A method of obtaining a pigment of titanium dioxide from titanium containing waste
(57) Abstract:The invention relates to a method for producing pigmentary titanium dioxide from titanium containing waste, which can be used in the manufacture of paints and as a component to create white. The invention consists in the interaction of such materials with concentrated hydrochloric acid density 1,145-is 1.175 g/cm3when the ratio of T: W 2: 7 in the calculation of the titanium to form a solution, which is diluted with double amount of water, and then treated with half the amount of ammonium hydroxide solution with mass fraction of 25%, then heated to boiling, defend, produce three decanting sludge, the sludge is dried at 60 to 90oC. This method allows you to get the product from waste. table 4. The invention relates to inorganic chemistry and metallurgy of titanium, in particular a process for the production of titanium dioxide from titanium containing waste (titanium chips, scraps, etc.,) for the subsequent production of titanium pigment for paint and varnish industries.A method of obtaining titanium dioxide (white E. F., Raskin I... Chemistry and technology of pigments. L.: Chemistry, 1974, S. 148-152), to the C, chlorination in the environment of molten chlorides (pages 148-149), cleaned from impurities (Al, V, Si) (page 150), obtaining TiCl4the hydrolysis of aqueous solutions (page 151). Vapor-phase hydrolysis proceeds manual (page 152); to reduce heating of the aqueous solution of TiCl4apply diluted HCl, which eliminates premature hydrolysis (page 151). During annealing of the hydrolysis product with the addition of mineralizers receive TiO2where 90% of the particles less than 1 micron. However, this TiO2has low resistance (page 152).The closest technical level and the achieved result is a method of obtaining titanium dioxide from ilmenite ore (the Method of obtaining titanium dioxide from ilmenite ore. Application 2405271, Germany/Sergey A. Berkovich , Oakvili, Outario (Kanada). N 2405271; Publ. 8.02.79, MCI CO G 23/06 (Inventions in the USSR and abroad. Inorganic chemistry. 1979, No. 6, V. 49, S. 14)).The feedstock is treated with concentrated hydrochloric acid. Requires precise dosing of the quantity of hydrochloric acid for the actions of its iron (III), iron (II) and titanium.This method has a low technical level, due to the necessity of transfer of iron (III) iron (II) using a reducing agent. Receiving the acessa, which generally leads to a reduction in the efficiency of the applied method.The disadvantages discussed above of technological processes of production of titanium dioxide determine the relevance of the solution is the development of a more perfect way to retrieve it.The technical result of the proposed method is to obtain pigment titanium dioxide in the process of interaction of such waste with hydrochloric acid, further diluting the resulting solution double the volume of water to accelerate the hydrolysis of TiCl4and further processing the resulting precipitate is half the volume of ammonium hydroxide solution with mass fraction of 25% for the best precipitation of titanium hydroxide, subsequent boiling of the solution to create more titanium hydroxide, decanting after sedimentation, filtration and drying at 60 to 90oC. This method allows you to create a new technology of production of titanium dioxide.The inventive method of obtaining titanium dioxide does not require complex hardware design, the use of any reducing agents for iron and provides a relatively high yield.Specified technical resurrected ammonium allows you to allocate a greater amount of titanium ions in the precipitate.Creating a new method of obtaining titanium dioxide on the basis of such wastes, when these actions, allows to obtain titanium dioxide rutile modification, with a particle size of 25-30 microns.With respect to T:W - 1:2 hydrochloric acid and 1:0.5 for solution of ammonium hydroxide at the boiling yield is 80-90%.The essence of the invention lies in the fact that such waste chips or scraps from processing of titanium and its alloys (W-00 W-20) with a titanium content of not less than 85% (T) is treated with concentrated hydrochloric acid (G) density 1,145-is 1.175 g/cm3. The resulting solution was diluted with double the volume of water to accelerate the hydrolysis titanoboa acids, then the residue is treated with half the amount of ammonium hydroxide solution with mass fraction of 25% for the best precipitation of titanium hydroxide, to produce boiling of the solution for the formation of titanium dioxide, decantation after settling, filtration. The precipitate is dried at a temperature of 60-90oC.The invention relates to the chemistry and technology of pigments based on titanium dioxide and can be used for a wide production paint promyshlennosti waste.The effectiveness of the proposed method and the proposed technological regime to achieve this goal is illustrated by the following examples.Example 1. Take such waste (crushed chips titanium alloy VT-I-O, the chemical composition of which is given in the table. 1), and add hydrochloric acid in the ratio 2:7 in the calculation contained in the sample titanium.Produce stirring. The obtained dark blue solution was diluted with double the volume of water to enhance the hydrolysis of the formed titanium salts (see table. 2).The residue is treated with half the amount of ammonium hydroxide solution with mass fraction of 25% for the best precipitation of titanium hydroxide (see tab. 3).The solution was heated to boiling, boil for 20 minutes to destroy fragile titanium hydroxide. Make 3 meals a day decanting after settling. A precipitate of titanium dioxide white. Filtered, then dried at 60 to 90oC. the result is titanium dioxide rutile modification with a particle size of 25-75 microns.Specific data according to the obtained results are shown in table. 2, 3.The smaller the ratio of T:W 2:5 in the experiments on the dissolution Titania the number of T:W 2:10 also does not allow to obtain the optimal size of the particles, also reduced the yield of 50-70%.The ratio of T: W 2:7 allows to obtain the optimal size of the particles (25:30 μm) and higher yield (50-90%).The use of smaller amounts of water does not allow you to bring the hydrolysis of titanium containing salt to produce the desired amount of titanium dioxide, increase the size of the particles (40-70 μm) and low yield (30-70%). More water dilutes the solution, without impacting on the reduction of particle size (30-60 µm) and increased yield (40-70%).We offer you the best option with a ratio of T:W 2:7 and if a double dilution water allows to obtain smaller particles (25-30 microns) and greater yield.An important role in obtaining pigment plays and the use of ammonium hydroxide solution (PL. 3).Greater volumetric ratio of solution : ammonium hydroxide solution gives larger sediment particles (40-60 μm) and low yield (60-80%).Small volumetric ratio of these components gives smaller particles (30-70 microns) and greater variation in percentage of yield.Sludge treatment half rotovoi products (70-90%).Example 2. In example 1 to produce the processing of such waste alloy W-20 (chemical composition shown in table. 4) hydrochloric acid.After two-fold dilution with water the resulting solution make processing the obtained precipitate with ammonium hydroxide solution as in example 1. The solution was heated to boiling, boil for 20 minutes Then produce decantation after settling, filtration and drying at 60 to 90oC. the result is titanium dioxide rutile modification with a particle size of 25-75 microns.The proposed method of obtaining titanium dioxide as a component included in paint products, such waste was first carried out by the authors, has a scientific novelty and is, according to the authors, the basis for issuance of a certificate of invention.For the claimed invention in the form as it is characterized in the claims, confirmed the possibility of its implementation using the above-described manufacturing methods, conditions and modes of its implementation.The method of producing titanium dioxide from titanium containing wastes as proposed in the present invention, it provides an implementation of C is umyshlenna applicability. A method of obtaining a pigment titanium dioxide rutile modification by interaction of such materials with concentrated hydrochloric acid density 1,145 - is 1.175 g/cm3when the ratio of T : W 2 : 7 in the calculation of the titanium to form a solution, wherein the titanium containing solution is diluted with double amount of water, and then treated with half the amount of ammonium hydroxide solution with mass fraction of 25%, heated to boiling, defend, produce three decanting the precipitate and drying at 60 - 90oC.
FIELD: mining industry.
SUBSTANCE: perovskite concentrate, which can be used for manufacture of pigment titanium dioxide for paints, paper, enamels, and plastics, is processed as follows. 1 kg of concentrate is treated under atmosphere conditions with concentrated HCl at 90-100оС for 10 to 20 h to solubilize 75-85% of titanium, radioactive, and other acid-soluble components. Concentration of HCl is then lowered by diluting it with 1-5% HCl solution until TiO2 concentration 50-100 g/L. Thermohydrolysis of solution at 100-105оС accompanied by distilling away HCl leads to residual HCl concentration 20-100 g/L. Distilled HCl is sent to processing of perovskite concentrate. Titanium-containing precipitate is separated from mother liquor, washed first with 15-37% HCl solution and then with water to pH 3. Washed precipitate is treated with aluminum acid phosphate with pH 2-4. Aluminum acid phosphate uptake (on conversion to Al2O3) constitutes 0.5 to 5.0% content of TiO2. Treated precipitate is separated and calcined at 850-870оС to give pigment titanium dioxide. From mother liquor (after separation of Ti-containing precipitate), radioactive components are isolated by 4-6-step extraction with tributyl phosphate. Organic phase-to-water phase ratio is (1.5-2.0):1. Degree of titanium recovery is at least 98%, whiteness at least 96.5 conv. units, brightening power 1650-1800 conv. units, spreading capacity 38.0-40.0 g/m2, oil capacity 25-27 g/100 g pigment. Yield of pigment TiO2 is 95.7-98.0%. Amount of radioactive precipitate does not exceed 0.06 kg.
EFFECT: optimized perovskite concentrate processing parameters.
12 cl, 4 ex
FIELD: catalyst preparation methods.
SUBSTANCE: catalyst containing crystalline anatase phase in amount at least 30% and nickel in amount 0.5 to 2% has porous structure with mean pore diameter 2 to 16 nm and specific surface at least 70 m2/g. When used to catalyze photochemical reaction of isolation of hydrogen from water-alcohol mixtures, it provides quantum yield of reaction 0.09-0.13. Preparation of titanium dioxide-based mesoporous material comprises adding titanium tetraalkoxide precursor and organic-nature template to aqueous-organic solvent, ageing reaction mixture to complete formation of spatial structure therefrom through consecutive sol and gel formation stages, separating reaction product, and processing it to remove template. Invention is characterized by that water-alcohol derivative contains no more than 7% water and template consists of at least one ligand selected from group of macrocyclic compounds, in particular oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or complexes of indicated macrocyclic compounds with metal ions selected from group of alkali metals or alkali-earth metal metals, or f-metals consisting, in particular, of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, and cerium used in amounts from 0.001 to 0.2 mole per 1 mole precursor. Sol is formed by stirring reaction mixture at temperature not higher than 35°C. Once formation of spaced structure completed, mixture is held at the same temperature in open vessel to allow free access of water steam and, when template is removed from the mixture, mixture is first treated with nickel salt solution and then with alkali metal borohydride solution until metallic nickel is formed.
EFFECT: increased sorption and photocatalytic properties of catalyst and enabled reproducibility of its property complex.
7 cl, 68 ex
FIELD: production of inorganic compounds.
SUBSTANCE: invention relates to production of titanium dioxide using chloride process , which is employed in radio-electronic industry to manufacture multiple types of composite ceramic materials and also employed as starting material from production of metal titanates. Synthesis of titanium dioxide having high-purity rutile modification involves thermal hydrolysis of titanium tetrachloride solution with concentration 60-70 g/dm3 TiO2 and containing titanium nuclei and polyacrylamide in amount 100-120 g per 1 kg TiO2 in initial solution. Hydrolysis is continued for 1.5-2 h, after which resulting titanium hydroxide is separated from filtrate, treated with 2-3% oxalic acid solution, then with distilled water, dried and calcined at 550-650°C.
EFFECT: reduced hydrolysis process time, accelerated filtration, reduced consumption of power on heat treatment of resulting precipitate, and reduced negative environmental impact.
1 dwg, 1 tbl, 11 ex
FIELD: chemical industry; methods of production of the catalytic agents of photochemical reaction and sorbents-catalysts of heterogeneous photochemical processes.
SUBSTANCE: the invention is pertaining to the field of chemical industry and may be used in production of the catalytic agents of photochemical reaction and the sorbents-catalysts of heterogeneous photochemical processes of oxidizing of the harmful organic compounds. The precursor in the form of titanium tetraalcoxide and template of the organic nature are introduced into the water-organic dissolvent. The mixture of the reactants is intermixed up to formation of the sol and is kept till the final formation of the special structure. The gained reaction product is separated and treated removal of the template using calcifying or the extraction by the alcohol after preliminary hydrothermal treatment. In preferential version of the invention the water-alcohol dissolvent is additionally introduced with the salt of lanthanum. The invention allows to produce the reproducible sorbent-photocatalyst with the high attributes: the crystal phase of the anatase - no less than 30 mass %, a mean diameter of the pores - 2-16 nanometers, the specific surface - no less than 70 m2/g, does not contain the non-desirable impurities.
EFFECT: the invention ensures production of the reproducible sorbent-photocatalyst with the high attributes of thee crystal phase of the anatase, the effective diameter of the pores, the specific surface at absence of the non-desirable impurities.
7 cl, 68 ex
FIELD: sulfate method of production of titanium dioxide from titanium-containing material.
SUBSTANCE: proposed method includes leaching-out of titanium-containing materials with sulfuric acid solution for obtaining lye, deposition of ferrous sulfate from lye, extraction of titanyl sulfate from lye by means of solvent, hydrolysis of extracted titanyl sulfate followed by roasting of solid phase obtained at hydrolysis stage. At least part of raffinate from extraction stage is used as part of leaching solution at initial leaching-out stage.
EFFECT: high degree of purity of titanium dioxide; reduced amount of acid; reduced power requirements.
20 cl, 2 dwg, 9 tbl, 13 ex
FIELD: industrial inorganic synthesis.
SUBSTANCE: invention relates to a sulfate process for titanium dioxide production from titanium-containing material. Process comprises leaching starting material to produce leaching lye containing acidic solution of titanyl sulfate, which is separated from the lye and then hydrolyzed to form hydrated titanium oxides further fired to produce desired titanium dioxide. Hydrolysis step is properly controlled to form hydrated titanium oxides with desired particle size distribution.
EFFECT: enhanced commercial process efficiency.
29 cl, 2 dwg, 9 tbl, 13 ex
FIELD: sulfate method of production of titanium dioxide from titanium-containing material.
SUBSTANCE: proposed method includes leaching-out of titanium-containing material by sulfuric acid solution, thus obtaining lye containing titanyl sulfate, separation of titanyl sulfate from lye, hydrolysis of titanyl sulfate for forming solid phase containing hydrated titanium oxides followed by roasting the solid phase obtained at the hydrolysis stage. Proposed method includes additional leaching-out stage for leaching-out of solid phase remaining after leaching-out of initial titanium-containing material by means of solution containing sulfuric acid.
EFFECT: enhanced efficiency of process.
24 cl, 2 dwg, 9 tbl, 13 ex
FIELD: light-sensitive catalysts.
SUBSTANCE: invention is directed to preparation of titanium dioxide-based catalysts for photocatalytic treatment of water and air polluted with organics and pathogenic floras. Invention provides a method comprising preparation of reaction solution containing mineral titanium salt, fluoride ion, and activation additive; hydrolysis of mineral titanium salt to form precipitate; washing and calcination of the precipitate. Activation additive utilized is ammonium hydroxide in 5-10% stoichiometric excess. Hydrolysis is conducted for 0.25-0.5 h at pH 10-13, while concentration of fluoride ion in reaction solution is maintained at least 5 wt % based on TiO2. Mineral titanium salt is selected from titanium tetrachloride, titanyl sulfate, and titanium-ammonium chloride.
EFFECT: increased degree of recovering titanium dioxide into target product, increased heat resistance and specific surface of photocatalytic anatase-modification titanium, and reduced process duration.
6 cl, 1 tbl, 14 ex