The biostimulant of a kind of humic acid biological yield stimulant preparation method and preparation
Technical field
The present invention relates to biostimulant, be specifically related to a kind of humic acid biological yield stimulant with and preparation method thereof, be the humic acids growth stimulant prepared through peroxide degradation by brown coal.
Background technology
Humic acids is the unbodied macromolecule organic of a class, is produced through microbiological deterioration by dead organisms material, is extensively present in the low-rank coal such as natural brown coal, weathered coal, peat and soil.Humic acids of many uses, can be used as water conditioner, coal water mixture stabilizing agent, petroleum assistant etc., and humic acids is used as the investigation and application widely that plant growth substance obtains especially in recent years.
The production mainly weathered coal nitric acid oxido-degradation of coal based humic acid, and be oxidized with strong oxidizers such as hydrogen peroxide, potassium permanganate, sulfuric acid.Humic acids is water insoluble is dissolved in alkali, therefore usually prepares in the basic conditions.But this method can not solve problems of dissolution during application, be particularly not suitable in a lot of fields adopting alkaline condition.Ammonium humate is a kind of fulvo acid, can be used as water soluble fertilizer, as nitrogenous fertilizer for plant provides nitrogenous source, usually uses in Chemical Mixed Fertilizer mode.The preparation of current ammonium humate adopts free humic acid and ammoniacal liquor to react to be prepared from.Zhao Rui, Zhang Baolin, in vast at " weathered coal hydrogen peroxide oxidation---the research of ammonification preparing humic acid ammonium " (" Xinyang Normal College's journal: natural science edition ", phase October the 4th in 2010) in, weathered coal is added in three-necked flask, ammoniacal liquor (or carbon ammonium) and hydrogen peroxide and appropriate distilled water, temperature of reaction is 50 DEG C, reaction times is 30min, measure ammonium humate content, and determine optimum proportion than being weathered coal: ammoniacal liquor (25% ammoniacal liquor): hydrogen peroxide (30% hydrogen peroxide): water=1:1.04:1.5:6.46 is optimum proportioning, the optimum reaction conditions is temperature of reaction 60 DEG C, time 60min.Its ammonium humate concentration obtained is at about 40g/L.
But humic acids transformation efficiency and yield problem in the transformation efficiency of humic acids in humic acids prepared by different preparation method and different low-rank coal is only paid close attention in existing research, the regulating effect of humic acids to plant-growth that different preparation method prepares does not have research, and be obtain certain certain effects be all at present adopt humic acids and other material mixtures are realized, this is due to not deep enough to the study mechanism of Plant-stimulating activity to humic acids on the one hand, and it is seldom relevant with composition research to the molecular structure of the humic acids prepared under different condition, as long as these all make the effect that it is believed that humic acids only relevant with its content, and limit people and remove to study humic acids prepared by different preparation method again to the difference of plant hormesis.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and technical problem to be solved is to provide a kind of method utilizing low-rank coal directly to prepare humic acid biological yield stimulant and the humic acid biological yield stimulant utilizing the method to obtain.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: after brown coal are pulverized, under Ag-Pt catalyzer exists, mix with the vitriol oil and hydrogen peroxide and react, then add water and S-WAT carry out refluxing, by the aqueous phase concentrate drying after backflow, obtain humic acid biological yield stimulant.
The organic content of described brown coal is not less than 70%, and the granularity of described brown coal powder is not less than 120 orders.
The mass ratio of described brown coal powder and the vitriol oil, hydrogen peroxide is that brown coal powder: the vitriol oil: hydrogen peroxide=100:2-3:180-240, described hydrogen peroxide is 8%-15% hydrogen peroxide.
The reaction conditions of described brown coal powder and the vitriol oil and hydrogen peroxide is: ultrasonic wave atmosphere, 70-90 DEG C, reaction 10-20min.
When the reaction product of described brown coal powder and the vitriol oil and hydrogen peroxide refluxes, the consumption of water and S-WAT is, mass ratio, water: hydrogen peroxide=2:1, S-WAT: brown coal powder=5-8:100.
Described reflux conditions is temperature 90-100 DEG C, and return time is 1-1.5h.
The method of described aqueous phase concentrate drying is lyophilize.
Present invention also offers the humic acid biological yield stimulant obtained based on aforesaid method.
The pH=5.5-6.5 of the high-quality humic acid biological yield stimulant obtained, water insoluble matter content is lower than 5%.
Compared with prior art the present invention has following beneficial effect.
1, the present invention adopts the vitriol oil to be other mineral acids as the effect of acidifying activator, comprises dilute sulphuric acid irreplaceable, cannot make the maximize conversion of the humic acids in low-rank coal.
2, be 50-70% with the fulvo acid content of method acidolysis of the present invention, catalyzed oxidation, cavitation effect reaction preparation, and for the full water-soluble product of whole active ion composition can be retained.Through simultaneous test, it is obviously better than existing ammonium humate product to plant-growth promotion effect, can improve plant antiradical activities, strengthens plant vigor, oil recovery enhancement.
Accompanying drawing explanation
Fig. 1 is the effect diagram of different concns humic acids to total protein content in leaf mustard block root.
Fig. 2 is the effect diagram of different concns humic acids to leaf mustard block root POD vigor.
Fig. 3 be No. 6 humic acids different concns to leaf mustard fruit POD isozyme sds gel electrophoresis figure (be followed successively by from left to right control group and 100,200,300,500mg/L humic acids treatment group).
Fig. 4 be No. 7 humic acids different concns to leaf mustard fruit POD isozyme sds gel electrophoresis figure (be followed successively by from left to right control group and 100,200,300,500mg/L humic acids treatment group).
Fig. 5 is the effect diagram of different concns humic acids to leaf mustard block root total sugar content.
Fig. 6 is the effect diagram of different concns humic acids to leaf mustard block root SOD vigor.
Fig. 7 is the effect diagram of different concns humic acids to leaf mustard block root VC content.
Fig. 8 is that the humic acids of different concns is to the effect diagram of eggplant pulp total protein content.
Fig. 9 is that the humic acids of different concns is to the effect diagram of eggplant pulp POD vigor.
Figure 10 is that the humic acids of different concns is to the effect diagram of eggplant pulp polyphenoloxidase content.
Figure 11 is that different concns No. 6 humic acidss are to the effect diagram of eggplant fruit girth.
Figure 12 is that different concns No. 7 humic acidss are to the effect diagram of eggplant fruit girth.
Figure 13 is that the humic acids of different concns is to the effect diagram of eggplant leaf CAT vigor.
Figure 14 is that the humic acids of different concns is on the impact of eggplant leaf chlorophyll b.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal selecting organic average content 75%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 10% hydrogen peroxide=100:2:200, after three is mixed, in ultrasonic cavitation effect, at 80 DEG C, reaction 10min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 5% is added, reflux 1h at 100 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Embodiment 2
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal of organic average content 70%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 8% hydrogen peroxide=100:3:220, after three is mixed, in ultrasonic cavitation effect, at 70 DEG C, reaction 18min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 5% is added, reflux 1.2h at 95 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Embodiment 3
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal selecting organic average content 70%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 10% hydrogen peroxide=100:2:180, after three is mixed, in ultrasonic cavitation effect, at 80 DEG C, reaction 15min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 7% is added, reflux 1.5h at 90 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Embodiment 4
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal selecting organic average content 70%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 12% hydrogen peroxide=100:3:230, after three is mixed, in ultrasonic cavitation effect, at 85 DEG C, reaction 15min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 5% is added, reflux 1.2h at 100 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Embodiment 5
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal selecting organic average content 70%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 14% hydrogen peroxide=100:2:190, after three is mixed, ultrasonic cavitation effect, 80 times DEG C, reaction 20min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 6% is added, reflux 1h at 95 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Embodiment 6
A kind of humic acid biological yield stimulant preparation method, comprise the following steps: the brown coal selecting organic average content 70%, be crushed to after granularity is not less than 120 orders, under Ag-Pt catalyzer exists, it is brown coal powder in mass ratio: the vitriol oil: 15% hydrogen peroxide=100:2:240, after three is mixed, in ultrasonic cavitation effect, at 90 DEG C, reaction 10min, then the water of hydrogen peroxide double weight and the S-WAT of brown coal powder weight 8% is added, reflux 1.2h at 90 DEG C, and backflow aqueous phase carries out concentrate drying, obtains humic acid biological yield stimulant.
Experimental example
In order to evaluate humic acid biological tethelin of the present invention and the difference of existing humic acids product in plant growth regulating effect, invention has been simultaneous test.
Test sample (No. 6 humic acidss): the sample selecting embodiment 1;
Control sample (No. 7 humic acidss): prepare as follows: produce weathered coal for raw material with Shanxi Yuanping City, and sulfuric acid, 10% hydrogen peroxide and distilled water weight ratio be 1:1.04:1.5:6.46 are optimum proportioning, the optimum reaction conditions is temperature of reaction 60 DEG C, time 60min.
1, on the impact of various nutrition and physical signs in leaf mustard block root
In 26 days Augusts in 2012, with test sample humic acids 100mg/L, 200mg/L, 300mg/L, 500mg/L aqueous solution, whole strain spraying process is carried out to leaf mustard Shandong shaven head leaf mustard kind Seedling Stage (four leaf phases); Control sample humic acids does same process with the leaf mustard experimental plot of same concentration to another sheet same breed, and every day, 17:30 ~ 18:00 carried out at dusk, every 2d process 1 time, and co-processing 5 times.To spray distilled water in contrast, the dose of sprinkling is completely moistening for degree with plant.The consistent plant of the final growth selection of each treatment group is as test materials.
The mensuration of leaf mustard block root being carried out to nutritive index is at block root collection period (November 5).The morning, 7:30 went to experimental plot to be taken out from soil by leaf mustard block root, and wash clean, peeling, it is stand-by to be placed on ice pan.The same area that block root is got in each process measures, and each processing sample repeats 3 times, and result gets its mean value.See Fig. 1-Fig. 6.
As can be seen from Figure 1, when humic acids concentration is 100mg/L, 200mg/L, 500mg/L, in the leaf mustard after sample preparation of the present invention, total protein content is all than control sample height about about a times, and when lower concentration 100mg/L, 200mg/L best results.
As seen from Figure 2, when four groups of humic acids concentration are 100mg/L, 200mg/L, 300mg/L, 500mg/L, in the leaf mustard block root of inventive samples process, POD vigor is all apparently higher than control sample, and effect is best when concentration is 200mg/L.
Contrasted from Fig. 3 and Fig. 4, No. 6 humic acidss of the present invention obviously detect POD isozyme when lower concentration 100mg/L, 200mg/L, 300mg/L.Illustrate that in the leaf mustard fruit of employing No. 6 humic acids process, POD isozyme content is higher than No. 7 humic acids process.
As can be seen from Fig. 5-Fig. 7, No. 6 humic acidss of the present invention obviously increase when lower concentration 100mg/L, 200mg/L the promoter action of total sugar content, VC and SOD vigor in leaf mustard block root and are better than No. 7 humic acidss.
Conclusion: by the mensuration of each nutrition and physical signs in leaf mustard block root with contrast and can find, the raising of humic acids of the present invention to leaf mustard nutrition content and the improvement result successful of physical signs, and better when lower concentration, be better than contrasting humic acids simultaneously.
2, humic acids different concns is on the impact of several nutrition of eggplant fruit and physical signs
From 12 days July in 2012, with No. 6 humic acids 100mg/L, 200mg/L, 400mg/L, 600mg/L, 800mg/L aqueous solution, whole strain spraying process is carried out to the large black round eggplant kind initial bloom stage of eggplant, No. 7 humic acidss do same process with same concentration to another sheet eggplant experimental plot, every day, 17:30 ~ 18:00 carried out at dusk, every 1d process 1 time, co-processing 5 times.To spray distilled water in contrast, the dose of sprinkling is completely moistening for degree with plant.The consistent plant of the final growth selection of each treatment group is as test materials.
The mensuration of eggplant pulp being carried out to nutrition and physical signs is in collection period (August 13).The morning, 7:30 won eggplant, with clear water, eggplant surface is cleaned, thieving paper blots the moisture on surface, with scalper, eggplant is cut, get eggplant pulp, reject seed, each sample repeats 3 times, the same position of the different eggplant of same concentration for the treatment of taken from by different sample, and the measurement result of nutrition and physical signs gets its mean value.
Choose the eggplant 30 of same concentration for the treatment of different plants when measuring eggplant girth (thickness), listing mark, from July 25, within every 5 days, measure a fruit girth, totally 4 times, record and get its mean value.
The results are shown in Figure shown in 8-12.
As seen from Figure 8, adopt No. 6 humic acidss of the present invention in tested concentration range, in eggplant pulp, the increasing degree of total protein content is all apparently higher than No. 7 contrast humic acidss.
As seen from Figure 9, No. 6 humic acidss of the present invention and No. 7 humic acidss, on the impact of POD vigor in eggplant pulp, all have promoter action when lower concentration, have restraining effect on the contrary when high density, and promoter action both when 200mg/L is the most remarkable, and the present invention is obviously better than control sample.
As seen from Figure 10, lower concentration humic acids has promoter action to polyphenol oxidase enzyme activity in eggplant pulp and the present invention is better than reference substance, and produces restraining effect when high density.
As can be seen from Figure 11-Figure 12, No. 6 and No. 7 humic acidss all have obvious promoter action to the increase of eggplant fruit, and are all most pronounced effects when concentration is 200mg/L, and No. 6 humic acidss of the present invention contrast humic acidss to the promoter action that fruit increases by being obviously better than No. 7.
3, different concns humic acids is on the impact of yellow mouth eggplant leaf physiological and biochemical index
From 12 days July in 2012, with No. 6 humic acids 100mg/L, 200mg/L, 400mg/L, 600mg/L, the 800mg/L aqueous solution carries out whole strain spraying process to the large black round eggplant kind initial bloom stage of eggplant, No. 7 humic acidss do same process with same concentration to another sheet eggplant experimental plot, every day, 17:30 ~ 18:00 carried out at dusk, every 1d process 1 time, and co-processing 5 times.To spray distilled water in contrast, the dose of sprinkling is completely moistening for degree with plant.The consistent plant of the final growth selection of each treatment group is as test materials.
The mensuration of carrying out physical signs to blade is the animated period (August 12) at plant strain growth.The morning, 7:30 taked blade, and wipe clean with the wet gauze examination of cleaning, leaf is avoided main lobe arteries and veins and drawn materials, and carries out the mensuration of physical signs, and each sample repeats 3 times, and the different leaves of different plants taken from by different sample, and the measurement result of physiological and biochemical index gets its mean value.
It the results are shown in Figure 13-14.Shown in Figure 13 and Figure 14, No. 6 humic acidss of the present invention and reference substance No. 7 humic acidss all have promoter action to CAT vigor and Chlorophyll-a Content in eggplant leaf, and when lower concentration 200mg/L, effect is optimum, and the present invention is better than reference substance.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore, no matter from that, above-mentioned embodiment of the present invention all can only be thought explanation of the present invention and can not limit invention, claims indicate scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.