Detoxification treatment method based on straw degradation products

Abstract

The invention provides a detoxification treatment method based on straw degradation products, and relates to the technical field of straw treatment. According to the detoxification treatment method based on the straw degradation product, a low-cost ecological treatment system is constructed through natural photo-thermal resource utilization and waste woven bag transformation, the synergistic effect of microbial electron transfer and photooxidation is achieved through day and night circulation, straw toxin is efficiently converted into a stable polymer under the mediation of humic acid, and the detoxification effect is achieved. The whole process does not need to externally add chemicals and extra energy sources, the operation is convenient, farmers only need to observe the color change of liquid and the state of hyacinth living plants to judge that detoxification is completed, a treatment product is directly converted into a soil conditioner coated with a slow release fertilizer core, toxin resource utilization is achieved, and the cost is reduced. And the photosynthetic efficiency of crops and the heavy metal passivation effect are synchronously improved, a closed-loop circulation treatment mode from toxin degradation, fertilizer returning to the field to soil remediation is finally formed, and the agricultural ecological benefits are improved.

Description

Technical Field

[0001] This invention relates to the field of straw treatment technology, specifically a detoxification treatment method based on straw degradation products. Background Technology

[0002] Straw is a general term for the stems and leaves (ears) of mature crops, typically referring to the residue remaining after the grains are harvested from wheat, rice, corn, potatoes, rapeseed, cotton, sugarcane, and other crops. Straw detoxification treatment is primarily conducted because some straw contains factors that hinder its utilization. For example, some straw may be contaminated with mold during growth and storage, producing mycotoxins. These toxins not only affect the nutritional value of the straw but also harm the health of animals that consume it, leading to illness or even death. Some straw contains naturally occurring toxic substances; for instance, sorghum and corn seedling straw contains hydrocyanic acid, which can cause poisoning in animals if fed directly. Detoxification treatment reduces the content of toxic and harmful substances in straw, improving its safety. It also improves palatability, making it more palatable for animals, and increases its digestibility and nutritional value, allowing for better digestion and absorption by animals. This achieves effective utilization of straw, turning waste into treasure and reducing resource waste and environmental pollution.

[0003] Currently, the existing methods for straw treatment are relatively simple and basic, mostly involving discarding, burying, or using it as animal feed. The indiscriminate discarding of straw is very common, with these discarded straws often accumulating in fields, roadsides, or idle corners for extended periods. In the natural environment, due to suitable air humidity and temperature conditions, mold easily grows and multiplies on these accumulated straws. While burying straw seems like an environmentally friendly method, the decomposition process in the soil can also provide a breeding ground for mold due to environmental factors. Furthermore, using straw as animal feed also presents problems. If straw is not stored properly, it can also be susceptible to mold. Once straw is contaminated with mold, it produces mycotoxins. These mycotoxins are highly stable and toxic, posing potential harm to the surrounding ecological environment, such as polluting soil and water sources and affecting the growth of surrounding vegetation. Moreover, if contaminated straw is consumed by animals, mycotoxins accumulate in their bodies, affecting their health and leading to problems such as stunted growth and development, and weakened immunity. More seriously, these animal products containing mycotoxins pose a threat to human health and have significant safety risks once they enter the human food chain. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a detoxification treatment method based on straw degradation products, which solves the problem of certain safety hazards associated with existing straw treatment methods.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a detoxification treatment method based on straw degradation products, comprising the following steps:

[0006] S1. Inject the straw degradation liquid into a porous container made of agricultural waste;

[0007] S2. The container is filled with a composite matrix composed of rice husk ash and bentonite, wherein the mass ratio of rice husk ash to bentonite is 60:40 to 70:30;

[0008] S3. Inoculate the container with a suspension of moss spores to create a rhizosphere micro-ecosystem;

[0009] S4. Alternate between the darkroom period processing and the Guangqi period processing:

[0010] The dark box treatment lasts for 12-16 hours under completely dark conditions to activate the electron transport chain of anaerobic microorganisms.

[0011] The photo-initiation treatment lasts for 8-12 hours under natural light conditions, triggering a photo-oxidation reaction;

[0012] S5. The polymerization and precipitation of toxic phenolic substances are achieved through natural pH fluctuations. The final humic-toxin copolymer has a phenylpropane structural unit to toxin molecule binding ratio of 1:0.3-1:0.5. The detoxified composite matrix is ​​directly used as the slow-release organic fertilizer core, wrapped in a biodegradable membrane and applied to farmland.

[0013] Preferably, the porous container is made from waste plastic woven bags through needle punching with a pore size of 0.5-2mm.

[0014] Preferably, the total filling amount of the composite matrix is ​​60-75% of the container volume, wherein the rice husk ash is pre-activated by calcination at 300-400℃.

[0015] Preferably, the moss spore suspension is prepared from field-collected *Bryophyte scaber*, with a spore density of 1×10⁻⁶. 5 -5×10 5 per mL.

[0016] Preferably, the alternating process is repeated for 3-5 natural day-night cycles, during which no external chemical reagents or energy input is required.

[0017] Preferably, the method further includes: planting hyacinths on the surface of a porous container as biological indicators, and determining that detoxification is complete when the survival rate of the hyacinths reaches 95%.

[0018] Preferably, the concentration of hydroquinone generated by the reduction of quinone substances during the dark chamber treatment is 0.8-1.2 mmol / L, and the reactive oxygen species generated during the photosynthetic treatment include superoxide anions and hydroxyl radicals.

[0019] This invention provides a detoxification treatment method based on straw degradation products. It has the following beneficial effects:

[0020] This invention provides a detoxification method based on straw degradation products. This technology utilizes natural diurnal cycle light and heat resources and agricultural waste to regenerate reaction vessels, resulting in low processing costs. Furthermore, it leverages toxin transformation pathways, generating hydroquinone reserves through microbial electron transfer during alternating dark-box periods, coupled with activated free radical reactions during the light-activated period. This causes phenolic toxins to specifically polymerize into stable macromolecules under humic acid mediation, achieving high detoxification efficiency. Simultaneously, it achieves closed-loop resource regeneration. During the process, waste plastic woven bags are transformed into microreactors, and straw toxins are converted into humic-coated slow-release fertilizer. Hyacinth live indicator forms a permanent biological monitoring system. In operation, farmers only need to observe the liquid color change from red to yellow and the survival status of the hyacinths to judge the completion rate. No testing equipment or professional skills are required. It also forms an ecological chain that increases yield and efficiency. After detoxification, liquid irrigation increases the photosynthetic rate of crops, has a high rate of heavy metal migration and conversion, and the slow-release fertilizer core continuously releases nutrients for a long time. Finally, a closed-loop cycle is constructed. The treatment bag is directly returned to the field to improve the soil structure, which can increase the soil organic matter and reduce the background value of straw toxins. Ultimately, a sustainable treatment method of treating toxins with waste and ecological benefits is achieved. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the method flow of the present invention. Detailed Implementation

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] like Figure 1 As shown, this embodiment of the invention provides a detoxification treatment method based on straw degradation products, including the following steps:

[0024] S1. Inject the straw degradation liquid into a porous container made of agricultural waste;

[0025] S2. Fill the container with a composite matrix consisting of rice husk ash and bentonite, wherein the mass ratio of rice husk ash to bentonite is 60:40 to 70:30;

[0026] S3. Inoculate the container with a suspension of moss spores to create a rhizosphere micro-ecosystem;

[0027] S4. Alternate between the darkroom period processing and the Guangqi period processing:

[0028] The dark box treatment lasts for 12-16 hours under completely dark conditions to activate the electron transport chain of anaerobic microorganisms.

[0029] The photocatalytic treatment lasts for 8-12 hours under natural light conditions, triggering the photo-oxidation reaction.

[0030] S5. The polymerization and precipitation of toxic phenolic substances are achieved through natural pH fluctuations. The final humic-toxin copolymer has a phenylpropane structural unit to toxin molecule binding ratio of 1:0.3-1:0.5. The detoxified composite matrix is ​​directly used as the slow-release organic fertilizer core, wrapped in a biodegradable membrane and applied to farmland.

[0031] The porous container is made from waste plastic woven bags through needle punching with a pore size of 0.5-2 mm. The total filling volume of the composite matrix is ​​60-75% of the container volume, with rice husk ash pre-activated by calcination at 300-400℃. The moss spore suspension is prepared from field-collected scaly moss, with a spore density of 1×10⁻⁶. 5 -5×10 5 The concentration of hyacinths was 0.8-1.2 mmol / L. The alternating treatment process was repeated for 3-5 natural day-night cycles without the need for external chemical reagents or energy input. The method further included planting hyacinths on the surface of a porous container as biological indicators; detoxification was considered complete when the hyacinth survival rate reached 95%. During the dark chamber treatment, the concentration of hydroquinone generated from the reduction of quinones was 0.8-1.2 mmol / L, and the reactive oxygen species generated during the light-induced period included superoxide anions and hydroxyl radicals.

[0032] First, prepare agricultural waste plastic woven bags and use specialized needles to evenly puncture them, creating 0.5-2mm perforated pores on the bag surface, with a puncture density of 15-20 pores per square centimeter. Activate rice husk ash by calcining it in a simple earthen kiln at 300-400℃ for 2 hours. After cooling, mix it with natural bentonite at a 60:40 mass ratio and fill the modified woven bags to 65% volume using a layered filling method, forming a composite matrix with diatom structure and ion exchange function. Collect scaly bryophyte communities from local fields and prepare a spore density of 1×10⁻⁶ using river water. 5 A suspension of 1 / mL was evenly sprayed onto the matrix surface until it was completely wetted.

[0033] The straw degradation liquid was injected into the bag using a siphon until the liquid level reached three-quarters of the bag's height. It was then transferred to a dark environment to begin the dark chamber treatment: the bag was completely covered with black agricultural film for 16 hours. During this period, the anaerobic microbial community inside the bag reduced quinones to hydroquinone, with an electron transfer efficiency of 0.8 mmol electrons / g matrix. Simultaneously, the pH value naturally decreased to 5.6-5.8. After removing the agricultural film, the photocatalytic treatment was initiated: the bag was exposed to natural light for 10 hours. Sunlight radiation activated the hydroquinone auto-oxidation chain reaction, producing superoxide anions (O2·⁻) at a concentration ≥150 μmol / L and hydroxyl radicals. At this time, the matrix temperature rose to 35-38℃ due to the photothermal effect, and the pH value returned to 7.1-7.3.

[0034] The above-mentioned diurnal cycle was performed continuously for three natural days. At the end of each cycle, samples were taken to observe the color change of the liquid: a gradual change from an initial reddish-brown to a light yellow indicated the progress of toxin conversion. After the third photoperiod, hyacinth seedlings were planted on the outer surface of the woven bags, and the natural diurnal rhythm was maintained for another two days. Real-time monitoring of plant growth was conducted: when the leaves remained upright and the length of new root sprouts was ≥1cm, detoxification was considered complete (equivalent to vanillin residue <50ppm). Finally, the entire treatment bag was immersed in a biodegradable starch film solution to form a 0.2mm coating, and then directly buried 20cm deep in the topsoil of farmland. The humus-toxin copolymer inside the bag slowly released nutrients, while the hyacinths continued to perform their biological monitoring function. The entire treatment process required no electricity or chemical additives. The detoxified liquid, when used in irrigation, increased the number of rice tillers by 18%, and the heavy metal bound state conversion rate reached 92%.

[0035] Table 1: Control Parameters and Efficiency of Detoxification Process

[0036] index Control range mean ± standard deviation Detection methods Duration of the black box period 12-16 h 14.2±1.3 h Light recorder Hydroquinone formation concentration 0.8-1.2 mmol / L 1.05±0.15 mmol / L HPLC-MS peak concentration of free radicals ≥150 μmol / L 187±23 μmol / L Electron paramagnetic resonance pH fluctuation range 5.6-7.3 5.75→7.22 In-situ pH sensor Toxin polymerization ratio (phenylpropane: toxin) 1:0.3-1:0.5 1:0.41 ¹³C-NMR

[0037] Table 2: Comparison of detoxification efficiency (with traditional methods)

[0038] Toxin types This technology has a high removal rate. Traditional chemical removal rate biological adsorption removal rate Testing standards Phenols 97.2±2.1％ 91.5±3.8％ 84.3±5.7％ GB 11989-2008 Furans 95.6±1.8％ 88.3±4.2％ 79.1±6.3％ HJ 639-2012 Aldehydes (calculated as vanillin) 96.4±1.5％ 90.2±3.1％ 81.7±5.9％ GB / T 21918-2008 Heavy metal (Cd) 92.7±3.3％ 85.1±4.7％ 78.5±6.8％ GB / T 17141-1997

[0039] Note: The passivated state ratio reached 86%, as confirmed by the BCR continuous extraction method.

[0040] Table 3: Resource Recycling and Economic Benefits

[0041] project This technology Traditional processing solution Calculation basis Energy consumption per ton 0 kWh 38.7 kWh Power grid benchmark reagent cost 0 yuan / ton 420 yuan / ton Average price of commercial enzymes Container cost Discarded woven bags (0 yuan) 316L stainless steel tank (¥8500) Market price Value-added product income Slow-release fertilizer cores: ¥230 / ton Hazardous waste disposal fee: ¥150 / ton Organic fertilizer market price Crop yield increase rate 18.3±2.5％ 5.2±1.8％ Rice yield measurement (10,000 mu)

[0042] Table 4: Quantitative Indicators of Environmental Benefits

[0043] parameter Before processing After processing Improvement rate Monitoring methods Soil organic matter (g / kg) 24.7±3.1 29.4±2.3 +19.0％ NY / T 1121.6-2006 Earthworm biomass (g / m²) 32.5±7.4 51.2±9.6 +57.5％ ISO 23611-1:2018 Background levels of straw toxins (mg / kg) 146±32 99±25 -32.2％ HJ 761-2015 Aquatic ecotoxicity (EC50) 15.8％ 83.5％ +428％ GB / T 27858-2011

[0044] Table 5: Reliability Verification of Biological Indicator Systems

[0045] Hyacinth survival rate Toxin residue compliance rate Detoxification completion misjudgment rate Continuous monitoring duration ≥95％ 100％ 0％ 60 days 90-95％ 92.3％ 7.7％ 45 days <90％ 58.6％ 41.4％ <30 days

[0046] Note: The compliance rate refers to the degree of agreement between the hyacinth condition and the GC-MS detection results (n=162 batches).

[0047] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A detoxification treatment method based on straw degradation products, characterized in that, Includes the following steps: S1. Inject the straw degradation liquid into a porous container made of agricultural waste; S2. The container is filled with a composite matrix composed of rice husk ash and bentonite, wherein the mass ratio of rice husk ash to bentonite is 60:40 to 70:30; S3. Inoculate the container with a suspension of moss spores to create a rhizosphere micro-ecosystem; S4. Alternate between the darkroom period processing and the Guangqi period processing: The dark box treatment lasts for 12-16 hours under completely dark conditions to activate the electron transport chain of anaerobic microorganisms. The photo-initiation treatment lasts for 8-12 hours under natural light conditions, triggering a photo-oxidation reaction; S5. The polymerization and precipitation of toxic phenolic substances are achieved through natural pH fluctuations. The final humic-toxin copolymer has a phenylpropane structural unit to toxin molecule binding ratio of 1:0.3-1:0.

5. The detoxified composite matrix is ​​directly used as the slow-release organic fertilizer core, wrapped in a biodegradable membrane and applied to farmland.

2. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The porous container is made from waste plastic woven bags through needle punching with a pore size of 0.5-2mm.

3. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The total filling amount of the composite matrix is ​​60-75% of the container volume, wherein the rice husk ash is pre-activated by calcination at 300-400℃.

4. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The moss spore suspension was prepared from *Bryophyte scaber* collected in the field, with a spore density of 1 × 10⁻⁶. 5 -5×10 5 per mL.

5. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The alternating treatment process repeats for 3-5 natural day-night cycles, during which no external chemical reagents or energy input is required.

6. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The method further includes: planting hyacinths on the surface of a porous container as biological indicators, and determining that detoxification is complete when the survival rate of the hyacinths reaches 95%.

7. The detoxification treatment method based on straw degradation products according to claim 1, characterized in that: The concentration of hydroquinone generated by the reduction of quinones during the dark chamber treatment is 0.8-1.2 mmol / L, and the reactive oxygen species generated during the photosynthetic treatment include superoxide anions and hydroxyl radicals.

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