CN120817649A - Biological degreasing and deodorizing agent for grease trap and preparation method thereof - Google Patents

Biological degreasing and deodorizing agent for grease trap and preparation method thereof

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Publication number
CN120817649A
CN120817649A CN202510906929.9A CN202510906929A CN120817649A CN 120817649 A CN120817649 A CN 120817649A CN 202510906929 A CN202510906929 A CN 202510906929A CN 120817649 A CN120817649 A CN 120817649A
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cicc
surfactant
oil
biological
deodorizing agent
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CN120817649B (en
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章玲
汤海云
胡丽
黄镜铭
夏芳
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Shanghai Kelong Cleaning Technology Co ltd
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Shanghai Kelong Cleaning Technology Co ltd
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/343Biological treatment of water, waste water, or sewage characterised by the microorganisms used for digestion of grease, fat, oil
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10Inorganic compounds
    • C02F2101/101Sulfur compounds
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
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    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/14Additives which dissolves or releases substances when predefined environmental conditions are reached, e.g. pH or temperature
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Abstract

The invention provides a biological oil and odor removal agent for an oil removal tank and a preparation method thereof, and belongs to the technical field of oil and odor removal agents. The slow-release microbial pellet comprises the following raw materials, by weight, 50-70 parts of slow-release microbial pellets, 15-25 parts of fermentation products and 5-10 parts of compound surfactants, wherein the compound surfactants comprise a first surfactant and a second surfactant, and the mass ratio of the first surfactant to the second surfactant is 3-5:10. The biological degreasing and deodorizing agent for the oil removal tank can separate and emulsify oil stains better, reduce oil stain residues, meanwhile, lipase hydrolyzes the oil stains to generate free fatty acid, related strains act on the fatty acid to promote further oxidation reaction to generate carbon dioxide and water, and the biological degreasing and deodorizing agent also has better antibacterial effect.

Description

Biological oil and odor removal agent for oil removal tank and preparation method thereof
Technical Field
The invention relates to the technical field of oil and odor removal agents, in particular to a biological oil and odor removal agent for an oil removal tank and a preparation method thereof.
Background
The rapid development of catering industry generates a large amount of waste water containing oil and fat, the oil and fat is cooled, solidified and attached to the inner wall of a pipeline after entering the drainage pipeline, so that the pipeline is narrow and even blocked, if a large amount of oil and fat enters a water body, an oil film is formed to block oxygen exchange, so that aquatic organisms are anoxic and dead, the ecology is destroyed, and the deposited oil and fat provide propagation environment for mice, cockroaches, mosquitoes and flies, bacteria are bred, and the disease propagation risk is increased. The oil separation tank for dining and drinking is used as key equipment for kitchen wastewater treatment, and has the core advantages that grease, suspended solids and food residues are separated from wastewater by a physical separation principle, so that the risk of blockage of a sewer pipeline is effectively reduced, the load of a sewage treatment plant is reduced, and meanwhile, the damage of direct discharge of the grease to the ecology of a water body is avoided. However, there are still significant pain points for its practical use:
1. the long-term retained grease is easy to decay and ferment in a high-temperature environment, and anaerobic bacteria are bred and malodorous gases such as hydrogen sulfide are released to influence the kitchen environment and the surrounding air quality;
2. The oil separation efficiency fluctuates, namely the traditional oil separation tank has poor separation effect on tiny oil drops, and the oil-water separation efficiency is low when the flow overload or the oil emulsification is serious;
3. the cleaning and maintenance are complex, the deposited grease (usually 1-2 times per week) needs to be cleaned manually and periodically, the operation process is dirty and easy to cause secondary pollution, and the equipment with unreasonable structural design also has the problem that dead angle deposited grease is difficult to clean thoroughly.
Because of these pain points in the oil separator, a more efficient method is needed to reduce grease and environmental odors entering the drain line.
Disclosure of Invention
The invention aims to provide a biological degreasing and deodorizing agent for an oil removal tank and a preparation method thereof, which can better separate and emulsify oil stains, reduce oil stain residues, simultaneously, carry out enzymolysis on the oil stains by lipase to generate free fatty acid, enable related strains to act on the fatty acid to promote further oxidation reaction to generate carbon dioxide and water, have better antibacterial effect, and can effectively avoid inactivation of the active bacteria by embedding the active bacteria in microspheres, so that the microsphere shells are slowly broken after the active bacteria are added into water, release the active bacteria slowly, play a common role, and realize better degreasing and deodorizing, and have wide application prospects.
The technical scheme of the invention is realized as follows:
The invention provides a biological oil and odor removal agent for an oil separation tank, which comprises the following raw materials, by weight, 50-70 parts of slow-release bacteria balls, 15-25 parts of fermentation products and 5-10 parts of compound surfactants, wherein the compound surfactants comprise a first surfactant and a second surfactant, the mass ratio of the first surfactant is 3-5:10, the first surfactant is C10-16 alkyl derivative benzenesulfonic acid or C12-15 fatty alcohol polyoxyethylene ether, and the structural formula of the second surfactant is shown as formula I:
A formula I;
Wherein m=3-6.
As a further improvement of the invention, the preparation method of the slow-release bacteria ball and the fermentation product is as follows:
S1, preparing a culture medium, namely adding triolein, glycerol, peptone, yeast extract, inorganic salt, alanine, methionine and glutathione into deionized water, and sterilizing to prepare the culture medium;
S2, activating strains, namely respectively inoculating pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 into an LB culture medium, and carrying out activation culture to obtain strain seed liquid;
S3, fermenting and culturing, namely inoculating strain seed liquid into a culture medium, fermenting and culturing, filtering, washing, freeze-drying to obtain enhanced thalli;
s4, preparing slow-release bacteria balls, namely dissolving gelatin and sodium alginate in water, adding enhanced bacteria, stirring and mixing uniformly, adding an emulsifying agent, dropwise adding fish oil, emulsifying, dropwise adding a calcium chloride solution, solidifying at normal temperature, centrifuging, washing, and freeze-drying to obtain the slow-release bacteria balls.
As a further improvement of the invention, the mass ratio of the triolein, the glycerol, the peptone, the yeast extract, the inorganic salt, the alanine, the methionine and the glutathione in the step S1 is 15-20:5-10:1-2:1-3:1-2:0.5-1:0.2-0.5:0.1-0.3, the inorganic salt comprises magnesium sulfate, calcium chloride and ferric chloride, the mass ratio is 2-4:3-5:1-3, the temperature of the activation culture in the step S2 is 25-30 ℃, the time is 100-200r/min, the bacterial content of the bacterial seed liquid is 10 8-109 cfu/mL.
As a further improvement of the invention, the seed liquid of the Pseudomonas fluorescens CICC 22031, the Pseudomonas putida CICC 20576, the Bacillus subtilis CICC 10732, the Bacillus licheniformis CICC 10291, the Bacillus thuringiensis CICC 20556 and the Bacillus bailii CICC 24560 in the step S3 is respectively inoculated with 0.5-1v/v, 1-1.5v/v and 1-1.5v/v, the temperature of the fermentation culture is 25-30 ℃ and 100-200r/min, the mass ratio of the gelatin, the sodium alginate, the enhanced thalli and the emulsifying agent in the step S4 is 7-10:8-12:5-10:0.1-0.3, and the emulsifying agent is at least one of tween-20, tween-40, tween-60, tween-80 and tween-85.
As a further improvement of the present invention, the synthesis method of the second surfactant is as follows:
T1, mixing dehydroabietic acid, a catalyst and thionyl chloride, heating and reacting to prepare an intermediate 1, wherein the structure is as follows:
;
T2, mixing and reacting the intermediate 1 with 3-dimethylaminopropylamine and alkali to prepare an intermediate 2, wherein the structure is as follows:
;
T3, mixing and reacting perfluoro octanoic acid and benzoyl chloride to prepare perfluoro octanoyl chloride, wherein the structure is CF 3(CF2)6 COCl;
t4, mixing and reacting perfluoro octanoyl chloride, 3-dimethylaminopropylamine and alkali to prepare an intermediate 3, wherein the structure is as follows:
;
And T5, mixing and reacting the intermediate 2, the intermediate 3 and dibromoalkane to obtain the product.
As a further improvement of the invention, the catalyst in the step T1 is 4-dimethylaminopyridine, the mol ratio of dehydroabietic acid to thionyl chloride is 1:1.2-1.5, the addition amount of the catalyst is 15-20% of the amount of dehydroabietic acid substances, the heating reaction temperature is 70-75 ℃ and the time is 2-4h, the mol ratio of the intermediate 1 to 3-dimethylaminopropylamine to the alkali in the step T2 is 1:1-1.2:2-4, the reaction time is 1-3h, and the alkali is triethylamine, naOH or KOH.
As a further improvement of the invention, the molar ratio of the perfluoro caprylic acid to the benzoyl chloride in the step T3 is 1:1-1.2, the molar ratio of the perfluoro caprylic acid chloride to the 3-dimethylaminopropylamine and the alkali in the step T4 is 1:1-1.2:2-4, the reaction time is 1-3h, and the alkali is triethylamine, naOH or KOH.
As a further improvement of the invention, the molar ratio of the intermediate 2, the intermediate 3 and the dibromoalkane in the step T5 is 1:1-1.1:1, the reaction temperature is 75-85 ℃ and the reaction time is 44-52h, and the dibromoalkane is at least one selected from 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane and 1, 6-dibromohexane.
The invention further provides a preparation method of the biological oil and odor removal agent for the oil removal tank, which comprises the following steps:
(1) Uniformly mixing the first surfactant and the second surfactant to prepare a composite surfactant;
(2) And uniformly mixing the slow-release fungus balls, the fermentation product and the composite surfactant to prepare the biological deoiling and deodorizing agent for the oil separation tank.
The invention further protects a use method of the biological oil and odor removal agent for the oil separation tank, wherein the biological oil and odor removal agent for the oil separation tank is added with water to prepare 5-10wt% of suspension, and the suspension is dripped into the oil separation tank for oil and odor removal treatment.
The invention has the following beneficial effects:
The culture medium is added with various components including glycerol and triolein as carbon sources, and glucose-free bacteria are added to maintain growth of the bacteria, so that the 'glucose effect' is avoided to inhibit lipase synthesis, the glycerol can also be used as an osmotic regulator, and under adverse environments such as high osmotic pressure, the glycerol can help the bacteria to maintain osmotic pressure balance in cells, prevent the cells from being damaged due to excessive water loss, and further improve the stress resistance of fermentation bacteria; the composite nitrogen source (comprising peptone and yeast extract) is adopted to control the carbon-nitrogen ratio, so that metabolic flow in the enzyme production period can be promoted to be converted into lipase synthesis, meanwhile, the peptone contains rich nitrogen sources and trace elements, thereby being beneficial to the growth and propagation of thalli, improving the survival rate and stress resistance of the thalli, and the yeast extract is rich in nutrients such as protein, amino acid, vitamin, mineral and the like, and can provide comprehensive nutrition for zymophytes, promote the growth and metabolism of the thalli and strengthen the stress resistance of the thalli. According to the invention, the inorganic salt is added with Mg 2+、Ca2+ to stabilize the enzyme structure, and Fe 3+ promotes the activity of an electron transfer chain and promotes the enzyme activity. The method has the advantages that alanine and methionine are added as amino acid precursors, the ribosome synthesis efficiency is enhanced, glutathione is an important antioxidant, active oxygen free radicals in bacteria can be eliminated, harm of oxidative stress to the bacteria is reduced, stability and functions of cells are maintained, stress resistance of fermentation bacteria is improved, the tolerance of yeast to active oxygen can be improved, potassium dihydrogen phosphate can provide phosphorus elements and potassium elements for the fermentation bacteria, the phosphorus elements and potassium elements participate in metabolic processes of the bacteria, acid-base balance and osmotic pressure in the cells are regulated, and stress resistance of the bacteria is enhanced.
Biological additives provide a large number of bacterial species that break down the grease in wastewater by producing a range of metabolic enzymes. In particular, lipase can effectively catalyze triglyceride to generate glycerol and free fatty acid, and because lipase is an interface activated enzyme, the lipase can only act on an oil (fat) -water interface, and when the lipase contacts an oil-water two-phase interface, the enzyme is in an activated state.
The bacillus comprises Pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus bailii CICC 24560, wherein bacillus produces enzymes to decompose fat into glycerol and fatty acid, pseudomonas further decomposes fatty acid, oxidizes unsaturated fatty acid to decompose the fatty acid into carbon dioxide and water under the condition of sufficient oxygen supply, and if single bacillus has risks such as excessive free fatty acid, calcium content in the surrounding environment is high, fatty acid calcium is easy to form and deposit in a drainage pipeline to gradually cause accumulation, so that the synergistic effect of the bacillus and the Pseudomonas can greatly improve the grease removing capability.
The invention further increases the interface effect, adopts the biological additive and the surfactant to compound, and the function of the surfactant can disperse large oil drops into micron-sized emulsion drops, thereby increasing the contact area of lipase and accelerating enzymolysis reaction. The biological additive can eliminate the foul gas such as hydrogen sulfide generated by the oil and fat putrefaction, and reduce the generation of peculiar smell.
The invention prepares the second surfactant with extremely strong aggregation capability, good water solubility, good foamability and good calcium soap dispersibility, the preparation method is simple, the synthesis condition is mild, the yield is high, the surfactant contains a rosin structure, the surfactant has antibacterial or antibacterial effects on fungi or other moulds in saprophytes, the peculiar smell is further reduced, the environment is purified, a section of hydrophobic flexible chain is introduced on a rigid skeleton of the rosin through an amide group, the fluorocarbon chain is introduced at the other end of the rigid skeleton, the surfactant has better hydrophobic and oleophobic properties, the oleophobic properties of the surfactant are much stronger than those of the hydrocarbon chain, so that the surfactant with the fluorocarbon chain is easier to approach and interact with the greasy dirt, the greasy dirt is better dissolved and dispersed, and the oil removing effect is remarkably improved. The surfactant containing fluorocarbon chains can be deeper into the oil stain, so that the oil stain is separated from the cleaning surface and emulsified, the oil stain residue is reduced, meanwhile, the fluorocarbon surfactant can reduce the oil-water interfacial tension, so that the interaction between the oil stain and water is weakened, the oil stain is easier to remove, a molecular film with low surface energy is formed in the aqueous solution, the surface tension of the solution is reduced, the surfactant can better wet the oil-containing surface, the contact area with the oil stain is increased, and good conditions are created for the subsequent oil removal process. The first surfactant and the second surfactant have a synergistic effect. Although the surfactant has a certain antibacterial effect and possibly has a certain negative effect on the active bacteria, the active bacteria can initially exert a high-efficiency biological degreasing and deodorizing effect after being prepared into a solution because the active agent is not contacted with the surfactant in the microspheres in the storage process.
The biological degreasing and deodorizing agent for the oil removal tank can better separate and emulsify oil stains, reduce oil stain residues, simultaneously, the lipase hydrolyzes the oil stains to generate free fatty acid, related strains act on the fatty acid to promote the fatty acid to further generate oxidation reaction, the generated carbon dioxide and water also have better antibacterial effect, the active bacteria can be effectively prevented from being inactivated by embedding the microspheres, and after the active bacteria are added into the water, the microsphere shells are slowly broken to release the active bacteria slowly, so that the combined action is achieved, the oil and the smell are better removed, and the application prospect is wide.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 preparation of sustained-release pellet and fermentation product
The method comprises the following steps:
S1, preparing a culture medium, namely adding 15g of triolein, 5g of glycerol, 1g of peptone, 1g of yeast extract, 1g of inorganic salt, 0.5g of alanine, 0.2g of methionine and 0.1g of glutathione into 250mL of deionized water, and sterilizing to prepare the culture medium;
The inorganic salt comprises magnesium sulfate, calcium chloride and ferric chloride, and the mass ratio is 2:3:1;
S2, activating strains, namely inoculating pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 into an LB culture medium respectively, and carrying out activation culture for 18 hours at 25 ℃ and 100r/min to obtain strain seed liquid with the bacterial content of 10 8-109 cfu/mL;
S3, fermenting and culturing, namely inoculating Pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and Bacillus berryis CICC 24560 strain seed liquid into a culture medium, wherein the inoculum sizes are respectively 0.5v/v, 1v/v, 25 ℃,100r/min, fermenting and culturing for 36h, filtering, washing, freeze-drying to obtain enhanced thalli, standing and layering filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product;
s4, preparing slow-release bacteria balls, namely dissolving 7g of gelatin and 8g of sodium alginate in 250mL of water, adding 5g of enhanced bacteria, stirring and mixing uniformly, adding 0.1g of tween-20, dropwise adding 500mL of fish oil, emulsifying for 15min at 8000r/min, dropwise adding 10mL of 5wt% of calcium chloride solution, solidifying for 30min at normal temperature, centrifuging, washing, and freeze-drying to obtain the slow-release bacteria balls.
Preparation example 2 preparation of sustained-release pellet and fermentation product
The method comprises the following steps:
S1, preparing a culture medium, namely adding 20g of triolein, 10g of glycerol, 2g of peptone, 3g of yeast extract, 2g of inorganic salt, 1g of alanine, 0.5g of methionine and 0.3g of glutathione into 250mL of deionized water, and sterilizing to prepare the culture medium;
the inorganic salt comprises magnesium sulfate, calcium chloride and ferric chloride, and the mass ratio is 4:5:3;
S2, activating strains, namely inoculating pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 into an LB culture medium respectively, and carrying out activation culture for 30 hours at the temperature of 30 ℃ and 200r/min to obtain strain seed liquid with the bacterial content of 10 8-109 cfu/mL;
S3, fermenting and culturing, namely inoculating Pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and Bacillus berryis CICC 24560 strain seed liquid into a culture medium, wherein the inoculation amount is respectively 1v/v, 1.5v/v, 30 ℃ and 200r/min, fermenting and culturing for 48 hours, filtering, washing and freeze-drying to obtain enhanced thalli, standing and layering filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product;
S4, preparing slow-release bacteria balls, namely dissolving 10g of gelatin and 12g of sodium alginate in 250mL of water, adding 10g of enhanced bacteria, stirring and mixing uniformly, adding 0.3g of tween-40, dropwise adding 500mL of fish oil, emulsifying for 15min at 8000r/min, dropwise adding 10mL of 5wt% of calcium chloride solution, solidifying for 30min at normal temperature, centrifuging, washing, and freeze-drying to obtain the slow-release bacteria balls.
Preparation example 3 preparation of sustained-release pellet and fermentation product
The method comprises the following steps:
s1, preparing a culture medium, namely adding 17g of triolein, 7g of glycerol, 1.5g of peptone, 2g of yeast extract, 1.5g of inorganic salt, 0.7g of alanine, 0.35g of methionine and 0.2g of glutathione into 250mL of deionized water, and sterilizing to prepare the culture medium;
the inorganic salt comprises magnesium sulfate, calcium chloride and ferric chloride, and the mass ratio is 3:4:2;
S2, activating strains, namely inoculating pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 into an LB culture medium respectively, and carrying out activation culture for 22 hours at the temperature of 27 ℃ and 150r/min to obtain strain seed liquid with the bacterial content of 10 8-109 cfu/mL;
S3, fermenting and culturing, namely inoculating Pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 strain seed liquid into a culture medium, wherein the inoculum sizes are respectively 0.7v/v, 1.2v/v, 27 ℃ and 150r/min, fermenting and culturing for 42h, filtering, washing and freeze-drying to obtain enhanced thalli, standing and layering filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product;
S4, preparing slow-release bacteria balls, namely dissolving 8.5g of gelatin and 10g of sodium alginate in 250mL of water, adding 7g of enhanced bacteria, stirring and mixing uniformly, adding 0.2g of tween-85, dropwise adding 500mL of fish oil, emulsifying for 15min at 8000r/min, dropwise adding 10mL of 5wt% calcium chloride solution, solidifying for 30min at normal temperature, centrifuging, washing, and freeze-drying to obtain the slow-release bacteria balls.
Comparative preparation example 1
The difference compared to preparation example 3 is that in step S3, pseudomonas is not inoculated.
The method comprises the following steps:
S3, fermenting and culturing bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus bailii CICC 24560
Inoculating the strain seed liquid into a culture medium, wherein the inoculum size is respectively 1.4/v%, 1.4v/v%, 1.2v/v%,27 ℃ and 150r/min, fermenting and culturing for 42h, filtering, washing, freeze-drying to obtain enhanced thalli, standing and layering the filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product.
Comparative preparation example 2
The difference compared to preparation example 3 is that the Bacillus was not inoculated in step S3.
The method comprises the following steps:
S3, fermenting and culturing, namely inoculating pseudomonas fluorescens CICC 22031 and pseudomonas putida CICC 20576 strain seed solutions into a culture medium, wherein the inoculum sizes are 2.6v/v%,27 ℃ and 150r/min respectively, fermenting and culturing for 42h, filtering, washing and freeze-drying to obtain enhanced thalli, standing and layering filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product.
Comparative preparation example 3
In comparison with preparation example 3, the difference is that step S4 is not performed.
S1, preparing a culture medium, namely adding 17g of triolein, 7g of glycerol, 1.5g of peptone, 2g of yeast extract, 1.5g of inorganic salt, 0.7g of alanine, 0.35g of methionine and 0.2g of glutathione into 250mL of deionized water, and sterilizing to prepare the culture medium;
the inorganic salt comprises magnesium sulfate, calcium chloride and ferric chloride, and the mass ratio is 3:4:2;
S2, activating strains, namely inoculating pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus berryis CICC 24560 into an LB culture medium respectively, and carrying out activation culture for 22 hours at the temperature of 27 ℃ and 150r/min to obtain strain seed liquid with the bacterial content of 10 8-109 cfu/mL;
S3, fermenting and culturing, namely inoculating Pseudomonas fluorescens CICC 22031, pseudomonas putida CICC 20576, bacillus subtilis CICC 10732, bacillus licheniformis CICC 10291, bacillus thuringiensis CICC 20556 and bacillus bailii CICC 24560 strain seed liquid into a culture medium, wherein the inoculation amount is 0.7v/v, 1.2v/v, 27 ℃ and 150r/min respectively, fermenting and culturing for 42h, filtering, washing, freeze-drying to obtain enhanced thalli, standing and layering filtrate, collecting a water layer, and freeze-drying to obtain a fermentation product.
PREPARATION EXAMPLE 4 Synthesis of second surfactant
The method comprises the following steps:
T1. 0.1mol dehydroabietic acid and 0.02mol 4-dimethylaminopyridine are mixed and added into a container, thionyl chloride is added dropwise, the mixture is heated to 75 ℃, the mixture is stirred and reacted for 3 hours, after the reaction is finished, excessive thionyl chloride is removed under reduced pressure, and the intermediate 1 is obtained, wherein the calculated value of ESI-MS is C 20H28ClO(M+H)+ 319.18, the measured value is 319.2, and the yield is 89%.
Nuclear magnetic results :1H NMR(300MHz,CDCl3)δ6.8-6.95(m,3H),3.15(m,1H),2.85(t,2H),1.84-1.90(m,4H),1.75(t,1H),1.62(t,2H),1.42(m,2H),1.37(s,3H),1.23-1.25(m,9H);
The synthetic route is as follows:
T2. 0.11mol of 3-dimethylaminopropylamine and 0.3mol of triethylamine are mixed and added into a container, 100mL of a methylene chloride solution containing 0.1mol of intermediate 1 is added, stirring reaction is carried out for 2h, the reaction product is washed 3 times with weak alkaline water, methylene chloride is extracted 3 times, methylene chloride and triethylamine are removed under reduced pressure, intermediate 2 is obtained, calculated value of ESI-MS is C 25H41N2O(M+H)+ 385.31, measured value is 385.3, and yield is 80%.
Nuclear magnetic results :1H NMR(300MHz,CDCl3)δ8.0(br,1H)6.85-6.99(m,3H),3.19-3.32(m,3H),2.85(t,2H),2.25-2.37(m,8H),1.84-1.90(m,4H),1.77(t,1H),1.60-1.69(t,4H),1.44(m,2H),1.37(s,3H),1.23-1.25(m,9H);
The synthetic route is as follows:
t3, mixing 0.1mol of perfluorooctanoic acid and 0.11mol of benzoyl chloride, heating to 80 ℃, stirring and reacting for 1h, and heating and collecting a fraction at 125-135 ℃ to obtain perfluorooctanoyl chloride, wherein the melting point is 74-75 ℃, and the yield is 96%;
The synthetic route is as follows:
T4. 0.11mol of 3-dimethylaminopropylamine and 0.3mol of triethylamine are mixed and added into a container, 100mL of chloroform solution of perfluorooctanoyl chloride is added, stirring reaction is carried out for 2h, the reaction product is washed 3 times with weak alkaline water, chloroform is used for extraction 3 times, dichloromethane and triethylamine are removed under reduced pressure, intermediate 3 is prepared, ESI-MS calculated value is C 13H14F15N2O(M+H)+ 499.08, measured value is 499.1, and yield is 83%.
The nuclear magnetic resonance result: 1H NMR(300MHz,CDCl3) δ8.0 (br, 1H), 3.25 (t, 2H), 2.39 (t, 2H), 2.14 (s, 6H), 1.58 (m, 2H).
The synthetic route is as follows:
T5. 0.1mol of intermediate 2, 0.11mol of intermediate 3 and 0.1mol of 1, 4-dibromobutane are added into a container, 200mL of ethanol is added, the mixture is heated to 80 ℃, the reaction is stirred for 50h, the solvent is removed under reduced pressure, ethyl acetate/ethanol is recrystallized for 3 times, washed and dried, and the product is obtained. ESI-MS calculated C 42H62Br2F15N4O2(M+H)+ 1097.29, found 1097.3, yield 75%.
Nuclear magnetic results :1H NMR(300MHz,CDCl3)δ8.0(br,2H),6.8-6.92(m,3H),3.15-3.35(m,25H),2.95(m,2H),1.92(m,4H),1.5-1.8(m,11H),1.12-1.27(m,14H).
The synthetic route is as follows:
Example 1
The embodiment provides a preparation method of a biological oil and odor removal agent for an oil removal tank, which comprises the following steps:
(1) Uniformly mixing C10-16 alkyl-derived benzenesulfonic acid and the second surfactant prepared in preparation example 4, wherein the mass ratio of the C10-16 alkyl-derived benzenesulfonic acid to the second surfactant is 3:10, so as to prepare a composite surfactant;
(2) 50g of the slow-release bacteria ball prepared in preparation example 1, 15g of the fermentation product prepared in preparation example 1 and 5g of the compound surfactant are uniformly mixed to prepare the biological oil and odor removal agent for the oil separation tank. The biological oil removal and odor removal agent for the oil removal tank is added with a mixed solution to prepare 5wt% of suspension, wherein the formula of the mixed solution is 1 wt% of magnesium sulfate, 1 wt% of calcium chloride, 1 wt% of ferric chloride, 1 wt% of phosphate buffer, 1 wt% of magnesium sulfate, 1 wt% of calcium chloride, 1 wt% of ferric chloride and 1 wt% of phosphate buffer. Dripping the solution into grease, carrying out oil removal and odor removal treatment for 12h, dripping 100mL of suspension into each 10mL of grease, drying the residual liquid, and analyzing the decomposition state of the grease components of the product by using a Fourier transform infrared spectrometer. The c=o stretching vibration of the ester bond (RCOOR') in the intact triglyceride exhibits a strong absorption peak at 1740 cm -1, and the c=o vibration peak of the free fatty acid shifts to a low frequency shift to 1700-1720 cm -1. The product after reaction has a peak near 1711cm -1, and the peak height area corresponding to the ester bond of 1746cm -1 is reduced, which shows that partial grease is decomposed into free fatty acid, carboxylic acid (-COOH) and glycerin (-OH) generated by decomposition can form a broad peak near 3300 and cm -1, and the peak intensity of the product after reaction at 3457cm -1 is greater than the intensity of the whole grease at 3471cm -1.
Example 2
The embodiment provides a preparation method of a biological oil and odor removal agent for an oil removal tank, which comprises the following steps:
(1) Uniformly mixing C10-16 alkyl-derived benzenesulfonic acid and the second surfactant prepared in preparation example 4, wherein the mass ratio of the C10-16 alkyl-derived benzenesulfonic acid to the second surfactant is 5:10, so as to prepare a composite surfactant;
(2) 70g of the slow-release bacteria ball prepared in preparation example 2, 25g of the fermentation product prepared in preparation example 2 and 10g of the composite surfactant are uniformly mixed to prepare the biological oil and odor removal agent for the oil separation tank.
Example 3
The embodiment provides a preparation method of a biological oil and odor removal agent for an oil removal tank, which comprises the following steps:
(1) Uniformly mixing C12-15 fatty alcohol-polyoxyethylene ether and the second surfactant prepared in preparation example 4, wherein the mass ratio of the C12-15 fatty alcohol-polyoxyethylene ether to the second surfactant is 4:10, so as to prepare a composite surfactant;
(2) And uniformly mixing 60g of the slow-release bacteria ball prepared in preparation example 3, 20g of the fermentation product prepared in preparation example 3 and 7g of the composite surfactant to prepare the biological oil and odor removal agent for the oil separation tank.
Comparative example 1
The difference compared with example 3 is that both the slow-release pellet and the fermentation product were prepared in comparative preparation 1.
Comparative example 2
The difference compared with example 3 is that both the slow-release pellet and the fermentation product were prepared in comparative preparation 2.
Comparative example 3
Compared with example 3, the difference is that the fermentation products are all prepared by comparative preparation 3, and the slow-release bacteria balls are replaced by the reinforced bacteria prepared by comparative preparation 3 with equal mass.
Comparative example 4
The difference compared with example 3 is that the compound surfactant is replaced by a single C12-15 fatty alcohol-polyoxyethylene ether.
Comparative example 5
The difference compared to example 3 is that the complex surfactant is replaced by the second surfactant prepared in preparation 4 alone.
Comparative example 6
The difference compared to example 3 is that no complex surfactant is added.
Test example 2 surface tension and Critical micelle concentration determination
The compound surfactant prepared in the embodiment 1-3 of the invention is prepared into solutions with different concentrations by taking deionized water as a solvent, the surface tension of the aqueous solution is measured at room temperature by utilizing an interface parameter integrated measuring instrument, the obtained data is made into a gamma-lgC curve, the inflection point of the curve is the critical micelle concentration (cmc) of the composition, and the surface tension at the critical micelle concentration is measured. A50 mg/L solution was prepared and the oil-water interfacial tension was measured at 65℃using a rotary drop interfacial tensiometer. The results are shown in Table 1.
TABLE 1
As shown in the table above, the composite surfactant prepared in the step (1) of the embodiment 1-3 has better surface performance.
Test example 2
The oil-separation tanks prepared in examples 1 to 3 or comparative examples 1 to 3 were prepared into 5wt% suspensions by adding a mixed solution of 1 wt% magnesium sulfate+1 wt% calcium chloride+1 wt% ferric chloride+1 wt% phosphate buffer+1 wt% magnesium sulfate+1 wt% calcium chloride+1 wt% ferric chloride+1 wt% phosphate buffer. And (3) dropwise adding 100mL of suspension into the grease per 10mL of grease, and carrying out oil and odor removal treatment for 12h. The remaining material was measured and the results are shown in Table 2.
TABLE 2
From the above table, the biological degreasing and deodorizing agent for the oil removal tank prepared in the embodiments 1 to 3 can effectively degrade grease.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1.一种隔油池用生物除油除味剂,其特征在于,包括以下重量份的原料:缓释菌球50-70份、发酵产物15-25份、复合表面活性剂5-10份,所述复合表面活性剂包括第一表面活性剂和第二表面活性剂,质量比为3-5:10;所述第一表面活性剂为C10-16烷基衍生化苯磺酸或C12-15脂肪醇聚氧乙烯醚,所述第二表面活性剂的结构式如式I所示:1. A biological degreasing and deodorizing agent for a grease trap, comprising the following raw materials in parts by weight: 50-70 parts of slow-release bacterial pellets, 15-25 parts of a fermentation product, and 5-10 parts of a composite surfactant, wherein the composite surfactant comprises a first surfactant and a second surfactant in a mass ratio of 3-5:10; the first surfactant is a C10-16 alkyl-derivatized benzenesulfonic acid or a C12-15 fatty alcohol polyoxyethylene ether, and the second surfactant has the structural formula shown in Formula I: 式I;Formula I; 其中,m=3-6。Among them, m=3-6. 2.根据权利要求1所述的隔油池用生物除油除味剂,其特征在于,所述缓释菌球和发酵产物的制备方法如下:2. The biological degreasing and deodorizing agent for grease traps according to claim 1, wherein the preparation method of the slow-release bacterial pellets and fermentation products is as follows: S1. 培养基的制备:将三油酸甘油酯、甘油、蛋白胨、酵母提取物、无机盐、丙氨酸、甲硫氨酸、谷胱甘肽加入去离子水中,灭菌,制得培养基;S1. Preparation of culture medium: triolein, glycerol, peptone, yeast extract, inorganic salts, alanine, methionine, and glutathione were added to deionized water and sterilized to prepare a culture medium; S2. 菌种的活化:将荧光假单胞菌CICC 22031、恶臭假单胞菌CICC 20576、枯草芽孢杆菌CICC 10732、地衣芽孢杆菌CICC 10291、苏云金芽孢杆菌CICC 20556和贝莱斯芽孢杆菌CICC 24560分别接种于LB培养基中,活化培养,制得菌种种子液;S2. Activation of bacterial strains: Pseudomonas fluorescens CICC 22031, Pseudomonas putida CICC 20576, Bacillus subtilis CICC 10732, Bacillus licheniformis CICC 10291, Bacillus thuringiensis CICC 20556, and Bacillus velez CICC 24560 were inoculated into LB medium and activated to obtain seed solutions; S3. 发酵培养:将菌种种子液接种于培养基中,发酵培养,过滤,洗涤,冷冻干燥,获得增强菌体;滤液静置分层,收集水层,冷冻干燥,制得发酵产物;S3. Fermentation culture: The seed liquid of the bacteria was inoculated into the culture medium, fermented, filtered, washed, and freeze-dried to obtain enhanced bacteria; the filtrate was allowed to stand for stratification, the aqueous layer was collected, and freeze-dried to obtain a fermentation product; S4. 缓释菌球的制备:将明胶和海藻酸钠溶于水中,加入增强菌体,搅拌混合均匀,加入乳化剂,滴加入鱼油中,乳化,滴加氯化钙溶液,常温固化,离心,洗涤,冷冻干燥,制得缓释菌球。S4. Preparation of sustained-release bacterial pellets: Dissolve gelatin and sodium alginate in water, add enhanced bacterial cells, stir and mix thoroughly, add emulsifier, add dropwise to fish oil, emulsify, add calcium chloride solution dropwise, solidify at room temperature, centrifuge, wash, and freeze-dry to produce sustained-release bacterial pellets. 3.根据权利要求2所述的隔油池用生物除油除味剂,其特征在于,步骤S1中所述三油酸甘油酯、甘油、蛋白胨、酵母提取物、无机盐、丙氨酸、甲硫氨酸、谷胱甘肽的质量比为15-20:5-10:1-2:1-3:1-2:0.5-1:0.2-0.5:0.1-0.3,所述无机盐包括硫酸镁、氯化钙、氯化铁,质量比为2-4:3-5:1-3;步骤S2中所述活化培养的温度为25-30℃,100-200r/min,时间为18-30h,所述菌种种子液的含菌量为108-109cfu/mL。3. The biological oil and odor remover for grease traps according to claim 2, characterized in that the mass ratio of triolein, glycerol, peptone, yeast extract, inorganic salt, alanine, methionine, and glutathione in step S1 is 15-20:5-10:1-2:1-3:1-2:0.5-1:0.2-0.5:0.1-0.3, and the inorganic salt includes magnesium sulfate, calcium chloride, and ferric chloride in a mass ratio of 2-4:3-5:1-3; the activation culture in step S2 is carried out at a temperature of 25-30°C, 100-200 r/min, and for 18-30 h, and the bacterial content of the bacterial seed liquid is 108-109 cfu/mL. 4.根据权利要求2所述的隔油池用生物除油除味剂,其特征在于,步骤S3中所述荧光假单胞菌CICC 22031、恶臭假单胞菌CICC 20576、枯草芽孢杆菌CICC 10732、地衣芽孢杆菌CICC 10291、苏云金芽孢杆菌CICC 20556和贝莱斯芽孢杆菌CICC 24560菌种种子液的接种量分别为0.5-1v/v%、0.5-1v/v%、0.5-1v/v%、0.5-1v/v%、1-1.5v/v%、1-1.5v/v%,所述发酵培养的温度为25-30℃,100-200r/min,发酵培养36-48h;步骤S4中所述明胶、海藻酸钠、增强菌体、乳化剂的质量比为7-10:8-12:5-10:0.1-0.3,所述乳化剂选自吐温-20、吐温-40、吐温-60、吐温-80、吐温-85中的至少一种。4. The biological oil and odor remover for a grease trap according to claim 2, wherein the Pseudomonas fluorescens CICC 22031, Pseudomonas putida CICC 20576, Bacillus subtilis CICC 10732, Bacillus licheniformis CICC 10291, Bacillus thuringiensis CICC 20556 and Bacillus velezensis CICC The inoculation amount of the 24560 strain seed liquid is 0.5-1v/v%, 0.5-1v/v%, 0.5-1v/v%, 0.5-1v/v%, 1-1.5v/v%, and 1-1.5v/v%, respectively; the fermentation temperature is 25-30°C, 100-200r/min, and the fermentation is carried out for 36-48h; the mass ratio of gelatin, sodium alginate, enhanced bacteria, and emulsifier in step S4 is 7-10:8-12:5-10:0.1-0.3, and the emulsifier is selected from at least one of Tween-20, Tween-40, Tween-60, Tween-80, and Tween-85. 5.根据权利要求1所述的隔油池用生物除油除味剂,其特征在于,所述第二表面活性剂的合成方法如下:5. The biological deoiling and deodorizing agent for grease traps according to claim 1, wherein the synthesis method of the second surfactant is as follows: T1. 将脱氢枞酸、催化剂和氯化亚砜混合加热反应,制得中间体1,结构如下:T1. Dehydroabietic acid, a catalyst, and thionyl chloride were mixed and heated to react to obtain intermediate 1, which has the following structure: ; T2. 将中间体1和3-二甲氨基丙胺、碱混合反应,制得中间体2,结构如下:T2. Intermediate 1 is reacted with 3-dimethylaminopropylamine and a base to obtain intermediate 2, which has the following structure: ; T3. 将全氟辛酸和苯甲酰氯混合反应,制得全氟辛酰氯,结构如下:CF3(CF2)6COCl;T3. Perfluorooctanoic acid and benzoyl chloride are mixed and reacted to produce perfluorooctanoyl chloride, which has the following structure: CF 3 (CF 2 ) 6 COCl; T4. 将全氟辛酰氯和3-二甲氨基丙胺、碱混合反应,制得中间体3,结构如下:T4. Perfluorooctanoyl chloride, 3-dimethylaminopropylamine, and a base are reacted to produce intermediate 3, which has the following structure: ; T5. 将中间体2、中间体3和二溴代烷混合反应,制得产物。T5. Intermediate 2, intermediate 3 and dibromoalkane are mixed and reacted to obtain the product. 6.根据权利要求5所述的隔油池用生物除油除味剂,其特征在于,步骤T1中所述催化剂为4-二甲氨基吡啶,所述脱氢枞酸和氯化亚砜的摩尔比为1:1.2-1.5,所述催化剂的添加量为脱氢枞酸物质的量的15-20%,所述加热反应的温度为70-75℃,时间为2-4h;步骤T2中所述中间体1和3-二甲氨基丙胺、碱的摩尔比为1:1-1.2:2-4,所述反应的时间为1-3h,所述碱为三乙胺、NaOH或KOH。6. The biological deoiler and deodorizer for grease traps according to claim 5, characterized in that, in step T1, the catalyst is 4-dimethylaminopyridine, the molar ratio of dehydroabietic acid to thionyl chloride is 1:1.2-1.5, the amount of the catalyst added is 15-20% of the amount of dehydroabietic acid, the temperature of the heating reaction is 70-75°C, and the time is 2-4 hours; in step T2, the molar ratio of the intermediate 1 to 3-dimethylaminopropylamine and the base is 1:1-1.2:2-4, the reaction time is 1-3 hours, and the base is triethylamine, NaOH, or KOH. 7.根据权利要求5所述的隔油池用生物除油除味剂,其特征在于,步骤T3中所述全氟辛酸和苯甲酰氯的摩尔比为1:1-1.2;步骤T4中所述全氟辛酰氯和3-二甲氨基丙胺、碱的摩尔比为1:1-1.2:2-4,所述反应的时间为1-3h,所述碱为三乙胺、NaOH或KOH。7. The biological deoiling and deodorizing agent for a grease trap according to claim 5, characterized in that the molar ratio of perfluorooctanoic acid to benzoyl chloride in step T3 is 1:1-1.2; the molar ratio of perfluorooctanoyl chloride to 3-dimethylaminopropylamine and the base in step T4 is 1:1-1.2:2-4; the reaction time is 1-3 hours, and the base is triethylamine, NaOH, or KOH. 8.根据权利要求5所述的隔油池用生物除油除味剂,其特征在于,步骤T5中所述中间体2、中间体3和二溴代烷的摩尔比为1:1-1.1:1,所述反应的温度为75-85℃,时间为44-52h,所述二溴代烷选自1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷中的至少一种。8. The biological deoiling and deodorizing agent for grease traps according to claim 5, characterized in that the molar ratio of the intermediate 2, intermediate 3 and dibromoalkane in step T5 is 1:1-1.1:1, the reaction temperature is 75-85°C, the reaction time is 44-52 hours, and the dibromoalkane is selected from at least one of 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane and 1,6-dibromohexane. 9.一种如权利要求1-8任一项所述的隔油池用生物除油除味剂的制备方法,其特征在于,包括以下步骤:9. A method for preparing the biological deoiling and deodorizing agent for grease traps according to any one of claims 1 to 8, characterized in that it comprises the following steps: (1)将第一表面活性剂和第二表面活性剂混合均匀,制得复合表面活性剂;(1) uniformly mixing the first surfactant and the second surfactant to prepare a composite surfactant; (2)将缓释菌球、发酵产物和复合表面活性剂混合均匀,制得隔油池用生物除油除味剂。(2) The slow-release bacterial pellets, fermentation products and composite surfactants are mixed evenly to prepare a biological degreasing and deodorizing agent for grease traps. 10.一种如权利要求1-8任一项所述的隔油池用生物除油除味剂的使用方法,其特征在于,将所述隔油池用生物除油除味剂加水配制成5-10wt%的混悬液,滴加入隔油池中,进行除油除味处理。10. A method for using the biological oil removal and deodorizing agent for a grease trap according to any one of claims 1 to 8, characterized in that the biological oil removal and deodorizing agent for a grease trap is added with water to form a 5-10 wt% suspension, which is then added dropwise to the grease trap for oil removal and deodorization.
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