Resin-based nano iron oxide reinforced microbial agent and preparation method therefor and use thereof
The resin-based nano-iron oxide reinforced microbial agent accelerates electron transfer and enzyme expression, enabling efficient kitchen waste degradation at room temperature, addressing inefficiencies in existing biodegradation methods by achieving rapid and complete conversion of waste into liquid metabolites.
Patent Information
- Authority / Receiving Office
- GB · GB
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-01-18
- Publication Date
- 2026-03-11
AI Technical Summary
Existing biodegradation methods for kitchen waste are inefficient, requiring long treatment periods and high temperatures, limiting their widespread application and effectiveness.
A resin-based nano-iron oxide reinforced microbial agent is prepared by mixing styrene, divinylbenzene, and an amino acid protein functional agent, followed by reaction with chloromethyl ether and trimethylamine, and then iron salt solution, to create a microbial ecosystem that accelerates electron transfer and enzyme expression, allowing for rapid degradation of kitchen waste at room temperature under aerobic and anoxic conditions.
The method achieves a 99% weight loss of kitchen waste in 3-5 hours with low energy consumption, producing liquid organic acid metabolites and enhancing enzyme activities, thus overcoming the inefficiencies of traditional biodegradation methods.
Abstract
Description
[0005] In view above technical problems, the present invention provides a resin-based nanoiron oxide reinforced microbial agent, and a preparation method therefor and use thereof.
[0006] In order to achieve the above objectives, the technical solutions adopted by the present invention are 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. The method includes the following steps: preparing the resin-based nano-iron oxide material and culturing the microbial agent, wherein the step of preparing the resin-based nano-iron oxide material includes: mixing styrene as a monomer, divinylbenzene as a cross-linking agent, an amino acid protein functional agent, and benzoyl peroxide as an initiator, controlling a temperature to be 80°C-100°C, stirring the above materials, and performing suspension polymerization for 6 h-10 h to obtain a polystyrene resin material marked as PS; taking the PS, adding chloromethyl ether and trimethylamine, and reacting the above materials at a reaction temperature of 40°C-65°C for 5 h-8 h to obtain an amino-modified polystyrene resin marked as PS-N; and taking the PS-N, adding an iron salt solution, then reacting the above materials under the stirring for 3 h-5 h at room temperature, filtering the obtained reaction product, placing the filtered product in a sodium hydroxide solution to undergo in-situ deposition for 5 h-8 h under the stirring, and then performing heat treatment at 60°C-80°C for 3 h-5 h to obtain the resin-based nano-iron oxide material; and the step of culturing the microbial agent includes: taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi to form a microbial flora, culturing the microbial flora in a culture medium at 10°C-35°C and 150 rpm-180 rpm under the shaking overnight, and collecting the product after culture to obtain the microbial agent.
[0008] Furthermore, in the step of preparing the resin-based nano-iron oxide material, the amount of each component is specifically as follows: 15-20 parts by mass of the styrene, 5-12 parts by mass of the divinylbenzene, 3-10 parts by mass of the amino acid protein functional agent, and 1-3 parts by mass of the benzoyl peroxide; 15-35 parts by mass of the chloromethyl ether and 5-20 parts by mass of the trimethylamine, wherein the solid-to-liquid ratio of the PS to the PS-N is 20 g / L-300 g / L; and 3-50 parts by mass of the iron salt solution and 1-5 parts of the sodium hydroxide solution, wherein the solid-to-liquid ratio of the PS-N to the resin-based nano-iron oxide material is 50 g / L-220 g / L; and the mass content of the nano-iron oxide in the resin-based nano-iron oxide material is 5%-30%.
[0009] Furthermore, the amino acid protein functional agent is one or more of lactoglobulin, serum protein, and lysozyme; an iron salt in the iron salt solution is one or more of FeCh, Fe(NO3)3, and Fe2(SO4)3.
[0010] Furthermore, in the microbial agent, the relative content of the Bacillus velezensis at a bacterial level is 88%-95%, and the relative content of the Saccharomyces cerevisiae at a fungal level is 93%-97%.
[0011] The present invention further provides a resin-based nano-iron oxide reinforced microbial agent prepared by the method for preparing a resin-based nano-iron oxide reinforced microbial agent.
[0012] The present invention also provides use of the resin-based nano-iron oxide reinforced microbial agent in degrading kitchen waste / kitchen garbage.
[0013] Furthermore, a method for degrading the kitchen waste / kitchen garbage includes: fully mixing the resin-based nano-iron oxide reinforced microbial agent and the kitchen waste / kitchen garbage, subsequently stirring at 40 r / min-60 r / min (stirring for 2 min-5 min and then standing for 5 min-10 min, and alternating the above operations), and reacting the above mixture at a reaction temperature of 15°C-30°C for 3 h-5 h to complete the degradation.
[0014] Furthermore, the specific addition amounts are as follows: 200 g / L-500 g / L of the kitchen waste / kitchen garbage, 30 g / L -50 g / L of the resin-based nano-iron oxide, and 5 g / L-20 g / L of the microbial agent, and the ratio of the resin-based nano-iron oxide to the microbial agent is 2.5-6.0.
[0015] Furthermore, the use includes controlling the alternation of the stirring and the standing at a ratio of 1-5 so as to ensure the aerobic and anoxic environments of the reaction system.
[0016] Furthermore, after the degradation is completed, the weight loss rate of the kitchen waste / kitchen garbage is 80%-99%, and solid organic matters are converted into a liquid organic acid metabolite. In the resin-based nano-iron oxide reinforced microbial agent, the activities of enzymes in the microbial agent reinforced by resin-based nano-iron oxide are respectively as follows: the amylase activity is 1.2 U / mL-3.5 U / mL, the cellulase activity is 0.8 U / mL-3.0 U / mL, the lipase activity is 0.5 U / mL-1.9 U / mL, the protease activity is 6.3 U / mL-12.8 U / mL, and the liquid metabolite BODs / CODcr is 0.50-0.90.
[0017] Compared with the prior art, the present invention provides a microorganism-enhanced method for treating kitchen waste by using nano-composite resin as a core, which has the following obvious advantages:
[0018] 1. The microbial agent has strong degradation capability, wherein Bacillus velezensis produces amylase and lipase at high yield, and can degrade starch, protein, fat and cellulose in kitchen waste simultaneously; and Saccharomyces cerevisiae can degrade cellulose at high efficiency, and the dominant fungi with high degradation capability provides a material basis for the high-efficiency degradation of the kitchen waste.
[0019] 2. In the present invention, styrene, divinylbenzene, and an amino acid protein functional agent are used as raw materials to prepare a polystyrene resin sphere, and then an amino modified polystyrene resin is developed under the action of chloromethyl ether and trimethylamine. Resin-based nano-iron oxide with the iron oxide loading capacity of 5%-30% is obtained by taking the polystyrene resin as a carrier and an iron salt as a functional agent through an alkali liquor deposition technology. The reinforcement effects of the resin-based nano-iron oxide are shown in the following four aspects: 1) the resin-based nano-iron oxide provides attachment sites for microorganisms, forms the micro-electric field environment to accelerate the proliferation rate of dominant strains, ensures the biomass of the microbial agent, and avoids multiple addition of the microbial agent; 2) the interface amino acid structure and quaternary amino strong charge effect of the nano composite material can reconstruct a microbial ecosystem, can effectively enrich Bacillus velezensis, Saccharomyces cerevisiae and the like, at the same time can enrich a phosphorus source, a nitrogen source and organic matters in kitchen, and provides the interface environment for efficient degradation and rapid propagation of microorganisms; 3) the specific micro-electric field environment of the nano composite material can accelerate the rapid transfer between nano-iron oxide electrons and microorganisms, accelerate the high-efficiency expression of degradation functional enzymes, and realize the purpose of high-efficiency and rapid degradation of kitchen waste; and 4) the system realizes the aerobic and facultative alternate reaction environment through intermittent stirring; and under the aerobic condition, aerobic microorganisms can decompose complex organic matters in the kitchen waste into intermediate metabolites; and under the anoxic condition, the nano-iron oxide can be used as an electron acceptor of facultative microorganisms, such that the facultative microorganisms are promoted to further decompose the intermediate metabolites to generate a liquid slurry with high biochemical properties. The alternate aerobic and anaerobic environments in the system fully exert the functions of different microorganisms in the microbial agent, and shorten the treatment period of the kitchen waste.
[0020] 3. The method for degrading kitchen waste related in the present invention can be operated at normal temperature, does not need additional heat, and can be realized by intermittent stirring under aerobic and facultative conditions. The reaction period is only 3 h-5 h, all organic kitchen waste is converted into liquid metabolic products, the waste loss rate is up to 99% or more, and the annual loss rate of the nano composite material is lower than 5%. The method has the advantages of low energy consumption, high efficiency and no secondary pollution, and can effectively solve the problems of reduction, harmlessness and recycling in the kitchen waste treatment industry.
[0021] 4. Different from the temperature limitation and requirement of most biological treatment methods, the temperature range suitable for the present invention is only 15°C-30°C, and the microbial activity is obviously reduced or lost when the temperature is below the lower limit or above the upper limit of this range. In the prior art, the temperature is usually suitable between 40°C and 80°C, and the differences are obvious. DETAILED DESCRIPTION OF EMBODIMENTS
[0022] The present inventors find that the biodegradation method is mainly based on microorganisms. Although many published patents and documents report microbial complexing agents for degrading kitchen waste, the low treatment efficiency is still a bottleneck limiting the wide application of the method. Generally, the treatment period of the kitchen waste is 24 h or more, such that one of the core problems of the biodegradation method is how to accelerate the rate of microbial degradation / conversion of the kitchen waste. In the biological removal process of the kitchen waste, organic matters in the kitchen waste generally need to undergo a complicated conversion process, which is essentially an electron transfer process of the organic matters to a final acceptor. In the process, the microorganisms decompose and metabolize the organic matters in the kitchen waste, and obtain energy by virtue of the electronic transfer process so as to complete accumulation of substances required by life and self-proliferation and multiplication, thereby reducing the kitchen waste. Therefore, accelerating the electron transfer process between the microorganisms is the key to improve the efficiency of the method. In the kitchen waste treatment, an anaerobic fermentation technology is the most main technical solution. A plurality of articles or patents report a method for improving the performance of the anaerobic fermentation process by adding carbon-based materials or metal oxides to enhance microbial electron transfer (such as CN113388648A, CN104529116A, and CN103773807A). But the method needs to be performed under a strict anaerobic condition. Besides, the strain activity is often required to be activated by high temperature (50°C-75°C). The degradation period of the kitchen waste is only shortened from original 25 d-30 d to 15 d-20 d, and the treatment efficiency of the kitchen waste is difficult to be fundamentally improved. Therefore, the research and development have low requirements on natural environment. Particularly, the method for rapidly degrading the kitchen waste has important practical significance and requirements under the aerobic or facultative conditions.
[0023] On this basis, the method provided by the present invention uses the microbial agent as a base and the resin-based nano-iron oxide as a core and a carrier. By utilizing the unique charged structure of the carrier and the mediation effect of the nano-iron oxide, microbial proliferation and electron transfer processes can be remarkably accelerated under facultative or aerobic conditions at room temperature (15°C-30°C), the activity of a functional enzyme of the microbial agent is improved, and the kitchen waste can be efficiently and quickly degraded within 3 h-5 h.
[0024] 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 includes a resin-based nano-iron oxide material and a microbial agent. The method includes the following steps: preparing the resin-based nano-iron oxide material and culturing the microbial agent,
[0025] wherein 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 a temperature to be 80°C-100°C, stirring the above materials, and performing suspension polymerization for 6 h-10 h to obtain a polystyrene resin material marked as PS;
[0026] taking the PS, adding chloromethyl ether and trimethylamine, and reacting the above materials at a reaction temperature of 40°C-65°C for 5 h-8 h to obtain an amino-modified polystyrene resin marked as PS-N; and
[0027] taking the PS-N, adding an iron salt solution, then reacting the above materials under the stirring for 3 h-5 h at room temperature, filtering the obtained reaction product, placing the filtered product in a sodium hydroxide solution to undergo in-situ deposition for 5 h-8 h under the stirring, and then performing heat treatment at 60°C-80°C for 3 h-5 h to obtain the resinbased nano-iron oxide material, wherein it should be noted that after the PS-N is added into the iron salt solution, the resin interface amino acid structure can form a protein iron complex with Fe; and
[0028] the step of culturing the microbial agent comprises: taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi to form a microbial flora, culturing the microbial flora in a culture medium at 10°C-35°C and 150 rpm-180 rpm under the shaking overnight, and collecting the product after culture to obtain the microbial agent. Preferably, the medium used may be a classical lysogeny broth (LB) medium.
[0029] A second aspect of the present invention further provides a resin-based nano-iron oxide reinforced microbial agent prepared by the method for preparing a resin-based nano-iron oxide reinforced microbial agent.
[0030] A third aspect of the present invention also provides use of the resin-based nano-iron oxide reinforced microbial agent in degrading kitchen waste / kitchen garbage.
[0031] Specifically, a method for degrading the kitchen waste / kitchen garbage includes: fully mixing the resin-based nano-iron oxide reinforced microbial agent and the kitchen waste / kitchen garbage, subsequently stirring at 40 r / min-60 r / min (stirring for 2 min-5 min and then standing for 5 min-10 min, and alternating the above operations), and reacting the above mixture at a reaction temperature of 15°C-30°C for 3 h-5 h to complete the degradation. It should be noted that after the resin-based nano-iron oxide reinforced microbial agent is fully mixed with the kitchen waste / kitchen garbage, the materials are directly stirred without any acclimation time.
[0032] The following describes the present invention in detail with reference to specific implementations.
[0033] Example 1
[0034] 75 g of a styrene monomer, 25 g of divinylbenzene, and 15 g of lactoglobulin were weighed and fully mixed, 5 g of benzoyl peroxide and 380 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 80°C, fully stirred, and subjected to suspension polymerization for 6 h to obtain a polystyrene resin material marked as PS15 (15 representing the mass fraction of the styrene, i.e., 15%); 20 g of PS15 was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (150 g of the chloromethyl ether, 50 g of the trimethylamine, and 800 g of water), and the reaction was performed at a reaction temperature of 40°C for 5 h to obtain an amino-modified polystyrene resin marked as PS15-N; and
[0035] 50 g of PS15-N was weighed, 30 g of FeCh, and 970 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 3 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 1% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 5 h, and then subjected to heat treatment for 3 h at 60°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 5%.
[0036] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 10°C and 150 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 88%, and the relative content of the Saccharomyces cerevisiae at a genus level was 93%, and the microorganisms were centrifugally collected.
[0037] 30 g of the resin-based nano-iron oxide material, 5 g of the microorganisms, and 200 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 40 r / min (the mixture was stirred for 2 min and then stood for 5 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 15°C for 3 h, wherein the weight loss rate of the kitchen waste was 80%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 1.2 U / mL, the cellulase activity was 0.8 U / mL, the lipase activity was 0.5 U / mL, the protease activity was 6.3 U / mL, and the liquid metabolite BOD5 / CODcr was 0.50.
[0038] Example 2
[0039] 100 g of a styrene monomer, 60 g of divinylbenzene, and 50 g of lactoglobulin were weighed and fully mixed, 15 g of benzoyl peroxide and 270 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 100°C, fully stirred, and subjected to suspension polymerization for 10 h to obtain a polystyrene resin material marked as PS20 (20 representing the mass fraction of the styrene, i.e., 20%).
[0040] According to the method, 300 g of PS20 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (350 g of the chloromethyl ether, 200 g of the trimethylamine, and 450 g of water), and the reaction was performed at a reaction temperature of 65°C for 8 h to obtain an amino-modified polystyrene resin marked as PS20-N.
[0041] 220 g of PS20-N was weighed, 500 g of FeCh, and 500 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 5 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 5% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 8 h, and then subjected to heat treatment for 5 h at 80°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 30%.
[0042] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 35°C and 180 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 95%, and the relative content of the Saccharomyces cerevisiae at a genus level was 97%, and the microorganisms were centrifugally collected.
[0043] 50 g of the resin-based nano-iron oxide material, 20 g of the microorganisms, and 500 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 60 r / min (the mixture was stirred for 5 min and then stood for 10 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 30°C for 5 h, wherein the weight loss rate of the kitchen waste was 99%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 3.5 U / mL, the cellulase activity was 3.0 U / mL, the lipase activity was 1.9 U / mL, the protease activity was 12.8 U / mL, and the liquid metabolite BODs / CODcr was 0.90.
[0044] Examples
[0045] 80 g of a styrene monomer, 30 g of divinylbenzene, and 20 g of lactoglobulin were weighed and fully mixed, 7 g of benzoyl peroxide and 363 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 85°C, fully stirred, and subjected to suspension polymerization for 6 h to obtain a polystyrene resin material marked as PSi6 (16 representing the mass fraction of the styrene, i.e., 16%).
[0046] According to the method, 50 g of PSi6 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (190 g of the chloromethyl ether, 80 g of the trimethylamine, and 730 g of water), and the reaction was performed at a reaction temperature of 40°C for 5 h to obtain an amino-modified polystyrene resin marked as PSie-N.
[0047] 80 g of PS16-N was weighed, 100 g of FeCh, and 900 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 3 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 1% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 5 h, and then subjected to heat treatment for 3 h at 60°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 8%.
[0048] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 10°C and 150 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 88%, and the relative content of the Saccharomyces cerevisiae at a genus level was 93%, and the microorganisms were centrifugally collected.
[0049] 30 g of the resin-based nano-iron oxide material, 8 g of the microorganisms, and 200 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 40 r / min (the mixture was stirred for 2 min and then stood for 5 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 15°C for 3 h, wherein the weight loss rate of the kitchen waste was 83%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 1.4 U / mL, the cellulase activity was 1.0 U / mL, the lipase activity was 0.7 U / mL, the protease activity was 6.8 U / mL, and the liquid metabolite BOD5 / CODCr was 0.60.
[0050] Example 4
[0051] 85 g of a styrene monomer, 35 g of divinylbenzene, and 25 g of lactoglobulin were weighed and fully mixed, 9 g of benzoyl peroxide and 346 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 90°C, fully stirred, and subjected to suspension polymerization for 7 h to obtain a polystyrene resin material marked as PS 17 (17 representing the mass fraction of the styrene, i.e., 17%).
[0052] According to the method, 100 g of PS17 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (230 g of the chloromethyl ether, 110 g of the trimethylamine, and 660 g of water), and the reaction was performed at a reaction temperature of 45°C for 6 h to obtain an amino-modified polystyrene resin marked as PS17-N.
[0053] 100 g of PS17-N was weighed, 150 g of FeCh, and 850 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 4 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 2% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 6 h, and then subjected to heat treatment for 4 h at 65°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 10%.
[0054] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 15°C and 160 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 90%, and the relative content of the Saccharomyces cerevisiae at a genus level was 93%, and the microorganisms were centrifugally collected.
[0055] 35 g of the resin-based nano-iron oxide material, 10 g of the microorganisms, and 250 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 45 r / min (the mixture was stirred for 3 min and then stood for 6 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 20°C for 4 h, wherein the weight loss rate of the kitchen waste was 85%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 1.8 U / mL, the cellulase activity was 1.5 U / mL, the lipase activity was 0.9 U / mL, the protease activity was 7.5 U / mL, and the liquid metabolite BOD5 / CODcr was 0.65.
[0056] Example 5
[0057] 90 g of a styrene monomer, 40 g of divinylbenzene, and 30 g of lactoglobulin were weighed and fully mixed, 11g of benzoyl peroxide and 329 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 95°C, fully stirred, and subjected to suspension polymerization for 8 h to obtain a polystyrene resin material marked as PSi8 (18 representing the mass fraction of the styrene, i.e., 18%).
[0058] According to the method, 150 g of PSi8 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (270 g of the chloromethyl ether, 140 g of the trimethylamine, and 590 g of water), and the reaction was performed at a reaction temperature of 50°C for 7 h to obtain an amino-modified polystyrene resin marked as PS18-N.
[0059] 130 g of PSi8-N was weighed, 200 g of FeCh, and 800 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 5 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 3% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 7 h, and then subjected to heat treatment for 5 h at 70°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 15%.
[0060] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 20°C and 170 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 92%, and the relative content of the Saccharomyces cerevisiae at a genus level was 94%, and the microorganisms were centrifugally collected.
[0061] 40 g of the resin-based nano-iron oxide material, 12 g of the microorganisms, and 300 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 50 r / min (the mixture was stirred for 4 min and then stood for 7 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 25°C for 5 h, wherein the weight loss rate of the kitchen waste was 88%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 2.5 U / mL, the cellulase activity was 2.0 U / mL, the lipase activity was 1.5 U / mL, the protease activity was 10.5 U / mL, and the liquid metabolite BOD5 / CODcr was 0.80.
[0062] Example 6
[0063] 95 g of a styrene monomer, 45 g of divinylbenzene, and 35 g of lactoglobulin were weighed and fully mixed, 13 g of benzoyl peroxide and 312 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 80°C, fully stirred, and subjected to suspension polymerization for 9 h to obtain a polystyrene resin material marked as PS 19 (19 representing the mass fraction of the styrene, i.e., 19%).
[0064] According to the method, 200 g of PS19 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (300 g of the chloromethyl ether, 170 g of the trimethylamine, and 530 g of water), and the reaction was performed at a reaction temperature of 55°C for 8 h to obtain an amino-modified polystyrene resin marked as PS19-N.
[0065] 160 g of PS19-N was weighed, 250 g of FeCh, and 750 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 3 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 4% (by mass) sodium hydroxide solution, fully stirred and subjected to in-sim deposition for 8 h, and then subjected to heat treatment for 5 h at 75°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 30%.
[0066] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 25°C and 180 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 94%, and the relative content of the Saccharomyces cerevisiae at a genus level was 95%, and the microorganisms were centrifugally collected.
[0067] 45 g of the resin-based nano-iron oxide material, 14 g of the microorganisms, and 350 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 55 r / min (the mixture was stirred for 5 min and then stood for 8 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 30°C for 5 h, wherein the weight loss rate of the kitchen waste was 90%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 3.0 U / mL, the cellulase activity was 3.0 U / mL, the lipase activity was 1.8 U / mL, the protease activity was 12.8 U / mL, and the liquid metabolite BODs / CODcr was 0.90.
[0068] Example 7
[0069] 85 g of a styrene monomer, 50 g of di vinylbenzene, and 40 g of lactoglobulin were weighed and fully mixed, 9 g of benzoyl peroxide and 316 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 90°C, fully stirred, and subjected to suspension polymerization for 10 h to obtain a polystyrene resin material marked as PSn (17 representing the mass fraction of the styrene, i .e., 17%).
[0070] According to the method, 250 g of PS17 obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (320 g of the chloromethyl ether, 50 g of the trimethylamine, and 630 g of water), and the reaction was performed at a reaction temperature of 60°C for 6 h to obtain an amino-modified polystyrene resin marked as PS17-N.
[0071] 190 g of PS17-N was weighed, 300 g of FeCh, and 700 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 4 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 5% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 6 h, and then subjected to heat treatment for 4 h at 80°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 25%.
[0072] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 30°C and 180 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 95%, and the relative content of the Saccharomyces cerevisiae at a genus level was 97%, and the microorganisms were centrifugally collected.
[0073] 50 g of the resin-based nano-iron oxide material, 16 g of the microorganisms, and 400 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 60 r / min (the mixture was stirred for 4 min and then stood for 9 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 25°C for 4 h, wherein the weight loss rate of the kitchen waste was 90%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 2.3 U / mL, the cellulase activity was 2.8 U / mL, the lipase activity was 1.7 U / mL, the protease activity was 10.4 U / mL, and the liquid metabolite BODs / CODcr was 0.70.
[0074] Example 8
[0075] 90 g of a styrene monomer, 55 g of divinylbenzene, and 45 g of lactoglobulin were weighed and fully mixed, 11 g of benzoyl peroxide and 299 g of water were added and fully stirred and mixed, and the mixture was slowly heated to 100°C, fully stirred, and subjected to suspension polymerization for 8 h to obtain a polystyrene resin material marked as PS 18 (18 representing the mass fraction of the styrene, i.e., 18%).
[0076] According to the method, 300 g of PSis obtained was weighed and added to a mixed solution of chloromethyl ether and trimethylamine (350 g of the chloromethyl ether, 200 g of the trimethylamine, and 450 g of water), and the reaction was performed at a reaction temperature of 65°C for 8 h to obtain an amino-modified polystyrene resin marked as PS18-N.
[0077] 220 g of PS18-N was weighed, 400 g of FeCh, and 600 g of water were added, the resin interface amino acid structure can form a protein iron complex with Fe, the materials were subjected reaction under stirring for 5 h at room temperature, and the reaction product was filtered, placed in 500 mL of a 3% (by mass) sodium hydroxide solution, fully stirred and subjected to in-situ deposition for 7 h, and then subjected to heat treatment for 4 h at 70°C to obtain a resin-based nano-iron oxide material, wherein the loading capacity of nano-iron oxide was 28%.
[0078] A microbial agent was a microbial flora taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi, and a classical LB medium was used for culture at 35°C and 180 rpm under shaking overnight. After being cultured, the relative content of the Bacillus velezensis at a genus level was 95%, and the relative content of the Saccharomyces cerevisiae at a genus level was 97%, and the microorganisms were centrifugally collected.
[0079] 40 g of the resin-based nano-iron oxide material, 18 g of the microorganisms, and 450 g of kitchen waste were added into a 1-L container to be fully mixed, the mixture was directly stirred at 50 r / min (the mixture was stirred for 4 min and then stood for 10 min, and the above operations were alternated) without any acclimation time so as to ensure the aerobic and anoxic environments of a reaction system, the mixture was subjected to the reaction at a reaction temperature of 25°C for 4 h, wherein the weight loss rate of the kitchen waste was 85%, and solid organic matters were converted into a liquid organic acid metabolite. The activities of enzymes in the microbial flora reinforced by the nano-iron oxide composite material were respectively as follows: the amylase activity was 2.3 U / mL, the cellulase activity was 2.8 U / mL, the lipase activity was 1.7 U / mL, the protease activity was 10.4 U / mL, and the liquid metabolite BOD5 / CODcr was 0.70.
[0080] Those of ordinary skill in the art should understand that the above embodiments are specific examples for implementing the present application. In practical applications, various changes may be made to the above embodiments in terms of form and details without departing from the spirit and scope of the present application. Any person skilled in the art may make changes and modifications to the embodiments without departing from the spirit and scope of the present application. Therefore, the protection scope of the present application should be subject to the scope defined by the claims.
Claims
1. 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 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 a temperature to be 80°C-100°C, stirring the above materials, and performing suspension polymerization for 6 h-10 h to obtain a polystyrene resin material marked as PS;taking the PS, adding chloromethyl ether and trimethylamine, and reacting the above materials at a reaction temperature of 40°C-65°C for 5 h-8 h to obtain an amino-modified polystyrene resin marked as PS-N; andtaking the PS-N, adding an iron salt solution, then reacting the above materials under the stirring for 3 h-5 h at room temperature, filtering the obtained reaction product, placing the filtered product in a sodium hydroxide solution to undergo in-situ deposition for 5 h-8 h under the stirring, and then performing heat treatment at 60°C-80°C for 3 h-5 h to obtain the resinbased nano-iron oxide material; andthe step of culturing the microbial agent comprises: taking Bacillus velezensis as dominant bacteria and Saccharomyces cerevisiae as dominant fungi to form a microbial flora, culturing the microbial flora in a culture medium at 1O°C-35°C and 150 rpm-180 rpm under the shaking overnight, and collecting the product after culture to obtain the microbial agent.
2. The method for preparing a resin-based nano-iron oxide reinforced microbial agent according to claim 1, wherein in the step of preparing the resin-based nano-iron oxide material, the amount of each component is specifically as follows: 15-20 parts by mass of the styrene, 5-12 parts by mass of the divinylbenzene, 3-10 parts by mass of the amino acid protein functional agent, and 1-3 parts by mass of the benzoyl peroxide;15-35 parts by mass of the chloromethyl ether and 5-20 parts by mass of the trimethylamine, wherein the solid-to-liquid ratio of the PS to the PS-N is 20 g / L-300 g / L; and3-50 parts by mass of the iron salt solution and 1-5 parts of the sodium hydroxide solution, wherein the solid-to-liquid ratio of the PS-N to the resin-based nano-iron oxide material is 50 g / L-220 g / L; andthe mass content of the nano-iron oxide in the resin-based nano-iron oxide material is 5%-30%.
3. The method for preparing a resin-based nano-iron oxide reinforced microbial agent according to claim 1, wherein the amino acid protein functional agent is one or more of lactoglobulin, serum protein, and lysozyme; andan iron salt in the iron salt solution is one or more of FeCh, Fe(NO3)3, and FealSCLh.
4. The method for preparing a resin-based nano-iron oxide reinforced microbial agent according to claim 1, wherein in the microbial agent, the relative content of the Bacillus velezensis at a bacterial level is 88%-95%, and the relative content of the Saccharomyces cerevisiae at a fungal level is 93%-97%.
5. A resin-based nano-iron oxide reinforced microbial agent prepared by the method for preparing a 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 reinforced microbial agent according to claim 5 in degrading kitchen waste / kitchen garbage.
7. The use according to claim 6, wherein a method for degrading the kitchen waste / kitchen garbage comprises:fully mixing the resin-based nano-iron oxide reinforced microbial agent and the kitchen waste / kitchen garbage, subsequently stirring at 40 r / min-60 r / min (stirring for 2 min-5 min and then standing for 5 min-10 min, and alternating the above operations), and reacting the above mixture at a reaction temperature of 15°C-30°C for 3 h-5 h to complete the degradation.
8. The use according to claim 7, wherein the specific addition amounts are as follows: 200 g / L-500 g / L of the kitchen waste / kitchen garbage, 30 g / L-50 g / L of the resin-based nano-iron oxide, and 5 g / L-20 g / L of the microbial agent, 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, further comprising controlling the alternation of the stirring and the standing at a ratio of 1-5.
10. The use according to claim 7, wherein after the degradation is completed, the weight loss rate of the kitchen waste / kitchen garbage is 80%-99%, and solid organic matters are converted into a liquid organic acid metabolite; and in the resin-based nano-iron oxide reinforced microbial agent, the activities of enzymes in the microbial agent reinforced by resinbased nano-iron oxide are respectively as follows: the amylase activity is 1.2 U / mL-3.5 U / mL, the cellulase activity is 0.8 U / mL-3.0 U / mL, the lipase activity is 0.5 U / mL-1.9 U / mL, the protease activity is 6.3 U / mL-12.8 U / mL, and the liquid metabolite BODs / CODcr is 0.50-0.90.
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