阅读说明：本技术 一种阳离子化腐殖酸及其制备方法和应用 (Cationized humic acid and preparation method and application thereof ) 是由 王晨 邱冠钧 牛育华 秋列维 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种阳离子化腐殖酸及其制备方法和应用,包括以下步骤制备：在反应瓶中加入N,N二甲基-1,3-丙二胺,再向其中加入10.0wt.％腐植酸和1wt.％的对甲苯磺酸,在130℃反应7h；反应结束后沉降离心,沉淀物多次洗涤离心,真空干燥至恒重便得阳离子化腐殖酸,将该阳离子化腐殖酸按一定质量比添加到普通磷肥肥料液中,对于作物进行喷洒。本发明通过阳离子化腐殖酸对普通磷肥进行改良,解决了磷肥中过磷酸钙容易被固定,移动速率慢等缺点,为作物提供发育的N、P等营养物质,其中腐殖酸可以提高作物的抗菌性,改良土壤结构、利于土壤团粒结构的形成等优点,可作为一种速效肥料应用。(The invention discloses cationized humic acid and a preparation method and application thereof, and the cationized humic acid comprises the following steps: adding N, N dimethyl-1, 3-propane diamine into a reaction bottle, adding 10.0 wt.% humic acid and 1 wt.% p-toluenesulfonic acid, and reacting at 130 ℃ for 7 h; and (3) after the reaction is finished, settling and centrifuging, washing and centrifuging the precipitate for multiple times, drying in vacuum until the weight is constant to obtain cationized humic acid, adding the cationized humic acid into common phosphorus fertilizer liquid according to a certain mass ratio, and spraying crops. The invention improves the common phosphate fertilizer by the cationized humic acid, solves the defects of easy fixation, slow moving speed and the like of calcium superphosphate in the phosphate fertilizer, provides developed N, P and other nutrient substances for crops, has the advantages of improving the antibacterial property of the crops, improving the soil structure, facilitating the formation of the soil aggregate structure and the like, and can be applied as a quick-acting fertilizer.)

1. A cationized humic acid characterized by the following structural formula:

2. the preparation method of the cationized humic acid is characterized by comprising the following steps of:

adding 8-12 wt.% humic acid and 0.8-1.2 wt.% p-toluenesulfonic acid into N, N dimethyl-1, 3-propane diamine, and fully reacting at 120-140 ℃; and (3) after the reaction is finished, settling and centrifuging, washing and centrifuging the precipitate for multiple times, and drying in vacuum to constant weight to obtain the cationized humic acid.

3. The process for the preparation of cationized humic acid according to claim 2 wherein: in the reaction, the humic acid is obtained by alkali-dissolving and acid-extracting lignite.

4. The process for the preparation of cationized humic acid according to claim 2 wherein: and reacting for 6-8 h in the reaction.

5. Use of cationized humic acid as fertilizer according to claim 1 as additive of phosphate fertilizer.

6. Use according to claim 5, characterized in that: the application method comprises the following steps:

dissolving a phosphate fertilizer in water, adjusting the pH to 5-6 by using phosphoric acid, and adding 2-10% of cationized humic acid according to the mass percentage to obtain improved phosphorus fertilizer liquid with the cationized humic acid fertilizer, which is used for directly spraying crops.

7. Use according to claim 6, characterized in that: the cationized humic acid fertilizer has the following structural formula:

Technical Field

The invention relates to the technical field of humic acid utilization, and particularly relates to cationized humic acid and a preparation method and application thereof.

Background

Water-soluble fertilizers are used as novel fertilizers and are increasingly widely applied to agricultural production. Compared with the traditional fertilizer, the water-soluble fertilizer has the characteristics of high nutrient content, good water solubility, wide practicability and the like. More and more attention is paid to the humic acid-containing water-soluble fertilizer.

Disclosure of Invention

The invention provides cationized humic acid and a preparation method and application thereof, and aims to provide a humic acid-containing water-soluble fertilizer with better antibacterial and fertilizer effects.

In order to achieve the purpose, the invention adopts the following technical scheme:

a cationized humic acid having the formula:

a preparation method of cationized humic acid comprises the following steps:

adding 8-12 wt.% humic acid and 0.8-1.2 wt.% p-toluenesulfonic acid into N, N dimethyl-1, 3-propane diamine, and fully reacting at 120-140 ℃; and (3) after the reaction is finished, settling and centrifuging, washing and centrifuging the precipitate for multiple times, and drying in vacuum to constant weight to obtain the cationized humic acid.

The humic acid is obtained by alkali-dissolving and acid-extracting lignite.

And reacting for 6-8 h in the reaction.

The cationized humic acid is applied as a fertilizer and is used as an additive of a phosphate fertilizer.

The using method comprises the following steps:

dissolving a phosphate fertilizer in water, adjusting the pH to 5-6 by using phosphoric acid, and adding 2-10% of cationized humic acid according to claim 1 by mass percent to obtain an improved phosphate fertilizer liquid with cationized humic acid fertilizer for directly spraying crops.

The cationized humic acid fertilizer has the following structural formula:

the preparation method of the cationized humic acid comprises the following synthesis equation:

a cationized humic acid fertilizer has the following synthesis equation:

compared with the prior art, the invention has the following advantages:

the cationized humic acid can be applied to common water-soluble phosphate fertilizers, overcomes the defects that calcium superphosphate in the phosphate fertilizers is easy to fix and slow in moving speed, provides developed N, P and other nutrient substances for crops, has the advantages of improving the antibacterial property of the crops, improving the soil structure, facilitating the formation of soil aggregate structure and the like, and can be applied as a quick-acting fertilizer.

According to the invention, humic acid is dispersed in N, N dimethyl-1, 3-propane diamine for reaction, reactants are two phases, the preparation and separation are simple, and the cationized humic acid capable of improving the antibacterial property and the fertilizer efficiency of crops is obtained. The cationized humic acid is added into a water-soluble phosphate fertilizer with the pH value of 5-6, a complex of the cationized humic acid and a dihydrogen phosphate radical can be formed in water, the defects that ordinary phosphate fertilizer calcium superphosphate is easily fixed and the like can be overcome, after fertilization, the cationized humic acid is decomposed in soil and can supplement N, P elements to the soil, the salicylic acid structure and the phenol structure in humic acid can improve the antibacterial property of crops, and the humic acid can act on the soil to improve the soil structure and promote the formation of a soil aggregate structure, so that the cationized humic acid can be used as an additive of a new phosphate fertilizer.

The invention improves the common phosphate fertilizer by the cationized humic acid, solves the defects of easy fixation, slow moving speed and the like of calcium superphosphate in the phosphate fertilizer, provides developed N, P and other nutrient substances for crops, has the advantages of improving the antibacterial property of the crops, improving the soil structure, facilitating the formation of the soil aggregate structure and the like, and can be applied as a quick-acting fertilizer.

Drawings

FIG. 1 is a schematic diagram showing the synthesis of cationized humic acid;

FIG. 2 is a diagram of the synthesis scheme of the application of cationized humic acid in fertilizer;

FIG. 3 is a test of the bacteriostasis of downy mildew by adding the cationized humic acid fertilizer liquid.

Fig. 4 is a graph showing the influence of the cationized humic acid fertilizer liquid and the non-cationized humic acid fertilizer liquid on the growth length of bean sprouts.

Detailed Description

The invention relates to cationized humic acid, which is prepared by the following specific steps:

the reaction equation for cationized humic acid added into common phosphate fertilizer is as follows:

according to the above reaction mechanism, the method comprises the steps of:

adding N, N dimethyl-1, 3-propane diamine into a three-neck flask, adding 8-12 wt.% humic acid and 0.8-1.2 wt.% p-toluenesulfonic acid, and reacting at 120-140 ℃ for 6-8 h; and (3) after the reaction is finished, settling and centrifuging, washing and centrifuging the precipitate for multiple times, and drying in vacuum to constant weight to obtain the cationized humic acid.

The second step is that: a cationized humic acid fertilizer has the following synthesis equation:

according to the above reaction mechanism, the method comprises the steps of:

dissolving a common phosphate fertilizer in water, adjusting the pH value to 5-6, adding 2%, 4%, 6%, 8% and 10% of cationized humic acid according to the mass ratio to obtain an improved phosphate fertilizer solution, and directly spraying the improved phosphate fertilizer solution to crops to be used as a fertilizer.

The present invention will be described in detail with reference to the following specific examples: