CN114940986A - Microbial agent for treating high-salt industrial wastewater and preparation method thereof - Google Patents
Microbial agent for treating high-salt industrial wastewater and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microbial agent for treating high-salt industrial wastewater, which comprises a shell, an embedding agent and a microbial inner core; the active ingredients of the microorganism inner core comprise bacillus amyloliquefaciens, bacillus megaterium, bacillus altitudinis and rhodotorula rubra; the embedding agent is polyvinyl alcohol; the main component of the shell is modified polyvinyl alcohol. The microbial agent provided by the invention can keep stronger biological activity in high-salt industrial wastewater, and further realize high-efficiency degradation of organic pollutants in the high-salt industrial wastewater.
Description
Technical Field
The invention belongs to the technical field of microbial agents, and relates to a microbial agent for treating high-salt industrial wastewater and a preparation method thereof.
Background
High-salt industrial wastewater refers to wastewater containing organic matters and salt with the total mass fraction of at least 1%, and the wastewater also contains a large amount of inorganic salt ions such as Cl besides organic pollutants - 、SO 2 -4 、Na + 、Ca 2+ Plasma with a plasma chamber. At present, the treatment of high-salt industrial wastewater mainly comprises a physical chemical method and a biological method. Among them, the conventional physicochemical method is difficult to handle and the treatment cost is high; although the biological treatment method has the characteristics of economy, high efficiency, harmlessness and the like, the salt in the high-salt industrial wastewater has a strong inhibiting effect on the growth of the conventional microorganisms, for example, the enzyme activity of the microorganisms is reduced due to the high-concentration salt, the toxic action of the high-concentration chloride ions is caused, and the like, so that the technical difficulty of treating the high-salt industrial wastewater by adopting the conventional biological method is high.
Disclosure of Invention
The invention aims to provide a microbial agent for treating high-salt industrial wastewater, which can keep stronger biological activity in the high-salt industrial wastewater so as to realize efficient degradation of organic pollutants in the high-salt industrial wastewater.
The invention also aims to provide a preparation method of the microbial agent for treating the high-salt industrial wastewater, which is simple and feasible and is suitable for popularization and application.
The above purpose of the invention is realized by the following technical scheme:
a microbial agent for treating high-salt industrial wastewater is characterized in that: comprises an outer shell, an embedding medium and a microorganism inner core; the active ingredients of the microorganism inner core comprise bacillus amyloliquefaciens, bacillus megaterium, bacillus highland and rhodotorula rubra; the embedding agent is polyvinyl alcohol; the shell is prepared from modified polyvinyl alcohol which is prepared from the following raw materials in parts by weight:
putting 100 parts of raw material polyvinyl alcohol into a reactor, adding water to dissolve the raw material polyvinyl alcohol into viscous transparent liquid at the temperature of 60-75 ℃, adding 2-5 parts of catalyst and 1-2 parts of cationization reagent, reacting for 6-8 hours, cooling to normal temperature, drying and crushing.
The inventor finds that the polyvinyl alcohol is modified by the cationization reagent at present, the prepared modified polyvinyl alcohol is generally used as a flocculating agent for treating wastewater, and the flocculating agent can destabilize and agglomerate fine suspended particles in the wastewater to form larger floccules, and then precipitate to realize solid-liquid separation. According to the invention, the raw materials adopted for preparing the shell are strictly selected and the proportion of the raw materials is controlled, so that the prepared cation modified polyvinyl alcohol has the advantages that the capability of inactivating microorganisms is greatly reduced due to the low content of cations, the flocculation capability of the cations on fine suspended particles is reduced, the rapid sedimentation of materials is avoided, the efficiency of treating organic matters in wastewater by using microorganisms is improved, meanwhile, the cations can shield negative charges nearby after the wastewater is thrown in, and the toxic action of inorganic salt ions such as high-concentration chloride ions on the microorganisms is reduced.
Specifically, the weight ratio of the microbial inner core to the embedding medium to the outer shell is 2-3: 4-6: 10 to 15.
The polyvinyl alcohol as the embedding agent has an alcoholysis degree of 75 to 99% and an average molecular weight of 110000 to 130000.
It is further clarified that the polyvinyl alcohol used as a raw material for producing the modified polyvinyl alcohol has an alcoholysis degree of 89 to 99% and an average molecular weight of 180000 to 200000. The stability and the reliability of the microbial inoculum in high-salt industrial wastewater are ensured by strictly controlling the alcoholysis degree and the average molecular weight of the polyvinyl alcohol used as the embedding agent and the raw material polyvinyl alcohol adopted in the preparation of the modified polyvinyl alcohol.
As a further definition, the catalyst is one or a mixture of two of sodium hydroxide and potassium hydroxide.
It is further understood that the cationizing agent may be one or any mixture of glycidyltrimethylammonium chloride and glycidyltriethylammonium chloride.
As a further definition, in the active ingredients of the microorganism inner core, the weight parts of bacillus amyloliquefaciens, bacillus megaterium, bacillus altitudinis and rhodotorula rubra are 2-5: 2-5: 4-10: 1 to 2.
As a further definition, the total effective bacteria concentration of the active ingredients of the inner core of the microorganism is at least 2 x 10 11 CFU/g。
The preparation method of the microbial agent for treating the high-salt industrial wastewater sequentially comprises the following preparation steps of:
(1) respectively inoculating each strain into a culture medium, carrying out amplification culture at 15-35 ℃ for 48-96 hours, carrying out centrifugal separation on each culture medium after culture to obtain wet bacteria, and mixing the obtained wet bacteria according to a proportion to obtain the inner core of the microorganism; wherein the components of the culture medium can adopt 6-10 g/L of glucose, 2-2.2 g/L of urea, 0.8-1.0 g/L of monopotassium phosphate, 0.1-0.2 g/L of magnesium sulfate and 8-12 g/L of sodium chloride;
(2) adding water into polyvinyl alcohol with alcoholysis degree of 75-99% and average molecular weight of 110000-130000 serving as embedding agent, heating for dissolving, cooling to 50 ℃ after dissolving, adding the inner core of the microorganism, and fully and uniformly mixing to obtain a mixed solution;
(3) dropwise adding the obtained mixed solution into a mixed solidification solution containing boric acid and calcium chloride through a solution dropwise adding device to form particles with the particle size of 2-3 mm, wherein the concentration of the calcium chloride in the mixed solidification solution is 0.15-0.25 mol/L, and the concentration of the boric acid is 0.1-0.15 mol/L; standing the obtained particles at room temperature for 1-2 h, and then cleaning the particles with sterile water for 2 times to obtain cured particles;
(3) putting a polyvinyl alcohol raw material with alcoholysis degree of 89-99% and average molecular weight of 180000-200000 into a reactor, adding water, dissolving at 60-75 ℃ to form viscous transparent liquid, adding a catalyst and a cationization reagent, reacting for 6-8 h, cooling to normal temperature, drying and crushing to obtain modified polyvinyl alcohol powder; and adding water into the obtained modified polyvinyl alcohol powder according to the proportion of 1:1.5, mixing and stirring to form a mud-like substance, then wrapping the mud-like substance on the outer layer of the solidified particles, molding into a spherical shape, and drying to obtain the microbial agent for treating the high-salt industrial wastewater.
The invention has the following beneficial effects:
the microbial agent for treating the high-salt industrial wastewater provided by the invention can keep stronger biological activity in the high-salt industrial wastewater and has efficient degradation effect on organic pollutants in the high-salt industrial wastewater.
(1) In the active ingredients of the microbial inner core, bacillus amyloliquefaciens, bacillus megaterium and bacillus altitudinis can synergistically and strongly decompose pollutants such as carbon series, nitrogen series, phosphorus series, sulfur series and the like in wastewater, and form a zoogloea, so that the resistance to adverse environment is enhanced, and the added metabolic secretion of the rhodotorula rubra can promote the biological activity of microbial strains;
(2) the polyvinyl alcohol used as the embedding agent has stable chemical property, no toxicity and extremely low biological toxicity, plays a good role in protecting the inner core of the microorganism, not only enhances the resistance of the polyvinyl alcohol to the adverse effect of the polyvinyl alcohol on the environment of high-salt industrial wastewater, but also realizes the separation of the inner core of the microorganism and the shell of which the main component is cation modified polyvinyl alcohol, and avoids the adverse effect of the shell on the inner core of the microorganism;
(3) the main component of the shell is cation modified polyvinyl alcohol, the cation content is ensured to be lower by controlling the selection of the raw materials, the capability of the shell to inactivate microorganisms is greatly reduced, the flocculation capability of the shell to fine suspended particles is reduced, the rapid sedimentation of materials is avoided, the efficiency of treating organic matters in wastewater by using microorganisms is improved, meanwhile, the cations can shield negative charges nearby after the wastewater is thrown in, and the toxic action of inorganic salt ions such as high-concentration chloride ions and the like to the microorganisms is reduced. Meanwhile, by strictly selecting the polyvinyl alcohol used as the embedding agent and the polyvinyl alcohol raw material adopted during the preparation of the modified polyvinyl alcohol, the microbial agent balances the contradiction between effective swelling and external high osmotic pressure resistance in the high-salt industrial wastewater, and the stability and reliability of the microbial agent in the high-salt industrial wastewater are ensured.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are merely exemplary of the invention and that all other embodiments that can be made by one skilled in the art without inventive faculty based on the embodiments described herein are within the scope of the invention.
Example 1
A preparation method of a microbial agent for treating high-salt industrial wastewater sequentially comprises the following preparation steps:
(1) respectively inoculating Bacillus amyloliquefaciens (Bacillus amyloliquefaciens CGMCC No.1.7463), Bacillus megaterium (Bacillus megaterium CGMCC 1.151), Bacillus altitudinis (Bacillus altitudinis CGMCC No.5948) and Rhodotorula rubra (Rhodotorula rubra CGMCC 2.670) into a culture medium, carrying out amplification culture at 25 ℃ for 48 hours, carrying out centrifugal separation on each culture medium after culture to obtain wet bacteria, and mixing the obtained Bacillus amyloliquefaciens wet bacteria, Bacillus megaterium wet bacteria, Bacillus altitudinis wet bacteria and Rhodotorula rubra wet bacteria according to the weight part ratio of 2: 2: 4: mixing at a ratio of 1 to obtain microorganism inner core with total effective bacteria concentration of 2 × 10 11 CFU/g; wherein, the components of the culture medium can adopt 6g/L glucose, 2.2g/L urea, 0.8g/L potassium dihydrogen phosphate, 0.1g/L magnesium sulfate and 8g/L sodium chloride;
(2) adding water into polyvinyl alcohol with alcoholysis degree of 75% and average molecular weight of 110000 as embedding agent, heating for dissolving, cooling to 50 deg.C after dissolving, adding the above microorganism core, and mixing to obtain mixed solution;
(3) dropwise adding the obtained mixed solution into a mixed solidification solution containing boric acid and calcium chloride through a solution dropwise adding device to form particles with the particle size of 2mm, wherein the concentration of the calcium chloride in the mixed solidification solution is 0.20mol/L, and the concentration of the boric acid in the mixed solidification solution is 0.1 mol/L; standing the obtained particles at room temperature for 2h, and then cleaning with sterile water for 2 times to obtain cured particles;
(3) putting 100 parts by weight of a polyvinyl alcohol raw material with alcoholysis degree of 89% and average molecular weight of 200000 into a reactor, adding water to dissolve the raw material at 65 ℃ to form viscous transparent liquid, adding 2 parts by weight of sodium hydroxide and 1.5 parts by weight of epoxypropyl trimethyl ammonium chloride, reacting for 7 hours, cooling to normal temperature, drying and crushing to obtain modified polyvinyl alcohol powder serving as a main material of a shell; and adding water into the obtained modified polyvinyl alcohol powder according to the proportion of 1:1.5, mixing and stirring to form a paste, then wrapping the paste on the outer layer of the solidified particles, carrying out die pressing to form a sphere, and drying to obtain the microbial agent for treating the high-salt industrial wastewater, wherein the weight ratio of an inner core of a microorganism, an embedding medium and an outer shell in the obtained microbial agent is 3:5: 10.
Example 2
A preparation method of a microbial agent for treating high-salt industrial wastewater sequentially comprises the following preparation steps:
(1) respectively inoculating Bacillus amyloliquefaciens (CGMCC No.1.7463), Bacillus megaterium (CGMCC 1.151), Bacillus altitudinis (CGMCC No.5948) and Rhodotorula rubra (CGMCC 2.670) into a culture medium, carrying out amplification culture at 35 ℃ for 96 hours, carrying out centrifugal separation on each culture medium to obtain wet bacteria, and mixing the obtained Bacillus amyloliquefaciens wet bacteria, Bacillus megaterium wet bacteria, Bacillus altitudinis wet bacteria and Rhodotorula rubra wet bacteria according to the weight ratio of 3:4: 8: mixing at a ratio of 2 to obtain microorganism inner core with total effective bacteria concentration higher than 2 × 10 11 CFU/g; wherein the components of the culture medium can adopt 8g/L glucose, 2g/L urea, 0.9g/L potassium dihydrogen phosphate, 0.2g/L magnesium sulfate and 10g/L sodium chloride;
(2) adding water into polyvinyl alcohol with alcoholysis degree of 99% and average molecular weight of 130000 as embedding agent, heating for dissolving, cooling to 50 deg.C after dissolving, adding the above microorganism inner core, and mixing thoroughly to obtain mixed solution;
(3) dropwise adding the obtained mixed solution into a mixed solidification solution containing boric acid and calcium chloride through a solution dropwise adding device to form particles with the particle size of 3mm, wherein the concentration of the calcium chloride in the mixed solidification solution is 0.25mol/L, and the concentration of the boric acid in the mixed solidification solution is 0.15 mol/L; standing the obtained particles at room temperature for 1h, and then cleaning with sterile water for 2 times to obtain cured particles;
(3) putting 100 parts by weight of a polyvinyl alcohol raw material with alcoholysis degree of 89% and average molecular weight of 180000 into a reactor, adding water to dissolve at 75 ℃ to form viscous transparent liquid, adding 5 parts by weight of potassium hydroxide and 2 parts by weight of glycidyl triethyl ammonium chloride, reacting for 6 hours, cooling to normal temperature, drying and crushing to obtain modified polyvinyl alcohol powder serving as a main material of a shell; and adding water into the obtained modified polyvinyl alcohol powder according to the proportion of 1:1.5, mixing and stirring to form a paste, then wrapping the paste on the outer layer of the solidified particles, carrying out die pressing to form a sphere, and drying to obtain the microbial agent for treating the high-salt industrial wastewater, wherein the weight ratio of an inner core of a microorganism, an embedding medium and an outer shell in the obtained microbial agent is 3:4: 10.
Example 3
A preparation method of a microbial agent for treating high-salt industrial wastewater sequentially comprises the following preparation steps:
(1) respectively inoculating Bacillus amyloliquefaciens (CGMCC No.1.7463), Bacillus megaterium (CGMCC 1.151), Bacillus altitudinis (CGMCC No.5948) and Rhodotorula rubra (CGMCC 2.670) into a culture medium, carrying out amplification culture at 15 ℃ for 60 hours, carrying out centrifugal separation on each culture medium to obtain wet bacteria, and carrying out centrifugal separation on the obtained Bacillus amyloliquefaciens wet bacteria, Bacillus megaterium wet bacteria, Bacillus altitudinis wet bacteria and Rhodotorula rubra wet bacteria according to the weight ratio of 4: 3: 10: mixing at a ratio of 1.5 to obtain microorganism inner core with total effective bacteria concentration higher than 2 × 10 11 CFU/g; wherein the culture medium comprises glucose 10g/L, urea 2.2g/L, potassium dihydrogen phosphate 1.0g/L, and magnesium sulfate 0.2g/L12g/L of sodium chloride;
(2) adding water into polyvinyl alcohol with alcoholysis degree of 89% and average molecular weight of 110000 as embedding agent, heating for dissolving, cooling to 50 deg.C after dissolving, adding the above microorganism inner core, and mixing thoroughly to obtain mixed solution;
(3) dropwise adding the obtained mixed solution into a mixed solidification solution containing boric acid and calcium chloride through a solution dropwise adding device to form particles with the particle size of 2mm, wherein the concentration of the calcium chloride in the mixed solidification solution is 0.15mol/L, and the concentration of the boric acid in the mixed solidification solution is 0.1 mol/L; standing the obtained particles at room temperature for 1h, and cleaning with sterile water for 2 times to obtain cured particles;
(3) putting 100 parts by weight of a polyvinyl alcohol raw material with alcoholysis degree of 89% and average molecular weight of 200000 into a reactor, adding water to dissolve at 60 ℃ to form viscous transparent liquid, adding 3 parts by weight of sodium hydroxide and 1 part by weight of epoxypropyl trimethyl ammonium chloride, reacting for 8 hours, cooling to normal temperature, drying and crushing to obtain modified polyvinyl alcohol powder serving as a main material of a shell; and adding water into the obtained modified polyvinyl alcohol powder according to the proportion of 1:1.5, mixing and stirring to obtain a sludge, then wrapping the sludge on the outer layer of the solidified particles, carrying out die pressing to obtain a spherical shape, and drying to obtain the microbial agent for treating the high-salt industrial wastewater, wherein the weight ratio of an inner core of a microorganism, an embedding medium and an outer shell in the microbial agent is 3:6: 12.
The invention also carried out the following application experiments:
the chemical wastewater produced by a certain chemical plant has the salt content of 2.8 percent, the COD of 1339mg/L and is high-salt refractory organic wastewater, the pH of the chemical wastewater is firstly adjusted to 7-8 during treatment, pre-aeration is carried out for 0.5-1 h, then the microbial agent for treating the high-salt industrial wastewater, which is prepared in the embodiment 1 of the invention, is added with the addition amount of 1 per mill, aeration is continuously carried out and regular detection is carried out, the reaction time is 12 days, the COD of the treated wastewater is less than 400mg/L, the appearance volume of the treated microbial agent particles is increased, and the integral integrity is good.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (9)
1. A microbial agent for treating high-salt industrial wastewater is characterized in that: comprises an outer shell, an embedding medium and a microorganism inner core; the active ingredients of the microorganism inner core comprise bacillus amyloliquefaciens, bacillus megaterium, bacillus altitudinis and rhodotorula rubra; the embedding agent is polyvinyl alcohol; the shell is prepared from the following raw materials in parts by weight:
putting 100 parts of raw material polyvinyl alcohol into a reactor, adding water to dissolve the raw material polyvinyl alcohol into viscous transparent liquid at the temperature of 60-75 ℃, adding 2-5 parts of catalyst and 1-2 parts of cationization reagent, reacting for 6-8 hours, cooling to normal temperature, drying and crushing.
2. The microbial inoculant for the treatment of high-salt industrial wastewater as claimed in claim 1, wherein: the weight ratio of the microbial inner core to the embedding agent to the outer shell is (2-3: 4-6): 10 to 15.
3. The microbial inoculant for the treatment of high-salinity industrial wastewater as claimed in claim 1 or 2, wherein: the polyvinyl alcohol used as the embedding agent has the alcoholysis degree of 75-99% and the average molecular weight of 110000-130000.
4. The microbial inoculant for the treatment of high-salinity industrial wastewater as claimed in any one of claims 1 to 3, wherein: the modified polyvinyl alcohol is prepared from the raw material polyvinyl alcohol, the alcoholysis degree of the polyvinyl alcohol is 89-99%, and the average molecular weight of the polyvinyl alcohol is 180000-200000.
5. The microbial agent for treating high-salt industrial wastewater as claimed in any one of claims 1 to 4, wherein: the catalyst is one or a mixture of sodium hydroxide and potassium hydroxide.
6. The microbial inoculant for the treatment of high-salinity industrial wastewater as claimed in any one of claims 1 to 5, wherein: the cationization reagent adopts one or any mixture of epoxypropyltrimethyl ammonium chloride or epoxypropyltriethyl ammonium chloride.
7. The microbial agent for treating high-salt industrial wastewater as claimed in any one of claims 1 to 6, wherein: in the active ingredients of the microorganism inner core, the weight parts of bacillus amyloliquefaciens, bacillus megaterium, bacillus highland and rhodotorula rubra are 2-5: 2-5: 4-10: 1 to 2.
8. The microbial agent for treating high-salt industrial wastewater as claimed in any one of claims 1 to 7, wherein: the total effective bacteria concentration of the active components of the microorganism inner core is at least 2 x 10 11 CFU/g。
9. The preparation method of the microbial agent for treating high-salt industrial wastewater as claimed in any one of claims 1 to 7, which comprises the following preparation steps in sequence:
(1) respectively inoculating each strain into a culture medium, carrying out amplification culture for 48-96 hours at 15-35 ℃, carrying out centrifugal separation on each culture medium after culture to obtain wet thalli, and mixing the obtained wet thalli according to a proportion to obtain the inner core of the microorganism; wherein the components of the culture medium can adopt 6-10 g/L of glucose, 2-2.2 g/L of urea, 0.8-1.0 g/L of monopotassium phosphate, 0.1-0.2 g/L of magnesium sulfate and 8-12 g/L of sodium chloride;
(2) adding water into the polyvinyl alcohol with the alcoholysis degree of 75-99% and the average molecular weight of 110000-130000 serving as the embedding agent, heating for dissolving, cooling to 50 ℃ after dissolving, adding the microorganism inner core, and fully and uniformly mixing to obtain a mixed solution;
(3) dropwise adding the obtained mixed solution into a mixed solidification solution containing boric acid and calcium chloride through a solution dropwise adding device to form particles with the particle size of 2-3 mm, wherein the concentration of the calcium chloride in the mixed solidification solution is 0.15-0.25 mol/L, and the concentration of the boric acid is 0.1-0.15 mol/L; standing the obtained particles at room temperature for 1-2 h, and then cleaning the particles with sterile water for 2 times to obtain cured particles;
(3) putting a polyvinyl alcohol raw material with alcoholysis degree of 89-99% and average molecular weight of 180000-200000 into a reactor, adding water, dissolving at 60-75 ℃ to form viscous transparent liquid, adding a catalyst and a cationization reagent, reacting for 6-8 h, cooling to normal temperature, drying and crushing to obtain modified polyvinyl alcohol powder; and adding water into the obtained modified polyvinyl alcohol powder according to the proportion of 1:1.5, mixing and stirring to form a paste, then wrapping the paste on the outer layer of the solidified particles, molding into a spherical shape, and drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432829A (en) * | 2022-08-31 | 2022-12-06 | 江西盖亚环保科技有限公司 | Biological filler, preparation method and application thereof in sewage treatment |
| CN116282496A (en) * | 2023-05-22 | 2023-06-23 | 广州市豫泉净水材料有限公司 | Composite carbon source production process |
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2022
- 2022-05-31 CN CN202210609050.4A patent/CN114940986A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432829A (en) * | 2022-08-31 | 2022-12-06 | 江西盖亚环保科技有限公司 | Biological filler, preparation method and application thereof in sewage treatment |
| CN116282496A (en) * | 2023-05-22 | 2023-06-23 | 广州市豫泉净水材料有限公司 | Composite carbon source production process |
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Application publication date: 20220826 |