CN115465955A - Composite material with microcapsule biodegradability and preparation method and application thereof - Google Patents

Composite material with microcapsule biodegradability and preparation method and application thereof Download PDF

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CN115465955A
CN115465955A CN202210597830.1A CN202210597830A CN115465955A CN 115465955 A CN115465955 A CN 115465955A CN 202210597830 A CN202210597830 A CN 202210597830A CN 115465955 A CN115465955 A CN 115465955A
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microcapsules
microcapsule
water
composite material
solution
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孟淼
高南
闫志强
彭琦
胡俊业
汪杰
甘萌萌
丁莉
朱红芳
郭欢
兰天齐
何润东
刘锋
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Shunde Polytechnic
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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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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
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    • C12R2001/89—Algae ; Processes using algae
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention relates to the technical field of water treatment, in particular to a composite material with microcapsules and biodegradability, and a preparation method and application thereof. The composite material with the microcapsule biodegradable property comprises a degradable porous material and microcapsules loaded on the degradable porous material, wherein the loading rate of the microcapsules on the degradable porous material is 3-50%; the capsule core of the microcapsule comprises sewage treatment bacteria. The composite material with the microcapsule biodegradability can improve the load rate of the microcapsule on the degradable porous material and improve the water purification efficiency.

Description

Composite material with microcapsule biodegradability and preparation method and application thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite material with microcapsules and biodegradability, and a preparation method and application thereof.
Background
Water pollution is one of the important environmental problems, and rivers, lakes and underground water are polluted by nitrogen, phosphorus, sulfur and the like to different degrees. Therefore, the degradation and removal of nitrogen, phosphorus and sulfur are important targets for ecological restoration of the polluted water body. The removal of nitrogen, phosphorus and sulfur in the water body can be mainly realized by microorganisms. The microbial micelles can provide good living environments for protozoa and micro metazoan by adsorbing and decomposing organic substances, for example, removing poison, providing food stuff, increasing dissolved oxygen, and the like.
Along with the increase of environmental protection demand and the development of degradable materials, the sewage treatment fieldHave begun to attempt to replace traditional non-degradable fillers with degradable fillers. For example, patent CN1562800A uses cellulose as raw material to prepare degradable microbial filler for wastewater treatment. However, the method has complex process, the foaming temperature needs 100-160 ℃, and meanwhile, the alkalization treatment is needed, and dangerous chemicals are needed. And in the carrier production process, a by-product H 2 S and CS 2 And the emission of harmful gases makes the fiber production process complicated and pollutes the environment. In the patent CN102603081A, fibers are prepared mainly through N-methylmorpholine-N-oxide, the mechanical property of the filler is further improved through a crosslinking modification technology, and meanwhile, the surface of the filler is treated to be positively charged, so that the adhesion and growth of microorganisms on the surface of the filler are facilitated. However, this method uses an irritant drug (N-methylmorpholine-N-oxide) and a strong base (sodium hydroxide), which is not only dangerous during the preparation but also has a certain irritating effect on the eyes, respiratory system and skin. In addition, the research on the preparation of the sewage purification filler by combining the microorganism immobilization technology with the coating material has been carried out, but the following defects exist: 1. the traditional microorganism immobilization technology adopts a direct coating method, namely, microorganisms are coated by a coating material, so that the coating material is easy to break and the microorganisms are lost; 2. the size of the microorganism directly injected into the coating material is relatively large, the contact area with sewage is small, and even gaps are blocked, so that the purification effect is reduced; 3. the technology for fixing the microorganisms in the coating material is complex, the steps are complicated, and the operation is required to be carried out under a high-pressure environment; 4. the microorganism has an adaptation process in a new environment, and the microorganism in the method has low survival rate or even can not survive under the condition of high-concentration polluted environment of black and odorous water body, thereby influencing the action effect of the microorganism; 5. the microbial growth environment changes along with the flow of the water body, such as unstable pH value and the like, and has the disadvantages of unsatisfactory propagation, easy shedding and slow degradation rate on black and odorous water.
Disclosure of Invention
Based on the above, there is a need for a composite material with microcapsule biodegradability, which can improve microcapsule loading rate and water purification rate, and a preparation method and application thereof.
An embodiment of the invention provides a degradable composite material with microcapsules, which comprises a degradable porous material and microcapsules loaded on the degradable porous material, wherein the loading rate of the microcapsules on the degradable porous material is 3% -50%; the microcapsule comprises a core containing sewage treatment bacteria.
In another embodiment of the present invention, there is also provided a method for preparing the above composite material with microcapsules, which comprises the following steps:
and dissolving the microcapsule in water to form a first solution, regulating the pH value of the first solution to be 4-5, and adding the degradable porous material to perform complex coacervation reaction.
In still another embodiment of the present invention, there is further provided a water purifying agent, wherein the raw material for preparing the water purifying agent comprises the above-mentioned composite material having microcapsules and being biodegradable.
According to the composite material with the biodegradable microcapsule, the microcapsule technology is adopted to coat the bacterial strains of the microorganisms such as the sewage treatment bacteria and the like in the capsule wall of the microcapsule through a complex coacervation method, so that a good living environment can be provided for the growth and the propagation of the sewage treatment bacterial strains, the loss of the sewage treatment bacterial strains is avoided, the survival rate of the microorganisms is effectively improved, the contact area of the microorganisms and sewage is increased, and the degradation of black and odorous sewage water is further improved. Meanwhile, the microcapsule is prepared by combining a complex coacervation method and the load of the microcapsule on the degradable porous material is realized by an in-situ method, on one hand, the degradable wall material is endowed with a certain cationic charge density by the complex coacervation method and acts with the degradable porous material with anionic charge, the load rate of the microcapsule is effectively improved, and on the other hand, the microcapsule is not subjected to secondary pollution, and meanwhile, the operation is simple and convenient and the cost is low.
In conclusion, when the composite material with the microcapsule biodegradability is used in aquatic ecological restoration engineering, sewage treatment bacteria can survive in a severe environment for a long time, the action time is long, the contact area of the microorganisms and the sewage is large, the composite material has high efficiency and durability, pollutants such as COD (chemical oxygen demand), total phosphorus content, ammonia nitrogen concentration and the like in a water body can be effectively reduced, and the composite material can play a positive role in the ecological restoration of the water body for a long time.
Drawings
FIG. 1 is a schematic diagram of the structure of microcapsules in a biodegradable composite material having microcapsules according to an embodiment of the present invention;
FIGS. 2 to 4 are COD of the composite material with microcapsule biodegradability prepared in example 1, respectively Mn 、NH 3 -N and TP index detection results;
FIG. 5 is an image microscopic view of the porous material obtained in example 2;
FIG. 6 is an image microscope of microcapsules in the composite with microcapsule biodegradability prepared in example 2;
FIG. 7 is an image microscopic view of the composite with microcapsule biodegradability prepared in example 2;
FIGS. 8 to 10 are COD values of the composite with microcapsule biodegradable prepared in example 2, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 11 to 13 are COD of the composite with microcapsule biodegradability prepared in example 3, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 14 to 16 are COD of the composite with microencapsulated biodegradable material prepared in example 4, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 17 to 19 are COD of the composite with microcapsule biodegradable prepared in example 5, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 20 to 22 are COD of the composite with microcapsule biodegradable prepared in example 6, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 23 to 25 are COD of the composite material with microcapsule biodegradability prepared in comparative example 1, respectively Mn 、NH 3 -N and TP index detection results;
FIGS. 26 to 28 are schematic views of the microcapsules prepared in comparative example 2COD of biodegradable composites Mn 、NH 3 -N and TP index detection results.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following more detailed description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Terms and definitions:
"loading" refers to the mass of microcapsules loaded on the degradable porous material, and "loading rate" refers to the mass percentage of the loading of the microcapsules to the sum of the microcapsule loading and the mass of the degradable porous material, and is calculated as follows:
the load factor = microcapsule load amount/(microcapsule load amount + mass of degradable porous material) × 100%.
Chemical Oxygen Demand (COD) is the equivalent amount of Oxygen consumed by a strong oxidant to chemically measure the amount of organic matter in water when the organic matter is oxidized by the strong oxidant. Under certain conditions, the amount of the oxidant consumed by oxidizing the reducing substances in 1L of water sample is taken as an index, the mg of oxygen required by the oxidation of the whole water sample is converted, and the mg/L represents the degree of pollution of the water (sewage and wastewater) by the reducing substances. COD Mn The index of potassium permanganate is used as an oxidant, and the COD is measured by using the potassium permanganate.
NH 3 N is an index of the ammonia nitrogen content in water (sewage, waste water), and the unit is usually mg/L. Ammonia nitrogen refers to free ammonia (NH) in water 3 ) And ammonium ion (NH) 4+ ) Nitrogen in the form thereof. Ammonia nitrogen is a nutrient in water, can cause water eutrophication, and is a main oxygen-consuming pollutant in the water.
TP is the index of total phosphorus content in water (sewage and wastewater), and is the result of determination after various forms of phosphorus are converted into orthophosphate by digesting a water sample.
The invention relates to a composite material with microcapsules capable of being biodegraded, which comprises a degradable porous material and microcapsules loaded on the degradable porous material, wherein the loading rate of the microcapsules on the degradable porous material is 3% -50%; the microcapsule core comprises sewage treatment bacteria. It will be appreciated that microcapsules generally comprise a wall and a core embedded or enclosed within the wall.
In some embodiments, the loading rate of the microcapsule on the degradable porous material may be any value between 3% and 50%, and may also be 5%, 7%, 10%, 12%, 13%, 15%, 18%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 40%.
It will be appreciated that microcapsules generally comprise a wall and a core embedded or enclosed within the wall. In order to improve the viability, stability and sustained release of the sewage treatment bacteria, one embodiment of the present invention places the sewage treatment bacteria in the core of the capsule and coats the core with the capsule wall.
In some embodiments, the particle size of the microcapsules may be anywhere between 10 μm and 500 μm, preferably anywhere between 10 μm and 100 μm, and may for example be 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 70 μm, 80 μm, 90 μm.
Degradable material is understood to mean a material that is degradable in both thermodynamic and kinetic terms over a period of time. The degradable porous material is a material with a network structure formed by interconnected or closed pores, and can be degraded under natural environmental conditions such as light, heat, water, pollutants, microorganisms, insects, mechanical force and the like. In some embodiments, the raw materials for preparing the degradable porous material comprise the following components in parts by mass:
80-100 parts of floating algae, 20-20 parts of saccharides, 12-28 parts of binder, 5-10 parts of foaming agent and 3-5 parts of cross-linking agent.
In some embodiments, the planktonic algae can be one or more of chlorella, scenedesmus obliquus, and gossypium hirsutum, preferably chlorella.
In some embodiments, the binder may be one or more of starch, polylactic acid, and sodium alginate, preferably starch and polylactic acid, starch and sodium alginate, or starch and polylactic acid and sodium alginate.
In some embodiments, the foaming agent may be a carbonate and/or bicarbonate, for example, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and the like, preferably sodium bicarbonate.
In some embodiments, the crosslinking agent is an inorganic salt and a weak acid having an acidity coefficient pKa greater than 4, wherein the inorganic salt may be calcium chloride and the weak acid may be acetic acid. Preferably, the mass ratio of the calcium chloride to the acetic acid is (1-10): (10-1).
In some embodiments, the degradable porous material may have a pore size of 500 μm to 10 μm 4 μ m, and specific surface area of 350m 2 /g～550m 2 /g。
In some embodiments, the wastewater treatment bacteria may be selected from one or more of bacillus subtilis, EM bacteria, and composite bacteria.
The Bacillus subtilis is a simple gram-positive aerobic bacterium, has excellent acid resistance, salt resistance, high temperature resistance and extrusion resistance, is a simple bacterium, is a dominant population in soil, and has abundant protease, lipase, amylase, cellulase and the like. The bacillus subtilis can strongly decompose carbon-series, nitrogen-series, phosphorus-series and sulfur-series pollutants, and the bacillus can also decompose complex polysaccharide, protein and water-soluble organic matters to form a dominant flora in a water environment.
The EM is a composite microbial strain which is prepared by separately culturing, fermenting and spray drying single strains of bifidobacterium, lactobacillus, bacillus (bacillus licheniformis, bacillus subtilis, bacillus mucilaginosus, bacillus thuringiensis and the like), photosynthetic bacteria, saccharomycetes, actinomycetes, acetic acid bacteria and the like by a special process. The EM bacteria can effectively degrade harmful substances such as ammoniacal nitrogen, methane, nitrite, hydrogen sulfide and the like in the water body, can decompose residual bait and organic matters in the water, and play roles in stabilizing the pH value of the water body, removing chemical residual toxicity in the water, purifying the water quality, keeping the balance of beneficial bacteria and plankton in the water and inhibiting the growth of harmful algae.
The composite bacteria are composite strains composed of mould, saccharomycetes, floc-producing bacteria, azotobacter, coccus, bacillus, nitrobacteria and the like. Wherein the yeast has the functions of decomposing fat and degrading phenol; the mould has strong oxidizing capacity and can oxidize nitrogenous substances such as protein, nucleic acid and the like in water; the floc-producing bacteria can form bacteria of floc, such as filamentous bacteria, escherichia coli, pseudomonas bacilli, fungi and the like, and have strong capability of oxidizing and decomposing organic matters and good settleability; the nitrogen-fixing bacteria are some bacteria which can live by utilizing nitrogen in air and waste water, such as nitrogen-fixing cyanobacteria.
In some embodiments, the raw materials for preparing the wall of the microcapsule comprise: within a pH value of 4-5, a first polymer material with positive charges and a second polymer material with negative charges, wherein the mass ratio of the first polymer material to the second polymer material can be (1-4): (4-1). The wall of the microcapsule is formed by electrostatic interaction between a first polymeric material having a positive charge and a second polymeric material having a negative charge under a specific pH condition.
In some embodiments, the first polymeric material may be one or more of gelatin type a, peach gum, xanthan gum, and gum arabic. The microcapsule wall is formed by selecting polymers from natural sources, and has the advantages of degradability, no pollution to the environment and the like.
In some embodiments, the second polymeric material may be one or more of maltodextrin, sodium carboxymethyl cellulose, sodium alginate, and sodium caseinate.
Another aspect of the present invention also relates to a preparation method of the composite material with microcapsules and biodegradability, which may specifically include steps S10 to S30 as follows:
step S10: placing the planktonic algae in a plant nutrient solution to make the algae cells enter an exponential growth phase and concentrating the algae cells; and
and dissolving the concentrated algae cells, the binder, the foaming agent and the cross-linking agent in water for cross-linking and curing to prepare the degradable porous material. It is understood that in some embodiments, step S10 may be omitted. The algae cells are used as a matrix, and the degradable porous material is formed by foaming and curing, so that the degradable porous material has good adsorption performance, can adsorb gas, microorganisms and the like, and is favorable for adsorption of sewage treatment bacteria in the microcapsules.
In some embodiments, the adhesive is selected from one or more of starch, polylactic acid and sodium alginate, and has the gelling effect, and is degradable and free of environmental pollution.
In some embodiments, the method of placing phytoplankton in a phytonutrient solution to bring algal cells into an exponential growth phase may specifically comprise the steps of:
s100: placing the floating algae in a plant nutrient solution, illuminating, and taking out the floating algae after the algae cells enter an exponential growth phase to prepare tested algae; and
s200: adjusting the volume concentration of the tested algae to 0.5-5%, placing the volume concentration in a plant nutrient solution, concentrating algae cells after the algae cells enter an exponential growth phase, and drying.
In some embodiments, the plant nutrient solution may be any plant nutrient solution commonly used in the art, and may be, for example, a hodgkin's nutrient solution, wherein the concentration of the hodgkin's nutrient solution may be 5% to 20% by mass.
In some embodiments, the method of concentrating algal cells may employ a number 25 plankton net for concentration.
In some embodiments, the step of dissolving the concentrated algae cells, the binder, the foaming agent and the cross-linking agent in water for cross-linking and curing may specifically be as follows:
adding a first binder into water, heating and dissolving, and then adding concentrated algae cells to form a first floccule, wherein the first binder is starch and polylactic acid;
dissolving a second binder in water, heating to form a second floccule, cooling, and adding a foaming agent, the first floccule and a cross-linking agent, wherein the second binder is sodium alginate.
In some embodiments, the time for the cross-linking curing is not limited, and may be, for example, 10min to 60min.
In some embodiments, the volume ratio of planktonic algae to phytonutrient solution can be 0.1% to 1%.
In some embodiments, the intensity of illumination may be 2000lx to 6000lx, the temperature may be 15 ℃ to 40 ℃, and the light-to-dark ratio may be (6 h to 18 h): (18 h-6 h).
Step S20: dissolving the capsule wall of the microcapsule in water to form a second solution, and adding bacterial sludge of the sewage treatment bacteria to form a first solution.
In some embodiments, the method further comprising obtaining a bacterial sludge of wastewater treatment bacteria may be any method commonly used in the art, such as by centrifugation.
In some embodiments, the mass concentration of the second solution may be any value between 0.5% and 5%, and may also be 1%, 1.5%, 2%, 3%, 4%, for example.
In some embodiments, the method further comprises the step of heating the second solution, wherein the heating temperature can be 20 ℃ to 50 ℃.
In some embodiments, the amount of the bacterial sludge of the sewage treatment bacteria can be calculated according to the content of the microcapsule wall, for example, 10 can be added per gram of the microcapsule wall 8 cfu～10 12 Bacterial sludge of cfu.
Step S30: regulating the pH value of the first solution to 4-5, adding a degradable porous material to perform complex coacervation reaction, and drying.
In some embodiments, the pH may be any value between 4 and 5, and may also be, for example, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9.
In some embodiments, the time for the complex coacervation reaction can be any value between 10min and 90 min.
The invention also relates to a water purifying agent, and the preparation raw materials of the water purifying agent comprise the biodegradable composite material with the microcapsules.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella liquid into a conical flask filled with 5% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as a tested chlorella of a culture experiment when chlorella cells enter an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 5%, putting the solution into a Hoagland nutrient solution with the volume concentration of 5% for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a drying oven with the temperature of 20 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 60 ℃ to form a floccule, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to the volume ratio of 1;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 10min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 10g of the frozen EM strain, mixing and diluting the EM strain with water according to the mass ratio of 1;
2) Respectively dissolving 10g of A-type gelatin and 10g of sodium caseinate in water to prepare a 10% A-type gelatin solution and a 10% sodium caseinate solution, and preserving heat at 35 ℃;
3) And (2) taking 5g of bacterial sludge obtained in the step 1), 50g of type A gelatin solution obtained in the step 2) and 50g of sodium caseinate solution at 35 ℃, uniformly mixing, adjusting the pH value to 4.3, immediately adding the porous material obtained in the step (1), inducing a complex coacervation reaction for 20min, and freeze-drying to obtain the biodegradable composite material with the microcapsules, wherein the structural schematic diagram of the microcapsules is shown in figure 1 and comprises a capsule core and a capsule wall. The size D50 of the microcapsules in the composite material with the biodegradable microcapsules was measured to be 12.426. Mu.m, and the loading rate of the microcapsules on the porous material was 28.5%. The following relevant performance tests were performed on it:
selecting 6 blue plastic boxes of 200L, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L of wastewater from 2 rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air volume of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the water level in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index being tested in 3 groups in parallel, and the average taken. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of-N and TP indicators are shown in FIGS. 2, 3 and 4, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant in two rivers is reduced by 35-45%, after 7 days, the concentration of each pollutant is reduced to 79-81%, and the composite material has a remarkable sewage purification effect.
Example 2
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella liquid into a conical flask filled with 10% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as a tested chlorella of a culture experiment when chlorella cells enter an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 3%, putting the solution into 10% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a drying oven with the temperature of 35 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form floccules to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 75 ℃ to form a floccule, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to a volume ratio of 1;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent in the step 5) for reaction for 30min, and washing the porous material with water after crosslinking and curing to obtain the porous material, wherein an imaging microscopic picture of the porous material is shown in fig. 5, and the multiple of an objective lens is 10 x;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 5g of the EM strain and 5g of the bacillus subtilis which are subjected to freezing preservation, mixing and diluting the EM strain and the bacillus subtilis with water according to the mass ratio of 1;
2) Respectively dissolving 5g of A-type gelatin and 5g of sodium alginate in water to prepare an A-type gelatin solution with the mass concentration of 5% and a sodium alginate solution with the mass concentration of 5%, and preserving heat at 35 ℃;
3) And (2) at the temperature of 20 ℃, uniformly mixing 3g of bacterial sludge obtained in the step 1), 50g of A type gelatin solution obtained in the step 2) and 50g of sodium alginate solution, adjusting the pH value to 4.5, immediately adding the porous material obtained in the step (1), inducing to carry out complex coacervation reaction for 60min, and carrying out freeze drying to obtain the microcapsule biodegradable composite material. An imaging microscope of the microcapsules in the composite material with the biodegradable microcapsules is shown in fig. 6, and an imaging microscope of the composite material with the biodegradable microcapsules is shown in fig. 7. The size D50 of the microcapsules in the composite material with the biodegradable microcapsules was measured to be 31.572. Mu.m, and the loading rate of the microcapsules on the porous material was 15.2%. The following relevant performance tests were performed on it:
selecting 6 200L blue plastic boxes, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L wastewater from 2 river rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air quantity of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the water level in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index group was examined in parallel for 3 groups and averaged. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of the-N and TP indicators are shown in FIGS. 8, 9 and 10, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant of two river rivers is reduced by about 23-27%, and after 7 days, the concentration of each pollutant is reduced to about 47-55%, so that the composite material has a remarkable sewage purification effect.
Example 3
(1) Preparation of degradable porous material
1) Transferring the chlorella solution into a conical flask filled with 20% Hoagland nutrient solution under aseptic condition, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as a tested chlorella of a culture experiment when chlorella cells enter an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 0.5%, putting the solution into a 20% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a 50 ℃ oven for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form floccules to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 90 ℃ to form a floccule, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to a volume ratio of 2;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 60min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 2g of the EM strain and 1g of the bacillus subtilis which are subjected to freezing preservation, mixing and diluting the EM strain and water according to the mass ratio of 1;
2) Weighing 1g of type A gelatin and 4g of sodium carboxymethylcellulose, respectively dissolving in water to prepare a type A gelatin solution with a mass concentration of 1% and a sodium carboxymethylcellulose solution with a mass concentration of 1%, and preserving heat at 35 ℃;
3) And (2) at the temperature of 20 ℃, uniformly mixing 2g of bacterial sludge obtained in the step 1), 100g of A-type gelatin solution obtained in the step 2) and 50g of sodium carboxymethylcellulose solution, adjusting the pH value to 4.6, immediately adding the porous material obtained in the step (1), inducing a complex coacervation reaction for 90min, and freeze-drying to obtain the microcapsule biodegradable composite material. The size D50 of the microcapsules in the composite material having the biodegradable microcapsules was measured to be 21.384 μm, and the loading rate of the microcapsules on the porous material was 8.4%. The following relevant performance tests were performed on it:
selecting 6 200L blue plastic boxes, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L wastewater from 2 river rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air quantity of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the horizontal plane in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index being tested in 3 groups in parallel, and the average taken. According to the quality standard of surface water environment (GB 3838-2002) in the quality standard of surface water environment, the microcapsule can be produced by coating the microcapsuleThe wastewater treated by the biodegradable composite material is subjected to water quality detection, COD Mn 、NH 3 The detection results of-N and TP indicators are shown in FIGS. 11, 12 and 13, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant of two river rivers is reduced by about 13-15%, and after 7 days, the concentration of each pollutant is reduced to about 25-28%, so that the composite material has a remarkable sewage purification effect.
Example 4
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella solution into a conical flask filled with 12% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as the tested chlorella of the culture experiment when the chlorella enters an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 1.0%, putting the solution into a 12% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into an oven with the temperature of 40 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 70 ℃ to form a floccule, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to the volume ratio of 5;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 30min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 3g of the EM strain which is subjected to freezing preservation, mixing and diluting the EM strain with water according to the mass ratio of 1;
2) Weighing 3g of type A gelatin, 3g of sodium alginate and 3g of Arabic gum, respectively dissolving in water to prepare a type A gelatin solution with the mass concentration of 3%, a sodium alginate solution with the mass concentration of 1% and an Arabic gum solution with the mass concentration of 1%, and preserving heat at 35 ℃;
3) And (2) uniformly mixing 5g of bacterial sludge obtained in the step 1), 100g of the type A gelatin solution obtained in the step 2), 100g of the sodium alginate solution and 100g of the Arabic gum solution at 20 ℃, adjusting the pH value to 4.8, immediately adding the porous material obtained in the step (1), inducing to carry out complex coacervation reaction for 60min, and carrying out freeze drying to obtain the microcapsule biodegradable composite material. The size D50 of the microcapsules in the composite material having the biodegradable microcapsules was measured to be 39.452 μm, and the loading rate of the microcapsules on the porous material was 27.4%. The following relevant performance tests were performed on it:
selecting 6 200L blue plastic boxes, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L wastewater from 2 river rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air quantity of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the water level in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index being tested in 3 groups in parallel, and the average taken. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of-N and TP indicators are shown in FIGS. 14, 15 and 16, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant in two rivers is reduced by about 40-50%, and after 7 days, the concentration of each pollutant can be reduced to about 80-85%, so that the composite material has a remarkable sewage purification effect.
Example 5
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella solution into a conical flask filled with 15% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as the tested chlorella of the culture experiment when the chlorella enters an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 1.2%, putting the solution into 15% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a drying oven with the temperature of 30 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 80 ℃ to form floccules, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to a volume ratio of 1;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 70min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 1g of the EM strain, 3g of the bacillus subtilis and 1g of the compound bacteria which are subjected to freezing preservation, mixing and diluting the EM strain and water according to the mass ratio of 1;
2) Weighing 2g of A-type gelatin and 2g of sodium alginate, respectively dissolving in water to prepare an A-type gelatin solution with the mass concentration of 2% and a sodium alginate solution with the mass concentration of 2%, and preserving heat at 35 ℃;
3) And (2) uniformly mixing 1g of bacterial sludge obtained in the step 1), 100g of A type gelatin solution obtained in the step 2) and 100g of sodium alginate solution at 20 ℃, adjusting the pH value to 4.8, immediately adding the porous material obtained in the step (1), inducing a complex coacervation reaction for 60min, and freeze-drying to obtain the microcapsule biodegradable composite material. The size D50 of the microcapsules in the composite material with the biodegradable microcapsules was measured to be 18.542. Mu.m, and the loading rate of the microcapsules on the porous material was 7.1%. The following relevant performance tests were performed on it:
selecting 6 blue plastic boxes of 200L, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L of wastewater from 2 rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air volume of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the horizontal plane in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index group was examined in parallel for 3 groups and averaged. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of-N and TP indicators are shown in FIGS. 17, 18 and 19, respectively. The result shows that the prepared composite material with the microcapsule and the biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant in two rivers is reduced by about 11-15%, and after 7 days, the concentration of each pollutant can be reduced to about 22-27%, so that the composite material has a remarkable sewage purification effect.
Example 6
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella solution into a conical flask filled with 10% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as the tested chlorella of the culture experiment when the chlorella cells enter an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 1.0%, putting the solution into 10% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a drying oven at 40 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 60 ℃ to form a floccule, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to the volume ratio of 1;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) for reaction for 30min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 5g of the frozen EM strain, mixing and diluting the EM strain with water according to the mass ratio of 1;
2) Weighing 1g of A-type gelatin and 4g of sodium alginate, respectively dissolving in water to prepare an A-type gelatin solution with a mass concentration of 1% and a sodium alginate solution with a mass concentration of 1%, and preserving heat at 35 ℃;
3) And (2) uniformly mixing 1g of bacterial sludge obtained in the step 1), 100g of A-type gelatin solution obtained in the step 2) and 50g of sodium alginate solution at 20 ℃, adjusting the pH value to 4.8, immediately adding the porous material obtained in the step (1), inducing complex coacervation reaction for 90min, and freeze-drying to obtain the microcapsule biodegradable composite material. The size D50 of the microcapsules in the composite material having the biodegradable microcapsules was measured to be 13.534 μm, and the loading rate of the microcapsules on the porous material was 21.9%. The following relevant performance tests were performed on it:
selecting 6 blue plastic boxes of 200L, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L of wastewater from 2 rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air volume of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively on day 3And 7 th day, sampling the water body in the plastic box 5cm away from the horizontal plane, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index being tested in 3 groups in parallel, and the average taken. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of the-N and TP indices are shown in fig. 20, 21, and 22, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can effectively remove phosphorus, ammonia nitrogen and COD in wastewater, after 3 days of reaction, the concentration of each pollutant in two rivers is reduced by about 31-34%, and after 7 days, the concentration of each pollutant can be reduced to about 64-66%, so that the composite material has a remarkable sewage purification effect.
Comparative example 1
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella solution into a conical flask filled with 1% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as the tested chlorella of the culture experiment when the chlorella enters an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 0.2%, putting the solution into a 1% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a 50 ℃ oven for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 90 ℃ to form floccules, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to the volume ratio of 1;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 60min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 2g of the EM strain and 1g of the bacillus subtilis which are subjected to freezing preservation, mixing and diluting the EM strain and water according to the mass ratio of 1;
2) Weighing 2g of A-type gelatin and 2g of sodium alginate, respectively dissolving in water to prepare an A-type gelatin solution with the mass concentration of 2% and a sodium alginate solution with the mass concentration of 2%, and preserving heat at 35 ℃;
3) And (2) taking 2g of bacterial sludge obtained in the step (1), 100g of A-type gelatin solution obtained in the step (2) and 100g of sodium alginate solution, uniformly mixing at 20 ℃, adjusting the pH value to 5.1, immediately adding the porous material obtained in the step (1), inducing to carry out complex coacervation reaction for 60min, and carrying out freeze drying to obtain the microcapsule biodegradable composite material. The average particle size of the porous material cannot be measured by a Malvern particle size analyzer, the porous material has multimodal distribution, and the loading rate of the microcapsules on the porous material is 1.5%. The following relevant performance tests were performed on it:
selecting 6 200L blue plastic boxes, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L wastewater from 2 river rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air quantity of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the horizontal plane in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index group was examined in parallel for 3 groups and averaged. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of-N and TP indicators are shown in FIGS. 23, 24 and 25, respectively. The results show that the prepared composite material with microcapsule biodegradability can not effectively remove phosphorus, ammonia nitrogen and COD in wastewater, and the reaction lasts for 3 days or 7 days or two daysThe concentrations of various pollutants in the river are not obviously purified.
Comparative example 2
(1) Preparation of degradable porous material
1) Under the aseptic condition, transferring the chlorella solution into a conical flask filled with 10% Hoagland's nutrient solution, then placing the conical flask into an illumination incubator for amplification culture, and taking out the chlorella as the tested chlorella of the culture experiment when the chlorella cells enter an exponential growth phase;
2) Preparing the tested algae prepared in the step 1) into a solution with the volume concentration of 3%, putting the solution into 10% Hoagland nutrient solution for amplification culture, concentrating algae cells by using a No. 25 plankton net when the algae cells enter an exponential growth phase, and putting the concentrated algae cells into a drying oven with the temperature of 40 ℃ for drying;
3) Adding starch and polylactic acid into water, heating and dissolving, adding the dried algae cells, and uniformly stirring to form a floccule to obtain a first mixture;
4) Mixing sodium alginate and water, heating to 70 ℃ to form floccules, cooling, adding sodium bicarbonate, and uniformly stirring to obtain a second mixture;
5) Dissolving calcium chloride in water, and mixing the calcium chloride solution and acetic acid according to a volume ratio of 15;
6) And mixing the first mixture and the second mixture, uniformly stirring, and pouring into a mold. Then adding the crosslinking reagent obtained in the step 5) to react for 60min, and washing the obtained product clean with water after crosslinking and curing to obtain a porous material;
(2) Preparation of biological microcapsule and load of biological microcapsule on degradable porous material
1) Taking 2g of the EM strain which is subjected to freezing preservation, mixing and diluting the EM strain with water according to the mass ratio of 1;
2) Weighing 1g of A-type gelatin and 1g of Arabic gum, respectively dissolving in water to prepare an A-type gelatin solution with the mass concentration of 0.1% and an Arabic gum solution with the mass concentration of 0.1%, and preserving heat at 35 ℃;
3) And (2) uniformly mixing 0.1g of bacterial sludge obtained in the step 1), 100g of A-type gelatin solution obtained in the step 2) and 100g of Arabic gum solution at 20 ℃, adjusting the pH value to 4.6, immediately adding the porous material obtained in the step (1), inducing to carry out complex coacervation reaction for 70min, and carrying out freeze drying to obtain the microcapsule biodegradable composite material. The size D50 of the microcapsules in the composite material having the biodegradable microcapsules was measured to be 2.583 μm, and the loading rate of the microcapsules on the porous material was 0.52%. The following relevant performance tests were performed on it:
selecting 6 blue plastic boxes of 200L, placing the composite material with the microcapsules and the biodegradability according to the volume ratio of 30%, respectively taking 150L of wastewater from 2 rivers (river 1 and river 2) and placing the wastewater in 3 plastic boxes, and adjusting the air volume of a fan to ensure that the dissolved oxygen of the wastewater in the boxes is 3mg/L. Respectively sampling the water body 5cm away from the horizontal plane in the plastic box on the 3 rd day and the 7 th day, and detecting the COD of the water body Mn 、NH 3 -N and TP indices, each index being tested in 3 groups in parallel, and the average taken. According to the quality standard of surface water environment (GB 3838-2002) in the surface water environment quality standard, the water quality of the wastewater treated by the composite material with the microcapsules which can be biologically degraded is detected, namely COD Mn 、NH 3 The detection results of-N and TP indices are shown in FIGS. 26, 27 and 28, respectively. The result shows that the prepared composite material with the microcapsule biodegradability can not effectively remove phosphorus, ammonia nitrogen and COD in wastewater, and the concentration of each pollutant of two river rivers is not obviously purified no matter the composite material is reacted for 3 days or 7 days.
The relevant parameters of the composite with microcapsules biodegradable in the various examples and comparative examples are shown in table 1:
TABLE 1
Figure BDA0003668803440000191
The test results in the table show that the composite material with the microcapsule biodegradability provided by the invention has a high-efficiency sewage purification effect and can effectively degrade COD (chemical oxygen demand), total phosphorus content and ammonia nitrogen concentration in a water body.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A composite material with microcapsule biodegradability is characterized by comprising a degradable porous material and microcapsules loaded on the degradable porous material, wherein the loading rate of the microcapsules on the degradable porous material is 3% -50%; the microcapsule comprises a core containing sewage treatment bacteria.
2. The composite material with microcapsules of claim 1, wherein the loading rate of the microcapsules on the degradable porous material is 5% to 30%.
3. Biodegradable composite material with microcapsules according to claim 1, characterized in that the microcapsules have a particle size comprised between 10 and 500 μm; preferably, the particle size of the microcapsule is 10-100 μm; the sewage treatment bacteria are selected from one or more of bacillus subtilis, EM (effective microorganisms) and composite bacteria.
4. The microcapsule biodegradable composite material as set forth in claim 1, wherein the raw material for preparing the degradable porous material comprises the following components in parts by mass:
80-100 parts of floating algae, 12-28 parts of binder, 5-10 parts of foaming agent and 3-5 parts of cross-linking agent; the floating algae is selected from one or more of chlorella, scenedesmus obliquus and gossypium hirsutum, the binder is one or more of starch, polylactic acid and sodium alginate, the foaming agent is carbonate and/or bicarbonate, the crosslinking agent is inorganic salt and weak acid, and the acidity coefficient pKa of the weak acid is more than 4; preferably, the mass ratio of the inorganic salt to the weak acid is (1-10): (10-1).
5. The biodegradable composite material with microcapsules according to any one of claims 1 to 4, characterized in that the wall of the microcapsules is prepared from raw materials comprising: within a pH value of 4-5, a first polymer material with positive charges and a second polymer material with negative charges, wherein the mass ratio of the first polymer material to the second polymer material is (1-4): (4-1).
6. The microencapsulated biodegradable composite material as claimed in claim 5, wherein the first polymer material is one or more of gelatin type A, peach gum, xanthan gum and gum arabic; and/or
The second polymer material is one or more of maltodextrin, sodium carboxymethyl cellulose, sodium alginate and sodium caseinate.
7. A process for the preparation of a composite material with microcapsules biodegradable, according to any of claims 1 to 6, characterized in that it comprises the following steps:
and dissolving the microcapsule in water to form a first solution, regulating the pH value of the first solution to be 4-5, and adding the degradable porous material to perform complex coacervation reaction.
8. The method for preparing a composite material with microcapsules biodegradable according to claim 7, characterized in that it further comprises a step of preparing said degradable porous material, in particular as follows:
placing planktonic algae in a phytonutrient solution to bring algae cells into an exponential growth phase and concentrating the algae cells; and
and dissolving the concentrated algae cells, the binder, the foaming agent and the cross-linking agent in water for cross-linking and curing.
9. The method for preparing a biodegradable composite material with microcapsules according to claim 7 or 8, characterized in that the step of dissolving the microcapsules in water to form a first solution is specifically as follows:
dissolving the capsule wall of the microcapsule in water to form a second solution, and adding bacterial sludge of the sewage treatment bacteria into the second solution; preferably, the mass concentration of the second solution is 0.5% to 5%.
10. A water purifying agent characterized in that a raw material for preparing the water purifying agent comprises the composite material with microcapsule biodegradability of any one of claims 1 to 6.
CN202210597830.1A 2022-05-30 2022-05-30 Composite material with microcapsule biodegradability and preparation method and application thereof Pending CN115465955A (en)

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