CN108178708A - A kind of selenium-rich organic carbon fertilizer and preparation method thereof - Google Patents
A kind of selenium-rich organic carbon fertilizer and preparation method thereof Download PDFInfo
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- CN108178708A CN108178708A CN201810073944.XA CN201810073944A CN108178708A CN 108178708 A CN108178708 A CN 108178708A CN 201810073944 A CN201810073944 A CN 201810073944A CN 108178708 A CN108178708 A CN 108178708A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
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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
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
Abstract
The invention discloses a kind of selenium-rich organic carbon fertilizer and preparation method thereof.The present invention is raw material using amino acid fermentation waste liquid and amino acid fermentation waste liquid and inorganic selenium, selenium-rich organic carbon fertilizer is produced, mainly using redox reaction, amino acid waste liquid is degraded to nanoscale small molecule organic matter, under weak basic condition, generation Organic Selenium is reacted with selenium compound.Present invention process is simple, and efficiently solving the problems, such as the recycling of amino acid fermentation waste liquid, production selenium-rich organic carbon fertilizer, only plant growth does not provide various required nutrients, plant health growing way is effectively kept, and effectively enhances the anti-adversity abilities such as crop drought resistance, waterlogging-resistant, disease-resistant.
Description
Technical field
The invention belongs to technical field of fertilizers, and in particular to a kind of selenium-rich organic carbon fertilizer and preparation method thereof.
Background technology
Selenium element oneself by the World Health Organization and Chinese Medical Association be set to the third-largest micronutrient health care after iodine, zinc member
Element.Medical research shows that selenium has the function of anti-oxidant, prevention canceration, toxin expelling, improves the various aspects such as immunity in human body,
Pre- preventing tumor, cardiovascular and cerebrovascular disease, diabetes, infection of the upper respiratory tract etc. also have unique effect.To crops selenium-supply, one
Aspect can improve the nutrition condition of crop in itself, promote the growth of crop, improve yield, while can increase corresponding agricultural product again
The content of middle selenium element provides the selenium-enriched food of safety to the mankind, to agricultural development and human body health is promoted all to have weight
The meaning wanted.But most liquid selenium-rich fertilizer is generally fermented using selenite or selenite currently on the market
Or after complexing agent, multiple foliage-spray is carried out, it is minimum to need to spray more than twice, to realize the production of Se-rich farm products.Its
It is primarily present following weakness：First, the residual of inorganic selenium is serious, there is potential murder by poisoning risk；Second is that the conversion ratio of agricultural product selenium
It is low, it is of high cost；Third, the application of foliar fertilizer and having burn seedlings risk in itself to plant；Fourth, heavy workload is repeatedly sprayed, people
Work is of high cost etc..
Research staff has carried out the improved technology scheme of organic selenium fertilizer and its preparation：As CN 101817710A are disclosed
" a kind of organic selenium-enriched liquid fertilizer and preparation method thereof ", core are to interrupt the skin chain of animal ceratin, swim amino acid
Organic selenizing amino acid is prepared from then being reacted in water with elemental nano-selenium powder, each component content is：Total animal ceratin water
Solve amino acid >=10wt%, the organic Se content 0.1-3wt% in terms of selenium, surfactant 2-3wt%, micro member needed for plant
Plain zinc >=1.0wt%, boron >=1.0wt%, Yu Weishui.This method cost is excessively high, and preparation requires process conditions height；CN
103304296A discloses " a kind of tobacco rod selenium-enriched organic fertilizer ", mainly utilizes cigarette pavilion, activation selenium mineral powder, fulvic acid and urine
Element is inoculated in raw material with the zymocyte liquid Jing Guo activation culture, by the method for biofermentation it is easy produce selenium-rich organic
Fertilizer.However, selenium-enriched organic fertilizer unbalanced nutrition prepared by this method, there is also a large amount of remaining hidden danger of inorganic selenium.
So urgent need outputs a kind of nutrition equilibrium and is not in the remaining selenium fertilizer of a large amount of selenium.
Invention content
To solve the above-mentioned problems, inventor is raw material using amino acid fermentation waste liquid and inorganic selenium, is produced
A kind of selenium-rich organic carbon fertilizer, preparation process is simple, and efficiently solves the problems, such as the recycling of amino acid fermentation waste liquid.
For this purpose, the present invention provides a kind of preparation method of selenium-rich organic carbon fertilizer, include the following steps：
(1) temperature of amino acid fermentation waste liquid is heated to 70-90 DEG C；
(2) it adds in reductant-oxidant and stirs 15-60 minutes；
(3) add in the pH adjusting agent pH of reaction system that step (2) is obtained and be adjusted to 7-8, then addition selenium source and
It is reacted 2-6 hours at a temperature of 70-90 DEG C；
(4) it adds in surfactant and stirs 1-2 hours, solution is uniformly dispersed to get selenium-rich organic carbon fertilizer.
In amino acids production, bulk fermentation waste water causes the serious pollution to environment from plant emissions.In amino acid wastewater
Rich in water-soluble organic matters such as a large amount of free amino acids.These waste water are unprocessed to be directly discharged into water body, wastes the same of resource
When cause environmental pollution and the destruction of the ecosystem.In addition, due to containing a large amount of free amino acids, albumen in amino acid wastewater
So seleno-amino acids etc. can be formed with selenium element reactant salt, inorganic states selenium is converted into for the substances such as matter, organic acid and reduced sugar
Organic Selenium.Organic Selenium eliminates the murder by poisoning risk of inorganic selenium salt, improves sorption enhanced utilization rate of the crop to selenium.Using
Amino acids fermented waste fluid produces Organic Selenium, these wastes can not only be effectively treated, but also can turn waste into wealth, and improves
Soil physico-chemical property and raising Se content are horizontal, increase selenium content of crops, yield and quality, have to Selenium deficiency area people's selenium-supply
Important meaning.
Selenium-rich organic carbon fertilizer of the present invention realizes waste water utilization, so as to save using amino acid fermentation waste liquid as main organic principle
About resource, and Environmental Safety.Using redox reaction, amino acid waste liquid is degraded to nanoscale small molecule organic matter, weak
Under alkaline condition, generation Organic Selenium is reacted with selenium compound, inorganic selenium is converted into Organic Selenium, produces selenium-rich organic carbon
Fertilizer.
Preferably, in the selenium-rich organic carbon fertilizer, the weight of solid content is based on described in the amino acid fermentation waste liquid
The percentage of the total weight of amino acid fermentation waste liquid is 30%-45%, wherein the solid content refers to that the amino acid fermentation gives up
The substance that liquid is formed after drying.
Preferably, amino acid fermentation waste liquid is nucleotide fermented waste fluid or Threonine Fermentation waste liquid in the step (1).
Preferably, reductant-oxidant is concentrated nitric acid or oxalic acid or hydrogen peroxide or potassium permanganate etc. in the step (2), is added
Enter the 0.2%-1% that amount is the amino acid fermentation waste liquid quality.
Preferably, pH adjusting agent is sodium hydroxide or potassium hydroxide in the step (3), makes reaction system alkali on the weak side
Property.
Preferably, selenium source is sodium selenite or sodium selenate or selenium mineral powder in the step (3), and dosage is sent out for the amino acid
The 1%-5% of ferment waste liquid quality.
Preferably, surfactant described in the step (4) is emulsifier or dispersant, and dosage is the amino acid
The 0.1-0.5% of fermented waste fluid quality.OP-10 can be used as emulsifier, and odium stearate can be used as dispersant.OP-10 ingredients
It is polyoxethylene octylphenyl phenol ether -10, there are excellent level dyeing, emulsification, wax control, inhibition, wetting, the spies such as diffusion, antistatic property
Property.
In addition, the present invention also provides a kind of selenium-rich organic carbon fertilizer prepared by the above method.
Preferably, the content of the selenium in the selenium-rich organic carbon fertilizer is 72.5-152.3mg/kg, and the content of selenium passes through national standard
GB5009.93-2010 is measured；The content of organic matter >=15%, free amino acid >=50g/kg.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) the recycling application of amino acid fermentation waste liquid rich in water-soluble amino acids small molecule, is given birth to selenium element reactant salt
Into Organic Selenium, the remaining potential murder by poisoning risk of inorganic selenium is reduced, and crop can be promoted to absorb fertilizer；
(2) selenium-rich organic carbon fertilizer has that nutrition is complete, utilization rate is high, good absorbing, quick, can crop Water soluble fertilizer or blade face
Fertilizer uses, and can simultaneously be used with most of pesticides and antiseptic；
(3) simple production process, reaction condition is mild, at low cost.
Specific embodiment
In order to make objects and advantages of the present invention more concise, the present invention will be explained with specific examples below
It is bright, but the present invention is only limitted to absolutely not these embodiments.Following embodiment is only more preferably embodiment, and be only used for explaining of the invention
State the present invention, it is impossible to be interpreted as limiting the scope of the present invention.It should be pointed out that it is all the present invention essence and principle it
Interior done all any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention.Therefore, it is of the invention
The protection domain of patent should be determined by the appended claims.
Prepare embodiment
Prepare embodiment 1
(1) double centner nucleotide fermented waste fluid fermented waste fluid is added in into reaction kettle, solid content is 40 kilograms, is added
Heat is to 90 DEG C；
(2) oxalic acid is added in as reductant-oxidant, and addition is 1 kilogram, is reacted 15 minutes, reaction solution grain size ＜
1000nm；
(3) it is 8 to add in sodium hydrate aqueous solution and adjust reaction solution pH as pH adjusting agent, adds in sodium selenite 0.4kg, and
It is reacted 1.5 hours at a temperature of 90 DEG C；
(4) 0.1 kilogram of OP-10 is slowly added to as emulsifier, is promoted the stabilization of selenium compound, after reacting 4 hours, is reacted
Terminate, reaction solution is finished product.
Prepare embodiment 2
(1) double centner Threonine Fermentation waste liquid fermented waste fluid is added in into reaction kettle, solid content is 45 kilograms, is added
Heat is to 70 DEG C；
(2) potassium permanganate is added in as reductant-oxidant, and addition is 1 kilogram, is reacted 30 minutes, reaction solution grain size ＜
1000nm；
(3) it is 8 to add in sodium hydroxide and adjust reaction solution pH as pH adjusting agent, adds in sodium selenite, and 70 DEG C of reactions 1.5 are small
When；
(4) 0.1 kilogram of odium stearate is slowly added to as dispersant, promotes the stabilization of selenium compound, after reaction 4 hours,
Reaction terminates, and reaction solution is finished product.
Prepare embodiment 3
(1) double centner nucleotide fermented waste fluid fermented waste fluid is added in into reaction kettle, solid content is 40 kilograms, is added
Heat is to 90 DEG C；
(2) oxalic acid is added in as reductant-oxidant, and addition is 1 kilogram, is reacted 30 minutes, reaction solution grain size ＜
1000nm；
(3) it is 7 to add in sodium hydroxide and adjust reaction solution pH as pH adjusting agent, adds in sodium selenite 0.9kg, 90 DEG C of reactions
1.5 hour；
(4) 0.1 kilogram of OP-10 is slowly added to as emulsifier, is promoted the stabilization of selenium compound, after reacting 4 hours, is reacted
Terminate, reaction solution is finished product.
Prepare embodiment 4
(1) double centner Threonine Fermentation waste liquid fermented waste fluid is added in into reaction kettle, solid content is 45 kilograms, is added
Heat is to 70 DEG C；
(2) potassium permanganate is added in as reductant-oxidant, and addition is 1 kilogram, is reacted 30 minutes, reaction solution grain size ＜
1000nm；
(3) it is 7 to add in sodium hydroxide and adjust reaction solution pH as pH adjusting agent, adds in sodium selenite 6kg, 70 DEG C of reactions
1.5 hour；
(4) 0.1 kilogram of odium stearate is slowly added to as dispersant, promotes the stabilization of selenium compound, after reaction 4 hours,
Reaction terminates, and reaction solution is finished product.
Comparative example 1
The present embodiment preparation method and step, originally identical with preparing 1 whole of embodiment, the difference lies in do not add in
Sodium selenite, it is specific as follows.
(1) double centner Threonine Fermentation waste liquid fermented waste fluid is added in into reaction kettle, solid content is 45 kilograms, is added
Heat is to 90 DEG C；
(2) potassium permanganate is added in as reductant-oxidant, and addition is 1 kilogram, is reacted 30 minutes, reaction solution grain size ＜
1000nm；
(3) it is 7-8 to add in sodium hydroxide and adjust reaction solution pH as pH adjusting agent, addition sodium selenite 13.5kg, 90 DEG C
Reaction 1.5 hours；
(4) 0.1 kilogram of odium stearate is slowly added to as dispersant, promotes the stabilization of selenium compound, after reaction 4 hours,
Reaction terminates, and reaction solution is finished product.
Comparative example 2
The present embodiment directly using solid content account for amino acid proportion be 45% nucleotide fermented waste fluid.
Comparative example 3
The present embodiment is directly using Organic Selenium foliar fertilizer on the market, wherein Se content 76mg/kg.
| Embodiment | Solid content accounts for the proportion % of amino acid | Inorganic selenium accounts for the proportion % of amino acid solid content | Amino acid waste liquid type |
| Embodiment 1 | 40 | 1 | Nucleotide |
| Embodiment 2 | 45 | 2 | Threonine |
| Embodiment 3 | 40 | 15 | Nucleotide |
| Embodiment 4 | 45 | 30 | Threonine |
| Comparative example 1 | 45 | Without selenium source | Nucleotide |
| Comparative example 2 | 45 | Nucleotide fermented waste fluid | Nucleotide |
| Comparative example 3 | 0 | Other liquid selenium-rich fertilizer | Other types |
Application Example
In the production of 1 potato of field test embodiment, liquid level sprays or pours twice, each dosage is selenium-rich organic carbon
It is 2.5kg/ mus fertile.
Test method：Field trial, sowing mid-November, when seedling grows to 3-4 leaves were carried out in Shenzhen in 2016
Seedling thinning field planting is carried out, this experiment sets 8 processing, and random district's groups is taken to arrange, are repeated three times.Each 50 square metres of test block, often
Ridge is set between district's groups between a test block, is influenced each other when preventing from spraying, the sample plot sets the protection row of 2m, and to each
The soil of test block sterilizes.Each area is tested by scheme requirement top dressing, other management measures are identical, by the examination of Ministry of Agriculture's specification
Requirement is tested to implement.Fertilising：Sprayed before field planting and after field planting of transplanting seedlings at interval of the sprinkling of whole strain in 7 days twice until end of pulling up seedlings,
During middle use 50kg is watered per 100g spraying preparations.
Blank：It does not apply fertilizer；
Processing 1：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 1；
Processing 2：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 2；
Processing 3：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 3；
Processing 4：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 4；
Processing 5：The selenium-rich organic carbon fertilizer 100g of the preparation of comparative example 1 is sprayed every time；
Processing 6：The nucleotide fermented waste fluid 100g of comparative example 2 is sprayed every time；
Processing 7：The selenium fertilizer 100g of the selection of comparative example 3 is sprayed every time.
| Project | Ripening fruits Se content | Yield/kg | Pre-set time picking time (my god) |
| Blank | 0.0009 | 105 | -- |
| Processing 1 | 0.0296 | 134 | 3 |
| Processing 2 | 0.0306 | 128 | 5 |
| Processing 3 | 0.0325 | 138 | 4 |
| Processing 4 | 0.0358 | 145 | 5 |
| Processing 5 | 0.0011 | 139 | 2 |
| Processing 6 | 0.0013 | 137 | 2 |
| Processing 7 | 0.0245 | 118 | 1 |
As seen from the above table：The potato picking time that the selenium-rich organic carbon fertilizer of embodiment 1-4 is prepared using the present invention shifts to an earlier date
2-5 days, while Se content relatively handles 7 selenium fertilizer and improves at least as 20.8%, yield compared with space management also improve at least
21.9%, it can be seen that selenium-rich organic carbon fertilizer of the present invention can increase yield, improve crop Se content.In addition, processing 1-6 is whole
Stem is sturdy compared with other processing in growth course after a field planting of transplanting seedlings, and growing way is more preferable, and is found after pulling up seedlings, compared with its blank and
It is more flourishing to handle 7 roots, illustrates that amino acid fermentation waste liquid can promote crop root to produce, improves yield.
In 2 cucumber production of field test embodiment, liquid level sprays or pours twice, and each dosage is selenium-rich organic carbon fertilizer
2.5kg/ mu.
Test method：In 2016 Shenzhen carry out field trial, mid-April seeding and seedling raising, when seedling grows to 3-4 leaves
Shi Jinhang transplants seedlings field planting, this experiment sets 8 processing, and random district's groups is taken to arrange, are repeated three times.Each 50 square metres of test block,
Ridge is set between district's groups between each test block, is influenced each other when preventing from spraying, the sample plot sets the protection row of 2m, and to every
The soil of a test block sterilizes.Each area is tested by scheme requirement top dressing, other management measures are identical, by Ministry of Agriculture's specification
Test requirements document is implemented.Fertilising：It transplants seedlings and sprays before being colonized and sprayed twice until knot of pulling up seedlings at interval of whole strain in 7 days after field planting of transplanting seedlings
Beam is watered 5kg per 10g spraying preparations when used.
Blank：It does not apply fertilizer；
Processing 1：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 1；
Processing 2：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 2；
Processing 3：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 3；
Processing 4：It sprays every time and prepares selenium-rich organic carbon fertilizer 100g prepared by embodiment 4；
Processing 5：The selenium-rich organic carbon fertilizer 100g of the preparation of comparative example 1 is sprayed every time；
Processing 6：The nucleotide fermented waste fluid 100g of comparative example 2 is sprayed every time；
Processing 7：The selenium fertilizer 100g of the selection of comparative example 3 is sprayed every time.
As seen from the above table：The cucumber picking time that the selenium-rich organic carbon fertilizer of embodiment 1-4 is prepared using the present invention shifts to an earlier date 3-5
My god, and entire fruiting period extends 2-5 days, while it is at least 21.5% that Se content, which relatively handles 7 selenium fertilizer and improves, yield compared with blank space
Reason also improves at least 21.7%, it can be seen that selenium-rich organic carbon fertilizer of the present invention can increase yield, improve crop Se content.This
Outside, stem is sturdy compared with other processing in growth courses of the processing 1-6 after field planting of entirely transplanting seedlings, and growing way is more preferable.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to the one of invention
A little modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, it although is used in this specification
Some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (9)
1. a kind of preparation method of selenium-rich organic carbon fertilizer, which is characterized in that it includes the following steps successively：
(1) temperature of amino acid fermentation waste liquid is heated to 70-90 DEG C；
(2) it adds in reductant-oxidant and stirs 15-60 minutes；
(3) it adds in pH adjusting agent and 7-8 is adjusted to the pH for the reaction system for obtaining step (2), then add in selenium source and in 70-
It is reacted 2-6 hours at a temperature of 90 DEG C；
(4) it adds in surfactant and stirs 1-2 hours up to selenium-rich organic carbon fertilizer.
A kind of 2. preparation method as described in claim 1, which is characterized in that the weight of solid content in the amino acid fermentation waste liquid
The percentage for measuring the total weight based on the amino acid fermentation waste liquid is 30%-45%, wherein the solid content refers to the ammonia
The substance that base acid fermentation waste liquid is formed after drying.
3. a kind of preparation method as claimed in claim 2, which is characterized in that amino acid fermentation waste liquid is in the step (1)
Nucleotide fermented waste fluid or Threonine Fermentation waste liquid.
4. a kind of preparation method as described in claim 1, which is characterized in that reductant-oxidant is dense nitre in the step (2)
One or more in acid, oxalic acid, hydrogen peroxide, potassium permanganate, dosage is the 0.2- of the amino acid fermentation waste liquid quality
1%.
5. a kind of preparation method as described in claim 1, which is characterized in that pH adjusting agent is hydroxide in the step (3)
Sodium or potassium hydroxide aqueous solution.
6. a kind of preparation method as described in claim 1, which is characterized in that selenium source is sodium selenite, selenium in the step (3)
Sour sodium or selenium mineral powder, dosage are the 1-5% of the amino acid fermentation waste liquid quality.
7. a kind of preparation method as described in claim 1, which is characterized in that step (4) surfactant is emulsifier
Or dispersant, dosage are the 0.1-0.5% of the amino acid fermentation waste liquid quality.
8. a kind of selenium-rich organic carbon fertilizer prepared by preparation method by described in any one of claim 1-7.
9. a kind of selenium-rich organic carbon as described in claim 8 fertilizer, which is characterized in that selenium in the selenium-rich organic carbon fertilizer
Content is 72.5-152.3mg/kg.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109574745A (en) * | 2018-12-10 | 2019-04-05 | 深圳市芭田生态工程股份有限公司 | A kind of selenium Liquid Fertilizer and preparation method thereof |
| CN110452058A (en) * | 2019-09-12 | 2019-11-15 | 湖北田头生物科技有限公司 | A method of organic carbon fertilizer is prepared with active dry yeasr black liquor |
| CN113387742A (en) * | 2021-05-21 | 2021-09-14 | 恩施德源健康科技发展有限公司 | Nano organic selenium fertilizer and preparation method and application thereof |
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| CN110452058A (en) * | 2019-09-12 | 2019-11-15 | 湖北田头生物科技有限公司 | A method of organic carbon fertilizer is prepared with active dry yeasr black liquor |
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