CN110105407B - Method for preparing fulvic acid by degrading fulvic acid and ulmic acid - Google Patents
Method for preparing fulvic acid by degrading fulvic acid and ulmic acid Download PDFInfo
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Abstract
The invention relates to a method for preparing fulvic acid by degrading black humic acid and ulmic acid, which comprises the steps of fully crushing the black humic acid and the ulmic acid into powder by a crusher, preparing degradation slurry by an oxidation method, treating the slurry by ultrasonic treatment, finally centrifugally separating the slurry after the ultrasonic treatment to obtain filter residue and supernatant, washing the filter residue by hot water for multiple times, mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding the supernatant to obtain the fulvic acid product. Compared with the prior art, the method can obviously improve the extraction rate and shorten the extraction time.
Description
Technical Field
The invention relates to the technical field of utilization of natural humic substances, in particular to a method for preparing fulvic acid by degrading black humic acid and fulvic acid.
Background
Humic Acid (HA) is a natural organic mixed substance and is composed of C, H, O, N, S and other elements, wherein, the Humic acid mainly comprises Humic acid, Humic acid black and Humic acid yellow. The humic acid is humic substance which can be dissolved in alkali solution and precipitated by acid solution, the molecular weight of the humic acid is larger than that of the humic acid, and the percentage content of each element in the molecular composition is as follows: c50-60, H2.8-6.6, O31-40, N2.6-6.0. Compared with fulvic acid, the fulvic acid and fulvic acid have the advantages of small acidity, slightly acidity and higher absorption capacity, monovalent salts of the fulvic acid and trivalent salts of the fulvic acid are dissolved in water, and the divalent salts and the trivalent salts of the fulvic acid are insoluble in water, so that the fulvic acid and the fulvic acid have significance for maintaining soil nutrients and forming soil structures.
The fulvic acid is a humus substance which is soluble in an alkali solution and an acid solution, the molecular weight of the fulvic acid is smaller than that of the fulvic acid and the fulvic acid, and the percentage content of each element in the molecular composition is as follows: c40-52, H4-6, O40-48, N2-6. The fulvic acid is strong in acidity, large in mobility and low in absorption, and monovalent, divalent and trivalent salts of the fulvic acid are dissolved in water, so that the fulvic acid plays an important role in promoting the decomposition of minerals and the release of nutrients.
Wherein, the fulvic acid is extracted from natural humus and is a group of substances which can be dissolved in alkali, acid and water, have smaller molecular weight and are yellow or brownish yellow in dilute solution. It is a kind of culture growth regulator, and can promote the growth of culture, raise the resistance of culture, increase yield and improve quality. The fulvic acid is the best core component for forming soil humus, is a small-molecular-weight and fully water-soluble organic aromatic substance generated by decomposition and decomposition of organic matters, is the best humic acid component in soil, and is the core substance for forming a soil granular structure.
The application and basic research of the fulvic acid are important research subjects at home and abroad in recent years, and although the storage amount of the humic acid in the nature is rich, the fulvic acid is very rare; the production and purification technology is difficult, the cost is high, and the yield of the fulvic acid is very low. The price of the commercially available fulvic acid is high, and the kilogram price of the fulvic acid with high purity reaches hundreds to thousands, even higher. Although the fulvic acid resource is less, the fulvic acid has many functions, so that the national ministry of health has listed fulvic acid as a secondary protection variety of the traditional Chinese medicine, and the search for a simple, cheap and efficient fulvic acid extraction method is particularly important.
The existing preparation methods of fulvic acid mainly comprise three major methods, namely an extraction method, a fermentation method and an electrodialysis method. Wherein the extraction method comprises alkali dissolution and acid precipitation, strong acid extraction, acetone sulfate method, ion exchange resin method, catalytic oxidation method, organic solvent extraction method, etc. The electrodialysis method is a deep purification method, which is generally used for further processing and purifying fulvic acid primary products, and removes metal ions combined with fulvic acid in a complex state under the action of an electric field, so that fulvic acid macromolecules and inorganic salt ash are separated, and the fulvic acid is purified.
The existing fulvic acid extraction methods have the following advantages and disadvantages: (1) the alkaline dissolution and acidification method is widely applied, but the extraction rate of the fulvic acid is low and is only about 8%, the extraction time is about 90 minutes, and the extraction time is long; (2) the catalytic oxygen decomposition is mainly carried out by nitric acid at present, so that the extraction rate of fulvic acid is improved, but the nitric acid causes great harm to the environment, and the reaction time is long, so that researchers substitute hydrogen peroxide for nitric acid oxygen decomposition in the aspect of reducing the pollution to the environment; (3) for organic solvent extractant electrodialysis, ion exchange method, etc., it is mainly used for extraction of high-purity fulvic acid, such as medical fulvic acid.
Chinese patent 201610847821.8 discloses a method for efficiently extracting fulvic acid substances from papermaking black liquor, which comprises the steps of adding a protective agent, an oxidant and a catalyst into papermaking black liquor at one time, heating to 60-90 ℃ in the stirring process, reacting for 30-90 minutes, and adjusting the pH value of the mixed liquor to 2-3 by using an acidizing solution; the mixed solution is told to be centrifuged for 30 minutes at 6000 r/min; standing, vacuum filtering, and removing precipitate impurities to obtain 37-40% fulvic acid solution. The method can fully utilize the largest pollutant black liquor in the papermaking industry as resources, reduce the pollution to the environment and the cost for treating the pollution, and has good environmental benefit; the fulvic acid substances of the colleagues paper money have wider application prospect in agriculture. However, the invention is limited to extracting fulvic acid substances in the paper-making night, and other domestic waste materials are not utilized.
Chinese patent CN1117036A discloses a humic acid of regenerated fulvic acid and a production method thereof, wherein the humic acid is micromolecule fulvic acid with the molecular weight below 350, which is obtained by chemically cutting macromolecules of the fulvic acid and the fulvic acid, and the humic acid has the same property with natural fulvic acid, is easy to dissolve in water, does not flocculate and is convenient to spray and absorb by crops. The production method is that sodium humate or turf is taken as raw material, Na is added into a reaction kettle2SO3、MnO2And NaOH chemical partitioning. The method is characterized by comprising the steps of re-extraction, separation, acidification, crystallization and drying, but the process flow of the patent is relatively complex, and more reagents and medicines are required to be added, so that the purity of the prepared product is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing fulvic acid by degrading fulvic acid and fulvic acid, wherein the method for preparing fulvic acid can obviously improve the extraction rate and shorten the extraction time.
The purpose of the invention can be realized by the following technical scheme:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 60-80 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid and the brown humic acid powder prepared in the step (1) according to the weight ratio of 1-3:1, and adding water to dilute the mixture to a solution state, wherein the weight ratio of the degradation material to the pure water is 1: 30-50; then preheating to 50-55 ℃, simultaneously performing microwave pretreatment with the frequency of 100-300MHz, putting the pretreated black humic acid and brown humic acid powder into a high-pressure kettle, adding a ferrous sulfate Fenton (Fenton) reagent and a catalyst into the high-pressure kettle, setting the pressure of the high-pressure kettle for degradation, and obtaining a degradation material, wherein the degradation time is 40-60 minutes;
further, the weight ratio of the ferrous sulfate Fenton (Fenton) reagent to the mixed powder of the black humic acid and the brown humic acid is 1: 150-250;
further, the catalyst may be titanium dioxide (TiO)2)；
Further, the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 300-400;
further, the pressure of the autoclave is set to be 0.3-0.5 MPa;
(3) ultrasonic treatment of the degradation material: injecting the degradation material prepared in the step (2) into an ultrasonic cleaner, adding pure water at the same time, wherein the weight ratio of the degradation material to the pure water is 1:10, uniformly mixing, and then carrying out ultrasonic treatment, wherein the ultrasonic frequency is 50KHz-100KHz, and fully stirring for 60-90 minutes while carrying out ultrasonic treatment to obtain the degradation material subjected to ultrasonic treatment;
(4) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (3) to obtain filter residue and supernatant, wherein the centrifugation speed is 600-1200r/min, washing the filter residue with hot water for 3-5 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
further, the temperature of the hot water is 60-80 ℃;
the step (2) can also adopt the following steps: uniformly mixing the black humic acid and the brown humic acid powder prepared in the step (1) according to the weight ratio of 1-3:1Uniformly mixing, adding pure water, preheating to 50-55 deg.C, pretreating with 100-300MHz microwave while preheating, adding catalyst into three-neck flask, stirring, and introducing oxidant O into one end of two-neck flask3And the other end is sealed by a water column, and the degradation time is 40-60 minutes, so that the degradation material is obtained.
Ultrasonic treatment of the degradation material: preheating the brown humic acid and the black humic acid in the step (1) to 50-55 ℃, adding water for diluting to a solution state, pretreating by using 100MHz-300MHz microwave, putting into a three-neck flask, adding a catalyst into the three-neck flask, stirring the middle bottle mouth, and introducing an oxidant O into one end of each of two end bottle mouths3The other end is sealed, and the degradation time is 40-60 minutes, so as to obtain the degraded material subjected to ultrasonic treatment;
further, the ratio of the water addition amount to the brown black humic acid is 30-50:1
Further, the catalyst may be titanium dioxide (TiO)2)；
Further, the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 300-400;
further, the oxidizing agent O3The volume concentration of (2) is 20%, and the dosage of the volume concentration is 0.4 times of the weight of the mixed powder of the humic acid and the palmitic acid.
Compared with the prior art, the invention has the following advantages:
1. compared with the prior art, the method for preparing the fulvic acid can obviously improve the extraction rate from 37-42% in the prior art to 60-67% in the invention. The reason is that the extraction of fulvic acid in the prior art is directly carried out by taking coal as a raw material, and the invention directly carries out oxidative degradation on macromolecular brown and black humic acid without utilization effect in the coal, so as to break macromolecular chains to a greater extent and enable the macromolecular brown and black humic acid to become micromolecular fulvic acid, thereby increasing the yield of fulvic acid in the coal with the same weight, in other words, the brown and black humic acid without utilization effect in the coal is changed into fulvic acid with beneficial effect.
2. Compared with the prior art, the method for preparing the fulvic acid can obviously shorten the extraction time from 90 minutes in the prior art to 60 minutes in the invention. The existing extraction process is directly directed at lignite treatment, but the process scheme is that brown humic acid and black humic acid in lignite are directly subjected to oxidative degradation, so that interference of non-humic acid (humins) components in coal is eliminated, the maximum degradation effect can be achieved, and the degradation time is not too long so as to prevent fulvic acid obtained by degradation from being oxidized.
3. The equipment adopted by the invention is common equipment in the industry, the raw materials are simple and easy to obtain, and the preparation cost of the fulvic acid is reduced.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A method for preparing fulvic acid by degrading fulvic acid and fulvic acid comprises the following specific steps:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 60 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid powder and the brown humic acid powder prepared in the step (1) according to the weight ratio of 2:1, adding water to dilute the mixture to a solution state, then placing the solution in a water bath kettle at 50 ℃ for preheating, simultaneously using microwave with the frequency of 200MHz for pretreatment, placing the pretreated black humic acid powder and the brown humic acid powder into a high-pressure kettle, adding a Fenton (Fenton) sulfate reagent and a catalyst into the high-pressure kettle, setting the pressure of the high-pressure kettle for degradation, and setting the degradation time to be 50 minutes to obtain a degraded material;
wherein the ratio of the water addition amount to the brown black humic acid is 40: 1;
wherein the weight ratio of the ferrous sulfate Fenton (Fenton) reagent to the mixed powder of the black humic acid and the brown humic acid is 1: 200;
whereinThe catalyst is titanium dioxide (TiO)2)；
Wherein the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 350;
wherein the pressure of the autoclave is set to be 0.3 MPa;
(3) ultrasonic treatment of the degradation material: injecting the degraded material prepared in the step (2) into an ultrasonic cleaner, adding pure water at the same time, wherein the weight ratio of the degraded material to the pure water is 1:10, uniformly mixing, and then performing ultrasonic treatment, wherein the ultrasonic frequency is 80KHz, and fully stirring for 80 minutes while performing the ultrasonic treatment to obtain the degraded material subjected to the ultrasonic treatment;
(4) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (3) to obtain filter residue and supernatant, wherein the centrifugation speed is 800r/min, washing the filter residue with hot water for 4 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
wherein the hot water temperature is 65 ℃.
The fulvic acid obtained in this example had an extraction yield of 67%.
Example 2
A method for preparing fulvic acid by degrading fulvic acid and fulvic acid comprises the following specific steps:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 70 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid powder and the brown humic acid powder prepared in the step (1) according to the weight ratio of 3:1, adding water to dilute the mixture to a solution state, then placing the solution in a 55-DEG C water bath kettle for preheating, simultaneously performing microwave pretreatment with the frequency of 100MHz, placing the pretreated black humic acid powder and the brown humic acid powder into a high-pressure kettle, adding a Fenton (Fenton) sulfate reagent and a catalyst into the high-pressure kettle, setting the pressure of the high-pressure kettle for degradation, and obtaining a degradation material, wherein the degradation time is 55 minutes;
wherein the ratio of the water addition amount to the brown black humic acid is 30: 1;
wherein the weight ratio of the ferrous sulfate Fenton (Fenton) reagent to the mixed powder of the black humic acid and the brown humic acid is 1: 150;
wherein the catalyst is titanium dioxide (TiO)2)；
Wherein the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 400;
wherein the pressure of the autoclave is set to be 0.5 MPa;
(3) ultrasonic treatment of the degradation material: injecting the degraded material prepared in the step (2) into an ultrasonic cleaner, adding pure water at the same time, wherein the weight ratio of the degraded material to the pure water is 1:10, uniformly mixing, and then performing ultrasonic treatment, wherein the ultrasonic frequency is 60KHz, and fully stirring for 70 minutes while performing the ultrasonic treatment to obtain the degraded material subjected to the ultrasonic treatment;
(4) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (3) to obtain filter residue and supernatant, wherein the centrifugation speed is 600r/min, washing the filter residue with hot water for 3 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
wherein the hot water temperature is 60 ℃.
The fulvic acid obtained in this example had an extraction yield of 61%.
Example 3
A method for preparing fulvic acid by degrading fulvic acid and fulvic acid comprises the following specific steps:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 70 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid powder and the brown humic acid powder prepared in the step (1) according to the weight ratio of 1:1, adding water to dilute the mixture to a solution state, then placing the solution in a water bath kettle at 52 ℃ for preheating, simultaneously using microwave with the frequency of 150MHz for pretreatment, placing the pretreated black humic acid powder and the brown humic acid powder into a high-pressure kettle, adding a Fenton (Fenton) sulfate reagent and a catalyst into the high-pressure kettle, setting the pressure of the high-pressure kettle for degradation, and obtaining a degradation material, wherein the degradation time is 40-60 minutes;
wherein the ratio of the water addition amount to the brown black humic acid is 40: 1;
wherein the weight ratio of the ferrous sulfate Fenton (Fenton) reagent to the mixed powder of the black humic acid and the brown humic acid is 1: 150;
wherein the catalyst is ferric oxide (Fe)2O3)；
Wherein the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 300;
wherein the pressure of the autoclave is set to be 0.5 MPa;
(3) ultrasonic treatment of the degradation material: injecting the degraded material prepared in the step (2) into an ultrasonic cleaner, adding pure water at the same time, wherein the weight ratio of the degraded material to the pure water is 1:10, uniformly mixing, and then performing ultrasonic treatment, wherein the ultrasonic frequency is 60KHz, and fully stirring for 65 minutes while performing the ultrasonic treatment to obtain the degraded material subjected to the ultrasonic treatment;
(4) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (3) to obtain filter residue and supernatant, wherein the centrifugation speed is 1200r/min, washing the filter residue with hot water for 3 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
wherein the hot water temperature is 80 ℃.
The fulvic acid obtained in this example had an extraction yield of 60%.
Example 4
A method for preparing fulvic acid by degrading fulvic acid and fulvic acid comprises the following specific steps:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 60 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid powder and the brown humic acid powder prepared in the step (1) according to the weight ratio of 2:1, adding water to dilute the mixture to a solution state, then placing the solution in a 52 ℃ water bath kettle for preheating, simultaneously using microwave with the frequency of 250MHz for pretreatment, placing the pretreated black humic acid powder and the brown humic acid powder into a three-neck flask, adding a catalyst into the three-neck flask, using a middle bottle opening for stirring, and using one end of two end bottle openings for introducing an oxidant O3The other end is sealed by a water column, and the degradation time is 45 minutes to obtainTo degraded material subjected to ultrasonic treatment;
wherein the ratio of the water addition amount to the brown black humic acid is 50: 1;
wherein the catalyst is titanium dioxide (TiO)2)；
Wherein the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 380;
wherein, the oxidant O3The volume concentration of the humic acid is 20 percent, and the dosage of the humic acid is 0.4 time of the weight of the mixed powder of the humic acid and the humic acid;
(3) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (2) to obtain filter residue and supernatant, wherein the centrifugation speed is 1000r/min, washing the filter residue with hot water for 3-5 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
wherein the hot water temperature is 75 ℃.
The fulvic acid obtained in this example had an extraction yield of 62%.
Example 5
A method for preparing fulvic acid by degrading fulvic acid and fulvic acid comprises the following specific steps:
(1) preparation of black humic acid and brown humic acid powder: respectively and fully crushing the humic acid and the humic acid into powder with the particle size of 60 meshes by a crusher;
(2) preparing a degradation material: uniformly mixing the black humic acid and the brown humic acid powder prepared in the step (1) according to the weight ratio of 3:1, adding water to dilute the mixture to a solution state, then placing the solution in a water bath kettle at 60 ℃ for preheating and simultaneously using microwave with the frequency of 250MHz for pretreatment, placing the pretreated black humic acid and the brown humic acid powder into a three-neck flask, adding a catalyst into the three-neck flask, using a middle bottle opening for stirring, and using one end of two end bottle openings for introducing an oxidant O3The other end of the material is sealed by a water column, and the degradation time is 45 minutes, so that the degraded material subjected to ultrasonic treatment is obtained;
wherein the ratio of the water addition amount to the brown black humic acid is 50: 1;
wherein the catalyst is titanium dioxide (TiO)2)；
Wherein the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1: 300;
wherein, the oxidant O3The concentration of the humic acid is 20 percent, and the dosage of the humic acid is 0.4 time of the weight of the mixed powder of the humic acid and the humic acid;
(3) centrifuging the degraded material subjected to ultrasonic treatment prepared in the step (2) to obtain filter residue and supernatant, wherein the centrifugation speed is 1000r/min, washing the filter residue with hot water for 3-5 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain a fulvic acid product;
wherein the hot water temperature is 50 ℃.
The fulvic acid obtained in this example had an extraction yield of 61%.
Comparative example 1
The only difference between this comparative example and example 1 is that the weight ratio of the black humic acid to the brown humic acid powder in step (1) is 4:1, and the other operation steps, conditions and material amount are the same as example 1.
The fulvic acid extraction yield obtained in this comparative example was 29%.
Comparative example 2
The comparative example is different from example 1 only in that the weight ratio of ferrous sulfate Fenton (Fenton) reagent to the mixed powder of black humic acid and brown humic acid in step (2) is 1:300, and other operation steps, conditions and material amount are the same as example 1.
The fulvic acid obtained in this comparative example had an extraction yield of 27%.
Comparative example 3
The only difference between this comparative example and example 1 is that the weight ratio of the catalyst to the mixed powder of humic acid black and humic acid brown in step (2) is 1:450, and the other operation steps, conditions and material amount are the same as example 1.
The fulvic acid obtained in this comparative example had an extraction rate of 32%.
Comparative example 4
The only difference between this comparative example and example 2 is that the weight ratio of the black humic acid to the brown humic acid powder in step (1) is 5:1, and the other operation steps, conditions and material amount are the same as example 2.
The fulvic acid obtained in this comparative example had an extraction rate of 31%.
Comparative example 5
The comparative example is different from example 3 only in that the weight ratio of ferrous sulfate Fenton (Fenton) reagent to the mixed powder of black humic acid and brown humic acid in step (2) is 1:100, and other operation steps, conditions and material amount are the same as example 3.
The fulvic acid obtained in this comparative example had an extraction rate of 30%.
Comparative example 6
The only difference between this comparative example and example 4 is that the weight ratio of the catalyst to the mixed powder of humic acid black and humic acid brown in step (2) is 1:500, and the other operation steps, conditions and material amount are the same as example 4.
The fulvic acid extraction yield obtained in this comparative example was 28%.
As can be seen from the examples 1 to 5 and the comparative examples 1 to 6, the method for preparing fulvic acid can remarkably improve the extraction rate of fulvic acid from 37 to 40 percent in the prior art to 60 to 67 percent, simultaneously shortens the extraction time from 90 minutes to 60 minutes in the prior art, and all equipment used in the extraction process is common equipment in the industry, so that the preparation cost of fulvic acid is reduced, and in addition, the extraction process is harmless to the environment.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A method for degrading humic acid and humic acid to prepare humic acid, which comprises:
(1) preparation of black humic acid and brown humic acid powder: crushing the humic acid and the humic acid into powder with the particle size of 60-80 meshes;
(2) preparing a degradation material: uniformly mixing the black humic acid and the brown humic acid powder according to the weight ratio of (1-3) to 1, simultaneously adding pure water, preheating, adopting microwave pretreatment, adding a ferrous sulfate Fenton reagent and a catalyst, and performing high-pressure degradation to obtain a degraded material; the catalyst is titanium dioxide, and the weight ratio of the catalyst to the mixed powder of the humic acid and the humic acid is 1 (300-400); the weight ratio of the ferrous sulfate Fenton reagent to the mixed powder of the black humic acid and the brown humic acid is 1 (150-250); the pressure of high-pressure degradation is 0.3-0.5MPa, and the time is 40-60 min;
(3) ultrasonic treatment of the degradation material: injecting the degradation material into an ultrasonic cleaner, adding pure water at the same time, uniformly mixing the degradation material and the pure water in a weight ratio of 1:10, performing ultrasonic treatment, and stirring for 60-90 minutes to obtain the ultrasonic-treated degradation material;
(4) and (3) centrifugally separating the degraded material subjected to ultrasonic treatment to obtain filter residue and supernatant, washing the filter residue with hot water for 3-5 times to obtain washing water, uniformly mixing the obtained washing water with the supernatant for treatment, and sequentially concentrating, drying, cooling and grinding to obtain the fulvic acid.
2. The method for degrading humic acid and humic acid to prepare fulvic acid according to claim 1, wherein step (2) further comprises the following steps:
uniformly mixing the black humic acid powder and the brown humic acid powder prepared in the step (1) according to the weight ratio of (1-3) to 1, adding pure water, wherein the weight ratio of the mixed powder to the pure water is 1 (30-50), preheating to 50-55 ℃, simultaneously performing pretreatment by using 100-plus-300 MHz microwave, then placing into a three-neck flask, adding catalyst titanium dioxide into the three-neck flask, stirring the middle bottle mouth, and introducing an oxidant O into one end of each of two end bottle mouths3The other end is sealed by a water column, and the degradation time is 40-60 minutes to obtain a degradation material; the oxidant O3The volume concentration of the humic acid is 20 percent, and the dosage of the humic acid is 0.4 times of the weight of the mixed powder of the humic acid and the humic acid.
3. The method for degrading humic acid and humic acid to prepare humic acid according to claim 1 wherein the frequency of ultrasonic treatment is 50-100 KHz.
4. The method for preparing fulvic acid by using fulvic acid and fulvic acid as claimed in claim 1, wherein the centrifugation speed is 600-1200 r/min.
5. The method for preparing fulvic acid by degrading fulvic acid and fulvic acid according to claim 1, wherein the hot water temperature for treating the filter residue is 60-80 ℃.
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