CN104446752B - A kind of copper-based nourishment protecting agent and its production method containing amino acid chelated calcium - Google Patents
A kind of copper-based nourishment protecting agent and its production method containing amino acid chelated calcium Download PDFInfo
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- CN104446752B CN104446752B CN201410624544.5A CN201410624544A CN104446752B CN 104446752 B CN104446752 B CN 104446752B CN 201410624544 A CN201410624544 A CN 201410624544A CN 104446752 B CN104446752 B CN 104446752B
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- calcium
- amino acid
- copper
- acid chelated
- protecting agent
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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
- 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
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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
- C05G5/00—Fertilisers characterised by their form
- C05G5/40—Fertilisers incorporated into a matrix
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to a kind of copper-based nourishment protecting agent containing amino acid chelated calcium and its production method.The present invention is on the basis of copper-based nourishment protecting agent; add amino acid chelated calcium; the calcium constituent and nitrogen being supplied to after spraying required for plant; because the form of calcium is in chelating or complex state; exist in suspension in stable state, be easy to be absorbed by plants after spraying, make product that there is trophism again while sterilization; the symptoms such as the calcium deficiency of crop can be corrected, crop anti-adversity and its yield and quality is improved.This copper-based nourishment protecting agent active constituent content containing amino acid chelated calcium is high, and suspension is good, plant surface adhesion force is strong, the uniformity is big, resistance of rainwater washing against, lasting medicine, can reduce spray number of times, significantly improves economic, society and ecological benefits.
Description
(1) technical field
The present invention relates to a kind of copper-based nourishment protecting agent containing amino acid chelated calcium and production method, belong to plant nutrient with
Plant protection product.
(2) background technology
Calcium is indispensable element important in plant, is the regulation and control person of plant main metabolic and development, it is to plant cell
Structure, physiological function and fruit development play the role of it is important, to improve fruit quality, increase Storage etc. also have it is important
Meaning.In soil, phosphorus and calcium are commonly formed synthos precipitation and cause phosphorus fixation especially in calacareous soil, and then drop
The validity of utilization rate and the calcium element of low phosphate fertilizer, influences yield, quality and the resistance of crop, in particular with facility cultivation
Development, a large amount of of phosphate fertilizer apply and crop yield is increased substantially, and physiological disturbance about some crop calcium deficiency or apply calcium
The report of volume increase gradually increases.Amino acid chelated calcium is led to by several amino acids and inorganic calcium salt or oxide, hydroxide etc.
A kind of organic calcium class material crossed chemosynthesis reaction and produced, so that absorption of the plant to calcium is substantially increased, with stable
Chemical property, high biological value, it is nontoxic the advantages of, supplementing calcium element and amino acid can be played dual parts of.Amino acid
As chelating agent, stability constant is moderate, is not disturbed by soil pH and other ions, and wherein calcium constituent is by chelating amino acids, no
Easily by soil fixing, it is easy to the absorption of crop.
Advantage of the invention is that on the basis of copper-based nutritious multifunctional is protectant, adding the amino acid chela that plant needs
Calcium is closed, making the active constituent content of this product, higher there is provided the more nutrition of plant.With ZL201110441906.3 (copper-based battalion
Support multifunctional foliage fertilizer and preparation method thereof) the main distinction be, present invention adds amino acid chelated calcium, to be more easy to by leaves of plants
Piece absorbs the calcium deficiency symptom for reducing and correcting plant there is provided the nitrogen required for plant and calcium constituent, improves the yield of product
And quality.
(3) content of the invention
To solve the above problems, the invention provides a kind of copper-based nourishment protecting agent and producer containing amino acid chelated calcium
Method, is to use Kocide SD colloid, dispersant, wetting agent, deflocculant of addition amino acid chelated calcium and different proportion etc., and
The copper-based nourishment protecting agent suspending agent product containing amino acid is prepared by sand mill technique, or is prepared by flash dryer technique
Copper-based nourishment protecting agent wettable powdery product containing amino acid chelated calcium, or prepared by spray drying tower process containing amino acid
Chelated calcium copper-based nourishment protecting agent dry suspending agent product.This product has nutrition and sterilization dual-use function.
A kind of copper-based nourishment protecting agent containing amino acid chelated calcium, in terms of the butt of powder product (weight ratio)：Contain ammonia
Base acid chelating calcium 40-46%；The content of remaining composition is：Kocide SD colloid 46-52%, auxiliary agent are dispersant D-425 alkyl
Naphthalene sulfonic acids condensation polymer sodium salt 3%, the mixture 2% of dispersant SPR Sulfonateses and phosphate ester salt analog anion surfactants,
The mixture 2% and deflocculant DC7 Sulfonateses and phosphate ester salt of wetting agent EFW alkylnaphthalene sulfonates and anion wetting agent
The mixture 1% of analog anion surfactants；Each component percentage composition sum is 100%；
Described amino acid chelated calcium is compound amino acid chelate calcium, calcium-glutamate chelate or aspartic acid chelating calcium.
The preparation method of described amino acid chelated calcium is：By amino acid and hydroxide in 75 ± 5 DEG C of water bath with thermostatic control
Calcium is soluble in water, and regulation pH is 7.5 ± 0.5, it is fully dissolved, the reaction time is 60min-90min, the amino acid and hydrogen
The mol ratio of calcium oxide is 2:1.
Copper-based nourishment protecting agent product prepared by the present invention can be suspending agent, dry suspending agent or wettable powder product.
In use, the protective agent product and water by weight 1:500-1000 is mixed, and the pH value of suspension is 7.0-8.0 after mixing.
A kind of copper-based nourishment protecting agent containing amino acid chelated calcium, its preparation method is as follows：
(1) copper sulphate of certain mass is slowly added into certain volume (quality of copper sulphate and ammoniacal liquor is with volume ratio
In ammoniacal liquor 1.2-1.3), not stopping stirring is completely dissolved it, forms the co-ordination complex solution of copper, the reaction time is 20-
30min；Then certain volume being added in the form of spraying into droplet, (sulfuric acid copper mass is with sodium hydroxide solution volume ratio as 1.6-
1.7) concentration is 5mol/L sodium hydroxide solution, and the time is 70-90min, makes the Kocide SD colloid average grain diameter of generation small
In 5 μm；Originally water washing Kocide SD suspension colloid 3-4 times is used afterwards, its pH value is reached 7.5 ± 0.5, through standing or centrifuging
Remove supernatant and obtain Kocide SD suspension colloid；Hydroxide is obtained by air-drying or being dried in baking oven of the temperature less than 45 DEG C
Copper hydrocolloid powder.
(2) in 75 ± 5 DEG C of water bath with thermostatic control that amino acid and calcium hydroxide is soluble in water, regulation pH is 7.5 ± 0.5,
It is set fully to dissolve, the reaction time is 60min-90min, the mol ratio of the amino acid and calcium hydroxide is 2:1, through centrifuging,
Purifying obtains amino acid chelated calcium fluid product.
(3) on the basis of accurate proportioning is calculated, add and match somebody with somebody in the Kocide SD hydrocolloid powder prepared in above-mentioned (1)
Square auxiliary agent dispersant, wetting agent, deflocculant etc..Add the chelating amino acids calcium solution prepared in above-mentioned (2).
(4) it is fully ground through sand mill after disperseing and obtains the copper-based nourishment protecting agent suspending agent production containing amino acid chelated calcium
Product.
(5) or on the basis of above-mentioned (3), raw material is obtained to the copper containing amino acid chelated calcium after flash dryer
Base nourishment protecting agent wettable powder product.
(6) or on the basis of above-mentioned (3), raw material is obtained into the copper-based battalion containing amino acid chelated calcium by spray drying tower
Support protective agent dry suspending agent product.
The method is characterized in that：
One of main points are：Change Bordeaux mixture preparation conventional formulation, it is traditional using ammonium hydroxide and sodium hydroxide substitution
Calcium hydroxide, it is to avoid the problem of calcium is with sulfate ion reaction generation calcium sulfate precipitation.Dispersant, wetting can so be reduced
The consumption of the auxiliary agents such as agent, is greatly lowered production cost.
The two of main points are：The copper sulphate of certain mass is slowly added in the ammoniacal liquor of certain volume, being continuously agitated makes it
The co-ordination complex to form copper is completely dissolved, the reaction time was controlled at 20-30 minutes.Sodium hydroxide solution is sprayed with droplet form
Enter, by controlling the concentration and spray velocity of sodium hydroxide solution, to control the granularity of Kocide SD suspension colloid, it is averaged
Particle diameter is less than 5 μm.Preparing after Kocide SD suspension colloid process terminates, with running water washing reaction product 3-4 times, making its pH
Value reaches 7.5 ± 0.5.Production equipment needed for the technological process is simple, and the reaction used time is short, can be controlled in 1.5-2 hours.
Third key point is：On the basis of accurate proportioning is calculated, added into above-mentioned Kocide SD hydrocolloid powder certain
The amino acid chelated calcium of amount and various auxiliary agents, can not only provide the calcium for being easy to absorb plain nutrition for plant growth, and in water
In easily scattered suspension it is good, be sprayed on after plant surface that adherence is strong, resistance of rainwater washing against is not only easy to use, and operation is simple,
And spray number of times and consumption can be reduced.
The effect of the present invention：
The present invention is on the basis of existing copper-based nourishment protecting agent, using the technology of preparing and production equipment of optimization, raw
Output price is low, the good copper-based nourishment protecting agent product containing amino acid chelated calcium of effect.This copper-based nourishment protecting agent product
Not only have and sterilize and intend bacterium effect, and nitrogen and calcium constituent can be provided for the growth of plant, easy to use, time and labour saving,
The waste and pollution of resource are reduced, with good economic and social benefit.
Product produced by the invention is compared with conventional copper-based nutritional multi-functional foliar fertilizer product, due to adding amino acid
Calcium is chelated, the calcium element of this Chelating state is easier to be absorbed by plants, more effectively the calcium deficiency symptom of correction crop, while can also be
Crop provides the amino acid organic nitrogen directly absorbed, and promotion is by the blade normal physiological function of disease or environment stress
Recover, improve crop anti-adversity, yield and quality.The experiment of this product is sprayed on the crops such as apple, grape, tomato, capsicum
As a result show, not only significantly reduce the generation of disease and add yield, and significantly improve the calcium content in fruit, sugar
Sour ratio, Vitamin C content etc., add keeping quality and exterior quality.Therefore, product of the present invention has copper-based nutrition protection in the past
Agent dramatically different advantage and feature.
(4) illustrate
Copper-based nourishment protecting agent product processes flow charts of the Fig. 1 containing amino acid chelated calcium.
In figure：1st, the copper sulphate of certain mass is weighed；2nd, it is slowly added into the ammoniacal liquor of certain volume, is constantly being stirred
Under conditions of mixing, it is set fully to react；3rd, the sodium hydroxide solution of finite concentration and certain volume is sprayed into the form of droplet
Into reactant 2；4th, washing Kocide SD colloid three to four times, makes untill its pH value reaches 7.5 ± 0.5, through standing or centrifuging
Supernatant is removed, Kocide SD suspension colloid is obtained；5th, gradually appropriate amino is added into above-mentioned Kocide SD suspension colloid
Acid chelating calcium liquid；6th, gradually to adding the auxiliary agents such as appropriate dispersant, wetting agent, deflocculant in 5, and it is sufficiently stirred for；7、
Mixture is ground or spray-dried or obtain copper-based nourishment protecting agent containing amino acid chelated calcium through expansion drying and produce
Product；8th, through being packaged as finished product after the assay was approved.
(5) embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The material can be obtained from open commercial sources unless otherwise instructed.
Embodiment 1：
5kg cupric sulfate pentahydrates (1) are weighed, are slowly added into the ammoniacal liquor that 6.5L concentration is 25%, not stopping stirring makes
It is completely dissolved, and forms the co-ordination complex solution of copper, and the reaction time is 20-30min (2)；Then in the form of spraying into droplet
5mol/L sodium hydroxide solution 10L are added, the time is 70-90min, the Kocide SD colloid average grain diameter of generation is less than 5 μm
(3)；Originally water washing Kocide SD suspension colloid 3-4 times is used afterwards, its pH value is reached 7.5 ± 0.5, is removed through standing or centrifuging
Supernatant is gone to obtain Kocide SD suspension colloid (4)；Dry through natural air drying or in baking oven of the temperature less than 45 DEG C and obtain hydrogen
Cupric oxide hydrocolloid powder；In 75 ± 5 DEG C of waters bath with thermostatic control, 140g glutamic acid and 35g calcium hydroxides are dissolved in 350mL water, adjusted
It is 7.5 ± 0.5 to save pH, it is fully dissolved, the reaction time is 60min-90min, and calcium-glutamate chelate is obtained through centrifugation, purifying
Fluid product；Kocide SD hydrocolloid powder 300g is weighed, above-mentioned glutamate chelate calcium solution (5) is added thereto；Add scattered
Agent D-425 (alkyl naphthalene sulfonic acid condensation polymer sodium salt) 15g, dispersant SPR (Sulfonates and phosphates anion surface active
The mixture of agent) 10g, wetting agent EFW (mixture of alkylnaphthalene sulfonate and anion wetting agent) 10g and deflocculant DC7
(mixtures of Sulfonates and phosphate ester salt analog anion surfactants) 5g (6)；By mixture through sand mill grinding distribution；
The copper-based nourishment protecting agent suspending agent product (7) (8) containing amino acid is obtained with 500mL water washings.Wherein, Kocide SD content is accounted for
Product dry basis 60%.
In gained suspending agent：Contain Cu%=39.18% by product butt；Containing Ca%=3.78%；This suspending agent product exists
Spraying concentration is 1 after adding water:Suspension pH during 500-1000 is 7.0-8.0.
Embodiment 2：
5kg cupric sulfate pentahydrates (1) are weighed, are slowly added into the ammoniacal liquor that 6.5L concentration is 25%, not stopping stirring makes
It is completely dissolved, and forms the co-ordination complex solution of copper, and the reaction time is 20-30min (2)；Then in the form of spraying into droplet
5mol/L sodium hydroxide solution 10L are added, the time is 70-90min, the Kocide SD colloid average grain diameter of generation is less than 5 μm
(3)；Originally water washing Kocide SD suspension colloid 3-4 times is used afterwards, its pH value is reached 7.5 ± 0.5, is removed through standing or centrifuging
Supernatant is gone to obtain Kocide SD suspension colloid (4)；Dry through natural air drying or in baking oven of the temperature less than 45 DEG C and obtain hydrogen
Cupric oxide hydrocolloid powder；In 75 ± 5 DEG C of waters bath with thermostatic control, 140g glutamic acid and 35g calcium hydroxides are dissolved in 350mL water, adjusted
It is 7.5 ± 0.5 to save pH, it is fully dissolved, the reaction time is 60min-90min, through centrifuging, purifying, be dried to obtain glutamic acid
Chelate calcium powder product；Kocide SD hydrocolloid powder 300g is weighed, above-mentioned calcium-glutamate chelate (5) is added thereto；Add and divide
(Sulfonates and phosphates anionic surface are lived by powder D-425 (alkyl naphthalene sulfonic acid condensation polymer sodium salt) 15g, dispersant SPR
The mixture of property agent) 10g, wetting agent EFW (mixture of alkylnaphthalene sulfonate and anion wetting agent) 10g and deflocculant
DC7 (mixtures of Sulfonates and phosphate ester salt analog anion surfactants) 5g (6)；Mixture is dodged through flash dryer
Steam stirring 20min and obtain the copper-based nourishment protecting agent wettable powder product (7) (8) containing calcium-glutamate chelate.Wherein, hydroxide
Copper content accounts for product dry basis 60%.
In gained wettable powder：Containing Cu%=39.18%；Containing Ca%=3.78%；This wettable powder product is adding
Spraying concentration is 1 after water:Suspension pH during 500-1000 is 7.0-8.0.
Embodiment 3：
Adition process such as embodiment 1, but it is otherwise varied on the additive of addition.Such as：Utilize aspartic acid and hydrogen-oxygen
Change calcium and prepare aspartic acid chelating calcium fluid product 350mL, other processes are with example 1.
In gained suspending agent：Contain Cu%=39.18% by product butt；Containing Ca%=3.78%；This suspending agent product exists
Spraying concentration is 1 after adding water:Suspension pH during 500-1000 is 7.0-8.0.
Embodiment 4：
Adition process such as embodiment 2, but it is otherwise varied on the additive of addition.Such as：Utilize aspartic acid and hydroxide
Calcium prepares aspartic acid chelating calcium 160g, and other processes are with example 2.
In gained wettable powder：Containing Cu%=39.18%；Containing Ca%=3.78%；This powder product sprays after adding the water
It is 1 to apply concentration:Suspension pH during 500-1000 is 7.0-8.0.
Embodiment 5：
Adition process such as embodiment 1, but it is otherwise varied on the additive of addition.Such as：Utilize compound amino acid and hydrogen
Calcium oxide prepares compound amino acid chelate calcium fluid product 350mL, and other processes are with example 1.
In gained suspending agent：Contain Cu%=39.18% by product butt；Containing Ca%=3.78%；This suspending agent product exists
Spraying concentration is 1 after adding water:Suspension pH during 500-1000 is 7.0-8.0.
Embodiment 6：
Adition process such as embodiment 2, but it is otherwise varied on the additive of addition.Such as：Utilize compound amino acid and hydrogen-oxygen
Change calcium and prepare compound amino acid chelate calcium 160g, other processes are with example 2.
In gained wettable powder：Containing Cu%=39.18%；Containing Ca%=3.78%；This powder product sprays after adding the water
It is 1 to apply concentration:Suspension pH during 500-1000 is 7.0-8.0.
Claims (1)
1. a kind of copper-based nourishment protecting agent containing amino acid chelated calcium, it is characterised in that in terms of the butt of its powder product：Contain
Percentage by weight 40-46% amino acid chelated calcium；Remaining component is Kocide SD colloid 46-52%, and auxiliary agent is dispersant D-
425 alkyl naphthalene sulfonic acid condensation polymer sodium salts 3%, dispersant SPR Sulfonateses and phosphate ester salt analog anion surfactants it is mixed
The mixture 2% of compound 2%, wetting agent EFW alkylnaphthalene sulfonates and anion wetting agent, deflocculant DC7 Sulfonateses and
The mixture 1% of phosphate ester salt analog anion surfactants；Each component weight is 100% than sum；
The preparation method of described amino acid chelated calcium is：It is in 75 ± 5 DEG C of water bath with thermostatic control that amino acid and calcium hydroxide is molten
Yu Shuizhong, regulation pH is 7.5 ± 0.5, it is fully dissolved, and reacts 60min-90min, and the amino acid and calcium hydroxide rub
You are than being 2:1；Described amino acid chelated calcium is compound amino acid chelate calcium, calcium-glutamate chelate or aspartic acid chelating calcium.
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| CN201410624544.5A CN104446752B (en) | 2014-11-07 | 2014-11-07 | A kind of copper-based nourishment protecting agent and its production method containing amino acid chelated calcium |
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| CN106117069A (en) * | 2016-06-17 | 2016-11-16 | 宜兴市前成生物有限公司 | A kind of method preparing L glutamate chelate potassium one water thing |
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| CN85108051A (en) * | 1985-10-30 | 1987-06-24 | 陶仲侃 | Synthetization technology of agriculture germicide " shuang xiao ling " |
| CN1056035C (en) * | 1993-04-07 | 2000-09-06 | 李善宽 | Agricultural multi-effect bactericide |
| CN1046185C (en) * | 1994-11-18 | 1999-11-10 | 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 |
| KR101120654B1 (en) * | 2009-06-15 | 2012-03-16 | 유섬근 | Method of preparing for concentrated bordeaux mixture |
| CN102515962B (en) * | 2011-12-26 | 2013-09-25 | 山东农业大学 | Copper-based nutritional multi-functional foliar fertilizer and preparation method thereof |
| CN102491851B (en) * | 2011-12-26 | 2013-10-16 | 山东农业大学 | Stable and available iron-containing copper-based nutritional foliar fertilizer and its preparation method |
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