HU195455B - Process for producing additives of micronutrient spray containing titanium-complex for improving soil - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to the preparation of a trace element containing tritium-containing titanium complex directly from rutile with alkaline excavation. The process is characterized in that 1 part by weight of rutile ore, milled to 50-150 micrometers, is excreted in bulk with 4-5 parts by weight of potassium hydroxide, the resulting metatitanate is ground to a particle size of 1 to 2 mm and then 25 to 35 parts by weight at up to 50 ° C. the solution is dissolved in water, the solution is separated, the residue is dissolved in 3 to 4 parts by weight of 1: 1 dilute sulfuric acid, the titanium (IV) sulphate solution is slowly neutralized with ammonium hydroxide solution at 40 ° C and the titanium (IV) hydroxide precipitate separated from the liquid, washed and then mixed in a solid state with 1.2-1.6 parts by weight of citric and / or tartaric acid, followed by 0.2-0.3 parts by weight of copper sulphate with ammonium hydroxide, after neutralization and neutralization. ammonium sulfate complex is added. -1-

Description

FIELD OF THE INVENTION The present invention relates to the production of a soil-based titanium complex containing trace element spray directly from rutile minerals.

The product obtained by the process according to the invention can be used primarily as a spray additive for foliar fertilization and can also be mixed with solid NPK fertilizers.

There are few references in the literature to the water-soluble compounds of titanium and to the increase of crop yield in agriculture. In the available literature, we found only one domestic work on titanium by dr. White and dr. For relevant experiments by Paizs in "Trace Elements in Agriculture 1982".

They have demonstrated, through their many years of experimentation, the very beneficial effect of titanium on crop plants. The titanium-based spray has been used to multiply apple, grape, tomato, sugar beet, and alfalfa and soy have also been tested, with good results.

It is interesting that the literature on modern agriculture practically does not provide data on titanium. According to an older literature reference (Károly Than), most of the fields contain about 0.5% of titanium oxide but are practically insoluble. Most plants also contain 0.3% of titanium oxide, can be detected in bone and meat.

The biological titanium binding thus appears to be justified in plant and animal terms.

dr. White and dr. The main ingredient of Paizs sprayer is titanium tetrachloride and ascorbic acid.

The known processes for the preparation of tetravalent titanium compounds, since they are easily and even water-soluble in contrast to trivalent titanium compounds, start from pure titanium metal, which makes the processes very complicated and costly since chlorination, sulfuric acid dissolution, neutralization, etc. stairs followed.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for the preparation of a quaternary titanium complex starting from the ore directly and without purification containing all the titanium in a stable water-soluble form. Thus, the resulting soil-based titanium complex trace element additive is completely water-soluble and stable, and in case of improper storage and treatment (heat effect) there is no conversion to the insoluble Ti (III) compound.

The rutile mineral used in the process of the present invention contains about 94 to 95% by weight of titanium oxide, containing from 1 to 2% by weight of iron oxide, 1.5 to 2% by weight of silica and other trace elements, Al ₂ O ₃ , MoO ₃ . 0.5% by volume. The impurities next to the titanium oxide, after being at most inert to the plants, are left in the system. After the concentration of titanium in the spray agent is approx. 1 gram, 4, so there is only one thousand percent contamination with titanium.

Our process is summarized in that a high purity can be produced in the metal phase TiO ₂ -containing omitting dúsítmányokból ores or the water-soluble titanium complex.

It has been found that the titanium (IV) complex, which is a complex of the metal with an oxide of organic oxide, preferably citrate and / or tartrate, retains its total water solubility when stabilized by the addition of a copper complex at a concentration of ten% by weight of the titanium compound. This copper complex is copper ammonium sulfate.

It has further been found that the tetravalent titanium complex, which is citrate and / or 'tartrate and completely water soluble, can be prepared directly from the ore without purification and metal conversion.

According to the present invention, 1 part by weight of rutile ore ground to 50-150 micrometre particle size is digested with 4-5 parts by weight of potassium hydroxide. separating the solution, dissolving the residue in 3-4 parts by weight of a 1: 1 diluent in sulfuric acid, slowly removing the resulting titanium (IV) sulfate solution with ammonium hydroxide solution at a temperature of not more than 40 ° C, separating the titanium (IV) hydroxide precipitate , washed and then mixed in a solid state with 1.2 to 1.6 parts by weight of citric and / or tartaric acid, and after cooling and neutralization, 0.2 to 0.3 parts by weight of crystalline water containing copper ammonium sulphate complex is prepared from ammonium hydroxide.

In our experiments potassium hydroxide was used to reveal the titanium dioxide content of rutile mineral. Potassium hydroxide was used for digestion instead of cheaper sodium hydroxide because eventually, potassium as potassium sulfate is recycled as a by-product for fertilization.

The reaction equation for the digestion only applies to titanium dioxide.

TiO ₂

It has been found that two moles of potassium hydroxide in the reaction equation are not sufficient for the smooth derivatization of titanium oxide digestion. We found that approx. four times as much potassium hydroxide is needed to digest the titanium. According to the reaction equation, potassium metatitanate is formed. Potassium metatitanate is partially soluble in water depending on temperature. According to the developed technologies the dissolution rate is approx. 8-10%.

Titanium is one of the changing elements. Two acids can be derived from titanium dioxide or titanium anhydride: the orthotonic acid: H. TiCT, and the metatitanoic acid: H ₂ TiO ₃ . The composition of the acids is not strictly expressed in the above formulas, even if they contain water, the amount of which depends on the method of preparation. The orthotenic acid H ₄ TiO _{4 is a} white precipitate formed when the cooled acidic solution of the titanates of the alkali metals (Na, K) is carefully mixed with alkalis. The white precipitate is readily soluble in sulfuric acid. Metatitanoic acid H, TiO _{3 is} formed when the diluted sulfuric acid olcate of orthotitanoic acid is kept near its boiling point; the precipitate formed is so-called insoluble in kensic acid.

The essence of our procedure is the determination and recognition of factors influencing the solubility and insolubility of titanium acids. This knowledge was also applied to the processing of rutile ore. As a result, the production of soluble titanium compounds is superseded so that the resulting orthotitanium form does not go into the metatitane form, since the latter compound is not

195,455 is desirable. Therefore, the maximum working temperature should not be higher than 45 -50 ° C.

The rutile ore is disintegrated in the form of a 50 to 150 micrometre particle size powder, which is carried out at 450 to 500 ° C using at least three, preferably four to five times, potassium hydroxide in nickel or high alloy steel.

The digester is electrically heated so it is easy to control. Place the potassium hydroxide in the nickel crucible in a heated oven, and at a temperature of 500 ° C, the potassium hydroxide is placed in the oven for approx. Melt in 10 to 15 minutes. The rutile is then added continuously to the molten potassium hydroxide while stirring. The duration of the excavation is 30-35 minutes. After this time, the slurry is poured onto an iron plate to facilitate further work. Due to the good viscosity of the material, we can pour it over a large surface. Instead of a cast iron plate, a water-cooled double-walled chill can be used - providing more controllable conditions. The cooled material is approx. Thickness 4-5 mm. Further, the cooled material is suitable for approx. Grind to a mesh size of 1-2 mm. The powder is then added in portions to a specified amount of tap water with constant mixing. The addition of the substance to water is controlled so that the temperature of the water does not rise above 50 ° C.

Reconstitute the solute with ca. It is advisable to settle for 10-12 hours. The solution containing the strong alkali is separated from the precipitate by decantation. The decanted alkaline solution contains the unused portion of the excess potassium hydroxide and the resulting potassium metatitanate approximately. 8-10%. Sulfuric acid was added to the solution containing the separated titanium and potassium hydroxide under strong cooling until pH = 2. Ammonium hydroxide is then added to the dilute weakly acidic solution at room temperature to bind excess sulfuric acid.

The reaction equations for the processes are as follows:

KOH + H SO ₄ = K SO ₄ + 2 Η O (2)

Ti (SO ₄ ) ₂ MNH ₄ O H = Ti (O H) _{4 +} 2 (NH ₄ ) ₂ SO ₄ (3)

The precipitate that remains after decantation consists of potassium metatanate and potassium hydroxide. This max. At 50 ° C, dissolve in 50% sulfuric acid in a refrigerated apparatus. After about 1 hour of dissolution, the solution (pH = 2) is filtered from the remaining silica and the unexposed rutile. After suitable dilution, the titanium-filtered solution is max. It is made alkaline with ammonium hydroxide at 40 ° C to pH 7, whereupon titanium is precipitated in the form of titanium hydroxide. The titanium hydroxide formed from the solution and the precipitate was filtered through a common filter. The potassium sulphate tube passes through the filtrate into ammonium sulphate. After washing the precipitate with water, the titanium hydroxide remains on the filter. The potassium sulphate and ammonium sulphate-containing filtrate can be recovered by evaporation in solid form or passed to the foliar manure without evaporation. The washed precipitate consists mainly of titanium hydroxide and is converted to the titanium complex with citric acid and sulfuric acid.

According to our experience, the titanium complex formed with citric acid or tartaric acid decomposes and in one to three weeks in the aqueous solution pencil fungi appear to be uneasy.

To prevent this, we add a copper complex to the titanium complex.

Copper causes the appearance and growth of molds.

Example: 25 I approx. Preparation of 10 g of titanium and copper containing titanium solution

1. Weigh 2 kg of potassium hydroxide and 0.5 kg of rutile mineral into a three-liter nickel crucible. The digestion temperature is 480-500 ° C. Exploration time 35 minutes.

2. After the material has been uncovered, the melt is poured onto an iron plate and after it has cooled, approx. Grind to 1-2 rnnr.

3. Add the cooled meal to 14 liters of tap water with constant stirring, ensuring that the temperature of the solution does not exceed 50 ° C. After standing for about 12 hours, the clear solution is separated from the precipitate by decantation, the decanted solution being separated by ca. 9.3 liters. This solution contains a portion of the potassium metatanate in solution and the amount of potassium hydroxide not used in digestion. The unused potassium hydroxide is neutralized with 50 liters of 1: 1 sulfuric acid under constant stirring at 50 ° C.

4. The precipitate that remains after decanting contains most of the potassium metatitanate formed, using 2 liters of 1: 1 sulfuric acid to convert it to titanium sulfate. After 35-40 minutes, the solution is made up to 15 liters with water and, after dissolution, filtered.

5. Mix the two solutions obtained by decantation and neutralized by precipitation with sulfuric acid and remaining after decantation and filtering with 2.3 L of 0.91 NH ₄ OH and titrating the solution as titanium. the hydroxide is separated off. The titanium hydroxide was filtered through a vacuum filter and the precipitate was washed with water at room temperature 3-4 times.

The filtered precipitate mainly contains titanium hydroxide and traces of impurities. The filtrate contains potassium in the form of potassium sulphate and ammonia in the form of ammonium sulphate. The filtered and washed titanium hydroxide precipitate was mixed with 0.75 kg solid citric acid. Citric acid can be replaced, in whole or in part, by boric acid. Thorough mixing and approx. After resting for 20-25 minutes, another 0.5 L of 1: 1 dilute sulfuric acid is added and after 4-5 hours the solution is filtered. Further, the filtered solution is neutralized with ammonium hydroxide besides litmus paper indicator. To the neutralized titanium solution was added an additional 100 g of water-containing copper sulfate with NHOH; After adding stabilized complex - (Cu, / 0H / ₂ SO ₄ ) followed by 200 cm ^{3 of} concentrated sulfuric acid, the solution is made up to 25 liters with clean water.

Material balance for the preparation of 100 liters of titanium complex solution:

Application: Formation: 1. Rutil 2 kg 1. 100 liters of titanium complex solution Ingredients: 2. Potassium hydroxide 8 kg Ti 9.68 g / l 3. Ammonium hydroxide 10 liters Cu 0.97 g / l 4. Sulfuric acid 7 kg H ₂ SO ₄ 14.50 g / l

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5. Citric acid 3 kg density 1.07 g / cm ³

6. Copper sulfate 0.4 kg 2. Q _? S0 ₄ * (NH ₄ ) ₂ S0 ₄ together

21.2 kg without water. EXAMPLES OF COMPARATIVE EFFECTS Example 2

In the Danube-Tisza Intercultural Area, Kecskemét area (Gold binding: K ^ = 37, humus = 1.11%, medium supply of main phosphorus and potassium) was sprayed three times at two-week intervals from July 1, according to the invention. solution of titanium in g / l. The experiment was repeated six times. The signal plant: 15 wine grapes of the stonecrop.

We evaluated the yield of 25 capital per plot.

Average yield of a productive capital, kg The average weight of 100 clusters is kg Sprayed capital 2.39 12.1 Non-sprayed capital 1.68 8.3 SZD _s % 0.5 3.5

The quality of the must resulting from the treatment is one of the following:

rint changed: Sugar content, Mm ₀ Acidity, q / 1 Sprayed capital 16.3 6.1 Non-sprayed capital 16.0 6.9 SzD ₅ % 0.1 0.8

Example 3

In the Kalocsa region (K ^ = 43, humus = 2.3, phosphorus medium, potassium medium supply), the following results were obtained on an average of 3 years. Spray with 500 l / ha of Example 1 spray before flowering and at the beginning of ripening.

Raw crop, q / ha

Sprayed parcels

Non - sprayed parcels

SzD _s 25%

Example 4

H ₂ cultivated with green peppers twice with the solution of Example 1 twice. April 25 and April We sprayed on 5th. Taking into account the yield of 90 m ² plot, the cumulative yield was as follows.

Cumulative yield, pcs / 90 m ² time sprayed parcel Not sprayed parcel April 10 780 730 May 10 2,200 2,000 June 10 7600 7,000 June 30 10500 10,000

Example 5

During canning tomato cultivation, the orchard of Nagykőrös was sprayed with the spray of Example 1 after the first flowering and then twice more at 2-week intervals. An average of five replicates gave the following results.

Average Out, q / ha Refrakdó Sprayed parcel 280 7.0 Not sprayed parcel 260 6.0 SZD _s % 15 0.7

A patent claim

Claims (1)

A patent claim A process for the preparation of a tritiated spray containing a titanium complex containing a soil substitute directly from rutile ore by digestion with potassium hydroxide, followed by By dissolving 35 metatitanates, characterized in that 1 part by weight of rutile ore, ground to 50-150 micrometres in size, is digested with 4-5 parts by weight of potassium hydroxide, the resulting metatitanate is ground to a particle size of 1-2 mm and then 25-35 parts by weight. Dissolve in water (C), separate and dissolve the residue in 3-4 parts by weight of dilute sulfuric acid (1: 1) and slowly neutralize the solution of titanium (IV) sulphate with ammonium hydroxide at 40 ° C. ) -hydroxide precipitate is separated from the liquid, washed and mixed in a solid state with 1.2-1.6 parts by weight of citric and / or tartaric acid, and after cooling and neutralization, 0.2-0.3 parts by weight of crystalline water containing copper sulphate is prepared with ammonium hydroxide. It is stabilized with 50 copper ammonium sulfate complexes.