CN107651758B - Method for preparing organic fertilizer by using starch wastewater - Google Patents

Method for preparing organic fertilizer by using starch wastewater Download PDF

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CN107651758B
CN107651758B CN201711126145.6A CN201711126145A CN107651758B CN 107651758 B CN107651758 B CN 107651758B CN 201711126145 A CN201711126145 A CN 201711126145A CN 107651758 B CN107651758 B CN 107651758B
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CN107651758A (en
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覃央央
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YINGCHENG SHINDOO CHEMICAL Co.,Ltd.
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C—CHEMISTRY; METALLURGY
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    • C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C05F17/50—Treatments combining two or more different biological or biochemical treatments, e.g. anaerobic and aerobic treatment or vermicomposting and aerobic treatment
    • C—CHEMISTRY; METALLURGY
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    • C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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    • C—CHEMISTRY; METALLURGY
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    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/004—Liquid waste from mechanical processing of material, e.g. wash-water, milling fluid, filtrate
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
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    • C02F2101/30—Organic compounds
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    • C02F2301/046—Recirculation with an external loop
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    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract

The invention provides a method for preparing an organic fertilizer by using starch wastewater. The starch wastewater is treated by using the honeycomb reaction chamber, and the special upper and lower flat plates of the honeycomb reaction chamber can effectively adsorb heavy metal ions in the starch wastewater; the honeycomb chamber structure is vertically clamped on the upper flat plate and the lower flat plate, the mesoporous silicon material is imprinted by the honeycomb chamber wall by utilizing protein imprinting to prepare a high-performance film, so that the mesoporous material can specifically adsorb protein, the specific pores of the mesoporous material can improve the protein adsorption capacity, and a certain adsorption effect on heavy metal ions is realized; the composite strain decomposes protein in the honeycomb chamber by using micro-aerobic aeration, so that protein macromolecules are converted into micromolecules, organic matters are converted into humic acid, the treated wastewater is used for preparing organic fertilizer, the content of bioactive substances is high, and meanwhile, the starch wastewater is effectively purified, so that the resource recycling is realized, and the method has a good development prospect.

Description

Method for preparing organic fertilizer by using starch wastewater
Technical Field
The invention belongs to the technical field of sewage treatment and organic fertilizer preparation, and particularly relates to a method for preparing an organic fertilizer by using starch wastewater.
Background
The starch wastewater is produced by producing starch or starch deep-processing products (starch sugar, glucose, starch derivatives and the like) by using agricultural products such as corn, potato, wheat, rice and the like as raw materials, generally belongs to high-concentration organic wastewater, and is one of main pollution sources causing environmental pollution. The main pollutants of the starch wastewater comprise suspended matters (SS), Chemical Oxygen Demand (COD), ammonia nitrogen (NH 3-N), Total Nitrogen (TN) and Total Phosphorus (TP). Meanwhile, starch wastewater contains a lot of protein, but the separation of the starch wastewater has a lot of difficulties. The prior starch wastewater treatment technology has the defects of incomplete treatment, high energy consumption, high investment, high operating cost and the like, and the two problems of environmental pollution and serious waste of organic matters are difficult to effectively solve.
The mesoporous silicon material has the characteristics of structure variability, accurate controllability of hydrolytic polycondensation reaction, surface modifiability and the like, and for the preparation of the adsorbent, the characteristics of the silicon-based mesoporous material are beneficial to preparing different types of adsorbents so as to adapt to different environmental requirements.
The molecular imprinting technology is widely applied to the fields of chromatographic separation, solid phase extraction, drug analysis, biosensor technology, catalytic synthesis and the like, and therefore, the molecular imprinting technology becomes one of the novel fields of chemistry and biology, and shows good application prospects. The molecular imprinting is to polymerize template molecules and a cross-linking agent in a polymer monomer solution to obtain a solid medium, and then elute and remove the template molecules in the medium by a physical or chemical method to obtain covalent Molecularly Imprinted Polymers (MIPs) which are imprinted with a target molecular spatial structure and binding sites and have higher selectivity. It is possible to envisage: a series of functional monomers meet template molecules in solution, and the functional monomers and the template molecules can be arranged in an ordered state complementary to the structure of the template molecules through hydrogen bonds, electrostatic interaction, hydrophobic interaction and other non-covalent interactions, so that covalent complexes are prepared or non-covalent addition products are formed between the functional monomers and the template molecules; the template molecule is removed from the polymer, and the space formerly occupied by the template molecule forms a remaining cavity within the polymer, which cavity desirably "remembers" the structure, size, and other physicochemical properties of the template under appropriate conditions, and effectively and selectively debonds template (or like) molecules.
Patent application No. CN200910236321.0, utilize sweet potato starch waste water production trichoderma microbial manure, the waste water that produces in the process of using sweet potato starch as main nutrient raw materials, adopt liquid and solid-state joint fermentation's method production trichoderma microbial manure has low in production cost, the characteristics of environment-friendly, the product can obviously improve soil environmental quality, improve crop output, and can prevent and treat multiple plant diseases, find effectual processing method for the large amount of high concentration waste water that produces in the high-efficient processing sweet potato starch production process simultaneously, reduce environmental pollution. Patent application No. CN201310468266.4, a method for producing liquid organic fertilizer by using starch wastewater, the wastewater discharged by producing corn starch or wheat starch is added into a closed container after removing impurities, lactobacillus acidophilus and saccharomyces cerevisiae are inoculated for fermentation, by the invention, the pollution of the wastewater to the environment can be effectively reduced, the waste utilization can be realized, the investment is small, the process is simple, the fertilizer efficiency is obvious, the production cost is low, the competitive advantage is strong, and the trial production potential is large. Patent application No. CN201610710440.5, utilize starch waste water production to be used for improving the method of liquid organic fertilizer in saline and alkaline land, through a series of advanced treatment such as filter screen filtration, anaerobism filtering pond fermentation, solar energy aeration biological filter fermentation, starch phosphate and the hydrolysis of polyphosphate ferric chloride, microbial fermentation agent fermentation, make starch waste water become the liquid microbial manure that is rich in beneficial microbial community and multiple secondary metabolite, improve the problem that secondary saline and alkaline land soil microbial community reduces after the use, can make secondary saline and alkaline land increase production 20% -30%, both saved the cost, also alleviated soil infertily, harden, salinization, compound energy-conservation, environmental protection, sustainable development's trend. Patent application No. CN201410015439.1, a method for preparing potato extract powder by using potato starch wastewater, which comprises the steps of firstly removing impurities from the potato starch wastewater and concentrating; then pumping the concentrated solution into an enzymolysis tank, respectively carrying out enzymolysis for three times by medium-temperature amylase, saccharifying enzyme and neutral protease (or compound protease), and then inactivating the enzyme; concentrating and spray drying the hydrolysate again to obtain the potato extract powder. The method prepares the potato extract powder containing a large amount of amino acids and peptide substances by utilizing the potato starch wastewater through a bioengineering method, changes waste into valuable, has low cost and high added value of products, has great competitive advantages, and solves the problems of starch wastewater treatment and discharge.
In the prior art, a lot of researches are carried out on the technology for producing available materials by utilizing starch wastewater treated by biological fermentation, but the pretreatment technology in most technologies is complex, substances such as heavy metals in the wastewater cannot be effectively removed, and meanwhile, the starch wastewater needs to be added for many times during biological fermentation, so that the labor is high, and the energy consumption is high. The mesoporous material and the molecular imprinting technology are combined to effectively purify the starch wastewater, and the technology for preparing the organic fertilizer is not reported.
Disclosure of Invention
Aiming at the problems of complex technology, low effect and the like of the starch wastewater treatment method in the prior art, the invention provides a method for preparing an organic fertilizer by treating starch wastewater in a honeycomb-like reaction chamber prepared by using a molecular imprinting mesoporous material, which is realized by the following steps:
a method for preparing organic fertilizer by using starch wastewater comprises the following steps:
(1) preparing a reaction chamber with a simulated honeycomb structure;
(2) installing a micro-aerobic aeration pipeline at the bottom of the wastewater reaction tank, and flatly paving the reaction chamber with the honeycomb-like structure on the aeration pipeline;
(3) inoculating fermentation strains in a bee room of a honeycomb reaction chamber, adding starch wastewater into a reaction tank I to enable the wastewater to be completely immersed in the honeycomb-like reaction chamber, continuously discharging the wastewater in the reaction tank I into a reaction tank II for biological reaction after the biological reaction lasts for 1-2 d, discharging the wastewater into the reaction tank I after the hydraulic retention time of the wastewater in the reaction tank II is 8-10 h, stopping the circulation and addition of the wastewater in the reaction tank I and the reaction tank II after the circulation reaction lasts for 6-8 d, uncovering an upper flat plate of the honeycomb-like reaction chamber, discharging the starch wastewater after fermentation, adding nitrogen and phosphorus auxiliary materials for blending, and obtaining the organic fertilizer.
The preparation method of the pseudo-honeycomb structure reaction chamber comprises the following steps:
preparing a honeycomb chamber by using a imprinted mesoporous material, preparing a honeycomb flat plate by using the mesoporous material, clamping the honeycomb chamber between the honeycomb flat plates, and assembling the honeycomb chamber vertical to the two flat plates to form a honeycomb-like structure reaction chamber, wherein the concrete preparation steps of each structure are as follows:
A. preparation of imprinted mesoporous material
(1) Weighing 2-3 parts of 3-aminopropyl-triethoxysilane and 2-4 parts of template protein solution at room temperature, dissolving in absolute ethanol, and dropwise adding 2-4 parts of 25% tetramethyl ammonium hydroxide aqueous solution by mass fraction to obtain solution A; meanwhile, 8-15 parts of polyethylene glycol 2000 and 400-750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; transferring the mixture into a watch glass, and standing at room temperature until the solvent is completely volatilized to obtain a product C;
(3) performing hydrothermal crystallization on the product C at the temperature of 60-80 ℃ for 10-20 hours, then placing the product C in a vacuum drying oven at the temperature of 35-40 ℃ for drying for 2-3 hours, taking out the product C, eluting the product C with 0.1-0.3 mol/L sodium chloride solution, and then refluxing the product C in an ethanol hydrochloric acid extract at the temperature of 60-70 ℃ for 1d to remove the template agent to obtain the imprinted mesoporous material;
B. preparation of Honeycomb Chambers
Taking 8-12 parts of imprinted mesoporous material, adding 20-24 parts of nylon 66 to prepare a structural material sheet, and winding the structural material sheet on a roller coated with polytetrafluoroethylene to prepare a honeycomb chamber;
the viscosity of the nylon 66 is 180-220 g/ml;
the viscosity of the nylon 66 influences the strength and resilience of the honeycomb chamber, so that the prepared honeycomb chamber has good pressure resistance and heat resistance, and the harmful effect of heat generated in the microbial fermentation process on the honeycomb reaction chamber under the long-term action is reduced.
C. Preparation of Honeycomb plates
(1) Weighing 2-3 parts of 3-aminopropyl tri-ethoxy silane and 2-4 parts of modified chitosan at room temperature, dissolving in absolute ethyl alcohol, and dropwise adding 2-4 parts of 25% by mass of tetramethyl ammonium hydroxide aqueous solution to obtain solution A; meanwhile, 8-15 parts of polyethylene glycol 2000 and 400-750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; pouring the mixture onto a glass plate to form a film, performing hydrothermal crystallization at 90-100 ℃ for 36-48 h, then placing the product in a vacuum drying oven at 35-40 ℃ to dry for 2-3 h, taking out, eluting with 0.1-0.3 mol/L sodium chloride solution, and then refluxing in 60-70 ℃ ethanol hydrochloric acid extract for 1d to remove the template agent to obtain a honeycomb flat plate;
(3) the honeycomb chamber is clamped between the honeycomb flat plates and is vertical to the two flat plates to assemble the reaction chamber with the pseudo-honeycomb structure.
The honeycomb flat plate prepared from the aminated mesoporous silicon material has good heavy metal ion adsorption performance and a function of killing pathogenic bacteria, wastewater firstly permeates into a bee room through the flat plate to carry out microbial fermentation reaction, and the effects of primarily removing the heavy metal ions and killing the pathogenic bacteria are firstly achieved, so that a good reaction environment is improved for microbial fermentation in the bee room.
As a further improvement of the invention, the wall thickness of the bee room is 0.5-1.5 mm, the inner diameter of the bee room pipe is 40-100 mm, the length of the bee room pipe is 120-400 mm, and the ratio of the length to the inner diameter of the bee room pipe is 3-4;
the honeycomb structure has good compression resistance and light weight, the honeycomb chamber has a large-area reaction space, the wall thickness and the diameter of the honeycomb chamber and the orientation of the wall of the honeycomb chamber determine the stability of the material, the wall thickness and the diameter of the honeycomb chamber determine the compression resistance and the hydraulic retention time of the whole reaction chamber, and when the ratio of the length of the tube to the inner diameter of the tube is 3-4, the hydraulic retention time can be kept for 1-2 days; the honeycomb-like structure reaction chamber prepared by combining the mesoporous material and the molecular imprinting technology has a special structure with good pressure resistance, can reduce the influence of turbulence generated by the flow of wastewater on microbial fermentation, and reduces the damage of water pressure on the reaction chamber; on the other hand, the honeycomb structure can provide a larger reaction space for microorganisms, the mesoporous material can be used for imprinting the material and can specifically identify and adsorb protein, and the mesoporous material has a large specific surface area, so that more and more effective enrichment of protein in wastewater is realized.
As a further improvement of the invention, the micro-aerobic aeration pipeline is a snakelike pipeline, the oxygen hole faces downwards, and the vertical distance between the pipeline and the pool bottom is 5-8 cm during installation; the concentration of dissolved oxygen in the reaction tank is 0.3-0.8 mg/L.
In the micro-aerobic aeration system, the good itch bacteria, the facultative bacteria and the anaerobic bacteria appear simultaneously, compared with the simple good itch or the anaerobic bacteria, the microorganism species in the micro-nutrient system are more comprehensive, and various microorganisms cooperate with one another to jointly complete the degradation function.
As a further improvement of the invention, the fermentation strain is bacillus megateriumBacillus megateriumAzotobacter fuscusAzotobacter chroococcumAspergillus versicolor, Aspergillus versicolorAspergillus versicolorBacillus licheniformisBacillus licheniformisOne or more of the above combinations; the inoculation amount of the bacillus megaterium is 5-8%, and the age of the bacillus megaterium is 12-18 h; the inoculation amount of azotobacter chroococcum is 2% -4%, and the seed age is 14-16 h; the inoculation amount of the aspergillus versicolor is 4-6%, and the seed age is 12-16 h; the inoculation amount of the bacillus licheniformis is 3% -5%, and the seed age is 13-16 h.
Bacillus megateriumBacillus megateriumThe protein decomposing bacteria can decompose most organic matters and proteins in the starch wastewater, are also organic phosphorus decomposing bacteria and can be used for manufacturing phosphorus bacterial fertilizers;
bacillus licheniformisBacillus licheniformisThe bacillus subtilis can decompose toxic and harmful substances in starch wastewater, has stronger protease and amylase activities, can promote starch hydrolysis, can grow in a severe environment, can exert the biological decomposition effect under the condition of micro-culture, can supply substances generated by starch decomposition to anaerobic azotobacter, azotobacter chroococcum and aspergillus versicolor for growth, and can kill pathogenic bacteria;
azotobacter fuscusAzotobacter chroococcumAspergillus versicolorAspergillus versicolorUnder the condition of micro-culture, organic nitrogen substances in the starch wastewater can be utilized for reproduction, the wastewater purification effect is achieved, and meanwhile, energy generated in the nitrogen fixation process can be supplied to other microorganisms for reproduction and growth.
As a further improvement of the invention, the template protein solution is prepared by the following steps:
a. taking a starch wastewater sample, standing a filtrate filtered by double-layer filter cloth for 2h, centrifuging for 15min at 6000r/min, taking a supernatant, adding a sodium hydroxide solution with the same volume and pH of 9-10, extracting for 60min, and centrifuging for 15min at 6000 r/min; taking the supernatant fluid 1;
b. adding hydrochloric acid solution with the same volume and pH value of 3-4.5 into the supernatant 1, precipitating for 10min, and then centrifuging for 15min at 8000r/min to precipitate crude protein;
c. dissolving the crude protein powder in 4-6 ml KH with pH of 6.22PO4-NaHPO4In a buffer solution, preparationForming a solution with the protein concentration of 0.15mmol/L, adding 0.2-0.5 part of acrylamide after the protein is completely dissolved, and standing for 8-10 h at 4 ℃;
d. adding 180-200 mu L of ammonium persulfate with the mass fraction of 10% into the overnight protein solution to obtain the template protein solution.
The starch wastewater protein is used as a template molecule, and the structure of the starch wastewater protein is from the same source, so that the protein can be better identified in starch wastewater treatment, the protein is enriched, and the microorganism can be better and more conveniently decomposed.
As a further improvement of the present invention, the 3-aminopropyl-triethoxysilane: tetramethyl ammonium hydroxide: polyethylene glycol 2000: ethyl orthosilicate: the molar ratio of the absolute ethyl alcohol is 0.20-0.30: (0.1-0.3): (0.07-0.1): 1: (50-75). Wherein the weight ratio of tetramethyl ammonium hydroxide: the optimal molar ratio of the ethyl orthosilicate is 0.25:1, and the optimal molar ratio varies from (0.1:1) to (0.3: 1).
3-aminopropyltriethoxysilane provides amino functional groups, tetraethoxysilane provides silicon sources to synthesize amino functionalized mesoporous silicon materials, and the amino functional groups can be combined with heavy metal ions in wastewater to achieve the effect of adsorbing the heavy metal ions.
PEG2000 is used as a template agent, is a non-ionic surfactant, is combined with a silicon source by a hydrogen bond, has a stable structure, has good compatibility with solvent ethanol, and is changed into a zigzag type from a long chain after being dissolved, so that the characteristics create favorable conditions for synthesizing an ordered mesoporous structure.
The mesoporous material prepared by taking PEG2000 as a surfactant has the advantages of uniform pore structure distribution, large average pore diameter and excellent heavy metal adsorption performance.
Tetramethyl ammonium hydroxide is used as an auxiliary template agent, not only can be used as a catalyst, but also can effectively reduce the bending and coiling of a long carbon chain, obviously improve the order of mesopores and increase the aperture.
The invention has the beneficial effects that:
1. the starch wastewater is utilized to prepare the organic fertilizer, so that the wastewater treatment effect is achieved, the number of active bacteria in the produced organic fertilizer is high, and double benefits of sewage recycling and organic fertilizer development are realized;
2. the honeycomb-like reaction chamber prepared by imprinting the mesoporous material has the advantages that the special material can adsorb heavy metal ions in wastewater, a safe reaction environment for microorganisms can be provided, and meanwhile, the mesoporous material can more effectively identify and aggregate proteins, so that the microorganisms can better decompose the proteins.
Drawings
Fig. 1 shows a reaction chamber with a honeycomb-like structure prepared by the present invention, wherein 1 and 2 are honeycomb plates, 3 is imprinted mesoporous honeycomb walls, and 4 is a honeycomb chamber providing a microbial reaction.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
Firstly, preparing a reaction chamber with a honeycomb-like structure:
A. preparation of imprinted mesoporous material
(1) Weighing 2 parts of 3-aminopropyl-triethoxysilane and 2 parts of template protein solution at room temperature, dissolving in absolute ethanol, and dropwise adding 2 parts of 25 mass percent tetramethylammonium hydroxide aqueous solution to obtain solution A; meanwhile, 8 parts of polyethylene glycol 2000 and 400 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; transferring the mixture into a watch glass, and standing at room temperature until the solvent is completely volatilized to obtain a product C;
(3) performing hydrothermal crystallization on the product C at the temperature of 60-80 ℃ for 10 hours, then placing the product C in a vacuum drying oven at the temperature of 35 ℃ for drying for 2 hours, taking out the product C, eluting the product C with 0.1-mol/L sodium chloride solution, and then refluxing the product C in an ethanol hydrochloric acid extract at the temperature of 60 ℃ for 1d to remove the template agent to obtain the imprinted mesoporous material;
B. preparation of Honeycomb Chambers
Taking 8 parts of imprinted mesoporous material, adding 20 parts of nylon 66 with the viscosity of 180g/ml to prepare a structural material sheet, and winding the structural material sheet on a roller coated with polytetrafluoroethylene to prepare a honeycomb chamber with the wall thickness of the honeycomb chamber of 0.5mm, the inner diameter of the honeycomb chamber pipe of 40mm and the length of the honeycomb chamber pipe of 120 mm;
C. preparation of Honeycomb plates
(1) Weighing 2 parts of 3-aminopropyl tri-ethoxysilane and 2 parts of modified chitosan, dissolving in absolute ethyl alcohol at room temperature, and dropwise adding 2 parts of 25 mass percent tetramethyl ammonium hydroxide aqueous solution to prepare a solution A; meanwhile, 8 parts of polyethylene glycol 2000 and 400 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 8 parts of tetraethoxysilane is added drop by drop, and the mixture is slowly stirred for 1 hour; pouring the mixture onto a glass plate to form a film, performing hydrothermal crystallization for 36h at 90 ℃, then placing the product in a vacuum drying oven at 35 ℃ to dry for 2h, taking out the product, eluting with 0.1mol/L sodium chloride solution, and then refluxing for 1d in an ethanol hydrochloric acid extract at 60 ℃ to remove the template agent to obtain a honeycomb flat plate;
(3) the honeycomb chamber is clamped between the honeycomb flat plates and is vertical to the two flat plates to assemble the reaction chamber with the pseudo-honeycomb structure.
Secondly, installing a micro-aerobic aeration pipeline at the bottom of the wastewater reaction tank, and paving the reaction chamber with the honeycomb-like structure on the aeration pipeline; the micro-oxygen concentration in the reaction tank is 0.3 mg/L.
Inoculating 5% of bacillus megatherium with the age of 12h, 3% of bacillus licheniformis with the age of 13h and 2% of azotobacter chroococcum with the age of 14h in a bee room 4 of a honeycomb reaction chamber, adding starch wastewater into a reaction tank I to enable the wastewater to be completely immersed in an upper plate 1 of the honeycomb-like reaction chamber, continuously discharging the wastewater in the reaction tank I into a reaction tank II for biological reaction after 1d of biological reaction, discharging the wastewater into the reaction tank I after the hydraulic retention time of the wastewater in the reaction tank II is 8h, stopping the circulation and addition of the wastewater in the reaction tank I and the reaction tank II after 6d of circulation reaction, uncovering the upper plate 1 of the honeycomb-like reaction chamber, and discharging the starch wastewater after fermentation to obtain the organic fertilizer;
in the organic fertilizer prepared by the embodiment, the total viable count is 1.4 multiplied by 108One per ml, and the total amino acid content is 188 g/L.
Example 2
Firstly, preparing a reaction chamber with a honeycomb-like structure:
A. preparation of imprinted mesoporous material
(1) Weighing 3 parts of 3-aminopropyl-triethoxysilane and 4 parts of template protein solution at room temperature, dissolving in absolute ethanol, and dropwise adding 3 parts of 25 mass percent tetramethylammonium hydroxide aqueous solution to obtain solution A; meanwhile, 15 parts of polyethylene glycol 2000 and 750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 12 parts of tetraethoxysilane is added drop by drop, and the mixture is slowly stirred for 1 hour; transferring the mixture into a watch glass, and standing at room temperature until the solvent is completely volatilized to obtain a product C;
(3) performing hydrothermal crystallization on the product C at 80 ℃ for 20h, then placing the product C in a vacuum drying oven at 40 ℃ for drying for 3h, taking out, eluting with 0.3mol/L sodium chloride solution, and then refluxing in an ethanol hydrochloric acid extract at 70 ℃ for 1d to remove the template agent to obtain the imprinted mesoporous material;
B. preparation of Honeycomb Chambers
Taking 12 parts of imprinted mesoporous material, adding 24 parts of nylon 66 with the viscosity of 220g/ml to prepare a structural material sheet, and winding the structural material sheet on a roller coated with polytetrafluoroethylene to prepare a honeycomb chamber with the wall thickness of 1.5mm, the inner diameter of the honeycomb chamber of 100mm and the length of a honeycomb chamber pipe of 400 mm;
C. preparation of Honeycomb plates
(1) Weighing 3 parts of 3-aminopropyl tri-ethoxysilane and 4 parts of modified chitosan, dissolving in absolute ethyl alcohol at room temperature, and dropwise adding 4 parts of 25 mass percent tetramethyl ammonium hydroxide aqueous solution to prepare a solution A; meanwhile, 15 parts of polyethylene glycol 2000 and 750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; pouring the mixture onto a glass plate to form a film, performing hydrothermal crystallization for 48h at 100 ℃, then placing the product in a vacuum drying oven at 40 ℃ to dry for 3h, taking out the product, eluting with 0.3mol/L sodium chloride solution, and then refluxing for 1d in an ethanol hydrochloric acid extract at 70 ℃ to remove the template agent to obtain a honeycomb flat plate;
(3) the honeycomb chamber is clamped between the honeycomb flat plates and is vertical to the two flat plates to assemble the reaction chamber with the pseudo-honeycomb structure.
Secondly, installing a micro-aerobic aeration pipeline at the bottom of the wastewater reaction tank, and paving the reaction chamber with the honeycomb-like structure on the aeration pipeline; the micro-oxygen concentration in the reaction tank is 0.8 mg/L.
Inoculating 8% of bacillus megaterium with the age of 18h, 3% of bacillus licheniformis with the age of 16h and 6% of aspergillus versicolor with the age of 16h into a bee room of a bee nest reaction chamber, adding starch wastewater into a reaction tank I to enable the wastewater to be completely immersed into an artificial bee nest reaction chamber, continuously discharging the wastewater in the reaction tank I into a reaction tank II for biological reaction after 2d of biological reaction, discharging the wastewater into the reaction tank I after the wastewater stays for 8-10 h in the reaction tank II, stopping the circulation and addition of the wastewater in the reaction tank I and the reaction tank II after 8d of circular reaction, uncovering an upper plate of the artificial bee nest reaction chamber, and discharging the starch wastewater after fermentation to obtain the organic fertilizer;
in the organic fertilizer prepared by the embodiment, the total viable count is 1.3 multiplied by 108One per ml, and the total amino acid content is 182 g/L.
Example 3
Firstly, preparing a reaction chamber with a honeycomb-like structure:
A. preparation of imprinted mesoporous material
(1) Weighing 2.3 parts of 3-aminopropyl-triethoxysilane and 3 parts of template protein solution at room temperature, dissolving in absolute ethanol, and dropwise adding 2.5 parts of 25% tetramethyl ammonium hydroxide aqueous solution to obtain solution A; meanwhile, 8 parts of polyethylene glycol 2000 and 500 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; transferring the mixture into a watch glass, and standing at room temperature until the solvent is completely volatilized to obtain a product C;
(3) performing hydrothermal crystallization on the product C at 64 ℃ for 18h, then placing the product C in a vacuum drying oven at 38 ℃ for drying for 3h, taking out, eluting with 0.2mol/L sodium chloride solution, and then refluxing in ethanol hydrochloric acid extract at 68 ℃ for 1d to remove the template agent, thereby obtaining the imprinted mesoporous material;
B. preparation of Honeycomb Chambers
Taking 10 parts of imprinted mesoporous material, adding 22 parts of nylon 66 with the viscosity of 200g/ml to prepare a structural material sheet, and winding the structural material sheet on a roller coated with polytetrafluoroethylene to prepare a honeycomb chamber with the wall thickness of 1mm, the inner diameter of the honeycomb chamber pipe of 60mm and the length of the honeycomb chamber pipe of 240 mm;
C. preparation of Honeycomb plates
(1) Weighing 2.3 parts of 3-aminopropyl tri-ethoxy silane and 4 parts of modified chitosan, dissolving in absolute ethyl alcohol at room temperature, and dropwise adding 2.5 parts of 25 mass percent tetramethyl ammonium hydroxide aqueous solution to prepare solution A; meanwhile, 8 parts of polyethylene glycol 2000 and 500 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; pouring the mixture onto a glass plate to form a film, performing hydrothermal crystallization at 88 ℃ for 36-48 h, then placing the product in a vacuum drying oven at 40 ℃ to dry for 3h, taking out the product, eluting the product with 0.2mol/L sodium chloride solution, and then refluxing the product in ethanol hydrochloric acid extract at 66 ℃ for 1d to remove the template agent to obtain a honeycomb flat plate;
(3) the honeycomb chamber is clamped between the honeycomb flat plates and is vertical to the two flat plates to assemble the reaction chamber with the pseudo-honeycomb structure.
Secondly, installing a micro-aerobic aeration pipeline at the bottom of the wastewater reaction tank, and paving the reaction chamber with the honeycomb-like structure on the aeration pipeline; the micro-oxygen concentration in the reaction tank is 0.6 mg/L.
Inoculating 6% of bacillus megaterium with the age of 14h, 3% of azotobacter chroococcum with the age of 15h, 5% of aspergillus versicolor with the age of 14h and 4% of bacillus licheniformis with the age of 14h in a bee room of a bee nest reaction chamber, adding starch wastewater into a reaction tank I to enable the wastewater to be completely immersed in the bee nest reaction chamber, continuously discharging the wastewater in the reaction tank I into a reaction tank II for biological reaction after 2d of biological reaction, discharging the wastewater into the reaction tank I after 10h of hydraulic retention time in the reaction tank II, stopping the circulation and addition of the wastewater in the reaction tank I and the reaction tank II after 8d of circulation reaction, uncovering an upper flat plate of the bee nest reaction chamber, and discharging the starch wastewater after fermentation to obtain the organic fertilizer;
by the present embodimentThe total viable count of the prepared organic fertilizer is 1.8 multiplied by 108The total amino acid content is 192 g/L.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (7)

1. A method for preparing an organic fertilizer by using starch wastewater is characterized by comprising the following steps:
(1) preparing a reaction chamber with a simulated honeycomb structure;
(2) installing a micro-aerobic aeration pipeline at the bottom of the wastewater reaction tank, and flatly paving the reaction chamber with the honeycomb-like structure on the aeration pipeline;
(3) inoculating fermentation strains in a bee chamber of a honeycomb reaction chamber, adding starch wastewater into a reaction tank I to enable the wastewater to be completely immersed in the honeycomb-like reaction chamber, continuously discharging the wastewater in the reaction tank I into a reaction tank II for biological reaction after the biological reaction lasts for 1-2 d, discharging the wastewater into the reaction tank I after the hydraulic retention time of the wastewater in the reaction tank II is 8-10 h, stopping the circulation and the addition of the wastewater in the reaction tank I and the reaction tank II after the circulation reaction lasts for 6-8 d, uncovering an upper flat plate of the honeycomb-like reaction chamber, discharging the fermented starch wastewater, adding auxiliary materials rich in nitrogen and phosphorus, and blending to obtain the organic fertilizer;
the preparation method of the pseudo-honeycomb structure reaction chamber comprises the following steps:
preparing a honeycomb chamber by using a imprinted mesoporous material, preparing a honeycomb flat plate by using the mesoporous material, clamping the honeycomb chamber between the honeycomb flat plates, and assembling the honeycomb chamber vertical to the two flat plates to form a honeycomb-like structure reaction chamber, wherein the concrete preparation steps of each structure are as follows:
A. preparation of imprinted mesoporous material
(1) Weighing 2-3 parts of 3-aminopropyl-triethoxysilane and 2-4 parts of template protein solution at room temperature, dissolving in absolute ethanol, and dropwise adding 2-4 parts of 25% tetramethyl ammonium hydroxide aqueous solution by mass fraction to obtain solution A; meanwhile, 8-15 parts of polyethylene glycol 2000 and 400-750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; transferring the mixture into a watch glass, and standing at room temperature until the solvent is completely volatilized to obtain a product C;
(3) performing hydrothermal crystallization on the product C at the temperature of 60-80 ℃ for 10-20 hours, then placing the product C in a vacuum drying oven at the temperature of 35-40 ℃ for drying for 2-3 hours, taking out the product C, eluting the product C with 0.1-0.3 mol/L sodium chloride solution, and then refluxing the product C in an ethanol hydrochloric acid extract at the temperature of 60-70 ℃ for 1d to remove the template agent to obtain the imprinted mesoporous material;
B. preparation of Honeycomb Chambers
Taking 8-12 parts of imprinted mesoporous material, adding 20-24 parts of nylon 66 to prepare a structural material sheet, and winding the structural material sheet on a roller coated with polytetrafluoroethylene to prepare a honeycomb chamber;
the viscosity of the nylon 66 is 180-220 g/ml;
C. preparation of Honeycomb plates
(1) Weighing 2-3 parts of 3-aminopropyl tri-ethoxy silane and 2-4 parts of modified chitosan at room temperature, dissolving in absolute ethyl alcohol, and dropwise adding 2-4 parts of 25% by mass of tetramethyl ammonium hydroxide aqueous solution to obtain solution A; meanwhile, 8-15 parts of polyethylene glycol 2000 and 400-750 parts of absolute ethyl alcohol are mixed and stirred to prepare a solution B;
(2) after reacting for 2 hours, A, B solution is fully mixed, 10 parts of ethyl orthosilicate is added drop by drop, and the mixture is slowly stirred for 1 hour; pouring the mixture onto a glass plate to form a film, performing hydrothermal crystallization at 90-100 ℃ for 36-48 h, then placing the product in a vacuum drying oven at 35-40 ℃ to dry for 2-3 h, taking out, eluting with 0.1-0.3 mol/L sodium chloride solution, and then refluxing in 60-70 ℃ ethanol hydrochloric acid extract for 1d to remove the template agent to obtain the honeycomb flat plate.
2. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the nitrogen and phosphorus auxiliary material is one of bran and soybean meal; adding 200-400 g of bran or 100-300 g of soybean meal according to 1L of fermented wastewater for blending.
3. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the wall thickness of the bee room is 0.5-1.5 mm, the inner diameter of the bee room pipe is 40-100 mm, the length of the bee room pipe is 120-400 mm, and the ratio of the length to the inner diameter of the bee room pipe is 3-4.
4. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the concentration of dissolved oxygen in the reaction tank is 0.3-0.8 mg/L.
5. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the fermentation strain is bacillus megateriumBacillus megateriumAzotobacter fuscusAzotobacter chroococcumAspergillus versicolor, Aspergillus versicolorAspergillus versicolorBacillus licheniformisBacillus licheniformisOne or more of the above combinations; the inoculation amount of the bacillus megaterium is 5-8%, and the age of the bacillus megaterium is 12-18 h; the inoculation amount of azotobacter chroococcum is 2% -4%, and the seed age is 14-16 h; the inoculation amount of the aspergillus versicolor is 4-6%, and the seed age is 12-16 h; the inoculation amount of the bacillus licheniformis is 3% -5%, and the seed age is 13-16 h.
6. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the preparation steps of the template protein solution are as follows:
a. taking a starch wastewater sample, standing a filtrate filtered by double-layer filter cloth for 2h, centrifuging for 15min at 6000r/min, taking a supernatant, adding a sodium hydroxide solution with the same volume and pH of 9-10, extracting for 60min, and centrifuging for 15min at 6000 r/min; taking the supernatant fluid 1;
b. adding hydrochloric acid solution with the same volume and pH value of 3-4.5 into the supernatant 1, precipitating for 10min, and then centrifuging for 15min at 8000r/min to precipitate crude protein;
c. dissolving the crude protein powder in 4-6 ml KH with pH of 6.22PO4-NaHPO4Preparing a solution with the protein concentration of 0.15mmol/L in a buffer solution, adding 0.2-0.5 part of acrylamide after the protein is completely dissolved, and standing at 4 ℃ for 8 percent~10h；
d. Adding 180-200 mu L of ammonium persulfate with the mass fraction of 10% into the overnight protein solution to obtain the template protein solution.
7. The method for preparing organic fertilizer by using starch wastewater as claimed in claim 1, wherein the method comprises the following steps: the 3-aminopropyl-triethoxysilane: tetramethyl ammonium hydroxide: polyethylene glycol 2000: ethyl orthosilicate: the molar ratio of the absolute ethyl alcohol is (0.20-0.30): (0.1-0.3): (0.07-0.1): 1: (50-75).
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