CN116119837A - Nitrifying bacteria biological nest containing nitrifying bacteria growth promoter, and preparation method and application thereof - Google Patents
Nitrifying bacteria biological nest containing nitrifying bacteria growth promoter, and preparation method and application thereof Download PDFInfo
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- CN116119837A CN116119837A CN202310063166.7A CN202310063166A CN116119837A CN 116119837 A CN116119837 A CN 116119837A CN 202310063166 A CN202310063166 A CN 202310063166A CN 116119837 A CN116119837 A CN 116119837A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention relates to the technical field of water treatment, and discloses a nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter, a preparation method and application thereof. The nitrifying bacteria biological nest comprises the following raw materials: nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure and redispersible emulsion powder; the basalt fiber with the skin-core structure comprises basalt fiber, a biological affinity modified layer and a calcium carbonate deposition layer from inside to outside. The preparation method of the nitrifying bacteria biological nest comprises the following steps: mixing a nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure, redispersible emulsion powder and water, molding, and then soaking in an acid solution to react calcium carbonate, thereby obtaining the nitrifying bacteria biological nest. In the nitrifying bacteria biological nest, the growth promoter released slowly inside can be fully contacted with nitrifying bacteria attached and grown in the nitrifying bacteria biological nest, so that a better nitrifying treatment effect can be realized when the nitrifying bacteria biological nest is used for wastewater treatment.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter, a preparation method and application thereof.
Background
In industrial, agricultural and animal husbandry production, the discharge of nitrogen-containing wastewater leads to the increase of nitrogen content in surface water and underground water, which is easy to cause eutrophication of water bodies and endanger human health and biodiversity. Biological denitrification is one of the common methods for innocent treatment of nitrogen-containing wastewater. Nitrifying bacteria include nitrifying bacteria and nitrifying bacteria, and can convert reduced nitrogen (such as ammonia nitrogen and organic nitrogen) into hydroxylamine, nitrate nitrogen or nitrite nitrogen, and are important steps of biological denitrification of wastewater.
The nitrifying bacteria biological nest refers to a solid medium or carrier which can be put into the nitrogenous wastewater to provide a place for nitrifying bacteria to grow and reproduce and fix nitrifying bacteria. The nitrifying bacteria biological nest is utilized, so that the growth and propagation of nitrifying bacteria can be promoted, and the loss of nitrifying bacteria is reduced, so that the nitrifying bacteria can maintain higher biomass and bioactivity in the nitrogenous wastewater to improve the denitrification effect, and meanwhile, the impact resistance of a biological denitrification system can be improved, the system can be quickly recovered from the denitrification chaotic state caused by impact load and sudden factors, and the long-term stability of nitrification is maintained.
The nitrifying bacteria growth promoter can provide nutrients for the growth and propagation of nitrifying bacteria and the nitrification, so that flora can be rapidly activated to promote biological denitrification. The growth promoter is loaded in the biological nest, so that the growth promoter is slowly released in the wastewater treatment process, and the growth promoter in the wastewater can be maintained at a relatively stable level during biological denitrification, so that the problem that the addition amount of the growth promoter is not easy to control is solved, organic matters and inorganic ions in the wastewater are prevented from remaining due to the fact that the initial release amount is too high, and a good denitrification effect is difficult to maintain due to the fact that the later release amount is insufficient.
The ideal bacterial biological nest has better adsorption performance on thalli, so that microorganisms can be enriched in the bacterial biological nest, and the bacterial biological nest has rich porosity and communicated pore passages, so that a bacterial growth promoter can circulate and be transmitted in the bacterial biological nest, and the bacterial growth and propagation are promoted. Patent CN106517504B discloses a slow-release carbon source filler, and a preparation method and application thereof, wherein the slow-release carbon source filler is prepared from agar, poly-beta-hydroxybutyric acid, a wetting dispersant, a filler, an enzymatic activity regulator, a processing modifier, a high polymer adhesive and a foaming agent, wherein the poly-beta-hydroxybutyric acid is used as a carbon source, the agar is used as a skeleton carrier for wrapping the carbon source, so that stable release of the carbon source can be realized, the problems of reduced metabolic function of microorganisms, reduced pollutant removal effect and the like caused by insufficient carbon source are overcome, and residual organic matters in effluent caused by excessive release of the carbon source are avoided. The patent utilizes the foaming agent to improve the porosity of the inside of the slow-release carbon source filler, but is difficult to greatly promote the circulation and transmission of the carbon source in the filler, and promote the growth and propagation of the carbon source by contacting bacteria, which can cause the poor treatment effect of the slow-release carbon source filler on wastewater.
Disclosure of Invention
The invention provides a nitrifying bacteria biological nest containing nitrifying bacteria growth promoters, a preparation method and application thereof, and aims to solve the technical problem that the bacterial growth promoters released from the inside of the existing bacterial biological nest cannot be effectively contacted with bacteria. In the nitrifying bacteria biological nest, the slowly released growth promoter in the biological nest can be fully contacted with nitrifying bacteria attached and grown in the biological nest to provide nutrition for the growth and propagation and nitrification of the nitrifying bacteria, so that a better nitrification treatment effect can be realized when the nitrifying bacteria biological nest is used for wastewater treatment.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter, the raw materials comprising the following components: nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure and redispersible emulsion powder; the basalt fiber with the skin-core structure comprises basalt fiber, a biological affinity modified layer and a calcium carbonate deposition layer from inside to outside.
In the nitrifying bacteria biological nest, the inorganic aggregate and the redispersible emulsion powder form a matrix of the biological nest, the nitrifying bacteria growth promoter is dispersed in the matrix, and the redispersible emulsion powder can form a film between the inorganic aggregates, plays a role of fixing the inorganic aggregates and slows down the release of the growth promoter. Compared with agar in the prior art (which needs to be dissolved at the temperature close to 100 ℃), the redispersible emulsion powder has lower film forming temperature and can not damage the components with poor thermal stability in the growth promoter.
The basalt fiber with the skin-core structure adopts a three-layer structure consisting of basalt fiber, a biological affinity modified layer and a calcium carbonate deposition layer, is dispersed in a matrix consisting of inorganic aggregate and redispersible latex powder, and can form a pore canal in a biological nest by utilizing the reaction of the calcium carbonate deposition layer at the outermost layer to dissolve out and release carbon dioxide under the action of an acid solution. By utilizing the basalt fibers with the skin-core structure, the slowly released growth promoter in the biological nest is beneficial to contact with nitrifying bacteria attached and grown in the biological nest, so that the nitrifying treatment effect of the nitrifying bacteria biological nest on wastewater is improved, and the specific mechanism is as follows:
(1) after the calcium carbonate is subjected to pore-forming, gaps are formed between the fibers and the matrix, so that space can be provided for enrichment of nitrifying bacteria, and the bioaffinity modification layer has good bioaffinity and is beneficial to adhesion of nitrifying bacteria, so that nitrifying bacteria can adhere to and grow on the bioaffinity modification layer on the surface of the basalt fibers to form a nitrifying bacteria film.
(2) In addition to providing space for enrichment of nitrifying bacteria, gaps formed between the fibers and the matrix can also provide space for circulation of growth promoters, so that the slowly released growth promoters can circulate along the fibers to provide nutrients for nitrifying bacteria films on the surfaces of the fibers; in addition, in the process of calcium carbonate pore-forming, the generated gas forms pore channels in the biological nest matrix, the pore channels are communicated with the surface of the fiber, and the slow released accelerant in the biological nest matrix can flow to the surface of the fiber along the pore channels to contact with the nitrifying bacteria film so as to promote the growth and nitrifying action of nitrifying bacteria.
3. In addition, in the pore-forming process of calcium carbonate, along with the release of carbon dioxide, a pore canal can be formed in the biological nest, the surface of the fiber is communicated with the outside, nitrifying bacteria can enter along the pore canal and then adhere to the surface of the biological affinity modified layer in the fiber, nitrifying bacteria films are formed, and wastewater can enter from the outside and contact with the nitrifying bacteria films adhered to the surface of the fiber.
Through the steps (1) - (3), the basalt fiber with the skin-core structure is added, so that the growth promoter slowly released in the biological nest can provide nutrients for nitrifying bacteria attached to the surface of the fiber, and the growth of the nitrifying bacteria and the nitrification of wastewater are promoted.
Preferably, the raw materials of the bioaffinity modification layer comprise the following components: nano silicon dioxide powder, nano calcium carbonate powder, an aminosilane coupling agent, a cationic surfactant and epoxy resin.
The basalt fiber surface has the characteristics of smoothness, hydrophobicity and negative charge, is unfavorable for bacterial adhesion, and when the basalt fiber surface is used for immobilizing bacteria, the surface of the basalt fiber needs to be subjected to bioaffinity modification. In the raw materials of the bioaffinity modification layer, the epoxy resin can improve the hydrophilicity of the basalt fiber surface; the nano silicon dioxide powder can form bulges on the surface of the bioaffinity modification layer, so that the surface roughness is improved; the nano calcium carbonate powder reacts and dissolves out and releases carbon dioxide in the pore-forming process of the calcium carbonate deposition layer, and pores are formed in the bioaffinity modification layer, so that the surface roughness of the nano calcium carbonate powder is further improved; the cationic surfactant can improve the Zeta potential of the surface of the bioaffinity modification layer and reduce the electrostatic repulsive force between the fiber surface and bacteria; the aminosilane coupling agent can enable the nano silicon dioxide powder and the nano calcium carbonate powder to be uniformly dispersed into the bioaffinity modification layer, and reduce the falling of the nano silicon dioxide powder. In summary, the bioaffinity modifying layer can improve the hydrophilicity, roughness and bioaffinity of the basalt fiber surface and promote the adhesion and film formation of nitrifying bacteria on the surface.
Preferably, the preparation method of the basalt fiber with the skin-core structure comprises the following steps:
(1) Dispersing nano silicon dioxide powder and nano calcium carbonate powder into a solvent, adding an aminosilane coupling agent into the solvent, and carrying out a grafting reaction to obtain modified particle dispersion;
in the step (1), amino groups can be grafted to the surfaces of the nano silicon dioxide powder and the nano calcium carbonate powder by using the siloxy groups in the aminosilane coupling agent.
(2) Adding a cationic surfactant and epoxy resin into the modified particle dispersion liquid, uniformly mixing, and performing ring-opening reaction to obtain a fiber modified liquid;
in the step (2), the amino groups on the surfaces of the nano silicon dioxide powder and the nano calcium carbonate powder react with epoxy groups in the epoxy resin, so that the nano silicon dioxide powder and the nano calcium carbonate powder can be connected to the epoxy resin, the powder can be uniformly dispersed in the bioaffinity modified layer, and the falling of the nano silicon dioxide powder in the use process of the biological nest is reduced.
(3) Immersing basalt fibers in fiber modification liquid, taking out after immersing, and drying to obtain modified basalt fibers; in the step (3), the fiber modification liquid forms a bioaffinity modification layer on the surface of the basalt fiber.
(4) Immersing the dried modified basalt fiber in the step (3) into a calcium bicarbonate solution immediately without cooling, and taking out the basalt fiber after immersing to obtain a basalt fiber with a skin-core structure;
in the step (4), the modified basalt fiber has higher temperature, and after being immersed in the calcium bicarbonate solution, the calcium bicarbonate can be decomposed into calcium carbonate on the surface of the fiber, so that a calcium carbonate deposition layer is formed.
Further, in the steps (1) to (2), the mass ratio of the nano silicon dioxide powder to the nano calcium carbonate powder to the aminosilane coupling agent to the cationic surfactant to the epoxy resin is 1:0.5 to 1.5:5 to 7:2 to 5: 50-80.
Further, in the step (1), the temperature of the grafting reaction is 70-80 ℃ and the time is 2-4 h.
Further, in the step (1), the ratio of the total mass of the nano silica powder and the nano calcium carbonate powder to the volume of the solvent is 1g: 90-110 mL.
Further, in the step (2), the temperature of the ring-opening reaction is 50-60 ℃ and the time is 3-4 h.
Further, in the step (3), the soaking time is 1-2 h.
Further, in the step (3), the temperature of the drying is 130-150 ℃.
Further, in the step (4), the concentration of the calcium bicarbonate solution is 12-16 wt%, and the soaking time is 20-30 min.
Preferably, the nitrifying bacteria growth promoter comprises the following components in parts by weight: 20-60 parts of magnesium salt, 40-100 parts of ferrous salt, 5-20 parts of manganese salt, 1-20 parts of copper salt, 1-10 parts of zinc salt, 1-20 parts of vitamin and 1-20 parts of rhamnolipid.
The formula can provide comprehensive nutrition for nitrifying bacteria, so that the nitrifying bacteria can grow and propagate rapidly in a short time, and the nitrifying effect of the nitrifying bacteria is promoted.
Further, the vitamins include one or more of vitamin B1, vitamin B2, and vitamin C.
Preferably, the inorganic aggregate comprises one or more of quartz sand, attapulgite, diatomite, bentonite and talcum powder.
Preferably, the nitrifying bacteria biological nest comprises the following raw materials in parts by weight: 10-20 parts of nitrifying bacteria growth promoter, 30-50 parts of inorganic aggregate, 5-13 parts of basalt fiber with a skin-core structure and 3.5-5.5 parts of redispersible emulsion powder.
In a second aspect, the invention provides a method for preparing the nitrifying bacteria biological nest, which comprises the following steps: mixing a nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure, redispersible emulsion powder and water, molding, and then soaking in an acid solution to react calcium carbonate, thereby obtaining the nitrifying bacteria biological nest.
In a third aspect, the invention provides the use of said nitrifying bacteria biological nest in wastewater treatment.
Compared with the prior art, the invention has the following advantages:
(1) According to the nitrifying bacteria biological nest, the special basalt fiber with the skin-core structure is adopted, so that the growth promoter slowly released in the biological nest can be fully contacted with nitrifying bacteria attached and grown in the biological nest, and the nitrifying treatment effect of the nitrifying bacteria biological nest on wastewater is improved;
(2) According to the basalt fiber with the skin-core structure, which is used in the invention, the nano calcium carbonate powder is added into the raw material of the bioaffinity modification layer, so that the roughness of the bioaffinity modification layer can be improved, and the attachment and film formation of nitrifying bacteria on the surface of the fiber are promoted.
Detailed Description
The invention is further described below with reference to examples.
General examples
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter, which comprises the following raw materials: nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure and redispersible emulsion powder; the basalt fiber with the skin-core structure comprises basalt fiber, a biological affinity modified layer and a calcium carbonate deposition layer from inside to outside.
In some embodiments, the nitrifying bacteria biological nest comprises the following raw materials in parts by weight: 10-20 parts of nitrifying bacteria growth promoter, 30-50 parts of inorganic aggregate, 5-13 parts of basalt fiber with a skin-core structure and 3.5-5.5 parts of redispersible emulsion powder.
In some embodiments, the preparation method of the basalt fiber with the skin-core structure comprises the following steps:
(1) Dispersing nano silicon dioxide powder and nano calcium carbonate powder into a solvent, adding an aminosilane coupling agent into the solvent, and performing a grafting reaction (the temperature is 70-80 ℃ and the time is 2-4 h) to prepare modified particle dispersion liquid; the ratio of the total mass of the nano silicon dioxide powder and the nano calcium carbonate powder to the volume of the solvent is 1g: 90-110 mL;
(2) Adding a cationic surfactant and epoxy resin into the modified particle dispersion liquid, uniformly mixing, and carrying out ring-opening reaction (the temperature is 50-60 ℃ and the time is 3-4 h) to obtain a fiber modified liquid; the mass ratio of the nano silicon dioxide powder to the nano calcium carbonate powder to the aminosilane coupling agent to the cationic surfactant to the epoxy resin is 1:0.5 to 1.5:5 to 7:2 to 5: 50-80 parts;
(3) Immersing basalt fiber into fiber modification liquid, taking out after immersing for 1-2 h, and drying (the temperature is 130-150 ℃ and the time is 0.5-1 h) to obtain modified basalt fiber;
(4) And (3) immediately immersing the dried modified basalt fiber in the step (3) in a 12-16 wt% calcium bicarbonate solution without cooling for 20-30 min, and taking out to obtain the basalt fiber with a skin-core structure.
In some embodiments, the nitrifying bacteria growth promoter comprises the following components in parts by weight: 20-60 parts of magnesium salt, 40-100 parts of ferrous salt, 5-20 parts of manganese salt, 1-20 parts of copper salt, 1-10 parts of zinc salt, 1-20 parts of vitamin and 1-20 parts of rhamnolipid.
Optionally, the vitamins include one or more of vitamin B1, vitamin B2, and vitamin C.
In some embodiments, the inorganic aggregate comprises one or more of quartz sand, attapulgite, diatomaceous earth, bentonite, and talc.
A method for preparing the nitrifying bacteria biological nest, which comprises the following steps: mixing a nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure, redispersible emulsion powder and water, molding, and then soaking in an acid solution to react calcium carbonate, thereby obtaining the nitrifying bacteria biological nest.
The application of the nitrifying bacteria biological nest in wastewater treatment.
Example 1
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 30 parts of magnesium sulfate, 60 parts of ferrous sulfate, 10 parts of manganese sulfate, 10 parts of copper sulfate, 5 parts of zinc sulfate, 15 parts of vitamins and 15 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
(2.1) weighing the following components in parts by weight: 1 part of nano silicon dioxide powder, 1 part of nano calcium carbonate powder, 5-7 parts of silane coupling agent KH-550, 2-5 parts of hexadecyl trimethyl ammonium chloride and 50-80 parts of epoxy resin;
(2.2) taking nano silicon dioxide powder and nano calcium carbonate powder according to a solid-to-liquid ratio of 1g:100mL of the modified particle dispersion is added into ethanol water solution (the volume ratio of ethanol to water is 1:1.5), after ultrasonic dispersion is carried out for 10min, silane coupling agent KH-550 is added into the solution, and the mixture is heated and refluxed for 3h at 75 ℃ to obtain modified particle dispersion;
(2.3) adding cetyl trimethyl ammonium chloride and epoxy resin into the modified particle dispersion liquid, stirring uniformly at a high speed, and stirring for 3.5 hours at 55 ℃ to obtain a fiber modified liquid;
(2.4) basalt fiber having a diameter of 13 μm was mixed in an amount of 1g:10mL of the fiber modified liquid is immersed in the fiber modified liquid according to the mass volume ratio of 1.5h, taken out after being immersed, dried for 0.5h at 140 ℃, and immediately mixed according to 1g: and immersing 20mL of the basalt fiber into 15wt% calcium bicarbonate solution according to the mass-volume ratio, taking out the basalt fiber after immersing for 30min, and drying the basalt fiber at 120 ℃ until the weight is constant, thus obtaining the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 15 parts of nitrifying bacteria growth promoter, 20 parts of quartz sand, 18 parts of attapulgite, 10 parts of basalt fiber with a skin-core structure, 4.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 15 parts of water;
(3.2) uniformly mixing all the raw materials by using a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g: immersing 20mL in 10wt% hydrochloric acid for 1.5h, taking out, washing with water to neutrality, and draining to obtain nitrifying bacteria biological nest.
Example 2
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 20 parts of magnesium sulfate, 100 parts of ferrous sulfate, 5 parts of manganese sulfate, 1 part of copper sulfate, 10 parts of zinc sulfate, 1 part of vitamin and 20 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
(2.1) weighing the following components in parts by weight: 1 part of nano silicon dioxide powder, 1.5 parts of nano calcium carbonate powder, 5-7 parts of silane coupling agent KH-550, 2-5 parts of hexadecyl trimethyl ammonium chloride and 50-80 parts of epoxy resin;
(2.2) taking nano silicon dioxide powder and nano calcium carbonate powder according to a solid-to-liquid ratio of 1g:100mL of the modified particle dispersion is added into ethanol water solution (the volume ratio of ethanol to water is 1:1.5), after ultrasonic dispersion is carried out for 10min, silane coupling agent KH-550 is added into the solution, and the mixture is heated and refluxed for 4h at 70 ℃ to obtain modified particle dispersion;
(2.3) adding hexadecyl trimethyl ammonium chloride and epoxy resin into the modified particle dispersion liquid, stirring uniformly at a high speed, and stirring for 3 hours at 60 ℃ to obtain a fiber modified liquid;
(2.4) basalt fiber having a diameter of 13 μm was mixed in an amount of 1g:10mL of the fiber modified liquid is immersed in the fiber modified liquid according to the mass volume ratio, the fiber modified liquid is taken out after being immersed for 1h, and the fiber modified liquid is dried for 0.5h at 150 ℃ and immediately mixed with 1g: and immersing 20mL of the basalt fiber into a 12wt% calcium bicarbonate solution according to the mass-volume ratio, taking out the basalt fiber after immersing for 30min, and drying the basalt fiber at 120 ℃ until the weight is constant, thus obtaining the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 10 parts of nitrifying bacteria growth promoter, 30 parts of quartz sand, 20 parts of attapulgite, 13 parts of skin-core structure basalt fiber, 5.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 20 parts of water;
(3.2) uniformly mixing all the raw materials by using a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g:20mL is immersed in 10wt% hydrochloric acid, taken out after being immersed for 2 hours, washed to be neutral by water, and drained, thus obtaining the nitrifying bacteria biological nest.
Example 3
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 60 parts of magnesium sulfate, 40 parts of ferrous sulfate, 20 parts of manganese sulfate, 20 parts of copper sulfate, 1 part of zinc sulfate, 20 parts of vitamins and 5 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
(2.1) weighing the following components in parts by weight: 1 part of nano silicon dioxide powder, 0.5 part of nano calcium carbonate powder, 5 to 7 parts of silane coupling agent KH-550, 2 to 5 parts of hexadecyl trimethyl ammonium chloride and 50 to 80 parts of epoxy resin;
(2.2) taking nano silicon dioxide powder and nano calcium carbonate powder according to a solid-to-liquid ratio of 1g:100mL of the modified particle dispersion is added into ethanol water solution (the volume ratio of ethanol to water is 1:1.5), after ultrasonic dispersion is carried out for 10min, silane coupling agent KH-550 is added into the solution, and the mixture is heated and refluxed for 2h at 80 ℃ to obtain modified particle dispersion;
(2.3) adding hexadecyl trimethyl ammonium chloride and epoxy resin into the modified particle dispersion liquid, stirring uniformly at a high speed, and stirring for 4 hours at 50 ℃ to obtain a fiber modified liquid;
(2.4) basalt fiber having a diameter of 13 μm was mixed in an amount of 1g: immersing 10mL of the fiber into the fiber modification liquid according to the mass-volume ratio, immersing for 2 hours, taking out, drying at 130 ℃ for 1 hour, and immediately mixing with 1g: and immersing 20mL of the basalt fiber into 16wt% calcium bicarbonate solution according to the mass-volume ratio, taking out the basalt fiber after immersing for 20min, and drying the basalt fiber at 120 ℃ until the weight is constant, thus obtaining the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 20 parts of nitrifying bacteria growth promoter, 15 parts of quartz sand, 15 parts of attapulgite, 5 parts of basalt fiber with a skin-core structure, 3.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 10 parts of water;
(3.2) uniformly mixing all the raw materials by using a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g:20mL is immersed in 10wt% hydrochloric acid, taken out after being immersed for 1h, washed to be neutral by water, and drained, thus obtaining the nitrifying bacteria biological nest.
Example 4
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 30 parts of magnesium sulfate, 60 parts of ferrous sulfate, 10 parts of manganese sulfate, 10 parts of copper sulfate, 5 parts of zinc sulfate, 15 parts of vitamins and 15 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
(2.1) weighing the following components in parts by weight: 1 part of nano silicon dioxide powder, 5-7 parts of silane coupling agent KH-550, 2-5 parts of hexadecyl trimethyl ammonium chloride and 50-80 parts of epoxy resin;
(2.2) taking nano silicon dioxide powder, wherein the solid-to-liquid ratio is 0.5g:100mL of the modified particle dispersion is added into ethanol water solution (the volume ratio of ethanol to water is 1:1.5), after ultrasonic dispersion is carried out for 10min, silane coupling agent KH-550 is added into the solution, and the mixture is heated and refluxed for 3h at 75 ℃ to obtain modified particle dispersion;
(2.3) adding cetyl trimethyl ammonium chloride and epoxy resin into the modified particle dispersion liquid, stirring uniformly at a high speed, and stirring for 3.5 hours at 55 ℃ to obtain a fiber modified liquid;
(2.4) basalt fiber having a diameter of 13 μm was mixed in an amount of 1g:10mL of the fiber modified liquid is immersed in the fiber modified liquid according to the mass volume ratio of 1.5h, taken out after being immersed, dried for 0.5h at 140 ℃, and immediately mixed according to 1g: and immersing 20mL of the basalt fiber into 15wt% calcium bicarbonate solution according to the mass-volume ratio, taking out the basalt fiber after immersing for 30min, and drying the basalt fiber at 120 ℃ until the weight is constant, thus obtaining the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 15 parts of nitrifying bacteria growth promoter, 20 parts of quartz sand, 18 parts of attapulgite, 10 parts of basalt fiber with a skin-core structure, 4.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 15 parts of water;
(3.2) uniformly mixing all the raw materials by using a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g: immersing 20mL in 10wt% hydrochloric acid for 1.5h, taking out, washing with water to neutrality, and draining to obtain nitrifying bacteria biological nest.
Comparative example 1
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 30 parts of magnesium sulfate, 60 parts of ferrous sulfate, 10 parts of manganese sulfate, 10 parts of copper sulfate, 5 parts of zinc sulfate, 15 parts of vitamins and 15 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparation of nitrifying bacteria biological nest:
(2.1) weighing according to parts by weight: 15 parts of nitrifying bacteria growth promoter, 20 parts of quartz sand, 18 parts of attapulgite, 3.5 parts of calcium carbonate, 4.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 15 parts of water;
(2.2) uniformly mixing all raw materials by a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(2.3) the biological nest blank is mixed according to 1g: immersing 20mL in 10wt% hydrochloric acid for 1.5h, taking out, washing with water to neutrality, and draining to obtain nitrifying bacteria biological nest.
Comparative example 2
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 30 parts of magnesium sulfate, 60 parts of ferrous sulfate, 10 parts of manganese sulfate, 10 parts of copper sulfate, 5 parts of zinc sulfate, 15 parts of vitamins and 15 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
(2.1) weighing the following components in parts by weight: 1 part of nano silicon dioxide powder, 1 part of nano calcium carbonate powder, 5-7 parts of silane coupling agent KH-550, 2-5 parts of hexadecyl trimethyl ammonium chloride and 50-80 parts of epoxy resin;
(2.2) taking nano silicon dioxide powder and nano calcium carbonate powder according to a solid-to-liquid ratio of 1g:100mL of the modified particle dispersion is added into ethanol water solution (the volume ratio of ethanol to water is 1:1.5), after ultrasonic dispersion is carried out for 10min, silane coupling agent KH-550 is added into the solution, and the mixture is heated and refluxed for 3h at 75 ℃ to obtain modified particle dispersion;
(2.3) adding cetyl trimethyl ammonium chloride and epoxy resin into the modified particle dispersion liquid, stirring uniformly at a high speed, and stirring for 3.5 hours at 55 ℃ to obtain a fiber modified liquid;
(2.4) basalt fiber having a diameter of 13 μm was mixed in an amount of 1g: immersing 10mL of the basalt fiber into the fiber modified liquid in a mass-volume ratio, immersing for 1.5h, taking out, and drying at 140 ℃ to constant weight to obtain the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 15 parts of nitrifying bacteria growth promoter, 20 parts of quartz sand, 18 parts of attapulgite, 10 parts of basalt fiber with a skin-core structure, 3.5 parts of calcium carbonate, 4.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 15 parts of water;
(3.2) uniformly mixing all the raw materials by using a mixer, injecting the obtained slurry into a mould, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g: immersing 20mL in 10wt% hydrochloric acid for 1.5h, taking out, washing with water to neutrality, and draining to obtain nitrifying bacteria biological nest.
Comparative example 3
A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter is prepared by the steps of:
(1) Preparation of nitrifying bacteria growth promoter:
(1.1) weighing the following components in parts by weight: 30 parts of magnesium sulfate, 60 parts of ferrous sulfate, 10 parts of manganese sulfate, 10 parts of copper sulfate, 5 parts of zinc sulfate, 15 parts of vitamins and 15 parts of rhamnolipid;
(1.2) separating particles and blocks of all raw materials by using a FAST-600 rotary vibrating screen, wherein the mesh number of the screen is 30 meshes, the particles can be directly used, and the blocks are required to be scattered by a pulverizer to be in the form of particles for use;
(1.3) uniformly mixing all the raw materials treated in the step (1.2) by a mixer to obtain the nitrifying bacteria growth promoter.
(2) Preparing basalt fiber with a skin-core structure:
immediately after heat treatment of basalt fiber with a diameter of 13 μm at 140 ℃ for 0.5h, 1g: and immersing 20mL of the basalt fiber into 15wt% calcium bicarbonate solution according to the mass-volume ratio, taking out the basalt fiber after immersing for 30min, and drying the basalt fiber at 120 ℃ until the weight is constant, thus obtaining the basalt fiber with the skin-core structure.
(3) Preparation of nitrifying bacteria biological nest:
(3.1) weighing according to parts by weight: 15 parts of nitrifying bacteria growth promoter, 20 parts of quartz sand, 18 parts of attapulgite, 10 parts of basalt fiber with a skin-core structure, 4.5 parts of ethylene-vinyl acetate copolymer emulsion powder and 15 parts of water;
(3.2) uniformly mixing all raw materials by using a mixer, injecting the obtained slurry into a rectangular mould with the thickness of 6cm multiplied by 3cm, drying and demoulding to obtain a biological nest blank;
(3.3) the biological nest blank is mixed according to 1g: immersing 20mL in 10wt% hydrochloric acid for 1.5h, taking out, washing with water to neutrality, and draining to obtain nitrifying bacteria biological nest.
Application example
The nitrifying bacteria biological nest prepared in examples 1 to 4 and comparative examples 1 to 3 is used for carrying out wastewater nitrifying treatment, and the specific process is as follows: 5L of production wastewater (COD is 1100mg/L, ammonia nitrogen concentration is 200 mg/L) of a pharmaceutical factory in Taizhou, zhejiang province is taken, 50g of biological nest and 1g of nitrifying bacillus bacteria agent are added, the content of dissolved oxygen in the wastewater is controlled to be 4.5+/-0.5 mg/L, and the temperature is 30+/-1 ℃ for wastewater nitrification treatment. The ammonia nitrogen content was detected by sampling at intervals from the start of the addition of the biological nest and the microbial inoculum, and the results are shown in Table 1.
TABLE 1 Ammonia nitrogen concentration in wastewater (in mg/L) over time
| 18h after adding | After adding for 48h | After being added for 66h | 90h after adding | 114h after adding | |
| No addition of biological nest | 199.0 | 196.8 | 193.6 | 189.9 | 184.5 |
| Example 1 | 181.2 | 128.6 | 88.7 | 31.6 | 8.4 |
| Example 2 | 182.9 | 134.3 | 96.0 | 36.2 | 9.6 |
| Example 3 | 190.4 | 144.5 | 106.3 | 47.5 | 20.7 |
| Example 4 | 190.8 | 146.0 | 110.5 | 56.2 | 26.8 |
| Comparative example 1 | 195.7 | 160.3 | 132.6 | 91.6 | 68.0 |
| Comparative example 2 | 193.3 | 154.6 | 119.2 | 69.4 | 45.3 |
| Comparative example 3 | 192.9 | 157.6 | 127.4 | 84.3 | 59.8 |
Comparing the effect of the biological nest of each example and comparative example in the above table on the nitrification treatment of wastewater, it can be seen that:
(1) The significantly higher ammonia nitrogen removal efficiency of examples 1-4 and comparative examples 1-3 compared to the absence of addition of the biological nest, demonstrates that nitrifying bacteria can be rapidly activated and their nitrification of wastewater promoted by the addition of the biological nest.
(2) The ammonia nitrogen removal efficiency of example 1 is obviously higher than that of comparative examples 1 and 2, which shows that compared with the calcium carbonate which is added with a pore-forming agent in a dispersing way, the calcium carbonate is deposited on the surface of basalt fiber with a skin-core structure, so that the effect of promoting the nitrification treatment of wastewater by biological nest can be improved. The reason is that: the calcium carbonate pore-forming on the surface of the basalt fiber with the skin-core structure can form a gap between the fiber and the matrix to provide a space for bacteria adhesion and growth promoter to circulate along the fiber, and gas generated in the calcium carbonate pore-forming process forms pore channels in the matrix, wherein the pore channels can communicate the surface of the fiber with the outside and the inside of the biological nest matrix. Through the mode, nitrifying bacteria can enter the biological nest and are enriched on the surface of the fiber, and meanwhile, the slowly released growth promoter is beneficial to contact with nitrifying bacteria on the surface of the fiber, so that wastewater can enter the biological nest and contact with nitrifying bacteria films on the surface of the fiber, and the growth and propagation of nitrifying bacteria and the nitrifying action on the wastewater are promoted.
(3) Compared with comparative example 3, the ammonia nitrogen removal efficiency of example 1 is higher, which shows that the effect of promoting the wastewater nitrification treatment by the biological nest can be improved by arranging the biological affinity modification layer on the surface of the basalt fiber. The reason is that: the basalt fiber surface has the characteristics of smoothness, hydrophobicity and negative charge, is unfavorable for bacterial adhesion, and after the bioaffinity modification layer is formed on the surface of the basalt fiber surface by modifying the surface of the basalt fiber surface by the method, the hydrophilicity, the roughness and the bioaffinity of the basalt fiber surface can be improved, and the adhesion and the film formation of nitrifying bacteria on the surface of the basalt fiber surface are promoted, so that the biological nest is favorable for playing the role of promoting the growth and the nitrifying metabolism of the nitrifying bacteria.
(4) Compared with example 4, the ammonia nitrogen removal efficiency of example 1 is significantly higher, which indicates that the effect of promoting the nitrification treatment of the wastewater by the biological nest can be improved by adding calcium carbonate into the bioaffinity modification layer. The reason is that: in the pore-forming process of the calcium carbonate deposition layer, the nano calcium carbonate powder in the bioaffinity modification layer also reacts to dissolve out and release carbon dioxide, and pores are formed in the bioaffinity modification layer, so that the surface roughness of the bioaffinity modification layer is improved, and the adhesion and film forming of nitrifying bacteria on the surface of the bioaffinity modification layer are further promoted.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A nitrifying bacteria biological nest containing a nitrifying bacteria growth promoter, characterized in that the raw materials comprise the following components: nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure and redispersible emulsion powder; the basalt fiber with the skin-core structure comprises basalt fiber, a biological affinity modified layer and a calcium carbonate deposition layer from inside to outside.
2. The nitrifying bacteria biological nest of claim 1, wherein the raw materials of said bioaffinity-modifying layer comprise the following components: nano silicon dioxide powder, nano calcium carbonate powder, an aminosilane coupling agent, a cationic surfactant and epoxy resin.
3. The nitrifying bacteria biological nest of claim 2, wherein said method for preparing said sheath-core structural basalt fiber comprises the steps of:
(1) Dispersing nano silicon dioxide powder and nano calcium carbonate powder into a solvent, adding an aminosilane coupling agent into the solvent, and carrying out a grafting reaction to obtain modified particle dispersion;
(2) Adding a cationic surfactant and epoxy resin into the modified particle dispersion liquid, uniformly mixing, and performing ring-opening reaction to obtain a fiber modified liquid;
(3) Immersing basalt fibers in fiber modification liquid, taking out after immersing, and drying to obtain modified basalt fibers;
(4) And (3) immediately immersing the dried modified basalt fiber in the step (3) into a calcium bicarbonate solution without cooling, and taking out after immersing to obtain the basalt fiber with the skin-core structure.
4. The nitrifying bacteria biological nest of claim 3, wherein in the steps (1) - (2), the mass ratio of the nano silicon dioxide powder, the nano calcium carbonate powder, the aminosilane coupling agent, the cationic surfactant and the epoxy resin is 1:0.5 to 1.5: 5-7: 2-5: 50-80.
5. The nitrifying bacteria biological nest of claim 3, wherein in step (3), the temperature of drying is 130-150 ℃.
6. The nitrifying bacteria biological nest of claim 3, wherein in the step (4), the concentration of the calcium bicarbonate solution is 12-16wt% and the soaking time is 20-30 min.
7. The nitrifying bacteria biological nest of claim 1, wherein said nitrifying bacteria growth promoter comprises the following components in parts by weight: 20-60 parts of magnesium salt, 40-100 parts of ferrous salt, 5-20 parts of manganese salt, 1-20 parts of copper salt, 1-10 parts of zinc salt, 1-20 parts of vitamin and 1-20 parts of rhamnolipid.
8. The nitrifying bacteria biological nest of claim 1, wherein the raw materials comprise the following components in parts by weight: 10-20 parts of nitrifying bacteria growth promoter, 30-50 parts of inorganic aggregate, 5-13 parts of basalt fiber with a skin-core structure and 3.5-5.5 parts of redispersible emulsion powder.
9. A method for preparing a nitrifying bacteria biological nest according to one of claims 1 to 8, characterized by comprising the following steps: mixing a nitrifying bacteria growth promoter, inorganic aggregate, basalt fiber with a skin-core structure, redispersible emulsion powder and water, molding, and then soaking in an acid solution to react calcium carbonate, thereby obtaining the nitrifying bacteria biological nest.
10. Use of the nitrifying bacteria biological nest according to one of claims 1 to 8 in wastewater treatment.
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| CN116789377B (en) * | 2023-08-18 | 2024-01-30 | 宿迁和天下建材科技有限公司 | Early-strength anti-cracking concrete admixture and preparation method thereof |
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