CN102531769A - Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process - Google Patents
Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process Download PDFInfo
- Publication number
- CN102531769A CN102531769A CN201110412087XA CN201110412087A CN102531769A CN 102531769 A CN102531769 A CN 102531769A CN 201110412087X A CN201110412087X A CN 201110412087XA CN 201110412087 A CN201110412087 A CN 201110412087A CN 102531769 A CN102531769 A CN 102531769A
- Authority
- CN
- China
- Prior art keywords
- titanium
- acid
- hydrocerol
- potassium
- metatitanic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a method for preparing potassium fulvate phosphate fertilizer containing organic titanium by a recrystallization process. The method is characterized by comprising the following steps of: neutralizing titanium salt ice water solution with a base to prepare a new precipitate metatitanic acid; replacing titanium chloride or sulfate with new precipitate metatitanic acid to be used as a raw material for synthesizing titanium citrate free of chloride or sulfate; synthesizing titanium citrate saturated solution with new precipitate metatitanic acid as a titanium source and citric acid as an acid solvent and chelating agent by a microwave hot-melt chelating process; and mixing dipotassium hydrogen phosphate containing crystal water with potassium fulvate according to a ratio, co-melting at the temperature not less than 40 DEG C to obtain potassium fulvate and potassium phosphate complex, maintaining the temperature of the potassium fulvate and potassium phosphate complex at the temperature of not less than 40 DEG C, adding titanium citric acid solution according to a ratio, uniformly mixing and cooling for recrystallization. According to the invention, aiming at the problem of low utilization rate of phosphate fertilizer, a humic acid phosphate fertilizer synergist and organic titanium for strongly promoting plants to absorb and transfer phosphorus element are integrated so as to form a double-effect phosphate fertilizer synergist.
Description
Technical field
The invention belongs to technical field of fertilizers, be specifically related to a kind of method that contains the phosphoric acid potash fertilizer of organic titanium with the recrystallizing technology preparation.
Background technology
Phosphorus is the necessary for plant growth nutritive element, and in agriculture prodn, phosphate fertilizer is second largest fertile the kind, and China has 74% arable soil to lack phosphorus, and application of P fertilizer has become to guarantee the requisite important measures of crop yield.
According to China's comprehensive scientific and technological level determination of agricultural at present, the utilization ratio of China's agricultural crops fertilising is merely about 30%, and this season utilization ratio of China's application of P fertilizer has only 10% ~ 20%, causes the pollution of a large amount of fertilizer loss wastes and environment.
How to improve the utilization ratio and the fertilizer efficiency of phosphate fertilizer, develop and reduce or, be focus and the difficult point that current chemical fertilizer and agronomy circle are competitively studied not by the long-acting efficient phosphate fertilizer of soil fixing.
In soil, humic acids is the constructor of soil granular tissue, and " warehouse " that rotate for fertilizer; In agriculture prodn, humic acids is base manure or the organic fertilizer that topdresses.It can improve Soil structure and physicochemical property, improves the fertile water retention capacity of guarantor of soil, promotes plant-growth, improves crop yield.
Xanthohumic acid is an integral part most active in the humic acids, and its molecular weight is less, and is soluble in water, and the deflocculate performance is good, and intramolecularly contains more active function groups, has very high chemically reactive and biological activity.
Xanthohumic acid is a kind of soil improvement agent, and tool one plant growth regulators still is synergistic agent, the sustained release dosage of mineral manure simultaneously again.
Xanthohumic acid has very strong sequestering power to the effect that nitrogen, phosphorus, potassic fertilizer have tangible fixed nitrogen phosphorus decomposing slowly-releasing potassium to trace elements such as boron, iron, manganese, copper, zinc, molybdenums, and xanthohumic acid is the complexing agent that mineral manure organises.
It is reported that xanthohumic acid and inorganic nitrogen, phosphorus, potassic fertilizer combination are used, and can obviously improve the absorption rate of crop to nitrogen, phosphorus, potassium.Make phosphate fertilizer utilization efficiency improve 8.4% ~ 44.1%; Make potassium utilization rate improve 17.7%; Mix use with carbon ammonium and ammoniacal liquor, its utilization ratio improves 3.37 times and 11.80 times respectively.
Patent documentation CN1151096C discloses by ammonium humic acids, superphosphate of lime, organism (rapeseed cake), phosphorus potassium microorganism active bacterium, phosphorus powder etc. and has formed,, the patented technology of the biological humic organic phosphatic fertiliser that warp batching, mixing, stacking slaking are processed;
Patent documentation CN100355706C discloses superfine ground phosphate rock and superfine humic acids and minor amounts of additives, and an amount of water prescription, mixing are handled through mechanical activation, and the patented technology of ultrafine activated phosphorusore compound fertilizer is processed in the material granulation;
Patent documentation CN101717317A discloses by sulfuric acid, liquefied ammonia, ammonium sulfate, monoammonium phosphate and by xanthohumic acid, ammonium thiosulfate, Dyhard RU 100 and has formed the patented technology of the fresh-keeping suppressor factor of control nitrogen through the long-acting slow-releasing diammonium phosphate of manufacturings such as batching, granulation;
Patent documentation CN101781145A discloses by potassium primary phosphate, vitriolate of tartar or Repone K, hydroxyethyl di-phosphate, xanthohumic acid, Ulmic acids, ammonium polyphosphate, Pottasium Hydroxide and ferrous sulfate, sodium tetraborate, manganous sulfate, zinc sulfate, copper sulfate, Sodium orthomolybdate etc. and has formed the fertile patented technology of liquid that contains rich phosphorus and potassium;
Patent documentation CN102086140A discloses with ammonium humate as acvator, processes the patented technology of efficient humic acids phosphoric acid two ammoniums with diammonium phosphate and ammonium humate mix, through granulation, ammonification, drying;
Above patent documentation discloses the technology of mixing fertile synergistic agent or acvator with humic acids as phosphate fertilizer and phosphorus potassium, phosphorus ammonium etc.
Humic acids (xanthohumic acid) has been obtained a collection of achievement as the history in existing more than 40 year of research of the synergistic agent of mineral manure such as phosphorus potassium, phosphorus ammonium, urea.Humic acids (xanthohumic acid) has activation, conversion, multi-efficiency such as moves phosphate fertilizer; Humic acids (xanthohumic acid) can suppress water-soluble phosphorus and in soil, be fixed; But the fixedly iron of titanium pigment, aluminium, calcium ion in the complexing soil make it lose the fixedly activity of phosphorus; But activation is fixed on the insoluble invalid phosphorus in the soil, and crop utilizes again; Can increase the miles of relative movement of available phosphorus in soil etc.
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.
Through retrieving disclosed patent documentation and memoir:
Do not find organic titanium and the compound report of xanthohumic acid as the phosphate fertilizer synergistic agent.
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 method that contains the xanthohumic acid potassiumphosphate of 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 method that contains the phosphoric acid potash fertilizer of 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 saturated solution not chloride, sulfonium ion with microwave hot melt chelating technology; The potassium hydrogenphosphate and the potassium fulvate proportional mixing that will contain crystal water; Congruent melting makes xanthohumic acid sylvite and potassium phosphate salt complex body in >=40 ℃ temperature; Xanthohumic acid sylvite and potassium phosphate salt complex body are incubated in >=40 ℃ of temperature; Add the Hydrocerol A titanium solution in proportion, mix, the cooling recrystallization.
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 ℃, and 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.
The described potassium hydrogenphosphate and the potassium fulvate proportional mixing that will contain crystal water, congruent melting makes xanthohumic acid sylvite and potassium phosphate salt complex body in >=40 ℃ temperature:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, and press potassium hydrogenphosphate: the part by weight of potassium fulvate=1:0.5 ~ 1.5 adds potassium fulvate powder mixing congruent melting, is the complex body of xanthohumic acid sylvite and potassium phosphate salt.
Described even by the mixed of 1:0.3 ~ 0.8 with weight ratio at the xanthohumic acid sylvite that is dissolved in self crystal water and potassium phosphate salt complex body and Hydrocerol A titanium solution, the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer that contains organic titanium.
Compare with prior art; The present invention has following advantage: the present invention is directed to the low problem of phosphate fertilizer utilization efficiency; With humic-acid kind phosphate fertilizer synergistic agent with have that strong promotion plant absorbs phosphoric and the organic titanium of running dissolves and is one, form two synergetic phosphate fertilizer synergistic agent.
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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, and press potassium hydrogenphosphate: the part by weight of potassium fulvate=1:1 adds potassium fulvate powder mixing congruent melting, is the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
Xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.5 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, and press potassium hydrogenphosphate: the part by weight of potassium fulvate=1:0.5 adds potassium fulvate powder mixing congruent melting, is the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
Xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.3 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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:
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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, and press potassium hydrogenphosphate: the part by weight of potassium fulvate=1:1.5 adds potassium fulvate powder mixing congruent melting, is the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
Xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.8 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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, the sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10% is controlled 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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, and press potassium hydrogenphosphate: the part by weight of potassium fulvate 1:1 adds potassium fulvate powder mixing congruent melting, is the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
At xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.5 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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, the sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10% is controlled 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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, add potassium fulvate powder mixing congruent melting in the ratio of potassium hydrogenphosphate: potassium fulvate=1:0.5 ~ 1.5, and be the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
Xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.3 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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, the sodium hydroxide solution neutralisation of sulphuric acid titanium solution with 10% is controlled 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; With cabinet type microwave stove hot melt chelating under 100 ℃ ~ 120 ℃ temperature of 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) manufacturing of xanthohumic acid sylvite-potassium phosphate salt complex body:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, add potassium fulvate powder mixing congruent melting in the part by weight ratio of potassium hydrogenphosphate: potassium fulvate=1:1.5, and be the complex body of xanthohumic acid sylvite and potassium phosphate salt.
(4) contain the manufacturing of the xanthohumic acid phosphoric acid potash fertilizer of organic titanium:
Xanthohumic acid sylvite-potassium phosphate salt complex body and Hydrocerol A titanium solution, the mixed of pressing 1:0.8 with weight ratio is even, and the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer 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 method for the xanthohumic acid phosphoric acid potash fertilizer 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, the potassium hydrogenphosphate that will contain crystal water and potassium fulvate proportional mixing, congruent melting makes xanthohumic acid sylvite and potassium phosphate salt complex body in >=40 ℃ temperature,
E, xanthohumic acid sylvite and potassium phosphate salt complex body are incubated in >=40 ℃ of temperature, add the Hydrocerol A titanium solution in proportion, mix, the cooling recrystallization.
2. according to claim 1ly a kind ofly contain the method for the xanthohumic acid phosphoric acid potash fertilizer 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 method for the xanthohumic acid phosphoric acid potash fertilizer 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 method for the xanthohumic acid phosphoric acid potash fertilizer 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. a kind of method that contains the xanthohumic acid phosphoric acid potash fertilizer of organic titanium with the recrystallizing technology preparation according to claim 1; It is characterized in that the described potassium hydrogenphosphate and the potassium fulvate proportional mixing that will contain crystal water, congruent melting makes xanthohumic acid sylvite and potassium phosphate salt complex body in >=40 ℃ temperature:
The potassium hydrogenphosphate that will contain 3 crystal water places >=40 ℃ temperature, add potassium fulvate powder mixing congruent melting with weight ratio in the ratio of potassium hydrogenphosphate: potassium fulvate=1:0.5 ~ 1.5, and be the complex body of xanthohumic acid sylvite and potassium phosphate salt.
6. a kind of method that contains the phosphoric acid potash fertilizer of organic titanium with the recrystallizing technology preparation according to claim 1; It is characterized in that described xanthohumic acid sylvite that is dissolved in self crystal water and potassium phosphate salt complex body and Hydrocerol A titanium solution are with the ratio of weight ratio in 1:0.3 ~ 0.8; Mix, the cooling recrystallization is separated out and is the xanthohumic acid phosphoric acid potash fertilizer that contains organic titanium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110412087XA CN102531769B (en) | 2011-12-13 | 2011-12-13 | Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110412087XA CN102531769B (en) | 2011-12-13 | 2011-12-13 | Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102531769A true CN102531769A (en) | 2012-07-04 |
| CN102531769B CN102531769B (en) | 2013-11-13 |
Family
ID=46339963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110412087XA Expired - Fee Related CN102531769B (en) | 2011-12-13 | 2011-12-13 | Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102531769B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250478A (en) * | 2020-10-29 | 2021-01-22 | 四川龙蟒福生科技有限责任公司 | Full-water-soluble titanium fertilizer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952563A (en) * | 1987-03-21 | 1990-08-28 | Rutgerswerke Ag | Waterfree application form of low molecular weight alkali huminates |
| CN1052302A (en) * | 1989-11-28 | 1991-06-19 | 北京有色金属研究总院 | Titanium compound for plant growing regulating agent and synthetic |
| CN101575245A (en) * | 2009-06-12 | 2009-11-11 | 陕西惠蕊德农业科技有限公司 | Organic titanium-potassium fertilizer and preparation method thereof |
-
2011
- 2011-12-13 CN CN201110412087XA patent/CN102531769B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952563A (en) * | 1987-03-21 | 1990-08-28 | Rutgerswerke Ag | Waterfree application form of low molecular weight alkali huminates |
| CN1052302A (en) * | 1989-11-28 | 1991-06-19 | 北京有色金属研究总院 | Titanium compound for plant growing regulating agent and synthetic |
| CN101575245A (en) * | 2009-06-12 | 2009-11-11 | 陕西惠蕊德农业科技有限公司 | Organic titanium-potassium fertilizer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐观峰，等: "用钨酸盐作助熔剂生长KTP晶体", 《人工晶体学报》 * |
| 陈吉书，等: "柠檬酸钛(Ⅳ)化合物的合成和热性质研究", 《云南大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250478A (en) * | 2020-10-29 | 2021-01-22 | 四川龙蟒福生科技有限责任公司 | Full-water-soluble titanium fertilizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102531769B (en) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103708964B (en) | Instant chelated solid water-soluble fertilizer | |
| CN101935243B (en) | High-water-solubility organic fertilizer | |
| CN104829342B (en) | A kind of method of allantoin waste water production composite fertilizer | |
| CN103130580B (en) | Production method of urea sulfuric acid multi-nutrient functional compound fertilizer | |
| CN103951509A (en) | Functional ecological potash fertilizer for agriculture and preparation method thereof | |
| CN102515917B (en) | Method for preparing organic titanium-containing ammonium borate fertilizer with recrystallization technology | |
| CN107892634A (en) | The cotton dedicated liquid set meal fertilizer and preparation method and application process of a kind of improved soil | |
| CN103193553A (en) | Production technology of water-soluble water retention drop irrigation slow release fertilizer | |
| CN102515924A (en) | Preparation method of chlorine-free compound fertilizer | |
| CN102557822B (en) | Method for preparing urea peroxide containing organic titanium by recrystallization process | |
| CN106748527A (en) | A kind of production method of organic water-soluble fertilizer | |
| CN103739406A (en) | Humic acid chelated boron, magnesium, zinc and iron fertilizer and preparation method thereof | |
| CN102649657B (en) | Production method for macroelement fully water-soluble fertilizer | |
| CN102442864A (en) | Acidic fertilizer capable of decomposing phosphorous, potassium and trace elements in soil | |
| CN102557825B (en) | Method for preparing trace element fertilizer containing organic titanium through microwave chelating process | |
| IL187811A (en) | Fertilizing method for agricultural irrigation | |
| CN102531769B (en) | Method for preparing potassium fulvate phosphate fertilizer containing organic titanium by recrystallization process | |
| CN102557818B (en) | Method for preparing fulvic acid ammonium phosphate fertilizer containing organic titanium through recrystallization process | |
| CN102531770B (en) | Method for preparing organic titanium-containing potassium borate fertilizer by recrystallization process | |
| CN107721472A (en) | A kind of enzyme liquid body phosphorus decomposing agent of bioactivation containing potassium fulvate and preparation method thereof | |
| CN102557823B (en) | Method for preparing organic titanium-chitosoligosaccharide ammonium salt biological fertilizer by salting-out process | |
| CN102557819B (en) | Method for preparing organic titanium-organic ammonium salt organic fertilizer by salting-out process | |
| CN104557185A (en) | Formula for organic-inorganic special fertilizer for walnut tree | |
| CN102531771B (en) | Method for preparing organic titanium-organic potassium salt organic fertilizer by salting-out process | |
| CN110079326B (en) | Preparation method of iron-containing soil conditioner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131113 Termination date: 20171213 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |