Wood vinegar and fulvic acid mixed liquid fertilizer and preparation method thereof

Abstract

The invention relates to the field of fertilizers, in particular to a pyroligneous liquor and fulvic acid mixed liquid fertilizer and a preparation method thereof.The pyroligneous liquor and fulvic acid mixed liquid fertilizer is prepared from, by weight, 30-35% of pyroligneous liquor, 25-40% of fulvic acid, 4-6% of amino acid, 5-7% of modified activated carbon and the balance water. The wood vinegar and fulvic acid mixed liquid fertilizer prepared by the invention has good antibacterial performance, and can promote the growth of crops, so that the yield is increased.

Description

Technical Field

[0001] The invention relates to the field of fertilizers, and in particular to a wood vinegar and humic acid mixed liquid fertilizer and a preparation method thereof. Background Art

[0002] In order to increase the yield of crops, fertilizers can be applied to crops to increase yield and growth. However, traditional solid chemical fertilizers are slowly absorbed by plants and have low utilization rates. In order to increase yields, large amounts of fertilizers are needed, which may cause soil acidification and compaction, and even affect the planting of the next crop of plants. Liquid fertilizers can quickly penetrate into the soil and are more easily absorbed by crops, thereby increasing fertilizer utilization rates. Liquid fertilizers are quick and easy to use and are suitable for large areas of farmland.

[0003] Patent CN110105147B discloses a liquid fertilizer prepared from inorganic nutrients, organic nutrients, water and metronidazole, which can prevent the liquid fertilizer from swelling in the bottle, has stable quality and high utilization rate. However, the invention uses metronidazole, and if the residue time after use is too long, it will affect the next crop.

[0004] Patent CN108002924B discloses a cold-resistant microbial liquid fertilizer. The cold-resistant microbial liquid fertilizer obtained by adding alginic acid, low-temperature-resistant bacteria, and trace elements can effectively improve the cold resistance of crops, improve the root zone ecological environment of crops, and promote crop growth. However, metal elements are added in this invention, which may not only pollute the soil after repeated use, but also affect the photosynthesis of plants.

[0005] Wood vinegar contains rich organic acids, phenols, esters, and ketone compounds, which can improve the physical and chemical properties and biological activity of the soil. Fulvic acid contains humic acid. Mixing them can increase the plant's absorption rate of nutrients, regulate plant growth metabolism, accelerate plant growth and development, improve soil quality and enhance plant immunity, and promote plant growth, gradually becoming one of the important ingredients for preparing liquid fertilizers.

[0006] Therefore, there is an urgent need in the market for a mixed liquid fertilizer containing wood vinegar which has no residue after use, does not pollute the soil and can promote plant growth. Summary of the invention

[0007] In view of the problems existing in the prior art, the purpose of the present invention is to obtain a wood vinegar humic acid mixed liquid fertilizer which has high utilization rate, good antibacterial property, no residue after use and no pollution to the soil.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] On one hand, the present invention provides a wood vinegar and fulvic acid mixed liquid fertilizer, which comprises the following raw materials, calculated by weight percentage of 100%, 30-35% of wood vinegar, 25-40% of fulvic acid, 4-6% of amino acid, 5-7% of modified activated carbon, and the balance is water.

[0010] In some embodiments, the amino acids are a combination of alanine, arginine, glycine, and lysine in a mass ratio of 1:(1-1.3):(0.5-1):(1.3-1.7).

[0011] In some embodiments, the preparation method of the modified activated carbon comprises the following steps: adding activated carbon and a silane coupling agent to ethanol, reacting at 50-60° C. for 5-6 hours, then adding potassium hydrogen phthalate and tetrahydrofuran, stirring at room temperature for 10-12 hours, filtering, and drying to obtain modified activated carbon.

[0012] Preferably, the silane coupling agent is distearoylphosphatidylethanolamine modified silane.

[0013] In some embodiments, the mass ratio of the activated carbon to potassium hydrogen phthalate is 1:(0.5-0.8).

[0014] The particle size of activated carbon is small, and there is a strong hydrogen bond between molecules, which makes it unstable in solution, with poor suspension and easy sedimentation. The present invention improves the dispersibility of activated carbon in water by modifying activated carbon. The obtained liquid fertilizer has uniform active ingredients, and the pipeline will not be blocked when used in drip irrigation. On the other hand, activated carbon has good affinity and good adsorption capacity for other active ingredients in fertilizer, making the prepared liquid fertilizer easier to absorb. In addition, activated carbon has a porous structure, which fixes some active ingredients in the pores, has a certain slow release effect, can improve the utilization rate of fertilizer, and can reduce the volatilization of wood vinegar, further improving the utilization rate of fertilizer; in addition, a silane coupling agent containing phosphorus is specifically used, and phosphorus is an important component of plant nuclear protein, phospholipids, and nucleic acids. It directly participates in fat and protein metabolism and plays a significant promoting role, enhances root development, and is conducive to reducing the maturity cycle of plants; in addition, potassium is added to regulate plant transpiration and maintain a certain water balance. The mass ratio of activated carbon to potassium hydrogen phthalate is limited to provide part of the potassium element for plants while avoiding the difficulty of fertilizer degradation due to the addition of benzene ring structure.

[0015] In some embodiments, the wood vinegar humic acid mixed liquid fertilizer further comprises 5-8% of modified glucose.

[0016] In some embodiments, the method for preparing the modified glucose comprises the following steps:

[0017] (1) Add benzofuran, trimethyl orthoformate and acetic anhydride to a reaction vessel, react at 108-115° C. for 22-24 hours, extract, and rotary evaporate to obtain a crude product. Dissolve the crude product in methanol at 70-80° C., heat under reflux for 20-40 minutes, cool to 0-5° C., filter, wash with ice methanol, and dry to obtain compound A;

[0018] (2) Compound A obtained in step (1) and sodium methoxide are added to a solvent, stirred at room temperature for 2.5-3.5 hours, cooled to -20 to -10°C, and then 2,5-dichlorothiazole and triethylenetetramine are added, stirred for 4.5-5.5 hours, extracted, and then purified by column chromatography to obtain compound B;

[0019] (3) Compound B obtained in step (2) and KHSO 4 Add to DMF, react at 143-148°C for 5-6h, cool to room temperature, add toluene, filter, wash, and recrystallize to obtain compound C;

[0020] (4) Dissolve the compound C obtained in step (3), glucose and 4-dimethylaminopyridine in dichloromethane, stir at 25-35° C. for 12-15 hours, extract, combine and collect the organic phases, rotary evaporate and dry to obtain modified glucose.

[0021] Glucose, as an organic substance, can be converted into humic acid under the action of soil microorganisms, thereby enhancing soil fertility and promoting the growth of crops. However, it can also provide nutrition for bacteria and may cause harm to plants. The present invention modifies glucose and uses it in liquid fertilizer, which not only has good antibacterial properties but also promotes the growth and development of crops. On the one hand, a possible reason is that it provides sulfur and nitrogen elements for crops, which can improve plant photosynthesis, promote plant root growth, and improve the yield and quality of plant crops; on the other hand, it may be due to the structure of methoxyacrylate, which has a certain inhibitory effect on harmful pathogens and improves the yield of crops.

[0022] In some embodiments, the mass ratio of benzofuran to trimethyl orthoformate in step (1) is 1:(11-12).

[0023] In some embodiments, the mass ratio of compound A, sodium methoxide, and 2,5-dichlorothiazole in step (2) is 1:(0.3-0.4):(0.9-1.1).

[0024] The present invention limits the mass ratio of benzofuran and trimethyl orthoformate so that benzofuran can react completely without consuming a large amount of trimethyl orthoformate, thereby saving costs. In addition, limiting the mass ratio of compound A, sodium methoxide and 2,5-dichlorothiazole can avoid the danger caused by excessively violent reactions on the one hand, and avoid excessive generation of impurities to affect the antibacterial property on the other hand.

[0025] In some embodiments, the mass ratio of compound C to glucose in step (4) is 1:(5-6.5).

[0026] The invention limits the mass ratio of compound C to glucose so that the modified glucose has certain antibacterial properties without affecting the dispersibility of glucose in water and the activity of microorganisms in soil, so that the glucose can still be effectively utilized by plants.

[0027] Another aspect of the present invention provides a method for preparing a wood vinegar humic acid mixed liquid fertilizer, comprising the following steps:

[0028] S1. Stir wood vinegar, fulvic acid, modified activated carbon and water at 40-50° C. for 1-2 hours to obtain a mixed solution;

[0029] S2. Add amino acids and modified glucose to the mixed solution obtained in step S1, and stir at room temperature for 10-20 minutes to obtain wood vinegar humic acid mixed liquid fertilizer.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The present invention obtains a wood vinegar humic acid mixed liquid fertilizer with high utilization rate, good antibacterial property, no residue after use, and suitable for various soils by adding amino acids and modified activated carbon.

[0032] (2) The present invention improves the dispersibility of activated carbon in water by modifying activated carbon. The obtained liquid fertilizer has uniform effective ingredients and will not clog the pipe when used in drip irrigation. On the other hand, the activated carbon has good affinity and good adsorption capacity for other effective ingredients in the fertilizer, making the prepared liquid fertilizer easier to absorb. In addition, the activated carbon has a porous structure, which fixes some effective ingredients in the pores and has a certain slow-release effect, which can improve the utilization rate of the fertilizer. In addition, it can reduce the volatilization of wood vinegar and further improve the utilization rate of the fertilizer.

[0033] (3) The specific use of phosphorus-containing silane coupling agents in the present invention can enhance root development, which is beneficial to shortening the maturity period of plants; in addition, potassium is added to participate in regulating plant transpiration and maintain a certain water balance. The mass ratio of activated carbon to potassium hydrogen phthalate is limited to provide plants with some potassium elements while avoiding the problem of fertilizer being difficult to degrade due to the addition of benzene ring structure.

[0034] (4) The present invention adds modified glucose, which is used in liquid fertilizer and not only has good antibacterial properties, but also promotes the growth and development of crops, thereby increasing the yield and quality of plant crops; in addition, due to the structure of methoxyacrylate, it has a certain inhibitory effect on harmful pathogens, thereby increasing the yield of crops. DETAILED DESCRIPTION

[0035] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0036] In the following examples and comparative examples, the compounds and related reagents used can be purchased from the market, wherein distearoylphosphatidylethanolamine modified silane was purchased from Xi'an Ruixi Biotechnology Co., Ltd.; activated carbon was purchased from Shanghai Hainuo Carbon Co., Ltd. with a particle size of 200 nm, and wood vinegar was extracted by our company.

[0037] Preparation Example 1

[0038] The preparation method of modified activated carbon-1 comprises the following steps: adding 1 g of activated carbon and 0.6 g of distearoylphosphatidylethanolamine-modified silane to 30 ml of anhydrous ethanol, reacting at 55° C. for 5.5 h, then adding 0.7 g of potassium hydrogen phthalate and 20 ml of anhydrous tetrahydrofuran, stirring at room temperature for 11 h, filtering and drying to obtain modified activated carbon-1.

[0039] Preparation Example 2

[0040] The preparation method of modified activated carbon-2 is the same as that of Preparation Example 1, except that the amount of potassium hydrogen phthalate added is 1 g.

[0041] Preparation Example 3

[0042] The preparation method of modified glucose-1 comprises the following steps:

[0043] (1) 1 g of benzofuran, 11.5 g of trimethyl orthoformate, and 3.5 g of acetic anhydride were added to a reaction vessel, reacted at 110° C. for 23 h, extracted, and rotary evaporated to obtain a crude product. The crude product was dissolved in 30 ml of anhydrous methanol at 75° C., heated under reflux for 30 min, cooled to 3° C., filtered, washed with 5° C. ice methanol, and dried to obtain compound A;

[0044] (2) Add 1 g of compound A obtained in step (1) and 0.37 g of sodium methoxide to 30 ml of toluene, stir at room temperature for 3 h, cool to -15°C, add 1 g of 2,5-dichlorothiazole and 0.2 g of triethylenetetramine, stir for 5 h, extract, and then purify by column chromatography to obtain compound B;

[0045] (3) 1 g of compound B obtained in step (2) and 1 g of KHSO 4Add 50 ml of DMF, react at 145°C for 5.5 h, cool to room temperature, add 100 ml of toluene, filter, wash, and recrystallize with 30 ml of anhydrous methanol to obtain compound C;

[0046] (4) Dissolve 1 g of compound C obtained in step (3), 6 g of glucose, and 0.4 g of 4-dimethylaminopyridine in 30 ml of dichloromethane, stir at 30° C. for 13 h, extract, combine and collect the organic phases, rotary evaporate, and dry to obtain modified glucose-1.

[0047] Preparation Example 4

[0048] The preparation method of modified glucose-2 is the same as that of Preparation Example 4, except that the amount of trimethyl orthoformate added is 10 g.

[0049] Preparation Example 5

[0050] The preparation method of modified glucose-3 is the same as that of Preparation Example 4, except that the amount of sodium methoxide added is 0.5 g.

[0051] Preparation Example 6

[0052] The preparation method of modified glucose-4 is the same as that of Preparation Example 4, except that the amount of 2,5-dichlorothiazole added is 1.3 g.

[0053] Preparation Example 7

[0054] The preparation method of modified glucose-5 is the same as that of Preparation Example 4, except that the amount of glucose added is 4 g.

[0055] Example 1

[0056] A wood vinegar and humic acid mixed liquid fertilizer comprises the following raw materials, calculated by weight percentage of 100%, including 33% wood vinegar, 35% humic acid, 5% amino acid, 6% modified activated carbon-1, and 21% water; the amino acids are a combination of alanine, arginine, glycine, and lysine, and the mass ratio is 1:1.2:0.7:1.5.

[0057] The preparation method of wood vinegar humic acid mixed liquid fertilizer of this embodiment comprises the following steps:

[0058] S1, stirring wood vinegar, fulvic acid, modified activated carbon-1 and water at 45° C. for 1.5 h to obtain a mixed solution;

[0059] S2. Add amino acids to the mixed solution obtained in step S1 and stir at room temperature for 15 minutes to obtain wood vinegar humic acid mixed liquid fertilizer.

[0060] Example 2

[0061] A wood vinegar and humic acid mixed liquid fertilizer comprises the following raw materials, calculated by weight percentage of 100%, including 30% wood vinegar, 25% humic acid, 4% amino acid, 5% modified activated carbon-1, and 36% water; the amino acids are a combination of alanine, arginine, glycine, and lysine, and the mass ratio is 1:1:0.5:1.3.

[0062] The preparation method of wood vinegar humic acid mixed liquid fertilizer of this embodiment comprises the following steps:

[0063] S1, stirring wood vinegar, fulvic acid, modified activated carbon-1 and water at 40° C. for 2 h to obtain a mixed solution;

[0064] S2. Add amino acids to the mixed solution obtained in step S1 and stir at room temperature for 10 min to obtain wood vinegar humic acid mixed liquid fertilizer.

[0065] Example 3

[0066] A wood vinegar and humic acid mixed liquid fertilizer comprises the following raw materials, calculated by weight percentage of 100%, including 35% wood vinegar, 40% humic acid, 6% amino acid, 7% modified activated carbon-1, and 12% water; the amino acids are a combination of alanine, arginine, glycine, and lysine, and the mass ratio is 1:1.3:1:1.7.

[0067] The preparation method of wood vinegar humic acid mixed liquid fertilizer of this embodiment comprises the following steps:

[0068] S1, stirring wood vinegar, fulvic acid, modified activated carbon-1 and water at 50° C. for 1 h to obtain a mixed solution;

[0069] S2. Add amino acids to the mixed solution obtained in step S1 and stir at room temperature for 20 minutes to obtain wood vinegar humic acid mixed liquid fertilizer.

[0070] Example 4

[0071] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of modified activated carbon-1 is replaced by modified activated carbon-2.

[0072] Example 5

[0073] A wood vinegar and humic acid mixed liquid fertilizer comprises the following raw materials, calculated by weight percentage of 100%, including 33% wood vinegar, 35% humic acid, 5% amino acid, 6% modified activated carbon-1, 7% modified glucose-1, and 14% water; the amino acids are a combination of alanine, arginine, glycine, and lysine, and the mass ratio is 1:1.2:0.7:1.5.

[0074] The preparation method of wood vinegar humic acid mixed liquid fertilizer of this embodiment comprises the following steps:

[0075] S1, stirring wood vinegar, fulvic acid, modified activated carbon-1 and water at 45° C. for 1.5 h to obtain a mixed solution;

[0076] S2. Add amino acids and modified glucose-1 to the mixed solution obtained in step S1 and stir at room temperature for 15 minutes to obtain wood vinegar humic acid mixed liquid fertilizer.

[0077] Example 6

[0078] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof. The specific implementation method is the same as that of Example 5, except that an equal amount of modified glucose-1 is replaced by modified glucose-2.

[0079] Example 7

[0080] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof. The specific implementation method is the same as that of Example 5, except that an equal amount of modified glucose-1 is replaced by modified glucose-3.

[0081] Example 8

[0082] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof. The specific implementation method is the same as that of Example 5, except that an equal amount of modified glucose-1 is replaced by modified glucose-4.

[0083] Example 9

[0084] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof. The specific implementation method is the same as that of Example 5, except that an equal amount of modified glucose-1 is replaced by modified glucose-5.

[0085] Example 10

[0086] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 5, except that an equal amount of modified glucose-1 is replaced by glucose.

[0087] Comparative Example 1

[0088] A wood vinegar humic acid mixed liquid fertilizer and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 5, except that an equal amount of modified activated carbon-1 is replaced by activated carbon.

[0089] Performance Testing

[0090] 1. Stability

[0091] Take 200 ml of the liquid fertilizer prepared in each example and comparative example, let it stand for 3 months, and observe whether it settles.

[0092] 2. Field trials

[0093] Experimental area: Aksu, Xinjiang; Variety: Junzao;

[0094] The liquid fertilizer prepared in the above embodiments and comparative examples was diluted with water to obtain a dilution, the mass ratio of liquid fertilizer to water was 1:950, and the roots of the jujube trees were fertilized during the initial flowering period, young fruit period and nucleation period. 1000 g of the dilution was applied per mu of land. At harvest time, 3 points were randomly arranged, 10 jujube trees were randomly selected, the number of jujubes per plant, the weight of single fruit, the yield per plant and the yield were measured, and the average value was taken.

[0095] The test results are shown in Table 1.

[0096] Table 1

[0097]

[0098] By comparing the experimental data of Examples 1-3 in Table 1, it can be seen that the wood vinegar humic acid mixed liquid fertilizer can make Jun jujube have a higher yield and higher stability; compared with Example 1, Example 4 shows that the change in the ratio of potassium hydrogen phthalate to activated carbon in modified activated carbon-2 may lead to a decrease in dispersibility, soil agglomeration, and a decrease in yield; compared with Example 1, Example 5 shows that the addition of modified glucose increases soil fertility and further increases the yield; compared with Example 1, Examples 6, 7, and 8 show that the ratio of benzofuran to trimethyl orthoformate and the compound A. Changing the ratio of sodium methoxide to 2,5-dichlorothiazole may result in more impurities in the prepared modified glucose, and the yield may decrease to a certain extent; comparing Example 9 with Example 5, it can be seen that the change in the ratio of compound C to glucose in modified glucose 5 may lead to a decrease in microbial activity in the soil and a decrease in yield; comparing Example 10 with Example 1, it can be seen that glucose may increase the activity of bacteria, resulting in a decrease in antibacterial activity and a decrease in yield; comparing Example 5 with Comparative Example 1, it can be seen that the fertilizer cannot be evenly absorbed due to the poor dispersibility of activated carbon, resulting in a decrease in yield.

[0099] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A wood vinegar humic acid mixed liquid fertilizer, characterized in that: The invention comprises the following raw materials in 100% by weight: 30-35% of wood vinegar, 25-40% of fulvic acid, 4-6% of amino acid, 5-7% of modified activated carbon, and the balance of water.

2. The wood vinegar humic acid mixed liquid fertilizer according to claim 1, characterized in that: The amino acids are a combination of alanine, arginine, glycine and lysine, with a mass ratio of 1:(1-1.3):(0.5-1):(1.3-1.7).

3. The wood vinegar humic acid mixed liquid fertilizer according to claim 1, characterized in that: The preparation method of modified activated carbon comprises the following steps: adding activated carbon and a silane coupling agent into ethanol, reacting at 50-60° C. for 5-6 hours, then adding potassium hydrogen phthalate and tetrahydrofuran, stirring at room temperature for 10-12 hours, filtering and drying to obtain modified activated carbon.

4. The wood vinegar humic acid mixed liquid fertilizer according to claim 3, characterized in that: The mass ratio of the activated carbon to potassium hydrogen phthalate is 1:(0.5-0.8).

5. The wood vinegar humic acid mixed liquid fertilizer according to claim 1, characterized in that: The wood vinegar humic acid mixed liquid fertilizer also includes 5-8% of modified glucose.

6. The wood vinegar humic acid mixed liquid fertilizer according to claim 5, wherein the preparation method of the modified glucose comprises the following steps: (1) Add benzofuran, trimethyl orthoformate and acetic anhydride to a reaction vessel, react at 108-115° C. for 22-24 hours, extract, and rotary evaporate to obtain a crude product. Dissolve the crude product in methanol at 70-80° C., heat under reflux for 20-40 minutes, cool to 0-5° C., filter, wash with ice methanol, and dry to obtain compound A; (2) Compound A obtained in step (1) and sodium methoxide are added to a solvent, stirred at room temperature for 2.5-3.5 hours, cooled to -20 to -10°C, and then 2,5-dichlorothiazole and triethylenetetramine are added, stirred for 4.5-5.5 hours, extracted, and then purified by column chromatography to obtain compound B; (3) Compound B obtained in step (2) and KHSO4 are added to DMF, reacted at 143-148° C. for 5-6 hours, cooled to room temperature, added with toluene, filtered, washed, and recrystallized to obtain compound C; (4) Dissolve the compound C obtained in step (3), glucose and 4-dimethylaminopyridine in dichloromethane, stir at 25-35° C. for 12-15 hours, extract, combine and collect the organic phases, rotary evaporate and dry to obtain modified glucose.

7. The wood vinegar humic acid mixed liquid fertilizer according to claim 6, characterized in that: In the step (1), the mass ratio of benzofuran to trimethyl orthoformate is 1:(11-12).

8. The wood vinegar humic acid mixed liquid fertilizer according to claim 6, characterized in that: In the step (2), the mass ratio of compound A, sodium methoxide and 2,5-dichlorothiazole is 1:(0.3-0.4):(0.9-1.1).

9. The wood vinegar humic acid mixed liquid fertilizer according to claim 6, characterized in that: In the step (4), the mass ratio of compound C to glucose is 1:(5-6.5).

10. A method for preparing the wood vinegar humic acid mixed liquid fertilizer according to any one of claims 5 to 9, characterized in that: The following steps are involved: S1. Stir wood vinegar, fulvic acid, modified activated carbon and water at 40-50° C. for 1-2 hours to obtain a mixed solution; S2. Add amino acids and modified glucose to the mixed solution obtained in step S1, and stir at room temperature for 10-20 minutes to obtain wood vinegar humic acid mixed liquid fertilizer.

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