CN102515917A - Method for preparing organic titanium-containing ammonium borate fertilizer with recrystallization technology - Google Patents
Method for preparing organic titanium-containing ammonium borate fertilizer with recrystallization technology Download PDFInfo
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Abstract
The invention relates to a method for preparing an organic titanium-containing ammonium borate fertilizer with a recrystallization technology. The method is characterized by: using alkali to neutralize the ice water solution of a titanium salt so as to prepare a new precipitate metatitanic acid; using the new precipitate metatitanic acid to substitute a chloride of titanium and a sulfate to serve as the raw material for synthesizing titanium citrate; taking the new precipitate metatitanic acid as a titanium source, and citric acid as a solvent and a chelating agent, employing a micro wave hot melting and chelating process to synthesize a saturated titanium citrate solution; conducting neutralization and salting-out on the saturated titanium citrate solution with powdered ammonium carbonate for preparing a composite salt of organic titanium-organic ammonium, mixing the powder of the organic titanium-organic ammonium composite salt with crystal water-containing ammonium tetraborate and carrying out eutectic melting so as to manufacturing the titanium-containing ammonium borate fertilizer. Due to the characteristic of titanium element to powerfully promote the absorption and running of nitrogen, phosphorus, potassium as well as other secondary elements and trace elements in plants, water soluble titanium citrate with superior stability obtained from micro wave hot melting and sufficient chelating can be used as a synergist for promoting ammonium borate fertilizer absorption and a crop growth accelerator.
Description
Technical field
The invention belongs to technical field of fertilizers, be specifically related to a kind of fertile method of manufacture of ammonium borate that becomes to contain organic titanium by organic titanium and boric acid ammonium salt complex group.
Background technology
Boron is one of 7 kinds of essential micronutrient elements of growth and development of plants, in plant growth and development process, plays irreplaceable physiological action, has participated in the many important physical active procedures of plant.
Boron deficiency is comparatively general in the soil in Chinese arable land, orchard, forest land, and according to the data statistics of the overall survey of soil for the second time of 1982 ~ 1986 years whole nations, national arable soil boron deficiency area is nearly more than 500,000,000 mu.Arable land, ground boron deficiency ratios such as Guizhou, Sichuan, Hubei, Hunan, Anhui, Jiangsu, Jiangxi, Yunnan, Henan, Shaanxi, Guangdong, Fujian, Guangxi, Jilin, Hebei, Shandong, Shanxi are all greater than 60%.
It is unusual that boron deficiency can cause growth and development of plants in the soil, as cause that rape " colored and unreal ", cotton " flower bud and do not spend ", peanut " flower and do not have benevolence ", wheat " are not harvested ", fruit tree fruit " insatiable hunger " and phenomenons such as " bud drop, fallen flowers, sheddings " occurs.
The novel boron micro-fertilizer of high-absorbility also is the focus of current research and development.
Titanium elements is described as " catalyzer of fertilizer ", and it can promote plant to nitrogen, phosphorus, potassium and other moderate-element, trace elements absorbed and running forcefully.Use the compound manure that contains titanium elements and both can reach additional plant nutrition, can greatly promote absorption and the utilization of plant again nutritive ingredient.
According to domestic and international research department the test-results of using the compound manure that contains organic titanium is shown: use the compound manure that contains organic titanium; Can be on the level of original plant to the fertilizer absorption rate; Improve absorption rate 20% ~ 30%, the compound manure that contains organic titanium is a kind of new-type fertilizer of high utilization rate.
Titanium elements still is a kind of very effective non-hormone plant-growth regulator:
Titanium elements can improve photosynthesis of plants, increases the chlorophyll content in the plant leaf;
The activity of plurality of enzymes (like px, katalase, nitrogenase, nitrate reductase, 2-6 Phosphoric acid esterase etc.) in the titanium elements ability activated plant body;
Titanium elements can promote to improve the resistance of crop, and strengthening immunity is significantly improved to the ability of the drought resisting of crop, waterlogging-resistant, cold-resistant, high temperature resistance, disease and insect resistance;
Titanium elements can promote crop precocious, increases agricultural output;
Titanium elements can improve the quality of agricultural-food, improves the content of various nutritive ingredients in the agricultural-food, reduces the odd fruit rate, makes fruit shape plentiful, lovely luster.
The compound manure that contains organic titanium is that trace element fertilizer is formed by water miscible organic titanium inner complex and common nitrogen, phosphorus, potassic fertilizer and other secondary nutrientses, is the new type functional fertilizer of a kind of plant nutrition and physiological regulation economic benefits and social benefits unification.
The use of the compound manure of organic titanium on farm crop do not receive area, soil and weather condition effect, is a kind of broad spectrum that is applicable to Different Crop, the functional fertilizer that consumption is low.
Patent documentation CN1052302A discloses the patented technology with titanium tetrachloride and the synthetic plant growth regulator of Hydrocerol A;
Patent documentation CN101838159A discloses the patented technology that contains the functional fertilizer of titanium complex with preparations such as titanium sulfate and tartrate, Hydrocerol A, oxysuccinic acid, mandelic acid, lactic acid.
Above patent documentation discloses direct muriate with water-soluble titanium; Or the vitriol of titanium is as the raw material of synthesizing citric acid organic titanium inner complex, and the weak point of its existence is will mix with a large amount of cl ionss or sulfonium ion in institute's synthetic Hydrocerol A organic titanium inner complex.
Through retrieving disclosed patent documentation and memoir:
Find to be employed in the frozen water with the report for preparing the metatitanic acid that can be dissolved in Hydrocerol A in the alkalescence with titanium salt; Do not find with the report of new deposition metatitanic acid as the titanium source of preparation lemon titanium; Do not find report with microwave hot melt chelating technology synthesizing citric acid titanium.
The organic titanium-boron fertilizer of forming by organic titanium, glucose, humic acids, four water, eight Sodium Tetraboratees, trolamine, biological titanium etc. of in the disclosed patent documentation that relates to organic titanium-boron fertilizer of retrieval, only having found the open class of patent documentation CN101575230B patent of invention; Wherein organic titanium is by butyl(tetra)titanate and methyl ethyl diketone 1:2 in molar ratio, and forms the organic chelated liquid of titaniums with 40 ~ 60 ℃ of microwave chelatings.
The organic titanium-boron fertilizer of finding to use stable superior, the water-soluble Hydrocerol A titanium that forms through the abundant chelating of microwave fusion and ammonium borate to be combined into.
Do not find the organic titanium inner complex is dissolved in the boric acid ammonium salt crystal water the fertile report of ammonium borate that contains organic titanium through the recrystallization preparation.
Summary of the invention
One of the object of the invention provides a kind of method of manufacture of Hydrocerol A titanium of not chloride, sulfonium ion;
Two of the object of the invention provides a kind of fertile method of ammonium borate that contains organic titanium with the recrystallizing technology preparation.
The object of the invention is realized through following technical scheme: the present invention is a kind of fertile method of ammonium borate that contains organic titanium with the recrystallizing technology preparation; It is characterized in that: with in the alkali with a kind of not chloride, sulfonium ion of frozen water formulations prepared from solutions of titanium salt, can be dissolved in the new deposition metatitanic acid of Hydrocerol A; With not chloride, sulfonium ion, can be dissolved in the new deposition metatitanic acid of Hydrocerol A, the muriate of instead of titanium, vitriol are as the raw material of the Hydrocerol A titanium of synthetic not chloride, sulfonium ion; With not chloride, sulfonium ion, the new deposition metatitanic acid that can be dissolved in Hydrocerol A is the titanium source, is sour solvent, sequestrant with Hydrocerol A, synthesizes Hydrocerol A titanium not chloride, sulfonium ion with microwave hot melt chelating technology; Hydrocerol A titanium saturated solution with the volatile salt powder neutralization preparation Hydrocerol A titanium-ammonium citrate composite salt of saltouing, is mixed Hydrocerol A titanium-ammonium citrate composite salt powder and to dissolve recrystallization altogether and prepare the ammonium borate fertilizer that contains organic titanium with the tetraboric acid ammonium that contains crystal water.
Described with in the alkali with the frozen water solution of titanium salt, the new deposition metatitanic acid of preparation, preparation according to the following steps:
A, the vitriol of the muriate of titanium or titanium is dissolved among the frozen water, with the neutralization of 10% ~ 30% sodium hydroxide solution, control pH is 7.0 ~ 8.0, and deposition is separated out oyster white gel metatitanic acid in≤5 ℃ cold water,
B, new sedimentary metatitanic acid are removed cl ions or sulfonium ion with distilled water wash,
After the new sedimentary metatitanic acid of c, washing removal cl ions or sulfonium ion removes the part planar water with whizzer, in time be used for acid and dissolve chelating.
Described new deposition metatitanic acid and Hydrocerol A are in the ratio proportioning of titanium: Hydrocerol A=1:2.5 ~ 4 mol ratios.
Described with microwave hot melt chelating technology according to the following steps:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
In titanium: the ratio proportioning of the mol ratio 1:2.5 of Hydrocerol A ~ 4, the Citric acid monohydrate Food grade of xln is dissolved in the planar water of new deposition metatitanic acid, stirring generates milky Hydrocerol A-metatitanic acid suspension mixed solution,
B, microwave hot melt chelating technology synthesizing citric acid titanium,
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; With operating frequency 915MHz or use operating frequency 2450MHz; The cabinet type microwave device of microwave power 1 ~ 10KW, or tunnel type micro wave equipment carries out radiation hot melt chelating, and the microwave thermal melting temperatur is controlled at 100 ℃ ~ 120 ℃; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed when glue also is in the hot melt state, becomes Hydrocerol A titanium saturated solution with distilled water diluting.
Described Hydrocerol A titanium saturated solution is saltoutd technology according to the following steps with Powdered carbonic acid ammonium neutralization:
The preparation of a, acid Hydrocerol A titanium-ammonium citrate composite salt:
Using volatile salt or solution of ammonium hydroxide to regulate pH Hydrocerol A titanium saturated solution is 1.5 ~ 2.5; Hydrocerol A titanium and organic ammonium salt crystallization are separated out; And ageing after 24 hours in≤25 ℃ of room temperatures; Remove surface adsorption water with 60 ℃ of hot blasts, be the composite salt of the acid Hydrocerol A titanium-ammonium citrate of leather hard
The preparation of b, Hydrocerol A titanium-ammonium citrate composite salt powder:
The ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt was removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
Described that the ammonium borate that contains organic titanium is processed in organic titanium-organic ammonium composite salt powder and the tetraboric acid ammonium proportional mixing congruent melting that contains crystal water is fertile, and its step is following:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.3 ~ 0.8, with acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water by mixing,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in >=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Compare with prior art; The present invention has following advantage: the present invention is directed to titanium elements and have strong promotion plant to nitrogen, phosphorus, potassium and other moderate-element; The characteristic of trace elements absorbed and running, stable superior, the water miscible Hydrocerol A titanium that will be processed by the abundant chelating of microwave hot melt is as fertile sorbefacient synergistic agent of ammonium borate and crop growth promoter.The present invention also is soluble in the crystal water of self to ten water tetraboric acid ammoniums, be prone to the characteristic of recrystallization after the cooling again, and Hydrocerol A titanium-ammonium citrate composite salt is dissolved in the ten water tetraboric acid ammoniums, and it is fertile to process the ammonium borate that contains organic titanium through recrystallization.
Embodiment
Below in conjunction with embodiment the present invention is elaborated, but do not limit the scope of the present invention.
Embodiment 1
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate the titanium tetrachloride hydrochloric acid soln; With in 10% the sodium hydroxide solution with the titanium tetrachloride hydrochloric acid soln; Control solution temperature≤5 ℃, pH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water;
B, new sedimentary metatitanic acid are removed cl ions with distilled water wash,
After the metatitanic acid of c, washing removal cl ions removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 8.7g in the prepared metatitanic acid of the titanium tetrachloride of 20ml; In titanium: the ratio proportioning of the mol ratio 1:3 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 115g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.5, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in>=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Embodiment 2
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate the titanium tetrachloride hydrochloric acid soln; With in 10% the sodium hydroxide solution with the titanium tetrachloride hydrochloric acid soln; Control solution temperature≤5 ℃, pH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water;
B, new sedimentary metatitanic acid are removed cl ions with distilled water wash,
After the metatitanic acid of c, washing removal cl ions removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 8.7g in the prepared metatitanic acid of the titanium tetrachloride of 20ml; In titanium: the ratio proportioning of the mol ratio 1:2.5 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 96g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.3, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in>=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Embodiment 3
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate the titanium tetrachloride hydrochloric acid soln; With in 10% the sodium hydroxide solution with the titanium tetrachloride hydrochloric acid soln; Control solution temperature≤5 ℃, pH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water;
B, new sedimentary metatitanic acid are removed cl ions with distilled water wash,
After the metatitanic acid of c, washing removal cl ions removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 8.7g in the prepared metatitanic acid of the titanium tetrachloride of 20ml; In titanium: the ratio proportioning of the mol ratio 1:4 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 153g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.8, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in>=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Embodiment 4
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10%; Control solution temperature≤5 ℃; PH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water
B, new sedimentary metatitanic acid are removed sulfonium ion with distilled water wash,
After the metatitanic acid of c, washing removal sulfonium ion removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 5g in the prepared metatitanic acid of 25g titanium sulfate; In titanium: the ratio proportioning of the mol ratio 1:3 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 65g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.5, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in >=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Embodiment 5
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10%; Control solution temperature≤5 ℃; PH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water
B, new sedimentary metatitanic acid are removed sulfonium ion with distilled water wash,
After the metatitanic acid of c, washing removal sulfonium ion removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 5g in the prepared metatitanic acid of 25g titanium sulfate; In titanium: the ratio proportioning of the mol ratio 1:2.5 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 54g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.3, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in >=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
Embodiment 6
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add 0 ℃ ~ 5 ℃ the frozen water of 1000ml; Under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10%; Control solution temperature≤5 ℃; PH value 7.0 ~ 8.0 precipitates metatitanic acid and separates out in≤5 ℃ cold water
B, new sedimentary metatitanic acid are removed sulfonium ion with distilled water wash,
After the metatitanic acid of c, washing removal sulfonium ion removes the part planar water with whizzer, promptly can be used for acid and dissolve chelating.
(2) preparation of Hydrocerol A titanium chelate:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
Titaniferous is 5g in the prepared metatitanic acid of 25g titanium sulfate; In titanium: the ratio proportioning of the mol ratio 1:3 of Hydrocerol A; Add Citric acid monohydrate Food grade crystallization powder 86g at metatitanic acid; Be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form Hydrocerol A-metatitanic acid suspended mixture
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; Cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature with 2450MHz frequency 1000W; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed becomes Hydrocerol A titanium saturated solution with distilled water diluting when glue is in the hot melt state.
(3) preparation of lemon acid titanium-ammonium citrate composite salt:
The preparation of a, acid Hydrocerol A titanium-Hydrocerol A ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-ammonium citrate composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-ammonium citrate composite salt powder.
(4) it is fertile to prepare the ammonium borate that contains organic titanium with recrystallizing technology:
A, with boric acid ammonium salt Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.8, acid Hydrocerol A titanium-ammonium citrate composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed,
B, with the acid Hydrocerol A titanium-ammonium citrate composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in >=80 ℃ of thermostat containers that contains 10 crystal water; Acid Hydrocerol A titanium-ammonium citrate composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and Hydrocerol A titanium, ammonium citrate recrystallization are separated out, be the functional fertilizer of the ammonium borate that contains organic titanium.
More than be embodiment of the present invention, all similar changes of doing according to above-mentioned design ought to belong to the content that contains of the present invention.
Claims (6)
1. one kind contains the fertile method of ammonium borate of organic titanium with recrystallizing technology preparation, it is characterized in that:
A, with in the alkali and a kind of not chloride, sulfonium ion of the frozen water formulations prepared from solutions of titanium salt, can be dissolved in the new deposition metatitanic acid of Hydrocerol A,
B, with not chloride, sulfonium ion, can be dissolved in the new deposition metatitanic acid of Hydrocerol A, the muriate of instead of titanium, vitriol be as the raw material of the Hydrocerol A titanium of synthetic not chloride, sulfonium ion,
C, not chloride, the sulfonium ion of usefulness, the new deposition metatitanic acid that can be dissolved in Hydrocerol A is the titanium source, is sour solvent, sequestrant with Hydrocerol A, synthesizes Hydrocerol A titanium saturated solution not chloride, sulfonium ion with microwave hot melt chelating technology,
D, with Hydrocerol A titanium saturated solution with the saltout composite salt of preparation organic titanium-organic ammonium of Powdered carbonic acid ammonium neutralization,
E, that organic titanium-organic ammonium composite salt powder and the tetraboric acid ammonium mixing congruent melting manufacturing that contains crystal water are contained the ammonium borate of organic titanium is fertile.
2. according to claim 1ly a kind ofly contain the fertile method of ammonium borate of organic titanium with recrystallizing technology preparation, it is characterized in that described with in the alkali with the frozen water solution of titanium salt, the new deposition metatitanic acid of preparation prepares according to the following steps:
A, the vitriol of the muriate of titanium or titanium is dissolved among the frozen water, with the neutralization of 10% ~ 30% sodium hydroxide solution, control pH is 7.0 ~ 8.0, and deposition is separated out oyster white gel metatitanic acid in≤5 ℃ cold water,
B, new sedimentary metatitanic acid are removed cl ions or sulfonium ion with distilled water wash,
After the new sedimentary metatitanic acid of c, washing removal cl ions or sulfonium ion removes the part planar water with whizzer, in time be used for acid and dissolve chelating.
3. according to claim 1ly a kind ofly contain the fertile method of ammonium borate of organic titanium, it is characterized in that described new deposition metatitanic acid and Hydrocerol A ratio proportioning in titanium: Hydrocerol A=1:2.5 ~ 4 mol ratios with recrystallizing technology preparation.
4. according to claim 1ly a kind ofly contain the fertile method of ammonium borate of organic titanium with recrystallizing technology preparation, it is characterized in that described with microwave hot melt chelating technology according to the following steps:
The preparation of a, Hydrocerol A-metatitanic acid suspension mixed solution:
In titanium: the ratio proportioning of the mol ratio 1:2.5 of Hydrocerol A ~ 4, the Citric acid monohydrate Food grade of xln is dissolved in the planar water of new deposition metatitanic acid, stirring generates milky Hydrocerol A-metatitanic acid suspension mixed solution,
B, microwave hot melt chelating technology synthesizing citric acid titanium:
Hydrocerol A-metatitanic acid suspension mixed solution is placed in the special disc type teflon resin reaction vessel; With operating frequency 915MHz or use operating frequency 2450MHz; The cabinet type microwave device of microwave power 1 ~ 10KW, or tunnel type micro wave equipment carries out radiation hot melt chelating, and the microwave thermal melting temperatur is controlled at 100 ℃ ~ 120 ℃; Reaction end is that milky suspension mixed solution becomes water white glue
The preparation of c, Hydrocerol A titanium saturated solution:
Hydrocerol A titanium glue with microwave hot melt chelating is processed when also being in the hot melt state, becomes Hydrocerol A titanium saturated solution with distilled water diluting.
5. according to claim 1ly a kind ofly contain the fertile method of ammonium borate of organic titanium, it is characterized in that described Hydrocerol A titanium saturated solution neutralizes with Powdered carbonic acid ammonium to saltout technology according to the following steps with recrystallizing technology preparation:
The preparation of a, acid Hydrocerol A titanium-organic ammonium salt:
Use pulverous volatile salt to regulate pH Hydrocerol A titanium saturated solution and be 1.5 ~ 2.5, make Hydrocerol A titanium and organic ammonium generate gelatinous acid Hydrocerol A titanium-organic ammonium composite salt and separate out,
B, the ageing in≤25 ℃ of room temperatures of gelatinous acid Hydrocerol A titanium-organic ammonium composite salt removed surface adsorption water with 60 ℃ of hot blasts after 24 hours, and this product is acid Hydrocerol A titanium-organic ammonium composite salt powder.
6. according to a kind of fertile method of ammonium borate that contains organic titanium with recrystallizing technology preparation of claim 1 art; It is characterized in that described that the ammonium borate that contains organic titanium is processed in organic titanium-organic ammonium composite salt powder and the tetraboric acid ammonium proportional mixing congruent melting that contains crystal water is fertile, its step is following:
A, with boric acid ammonium salt and Hydrocerol A titanium-ammonium citrate composite salt, with the ratio proportioning of weight ratio 1:0.3 ~ 0.8, acid organic titanium-organic ammonium composite salt powder and the tetraboric acid ammonium that contains 10 crystal water are mixed in proportion,
B, with the acid organic titanium-organic ammonium composite salt powder of leather hard and the tetraboric acid ammonium mixture congruent melting in >=80 ℃ of thermostat containers that contains 10 crystal water; Acid organic titanium-organic ammonium composite salt is dissolved in 10 crystal water of tetraboric acid ammonium; And generation acid-base neutralisation reaction; Making final control pH value is 5.5 ~ 6.5
C, reaction product is cooled to room temperature, boric acid ammonium salt and organic titanium, organic ammonium recrystallization are separated out, it is fertile to be the ammonium borate that contains organic titanium.
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| CN106431679A (en) * | 2016-10-08 | 2017-02-22 | 东莞市农立农业科技有限公司 | Preparation method of titanium citrate liquid |
| CN106478155A (en) * | 2016-09-27 | 2017-03-08 | 武汉富强科技发展有限责任公司 | High-load readily soluble blade face boron fertilizer and preparation method thereof |
| CN109776218A (en) * | 2019-03-25 | 2019-05-21 | 山西省农业科学院农业环境与资源研究所 | A kind of Jian Kuo pea regulation special fertilizer |
| CN109824506A (en) * | 2019-04-06 | 2019-05-31 | 河南工业大学 | The preparation method of one plant growth regulators Titanium Citrate ammonium |
| CN109896951A (en) * | 2019-04-06 | 2019-06-18 | 河南工业大学 | The preparation method of one plant growth regulators Titanium Citrate potassium (photosensitizer) |
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