Resin-based nano-iron oxide enhanced microbial inoculant and its preparation method and application

Abstract

The present invention relates to a resin-based nano-iron oxide enhanced microbial inoculant, its preparation method and application. After mixing the resin-based nano-iron oxide, the microbial inoculant and kitchen waste, at room temperature, the resin-based nano-iron oxide can enhance the degradation of kitchen waste by the microbial inoculant through multiple functions such as accelerating microbial proliferation, inducing the highly active expression of functional proteases, and accelerating the electron transfer process. The alternation of aerobic and anaerobic environments can give full play to the role of the microbial inoculant, and the metabolites have high biodegradability. After a reaction at room temperature for 3 to 5 hours, the weight loss rate of kitchen waste can reach 80% to 99%. The technology of the present invention is simple, has low energy consumption and no secondary pollution, and can effectively achieve the goals of reducing, recycling and harmless treatment of kitchen waste.

Description

Technical Field

[0001] The invention relates to the technical field of kitchen waste treatment, and in particular to a resin-based nano iron oxide reinforced microbial agent and a preparation method and application thereof. Background Art

[0002] Kitchen waste has high organic matter content, high water content, and rich nutrition, and is very easy to corrupt and cause secondary pollution. Strengthening the research and application of kitchen waste treatment technology and achieving harmless and resourceful treatment of kitchen waste is an urgent problem to be solved in the context of garbage classification.

[0003] At present, the main methods for treating kitchen waste are: incineration, crushing and direct discharge, aerobic composting, anaerobic fermentation, etc. Although incineration is simple and efficient, it requires pre-dehydration and the addition of auxiliary fuels, which is easy to produce harmful gases such as dioxins; crushing and direct discharge only produce kitchen waste sewage and sludge, which is easy to burden the sewage treatment system; aerobic composting has the advantages of easy operation and low cost, and can convert kitchen waste into organic fertilizer, but this method occupies a large area, has a long treatment cycle, and is easy to produce secondary pollution such as odor and leachate; although anaerobic fermentation has less secondary pollution and can be converted into biogas for energy utilization, it has problems such as complex pretreatment, large area, high investment cost, and long overall process chain. Importantly, these centralized treatment modes are increasingly difficult to adapt to the needs of the development of the situation. Biodegradation is currently a hot research topic in kitchen waste treatment. Compared with the above traditional methods, it has the advantages of low cost, low energy consumption, environmental friendliness, and no secondary pollution.

[0004] Therefore, the use of small and medium-sized food waste treatment equipment with biodegradation as the core to treat food waste on-site, quickly and efficiently will become the development direction of the food waste treatment industry in the future. Summary of the invention

[0005] In view of the above technical problems, the present invention provides a resin-based nano-iron oxide-reinforced microbial agent and a preparation method and application thereof.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] The present invention provides a method for preparing a resin-based nano iron oxide reinforced microbial agent, wherein the resin-based nano iron oxide reinforced microbial agent comprises a resin-based nano iron oxide material and a microbial agent, and the method comprises the following steps: preparing the resin-based nano iron oxide material and culturing the microbial agent; wherein, in the step of preparing the resin-based nano iron oxide material, the method comprises: using styrene as a monomer, divinylbenzene as a cross-linking agent, an amino acid protein functional agent, and benzoyl peroxide as an initiator, mixing, controlling the temperature to 80°C to 100°C, stirring, and suspending the polymerization reaction for 6h to 10h to obtain A polystyrene resin material is referred to as PS; the PS is added with chloromethyl ether and trimethylamine, the reaction temperature is controlled at 40°C to 65°C, and the reaction time is 5h to 8h to obtain an amino-modified polystyrene resin, referred to as PS-N; the PS-N is added with an iron salt solution, stirred for reaction at room temperature for 3h to 5h, filtered and placed in a sodium hydroxide solution, stirred for in-situ deposition for 5h to 8h, and then heat treated at 60°C to 80°C for 3h to 5h to obtain the resin-based nano iron oxide material; in the step of culturing the microbial agent, the bacteria are Bacillus velezensis as the dominant genus, and the fungi are Saccharomyces cerevisiae as the dominant genus to form a microbial flora, and cultured with a culture medium under the conditions of 10°C to 35°C and 150rpm to 180rpm, shaken overnight and collected to obtain the microbial agent.

[0008] Furthermore, in the step of preparing the resin-based nano iron oxide material, the specific amount of each component is: 15 to 20 parts by mass of styrene, 5 to 12 parts by mass of divinylbenzene, 3 to 10 parts by mass of amino acid protein functional agent, 1 to 3 parts by mass of benzoyl peroxide; 15 to 35 parts by mass of chloromethyl ether, 5 to 20 parts by mass of trimethylamine, the solid-liquid ratio of PS to PS-N is 20 g / L to 300 g / L; 3 to 50 parts by mass of iron salt solution, 1 to 5 parts by mass of sodium hydroxide solution, the solid-liquid ratio of PS-N to the resin-based nano iron oxide material is 50 g / L to 220 g / L; the mass content of nano iron oxide in the resin-based nano iron oxide material is 5% to 30%.

[0009] Furthermore, the amino acid protein functional agent is one or more of lactoglobulin, serum protein, and lysozyme protein; the iron salt in the iron salt solution is FeCl 3 、Fe(NO 3 ) 3 , Fe 2 (SO 4 ) 3 One or more of .

[0010] Furthermore, in the microbial agent, the relative content of Bacillus Velezii at the bacterial level is 88% to 95%, and the relative content of Saccharomyces cerevisiae at the fungal level is 93% to 97%.

[0011] The present invention also provides a resin-based nano-iron oxide reinforced microbial agent prepared by the above-mentioned method for preparing the resin-based nano-iron oxide reinforced microbial agent.

[0012] The present invention also provides the use of the above-mentioned resin-based nano-iron oxide-enhanced microbial agent in degrading kitchen waste / restaurant waste.

[0013] Furthermore, the method for degrading kitchen waste / restaurant waste comprises: fully mixing the resin-based nano-iron oxide-enhanced microbial agent and the kitchen waste / restaurant waste, stirring at 40 to 60 r / min, controlling the stirring to be 2 min to 5 min and then standing for 5 min to 10 min, alternating between the two, and controlling the reaction temperature to be 15° C. to 30° C., and completing the degradation after 3 h to 5 h of reaction.

[0014] Furthermore, the specific addition amounts are: kitchen waste / restaurant kitchen waste is 200g / L~500g / L, the resin-based nano-iron oxide is 30g / L~50g / L, the microbial agent is 5g / L~20g / L, and the ratio of the resin-based nano-iron oxide to the microbial agent is 2.5~6.0.

[0015] Furthermore, the method further comprises: controlling stirring and standing to be performed alternately, with the stirring and standing ratio being 1 to 5, thereby ensuring an aerobic and anoxic environment of the reaction system.

[0016] Furthermore, after the degradation is completed, the weight loss rate of kitchen waste / restaurant kitchen waste is 80%-99%, and the solid organic matter is converted into liquid organic acid metabolites. In the resin-based nano-iron oxide-enhanced microbial agent, the enzyme activity in the microbial agent after being enhanced by the resin-based nano-iron oxide can reach 1.2U / mL to 3.5U / mL for amylase, 0.8U / mL to 3.0U / mL for cellulase, 0.5U / mL to 1.9U / mL for lipase, 6.3U / mL to 12.8U / mL for protease, and the metabolic liquid product BOD 5 / COD Cr It is 0.50~0.90.

[0017] The present invention provides a microbial enhanced kitchen waste treatment method with nanocomposite resin as the core, which has the following obvious advantages over the prior art:

[0018] 1. Microbial agents have strong degradation ability. Among them, Bacillus Velezii produces high levels of amylase and lipase, which can simultaneously degrade starch, protein, fat and cellulose in kitchen waste. Saccharomyces cerevisiae can efficiently degrade cellulose. The dominant bacterial genera with high degradation ability provide a material basis for the efficient degradation of kitchen waste.

[0019] 2. The present invention uses styrene, divinylbenzene and amino acid protein as raw materials to prepare polystyrene resin spheres, and then develops amino-modified polystyrene resin under the action of chloromethyl ether and trimethylamine. The above polystyrene resin is used as a carrier and iron salt is used as a functional agent. Through alkali liquid precipitation technology, resin-based nano iron oxide with an iron oxide loading of 5%-30% is obtained. The strengthening effect of resin-based nano-iron oxide is reflected in the following four aspects: 1) It provides attachment sites for microorganisms. The micro-electric field environment formed can accelerate the proliferation rate of dominant bacteria, ensure the biomass of microbial agents, and avoid multiple additions of microbial agents; 2) The amino acid structure and strong charging effect of quaternary amino groups on the interface of nano-composite materials can reconstruct the microbial ecosystem. On the one hand, it can effectively enrich Bacillus velez, Saccharomyces cerevisiae, etc., and on the other hand, it can enrich phosphorus sources, nitrogen sources and organic matter in food waste, providing an interface environment for efficient degradation and rapid reproduction for microorganisms; 3) The unique micro-electric field environment of nano-composite materials can accelerate the rapid transfer of nano-iron oxide electrons and microorganisms, accelerate the efficient expression of degradation functional enzymes, and achieve the purpose of efficient and rapid degradation of kitchen waste; 4) The system realizes an alternating reaction environment of aerobic and facultative oxygen through intermittent stirring. Under aerobic conditions, aerobic microorganisms can decompose complex organic matter in kitchen waste into intermediate metabolites; under anaerobic conditions, nano-iron oxide can serve as an electron acceptor for facultative microorganisms, prompting facultative microorganisms to further decompose intermediate metabolites to generate a slurry with high biodegradability. The alternation of aerobic and anoxic environments in the system fully brings out the role of different microorganisms in the microbial agent and shortens the treatment cycle of kitchen waste.

[0020] 3. The kitchen waste degradation method involved in the present invention can be operated at room temperature without the need for additional heat. It can be achieved through intermittent stirring under aerobic and anaerobic conditions. The reaction cycle is only 3h to 5h. All organic kitchen waste is converted into liquid metabolites. The waste reduction rate is as high as over 99%, and the annual loss rate of nano-composite materials is less than 5%. It shows the advantages of low energy consumption, high efficiency, and no secondary pollution. It can effectively solve the problems of reduction, harmlessness, and resource utilization in the kitchen waste treatment industry.

[0021] 4. Unlike most biological treatment methods that have temperature restrictions and requirements, the suitable temperature range of the present invention is only 15℃~30℃. Below or above this temperature range, the activity of microorganisms will be significantly reduced or eliminated. The existing technology usually uses a temperature of 40℃~80℃, which is significantly different. DETAILED DESCRIPTION

[0022] The inventors found that the biodegradation method is a treatment method centered on microorganisms. Although a large number of microbial composite agents for degrading kitchen waste have been reported in published patents and literature, low treatment efficiency is still a bottleneck that limits the widespread application of this method. Generally speaking, the kitchen waste treatment cycle is more than 24 hours, so one of the core issues of the biodegradation method is how to speed up the rate of microbial degradation / conversion of kitchen waste. In the biological removal process of kitchen waste, the organic matter in kitchen waste generally needs to undergo a complex transformation process, the essence of which is the electron transfer process from organic matter to the final receptor. In this process, microorganisms decompose and metabolize the organic matter in kitchen waste, and obtain energy through the electron transfer process, complete the accumulation of substances required for life and self-proliferation, thereby achieving the purpose of reducing the amount of kitchen waste. Therefore, accelerating the electron transfer process between microorganisms is the key to improving the efficiency of this method. In the treatment of kitchen waste, anaerobic fermentation technology is the most important technical solution. Many articles or patents have reported methods of improving the performance of anaerobic fermentation processes by adding carbon-based materials or metal oxides to enhance microbial electron transfer (such as CN113388648A, CN104529116A, CN103773807A). However, this method must be carried out under strict anaerobic conditions and often requires the use of high temperatures to activate the activity of bacteria (50°C to 75°C). The degradation cycle of kitchen waste is only shortened from the original 25d to 30d to 15d to 20d, which makes it difficult to fundamentally improve the treatment efficiency of kitchen waste. Therefore, the research and development of methods that have low requirements for the natural environment, especially under aerobic or facultative aerobic conditions, and can quickly degrade kitchen waste has important practical significance and needs.

[0023] Based on this, the method provided by the present invention is based on microbial agents, with resin-based nano-iron oxide as the core and carrier. With the help of the unique charged structure of the carrier and the mediating effect of nano-iron oxide, it can significantly accelerate the microbial proliferation and electron transfer process under facultative or aerobic conditions and room temperature conditions (15°C to 30°C), and improve the activity of the functional enzymes of the agent, thereby achieving efficient and rapid degradation of kitchen waste within 3h to 5h.

[0024] The first aspect of the present invention provides a method for preparing a resin-based nano-iron oxide reinforced microbial agent, wherein the resin-based nano-iron oxide reinforced microbial agent comprises a resin-based nano-iron oxide material and a microbial agent, and the method comprises the following steps: preparing a resin-based nano-iron oxide material and culturing a microbial agent;

[0025] The step of preparing the resin-based nano iron oxide material includes: mixing styrene as a monomer, divinylbenzene as a cross-linking agent, amino acid protein functional agent, and benzoyl peroxide as an initiator, controlling the temperature to 80° C. to 100° C., stirring, and suspending the polymerization reaction for 6 h to 10 h to obtain a polystyrene resin material, which is recorded as PS;

[0026] Take the PS, add chloromethyl ether and trimethylamine, control the reaction temperature at 40°C to 65°C, and the reaction time at 5h to 8h to obtain an amino-modified polystyrene resin, which is recorded as PS-N;

[0027] Take the PS-N, add the iron salt solution, stir and react at room temperature for 3h to 5h, filter and place in a sodium hydroxide solution, stir and deposit in situ for 5h to 8h, and then heat treat at 60°C to 80°C for 3h to 5h to obtain the resin-based nano iron oxide material; it should be noted that after the iron salt solution is added to PS-N, the amino acid structure on the resin interface can form a protein iron complex with Fe.

[0028] In the step of culturing the microbial agent, the bacteria are Bacillus Velezii as the dominant genus, and the fungi are Saccharomyces cerevisiae as the dominant genus, forming a microbial flora, and culturing in a culture medium under the conditions of 10°C to 35°C and 150rpm to 180rpm, shaking overnight and collecting to obtain the microbial agent. Preferably, the culture medium used can be a classic lysing broth culture medium.

[0029] The second aspect of the present invention also provides a resin-based nano-iron oxide-reinforced microbial agent prepared by the above-mentioned method for preparing the resin-based nano-iron oxide-reinforced microbial agent.

[0030] The third aspect of the present invention also provides the use of the above-mentioned resin-based nano-iron oxide-enhanced microbial agent in the degradation of kitchen waste / restaurant waste.

[0031] Specifically, the method for degrading kitchen waste / restaurant kitchen waste comprises: after fully mixing the resin-based nano-iron oxide-enhanced microbial agent and kitchen waste / restaurant kitchen waste, stirring at 40 to 60 r / min, controlling the stirring for 2 to 5 minutes and then standing for 5 to 10 minutes, alternating, and controlling the reaction temperature to be 15° C. to 30° C., and completing the degradation after 3 to 5 hours of reaction. It should be noted that after fully mixing the resin-based nano-iron oxide-enhanced microbial agent and kitchen waste / restaurant kitchen waste, no acclimation time is required, and direct stirring is sufficient.

[0032] The present invention is described in detail below in conjunction with specific implementation modes.

[0033] Example 1

[0034] Weigh 75g of styrene monomer, 25g of divinylbenzene, 15g of lactoglobulin, mix thoroughly, add 5g of benzoyl peroxide, add 380g of water and stir thoroughly, slowly heat to 80℃, stir thoroughly, and perform suspension polymerization for 6h to obtain polystyrene resin material, recorded as PS 15(15 represents 15% styrene mass fraction); weigh 20g PS 15 Add chloromethyl ether and trimethylamine mixed solution (including 150g chloromethyl ether and 50g trimethylamine, 800g water), control the reaction temperature at 40℃, and the reaction time for 5h to obtain amino-modified polystyrene resin, recorded as PS 15 -N;

[0035] Weigh 50g PS 15 -N, add 30g FeCl 3 and 970g of water, the amino acid structure on the resin interface can form a protein-iron complex with Fe, the reaction is stirred at room temperature for 3h, filtered and placed in 500mL of 1% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 5h, and then heat treated at 60°C for 3h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 5%.

[0036] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 10°C and 150rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 88%, and the relative content of Saccharomyces cerevisiae at the genus level is 93%, and the microbial cells are collected by centrifugation.

[0037] In a 1L container, add 30g of resin-based nano-iron oxide material, 5g of microbial cells and 200g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 40r / min. Stir for 2min and then stand for 5min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 15°C. After 3h of reaction, the weight loss rate of kitchen waste is 80%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 1.2U / mL of amylase activity, 0.8U / mL of cellulase activity, 0.5U / mL of lipase activity, 6.3U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.50.

[0038] Example 2

[0039] Weigh 100g styrene monomer, 60g divinylbenzene, 50g lactoglobulin, mix thoroughly, add 15g benzoyl peroxide, add 270g water and stir thoroughly, slowly heat to 100℃, stir thoroughly, and carry out suspension polymerization reaction for 10h to obtain polystyrene resin material, recorded as PS 20 (20 represents 20% styrene mass fraction).

[0040] According to the above method, the obtained PS 20 Weigh 300g and add it to a mixed solution of chloromethyl ether and trimethylamine (350g of chloromethyl ether and 200g of trimethylamine, 450g of water), control the reaction temperature to 65°C, and the reaction time to 8h to obtain amino-modified polystyrene resin, recorded as PS 20 -N.

[0041] Weigh 220g PS 20 -N, add 500g FeCl 3 and 500g of water, the amino acid structure on the resin interface can form a protein iron complex with Fe, the reaction is stirred at room temperature for 5h, filtered and placed in 500mL of 5% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 8h, and then heat treated at 80℃ for 5h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 30%.

[0042] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 35°C and 180rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 95%, and the relative content of Saccharomyces cerevisiae at the genus level is 97%, and the microbial cells are collected by centrifugation.

[0043] In a 1L container, add 50g of resin-based nano-iron oxide material, 20g of microbial cells and 500g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 60r / min. Stir for 5min and then stand for 10min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 30℃. After 5h of reaction, the weight loss rate of kitchen waste is 99%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 3.5U / mL of amylase activity, 3.0U / mL of cellulase activity, 1.9U / mL of lipase activity, 12.8U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.90.

[0044] Example 3

[0045] Weigh 80g of styrene monomer, 30g of divinylbenzene, 20g of lactoglobulin, mix thoroughly, add 7g of benzoyl peroxide, add 363g of water and stir thoroughly, slowly heat to 85℃, stir thoroughly, and perform suspension polymerization for 6h to obtain polystyrene resin material, recorded as PS 16 (16 represents 16% mass fraction of styrene).

[0046] According to the above method, the obtained PS 16 Weigh 50g and add it into a mixed solution of chloromethyl ether and trimethylamine (including 190g chloromethyl ether and 80g trimethylamine, 730g water), control the reaction temperature to 40℃, and the reaction time to 5h to obtain amino-modified polystyrene resin, recorded as PS 16 -N.

[0047] Weigh 80g PS 16 -N, add 100g FeCl 3 and 900g of water, the amino acid structure on the resin interface can form a protein-iron complex with Fe, the reaction is stirred at room temperature for 3h, filtered and placed in 500mL of 1% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 5h, and then heat treated at 60°C for 3h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 8%.

[0048] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 10°C and 150rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 88%, and the relative content of Saccharomyces cerevisiae at the genus level is 93%, and the microbial cells are collected by centrifugation.

[0049] In a 1L container, add 30g of resin-based nano-iron oxide material, 8g of microbial cells and 200g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 40r / min. Stir for 2min and then stand for 5min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 15°C. After 3h of reaction, the weight loss rate of kitchen waste is 83%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 1.4U / mL of amylase activity, 1.0U / mL of cellulase activity, 0.7U / mL of lipase activity, 6.8U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.60.

[0050] Example 4

[0051] Weigh 85g of styrene monomer, 35g of divinylbenzene, 25g of lactoglobulin, mix thoroughly, add 9g of benzoyl peroxide, add 346g of water and stir thoroughly, slowly heat to 90°C, stir thoroughly, and perform suspension polymerization for 7h to obtain polystyrene resin material, recorded as PS 17 (17 represents 17% mass fraction of styrene).

[0052] According to the above method, the obtained PS17 Weigh 100g and add it to a mixed solution of chloromethyl ether and trimethylamine (including 230g chloromethyl ether and 110g trimethylamine, 660g water), control the reaction temperature to 45°C, and the reaction time to 6h to obtain amino-modified polystyrene resin, recorded as PS 17 -N.

[0053] Weigh 100g PS 17 -N, add 150g FeCl 3 and 850g of water, the amino acid structure on the resin interface can form a protein iron complex with Fe, the reaction is stirred at room temperature for 4h, filtered and placed in 500mL of 2% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 6h, and then heat treated at 65°C for 4h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 10%.

[0054] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 15°C and 160rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 90%, and the relative content of Saccharomyces cerevisiae at the genus level is 93%, and the microbial cells are collected by centrifugation.

[0055] In a 1L container, add 35g of resin-based nano-iron oxide material, 10g of microbial cells and 250g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 45r / min. Stir for 3min first and then stand for 6min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 20℃. After 4h of reaction, the weight loss rate of kitchen waste is 85%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 1.8U / mL of amylase activity, 1.5U / mL of cellulase activity, 0.9U / mL of lipase activity, 7.5U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.65.

[0056] Example 5

[0057] Weigh 90g of styrene monomer, 40g of divinylbenzene, 30g of lactoglobulin, mix thoroughly, add 11g of benzoyl peroxide, add 329g of water and stir thoroughly, slowly heat to 95°C, stir thoroughly, and perform suspension polymerization for 8h to obtain polystyrene resin material, recorded as PS 18 (18 represents 18% mass fraction of styrene).

[0058] According to the above method, the obtained PS18 Weigh 150g and add it to a mixed solution of chloromethyl ether and trimethylamine (including 270g chloromethyl ether and 140g trimethylamine, 590g water), control the reaction temperature to 50°C, and the reaction time to 7h to obtain amino-modified polystyrene resin, recorded as PS 18 -N.

[0059] Weigh 130g PS 18 -N, add 200g FeCl 3 and 800g of water, the amino acid structure on the resin interface can form a protein iron complex with Fe, the reaction is stirred at room temperature for 5h, filtered and placed in 500mL of 3% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 7h, and then heat treated at 70°C for 5h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 15%.

[0060] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 20°C and 170rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 92%, and the relative content of Saccharomyces cerevisiae at the genus level is 94%, and the microbial cells are collected by centrifugation.

[0061] In a 1L container, add 40g of resin-based nano-iron oxide material, 12g of microbial cells and 300g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 50r / min. Stir for 4min and then stand for 7min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 25°C. After 5h of reaction, the weight loss rate of kitchen waste is 88%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 2.5U / mL of amylase activity, 2.0U / mL of cellulase activity, 1.5U / mL of lipase activity, 10.5U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.80.

[0062] Example 6

[0063] Weigh 95g of styrene monomer, 45g of divinylbenzene, 35g of lactoglobulin, mix thoroughly, add 13g of benzoyl peroxide, add 312g of water and stir thoroughly, slowly heat to 80°C, stir thoroughly, and perform suspension polymerization for 9h to obtain polystyrene resin material, recorded as PS 19 (19 represents 19% mass fraction of styrene).

[0064] According to the above method, the obtained PS19 Weigh 200g and add it to a mixed solution of chloromethyl ether and trimethylamine (300g of chloromethyl ether and 170g of trimethylamine, 530g of water), control the reaction temperature to 55°C, and the reaction time to 8h to obtain amino-modified polystyrene resin, recorded as PS 19 -N.

[0065] Weigh 160g PS 19 -N, add 250g FeCl 3 and 750g of water, the amino acid structure on the resin interface can form a protein-iron complex with Fe, the reaction is stirred at room temperature for 3h, filtered and placed in 500mL of 4% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 8h, and then heat treated at 75°C for 5h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 30%.

[0066] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 25°C and 180rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 94%, and the relative content of Saccharomyces cerevisiae at the genus level is 95%, and the microbial cells are collected by centrifugation.

[0067] In a 1L container, add 45g of resin-based nano-iron oxide material, 14g of microbial cells and 350g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 55r / min. Stir for 5min and then stand for 8min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 30℃. After 5h of reaction, the weight loss rate of kitchen waste is 90%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 3.0U / mL of amylase activity, 3.0U / mL of cellulase activity, 1.8U / mL of lipase activity, 12.8U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.90.

[0068] Example 7

[0069] Weigh 85g of styrene monomer, 50g of divinylbenzene, 40g of lactoglobulin, mix thoroughly, add 9g of benzoyl peroxide, add 316g of water and stir thoroughly, slowly heat to 90℃, stir thoroughly, and perform suspension polymerization for 10h to obtain polystyrene resin material, recorded as PS 17 (17 represents 17% mass fraction of styrene).

[0070] According to the above method, the obtained PS17 Weigh 250g and add it to a mixed solution of chloromethyl ether and trimethylamine (320g chloromethyl ether and 50g trimethylamine, 630g water), control the reaction temperature to 60°C, and the reaction time to 6h to obtain amino-modified polystyrene resin, recorded as PS 17 -N.

[0071] Weigh 190g PS 17 -N, add 300g FeCl 3 and 700g of water, the amino acid structure on the resin interface can form a protein-iron complex with Fe, the reaction is stirred at room temperature for 4h, filtered and placed in 500mL of 5% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 6h, and then heat treated at 80℃ for 4h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 25%.

[0072] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 30°C and 180rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 95%, and the relative content of Saccharomyces cerevisiae at the genus level is 97%, and the microbial cells are collected by centrifugation.

[0073] In a 1L container, add 50g of resin-based nano-iron oxide material, 16g of microbial cells and 400g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 60r / min. Stir for 4min and then stand for 9min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 25℃. After 4h of reaction, the weight loss rate of kitchen waste is 90%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 2.3U / mL of amylase activity, 2.8U / mL of cellulase activity, 1.7U / mL of lipase activity, 10.4U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.70.

[0074] Example 8

[0075] Weigh 90g styrene monomer, 55g divinylbenzene, 45g lactoglobulin, mix thoroughly, add 11g benzoyl peroxide, add 299g water and stir thoroughly, slowly raise the temperature to 100℃, stir thoroughly, and carry out suspension polymerization reaction for 8h to obtain polystyrene resin material, recorded as PS 18 (18 represents 18% mass fraction of styrene).

[0076] According to the above method, the obtained PS18 Weigh 300g and add it to a mixed solution of chloromethyl ether and trimethylamine (350g of chloromethyl ether and 200g of trimethylamine, 450g of water), control the reaction temperature to 65°C, and the reaction time to 8h to obtain amino-modified polystyrene resin, recorded as PS 18 -N.

[0077] Weigh 220g PS 18 -N, add 400g FeCl 3 and 600g of water, the amino acid structure on the resin interface can form a protein-iron complex with Fe, the reaction is stirred at room temperature for 5h, filtered and placed in 500mL of 3% sodium hydroxide solution by mass fraction, fully stirred and deposited in situ for 7h, and then heat treated at 70℃ for 4h to obtain a resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 28%.

[0078] The microbial agent is a microbial flora with Bacillus velez as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi, and is cultured in a classic LB medium. The culture conditions are 35°C and 180rpm shaking overnight. After cultivation, the relative content of Bacillus velez at the genus level is 95%, and the relative content of Saccharomyces cerevisiae at the genus level is 97%, and the microbial cells are collected by centrifugation.

[0079] In a 1L container, add 40g of resin-based nano-iron oxide material, 18g of microbial cells and 450g of kitchen waste and mix them thoroughly. No acclimatization time is required. Stir directly at 50r / min. Stir for 4min and then stand for 10min, alternating to ensure the aerobic and anoxic environment of the reaction system. Control the reaction temperature at 25℃. After 4h of reaction, the weight loss rate of kitchen waste is 85%, and solid organic matter is converted into liquid organic acid metabolites. After being strengthened by nano-iron oxide composite materials, the enzyme activities of the microbial flora can reach 2.3U / mL of amylase activity, 2.8U / mL of cellulase activity, 1.7U / mL of lipase activity, 10.4U / mL of protease activity, and the metabolic liquid product BOD 5 / COD Cr is 0.70.

[0080] Those skilled in the art can understand that the above-mentioned embodiments are specific examples for implementing the present application, and in practical applications, various changes can be made to them in form and detail without departing from the spirit and scope of the present application. Any person skilled in the art can make their own changes and modifications without departing from the spirit and scope of the present application, so the scope of protection of the present application shall be based on the scope defined in the claims.

Claims

1. A method for preparing a resin-based nano-iron oxide-reinforced microbial agent, It is characterized in that The resin-based nano iron oxide reinforced microbial agent comprises a resin-based nano iron oxide material and a microbial agent, and the method comprises the following steps: preparing the resin-based nano iron oxide material and culturing the microbial agent; The step of preparing the resin-based nano iron oxide material includes: mixing styrene as a monomer, divinylbenzene as a cross-linking agent, amino acid protein functional agent, and benzoyl peroxide as an initiator, controlling the temperature to 80° C. to 100° C., stirring, and suspending the polymerization reaction for 6 h to 10 h to obtain a polystyrene resin material, which is recorded as PS; Take the PS, add chloromethyl ether and trimethylamine, control the reaction temperature at 40°C to 65°C, and the reaction time at 5h to 8h to obtain an amino-modified polystyrene resin, which is recorded as PS-N; Take the PS-N, add the iron salt solution, stir and react at room temperature for 3h to 5h, filter and place in a sodium hydroxide solution, stir and deposit in situ for 5h to 8h, and then heat treat at 60°C to 80°C for 3h to 5h to obtain the resin-based nano iron oxide material; The step of culturing the microbial agent includes: using Bacillus Velezii as the dominant genus of bacteria and Saccharomyces cerevisiae as the dominant genus of fungi to form a microbial flora, using a culture medium for culturing, the culture conditions are 10°C to 35°C, 150rpm to 180rpm, shaking overnight and collecting, to obtain the microbial agent.

2. The method for preparing the resin-based nano-iron oxide-reinforced microbial agent according to claim 1, It is characterized in that In the step of preparing the resin-based nano iron oxide material, the specific amount of each component is: 15 to 20 parts by mass of styrene, 5 to 12 parts by mass of divinylbenzene, 3 to 10 parts by mass of amino acid protein functional agent, and 1 to 3 parts by mass of benzoyl peroxide; 15 to 35 parts by mass of chloromethyl ether, 5 to 20 parts by mass of trimethylamine, the solid-liquid ratio of PS to PS-N being 20 g / L to 300 g / L; 3 to 50 parts by weight of iron salt solution, 1 to 5 parts by weight of sodium hydroxide solution, the solid-liquid ratio of the PS-N to the resin-based nano-iron oxide material is 50 g / L to 220 g / L; The mass content of nano iron oxide in the resin-based nano iron oxide material is 5% to 30%.

3. The method for preparing the resin-based nano-iron oxide-reinforced microbial agent according to claim 1, It is characterized in that The amino acid protein functional agent is one or more of lactoglobulin, serum protein, and lysozyme protein; The iron salt in the iron salt solution is FeCl 3 、Fe(NO 3 ) 3 , Fe 2 (SO 4 ) 3 One or more of .

4. The method for preparing the resin-based nano-iron oxide-reinforced microbial agent according to claim 1, It is characterized in that In the microbial agent, the relative content of Bacillus Velezii at the bacterial level is 88% to 95%, and the relative content of Saccharomyces cerevisiae at the fungal level is 93% to 97%.

5. The resin-based nano-iron oxide reinforced microbial agent obtained by the method for preparing the resin-based nano-iron oxide reinforced microbial agent according to any one of claims 1 to 4.

6. Use of the resin-based nano-iron oxide-enhanced microbial agent as claimed in claim 5 in degrading kitchen waste / restaurant waste.

7. The use according to claim 6, It is characterized in that The method for degrading kitchen waste / restaurant kitchen waste comprises: After the resin-based nano-iron oxide-enhanced microbial agent and kitchen waste / restaurant kitchen waste are fully mixed, they are stirred at 40-60 r / min, and the stirring is controlled to be 2-5 minutes first and then to stand for 5-10 minutes, alternating, and the reaction temperature is controlled to be 15° C.-30° C. After 3-5 hours of reaction, the degradation is completed.

8. The use according to claim 7, It is characterized in that The specific addition amounts are: kitchen waste / restaurant kitchen waste is 200g / L~500g / L, the resin-based nano-iron oxide is 30g / L~50g / L, the microbial agent is 5g / L~20g / L, and the ratio of the resin-based nano-iron oxide to the microbial agent is 2.5~6.

0.

9. The use according to claim 7, It is characterized in that Also includes: Control the stirring and standing alternately, and the stirring and standing ratio is 1 to 5.

10. The use according to claim 7, It is characterized in that After the degradation is completed, the weight loss rate of kitchen waste / restaurant kitchen waste is 80%-99%, and the solid organic matter is converted into liquid organic acid metabolites; in the resin-based nano-iron oxide-enhanced microbial agent, the enzyme activities in the microbial agent after being enhanced by the resin-based nano-iron oxide can reach 1.2U / mL to 3.5U / mL for amylase, 0.8U / mL to 3.0U / mL for cellulase, 0.5U / mL to 1.9U / mL for lipase, 6.3U / mL to 12.8U / mL for protease, and the metabolic liquid product BOD 5 / COD Cr It is 0.50~0.90.