CN107698329A - A kind of anion silicon titanium fertilizer and preparation method thereof - Google Patents

A kind of anion silicon titanium fertilizer and preparation method thereof Download PDF

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Publication number
CN107698329A
CN107698329A CN201711032584.0A CN201711032584A CN107698329A CN 107698329 A CN107698329 A CN 107698329A CN 201711032584 A CN201711032584 A CN 201711032584A CN 107698329 A CN107698329 A CN 107698329A
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parts
powder
micron
anion
silicon titanium
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Chinese (zh)
Inventor
王震
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Huambo Science And Technology (beijing) Co Ltd
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Huambo Science And Technology (beijing) Co Ltd
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Priority to CN201711032584.0A priority Critical patent/CN107698329A/en
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B17/00Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G5/00Fertilisers characterised by their form
    • C05G5/20Liquid fertilisers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)

Abstract

In anion silicon titanium fertilizer provided by the invention, because the presence of anion water to be rich in anion and oxonium ion in the anion silicon titanium fertilizer;Simultaneously rich in multiple elements such as silicon, titanium, boron, iron, manganese, zinc, copper;Due to the porous of zeolite so that anion silicon titanium fertilizer can be formed into needle prick shape on the blade face of crops in use, expel insect, adsorbed simultaneously decomposing harmful substances, improved the anti-epidemic disease power of plant;In addition there is zeolite releasing far infrared energy to act on, it is micromolecular water by macromolecular water decomposition, plant nutrient is promoted to absorb, improve crop quality, polypeptide also can speed up the penetrance to cell membrane, strengthen absorbability, and enhancing electric charge produces energy with ground magnetic interaction, promote crops metabolism, lift crop disease-resistant ability.Silicon titanium elements are rich in anion silicon titanium fertilizer provided by the invention, improve the photosynthesis of crops, improve the micro- absorptivity and content in crops.

Description

A kind of anion silicon titanium fertilizer and preparation method thereof
Technical field
The invention belongs to chemical fertilizer field, and in particular to a kind of anion silicon titanium fertilizer and preparation method thereof.
Background technology
The referred to as micro- fertilizer of trace element fertilizer, it is the micro member needed for the offers such as crops, forest, herbage, fruit tree, vegetables growth Element.China, which promotes micro- fertilizer, mainly to be had:Boron fertilizer, molydbenum fertilizer, zinc fertilizer, copper fertilizer, manganese fertilizer, iron fertilizer.They are in crops, forest, herbage, fruit Applied on tree, vegetables, there is mutual irreplaceable effect.Micro- fertilizer, effect of increasing production are applied for nutritional deficiency soil and sensitive plant It is very notable.
Micro- nutriment in a fertilizer class is varied.Form and divide by nutrient, be broadly divided into following three class:(1) the micro- fertilizer of simple substance.This kind of fertilizer Material typically belongs to such containing only a kind of trace element required for crop, such as zinc sulfate, ferrous sulfate.(2) compound trace element fertilizer.This A kind of fertilizer is more to be added one or more trace elements when manufacture fertilizer and is made, it include a great number of elements with it is micro- with It is and compound between trace element and trace element.For example, zinc ammonium phosphate, ammonium phosphate manganese etc..This kind of fertilizer, applied once is simultaneously Several nutrients are fed, compare saving of labor, but be difficult to and suit measures to local conditions.(3) micro- fertilizer is mixed.This kind of fertilizer is to manufacture or applying When, various straight fertilizers are mixed by its needs.Its advantage is that composition is flexible.According to various regions soil test data, crop Regulation of fertilizer requirement, formed by field test, therefore economic benefit is obvious after Fertilizer application, but configure complicated.
The fertility for having not only broken up soil is excessively used in chemical fertilizer since throughout the year, is also greatly reduced agricultural products quality, Cry more and more higher of the people to pollution-free food.
Silicon is the important nutrient of crops composition, is considered fourth element after N P and K by international soil circle.Silicon Fertilizer is a kind of quality fertilizer, health care fertilizer and plant modulability fertilizer well, is the incomparable one kind of other chemical fertilizer Novel and multifunctional fertilizer.Silicon titanium fertilizer can both make fertilizer, there is provided nutrient, can be used as soil conditioner, improved soil again.In addition, also Have the effect of diseases prevention, insect prevention and attenuation concurrently.With outstanding advantages of its is nontoxic, tasteless, never degenerate, be not lost in, nuisanceless, will turn into Develop the high-efficiency high-quality fertilizer of green ecological agricultural.But the titaniferous amount in soil is generally 0.3-0.6%, and with oxide Or the form of insoluble salt is present, plant is difficult to absorb.Micro- single, plant be present in titanium fertilizer in the market Utilization rate it is low the shortcomings that.
The content of the invention
In order to solve the technical problem of the above, the present invention provides one kind and is with anion water, polypeptide, medical stone and zeolite etc. Primary raw material, it is nutritious by containing various trace elements made of biology chelating technique compounding, easily absorbed by crops Anion silicon titanium fertilizer.
The nutriment that protein, polypeptide and amino acid are not only animal and needed by human body is wanted, and the essence needed for plant China, it is generally the case that the amino acid being connected more than 100 peptide bonds is referred to as protein by people, by more than 2, less than 100 The amino acid that peptide bond is connected is referred to as polypeptide.Polypeptides matter in plant has promotion cytoactive, accelerates crop wound to be cured The effect of conjunction, meanwhile, polypeptide has important regulative in the growing of plant, reproduction and reply external environment.Therefore Present invention addition polypeptide, the effect of silicon titanium fertilizer is improved, when as foliar fertilizer, the activity of crop plant cells is improved, increases farming The yield of thing;When as soaking seed fertile, increase the stimulation to seed, shorten seed dormancy phase, accelerate seed germination, be that crop carries The trophophase is advanced into, increases the absorption to other nutrients, improves the yield of crops.
The anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, include the component of following parts by weight:
Anion water 40-50 parts;
Medical stone powder and micron 2-15 parts;
Zeolite powder and micron 5-10 parts;
Micron selenium 0.5-2 parts;
Ammonium sulfate 2-5 parts;
Apatite powder and micron 2-5 parts;
Silica powder and micron 1-3 parts;
Titanium dioxide micrometer powder 1-3 parts;
Polypeptide 2-5 parts.
The anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide.
The main chemical compositions of medical stone in anion silicon titanium fertilizer provided by the invention are inorganic alumino-silicates, wherein Including SiO2、Al2O3、Fe2O3、FeO、MgO、CaO、K2O、Na2O、TiO2、P2O5, MnO etc., also containing needed for animal all often Secondary element, such as:K, the trace element such as Na, Ca, Mg, Cu, Mo and rare earth element, as many as about 58 kinds.
The anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that the component also includes:Chelating agent 20-30 parts.Further, the chelating agent is ascorbic acid.
The anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that the component also includes:Adjusted with pH The pH of silicon titanium fertilizer is adjusted to 5.5-6.5 by agent, the pH adjusting agent, and further, the pH adjusting agent is hydroxide Potassium and/or potassium carbonate.
The anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that the pH of the silicon titanium fertilizer is 5.5- 6.5。
The preparation method of anion silicon titanium fertilizer, methods described include following step according to obtained by the specific embodiment of the invention Suddenly:
(1) medical stone, zeolite, apatite are weighed respectively, crushes, then adds ammonium sulfate, are well mixed, are mixed Powder;
(2) mixed powder obtained in step (1) is heated to 300-400 DEG C in blowing air or oxygen, is incubated 20- 40min, micron level is then crushed to, obtains mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, chelating agent and pH adjusting agent are added, adjusts the pH to 5.5-6.5 of solution, heating, chelating is complete, adds polypeptide, It is well mixed, obtain the anion silicon titanium fertilizer.
The preparation method of anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that in step (1), institute The particle diameter for stating mixed powder is 0.1-1cm.
The preparation method of anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that in step (2), institute The particle diameter for stating mixture powder and micron is 10-100 μm.
The preparation method of anion silicon titanium fertilizer according to obtained by the specific embodiment of the invention, it is preferable that, will in step (1) The mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added in anion water, is added Enter chelating agent and pH adjusting agent, adjust the pH to 5.5-6.5 of solution, be heated to 40-50 DEG C.
Beneficial effects of the present invention are:
In anion silicon titanium fertilizer provided by the invention, because the presence of anion water causes richness in the anion silicon titanium fertilizer Containing anion and oxonium ion;Simultaneously rich in multiple elements such as silicon, titanium, boron, iron, manganese, zinc, copper, due to the porous of zeolite so that Anion silicon titanium fertilizer can be formed into needle prick shape on the blade face of crops in use, expelled insect, adsorbed and decomposed Evil material, improves the anti-epidemic disease power of plant;In addition there is zeolite releasing far infrared energy to act on, and be small molecule by macromolecular water decomposition Water, promoting plant nutrient to absorb, improve crop quality, polypeptide also can speed up the penetrance to cell membrane, strengthen absorbability, Strengthen electric charge and produce energy with ground magnetic interaction, promote crops metabolism, lift crop disease-resistant ability.The present invention provides Anion silicon titanium fertilizer in be rich in silicon titanium elements, improve the photosynthesis of crops, improve the micro- suction in crops Yield and content.
Anion silicon titanium fertilizer provided by the invention is using anion water as carrier, by the lot of trace member needed for crop growth Plain fertilizer carries out micronization processes and high temperature oxidation process so that various trace elements are preferably dissolved in anion water;Utilize life The method of thing chelating, trace element and chelant ties obtain chelating liquid, and add polypeptide, obtain a kind of raising farming Produce amount, reduce the anion silicon titanium fertilizer of diseases and pests of agronomic crop.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Base Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned Other embodiment, belong to the scope that the present invention is protected.
Embodiment 1
Anion silicon titanium fertilizer, include the component of following parts by weight:
40 parts of anion water;
2 parts of medical stone powder and micron;
5 parts of zeolite powder and micron;
0.5 part of selenium of micron;
2 parts of ammonium sulfate;
2 parts of apatite powder and micron;
1 part of silica powder and micron;
1 part of titanium dioxide micrometer powder;
2 parts of polypeptide.
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, 0.1cm is crushed to, then adds ammonium sulfate, are well mixed, are obtained To mixed powder;
(2) mixed powder obtained in step (1) is heated to 300 DEG C in blowing air or oxygen, is incubated 40min, so After be crushed to 10 μm, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, polypeptide is added, is well mixed, obtains the anion silicon titanium fertilizer.
Embodiment 2
Anion silicon titanium fertilizer, include the component of following parts by weight:
50 parts of anion water;
15 parts of medical stone powder and micron;
10 parts of zeolite powder and micron;
2 parts of selenium of micron;
5 parts of ammonium sulfate;
5 parts of apatite powder and micron;
3 parts of silica powder and micron;
3 parts of titanium dioxide micrometer powder;
5 parts of polypeptide.
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, 1cm is crushed to, then adds ammonium sulfate, are well mixed, are obtained Mixed powder;
(2) mixed powder obtained in step (1) is heated to 400 DEG C in blowing air or oxygen, is incubated 20min, so After be crushed to 100 μm, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, polypeptide is added, is well mixed, obtains the anion silicon titanium fertilizer.
Embodiment 3
Anion silicon titanium fertilizer, include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide.
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, 0.5cm is crushed to, then adds ammonium sulfate, are well mixed, are obtained To mixed powder;
(2) mixed powder obtained in step (1) is heated to 350 DEG C in blowing air or oxygen, is incubated 35min, so After be crushed to 50 μm, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, polypeptide is added, is well mixed, obtains the anion silicon titanium fertilizer.
Embodiment 4
Anion silicon titanium fertilizer, include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide;
20 parts of ascorbic acid;
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, crushes, then adds ammonium sulfate, are well mixed, are mixed Powder;
(2) mixed powder obtained in step (1) is heated to 350 DEG C in blowing air or oxygen, is incubated 30min, so After be crushed to micron level, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, ascorbic acid is added, adjusts the pH to 6 of solution, heating, chelating is complete, adds polypeptide, is well mixed, obtains The anion silicon titanium fertilizer.
Embodiment 5
Anion silicon titanium fertilizer, include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide;
30 parts of ascorbic acid;
Potassium hydroxide and potassium carbonate, the pH of the silicon titanium fertilizer is 5.5.
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, 0.1cm is crushed to, then adds ammonium sulfate, are well mixed, are obtained To mixed powder;
(2) mixed powder obtained in step (1) is heated to 350 DEG C in blowing air or oxygen, is incubated 30min, so After be crushed to 50 μm, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, ascorbic acid, potassium hydroxide and potassium carbonate are added, the pH to 6.5 of solution is adjusted, is heated to 40 DEG C, has chelated Entirely, polypeptide is added, is well mixed, obtains the anion silicon titanium fertilizer.
Embodiment 6
Anion silicon titanium fertilizer, include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide;
20 parts of ascorbic acid;
And sodium hydroxide, the pH of the silicon titanium fertilizer is 5.5.
The preparation method of above-mentioned anion silicon titanium fertilizer, the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, 0.1cm is crushed to, then adds ammonium sulfate, are well mixed, are obtained To mixed powder;
(2) mixed powder obtained in step (1) is heated to 350 DEG C in blowing air or oxygen, is incubated 30min, so After be crushed to 50 μm, obtain mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to In anion water, ascorbic acid and potassium hydroxide are added, adjusts the pH to 6 of solution, is heated to 50 DEG C, chelating is complete, adds more Peptide, it is well mixed, obtains the anion silicon titanium fertilizer.
Test example
According to NY/T 1977-2010《Water-soluble fertilizer total nitrogen, phosphorus, the measure of potassium content》;NY/T 1974-2010《It is water-soluble Fertilizer copper, zinc, boron, the measure of molybdenum content》;NY/T 1117-2010《Water-soluble fertilizer calcium, magnesium, sulphur, the measure of chlorinity》;NY/T 1972-2010《Water-soluble fertilizer sodium, selenium, the measure of silicone content》;NY/T 1978-2010《Fertilizer mercury, arsenic, cadmium, lead, chromium content Measure》, the anion silicon titanium fertilizer that embodiment 6 obtains is tested, the results are shown in Table 1.
The anion silicon titanium fertilizer assay of table 1
It can be seen that in anion silicon titanium fertilizer provided by the invention from the assay of table 1 and grown rich in multiple kinds of crops Required trace element.
In the cultivating process of crops can using anion silicon titanium provided by the invention fertilizer as foliar fertilizer to crops The supplement of trace element is carried out, also can carry out seed soaking use before proportion of crop planting.Promote crop growth, to soil and Person poultry harmless, and there is significant effect of increasing production.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (10)

1. a kind of anion silicon titanium fertilizer, it is characterised in that include the component of following parts by weight:
Anion water 40-50 parts;
Medical stone powder and micron 2-15 parts;
Zeolite powder and micron 5-10 parts;
Micron selenium 0.5-2 parts;
Ammonium sulfate 2-5 parts;
Apatite powder and micron 2-5 parts;
Silica powder and micron 1-3 parts;
Titanium dioxide micrometer powder 1-3 parts;
Polypeptide 2-5 parts.
2. anion silicon titanium fertilizer according to claim 1, it is characterised in that include the component of following parts by weight:
45 parts of anion water;
10 parts of medical stone powder and micron;
8 parts of zeolite powder and micron;
1.5 parts of selenium of micron;
4.5 parts of ammonium sulfate;
3 parts of apatite powder and micron;
2.5 parts of silica powder and micron;
2.5 parts of titanium dioxide micrometer powder;
4 parts of polypeptide.
3. anion silicon titanium fertilizer according to claim 1 or 2, it is characterised in that the component also includes:Chelating agent 20- 30 parts.
4. anion silicon titanium fertilizer according to claim 3, it is characterised in that the chelating agent is ascorbic acid.
5. anion silicon titanium fertilizer according to claim 4, it is characterised in that the component also includes:PH adjusting agent, it is described The pH of silicon titanium fertilizer is adjusted to 5.5-6.5 by pH adjusting agent.
6. anion silicon titanium according to claim 5 fertilizer, it is characterised in that the pH adjusting agent be potassium hydroxide and/or Potassium carbonate.
7. the preparation method of the anion silicon titanium fertilizer described in claim 6, it is characterised in that the described method comprises the following steps:
(1) medical stone, zeolite, apatite are weighed respectively, crushes, then adds ammonium sulfate, are well mixed, are obtained mixed powder;
(2) mixed powder obtained in step (1) is heated to 300-400 DEG C in blowing air or oxygen, is incubated 20-40min, Then micron level is crushed to, obtains mixture powder and micron;
(3) the mixture powder and micron obtained in silica powder and micron, titanium dioxide micrometer powder and step (2) is added to bear from In sub- water, chelating agent and pH adjusting agent are added, adjusts the pH to 5.5-6.5 of solution, heating, chelating is complete, adds polypeptide, mixing Uniformly, the anion silicon titanium fertilizer is obtained.
8. the preparation method of anion silicon titanium fertilizer according to claim 7, it is characterised in that in step (1), the mixing The particle diameter of powder is 0.1-1cm.
9. the preparation method of anion silicon titanium fertilizer according to claim 7, it is characterised in that in step (2), the mixing The particle diameter of thing powder and micron is 10-100 μm.
10. the preparation method of anion silicon titanium fertilizer according to claim 7, it is characterised in that in step (1), by dioxy The mixture powder and micron obtained in SiClx powder and micron, titanium dioxide micrometer powder and step (2) is added in anion water, adds chela Mixture and pH adjusting agent, the pH to 5.5-6.5 of solution is adjusted, is heated to 40-50 DEG C.
CN201711032584.0A 2017-10-27 2017-10-27 A kind of anion silicon titanium fertilizer and preparation method thereof Pending CN107698329A (en)

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Publication number Priority date Publication date Assignee Title
CN112409030A (en) * 2020-11-26 2021-02-26 绘农科技农业控股(深圳)有限公司 Novel water-soluble fertilizer production process
CN113443939A (en) * 2021-07-30 2021-09-28 温炫亮 Molecular type nano silicon-titanium fertilizer and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409030A (en) * 2020-11-26 2021-02-26 绘农科技农业控股(深圳)有限公司 Novel water-soluble fertilizer production process
CN113443939A (en) * 2021-07-30 2021-09-28 温炫亮 Molecular type nano silicon-titanium fertilizer and preparation method thereof

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Application publication date: 20180216

WD01 Invention patent application deemed withdrawn after publication