CN106032333A - Humic acid composition and preparation method thereof - Google Patents
Humic acid composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a humic acid composition. The humic acid composition is prepared from, by weight, 19.6-49.3 parts of fulvic acid, 0.4-5.2 parts of ulmic acid and 0-1.8 parts of humic acid. A preparation method comprises the steps that oil crop straw is subjected to prepared material treatment and then subjected to liquid-phase circulating hydrolysis in a ammonium sulfite solution to obtain hydrolysate; the hydrolysate is subjected to multiple-effect evaporation and concentration until the solid concentration is 50%-65%, and a concentrated solution is obtained; the concentrated solution is stirred and then subjected to spraying granulation, and the humic acid composition is obtained. According to the preparation method, lignin in the oil crop straw is decomposed through circulating hydrolysis on the oil crop straw to obtain the humic acid composition with the very high fulvic acid content. The humic acid composition is reasonable in component proportion and beneficial for increasing the crop yield.
Description
Technical field
The present invention relates to humic acid study, a kind of humic acids compositions and the preparation method of said composition.
Background technology
Humic acids (Humic acid, HA), a kind of natural organic high-molecular compound, be humus mainly comprise portion
Point.Animals and plants remains such as lignins, under microorganism and geophysics, chemical action, through a series of decomposition and
Convert the class macromole organic monoacid mixture formed.Humic acids is not a single acid, but complicated containing
There is the mixture of the group such as carboxyl, phenolic hydroxyl group, so this mixture shows the character of binary acid or ternary acid once in a while.Rotten
Phytic acid is usual and ion forming complex in nature.
Humic acids, as organic matter raw material, is widely used in agriculture, woods, herds, oil, chemical industry, building materials, medicine, defends
The every field such as life, environmental protection.Now belong to direct or indirect application humic-acid-type substances has five aspects, can be summarized as 70
Individual trifle.The major product of China's exploitation has fertilizer, pesticide, veterinary drug, drought resistance agent, feed additive；Medicine, health care
Product, cosmetics；Petroleum assistant, industrial water conditioning agent, coal water mixture stabilizing agent, accumulator extender, ceramic additive,
More than 100 kind such as easer, has basically constituted the integral framework of China Humic Acid series products.
Humic acids is divided into humic acid, ulmic acid, fulvic acid, wherein humic acid proportion by dissolubility and molecular size range
Maximum, its molecular weight is maximum, more than 105The order of magnitude, is dissolved in alkali and water insoluble, sour, ethanol and acetone；Hymatomalenic acid
Molecular weight is relatively big, is 104-105The order of magnitude, is dissolved in alkali, ethanol and acetone；Fulvic acid molecular weight, is 103The order of magnitude,
It is dissolved in acid, alkali and water.In these three component in addition to fulvic acid, humic acid, ulmic acid be transformed into potassium, sodium equivalent metal or
Ammonium salt can be dissolved in water, the aobvious alkalescence of these saline solutions.And fulvic acid can be directly dissolved in water, its aqueous solution is faintly acid.
CN103275333A discloses a kind of crop material and extracts class humic acids and compound fertilizer's preparation method thereof, by extracting
Humic acids in rice straw and fulvic acid, optimize the utilization rate of resource, indirectly decreases rice straw to environment
Polluting, meanwhile, the compound fertilizer utilizing the class humic acids extracted to prepare can improve the production environment of crop, for the life of crop
The more nutrient of long offer, strengthens the resistance of crop.
CN101040622 discloses a kind of preparation side utilizing straw to produce composite humic acid plant growth regulator
Method, one or more mixture in agricultural crop straw corn straw, Sorghum vulgare Pers. stalk, wheat straw, rice straw stem stalk are entered by it
Row is pulverized, batch mixing, and then sterilizing 10-30 minute under 80-90 DEG C of high temperature is down to 35-40 DEG C and is fermented, add quick-acting
Bacterium is fermented 10-20 days, produces extracting solution；This invention is mixed liquor, can preserve for a long time at normal temperatures, utilize corn stalk
The plant caulomes such as stalk, wheat straw, rice straw are raw material, and the product produced has nutrition, health care, can swash plant
Living plant physiological function, enhancing immunity, there is antibacterial action of substantially curing the disease, the present invention improves yield, has more significant
Economic benefit and social efficiency.
CN 200710180056.X discloses production method and the application thereof of a kind of agricultural enzyme microorganism culture medium, described culture medium
With weathered coal as raw material, component: humic acids 30-70G, fulvic acid 4-30G, ulmic acid 2-20G, humic acid 2-20G；Ash
Part 4-15%, C/N than 25-30: 1, organic 40-80%, N.P.K 3-4%；Formula contains: humic acids 40-70%, fulvic acid
6-30%, ulmic acid 3-15%, humic acid 3-15%；By raw material 800-1000 gram and sterilized water 400-500 gram stirring during production,
Adding original seed 1-2G, regulation pH value is 6-7, controls incubator temperature 48-60 DEG C, humidity 75-85 DEG C, and oxygen is appropriate, shading
Ferment 48-72 hour.The enzymatic microorganism obtained is containing multiple organic acid, several amino acids, multiple oxygen-containing functional group, multiple
Biological element etc., make probiotics bacterium live reach 90-260 hundred million/gram, surpass far away GB 0.2 hundred million/gram standard, this bacterium also may be used simultaneously
Producing three grades of bacterial manure is that land for growing field crops is suitable for horticultural gardening, excellent.Chemical fertilizer, pesticide vicious cycle can be made after application to life
State benign cycle changes, and highlights technological progress.The agricultural enzyme microorganism culture medium poorly water-soluble using the method to produce, is dissolved in
Easily generating flocculent deposit during water, bioavailability is low, and its production cycle is long, and cost is high.Fulvic acid, ulmic acid,
How rational proportion is to improve crop yield for humic acid, and prior art does not provide the enlightenment of any technology.
In view of this, the special proposition present invention.
Summary of the invention
It is an object of the invention to a kind of humic acids compositions, this humic acids compositions assembles rationally, is conducive to carrying further
High crop yield.
For realizing the purpose of the present invention, the present invention adopts the following technical scheme that
A kind of humic acids compositions, it is characterised in that: including:
Fulvic acid 19.6-49.3 weight portion；Ulmic acid 0.4-5.2 weight portion；Humic acid 0-1.8 weight portion.
The fulvic acid of humic acids compositions molecular weight of the present invention and ulmic acid content are high, and the humic acid that molecular weight is bigger contains
Measure low, within after humic acid fertilizer is dissolved in water 5 hours, have no flocculent deposit.Humic acids of the present invention passes through fulvic acid, and palm fibre is rotten
Acid, the rational proportion of humic acid makes humic acids compositions be difficult to flocculation, and resistance to hard water is strong, and bioavailability is high, improves
Crop yield.
Organic composition in humic acids compositions of the present invention includes fulvic acid, ulmic acid, humic acid and a small amount of other
Organic impurities, other organic impuritiess described are pectin and saccharide.Humic acids compositions good water solubility of the present invention, it is possible to strengthen
The crumb structure of soil, makes loosing soil, promotes that crop is to the absorption of mineral and utilization.
The most described humic acids compositions includes fulvic acid 20.9-48.5 weight portion；Ulmic acid 0.4-4.8 weight portion；Humic acid
0-1.6 weight portion.
The most described humic acids compositions includes fulvic acid 20.9-47.8 weight portion；Ulmic acid 0.4-4.1 weight portion；Black corruption
Acid 0-1.5 weight portion.
Described humic acids compositions also includes ammonium or ammonium ion 4.1-9.5 weight portion, potassium 2.08-3.58 weight portion, chlorine 0.43-1.59
Weight portion, sodium 0-1.13 weight portion.
The most described humic acids compositions also includes ammonium or ammonium ion 4.2-8.9 weight portion, potassium 2.08-3.13 weight portion, chlorine
0.43-1.36 weight portion, sodium 0.23-0.96 weight portion.
The most described humic acids compositions also includes ammonium or ammonium ion 4.4-8.7 weight portion, potassium 2.68-2.9 weight portion, chlorine
0.44-0.94 weight portion, sodium 0.38-0.41 weight portion.
Described humic acids compositions also includes calcium 0.07-0.19 weight portion, magnesium 0.22-0.39 weight portion, ferrum 0-0.05 weight portion,
Zinc 0-0.02 weight portion.
The most described humic acids compositions also includes calcium 0.08-0.16 weight portion, magnesium 0.28-0.34 weight portion, ferrum 0.01-0.05
Weight portion, zinc 0.01-0.02 weight portion.
The present invention is by calcium, magnesium, ferrum, the rational proportion of zinc, and applicable crop absorbs.Ammonium or ammonium ion, sodium,
Potassium, calcium, magnesium, ferrum, zinc are combined formation salt, or and yellow humic with inferior sulfate radical, sulfate radical, nitrate anion or salt acid ion
Acid, ulmic acid or humic acid complexation.
Inorganic salts material in humic acids compositions and fulvic acid, ulmic acid, one piece of use of humic acid have Synergistic
Effect.Humus acid can improve the permeability of plant cell and cytoplasmic permeability, promotes that plant is to water and nutrient
Absorb and internal balance, add the plant assimilation effect to various soluble inorganic salts.
In humus acid composition, various soluble inorganic salt materials can promote phytoenzyme activity, various enzymes in plant
Increased activity, metabolism reinforcement, the growth promoter of plant is healthy and strong, and nutrition is complete abundant, the beneficially conjunction of material
Becoming, transfer and accumulate, yield and quality all can improve.
Containing acidic groups 1.33-2.15mmol/g in described humic acids compositions, carboxyl 0.21-0.59mmol/g, phenolic hydroxyl group
1.12-1.56mmol/g。
Containing acidic groups 1.55-1.81mmol/g in the most described humic acids compositions, carboxyl 0.32-0.45mmol/g, phenol
Hydroxyl 1.23-1.36mmol/g.
Containing acidic groups 1.68mmol/g in the most described humic acids compositions, carboxyl 0.38mmol/g, phenolic hydroxyl group
1.30mmol/g。
The a part of generation humate that combines with ammonium ion or other metal ions of the acidic-group of humic acids of the present invention, separately
A part is free acidic-group.The method that the present invention uses prior art conventional is measured in humic acids compositions free
Acidic-group.Described total acidic group is total acidic group free in humic acids compositions, and described carboxyl is humic acids group
Carboxyl free in compound, described phenolic hydroxyl group is phenolic hydroxyl group free in humic acids compositions.
The acidic-group of humic acids such as carboxyl and phenolic hydroxyl group possess chela (network) and close ability metal ion, it is possible to be greatly improved
The biological effectiveness of metal ion.Acidic-group maintains moisture, solubilized inorganic fertilizer and then reduce him at the root of crop
Scatter and disappear；Reduce phosphorus and calcium, ferrum, magnesium, the reaction of aluminum, or they are converted into can be absorbed by plants from invalid state
The form utilized；The noxious substance in earth can be reduced.Earth physicochemical character can be improved, improve fertilizer efficiency, activate mud
Soil nutrient, thus the growing environment of Crop Improvement, humic acids self also possesses enhancement crop root growth simultaneously, adds and pretends
Thing to the absorption of nutrient, save bit by bit and transport, promote Repiration, improve the activity of enzyme, improve plant stress-resistance ability
Etc. multiple biological activity.The present invention is it was discovered by researchers that acidic-group and sodium ion or other ions in humic acids compositions
The acidic-group that part is free is there is also, it is possible to extend the action time of humic acids compositions, make fertilizer efficiency slowly release after in conjunction with
Put, according to the psychological need of crop to reach to balance dynamically.When humic acids compositions of the present invention is applied to acid ground,
Free acidic-group first chelated mineral cation is beneficial to absorbing of root；Then the acidity being combined with sodium ion
Group can progressively discharge sodium ion, becomes free acidic-group, and further chelated mineral cation is beneficial to root
Absorb.
A kind of humic acids compositions, is prepared by oil crop straw high-temperature heating liquid-phase hydrolysis in ammonium sulfite solution.
Oil crop straw refers to the straw to squeeze an oils and fats class crop as main uses.This kind of crop includes but does not limits
In Semen sojae atricolor, Semen arachidis hypogaeae, Semen Sesami, Helianthi, Semen Gossypii, Semen Ricini, Fructus Perillae, oil seed flax and Fructus Cannabis etc..
Oil crop straw be mainly composed of cellulose, hemicellulose and lignin.Lignin, also known as lignin, is a kind of
Native three dimensional net high-polymer polymer, constitutes the main component of plant cell wall together with cellulose and hemicellulose, is
In plant kingdom, content is only second to a family macromolecule organic substance of cellulose, is the Renewable resource of a kind of great potential.
Oil crop can be by lignin dissolution therein and hydrolyze under conditions of high-temperature liquid-phase heating in ammonium sulfite solution
Fulvic acid, ulmic acid and humic acid for little molecule.
The preparation method of a kind of humic acids compositions, comprises the steps:
(1) process that carries out oil crop straw getting the raw materials ready obtains oil crop stalk；
(2) it is continuously added in reactor after oil crop stalk being contacted with ammonium sulfite solution, is continuously added to simultaneously
Stock solution A of 90-105 DEG C and circulation stock solution B of 160-180 DEG C, the consumption of ammonium sulfite is oil crop stalk over dry
The 18-30% of material amount, the consumption of reactor sulfite ammonium salt solution+stock solution A+ circulation stock solution B is that oil crop straw is former
Expect exhausted amount of dry matter 6.5-10 times, reactor pressure is 0.6-0.8MPa；
(3) it is incubated 40-180min after reactor temperature being warming up to 160-180 DEG C and forms serosity A；
(4) the partial reaction liquid in serosity A being discharged formation serosity B, the reactant liquor of discharge joins in circulation original fluid container,
And it is warming up to 160-180 DEG C, as circulation stock solution B in step (2) in circulation original fluid container；
(5) adding cold cleaning mixture in serosity B, washing displacement obtains serosity C and hydrolyzed solution, by many after hydrolyzed solution heat exchange
Effect evaporation slurry-spraying pelletizing obtains humic acids compositions；
(6) after serosity C spurts plasma discharge, shove obtains stock solution A and serosity D, stock solution A is used in step (2)；
(7) obtain serosity D and cold cleaning mixture by adding washing in serosity D after water heat exchange, cold cleaning mixture is used for step
(5) in.
In straw, lignin carrys out sclereid wall, so lignin is positioned at the fibre of plant cellulose by forming intertexture net
Between dimension.Sodium sulfite solution is penetrated in the plant cell wall of oil crop by the present invention under the high temperature conditions, thin with plant
Lignin generation sulfonating reaction in cell wall, introduces sulfonic group in lignin and generates the lignosulfonate being dissolved in water.Due to
Lignosulfonate molecular weight is big, is interweaved in hydrolyzed solution between lignosulfonate long-chain molecule, and hydrolyzed solution viscosity rises rapidly,
The lignin of dissolution is easily attached on the surface of Plant fiber, stops the further dissolution of lignin of plant cell pars intramuralis.
In order to reduce the viscosity of hydrolyzed solution, making sulfonating reaction carry out further, the present invention uses the method for circulation hydrolysis,
While sulfonating reaction, lignosulfonate is hydrolyzed.Circulation stock solution B circulates heating under the high temperature conditions, can prevent
Only the lignin of long-chain is attached on plant fibre surface, improves the dissolution efficiency of lignin；Lignosulfonate macromole can be made
Easily the effect at ammonium sulfite issues heat splitting action, makes the viscosity of circulation stock solution B irreversibly reduce；After hydrolysis
The humic acids molecular weight obtained, fulvic acid content is high, and lignosulfonate degradation efficiency is high；After hydrolyzed solution viscosity reduces
Further promote the dissolution of plant cell wall inner timber quality, improve the solid content of hydrolyzed solution；Recycle heat utilizes,
Improve the utilization rate of the energy；Use circulation stock solution B liquid phase heating, it is to avoid introduce the chemical reaction shadow that steam generation is fierce
The stability of acoustic system, lignin uniform hydrolyses is thorough.
Preparation method stock solution A of humic acids compositions of the present invention, circulation stock solution B and the circulation recycling of cold cleaning mixture improve
The utilization rate of the energy and water, in the hydrolyzed solution finally given, solid inclusion content is high, for 6-12%, wherein Organic substance and nothing
The concentration of machine thing ratio is for 1.5-2:1, and the yield of humic acids compositions is high.
In step (2), substitute stock solution A and circulation stock solution B with hot water respectively during reaction first.
In described step (3), outside reactor, it is provided with heater, by heater outer circulation and the circulation of circulation stock solution B
Reactor temperature is warming up to 160-180 DEG C.
The described blade got the raw materials ready as oil crop crushed stalk obtains a length of 20mm-60mm qualification rate >=92%, by grass
Sheet washing desliming is husky, is dehydrated to over dry content of material more than 15%, and addition screw feeder compresses and continues dehydration and obtains absolutely
Dry matter content is the oil crop stalk of 35-45%.
The temperature of described hydrolyzed solution is 130-145 DEG C, and hydrolyzed solution and normal-temperature water heat exchange are to 75-80 DEG C of multiple-effect evaporation whitewashing later
Pelletize obtains humic acids compositions, and normal-temperature water heat exchange is warming up to 70-80 DEG C in step (7).
In described step (6), the temperature of stock solution A is 120-140 DEG C, heat exchange be cooled to 90-105 DEG C after for step (2)
In.
Described hydrolyzed solution multiple-effect evaporation is 50-65% to solid concentration, obtains the concentrated solution that temperature is 100-110 DEG C, will
After concentrated solution stirring, slurry-spraying pelletizing obtains humic acids compositions.
After using technique scheme, the present invention compared with prior art has the advantages that
The present invention is by hydrolyzing, by whole for the lignin in oil crop straw water the ammonium sulfite of oil crop straw
Solution obtains humic acids compositions, can comprise the substantial amounts of indispensable element favourable to plant growing or micro-in humic acids compositions
Secondary element, can be fabricated to be suitable for different plant growing or the compositions of area needs.Produce after the hydrolysis of oil crop straw
Containing cellulose and hemicellulose in solid residue, can be used for papermaking or prepare fermentable sugars.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention
Detailed description of the invention
Embodiment 1
(1) take sesame stalk, Semen Ricini stalk, Semen arachidis hypogaeae bar, cotton stalk, each portion of Semen sojae atricolor bar respectively, pulverize and obtain a length of 60mm
Blade, it is husky that blade washs desliming, is dehydrated to over dry content of material more than 15%, adds screw feeder and compress and continue
Continuous dehydration obtains the oil crop stalk that over dry content of material is 35-45%；
(2) after oil crop stalk being mixed with ammonium sulfite solution, it is continuously added in reactor, adds continuously simultaneously
Entering stock solution A of 90-105 DEG C and circulation stock solution B of 175 DEG C, the consumption of ammonium sulfite is oil crop stalk over dry
The 18% of material amount, the consumption of ammonium sulfite solution+stock solution A+ circulation stock solution B is oil crop stalk over dry materials
6.5 times of amount, reactor pressure is 0.7MPa；
(3) it is incubated 120min after reactor temperature being warming up to 175 DEG C and forms serosity A；
(4) the partial reaction liquid in serosity A being discharged formation serosity B, the reactant liquor of discharge joins in circulation original fluid container,
And it is warming up to 175 DEG C, as circulation stock solution B in step (2) in circulation original fluid container；
(5) adding cold cleaning mixture in serosity B, washing displacement obtains serosity C and hydrolyzed solution, by the 70-80 of hydrolyzed solution heat exchange
After DEG C, it is 55% that multi-effect evaporator is concentrated into solid concentration, obtains the concentrated solution that temperature is 100-110 DEG C, by concentrated solution
After stirring, slurry-spraying pelletizing obtains humic acids compositions；
(6) after serosity C spurts plasma discharge, shove obtains stock solution A and serosity D, will be used for step (2) after the heat exchange of stock solution A
In；
(7) normal-temperature water is added washing acquisition serosity D and cold cleaning mixture in serosity D with hydrolyzed solution heat exchange after 75-80 DEG C,
Cold cleaning mixture is used in step (5).
Through measuring, in humic acids compositions, each content of material (by weight), acidic groups, carboxyl, phenolic hydroxyl group contain
Amount (mmol/g) see table.
Table 1
| Sesame stalk | Semen Ricini stalk | Semen arachidis hypogaeae bar | Cotton stalk | Semen sojae atricolor bar | |
| Fulvic acid | 19.60 | 45.17 | 37.78 | 47.8 | 20.09 |
| Ulmic acid | 2.17 | 3.52 | 3.14 | 4.1 | 0.4 |
| Humic acid | 0 | 0.97 | 0.89 | 1.48 | 0 |
| Potassium | 3.27 | 3.58 | 2.07 | 2.90 | 2.68 |
| Ammonium | 9.50 | 8.90 | 4.13 | 8.89 | 4.25 |
| Chlorine | 0.43 | 0.89 | 1.01 | 0.93 | 0.6 |
| Sodium | 0.23 | 1.13 | 0.48 | 0.87 | 0.42 |
| Calcium | 0.19 | 0.18 | 0.08 | 0.16 | 0.07 |
| Magnesium | 0.39 | 0.22 | 0.25 | 0.29 | 0.28 |
| Ferrum | 0.01 | 0.04 | 0.05 | 0 | 0.04 |
| Zinc | 0.02 | 0.02 | 0.01 | 0 | 0.01 |
| Acidic groups | 1.86mmol/g | 1.61mmol/g | 1.74mmol/g | 1.68mmol/g | 1.89mmol/g |
| Carboxyl | 0.59mmol/g | 0.38mmol/g | 0.42mmol/g | 0.38mmol/g | 0.33mmol/g |
| Phenolic hydroxyl group | 1.27mmol/g | 1.23mmol/g | 1.32mmol/g | 1.30mmol/g | 1.56mmol/g |
Embodiment 2
(1) take sesame stalk, Semen Ricini stalk, Semen arachidis hypogaeae bar, cotton stalk, each portion of Semen sojae atricolor bar respectively, pulverize and obtain a length of 60mm
Blade, it is husky that blade washs desliming, is dehydrated to over dry content of material more than 15%, adds screw feeder and compress and continue
Continuous dehydration obtains the oil crop stalk that over dry content of material is 35-45%；
(2) after oil crop stalk being mixed with ammonium sulfite solution, it is continuously added in reactor, adds continuously simultaneously
Entering stock solution A of 90-105 DEG C and circulation stock solution B of 160 DEG C, the consumption of ammonium sulfite is oil crop stalk over dry
The 18% of material amount, the consumption of ammonium sulfite solution+stock solution A+ circulation stock solution B is oil crop stalk over dry materials
10 times of amount, reactor pressure is 0.6MPa；
(3) it is incubated 60min after reactor temperature being warming up to 160 DEG C and forms serosity A；
(4) the partial reaction liquid in serosity A being discharged formation serosity B, the reactant liquor of discharge joins in circulation original fluid container,
And it is warming up to 160 DEG C, as circulation stock solution B in step (2) in circulation original fluid container；
(5) adding cold cleaning mixture in serosity B, washing displacement obtains serosity C and hydrolyzed solution, by the 70-80 of hydrolyzed solution heat exchange
After DEG C, it is 65% that multi-effect evaporator is concentrated into solid concentration, obtains the concentrated solution that temperature is 100-110 DEG C, by concentrated solution
After stirring, slurry-spraying pelletizing obtains humic acids compositions；
(6) after serosity C spurts plasma discharge, shove obtains stock solution A and serosity D, will be used for step (2) after the heat exchange of stock solution A
In；
(7) normal-temperature water is added washing acquisition serosity D and cold cleaning mixture in serosity D with hydrolyzed solution heat exchange after 75-80 DEG C,
Cold cleaning mixture is used in step (5).
Through measuring, in humic acids compositions, each content of material (by weight), acidic groups, carboxyl, phenolic hydroxyl group contain
Amount (mmol/g) see table.
Table 2
| Sesame stalk | Semen Ricini stalk | Semen arachidis hypogaeae bar | Cotton stalk | Semen sojae atricolor bar | |
| Fulvic acid | 36.54 | 49.30 | 32.95 | 48.13 | 37.38 |
| Ulmic acid | 0.97 | 0.86 | 3.78 | 5.20 | 0.87 |
| Humic acid | 0.54 | 0.96 | 1.48 | 1.13 | 0.76 |
| Ammonium | 9.32 | 7.95 | 8.59 | 7.55 | 8.64 |
| Potassium | 2.08 | 2.74 | 2.86 | 2.96 | 2.98 |
| Chlorine | 0.94 | 1.04 | 0.43 | 0.76 | 0.98 |
| Sodium | 0.36 | 0.40 | 0.38 | 1.13 | 0.58 |
| Calcium | 0.16 | 0.14 | 0.07 | 0.13 | 0.19 |
| Magnesium | 0.22 | 0.26 | 0.36 | 0.38 | 0.29 |
| Ferrum | 0.05 | 0.03 | 0.01 | 0 | 0.03 |
| Zinc | 0.02 | 0.01 | 0.01 | 0 | 0.02 |
| Acidic groups | 1.60mmol/g | 1.50mmol/g | 1.76mmol/g | 1.73mmol/g | 1.76mmol/g |
| Carboxyl | 0.37mmol/g | 0.35mmol/g | 0.42mmol/g | 0.37mmol/g | 0.46mmol/g |
| Phenolic hydroxyl group | 1.23mmol/g | 1.15mmol/g | 1.34mmol/g | 1.36mmol/g | 1.30mmol/g |
Embodiment 3
(1) sesame stalk and Semen Ricini stalk 1:1 mixture, sesame stalk and Semen arachidis hypogaeae bar 1:1 mixture, Semen Ricini stalk and flower are taken respectively
Raw bar 1:1 mixture, Semen arachidis hypogaeae bar and cotton stalk 1:1 mixture, cotton stalk and Semen sojae atricolor bar 1:1 mixture, Semen Ricini stalk, Semen arachidis hypogaeae bar
With the cotton stalk each portion of 1:1:1 mixture, number consecutively is No. 1-6 respectively, pulverizes the blade obtaining a length of 40mm, will
Blade washing desliming is husky, is dehydrated to over dry content of material more than 15%, and addition screw feeder compresses and continues dehydration and obtains
Over dry content of material is the oil crop stalk of 35-45%；
(2) after oil crop stalk being mixed with ammonium sulfite solution, it is continuously added in reactor, adds continuously simultaneously
Entering stock solution A of 90-105 DEG C and circulation stock solution B of 180 DEG C, the consumption of ammonium sulfite is oil crop stalk over dry
The 30% of material amount, the consumption of ammonium sulfite solution+stock solution A+ circulation stock solution B is oil crop stalk over dry materials
10 times of amount, reactor pressure is 0.8MPa；
(3) it is incubated 40min after reactor temperature being warming up to 180 DEG C and forms serosity A；
(4) the partial reaction liquid in serosity A being discharged formation serosity B, the reactant liquor of discharge joins in circulation original fluid container,
And it is warming up to 180 DEG C, as circulation stock solution B in step (2) in circulation original fluid container；
(5) adding cold cleaning mixture in serosity B, washing displacement obtains serosity C and hydrolyzed solution, by the 70-80 of hydrolyzed solution heat exchange
After DEG C, it is 60% that multi-effect evaporator is concentrated into solid concentration, obtains the concentrated solution that temperature is 100-110 DEG C, by concentrated solution
After stirring, slurry-spraying pelletizing obtains humic acids compositions；
(6) after serosity C spurts plasma discharge, shove obtains stock solution A and serosity D, will be used for step (2) after the heat exchange of stock solution A
In；
(7) normal-temperature water is added washing acquisition serosity D and cold cleaning mixture in serosity D with hydrolyzed solution heat exchange after 75-80 DEG C,
Cold cleaning mixture is used in step (5).
Through measuring, in humic acids compositions, each content of material (by weight), acidic groups, carboxyl, phenolic hydroxyl group contain
Amount (mmol/g) see table.
Table 3
Embodiment 4
(1) sesame stalk and Semen Ricini stalk 1:1 mixture, sesame stalk and Semen arachidis hypogaeae bar 1:1 mixture, Semen Ricini stalk and flower are taken respectively
Raw bar 1:1 mixture, Semen arachidis hypogaeae bar and cotton stalk 1:1 mixture, cotton stalk and Semen sojae atricolor bar 1:1 mixture, Semen Ricini stalk, Semen arachidis hypogaeae bar
With the cotton stalk each portion of 1:1:1 mixture, number consecutively is No. 7-12 respectively, pulverizes the blade obtaining a length of 20mm,
Blade washing desliming husky, be dehydrated to over dry content of material more than 15%, addition screw feeder compresses and continues dehydration and obtains
Obtain the oil crop stalk that over dry content of material is 35-45%；
(2) after oil crop stalk being mixed with ammonium sulfite solution, it is continuously added in reactor, adds continuously simultaneously
Entering stock solution A of 90-105 DEG C and circulation stock solution B of 170 DEG C, the consumption of ammonium sulfite is oil crop stalk over dry
The 30% of material amount, the consumption of ammonium sulfite solution+stock solution A+ circulation stock solution B is oil crop stalk over dry materials
10 times of amount, reactor pressure is 0.7MPa；
(3) it is incubated 40min after reactor temperature being warming up to 170 DEG C and forms serosity A；
(4) the partial reaction liquid in serosity A being discharged formation serosity B, the reactant liquor of discharge joins in circulation original fluid container,
And it is warming up to 170 DEG C, as circulation stock solution B in step (2) in circulation original fluid container；
(5) adding cold cleaning mixture in serosity B, washing displacement obtains serosity C and hydrolyzed solution, by the 70-80 of hydrolyzed solution heat exchange
After DEG C, it is 60% that multi-effect evaporator is concentrated into solid concentration, obtains the concentrated solution that temperature is 100-110 DEG C, by concentrated solution
After stirring, slurry-spraying pelletizing obtains humic acids compositions；
(6) after serosity C spurts plasma discharge, shove obtains stock solution A and serosity D, will be used for step (2) after the heat exchange of stock solution A
In；
(7) normal-temperature water is added washing acquisition serosity D and cold cleaning mixture in serosity D with hydrolyzed solution heat exchange after 75-80 DEG C,
Cold cleaning mixture is used in step (5).
Through measuring, in humic acids compositions, each content of material (by weight), acidic groups, carboxyl, phenolic hydroxyl group contain
Amount (mmol/g) see table.
Table 4
Embodiment in above-described embodiment can be further combined or replace, and embodiment is only preferred to the present invention
Embodiment is described, and is not defined the spirit and scope of the present invention, before without departing from design philosophy of the present invention
Put, the various changes and modifications that in this area, technical scheme is made by professional and technical personnel, belong to this
Bright protection domain.
Experimental example 1
Taian Institute of Agricultural Sciences in 2012 is experimental field scheduled that to demonstrate in large area field, and demonstration result is as follows:
1. test material method
1.1 test periods and place
Test period: in March, 2012 is to July
Test site: Taian Institute of Agricultural Sciences is experimental field.
1.2 experimental field basic conditions
Experimental field soil types is grassy marshland, and quality is middle flesh, and soil pH is 5.80-6.14.
1.3 for examination fertilizer
Humus acid composition prepared by the embodiment of the present invention 1, by patent CN200710180056.X agricultural ferment
Humic acid biological fertilizer prepared by the production method of bacterium and Application Example 1 method thereof
1.4 for studying thing
Plantula Brassicae chinensis: long stalk is white；Fructus Cucumidis sativi: Hui Feng F1
1.5 EXPERIMENTAL DESIGN and method
Test processes:
Check plot: use CN200710180056.X humic acid biological fertilizer on the basis of conventional fertilizer application
Demonstration area: use humic acids compositions of the present invention on the basis of conventional fertilizer application
1.6 test Term Fertilization methods
Plantula Brassicae chinensis: humic acids compositions of the present invention and humic acid biological fertilizer are dissolved in water by the concentration of 100g/L respectively
After in, spray after Plantula Brassicae chinensis is emerged respectively.Total sprays fertile three times, each 50ml/ mu.Fructus Cucumidis sativi: every after transplanting slow Seedling
Uniformly sprayed with 1000 times of diluent blade faces every 7-15 days, totally three times, each consumption 50ml/ mu.
1.7 field management
Plantula Brassicae chinensis: first doing furrow before sowing, furrow are wide 1 meter, and the farm manure fully become thoroughly decomposed and fertilizer special for vegetable are done base manure wholely
Disposable bottom application is buried, and then ploughs and does furrow, and April 8 was sowed, and starts April 15 to spray for the first time and plants containing corruption of the present invention
Acid composition and clear water, every spray in 7 days once, spray 3 times, each consumption 50 milliliter/mu 800 times, May 17 continuously
Day starts to gather.In terms of actual production
Fructus Cucumidis sativi: after front stubble Fructus Cucumidis sativi results, plough deeply, accomplish intensive cultivation.Pot for growing seedlings nursery, January 10 is used to broadcast
Kind.Every mu of booth needs 2600 alms bowls.February 28 survival after transplant.Line-spacing 90 centimetres, spacing in the rows 23 centimetres, ridge length 6.5 meters,
28 strains/ridge, covering with plastic film.Water permeable during field planting, suitably water after slow Seedling.Alternately make with TBZ suspending agent and iprodione
With preventing and treating gray mold, with killing to prevent and treat bacterial angular leaf spot with agricultural streptomycin.Other management are with producing field.Fructus Cucumidis sativi
Period of duration, each process sprays 3 test fertilizer and clear water by EXPERIMENTAL DESIGN.Fructus Cucumidis sativi started to adopt on March 20th, 2012
Receive, end of gathering June 30.Single receipts are singly adopted in each region, and meter is real to be produced.
2. test result analysis
2.1 Plantula Brassicae chinensis
2.1.1 different disposal is to Plantula Brassicae chinensis rice growth character
As can be seen from Table 5, after spraying containing humic acids compositions of the present invention, the plant height of Plantula Brassicae chinensis, there is a certain degree of increase.
Plant height increases 2.8cm, and the number of blade increases by 3.4.Can promote little it can therefore be seen that spray containing humic acid water-soluble fertilizer
The growth of Chinese cabbage.
Table 5 Plantula Brassicae chinensis Growth Character application form
| Process | Emerge | Plant height (cm) | Leaf color | The number of blade |
| Check plot | 4.12 | 21.9 | Green | 10.1 |
| Demonstration area | 4.12 | 23.1 | Dark green | 13.5 |
2.1.2 the different disposal impact on yield of pakchoi
As seen from Table 6, after spraying containing humic acids compositions of the present invention, yield of pakchoi increases.Actual through field
Yield, demonstration area per mu yield 2159kg, ratio check plot 2021kg, increase 143kg, rate of growth is 7.08%.
Table 6 yield of pakchoi application form
2.2 Fructus Cucumidis sativi
2.2.1 different disposal is to Fructus Cucumidis sativi rice growth character
As can be seen from Table 7, after spraying containing humic acids compositions of the present invention, the plant height of Fructus Cucumidis sativi, single fruit weight and fruit transverse diameter are all
There is a certain degree of increase.Plant height increases 5.0cm；Single fruit weight increases 4.2g, and individual plant fruit number increases by 0.4, sugar content increasing
Add 0.09 percentage point.Between leaf color processes, difference is inconspicuous.
Table 7 Fructus Cucumidis sativi Growth Character application form
2.2.2 the different disposal impact on cucumber yield
As seen from Table 8, after spraying containing humic acids compositions of the present invention, cucumber yield increases.The actual product through field
Amount, demonstration area yield 5382kg, ratio check plot 5031kg, increase 351kg, rate of growth is 6.98%.
Table 8 cucumber yield application form
2.3 Economic and Efficiency Analysis
Plantula Brassicae chinensis calculates with local average market valency valency 1.6 yuan/kilogram, check plot per mu yield 2021kg, and per mu yield is worth 3233.6 yuan,
Spraying containing humic acids compositions per mu yield 2159kg of the present invention, per mu yield is worth 3454.4 yuan, sprays humic acids compositions of the present invention
220.8 yuan are increased income than check plot mu.
Fructus Cucumidis sativi calculates with local wholesale price 2.00 yuan/kilogram, check plot per mu yield 5031kg, and per mu yield is worth 10062 yuan, sprays and contain
Humic acids compositions per mu yield 5382kg of the present invention, per mu yield is worth 10764 yuan, uses humic acids compositions of the present invention than comparison
District's mu increases income 702 yuan.
3. conclusion (of pressure testing)
Use and can improve crop growth character containing humic acids compositions of the present invention, main performance Plantula Brassicae chinensis plant is high, blade is many,
Plant strain growth is healthy and strong, and field growing way is the most neat；Fructus Cucumidis sativi result is many, result is the most neat.
Use containing humic acids compositions crop yield potentiation of the present invention notable.
Claims (9)
1. a humic acids compositions, it is characterised in that: including:
Fulvic acid 19.6-49.3 weight portion, ulmic acid 0.4-5.2 weight portion, humic acid 0-1.8 weight portion.
A kind of humic acids compositions the most according to claim 1, it is characterised in that: described humic acids compositions includes
Fulvic acid 20.9-48.5 weight portion, ulmic acid 0.4-4.8 weight portion, humic acid 0-1.6 weight portion.
A kind of humic acids compositions the most according to claim 2, it is characterised in that: described humic acids compositions includes
Fulvic acid 20.9-47.8 weight portion, ulmic acid 0.4-4.1 weight portion, humic acid 0-1.5 weight portion.
4. according to a kind of humic acids compositions described in claim 1-3 any one, it is characterised in that: described humic acids
Compositions also includes ammonium or ammonium ion 4.1-9.5 weight portion, potassium 2.08-3.58 weight portion, chlorine 0.43-1.59 weight portion, sodium
0-1.13 weight portion.
A kind of humic acids compositions the most according to claim 4, it is characterised in that: described humic acids compositions includes
Ammonium or ammonium ion 4.2-8.9 weight portion, potassium 2.08-3.13 weight portion, chlorine 0.43-1.36 weight portion, sodium 0.23-0.96 weight
Part.
A kind of humic acids compositions the most according to claim 5, it is characterised in that: described humic acids compositions is also wrapped
Include ammonium or ammonium ion 4.4-8.7 weight portion, potassium 2.68-2.9 weight portion, chlorine 0.44-0.94 weight portion, sodium 0.38-0.41 weight
Amount part.
A kind of humic acids compositions the most according to claim 4, it is characterised in that: described humic acids compositions is also wrapped
Include calcium 0.07-0.19 weight portion, magnesium 0.22-0.39 weight portion, ferrum 0-0.05 weight portion, zinc 0-0.02 weight portion.
A kind of humic acids compositions the most according to claim 7, it is characterised in that: described humic acids compositions is also wrapped
Include calcium 0.08-0.16 weight portion, magnesium 0.28-0.34 weight portion, ferrum 0.01-0.05 weight portion, zinc 0.01-0.02 weight portion.
9. according to a kind of humic acids compositions described in claim 1-8 any one, it is characterised in that: described humic acids
Compositions is prepared by oil crop straw high-temperature heating liquid-phase hydrolysis in ammonium sulfite solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111747779A (en) * | 2019-03-29 | 2020-10-09 | 崔强 | Preparation method and application of fulvic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486796A (en) * | 2008-01-16 | 2009-07-22 | 山东泉林纸业有限责任公司 | Method for extracting fulvic acid from straw pulp black liquor |
| CN101486797A (en) * | 2008-01-16 | 2009-07-22 | 山东泉林纸业有限责任公司 | Method for extracting fulvic acid from straw pulp black liquor by ammonium sulfite method |
| CN101906729A (en) * | 2009-05-08 | 2010-12-08 | 山东泉林纸业有限责任公司 | Method for continuously cooking grass raw materials and equipment used in same |
| CN103922818A (en) * | 2014-03-10 | 2014-07-16 | 北京嘉博文生物科技有限公司 | Technology for producing biological humic acid by utilization of sugar-making filter mud and process |
-
2015
- 2015-03-20 CN CN201510126053.2A patent/CN106032333A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486796A (en) * | 2008-01-16 | 2009-07-22 | 山东泉林纸业有限责任公司 | Method for extracting fulvic acid from straw pulp black liquor |
| CN101486797A (en) * | 2008-01-16 | 2009-07-22 | 山东泉林纸业有限责任公司 | Method for extracting fulvic acid from straw pulp black liquor by ammonium sulfite method |
| CN101906729A (en) * | 2009-05-08 | 2010-12-08 | 山东泉林纸业有限责任公司 | Method for continuously cooking grass raw materials and equipment used in same |
| CN103922818A (en) * | 2014-03-10 | 2014-07-16 | 北京嘉博文生物科技有限公司 | Technology for producing biological humic acid by utilization of sugar-making filter mud and process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747779A (en) * | 2019-03-29 | 2020-10-09 | 崔强 | Preparation method and application of fulvic acid |
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