CN111849504A - Preparation method of biological activated vinegar residue biochar, product and application thereof - Google Patents
Preparation method of biological activated vinegar residue biochar, product and application thereof Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
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- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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Abstract
The invention discloses a preparation method of biological activated vinegar residue biochar, a product and application thereof, wherein the preparation method comprises the following steps of vinegar residue modification pretreatment: mixing the vinegar residue and a KOH solution, and soaking for 12 hours to ensure that the pH value of the soaked vinegar residue reaches 6.5, thereby obtaining pretreated vinegar residue; drying and dehydrating the vinegar residue, crushing the dried vinegar residue, sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18mm, heating the crushed vinegar residue under the nitrogen atmosphere, cooling to obtain vinegar residue biochar, putting the carbonized vinegar residue biochar in an earthworm intestinal tract in-vitro artificial simulator, fermenting for 7-10 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar with hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar to obtain the biologically activated vinegar residue biochar with the particle size of less than 4 mm. Compared with the original unmodified vinegar residue biochar, the finally formed biological activated vinegar residue biochar can passivate the content of the TPLC-state Cd (II), the TPLC-state Cu (II) and the DDTs in the soil to 42.69 percent, 52 percent and 38.92 percent of the initial value.
Description
The invention belongs to the technical field of fertilizer application, and particularly relates to a preparation method of biological activated vinegar residue biochar, a product and application thereof.
Background
The biochar is a stable solid product generated by high-temperature (300-1000 ℃) thermal degradation of an organic biomass material under the anoxic or anaerobic condition, has the characteristics of being porous, large in specific surface area, high in fragrance degree and the like, contains some nutrient elements required by plant growth, and has certain pH buffering capacity and cation exchange capacity. The vinegar residue is an important agricultural byproduct in the vinegar brewing process, mainly consists of rice hulls and other components such as bran, sorghum hulls, bacterial sludge and the like. The vinegar residues have the characteristics of high water content, strong acidity, rich organic matters and the like, and the local ecology can be seriously damaged by the traditional incineration, landfill or direct placement in the environment.
The sources of farmland soil pollutants are mainly as follows: mineral development, industrial development, urban construction, garbage disposal, vehicle transportation, agricultural production and the like, and the existence of the pollutants in the soil can not only reduce the yield of crops and lower the product quality, but also harm human health through the enrichment effect of a food chain, and is urgent to regulate the soil.
Therefore, there is a need in the art for a bio-activated vinegar residue biochar capable of passivating soil pollutants and a preparation method thereof.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
Therefore, the invention aims to overcome the defects of the existing preparation method of the biological activated vinegar residue biochar and provide a preparation method of the biological activated vinegar residue biochar.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of biological activated vinegar residue biochar comprises the following steps of vinegar residue modification pretreatment: mixing the vinegar residue and a KOH solution, and soaking for 12 hours to ensure that the pH value of the soaked vinegar residue reaches 6.5, thereby obtaining pretreated vinegar residue; drying and dehydrating the vinegar residue: drying the pretreated vinegar residue with hot air at 60-80 ℃ to constant weight to obtain dried vinegar residue; crushing the dried vinegar residues: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm; carbonizing vinegar residues: heating the crushed vinegar residue in nitrogen atmosphere, and cooling to obtain vinegar residue biochar; biological activation of vinegar residue biochar: putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 7-10 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar; the in-vitro artificial earthworm intestinal tract simulator is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:1 in the container and fermenting for 48-72 hours at 20-25 ℃ and pH of 6.3-6.8 under a light-proof anaerobic condition.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: and putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator for co-fermentation for 7-10 days, wherein the co-fermentation conditions are as follows: the temperature is 20-25 ℃, and the pH is 7.0-7.5.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: the mass ratio of the carbonized vinegar residue biochar to the common fermentation product in the earthworm intestinal tract in-vitro artificial simulator is 7-8: 2-3.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: and mixing the vinegar residue and a KOH solution, wherein the concentration of the KOH solution is 1.6-2.5 g/L, and the mass ratio of the vinegar residue to the KOH solution is 1: 1.5-1: 2.5.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: and (3) carrying out drying and dehydration treatment on the vinegar residue, wherein the water content of the dried vinegar residue is less than 5%.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: carbonizing the vinegar residues, wherein the temperature rise rate during carbonization is 10 ℃/min, the carbonization temperature is 700 ℃, and the retention time at the carbonization temperature is 2 h; and the temperature is naturally reduced to room temperature after being reduced to 300 ℃ at the speed of 10 ℃/min.
As a preferred scheme of the preparation method of the biological activated vinegar residue biochar, the method comprises the following steps: the earthworms comprise adult Eisenia foetida.
The invention also aims to overcome the defects of the prior art and provide a biological activated vinegar residue biochar product prepared by the preparation method of the biological activated vinegar residue biochar.
The invention also aims to overcome the defects of the prior art and provide the application of the biological activated vinegar residue biochar product in the soil conditioner.
As a preferable aspect of the application of the present invention, wherein: the preparation method of the soil conditioner comprises the steps of mixing the biologically activated vinegar residue biochar, the calcium magnesium potassium fertilizer and the diatomite, stirring and crushing at the constant temperature of 30 ℃, drying by hot air at the temperature of 55 ℃ to constant weight, and crushing to obtain the soil conditioner with the particle size of less than 4 mm; wherein the compound mass ratio of the vinegar residue biochar, the calcium-magnesium-potassium fertilizer and the diatomite is 8:1
The invention has the beneficial effects that:
(1) the invention provides a method for modifying vinegar residue biochar before carbonization by using low-concentration KOH, the formed modified vinegar residue biochar has the capacity of efficiently adsorbing heavy metals, and compared with the original unmodified vinegar residue biochar, the capacity of adsorbing Cd (II) and Cu (II) of the modified vinegar residue biochar is improved by 3.13 times and 1.57 times.
(2) According to the biologically activated vinegar residue biochar, biological activation is carried out on the vinegar residue biochar by using an earthworm intestinal tract in-vitro artificial simulator, beneficial soil microorganisms rich in earthworm intestinal tracts are used for promoting degradation of soil pollutants, regulating soil flora and accelerating decomposition of soil organic matters to enable the soil organic matters to be in a plant available form; the porous structure of the biochar can provide a colonization site for earthworm intestinal microorganisms, and the abundant functional groups can well fix extracellular enzymes on the biochar, so that the biologically activated vinegar residue biochar is rich in enzymes and beneficial microorganisms, can passivate soil pollutants, and can improve soil to promote crop growth;
the prepared biological activated vinegar residue biochar has higher soil extracellular enzyme activity, and the activities of beta-glucosidase, alkaline phosphatase and carboxylesterase respectively reach 1.39, 2.14 and 5.12 mu mol/h/g biochar; according to the invention, the time for treating and activating the biochar by using the live earthworm intestinal tract artificial simulator can be greatly shortened, in addition, the toxic and side effects of high-content biochar on the earthworm can be avoided, the beta-glucosidase and alkaline phosphatase of the biochar treated by the process have higher enzyme activity, and the biological activation of the invention is simpler and more efficient.
(3) The vinegar residue biochar forms a developed pore structure and a huge specific surface area in the carbonization process, can provide a large number of reaction sites for adsorption and passivation of heavy metals in soil, and can improve the soil hardening condition and increase the water retention capacity of the soil; in addition, because the vinegar residue contains a large amount of organic matters, a considerable amount of oxygen-containing functional groups can be formed during pyrolysis, and the oxygen-containing functional groups can complex heavy metal pollutants or organic pesticide residues in soil, so that the negative effects of the soil pollutants on crops are reduced; after the biological activated vinegar residue charcoal acts on soil, the contents of alkaline hydrolysis nitrogen, quick-acting phosphorus and quick-acting potassium in the soil are respectively increased by 144.8%, 173.9% and 136.7% compared with a control group, the content of organic chlorine is 38.92% of the control group, and the contents of TPLC state cadmium and copper are respectively 42.69% and 52% of the control group; the tomatoes are planted on the soil treated by the biological activated vinegar residue biochar, so that the maturation period of the tomatoes is advanced by 11 days, and the sensory quality of the tomatoes is remarkably improved. The biological activated vinegar residue charcoal prepared by the method can efficiently adsorb heavy metals, is rich in high enzyme activity, and can effectively passivate soil pollutants after acting on soil, improve soil fertility and improve crop quality. The preparation process of the biological activated vinegar residue biochar is simple, the raw materials are low in price and easy to obtain, and the requirement on production equipment is low.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a graph comparing the change of soil pH over 28 days when different biochar acts on soil in the practice of the invention.
FIG. 2 is a graph showing the content of alkaline hydrolyzable nitrogen, available phosphorus and available potassium in soil when different biochar acts on the soil in the embodiment of the present invention.
FIG. 3 is a graph showing the content change of TPLC-state cadmium, copper and DDTs in soil when different biochar acts on the soil in the implementation of the invention.
FIG. 4 is a graph showing the sensory scores of tomatoes planted on soil with different biochar in the practice of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The method comprises the following steps of (1) measuring the cadmium and the copper of the biochar: respectively mixing 0.1g of biochar with 50mL of 500mg/L Cd (II) and Cu (II) solutions, balancing for 24 hours at 30 ℃ under the condition of 180rmp, filtering by a 0.45-micrometer microporous filter membrane, measuring the content of Cd and Cu in the filtrate by ICP-MS, and calculating the content of Cd (II) and Cu (II) adsorbed by each gram of biochar.
The method for measuring the TPLC form cadmium and the TPLC form copper in the soil comprises the following steps: the heavy metals in the form of TPLC in the soil are determined by an EPA method 1311. The specific operation is as follows, 2g soil is mixed with 40mL TCLP extract, the mixed solution is centrifuged for 5min under 3000r/min, then supernatant fluid is taken, the supernatant fluid is filtered by a 0.45 μm microporous membrane, and the content of Cd and Cu in the filtrate is determined by ICP-MS.
In the invention, the determination of alkaline hydrolysis nitrogen and quick-acting phosphorus and potassium is as follows: the alkaline hydrolysis nitrogen is determined by adopting a 1.0mol/LNaOH diffusion method and adopting NaHCO3Leaching-molybdenum-antimony colorimetry to determine available phosphorus, and flame photometry to determine available potassium.
The invention relates to a method for measuring the activity of soil extracellular enzyme: taking a 2g soil sample, using ultrapure water to fix the volume to 100mL, mixing uniformly, centrifuging and taking supernatant. mu.L of the supernatant was added dropwise to a 96-well plate and mixed with 140. mu.L of 0.1M (pH 7.4) Tris-HCl, and 10. mu.L of 1-naphthyl butyrate, 4-nitrophenyl phosphate and 4-nitrophenyl-beta-D-glucopyranoside were added to measure the activities of carboxylesterase (EC 3.1.1.1), alkaline phosphatase (EC 3.1.3.1) and beta-glucosidase (EC 3.2.1.21), respectively. The 96-well plate is placed on a constant temperature shaking table at 20 ℃ and is shaken for 15 minutes, and the detection is carried out by a UVM340 microplate reader.
Sensory evaluation and analysis in the invention: 10 trained professionals (male: female: 1) were selected to evaluate and score the color, aroma, flavor, shape, texture and general preference of edible parts of tomatoes coated with different kinds of soil conditioners described in the examples.
In the invention: hot air equipment: GZX-9070MBE, Shanghai Bochen industries, Inc. medical facilities; a tube furnace: OTF-1200X, Combined Fertilizer and Crystal Material technology, Inc.; ICP-MS QP2010 Plus, Shimadzu corporation; a pulverizer: FZ-102, Tensted instruments, Inc., Tianjin; vinegar residue: the vinegar residue is provided by Shanxi Shuangyuan vinegar industry, Inc.; earthworms: earthworms are purchased from Xin Yida earthworm farms; humus soil: it is commercially available.
Other raw materials are not specially described and are all generally sold in the market.
Example 1:
the embodiment provides a preparation method of rice straw biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: cutting the rice straws into 5cm small sections, and drying the rice straws by hot air at the temperature of 60 ℃ to constant weight to obtain dried rice straws;
(2) crushing the dried raw materials: crushing the dried rice straw, and sieving the crushed rice straw with a 80-mesh sieve to obtain rice straw powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: heating the crushed rice straws to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, and washing with deionized water until the pH of washing water is stable to obtain the rice straw biochar.
Example 2:
the embodiment provides a preparation method of vinegar residue biochar, which comprises the following steps:
(1) drying and dehydrating the raw materials: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue;
(2) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(3) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, and washing with deionized water until the pH of washing water is stable, thus obtaining the original vinegar residue biochar.
The biochar described in example 1 and example 2 was used to adsorb Cd (II) and Cu (II) respectively in aqueous solution under the same conditions, and the results are shown in Table 1.
TABLE 1 pH and maximum adsorption of heavy metals of Rice straw biochar and Vinegar residue biochar
As can be seen from Table 1, the adsorption capacity of the vinegar residue biochar to Cd (II) and Cu (II) is greater than that of the rice straw biochar, which is enough to show the feasibility of preparing the biochar by using the vinegar residue as a raw material.
Example 3:
the embodiment provides a preparation method of modified vinegar residue biochar before carbonization, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is 6.5.
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar 1 before carbonization.
The biochar described in example 2 and example 3 was used to adsorb Cd (II) and Cu (II) respectively in aqueous solution under the same conditions, and the results are shown in Table 2.
TABLE 2 maximum adsorption of heavy metals for the modified and unmodified vinegar residue biochar before carbonization
As can be seen from Table 2, the adsorption capacity of the modified vinegar residue biochar on Cd (II) and Cu (II) is 3.13 times and 1.57 times that of the modified vinegar residue biochar before modification, which is enough to illustrate the advantages of the modified vinegar residue biochar before carbonization.
Example 5:
the embodiment provides a preparation method of modified vinegar residue biochar before carbonization, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: mixing 1 part of vinegar residue and 2.5 parts of water solution, and soaking for 12h to obtain the pH value of the soaked vinegar residue of 4.23.
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar 0 before carbonization.
Example 6:
the embodiment provides a preparation method of modified vinegar residue biochar before carbonization, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution are soaked for 12 hours, so that the pH value of the soaked vinegar residue is 8.95.
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar 2 before carbonization.
Example 7:
the embodiment provides a preparation method of modified vinegar residue biochar before carbonization, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution are soaked for 12 hours, so that the pH value of the soaked vinegar residue is 11.63.
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue;
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar 3 before carbonization.
The maximum adsorption amount of the vinegar residue biochar to the heavy metal obtained by treating the vinegar residue before carbonization with KOH solutions of different concentrations is shown in Table 3.
TABLE 3 maximum adsorption of heavy metals of modified vinegar residue biochar before carbonization at different KOH concentrations
As is apparent from Table 3, it was found that the heavy metal adsorption capacity of the vinegar residue biochar obtained by immersing the vinegar residue in a KOH solution of 1.6g/L for 12 hours was the highest, while the heavy metal adsorption capacity of the vinegar residue biochar treated with a higher KOH concentration was rather decreased, which was an unexpected finding of the present inventors. Therefore, the best scheme of modifying before carbonization is preferably obtained by soaking the vinegar residue in 1.6g/L KOH solution for 12 hours so that the soaked vinegar residue is neutral (6.5).
Example 8:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 2:1 in the container and fermenting for 48 hours at the temperature of 20-25 ℃ and the pH value of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
Example 9:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:1 in the container and fermenting for 48 hours at the temperature of 20-25 ℃ and the pH value of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
Example 10:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:2 in the container and fermenting for 48 hours at the temperature of 20-25 ℃ and the pH value of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
The earthworm intestinal canal in-vitro artificial simulator obtained by mixing and co-fermenting the earthworm homogenate and humus according to different mass proportions is used for biologically activating biochar, and the enzyme activity conditions of beta-glucosidase, alkaline phosphatase and carboxylesterase in the biochar are shown in table 4.
TABLE 4 enzymatic Activity of the biologically activated Vinegar residue biochar obtained from different ratios of earthworm homogenate to humus
As can be seen from table 4, when the ratio of the earthworm homogenate to the humus soil was 1:1, the enzymatic activities of beta-glucosidase, alkaline phosphatase and carboxylesterase of the biologically activated vinegar residue biochar are highest, and when the ratio of the earthworm homogenate to the humus is 2:1, the nutrition required by fermentation is insufficient, the survival competition among microorganisms is violent, and the power for secreting corresponding enzymes is insufficient, so that the enzyme activity for activating the biochar is not high; the ratio of the earthworm homogenate to the humus is 1:2, the amount of the added initial bacteria is insufficient, so that the fermentation is relatively slow, and a good biological activation effect cannot be achieved. Thus, the ratio of earthworm homogenate to humus is 1: the earthworm intestinal tract in-vitro artificial simulator in 1 hour is most suitable for the biological activation of the vinegar residue biochar.
Example 11:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:1 in the container and fermenting for 24 hours at the temperature of 20-25 ℃ and the pH value of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
Example 12:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:2 in the container and fermenting for 48 hours at the temperature of 20-25 ℃ and the pH value of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
Example 13:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:2 in the container and fermenting for 72 hours at the temperature of 20-25 ℃ and the pH of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
Example 14:
the embodiment provides a preparation method of biological activated vinegar residue biochar, which comprises the following steps:
(1) modifying the vinegar residue biochar before carbonization: 1 part of vinegar residue and 2.5 parts of KOH solution (the concentration of the KOH solution is 1.6g/L) are soaked for 12 hours, so that the pH value of the vinegar residue after soaking is neutral (6.5).
(2) Drying and dehydrating: drying the vinegar residue with hot air at 60 deg.C to constant weight to obtain dried vinegar residue (water content of dried vinegar residue is less than 5%);
(3) crushing the dried raw materials: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
(4) carbonizing treatment: heating the crushed vinegar residue to 700 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, keeping the temperature for 2h, then cooling to 300 ℃ at a speed of 10 ℃/min, then naturally cooling to room temperature, washing with deionized water until the pH of washing water is stable, and obtaining the modified vinegar residue biochar before carbonization;
(4) the biological activation process of the vinegar residue biochar comprises the following steps:
putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 8 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
wherein, the co-fermentation conditions are as follows: the temperature is 25 ℃, and the pH is 7.0;
the in-vitro artificial simulator for the earthworm intestinal tracts is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:2 in the container and fermenting for 86 hours at the temperature of 20-25 ℃ and the pH of 6.3-6.8 under the dark anaerobic condition. Before fermentation, the simulator is subjected to online CIP cleaning and SIP sterilization (121 ℃/0.1MPa), the humus soil is subjected to sterilization treatment (121 ℃/0.1MPa) before fermentation, the earthworms are adult Eisenia foetida, the earthworms are subjected to 75% ethanol washing on the outer surface before homogenization to remove in-vitro bacteria, and then are crushed and co-fermented with the humus soil under aseptic operation.
The in vitro artificial simulator for intestinal tracts of earthworms, which is obtained by co-fermenting the earthworm homogenate and humus at different fermentation times, is used for biologically activating biochar, and the enzyme activity conditions of beta-glucosidase, alkaline phosphatase and carboxylesterase in the biochar are shown in table 5.
TABLE 5 enzymatic Activity of earthworm homogenate and Humus soil for biological activation of vinegar residue biochar at different co-fermentation times
As can be seen from Table 5, the enzyme activity of the formed bio-activated vinegar residue biochar is the highest within 48-72 h. When the fermentation time is 24 hours, the fermentation time is too short to generate enough enzyme, and the enzyme is inactivated corresponding to too long fermentation time, so that the enzyme activity of the formed biochar is reduced. Therefore, 48-72 h is the optimal co-fermentation time of the earthworm homogenate and humus.
Example 15:
and (3) putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator for fermentation for 3 days under the conditions of example 9, wherein the other conditions are the same as those of example 9, so as to obtain the biologically-activated vinegar residue biochar.
Example 16:
and (3) putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator for fermentation for 15 days under the conditions of example 9, wherein the other conditions are the same as those of example 9, so as to obtain the biologically-activated vinegar residue biochar.
Example 17:
under the conditions of example 9, live earthworms are replaced by the earthworm homogenate to carry out co-fermentation with humus under the same conditions, and then biochar is placed in the earthworm homogenate to be fermented for 8 days to obtain the bio-activated vinegar residue biochar.
Example 18:
the original vinegar residue biochar prepared in example 2 was placed in an earthworm intestinal tract in vitro artificial simulator for fermentation for 8 days under the conditions of example 9, and the other conditions were the same as those of example 9, to obtain the bio-activated vinegar residue biochar.
The biochar prepared in example 3, example 9, example 15, example 16, example 17 and example 18 was measured for β -glucosidase, alkaline phosphatase, and carboxylesterase activities under the same conditions, and the results are shown in table 6.
TABLE 6 beta-glucosidase, alkaline phosphatase, Carboxylic acid esterase activities of different biochar
As can be seen from Table 4, the vinegar residue biochar is rich in enzyme activity after being biologically activated, the active enzymes can participate in the conversion of nutrient substances in soil, the enzyme activity of the biologically activated vinegar residue biochar is the highest when the fermentation time is 8 days, and the activities of beta-glucosidase, alkaline phosphatase and carboxylesterase respectively reach 1.39, 2.14 and 5.12 mu mol/h/g biochar, namely the biological activation effect at the activation time is the best. In addition, the vinegar residue biochar is biologically activated by the live earthworms, the activity of each group of enzymes is lowest, and the biochar can not activate the vinegar residue biochar well probably because the normal living activity habits of the earthworms are influenced by the biochar. Therefore, compared with the biological activation behavior of live earthworms, the artificial earthworm intestinal tract in vitro simulator has more efficient biological activation effect.
Example 19:
the unmodified vinegar residue biochar, the modified vinegar residue biochar before carbonization, and the biologically activated vinegar residue biochar described in example 2, example 3, and example 9 were named biochar 1, biochar 2, and biochar 3, respectively.
Taking a series of polyethylene pots, adding 15 kg of soil (soil is taken from a certain farmland in Tianjin coastal new areas) into each pot, applying biochar to the soil at an application rate of 2% of the mass ratio of the soil, taking the soil without biochar as a control group, and supplementing water into each pot every week to keep the soil moisture at 70%.
FIG. 1 is a graph comparing the change of soil pH over 28 days when different biochar acts on the soil. As can be seen from fig. 1, compared with the control group, the biochar of different types can effectively alleviate the problem of soil acidification, the effect of alleviating pH change by the biologically activated vinegar residue biochar is mildest, the original pH value of the soil can be maintained to a greater extent, the acidification problem can be alleviated, and the excessive alkali change of the soil can be avoided. The effect can be benefited by the double action effect of a large amount of alkaline mineral components contained in the biochar and oxygen-containing functional groups formed on the surface of the biochar after biological activation.
FIG. 2 is a graph comparing the contents of alkaline-hydrolyzable nitrogen, quick-acting phosphorus and quick-acting potassium in soil when different biochar acts on the soil. As can be seen from the second graph, the contents of the alkaline hydrolysis nitrogen, the quick-acting phosphorus and the quick-acting potassium in the soil after the action of the biochar of different types are all increased, wherein the action effect of the biochar of the biologically activated vinegar residue is most obvious, and the contents of the alkaline hydrolysis nitrogen, the quick-acting phosphorus and the quick-acting potassium are respectively increased by 144.8%, 173.9% and 136.7% compared with the control group. Therefore, the vinegar residue biochar is rich in active enzymes after being biologically activated, and the active enzymes can further promote the conversion of nutrient substances in soil, so that the content of nitrogen, phosphorus and potassium available to plants is increased.
Fig. 3 shows the content changes of TPLC state cadmium, copper and DDTs in soil when different biochar acts on soil, as can be seen from fig. 3, different biochar can effectively passivate the content of effective heavy metal in soil, the vinegar residue biochar after biological activation has more obvious effect of degrading organochlorine pesticide, the content of organochlorine after passivation is 55.6% of that of the modified group after carbonization and 38.92% of that of the control group, and it is possible that enzyme and microbial flora introduced after biological activation are beneficial to the degradation of organochlorine pesticide. The modified vinegar residue biochar has obvious passivation effect on heavy metals, the content of TPLC-state cadmium and copper after passivation is only 57.9% and 56.8% of that of a control group, and the content of TPLC-state cadmium and copper after biological activation is 73.7% and 91.5% of that before biological activation. Therefore, the vinegar residue biochar has obvious passivation effect on soil pollutants after modification and biological activation.
Example 20:
the unmodified vinegar residue biochar, the modified vinegar residue biochar before carbonization, and the biologically activated vinegar residue biochar described in example 2, example 3, and example 9 were named biochar 1, biochar 2, and biochar 3, respectively.
Mixing biochar (biochar 1, biochar 2 and biochar 3), calcium-magnesium-potassium fertilizer and diatomite, stirring and crushing at the constant temperature of 30 ℃, drying by hot air at the temperature of 55 ℃ to constant weight, and crushing until the particle size is less than 4mm to obtain the soil conditioner (conditioner 1, conditioner 2 and conditioner 3); wherein the compounding mass ratio of the vinegar residue biochar, the calcium magnesium potassium fertilizer and the diatomite is 8:1: 1.
Taking a series of polyethylene pots, adding 15 kg of soil (the soil is taken from a certain farmland in Tianjin coastal new areas) into each pot, applying the conditioner to the soil at an application amount of 2% of the soil mass ratio, taking the soil without the conditioner as a control group, supplementing water into each pot every week to keep the soil moisture at 70%, sowing 5 tomato seeds into each polyethylene pot after balancing for 2 months, keeping the seedlings with the best activity in each pot when the germinated seedlings of the seeds grow to 10cm high, and pulling out the rest. Watering is not carried out regularly during the growth period of the tomatoes, but the treatment consistency among groups is ensured, the date that the first tomato of each group turns red is recorded, and the tomato fruits of each group are picked randomly for sensory evaluation after the tomato fruits of all groups are ripe.
Table 5 shows the days of premature ripening of tomatoes under the action of different biochar types, and conditioners prepared from biochar 1, biochar 2 and biochar 3 in examples 2, 3 and 8 can lead the ripening period of tomatoes to 2 days, 5 days and 11 days respectively.
Probably, the tomato roots can grow better due to the fact that the soil is looser after the porous charcoal is applied, and the developed roots can absorb more nutrient substances to promote the growth of tomato plants and fruits, so that tomatoes applied with the charcoal group can be ripe 2-11 days in advance, and the table 7 shows that the tomato roots are rich in nutrients.
TABLE 7 days of premature ripening of tomatoes under the action of different types of biochar
FIG. 4 is a graph of sensory scores of tomatoes planted with different biochar applied to soil at a 2% application rate, compared with a control group, the tomatoes of different treatment groups have reduced acid taste, obviously improved sweet taste, enriched flavor, greatly improved overall preference, and the crop quality is regulated and controlled by multiple factors, after vinegar residue biochar acts on soil, the content of soil pollutants is obviously reduced, the toxic action of the tomato plants by the pollutants is reduced, in addition, the biologically activated charcoal contains a large amount of enzymes and microbial strains, which can change the soil micro-ecology to a benign direction after acting on the soil, the circulation of soil nutrient substances is smoother, so that the plants can absorb more nutrient elements, in addition, the biochar has the characteristic of being porous, the modification before carbonization is beneficial to enlarging the aperture of the biochar, the soil is looser after the modification acts on the soil, and the growth extension of plant roots is facilitated. In a word, the improvement of the crop quality is the macroscopic embodiment that the vinegar residue biochar improves the soil and passivates soil pollutants.
In conclusion, the invention provides the vinegar residue biochar modified by using the low-concentration KOH before carbonization, and then biologically activated by using the earthworm intestinal tract in-vitro artificial simulator, so that the formed vinegar residue biochar has the capability of efficiently adsorbing heavy metals, and compared with the original unmodified vinegar residue biochar, the capability of adsorbing Cd (II) and Cu (II) of the modified vinegar residue biochar is improved by 3.13 times and 1.57 times. In addition, the vinegar residue biochar after biological activation has higher soil extracellular enzyme activity, and the activities of beta-glucosidase, alkaline phosphatase and carboxylesterase respectively reach 1.39, 2.14 and 5.12 mu mol/h/g biochar. After the biological activated vinegar residue charcoal acts on soil, the contents of alkaline hydrolysis nitrogen, quick-acting phosphorus and quick-acting potassium in the soil are respectively increased by 144.8%, 173.9% and 136.7% compared with a control group, the content of organic chlorine is 38.92% of the control group, and the contents of TPLC state cadmium and copper are respectively 42.69% and 52% of the control group. The tomatoes are planted on the soil treated by the biological activated vinegar residue biochar, so that the maturation period of the tomatoes is advanced by 11 days, and the sensory quality of the tomatoes is remarkably improved. The biological activated vinegar residue charcoal prepared by the method can efficiently adsorb heavy metals, is rich in high enzyme activity, and can effectively passivate soil pollutants after acting on soil, improve soil fertility and improve crop quality.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of biological activated vinegar residue biochar is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
modifying and pretreating vinegar residues: mixing the vinegar residue and a KOH solution, and soaking for 12 hours to ensure that the pH value of the soaked vinegar residue reaches 6.5, thereby obtaining pretreated vinegar residue;
drying and dehydrating the vinegar residue: drying the pretreated vinegar residue with hot air at 60-80 ℃ to constant weight to obtain dried vinegar residue;
crushing the dried vinegar residues: crushing the dried vinegar residue, and sieving the crushed vinegar residue with a 80-mesh sieve to obtain vinegar residue powder with the particle size of less than 0.18 mm;
carbonizing vinegar residues: heating the crushed vinegar residue in nitrogen atmosphere, and cooling to obtain vinegar residue biochar;
biological activation of vinegar residue biochar: putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator, fermenting for 7-10 days to obtain biologically activated vinegar residue biochar, drying the biologically activated vinegar residue biochar by hot air at 55 ℃ to constant weight, and crushing the biologically activated vinegar residue biochar until the particle size is less than 4mm to obtain the biologically activated vinegar residue biochar;
the in-vitro artificial earthworm intestinal tract simulator is a container containing a co-fermentation product of earthworm homogenate and humus, wherein the co-fermentation product is prepared by mixing the earthworm homogenate and the humus in a mass ratio of 1:1 in the container and fermenting for 48-72 hours at 20-25 ℃ and pH of 6.3-6.8 under a light-proof anaerobic condition.
2. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: and putting the carbonized vinegar residue biochar into an earthworm intestinal tract in-vitro artificial simulator for co-fermentation for 7-10 days, wherein the co-fermentation conditions are as follows: the temperature is 20-25 ℃, and the pH is 7.0-7.5.
3. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: the mass ratio of the carbonized vinegar residue biochar to the common fermentation product in the earthworm intestinal tract in-vitro artificial simulator is 7-8: 2-3.
4. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: and mixing the vinegar residue and a KOH solution, wherein the concentration of the KOH solution is 1.6-2.5 g/L, and the mass ratio of the vinegar residue to the KOH solution is 1: 1.5-1: 2.5.
5. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: and (3) carrying out drying and dehydration treatment on the vinegar residue, wherein the water content of the dried vinegar residue is less than 5%.
6. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: carbonizing the vinegar residues, wherein the temperature rise rate during carbonization is 10 ℃/min, the carbonization temperature is 700 ℃, and the retention time at the carbonization temperature is 2 h; and the temperature is naturally reduced to room temperature after being reduced to 300 ℃ at the speed of 10 ℃/min.
7. The method for preparing bio-activated vinegar residue biochar as claimed in claim 1, wherein: the earthworms comprise adult Eisenia foetida.
8. A bio-activated vinegar residue biochar product prepared by the method for preparing the bio-activated vinegar residue biochar as claimed in any one of claims 1 to 7.
9. The use of the bio-activated sludge biochar product of claim 8 in a soil conditioner.
10. The use of biologically activated vinegar residue biochar in a soil conditioner as claimed in claim 9, wherein: the soil conditioner and the preparation method thereof comprise the following steps,
mixing the biologically activated vinegar residue biochar, the calcium-magnesium-potassium fertilizer and the diatomite, stirring and crushing at the constant temperature of 30 ℃, drying by hot air at the temperature of 55 ℃ to constant weight, and crushing until the particle size is less than 4mm to obtain the soil conditioner; wherein the compounding mass ratio of the vinegar residue biochar, the calcium magnesium potassium fertilizer and the diatomite is 8:1: 1.
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