the porous material and application of the porous material as an attachment carrier of microorganisms in sewage treatment. In a word, the invention provides a porous material which can provide a larger living environment for microorganisms, enrich the microorganisms, has good performance and is suitable for water pollution treatment, and the material can stably exist in a flowing water body, can be automatically degraded without special treatment, and opens up a new road for the field of water pollution treatment.

Description

Porous polymer material and preparation method and application thereof
Technical Field
The invention relates to the field of materials, in particular to a porous polymer material and a preparation method and application thereof.
Background
Water is one of indispensable conditions for the survival of terrestrial organisms, and no life exists after leaving the water source. However, as the world population increases and the industrialization process accelerates, on the one hand, the human demand for water resources expands at an alarming rate; on the other hand, increasingly water pollutes water resources available for human beings when eating silkworm. Therefore, the reasonable utilization and protection of the current earth water source are extremely important.
Conservation of water resources begins with the disposal of contaminated water sources. The source of water pollution mainly comes from domestic water, industrial wastewater and agricultural wastewater, and a large amount of pollutants exist in the water, and if the water is directly discharged into a natural water body without treatment, the water pollution inevitably causes serious pollution and deterioration of water resources. The nitrogen-containing compound is one of the common pollutants in the sewage, and the pollution of the nitrogen-containing sewage to natural water bodies is more serious in recent years. The nitrogen mainly comes from human daily domestic garbage and industrial and agricultural wastewater, the main forms of the nitrogen are organic nitrogen, ammonia nitrogen, nitric acid nitrogen and nitrous acid nitrogen, and the nitrogen in various forms can be mutually converted under different water body conditions, so that secondary pollution is often caused, and the treatment is difficult. Excessive nitrogen level in the water body can affect the survival of aquatic animals, the eutrophication phenomenon of massive proliferation of aquatic plants can also occur, and the human health is more harmful to drinking. Therefore, the efficient removal of nitrogen pollution existing in natural water is an urgent problem to be solved.
At the present stage, there are three main methods for sewage treatment in the industry: physical, chemical and biological methods. The physical method is to separate the suspended pollutants in the wastewater by using physical action. The chemical principle is a treatment method which utilizes the principle and method of chemical reaction to separate and recycle the pollutants in the wastewater or change the properties of the pollutants to change the pollutants from harmful to harmless. The biological method mainly utilizes the life activity process of microorganisms to transfer and convert pollutants in the wastewater, thereby purifying the wastewater. The physical method and the chemical method usually need to use large-scale instruments or add other medicaments when being implemented, so that the method has the defects of high cost, complex process, low treatment efficiency and the like, and the biological treatment method is the most common method in sewage treatment due to the characteristics of simplicity, convenience, easiness, good treatment effect and the like.
As described above, the biological treatment method requires the use of life activities of microorganisms and the like to consume or convert these pollutants, thereby removing the pollutants from the water body. The effectiveness of the biological treatment is therefore directly dependent on the action exerted by the microorganisms used. The method is mainly used for removing nitrogen pollution in the water body by depending on the combined action of some nitrifying bacteria and denitrifying bacteria, wherein the nitrifying bacteria convert nitrogen in various forms into nitrate nitrogen through nitrification, and the denitrifying bacteria convert the nitrate nitrogen into nitrogen through denitrification, so that the nitrogen pollution in the water body is removed. The role played by denitrifying bacteria directly determines the nitrogen removal capacity of the process.
Because the existing commonly used denitrifying bacteria are heterotrophic bacteria, if the denitrifying bacteria are expected to complete the nitrogen removal process, certain energy is often required to be provided for the denitrifying bacteria, and the energy supply to the denitrifying bacteria is mainly realized by adding a carbon source into a water body in the prior art. Compared with liquid carbon sources, solid carbon sources have the advantages of being not easy to run off along with water, not easy to cause secondary pollution and the like, and become the most common carbon source type. And the solid carbon source also has a surface with a certain area, and can be provided for a living place of denitrifying bacteria, so that the denitrifying bacteria can form a bacterial film on the surface of the denitrifying bacteria, thereby being not easily influenced by external conditions such as water flow and the like, and better performing a nitrogen removal process. Therefore, the selection of a proper solid carbon source and the modification of the solid carbon source to make the solid carbon source have a larger surface area for the attachment of bacteria become the key point of the biological treatment method.
Chinese patent application CN104140522A discloses a degradable polyhydroxyalkanoate, which is prepared by selecting renewable resources without load on environment as main monomers and respectively performing condensation polymerization with bio-based monomers to prepare a novel degradable polyhydroxyalkanoate, but the scheme is only to polymerize and mix different monomers, and there is no description about the use of materials. The other chinese patent application CN102921047A discloses a method for preparing porous biomaterial, which comprises physically removing impurities from the tissue by using collagen material derived from natural tissue, and preparing porous material by a series of steps such as pretreatment, swelling treatment, osmotic pressure adjustment, chemical crosslinking, washing, and freeze-drying, wherein the pores of the material are derived from the collagen material itself and are formed by simple physical processing. But the material cannot stably exist in the water body because the material is derived from biological tissues.
Disclosure of Invention
The invention aims to provide a porous material, a preparation method and application thereof, so as to solve the problem that a carrier material which has good performance, can provide a larger living environment for microorganisms and is suitable for water pollution treatment is lacked in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
according to a first aspect of the present invention, there is provided a porous material comprising: the disperse phase A, the middle part B and the continuous phase C are all polymer materials, and the disperse phase A is distributed in the continuous phase C in the form of tiny particles through the bonding effect of the middle part B. The dispersed phase A is distributed in the continuous phase C in the form of tiny particles through the bonding effect of the middle part B, the aperture ratio of the porous material is 10-85%, the closed pore ratio is 0-10%, and the specific surface area is 50-900 m2/g。
Preferably, pores are present between the dispersed phase a and the continuous phase C, and at least a part of the outer surface of the dispersed phase a distributed in the form of fine particles is bonded to the inner and outer surfaces of the continuous phase C by the adhesive action of the intermediate portion B.
The continuous phase is a substance for dispersing other substances in a system, and the dispersed phase is a substance dispersed in another substance by being dispersed as fine particles. The substance C for half-wrapping the dispersed phase A and the intermediate portion B is called a continuous phase, and the substance A dispersed in the continuous phase C and bonded to the surface of C by the action of the intermediate portion B is called a dispersed phase.
Preferably, the softening temperature of the material used for the intermediate portion B is lower than the softening temperature of the material used for the continuous phase C, and the softening temperature of the material used for the continuous phase C is lower than the softening temperature of the material used for the dispersed phase A.
The softening temperature is a temperature at which the three polymer materials A, B and C used begin to soften, i.e., a temperature at which the state of the polymer materials gradually changes from a solid state to a liquid state. The softening temperature corresponds to the melting point (Tm) for semi-crystalline polymers and the glass transition temperature (Tg) for amorphous polymers. The softening temperature value of each material can be determined by Differential Scanning Calorimetry (DSC).
Preferably, the cooling shrinkage of the intermediate portion B is greater than the cooling shrinkage of the dispersed phase a and the continuous phase C. More preferably, the cooling shrinkage of the intermediate portion B is greater than the cooling shrinkage of the dispersed phase a, and the cooling shrinkage of the dispersed phase a is greater than the cooling shrinkage of the continuous phase C.
The cooling shrinkage rate is a volume shrinkage rate of a melt of a material in a process of cooling the melt from a liquid state at a melting point temperature to a room temperature to a solid state. The cooling shrinkage rate is referred to the 9 th part of plastic unsaturated polyester resin (up-r) in the national standard GB/T24148.9-2014: the total volume shrinkage was measured by the method described in "measurement of Total volume shrinkage".
Further, the outer surface of the continuous phase C has a number of channels connected to the dispersed phase a, said channels communicating with the pores present between the dispersed phase a and the continuous phase C.
Preferably, the polymeric material is a biodegradable material.
The dispersed phase A, the middle part B and the continuous phase C are respectively one or more than one of polyester, polyethylene glycol, poly (butylene adipate/terephthalate), polyvinyl alcohol, polysaccharide, starch, cellulose, chitin and collagen.
It should be understood that the three materials of the dispersed phase a, the middle part B and the continuous phase C are different from each other, but since the names of these materials are general names of a class of materials, the three materials may be different materials in the same class of materials, even different brands of products of the same material, as long as they are not completely the same.
It should also be understood that the three parts of the dispersed phase a, the intermediate part B and the continuous phase C may also be a mixture of several materials in terms of material selection.
Wherein, the polyester is a general name of a polymer obtained by condensation polymerization of polyalcohol and polybasic acid, preferably, the polyester is selected from one or more of polyhydroxyalkanoate, polylactic acid, polycaprolactone and butanediol ester copolymer. The polyhydroxyalkanoate is an intracellular polyester synthesized by many bacteria, and exists mainly as a storage substance of a carbon source and an energy source in an organism.
The polyhydroxyalkanoate is selected from one or more of poly 3-hydroxybutyrate, poly 3-hydroxyvalerate, poly 3-hydroxyhexanoate, poly 3-hydroxyoctanoate, poly hydroxybutanoate valerate and poly 3-hydroxybutyrate 4-hydroxybutyrate.
The polysaccharide is selected from one or more of starch, glycogen, cellulose, chitin, inulin and agar.
The disperse phase A is preferably a material which exists in a relatively uniform powder or particle state so as to be convenient for processing and forming, the sphericity of the disperse phase A is greater than 0.7, the particle size is 0.1-1 micron, and the particle size distribution coefficient is less than 1.2.
The intermediate part B is preferably a material which has a certain adhesive effect after melting and resolidification, so that the dispersed phase A can be better bonded to the inner surface of the continuous phase C.
The continuous phase C is preferably a material with a slightly higher mechanical strength to ensure that the final product has a strength that meets the use conditions.
Wherein, the sphericity refers to the ratio of the surface area of a sphere having the same volume as an object to the surface area of the object, and the more the sphericity is close to 1, the more the shape is close to a regular sphere, and the parameter can be determined by a particle image analyzer. In the present invention, for the biodegradable material used for the dispersed phase a, particles of the material a having a sphericity of 0.95 are most preferable. The particle size refers to the diameter of the particles and can be measured by a laser particle sizer. In the present invention, for the biodegradable material used in the dispersed phase A, particles having a particle size of 0.5 μm are most preferable. The particle size distribution coefficient is used for representing the uniformity of particle diameter distribution, the closer the particle size distribution coefficient of the particles is to 1, the more uniform the size distribution of the particles is, and the parameter can also be tested by a laser particle sizer. In the present invention, for the biodegradable material used for the dispersed phase a, particles having a particle size distribution coefficient of 1.05 are most preferable.
The porous material has an aperture ratio of 10-85%, a closed-cell ratio of 0-10%, and a specific surface area of 50-900 m2(ii) in terms of/g. Preferably, the porous material has an open porosity of 30 to 85%, a closed porosity of 0 to 2%, and a specific surface area of 100 to 900m2/g。
The porosity and the specific surface area of the porous material are large, and the porosity data refers to the part 1 of the measurement of the pore size distribution and the porosity of a solid material by a GB/T21650.1-2008 mercury intrusion method and a gas adsorption method in the national standard: the specific surface area is measured by the method in mercury intrusion method, and the specific surface area is measured by the gas adsorption BET method in GB/T19587-. The open porosity is the proportion of the volume of the pores which are present inside the material and are in communication with the outside to the total volume of the material, and the material obtained by the present invention has an open porosity of 85% most preferably. The closed porosity is the ratio of the volume of closed pores which exist in the material but are not communicated with the outside to the total volume of the material, and the material obtained by the invention has the most preferable closed porosity of 1%. The specific surface area is the total surface area per unit mass of the object, and for the material obtained by the invention, the specific surface area is most preferably 900m2/g。
According to a second aspect of the present invention, there is provided a method of preparing a porous material, the method comprising the steps of: 1) adding the polymer material used by the middle part B into a solvent, heating and stirring to dissolve the polymer material to obtain a solution of the material used by the middle part B as a first coating liquid; 2) mixing the polymer material used by the disperse phase A and the first coating liquid according to a certain proportion, uniformly coating, and putting the mixture into a vacuum drying oven to remove the solvent to obtain a first coating product; 3) adding the polymer material used by the continuous phase C into water, heating and stirring to dissolve the polymer material to obtain a solution of the continuous phase C as a second coating liquid; 4) mixing the first coating product obtained in the step 2) and the second coating liquid obtained in the step 3) according to a certain proportion, uniformly coating, and putting the mixture into a vacuum drying oven to remove the solvent to obtain a second coating product; 5) putting the second coating product obtained in the step 4) into a container with a certain shape, putting the container into a drying box, applying a certain pressure on the container, raising the temperature to be above the softening temperature of the continuous phase C and below the softening temperature of the dispersed phase A for a period of time, and slowly cooling to obtain a final coating product; 6) putting the final coating product obtained in the step 5) into a container, and vacuumizing the final coating product to obtain the porous material.
Among them, there are many solvents used in step 1), such as water, ethanol, dichloromethane, chloroform, acetone, ethyl acetate, N-dimethylformamide, tetrahydrofuran, toluene, and dimethylsulfoxide, and it should be understood that any solvent capable of dissolving the polymer used may be used, and various solvents may be selected according to the solubility of the material used for the intermediate portion B.
In the step 6), the aperture ratio of the porous material can be further improved, the closed-cell ratio is further reduced, and the use performance of the porous material is favorably improved.
In the preparation process of the porous material, the second coating product is required to be heated to a certain temperature which is higher than the softening temperature of the continuous phase C and lower than the softening temperature of the dispersed phase A, and then the material is cooled to room temperature to obtain the product. During this cooling process:
1. preferably, the cooling shrinkage of the continuous phase C is minimal, since the melting point of this portion is lower than but closest to the temperature to which the system is heated, so that upon cooling the portion is initially cooled to set the defining frame, and a smaller cooling shrinkage may leave a larger internal space for the product frame;
2. it is also preferable that the cooling shrinkage of the dispersed phase a is intermediate between the continuous phase C and the intermediate portion B, since this portion is not melted during the production of the product, but a certain cooling shrinkage may leave a larger space between the dispersed phase a and the continuous phase C as a framework;
3. more preferably, the cooling shrinkage of the intermediate part B is maximized, since the melting point of this part is the lowest, so that the shape is fixed during cooling, and the maximum cooling shrinkage can maximize the porosity between the dispersed phase a and the continuous phase C, thereby increasing the porosity of the material.
In the present invention, since the softening temperature of the material for the intermediate portion B is lower than that of the material for the continuous phase C and the softening temperature of the material for the continuous phase C is lower than that of the material for the dispersed phase a, in the step 5), in the process of raising the temperature to the temperature higher than the softening temperature of the continuous phase C and lower than the softening temperature of the dispersed phase a, the intermediate portion B is first softened and melted to coat the surface of the dispersed phase a, and then the continuous phase C is gradually melted and softened to coat the coated product of the intermediate portion B and the dispersed phase a again.
Therefore, in this production method, it is preferable that the cooling shrinkage of the intermediate portion B is larger than those of the dispersed phase a and the continuous phase C. More preferably, the cooling shrinkage of the intermediate portion B is greater than the cooling shrinkage of the dispersed phase a, and the cooling shrinkage of the dispersed phase a is greater than the cooling shrinkage of the continuous phase C.
According to a third aspect of the present invention, there is also provided the use of a porous material as an attachment carrier for microorganisms in wastewater treatment.
On one hand, the material used by the carrier can be used as a carbon source for bacteria to carry out a nitrogen removal process; on the other hand, the porous structure of the carrier can supply bacteria living places, so that bacteria can be attached and gathered on the inner pores and the outer surface of the carrier, thereby improving the concentration of the bacteria in unit water body and improving the efficiency of sewage treatment.
Compared with the prior art, the porous material and the preparation method and the application thereof provided by the invention have the following remarkable beneficial effects:
firstly, the porous material provided by the invention has a large number of pores for microorganisms to attach and live, and the microorganisms can enter the pores to be gathered to form a bacterial film, so that the concentration of the microorganisms in a unit water body is improved, bacteria are not easy to be washed away by water flow, and the sewage treatment efficiency can be improved.
Secondly, the porous material provided by the invention is in a solid state and can stably exist in a flowing water body, and a carbon source is provided for the nitrogen removal microorganisms to maintain the life activities of the nitrogen removal microorganisms, so that the nitrogen removal behaviors of the microorganisms are continued all the time, and the nitrogen pollution in the water body is gradually removed.
And thirdly, the porous material is prepared by using the biodegradable material, so that the residual material of the porous material left in the water body can be automatically degraded without special treatment, and secondary pollution of the water body is avoided.
Finally, the pores of the porous material provided by the invention are attached by microorganisms, and simultaneously, the microorganisms consume part of the material along with the prolonging of the time, so the pores gradually become larger along with the passing of the time until the material is finally consumed, in the process, the amount of bacteria contained in the pores gradually increases, and the treatment efficiency of the system also gradually increases.
In a word, the invention provides a porous material which can provide a larger living environment for microorganisms, enrich the microorganisms, has good performance and is suitable for water pollution treatment, the material can stably exist in a flowing water body, can be automatically degraded without special treatment, the amount of bacteria contained in pores is gradually increased along with the prolonging of time, the treatment efficiency of a system is also gradually increased, and a new way is opened up for the field of water pollution treatment.
Drawings
Fig. 1 is a cross-sectional view of a porous material according to a preferred embodiment of the present invention, wherein:
1-dispersed phase a; 2-middle part B; 3-continuous phase C.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
1.1 adding polyvinyl alcohol (softening temperature is 220 ℃ and cooling shrinkage rate is 5%) used by the middle part B into water, heating and stirring to dissolve the polyvinyl alcohol to obtain a solution of a material used by the middle part B as a first coating liquid;
1.2 grinding polyethylene glycol (softening temperature is 50 ℃, cooling shrinkage rate is 8%) used by the disperse phase A into powder (average sphericity of the powder is 0.5, average particle size is 0.9 micron, particle size distribution coefficient is 1.5), mixing the powder with a first coating liquid according to a certain proportion, uniformly coating, putting the powder into a vacuum drying oven, and completely removing moisture to obtain a first coating product;
1.3 diluting the acrylic resin (solid content is styrene-acrylate copolymer, softening temperature is 90 ℃, cooling shrinkage is 1%) emulsion used for the continuous phase C, and then ultrasonically oscillating the emulsion into uniform emulsion to obtain the emulsion of the continuous phase C as a second coating liquid;
1.4, uniformly mixing and coating the first coating product obtained in the step 1.2 and the second coating liquid obtained in the step 1.3 according to a certain proportion, and putting the mixture into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
1.5 putting the second coated product obtained in the step 1.4 into a container with a certain shape, putting the container into a drying oven, applying a certain pressure on the container, raising the temperature to 230 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and cooling to room temperature to obtain the porous material.
Example 2
2.1 adding polyethylene glycol (softening temperature is 50 ℃, cooling shrinkage rate is 8%) used by the middle part B into water, heating and stirring to dissolve the polyethylene glycol to obtain a solution of a material used by the middle part B as a first coating liquid;
2.2, uniformly mixing and coating polyvinylpyrrolidone powder (the softening temperature is 130 ℃, the cooling shrinkage rate is 6%, the average sphericity of the powder is 0.55, the average particle size is 0.85 micrometer, and the particle size distribution coefficient is 1.52) used by the disperse phase A and first coating liquid according to a certain proportion, putting the mixture into a vacuum drying oven, and completely removing moisture to obtain a first coating product;
2.3 adding polycaprolactone (softening temperature is 62 ℃, cooling shrinkage is 10%) used by the continuous phase C into dichloromethane, sealing and stirring to dissolve the polycaprolactone to obtain a second coating liquid;
2.4 mixing the first coating product obtained in the step 2.2 and the second coating liquid obtained in the step 2.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
2.5 putting the second coated product obtained in the step 2.4 into a container with a certain shape, putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 80 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and cooling to room temperature to obtain the porous material.
Example 3
3.1 adding the material used in the middle part B, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the material to obtain a solution of the material used in the middle part B as a first coating liquid;
3.2, uniformly mixing and coating polyvinyl alcohol powder (the softening temperature is 220 ℃, the cooling shrinkage rate is 5%, the average sphericity of the powder is 0.6, the average particle size is 0.7 micron, and the particle size distribution coefficient is 1.45) used by the disperse phase A and the first coating liquid according to a certain proportion, putting the mixture into a vacuum drying oven, and completely removing the solvent to obtain a first coating product;
3.3 diluting the acrylic resin (containing solid styrene-acrylate copolymer with softening temperature of 90 ℃ and cooling shrinkage of 1%) emulsion used for the continuous phase C, and then ultrasonically oscillating the emulsion into uniform emulsion to obtain the emulsion of the continuous phase C as a second coating liquid;
and 3.4, uniformly mixing and coating the first coating product obtained in the step 3.2 and the second coating liquid obtained in the step 3.3 according to a certain proportion, and putting the mixture into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
3.5 putting the second coated product obtained in the step 3.4 into a container with a certain shape, putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 100 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and cooling to room temperature to obtain the porous material.
Example 4
4.1 adding the material used in the middle part B, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the material to obtain a solution of the material used in the middle part B as a first coating liquid;
4.2, uniformly mixing and coating polyvinylpyrrolidone powder (the softening temperature is 130 ℃, the cooling shrinkage rate is 6%, the average sphericity of the powder is 0.55, the average particle size is 0.85 micrometer, and the particle size distribution coefficient is 1.52) used by the disperse phase A and the first coating liquid according to a certain proportion, putting the mixture into a vacuum drying oven, and completely removing moisture to obtain a first coating product;
4.3 diluting the acrylic resin (containing solid styrene-acrylate copolymer with softening temperature of 90 ℃ and cooling shrinkage of 1%) emulsion used for the continuous phase C, and ultrasonically oscillating the emulsion into uniform emulsion to obtain the emulsion of the continuous phase C as a second coating liquid;
4.4, uniformly mixing and coating the first coating product obtained in the step 4.2 and the second coating liquid obtained in the step 4.3 according to a certain proportion, and putting the mixture into a vacuum drying oven to completely remove the solvent to obtain a second coating product;
4.5 putting the second coating product obtained in the step 4.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 100 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling to the room temperature at the speed of 1 ℃/min to obtain the porous material.
Example 5
5.1 adding the material used in the middle part B, namely polyethylene glycol (the softening temperature is 50 ℃, and the cooling shrinkage rate is 8%) into water, stirring to dissolve the polyethylene glycol to obtain a solution of the material used in the middle part B as a first coating liquid;
5.2 mixing the poly-3-hydroxybutyrate powder (the softening temperature is 175 ℃, the cooling shrinkage is 5%, the average sphericity of the powder is 0.58, the average particle size is 0.8 micron, the particle size distribution coefficient is 1.47) used by the disperse phase A and the first coating liquid according to a certain proportion, uniformly coating, putting into a vacuum drying oven, and completely removing moisture to obtain a first coating product;
5.3 diluting the acrylic resin (containing solid styrene-acrylate copolymer with softening temperature of 90 ℃ and cooling shrinkage of 1%) emulsion used for the continuous phase C, and ultrasonically oscillating the emulsion into uniform emulsion to obtain the emulsion of the continuous phase C as a second coating liquid;
and 5.4, uniformly mixing and coating the first coating product obtained in the step 5.2 and the second coating liquid obtained in the step 5.3 according to a certain proportion, and putting the mixture into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
5.5 putting the second coating product obtained in the step 5.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 100 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the speed of 1 ℃/min to obtain a final coating product;
5.6 putting the final coating product obtained in the step 5.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
The cross-sectional view of the porous material is shown in fig. 1, and it can be seen from the figure that the dispersed phase a is distributed in the continuous phase C in the form of fine particles through the bonding effect of the intermediate part B, pores exist between the dispersed phase a and the continuous phase C, the outer surface of the continuous phase C has a plurality of channels connected to the dispersed phase a, and the channels are communicated with the pores existing between the dispersed phase a and the continuous phase C.
Example 6
6.1 adding the biodegradable material selected by the middle part B, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the polycaprolactone to obtain a solution of the material used by the middle part B as a first coating liquid;
6.2 mixing the biodegradable material used in the disperse phase A, namely poly-3-hydroxybutyrate powder particles (the softening temperature is 175 ℃, the cooling shrinkage rate is 5%, the average sphericity of the powder is 0.56, the average particle size is 0.82 micron, the particle size distribution coefficient is 1.48) and the first coating liquid according to a certain proportion, uniformly coating, putting into a vacuum drying oven, and completely removing the solvent to obtain a first coating product;
6.3 adding a biodegradable material used for the continuous phase C, namely poly (butylene adipate/terephthalate) (the softening temperature is 115 ℃ and the cooling shrinkage rate is 0.8%) into the trichloromethane, sealing and stirring to dissolve the mixture to obtain a solution of the continuous phase C as a second coating liquid;
6.4 mixing the first coating product obtained in the step 6.2 and the second coating liquid obtained in the step 6.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
6.5 putting the second coating product obtained in the step 6.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 120 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain a final coating product;
6.6 putting the final coating product obtained in the step 6.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 7
7.1 adding the biodegradable material selected by the middle part B, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the polycaprolactone to obtain a solution of the material used by the middle part B as a first coating liquid;
7.2 mixing the biodegradable material used in the disperse phase A, namely poly 3-hydroxybutyrate valerate powder particles (the softening temperature is 170 ℃, the cooling shrinkage rate is 6%, the average sphericity of the powder is 0.6, the average particle size is 0.78 micron, the particle size distribution coefficient is 1.35) and the first coating liquid according to a certain proportion, uniformly coating, putting into a vacuum drying oven, and completely removing the solvent to obtain a first coating product;
7.3 adding a biodegradable material used for the continuous phase C, namely poly (butylene adipate/terephthalate) (the softening temperature is 115 ℃, and the cooling shrinkage rate is 0.8%) into the trichloromethane, sealing and stirring to dissolve the mixture to obtain a solution of the continuous phase C as a second coating liquid;
7.4 mixing the first coating product obtained in the step 7.2 and the second coating liquid obtained in the step 7.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
7.5 putting the second coating product obtained in the step 7.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 120 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain a final coating product;
7.6 putting the final coating product obtained in the step 7.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 8
8.1 adding the biodegradable material selected for the middle part B, namely polyethylene glycol (the softening temperature is 50 ℃, and the cooling shrinkage rate is 8%) into water, stirring to dissolve the polyethylene glycol to obtain a solution of the material for the middle part B as a first coating liquid;
8.2 sieving and other treatments are carried out on biodegradable materials used in the disperse phase A, namely mixed powder particles (the softening temperature is 173 ℃, the cooling shrinkage rate is 5.5%) of poly 3-hydroxybutyrate and poly 3-hydroxybutyrate valerate, and through the test of a particle image analyzer laser particle sizer, powder particles with the average sphericity of 0.75, the average particle size of 0.92 microns and the particle size distribution coefficient of 1.15 are selected and obtained, and the powder particles and the first coating liquid are mixed according to a certain proportion and coated uniformly, and are put into a vacuum drying oven to remove moisture, so as to obtain a first coating product;
8.3 adding a biodegradable material used for the continuous phase C, namely polylactic acid (the softening temperature is 160 ℃, and the cooling shrinkage rate is 0.3%) into the trichloromethane, sealing and stirring to dissolve the polylactic acid to obtain a solution of the continuous phase C as a second coating liquid;
8.4 mixing the first coating product obtained in the step 8.2 and the second coating liquid obtained in the step 8.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
8.5 putting the second coating product obtained in the step 8.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 160 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain a final coating product;
8.6 putting the final coating product obtained in the step 8.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 9
9.1 adding the biodegradable material selected by the middle part B, namely the mixture of polycaprolactone and poly (adipic acid)/butylene terephthalate (the complete softening temperature is 115 ℃, the average cooling shrinkage is about 10%) into trichloromethane, sealing and stirring to dissolve the mixture to obtain a solution of the material used by the middle part B as a first coating liquid;
9.2 sieving and other treatments are carried out on biodegradable materials used in the disperse phase A, namely powder particles (the softening temperature is 170 ℃ and the cooling shrinkage rate is 6%) of poly-3-hydroxybutyrate valerate, and the powder particles are selected to obtain powder particles with the average sphericity of 0.75, the average particle size of 0.94 microns and the particle size distribution coefficient of 1.13 through the test of a laser particle sizer of a particle image analyzer and are mixed with first coating liquid according to a certain proportion for uniform coating, and the powder particles and the first coating liquid are put into a vacuum drying oven to remove moisture, so as to obtain a first coating product;
9.3 adding a biodegradable material used for the continuous phase C, namely polylactic acid (the softening temperature is 160 ℃, and the cooling shrinkage rate is 0.3%) into the trichloromethane, sealing and stirring to dissolve the polylactic acid to obtain a solution of the continuous phase C as a second coating liquid;
9.4 mixing the first coating product obtained in the step 9.2 and the second coating liquid obtained in the step 9.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
9.5 putting the second coating product obtained in the step 9.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 160 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the mixture to room temperature at the speed of 1 ℃/min to obtain the porous material;
9.6 putting the final coating product obtained in the step 9.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 10
10.1 adding a biodegradable material selected by the middle part B, namely polyethylene glycol (the softening temperature is 50 ℃, and the cooling shrinkage rate is 8%) into water, stirring to dissolve the polyethylene glycol to obtain a solution of the material used by the middle part B as a first coating liquid;
10.2, sieving and other treatment are carried out on biodegradable materials used in the disperse phase A, namely powder particles of poly 3-hydroxybutyrate valerate (the softening temperature is 170 ℃ and the cooling shrinkage rate is 6%), and through the test of a particle image analyzer laser particle sizer, powder particles with the average sphericity of 0.72, the average particle size of 0.9 micron and the particle size distribution coefficient of 1.18 are selected and obtained, and the powder particles and the first coating liquid are mixed and coated uniformly according to a certain proportion and are put into a vacuum drying oven to remove moisture, so as to obtain a first coating product;
10.3 adding a biodegradable material used for the continuous phase C, namely poly (butylene adipate/terephthalate) (the softening temperature is 115 ℃, and the cooling shrinkage rate is 0.8%) into the trichloromethane, sealing and stirring to dissolve the mixture to obtain a solution of the continuous phase C as a second coating liquid;
10.4 mixing the first coating product obtained in the step 10.2 and the second coating liquid obtained in the step 10.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
10.5 putting the second coating product obtained in the step 10.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 120 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain a final coating product;
10.6, putting the final coating product obtained in the step 10.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 11
11.1 adding the biodegradable material selected by the middle part B, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the polycaprolactone to obtain a solution of the material used by the middle part B as a first coating liquid;
11.2, sieving and other treatment are carried out on biodegradable materials used in the disperse phase A, namely powder particles of poly-3-hydroxybutyrate (the softening temperature is 175 ℃ and the cooling shrinkage rate is 5%), and through the test of a laser particle sizer of a particle image analyzer, the powder particles with the average sphericity of 0.85, the average particle size of 0.7 micron and the particle size distribution coefficient of 1.1 are selected and obtained, and the powder particles and the first coating liquid are mixed and coated uniformly according to a certain proportion and are put into a vacuum drying oven to completely remove the solvent, so as to obtain a first coating product;
11.3 adding a biodegradable material used for the continuous phase C, namely poly (butylene adipate/terephthalate) (the softening temperature is 115 ℃, and the cooling shrinkage rate is 0.8%) into the trichloromethane, sealing and stirring to dissolve the mixture to obtain a solution of the continuous phase C as a second coating liquid;
11.4, uniformly mixing and coating the first coating product obtained in the step 11.2 and the second coating liquid obtained in the step 11.3 according to a certain proportion, and putting the mixture into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
11.5 putting the second coating product obtained in the step 11.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 120 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain a final coating product;
11.6 putting the final coating product obtained in the step 11.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Example 12
12.1 adding the biodegradable material selected for the middle part B, namely polyethylene glycol (the softening temperature is 50 ℃, and the cooling shrinkage rate is 8%) into water, heating and stirring to dissolve the biodegradable material to obtain a solution of the material for the middle part B as a first coating liquid;
12.2 sieving and other treatment are carried out on biodegradable materials used in the disperse phase A, namely powder particles of poly 3-hydroxybutyrate valerate (the softening temperature is 170 ℃ and the cooling shrinkage rate is 6%), and through the test of a particle image analyzer and a laser particle sizer, the powder particles with the average sphericity of 0.95, the average particle size of 0.5 micron and the particle size distribution coefficient of 1.05 are selected and obtained, and are mixed with the first coating liquid according to a certain proportion and coated uniformly, and the mixture is put into a vacuum drying oven to remove moisture, so as to obtain a first coating product;
12.3 adding a biodegradable material used for the continuous phase C, namely polylactic acid (the softening temperature is 160 ℃, and the cooling shrinkage rate is 0.3%) into dichloromethane, sealing and stirring to dissolve the polylactic acid to obtain a solution of the continuous phase C as a second coating liquid;
12.4 mixing the first coating product obtained in the step 12.2 and the second coating liquid obtained in the step 12.3 according to a certain proportion, uniformly coating, and putting into a vacuum drying oven to completely remove the solvent to obtain a second coating product.
12.5 putting the second coating product obtained in the step 12.4 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 165 ℃ to melt the middle part B and the continuous phase C, keeping the temperature for 60min, and then slowly cooling to room temperature at the rate of 1 ℃/min at room temperature to obtain the final coating product;
12.6 putting the final coating product obtained in the step 12.5 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the porous material.
Comparative example 1
13.1 adding the material used by the continuous phase C, namely polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%) into dichloromethane, sealing and stirring to dissolve the polycaprolactone to obtain a solution of the material used by the continuous phase C as a first coating liquid;
13.2 sieving the biodegradable material powder used in the dispersed phase A, namely poly 3-hydroxybutyrate valerate (softening temperature is 170 ℃, cooling shrinkage is 0.5%) powder particles, and selecting the powder particles with the average sphericity of 0.95, the average particle size of 0.5 and the particle size distribution coefficient of 1.05 through the tests of a particle image analyzer and a laser particle sizer, uniformly mixing and coating the powder particles with the first coating liquid according to a certain proportion, putting the powder particles into a vacuum drying oven to remove moisture, and obtaining a first coating product;
13.3 putting the first coating product obtained in the step 13.2 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 80 ℃ to melt the continuous phase C, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain the final coating product;
13.4 putting the final coating product obtained in the step 13.3 into a container capable of forming negative pressure, and vacuumizing the final coating product to obtain the material.
Comparative example 2
14.1 adding the material used in the middle part B, namely polyethylene glycol (softening temperature is 50 ℃, cooling shrinkage rate is 8%) into water, stirring to dissolve the material to obtain a solution of the material used in the middle part B as a first coating liquid;
14.2, sieving and other treatment are carried out on biodegradable material powder used in the disperse phase A, namely powder particles of poly-3-hydroxybutyrate (the softening temperature is 175 ℃ and the cooling shrinkage rate is 0.7%), and through the test of a particle image analyzer laser particle sizer, powder particles with the average sphericity of 0.95, the average particle size of 0.5 and the particle size distribution coefficient of 1.05 are selected and obtained, and the powder particles and the first coating liquid are mixed according to a certain proportion and coated uniformly, and then the mixture is put into a vacuum drying oven to completely remove the solvent, so as to obtain a first coating product;
14.3 putting the first coating product obtained in the step 14.2 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 70 ℃, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain the final coating product;
14.4 placing the final coated product obtained in 14.3 into a container capable of forming negative pressure, and vacuumizing the final coated product to obtain the material.
Comparative example 3
15.1 adding the material used in the middle part B, namely polyethylene glycol (the softening temperature is 50 ℃, and the cooling shrinkage rate is 8%) into water, stirring to dissolve the polyethylene glycol to obtain a solution of the material used in the middle part B as a first coating liquid;
15.2, sieving and other treatment are carried out on the biodegradable material powder used for the continuous phase C, namely powder particles obtained by crushing polycaprolactone (the softening temperature is 62 ℃ and the cooling shrinkage rate is 10%), and the powder particles are tested by a particle image analyzer and a laser particle sizer to obtain powder particles with the average sphericity of 0.95, the average particle size of 0.5 and the particle size distribution coefficient of 1.05, and the powder particles and the first coating liquid are mixed and coated uniformly according to a certain proportion and then are put into a vacuum drying oven to remove moisture, so as to obtain a first coating product;
15.3 putting the first coating product obtained in the step 15.2 into a container with a certain shape, then putting the container into a drying box, applying a certain pressure on the container, raising the temperature to 70 ℃, keeping the temperature for 60min, and then slowly cooling the product to room temperature at the rate of 1 ℃/min to obtain the final coating product;
15.4 placing the final coated product obtained in 15.3 into a container capable of forming negative pressure, and vacuumizing the final coated product to obtain the material.
According to the comparative examples 1, 2 and 3, it can be seen that the porous material provided by the present invention has the disadvantages of the dispersed phase a, the intermediate portion B and the continuous phase C.
Finally, the invention carries out the comparative test of the physical property and the nitrogen removal effect on the raw materials used in the examples 1 to 12 and the comparative examples 1 to 3 and the obtained porous materials, and the test instrument or the method is as follows:
1) testing of softening point of raw material: differential Scanning Calorimetry (DSC);
2) testing the sphericity of the powder: a particle image analyzer;
3) testing of powder particle size and particle size distribution coefficient: marvens laser particle sizer Zetasizer Nano ZS;
4) testing of the thermal shrinkage of the material: referring to the national Standard GB/T24148.9-2014 Plastic unsaturated polyester resin (up-r) part 9: the total volume shrinkage rate was measured by the method described in "(determination of total volume shrinkage rate)";
5) and (3) porosity testing: the pore size distribution and porosity of the solid material are measured by referring to the GB/T21650.1-2008 mercury intrusion method and the gas adsorption method part 1: the method in mercury intrusion method is used for measurement;
6) specific surface area test: the determination is carried out according to the method in the national standard GB/T19587-2004 gas adsorption BET method for determining the specific surface area of the solid substance;
7) nitrate nitrogen content test: the determination is carried out according to the method in the national environmental protection standard HJ 636 and 2012 ultraviolet spectrophotometry for determining total nitrogen in water quality of alkaline potassium persulfate digestion.
The porous materials prepared in examples 1 to 12 and the materials prepared in comparative examples 1 to 3 were sampled, and a denitrification bacterial method was used for a denitrification test. The specific implementation method comprises the following steps: a glass column with connectors at the upper end and the lower end is taken as a reactor, and water flow containing 50mg/L nitrate nitrogen is introduced from the connector at the lower end of the glass column and flows out from the connector at the upper end. Adding each prepared material into 13 glass column cavities, keeping the same mass, adding activated denitrifying bacteria liquid accounting for 1 percent of the volume of the material into each reactor, keeping a lower water flow rate of 1L/h at the beginning stage to enable bacteria to grow and attach on the surface and in pores of the material, and then gradually adjusting the water flow rate to 10L/h to carry out the treatment process. And testing the nitrogen content data of the outlet water of the upper end of the reactor every 12 h.
The open, closed and specific surface area data of the material, as well as the data of the nitrogen content test, are summarized in the following table:
TABLE Experimental data for open cell content, closed cell content, specific surface area, and nitrogen content for each of the example and comparative example materials
Open cell content% Percentage of closed cells/%) Specific surface area/(m)2/g) Stable nitrate nitrogen concentration/(mg/L) Average nitrogen removal rate/(mg/(L x h))
Example 1 24 10 95 33 0.2
Example 2 25 8 130 27 0.24
Example 3 57 7 309 10 0.39
Example 4 65 9 351 11 0.41
Example 5 73 1 520 6 0.5
Example 6 78 2 786 5 0.9
Example 7 75 1 740 5.5 0.85
Example 8 76 1 750 6 0.8
Example 9 78 2 770 5 0.85
Example 10 79 1 806 2 0.92
Example 11 80 2 850 1 0.98
Example 12 85 1 890 0 1.1
Comparative example 1 10 3 51 40 0.1
Comparative example 2 12 2 62 39 0.11
Comparative example 3 15 3 70 37 0.15
Comparing the data in the table above, it can be seen that, from example 1 to example 12, the prepared porous materials each have a gradually increasing trend of the open pore ratio, a gradually decreasing trend of the closed pore ratio, which is substantially maintained at 1-2%, and a gradually increasing specific surface area, and accordingly the nitrogen removal performance of the material is gradually improved. In which examples 11 and 12 exhibited the best performance. Meanwhile, 3 comparative examples lack one component of the dispersed phase A, the middle part B and the continuous phase C respectively, and are poorer in material property and use effect than the materials of examples 1-12.
In addition, it can be found that the closed pore ratio of the porous materials of examples 5 to 12 is significantly reduced compared to that of examples 1 to 4, and thus, the evacuation treatment in step 6) can further increase the open pore ratio of the porous material, further reduce the closed pore ratio, and is beneficial to improving the service performance of the porous material.
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.

Claims (7)

1. A porous material, characterized in that it comprises: the porous material is characterized by comprising a dispersed phase A, a middle part B and a continuous phase C, wherein the dispersed phase A, the middle part B and the continuous phase C are all polymer materials, the dispersed phase A is distributed in the continuous phase C in a form of tiny particles through the bonding effect of the middle part B, the aperture ratio of the porous material is 10-85%, the closed pore ratio is 0-10%, the specific surface area is 50-900 m2/g, the softening temperature of the middle part B is lower than that of the continuous phase C, the softening temperature of the continuous phase C is lower than that of the dispersed phase A, the cooling shrinkage rate of the middle part B is larger than that of the dispersed phase A, and the cooling shrinkage rate of the dispersed phase A is larger than that of the continuous phase C.
2. The porous material according to claim 1, wherein pores exist between the dispersed phase A and the continuous phase C, and at least a part of the outer surface of the dispersed phase A distributed in the form of fine particles is bonded to the inner and outer surfaces of the continuous phase C by the adhesive action of the intermediate portion B.
3. The porous material according to claim 2, wherein the outer surface of the continuous phase C has a number of channels connected to the dispersed phase a, said channels communicating with the pores present between the dispersed phase a and the continuous phase C.
4. The porous material according to claim 1, wherein the dispersed phase A, the middle part B and the continuous phase C are selected from one or more of polyhydroxyalkanoate, polylactic acid, polycaprolactone, butanediol ester copolymer, polyethylene glycol, polybutylene adipate/terephthalate, polyvinyl alcohol, polysaccharide and collagen.
5. Porous material according to claim 4, wherein said polyhydroxyalkanoate is selected from one or more of poly-3-hydroxybutyrate, poly-3-hydroxyvalerate, poly-3-hydroxyhexanoate, poly-3-hydroxyoctanoate, polyhydroxybutyrate valerate, poly-3-hydroxybutyrate-4-hydroxybutyrate, and said polysaccharide is selected from one or more of starch, glycogen, cellulose, chitin, inulin, agar.
6. A method for preparing a porous material according to any one of claims 1 to 5, comprising the steps of:
1) adding the polymer material used by the middle part B into a solvent, heating and stirring to dissolve the polymer material to obtain a solution of the material used by the middle part B as a first coating liquid;
2) mixing the polymer material used by the disperse phase A and the first coating liquid according to a certain proportion, uniformly coating, and putting the mixture into a vacuum drying oven to remove the solvent to obtain a first coating product;
3) adding the polymer material used by the continuous phase C into water, heating and stirring to dissolve the polymer material to obtain a solution of the continuous phase C as a second coating liquid;
4) mixing the first coating product obtained in the step 2) and the second coating liquid obtained in the step 3) according to a certain proportion, uniformly coating, and putting the mixture into a vacuum drying oven to remove the solvent to obtain a second coating product;
5) putting the second coating product obtained in the step 4) into a container with a certain shape, putting the container into a drying box, applying a certain pressure on the container, raising the temperature to be above the softening temperature of the continuous phase C and below the softening temperature of the dispersed phase A for a period of time, and slowly cooling to obtain a final coating product;
6) putting the final coating product obtained in the step 5) into a container, and vacuumizing the final coating product to obtain the porous material.
7. Use of a porous material according to any one of claims 1 to 5 as an attachment carrier for microorganisms in sewage treatment.
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CN108529739B (en) * 2018-04-25 2021-03-05 上海祺宇生物科技有限公司 Porous composite microbial carrier and preparation method thereof
CN108726688B (en) * 2018-04-25 2021-05-04 上海祺宇生物科技有限公司 Porous carrier for water treatment and preparation method thereof
CN109231442B (en) * 2018-04-26 2020-04-21 知和环保科技有限公司 Drawer type reactor for removing nitrate nitrogen in water

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