CN107827594A - A kind of humic acid Water soluble fertilizer of long-acting stabilization and preparation method thereof - Google Patents
A kind of humic acid Water soluble fertilizer of long-acting stabilization and preparation method thereof Download PDFInfo
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- CN107827594A CN107827594A CN201711233414.9A CN201711233414A CN107827594A CN 107827594 A CN107827594 A CN 107827594A CN 201711233414 A CN201711233414 A CN 201711233414A CN 107827594 A CN107827594 A CN 107827594A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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Abstract
The invention belongs to fertilizer field, more particularly to a kind of humic acid Water soluble fertilizer of long-acting stabilization and preparation method thereof.The present invention is combined carbon dust under ultrasonic state with EDTA, enable carbon dust dispersed in water, it is and soluble in water, adsorption capacity by carbon dust to humic acid, makes humic acid be wrapped up by carbon dust, and avoiding humic acid from being reacted with metal ion causes to precipitate, and the EDTA combined with carbon dust can one step ahead with complexing of metal ion, stable soluble complexes are formed, the humic acid Water soluble fertilizer for enabling to finally give dissolves rapidly in water, and is kept for the long period fail to understand explict occurrence precipitation.
Description
Technical field
The invention belongs to fertilizer field, more particularly to a kind of humic acid Water soluble fertilizer of long-acting stabilization and preparation method thereof.
Background technology
Water soluble fertilizer is a kind of multielement compound fertilizer that can be dissolved completely in water, relative to traditional peroxophosphoric acid
The non-full water-soluble fertilizer such as calcium, granulated compound fertilizer and sustained release kind, due to its have instant, absorptivity is high, it is quick, without residue,
Using the remarkable advantage such as convenient, swift and violent development has been obtained.Especially in the ring in face of being on the rise caused by greenhouse effects
In the case of border protection and water resources shortage, drip irrigation system, the novel fertilizer application with fertile function of significantly economizing on water, save such as sprinkling irrigation is sprayed
Mode starts to be widely applied, the person that the makes agricultural fertilizer basic change to the noegenesis of fertilizer.Water soluble composite fertilizer is made
For the main flow of current fertigation, although can economize on water, save fertilizer, save man-hour.
Humic acid Zuo is the organic substance of Yi Zhong Green colors, and its raw material is easy to get and does not produce secondary pollution, agriculturally to changing
Good native Reel, raising crop anti-adversity, improvement quality of agricultural product etc. have important application value.With the green industry in China
With the development of global low-carbon economy, the market space of humic acids technology and product is huge, and humic acids new-type fertilizer industry will
Get more preferable development.Disclosed various humic acid fertilizer products are divided into solid and liquid two types mostly in the market,
Universal is all the humic acid macroelement fertilizer than lower end, be typically simply mixed using humate and the big fertilizer of N P and K and
Into, thus there is single varieties, nutrient content is low, poorly water-soluble, water-soluble speed is not fast enough, precipitation is more, sedimentation stability is poor
And the shortcomings such as added value is low.
Therefore, it is less if a kind of dissolution velocity fast, good water solubility, precipitation can develop, and dissolving can be kept for a long time
Humic acid water-soluble fertilizer, to promoting China's chemical fertilizer industry to realize industry restructuring and increasing farmers' income with highly important
Meaning.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of humic sour water of long-acting stabilization
Molten fertilizer and preparation method thereof, it is achieved particular by following art scheme：
A kind of preparation method of the humic acid Water soluble fertilizer of long-acting stabilization, comprises the following steps：
(1) urea 650-800 parts, ammonium sulfate 210-250 parts, nitre phosphorus ammonium 120-130 parts, sulfuric acid boron are weighed by weight
45-50 parts, potassium dihydrogen phosphate 280-320 parts, ammonium hydrogen carbonate 250-270 parts, humic acid 280-320 parts, EDTA30-50 parts, carbon
Powder 45-65 parts；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 80-100 mesh, humic
Acid, carbon dust were crushed to more than 200 mesh and sieved；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the 5-15 times of water measured, be heated to 85-95 DEG C, added
EDTA, stir, be ultrasonically treated 2-4h, add humic acid, continue ultrasonic 10-30min；
(4) mixture in reactor is concentrated and dried, was crushed to more than 100 mesh and sieves, and obtained being modified humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 40-60min to 130-150 DEG C；
(6) it will pack, produce after mixture drying, crushing.
Preferably, it is by weight, to take 1400 parts of urea, 230 parts of ammonium sulfate, 125 parts of nitre phosphorus ammonium, sulfuric acid boron 47.5
Part, 300 parts of potassium dihydrogen phosphate, 260 parts of ammonium hydrogen carbonate, 300 parts of humic acid, EDTA40 parts, 55 parts of carbon dust.
The carbon dust, is only made up of carbon molecules or carbon atom.As in carbon dust carry other impurities can influence its with
EDTA Percentage bound, and influence adsorption capacity of the carbon dust to humic acid.
The step (2), carbon dust was crushed to more than 10000 mesh and sieved, and can further lift carbon dust and EDTA knot
Conjunction rate, make the enhanced dissolution rate of the Water soluble fertilizer of last gained, stabilization time increase.
The supersound process, handled with frequency 30-40kHz, power 200-300W ultrasonic wave, make carbon dust and
EDTA is more scattered, can improve carbon dust and EDTA Percentage bound.Preferably, the 3s that often works is ultrasonically treated, is spaced 3s, Ke Yiti
Rise carbon dust and EDTA dispersion efficiency.85-95 DEG C of temperature is controlled during supersound process, moisture rapid steaming can be avoided
It is dry, substantial amounts of heat can be produced due to being ultrasonically treated, if do not controlled temperature that water can be caused quickly to be evaporated, influences carbon dust and EDTA
Meltage, influence its combination.
Further preferably, the step (5), after the completion of stirring, mixture is put into high pressure homogenizer and carried out at homogeneous
Reason.Homogeneous is also referred to as homogenized, and is to make dispersion micronized, the processing procedure of homogenization in suspension (or emulsion) system, this
Kind processing plays a part of to reduce dispersion yardstick and raising dispersion distributing homogeneity simultaneously.
Preferable drying mode is spray-dried after condensing crystallizing.Spray drying is that systematization technique is applied to material
A kind of dry method.In hothouse by solvent or diluent after atomization, in the contact with hot-air, moisture rapid vaporization, produce
To dry products.The method can directly make solution, emulsion dry powdering or particulate preparation.
The present invention is combined carbon dust under ultrasonic state with EDTA, enables carbon dust dispersed in water, and soluble in water,
Adsorption capacity by carbon dust to humic acid, makes humic acid be wrapped up by carbon dust, avoids humic acid from being reacted with metal ion and leads
Precipitation is caused, and the EDTA combined with carbon dust can be formed stable soluble complexes, made most one step ahead with complexing of metal ion
The humic acid Water soluble fertilizer obtained eventually can dissolve rapidly in water, and be kept for the long period fail to understand explict occurrence precipitation.
Compared with prior art, the technique effect of the invention is embodied in：
The present invention is combined carbon dust under ultrasonic state with EDTA, enables carbon dust dispersed in water, and soluble in water,
Adsorption capacity by carbon dust to humic acid, makes humic acid be wrapped up by carbon dust, avoids humic acid from being reacted with metal ion and leads
Precipitation is caused, and the EDTA combined with carbon dust can be formed stable soluble complexes, made most one step ahead with complexing of metal ion
The humic acid Water soluble fertilizer obtained eventually can dissolve rapidly in water, and be kept for the long period fail to understand explict occurrence precipitation.
Embodiment
Limited with reference to specific embodiment technical scheme is further, but claimed
Scope is not only limited to made description.
Embodiment 1
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 1400kg, ammonium sulfate 230kg, nitre phosphorus ammonium 125kg, sulfuric acid boron 47.5kg, potassium dihydrogen phosphate are weighed
300kg, ammonium hydrogen carbonate 260kg, humic acid 300kg, EDTA40kg, carbon dust 55kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 90 mesh, humic acid,
Carbon dust was crushed to 300 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 10 times of amounts, be heated to 90 DEG C, add EDTA,
Stir, be ultrasonically treated 3h, add humic acid, continue ultrasonic 20min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 50min to 140 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
Embodiment 2
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 650kg, ammonium sulfate 210kg, nitre phosphorus ammonium 120kg, sulfuric acid boron 45kg, biphosphate are weighed by weight
Potassium 280kg, ammonium hydrogen carbonate 250kg, humic acid 280kg, EDTA30kg, carbon dust 45kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 80 mesh, humic acid,
Carbon dust was crushed to 200 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 5 times of amounts, be heated to 85 DEG C, add EDTA,
Stir, be ultrasonically treated 2h, add humic acid, continue ultrasonic 10min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 40min to 130 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
Embodiment 3
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 800kg, ammonium sulfate 250kg, nitre phosphorus ammonium 130kg, sulfuric acid boron 50kg, biphosphate are weighed by weight
Potassium 320kg, ammonium hydrogen carbonate 270kg, humic acid 320kg, EDTA50kg, carbon dust 65kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 100 mesh, humic acid,
Carbon dust was crushed to 400 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 15 times of amounts, be heated to 95 DEG C, add EDTA,
Stir, be ultrasonically treated 4h, add humic acid, continue ultrasonic 30min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 60min to 150 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
Embodiment 4
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 1400kg, ammonium sulfate 230kg, nitre phosphorus ammonium 125kg, sulfuric acid boron 47.5kg, potassium dihydrogen phosphate are weighed
300kg, ammonium hydrogen carbonate 260kg, humic acid 300kg, EDTA40kg, carbon dust 55kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 90 mesh, humic acid powder
300 mesh sieves were broken to, carbon dust is crushed to 10000 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 10 times of amounts, be heated to 90 DEG C, add EDTA,
Stir, be ultrasonically treated 3h, add humic acid, continue ultrasonic 20min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 50min to 140 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
Embodiment 5
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 1400kg, ammonium sulfate 230kg, nitre phosphorus ammonium 125kg, sulfuric acid boron 47.5kg, potassium dihydrogen phosphate are weighed
300kg, ammonium hydrogen carbonate 260kg, humic acid 300kg, EDTA40kg, carbon dust 55kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 90 mesh, humic acid,
Carbon dust was crushed to 300 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 10 times of amounts, be heated to 90 DEG C, add EDTA,
Stir, be ultrasonically treated 3h, add humic acid, continue ultrasonic 20min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 50min to 140 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
The supersound process, handled with frequency 30-40kHz, power 200-300W ultrasonic wave, often work 3s,
3s is spaced, and 85-95 DEG C of temperature is controlled during being ultrasonically treated.
Embodiment 6
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 1400kg, ammonium sulfate 230kg, nitre phosphorus ammonium 125kg, sulfuric acid boron 47.5kg, potassium dihydrogen phosphate are weighed
300kg, ammonium hydrogen carbonate 260kg, humic acid 300kg, EDTA40kg, carbon dust 55kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 90 mesh, humic acid,
Carbon dust was crushed to 300 mesh sieves；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the water of 10 times of amounts, be heated to 90 DEG C, add EDTA,
Stir, be ultrasonically treated 3h, add humic acid, continue ultrasonic 20min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 50min, mixture is put into high pressure homogenizer and carried out to 140 DEG C
Homogenization；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
The carbon dust, is only made up of carbon molecules or carbon atom.
Comparative example 1
A kind of humic acid Water soluble fertilizer of long-acting stabilization, is prepared via a method which：
(1) urea 1400kg, ammonium sulfate 230kg, nitre phosphorus ammonium 125kg, sulfuric acid boron 47.5kg, potassium dihydrogen phosphate are weighed
300kg, ammonium hydrogen carbonate 260kg, humic acid 300kg, EDTA40kg；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 90 mesh, humic acid powder
It was broken to 300 mesh sieves；
(3) 550L water is added into ultrasonic reaction kettle, is heated to 90 DEG C, EDTA is added, stirs, is ultrasonically treated 3h,
Humic acid is added, continues ultrasonic 20min；
(4) it will be spray-dried in reactor after mixture condensing crystallizing, be crushed to more than 100 mesh and sieve, and changed
Property humic acid；
(5) by the urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid
Add in ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 50min to 140 DEG C；
(6) pack, produce after being spray-dried, crushed after mixture condensing crystallizing.
By embodiment 1-6, the humic acid Water soluble fertilizer of the long-acting stabilization of the gained of comparative example 1, commercially available humic acid Water soluble fertilizer difference
1kg is taken, is dissolved with the standard hard water of 500 times of times of weight, record is completely dissolved the time, stands 4h, is filtered, separated using filter paper
Filtrate, precipitation is dried to constant weight, records Sediment weight, then proceeded to stand 48h, filtered using filter paper, separating filtrate, will be heavy
Shallow lake is dried to constant weight, records Sediment weight.
Contrast understands that the humic acid Water soluble fertilizer of long-acting stabilization of the invention, dissolution velocity is fast, precipitation capacity is few, after standing 48h
Also occur without precipitation too much, be advantageous to make full use of raw material, and convenient fertilising.
Finally it is pointed out that above example is only the more representational example of the present invention.Obviously, technology of the invention
Scheme is not limited to above-described embodiment, can also there is many deformations.One of ordinary skill in the art can be from disclosed by the invention
All deformations that content is directly exported or associated, are considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the humic acid Water soluble fertilizer of long-acting stabilization, it is characterised in that comprise the following steps：
(1) urea 650-800 parts, ammonium sulfate 210-250 parts, nitre phosphorus ammonium 120-130 parts, sulfuric acid boron 45-50 are weighed by weight
Part, potassium dihydrogen phosphate 280-320 parts, ammonium hydrogen carbonate 250-270 parts, humic acid 280-320 parts, EDTA30-50 parts, carbon dust 45-
65 parts；
(2) urea, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate are crushed to 80-100 mesh, humic acid,
Carbon dust was crushed to more than 200 mesh and sieved；
(3) carbon dust crushed is put into ultrasonic reaction kettle, adds the 5-15 times of water measured, be heated to 85-95 DEG C, added
EDTA, stir, be ultrasonically treated 2-4h, add humic acid, continue ultrasonic 10-30min；
(4) mixture in reactor is concentrated and dried, was crushed to more than 100 mesh and sieves, and obtained being modified humic acid；
(5) urea crushed, ammonium sulfate, nitre phosphorus ammonium, sulfuric acid boron, potassium dihydrogen phosphate, ammonium hydrogen carbonate, modified humic acid are added
In ultrasonic reaction kettle, adjustment temperature of reaction kettle stirs 40-60min to 130-150 DEG C；
(6) it will pack, produce after mixture drying, crushing.
2. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1, it is characterised in that the step
(1) it is, to weigh 1400 parts of urea, 230 parts of ammonium sulfate, 125 parts of nitre phosphorus ammonium, 47.5 parts of sulfuric acid boron, potassium dihydrogen phosphate by weight
300 parts, 260 parts of ammonium hydrogen carbonate, 300 parts of humic acid, EDTA40 parts, 55 parts of carbon dust.
3. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1 or 2, it is characterised in that described
Carbon dust, only it is made up of carbon molecules or carbon atom.
4. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1 or 2, it is characterised in that described
Step (2), carbon dust was crushed to more than 10000 mesh and sieved.
5. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1 or 2, it is characterised in that described
Be ultrasonically treated, handled with frequency 30-40kHz, power 200-300W ultrasonic wave.
6. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 5, it is characterised in that the ultrasound
Processing, often work 3s, is spaced 3s.
7. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 5, it is characterised in that the ultrasound
85-95 DEG C of temperature is controlled during processing.
8. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1 or 2, it is characterised in that described
Step (5), after the completion of stirring, mixture is put into high pressure homogenizer and carries out homogenization.
9. the preparation method of the humic acid Water soluble fertilizer of long-acting stabilization according to claim 1 or 2, it is characterised in that described
Drying is spray-dried after condensing crystallizing.
10. it is prepared by the preparation method of the humic acid Water soluble fertilizer of the long-acting stabilization described in claim 1-9 long-acting steady
Fixed humic acid Water soluble fertilizer.
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| CN108440144A (en) * | 2018-05-30 | 2018-08-24 | 安徽辉隆集团五禾生态肥业有限公司 | With anti-caking, the compound fertilizer of slow release effect and preparation method |
| CN112028694A (en) * | 2020-09-21 | 2020-12-04 | 河南鄂中肥业有限公司 | Special compound microbial fertilizer for garlic with effects of strengthening seedlings and promoting roots and preparation method thereof |
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Application publication date: 20180323 |