Resin-based NANO iron oxide reinforced microbial agent and preparation method therefor and use thereof

Abstract

A resin-based nano iron oxide reinforced microbial agent and a preparation method therefor and the use thereof. After resin-based nano iron oxide is mixed with a microbial agent and kitchen waste, the resin-based nano iron oxide at room temperature can enhance the degradation of the microbial agent to the kitchen waste by means of multiple functions of accelerating microbial proliferation, inducing high-activity expression of functional proteases, accelerating an electron transfer process, etc. The effect of the microbial agent can be fully exerted by means of alternating aerobic and anoxic environments, the biodegradability of metabolites is high, and the weight reduction rate of kitchen waste can reach 80%-99% by reacting under the room temperature condition for 3-5 hours. The energy consumption is low, secondary pollution is avoided, and the aims of reduction, recycling and harmlessness treatment of kitchen waste can be effectively achieved.

Description

Resin-based nano-iron oxide-enhanced microbial agent and its preparation method and application Technical Field

[0001] The present 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] In recent years, with the full implementation of household waste sorting, my country's food waste collection and transportation volume has surged. Food waste is high in organic matter, water, and nutrients, making it prone to spoilage and causing secondary pollution. Statistics show that in 2020, my country generated nearly 130 million tons of food waste, but only 20% of this total was processed. Strengthening the research and application of food waste treatment technologies and achieving harmless and resource-based treatment of food waste are urgent issues to be addressed in the context of waste sorting.

[0003] Currently, the main methods for treating food waste include incineration, pulverization and direct discharge, aerobic composting, and anaerobic fermentation. While incineration is simple and highly efficient, it requires pre-dehydration and the addition of auxiliary fuel, which can easily produce harmful gases such as dioxins. Pulverization and direct discharge simply turn food waste into sewage and sludge, which can easily burden sewage treatment systems. Aerobic composting offers advantages such as ease of operation and low cost, converting food waste into organic fertilizer. However, this method requires a large footprint, has a long treatment cycle, and is prone to secondary pollution such as odor and leachate. While anaerobic fermentation reduces secondary pollution and can convert food waste into biogas for energy utilization, it also presents challenges such as complex pretreatment, large land requirements, high investment costs, and a long overall process chain. Importantly, these centralized treatment models are increasingly unable to adapt to evolving circumstances. At the 2020 National People's Congress, deputies to the National People's Congress proposed promoting decentralized food waste treatment in both urban and rural areas nationwide, and formulating policies to encourage and promote the adoption of small-scale, decentralized food waste treatment methods. Biodegradation is currently a research hotspot for kitchen waste treatment. Compared with the above-mentioned 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 based on biodegradation as the core to carry out on-site, rapid and efficient treatment of food waste will become the future development direction of the food waste treatment industry.

[0005] Summary of the Invention

[0006] In response to the above technical problems, the present invention provides a resin-based nano-iron oxide-enhanced microbial agent and its preparation method and application.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] 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: mixing styrene as a monomer, divinylbenzene as a cross-linking agent, an amino acid protein functional agent, and benzoyl peroxide as an initiator, controlling the temperature at 80°C to 100°C, stirring, and performing suspension polymerization for 6h to 10h to obtain A polystyrene resin material is referred to as PS. The PS is added with chloromethyl ether and trimethylamine, and the reaction temperature is controlled at 40° C. to 65° C. for 5 h to 8 h to obtain an amino-modified polystyrene resin, referred to as PS-N. The PS-N is added with an iron salt solution, stirred and reacted at room temperature for 3 h to 5 h, filtered and placed in a sodium hydroxide solution, stirred and deposited in situ for 5 h to 8 h, and then heat-treated at 60° C. to 80° C. for 3 h to 5 h to obtain the resin-based nano-iron oxide material. The step of culturing the microbial agent includes: using Bacillus velezensis as the dominant bacterial genus and Saccharomyces cerevisiae as the dominant fungal genus to form a microbial flora, and culturing the microbial flora using a culture medium under the conditions of 10° C. to 35° C. and 150 rpm to 180 rpm, shaking overnight and collecting the microbial agent.

[0009] Furthermore, in the step of preparing the resin-based nano-iron oxide material, the specific amounts of the components used are: 15 to 20 parts by mass of styrene, 5 to 12 parts by mass of divinylbenzene, 3 to 10 parts by mass of an 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 the PS to PS-N being 20 g / L to 300 g / L; 3 to 50 parts by mass of an iron salt solution, 1 to 5 parts by mass of a sodium hydroxide solution, the solid-liquid ratio of the PS-N to the resin-based nano-iron oxide material being 50 g / L to 220 g / L; and the mass content of the nano-iron oxide in the resin-based nano-iron oxide material being 5% to 30%.

[0010] 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 one or more of FeCl3, Fe(NO3)3, and Fe2(SO4)3.

[0011] Furthermore, in the microbial agent, the relative content of Bacillus velezensis at the bacterial level is 88% to 95%, and the relative content of Saccharomyces cerevisiae at the fungal level is 93% to 97%.

[0012] The present invention also provides a resin-based nano-iron oxide-enhanced microbial agent prepared by the above-mentioned method for preparing the resin-based nano-iron oxide-enhanced microbial agent.

[0013] 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.

[0014] Furthermore, the method for degrading kitchen waste / restaurant waste includes: 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 time to be 2 to 5 minutes and then standing for 5 to 10 minutes, alternating between the two steps, and controlling the reaction temperature to be 15° C. to 30° C., and completing the degradation after 3 to 5 hours of reaction.

[0015] Furthermore, the specific addition amount is: 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.

[0016] Furthermore, the method further comprises: controlling stirring and standing alternately, with a stirring to standing ratio of 1 to 5, thereby ensuring an aerobic and anoxic environment of the reaction system.

[0017] 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 amylase activity of 1.2U / mL to 3.5U / mL, cellulase activity of 0.8U / mL to 3.0U / mL, lipase activity of 0.5U / mL to 1.9U / mL, protease activity of 6.3U / mL to 12.8U / mL, and metabolic liquid product BOD5 / COD Cr It is 0.50~0.90.

[0018] 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 existing technology:

[0019] 1. Microbial agents have strong degradation capabilities. Among them, Bacillus Velezii produces a high amount 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 capabilities provide a material basis for the efficient degradation of kitchen waste.

[0020] 2. This invention uses styrene, divinylbenzene, and amino acid protein as raw materials to prepare polystyrene resin spheres. Then, amino-modified polystyrene resin is developed in the presence of chloromethyl ether and trimethylamine. Using this polystyrene resin as a carrier and iron salt as a functional agent, an alkaline solution precipitation technique is used to produce resin-based nano-iron oxide with an iron oxide loading of 5%-30%. The reinforcing effect of resin-based nano-iron oxide is manifested in the following four aspects: 1) It provides attachment sites for microorganisms, and the resulting micro-electric field environment accelerates the proliferation rate of dominant bacterial species, ensuring the biomass of the microbial agent and avoiding the need for multiple additions of the microbial agent. 2) The amino acid structure and strong charging effect of the quaternary amino group at the interface of the nano-composite material can reconstruct the microbial ecosystem. On the one hand, it can effectively enrich Bacillus velezensis and Saccharomyces cerevisiae, and on the other hand, it can enrich phosphorus, nitrogen and organic matter in food waste, providing an interface environment for efficient degradation and rapid reproduction of microorganisms. 3) The unique micro-electric field environment of the nano-composite material can accelerate the rapid transfer of electrons between the nano-iron oxide and microorganisms, accelerating the efficient expression of functional degradation enzymes, and achieving the goal of efficient and rapid degradation of food waste. 4) The system achieves an alternating aerobic and facultative anaerobic reaction environment through intermittent stirring. Under aerobic conditions, aerobic microorganisms can decompose complex organic matter in food waste into intermediate metabolites. Under anaerobic conditions, the nano-iron oxide acts as an electron acceptor for facultative microorganisms, prompting them to further decompose the intermediate metabolites to produce a highly biodegradable slurry. 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.

[0021] 3. The kitchen waste degradation method involved in the present invention can operate 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 3 to 5 hours. 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 exhibits 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.

[0022] 4. Unlike most biological treatment methods that have temperature restrictions and requirements, the suitable temperature range for this invention is only 15°C to 30°C. Below or above this temperature range, microbial activity is significantly reduced or even eliminated. Existing technologies generally use temperatures between 40°C and 80°C, which is a significant difference. DETAILED DESCRIPTION

[0023] The inventors have found that the biodegradation method is a treatment method centered on microorganisms. Although a large number of microbial complexes for degrading kitchen waste have been reported in published patents and literature, the low treatment efficiency is still a bottleneck limiting 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 conversion process, the essence of which is the electron transfer process from organic matter to the final acceptor. 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 their own proliferation and reproduction, 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, and CN103773807A). However, this method must be carried out under strictly anaerobic conditions and often requires the use of high temperatures (50°C to 75°C) to activate the activity of the bacteria. The kitchen waste degradation cycle is only shortened from the original 25d to 30d to 15d to 20d, making 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, that can quickly degrade kitchen waste has important practical significance and demand.

[0024] 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), thereby improving the activity of the functional enzymes of the agent, and thus achieving efficient and rapid degradation of kitchen waste within 3h to 5h.

[0025] A 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. The method comprises the following steps: preparing the resin-based nano-iron oxide material and culturing the microbial agent;

[0026] The step of preparing the resin-based nano-iron oxide material comprises: mixing styrene as a monomer, divinylbenzene as a cross-linking agent, an amino acid protein functional agent, and benzoyl peroxide as an initiator, controlling the temperature at 80° C. to 100° C., stirring, and performing suspension polymerization for 6 h to 10 h to obtain a polystyrene resin material, referred to as PS;

[0027] Take the PS, add chloromethyl ether and trimethylamine, control the reaction temperature at 40°C to 65°C, and the reaction time for 5h to 8h to obtain an amino-modified polystyrene resin, which is recorded as PS-N;

[0028] Take the PS-N, add the iron salt solution, stir and react at room temperature for 3h to 5h, filter and place in sodium hydroxide solution, stir and deposit in situ for 5h to 8h, and then heat treat at 60℃ to 80℃ 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 at the resin interface can form a protein-iron complex with Fe.

[0029] The step of culturing the microbial agent includes: using Bacillus velezensis as the dominant bacterial genus and Saccharomyces cerevisiae as the dominant fungal genus to form a microbial flora, culturing the microbial flora in a culture medium at 10° C. to 35° C. and 150 rpm to 180 rpm, shaking the microbial flora overnight, and collecting the microbial flora to obtain the microbial agent. Preferably, the culture medium used can be a classic lysing broth medium.

[0030] The second aspect of the present invention also provides a resin-based nano-iron oxide-enhanced microbial agent prepared by the above-mentioned method for preparing the resin-based nano-iron oxide-enhanced microbial agent.

[0031] 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.

[0032] Specifically, the method for degrading kitchen waste / restaurant waste comprises: thoroughly mixing the resin-based nano-iron oxide-enhanced microbial agent with the kitchen waste / restaurant waste, stirring at 40-60 rpm, alternating between stirring for 2-5 minutes and then standing for 5-10 minutes, and controlling the reaction temperature to be between 15°C and 30°C. Degradation is completed after 3-5 hours of reaction. It should be noted that after the resin-based nano-iron oxide-enhanced microbial agent and the kitchen waste / restaurant waste are thoroughly mixed, no acclimation time is required and direct stirring is sufficient.

[0033] The present invention is described in detail below with reference to specific embodiments.

[0034] Example 1

[0035] 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 carry out suspension polymerization for 6h to obtain polystyrene resin material, recorded as PS 15 (15 represents 15% styrene mass fraction); weigh 20g PS 15Add 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;

[0036] Weigh 50g PS 15 -N, add 30g FeCl3 and 970g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 3h, filter and place in 500mL of 1% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 5h, and then heat treat at 60℃ for 3h to obtain resin-based nano-iron oxide material, where the loading amount of nano-iron oxide is 5%.

[0037] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus velezensis and a fungal consortium dominated by Saccharomyces cerevisiae, cultured in classic LB medium at 10°C and shaken at 150 rpm overnight. After incubation, the relative content of Bacillus velezensis at the genus level was 88%, and the relative content of Saccharomyces cerevisiae at the genus level was 93%. The microbial cells were then collected by centrifugation.

[0038] 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 acclimation time is required. Stir directly at 40r / min. Stir for 2min and then let it 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 BOD5 / COD Cr is 0.50.

[0039] Example 2

[0040] Weigh 100g of styrene monomer, 60g of divinylbenzene, 50g of lactoglobulin, mix thoroughly, add 15g of benzoyl peroxide, add 270g of 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).

[0041] According to the above method, the obtained PS 20Weigh 300g and add it into a mixed solution of chloromethyl ether and trimethylamine (350g of chloromethyl ether, 200g of trimethylamine, and 450g of water). Control the reaction temperature to 65°C and the reaction time to 8h to obtain amino-modified polystyrene resin, which is recorded as PS. 20 -N.

[0042] Weigh 220g PS 20 -N, add 500g FeCl3 and 500g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 5h, filter and place in 500mL of 5% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 8h, and then heat treat at 80℃ for 5h to obtain resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 30%.

[0043] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus Velez-Oleracea and a fungal consortium dominated by Saccharomyces cerevisiae. The culture was performed using classic LB medium. The culture conditions were 35°C and shaken at 180 rpm overnight. After incubation, the relative content of Bacillus Velez-Oleracea at the genus level was 95%, and the relative content of Saccharomyces cerevisiae at the genus level was 97%. The microbial cells were then collected by centrifugation.

[0044] 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 acclimation time is required. Stir directly at 60r / min. Stir for 5min and then let it stand for 10min, alternating to ensure the aerobic and anoxic environment of the reaction system. The reaction temperature is controlled 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 BOD5 / COD Cr is 0.90.

[0045] Example 3

[0046] 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 carry out suspension polymerization for 6h to obtain polystyrene resin material, recorded as PS 16 (16 represents 16% by mass fraction of styrene).

[0047] According to the above method, the obtained PS 16Weigh 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 at 40℃ and the reaction time for 5h to obtain amino-modified polystyrene resin, which is recorded as PS. 16 -N.

[0048] Weigh 80g PS 20 -N, add 100g FeCl3 and 900g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 3h, filter and place in 500mL of 1% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 5h, and then heat treat at 60℃ for 3h to obtain resin-based nano-iron oxide material, where the loading amount of nano-iron oxide is 8%.

[0049] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus velezensis and a fungal consortium dominated by Saccharomyces cerevisiae, cultured in classic LB medium at 10°C and shaken at 150 rpm overnight. After incubation, the relative content of Bacillus velezensis at the genus level was 88%, and the relative content of Saccharomyces cerevisiae at the genus level was 93%. The microbial cells were then collected by centrifugation.

[0050] In a 1L container, 30g of resin-based nano-iron oxide material, 8g of microbial cells and 200g of kitchen waste were added and fully mixed. No acclimation time was required. The mixture was stirred at 40r / min. The stirring was controlled to be 2min first and then allowed to stand for 5min, alternating to ensure the aerobic and anoxic environment of the reaction system. The reaction temperature was controlled at 15°C. After 3h of reaction, the weight loss rate of kitchen waste was 83%, and solid organic matter was converted into liquid organic acid metabolites. After being strengthened by the nano-iron oxide composite material, the enzyme activity 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 BOD5 / COD Cr is 0.60.

[0051] Example 4

[0052] 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℃, stir thoroughly, and carry out suspension polymerization for 7h to obtain polystyrene resin material, recorded as PS 17 (17 represents 17% by mass fraction of styrene).

[0053] According to the above method, the obtained PS 17Weigh 100g and add it into a mixed solution of chloromethyl ether and trimethylamine (including 230g chloromethyl ether, 110g trimethylamine, and 660g water). Control the reaction temperature at 45°C and the reaction time for 6h to obtain amino-modified polystyrene resin, which is recorded as PS. 17 -N.

[0054] Weigh 100g PS 20 -N, add 150g FeCl3 and 850g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 4h, filter and place in 500mL of 2% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 6h, and then heat treat at 65℃ for 4h to obtain resin-based nano-iron oxide material, where the loading amount of nano-iron oxide is 10%.

[0055] The microbial inoculant consisted of a bacterial consortium dominated by Bacillus Velez-Oleracea and a fungal consortium dominated by Saccharomyces cerevisiae, cultured in classic LB medium at 15°C and shaken at 160 rpm overnight. After incubation, the relative content of Bacillus Velez-Oleracea at the genus level was 90%, and the relative content of Saccharomyces cerevisiae at the genus level was 93%. The microbial cells were then collected by centrifugation.

[0056] 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 acclimation time is required. Stir directly at 45r / min. Stir for 3min first and then let it 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 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 BOD5 / COD Cr is 0.65.

[0057] Example 5

[0058] 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℃, stir thoroughly, and carry out suspension polymerization for 8h to obtain polystyrene resin material, recorded as PS 18 (18 represents 18% by mass fraction of styrene).

[0059] According to the above method, the obtained PS 18Weigh 150g and add it into a mixed solution of chloromethyl ether and trimethylamine (including 270g chloromethyl ether, 140g trimethylamine, and 590g water). Control the reaction temperature to 50℃ and the reaction time to 7h to obtain amino-modified polystyrene resin, which is recorded as PS. 18 -N.

[0060] Weigh 130g PS 20 -N, add 200g FeCl3 and 800g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 5h, filter and place in 500mL of 3% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 7h, and then heat treat at 70℃ for 5h to obtain resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 15%.

[0061] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus Velez-Oleracea and a fungal consortium dominated by Saccharomyces cerevisiae. The culture was performed using classic LB medium. The culture conditions were 20°C, with shaking at 170 rpm overnight. After incubation, the relative content of Bacillus Velez-Oleracea at the genus level was 92%, and the relative content of Saccharomyces cerevisiae at the genus level was 94%. The microbial cells were then collected by centrifugation.

[0062] 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 acclimation time is required. Stir directly at 50r / min. Stir for 4min and then let it stand for 7min, alternating to ensure the aerobic and anoxic environment of the reaction system. The reaction temperature is controlled at 25℃. 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 BOD5 / COD Cr is 0.80.

[0063] Example 6

[0064] 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℃, stir thoroughly, and carry out suspension polymerization for 9h to obtain polystyrene resin material, recorded as PS 19 (19 represents 19% by mass fraction of styrene).

[0065] According to the above method, the obtained PS 19Weigh 200g and add it into 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, which is recorded as PS. 19 -N.

[0066] Weigh 160g PS 20 -N, add 250g FeCl3 and 750g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 3h, filter and place in 500mL of 4% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 8h, and then heat treat at 75℃ for 5h to obtain resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 30%.

[0067] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus Velez-O'Neb. and a fungal consortium dominated by Saccharomyces cerevisiae. The culture was performed using classic LB medium. The culture conditions were 25°C, with shaking at 180 rpm overnight. After incubation, the relative content of Bacillus Velez-O'Neb. at the genus level was 94%, and the relative content of Saccharomyces cerevisiae at the genus level was 95%. The microbial cells were then collected by centrifugation.

[0068] 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 acclimation time is required. Stir directly at 55r / min. Stir for 5min and then let it 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 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 BOD5 / COD Cr is 0.90.

[0069] Example 7

[0070] 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 carry out suspension polymerization for 10h to obtain polystyrene resin material, recorded as PS 17 (17 represents 17% by mass fraction of styrene).

[0071] According to the above method, the obtained PS 17Weigh 250g and add it into a mixed solution of chloromethyl ether and trimethylamine (320g of chloromethyl ether and 50g of trimethylamine, 630g of water). Control the reaction temperature to 60℃ and the reaction time to 6h to obtain amino-modified polystyrene resin, which is recorded as PS. 17 -N.

[0072] Weigh 190g PS 17 -N, add 300g FeCl3 and 700g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 4h, filter and place in 500mL of 5% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 6h, and then heat treat at 80℃ for 4h to obtain resin-based nano-iron oxide material, in which the loading amount of nano-iron oxide is 25%.

[0073] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus Velez-Oleracea and a fungal consortium dominated by Saccharomyces cerevisiae. The culture was performed using classic LB medium. The culture conditions were 30°C and shaken at 180 rpm overnight. After incubation, the relative content of Bacillus Velez-Oleracea at the genus level was 95%, and the relative content of Saccharomyces cerevisiae at the genus level was 97%. The microbial cells were then collected by centrifugation.

[0074] 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 acclimation time is required. Stir directly at 60r / min. Stir for 4min and then let it stand for 9min, alternating to ensure the aerobic and anoxic environment of the reaction system. The reaction temperature is controlled 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 BOD5 / COD Cr is 0.70.

[0075] Example 8

[0076] Weigh 90g of styrene monomer, 55g of divinylbenzene, 45g of lactoglobulin, mix thoroughly, add 11g of benzoyl peroxide, add 299g of water and stir thoroughly, slowly heat to 100℃, stir thoroughly, and carry out suspension polymerization reaction for 8h to obtain polystyrene resin material, recorded as PS 18 (18 represents 18% by mass fraction of styrene).

[0077] According to the above method, the obtained PS 18Weigh 300g and add it into a mixed solution of chloromethyl ether and trimethylamine (350g of chloromethyl ether, 200g of trimethylamine, and 450g of water). Control the reaction temperature to 65°C and the reaction time to 8h to obtain amino-modified polystyrene resin, which is recorded as PS. 18 -N.

[0078] Weigh 220g PS 20 -N, add 400g FeCl3 and 600g water, the amino acid structure on the resin interface can form a protein iron complex with Fe, stir and react at room temperature for 5h, filter and place in 500mL of 3% sodium hydroxide solution by mass fraction, stir well and deposit in situ for 7h, and then heat treat at 70℃ for 4h to obtain resin-based nano-iron oxide material, in which the loading capacity of nano-iron oxide is 28%.

[0079] The microbial inoculum consisted of a bacterial consortium dominated by Bacillus Velez-Oleracea and a fungal consortium dominated by Saccharomyces cerevisiae. The culture was performed using classic LB medium. The culture conditions were 35°C and shaken at 180 rpm overnight. After incubation, the relative content of Bacillus Velez-Oleracea at the genus level was 95%, and the relative content of Saccharomyces cerevisiae at the genus level was 97%. The microbial cells were then collected by centrifugation.

[0080] 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 acclimation time is required. Stir directly at 50r / min. Stir for 4min and then let it stand for 10min, alternating to ensure the aerobic and anoxic environment of the reaction system. The reaction temperature is controlled at 25°C. 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 the nano-iron oxide composite material, the enzyme activity 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 BOD5 / COD Cr is 0.70.

[0081] Those skilled in the art will appreciate that the above-described embodiments are specific examples for implementing the present application, and that in actual applications, various changes in form and detail may be made thereto without departing from the spirit and scope of the present application. Any person skilled in the art may make changes and modifications without departing from the spirit and scope of the present application. Therefore, the scope of protection of the present application shall be subject to the scope defined in the claims.

Claims

1. A method for preparing a resin-based nano-iron oxide-reinforced microbial agent, 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-enhanced microbial inoculant according to claim 1, 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, 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 one or more of FeCl3, Fe(NO3)3, and Fe2(SO4)3.

4. The method for preparing the resin-based nano-iron oxide-reinforced microbial agent according to claim 1, 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, 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, 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, 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, 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 BOD5 / COD Cr It is 0.50~0.90.