CN105585342B - Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment - Google Patents
Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment Download PDFInfo
- Publication number
- CN105585342B CN105585342B CN201610184724.5A CN201610184724A CN105585342B CN 105585342 B CN105585342 B CN 105585342B CN 201610184724 A CN201610184724 A CN 201610184724A CN 105585342 B CN105585342 B CN 105585342B
- Authority
- CN
- China
- Prior art keywords
- microelement
- methylenephosphonic acid
- amino trimethylene
- fertilizer
- sulfate
- 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.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The present invention discloses a kind of amino trimethylene methylenephosphonic acid chelate and preparation method thereof containing microelement；Amino trimethylene methylenephosphonic acid chelated microelement fertilizer and preparation method thereof is also provided.The present invention uses amino trimethylene methylenephosphonic acid ATMP for organic nitrogen-phosphorous chelating agent, and chelated microelement, therefore tri- kinds of nutrients containing N, P, K on chelate molecular structure again, meets nutrition smog chelating agent requirement after being neutralized with aqueous slkali；The amino trimethylene methylenephosphonic acid chelate of the microelement of preparation can be used as a kind of excellent metal element chelate fertilizer raw material.Meanwhile amino trimethylene methylenephosphonic acid ATMP is shared with the lone pair electrons of phosphorus atoms and oxygen atom and microelement and is formed chelate, stability constant is adapted to the soil environment of meta-alkalescence 10 or more.The present invention produces amino trimethylene methylenephosphonic acid chelated microelement fertilizer assembly line can be achieved, it is ensured that different microelements are uniformly mixed, and significantly improve the absorption efficiency of fertilizer.
Description
The present invention relates to fertilizer field more particularly to a kind of amino trimethylene methylenephosphonic acids containing microelement for technical field
Chelate and preparation method thereof；The invention further relates to amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof
And Preparation equipment.
For background technique with the increase of farm output, applying quantity of chemical fertilizer is constantly soaring.And for a long time, China generally deposits
The phenomenon that attention a great number of elements despises microelement, cause Trace Elements in Soil content too low, it is raw not to be able to satisfy crop
Long needs also affect the absorption efficiency of macroelement fertilizer.In recent years, trace-element fertilizer is especially paid attention to how
Crop is promoted to have become the important topic of fertilizer industry to the absorption of microelement.Several main metal trace elements, as zinc,
Manganese, iron, copper etc., in soil of the pH value greater than 6, ionic state metal trace element easily forms the hydroxide precipitating for being insoluble in water
And can not be absorbed and used, and with chelating agent and metal ion-chelant, being formed to the stronger chelate of pH value adaptability is solution
The certainly effective way of this problem.
In order to obtain microelement chelate that is cheap and haveing excellent performance, some publications are using amino acid as main
Chelating agent, such as Patent No. CN95120857.8, patent name is " mixed amino-acid complex state multielement micro-fertilizer and its manufacturer
Method " patent of invention, disclose mixed amino-acid complex state multielement micro-fertilizer, by 17 kinds of amino acid, various trace elements, mixing
Rare earth element, potassium, boron, nitrogen, fulvic acid, micro iodine and surfactant composition.Its manufacturing method will contain kilnitamin
Industrial wastewater removal of impurities evaporation obtains amino acid concentrate, in nitric acid or hydrochloric acid medium, respectively with mischmetal salt and a variety of micro-
Secondary element salt carries out complex reaction, obtains corresponding amino acids metal nitrate (or chloride) complex, then with assisted solution
It is mixed to prepare micro- fertilizer.The chelating agent that the patent obtains is although at low cost, dissolubility is good, but the chelating agent of mixture composition is due to each
Optimal ph when chelatropic reaction occurs of kind of raw material, temperature and different from the molar ratio of microelement, are difficult to after mixed whole
Optimal technique process is obtained on body；And the chelating constant K formed is lower, is difficult to keep chelating shape in environment of the pH greater than 7
State.
Patent No. CN200410065458.1, patent name are " the compound middle trace element chelated fertilizer of one kind and its life
Production method " patent of invention in, a kind of compound middle trace element chelated fertilizer and its production method are disclosed, using containing amino acid
After industrial wastewater or waste eggshell white matter are hydrolyzed to amino acid, microelement inorganic salts are added and carry out chelatropic reaction, add humic
The sour free middle and trace element out of sodium chelating is formed with amino acid, the double chelant ties fertilizer of humic acid.Make there are also some patents
As chelating agent after using a variety of organic acids to mix, for example, Patent No. CN200710107078.3, patent name is a kind of " chela
Close zinc fertilizer and preparation method thereof " patent of invention, disclose a kind of fertilizer of chelated zinc, the fertilizer of chelated zinc is in 1~2% (quality hundred
Point content) catalyst action under, after chelatropic reaction occurs by 58~69% inorganic zinc raw material and 30~40% chelating agent
It is made；Wherein, the chelating agent includes the component of following mass ratios: oxalic acid, malic acid, citric acid, maleic acid, sorbose
Alcohol, gallic acid, lactic acid etc., stability is moderate, it is at low cost and can under solid state shape with zinc carry out chelatropic reaction.It is above-mentioned
In two existing patents, due to small molecular organic acids such as amino acid and malic acid, it is common that by nitrogen-atoms, the oxygen atom in molecule
Deng lone pair electrons and the unoccupied orbital of microelement form share electron pair and chelatropic reaction occur, the chelating constant K of formation compared with
It is low, sequestering properties are difficult to keep in environment of the pH value greater than 7.
In addition, number of patent application is 200610030505.8, patent name is " complete-element chelating highly effective trace fertilizer and its manufacturer
Method " patent of invention, disclose a series of complete-element chelating highly effective trace fertilizers and its system containing microelement needed for multiple kinds of crops
Make method.The invention uses tetra- acid solution of EDTA and copper, zinc, manganese, iron etc. to react the method for generating full element chelating fertilizer.EDTA system
Chelating agent has higher stability constant K, but itself does not have fertilizer efficiency, and is difficult to degrade, and easily causes Soil Environmental Pollution, in addition
It is expensive, therefore there are a degree of limitations in application.
Amino trimethylene methylenephosphonic acid (ATMP) is a kind of water-soluble phosphate, shown in molecular formula such as formula (II):
ATMP can form stable chelate, chemical stabilization with various metals ion chelatings such as copper, zinc, iron, manganese, calcium, magnesium
Property it is high, it is preferable to carbonate scale inhibition effect, be readily biodegradable.ATMP is currently used primarily in thermal power plant, oil plant follows
Ring cooling water, oil field reinjection water system can play the role of reducing metal equipment or corrosion of piping and fouling, and at present there is no works
The report applied for middle and trace element chelating agent in chemical fertilizer field.
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of stability constant height, nutrition for summary of the invention
Comprehensively, and be suitable for meta-alkalescence soil amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and preparation
Equipment, the present invention also provides a kind of amino trimethylene methylenephosphonic acid chelate and preparation method thereof containing microelement.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of amino trimethylene methylenephosphonic acid chelate containing microelement, shown in molecular formula such as formula (I):
Wherein, A is one of following metal ion: zinc, manganese, copper or iron.
The preparation method of the present invention also provides a kind of amino trimethylene methylenephosphonic acid chelate containing microelement comprising with
Lower step:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 50% being added in reaction flask, adds alkali to adjust molten
The pH value of liquid is 5-7；
Step 2: being warming up to 40 DEG C~50 DEG C, the sulfuric acid salt water containing microelement that concentration is 20%~50% is slowly added dropwise
Solution；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；It is micro- in the sulfate solution
Secondary element is one of the following: zinc, manganese, copper or iron；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min-100r/min obtains the ammonia containing microelement
Base Sanya methylenephosphonic acid chelate.
Since amino trimethylene methylenephosphonic acid has contained two kinds of nutrients of N and P, by carrying out neutralization reaction with lye,
It may be incorporated into other nutrients, such as neutralized by the way that potassium hydroxide solution is added, potassium nutrition element can be introduced.In this way
The amino trimethylene methylenephosphonic acid chelate containing microelement of preparation, due to tri- kinds of nutrients containing N, P, K on molecular structure, battalion
It supports comprehensive；And compared with amino acids chelating agent, the sequestering power of amino trimethylene methylenephosphonic acid is stronger, the chelating constant K of formation
Higher, Stability of Chelate is more preferable.
Further, the alkali being added in the step 1 is potassium hydroxide aqueous solution, provides K ion for chelating agent.
Further, the microelement in the sulfate solution is if manganese, then sulfate is manganese sulfate monohydrate, step
In 1 plus alkali adjusts the pH value 6-7 of solution；
For microelement in the sulfate solution if zinc, then sulfate is white vitriol, adds alkali tune in step 1
Save the pH value 6-7 of solution；
For microelement in the sulfate solution if iron, then sulfate is ferrous sulfate heptahydrate, adds alkali in step 1
Adjust the pH value 5.5-6 of solution；
For microelement in the sulfate solution if copper, then sulfate is cupric sulfate pentahydrate, adds alkali tune in step 1
Save the pH value 5-5.5 of solution.
The difference of the microelement as contained in sulfate after sulfate solution is reacted with alkali, controls the pH of solution
It is worth also different.For example, the microelement in sulfate solution if iron, then adjusts the pH value of solution after neutralization reaction
5.5-6, this is because the capacity of chelates ferric ions is maximum under this pH value condition；And the microelement in sulfate solution
If zinc, then the pH value 6-7 of solution is adjusted after neutralization reaction, this is because chelated zinc ions capacity is maximum under the conditions of this pH.
When microelement is manganese or copper, the control principle of pH value is same as described above.
Invention additionally discloses a kind of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising described contains micro member
The amino trimethylene methylenephosphonic acid chelate of element.
The invention also discloses a kind of preparation methods of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising with
Lower step:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 40%~50% being added in each reaction kettle, adds
The pH value that alkali adjusts solution is 5-7,
Step 2: being warming up to 40 DEG C~50 DEG C, it is 20%~50% that a kind of concentration is slowly added dropwise respectively into each reaction kettle
Sulfate solution containing microelement；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；Institute
Stating the microelement in sulfate solution is one of the following: zinc, manganese, copper or iron；The sulphur containing different microelements
Acid salt aqueous solution is reacted in different reaction kettles respectively；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min~100r/min is obtained various containing micro member
The amino trimethylene methylenephosphonic acid chelate of element；
Step 4: the amino trimethylene methylenephosphonic acid chelate respectively containing microelement being transported to buffering in proportion with metering pump
It is uniformly mixed, is then transported in compound fertilizer's reactor again, after mixing with other composite fertilizer materials in reactor in tank
It is granulated, obtains amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
In the above preparation method, pass through the operation of step 4, it is ensured that the amino trimethylene methene containing different microelements
Phosphonic acids chelate is uniformly mixed, it is also ensured that amino trimethylene methylenephosphonic acid chelate and other composite fertilizer materials containing microelement
It is uniformly mixed, the absorption efficiency of fertilizer is significantly improved, to guarantee fertilizer efficiency.
Further, the step 4 specifically includes:
Step 41: the various amino trimethylene methylenephosphonic acid chelates containing microelement being conveyed into buffering in proportion with metering pump
It is uniformly mixed in tank, is then transported at compound fertilizer's reactor inlet again,
Step 42: being sprayed the amino trimethylene methylenephosphonic acid chelate containing microelement being uniformly mixed by atomization distributor
Enter in compound fertilizer's reactor；
Step 43: in the uniformly mixed amino trimethylene methylenephosphonic acid chelate containing microelement and compound fertilizer's reactor
Other composite fertilizer materials are granulated after mixing, obtain amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
By step 41, can be mixed in surge tank the amino trimethylene methylenephosphonic acid chelate by various containing microelement in advance
It closes uniformly, amino trimethylene methylenephosphonic acid chelate is then sprayed by compound fertilizer's reactor by the atomization distributor in step 42
In, consequently facilitating being uniformly mixed with other composite fertilizer materials in compound fertilizer's reactor.
Further, other composite fertilizer materials in the step 4 are one of the following or two or more mixing: urine
Element, potassium sulfate or monoammonium phosphate.
The present invention also provides a kind of Preparation equipments of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising alkali soluble
Liquid storage tank, more than two chelating agent reaction kettles, more than two metering pumps, surge tank, flowmeter, atomization distributor and compound
Fertile reactor, the output end of the alkali soluble liquid storage tank are connect with the input terminal of each chelating agent reaction kettle respectively, and each chelating agent is anti-
Kettle is answered to be connected separately with corresponding metering pump, the output end of metering pump is connect with the input terminal of surge tank, the output of surge tank
End is connect by flowmeter with the input terminal for being atomized distributor, and the output end of distributor and the input terminal of compound fertilizer's reactor are atomized
Connection.
The present invention uses above-mentioned equipment, and the preparation of chelate and the production of compound fertilizer are combined, realize assembly line
Produce compound fertilizer, it is ensured that be uniformly mixed, can also protect between different microelements, between microelement and other composite fertilizer materials
The flexibility for demonstrate,proving trace element formula (prepares the amino three of a variety of microelements containing feature by multiple chelating agent reaction kettles simultaneously
Then sub- methylenephosphonic acid chelate can select the amino trimethylene methylenephosphonic acid chelating containing microelement in need according to demand
Object carries out preparing fertilizer), to adapt to the different demands of different regions Different Crop.
Further, the Preparation equipment of amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the invention further includes
The output end of elevator, surge tank is connected by the input terminal of flowmeter and elevator, and the output end of elevator and atomization are distributed
The input terminal of device connects.
The invention has the benefit that
1. being highly acid, after being neutralized with aqueous slkali since amino trimethylene methylenephosphonic acid ATMP is organic nitrogen-phosphorous chelating agent
Chelated microelement again, therefore tri- kinds of nutrients containing N, P, K on chelate molecular structure, meet nutrition smog chelating agent and want
It asks；It is former that the amino trimethylene methylenephosphonic acid chelate of the microelement of preparation can be used as a kind of excellent metal element chelate fertilizer
Material.
2. amino trimethylene methylenephosphonic acid ATMP is shared with the lone pair electrons of phosphorus atoms and oxygen atom and microelement and is formed chela
Object is closed, stability constant is adapted to the soil environment of meta-alkalescence 10 or more.
3, the achievable assembly line of the present invention amino trimethylene methylenephosphonic acid chelated microelement fertilizer is produced, it is ensured that no
It is uniformly mixed between microelement, between microelement and other composite fertilizer materials, the absorption efficiency of fertilizer is significantly improved, to protect
Demonstrate,prove fertilizer efficiency.
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments for Detailed description of the invention:
Fig. 1 is the Preparation equipment structural schematic diagram of amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the present invention.
The present invention will be further described in detail with reference to the specific embodiments for specific embodiment.
A kind of amino trimethylene methylenephosphonic acid chelate containing microelement, shown in molecular formula such as formula (I):
Wherein, A is one of following metal ion: zinc, manganese, copper or iron.
The present invention provides a kind of preparation method of amino trimethylene methylenephosphonic acid chelate containing microelement comprising following
Step:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 40%~50% being added in a kettle, adds alkali
The pH value for adjusting solution is 5-7；
Step 2: being warming up to 40 DEG C~50 DEG C, the sulfuric acid salt water containing microelement that concentration is 20%~50% is slowly added dropwise
Solution；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；It is micro- in the sulfate solution
Secondary element is one of the following: zinc, manganese, copper or iron；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min~100r/min is obtained containing microelement
Amino trimethylene methylenephosphonic acid chelate.
Embodiment 1
A kind of preparation method of the amino trimethylene methylenephosphonic acid chelate containing microelement comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution 120g that concentration is 42% being added in reaction flask, is added dense
Degree is 6-7 for the pH value of 50% potassium hydroxide aqueous solution 90g adjusting ATMP solution；
Step 2: 50 DEG C are warming up to, the manganese sulfate monohydrate aqueous solution containing manganese microelement that concentration is 50% is slowly added dropwise,
Solution reaction situation is observed, when solution becomes cloudy, and has white precipitate generation, stops that manganese sulfate monohydrate aqueous solution is added dropwise, adds
The manganese sulfate solution entered is 47g；
Step 3: the insulation reaction 1h under the mixing speed of 50r/min obtains the amino trimethylene methene containing manganese microelement
Phosphonic acids chelate, effectively chelating manganese content is 3.0%.
Embodiment 2
A kind of preparation method of the amino trimethylene methylenephosphonic acid chelate containing microelement comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution 175g that concentration is 43% being added in reaction flask, is added dense
Degree is 6-7 for the pH value of 50% potassium hydroxide aqueous solution 128g adjusting ATMP solution；
Step 2: 47 DEG C are warming up to, the white vitriol aqueous solution containing zinc microelement that concentration is 20% is slowly added dropwise,
Solution reaction situation is observed, when solution becomes cloudy, and has white precipitate generation, stops that white vitriol aqueous solution is added dropwise, adds
The zinc sulfate solution quality entered is 278.5g；
Step 3: the insulation reaction 0.5h under the mixing speed of 100r/min obtains the amino trimethylene first containing zinc microelement
Phosphonic acids chelate is pitched, effectively chelating Zn content is 3.2%.
Embodiment 3
A kind of preparation method of the amino trimethylene methylenephosphonic acid chelate containing microelement comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution 150g that concentration is 40% being added in reaction flask, is added dense
Degree is 5.5-6 for the pH value of 50% potassium hydroxide aqueous solution 98g adjusting ATMP solution；
Step 2: being warming up to 45 DEG C, it is water-soluble that the ferrous sulfate heptahydrate containing iron microelement that concentration is 40% is slowly added dropwise
Liquid observes solution reaction situation, when solution becomes cloudy, and has greenish precipitate generation, stops that ferrous sulfate heptahydrate water is added dropwise
Solution, addition ferrous sulfate aqueous solution quality are 126g；
Step 3: the insulation reaction 0.9h under the mixing speed of 60r/min obtains the amino trimethylene first containing iron microelement
Phosphonic acids chelate is pitched, effectively chelating iron content is 3.4%.
Embodiment 4
A kind of preparation method of the amino trimethylene methylenephosphonic acid chelate containing microelement comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution 96g that concentration is 50% being added in a kettle, is added dense
Degree is 5-5.5 for the pH value of 50% potassium hydroxide aqueous solution 116g adjusting ATMP solution；
Step 2: 40 DEG C are warming up to, the cupric sulfate pentahydrate aqueous solution containing cu microelements that concentration is 50% is slowly added dropwise,
Solution reaction situation is observed, when solution becomes cloudy, and has blue-green precipitating to generate, stops that cupric sulfate pentahydrate aqueous solution is added dropwise,
Addition cupric sulfate pentahydrate aqueous solution quality is 86g；
Step 3: the insulation reaction 0.8h under the mixing speed of 70r/min obtains the amino trimethylene first containing cu microelements
Phosphonic acids chelate is pitched, effectively chelating copper content is 3.4%.
Invention additionally discloses a kind of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising above-mentioned contains micro member
The amino trimethylene methylenephosphonic acid chelate of element.In amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the invention, it will contain micro-
The amino trimethylene methylenephosphonic acid chelate of secondary element carries out mixing granulation by various demands with other various composite fertilizer materials and obtains.
Other various composite fertilizer materials are added according to user demand, can be one of urea, potassium sulfate or monoammonium phosphate or two
Kind or more mixing, can also be other composite fertilizer materials, the ratio users of specific various raw materials can according to soil demand into
Row mixing.
The invention also discloses a kind of preparation methods of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising with
Lower step:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 40%~50% being added in each reaction kettle, adds
The pH value that alkali adjusts solution is 5-7,
Step 2: being warming up to 40 DEG C~50 DEG C, it is 20%~50% that a kind of concentration is slowly added dropwise respectively into each reaction kettle
Sulfate solution containing microelement；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；Institute
Stating the microelement in sulfate solution is one of the following: zinc, manganese, copper or iron；The sulphur containing different microelements
Acid salt aqueous solution is reacted in different reaction kettles respectively；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min~100r/min is obtained various containing micro member
The amino trimethylene methylenephosphonic acid chelate of element；
Step 4: the amino trimethylene methylenephosphonic acid chelate respectively containing microelement being transported to buffering in proportion with metering pump
It is uniformly mixed, is then transported in compound fertilizer's reactor again, after mixing with other composite fertilizer materials in reactor in tank
It is granulated, obtains amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
The step 4 specifically includes:
Step 41: the amino trimethylene methylenephosphonic acid chelate respectively containing microelement being conveyed into surge tank in proportion with metering pump
In be uniformly mixed, be then transported at compound fertilizer's reactor inlet again,
Step 42: being sprayed the amino trimethylene methylenephosphonic acid chelate containing microelement being uniformly mixed by atomization distributor
Enter in compound fertilizer's reactor；
Step 43: in the uniformly mixed amino trimethylene methylenephosphonic acid chelate containing microelement and compound fertilizer's reactor
Other composite fertilizer materials are granulated after mixing, obtain amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
Embodiment 5
A kind of preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising following steps:
Step 1 first presses embodiment 1, embodiment 2, preparation method described in embodiment 3, is amplified to three reaction kettles respectively
In produced, respectively obtain the amino trimethylene methylenephosphonic acid chelate containing manganese, zinc and iron microelement；It is controlled in flowmeter
Under traffic conditions, the amino trimethylene methylenephosphonic acid chelate containing manganese, zinc and iron microelement is pressed to the stream of 3:5:2 with metering pump
Amount ratio is respectively delivered in surge tank, is sufficiently mixed, is obtained the ATMP amino trimethylene methene phosphine containing manganese, zinc and iron microelement
Sour chelate；
Step 2: in the case where compound fertilizer's yield is the scale of 300t/d, manganese, zinc and iron will be contained with the rate metering pump of 38t/d
The amino trimethylene methylenephosphonic acid chelate of microelement is transported to the inlet of compound fertilizer's reactor from surge tank,
Step 3: the amino trimethylene methylenephosphonic acid containing manganese, zinc and iron microelement that will be uniformly mixed by atomization distributor
Chelate sprays into compound fertilizer's reactor；
Step 4: the amino trimethylene methylenephosphonic acid chelate containing manganese, zinc and iron microelement and mentioning in compound fertilizer's reactor
Other composite fertilizer materials (urea and potassium sulfate, monoammonium phosphate) of preceding addition are granulated after mixing；Obtain 15-15-15S
Amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc, iron fertilizer.Wherein, the amino trimethylene methylenephosphonic acid chelating is micro
Manganese, zinc, iron total content are 0.5% in element fertilizer；Manganese, zinc, iron content are respectively 0.15%, 0.25%, 0.1%, the proportion
Fertilizer is well suited to the application of the ground field crop such as Liaoning.
Embodiment 6
A kind of preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer comprising following steps:
Step 1 first presses embodiment 1, embodiment 2, preparation method as described in example 4, is amplified to three reaction kettles respectively
In produced, respectively obtain the amino trimethylene methylenephosphonic acid chelate containing manganese, zinc and cu microelements；It controls and flows in flowmeter
In the case of amount, the amino trimethylene methylenephosphonic acid chelate containing manganese, zinc and cu microelements is flowed by 13.5:8.7:1 with metering pump
Amount ratio is respectively delivered in surge tank, is sufficiently mixed, is obtained the ATMP amino trimethylene methylenephosphonic acid chela containing zinc and iron microelement
Close object；
Step 2: in the case where compound fertilizer's yield is the scale of 300t/d, manganese, zinc and copper will be contained with the rate metering pump of 38t/d
The amino trimethylene methylenephosphonic acid chelate of microelement is transported to the inlet of compound fertilizer's reactor from surge tank,
Step 3: the amino trimethylene methylenephosphonic acid containing manganese, zinc and cu microelements that will be uniformly mixed by atomization distributor
Chelate sprays into compound fertilizer's reactor；
Step 4: shifting to an earlier date in amino trimethylene methylenephosphonic acid chelate and compound fertilizer's reactor containing zinc and iron microelement
Other composite fertilizer materials (potassium sulfate and monoammonium phosphate) being added are granulated after mixing, obtain 15-5-25S amino trimethylene
The fertilizer of methylenephosphonic acid chelated microelement zinc, iron.Wherein, in the amino trimethylene methylenephosphonic acid chelated microelement fertilizer
Manganese, zinc, copper total content are 0.5%；Manganese, zinc, copper content are respectively 0.28%, 0.2%, 0.02%, and the fertilizer of the proportion is well suited to
The application of the ground field crop such as Zhejiang, Guangxi.
Embodiment 7
As shown in Figure 1, the present invention also provides a kind of Preparation equipment of amino trimethylene methylenephosphonic acid chelated microelement fertilizer,
It include alkali soluble liquid storage tank 1, more than two chelating agent reaction kettles 2, more than two metering pumps 3, surge tank 4, flowmeter 5,
Elevator 6, atomization distributor 7 and compound fertilizer's reactor 8, the output end of the alkali soluble liquid storage tank 1 are reacted with each chelating agent respectively
The input terminal of kettle 2 connects, and each chelating agent reaction kettle 2 is connected separately with corresponding metering pump 3, the output end of metering pump 3 with
The input terminal of surge tank 4 connects, and the output end of surge tank 4 is connect by flowmeter 5 with the input terminal of elevator 6, elevator 6
Output end is connect with the input terminal of atomization distributor 7, and the input terminal of the output end and compound fertilizer's reactor 8 that are atomized distributor 7 connects
It connects.
Carry out preparing fertilizer using above equipment the following steps are included:
1) amino trimethylene methylenephosphonic acid ATMP aqueous solution is first added in each chelating agent reaction kettle 2, is then stored up from aqueous slkali
Conveying aqueous slkali in tank 1 and adjusting the pH value of ATMP solution into each chelating agent reaction kettle 2 is 5-7；
It 2), will be containing various microelements after the amino trimethylene methylenephosphonic acid chelate containing various microelements is prepared
Amino trimethylene methylenephosphonic acid chelate is respectively delivered to be uniformly mixed in surge tank 4 in proportion；
3): with metering pump 3 that the mixed amino trimethylene methylenephosphonic acid chelate containing microelement is defeated from surge tank 4
Out, and successively the inlet of compound fertilizer's reactor 8 is transported to by flowmeter 5 and elevator 6,
4): the amino trimethylene methylenephosphonic acid chelate containing various microelements that will be uniformly mixed by atomization distributor 7
It sprays into compound fertilizer's reactor 8；
5): amino trimethylene methylenephosphonic acid chelate containing various microelements in compound fertilizer reactor 8 other are compound
Fertile raw material is granulated after mixing, obtains the fertilizer that amino trimethylene methylenephosphonic acid chelates various microelements.
Embodiment 8
The fertilizer of amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc and iron that embodiment 5 is prepared carries out fertilizer
Effect test, concrete condition are as follows:
Test site: a corn field in the disasters in Jianping County, Liaoning elm woods town sub- village of South Platform carries out, and topography is flat, irrigation side
Just, soil fertility is medium, and microelement more lacks.
Test the date: in April, 2015-September
For studying object: trial crops are red No. 402 beautiful.
Model field, control field area: each 3 mu；
Test process:
Processing 1: it is that (meaning of 15-15-15 is nitrogen, phosphorus, potash fertilizer content to common 15-15-15S that control field, which applies base manure,
Respectively 15%, S indicates that compound fertilizer is sulfur fertilizer) compound fertilizer, 50 kgs/acre；Big bell mouth stage imposes 10 kgs/acre of urea, altogether
60 kgs/acre of meter；
Processing 2: apply the fertilizer of amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc and iron made from example 5 to model field
Material 15-15-15S (meaning of 15-15-15 be nitrogen, phosphorus, potash fertilizer content are respectively that 15%, S indicates that compound fertilizer is sulfur fertilizer), 50 public affairs
Pound/acre, big bell mouth stage imposes 10 kgs/acre of urea, amounts to 60 kgs/acre；
Experimental result is as shown in table 1.
1 model field of table with compare field cost and the benefit table of comparisons
As shown in Table 1, as applying amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc and iron made from embodiment 5
Fertilizer, model field than control field per acre fecund 105.5 kilograms, rate of growth increases income 219 yuan of (corn prices up to 15.5% per acre
2.2 yuan/kilogram), there is good effect of increasing production.
Claims (7)
1. a kind of amino trimethylene methylenephosphonic acid chelate containing microelement, it is characterised in that: shown in its molecular formula such as formula (I):
Wherein, A is one of following metal ion: zinc, manganese, copper or iron.
2. a kind of preparation method of the amino trimethylene methylenephosphonic acid chelate containing microelement as described in claim 1, special
Sign is comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 40%~50% being added in reaction flask, alkali is added to adjust
The pH value of solution is 5-7；
Step 2: being warming up to 40 DEG C~50 DEG C, it is water-soluble that the sulfate containing microelement that concentration is 20%~50% is slowly added dropwise
Liquid；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；It is micro in the sulfate solution
Element is one of the following: zinc, manganese, copper or iron；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min~100r/min obtains the amino containing microelement
Sanya methylenephosphonic acid chelate；
The alkali being added in the step 1 is potassium hydroxide aqueous solution.
3. the preparation method of the amino trimethylene methylenephosphonic acid chelate according to claim 2 containing microelement, feature
Be: for the microelement in the sulfate solution if manganese, then sulfate is manganese sulfate monohydrate, adds alkali to adjust in step 1
The pH value 6-7 of solution；
For microelement in the sulfate solution if zinc, then sulfate is white vitriol, adds alkali to adjust in step 1 molten
The pH value 6-7 of liquid；
For microelement in the sulfate solution if iron, then sulfate is ferrous sulfate heptahydrate, adds alkali to adjust in step 1
The pH value 5.5-6 of solution；
For microelement in the sulfate solution if copper, then sulfate is cupric sulfate pentahydrate, adds alkali to adjust in step 1 molten
The pH value 5-5.5 of liquid.
4. a kind of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, it is characterised in that: it includes described in claim 1 contains
The amino trimethylene methylenephosphonic acid chelate of microelement.
5. a kind of preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer as claimed in claim 4, feature
It is comprising following steps:
Step 1: the amino trimethylene methylenephosphonic acid ATMP aqueous solution that concentration is 40%~50% being added in each reaction kettle, adds alkali tune
The pH value for saving solution is 5-7,
Step 2: being warming up to 40 DEG C~50 DEG C, it is 20%~50% containing micro- that a kind of concentration is slowly added dropwise respectively into each reaction kettle
The sulfate solution of secondary element；When solution becomes cloudy, and has precipitating to generate, stop that sulfate solution is added dropwise；The sulphur
Microelement in acid salt aqueous solution is one of the following: zinc, manganese, copper or iron；
Step 3: the insulation reaction 0.5-1h under the mixing speed of 50r/min~100r/min obtains the amino containing microelement
Sanya methylenephosphonic acid chelate；
Step 4: the various amino trimethylene methylenephosphonic acid chelates containing microelement being transported to surge tank in proportion with metering pump
In be uniformly mixed, be then transported in compound fertilizer's reactor, be uniformly mixed with other composite fertilizer materials in reactor laggard again
Row is granulated, and obtains amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
6. the method for amino trimethylene methylenephosphonic acid chelated microelement fertilizer according to claim 5, which is characterized in that institute
Step 4 is stated to specifically include:
Step 41: the amino trimethylene methylenephosphonic acid chelate containing microelement being conveyed in surge tank in proportion with metering pump and is mixed
Uniformly, it is then transported at compound fertilizer's reactor inlet again,
Step 42: being sprayed into the amino trimethylene methylenephosphonic acid chelate containing microelement being uniformly mixed again by atomization distributor
In the reactor of Hefei；
Step 43: other in the uniformly mixed amino trimethylene methylenephosphonic acid chelate containing microelement and compound fertilizer's reactor
Composite fertilizer material is granulated after mixing, obtains amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
7. the preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer according to claim 5 or 6, feature
Be, other composite fertilizer materials in the step 4 be one of the following or two or more mixing: urea, potassium sulfate or
Monoammonium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184724.5A CN105585342B (en) | 2016-03-29 | 2016-03-29 | Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184724.5A CN105585342B (en) | 2016-03-29 | 2016-03-29 | Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105585342A CN105585342A (en) | 2016-05-18 |
| CN105585342B true CN105585342B (en) | 2019-07-16 |
Family
ID=55925286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610184724.5A Active CN105585342B (en) | 2016-03-29 | 2016-03-29 | Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105585342B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266205A (en) * | 2017-07-28 | 2017-10-20 | 陕西彤山生物科技有限公司 | A kind of water soluble fertilizer that for drip irrigation system there is dredging pipeline anti-clogging to act on and its application method |
| CN116063121A (en) * | 2021-10-29 | 2023-05-05 | 沈阳化工研究院有限公司 | Environment-friendly chelated element compound fertilizer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5462671A (en) * | 1994-09-08 | 1995-10-31 | Hydrochem Industrial Services, Inc. | Method of removing heavy metals from solutions of amino-carboxylic acids for disposal purposes |
| CN1468831A (en) * | 2002-07-18 | 2004-01-21 | 邵建华 | Application of amino acid-trace element chelate in composite fertilizer |
| WO2014155388A1 (en) * | 2013-03-28 | 2014-10-02 | Subramanyam Sundaresan | A composition for fertigation |
| CN105294314A (en) * | 2015-12-01 | 2016-02-03 | 沈阳化工研究院有限公司 | Chelated fertilizer and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788181A (en) * | 2015-04-01 | 2015-07-22 | 中化化肥有限公司 | Production method of multielement microelement amino acid chelating fertilizer |
| CN204529697U (en) * | 2015-04-01 | 2015-08-05 | 福建中化智胜化肥有限公司 | A kind of production equipment of more trace elements chelating fertilizer |
-
2016
- 2016-03-29 CN CN201610184724.5A patent/CN105585342B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5462671A (en) * | 1994-09-08 | 1995-10-31 | Hydrochem Industrial Services, Inc. | Method of removing heavy metals from solutions of amino-carboxylic acids for disposal purposes |
| CN1468831A (en) * | 2002-07-18 | 2004-01-21 | 邵建华 | Application of amino acid-trace element chelate in composite fertilizer |
| WO2014155388A1 (en) * | 2013-03-28 | 2014-10-02 | Subramanyam Sundaresan | A composition for fertigation |
| CN105294314A (en) * | 2015-12-01 | 2016-02-03 | 沈阳化工研究院有限公司 | Chelated fertilizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105585342A (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101100404B (en) | Liquid type tea leaf surface composite fertilizer and preparation method thereof | |
| CN103708964B (en) | Instant chelated solid water-soluble fertilizer | |
| CN102557838A (en) | Multi-functional slow-release urea fertilizer and preparation method | |
| CN102584495B (en) | Slow-release urea containing gamma-polyglutamic acid and urease inhibitor and preparation method thereof | |
| CN100430342C (en) | Dedicated liquid composite fertilizer for vegetables drop irrigation and preparation method thereof | |
| CN104829342A (en) | Method for producing compound fertilizer from allantoin wastewater | |
| CN107226733A (en) | New multicomponent element ecology chelation fertilizer and its manufacture method | |
| CN105585342B (en) | Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment | |
| CN103360183B (en) | Synergistic urea containing multiple trace elements and preparation method of synergistic urea | |
| CN107814644A (en) | A kind of clear liquid type a great number of elements Water soluble fertilizer of low-temperature stabilization and preparation method thereof | |
| CN113248322B (en) | Preparation method of soluble medium-trace element fertilizer | |
| CN104803793B (en) | Biologically active polypeptide prepares hard water resistance Water soluble fertilizer containing humic acid and method and application | |
| CN109704818B (en) | DAP compound fertilizer and preparation method thereof | |
| CN104788181A (en) | Production method of multielement microelement amino acid chelating fertilizer | |
| CN1994980A (en) | Liquid foliage fertilizer and its producing method | |
| CN105367137B (en) | A kind of more trace elements chelating fertilizer and preparation method thereof | |
| CN111662098A (en) | Monoammonium phosphate suspension fertilizer containing medium trace elements and preparation method thereof | |
| CN116693342A (en) | Preparation method of stable synergistic liquid fertilizer containing polymerized phosphorus and fertilizer | |
| CN105294314B (en) | A kind of chelating fertilizer and preparation method thereof | |
| CN100361940C (en) | Spray-assistant drip irrigation bolt head cleaning-type concentrated fertilizer and preparation method thereof | |
| CN109438266B (en) | Environment-friendly iminodisuccinic acid chelated metal salt | |
| CN211896726U (en) | Device for producing nitro-sulfenyl water-soluble fertilizer | |
| CN109503238A (en) | A kind of preparation method of the liquid fertilizer of Water soluble fertilizer containing high-activity humic acid | |
| CN107827680A (en) | A kind of zinc-base activated water-soluble compound trace element fertilizer and preparation method thereof | |
| CN1785927A (en) | Composite intermediate and microelement chelated fertilizer and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221118 Address after: 100069 18th floor, building 17, yard 2, xitieying Middle Road, Fengtai District, Beijing Patentee after: SINOFERT HOLDING Ltd. Patentee after: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: No. 188, Banwei, Yong'an City, Sanming City, Fujian Province, 366000 Patentee before: FUJIAN SINOCHEM ZHISHENG FERTILIZER Co.,Ltd. Patentee before: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |