CN112897709B - Slow-release microbial agent and application thereof in sewage treatment - Google Patents
Slow-release microbial agent and application thereof in sewage treatment Download PDFInfo
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Abstract
The invention discloses a slow-release microbial agent and application thereof in sewage treatment, belongs to the field of preparation of microbial agents, and discloses a slow-release microbial agent, which comprises the following components in part by weight: the slow release carrier is a porous activated mixture and a slow release film coated on the porous activated mixture, and the mass fraction of the slow release film is that the porous activated mixture contains a porous material; and the microbial bacteria are supported on the porous material. The porous material prepared by the invention has good porosity and large specific surface area which is 350m2More than g, high pore volume of 0.690cm3More than g, good adsorption performance, and nitrogen adsorption capacity of more than 8.4 mg/g; the slow-release microbial agent obtained by the invention has good slow-release performance and long-term slow-release performance.
Description
Technical Field
The invention belongs to the field of preparation of microbial agents, and particularly relates to a slow-release microbial agent and application thereof in sewage treatment.
Background
With the rapid development of economy in China, the living standard of people is continuously improved, the yield of a large amount of industrial sewage and domestic sewage is increased day by day, and the traditional treatment mode not only easily causes secondary pollution, but also wastes resources. In recent years, the technology of treating the garbage by using a biological method is mature day by day, the garbage treated by the biological method is thorough in treatment, free of secondary pollution and good in safety, the transportation cost and the labor cost are reduced, and the treated product can be used for preparing organic fertilizer and is beneficial to recycling of resources.
The microorganism bacterium agent has the fatal defect that the microorganism bacterium agent is easy to be influenced by external environment change, such as ultraviolet rays in the nature and the like, can kill microorganisms, and is killed before the microorganism bacterium reaches a target place. The microorganism is prepared into the slow release microbial inoculum, so that the resistance of the microorganism to the change of the external environment can be enhanced, the application effect of the microbial inoculum is improved, and the long-term effective treatment effect can be generated due to the improvement of the slow release performance.
Disclosure of Invention
The invention aims to provide a slow-release microbial agent with good slow-release effect and good long-term slow-release performance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a sustained release microbial inoculant comprising:
the slow release carrier is a porous activated mixture and a slow release film coated on the porous activated mixture, the porous activated mixture contains a porous material, and the specific surface area of the porous material is 350m2More than g;
and the microbial bacteria are supported on the porous material.
Preferably, the porous activation mixture further comprises an inorganic material.
Preferably, the sustained release membrane comprises a cross-linked alginate and a wax film material.
Preferably, the porous material is obtained by modifying and carbonizing a biological material.
Preferably, the biological material is modified by an alkaline solution containing diosmetin-7-glucoside.
The invention discloses application of the slow-release microbial agent in sewage treatment, wherein the slow-release effective time of the microbial agent reaches more than 7 days.
The invention aims to provide a porous material which can be used as a carrier of a slow-release microbial inoculum and has large specific surface area and high pore volume, and a preparation method of a slow-release microbial inoculum with good slow-release performance and good long-term slow-release performance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a slow-release microbial agent comprises the following steps:
carrying out a carbonization process on the biological material to obtain a porous material;
mixing the microbial liquid with a porous material to obtain a porous microbial adsorption mixture;
the slow-release microbial agent is prepared from the porous microbial adsorption mixture, an inorganic material, a membrane material solution and calcium chloride through a preparation process.
Preferably, the biological material comprises at least one of corn stover, rice straw, corn cobs.
Preferably, the inorganic material is at least one of perlite, fine clay, bentonite, diatomaceous earth, vermiculite powder and yellow cotton soil.
Preferably, the wax film material is at least one of paraffin, liquid paraffin, shellac, xanthan gum.
Preferably, the porous material is prepared by: soaking the biological material in an acidic solution for 1-3h, filtering and washing to obtain an acidified biological material, soaking the acidified biological material in an alkaline solution for 1-3h, filtering and washing to remove surface alkali liquor residue to obtain an alkalized biological material, and then treating in a muffle furnace at the temperature of 500-600 ℃ for 1-5h to obtain a pretreated porous material; the porous material is charcoal, and the addition amount of the biological material is 5-10 wt% of the acid solution; the acid solution is a mixed solution of nitric acid and phosphoric acid, the content of the nitric acid in the acid solution is 2-5 wt%, and the content of the phosphoric acid in the acid solution is 10-15 wt%; the alkaline solution is 2-5 wt% sodium hydroxide solution, and the addition amount of the acidified biological material is 5-10 wt% of the alkaline solution.
More preferably, the alkaline solution contains diosmetin-7-glucoside, and the addition amount of diosmetin-7-glucoside is 0.5-4 wt% of the alkaline solution. When the porous material is treated by an alkaline solution containing diosmetin-7-glucoside, diosmetin-7-glucoside is immersed into the biological material, through the interaction force between diosmetin-7-glucoside and functional groups in the biological material, diosmetin-7-glucoside is tightly combined in the biological material, the distribution is more stable, in the next high-temperature carbonization process, the conversion efficiency of the biochar is improved, the biochar with a high specific surface area is obtained, the pore volume of the biochar is improved, and when the slow-release microbial agent is prepared, the adsorption capacity of the microbial agent is improved.
More preferably, the biological material comprises at least one of corn stover, rice straw, corn cobs.
Preferably, the porous microbial adsorption mixture: will be micro-grownAnd mixing the biological liquid with the porous material to obtain a porous microorganism adsorption mixture. The number of viable bacteria in the porous microorganism adsorption mixture is 3 × 1010-10×1010CFU/g。
Preferably, the microorganism bacterium is at least one of chrysobacillus indolenini, pseudomonas putida and acinetobacter iwoffii.
More preferably, the microorganism bacteria in the microorganism bacteria liquid are the mixture of any two of chrysobacillus indoligenes, pseudomonas putida and acinetobacter iwoffii, and the two microorganism bacteria in the microorganism bacteria liquid are mixed in a ratio of 1: mixing with viable bacteria 0.1-10.
More preferably, the microorganism bacteria in the microorganism bacteria liquid are a mixture of three kinds of chrysobacillus indolenini, pseudomonas putida and acinetobacter iwoffii, and the ratio of the three kinds of microorganism bacteria in the microorganism bacteria liquid is 1: 0.1-10: mixing with viable bacteria 0.1-10.
Preferably, the slow-release microbial agent is prepared by the following steps: uniformly mixing the porous microorganism adsorption mixture with an inorganic material and drying to obtain a porous activation mixture, adding the porous activation mixture into a membrane material solution containing alginate and a wax membrane material, uniformly mixing and drying, and adding a calcium chloride solution to obtain a slow-release microbial agent; the inorganic material is diatomite, and the addition amount of the inorganic material is 10-20 wt% of the porous microorganism adsorption mixture; alginate is sodium alginate, wax membrane material is xanthan gum, the usage amount of alginate is 3-5 wt% of the porous activation mixture, and the usage amount of wax membrane material is 2-8 wt% of the porous activation mixture; the amount of calcium chloride used is 0.6-1.2 wt% of the porous activation mixture.
Preferably, the membrane material solution contains dihydroxypropyl PABA ethyl ester and methyl-penta polyethylene glycol-succinimidyl acrylate, the addition amount of the dihydroxypropyl PABA ethyl ester is 0.3-3 wt% of the membrane material solution, and the addition amount of the methyl-penta polyethylene glycol-succinimidyl acrylate is 0.5-2 wt% of the membrane material solution. When the slow release membrane is formed, the dihydroxypropyl PABA ethyl ester and the methyl-pentapolyethylene glycol-succinimidyl acrylate are combined with the components in the membrane material solution to form a fine slow release membrane layer, the embedding effect is good, the slow release effect of the microbial agent is further improved, and the long-term slow release performance is enhanced.
The invention adopts the biological material which is treated by the alkali liquor containing diosmetin-7-glucoside and is carbonized to prepare the porous material, and prepares the slow-release microbial agent by mixing and adsorbing the microbial liquid and the porous material and then mixing the microbial liquid and the inorganic material and the membrane material solution, thereby having the following beneficial effects: the porous material has good porosity performance and large specific surface area which is 350m2More than g, high pore volume of 0.690cm3More than g, good adsorption performance, and nitrogen adsorption capacity of more than 8.4 mg/g; has good slow release performance and long-term slow release performance. Therefore, the invention is a porous material with large specific surface area and high pore volume which can be used as a carrier of the slow-release microbial inoculum and a preparation method of the slow-release microbial inoculum with good slow-release performance and good long-term slow-release performance.
Drawings
FIG. 1 is a graph showing results of specific surface area of biochar;
FIG. 2 is a graph showing the results of pore volume of biochar;
FIG. 3 is a graph showing the results of nitrogen adsorption amount of biochar;
FIG. 4 is a graph showing the results of the sustained release performance of the sustained release microbial agent;
FIG. 5 is a graph showing the results of the long-term sustained-release performance of the sustained-release microbial agent.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the preservation number of chrysobacillus indogenes (Chryseobacterium indices) used in the embodiment of the invention is CCTCCNO: m2018651; pseudomonas putida (Pseudomonas putida) with deposit number ATCC 49128; acinetobacter lwofiis (Acinetobacter lwofiis) was deposited under accession number CICC 23693.
Example 1:
a preparation method of a slow-release microbial agent,
preparing a porous material: soaking the biological material in an acidic solution for 2h, filtering, washing to obtain an acidified biological material, soaking the acidified biological material in an alkaline solution for 2h, filtering, washing to remove surface alkali liquor residue to obtain an alkalified biological material, and treating in a muffle furnace at 500 ℃ for 3h to obtain a pretreated porous material; the porous material is charcoal, and the adding amount of the biological material is 10 wt% of the acid solution; the acid solution is a mixed solution of nitric acid and phosphoric acid, the content of the nitric acid in the acid solution is 4 wt%, and the content of the phosphoric acid in the acid solution is 12 wt%; the alkaline solution is 5 wt% sodium hydroxide solution, and the amount of acidified biomaterial added is 10 wt% of the alkaline solution.
Porous microbial adsorption mixture: and (3) mixing the microbial liquid with the pretreated porous material to obtain a porous microbial adsorption mixture. The microbial bacteria in the microbial bacteria liquid are the mixture of three kinds of chrysobacillus indolenini, pseudomonas putida and acinetobacter iwoffii, and the ratio of the three kinds of microbial bacteria in the microbial bacteria liquid is 1: 0.5: 2, the number of the live bacteria in the porous microorganism adsorption mixture is 5 multiplied by 1010CFU/g。
Preparing a slow-release microbial agent: uniformly mixing the porous microorganism adsorption mixture with an inorganic material and drying to obtain a porous activation mixture, adding the porous activation mixture into a membrane material solution containing alginate and a wax membrane material, uniformly mixing and drying, and adding a calcium chloride solution to obtain a slow-release microbial agent; the inorganic material is diatomite, and the addition amount of the inorganic material is 15 wt% of the porous microorganism adsorption mixture; the alginate is sodium alginate, the wax film material is xanthan gum, the usage amount of the alginate is 4 wt% of the porous activation mixture, and the usage amount of the wax film material is 4 wt% of the porous activation mixture; calcium chloride was used in an amount of 1 wt% of the porous activation mixture.
Example 2:
this example is different from example 1 only in that the alkaline solution contains diosmetin-7-glucoside, and the addition amount of diosmetin-7-glucoside is 1.8 wt% of the alkaline solution.
Example 3:
this example is different from example 1 only in that the alkaline solution contains diosmetin-7-glucoside, and the added amount of diosmetin-7-glucoside is 3.4 wt% of the alkaline solution.
Example 4:
compared with the embodiment 3, the difference of the embodiment is only that the film material solution contains dihydroxypropyl PABA ethyl ester and methyl-penta-polyethylene glycol-acrylic acid succinimide ester, the addition amount of the dihydroxypropyl PABA ethyl ester is 0.6 wt% of the film material solution, and the addition amount of the methyl-penta-polyethylene glycol-acrylic acid succinimide ester is 0.9 wt% of the film material solution.
Example 5:
compared with example 3, the difference of this example is that the membrane material solution contains dihydroxypropyl PABA ethyl ester and methyl-penta polyethylene glycol-succinimidyl acrylate, the addition amount of dihydroxypropyl PABA ethyl ester is 1.3 wt% of the membrane material solution, and the addition amount of methyl-penta polyethylene glycol-succinimidyl acrylate is 1.5 wt% of the membrane material solution.
Example 6:
this example is different from example 5 only in that the membrane material solution does not contain methyl-penta polyethylene glycol-acrylic acid succinimidyl ester.
Example 7:
this example is different from example 5 only in that no dihydroxypropyl PABA ethyl ester is contained in the membrane material solution.
Test example 1:
1. biochar pore status testing
Test samples: biochar obtained in each example.
The specific surface area, pore volume and other pore conditions of the biochar are measured by a physical adsorption instrument. Drying the ground and sieved biochar sample at 100 ℃ for 24h, degassing for 4h at 200 ℃ by using a nitrogen adsorption medium, and measuring the specific surface area and the gap of the biochar sample under 77K liquid nitrogen.
The results of the measurement of the specific surface area of biochar are shown in FIG. 1, in which the specific surface area of biochar obtained in example 1 was 358m2(g), the specific surface area of the biochar obtained in example 2 was 404m2The specific surface area of the porous material after being treated by the alkali liquor containing diosmetin-7-glucoside and then treated by the muffle furnace is increased and is increased by 12 in example 2 compared with example 185 percent; the specific surface area of the biochar obtained in example 3 was 437m2Example 3 compared with example 2 shows that the specific surface area of the biochar can be further increased by increasing the using amount of diosmetin-7-glucoside in the alkali liquor, and compared with example 1, the specific surface area is increased by 22.07%.
The results of the pore volume test of the biochar are shown in FIG. 2, in which the pore volume of the biochar obtained in example 1 was 0.694cm3Per g, the pore volume of the biochar obtained in example 2 was 0.739cm3Compared with the example 1, the example 2 shows that the pore volume of the porous material is increased and improved by 6.48 percent after the porous material is treated by the lye containing diosmetin-7-glucoside and then treated by a muffle furnace; the pore volume of the biochar obtained in example 3 was 0.762cm3The comparison of example 3 and example 2 shows that the increase of the dosage of diosmetin-7-glucoside in the alkali liquor can further increase the pore volume of the biochar, and the pore volume is improved by 9.80 percent compared with example 1.
The results of the measurement of the nitrogen adsorption amount of the biochar are shown in fig. 3, wherein the nitrogen adsorption amount of the biochar obtained in example 1 is 8.47mg/g, the nitrogen adsorption amount of the biochar obtained in example 2 is 9.35mg/g, and the nitrogen adsorption amount of the porous material treated by the muffle furnace after being treated by the alkali solution containing diosmetin-7-glucoside is increased in example 2 compared with example 1; the nitrogen adsorption amount of the biochar obtained in example 3 is 9.82mg/g, and compared with example 2, the nitrogen adsorption amount of the biochar can be further increased by increasing the usage amount of diosmetin-7-glucoside in the alkali liquor in example 3.
The porous material obtained by the invention has good porosity performance and large specific surface area which is 350m2More than g, high pore volume of 0.690cm3More than g, good adsorption performance, and nitrogen adsorption capacity of more than 8.4mg/g
Test example 2:
1. test of sustained Release Performance
Test samples: the slow-release biological agent obtained in each embodiment.
Testing a water sample: COD value of the sewage is 78.19 mg/L.
And (3) testing conditions are as follows: the test container is a toughened glass cylinder with the length, width and height of 0.6m, 0.4m and 0.5m respectively, and the experimental water body is kept in a flowing state in a circulating mode. Respectively adding the slow-release microbial agent into a test group, wherein the adding amount is 1.2kg/m2. After the operation test is carried out for 1d, detecting the COD value of the water sample; and after the operation is continued for 6d, draining the water sample in the container, adding the water sample with the same initial COD value in the same batch again, and after the operation is continued for 1d, detecting the COD value of the water sample.
The result of the slow release performance test of the slow release microbial agent is shown in fig. 4, the COD value of the slow release microbial agent in example 3 after the slow release microbial agent is treated for 1d of sewage is 64.09mg/L, the COD value of the slow release microbial agent in example 4 after the slow release microbial agent is treated for 1d of sewage is 65.71mg/L, the COD value of the slow release microbial agent in example 5 after the slow release microbial agent is treated for 1d of sewage is 66.93mg/L, and compared with example 3, in examples 4 to 5, it is shown that the slow release performance of the microbial agent is improved by adding dihydroxypropyl PABA ethyl ester and methyl-pentapolyethylene glycol-succinimidyl acrylate into a membrane material solution; example 5 compared to examples 6-7 shows that the effect of using dihydroxypropyl PABA ethyl ester and methyl-pentapolyethylene glycol-acrylic acid succinimide ester together is better than the effect of using dihydroxypropyl PABA ethyl ester or methyl-pentapolyethylene glycol-acrylic acid succinimide ester separately.
The long-term slow-release performance test result of the slow-release microbial agent is shown in fig. 5, the COD value of the slow-release microbial agent in example 3 after running for 7 days and treating sewage again for 1d is 64.14mg/L, the COD value of the slow-release microbial agent in example 4 after running for 7 days and treating sewage again for 1d is 66.35mg/L, the COD value of the slow-release microbial agent in example 5 after running for 7 days and treating sewage again for 1d is 67.84mg/L, and compared with example 3, the examples 4-5 show that the addition of dihydroxypropyl PABA ethyl ester and methyl-penta-polyethylene glycol-succinimidyl acrylate in the membrane material solution improves the long-term slow-release performance of the microbial agent; example 5 shows that the effect of using dihydroxypropyl PABA ethyl ester and methyl-pentapolyethylene glycol-succinimidyl acrylate together is better than the effect of using dihydroxypropyl PABA ethyl ester or methyl-pentapolyethylene glycol-succinimidyl acrylate separately, compared to examples 6-7.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (9)
1. A sustained-release microbial inoculant comprising:
the slow release carrier is a porous activation mixture and a slow release film coated on the porous activation mixture, the porous activation mixture contains a porous material, and the specific surface area of the porous material is 350m2More than g; the porous activation mixture is obtained by mixing a porous microorganism adsorption mixture with an inorganic material and drying, and the porous microorganism adsorption mixture is obtained by mixing a microorganism liquid with a porous material;
the microorganism bacteria are loaded on the porous material;
the slow release membrane is prepared from a membrane material solution, wherein the membrane material solution contains dihydroxypropyl PABA ethyl ester and methyl-pentapolyethylene glycol-succinimidyl acrylate, the addition amount of the dihydroxypropyl PABA ethyl ester is 0.3-3 wt% of the membrane material solution, and the addition amount of the methyl-pentapolyethylene glycol-succinimidyl acrylate is 0.5-2 wt% of the membrane material solution.
2. The sustained-release microbial preparation according to claim 1, wherein: the slow release film comprises cross-linked alginate and a wax film material.
3. The sustained-release microbial agent according to claim 2, wherein: the wax film material is at least one of petrolatum, liquid paraffin, shellac and xanthan gum.
4. The sustained-release microbial agent according to claim 1, wherein: the porous material is obtained by modifying and carbonizing a biological material.
5. The sustained-release microbial agent according to claim 4, wherein: the biological material is modified by an alkaline solution containing diosmetin-7-glucoside.
6. Use of the slow-release microbial agent of any one of claims 1 to 5 in sewage treatment, wherein: the effective time of the slow release of the microbial inoculum reaches more than 7 days.
7. A method for preparing the sustained-release microbial agent of any one of claims 1 to 5, comprising:
carrying out a carbonization procedure on the biological material to obtain a porous material;
mixing the microbial liquid with a porous material to obtain a porous microbial adsorption mixture;
the slow-release microbial agent is prepared from the porous microbial adsorption mixture, an inorganic material, a membrane material solution and calcium chloride through a preparation process.
8. The method for preparing a sustained-release microbial inoculant according to claim 7, wherein the method comprises the following steps: the biological material comprises at least one of corn stalks, rice straw stalks and corncobs.
9. The method for preparing a sustained-release microbial inoculant according to claim 7, wherein the method comprises the following steps: the inorganic material is at least one of perlite, fine clay, bentonite, diatomite, vermiculite powder and yellow cotton soil.
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| CN116078806A (en) * | 2022-12-09 | 2023-05-09 | 杭州楠大环保科技有限公司 | Method for adjusting carbon-nitrogen-phosphorus ratio in polluted soil |
| CN116854260B (en) * | 2023-07-28 | 2024-04-26 | 杭州洁神环境科技股份有限公司 | Sustained-release sewage treatment agent and preparation method thereof |
| CN117023811B (en) * | 2023-07-28 | 2024-06-18 | 杭州洁神环境科技股份有限公司 | Degradable slow-release microsphere for water treatment and preparation method thereof |
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