CN114957702A - Preparation method of high-activity humic acid - Google Patents
Preparation method of high-activity humic acid Download PDFInfo
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Abstract
The invention discloses a preparation method of high-activity humic acid, which comprises the steps of grinding raw materials of lignite and agricultural and forestry waste, and uniformly mixing to prepare a mixed raw material; taking the mixed raw materials into an oxidizing solution, and performing sufficient thermal oxidation at 70-90 ℃; filtering and separating liquid phase and solid phase, and repeatedly washing the solid phase with deionized water until the residue is neutral; adding 3% KOH into the obtained residue, extracting for 90min at 80 ℃ in a constant temperature oscillator, cooling to room temperature, performing suction filtration, repeatedly washing the residue with deionized water, and centrifuging until the solution is colorless; adding a hydrochloric acid solution into the filtrate to adjust the pH value to 1-2, and standing for 20-24 h; centrifuging, and drying the solid product at 40-60 ℃ to constant weight to obtain high-activity humic acid; wherein the content of oxygen-containing functional groups in the high-activity humic acid is 12.72 mmol/g ‑1 . The invention provides a preparation method of high-activity humic acid, which prepares composite HA by carrying out co-thermal oxidation on lignite and agricultural and forestry waste to obtain the composite HA with rich oxygen-containing functional groups and high activity.
Description
Technical Field
The invention belongs to the field of humic acid preparation, and particularly relates to a preparation method of high-activity humic acid.
Background
Humic acid is a natural macromolecular mixture formed by randomly linking various functional groups such as carboxyl, quinonyl and phenolic hydroxyl by one or more condensed ring aromatic nuclei through bridge bonds. The structural characteristics enable HA (humic acid) to have the characteristics of acidity, hydrophilicity, complexation, adsorptivity, ion exchange and the like, so that HA (humic acid) can be applied to industries such as agriculture, industry, animal husbandry, medicine and the like, and HAs considerable prospect.
According to the development, there are two main categories of HA: mineral HA and biochemical HA. Although the mineral HA is easily obtained, the problems of incomplete HA extraction and large molecular weight exist. According to previous studies, HNO 3 The extraction rate of the ore source HA in the lignite can be promoted by carrying out pretreatment on the lignite through chemical methods such as oxidation, hydrogen peroxide activation, ammonolysis, catalytic activation, hydrothermal treatment, ultrasonic treatment, electrochemical chlorination and the like. Lignite, weathered coal and peat belong to non-renewable resources, while agricultural waste resources in China are rich, and biochemical HA is developed by utilizing the waste resources, so that the lignite, weathered coal and peat become an important channel for agricultural resource utilization and functionalization, and the characteristic of recycling of environment-friendly renewable resources is formed. In recent years, research on the preparation/extraction of biochemical HA HAs been mainly focused on China, and most of the research HAs been conducted with rice/grass straws as raw materials and few reports.
The principle of preparing HA by a chemical method is that straws are subjected to a series of physical treatments, and chemical reagents are used for hydrolyzing, catalyzing and oxidizing the straws so that lignocellulose in the straws is broken and oxidized to finally generate HA. The chemical oxidation method can not only improve the yield of biochemical HA prepared by biomass, but also improve the yield of ore source HA prepared by lignite. Biochemical HA and mineral HA have their own advantages and disadvantages.
At present, no report is available on the research on the improvement of the activity of humic acid.
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.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of high-activity humic acid.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing high-activity humic acid comprises,
grinding and uniformly mixing the raw materials of the lignite and the agricultural and forestry wastes to prepare a mixed raw material;
taking the mixed raw materials into an oxidizing solution, and performing sufficient thermal oxidation at 70-90 ℃;
filtering and separating liquid phase and solid phase, and repeatedly washing the solid phase with deionized water until the residue is neutral;
adding 3% KOH into the obtained residue, extracting for 90min at 80 ℃ in a constant temperature oscillator, cooling to room temperature, performing suction filtration, repeatedly washing the residue with deionized water, and centrifuging until the solution is colorless;
adding a hydrochloric acid solution into the filtrate to adjust the pH value to 1-2, and standing for 20-24 h;
centrifuging, and drying the solid product at 40-60 ℃ to constant weight to obtain high-activity humic acid; wherein the content of oxygen-containing functional groups in the high-activity humic acid is 12.72 mmol/g -1 。
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the lignite is Heilongjiang lignite or Yunnan lignite.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the agricultural and forestry waste raw material is straw, fruit shell or wood dust.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: grinding to 50-80 meshes.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the mixed raw materials comprise the following raw materials in a mass ratio of 1:1 to 2.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the mass ratio of the raw materials of the lignite and the agricultural and forestry waste is 1: 1.
as a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the oxidizing solution is HNO 3 、H 2 O 2 、H 2 SO 4 One or two of the solutions.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the mass volume ratio g of the mixed raw material to the oxidizing solution is as follows: the mL is 1: 10-20.
As a preferred scheme of the preparation method of the high-activity humic acid, the preparation method comprises the following steps: the thermal oxidation time is 30-90 min.
The invention aims to overcome the defects in the prior art and provide a product prepared by a preparation method of high-activity humic acid, wherein the content of oxygen-containing functional groups in the product is 12.72 mmol/g -1 。
The invention has the beneficial effects that:
the invention provides a preparation method of high-activity humic acid, which adopts lignite and agricultural and forestry waste to prepare composite HA through co-thermal oxidation to obtain composite HA with rich oxygen-containing functional groups and high activity, wherein the content of the oxygen-containing functional groups in the high-activity humic acid is 12.72 mmol.g -1 The positive synergistic effect is generated by adopting the activation of an oxidant and the co-thermal oxidation of the lignite and the biomass, active oxygen atoms generated by the oxidant possibly attack the molecular structures of the lignite and the wheat straws, and hydrogen bonds among molecules of the wheat straw cellulose and the hemicellulose are rearranged and the glycosidic bonds are broken to generate a large amount of alkyl free radicals; the condensed aromatic ring of lignite gradually generates phenolic hydroxyl and is gradually oxidized into quinonyl and carboxyl, and the two are simultaneously accompanied with nitro substitution reaction, and the two generate oxygen-containing oxygen under the synergistic actionThe compound HA HAs rich functional groups and high activity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 is a process flow diagram according to an embodiment of the present invention;
FIG. 2 is an FTIR plot of a complex HA obtained in an example of the present invention;
FIG. 3 shows a composite HA obtained in the example of the present invention 13 C NMR chart.
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 raw materials of the invention are all common commercial products.
Example 1:
grinding the black Longjiang brown coal to 80 meshes, grinding the wheat straws to 50 meshes, uniformly mixing the raw materials according to the mass ratio of (dry basis) 1:1 to obtain a raw material, and mixing the raw material with 10% of HNO 3 Mixing at a solid-to-liquid ratio (g: mL) of 1:20Fully oxidizing at 80 ℃ and 150rpm for 60 min;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water;
drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
the obtained residue is subjected to alkali dissolution and acid precipitation to prepare the high-activity humic acid, and the test result shows that: the experimental yield of complex HA was 20.72%.
Process flow diagram, see fig. 1.
Example 2:
grinding the black Longjiang brown coal to 80 meshes, grinding the wheat straws to 50 meshes, uniformly mixing the raw materials according to the mass ratio (dry basis) of 2:1, and mixing the raw materials with 10% of HNO 3 Mixing according to solid-to-liquid ratio (g: mL) of 1:15, and fully oxidizing at 80 deg.C and 150rpm for 30 min;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water;
drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and performing alkali dissolution and acid precipitation on the obtained residues to obtain the high-activity humic acid. The test result shows that: the experimental yield of complex HA was 19.57%.
Example 3:
grinding black Longjiang brown coal to 80 meshes, grinding miscellaneous tree to 50 meshes, uniformly mixing the raw materials according to the mass ratio of (dry basis) 1:1 to obtain raw materials, and mixing the raw materials with 15% of HNO 3 Fully oxidizing for 90min at 70 ℃ and 150rpm according to the solid-to-liquid ratio (g: mL) of 1: 20;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water;
drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and performing alkali dissolution and acid precipitation on the obtained residues to obtain the high-activity humic acid. The test result shows that: the experimental yield of complex HA was 19.05%.
Example 4:
grinding the wax-extracted Heilongjiang lignite to 80 meshes, grinding the rice straws to 60 meshes, uniformly mixing the raw materials according to the mass ratio (dry basis) of 1:2, and mixing the raw materials with 5%H 2 O 2 Fully oxidizing at 80 ℃ and 150rpm for 60min according to the solid-to-liquid ratio (g: mL) of 1: 10;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water; drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and performing alkali dissolution and acid precipitation on the obtained residues to obtain the high-activity humic acid. The test result shows that: the experimental yield of complex HA was 13.53%.
Example 5:
grinding the small Longtan lignite to 80 meshes, grinding the sandwood to 50 meshes, uniformly mixing the raw materials according to the mass ratio of (dry basis) 1:1, and mixing the raw materials with 5% of H 2 SO 4 Fully oxidizing at 80 ℃ and 150rpm for 60min according to the solid-to-liquid ratio (g: mL) of 1: 15;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water; drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and performing alkali dissolution and acid precipitation on the obtained residues to obtain the high-activity humic acid. The test result shows that: the experimental yield of complex HA was 30.69%.
Example 6:
grinding Showa brown coal to 80 meshes, grinding walnut shells to 50 meshes, uniformly mixing the materials according to the mass ratio of (dry basis) 3:2 to obtain the raw material, and mixing the raw material with 5% of H 2 SO 4 Fully oxidizing at 90 ℃ and 150rpm for 90min according to a solid-to-liquid ratio (g: mL) of 1: 20;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water; drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid; and carrying out alkali dissolution and acid precipitation on the obtained residues to prepare the high-activity humic acid. The test result shows that: the experimental yield of complex HA was 21.02%.
Comparative example 1:
grinding the black Longjiang brown coal to 80 meshes as a raw material, and mixing the raw material with 10% of HNO 3 Mixing according to solid-to-liquid ratio (g: mL) of 1:20, and fully oxidizing at 80 ℃ and 150rpm for 60 min;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water;
drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and carrying out alkali dissolution and acid precipitation on the obtained residues to obtain humic acid, namely: pure mineral HA.
Comparative example 2:
grinding wheat straw to 50 meshes as a raw material, mixing the raw material with 10% of HNO 3 Mixing according to solid-to-liquid ratio (g: mL) of 1:20, and fully oxidizing at 80 ℃ and 150rpm for 60 min;
filtering and separating liquid phase and solid phase, and repeatedly washing residues to be neutral by using deionized water;
drying the obtained filtrate at 40-60 ℃ to constant weight to obtain crude fulvic acid;
and carrying out alkali dissolution and acid precipitation on the obtained residues to obtain humic acid, namely: pure wheat straw HA.
Performing infrared spectrum and solid carbon nuclear magnetic characteristic analysis on the obtained compound HA obtained in the example 1, and comparing the compound HA with pure mineral HA and pure wheat straw HA to obtain results shown in figures 2 and 3;
the results show that: from the comparison results of FIG. 2, the complex HA was found to be red at about 1720cm -1 、1640cm -1 Distinct characteristic peaks appear. The composite HA HAs more oxygen-containing functional groups such as carboxyl, phenolic hydroxyl, ketone group, aldehyde group and the like, and HAs higher activity than that of the mineral HA and biochemical HA.
The results show that: from the comparison of FIG. 3, using f O Denotes the carbon content of the oxygen-containing functional group in HA, i.e. f O ＝f COO +f CO +f a O +f al OO +f al O In mineral HA, wheat straw HA and composite HA f O The contents are 35.59%, 38.99% and 41.87%, respectively, and f in the compound HA _ E O The content is higher than that of the compound HA-T, and further shows that the compound HA HAs more carbon connected with oxygen and stronger activity.
The obtained composite HA of example 1, pure mineral HA and pure wheat straw HA were measured for total acidic groups and carboxyl groups in HA by alkaline-soluble barium chloride precipitation potentiometric titration and microdialysis, and phenolic hydroxyl group content was obtained by subtraction method, and acidic functional group measurement was performed for comparison, and the experimental results are shown in table 1.
TABLE 1 humic acid product containing oxygen-containing functional groups mmol g -1
The results show that: the contents of carboxyl, phenolic hydroxyl and total acidic groups of the ore source HA and the wheat straw HA are relatively close, and the content of oxygen-containing functional groups in the composite HA is obviously greater than that in the ore source HA and the wheat straw HA.
Indicating that the addition of the biomass adopts a co-thermal oxidation method to improve the content of the composite HA total acid groups and increase the content of hydrophilic groups. The composite HA HAs stronger hard water resistance, can reduce flocculation in practical application and HAs better product effect.
By combining the composite HA, the mineral HA and the wheat straw HA in the example 1, the characterization and analysis can obtain: the positive synergistic effect is generated by adopting the oxidizing agent for activation and the co-thermal oxidation of the lignite and the biomass.
Active oxygen atoms generated by the oxidant attack molecular structures of lignite and wheat straws, hydrogen bond rearrangement and glycosidic bond fracture among molecules of wheat straw cellulose and hemicellulose generate a large amount of alkyl free radicals; the condensed aromatic ring of lignite gradually generates phenolic hydroxyl and is gradually oxidized into quinonyl and carboxyl, and meanwhile, nitro substitution reaction is carried out. The compound HA with rich oxygen-containing functional groups and high activity is generated.
The invention provides a preparation method of high-activity humic acid, which adopts lignite and agricultural and forestry waste to prepare composite HA through co-thermal oxidation to obtain composite HA with rich oxygen-containing functional groups and high activity, wherein the content of the oxygen-containing functional groups in the high-activity humic acid is 12.72 mmol.g -1 The positive synergistic effect is generated by adopting the activation of an oxidant and the co-thermal oxidation of the lignite and the biomass, active oxygen atoms generated by the oxidant possibly attack the molecular structures of the lignite and the wheat straws, and hydrogen bonds among molecules of the wheat straw cellulose and the hemicellulose are rearranged and the glycosidic bonds are broken to generate a large amount of alkyl free radicals; the condensed aromatic ring of the lignite gradually generates phenolic hydroxyl and is gradually coatedThe compound HA is oxidized into a quinonyl group and a carboxyl group, and simultaneously, the quinonyl group and the carboxyl group are accompanied by nitro substitution reaction, and the quinonyl group and the carboxyl group have synergistic effect to generate the compound HA with rich oxygen-containing functional groups and high activity.
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 is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to 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 high-activity humic acid is characterized by comprising the following steps: comprises the steps of (a) preparing a substrate,
grinding and uniformly mixing the raw materials of the lignite and the agricultural and forestry wastes to prepare a mixed raw material;
taking the mixed raw materials into an oxidizing solution, and performing sufficient thermal oxidation at 70-90 ℃;
filtering and separating liquid phase and solid phase, and repeatedly washing the solid phase with deionized water to neutrality;
adding 3% KOH into the obtained residue, extracting for 90min at 80 ℃ in a constant temperature oscillator, cooling to room temperature, performing suction filtration, repeatedly washing the residue with deionized water, and centrifuging until the solution is colorless;
adding a hydrochloric acid solution into the filtrate to adjust the pH value to 1-2, and standing for 20-24 h;
centrifuging, and drying the solid product at 40-60 ℃ to constant weight to obtain high-activity humic acid; wherein the content of oxygen-containing functional groups in the high-activity humic acid is 12.72 mmol/g -1 。
2. The method for preparing high-activity humic acid according to claim 1, wherein: the lignite is Heilongjiang lignite or Yunnan lignite.
3. The method for preparing highly active humic acid according to claim 1, wherein: the agricultural and forestry waste raw material is straw, fruit shell or wood dust.
4. The method for preparing highly active humic acid according to claim 1, wherein: and grinding to 50-80 meshes.
5. The method for preparing highly active humic acid according to any one of claims 1 to 4, wherein: the mixed raw material comprises the following raw materials in a mass ratio of 1:1 to 2.
6. The method for preparing high-activity humic acid according to claim 5, wherein: the mass ratio of the raw materials of the lignite and the agricultural and forestry waste is 1: 1.
7. the method for preparing highly active humic acid according to claim 1, wherein: the oxidizing solution is HNO 3 、H 2 O 2 、H 2 SO 4 One or two of the solutions.
8. The method for preparing highly active humic acid according to claim 7, wherein: the mass volume ratio g of the mixed raw material to the oxidizing solution is as follows: the mL is 1: 10-20.
9. The method for preparing highly active humic acid according to claim 1, wherein: the thermal oxidation time is 30-90 min.
10. The product prepared by the preparation method of the high-activity humic acid of any one of claims 1 to 9, which is characterized in that: the content of oxygen-containing functional groups in the product is 12.72 mmol-g -1 。
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Cited By (3)
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| CN115611683A (en) * | 2022-10-31 | 2023-01-17 | 华南理工大学 | Method for preparing water-soluble fertilizer containing super-mineral humic acid by using agriculture and forestry biomass solid waste |
| CN116987283A (en) * | 2023-06-28 | 2023-11-03 | 常州大学 | Preparation method of agricultural potassium humate and agricultural potassium humate product |
| CN117586528A (en) * | 2023-11-03 | 2024-02-23 | 中化化肥有限公司 | Modified humic acid, preparation method thereof and application of modified humic acid |
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| CN117586528A (en) * | 2023-11-03 | 2024-02-23 | 中化化肥有限公司 | Modified humic acid, preparation method thereof and application of modified humic acid |
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