CN104446751A - Copper-based nutrition protective agent containing amino acids and preparation method thereof - Google Patents
Copper-based nutrition protective agent containing amino acids and preparation method thereof Download PDFInfo
- Publication number
- CN104446751A CN104446751A CN201410624480.9A CN201410624480A CN104446751A CN 104446751 A CN104446751 A CN 104446751A CN 201410624480 A CN201410624480 A CN 201410624480A CN 104446751 A CN104446751 A CN 104446751A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- copper
- agent
- amino acids
- protective agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- 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
- C05G5/40—Fertilisers incorporated into a matrix
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a copper-based nutrition protective agent containing amino acids and a preparation method thereof. According to the copper-based nutrition protective agent containing the amino acids disclosed by the invention, as based on the copper-based nutrition protective agent, amino acids in different types or compound amino acids are added, the copper-based nutrition protective agent containing the amino acids can provide nitrogen elements to plants in a mode of amino acid nitrogen and is easy to be absorbed by the plants after being sprayed, so that the copper-based nutrition protective agent containing the amino acids has the nutrition function while carrying out sterilization, is capable of promoting growth and development of crops, improving the stress resistance and the quality of the crops and increasing the yield of the crops. The copper-based nutrition protective agent containing the amino acids is high in content of the effective components, good in suspension property, strong in adhesion and large in uniformly on the surfaces of the plants and durable in pesticide effect and is capable of resisting rainwash, reducing spraying times and remarkably increasing economical, social and ecological benefits.
Description
(1) technical field
The present invention relates to a kind of containing amino acid whose copper base nourishment protecting agent and preparation method, belong to plant nutrition and plant protection product.
(2) background technology
Amino acid is organic nitrogen compound main in soil, accounts for the 15%-60% of total soil nitrogen.Plant can absorb amino acid, and amino acid is distinguished because amino acid is different with floristics to some extent to the effect of plant.Amino acid can directly enter in plant, is directly absorbed, improve the output of some crops, quality etc. by celery, rye grass, wheat etc.At present, the series product such as amino acids sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator are had.But also report is rarely had for the application of amino acid in copper base nourishment protecting agent, needs experimental study, more useful product is grown to Different Crop for producing theoretical foundation and technical support are provided.
The patent that domestic and international relevant amino acid is applied to crop at present relates generally to foliage fertilizer, composite fertilizer and Water soluble fertilizer field, as CN1413960A (a kind of ammino acid liquid fertilizer), CN102134170B (a kind of potato amino acid organic and inorganic compound fertilizer dedicated and manufacture method), CN102614244B (natural plant amino acid nutrient solution and preparation method thereof), CN103086793A (a kind of Amino-acid water-soluble bio-fertilizer and preparation method thereof), CN103183573A (a kind of Ecological slow-release fertilizer of polymerization amino acid), EP2415737A1 (Method for manufacturing amino acid liquid fertilizer usinglivestock blood and amino acid liquid fertilizer manufactured thereby) etc.Advantage of the present invention is, on the protectant basis of copper base nutritious multifunctional, to add the amino acid of plant needs, make the active constituent content of this product higher.Be present invention adds amino acid with the key distinction of ZL201110441906.3 (copper base nutritional multi-functional foliar fertilizer and preparation method thereof), more easily absorbed by plant leaf, improve the yield and quality of product.
(3) summary of the invention
For solving the problem; the invention provides a kind of containing amino acid whose copper base nourishment protecting agent and preparation method; adopt self-control copper hydroxide colloid; add the dispersion agent, wetting agent, deflocculation agent etc. of amino acid and different ratios; and through the preparation of sand mill technique containing amino acid whose copper base nourishment protecting agent suspension agent product; or through the preparation of flash dryer technique containing amino acid whose copper base nourishment protecting agent wetting properties powder-like product, or through spray drying tower process preparation containing amino acid whose copper base nourishment protecting agent dry suspension product.This product has nutrition and sterilization dual-use function.
A kind of containing amino acid whose copper base nourishment protecting agent, in the butt of its powder-like product (weight ratio), the single-phase amino acid containing 40-46% or aminoacids complex; The mixture 2% that all the other compositions are copper hydroxide colloid 46-52%, auxiliary agent is dispersion agent D-425 alkyl naphthalene sulfonic acid polycondensate sodium salt 3%, dispersion agent SPR Sulfonates and phosphate ester salt analog anion surfactants, wetting agent are the mixture 2% of EFW sulfonated alkyl naphathalene and negatively charged ion wetting agent and the mixture 1% of deflocculation agent DC7 Sulfonates and phosphate ester salt analog anion surfactants; Each component concentration per-cent sum is 100%; Described amino acid is single-phase amino acid or aminoacids complex; Described single-phase amino acid is L-glutamic acid, aspartic acid, glycine or Serine; Described aminoacids complex is the commercially available mixture containing multiple amino acids such as L-glutamic acid, aspartic acid, glycine, Serines.
During use, this protective material product mixes by weight 1:500-1000 with water, and after mixing, the pH value of suspension is 7.0-8.0.
A kind of containing amino acid whose copper base nourishment protecting agent, its making method is as follows:
(1) copper sulfate of certain mass is slowly joined in the ammoniacal liquor (quality of copper sulfate and ammoniacal liquor and volume ratio are 1.2-1.3) of certain volume, not stopping stirring makes it dissolve completely, form the co-ordination complex solution of copper, the reaction times is 20-30min; Then add with the form spraying into droplet the sodium hydroxide solution (copper sulfate quality and sodium hydroxide solution volume ratio are for 1.6-1.7) that concentration is 5mol/L, the time is 70-90min, makes the copper hydroxide colloid median size of generation be less than 5 μm; Use tap water copper hydroxide suspension colloid 3-4 time afterwards, make its pH value reach 7.5 ± 0.5, obtain copper hydroxide suspension colloid through standing or centrifugal removing supernatant liquor; By air-dry or in the baking oven of temperature lower than 45 DEG C dry obtain copper hydroxide hydrocolloid powder.
(2) on the basis calculating accurate proportioning, in above-mentioned copper hydroxide hydrocolloid powder, add amino acid, the amino acid added can be aminoacids complex or different types of single-phase amino acid.
(3) formulation adjuvant dispersion agent, wetting agent, deflocculation agent etc. are added.
(4) on the basis of above-mentioned (3), stir through flash dryer and obtain containing amino acid whose copper base nourishment protecting agent powder-like product.
(5) or on the basis of above-mentioned (3), then add water, obtain after the abundant grinding distribution of sand mill containing amino acid whose copper base nourishment protecting agent suspension agent product.
(6) or on the basis of above-mentioned (5), suspension agent product is obtained containing amino acid whose copper base nourishment protecting agent dry suspension product through spray-drying tower.
Main points of the present invention are:
One of main points are: change Bordeaux mixture preparation conventional formulation, use ammonium hydroxide and sodium hydroxide to replace traditional calcium hydroxide, avoid calcium and sulfate ion reacts the problem generating calcium sulfate precipitation.The consumption of the auxiliary agent such as dispersion agent, wetting agent can be reduced like this, significantly reduce production cost.
Two of main points are: slowly added in the ammoniacal liquor of certain volume by the copper sulfate of certain mass, and ceaselessly stir and make it dissolve the co-ordination complex forming copper completely, the reaction times controls at 20-30 minute.Sodium hydroxide solution sprays into droplet form, by controlling concentration and the spray velocity of sodium hydroxide solution, controlling the granularity of copper hydroxide suspension colloid, making its median size be less than 5 μm.After preparation copper hydroxide suspension colloid end of processing, by tap water reaction product 3-4 time, its pH value is made to reach 7.5 ± 0.5.Production unit needed for this technical process is simple, and the reaction used time is short, can be controlled in 1.5-2 hour.
Three of main points are: on the basis calculating accurate proportioning, a certain amount of amino acid and various auxiliary agent is added in above-mentioned copper hydroxide hydrocolloid powder, the amino acid added can be aminoacids complex or various single-phase amino acid etc., not only can Promoting plant growth, and in water, easy dispersion suspension is good, and after being sprayed on plant surface, tackiness is strong, resistance of rainwater washing against, not only easy to use, operation is simple, and can reduce spray medicine number of times and consumption.
Effect of the present invention:
The present invention, on the basis of existing copper base nourishment protecting agent, adopts simple production technology and production unit, produce price low, effective containing amino acid whose copper base nourishment protecting agent product.This copper base nourishment protecting agent product not only has sterilization and intends bacterium effect, and can provide amino-acid nitrogen for the growth of plant, and easy to use, time and labour saving, has good economic and social benefit.
The product that the present invention produces is compared with copper base nourishment protecting agent product in the past; owing to adding different types of amino acid or aminoacids complex; can be crop and the organic nitrogen directly absorbed is provided; promote the recovery of the blade normal physiological function being subject to disease or environment stress, improve resistance, disease resistance and quality of agricultural product.The test-results that apple, grape, tomato spray this product shows, not only reduces the generation of disease, and significantly improves the sugar-acid ratio, Vitamin C content etc. in fruit, adds keeping quality and exterior quality.Therefore, product of the present invention has the advantage and feature that copper base nourishment protecting agent was significantly different in the past.
(4) accompanying drawing explanation
Fig. 1 is containing amino acid whose copper base nourishment protecting agent product preparation process schema.
In figure: the copper sulfate 1, taking certain mass; 2, it is slowly joined in the ammoniacal liquor of certain volume, under the condition constantly stirred, make it fully react; 3, certain density sodium hydroxide solution is injected in reactant 2 with the form of droplet; 4, washing copper hydroxide colloid three to four times, make its pH value reach till 7.5 ± 0.5, through leaving standstill or centrifugal removing supernatant liquor, obtaining copper hydroxide suspension colloid; 5, by air-dry or in the baking oven of temperature lower than 45 DEG C dry obtain copper hydroxide hydrocolloid powder.6, in above-mentioned copper hydroxide hydrocolloid powder, the auxiliary agent such as appropriate amino acid and appropriate dispersion agent, wetting agent, deflocculation agent is added; 7, mixture is obtained containing amino acid whose copper base nourishment protecting agent powder-like product through flash dryer stirring; Or add appropriate water and obtain containing amino acid whose copper base nourishment protecting agent suspension agent product after the abundant grinding distribution of sand mill; Or spray-dried the obtaining of suspension agent product contains amino acid whose copper base nourishment protecting agent product; 8, through being namely packaged as finished product after the assay was approved.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Embodiment 1:
Take 5kg cupric sulfate pentahydrate (1); It slowly being joined 6.5L concentration is in the ammoniacal liquor of 25%, does not stop stirring and makes it dissolve completely, and form the co-ordination complex solution of copper, the reaction times is 20-30min (2); Then add 5mol/L sodium hydroxide solution 10L with the form spraying into droplet, the time is 70-90min, and the copper hydroxide colloid median size of generation is less than 5 μm (3); Use tap water copper hydroxide suspension colloid 3-4 time afterwards, make its pH value reach 7.5 ± 0.5, obtain copper hydroxide suspension colloid (4) through standing or centrifugal removing supernatant liquor; Through natural air drying or in the baking oven of temperature lower than 45 DEG C dry obtain copper hydroxide hydrocolloid powder (5); Take copper hydroxide hydrocolloid powder 300g, add aminoacids complex 160g wherein, add dispersion agent D-425 (alkyl naphthalene sulfonic acid polycondensate sodium salt) 15g, dispersion agent SPR (mixture of Sulfonates and phosphate ester salt analog anion surfactants) 10g, wetting agent EFW (mixture of sulfonated alkyl naphathalene and negatively charged ion wetting agent) 10g and deflocculation agent DC7 (mixture of Sulfonates and phosphate ester salt analog anion surfactants) 5g (6); Add 333.3mL water; By mixture through sand mill grinding distribution; Obtain containing amino acid whose copper base nourishment protecting agent suspension agent product (7) with 500mL water washing.Wherein, copper hydroxide content accounts for product dry basis 60%.
In gained suspension agent: by dry basis, containing Cu%=39.18%.The suspension pH of this suspension agent product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Embodiment 2:
Take 5kg cupric sulfate pentahydrate (1); It slowly being joined 6.5L concentration is in the ammoniacal liquor of 25%, does not stop stirring and makes it dissolve completely, and form the co-ordination complex solution of copper, the reaction times is 20-30min (2); Then add 5mol/L sodium hydroxide solution 10L with the form spraying into droplet, the time is 70-90min, and the copper hydroxide colloid median size of generation is less than 5 μm (3); Use tap water copper hydroxide suspension colloid 3-4 time afterwards, make its pH value reach 7.5 ± 0.5, obtain copper hydroxide suspension colloid (4) through standing or centrifugal removing supernatant liquor; Through natural air drying or in the baking oven of temperature lower than 45 DEG C dry obtain copper hydroxide hydrocolloid powder (5); Take copper hydroxide hydrocolloid powder 300g, add aminoacids complex 160g wherein, add dispersion agent D-425 (alkyl naphthalene sulfonic acid polycondensate sodium salt) 15g, dispersion agent SPR (mixture of Sulfonates and phosphate ester salt analog anion surfactants) 10g, wetting agent EFW (mixture of sulfonated alkyl naphathalene and negatively charged ion wetting agent) 10g and deflocculation agent DC7 (mixture of Sulfonates and phosphate ester salt analog anion surfactants) 5g (6); Mixture is stirred 20min through flash dryer obtain containing amino acid whose copper base nourishment protecting agent wettable powder product (7) (8).Wherein, copper hydroxide content accounts for product dry basis 60%.
In gained wettable powder: containing Cu%=39.18%.The suspension pH of this wettable powder product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Embodiment 3:
Adition process as embodiment 1, but is distinguished to some extent on the amino acid added.As: add L-glutamic acid 160g, other processes are with example 1.
In gained suspension agent: by dry basis, containing Cu%==39.18%.The suspension pH of this suspension agent product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Embodiment 4:
Adition process as embodiment 2, but is distinguished to some extent on the amino acid added.As: add L-glutamic acid 160g, other processes are with example 2.
In gained wettable powder: containing Cu%=39.18%; Containing L-glutamic acid %=32%; The suspension pH of this wettable powder product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Embodiment 5:
Adition process as embodiment 1, but is distinguished to some extent on the amino acid added.As: add aspartic acid 160g, other processes are with example 1.
In gained suspension agent: by dry basis, containing Cu%==39.18%.The suspension pH of this suspension agent product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Embodiment 6:
Adition process as embodiment 2, but is distinguished to some extent on the amino acid added.As: add aspartic acid 160g, other processes are with example 2.
In gained wettable powder: containing Cu%=39.18%; Containing aspartic acid %=32%; The suspension pH of this wettable powder product when spraying concentration is 1:500-1000 is after adding the water 7.0-8.0.
Claims (2)
1., containing an amino acid whose copper base nourishment protecting agent, it is characterized in that, in the butt of its powder-like product, the amino acid containing weight ratio 40-46%; Described amino acid is single-phase amino acid or aminoacids complex; Described single-phase amino acid is L-glutamic acid, aspartic acid, glycine or Serine; Described aminoacids complex is the mixture of the multiple amino acids containing L-glutamic acid, aspartic acid, glycine, Serine.
2. as claimed in claim 1 a kind of containing amino acid whose copper base nourishment protecting agent; it is characterized in that; with the butt of its powder-like product with mass ratio range, all the other components are copper hydroxide colloid 46-52%, auxiliary agent is dispersion agent D-425 alkyl naphthalene sulfonic acid polycondensate sodium salt 3%, dispersion agent SPR Sulfonates and phosphate ester salt analog anion surfactants mixture 2%, wetting agent EFW sulfonated alkyl naphathalene and the mixture 2% of negatively charged ion wetting agent and the mixture 1% of deflocculation agent DC7 Sulfonates and phosphate ester salt analog anion surfactants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410624480.9A CN104446751B (en) | 2014-11-07 | 2014-11-07 | A kind of copper-based nourishment protecting agent containing amino acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410624480.9A CN104446751B (en) | 2014-11-07 | 2014-11-07 | A kind of copper-based nourishment protecting agent containing amino acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104446751A true CN104446751A (en) | 2015-03-25 |
| CN104446751B CN104446751B (en) | 2017-09-15 |
Family
ID=52893594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410624480.9A Expired - Fee Related CN104446751B (en) | 2014-11-07 | 2014-11-07 | A kind of copper-based nourishment protecting agent containing amino acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104446751B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108051A (en) * | 1985-10-30 | 1987-06-24 | 陶仲侃 | Synthetization technology of agriculture germicide " shuang xiao ling " |
| US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
| CN1080118A (en) * | 1993-04-07 | 1994-01-05 | 李善宽 | Agricultural multi-effect bactericide |
| CN1104851A (en) * | 1994-11-18 | 1995-07-12 | 张星辰 | Acetic acid, glutaminic acid and copper ammoniate bactericidal agent and its preparing method |
| CN1454480A (en) * | 2002-04-29 | 2003-11-12 | 黄安辉 | Preparation having glutamic copper complex as active principle with bacteriacide and foliage fertilizer effect |
| KR20100134166A (en) * | 2009-06-15 | 2010-12-23 | 유섬근 | Method of preparing for concentrated bordeaux mixture |
| CN102491851A (en) * | 2011-12-26 | 2012-06-13 | 山东农业大学 | Stable and available iron-containing copper-based nutritional foliar fertilizer and its preparation method |
| CN102515962A (en) * | 2011-12-26 | 2012-06-27 | 山东农业大学 | Copper-based nutritional multi-functional foliar fertilizer and preparation method thereof |
-
2014
- 2014-11-07 CN CN201410624480.9A patent/CN104446751B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108051A (en) * | 1985-10-30 | 1987-06-24 | 陶仲侃 | Synthetization technology of agriculture germicide " shuang xiao ling " |
| US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
| CN1080118A (en) * | 1993-04-07 | 1994-01-05 | 李善宽 | Agricultural multi-effect bactericide |
| CN1104851A (en) * | 1994-11-18 | 1995-07-12 | 张星辰 | Acetic acid, glutaminic acid and copper ammoniate bactericidal agent and its preparing method |
| CN1454480A (en) * | 2002-04-29 | 2003-11-12 | 黄安辉 | Preparation having glutamic copper complex as active principle with bacteriacide and foliage fertilizer effect |
| KR20100134166A (en) * | 2009-06-15 | 2010-12-23 | 유섬근 | Method of preparing for concentrated bordeaux mixture |
| CN102491851A (en) * | 2011-12-26 | 2012-06-13 | 山东农业大学 | Stable and available iron-containing copper-based nutritional foliar fertilizer and its preparation method |
| CN102515962A (en) * | 2011-12-26 | 2012-06-27 | 山东农业大学 | Copper-based nutritional multi-functional foliar fertilizer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘备 等: "铜基营养保护剂对苹果生长及果实品质的影响", 《北方园艺》 * |
| 唐孟成等: "废蚕丝制取氨基酸合铜农药的研究", 《桑蚕通报》 * |
| 徐睿 等: "砂磨机制备铜基营养保护剂悬浮剂的工艺优化", 《农药学学报》 * |
| 徐睿 等: "铜基营养保护剂悬浮浓度快速测定方法的研究", 《中国测试》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104446751B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102153417A (en) | Quick-acting striking root leaf fertilizer | |
| CN105646028A (en) | Kiwi fruit foliar spraying fertilizer | |
| CN108558524A (en) | A kind of multifunctional nano titanium dioxide composite foliage fertilizer | |
| CN104098378A (en) | High-efficiency slow-release compound fertilizer containing Crotalaria pallida | |
| CN103360146A (en) | High potassium washing fertilizer containing amino acid chelated medium and trace elements | |
| CN104030791A (en) | Soil-hardening-resisting growth-promoting sustained-release composite fertilizer | |
| CN104030799B (en) | A kind of long-acting slow-release compound fertilizers of water conservation drought resisting | |
| CN102795905A (en) | Preparation method of microelement type major element liquid water-soluble fertilizer | |
| CN105399544A (en) | Slow release composite fertilizer and preparation method thereof | |
| CN103708889B (en) | A kind of composite full water-soluble punching fertilising processed and preparation method | |
| CN109251082A (en) | A kind of humic acid foliar fertilizer and preparation method thereof | |
| CN104478620A (en) | Acetal-containing vegetable leaf fertilizer and preparation method thereof | |
| CN102515962B (en) | Copper-based nutritional multi-functional foliar fertilizer and preparation method thereof | |
| CN109400330A (en) | A kind of Chinese prickly ash special foliar fertilizer and preparation method thereof | |
| CN101898918B (en) | Chelated controlled-release compound fertilizer and preparation method thereof | |
| CN103772053B (en) | A kind of synergistic agent for urea and preparation method thereof and using method | |
| CN104788181A (en) | Production method of multielement microelement amino acid chelating fertilizer | |
| CN102491851A (en) | Stable and available iron-containing copper-based nutritional foliar fertilizer and its preparation method | |
| CN105237312A (en) | Controlled-release fertilizer for sugarcane and preparation method thereof | |
| CN109111290A (en) | A kind of organic-inorganic special type water-soluble fertilizer | |
| CN104446751A (en) | Copper-based nutrition protective agent containing amino acids and preparation method thereof | |
| CN104446752B (en) | A kind of copper-based nourishment protecting agent and its production method containing amino acid chelated calcium | |
| CN103951506B (en) | A kind of water-soluble fertilizer containing mushroom proteoglycan | |
| CN106116740A (en) | A kind of flowers multifunctional and nutritional element effervescent tablet and preparation method thereof | |
| CN105272724A (en) | Preparation method of water-soluble liquid taurine amino acid accelerating type high efficiency nitrogenous fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170915 Termination date: 20201107 |