CN105585342A - Amino tri(methylene phosphonic acid) chelated trace-element fertilizer and preparation method and preparation equipment thereof - Google Patents
Amino tri(methylene phosphonic acid) chelated trace-element fertilizer and preparation method and preparation equipment thereof Download PDFInfo
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- C05—FERTILISERS; MANUFACTURE THEREOF
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Abstract
The invention discloses an amino tri(methylene phosphonic acid) chelate containing trace elements and a preparation method of the amino tri(methylene phosphonic acid) chelate, and further provides an amino tri(methylene phosphonic acid) chelated trace-element fertilizer and a preparation method thereof. Amino tri(methylene phosphonic acid) (ATMP) is adopted as an organic nitrogen-phosphorus chelating agent, the trace elements are chelated after amino tri(methylene phosphonic acid) is neutralized with an alkaline solution, therefore, the molecular structure of the chelate contains three nutrient elements of N, P and K, and the chelate meets the requirements of a nutrition-comprehensive type chelating agent; the prepared amino tri(methylene phosphonic acid) chelate containing the trace elements can serve as a good metallic element chelate fertilizer raw material. Meanwhile, amino tri(methylene phosphonic acid) (ATMP) share lone pair electrons of phosphorus atoms and oxygen atoms with the trace elements to form the chelate, the stability constant of the chelate is 10 or above, and the chelate can adapt to a slight alkaline soil environment. Accordingly, flow line production of the amino tri(methylene phosphonic acid) chelated trace-element fertilizer can be achieved, it can be guaranteed that the different trace elements are mixed uniformly, and the absorption efficiency of the fertilizer is significantly improved.
Description
Technical field the present invention relates to fertilizer field, relates in particular to a kind of containing micro-amino trimethylene methene phosphineAcid chelate and preparation method thereof; The invention still further relates to amino trimethylene methylenephosphonic acid chelated microelement fertilizer andIts preparation method and Preparation equipment.
Background technology is along with the increase of farm output, and applying quantity of chemical fertilizer is constantly soaring. And for a long time, China is generalDespise micro-phenomenon all over existing attention a great number of elements, cause Trace Elements in Soil content too low, noCan meet the needs of plant growth, also affect the absorption efficiency of macroelement fertilizer. In recent years, trace elementFertilizer is especially paid attention to, and how to promote crop micro-absorption to be become to the important class of fertilizer industryTopic. Several main metal trace elements, as zinc, manganese, iron, copper etc., in pH value is greater than 6 soil,Ionic state metal trace element easily formation is insoluble in the precipitation of hydroxide of water and cannot be absorbed and used, and uses chelaMixture and metal ion-chelant, forming is having of addressing this problem to the stronger chelate of pH value adaptive capacityEffect approach.
In order to obtain the microelement chelate of cheapness and excellent performance, some publications adopt amino acid conductMain chelating agent, if the patent No. is CN95120857.8, patent name is that " mixed amino-acid complex state is manyUnit micro-fertilizer and manufacture method thereof " patent of invention, mixed amino-acid complex state multielement micro-fertilizer is disclosed, its by17 seed amino acids, various trace elements, mixed rare-earth elements, potassium, boron, nitrogen, fulvic acid, micro iodine andSurfactant composition. Its manufacture method is to obtain amino acid containing mixing amino acid whose industrial wastewater removal of impurities evaporationConcentrate, in nitric acid or hydrochloric acid medium, coordinates instead with mishmetal salt and various trace elements salt respectivelyShould, obtain corresponding amino acids metal nitrate (or chloride) complex, then mix with assisted solution make micro-Fertile. Although the chelating agent cost that this patent obtains is low, dissolubility good, the chelating agent of mixture composition is due to respectivelyOptimum pH value in the time there is chelatropic reaction of kind of raw material, temperature be with different from micro-mol ratio, mixtureAfter be difficult to obtain on the whole optimum process condition; And the chelating constant K forming is lower, is greater than 7 at PHEnvironment in be difficult to keep chelating state.
The patent No. is CN200410065458.1, and patent name is " a kind of compound middle trace element chelated fertilizerAnd production method " patent of invention in, a kind of compound middle trace element chelated fertilizer and producer thereof are disclosedMethod, after adopting and being amino acid containing amino acid industrial wastewater or discarded proteolysis, adds micro-inorganic saltsCarry out chelatropic reaction, then add sodium humate chelating to dissociate in, trace element, form with amino acid, corruptionGrow the two chelating agent chelating fertilizers of acid. After also having some patents to use multiple organic acid to mix as chelating agent, for example,The patent No. is CN200710107078.3, and patent name is sending out of " a kind of fertilizer of chelated zinc and preparation method thereof "Bright patent, discloses a kind of fertilizer of chelated zinc, and described fertilizer of chelated zinc is the catalyst at 1～2% (quality percentage composition)Under effect, after the inorganic zinc raw material by 58～69% and 30～40% chelating agent generation chelatropic reaction, make;Wherein, described chelating agent comprises the component of following mass ratio: oxalic acid, malic acid, citric acid, maleic acid,D-sorbite, gallic acid, lactic acid etc., its stability is moderate, and cost is low and can be under solid state shape and zincCarry out chelatropic reaction. In above-mentioned two existing patents, due to the small molecular organic acid such as amino acid and malic acid, generalAll over being to form shared electron by the lone pair electrons of nitrogen-atoms, oxygen atom etc. in molecule and micro-unoccupied orbitalTo and there is chelatropic reaction, the chelating constant K of formation is lower, is difficult to keep in pH value is greater than 7 environmentChelating state.
In addition, number of patent application is 200610030505.8, patent name be " complete-element chelating highly effective trace fertilizer andManufacture method " patent of invention, a series of complete-element chelatings that contain the required trace element of multiple kinds of crops are disclosedHighly effective trace fertilizer and manufacture method thereof. This invention adopts EDTA tetracid solution to react raw with copper, zinc, manganese, iron etc.Help the method for element chelating fertilizer. EDTA is that chelating agent has higher stability constant K, but itself does not possessFertilizer efficiency, hard degradation again, easily causes Soil Environmental Pollution, in addition expensive, therefore in application, has oneDetermine the limitation of degree.
Amino trimethylene methylenephosphonic acid (ATMP) is a kind of water-soluble phosphate, and molecular formula is suc as formula shown in (II):
ATMP can form stable chelate with many kinds of metal ions chelatings such as copper, zinc, iron, manganese, calcium, magnesium,Chemical stability is high, better to carbonate scale inhibition effect, is easy to biodegradation. ATMP is mainly used in fire at presentThe recirculated cooling water of power power plant, oil plant, oil field reinjection water system, can play and reduce hardware or pipeThe effect of road corrosion and fouling, at present temporarily without as in, the trace element chelated dose of report of applying in chemical fertilizer field.
Summary of the invention is in order to overcome the deficiencies in the prior art, the object of this invention is to provide a kind of stability constant high,Comprehensive nutrition, and can adapt to meta-alkalescence soil amino trimethylene methylenephosphonic acid chelated microelement fertilizer and systemPreparation Method and Preparation equipment, the present invention also provide a kind of containing micro-amino trimethylene methylenephosphonic acid chelate andIts preparation method.
To achieve these goals, technical scheme of the present invention is:
Containing a micro-amino trimethylene methylenephosphonic acid chelate, its molecular formula is suc as formula shown in (I):
Wherein, A is the one in following metal ion: zinc, manganese, copper or iron.
The present invention also provides a kind of preparation method containing micro-amino trimethylene methylenephosphonic acid chelate, its bagDraw together following steps:
Step 1: adding concentration in reaction bulb is 50% the amino trimethylene methylenephosphonic acid ATMP aqueous solution, addsThe pH value of alkali regulator solution is 5-7;
Step 2: be warming up to 40 DEG C～50 DEG C, slowly drip concentration and be 20%～50% containing micro-sulfuric acidSaline solution; When solution becomes muddy, and while having precipitation to generate, stop dripping sulfate solution; Described sulfuric acidTrace element in saline solution is the one in following: zinc, manganese, copper or iron;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min-100r/min, obtains containing trace unitThe amino trimethylene methylenephosphonic acid chelate of element.
Because amino trimethylene methylenephosphonic acid has contained N and two kinds of nutrients of P, in carrying out with alkali lyeAnd reaction, can also introduce other nutrients, for example, by adding potassium hydroxide solution to neutralize, can drawEnter potassium nutrition element. Like this preparation containing micro-amino trimethylene methylenephosphonic acid chelate, due to molecule knotOn structure, contain N, P, tri-kinds of nutrients of K, comprehensive nutrition; And compare amino three with amino acids chelating agentThe sequestering power of sub-methylenephosphonic acid is stronger, and the chelating constant K of formation is higher, and Stability of Chelate is better.
Further, the alkali adding in described step 1 is potassium hydroxide aqueous solution, for chelating agent provides K ion.
Further, if the trace element manganese in described sulfate solution, sulfate is manganese sulfate monohydrate,In step 1, add the pH value 6-7 of alkali regulator solution;
If the trace element zinc in described sulfate solution, sulfate is white vitriol, step 1In add the pH value 6-7 of alkali regulator solution;
If the trace element iron in described sulfate solution, sulfate is ferrous sulfate heptahydrate, step 1In add the pH value 5.5-6 of alkali regulator solution;
If the trace element copper in described sulfate solution, sulfate is cupric sulfate pentahydrate, step 1In add the pH value 5-5.5 of alkali regulator solution.
Due to micro-difference contained in sulfate, after sulfate solution and alkali reaction, control solutionPH value also different. For example, if the trace element iron in sulfate solution, after neutralization reactionThe pH value 5.5-6 of regulator solution, this is because under this pH value condition, the capacity maximum of chelated iron ion;And if trace element zinc in sulfate solution, the pH value 6-7 of regulator solution after neutralization reaction, thisBecause under this PH condition, chelated zinc ion capacity maximum. When trace element is manganese or copper, its pH valueControl principle same as described above.
The present invention also discloses a kind of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and it comprises described containing micro-The amino trimethylene methylenephosphonic acid chelate of secondary element.
The invention also discloses a kind of preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, its bagDraw together following steps:
Step 1: adding concentration in each reactor is 40%～50% amino trimethylene methylenephosphonic acid ATMP waterSolution, the pH value that adds alkali regulator solution is 5-7,
Step 2: be warming up to 40 DEG C～50 DEG C, toward slowly dripping respectively a kind of concentration in each reactor be20%～50% containing micro-sulfate solution; When solution becomes muddy, and while having precipitation to generate, stopOnly drip sulfate solution; Trace element in described sulfate solution is the one in following: zinc, manganese,Copper or iron; The described sulfate solution containing different trace elements, reacts at different reactors respectively;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min～100r/min, obtains various containing micro-The amino trimethylene methylenephosphonic acid chelate of secondary element;
Step 4: will respectively contain micro-amino trimethylene methylenephosphonic acid chelate with measuring pump and be transported in proportionIn surge tank, mix, and then be transported in composite fertilizer's reactor, former with other composite fertilizers in reactorAfter material mixes, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
In above-mentioned preparation method, by the operation of step 4, can ensure the amino three containing different trace elementsSub-methylenephosphonic acid chelate mixes, also can ensure containing micro-amino trimethylene methylenephosphonic acid chelate withOther composite fertilizer materials mix, and significantly improve the absorption efficiency of fertilizer, thereby ensure fertilizer efficiency.
Further, described step 4 specifically comprises:
Step 41: with measuring pump by various defeated in proportion containing micro-amino trimethylene methylenephosphonic acid chelateSend in surge tank and mix, and then be transported to reactor inlet place of composite fertilizer,
Step 42: by atomization distributor by mix containing micro-amino trimethylene methylenephosphonic acid chelaCompound sprays in composite fertilizer's reactor;
Step 43: what mix reacts with composite fertilizer containing micro-amino trimethylene methylenephosphonic acid chelateAfter other composite fertilizer materials in device mix, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelating trace unitFertilizer.
By step 41, can cushion containing micro-amino trimethylene methylenephosphonic acid chelate various in advanceIn tank, mix, then by the atomization distributor in step 42, amino trimethylene methylenephosphonic acid chelate is sprayedEnter in composite fertilizer's reactor, thereby be convenient to mix with other composite fertilizer materials in composite fertilizer reactor.
Further, other composite fertilizer materials in described step 4 are one or more mixed in followingClose: urea, potassium sulfate or MAP.
The present invention also provides a kind of Preparation equipment of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and it comprisesAqueous slkali storage tank, plural chelating agent reactor, plural measuring pump, surge tank, flowmeter,Atomization distributor and composite fertilizer's reactor, the output of described aqueous slkali storage tank is respectively with each chelating agent reactorInput connect, each chelating agent reactor is connected with respectively corresponding measuring pump, metering delivery side of pump all withThe input of surge tank connects, and the output of surge tank is connected with the input of atomization distributor by flowmeter,The output of atomization distributor is connected with the input of composite fertilizer's reactor.
The present invention adopts above-mentioned equipment, and the production of the preparation of chelate and composite fertilizer is combined, and realizes streamWaterline production composite fertilizer, can ensure between different trace elements, mix between trace element and other composite fertilizer materialsThe flexibility that evenly, can also ensure trace element formula (is prepared multiple by multiple chelating agent reactors simultaneouslyContaining the amino trimethylene methylenephosphonic acid chelate of feature trace element, then can be according to demand, select to contain needsThe amino trimethylene methylenephosphonic acid chelate of trace element is prepared fertilizer), thus adapt to the different works in different regionsThe different demands of thing.
Further, the Preparation equipment of amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the present invention, it is alsoComprise elevator, the output of surge tank is connected with the input of elevator by flowmeter, the output of elevatorEnd is connected with the input of atomization distributor.
Beneficial effect of the present invention is:
1. because amino trimethylene methylenephosphonic acid ATMP is organic nitrogen-phosphorus type chelating agent, be highly acid, molten with alkaliIn liquid and after chelated microelement again, therefore on chelate molecular structure containing N, P, tri-kinds of nutrients of K,Meet the requirement of comprehensive nutrition type chelating agent; The micro-amino trimethylene methylenephosphonic acid chelate of preparation can be doneFor a kind of good metal element chelate fertilizer raw material.
2. amino trimethylene methylenephosphonic acid ATMP shares with trace element with the lone pair electrons of phosphorus atoms and oxygen atomForm chelate, its stability constant, more than 10, can adapt to the soil environment of meta-alkalescence.
3, the present invention can realize streamline and produce amino trimethylene methylenephosphonic acid chelated microelement fertilizer, canEnsure between different trace elements, mix between trace element and other composite fertilizer materials, significantly improve fertilizerAbsorption efficiency, thus fertilizer efficiency ensured.
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments for brief description of the drawings:
Fig. 1 is the Preparation equipment structural representation of amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the present invention.
The present invention is further detailed explanation below in conjunction with detailed description of the invention for detailed description of the invention.
Containing a micro-amino trimethylene methylenephosphonic acid chelate, its molecular formula is suc as formula shown in (I):
Wherein, A is the one in following metal ion: zinc, manganese, copper or iron.
The invention provides a kind of preparation method containing micro-amino trimethylene methylenephosphonic acid chelate, it comprisesFollowing steps:
Step 1: adding concentration in reactor is that 40%～50% amino trimethylene methylenephosphonic acid ATMP is water-solubleLiquid, the pH value that adds alkali regulator solution is 5-7;
Step 2: be warming up to 40 DEG C～50 DEG C, slowly drip concentration and be 20%～50% containing micro-sulfuric acidSaline solution; When solution becomes muddy, and while having precipitation to generate, stop dripping sulfate solution; Described sulfuric acidTrace element in saline solution is the one in following: zinc, manganese, copper or iron;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min～100r/min, obtains containing trace unitThe amino trimethylene methylenephosphonic acid chelate of element.
Embodiment 1
Containing a preparation method for micro-amino trimethylene methylenephosphonic acid chelate, it comprises the following steps:
Step 1: adding concentration in reaction bulb is 42% the amino trimethylene methylenephosphonic acid ATMP aqueous solution120g, adding concentration is that to regulate the pH value of ATMP solution be 6-7 for 50% potassium hydroxide aqueous solution 90g;
Step 2: be warming up to 50 DEG C, slowly drip concentration and be 50% the manganese sulfate monohydrate water containing manganese microelementSolution, observes solution reaction situation, and when solution becomes muddy, and adularescent precipitation is while generating, stops dripping a waterManganese sulfate solution, the manganese sulfate solution adding is 47g;
Step 3: insulation reaction 1h under the mixing speed of 50r/min, obtains the amino three containing manganese microelementSub-methylenephosphonic acid chelate, effectively Chelated Manganese content is 3.0%.
Embodiment 2
Containing a preparation method for micro-amino trimethylene methylenephosphonic acid chelate, it comprises the following steps:
Step 1: adding concentration in reaction bulb is 43% the amino trimethylene methylenephosphonic acid ATMP aqueous solution175g, adding concentration is that to regulate the pH value of ATMP solution be 6-7 for 50% potassium hydroxide aqueous solution 128g;
Step 2: be warming up to 47 DEG C, slowly drip concentration and be 20% the white vitriol water containing zinc microelementSolution, observes solution reaction situation, and when solution becomes muddy, and adularescent precipitation is while generating, stops dripping seven waterZinc sulfate solution, the zinc sulfate solution quality adding is 278.5g;
Step 3: insulation reaction 0.5h under the mixing speed of 100r/min, obtains the ammonia containing zinc microelementBase Sanya methylenephosphonic acid chelate, effectively chelated zinc content is 3.2%.
Embodiment 3
Containing a preparation method for micro-amino trimethylene methylenephosphonic acid chelate, it comprises the following steps:
Step 1: adding concentration in reaction bulb is 40% the amino trimethylene methylenephosphonic acid ATMP aqueous solution150g, adding concentration is that to regulate the pH value of ATMP solution be 5.5-6 for 50% potassium hydroxide aqueous solution 98g;
Step 2: be warming up to 45 DEG C, slowly drip concentration and be 40% the ferrous sulfate heptahydrate containing iron microelementThe aqueous solution, observes solution reaction situation, when solution becomes muddy, and has light green color to precipitate while generation, stops drippingThe ferrous sulfate heptahydrate aqueous solution, adding ferrous sulfate aqueous solution quality is 126g;
Step 3: insulation reaction 0.9h under the mixing speed of 60r/min, obtains the amino containing iron microelementSanya methylenephosphonic acid chelate, effectively chelated iron content is 3.4%.
Embodiment 4
Containing a preparation method for micro-amino trimethylene methylenephosphonic acid chelate, it comprises the following steps:
Step 1: adding concentration in reactor is 50% amino trimethylene methylenephosphonic acid ATMP aqueous solution 96g,Adding concentration is that to regulate the pH value of ATMP solution be 5-5.5 for 50% potassium hydroxide aqueous solution 116g;
Step 2: be warming up to 40 DEG C, slowly drip concentration and be 50% the cupric sulfate pentahydrate water containing cu microelementsSolution, observes solution reaction situation, when solution becomes muddy, and has blue-green to precipitate while generation, stops dripping fiveThe brochanite aqueous solution, adding cupric sulfate pentahydrate aqueous solution quality is 86g;
Step 3: insulation reaction 0.8h under the mixing speed of 70r/min, obtains the amino containing cu microelementsSanya methylenephosphonic acid chelate, effectively chelated copper content is 3.4%.
The present invention also discloses a kind of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and it comprises above-mentioned containing micro-The amino trimethylene methylenephosphonic acid chelate of secondary element. Amino trimethylene methylenephosphonic acid chelated microelement fertilizer of the present inventionIn material, the amino trimethylene methylenephosphonic acid chelate containing micro-and other various composite fertilizer materials are pressed to various needAsk and carry out mixing granulation and obtain. Other various composite fertilizer materials add according to user's request, can be urea,The mixing of one or more in potassium sulfate or MAP, can also be other composite fertilizer materials, concreteThe ratio user of various raw materials can mix according to soil demand.
The invention also discloses a kind of preparation method of amino trimethylene methylenephosphonic acid chelated microelement fertilizer, its bagDraw together following steps:
Step 1: adding concentration in each reactor is 40%～50% amino trimethylene methylenephosphonic acid ATMP waterSolution, the pH value that adds alkali regulator solution is 5-7,
Step 2: be warming up to 40 DEG C～50 DEG C, toward slowly dripping respectively a kind of concentration in each reactor be20%～50% containing micro-sulfate solution; When solution becomes muddy, and while having precipitation to generate, stopOnly drip sulfate solution; Trace element in described sulfate solution is the one in following: zinc, manganese,Copper or iron; The described sulfate solution containing different trace elements, reacts at different reactors respectively;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min～100r/min, obtains various containing micro-The amino trimethylene methylenephosphonic acid chelate of secondary element;
Step 4: will respectively contain micro-amino trimethylene methylenephosphonic acid chelate with measuring pump and be transported in proportionIn surge tank, mix, and then be transported in composite fertilizer's reactor, former with other composite fertilizers in reactorAfter material mixes, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
Described step 4 specifically comprises:
Step 41: will respectively contain micro-amino trimethylene methylenephosphonic acid chelate with measuring pump and carry in proportionIn surge tank, mix, and then be transported to reactor inlet place of composite fertilizer,
Step 42: by atomization distributor by mix containing micro-amino trimethylene methylenephosphonic acid chelaCompound sprays in composite fertilizer's reactor;
Step 43: what mix reacts with composite fertilizer containing micro-amino trimethylene methylenephosphonic acid chelateAfter other composite fertilizer materials in device mix, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelating trace unitFertilizer.
Embodiment 5
A preparation method for amino trimethylene methylenephosphonic acid chelated microelement fertilizer, it comprises the following steps:
Step 1, first press the preparation method described in embodiment 1, embodiment 2, embodiment 3, be amplified to respectivelyIn three reactors, produce, obtain respectively the amino trimethylene methylenephosphonic acid containing manganese, zinc and iron microelementChelate; In flowmeter control flow situation, with measuring pump will be containing the amino of manganese, zinc and iron microelementSanya methylenephosphonic acid chelate is transported to respectively in surge tank by the flow-rate ratio of 3:5:2, fully mixes, and obtainsContaining the ATMP amino trimethylene methylenephosphonic acid chelate of manganese, zinc and iron microelement;
Step 2: under the scale that is 300t/d in composite fertilizer's output, with the speed of 38t/d with measuring pump will containing manganese,The amino trimethylene methylenephosphonic acid chelate of zinc and iron microelement is transported to composite fertilizer's reactor from surge tankPorch,
Step 3: by atomization distributor by mix containing the amino trimethylene first of manganese, zinc and iron microelementFork phosphonic acids chelate sprays in composite fertilizer's reactor;
Step 4: containing amino trimethylene methylenephosphonic acid chelate and composite fertilizer's reactor of manganese, zinc and iron microelementIn other composite fertilizer materials that add in advance (urea and potassium sulfate, MAP) make after mixingGrain; Obtain the fertilizer of 15-15-15S amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc, iron. Wherein,In described amino trimethylene methylenephosphonic acid chelated microelement fertilizer, manganese, zinc, iron total content are 0.5%; Manganese, zinc,Iron content is respectively 0.15%, 0.25%, 0.1%, and the fertilizer of this proportioning is suitable for the ground field crops such as Liaoning and uses.
Embodiment 6
A preparation method for amino trimethylene methylenephosphonic acid chelated microelement fertilizer, it comprises the following steps:
Step 1, first press the preparation method described in embodiment 1, embodiment 2, embodiment 4, be amplified to respectivelyIn three reactors, produce, obtain respectively the amino trimethylene methylenephosphonic acid chela containing manganese, zinc and cu microelementsCompound; In flowmeter control flow situation, with measuring pump will be containing the amino trimethylene of manganese, zinc and cu microelementsMethylenephosphonic acid chelate is transported to respectively in surge tank by 13.5:8.7:1 flow-rate ratio, fully mixes, and is containedThe ATMP amino trimethylene methylenephosphonic acid chelate of zinc and iron microelement;
Step 2: under the scale that is 300t/d in composite fertilizer's output, with the speed of 38t/d with measuring pump will containing manganese,The amino trimethylene methylenephosphonic acid chelate of zinc and cu microelements is transported to composite fertilizer's reactor from surge tankPorch,
Step 3: by atomization distributor by mix containing the amino trimethylene first of manganese, zinc and cu microelementsFork phosphonic acids chelate sprays in composite fertilizer's reactor;
Step 4: containing in the amino trimethylene methylenephosphonic acid chelate of zinc and iron microelement and composite fertilizer's reactorAfter other composite fertilizer materials (potassium sulfate and MAP) that add in advance mix, carry out granulation, obtainThe fertilizer of 15-5-25S amino trimethylene methylenephosphonic acid chelated microelement zinc, iron. Wherein, described amino trimethylene firstIn fork phosphonic acids chelated microelement fertilizer, manganese, zinc, copper total content are 0.5%; Manganese, zinc, copper content is respectively 0.28%,0.2%, 0.02%, the fertilizer of this proportioning is suitable for the ground such as Zhejiang, Guangxi field crop and uses.
Embodiment 7
As shown in Figure 1, the present invention also provides a kind of preparation of amino trimethylene methylenephosphonic acid chelated microelement fertilizerEquipment, it comprise aqueous slkali storage tank 1, plural chelating agent reactor 2, plural measuring pump 3,Surge tank 4, flowmeter 5, elevator 6, atomization distributor 7 and composite fertilizer's reactor 8, described aqueous slkali storageThe output of tank 1 is connected with the input of each chelating agent reactor 2 respectively, and each chelating agent reactor 2 respectivelyBe connected with corresponding measuring pump 3, the output of measuring pump 3 is all connected with the input of surge tank 4, surge tank4 output is connected with the input of elevator 6 by flowmeter 5, and output and the atomization of elevator 6 divideThe input of cloth device 7 connects, and the output of atomization distributor 7 is connected with the input of composite fertilizer reactor 8.
Adopting the said equipment to be prepared fertilizer comprises the following steps:
1) first in each chelating agent reactor 2, add the amino trimethylene methylenephosphonic acid ATMP aqueous solution, then fromIn aqueous slkali storage tank 1, carry aqueous slkali to regulate the pH value of ATMP solution to be in each chelating agent reactor 25-7；
2) prepare containing after the amino trimethylene methylenephosphonic acid chelate of various trace elements, will be containing various traceThe amino trimethylene methylenephosphonic acid chelate of element is transported to respectively in surge tank 4 and mixes in proportion;
3): use measuring pump 3 to contain micro-amino trimethylene methylenephosphonic acid chelate from surge tank by mixedOutput in 4, and be transported to successively the porch of composite fertilizer's reactor 8 through flowmeter 5 and elevator 6,
4): by atomization distributor 7 by mix containing the amino trimethylene methylenephosphonic acid chela of various trace elementsCompound sprays in composite fertilizer's reactor 8;
5): containing other in amino trimethylene methylenephosphonic acid chelate and composite fertilizer's reactor 8 of various trace elementsAfter composite fertilizer material mixes, carry out granulation, obtain the fertilizer of the various trace elements of amino trimethylene methylenephosphonic acid chelatingMaterial.
Embodiment 8
The fertilizer of amino trimethylene methylenephosphonic acid chelated microelement manganese, zinc and the iron that embodiment 5 is prepared entersRow manure trial, concrete condition is as follows:
Test site a: corn field in the sub-village of South Platform, elm woods town, disasters in Jianping County, Liaoning carries out, and physical features is smooth,It is convenient to irrigate, and soil fertility is medium, and trace element comparatively lacks.
The experiment date: in April, 2015-September
For studying thing: trial crops is red beautiful No. 402.
Model field, contrast field area: each 3 mu;
Test is processed:
Process 1: contrast field apply base manure be common 15-15-15S (implication of 15-15-15 be nitrogen, phosphorus,Potash fertilizer content is respectively 15%, S and represents that composite fertilizer is sulfur fertilizer) composite fertilizer, 50 kgs/acre; The typhon mouth phaseImpose 10 kgs/acre, urea, amount to 60 kgs/acre;
Process 2: to model field apply amino trimethylene methylenephosphonic acid chelated microelement manganese that example 5 makes, zinc and(implication of 15-15-15 is that nitrogen, phosphorus, potash fertilizer content are respectively 15%, S and represent for the fertilizer 15-15-15S of ironComposite fertilizer is sulfur fertilizer), 50 kgs/acre, the typhon mouth phase imposes 10 kgs/acre, urea, amounts to 60 kgs/acre;
Experimental result is as shown in table 1.
Table 1 model field with contrast field cost and the benefit table of comparisons
As shown in Table 1, by apply amino trimethylene methylenephosphonic acid chelated microelement manganese that embodiment 5 makes,The fertilizer of zinc and iron, model field is than 105.5 kilograms of every mu, field of contrast fecund, and rate of growth reaches 15.5%, every mu of increasingReceive 219 yuan (2.2 yuan/kilogram of corn prices), there is good effect of increasing production.
Claims (10)
1. containing a micro-amino trimethylene methylenephosphonic acid chelate, it is characterized in that: its molecular formula asShown in formula (I):
Wherein, A is the one in following metal ion: zinc, manganese, copper or iron.
2. the preparation containing micro-amino trimethylene methylenephosphonic acid chelate as claimed in claim 1Method, is characterized in that, it comprises the following steps:
Step 1: adding concentration in reaction bulb is 40%～50% the amino trimethylene methylenephosphonic acid ATMP aqueous solution,The pH value that adds alkali regulator solution is 5-7;
Step 2: be warming up to 40 DEG C～50 DEG C, slowly drip concentration and be 20%～50% containing micro-sulfuric acidSaline solution; When solution becomes muddy, and while having precipitation to generate, stop dripping sulfate solution; Described sulfuric acidTrace element in saline solution is the one in following: zinc, manganese, copper or iron;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min～100r/min, obtains containing traceThe amino trimethylene methylenephosphonic acid chelate of element.
3. the preparation side containing micro-amino trimethylene methylenephosphonic acid chelate according to claim 2Method, is characterized in that: the alkali adding in described step 1 is potassium hydroxide aqueous solution.
4. the preparation side containing micro-amino trimethylene methylenephosphonic acid chelate according to claim 2Method, is characterized in that: if the trace element manganese in described sulfate solution, sulfate is sulfuric acid monohydrateManganese, adds the pH value 6-7 of alkali regulator solution in step 1;
If the trace element zinc in described sulfate solution, sulfate is white vitriol, step 1In add the pH value 6-7 of alkali regulator solution;
If the trace element iron in described sulfate solution, sulfate is ferrous sulfate heptahydrate, step 1In add the pH value 5.5-6 of alkali regulator solution;
If the trace element copper in described sulfate solution, sulfate is cupric sulfate pentahydrate, step 1In add the pH value 5-5.5 of alkali regulator solution.
5. an amino trimethylene methylenephosphonic acid chelated microelement fertilizer, is characterized in that: it comprises that right willAsk the micro-amino trimethylene methylenephosphonic acid chelate that contains described in 1.
6. the preparation side of an amino trimethylene methylenephosphonic acid chelated microelement fertilizer as claimed in claim 5Method, is characterized in that, it comprises the following steps:
Step 1: adding concentration in each reactor is 40%～50% the amino trimethylene methylenephosphonic acid ATMP aqueous solution,The pH value that adds alkali regulator solution is 5-7,
Step 2: being warming up to 40 DEG C～50 DEG C, is 20%～50% toward slowly dripping a kind of concentration respectively in each reactorContaining micro-sulfate solution; When solution becomes muddy, and while having precipitation to generate, stop dripping sulfuric acidSaline solution; Trace element in described sulfate solution is the one in following: zinc, manganese, copper or iron;
Step 3: insulation reaction 0.5-1h under the mixing speed of 50r/min～100r/min, obtains various containingThe amino trimethylene methylenephosphonic acid chelate of trace element;
Step 4: carry in proportion containing micro-amino trimethylene methylenephosphonic acid chelate various with measuring pumpIn surge tank, mix, and then be transported in composite fertilizer's reactor, with other composite fertilizers in reactorAfter raw material mixes, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelated microelement fertilizer.
7. the method for amino trimethylene methylenephosphonic acid chelated microelement fertilizer according to claim 6, itsBe characterised in that, described step 4 specifically comprises:
Step 41: with measuring pump by various defeated in proportion containing micro-amino trimethylene methylenephosphonic acid chelateSend in surge tank and mix, and then be transported to reactor inlet place of composite fertilizer,
Step 42: by atomization distributor by mix containing micro-amino trimethylene methylenephosphonic acid chelaCompound sprays in composite fertilizer's reactor;
Step 43: what mix reacts with composite fertilizer containing micro-amino trimethylene methylenephosphonic acid chelateAfter other composite fertilizer materials in device mix, carry out granulation, obtain amino trimethylene methylenephosphonic acid chelating trace unitFertilizer.
8. according to the preparation of the amino trimethylene methylenephosphonic acid chelated microelement fertilizer described in claim 6 or 7Method, is characterized in that, other composite fertilizer materials in described step 4 are one or more in followingMixing: urea, potassium sulfate or MAP.
9. a Preparation equipment for amino trimethylene methylenephosphonic acid chelated microelement fertilizer, is characterized in that: itsComprise aqueous slkali storage tank, plural chelating agent reactor, plural measuring pump, surge tank, flowMeter, atomization distributor and composite fertilizer's reactor, the output of described aqueous slkali storage tank reacts with each chelating agent respectivelyThe input of still connects, and each chelating agent reactor is connected with respectively corresponding measuring pump, metering delivery side of pumpAll be connected with the input of surge tank, the output of surge tank connects by the input of flowmeter and atomization distributorConnect, the output of atomization distributor is connected with the input of composite fertilizer's reactor.
10. the preparation of amino trimethylene methylenephosphonic acid chelated microelement fertilizer according to claim 9 is establishedStandby, it is characterized in that: it also comprises elevator, the output of surge tank is by the input of flowmeter and elevatorEnd connects, and the output of elevator is connected with the input of atomization distributor.
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| 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 |
| CN116063121B (en) * | 2021-10-29 | 2025-04-11 | 沈阳化工研究院有限公司 | Environmentally friendly chelated element compound fertilizer and preparation method thereof |
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| CN105585342B (en) | 2019-07-16 |
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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. |