CN111099745B - Efficient electrospun fiber biological membrane and preparation method thereof - Google Patents
Efficient electrospun fiber biological membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-efficiency electrospun fiber biological membrane and a preparation method thereof, wherein the biological membrane comprises a base material, the base material is used as a bottom material, N layers of high molecular polymer nano-fiber membranes are covered on the base material, N is more than or equal to 1 and less than or equal to 4, and liquid adhesive dissolved with composite strains is sprayed on the upper surface of at least one of the base material and the N layers of high molecular polymer nano-fiber membranes. The invention adopts the substrate and the electrospun membrane to form the biological membrane, the electrospun membrane covers the surface of the substrate, the bulkiness of the surface of the substrate and the bulkiness of the electrospun membrane are fully superposed, a plurality of three-dimensional small spaces are provided for the survival of bacteria and are not easy to fall off, and the biofilm formation amount of the biological membrane is increased. The covering of the electrospun membrane also plays a role in protecting the base material or the lower electrospun membrane, and simultaneously provides a good environment for the survival of bacteria due to the water absorption of the electrospun membrane.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a high-efficiency electrospun fiber biological membrane and a preparation method thereof.
Background
The micro-polluted water generally refers to water containing more types of pollutants, more complex properties and lower concentration. With the rapid development of industrial and agricultural in China, the pollution of pollutants discharged by people in the life and production processes to the quality of source water is more and more serious, and the problem of drinking water supply safety is widely regarded. At present, most of water plants in the world adopt conventional flocculation, sedimentation, filtration, disinfection and other treatment processes, and the conventional treatment processes mainly remove suspended matters, colloidal substances and bacteria in water and have low removal efficiency on soluble organic matters, ammonia nitrogen, nitrate nitrogen and the like in water. Therefore, the treatment technology of the slightly polluted source water has become an important and urgent research subject.
The advanced treatment technology of micro-polluted water mainly comprises an activated sludge method, a biological membrane hanging method and the like, wherein the biological membrane hanging method adopts a cell immobilization technology to fix microorganisms for sewage treatment on a matrix (biological membrane), and the matrix is reused for sewage treatment, so that the method has the advantages of simple and convenient operation, easy recovery, stable activity, strong adaptability and the like. One of the key factors of the microbial curing technology is to select a proper biological carrier (biological filler), and the existing biological filler has the problems of too small specific surface, too poor affinity and compatibility with microorganisms, serious film formation amount insufficiency and low efficiency. In addition, strains are required to be implanted into the conventional biological filler before use, and water treatment by a biological biofilm formation method cannot be performed under the condition that the strains cannot be implanted.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide an efficient electrospun fiber biofilm and a preparation method thereof, which significantly increase the specific surface of the biofilm and the hydrophilicity of the biofilm, so that the biofilm becomes a hydrophilic substance, and meanwhile, the biofilm can be used under the condition that a strain cannot be implanted.
The invention adopts the specific technical scheme that:
the efficient electrospun fiber biological membrane comprises a base material, wherein the base material is used as a bottom material, N layers of high molecular polymer nano fiber membranes are covered on the base material, N is more than or equal to 1 and less than or equal to 4, and liquid binders dissolved with composite strains are sprayed on the upper surfaces of at least one of the base material and the N layers of high molecular polymer nano fiber membranes.
Preferably, the polymer nanofiber membrane raw material is selected from Polyacrylonitrile (PAN), polyethersulfone resin (PES), polyamide 6(PA6), and polyvinylidene fluoride (PVDF), and each layer of polymer nanofiber membrane raw material is the same or different.
Preferably, the biofilm further comprises one or more of the following characteristics: firstly, the base material is a polyester base material; secondly, the high molecular polymer nanofiber membrane is formed by dissolving a high molecular polymer in an organic solvent to obtain a high molecular polymer solution, and then attaching the solution to the high molecular polymer nanofiber membrane on the upper layer or the lower layer of the base material through an electrostatic spinning process; thirdly, the liquid adhesive dissolved with the composite strains is dotted on the upper surface of the base material and/or each layer of the high molecular polymer nanofiber membrane in an airflow spraying or ultrasonic spraying mode; fourthly, the liquid binder is prepared from water, liquid egg white and starch according to a mass ratio of 5: 4: 1 in proportion; fifthly, in the liquid binder dissolved with the composite strain, the mass ratio of the composite strain to the liquid binder is 1: 35-45.
Preferably, the biofilm further comprises one or more of the following characteristics: firstly, when preparing a high molecular polymer nanofiber membrane, the concentration of a PAN solution is 8-12%, the concentration of a PES solution is 22-26%, the concentration of a PA6 solution is 20-25%, and the concentration of a PVDF solution is 8-12%; II, the organic solvent is N, N-Dimethylformamide (DMF) or formic acid; thirdly, in the liquid binder dissolved with the composite strain, the mass ratio of the composite strain to the liquid binder is 1: 40; fourthly, the polyester substrate is selected from PET, PBT and polyarylate; and fifthly, the electrostatic spinning process is a wet electrostatic spinning process or a melt electrostatic spinning process.
More preferably, the substrate is 3.2493mm-4.2350 mm; the total thickness of the high molecular polymer nanofiber membrane layer is 0.22um-0.34 um.
Correspondingly, the invention also provides a method for preparing the high-efficiency electrospun fiber biological membrane, which is characterized by comprising the following steps:
(1) preparing each high molecular polymer solution according to the proportion, firstly putting high molecular polymer powder into a glass beaker, then putting into an organic solvent, and uniformly stirring by using a mechanical stirrer at normal temperature to prepare each high molecular polymer solution;
(2) preparing a liquid binder dissolved with composite strains according to a ratio, putting liquid binder powder into a glass beaker, then putting the composite strains, and slowly stirring at normal temperature to prepare the liquid binder dissolved with the composite strains;
(3) starting the gas permeation combination device by taking the base material as a base material to enable the surface of the base material to have wet viscous airflow to pass through and form a wet viscous airflow space;
(4) in a wet viscous airflow space, selecting whether to decorate the liquid adhesive dissolved with the composite strains on the upper surface of the substrate in an airflow spraying or ultrasonic spraying manner according to the requirements of the prepared high-efficiency electrospun fiber biomembrane;
(5) in the wet viscous airflow space, starting an electrostatic spinning device to spray a high molecular polymer solution to the surface of the base material sprayed with the liquid binder, and electrospinning to form a high molecular polymer nanofiber membrane;
(6) in a wet viscous airflow space, selecting whether to decorate the liquid adhesive dissolved with the composite strains on the upper surface of the high molecular polymer nanofiber membrane electrospun in the last step in an airflow spraying or ultrasonic spraying manner according to the requirements of the prepared high-efficiency electrospun fiber biofilm;
(7) in the wet viscous airflow space, selecting whether to repeat the step (5) and/or the step (6) or not according to the requirement of the prepared high-efficiency electrospun fiber biological membrane;
(8) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage.
Preferably, in the preparation method, in the process of preparing the high molecular polymer solution, the stirring speed of the mechanical stirrer is 600r/min, and the stirring time is 6 hours.
Preferably, in the preparation method, in the process of preparing the liquid binder dissolved with the composite strain, the stirring speed is 200r/min, and the stirring time is 6 hours.
Gas permeation phase bonding method: by using the principle of gas permeation, the electrospun membrane can be better combined with a substrate under the condition of no damage under the constant temperature by using gas as a carrier to convey some special combinations.
The ultrasonic compounding machine is used for transmitting high-frequency vibration waves to the surfaces of two or more materials to be welded, and under the condition of pressurization, the surfaces of the materials are mutually rubbed to form fusion between molecular layers, so that the fusion of materials such as cloth and cloth, cloth and chemical fiber cotton, plastic film and plastic film, and the fusion of fabrics and materials such as glue-spraying cotton, non-woven fabrics and sponge are achieved, and the welding is completed. Its advantages are high speed, saving energy, high fusion strength, high electric conductivity, no spark and cold state processing. Based on this, the invention adopts the fixation of ultrasonic compounding to the edge of the biological membrane.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the substrate and the electrospun membrane to form the biological membrane, the electrospun membrane covers the surface of the substrate, the bulkiness of the surface of the substrate and the bulkiness of the electrospun membrane are fully superposed, a plurality of three-dimensional small spaces are provided for the survival of bacteria and are not easy to fall off, and the biofilm formation amount of the biological membrane is increased. The covering of the electrospun membrane also plays a role in protecting the base material or the lower electrospun membrane, and simultaneously provides a good environment for the survival of bacteria due to the water absorption of the electrospun membrane.
2. According to the invention, the liquid binder dissolved with the composite strains is sprayed on the base material and/or the electrospun membrane, so that the utilization rate of the whole biofilm is improved, the starting efficiency of the biofilm is influenced because the free permeation speed of the inoculated strains is slightly slow, and the overall efficiency is reduced, the starting efficiency of the biofilm can be improved by spraying the liquid binder dissolved with the composite strains, so that the overall efficiency is improved, and the liquid binder enhances the binding property between the membrane and the base material or between the membrane and the membrane, so that the membrane is not easy to fall off.
3. The invention sprays the liquid adhesive with the compound strain dissolved on the base material and/or the electrospinning film, and can still adopt a biological biofilm formation method for water treatment under the condition that the strain can not be inoculated.
4. In the process of preparing the biological membrane, the invention uses two special processing devices, namely a gas permeation combination device and an ultrasonic combination device, wherein the gas permeation combination device can strengthen the combination property between the three layers of membranes, and the ultrasonic combination device can fix the three layers of membranes so that the structure of the three layers of membranes cannot be scattered when the three layers of membranes are scoured.
Drawings
FIG. 1 is a schematic structural diagram of the high-efficiency electrospun fiber biological membrane described in example 1
FIG. 2 schematic diagram of the electrospinning process
FIG. 3 schematic diagram of spraying composite liquid process
In the figure: 1-a polyester substrate; 2-mixed liquid film; 3-PAN electrospun membrane; 4-PES electrospun membrane; 5-electrostatic spinning machine; 6-spraying machine; 7-receiving a plate; 8-mixed liquid of liquid binder and composite strain; 9-electrospinning
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
Example 1
Referring to fig. 1, the present embodiment provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PES electrospun membrane), including a substrate, the substrate is used as a base material, the PAN electrospun membrane is covered on the substrate, the PAN electrospun membrane is covered with PES electrospun membrane, wherein a liquid binder dissolved with a composite strain is sprayed on the upper surface of the substrate; and the upper surface of the PAN electrospun membrane is sprayed with a liquid binder dissolved with the composite strain.
The preparation method of the high-efficiency electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 24% PES solution, taking 480g of PES powder and 1520g of DMF (N, N-dimethylformamide) solvent, putting the PES powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PES powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) preparing a mixed solution according to the ratio of 40: 1, preparing a liquid binder and a composite strain (nitrobacteria: denitrifying bacteria: bacillus: pseudomonas: 5: 4: 6) according to a mass ratio of 2250g of the liquid binder and 50g of the composite strain, firstly adding the liquid binder and then adding the composite strain, stirring at a rotating speed of 200r/min for 6 hours at normal temperature by using a mechanical stirrer, and constantly paying attention to the fact that the temperature of a beaker is not higher than 40 ℃;
(4) processing of the biological membrane is horizontal processing, a polyester substrate (PET) is used as a horizontal winding material, a gas permeation combination device is started to horizontally flow through the whole processed polyester substrate, so that wet viscous airflow passes through the surface of the substrate, the surface of the substrate has high adsorbability, a wet viscous airflow space is formed, and as shown in figure 3, a liquid adhesive dissolved with composite strains is sprayed on the surface of the substrate;
(5) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PAN solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) after the step (4) is completed, covering the PAN electrospun membrane as shown in fig. 2, and spraying a liquid binder dissolved with the composite strains on the surface of the PAN electrospun membrane as shown in fig. 3;
(6) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PES solution to the polyester substrate (which passes through the polyester substrate horizontally) after the step (5) is completed, and covering the PES electrospun membrane as shown in FIG. 2;
(7) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage, wherein the compound strain can survive for 4 months.
In this example, PAN (polyacrylonitrile), which is a chemical substance, is obtained by radical polymerization of acrylonitrile, which is a monomer. The polyacrylonitrile has the advantages of good weather resistance and sun resistance, and can keep 77 percent of the original strength after being placed outdoors for 18 months. It is also resistant to chemical agents, in particular inorganic acids, bleaching powders, hydrogen peroxide and organic agents in general. PAN has compatibility and affinity with microorganisms, and the PAN electrospun membrane prepared by electrostatic spinning has a very fluffy fiber structure, has the characteristics of large specific surface area (1000 times of fibers of conventional fibers), high porosity and large length-diameter ratio, so that the strain can have more living space, and the biofilm formation amount is increased greatly. And the combination of the electrospun membrane and the substrate has a plurality of three-dimensional small spaces for the bacteria to live and is not easy to fall off. The electrospinning diameter is closer to the size of bacteria than the traditional filler, and the electrospinning is more suitable for the survival of the bacteria. PES (polyether sulfone resin) has good chemical resistance and is resistant to common organic solvents except chlorinated hydrocarbons, ketones and acids. Is stable to common acids, alkalis, aliphatic hydrocarbons, oils and alcohols, etc. Good steam and superheated water (150-. Elongation percentage: 40% -80%, density: 1.37 to 1.51g/cm3, flexural strength: 130MPa, intrinsic viscosity: 0.6dL/g, impact strength (notched): >78.0J/m, water absorption: (23 ℃, 4h) < 0.40%, tensile strength: >85.0 MPa. The PES electrospun membrane prepared by electrostatic spinning not only plays a role in protecting the PAN electrospun membrane, but also provides a good environment for the survival of bacteria due to the excellent hydrophilic property of the PES electrospun membrane.
Example 2
Referring to fig. 1, the present embodiment provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PES electrospun membrane), which is different from that of embodiment 1 in that: the concentration of the prepared PAN solution is 8%, the concentration of the prepared PES solution is 22%, and the mass ratio of the liquid binder to the composite strain is 35: 1.
Example 3
Referring to fig. 1, the present embodiment provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PES electrospun membrane), which is different from that of embodiment 1 in that: the concentration of the prepared PAN solution is 12%, the concentration of the prepared PES solution is 26%, and the mass ratio of the liquid binder to the composite strain is 45: 1.
Example 4
The embodiment provides a high-efficiency electrospun fiber biological membrane (a substrate, mixed liquid, a PAN electrospun membrane, mixed liquid, a PES electrospun membrane and a PA6 electrospun membrane), which comprises a substrate, wherein the substrate is used as a bottom material, the PAN electrospun membrane is covered on the substrate, the PES electrospun membrane is covered on the PAN electrospun membrane, the PA6 electrospun membrane is covered on the PES electrospun membrane, and a liquid binder dissolved with composite strains is sprayed on the upper surface of the substrate; and the upper surface of the PAN electrospun membrane is sprayed with a liquid binder dissolved with the composite strain.
The preparation method of the high-efficiency electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 24% PES solution, taking 480g of PES powder and 1520g of DMF (N, N-dimethylformamide) solvent, putting the PES powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PES powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) preparing 22.5% PA6 solution, taking 450g of PA6 powder and 1550g of formic acid (chemical formula HCOOH, molecular formula CH2O2) solvent, putting the PA6 powder into a glass beaker firstly and then putting the formic acid solvent in order to prevent the PA6 powder from being excessively suspended on the liquid surface, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(4) preparing a mixed solution according to the ratio of 40: 1, preparing a liquid binder and a composite strain (nitrobacteria: denitrifying bacteria: bacillus: pseudomonas: 5: 4: 6) according to a mass ratio of 2250g of the liquid binder and 50g of the composite strain, firstly adding the liquid binder and then adding the composite strain, stirring at a rotating speed of 200r/min for 6 hours at normal temperature by using a mechanical stirrer, and constantly paying attention to the fact that the temperature of a beaker is not higher than 40 ℃;
(5) processing the biological membrane is horizontal processing, taking a polyester substrate (PET) as a horizontal winding material, starting a gas permeation combination device to horizontally flow through the whole processed polyester substrate, enabling the surface of the substrate to have wet viscous airflow to pass through, enabling the surface of the substrate to have higher adsorbability, forming a wet viscous airflow space, and spraying a liquid adhesive dissolved with a composite strain on the surface of the substrate;
(6) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PAN solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) after the step (5) is completed, covering the PAN electrospun membrane, and spraying a liquid binder dissolved with the composite strains on the surface of the PAN electrospun membrane;
(7) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PES solution to the polyester substrate (which passes through the polyester substrate in the horizontal direction) after the step (6) is completed, and covering a PES electrospun membrane;
(8) in the wet viscous airflow space, an electrostatic spinning device is started to spray the PA6 solution to the polyester substrate (passing through the polyester substrate horizontally) which is finished in the step (7), so that the polyester substrate is covered with the PA6 electrospun membrane;
(9) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage, wherein the compound strain can survive for 4 months.
Example 5
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PES electrospun membrane + PA6 electrospun membrane), which is different from example 4 in that: the concentration of the prepared PAN solution is 8%, the concentration of the prepared PES solution is 22%, the concentration of the prepared PA6 solution is 20%, and the mass ratio of the liquid binder to the composite strain is 35: 1.
Example 6
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PES electrospun membrane + PA6 electrospun membrane), which is different from example 4 in that: the concentration of the prepared PAN solution is 12%, the concentration of the prepared PES solution is 26%, the concentration of the prepared PA6 solution is 25%, and the mass ratio of the liquid binder to the composite strain is 45: 1.
Example 7
This example provides a high efficiency electrospun fibrous biofilm (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane).
The preparation method of the high-efficiency electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 22.5% PA6 solution, taking 450g of PA6 powder and 1550g of formic acid (chemical formula HCOOH, molecular formula CH2O2) solvent, putting the PA6 powder into a glass beaker firstly and then putting the formic acid solvent in order to prevent the PA6 powder from being excessively suspended on the liquid surface, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) preparing 10% PVDF solution, taking 200g of PVDF powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PVDF powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PVDF powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(4) preparing a mixed solution according to the ratio of 40: 1, preparing a liquid binder and a composite strain (nitrobacteria: denitrifying bacteria: bacillus: pseudomonas: 5: 4: 6) according to a mass ratio of 2250g of the liquid binder and 50g of the composite strain, firstly adding the liquid binder and then adding the composite strain, stirring at a rotating speed of 200r/min for 6 hours at normal temperature by using a mechanical stirrer, and constantly paying attention to the fact that the temperature of a beaker is not higher than 40 ℃;
(5) processing of the biological membrane is horizontal processing, a polyester substrate (PBT) is used as a horizontal winding material, a gas permeation combination device is started to horizontally flow through the whole processed polyester substrate, so that moist viscous airflow passes through the surface of the substrate, the surface of the substrate has high adsorbability, a moist viscous airflow space is formed, and a liquid adhesive dissolved with composite strains is sprayed on the surface of the substrate;
(6) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PAN solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) after the step (5) is completed, covering the PAN electrospun membrane, and spraying a liquid binder dissolved with the composite strains on the surface of the PAN electrospun membrane;
(7) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PA6 solution to the polyester substrate (passing through the polyester substrate horizontally) which has finished the step (6), so that the polyester substrate is covered with a PA6 electrospun membrane;
(8) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PVDF solution to the polyester substrate (which passes through the polyester substrate in the horizontal direction) which is subjected to the step (7), so that the PVDF electrospun membrane can be covered;
(9) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage, wherein the compound strain can survive for 4 months.
Example 8
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 4 in that: the concentration of the prepared PAN solution is 8%, the concentration of the prepared PA6 solution is 20%, the concentration of the prepared PVDF solution is 8%, and the mass ratio of the liquid binder to the composite strain is 35: 1.
Example 9
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 4 in that: the concentration of the prepared PAN solution is 12%, the concentration of the prepared PA6 solution is 25%, the concentration of the prepared PVDF solution is 12%, and the mass ratio of the liquid binder to the composite strain is 45: 1.
Example 10
This example provides a high efficiency electrospun fibrous biofilm (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane).
The preparation method of the high-efficiency electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 22.5% PA6 solution, taking 450g of PA6 powder and 1550g of formic acid (chemical formula HCOOH, molecular formula CH2O2) solvent, putting the PA6 powder into a glass beaker firstly and then putting the formic acid solvent in order to prevent the PA6 powder from being excessively suspended on the liquid surface, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) preparing 10% PVDF solution, taking 200g of PVDF powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PVDF powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PVDF powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(4) preparing a mixed solution according to the ratio of 40: 1, preparing a liquid binder and a composite strain (nitrobacteria: denitrifying bacteria: bacillus: pseudomonas: 5: 4: 6) according to a mass ratio of 2250g of the liquid binder and 50g of the composite strain, firstly adding the liquid binder and then adding the composite strain, stirring at a rotating speed of 200r/min for 6 hours at normal temperature by using a mechanical stirrer, and constantly paying attention to the fact that the temperature of a beaker is not higher than 40 ℃;
(5) processing of the biological membrane is horizontal processing, a polyester substrate (polyarylate) is used as a horizontal winding material, a gas permeation combination device is started to horizontally flow through the whole processed polyester substrate, so that wet viscous airflow passes through the surface of the substrate, the surface of the substrate has high adsorbability, a wet viscous airflow space is formed, and a liquid binder dissolved with composite strains is sprayed on the surface of the substrate;
(6) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PAN solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) after the step (5) is completed, covering the PAN electrospun membrane, and spraying a liquid binder dissolved with the composite strains on the surface of the PAN electrospun membrane;
(7) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PA6 solution to the polyester substrate (passing through the polyester substrate horizontally) which has finished the step (6), so that the polyester substrate is covered with a PA6 electrospun membrane;
(8) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PVDF solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) which is subjected to the step (7), covering the PVDF electrospun membrane, and spraying a liquid binder dissolved with the composite strain on the surface of the PVDF electrospun membrane;
(9) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage, wherein the compound strain can survive for 4 months.
Example 11
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 10 in that: the concentration of the prepared PAN solution is 8%, the concentration of the prepared PA6 solution is 20%, the concentration of the prepared PVDF solution is 8%, and the mass ratio of the liquid binder to the composite strain is 35: 1.
Example 12
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 10 in that: the concentration of the prepared PAN solution is 12%, the concentration of the prepared PA6 solution is 25%, the concentration of the prepared PVDF solution is 12%, and the mass ratio of the liquid binder to the composite strain is 45: 1.
Example 13
This example provides a highly efficient electrospun fibrous biofilm (substrate + PAN electrospun membrane + PA6 electrospun membrane + PVDF electrospun membrane + mixed solution).
The preparation method of the high-efficiency electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 22.5% PA6 solution, taking 450g of PA6 powder and 1550g of formic acid (chemical formula HCOOH, molecular formula CH2O2) solvent, putting the PA6 powder into a glass beaker firstly and then putting the formic acid solvent in order to prevent the PA6 powder from being excessively suspended on the liquid surface, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) preparing 10% PVDF solution, taking 200g of PVDF powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PVDF powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PVDF powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(4) preparing a mixed solution according to the ratio of 40: 1, preparing a liquid binder and a composite strain (nitrobacteria: denitrifying bacteria: bacillus: pseudomonas: 5: 4: 6) according to a mass ratio of 2250g of the liquid binder and 50g of the composite strain, firstly adding the liquid binder and then adding the composite strain, stirring at a rotating speed of 200r/min for 6 hours at normal temperature by using a mechanical stirrer, and constantly paying attention to the fact that the temperature of a beaker is not higher than 40 ℃;
(5) processing of the biological membrane is horizontal processing, a polyester substrate (polyarylate) is used as a horizontal winding material, a gas permeation combination device is started to horizontally flow through the whole processed polyester substrate, so that wet viscous airflow passes through the surface of the substrate, and the surface of the substrate has high adsorbability, thereby forming a wet viscous airflow space;
(6) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PAN solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) after the step (5) is completed, and covering the polyester substrate with the electrospun membrane of PAN;
(7) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PA6 solution to the polyester substrate (passing through the polyester substrate horizontally) which has finished the step (6), so that the polyester substrate is covered with a PA6 electrospun membrane;
(8) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PVDF solution to the polyester substrate (the polyester substrate passes through in the horizontal direction) which is subjected to the step (7), covering the PVDF electrospun membrane, and spraying a liquid binder dissolved with the composite strain on the surface of the PVDF electrospun membrane;
(9) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage, wherein the compound strain can survive for 4 months.
Example 14
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 13 in that: the concentration of the prepared PAN solution is 8%, the concentration of the prepared PA6 solution is 20%, the concentration of the prepared PVDF solution is 8%, and the mass ratio of the liquid binder to the composite strain is 35: 1.
Example 15
This example provides a high-efficiency electrospun fiber biological membrane (substrate + mixed solution + PAN electrospun membrane + mixed solution + PA6 electrospun membrane + PVDF electrospun membrane), which is different from example 13 in that: the concentration of the prepared PAN solution is 12%, the concentration of the prepared PA6 solution is 25%, the concentration of the prepared PVDF solution is 12%, and the mass ratio of the liquid binder to the composite strain is 45: 1.
Comparative example 1
Referring to fig. 1, the present comparative example provides an electrospun fiber biological membrane (substrate + PAN electrospun membrane + PES electrospun membrane) comprising a polyester substrate, the polyester substrate (PET) is used as a base material, and the PAN electrospun membrane is covered with the PES electrospun membrane.
The preparation method of the electrospun fiber biological membrane comprises the following steps:
(1) preparing 10% PAN solution, taking 200g of PAN powder and 1800g of DMF (N, N-dimethylformamide) solvent, putting the PAN powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PAN powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature at the rotating speed of 600r/min by using a mechanical stirrer after the PAN powder is put into the glass beaker;
(2) preparing 24% PES solution, taking 480g of PES powder and 1520g of DMF (N, N-dimethylformamide) solvent, putting the PES powder into a glass beaker firstly and then putting the DMF solvent in order to prevent the PES powder from being excessively suspended on the liquid level, and stirring for 6 hours at normal temperature by using a mechanical stirrer at the rotating speed of 600r/min after the completion;
(3) processing of the biological membrane is horizontal processing, a polyester substrate (PET, PBT, polyarylate) is used as a horizontal rolling material, a gas permeation combination device is started to horizontally flow through the whole processed polyester substrate, so that wet viscous airflow passes through the surface of the substrate, and the surface of the substrate has high adsorbability, and a wet viscous airflow space is formed;
(4) in the wet viscous airflow space, starting the electrostatic spinning device to spray the PAN solution to the polyester substrate (passing the polyester substrate horizontally) which is finished by the step (3), and covering the polyester substrate with the electrospun membrane of PAN as shown in FIG. 2;
(5) in the wet viscous airflow space, starting an electrostatic spinning device to spray the PES solution to the polyester substrate (which passes through the polyester substrate horizontally) after the step (4) is completed, and covering the PES electrospun membrane as shown in FIG. 2;
(6) fixing the edge of the biological membrane by ultrasonic compounding.
The biofilms provided in examples 1, 4, 7, 10, 13 and comparative example 1 were subjected to a performance test by:
firstly, according to the following steps of glucose: urea: calcium superphosphate is 100: 5:1, 106g of solute was weighed out, and then the solute was dissolved in 50L of water, thereby obtaining a culture solution. The whole culture solution was poured into an aeration tank, and then a tenth of the amount of sludge (sludge in a sewage ditch is preferred, but ordinary sludge is also acceptable in this test), which was added to water, was added with 20g of the strain (nitrifying bacteria: denitrifying bacteria: Bacillus sp.: Pseudomonas sp.: 5: 4: 6), dissolved in clear water, and aerated for 30 minutes to recover the activity, and then poured into the aeration tank, and 100g of glucose was added at regular intervals every day. Finally, aeration is stopped after aeration (namely, only aeration is carried out without injecting culture solution) is carried out for two days, standing and settling are carried out for 1h, then about 1/5 of upper layer wastewater in the tank is discharged, and the same amount of fresh tap water is injected. The three processes of aeration, static sedimentation and water inlet are repeated in this way, sludge can be primarily cultured in two weeks, when the sludge concentration in the aeration tank reaches 1 g/L, aeration can be continuously carried out, and when the sludge concentration reaches 10 g/L required by the process, the biological membranes provided by the examples 1, 4, 7, 10 and 13 and the comparative example 1 are respectively fixed by the support and are placed in the tank for a membrane hanging test. The results are shown in table 1:
TABLE 1
As is clear from Table 1, the amount of biofilm formed in the mixed solution of the liquid binder and the composite bacterial strain in example 1 was larger than the average amount of biofilm formed in the mixed solution of the control example 1200g/m2The above. The biological membrane provided by the invention has good membrane hanging effect.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
Although the embodiments have been described, once the basic inventive concept is obtained, other variations and modifications of these embodiments can be made by those skilled in the art, so that the above embodiments are only examples of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes using the contents of the present specification and drawings, or any other related technical fields, which are directly or indirectly applied thereto, are included in the scope of the present invention.
Claims (12)
1. The efficient electrospun fiber biological membrane is characterized by comprising a base material, wherein the base material is used as a bottom material, N layers of high molecular polymer nanofiber membranes are covered on the base material, N is more than or equal to 1 and less than or equal to 4, and a liquid binder dissolved with a composite strain is sprayed on the upper surface of at least one of the base material and the N layers of high molecular polymer nanofiber membranes; the preparation method comprises the following steps:
(1) preparing each high molecular polymer solution according to the proportion, firstly putting high molecular polymer powder into a glass beaker, then putting into an organic solvent, and uniformly stirring by using a mechanical stirrer at normal temperature to prepare each high molecular polymer solution;
(2) preparing a liquid binder dissolved with composite strains according to a ratio, putting liquid binder powder into a glass beaker, then putting the composite strains, and slowly stirring at normal temperature to prepare the liquid binder dissolved with the composite strains;
(3) starting the gas permeation combination device by taking the base material as a base material to enable the surface of the base material to have wet viscous airflow to pass through and form a wet viscous airflow space;
(4) in a wet viscous airflow space, selecting whether to decorate the liquid adhesive dissolved with the composite strains on the upper surface of the substrate in an airflow spraying or ultrasonic spraying manner according to the requirements of the prepared high-efficiency electrospun fiber biomembrane;
(5) in the wet viscous airflow space, starting an electrostatic spinning device to spray a high molecular polymer solution to the surface of the base material sprayed with the liquid binder, and electrospinning to form a high molecular polymer nanofiber membrane;
(6) in a wet viscous airflow space, selecting whether to decorate the liquid adhesive dissolved with the composite strains on the upper surface of the high molecular polymer nanofiber membrane electrospun in the last step in an airflow spraying or ultrasonic spraying manner according to the requirements of the prepared high-efficiency electrospun fiber biofilm;
(7) in the wet viscous airflow space, selecting whether to repeat the step (5) and/or the step (6) or not according to the requirement of the prepared high-efficiency electrospun fiber biological membrane;
(8) fixing the edge of the biological membrane by ultrasonic compounding, and then placing the biological membrane in an environment at 4 ℃ for ice storage.
2. The efficient electrospun fiber biological membrane of claim 1, wherein the high molecular polymer nanofiber membrane raw material is selected from Polyacrylonitrile (PAN), polyethersulfone resin (PES), polyamide 6(PA6) and polyvinylidene fluoride (PVDF), and each layer of high molecular polymer nanofiber membrane raw material is the same or different.
3. The efficient electrospun fiber biological membrane according to claim 1 or 2, wherein the substrate is a polyester substrate.
4. The efficient electrospun fiber biological membrane according to claim 1 or 2, wherein the liquid binder is prepared from water, liquid egg white and starch according to a mass ratio of 5: 4: 1, and mixing the components in a ratio of 1.
5. The efficient electrospun fiber biological membrane according to claim 1 or 2, wherein the mass ratio of the composite bacterial species to the liquid binder in the liquid binder dissolved with the composite bacterial species is 1: 35-45.
6. A high efficiency electrospun fiber biofilm according to claim 3 wherein said polyester substrate is selected from PET, PBT, polyarylate.
7. The efficient electrospun fiber biological membrane of claim 1, wherein when the high polymer nanofiber membrane is prepared, the concentration of the PAN solution is 8% -12%, the concentration of the PES solution is 22% -26%, the concentration of the PA6 solution is 20% -25%, and the concentration of the PVDF solution is 8% -12%.
8. The highly efficient electrospun fiber biological membrane according to claim 1, wherein the organic solvent is N, N-Dimethylformamide (DMF) or formic acid.
9. The efficient electrospun fiber biological membrane of claim 5, wherein the mass ratio of the composite bacterial species to the liquid binder in the liquid binder dissolved with the composite bacterial species is 1: 40.
10. A body height according to claim 8 or 9The electrospun fiber biomembrane is characterized in that the thickness of the substrate is 3.2493-4.2350 mm, and the gram weight is 276g/m2-366g/m2(ii) a The total thickness of the high molecular polymer nano fiber film layer is 0.22um-0.34um, and the gram weight is 0.0601g/m2-0.1803g/m2。
11. The highly efficient electrospun fiber biological membrane according to claim 1, wherein the stirring speed of a mechanical stirrer is 600r/min and the stirring time is 6 hours in the process of preparing the high molecular polymer solution.
12. The efficient electrospun fiber biological membrane of claim 1, wherein in the process of preparing the liquid binder dissolved with the composite bacterial strain, the stirring speed is 200r/min, and the stirring time is 6 hours.
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