CN102531772B - Method for preparing organic titanium-plant vinegar ammonium salt organic fertilizer - Google Patents
Method for preparing organic titanium-plant vinegar ammonium salt organic fertilizer Download PDFInfo
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- CN102531772B CN102531772B CN201110412121.3A CN201110412121A CN102531772B CN 102531772 B CN102531772 B CN 102531772B CN 201110412121 A CN201110412121 A CN 201110412121A CN 102531772 B CN102531772 B CN 102531772B
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Abstract
The invention relates to a method for preparing organic titanium-plant vinegar ammonium salt organic fertilizer. The method is characterized in that new sediment metatitanic acid is prepared by using alkali to neutralize ice water solution of titanium salt; the metatitanic acid is used to replace titanic chloride and sulfate as raw materials for the synthesis of citricacide-titatnium chelate; the new sediment metatitanic acid is used as a titanium source, the citric acid is used as acid solvent and chelant, and a microwave hot melting chelate technology is used to synthesize the citricacide-titatnium chelate; and then the saturated solution of citricacide-titatnium chelate is subjected to neutralization and salting-out by the alkaline plant vinegar composite ammonium to prepare the organic titanium-plant vinegar ammonium salt organic fertilizer. The citricacide-titatnium chelate prepared by the microwave hot melting chelate technology with excellent stability and water solubility is used as synergist of plant vinegar ammonium organic fertilizer and crop growth promoter.
Description
Technical field
The invention belongs to technical field of fertilizers, be specifically related to a kind of by organic titanium-the plant manufacture method of vinegar ammonium salt fertilizer.
Background technology
Fertilizer is the strategic materials that ensure national food safety, keeps and increase fertility of land realizing the basic substance of agricultural sustainable development.
Chemical fertilizer is still the important production means of current agriculture production, plant is very low to the chemical fertilizer absorption rate in soil, according to China's comprehensive scientific and technological level determination of agricultural at present, the utilization ratio of China's agricultural crops fertilising is only 30% left and right, causes the pollution of a large amount of fertilizer loss wastes and environment.
The new-type fertilizer research and development of high-absorbility are the technological innovation focuses of current technical field of fertilizers, countries in the world to the low problem of chemical fertilizer absorption rate in soil, have been dropped into a large amount of human and material resources, the new-type fertilizer of research and development high-absorbility energetically for plant.
Titanium elements is described as " catalyzer of fertilizer ", and it can promote the peanut of plant to nitrogen, phosphorus, potassium and other moderate-element, trace element forcefully.Use containing the compound manure of titanium elements and both can reach supplementary plant nutrition, can greatly promote again absorption and the utilization of Plant To Nutrient composition.
Show using containing the test-results of the compound manure of organic titanium according to domestic and international research department: use the compound manure containing organic titanium, can original plant to the level of fertilizer absorption rate on, improving absorption rate 20% ~ 30%, is a kind of new-type fertilizer of high utilization rate containing the compound manure of organic titanium.
Titanium elements or a kind of very effective non-hormone plant-growth regulator:
Titanium elements can improve the photosynthesis of plant, increases the chlorophyll content in plant leaf;
The activity of plurality of enzymes (as peroxidase, catalase, nitrogenase, nitrate reductase, 2-6 Phosphoric acid esterase etc.) in titanium elements energy activated plant body;
Titanium elements can promote to improve the resistance of crop, strengthening immunity, and the ability of drought resisting to crop, waterlogging-resistant, cold-resistant, high temperature resistance, disease and insect resistance is significantly improved;
Titanium elements can promote crop precocity, increases agricultural output;
Titanium elements can improve the quality of agricultural-food, improves the content of various nutritive ingredients in agricultural-food, reduces odd fruit rate, makes fruit shape plentiful, lovely luster.
Containing the compound manure of organic titanium, be that trace element fertilizer forms, and is the new type functional fertilizer that a kind of plant nutrition and physiological regulation economic benefits and social benefits are unified by water miscible Organo-Titanate Chelates and common N,P,K fertilizers and other secondary nutrientses.
The use of the compound manure of organic titanium on farm crop is not subject to the impact of area, soil and weather condition, is a kind of broad spectrum that is applicable to Different Crop, the multi-Functional Fertilizers that consumption is low.
Patent documentation CN1052302A discloses the patented technology with titanium tetrachloride and the synthetic plant growth regulator of citric acid;
Patent documentation CN101838159A discloses the patented technology containing the multi-Functional Fertilizers of titanium complex with preparations such as titanium sulfate and tartrate, citric acid, oxysuccinic acid, mandelic acid, lactic acid.
Above patent documentation discloses the direct muriate by water-soluble titanium, or the vitriol of titanium is as the raw material of synthesizing citric acid Organo-Titanate Chelates, the weak point of its existence is will be assorted with a large amount of chlorions or sulfonium ion in the citric acid Organo-Titanate Chelates of synthesized.
Planting vinegar is to form fluent meterial by the vegetable materials such as timber, shell, bamboo wood, stalk, husk and the condensation of industrial wood waste pyrolysis gas compound thereof, and its main component is the crude substance such as organic acid, phenols, ketone, aldehydes, alcohols and heterocyclic.
Plant in vinegar, made by timber, shell for wooden vinegar; What be made up of bamboo wood is bamboo vinegar; What be made up of stalk, husk is careless vinegar (claiming again stalk vinegar).Plant that vinegar can be used as organic pesticide (sterilant, Insecticides (tech) & Herbicides (tech)) and fertilizer in Organic farming, soil improvement agent uses.
Plant in the organic fertilizer of vinegar composition and there is strong seepage force owing to planting vinegar composition, can improve fertilizer efficiency 30% ~ 50%, plant vinegar simultaneously and can also improve the function of stress resistance of plant, diseases prevention to crop, antibacterial, expelling parasite has good effect, is a kind of multi-functional organic fertilizer.
Plant vinegar fertilizer and can double as again soil conditioner, can promote the growth of aerobic bacteria in soil, suppress harmful microbe breeding, be released in the nutritive element being cured in soil, also can improve again soil microorganisms structure, effectively reduce the generation of soil source disease, there is good effect to solving soil continuous cropping obstacle, and can alleviate the soil salinization, inferior degree of salinity, play the effect that regulates soil pH value, promote plant root system development, improve the transplanting success of plant.
Plant vinegar ammonium salt compound and be by wooden vinegar or bamboo vinegar or careless vinegar and alkaline ammonium salt and carry out acid-base reaction generation as volatile salt, ammonium hydroxide.
Planting vinegar ammonium salt compound is a kind of novel organic ammonium salt, and advantage and effect that it has possessed all inorganic nitrogenous fertilizers, have both and have supplementary nitrogen and plant the organotrophic double effects of vinegar.Plant vinegar ammonium salt compound compared with the traditional inorganic nitrogenous fertilizer such as ammonium chloride, ammonium sulfate, do not have sulfate radical and chlorion residual in soil, can not cause the acidifying of soil to harden, eliminate traditional nitrogenous fertilizer such as ammonium chloride, ammonium sulfate and made the restrictive factor of amount in raising, also can not cause the decline of potato, beet, quality of tobacco.Plant vinegar ammonium salt compound simultaneously and there is the function that significantly improves crop anti-adversity, can obviously strengthen that crop is cold-resistant, the ability of disease and insect resistance.
Patent documentation CN1225983C discloses the patented technology of the wooden vinegar multiple effect plant-growth accelerator being made up of wooden vinegar, urea, potassium primary phosphate, humic acids, citric acid, lactic acid, boric acid, ammonium molybdate, zinc sulfate, manganous sulfate, copper sulfate, ferrous sulfate, magnesium sulfate, disodium salt etc.;
Patent documentation CN100421562C disclose there is coordinate plant growth and necessarily antibacterial, sterilization, the bamboo vinegar of anthelminthic effect is matrix, adds the protectant patented technology of bamboo vinegar liquid plant nutrition of the compositions such as urea, potassium primary phosphate, saltpetre, magnesium sulfate, ferrous sulfate, manganous sulfate, zinc sulfate, copper sulfate, borax, ammonium molybdate;
Patent documentation CN100364934C discloses take wood (grass) vinegar liquid as matrix, adds the patented technology of wood (grass) the vinegar liquid fertilizer of the compositions such as urea, potassium primary phosphate, saltpetre, nitrocalcite, magnesium sulfate, ferrous sulfate, manganous sulfate, zinc sulfate, copper sulfate, borax or boric acid, Sodium orthomolybdate or ammonium molybdate and rare earth element, humic acids;
Patent documentation CN101176474A discloses by bamboo vinegar, wooden vinegar or careless vinegar liquid and traditional chemical herbicide and has formed biogenic steriland herbicide, and has both Promoting plant growth, the patented technology of improvement soil effect;
Patent documentation CN101263810A discloses by the patented technology of planting vinegar and inert ingredient, macroelement, trace element, sequestrant etc. and form pesticides antidote;
It is main that patent documentation CN101606536A discloses by wood vinegar, with the patented technology of the soil disinfectant of the composition such as copper sulfate, ferrous sulfate, avermitilis strain;
Patent documentation CN1647635A discloses the patented technology of preparing bamboo vinegar liquid compound salt preservative and freshness keeping agent with calcium oxide (unslaked lime) processing bamboo vinegar liquid;
Patent documentation CN100368509C discloses the patented technology with the preparation of alkaline matter for processing plant vinegar liquid with multifunction green agriculture products such as supplying with full nutrition, coordinate plant growth growth, bactericidal and disinfest;
The published patent of planting vinegar (wooden vinegar, bamboo vinegar, careless vinegar) liquid that relates to has been applied to the fields such as the upper weedicide of plant growth promoter, plant nutrition protective material, liquid fertilizer and agricultural, pesticides antidote, soil disinfectant, antisepsis antistaling agent and multifunctional green agriculture product above.
Through retrieving published patent documentation and academic paper:
Do not find to adopt in frozen water with the report of preparing the metatitanic acid that can be dissolved in citric acid in alkalescence with titanium salt; Do not find newly to precipitate the report of metatitanic acid as the titanium source of preparation lemon titanium; Do not find the report with microwave hot melt chelating technique synthesizing citric acid titanium.
Through retrieving published patent documentation and academic paper:
Do not find by organic titanium and the report of multifunctional organic fertilizer of planting vinegar composite salt combination; Do not find using alkalescence (pH >=8) plant vinegar ammonium salt compound as analysing salt neutralizing agent, salting out is prepared organic titanium-the plant report of vinegar ammonium salt compound multifunctional fertilizers.
Summary of the invention
One of object of the present invention, is to provide a kind of manufacture method of Titanium Citrate of not chloride, sulfonium ion;
Two of object of the present invention, is to provide a kind of organic titanium of not chloride, sulfonium ion-the plant manufacture method of the compound multifunctional organic fertilizer of vinegar ammonium salt.
Object of the present invention is achieved through the following technical solutions: the present invention is that a kind of use technique of saltouing is prepared organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer, it is characterized in that: with preparing with the frozen water solution of titanium salt in alkali, one is not chloride, sulfonium ion, can be dissolved in the new precipitation metatitanic acid of citric acid; With not chloride, sulfonium ion, can be dissolved in the new precipitation metatitanic acid of citric acid, the muriate of instead of titanium, vitriol are as the raw material of the Titanium Citrate of synthetic not chloride, sulfonium ion; With not chloride, sulfonium ion, the new precipitation metatitanic acid that can be dissolved in citric acid is titanium source, take citric acid as acid-soluble dose, sequestrant, uses microwave hot melt chelating technique to synthesize Titanium Citrate not chloride, sulfonium ion; Titanium Citrate saturated solution is planted to the compound ammonium salting out of vinegar by alkalescence and prepare organic titanium-plant vinegar ammonium salt fertilizer.
Described uses in alkali and the frozen water solution of titanium salt, the new precipitation metatitanic acid of preparation, according to the following steps preparation:
A, the vitriol of the muriate of titanium or titanium is dissolved among frozen water, with 10% ~ 30% sodium hydroxide solution neutralization, controlling pH is 7.0 ~ 8.0, Precipitation oyster white gel metatitanic acid in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes chlorion or sulfonium ion with distilled water wash;
The metatitanic acid that the new precipitation of chlorion or sulfonium ion is removed in c, washing removes after part planar water with whizzer, in time for acid-soluble chelating.
Described new precipitation metatitanic acid and citric acid are in titanium: the ratio proportioning of citric acid=1:2.5 ~ 4 mol ratio.
Described uses microwave hot melt chelating technique according to the following steps:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In titanium: the ratio proportioning of mol ratio 1:2.5 ~ 4 of citric acid, the Citric acid monohydrate Food grade of xln is dissolved in the planar water of new precipitation metatitanic acid, stir and generate milky citric acid-metatitanic acid suspension mixed solution;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in 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, 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, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, during also in hot melt state, is diluted with distilled water into Titanium Citrate saturated solution at glue.
Described Titanium Citrate saturated solution is saltoutd technique according to the following steps with the vinegar ammonium salt of planting of alkalescence:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound;
C, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-plant vinegar ammonium salt compound and Carbon Dioxide ammonium is mixed in proportion, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
Technology of the present invention be for direct with the muriate of titanium or the vitriol of titanium the raw material as synthesizing citric acid titanium, can make to mix the defect that has chlorion or sulfonium ion in the organic titanium of synthesized, propose the raw material as synthetic organic titanium with the metatitanic acid of not chloride, sulfonium ion.
Compared with the prior art, the present invention is using superior, water miscible the stability of being made up of the abundant chelating of microwave hot melt Titanium Citrate as synergistic agent and the plant growth promotor of planting vinegar ammonium fertilizer, will plant the various activity of vinegar fertilizer and the various activity of organic titanium are superimposed.
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 the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate titanium tetrachloride hydrochloric acid soln, with in 10% sodium hydroxide solution and titanium tetrachloride hydrochloric acid soln, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes chlorion with distilled water wash;
The metatitanic acid that chlorion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of the titanium tetrachloride of 20ml, titaniferous is 8.7g, in titanium: the ratio proportioning of the mol ratio 1:3 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
C, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:1.0 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
embodiment 2
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate titanium tetrachloride hydrochloric acid soln, with in 10% sodium hydroxide solution and titanium tetrachloride hydrochloric acid soln, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes chlorion with distilled water wash;
The metatitanic acid that chlorion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of the titanium tetrachloride of 20ml, titaniferous is 8.7g, in titanium: the ratio proportioning of the mol ratio 1:2.5 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
?c, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:0.8 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
embodiment 3
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, be added dropwise to 10ml hydrochloric acid and 20ml titanium tetrachloride, generate titanium tetrachloride hydrochloric acid soln, with in 10% sodium hydroxide solution and titanium tetrachloride hydrochloric acid soln, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes chlorion with distilled water wash;
The metatitanic acid that chlorion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of the titanium tetrachloride of 20ml, titaniferous is 8.7g, in titanium: the ratio proportioning of the mol ratio 1:4 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
?c, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:1.5 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
embodiment 4
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, with 10% sodium hydroxide solution neutralisation of sulphuric acid titanium solution, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes sulfonium ion with distilled water wash;
The metatitanic acid that sulfonium ion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of 25g titanium sulfate, titaniferous is 5g, in titanium: the ratio proportioning of the mol ratio 1:3 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
C, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:1.0 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
embodiment 5
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, with 10% sodium hydroxide solution neutralisation of sulphuric acid titanium solution, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes sulfonium ion with distilled water wash;
The metatitanic acid that sulfonium ion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of 25g titanium sulfate, titaniferous is 5g, in titanium: the ratio proportioning of the mol ratio 1:2.5 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
C, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:0.8 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
embodiment 6
(1) preparation of metatitanic acid:
A, in the beaker of 1500ml, add the frozen water of 0 ℃ ~ 5 ℃ of 1000ml, under the stirring of electric mixer, add 25g titanium sulfate stirring and dissolving, with 10% sodium hydroxide solution neutralisation of sulphuric acid titanium solution, control solution temperature≤5 ℃, pH value 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of b, new precipitation, removes sulfonium ion with distilled water wash;
The metatitanic acid that sulfonium ion is removed in c, washing removes after part planar water with whizzer, can be used for acid-soluble chelating.
(2) preparation of Titanium Citrate inner complex:
The preparation of a, citric acid-metatitanic acid suspension mixed solution:
In the prepared metatitanic acid of 25g titanium sulfate, titaniferous is 5g, in titanium: the ratio proportioning of the mol ratio 1:3 of citric acid, 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 citric acid-metatitanic acid suspended mixture;
B, microwave hot melt chelating technique synthesizing citric acid titanium:
Citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, with cabinet type microwave stove hot melt chelating at the temperature of 100 ℃ ~ 120 ℃ of 2450MHz frequency 1000W, reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, is diluted with distilled water into Titanium Citrate saturated solution during in hot melt state at glue.
(3) prepare organic titanium-the plant method of vinegar ammonium salt Multifunctional organic fertilizer by the technique of saltouing:
A, alkalescence are planted the preparation of vinegar ammonium salt compound:
To plant vinegar (containing wooden vinegar, bamboo vinegar, careless vinegar), to regulate pH with volatile salt or solution of ammonium hydroxide be 8.0 ~ 12.0, and clarification filtration is removed the materials such as tar, benzopyrene, and filtrate is that alkalescence is planted vinegar ammonium salt compound;
B, acid Titanium Citrate-the plant preparation of vinegar ammonium salt compound:
Titanium Citrate saturated solution is regulated to pH to 1.5 ~ 2.5 with the vinegar ammonium salt compound of planting of alkalescence, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt compound
C, organic titanium-the plant preparation of vinegar ammonium salt compound multifunctional organic fertilizer:
By the Titanium Citrate of leather hard-planting vinegar ammonium salt compound mixes by the part by weight of 1.0:1.5 with Carbon Dioxide ammonium, finally controlling its pH is 5.5 ~ 6.5, dries and make organic titanium-plant vinegar ammonium salt compound Multifunctional organic fertilizer in the baking oven of 60 ℃ ± 5 ℃.
Be more than embodiments 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 (1)
1. prepare organic titanium-plant a method for vinegar ammonium salt fertilizer by the technique of saltouing, it is characterized in that:
A, with in alkali and the frozen water solution of titanium salt prepare that one is not chloride, sulfonium ion, can be dissolved in the new precipitation metatitanic acid of citric acid; Described uses in alkali and the frozen water solution of titanium salt, the new precipitation metatitanic acid of preparation, according to the following steps preparation:
A-1, the vitriol of the muriate of titanium or titanium is dissolved among 0-5 ℃ of frozen water, with 10% sodium hydroxide solution neutralization, controlling pH is 7.0 ~ 8.0, makes metatitanic acid Precipitation in the cold water of≤5 ℃;
The metatitanic acid of a-2, new precipitation, removes chlorion or sulfonium ion with distilled water wash;
The new precipitation metatitanic acid that chlorion or sulfonium ion are removed in a-3, washing removes after part planar water with whizzer, can be used for acid-soluble chelating;
B, with not chloride, sulfonium ion, can be dissolved in the new precipitation metatitanic acid of citric acid, the muriate of instead of titanium, vitriol are as the raw material of the Titanium Citrate of synthetic not chloride, sulfonium ion;
C, not chloride, the sulfonium ion of use, the new precipitation metatitanic acid that can be dissolved in citric acid is titanium source, take citric acid as acid-soluble dose, sequestrant, uses microwave hot melt chelating technique to synthesize Titanium Citrate not chloride, sulfonium ion; Described uses microwave hot melt chelating technique according to the following steps:
The preparation of c-1, citric acid-metatitanic acid suspension mixed solution: in titanium: mol ratio 1:3, the 1:2.5 of citric acid or the ratio proportioning of 1:4, add Citric acid monohydrate Food grade crystallization powder at metatitanic acid, be stirred in the planar water that solid citric acid is dissolved in metatitanic acid with electric mixer, form citric acid-metatitanic acid suspension mixed solution;
C-2, microwave hot melt chelating technique synthesizing citric acid titanium: citric acid-metatitanic acid suspension mixed solution is placed in special disc type teflon resin reaction vessel, use operating frequency 2450MHz, the cabinet type microwave stove of microwave power 1000W is hot melt chelating at the temperature of 100 ℃ ~ 120 ℃, and reaction end is that milky suspension mixed solution becomes water white glue;
The preparation of c-3, Titanium Citrate saturated solution:
The Titanium Citrate glue that microwave hot melt chelating is made, during also in hot melt state, is diluted with distilled water into Titanium Citrate saturated solution at glue;
D, by Titanium Citrate for saturated solution the vinegar ammonium salt salting out of planting of pH8.0 ~ 12.0 prepare organic titanium-plant vinegar ammonium salt Multifunctional organic fertilizer; Described Titanium Citrate for saturated solution pH8.0 ~ 12.0 plant vinegar ammonium salt salting out technique according to the following steps:
The preparation of planting vinegar ammonium salt of d-1, pH8.0 ~ 12.0:
To plant vinegar volatile salt or solution of ammonium hydroxide, to regulate pH be 8.0 ~ 12.0, and clarification filtration is removed tar, benzopyrene material, and what filtrate was pH8.0 ~ 12.0 plants vinegar ammonium salt;
D-2, acid Titanium Citrate-the plant preparation of vinegar ammonium salt:
By Titanium Citrate for saturated solution pH8.0 ~ 12.0 plant vinegar ammonium salt regulate pH to 1.5 ~ 2.5, make Titanium Citrate and plant vinegar ammonium salt compound formation gel object and separate out, in≤25 ℃ of room temperatures, ageing is after 24 hours, remove surface adsorption water at 60 ℃ of hot blasts, form and be the acid Titanium Citrate of leather hard-the plant composite salt of vinegar ammonium salt;
D-3, organic titanium-the plant preparation of vinegar ammonium salt multifunctional organic fertilizer:
By the acid Titanium Citrate of leather hard-planting vinegar ammonium salt mixes by the part by weight of 1.0:0.8 or 1.0:1.0 or 1.0:1.5 with Carbon Dioxide ammonium, final its pH of control is 5.5 ~ 6.5, in the baking oven of 60 ℃ ± 5 ℃, dry, make organic titanium-plant vinegar ammonium salt Multifunctional organic fertilizer.
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| CN109612870B (en) * | 2018-01-25 | 2021-06-15 | 浙江农林大学 | Method for conveniently measuring total organic matter and moisture content of plant vinegar |
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