Plant curing liquid containing plant-derived wood vinegar and preparation method thereof

Abstract

The present invention relates to the technical field of plant curing liquid preparation, and in particular to a plant curing liquid containing plant-derived wood vinegar and a preparation method thereof. The preparation method comprises the following steps: preparing activated biochar; 4,4'-(hexafluoroisopropylene) diphthalic anhydride grafting and modifying the activated biochar; preparing self-assembled silk fibroin-modified carboxyl biochar; and preparing a plant curing liquid containing plant-derived wood vinegar. The present invention modifies the carboxyl-modified biochar by self-assembling silk fibroin. The self-assembly structure of the silk fibroin can increase the hydrophilicity of the biochar. After the silk fibroin is attached to the surface of the biochar, the self-assembly silk fibroin-modified carboxyl biochar has better dispersibility and compatibility in an aqueous environment due to the hydrophilicity of the silk fibroin. In addition, the self-assembly of the silk fibroin can form a porous structure, thereby improving its adsorption capacity, thereby improving the loading capacity of the effective ingredients in the wood vinegar.

Description

Technical Field

[0001] The invention relates to the technical field of plant curing liquid preparation, and in particular to a plant curing liquid containing plant-derived wood vinegar and a preparation method thereof. Background Art

[0002] Wood vinegar is a reddish-brown aqueous solution produced during the pyrolysis of wood. Its main components include organic acids, phenols, esters, water, and various minerals and vitamins. It is formed by heating wood in anoxic conditions, causing the organic matter in the wood to decompose and condense. The organic acids, phenols, and minerals in wood vinegar stimulate cell growth, promoting photosynthesis and nutrient absorption in plants, thereby promoting seed germination and seedling growth. Therefore, adding wood vinegar to plant maintenance solutions can better promote plant germination and growth.

[0003] However, the phenols and organic acids in wood vinegar contain a large number of active functional groups, such as hydroxyl and carboxyl groups, which are easily oxidized by oxygen. Furthermore, exposure of the curing solution to air, especially under conditions such as high temperature and light, can accelerate the oxidation of the phenolic and organic acids in the wood vinegar, thereby reducing the content of the active ingredients in the curing solution and affecting its effectiveness. Therefore, existing techniques often separate the phenolic acids from wood vinegar through various procedures and store them separately. However, the cost of separating organic and phenolic acids separately is high, the yield is low, and the components in wood vinegar are complex and synergistic. Therefore, the effect of separating these separately on improving plant growth and survival is not significant. Therefore, the present invention provides a plant curing solution containing plant-derived wood vinegar and a preparation method thereof to address the above-mentioned problems. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a plant curing liquid containing plant-derived wood vinegar and a preparation method thereof.

[0005] A method for preparing a plant curing liquid containing plant-derived wood vinegar comprises the following steps:

[0006] S1. Preparation of activated biochar:

[0007] Weigh zinc chloride and deionized water, stir until uniformly mixed, then add biochar, and calcine in a tubular furnace to obtain activated biochar;

[0008] S2, 4,4'-(hexafluoroisopropylene) diphthalic anhydride grafted modified activated biochar:

[0009] 4,4'-(Hexafluoroisopropylene) diphthalic anhydride and N,N-dimethylformamide were added to a reaction flask and mixed evenly, and then activated biochar was added and microwave-treated to obtain carboxyl-grafted biochar;

[0010] S3. Preparation of self-assembled silk fibroin modified carboxyl biochar:

[0011] The silk fibroin fibers were dissolved in a lithium bromide solution and stirred for reaction, followed by dialysis to obtain a self-assembled silk fibroin solution. The self-assembled silk fibroin solution was mixed with a NaOH solution, and carboxyl-grafted biochar was added. The mixture was magnetically stirred in a microwave reactor to obtain self-assembled silk fibroin-modified carboxyl biochar.

[0012] S4, preparing a plant curing solution containing plant-derived wood vinegar:

[0013] The self-assembled silk fibroin modified carboxyl biochar is soaked in wood vinegar to obtain a suspension, sodium alginate is dissolved in deionized water, the suspension is added, ultrasonicated, and then diluted with water to obtain a plant curing solution containing plant-derived wood vinegar.

[0014] Furthermore, step S1 of preparing activated biochar comprises the following steps:

[0015] Weigh 1-3 parts by mass of zinc chloride and 20-25 parts by mass of deionized water, stir until uniformly mixed, then add 2-4 parts by mass of biochar, let stand for 2-3 hours, then heat to 105-110°C, evaporate the water for 15-20 minutes, then calcine in a tube furnace at 600-800°C under a nitrogen atmosphere for 2-3 hours, cool to room temperature 22-24°C with the furnace, then add 30-35 parts by mass of deionized water, boil for 2-3 hours to remove water, and dry the solid product in an oven at 110-120°C to constant weight to obtain activated biochar.

[0016] Furthermore, in step S2, 4,4'-(hexafluoroisopropylene) diphthalic anhydride is grafted to modify the activated biochar, comprising the following steps:

[0017] 50 parts by mass of 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 100-120 parts by mass of N,N-dimethylformamide are added to a reaction bottle and mixed evenly, and then 1-5 parts by mass of activated biochar are added. The mixture is microwave-treated for 10-20 minutes, taken out, heated to 50-55°C, and stirred at a speed of 350-400 r / min for 10-20 minutes. The reaction product is filtered, and the solid matter is vacuum-dried at 60-65°C to obtain carboxyl-grafted biochar.

[0018] Furthermore, step S3 of preparing self-assembled silk fibroin-modified carboxyl biochar comprises the following steps:

[0019] S3.1. Dissolve silk fibroin in a 9-9.5 mol / L lithium bromide solution at a material-to-liquid ratio of 10 g silk fibroin to (100-120) mL lithium bromide solution. Heat the mixture to 60-65°C and stir for 40-50 min. Allow to cool to room temperature (22-24°C). Then, dialyze the mixture in deionized water at 0-4°C for 72-75 h to obtain a self-assembled silk fibroin solution.

[0020] S3.2. Mix 1-3 parts by mass of self-assembled silk fibroin solution with 80-100 parts by mass of NaOH solution, then add 1-2 parts by mass of carboxyl-grafted biochar, magnetically stir in a microwave reactor for 30-40 minutes, then filter to remove the liquid, wash with 0.1 mol / L NaOH solution 3-4 times, then wash with deionized water until neutral, and dry at 65-70°C to obtain self-assembled silk fibroin modified carboxyl biochar.

[0021] Furthermore, in step S4, preparing a plant curing solution containing plant-derived wood vinegar comprises the following steps:

[0022] S4.1. Soak the self-assembled silk fibroin-modified carboxylated biochar in wood vinegar for 24-26 hours, with a material-to-liquid ratio of 1 g wood vinegar to (10-20) mL of self-assembled silk fibroin-modified carboxylated biochar, to obtain a suspension.

[0023] S4.2. Dissolve 1-5 parts by volume of sodium alginate in 20-30 parts by volume of deionized water preheated to 50-60°C, add 3-4 parts by volume of the suspension, sonicate for 10-15 minutes, adjust the pH value of the system to 6-7, and then add 50-80 times the total volume of water to dilute the solution to obtain a plant-derived wood vinegar-containing plant-derived wood vinegar.

[0024] Furthermore, the specific steps for preparing biochar are as follows:

[0025] Cut rice straw into small pieces, wash it with deionized water, put it into an oven, and dry it at 60-65℃ for 24-25 hours. The dried material is crushed in a powder grinder to obtain straw powder. The straw powder is placed in a ceramic cochlea, compacted, covered with a lid, and placed in a muffle furnace that has been introduced with nitrogen to exhaust the air in the furnace. It is carbonized in anoxic conditions at 500-700℃ for 2-3 hours, cooled to room temperature, and then taken out to obtain biochar.

[0026] Furthermore, the specific preparation steps of silk fibroin fiber are as follows:

[0027] The silk was immersed in a papain solution at a material-liquid ratio of 1 g: (45-50) mL, with a mass concentration of 3-3.2 g / L and a pH value of 6, and treated in a water bath at 80-85°C for 1-1.5 hours, washed and pulled, and then dried at 60-65°C to obtain a primary degumming intermediate;

[0028] The primary degumming intermediate is immersed in 8-8.5 mol / L urea solution, with the material-liquid ratio of the primary degumming intermediate to the urea solution being 1 g: (30-40) mL, and treated in a 90-95°C water bath for 3-4 hours. After washing, the secondary degumming intermediate is dried to a constant weight to obtain the secondary degumming intermediate.

[0029] The secondary degumming intermediate is mixed with a sodium carbonate solution at a material-liquid ratio of 12 g: (500-550) mL, the concentration of the sodium carbonate solution is 0.5-0.6 g / L, the mixture is boiled for 30-35 minutes, and the mixture is washed with deionized water, which is repeated three times, and the silk fiber is dried.

[0030] Furthermore, the molecular weight cut-off of the dialysis bag during dialysis is 8-14 kDa.

[0031] Furthermore, the power of the microwave reactor is 400 W, and the speed of the magnetic stirring is 350 r / min.

[0032] A plant curing liquid containing plant-derived wood vinegar is prepared by the above-mentioned method for preparing the plant curing liquid containing plant-derived wood vinegar.

[0033] Compared with the prior art, the present invention has at least the following beneficial effects:

[0034] 1. The present invention uses 4,4'-(hexafluoroisopropylene) diphthalic anhydride to graft the biopeptide activated by zinc chloride. The 4,4'-(hexafluoroisopropylene) diphthalic anhydride molecule contains a variety of groups, and these groups can react with active sites such as hydroxyl or amino groups on the surface of biochar, thereby introducing more carboxyl groups and hexafluoroisopropylene groups on the surface of biochar, increasing the functional group density on the surface of biochar, thereby improving the adsorption capacity of biochar. In addition, 4,4'-(hexafluoroisopropylene) diphthalic anhydride has low toxicity, is more environmentally friendly and stable, and 4,4'- The process of grafting modification of (hexafluoroisopropylene) diphthalic anhydride and biochar is relatively simple, does not require the use of excessive organic solvents, and can reduce production costs. The carboxyl-grafted biochar prepared by the grafting reaction of 4,4'-(hexafluoroisopropylene) diphthalic anhydride not only has carboxyl groups, but also contains hexafluoroisopropylene groups. The introduction of carboxyl groups can provide a large number of adsorption sites for organisms, thereby assisting biochar in loading the components in wood vinegar that promote plant growth and improve plant stress resistance, and provide plants with the effect of promoting growth and improving survival rate when applied to plants.

[0035] 2. The present invention modifies carboxyl-modified biochar by self-assembling silk fibroin. The self-assembly structure of silk fibroin can increase the hydrophilicity of biochar. After the silk fibroin is attached to the surface of the biochar, the hydrophilicity of the silk fibroin makes the self-assembled silk fibroin-modified carboxyl biochar have better dispersibility and compatibility in an aqueous environment. In addition, the self-assembly of silk fibroin can form a porous structure, which can increase the specific surface area of ​​the biochar, thereby improving its adsorption capacity, thereby improving the loading capacity for the effective ingredients in the wood vinegar. In addition, the silk fibroin also has good biodegradability and can slowly decompose after application, without causing excessive burden on the planting soil, and is environmentally friendly.

[0036] 3. The present invention prepares a plant curing solution by compounding wood vinegar, biochar and sodium alginate, which can bring into play the synergistic effect of the three. The wood vinegar contains organic acids, alcohols, phenols and trace elements that promote plant growth and improve stress resistance. Biochar is the main carrier. After the biochar is loaded with wood vinegar, a degradable gel film is formed by sodium alginate to reduce volatilization. The wood vinegar provides quick-acting organic nutrients, the biochar adsorbs and slowly releases nutrients, and the sodium alginate chelates trace elements to form a "fast-slow-stable" three-level nutrient release mode. At the same time, sodium alginate has a certain chelating effect and can combine with metal ions to improve the utilization rate of trace elements. The metal ions are chelated by sodium alginate and can be absorbed by plants to enhance the absorption capacity of the leaves and roots, thereby further improving the absorption of the plant curing solution by the plants, thereby promoting plant growth and stress resistance and improving the survival rate of the plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The present invention is a flow chart of a method for preparing a plant curing liquid containing plant-derived wood vinegar. DETAILED DESCRIPTION

[0038] The following describes in detail a plant care solution containing plant-derived wood vinegar and a preparation method thereof provided by the present invention, in conjunction with the accompanying drawings and specific examples. It is also noted that, to provide a more detailed description, the following examples are best and preferred embodiments. For some known techniques, those skilled in the art may also adopt other alternatives to implement the invention. Furthermore, the accompanying drawings are provided solely for the purpose of describing the embodiments in greater detail and are not intended to limit the present invention.

[0039] Example 1:

[0040] A method for preparing a plant curing liquid containing plant-derived wood vinegar, such as Figure 1 As shown, the following steps are included:

[0041] S1. Preparation of activated biochar:

[0042] Cut rice straw into 5-6 cm segments, wash with deionized water, and place in an oven to dry at 60°C for 24 hours. The dried material is crushed in a powder grinder to obtain straw powder. The straw powder is placed in a ceramic cochlea, compacted, covered, and placed in a muffle furnace that has been purged of nitrogen to remove all air. Carbonize at 500°C for 2 hours in anoxic conditions, cool to room temperature, and then remove to obtain biochar.

[0043] Weigh 1 part by mass of zinc chloride and 20 parts by mass of deionized water, stir until uniformly mixed, then add 2 parts by mass of biochar, let it stand for 2 hours, then heat to 105°C, evaporate the water for 15 minutes, and then calcine in a tube furnace at 600°C under a nitrogen atmosphere for 2 hours, cool to room temperature 22°C with the furnace, then add 30 parts by mass of deionized water, boil for 2 hours to remove water, and dry the solid product in an oven at 110°C to constant weight to obtain activated biochar.

[0044] S2, 4,4'-(hexafluoroisopropylene) diphthalic anhydride grafted modified activated biochar:

[0045] 50 parts by mass of 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 100 parts by mass of N,N-dimethylformamide were added to a reaction bottle and mixed evenly, and then 1 part by mass of activated biochar was added. The mixture was microwave-treated for 10 minutes, taken out, heated to 50°C, and stirred at a speed of 350 r / min for 10 minutes. The reaction product was filtered, and the solid matter was vacuum-dried at 60°C to obtain carboxyl-grafted biochar.

[0046] S3. Preparation of self-assembled silk fibroin modified carboxyl biochar:

[0047] S3.1. Soak the silk in a papain solution at a material-liquid ratio of 1 g:45 mL, with a mass concentration of 3 g / L and a pH of 6. Treat in an 80°C water bath for 1 h, wash and pull, and then dry at 60°C to obtain a primary degumming intermediate.

[0048] The primary degumming intermediate was immersed in 8 mol / L urea solution, with the material-liquid ratio of the primary degumming intermediate to the urea solution being 1 g:30 mL, and treated in a 90°C water bath for 3 h. After washing, the secondary degumming intermediate was dried to a constant weight to obtain the secondary degumming intermediate.

[0049] The secondary degumming intermediate was mixed with sodium carbonate solution at a material-liquid ratio of 12 g:500 mL, with a sodium carbonate solution concentration of 0.5 g / L, boiled for 30 min, washed with deionized water, repeated three times, and dried to obtain silk fibroin fibers;

[0050] The silk fibroin fibers were dissolved in a 9 mol / L lithium bromide solution at a material-liquid ratio of 10 g of silk fibroin fibers to 100 mL of lithium bromide solution. The solution was then heated to 60°C and stirred for 40 minutes. The solution was then allowed to cool to room temperature (22°C). The solution was then dialyzed in deionized water at 0°C for 72 hours using a dialysis bag with a molecular weight cutoff of 8 kDa to obtain a self-assembled silk fibroin solution.

[0051] S3.2. Mix 1 part by mass of self-assembled silk fibroin solution with 80 parts by mass of NaOH solution, then add 1 part by mass of carboxyl-grafted biochar, and magnetically stir in a microwave reactor for 30 minutes. The power of the microwave reactor is 400 W, and the magnetic stirring speed is 350 r / min. Then filter to remove the liquid, wash with 0.1 mol / L NaOH solution three times, and then wash with deionized water until neutral, and dry at 65°C to obtain self-assembled silk fibroin modified carboxyl biochar.

[0052] S4, preparing a plant curing solution containing plant-derived wood vinegar:

[0053] S4.1. Soaking the self-assembled silk fibroin-modified carboxyl biochar in wood vinegar for 24 h at a material-to-liquid ratio of 1 g of wood vinegar to 10 mL of self-assembled silk fibroin-modified carboxyl biochar to obtain a suspension;

[0054] S4.2. Dissolve 1 part by volume of sodium alginate in 20 parts by volume of deionized water preheated to 50°C, add 3 parts by volume of the suspension, sonicate for 10 minutes, adjust the pH value of the system to 6, and then add 50 times the total volume of water to dilute the system to obtain a plant care solution containing plant-derived wood vinegar.

[0055] Example 2:

[0056] A method for preparing a plant curing liquid containing plant-derived wood vinegar, such as Figure 1 As shown, the following steps are included:

[0057] S1. Preparation of activated biochar:

[0058] Cut rice straw into 5-6 cm segments, wash with deionized water, and place in an oven to dry at 60°C for 24 hours. The dried material is crushed in a powder grinder to obtain straw powder. The straw powder is placed in a ceramic cochlea, compacted, covered, and placed in a muffle furnace that has been purged of nitrogen to remove all air. Carbonize at 500°C for 2 hours in anoxic conditions, cool to room temperature, and then remove to obtain biochar.

[0059] Weigh 3 parts by mass of zinc chloride and 25 parts by mass of deionized water, stir until uniformly mixed, then add 2 parts by mass of biochar, let it stand for 2 hours, then heat to 105°C, evaporate the water for 15 minutes, and then calcine in a tube furnace at 600°C under a nitrogen atmosphere for 2 hours, cool to room temperature 22°C with the furnace, then add 35 parts by mass of deionized water, boil for 2 hours to remove water, and dry the solid product in an oven at 110°C to constant weight to obtain activated biochar.

[0060] S2, 4,4'-(hexafluoroisopropylene) diphthalic anhydride grafted modified activated biochar:

[0061] 50 parts by mass of 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 120 parts by mass of N,N-dimethylformamide were added to a reaction bottle and mixed evenly, and then 5 parts by mass of activated biochar were added and microwave-treated for 10 minutes. After being taken out, the temperature was raised to 50°C and stirred at a speed of 350 r / min for 10 minutes. The reaction product was filtered and the solid matter was vacuum-dried at 60°C to obtain carboxyl-grafted biochar.

[0062] S3. Preparation of self-assembled silk fibroin modified carboxyl biochar:

[0063] S3.1. Soak the silk in a papain solution at a material-liquid ratio of 1 g:45 mL, with a mass concentration of 3 g / L and a pH of 6. Treat in an 80°C water bath for 1 h, wash and pull, and then dry at 60°C to obtain a primary degumming intermediate.

[0064] The primary degumming intermediate was immersed in 8 mol / L urea solution, with the material-liquid ratio of the primary degumming intermediate to the urea solution being 1 g:30 mL, and treated in a 90°C water bath for 3 h. After washing, the secondary degumming intermediate was dried to a constant weight to obtain the secondary degumming intermediate.

[0065] The secondary degumming intermediate was mixed with sodium carbonate solution at a material-liquid ratio of 12 g:500 mL, with a sodium carbonate solution concentration of 0.5 g / L, boiled for 30 min, washed with deionized water, repeated three times, and dried to obtain silk fibroin fibers;

[0066] The silk fibroin fibers were dissolved in a 9 mol / L lithium bromide solution at a material-liquid ratio of 10 g of silk fibroin fibers to 100 mL of lithium bromide solution. The solution was then heated to 60°C and stirred for 40 minutes. The solution was then allowed to cool to room temperature (22°C). The solution was then dialyzed in deionized water at 0°C for 72 hours using a dialysis bag with a molecular weight cutoff of 8 kDa to obtain a self-assembled silk fibroin solution.

[0067] S3.2. Mix 3 parts by mass of self-assembled silk fibroin solution with 100 parts by mass of NaOH solution, then add 2 parts by mass of carboxyl-grafted biochar, and magnetically stir in a microwave reactor for 30 minutes. The power of the microwave reactor is 400 W, and the magnetic stirring speed is 350 r / min. Then filter to remove the liquid, wash with 0.1 mol / L NaOH solution three times, and then wash with deionized water until neutral, and dry at 65°C to obtain self-assembled silk fibroin modified carboxyl biochar.

[0068] S4, preparing a plant curing solution containing plant-derived wood vinegar:

[0069] S4.1. Soaking the self-assembled silk fibroin-modified carboxyl biochar in wood vinegar for 24 h at a material-to-liquid ratio of 1 g of wood vinegar to 20 mL of self-assembled silk fibroin-modified carboxyl biochar to obtain a suspension;

[0070] S4.2. Dissolve 5 parts by volume of sodium alginate in 30 parts by volume of deionized water preheated to 50°C, add 4 parts by volume of the suspension, sonicate for 10 minutes, adjust the pH value of the system to 6, and then add 80 times the total volume of water to dilute the system to obtain a plant care solution containing plant-derived wood vinegar.

[0071] Example 3:

[0072] A method for preparing a plant curing liquid containing plant-derived wood vinegar, such as Figure 1 As shown, the following steps are included:

[0073] S1. Preparation of activated biochar:

[0074] Cut rice straw into 5-6 cm segments, wash with deionized water, and place in an oven to dry at 60°C for 24 hours. The dried material is crushed in a powder grinder to obtain straw powder. The straw powder is placed in a ceramic cochlea, compacted, covered, and placed in a muffle furnace that has been purged of nitrogen to remove all air. Carbonize at 500°C for 2 hours in anoxic conditions, cool to room temperature, and then remove to obtain biochar.

[0075] Weigh 1 part by mass of zinc chloride and 20 parts by mass of deionized water, stir until uniformly mixed, then add 2 parts by mass of biochar, let it stand for 3 hours, then heat to 110°C, evaporate the water for 20 minutes, and then calcine in a tube furnace at 800°C under a nitrogen atmosphere for 3 hours, cool to room temperature 22°C with the furnace, then add 30 parts by mass of deionized water, boil for 3 hours to remove water, and dry the solid product in an oven at 120°C to constant weight to obtain activated biochar.

[0076] S2, 4,4'-(hexafluoroisopropylene) diphthalic anhydride grafted modified activated biochar:

[0077] 50 parts by mass of 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 100 parts by mass of N,N-dimethylformamide were added to a reaction bottle and mixed evenly, and then 1 part by mass of activated biochar was added. The mixture was microwave-treated for 10 minutes, taken out, heated to 55°C, and stirred at a speed of 400 r / min for 20 minutes. The reaction product was filtered, and the solid matter was vacuum-dried at 60°C to obtain carboxyl-grafted biochar.

[0078] S3. Preparation of self-assembled silk fibroin modified carboxyl biochar:

[0079] S3.1. Soak the silk in a papain solution at a material-liquid ratio of 1 g:50 mL, with a mass concentration of 3.2 g / L and a pH of 6. Treat in an 85°C water bath for 1.5 h, wash and pull, and then dry at 65°C to obtain a primary degumming intermediate.

[0080] The primary degumming intermediate was immersed in 8.5 mol / L urea solution at a material-liquid ratio of 1 g of the primary degumming intermediate to the urea solution of 40 mL, and treated in a 95°C water bath for 4 h. After washing, the secondary degumming intermediate was dried to a constant weight.

[0081] The secondary degumming intermediate was mixed with sodium carbonate solution at a material-liquid ratio of 12 g:550 mL, with a sodium carbonate solution concentration of 0.6 g / L, boiled for 35 min, washed with deionized water, repeated three times, and dried to obtain silk fibroin fibers;

[0082] The silk fibroin fibers were dissolved in a 9 mol / L lithium bromide solution at a material-liquid ratio of 10 g of silk fibroin fibers to 100 mL of lithium bromide solution. The solution was then heated to 60°C and stirred for 40 minutes. The solution was then allowed to cool to room temperature (22°C). The solution was then dialyzed in deionized water at 0°C for 72 hours using a dialysis bag with a molecular weight cutoff of 8 kDa to obtain a self-assembled silk fibroin solution.

[0083] S3.2. Mix 1 part by mass of self-assembled silk fibroin solution with 80 parts by mass of NaOH solution, then add 1 part by mass of carboxyl-grafted biochar, and magnetically stir in a microwave reactor for 30 minutes. The power of the microwave reactor is 400 W, and the magnetic stirring speed is 350 r / min. Then filter to remove the liquid, wash with 0.1 mol / L NaOH solution three times, and then wash with deionized water until neutral, and dry at 65°C to obtain self-assembled silk fibroin modified carboxyl biochar.

[0084] S4, preparing a plant curing solution containing plant-derived wood vinegar:

[0085] S4.1. Soaking the self-assembled silk fibroin-modified carboxyl biochar in wood vinegar for 26 h, with a material-liquid ratio of wood vinegar to self-assembled silk fibroin-modified carboxyl biochar of 1 g:10 mL, to obtain a suspension;

[0086] S4.2. Dissolve 1 part by volume of sodium alginate in 20 parts by volume of deionized water preheated to 60°C, add 3 parts by volume of the suspension, sonicate for 15 minutes, adjust the pH value of the system to 7, and then add 50 times the total volume of water to dilute the system to obtain a plant care solution containing plant-derived wood vinegar.

[0087] Comparative Example 1:

[0088] Compared with Example 1, the difference of Comparative Example 1 is that step S2 is not performed, and biochar is used to replace the carboxyl-grafted biochar in step S3.2, specifically "S3.2, 1 part by mass of self-assembled silk fibroin solution is mixed with 80 parts by mass of NaOH solution, and then 1 part by mass of biochar is added, and magnetic stirring is carried out in a microwave reactor for 30 minutes. The power of the microwave reactor is 400 W, and the magnetic stirring speed is 350 r / min. Then, the liquid is filtered to remove, and the mixture is washed three times with 0.1 mol / L NaOH solution, and then washed with deionized water until neutral, and dried at 65°C to obtain self-assembled silk fibroin modified biochar". In the subsequent steps, self-assembled silk fibroin modified biochar is used instead of self-assembled silk fibroin modified carboxyl biochar, and the other steps remain unchanged. The obtained plant curing solution containing plant-derived wood vinegar is recorded as Comparative Example 1.

[0089] Comparative Example 2:

[0090] Compared with Example 1, the difference of Comparative Example 2 is that step S3 is not performed, and in step S4.1, carboxyl-grafted biochar is used instead of self-assembled silk fibroin-modified carboxyl biochar, specifically "S4.1, soaking the carboxyl-grafted biochar in wood vinegar for 24 hours, the material-liquid ratio of wood vinegar to carboxyl-grafted biochar is 1 g:10 mL, and a suspension is obtained", and the other steps remain unchanged. The obtained plant curing solution containing plant-derived wood vinegar is recorded as Comparative Example 2.

[0091] Comparative Example 3:

[0092] Compared with Example 1, the difference of Comparative Example 3 is that in step S4.1, biochar is used instead of self-assembled silk fibroin modified carboxyl biochar, specifically "S4.1, soaking biochar in wood vinegar for 24 hours, the material-liquid ratio of wood vinegar to biochar is 1 g:10 mL, and a suspension is obtained", and the other steps remain unchanged. The obtained plant curing solution containing plant-derived wood vinegar is recorded as Comparative Example 3.

[0093] Comparative Example 4:

[0094] Compared with Example 1, the difference of Comparative Example 4 is that self-assembled silk fibroin-modified carboxyl biochar is not added in step S4. Specifically, "S4.1, dissolving 1 volume part of sodium alginate in 20 volume parts of deionized water preheated to 50°C in advance, adding 3 volume parts of wood vinegar, ultrasonicating for 10 minutes, adjusting the pH value of the system to 6, and then adding 50 times the total volume of water to dilute the system to obtain a plant curing solution containing plant-derived wood vinegar", and the other steps remain unchanged. The obtained plant curing solution containing plant-derived wood vinegar is recorded as Comparative Example 4.

[0095] Comparative Example 5:

[0096] Compared with Example 1, the difference of Comparative Example 5 is that sodium alginate is not added in step S4, specifically, "S4.1, soaking the self-assembled silk fibroin modified carboxyl biochar in wood vinegar for 24 hours, with the material-liquid ratio of wood vinegar to self-assembled silk fibroin modified carboxyl biochar being 1 g:10 mL, to obtain a suspension;

[0097] S4.2. Ultrasonicate the suspension for 10 minutes to adjust the pH value of the system to 6, and then dilute it with 50 times the total volume of water to obtain a plant curing solution containing plant-derived wood vinegar. The remaining steps remain unchanged, and the obtained plant curing solution containing plant-derived wood vinegar is recorded as Comparative Example 5.

[0098] Comparative Example 6:

[0099] Comparative Example 6 is a commercially available curing solution for plant seeds.

[0100] Chinese cabbage seeds were sown in 9 experimental plots of 3 m×8 m. After sowing, Examples 1-3 and Comparative Examples 1-6 were sprayed into the crop soil during the germination period. After the Chinese cabbage germinated, the survival rate of the Chinese cabbage was calculated, as shown in Table 1.

[0101] After the Chinese cabbage matures, collect and calculate its average yield (kg / m 2 ), as shown in Table 2.

[0102] Table 1

[0103]

[0104] Table 2

[0105]

[0106] As can be seen from Table 1, the survival rates in Examples 1-3 are above 97.3%, which are all higher than those in the comparative examples. Moreover, comparative example 6 is a commercially available plant seed curing solution. The survival rate of the plant curing solution prepared by the present invention after application is higher than that of the commercially available product, indicating that the present invention has a better effect of promoting plant growth and improving the survival rate.

[0107] As can be seen from Table 2, the output of Examples 1-3 is 2.39 kg / m 2 The above values ​​are all higher than those in the comparative example. It can be seen that the raw materials of the present invention can exert a synergistic effect after being treated by the present invention and applied, thereby promoting plant growth. Moreover, the promoting effect of the present invention on plant growth is better than that of the comparative example 6 of the commercially available product.

[0108] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention.

Claims

1. A method for preparing a plant curing liquid containing plant-derived wood vinegar, characterized in that: The steps include: S1: Preparation of activated biochar Weigh 1-3 parts by mass of zinc chloride and 20-25 parts by mass of deionized water, stir until uniformly mixed, then add 2-4 parts by mass of biochar, let stand for 2-3 hours, then heat to 105-110°C, evaporate the water for 15-20 minutes, then calcine in a tube furnace at 600-800°C under a nitrogen atmosphere for 2-3 hours, cool to room temperature 22-24°C with the furnace, then add 30-35 parts by mass of deionized water, boil for 2-3 hours to remove water, and dry the solid product in an oven at 110-120°C to constant weight to obtain activated biochar; S2: Activated biochar grafted with 4,4'-(hexafluoroisopropylene) diphthalic anhydride 50 parts by mass of 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 100-120 parts by mass of N,N-dimethylformamide were added to a reaction flask and mixed evenly, and then 1-5 parts by mass of activated biochar were added. The mixture was microwave-treated for 10-20 minutes, and then the mixture was taken out and heated to 50-55°C, stirred at a speed of 350-400 r / min for 10-20 minutes, the reaction product was filtered, and the solid matter was vacuum-dried at 60-65°C to obtain carboxyl-grafted biochar; S3: Preparation of self-assembled silk fibroin-modified carboxyl biochar The silk was immersed in a papain solution at a material-liquid ratio of 1 g: (45-50) mL, with a mass concentration of 3-3.2 g / L and a pH value of 6, and treated in a water bath at 80-85°C for 1-1.5 hours, washed and pulled, and then dried at 60-65°C to obtain a primary degumming intermediate; The primary degumming intermediate is immersed in 8-8.5 mol / L urea solution, with the material-liquid ratio of the primary degumming intermediate to the urea solution being 1 g: (30-40) mL, and treated in a 90-95°C water bath for 3-4 hours. After washing, the secondary degumming intermediate is dried to a constant weight to obtain the secondary degumming intermediate. The secondary degumming intermediate was mixed with sodium carbonate solution at a material-liquid ratio of 12 g: (500-550) mL, the concentration of the sodium carbonate solution was 0.5-0.6 g / L, boiled for 30-35 min, washed with deionized water, repeated three times, and dried to obtain silk fibroin fibers; The silk fibroin fibers were dissolved in a lithium bromide solution and stirred for reaction, followed by dialysis to obtain a self-assembled silk fibroin solution. The self-assembled silk fibroin solution was mixed with a NaOH solution, and carboxyl-grafted biochar was added. The mixture was magnetically stirred in a microwave reactor to obtain self-assembled silk fibroin-modified carboxyl biochar. S4: Preparation of plant care solution containing plant-derived wood vinegar S4.1: Soak the self-assembled silk fibroin-modified carboxylated biochar in wood vinegar for 24-26 hours, with a wood vinegar to self-assembled silk fibroin-modified carboxylated biochar material-to-liquid ratio of 1 g:(10-20) mL to obtain a suspension; S4.2: Dissolve 1-5 parts by volume of sodium alginate in 20-30 parts by volume of deionized water preheated to 50-60°C, add 3-4 parts by volume of the suspension, sonicate for 10-15 minutes, adjust the pH value of the system to 6-7, and then dilute with 50-80 times the total volume of water to obtain a plant care solution containing plant-derived wood vinegar.

2. The method for preparing a plant curing solution containing plant-derived wood vinegar according to claim 1, wherein: Step S3 is to prepare self-assembled silk fibroin modified carboxyl biochar, comprising the following steps: S3.1: Dissolve silk fibroin in 9-9.5 mol / L lithium bromide solution at a material-to-liquid ratio of 10 g silk fibroin to (100-120) mL lithium bromide solution. Heat to 60-65°C, stir, and react for 40-50 min. Allow to cool to room temperature (22-24°C). Then, dialyze in deionized water at 0-4°C for 72-75 h to obtain a self-assembled silk fibroin solution. S3.2: Mix 1-3 parts by mass of self-assembled silk fibroin solution with 80-100 parts by mass of NaOH solution, then add 1-2 parts by mass of carboxyl-grafted biochar, magnetically stir in a microwave reactor for 30-40 minutes, then filter to remove the liquid, wash with 0.1 mol / L NaOH solution 3-4 times, then wash with deionized water until neutral, and dry at 65-70°C to obtain self-assembled silk fibroin modified carboxyl biochar.

3. A method for preparing a plant curing solution containing plant-derived wood vinegar according to claim 2, wherein: The specific steps for preparing biochar are: Cut rice straw into small pieces, wash it with deionized water, put it into an oven, and dry it at 60-65℃ for 24-25 hours. The dried material is crushed in a powder grinder to obtain straw powder. The straw powder is placed in a ceramic crucible, compacted, covered, and placed in a muffle furnace that has been filled with nitrogen to exhaust the air in the furnace. It is carbonized in anoxic conditions at 500-700℃ for 2-3 hours, cooled to room temperature, and then taken out to obtain biochar.

4. The method for preparing a plant curing solution containing plant-derived wood vinegar according to claim 3, wherein: The molecular weight cut-off of the dialysis bag during dialysis is 8-14 kDa.

5. The method for preparing a plant curing liquid containing plant-derived wood vinegar according to claim 4, wherein: The power of the microwave reactor was 400 W, and the speed of the magnetic stirring was 350 r / min.

6. A plant care solution containing plant-derived wood vinegar, characterized in that: The plant curing liquid is prepared by the method for preparing the plant curing liquid containing plant-derived wood vinegar according to any one of claims 1 to 5.

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