CN110105407A - A method of degradation humic acid and ulmic acid are to prepare fulvic acid - Google Patents
A method of degradation humic acid and ulmic acid are to prepare fulvic acid Download PDFInfo
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Abstract
Method the present invention relates to a kind of degradation humic acid and ulmic acid to prepare fulvic acid, humic acid, ulmic acid are sufficiently pulverized into powder with pulverizer, then with the method preparation degradation slurry of oxidation, again with ultrasonic treatment slurry, the slurry being ultrasonically treated finally is centrifugally separating to obtain filter residue and supernatant, filter residue is washed repeatedly with hot water, and obtained wash water is mixed with above-mentioned supernatant and is handled, and supernatant is successively concentrated, dry, cooling, grinds obtained fulvic acid product.Compared with prior art, the present invention is remarkably improved recovery rate, shortens extraction time.
Description
Technical field
The present invention relates to the utilization technical fields of natural source humus, more particularly, to a kind of degradation humic acid and ulmic acid
Method to prepare fulvic acid.
Background technique
Humic acid (Humic acid, abbreviation HA) is a kind of natural organic mixture matter, is by the elements group such as C, H, O, N, S
At wherein based on ulmic acid, humic acid and fulvic acid.Ulmic acid and humic acid are that one kind can be dissolved in aqueous slkali and by acid solution
The humic matter precipitated, molecular weight are bigger than fulvic acid, and the percentage composition of each element is respectively in molecular composition: C50~
60, H2.8~6.6, O 31~40, N2.6~6.0.Ulmic acid and humic acid are smaller than the acidity of fulvic acid, are in subacidity, absorb
Capacity is higher, its monovalence salt is dissolved in water, and divalent and trivalent species are not soluble in water, this holding and soil knot to soil nutrient
The formation of structure is all meaningful.
Fulvic acid is that one kind had not only been dissolved in aqueous slkali but also had been dissolved in the humic matter of acid solution, and molecular weight is than humic acid and palm fibre
Rotten acid is small, and the percentage composition of each element is respectively in molecular composition: C40~52, H4~6, O40~48, N2~6.Fulvic acid is in
Highly acid, mobility is big, and absorption is low, its monovalence, divalent, trivalent species are dissolved in water therefore fulvic acid divides promotion mineral
The release of solution and nutrient plays a significant role.
Wherein, fulvic acid is extracted from natural humus, be a kind of one group of molecular weight that can be dissolved in alkali, acid and water compared with
Small, weak solution is in the substance of yellow or brown color.It is that one kind grows object growth regulator, can promote to grow object growth, can improve and grow
Object is degeneration-resistant, volume increase and improving quality.Fulvic acid is to constitute the best core component of agron, is that organic matter decomposition is decomposed again
The molecular weight of generation is small, complete water-soluble organic aromatic substance, is humic sour component best in soil, is to form soil group
The core substance of kernel structure.
The application and basic research of fulvic acid are recent domestic important subjects, although humic acid is in nature
Rich reserves, but fulvic acid is but very rare；Production, purification technique difficulty are big, and cost is also higher, leads to the production of fulvic acid
Amount is few.Commercially available fulvic acid is expensive, and fulvic acid kilogram price with high purity is even higher up to hundreds of to thousands of.Although yellow
Rotten acid resource is few, but has many functions, therefore fulvic acid is classified as national Chinese medicine second class protection product by health ministry
Kind, therefore seek a kind of easy and Cheap highly effective extracting method of fulvic acid and seem to be even more important.
The preparation method of fulvic acid mainly has extraction method, fermentation method, electroosmose process three categories at present.Wherein, extraction method is again
It include that alkali-soluble acid analysis method, strong acid extraction process, sulfuric acid acetone method, ion-exchange-resin process, catalysis oxygen solution and organic solvent mention
The methods of follow the example of.And electroosmose process belongs to a kind of method of depth purification, is commonly used in fulvic acid early-products and further adds
Work purification, under the action of electric field with fulvic acid with complex status ins conjunction with metal ion remove, make fulvic acid macromolecular with
Inorganic salts ash content is separated, and realizes the purification of fulvic acid.
Existing extracting method of fulvic acid respectively has its advantage and disadvantage: (1) alkali-soluble acid analysis method is used relatively broad, but fulvic acid mentions
Take rate low, only 8% or so, extraction time needs 90 minutes or so, and extraction time is longer；(2) catalysis oxygen solution mainly uses now
Nitric acid carries out oxygen solution, improves the recovery rate of fulvic acid, but nitric acid causes huge harm to environment, and the reaction time is longer,
There is researcher to replace nitric acid oxygen with hydrogen peroxide in this respect, alleviates the pollution to environment；(3) for organic solvent extractant
Electrodialysis, ion-exchange etc. are mainly used for the extraction of high-purity fulvic acid, such as medical xanthonumic acid.
Chinese patent 201610847821.8 discloses a kind of side of high efficiency extraction fulvic acid substance from black liquid
Method, the invention are that protective agent, oxidant and catalyst are once added into papermaking night, are warming up to 60-90 DEG C in whipping process,
Adjusting pH of mixed with souring soln after reaction 30-90 minutes is 2-3；Tell mixed liquor 6000r/min to centrifugation 30 minutes；It is quiet
It is filtered by vacuum after only, removes precipitated impurities, obtain the fulvic acid substance solution that concentration is 37-40%.The invention can be with
It allows the maximum pollutant black liquor of paper industry to obtain sufficient resource utilization, reduces what it polluted the pollution of environment and processing
Cost has good environmental benefit；The fulvic acid substance of colleague's bank note agriculturally has more wide application prospect.
But the invention is only limitted to extract fulvic acid substance in papermaking night, does not use waste materials other in life.
Chinese patent CN1117036A discloses the humic acid and its production method of a kind of regenerated xanthohumic acid, which is
The molecular weight that the macromolecular of ulmic acid and humic acid is cut into through chemical method is in 350 small molecule fulvic acids below, property
Matter is consistent with natural fulvic acid, but soluble easily in water, does not flocculate, convenient for spraying and being absorbed by crops.Its production method be with
Rotten sodium or turf are raw material, and Na is added in a kettle2SO3、MnO2Divide with NaOH chemistry.It extracts, separate, be acidified, tie again
Crystalline substance is dried, but the patent process flow is relative complex, and needs to be added more reagent and drug, reduces system
The purity of standby obtained product.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of degradation ulmic acid and
Method of the humic acid to prepare fulvic acid, recovery rate can significantly be improved by preparing fulvic acid with this method, shorten extraction time.
The purpose of the present invention can be achieved through the following technical solutions:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 60-80 mesh powder；
(2) preparation of degraded polypropylene: first by humic acid made from step (1) and ulmic acid powder according to the weight ratio of 1-3:1
It is uniformly mixed, is diluted with water to solution state, wherein the weight ratio of degraded polypropylene and pure water is 1:30-50；Then it is preheated to 50-55
DEG C, the Microwave Pretreatment that preheating while is 100MHz-300MHz with frequency, by pretreated humic acid and ulmic acid powder
Be put into autoclave, be added ferrous sulfate Fenton (Fenton) reagent and catalyst into autoclave, setting autoclave pressure into
Row degradation, degradation time are 40-60 minutes, obtain degraded polypropylene；
Further, the weight ratio of ferrous sulfate Fenton (Fenton) reagent and humic acid and ulmic acid mixed-powder
For 1:150-250；
Further, the catalyst can be titanium dioxide (TiO2)；
Further, the weight ratio of the catalyst and humic acid and ulmic acid mixed-powder is 1:300-400；
Further, the pressure of the setting autoclave is 0.3-0.5MPa；
(3) it is ultrasonically treated degraded polypropylene: degraded polypropylene made from step (2) being injected in ultrasonic cleaner, while being added pure
Water, wherein the weight ratio of degraded polypropylene and pure water is 1:10, is ultrasonically treated after mixing, supersonic frequency 50KHz-
100KHz is sufficiently stirred 60-90 minutes, the degraded polypropylene being ultrasonically treated while ultrasonic treatment；
(4) step (3) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 600-1200r/min, and filter residue washs 3-5 times with hot water and obtains wash water, obtained wash water is mixed with above-mentioned supernatant
Even to be handled, fulvic acid product is made in successively concentrated, dry, cooling, grinding；
Further, the hot water temperature is 60-80 DEG C；
Step (2) can also use following steps: by humic acid made from step (1) and ulmic acid powder according to 1-3:1
Weight ratio be uniformly mixed, be added pure water, wherein the weight ratio of mixed-powder and pure water be 1:30-50, be preheated to 50-55 DEG C,
With being put into three-necked flask after 100MHz-300MHz Microwave Pretreatment while preheating, catalyst is added into three-necked flask, in
Between bottleneck for stirring, both ends bottleneck one end is for being passed through oxidant O3, the other end seals with water column, degradation time 40-60
Minute, obtain degraded polypropylene.
Ultrasonic treatment degraded polypropylene: while step (1) palm fibre, black humic acid are preheated to 50-55 DEG C, it is diluted with water to solution
Catalyst, intermediate bottle are added into three-necked flask with being put into three-necked flask after 100MHz-300MHz Microwave Pretreatment for state
Mouth is for stirring, and both ends bottleneck one end is for being passed through oxidant O3, the other end seals, and degradation time is 40-60 minutes, is surpassed
The degraded polypropylene of sonication；
Further, amount of water and dark brown humic acid ratio are 30-50:1
Further, the catalyst can be titanium dioxide (TiO2)；
Further, the weight ratio of the catalyst and humic acid and ulmic acid mixed-powder is 1:300-400；
Further, the oxidant O3Volumetric concentration be 20%, dosage is rotten acid and ulmic acid mixed-powder weight
0.4 times.
Compared with prior art, the invention has the following advantages that
1. the present invention prepares fulvic acid can significantly improve recovery rate compared with the prior art, by prior art 37-42%
It is increased to 60-67% of the invention., this is because the extraction of prior art fulvic acid is all that the coal that uses is direct for raw material
It extracts, and what the present invention took is directly to aoxidize the macromolecular for not having utilizing status in coal palm fibre, black humic acid
Degradation, more interrupts macromolecular chain and makes small molecule fulvic acid, to increase fulvic acid in identical weight coal
Yield, in other words not having brown, the black humic acid of utilizing status to become the fulvic acid for having utilizing status in coal.
2. the present invention, which prepares fulvic acid, can significantly shorten extraction time compared with the prior art, by 90 points of the prior art
Clock shortens to of the invention 60 minutes., this is because existing extraction process is directly against lignite processing, and this technique side
Case is that directly palm fibre, the progress oxidative degradation of black humic acid in lignite are eliminated non-humic acid (humin) ingredient in coal and done
It disturbs, can achieve maximization degradation effect, the fulvic acid that degradation time too long should not prevent degradation from obtaining is oxidized.
3. the equipment that the present invention uses is all equipment common in industry, raw material is simple and easy to get, reduces the system of fulvic acid
Standby cost.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A method of degradation ulmic acid and humic acid are to prepare fulvic acid, the specific steps are as follows:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 60 mesh powders；
(2) preparation of degraded polypropylene: first that humic acid made from step (1) and ulmic acid powder is mixed according to the weight ratio of 2:1
It closes uniformly, is diluted with water to solution state, being subsequently placed in while preheating in 50 DEG C of water-bath with frequency is the micro- of 200MHz
Wave pretreatment, pretreated humic acid and ulmic acid powder are put into autoclave, and it is fragrant that ferrous sulfate is added into autoclave
Pause (Fenton) reagent and catalyst, and setting autoclave pressure is degraded, and degradation time is 50 minutes, obtains degraded polypropylene；
Wherein, amount of water and dark brown humic acid ratio are 40:1；
Wherein, the weight ratio of ferrous sulfate Fenton (Fenton) reagent and humic acid and ulmic acid mixed-powder is 1:200；
Wherein, catalyst is titanium dioxide (TiO2)；
Wherein, the weight ratio of catalyst and humic acid and ulmic acid mixed-powder is 1:350；
Wherein, the pressure that autoclave is arranged is 0.3MPa；
(3) it is ultrasonically treated degraded polypropylene: degraded polypropylene made from step (2) being injected in ultrasonic cleaner, while being added pure
Water, wherein the weight ratio of degraded polypropylene and pure water is 1:10, is ultrasonically treated after mixing, supersonic frequency 80KHz, super
It is sufficiently stirred while sonication 80 minutes, the degraded polypropylene being ultrasonically treated；
(4) step (3) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 800r/min, and filter residue washs 4 times with hot water and obtains wash water, obtained wash water is uniformly mixed with above-mentioned supernatant and is located
Fulvic acid product is made in reason, successively concentrated, dry, cooling, grinding；
Wherein, hot water temperature is 65 DEG C.
The recovery rate of fulvic acid made from the embodiment is 67%.
Embodiment 2
A method of degradation ulmic acid and humic acid are to prepare fulvic acid, the specific steps are as follows:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 70 mesh powders；
(2) preparation of degraded polypropylene: first that humic acid made from step (1) and ulmic acid powder is mixed according to the weight ratio of 3:1
It closes uniformly, is diluted with water to solution state, being subsequently placed in while preheating in 55 DEG C of water-bath with frequency is the micro- of 100MHz
Wave pretreatment, pretreated humic acid and ulmic acid powder are put into autoclave, and it is fragrant that ferrous sulfate is added into autoclave
Pause (Fenton) reagent and catalyst, and setting autoclave pressure is degraded, and degradation time is 55 minutes, obtains degraded polypropylene；
Wherein, amount of water and dark brown humic acid ratio are 30:1；
Wherein, the weight ratio of ferrous sulfate Fenton (Fenton) reagent and humic acid and ulmic acid mixed-powder is 1:150；
Wherein, catalyst is titanium dioxide (TiO2)；
Wherein, the weight ratio of catalyst and humic acid and ulmic acid mixed-powder is 1:400；
Wherein, the pressure that autoclave is arranged is 0.5MPa；
(3) it is ultrasonically treated degraded polypropylene: degraded polypropylene made from step (2) being injected in ultrasonic cleaner, while being added pure
Water, wherein the weight ratio of degraded polypropylene and pure water is 1:10, is ultrasonically treated after mixing, supersonic frequency 60KHz, super
It is sufficiently stirred while sonication 70 minutes, the degraded polypropylene being ultrasonically treated；
(4) step (3) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 600r/min, and filter residue washs 3 times with hot water and obtains wash water, obtained wash water is uniformly mixed with above-mentioned supernatant and is located
Fulvic acid product is made in reason, successively concentrated, dry, cooling, grinding；
Wherein, hot water temperature is 60 DEG C.
The recovery rate of fulvic acid made from the embodiment is 61%.
Embodiment 3
A method of degradation ulmic acid and humic acid are to prepare fulvic acid, the specific steps are as follows:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 70 mesh powders；
(2) preparation of degraded polypropylene: first that humic acid made from step (1) and ulmic acid powder is mixed according to the weight ratio of 1:1
It closes uniformly, is diluted with water to solution state, being subsequently placed in while preheating in 52 DEG C of water-bath with frequency is the micro- of 150MHz
Wave pretreatment, pretreated humic acid and ulmic acid powder are put into autoclave, and it is fragrant that ferrous sulfate is added into autoclave
Pause (Fenton) reagent and catalyst, and setting autoclave pressure is degraded, and degradation time is 40-60 minutes, obtains degraded polypropylene；
Wherein, amount of water and dark brown humic acid ratio are 40:1；
Wherein, the weight ratio of ferrous sulfate Fenton (Fenton) reagent and humic acid and ulmic acid mixed-powder is 1:150；
Wherein, catalyst is di-iron trioxide (Fe2O3)；
Wherein, the weight ratio of catalyst and humic acid and ulmic acid mixed-powder is 1:300；
Wherein, the pressure that autoclave is arranged is 0.5MPa；
(3) it is ultrasonically treated degraded polypropylene: degraded polypropylene made from step (2) being injected in ultrasonic cleaner, while being added pure
Water, wherein the weight ratio of degraded polypropylene and pure water is 1:10, is ultrasonically treated after mixing, supersonic frequency 60KHz, super
It is sufficiently stirred while sonication 65 minutes, the degraded polypropylene being ultrasonically treated；
(4) step (3) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 1200r/min, and filter residue washs 3 times with hot water and obtains wash water, and obtained wash water is uniformly mixed progress with above-mentioned supernatant
Fulvic acid product is made in processing, successively concentrated, dry, cooling, grinding；
Wherein, hot water temperature is 80 DEG C.
The recovery rate of fulvic acid made from the embodiment is 60%.
Embodiment 4
A method of degradation ulmic acid and humic acid are to prepare fulvic acid, the specific steps are as follows:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 60 mesh powders；
(2) preparation of degraded polypropylene: first that humic acid made from step (1) and ulmic acid powder is mixed according to the weight ratio of 2:1
It closes uniformly, is diluted with water to solution state, being subsequently placed in while preheating in 52 DEG C of water-bath with frequency is the micro- of 250MHz
Wave pretreatment, pretreated humic acid and ulmic acid powder are put into three-necked flask, is added and urges into three-necked flask
Agent, intermediate bottleneck is for stirring, and both ends bottleneck one end is for being passed through oxidant O3, the other end seals with water column, degradation time
It is 45 minutes, the degraded polypropylene being ultrasonically treated；
Wherein, amount of water and dark brown humic acid ratio are 50:1；
Wherein, catalyst is titanium dioxide (TiO2)；
Wherein, the weight ratio of catalyst and humic acid and ulmic acid mixed-powder is 1:380；
Wherein, oxidant O3Volumetric concentration be 20%, dosage is 0.4 times of rotten acid and ulmic acid mixed-powder weight；
(3) step (2) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 1000r/min, and filter residue washs 3-5 times with hot water and obtain wash water, obtained wash water is uniformly mixed with above-mentioned supernatant into
Fulvic acid product is made in row processing, successively concentrated, dry, cooling, grinding；
Wherein, hot water temperature is 75 DEG C.
The recovery rate of fulvic acid made from the embodiment is 62%.
Embodiment 5
A method of degradation ulmic acid and humic acid are to prepare fulvic acid, the specific steps are as follows:
(1) humic acid and ulmic acid sufficiently the preparation of humic acid and ulmic acid powder: are crushed into granulating with pulverizer respectively
Diameter is 60 mesh powders；
(2) preparation of degraded polypropylene: first that humic acid made from step (1) and ulmic acid powder is mixed according to the weight ratio of 3:1
It closes uniformly, is diluted with water to solution state, being subsequently placed in while preheating in 60 DEG C of water-bath with frequency is the micro- of 250MHz
Wave pretreatment, pretreated humic acid and ulmic acid powder are put into three-necked flask, is added and urges into three-necked flask
Agent, intermediate bottleneck is for stirring, and both ends bottleneck one end is for being passed through oxidant O3, the other end seals with water column, degradation time
It is 45 minutes, the degraded polypropylene being ultrasonically treated；
Wherein, amount of water and dark brown humic acid ratio are 50:1；
Wherein, catalyst is titanium dioxide (TiO2)；
Wherein, the weight ratio of catalyst and humic acid and ulmic acid mixed-powder is 1:300；
Wherein, oxidant O3Concentration be 20%, dosage is 0.4 times of rotten acid and ulmic acid mixed-powder weight；
(3) step (2) degraded polypropylene obtained being ultrasonically treated is centrifugally separating to obtain filter residue and supernatant, wherein centrifugation speed
Degree is 1000r/min, and filter residue washs 3-5 times with hot water and obtain wash water, obtained wash water is uniformly mixed with above-mentioned supernatant into
Fulvic acid product is made in row processing, successively concentrated, dry, cooling, grinding；
Wherein, hot water temperature is 50 DEG C.
The recovery rate of fulvic acid made from the embodiment is 61%.
Comparative example 1
The comparative example is with embodiment 1 only difference is that the weight ratio of humic acid and ulmic acid powder is in step (1)
4:1, other operating procedures, condition and substance dosage are and embodiment 1 is identical.
The recovery rate of fulvic acid made from the comparative example is 29%.
Comparative example 2
The comparative example with embodiment 1 only difference is that in step (2) ferrous sulfate Fenton (Fenton) reagent with it is black
The weight ratio of rotten acid and ulmic acid mixed-powder is 1:300, other operating procedures, condition and substance dosage are and 1 phase of embodiment
Together.
The recovery rate of fulvic acid made from the comparative example is 27%.
Comparative example 3
The comparative example and embodiment 1 are only difference is that catalyst and humic acid and ulmic acid mixed powder in step (2)
The weight ratio at end is 1:450, other operating procedures, condition and substance dosage are and embodiment 1 is identical.
The recovery rate of fulvic acid made from the comparative example is 32%.
Comparative example 4
The comparative example is with embodiment 2 only difference is that the weight ratio of humic acid and ulmic acid powder is in step (1)
5:1, other operating procedures, condition and substance dosage are and embodiment 2 is identical.
The recovery rate of fulvic acid made from the comparative example is 31%.
Comparative example 5
The comparative example with embodiment 3 only difference is that in step (2) ferrous sulfate Fenton (Fenton) reagent with it is black
The weight ratio of rotten acid and ulmic acid mixed-powder is 1:100, other operating procedures, condition and substance dosage are and 3 phase of embodiment
Together.
The recovery rate of fulvic acid made from the comparative example is 30%.
Comparative example 6
The comparative example and embodiment 4 are only difference is that catalyst and humic acid and ulmic acid mixed powder in step (2)
The weight ratio at end is 1:500, other operating procedures, condition and substance dosage are and embodiment 4 is identical.
The recovery rate of fulvic acid made from the comparative example is 28%.
By embodiment 1-5 and comparative example 1-6 it is found that the method for preparing fulvic acid using the present invention, is remarkably improved Huang
The recovery rate of rotten acid, is increased to 60-67% by prior art 37-40%, while shortening extraction time, is divided by the prior art 90
Clock shortens to 60 minutes, and equipment used in extraction process is all industry conventional equipment, reduces the preparation of fulvic acid
Cost, in addition, extraction process is safe from harm to environment.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. the method for a kind of degradation humic acid and ulmic acid to prepare fulvic acid characterized by comprising
(1) preparation of humic acid and ulmic acid powder: it is 60-80 mesh powder that humic acid and ulmic acid, which are ground into partial size,；
(2) preparation of degraded polypropylene: humic acid and ulmic acid powder being uniformly mixed, while pure water is added, and are preheated and used microwave
Pretreatment is added ferrous sulfate Fenton reagent and catalyst, obtains degraded polypropylene by high pressure drop solution；
(3) it is ultrasonically treated degraded polypropylene: degraded polypropylene being injected in ultrasonic cleaner, while pure water is added, degraded polypropylene and pure water
Weight ratio is 1:10, is ultrasonically treated after mixing, while being stirred 60-90 minutes, the degraded polypropylene being ultrasonically treated；
(4) degraded polypropylene of ultrasonic treatment is centrifugally separating to obtain filter residue and supernatant, wherein filter residue washs 3-5 times with hot water and obtains
Obtained wash water is uniformly mixed with above-mentioned supernatant and handles by wash water, and Huang is made in successively concentrated, dry, cooling, grinding
Rotten acid.
2. the method for a kind of degradation humic acid and ulmic acid according to claim 1 to prepare fulvic acid, feature exist
In step (2) can also use following steps:
Humic acid made from step (1) and ulmic acid powder are uniformly mixed according to the weight ratio of 1-3:1, pure water is added, wherein
The weight ratio of mixed-powder and pure water is 1:30-50, is preheated to 50-55 DEG C, and preheating while is pre- with 100MHz-300MHz microwave
It is put into three-necked flask after processing, catalyst is added into three-necked flask, for stirring, both ends bottleneck one end is used for intermediate bottleneck
It is passed through oxidant O3, the other end seals with water column, and degradation time is 40-60 minutes, obtains degraded polypropylene.
3. the method for a kind of degradation humic acid and ulmic acid according to claim 1 or 2 to prepare fulvic acid, feature
It is, ferrous sulfate Fenton reagent and the humic acid and the weight ratio of ulmic acid mixed-powder stated is 1:150-250.
4. the method for a kind of degradation humic acid and ulmic acid according to claim 1 or 2 to prepare fulvic acid, feature
It is, the catalyst is titanium dioxide, and catalyst is 1:300-400 with the weight ratio of humic acid and ulmic acid mixed-powder.
5. the method for a kind of degradation humic acid and ulmic acid according to claim 2 to prepare fulvic acid, feature exist
In the oxidant O3Volumetric concentration be 20%, dosage is 0.4 times of humic acid and ulmic acid mixed-powder weight.
6. the method for a kind of degradation humic acid and ulmic acid according to claim 1 to prepare fulvic acid, feature exist
In the pressure of high pressure degradation is 0.3-0.5Mpa, time 40-60min.
7. the method for a kind of degradation humic acid and ulmic acid according to claim 1 to prepare fulvic acid, feature exist
In the frequency of ultrasonic treatment is 50KHz-100KHz.
8. the method for a kind of degradation humic acid and ulmic acid according to claim 1 to prepare fulvic acid, feature exist
In the speed of centrifuge separation is 600-1200r/min.
9. the method for a kind of degradation humic acid and ulmic acid according to claim 1 to prepare fulvic acid, feature exist
In the hot water temperature for handling filter residue is 60 DEG C -80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116589700A (en) * | 2023-05-19 | 2023-08-15 | 内蒙古蒙土生态环保科技有限公司 | Method for purifying fulvic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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