CN112174335A - Porous slow-release wax loaded with microbial carbon source and preparation method and application thereof - Google Patents
Porous slow-release wax loaded with microbial carbon source and preparation method and application thereof Download PDFInfo
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- CN112174335A CN112174335A CN202010961059.2A CN202010961059A CN112174335A CN 112174335 A CN112174335 A CN 112174335A CN 202010961059 A CN202010961059 A CN 202010961059A CN 112174335 A CN112174335 A CN 112174335A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/308—Biological phosphorus removal
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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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Abstract
The invention relates to the field of water treatment, and discloses a porous slow-release wax loaded with a microbial carbon source, and a preparation method and application thereof. The porous slow-release wax comprises: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside. The porous slow-release wax can slowly release a carbon source, does not cause the increase of COD (chemical oxygen demand) of a water body, can provide a continuous, as-needed and controllable carbon source for beneficial microorganisms, keeps the balance of carbon, nitrogen and phosphorus, and is beneficial to the growth and the propagation of the beneficial microorganisms; in addition, the porous slow-release wax can form a through three-dimensional network pore canal, so that beneficial microorganisms in the water body can grow and propagate on the pore walls, the contact area of the microorganisms and the water body is increased, and the water treatment efficiency is improved.
Description
Technical Field
The invention relates to the field of water treatment, in particular to porous slow-release wax loaded with a microbial carbon source and a preparation method and application thereof.
Background
Nitrogen and phosphorus are important nutrient sources of organisms, and eutrophication of water bodies is easily caused by excessive content of nitrogen and phosphorus in the water bodies. The nitrogen and phosphorus pollution sources are more, and the industrial and mining enterprise wastewater, the livestock and poultry breeding wastewater and the domestic wastewater have higher nitrogen and phosphorus contents. At present, nitrogen and phosphorus pollution becomes an important problem for preventing and treating water pollution.
Microorganisms such as ammonia oxidizing bacteria, nitrosobacteria, nitrifying bacteria and denitrifying bacteria can convert ammonia nitrogen, nitrite nitrogen, nitrate and organic nitrogen in the water body into nitrogen to overflow from the water body, so that the nitrogen content in the water body is reduced; the microorganisms can absorb phosphorus in the normal growth process to meet physiological needs, the microorganisms such as phosphorus accumulating bacteria and the like can absorb the phosphorus in excess to form intracellular polymeric phosphate, and the phosphorus content in the water body can be reduced by utilizing the absorption and conversion of the microorganisms on the phosphorus. Compared with a physical and chemical method, the method for removing nitrogen and phosphorus from the water body by using the microorganisms has the advantages of low treatment cost and less secondary pollution to the environment, is favored by researchers at home and abroad, and is widely applied to sewage treatment and polluted water body treatment.
In the process of microbial nitrogen and phosphorus removal, a large amount of organic carbon sources are consumed for microbial phosphorus uptake, and organic matters with a certain concentration are also required for denitrification to serve as electron donors, but the problem of insufficient carbon sources generally exists in domestic wastewater and polluted water bodies, so that additional carbon sources need to be added to meet the carbon source requirements of microbial phosphorus uptake, denitrification and the like. Chinese patent publication No. CN106830365A discloses a method for biologically decontaminating and purifying water, comprising the following steps: firstly, stirring and separating sludge: adopting movable sludge aeration equipment to re-precipitate sludge at the bottom of the treated rivers and lakes; then, a microorganism survival carrier system is established: putting a carbon source and a microbial bed in the treated rivers and lakes to provide environments for propagation, parasitism and growth of dominant floras; culturing and putting dominant flora: extracting microorganisms with water quality purifying function in river and lake water bodies to form dominant bacterial communities to be thrown into a polluted water body engineering section; installing water body aeration equipment; and finally, the self-purification function of the water body is improved: the dominant flora is rapidly propagated under the action of aeration, nitrifies and degrades sludge and organic matters in water in situ, degrades and converts ammonia, nitrogen and phosphorus pollutants. In the method, the COD in the water body is increased in a short period by directly adding the carbon source, so that the water body is anoxic and the water quality is deteriorated, beneficial microorganisms can grow and reproduce quickly only when the carbon nitrogen phosphorus ratio is in a proper range, and the problems of microorganism metabolism imbalance and the like caused by excessively high early and excessively low later organic carbon content in the water body by directly adding the carbon source are solved, so that the growth and the reproduction of the beneficial microorganisms are not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a porous slow-release wax loaded with a microbial carbon source, and a preparation method and application thereof. The porous slow-release wax can slowly release a carbon source, does not cause the increase of COD (chemical oxygen demand) of a water body, can provide a continuous, as-needed and controllable carbon source for beneficial microorganisms, keeps the balance of carbon, nitrogen and phosphorus, and is beneficial to the growth and the propagation of the beneficial microorganisms; in addition, the porous slow-release wax can form a through three-dimensional network pore canal, so that beneficial microorganisms in the water body can grow and propagate on the pore walls, the contact area of the microorganisms and the water body is increased, and the water treatment efficiency is improved.
The specific technical scheme of the invention is as follows:
a porous slow release wax loaded with a microbial carbon source comprising:
a waxy carrier, a source of wax,
a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the waxy carrier,
a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
After the product is put into a water body to be treated (high nitrogen and high phosphorus), the waxy carrier can be used as a growth and propagation place of beneficial microorganisms (such as bacillus) in the water body, and plays a role in promoting and enriching the beneficial microorganisms; meanwhile, the loaded carbon source is water-insoluble, so that the carbon source can be slowly released in water for a long time, the carbon source substances are complemented with a nitrogen source, a phosphorus source and the like in a water body to serve as a nutrient source of beneficial microorganisms, the growth and the propagation of the beneficial microorganisms are promoted, and finally a layer of microbial film (the number of bacteria cultured on the surface of the waxy carrier can be 9.16 times that of bacteria cultured on the surface of a common filter medium) is formed on the contact surface of the waxy carrier and the water body. The beneficial microorganisms can take nitrogen and phosphorus sources in the water body as nutrient substances in the growth and propagation process, and can effectively reduce indexes such as ammonia nitrogen, total phosphorus and the like in the water body. In addition, a large amount of enzyme is generated after the beneficial microorganisms grow and reproduce, and nitrogen sources and phosphorus sources of macromolecules in the water body can be decomposed into biological nitrate and polyphosphate which can be utilized by nitrobacteria and polyphosphate converting bacteria, so that reactions such as nitrification and denitrification are improved, and indexes such as ammonia nitrogen, total nitrogen and total phosphorus in the water body are reduced. Therefore, the product can be used for water body treatment (such as riverways, ocean lakes, wastewater ponds of factories, culture tail water and the like), and compared with the traditional water body treatment method for directly throwing the carbon source, the product can provide a growth and reproduction place for beneficial microorganisms, the carbon source is slowly released, COD (chemical oxygen demand) in the water body cannot be increased, a continuous, on-demand and controllable carbon source can be provided for the beneficial microorganisms, the carbon-nitrogen-phosphorus balance is kept, and the growth and reproduction of the beneficial microorganisms are facilitated.
On the other hand, after the waxy carrier is soaked in water, the polyvinyl alcohol fiber net with a three-dimensional network structure is dissolved in water, through three-dimensional network pore passages are formed in the waxy carrier and communicated with the outside, and water can enter the pore passages to grow and propagate beneficial microorganisms in a water body on the pore walls, so that the contact area of the microorganisms and the water body can be increased, and the water treatment effect is improved.
Although the porosity of the holes prepared by the conventional hole making process (such as adding sodium chloride into a wax block and forming the holes after dissolving the sodium chloride in water) can be controlled at a high level, the holes are independent from each other and cannot be communicated, so that the water cannot permeate into a wax carrier, beneficial microorganisms in a water body cannot enter the holes to grow and breed, and the microorganisms growing in the holes cannot be fully contacted with the water body to play a role in purifying water. Therefore, compared with the traditional hole making process, the invention can realize the communication between the holes, increase the contact area of the wax carrier and the water body and further improve the water treatment effect. In addition, compared with the traditional hole making process, the method has controllable porosity, can prevent the too high porosity from causing the too fast release of carbon source substances, can prevent the increase of COD (chemical oxygen demand) in the water body and the damage of carbon nitrogen phosphorus balance caused by the carbon source which is not utilized at the initial feeding stage, is not beneficial to the growth and the propagation of beneficial microorganisms, and can also prevent the too low porosity from causing the too small contact area between the waxy carrier and the water body and influencing the water treatment efficiency.
Preferably, the waxy carrier comprises the following raw materials in parts by weight: 70-75 parts of soft wax, 20 parts of paraffin wax and 5-10 parts of microcrystalline wax, wherein the total amount is 100 parts; the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5-20 parts of engine oil and 1-2 parts of PHBV; the auxiliary agent comprises the following raw materials in parts by weight: 1-2 parts of rhamnolipid and 1-2 parts of water; the polyvinyl alcohol fiber net accounts for 30-40% of the weight of the waxy carrier.
Further, the engine oil, the PHBV, the rhamnolipid and the water are respectively 15 parts, 1 part and 1 part by weight.
The PHBV refers to a copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate, and is a microbial degradable material. The PHBV and the engine oil can be used as a microbial carbon source, and the PHBV and the engine oil are combined, so that the method has the following advantages: compared with PHBV, the engine oil is easier to release and is easier to be utilized by microorganisms, so the combination of the engine oil and the PHBV can ensure that the microorganisms have time selectivity when the carbon source is utilized, and is beneficial to the long-acting slow release of the carbon source.
Besides two basic substances, namely a waxy carrier and a carbon source, rhamnolipid can be used as a surfactant, so that the components are better fused; the water can improve the fluidity of the wax liquid, promote the mixing of all the components and enable the porous slow-release wax to better adapt to the water environment.
Preferably, the melting point of the soft wax is 45-50 ℃, the melting point of the paraffin wax is 55-65 ℃, and the melting point of the microcrystalline wax is 60-80 ℃.
Preferably, the polyvinyl alcohol fibers have a diameter of 0.5 to 1.5 mm.
Preferably, the polyvinyl alcohol fiber is a modified polyvinyl alcohol fiber, and the preparation method is as follows:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol and urea into dimethyl sulfoxide in a protective atmosphere, heating to 80-90 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinositide, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinositide is 1: 4-6, and reacting for 10-15 min under 250-300W microwaves; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 100-110 ℃, spraying the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-10-0 ℃ to form jelly-like nascent fibers; and (3) primarily stretching the jelly-like nascent fiber, extracting with methanol, applying oil, drying, stretching, heat setting, and twisting again to obtain the modified polyvinyl alcohol fiber.
Compared with the method of firstly dissolving the polyvinyl alcohol fibers in warm water and then putting the dissolved polyvinyl alcohol fibers into the water body to be treated, the method of directly putting the carbon source in the porous slow-release wax can prevent the carbon source from being quickly released at the initial stage of putting, and as beneficial microorganisms at the initial stage of putting are not propagated in a large amount, the unused carbon source can cause the increase of COD in the water body and destroy the balance of carbon and nitrogen, which is not beneficial to the growth and propagation of the beneficial microorganisms, and in addition, the method can cause the insufficient release of the carbon source at the later stage and the death of the beneficial microorganisms in a large amount. Therefore, the direct feeding can obtain better water treatment effect. However, the dissolution temperature of common polyvinyl alcohol is usually above 80 ℃, and the dissolution in normal temperature water is too slow, so that the contact area between the interior of the porous slow-release wax and the water is small, and the water treatment efficiency is limited; polyvinyl alcohol having a low degree of polymerization has a low dissolution temperature, but is poor in spinnability and difficult to be made into fibers.
Aiming at the problems, the invention utilizes 1, 3-diphosphinositide to modify polyvinyl alcohol, phosphate groups in the 1, 3-diphosphinositide and hydroxyl groups in the polyvinyl alcohol are subjected to esterification reaction under the catalysis of urea, so that the 1, 3-diphosphinositide is grafted to a polyvinyl alcohol side chain, and the water solubility of the polyvinyl alcohol can be improved by the hydroxyl groups in the 1, 3-diphosphinositide, thereby accelerating the dissolution speed of the polyvinyl alcohol in a normal-temperature water body, enabling the porous slow-release wax to be directly put into a water body to be treated, gradually dissolving the modified polyvinyl alcohol fiber in the water body, preventing the carbon source from being excessively released at the initial stage of putting, and not limiting the improvement of the water treatment efficiency due to too slow dissolution.
In the invention, too large grafting amount of the 1, 3-diphosphinositol can cause the modified polyvinyl alcohol to be dissolved in water too fast, so that the carbon source is excessively released at the early stage of feeding, and the water treatment effect is influenced; too small a graft amount of inositol-1, 3-bisphosphate leads to too slow dissolution of the modified polyvinyl alcohol, which affects the water treatment efficiency. The mass ratio of the polyvinyl alcohol to the inositol 1, 3-diphosphate is controlled within the range of 1: 4-6, so that the modified polyvinyl alcohol has a proper dissolving speed, and a good water treatment effect is obtained.
Preferably, the polymerization degree of the polyvinyl alcohol is 1000 to 2000.
Preferably, in the step (i), the mass ratio of the polyvinyl alcohol to the urea is 1: 6-6.5.
Preferably, in the step (i), the aqueous solution of inositol 1, 3-diphosphate has a mass fraction of 70 to 80%.
Preferably, in the step (ii), the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1: 1.5-2.5: 2.5-3.5.
A method of making the porous slow release wax comprising the steps of:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net with a three-dimensional network structure;
(2) heating and melting soft wax, paraffin wax and microcrystalline wax, adding engine oil and water, stirring uniformly, cooling and agglomerating to obtain wax blocks;
(3) heating the wax block again to melt, fully stirring in the melting process until the wax block is completely melted, adding PHBV and rhamnolipid, and fully mixing to obtain a wax liquid;
(4) pouring the wax liquid into a mold filled with a polyvinyl alcohol fiber net, and agglomerating at 0-4 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
Preferably, in the step (2) and the step (3), the temperature for heating and melting is 60-80 ℃.
A method of water treatment using the porous slow release wax comprising the steps of: soaking the porous slow-release wax in water at the temperature of 35-40 ℃ for 3-6 h, and then putting the wax into a water body to be treated; or directly putting the porous slow-release wax into the water body to be treated.
Compared with the prior art, the invention has the following advantages:
(1) the carbon source can be slowly released, the COD of the water body can not be increased, a continuous, on-demand and controllable carbon source can be provided for beneficial microorganisms, the carbon nitrogen phosphorus balance is kept, and the growth and the propagation of the beneficial microorganisms are facilitated;
(2) by adding the polyvinyl alcohol fiber net into the wax carrier, a through three-dimensional network pore canal can be formed inside the wax block, beneficial microorganisms in the water body can grow and propagate on the pore wall, the contact area of the microorganisms and the water body is increased, and the water treatment efficiency is improved;
(3) through carrying out the grafting modification on the 1, 3-diphosphinosite on the polyvinyl alcohol, the dissolving speed of the polyvinyl alcohol in a normal-temperature water body can be accelerated, the porous slow-release wax can be directly put into a water body to be treated, and the modified polyvinyl alcohol fiber is gradually dissolved in the water body, so that the excessive release of a carbon source at the initial stage of putting is prevented, and the water treatment efficiency cannot be limited due to the excessively slow dissolution.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70-75 parts of soft wax with the melting point of 45-50 ℃, 20 parts of paraffin with the melting point of 55-65 ℃, 5-10 parts of microcrystalline wax with the melting point of 60-80 ℃, and 100 parts of the total amount;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5-20 parts of engine oil and 1-2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1-2 parts of rhamnolipid and 1-2 parts of water;
the polyvinyl alcohol fiber net accounts for 30-40% of the weight of the waxy carrier; the diameter of the polyvinyl alcohol fiber is 0.5-1.5 mm.
The porous slow-release wax is prepared by the following steps:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net with a three-dimensional network structure;
(2) heating and melting soft wax, paraffin wax and microcrystalline wax at 60-80 ℃, adding engine oil and water, stirring uniformly, and cooling and agglomerating to obtain wax blocks;
(3) heating the wax block again at 60-80 ℃ for melting, fully stirring in the melting process, adding PHBV and rhamnolipid after the wax block is completely melted, and fully mixing to obtain wax liquid;
(4) pouring the wax liquid into a mold filled with a fiber net, and caking at 0-4 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The water treatment is carried out by utilizing the porous slow-release wax, and the specific method comprises the following steps: soaking the porous slow-release wax in water at the temperature of 35-40 ℃ for 3-6 h, and then putting the wax into a water body to be treated; or directly putting the porous slow-release wax into the water body to be treated.
Optionally, the polyvinyl alcohol fibers are modified polyvinyl alcohol fibers, and the preparation method is as follows:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol with the polymerization degree of 1000-2000 and urea into dimethyl sulfoxide according to the mass ratio of 1: 6-6.5 in a protective atmosphere, heating to 80-90 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinositide with the mass fraction of 70-80%, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinositide is 1: 4-6, and reacting for 10-15 min under 250-300W microwaves; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 100-110 ℃, wherein the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1: 1.5-2.5: 2.5-3.5, spraying the solution through a spinneret orifice, and cooling the solution in a coagulation bath at the temperature of-10-0 ℃ to obtain jelly-like nascent fibers; and (3) primarily stretching the jelly-like nascent fiber, extracting with methanol, applying oil, drying, stretching, heat setting, and twisting again to obtain the modified polyvinyl alcohol fiber.
Example 1
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the polyvinyl alcohol fiber is 0.5 mm.
The porous slow-release wax is prepared by the following steps:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net, wherein the fiber net has a triaxial orthogonal three-dimensional network structure, and the distances among the polyvinyl alcohol fibers in three axial directions are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The water treatment is carried out by utilizing the porous slow-release wax, and the specific method comprises the following steps: soaking the porous slow-release wax in water at 35 ℃ for 6h, and then putting the wax into a water body to be treated.
Example 2
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the polyvinyl alcohol fiber is 0.5 mm.
The porous slow-release wax is prepared by the following steps:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net, wherein the fiber net has a triaxial orthogonal three-dimensional network structure, and the distances among the polyvinyl alcohol fibers in three axial directions are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The porous slow-release wax is used for water treatment, and the specific steps are as follows: directly putting the porous slow-release wax into the water body to be treated.
Example 3
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 72 parts of soft wax with the melting point of 48 ℃, 20 parts of paraffin with the melting point of 60 ℃ and 8 parts of microcrystalline wax with the melting point of 70 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 15 parts of engine oil and 1 part of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1 part of rhamnolipid and 1 part of water;
the polyvinyl alcohol fiber net accounts for 35% of the weight of the waxy carrier; the diameter of the polyvinyl alcohol fiber is 1 mm.
The porous slow-release wax is prepared by the following steps:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net, wherein the fiber net has a triaxial orthogonal three-dimensional network structure, and the distances among the polyvinyl alcohol fibers in three axial directions are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 2 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The water treatment is carried out by utilizing the porous slow-release wax, and the specific method comprises the following steps: soaking the porous slow-release wax in water at 40 ℃ for 5h, and then putting the wax into a water body to be treated.
Example 4
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 75 parts of soft wax with the melting point of 50 ℃, 20 parts of paraffin with the melting point of 65 ℃ and 5 parts of microcrystalline wax with the melting point of 80 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 20 parts of engine oil and 1.5 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 2 parts of rhamnolipid and 1.5 parts of water;
the polyvinyl alcohol fiber net accounts for 40% of the weight of the waxy carrier; the diameter of the polyvinyl alcohol fiber is 1.5 mm.
The porous slow-release wax is prepared by the following steps:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net, wherein the fiber net has a triaxial orthogonal three-dimensional network structure, and the distances among the polyvinyl alcohol fibers in three axial directions are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 4 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The water treatment is carried out by utilizing the porous slow-release wax, and the specific method comprises the following steps: soaking the porous slow-release wax in water at 40 ℃ for 6h, and then putting the wax into a water body to be treated.
Example 5
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and an improved polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the modified polyvinyl alcohol fiber in the modified polyvinyl alcohol fiber net extends to the surface of the waxy carrier and is communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the modified polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the modified polyvinyl alcohol fiber is 0.5 mm.
The preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol with the polymerization degree of 1500 and urea into dimethyl sulfoxide according to the mass ratio of 1:6 in a protective atmosphere, heating to 85 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinosite with the mass fraction of 75%, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinosite is 1:4, and reacting for 12min under 300W microwave; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 105 ℃, wherein the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1:2:3, spraying out the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-5 ℃ to obtain jelly-like nascent fiber; performing primary stretching on the jelly-like primary fiber at room temperature, wherein the stretching multiple is 6 times; then extracting for 0.5h by using methanol by adopting a counter-current extraction method, oiling, and drying at 55 ℃; and then carrying out stretching and heat setting at the temperature of 200 ℃, the heat shrinkage rate of 15 percent and the stretching multiple of 5 times, and carrying out re-twisting to obtain the modified polyvinyl alcohol fiber.
The porous slow-release wax is prepared by the following steps:
(1) fixing the modified polyvinyl alcohol fibers in a mold to form a modified polyvinyl alcohol fiber net, wherein the fiber net has a three-axis orthogonal three-dimensional network structure, and the distances among the modified polyvinyl alcohol fibers in the three axes are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The porous slow-release wax is used for water treatment, and the specific steps are as follows: directly putting the porous slow-release wax into the water body to be treated.
Example 6
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and an improved polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the modified polyvinyl alcohol fiber in the modified polyvinyl alcohol fiber net extends to the surface of the waxy carrier and is communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the modified polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the modified polyvinyl alcohol fiber is 0.5 mm.
The preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol with the polymerization degree of 1500 and urea into dimethyl sulfoxide according to the mass ratio of 1:6 in a protective atmosphere, heating to 85 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinosite with the mass fraction of 75%, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinosite is 1:6, and reacting for 12min under 300W microwave; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 105 ℃, wherein the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1:2:3, spraying out the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-5 ℃ to obtain jelly-like nascent fiber; performing primary stretching on the jelly-like primary fiber at room temperature, wherein the stretching multiple is 6 times; then extracting for 0.5h by using methanol by adopting a counter-current extraction method, oiling, and drying at 55 ℃; and then carrying out stretching and heat setting at the temperature of 200 ℃, the heat shrinkage rate of 15 percent and the stretching multiple of 5 times, and carrying out re-twisting to obtain the modified polyvinyl alcohol fiber.
The porous slow-release wax is prepared by the following steps:
(1) fixing the modified polyvinyl alcohol fibers in a mold to form a modified polyvinyl alcohol fiber net, wherein the fiber net has a three-axis orthogonal three-dimensional network structure, and the distances among the modified polyvinyl alcohol fibers in the three axes are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The porous slow-release wax is used for water treatment, and the specific steps are as follows: directly putting the porous slow-release wax into the water body to be treated.
Example 7
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and an improved polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the modified polyvinyl alcohol fiber in the modified polyvinyl alcohol fiber net extends to the surface of the waxy carrier and is communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the modified polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the modified polyvinyl alcohol fiber is 0.5 mm.
The preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol with the polymerization degree of 1500 and urea into dimethyl sulfoxide according to the mass ratio of 1:6 in a protective atmosphere, heating to 85 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinosite with the mass fraction of 75%, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinosite is 1:3, and reacting for 12min under 300W microwave; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 105 ℃, wherein the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1:2:3, spraying out the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-5 ℃ to obtain jelly-like nascent fiber; performing primary stretching on the jelly-like primary fiber at room temperature, wherein the stretching multiple is 6 times; then extracting for 0.5h by using methanol by adopting a counter-current extraction method, oiling, and drying at 55 ℃; and then carrying out stretching and heat setting at the temperature of 200 ℃, the heat shrinkage rate of 15 percent and the stretching multiple of 5 times, and carrying out re-twisting to obtain the modified polyvinyl alcohol fiber.
The porous slow-release wax is prepared by the following steps:
(1) fixing the modified polyvinyl alcohol fibers in a mold to form a modified polyvinyl alcohol fiber net, wherein the fiber net has a three-axis orthogonal three-dimensional network structure, and the distances among the modified polyvinyl alcohol fibers in the three axes are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The porous slow-release wax is used for water treatment, and the specific steps are as follows: directly putting the porous slow-release wax into the water body to be treated.
Example 8
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier, and an improved polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the modified polyvinyl alcohol fiber in the modified polyvinyl alcohol fiber net extends to the surface of the waxy carrier and is communicated with the outside.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1.5 parts of rhamnolipid and 2 parts of water;
the modified polyvinyl alcohol fiber net accounts for 30% of the weight of the waxy carrier; the diameter of the modified polyvinyl alcohol fiber is 0.5 mm.
The preparation method of the modified polyvinyl alcohol fiber comprises the following steps:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol with the polymerization degree of 1500 and urea into dimethyl sulfoxide according to the mass ratio of 1:6 in a protective atmosphere, heating to 85 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinosite with the mass fraction of 75%, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinosite is 1:7, and reacting for 12min under 300W microwave; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 105 ℃, wherein the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1:2:3, spraying out the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-5 ℃ to obtain jelly-like nascent fiber; performing primary stretching on the jelly-like primary fiber at room temperature, wherein the stretching multiple is 6 times; then extracting for 0.5h by using methanol by adopting a counter-current extraction method, oiling, and drying at 55 ℃; and then carrying out stretching and heat setting at the temperature of 200 ℃, the heat shrinkage rate of 15 percent and the stretching multiple of 5 times, and carrying out re-twisting to obtain the modified polyvinyl alcohol fiber.
The porous slow-release wax is prepared by the following steps:
(1) fixing the modified polyvinyl alcohol fibers in a mold to form a modified polyvinyl alcohol fiber net, wherein the fiber net has a three-axis orthogonal three-dimensional network structure, and the distances among the modified polyvinyl alcohol fibers in the three axes are equal;
(2) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(3) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(4) pouring the wax liquid into a mould filled with a fiber net, and caking at 0 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
The porous slow-release wax is used for water treatment, and the specific steps are as follows: directly putting the porous slow-release wax into the water body to be treated.
Comparative example 1
A porous slow release wax loaded with a microbial carbon source comprising: the wax carrier, and a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the wax carrier.
The waxy carrier comprises the following raw materials in parts by weight: 70 parts of soft wax with the melting point of 45 ℃, 20 parts of paraffin wax with the melting point of 55 ℃ and 10 parts of microcrystalline wax with the melting point of 60 ℃;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5 parts of engine oil and 2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1 part of rhamnolipid and 2 parts of water.
The slow release wax is prepared by the following steps:
(1) heating soft wax, paraffin wax and microcrystalline wax at 80 ℃ for melting, adding engine oil and water, stirring uniformly, and cooling for agglomeration to obtain wax blocks;
(2) heating the wax block again at 80 deg.C for melting, stirring thoroughly during melting process, adding PHBV and rhamnolipid, mixing thoroughly to obtain wax liquid;
(3) pouring the wax liquid into a mould, and agglomerating at 0 ℃ to obtain the slow-release wax loaded with the microbial carbon source.
The water treatment is carried out by utilizing the slow-release wax, and the specific method comprises the following steps: and soaking the slow-release wax in water at 70 ℃ for 5 hours, and then putting the slow-release wax into the water body to be treated.
The sizes of the microbial carbon source slow-release waxes in the embodiments 1-8 and the comparative example 1 are 35cm multiplied by 25cm, the water source to be treated is culture tail water for culturing Penaeus vannamei Boone, and each 3m of the culture tail water is3Throwing about 1kg of wax block. After the slow-release wax is put into the water body to be treated for 24 hours and 48 hours, the water is respectively measuredThe contents of ammonia nitrogen, nitric acid nitrogen and nitrous acid nitrogen in the body are shown in table 1.
TABLE 1
1Blank: no slow-release wax is added;
2directly adding a carbon source: i.e. no waxy carrier is used; the kind and amount of carbon source charged were the same as those of the carbon source in the controlled-release wax charged in comparative example 1.
From table 1, the content of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the water body of comparative example 1 decreased faster than that in the case of directly feeding the carbon source, which indicates that the water treatment efficiency can be improved by loading the carbon source with the waxy carrier, because: compared with the traditional water body treatment method for directly feeding the carbon source, the waxy carrier can provide a growth and propagation place for beneficial microorganisms, can slowly release the carbon source, cannot cause the increase of COD (chemical oxygen demand) in the water body, can provide a continuous, on-demand and controllable carbon source for the beneficial microorganisms, keeps the carbon nitrogen phosphorus balance, and is beneficial to the growth and propagation of the beneficial microorganisms.
Example 1 a polyvinyl alcohol fiber web was added to the slow release wax based on comparative example 1. From table 1, the content of ammonia nitrogen, nitric acid nitrogen and nitrous acid nitrogen in the water body in example 1 is reduced rapidly, which shows that the water treatment efficiency of the slow-release wax can be effectively improved by adding the polyvinyl alcohol fiber in the invention, because: after the polyethylene fiber net is dissolved, interconnected reticular pores are formed in the slow-release wax, the pores are communicated with the outside, and water can enter the pores, so that beneficial microorganisms in the water can grow and reproduce on the pore walls, and the contact area between the microorganisms growing in the slow-release wax and the water can be increased, thereby improving the water treatment efficiency.
The porous slow-release wax prepared in example 1 is the same as the porous slow-release wax prepared in example 2, in example 1, the porous slow-release wax is soaked in warm water to dissolve polyvinyl alcohol fibers, and then the porous slow-release wax is put into a water body, and in example 2, the polyvinyl alcohol fibers are directly put into the water body. As seen from Table 1, the content of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the water body of example 1 decreased rapidly, and the content of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the water body of example 2 decreased at a rate close to that of comparative example 1. The reason is that: the dissolution speed of the polyvinyl alcohol fiber in a normal-temperature water body is very low, so that the improvement effect of the polyvinyl alcohol fiber on the water treatment efficiency is limited.
Based on example 2, examples 5 and 6 graft-modified polyvinyl alcohol fibers with inositol 1, 3-bisphosphate. From table 1, the decrease rate of the ammonia nitrogen, nitric acid nitrogen and nitrous acid nitrogen contents in the water bodies of examples 5 and 6 is greater than that of examples 1 and 2, which shows that the water treatment efficiency of the porous slow-release wax can be improved by grafting a proper amount of inositol 1, 3-diphosphate on the polyvinyl alcohol fibers, and the water treatment efficiency can be higher by adopting the modified polyethylene fibers and adopting a direct feeding manner compared with the mode of firstly dissolving and then feeding, because: the water solubility of the polyvinyl alcohol can be improved by a large amount of hydroxyl in the 1, 3-inositol diphosphate, the dissolving speed of the polyvinyl alcohol in a normal-temperature water body is accelerated, the porous slow-release wax can be directly put into a water body to be treated, the modified polyvinyl alcohol fiber is gradually dissolved in the water body, the growth and the propagation of beneficial microorganisms which are influenced by excessive release of a carbon source at the initial stage of putting can be prevented, and the improvement of water treatment efficiency cannot be limited due to too slow dissolution.
In the process of preparing modified polyvinyl alcohol, the mass ratios of polyvinyl alcohol to inositol 1, 3-bisphosphate in examples 5 to 8 were 1:4, 1:6, 1:3, and 1:7, respectively. From Table 1, the decrease rates of the ammonia nitrogen, nitrate nitrogen and nitrite nitrogen contents in the water bodies of examples 7 and 8 are lower than those of examples 5 and 6, which shows that the water treatment efficiency of the porous slow-release wax is affected by the excessive or insufficient grafting amount of the inositol 1, 3-diphosphate, because: too large grafting amount of the 1, 3-inositol diphosphate can cause the modified polyvinyl alcohol to be dissolved in water too fast, so that the carbon source is excessively released at the early stage of putting, the growth and the propagation of beneficial microorganisms are influenced, and the water treatment effect is further influenced; too small a graft amount of inositol-1, 3-bisphosphate leads to too slow dissolution of the modified polyvinyl alcohol, which affects the water treatment efficiency.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A porous slow release wax loaded with a microbial carbon source, comprising:
a waxy carrier, a source of wax,
a water-insoluble microbial carbon source and an auxiliary agent which are distributed in the waxy carrier,
a polyvinyl alcohol fiber net which is distributed in the wax carrier and has a three-dimensional network structure; and the polyvinyl alcohol fibers in the polyvinyl alcohol fiber net extend to the surface of the wax carrier and are communicated with the outside.
2. The porous slow release wax of claim 1,
the waxy carrier comprises the following raw materials in parts by weight: 70-75 parts of soft wax, 20 parts of paraffin wax and 5-10 parts of microcrystalline wax, wherein the total amount is 100 parts;
the water-insoluble microbial carbon source comprises the following raw materials in parts by weight: 5-20 parts of engine oil and 1-2 parts of PHBV;
the auxiliary agent comprises the following raw materials in parts by weight: 1-2 parts of rhamnolipid and 1-2 parts of water;
the polyvinyl alcohol fiber net accounts for 30-40% of the weight of the waxy carrier.
3. The porous slow-release wax of claim 2, wherein the soft wax has a melting point of 45 to 50 ℃, the paraffin wax has a melting point of 55 to 65 ℃, and the microcrystalline wax has a melting point of 60 to 80 ℃.
4. The porous slow-release wax of claim 1, wherein the polyvinyl alcohol fibers have a diameter of 0.5 to 1.5 mm.
5. The porous slow-release wax as claimed in claim 1, 2 or 4, wherein the polyvinyl alcohol fiber is a modified polyvinyl alcohol fiber prepared by the following method:
(i) preparing modified polyvinyl alcohol: adding polyvinyl alcohol and urea into dimethyl sulfoxide in a protective atmosphere, heating to 80-90 ℃, stirring for dissolving, dropwise adding an aqueous solution of 1, 3-diphosphinositide, wherein the mass ratio of the polyvinyl alcohol to the 1, 3-diphosphinositide is 1: 4-6, and reacting for 10-15 min under 250-300W microwaves; after the reaction is finished, filtering to remove the precipitate, adding absolute ethyl alcohol into the filtrate to precipitate the product, dissolving the precipitate in water, adding absolute ethyl alcohol to precipitate, filtering, and drying the solid to obtain modified polyvinyl alcohol;
(ii) preparing modified polyvinyl alcohol fiber: dissolving modified polyvinyl alcohol in a mixed solution of water and dimethyl sulfoxide at the temperature of 100-110 ℃, spraying the solution through a spinneret orifice, and cooling the solution in a coagulating bath at the temperature of-10-0 ℃ to form jelly-like nascent fibers; and (3) primarily stretching the jelly-like nascent fiber, extracting with methanol, applying oil, drying, stretching, heat setting, and twisting again to obtain the modified polyvinyl alcohol fiber.
6. The porous slow-release wax of claim 1, wherein the degree of polymerization of the polyvinyl alcohol is 1000 to 2000.
7. The porous slow release wax of claim 5 wherein in step (i):
the mass ratio of the polyvinyl alcohol to the urea is 1: 6-6.5; and/or
The mass fraction of the aqueous solution of the 1, 3-diphosphinositide is 70-80%.
8. The porous slow release wax of claim 5 wherein in step (ii): the mass ratio of the modified polyvinyl alcohol to the water to the dimethyl sulfoxide is 1: 1.5-2.5: 2.5-3.5.
9. A process for preparing a porous slow release wax according to any of claims 2 to 8, comprising the steps of:
(1) fixing polyvinyl alcohol fibers in a mold to form a polyvinyl alcohol fiber net with a three-dimensional network structure;
(2) heating and melting soft wax, paraffin wax and microcrystalline wax, adding engine oil and water, stirring uniformly, cooling and agglomerating to obtain wax blocks;
(3) heating the wax block again to melt, fully stirring in the melting process until the wax block is completely melted, adding PHBV and rhamnolipid, and fully mixing to obtain a wax liquid;
(4) pouring the wax liquid into a mold filled with a polyvinyl alcohol fiber net, and agglomerating at 0-4 ℃ to obtain the porous slow-release wax loaded with the microbial carbon source.
10. A method for water treatment using the porous slow-release wax as claimed in any one of claims 1 to 8, comprising the steps of: soaking the porous slow-release wax in water at the temperature of 35-40 ℃ for 3-6 h, and then putting the wax into a water body to be treated; or directly putting the porous slow-release wax into the water body to be treated.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116617806A (en) * | 2023-05-23 | 2023-08-22 | 迁安市宏奥工贸有限公司 | Method for treating waste gas of coking plant |
| CN116621330A (en) * | 2023-07-10 | 2023-08-22 | 合肥学院 | Biological filler for slowly releasing carbon source and preparation method and application thereof |
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| CN102031572A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Preparation technique of water-soluble polyvinyl alcohol fiber and application thereof |
| CN105366793A (en) * | 2007-05-01 | 2016-03-02 | 海洋易洁公司 | Water treatment composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366793A (en) * | 2007-05-01 | 2016-03-02 | 海洋易洁公司 | Water treatment composition |
| CN102031572A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Preparation technique of water-soluble polyvinyl alcohol fiber and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116617806A (en) * | 2023-05-23 | 2023-08-22 | 迁安市宏奥工贸有限公司 | Method for treating waste gas of coking plant |
| CN116617806B (en) * | 2023-05-23 | 2023-11-03 | 迁安市宏奥工贸有限公司 | Method for treating waste gas of coking plant |
| CN116621330A (en) * | 2023-07-10 | 2023-08-22 | 合肥学院 | Biological filler for slowly releasing carbon source and preparation method and application thereof |
| CN116621330B (en) * | 2023-07-10 | 2024-05-07 | 合肥学院 | Biological filler for slowly releasing carbon source and preparation method and application thereof |
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