CN113248004B - Preparation method of sewage treatment microbial carrier - Google Patents
Preparation method of sewage treatment microbial carrier Download PDFInfo
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- CN113248004B CN113248004B CN202110369376.XA CN202110369376A CN113248004B CN 113248004 B CN113248004 B CN 113248004B CN 202110369376 A CN202110369376 A CN 202110369376A CN 113248004 B CN113248004 B CN 113248004B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of sewage treatment, in particular to a preparation method of a sewage treatment microbial carrier, which comprises forming, crosslinking, modifying and restructuring; because acid reagents participating in reaction in the chemical crosslinking process can remain in a finished product to influence the activity of microorganisms, and meanwhile, the hardening time of a carrier is long, so that the adhesion phenomenon is easy to generate, in the finished product prepared by a physical crosslinking method, the microorganisms are mixed with a neutral high-molecular solution, and the carrier material is directly prepared by utilizing circulating cooling, so that the pore forming rate is high, the water content is large, the influence on the activity of the microorganisms is avoided, but the condition of poor stability is caused by large water solubility; therefore, the additive components mixed in the preparation method are used for modifying the polyvinyl alcohol resin, and the adjustment operation of temperature in the circulating temperature rise and reduction process is matched, so that the bearing performance of the finished product morphological structure on microorganisms is improved, and the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method of a sewage treatment microbial carrier.
Background
The design and preparation of the novel carrier material are important aspects of research and development of wastewater treatment technology, the high polymer material is applicable to the complex water quality condition of sewage treatment due to excellent weather resistance and physical strength of the high polymer material, the hydrophilicity of the high polymer material can provide an excellent microenvironment for the metabolic proliferation of the microbial carrier, and the strength and the chemical stability of the high polymer material as the microbial carrier can be further improved after the high polymer material is subjected to chemical crosslinking or hardening modification treatment, so that the stability of the carrier in the sewage treatment process is ensured.
At present, the method for preparing the microbial carrier by using the high polymer material comprises a chemical crosslinking method and a physical crosslinking method, wherein the carrier product prepared by the chemical crosslinking method has high strength and long service life, but an acid reagent participating in the reaction in the chemical crosslinking process can remain in a finished product to influence the activity of microorganisms, and the carrier has long hardening time and is easy to generate a sticky phenomenon; in the finished product prepared by the physical crosslinking method, the carrier material is directly prepared by mixing the microorganisms with the neutral polymer solution and utilizing the circulating refrigeration, the porosity is high, the water content is large, the influence on the activity of the microorganisms is avoided, but the stability is poor due to the large water solubility.
For example, a Chinese patent with application number CN202010316341.5 discloses a microorganism carrier for sewage treatment, which is composed of a magnetic carbon fiber bracket and a polypyrrole film layer with microorganism fixed on the surface; the magnetic carbon fiber support is formed by weaving composite fiber bundles and is obtained by pre-oxidation and carbonization treatment; the composite fiber is polyacrylonitrile fiber doped with graphene, and magnetic iron oxide nanoparticles are uniformly distributed on the surface and in the composite fiber; according to the technical scheme, the iron oxide nanoparticles generated in situ have good photocatalytic activity, and can also promote local graphitization of carbon fibers and improve the conductivity of the carbon fibers in a synergistic manner with graphene; the magnetic carbon fiber support is used as a working electrode, and the polypyrrole film is electrochemically deposited on the magnetic carbon fiber support, so that effective fixation of microorganisms is realized, embedding is avoided, microorganism loading and proliferation are facilitated, iron oxide photocatalyst and microorganisms are in full contact with pollutants in sewage, photocatalytic degradation and microbial treatment are performed synchronously, and the sewage treatment efficiency is greatly improved; however, the technical scheme does not solve the water solubility problem of the prepared microbial carrier, and the process of photocatalysis is weakened in the water body of sewage, so that the biological activity of the microbes is limited.
In view of the above, the invention provides a preparation method of a sewage treatment microbial carrier, which solves the above technical problems.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a preparation method of a sewage treatment microbial carrier, which is characterized in that polyvinyl alcohol resin is modified by additive components mixed in the preparation method, and the carrying performance of a finished product morphological structure on microbes is improved by matching with the temperature regulation operation in the circulating temperature rise and temperature reduction process, so that the application effect of the preparation method of the sewage treatment microbial carrier is improved.
The invention relates to a preparation method of a sewage treatment microbial carrier, which comprises the following steps:
s1, forming: taking polyvinyl alcohol resin as a preparation raw material of a microbial carrier, adding alginate into the polyvinyl alcohol resin in a molten state of the polyvinyl alcohol resin molding, controlling the weight ratio of the alginate in the polyvinyl alcohol resin to be 0.6-2.2%, mixing and dissolving the alginate and the polyvinyl alcohol resin for more than 20min, dripping saturated boric acid solution containing calcium chloride into the mixture within 5min before the mixing is finished, forming a gel state after the mixture is naturally cooled, scattering and separating the gel-state polyvinyl alcohol resin into small balls with the diameter of 7-17mm by a stirrer, and circularly heating and cooling the stacked polyvinyl alcohol resin small balls;
s2, crosslinking: embedding microorganisms in polyethylene film balls, mixing the polyethylene film balls with acrylamide, adding the mixture into spherical polyvinyl alcohol resin subjected to cyclic heating and cooling in S1, wherein the size of the microorganisms embedded in the polyethylene film balls is controlled to be 30-60% of that of polyvinyl alcohol resin pellets, so that the content of the microorganisms in the finally added polyethylene film balls accounts for 40-70% of that of the polyvinyl alcohol resin, and gradually reducing the upper limit of the temperature of the cyclic heating and cooling to a room temperature state in the process of adding the polyethylene film balls;
s3, modification: in the process of adding the polyethylene film balls in S2, adding quartz sand particles, controlling the particle diameter of the quartz sand particles to be 0.5-0.9mm and accounting for 10-25% of the weight of the polyethylene film balls, performing ball milling treatment on the quartz sand particles, and simultaneously adding an equivalent amount of foaming agent to ensure that the density of the finally prepared polyvinyl alcohol resin pellets is 1.04-1.18g/cm 3 ；
S4, restructuring: respectively recording the upper limit and the lower limit of the temperature of the cyclic heating and cooling in the S1 as Tmin and Tmax, recording the room temperature as T0, recording the difference value of the Tmin and the T0 as T1, reducing the Tmin of the temperature of the cyclic heating and cooling by 10-20 ℃ after the process in the S1-S3 is completed, adjusting the Tmax to be the temperature parameter of T0+ T1, and then performing the cyclic heating and cooling for 30-40min;
in the prior art, a method for preparing a microbial carrier by using a high polymer material comprises a chemical crosslinking method and a physical crosslinking method, wherein a carrier product prepared by the chemical crosslinking method has high strength and long service life, but an acid reagent participating in a reaction in a chemical crosslinking process can remain in a finished product to influence the activity of microorganisms, the carrier has long hardening time and is easy to generate a sticking phenomenon, and in a finished product prepared by the physical crosslinking method, the microorganisms are mixed with a neutral high polymer solution, and the carrier material is directly prepared by using circulating cooling, has high porosity and large water content, avoids the influence on the activity of the microorganisms, but has poor stability due to high water solubility;
therefore, the added alginate and calcium chloride react in a saturated boric acid solution to generate calcium alginate, the surface performance of the polyvinyl alcohol resin is improved, a hard layer is formed on the surface of the globular polyvinyl alcohol resin in the circulating temperature rise and drop process, the adhesion degree between the globular polyvinyl alcohol resin is reduced, and the polyvinyl alcohol resin in the circulating temperature drop process keeps the shape of the globule; adding acrylamide to reduce the water-soluble expansibility of the polyvinyl alcohol resin, and uniformly mixing the added microorganisms into small spheres of the vinyl-based pure resin in the circulating temperature rise and reduction process by utilizing the fact that the polyethylene film spheres are lower than the melting point of the polyvinyl alcohol resin, so that the finally formed carrier is convenient to adhere to the microorganisms; the quartz sand particles are added to improve the physical property of the prepared microorganism carrier, so that the floating problem of the carrier caused by gas generated by metabolism of microorganisms in the sewage process is avoided, and arc-shaped bulges are formed on the surface of polyvinyl alcohol resin after the quartz sand particles are subjected to ball milling treatment, so that the surface area of the carrier is increased, and the attachment of microorganisms and the contact effect between the microorganisms and the sewage are facilitated; after the temperature of the cyclic heating and cooling is adjusted, pores are generated by the polyethylene resin under the cyclic reciprocating expansion deformation, so that the finally prepared carrier is convenient to enhance the attachment capacity to microorganisms; according to the invention, additive components mixed in the preparation method are utilized to modify polyvinyl alcohol resin, and the temperature is adjusted in the circulating heating and cooling process, so that the bearing performance of the finished product morphological structure on microorganisms is improved, and the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
Preferably, genipin is also added into the saturated boric acid in the molding process, the addition process of the genipin is in a temperature rise stage of cyclic temperature rise and temperature drop of the polyvinyl alcohol resin, and the genipin is used as a cross-linking agent in the reaction of the polyvinyl alcohol resin; the strength of calcium alginate in the hard layer on the surface of the polyvinyl alcohol resin bead is enhanced through the crosslinking effect of genipin, so that the acid resistance and the high-temperature resistance of the crosslinked carrier are enhanced, genipin generated by natural organisms replaces glutaraldehyde to serve as a crosslinking agent, the influence of the toxicity of the residual crosslinking agent on the carrier on the metabolism and proliferation of microorganisms is avoided, the hydrophilicity of hydroxyl groups in the carrier is inhibited through a covalent crosslinking network formed by the genipin and the polyvinyl alcohol resin carrier, the stability of the carrier is enhanced, and the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
Preferably, in the molding process, after saturated boric acid is added to form a gel state, 0.55-0.75mol/L sodium phosphate solution is added to completely submerge the polyvinyl alcohol resin in a temperature-rising state; the added metal ions in the sodium phosphate form coordinate bond crosslinking with hydroxyl in the polyvinyl alcohol resin, so that the hydrophobicity of the polyvinyl alcohol resin carrier is further enhanced, meanwhile, the sodium phosphate solution submerges the polyvinyl alcohol resin, the aqueous solution in the polyvinyl alcohol resin is softened, the process of forming calcium alginate precipitate in the polyvinyl alcohol resin is slowed down, the rate of forming gel in the polyvinyl alcohol resin is convenient to control, the uniformity of gel finished products in the polyvinyl alcohol resin is enhanced, and the polyvinyl alcohol resin beads with evenly distributed strength are formed, so that the application effect of the preparation method of the sewage treatment microbial carrier is improved.
Preferably, in the crosslinking step, the step of embedding the microorganisms in the polyethylene film spheres is as follows:
I. blowing an open polyethylene film ball through a die head with the diameter of 6mm, then spraying powder containing microorganisms into the polyethylene film ball through an air gun to attach the microorganism powder to the inner wall of the polyethylene film ball, controlling the adding amount of the microorganism powder to be less than 20% of the internal volume of the polyethylene film ball, and then carrying out heat sealing on the opening of the polyethylene film ball;
II. And (3) when the polyvinyl alcohol resin is in a stage of temperature reduction in temperature rise and temperature reduction, adding the polyethylene ball film prepared in the step I into the polyvinyl alcohol resin, enabling the polyethylene ball film to be attached to the polyvinyl alcohol resin, and enabling the sealed polyethylene film balls to be exploded in the polyvinyl alcohol resin in the process of cyclic temperature rise and temperature reduction to form a cavity structure.
Preferably, a spherical cage made of wood fibers is added in the polyethylene film ball, and the spherical cage is installed inside the polyethylene film ball through an opening of the polyethylene film ball; cellulase is also mixed in the microbial powder; the wood spherical cage added in the polyethylene spherical membrane is used for avoiding extrusion and cracking caused by shrinkage in a cooling state of the polyvinyl alcohol resin and losing the function of exploding a cavity in the polyvinyl alcohol resin, and the cellulase mixed in the microbial powder can decompose the wood spherical cage along with microorganisms in a sewage treatment process, so that an additional glucose source is provided for the microorganisms, the metabolic activity of the microorganisms is enhanced, and a solid sediment can be generated by metal ions of a polyvinyl alcohol resin carrier participating in a reaction with the sewage treatment process to replace the spherical cage to support the cavity of the polyvinyl alcohol resin, thereby improving the application effect of the preparation method of the sewage treatment microbial carrier.
Preferably, a magnetic column is further added into the polyethylene film ball, and two ends of the magnetic column are clamped in the spherical cage; the distribution of microorganisms in the polyvinyl alcohol resin carrier in metabolism is biased to magnetic field distribution through the magnetic columns arranged in the spherical cages, and the distribution state of a complex containing a magnetic material can be generated in the water treatment process, so that the application effect of the preparation method of the sewage treatment microbial carrier is stabilized.
The invention has the following beneficial effects:
1. according to the invention, through the additive components mixed in the preparation method, the polyvinyl alcohol resin is modified, and the temperature is adjusted in the process of circulating temperature rise and temperature reduction, so that the bearing performance of the finished product morphological structure on microorganisms is improved; the covalent cross-linked network formed by the added genipin and the polyvinyl alcohol resin carrier inhibits the hydrophilicity of hydroxyl groups in the covalent cross-linked network, and enhances the stability of the carrier.
2. According to the invention, metal ions in sodium phosphate and hydroxyl groups in polyvinyl alcohol resin form coordinate bond crosslinking, so that the hydrophobicity of a polyvinyl alcohol resin carrier is further enhanced, the aqueous solution in the polyvinyl alcohol resin carrier is softened, the rate of forming gel in the polyvinyl alcohol resin is conveniently controlled, the uniformity of a gel finished product in the polyvinyl alcohol resin carrier is enhanced, and the polyvinyl alcohol resin beads with evenly distributed strength are formed.
3. The invention avoids the phenomenon that the polyvinyl alcohol resin is reduced in a cooling state and is extruded and broken by adding the wooden spherical cage in the polyethylene spherical membrane, so that the effect of exploding a cavity in the polyvinyl alcohol resin is lost, and meanwhile, the cellulase mixed in the microbial powder can decompose the wooden spherical cage along with the microbes in the sewage treatment process, thereby providing an additional glucose source for the microbes and enhancing the metabolic activity of the microbes.
Drawings
The invention is further described with reference to the following figures and embodiments.
FIG. 1 is a flow chart of a method for preparing a microorganism carrier for wastewater treatment according to the present invention;
FIG. 2 is a flow chart of the microorganism embedding step of the polyethylene film ball of the present invention;
Detailed Description
The present invention will be further described with reference to the following detailed description so that the technical means, the creation features, the achievement purposes and the effects of the present invention can be easily understood.
As shown in FIGS. 1-2, the method for preparing a microorganism carrier for sewage treatment according to the present invention comprises the following steps:
s1, forming: taking polyvinyl alcohol resin as a preparation raw material of a microbial carrier, adding alginate into the polyvinyl alcohol resin in a molten state of the polyvinyl alcohol resin molding, controlling the weight ratio of the alginate in the polyvinyl alcohol resin to be 0.6-2.2%, mixing and dissolving the alginate and the polyvinyl alcohol resin for more than 20min, dripping saturated boric acid solution containing calcium chloride into the mixture within 5min before the mixing is finished, forming a gel state after the mixture is naturally cooled, scattering and separating the gel-state polyvinyl alcohol resin into small balls with the diameter of 7-17mm by a stirrer, and circularly heating and cooling the stacked small polyvinyl alcohol resin balls;
s2, crosslinking: embedding microorganisms in polyethylene film balls, mixing the polyethylene film balls with acrylamide, adding the mixture into spherical polyvinyl alcohol resin subjected to cyclic heating and cooling in S1, wherein the size of the microorganisms embedded in the polyethylene film balls is controlled to be 30-60% of that of polyvinyl alcohol resin beads, so that the content of the microorganisms in the finally added polyethylene film balls accounts for 40-70% of that of the polyvinyl alcohol resin, and gradually reducing the upper limit of the temperature of cyclic heating and cooling to a room temperature state in the process of adding the polyethylene film balls;
s3, modification: in the process of adding the polyethylene film balls in S2, adding quartz sand particles, controlling the particle diameter of the quartz sand particles to be 0.5-0.9mm and accounting for 10-25% of the weight of the polyethylene film balls, performing ball milling treatment on the quartz sand particles, and simultaneously adding an equivalent amount of foaming agent to ensure that the density of the finally prepared polyvinyl alcohol resin pellets is 1.04-1.18g/cm 3 ；
S4, restructuring: respectively recording the upper limit and the lower limit of the temperature of the cyclic heating and cooling in the S1 as Tmin and Tmax, recording the room temperature as T0, recording the difference value of the Tmin and the T0 as T1, reducing the Tmin of the temperature of the cyclic heating and cooling by 10-20 ℃ after the process in the S1-S3 is completed, adjusting the Tmax to be the temperature parameter of T0+ T1, and then performing the cyclic heating and cooling for 30-40min;
in the prior art, a method for preparing a microbial carrier by using a high polymer material comprises a chemical crosslinking method and a physical crosslinking method, wherein a carrier product prepared by the chemical crosslinking method is high in strength and long in service life, but an acid reagent participating in a reaction in a chemical crosslinking process can remain in a finished product to influence the activity of microorganisms, the carrier is long in hardening time and easy to generate a sticking phenomenon, and in a finished product prepared by the physical crosslinking method, the carrier material is directly prepared by mixing the microorganisms with a neutral high polymer solution and utilizing circulating cooling, and is high in porosity and water content, so that the influence on the activity of the microorganisms is avoided, but the high water solubility of the carrier material can cause a poor stability condition;
therefore, the added alginate and calcium chloride react in a saturated boric acid solution to generate calcium alginate, the surface performance of the polyvinyl alcohol resin is improved, and in the process of circularly heating and cooling, a hard layer is formed on the surface of the polyvinyl alcohol resin in a pellet shape, so that the adhesion degree between the polyvinyl alcohol resin and the polyvinyl alcohol resin is reduced, and the polyvinyl alcohol resin in the circularly cooling keeps the shape of the pellet; adding acrylamide to reduce the water-soluble expansibility of the polyvinyl alcohol resin, and uniformly mixing the added microorganisms into small spheres of the vinyl-based pure resin in the circulating temperature rise and reduction process by utilizing the fact that the polyethylene film spheres are lower than the melting point of the polyvinyl alcohol resin, so that the finally formed carrier is convenient to adhere to the microorganisms; the quartz sand particles are added to improve the physical property of the prepared microorganism carrier, so that the problem that the carrier floats upwards due to gas generated by metabolism of microorganisms in the sewage process is avoided, and arc-shaped bulges are formed on the surface of polyvinyl alcohol resin after the quartz sand particles are subjected to ball milling treatment, so that the surface area of the carrier is increased, and the attachment of microorganisms and the contact effect between the microorganisms and the sewage are facilitated; after the temperature of the cyclic heating and cooling is adjusted, pores are generated by the polyethylene resin under the cyclic reciprocating expansion deformation, so that the finally prepared carrier is convenient to enhance the attachment capacity to microorganisms; according to the invention, additive components mixed in the preparation method are utilized to modify polyvinyl alcohol resin, and the temperature is adjusted in the circulating heating and cooling process, so that the bearing performance of the finished product morphological structure on microorganisms is improved, and the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
In one embodiment of the present invention, genipin is further added to the saturated boric acid in the molding step, wherein the genipin is added in the heating stage of the cyclic heating and cooling of the polyvinyl alcohol resin, and is used as a crosslinking agent in the reaction of the polyvinyl alcohol resin; the strength of calcium alginate in the hard layer on the surface of the polyvinyl alcohol resin bead is enhanced through the crosslinking effect of genipin, so that the acid resistance and the high-temperature resistance of the crosslinked carrier are enhanced, genipin generated by natural organisms replaces glutaraldehyde to be used as a crosslinking agent, the influence of the toxicity of the residual crosslinking agent on the metabolism and proliferation of microorganisms is avoided, the hydrophilicity of hydroxyl in the carrier is inhibited through a covalent crosslinking network formed by the genipin and the polyvinyl alcohol resin carrier, the stability of the carrier is enhanced, and the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
In one embodiment of the present invention, in the molding step, after saturated boric acid is added to form a gel state, 0.55 to 0.75mol/L sodium phosphate solution is added thereto to completely submerge the polyvinyl alcohol resin in a temperature-raised state; the hydrophobicity of the polyvinyl alcohol resin carrier is further enhanced by forming coordination bond crosslinking with hydroxyl in the polyvinyl alcohol resin through metal ions in the added sodium phosphate, the polyvinyl alcohol resin is submerged by the sodium phosphate solution, the aqueous solution in the polyvinyl alcohol resin is softened, the process of forming calcium alginate precipitate in the polyvinyl alcohol resin is reduced, the rate of forming gel in the polyvinyl alcohol resin is conveniently controlled, the uniformity of gel finished products in the polyvinyl alcohol resin is enhanced, and the polyvinyl alcohol resin balls with evenly distributed strength are formed, so that the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
In one embodiment of the present invention, in the crosslinking step, the polyethylene film spheres are embedded with microorganisms in the following steps:
I. blowing an open polyethylene film ball through a die head with the diameter of 6mm, spraying powder containing microorganisms into the polyethylene film ball through an air gun to attach the microorganism powder to the inner wall of the polyethylene film ball, controlling the addition of the microorganism powder to be less than 20% of the internal volume of the polyethylene film ball, and then carrying out heat sealing on the opening of the polyethylene film ball;
II. And when the polyvinyl alcohol resin is in the stage of temperature reduction in temperature rise and temperature reduction, adding the polyethylene ball film prepared in the step I into the polyvinyl alcohol resin, so that the polyethylene ball film is attached to the polyvinyl alcohol resin, and the sealed polyethylene ball film is exploded in the polyvinyl alcohol resin in the process of cyclic temperature rise and temperature reduction to form a cavity structure.
As an embodiment of the invention, a spherical cage made of wood fiber is added in the polyethylene film ball, and the spherical cage is installed in the polyethylene film ball through an opening of the polyethylene film ball; cellulase is also mixed in the microbial powder; the wood spherical cage added into the polyethylene spherical membrane can avoid extrusion and cracking caused by shrinkage in a temperature reduction state of the polyvinyl alcohol resin, and the effect of exploding a cavity in the polyvinyl alcohol resin is lost, meanwhile, cellulase mixed into the microbial powder can decompose the wood spherical cage along with microorganisms in a sewage treatment process, so that an additional glucose source is provided for the microorganisms, the metabolic activity of the microorganisms is enhanced, and metal ions of a polyvinyl alcohol resin carrier participating in reaction with the sewage treatment process can generate solid sediments to replace the spherical cage to support the cavity of the polyvinyl alcohol resin, so that the application effect of the preparation method of the sewage treatment microorganism carrier is improved.
According to one embodiment of the invention, the polyethylene film ball is additionally provided with a magnetic column, and two ends of the magnetic column are clamped in the ball-shaped cage; the distribution of microorganisms metabolized in the polyvinyl alcohol resin carrier is biased to magnetic field distribution through the magnetic columns arranged in the spherical cages, and the distribution state of a complex containing a magnetic material can be generated in the water treatment process, so that the application effect of the preparation method of the sewage treatment microorganism carrier is stabilized.
The specific working process is as follows:
the added alginate and calcium chloride react in a saturated boric acid solution to generate calcium alginate, so that the surface performance of polyvinyl alcohol resin is improved, a hard layer is formed on the surface of the globular polyvinyl alcohol resin in the circulating temperature rise and drop process, the adhesion degree between the globular polyvinyl alcohol resin is reduced, and the polyvinyl alcohol resin in the circulating temperature drop process keeps the shape of the globule; acrylamide is added to reduce the water-soluble expansibility of the polyvinyl alcohol resin, and the polyethylene film balls are lower than the melting point of the polyvinyl alcohol resin, so that the added microorganisms are uniformly mixed into the small balls of the vinyl pure resin in the circulating temperature rise and reduction process, and the finally formed carrier is convenient to adhere to the microorganisms; the physical property of the prepared microorganism carrier is improved by adding the quartz sand particles, the floating problem of the carrier caused by gas generated by metabolism of microorganisms in the sewage process is avoided, and the arc-shaped bulges formed on the surface of the polyvinyl alcohol resin after the quartz sand particles are subjected to ball milling treatment increase the surface area of the carrier, thereby facilitating the attachment of microorganisms and the contact effect between the microorganisms and the sewage; after the temperature of the cyclic heating and cooling is adjusted, pores are generated by the polyethylene resin under the cyclic reciprocating expansion and contraction deformation, so that the finally prepared carrier is convenient to enhance the attachment capacity to microorganisms; the strength of calcium alginate in a hard layer on the surface of the polyvinyl alcohol resin bead is enhanced through the crosslinking effect of genipin, so that the acid resistance and high-temperature resistance of the crosslinked carrier are enhanced, genipin generated by natural organisms replaces glutaraldehyde to be used as a crosslinking agent, the influence of the toxicity of the residual crosslinking agent on the metabolism and proliferation of microorganisms is avoided, and the hydrophilicity of hydroxyl groups in the covalent crosslinking network formed by genipin and the polyvinyl alcohol resin carrier is inhibited, so that the stability of the carrier is enhanced; the added metal ions in the sodium phosphate and the hydroxyl in the polyvinyl alcohol resin form coordinate bond crosslinking, so that the hydrophobicity of a polyvinyl alcohol resin carrier is further enhanced, meanwhile, the sodium phosphate solution submerges the polyvinyl alcohol resin, the aqueous solution in the polyvinyl alcohol resin is softened, the process of forming calcium alginate precipitate in the polyvinyl alcohol resin is slowed down, the rate of forming gel in the polyvinyl alcohol resin is convenient to control, the uniformity of a gel finished product in the polyvinyl alcohol resin is enhanced, and small balls of the polyvinyl alcohol resin with evenly distributed strength are formed; the wooden spherical cage added in the polyvinyl alcohol spherical membrane avoids extrusion and cracking caused by shrinkage in a polyvinyl alcohol resin cooling state, and loses the function of exploding a cavity in the polyvinyl alcohol resin, and meanwhile, the cellulase mixed in the microbial powder can decompose the wooden spherical cage along with microorganisms in a sewage treatment process, so that an additional glucose source is provided for the microorganisms, the metabolic activity of the microorganisms is enhanced, and metal ions of a polyvinyl alcohol resin carrier participating in reaction in the sewage treatment process can generate solid sediments to replace the spherical cage to support the cavity of the polyvinyl alcohol resin; the magnetic columns arranged in the spherical cages make the metabolic distribution of microorganisms in the polyvinyl alcohol resin carrier biased to the magnetic field distribution, and can also guide the distribution state of a complex containing a magnetic material generated in the water treatment process.
To verify the practical application effect of the present invention, the following experiments were performed:
providing a sewage treatment microbial carrier preparation method for a microbial carrier manufacturer, respectively producing microbial carriers with different qualities, and applying the microbial carriers to a preset sewage tank for testing; respectively using a carrier produced by the microbial carrier preparation method of the invention, glutaraldehyde instead of genipin as a cross-linking agent, a carrier produced by the microbial carrier preparation method of the invention without adding a spherical cage, cellulase and a certain brand of microbial carrier on the market, respectively recording the treatment time of the microbial carrier on sewage with pH <1 and the survival state of the microbe by taking the certain brand of microbial carrier on the market as reference, wherein the survival state of the microbe is obtained by recovering the carrier after the sewage is treated into a culture solution, recording the change rate of the dry weight after the microbial carrier is taken out, simultaneously carrying out an experiment of 10 carrier samples, and recording the change data of each carrier sample;
experimental group 1, vectors produced using the microbial vector preparation method of the present invention:
experiment group 2, using the carrier produced by the microbial carrier preparation method of the present invention and replacing genipin with glutaraldehyde as a cross-linking agent:
experiment group 3, using the vector produced by the microbial vector preparation method of the present invention without adding spherical cages and cellulase:
experimental group 4, using a certain brand of microbial carrier on the market:
as can be seen from the experimental groups, the sewage treatment effect and the dry weight change of the microbial carriers in the culture solution are improved along with the increase of time;
in the first experimental group, the carrier produced by the preparation method of the microbial carrier has the best treatment rate on sewage and survival state of microbes;
in the second experimental group, the carrier produced by the microbial carrier preparation method is used, and glutaraldehyde is used as a cross-linking agent instead of genipin, so that the sewage treatment effect is weakened after 24 hours, the microbial survival rate is poor, the toxicity generated by glutaraldehyde serving as the cross-linking agent remaining in a carrier material can be inferred, and the activity of microbes is reduced;
in the third experimental group, the carrier produced by the microbial carrier preparation method is used, and no spherical cage or cellulase is added, so that the effect on sewage treatment is poor, the survival state of the microbes is slightly lower than that of the first experimental group, and the microbes filled in the carrier can be inferred to be not effectively involved in the reaction of water treatment;
in the fourth experiment group, a certain brand of microorganism carrier on the market is used, the effect on sewage treatment is slightly lower than that of the first experiment group, and the survival state of the microorganism is poor, so that the microorganism carrier is used as a reference group for producing the carrier by the microorganism carrier preparation method;
in conclusion, the carrier produced by the preparation method of the microbial carrier can be found, so that the survival state of the microbes is greatly improved, a good sewage treatment effect is maintained, the microbes added into the carrier can be recycled, and the application effect of the preparation method of the microbial carrier is improved.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a sewage treatment microbial carrier is characterized by comprising the following steps: the method comprises the following steps:
s1, forming: taking polyvinyl alcohol resin as a preparation raw material of a microbial carrier, adding alginate into the polyvinyl alcohol resin in a molten state of the polyvinyl alcohol resin molding, controlling the weight ratio of the alginate in the polyvinyl alcohol resin to be 0.6-2.2%, mixing and dissolving the alginate and the polyvinyl alcohol resin for more than 20min, dripping saturated boric acid solution containing calcium chloride into the mixture within 5min before the mixing is finished, forming a gel state after the mixture is naturally cooled, scattering and separating the gel-state polyvinyl alcohol resin into small balls with the diameter of 7-17mm by a stirrer, and circularly heating and cooling the stacked small polyvinyl alcohol resin balls;
s2, crosslinking: embedding microorganisms in polyethylene film balls, mixing the polyethylene film balls with acrylamide, adding the mixture into spherical polyvinyl alcohol resin subjected to cyclic heating and cooling in S1, wherein the size of the microorganisms embedded in the polyethylene film balls is controlled to be 30-60% of that of polyvinyl alcohol resin pellets, so that the content of the microorganisms in the finally added polyethylene film balls accounts for 40-70% of that of the polyvinyl alcohol resin, and gradually reducing the upper limit of the temperature of the cyclic heating and cooling to a room temperature state in the process of adding the polyethylene film balls;
s3, modification: in the process of adding the polyethylene film balls in S2, adding quartz sand particles, controlling the particle size of the quartz sand particles to be 0.5-0.9mm, accounting for 10-25% of the weight of the polyethylene film balls, performing ball milling treatment on the quartz sand particles, and simultaneously adding an equivalent amount of foaming agent to ensure that the density of the finally prepared polyvinyl alcohol resin pellets is 1.04-1.18g/cm < 3 >;
s4, restructuring: respectively marking the upper limit and the lower limit of the temperature of the cyclic heating and cooling in the S1 as Tmin and Tmax, marking the room temperature as T0, marking the difference value of the Tmin and the T0 as T1, reducing the Tmin of the temperature of the cyclic heating and cooling by 10-20 ℃ after the working procedures in the S1-S3 are completed, adjusting the Tmax to be the temperature parameter of T0+ T1, and then performing the cyclic heating and cooling for 30-40min;
in the cross-linking procedure, the steps of embedding microorganisms in the polyethylene film spheres are as follows:
I. blowing an open polyethylene film ball through a die head with the diameter of 6mm, spraying powder containing microorganisms into the polyethylene film ball through an air gun to attach the microorganism powder to the inner wall of the polyethylene film ball, controlling the addition of the microorganism powder to be less than 20% of the internal volume of the polyethylene film ball, and then carrying out heat sealing on the opening of the polyethylene film ball;
II. And when the polyvinyl alcohol resin is in the stage of temperature reduction in temperature rise and temperature reduction, adding the polyethylene ball film prepared in the step I into the polyvinyl alcohol resin, so that the polyethylene ball film is attached to the polyvinyl alcohol resin, and the sealed polyethylene film balls are exploded in the polyvinyl alcohol resin in the process of cyclic temperature rise and temperature reduction to form a cavity structure.
2. The method for preparing the sewage treatment microbial carrier according to claim 1, wherein the method comprises the following steps: and genipin is also added into the saturated boric acid in the molding procedure, the addition process of the genipin is in the temperature rise stage of the cyclic temperature rise and temperature drop of the polyvinyl alcohol resin, and the genipin is used as a cross-linking agent in the reaction of the polyvinyl alcohol resin.
3. The method for preparing the sewage treatment microbial carrier according to claim 2, wherein the method comprises the following steps: in the molding procedure, after saturated boric acid is added to form a gel state, 0.55-0.75mol/L sodium phosphate solution is added to completely submerge the polyvinyl alcohol resin in a temperature-rising state.
4. The method for preparing a wastewater treatment microbial carrier according to claim 1, wherein the method comprises the following steps: the polyethylene film ball is also added with a spherical cage made of wood fibers, and the spherical cage is arranged in the polyethylene film ball through an opening of the polyethylene film ball; cellulase is also mixed in the microbial powder.
5. The method for preparing a sewage treatment microbial carrier according to claim 4, wherein the method comprises the following steps: and a magnetic column is added in the polyethylene film ball, and two ends of the magnetic column are clamped in the spherical cage.
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