Zircon concentrate processing method. RU patent 2450974.
|
Composition based on zirconium oxide, titanium oxide or mixed zirconium and titanium oxide, deposited on silicon oxide support, methods of producing said composition and use thereof as catalyst / 2448908 Invention can be used in inorganic chemistry. The catalytic composition contains at least one oxide on a support, which is based on zirconium oxide, titanium oxide or a mixed zirconium and titanium oxide, deposited on a silicon oxide-based support. After firing at 900°C for 4 hours, the oxide on the support has the form of particles deposited on a support and size of said particles is not greater than 5 nm if the oxide on the support is based on zirconium oxide, not greater than 10 nm if the oxide on the support is based on titanium oxide and not greater than 8 nm if the oxide on the support is based on a mixed zirconium and titanium oxide. After firing at 1000°C for 4 hours, particle size is not greater than 7 nm if the oxide on the support is based on zirconium oxide, not greater than 19 nm if the oxide on the support is based on titanium oxide and not greater than 10 nm if the oxide on the support is based on a mixed zirconium and titanium oxide. |
 Zirconium oxide and way of its production / 2442752invention refers to powdered zirconium oxide, way of its production and its application in fuel cells, notably for production of electrolyte substances for ceramic fuel cells. The powdered zirconium oxide containing up to 10 mole % of at least one metal oxide from the scandium, yttrium groups, the group of rare-earth elements and/or their mixtures is characterized by the extension density from 1.2 to 2.5 g/cm³ measured according to ASTM B 417. |
 Composition based on zirconium oxide, yttrium oxide and tungsten oxide, method of production and use as catalyst or catalyst support / 2440299Composition contains 1-20% yttrium oxide, 1-30% tungsten oxide and zirconium oxide - the rest. The specific surface area of the composition is at least equal to 20 m2/g after calcination for 4 hours at 900°C. |
 Zirconium hydroxide / 2434810Invention relates to chemistry and can be used in catalytic processes. Amorphous zirconium hydroxide has surface area of at least 300 m2/g, total pore volume of at least 0.70 cm3/g and average pore size from 5 nm to 15 nm. First, an aqueous solution containing sulphate anions and a zirconium salt with the ratio ZrC2:SO3 ranging from 1:0.40 to 1:0.52 are obtained. The solution is then cooled to temperature lower than 25°C. Alkali is then added to precipitate amorphous zirconium hydroxide which is then filtered and washed with water or alkali to remove residual sulphate and chloride. The washed residue undergoes thermal treatment at excess pressure of not less than 3 bars and dried. |
|
Method of producing mineral material using zirconium oxide grinding beads containing cerium oxide, obtained products and use thereof / 2432376 In order to obtain ground mineral material a) at least one mineral material which is optionally in form of aqueous suspension is taken, b) said material is ground, c) the ground material obtained at step (b) is optionally sieved and/or concentrated, d) the ground material obtained at step (b) or (c) is optionally dried. The grinding step (b) is carried out in the presence of zirconium oxide grinding beads containing cerium oxide, having cerium oxide content between 14 and 20% of the total weight of said beads, preferably between 15 and 18% of the total weight of said beads, and more preferably approximately 16% of the total weight of said beads. The average size of grains after sintering grains which form said beads with average diameter less than 1 mcm is preferably less than 0.5 mcm and more preferably less than 0.3 mcm. The obtained ground mineral material is in form of aqueous suspension, wherein the weight ratio ZrO2/CeO2 is equal to 4-6.5, preferably 4.6-5.7 and more preferably 5.3. |
|
Method of producing nanocrystalline powder of metal oxides / 2425803 Method involves production of metal hydroxides via reverse precipitation, drying and calcination. To prevent local change in pH of the solution of the precipitation agent, the reverse precipitation method involves ultrasonic treatment of the solution of metal salts in an atomising nozzle through which the said solution passes before reacting with the solution of the precipitation agent. The solution of metal salts undergoes ultrasonic treatment which enables to disperse the solution to droplets with size smaller than 1.0 mcm. |
|
Composition for making thin films based on system of double oxides of zirconium and zinc / 2411187 Invention relates to production of thin-film materials used in illumination, construction and electronics. The composition for making thin films based on a system of double oxides of zirconium and zinc contains the following components, wt %: zirconium oxochloride 4.0-8.6; zinc nitrate 3.8-7.6; pre-distilled and dried to 96 wt % ethyl alcohol - the rest. The film-forming solution of the said composition is deposited onto a substrate by centrifuging and subjected to step-by-step thermal treatment. |
 Method of obtaining nanodispersed metal oxides / 2407705Invention can be used in production of refractory ceramic matrices of composite materials and high-temperature coatings. A solution of β-diketonates of one or more metals with concentration of 1·10-3-1 mol/l in an organic solvent or mixture of solvents in the presence of an alcohol undergoes thermal treatment at 95-250 °C for 0.1-8 hours to obtain solutions of alkoxo-β-diketones of corresponding metals. Hydrolysis is then carried out at 15-95°C for 0.05-240 hours with hydrolysing solutions, which are either water, organic solvents or mixture of solvents containing water or a mixture of organic solvents and water to form transparent gels. Further, the gels are dried at 15-250°C and pressure of 1·10-4-1 atm until constant weight. Thermal treatment of xerogels to form nanocrystalline metal oxides is carried out in an oxygen-containing atmosphere at 350-750°C for 0.5-24 hours. |
|
Zirconium oxide- and cerium oxide based composition with increased reducing power and stable specific surface, method of its producing and using for exhaust gas treatment / 2407584 Invention can be used for exhaust gas after burning in ICE. Aqueous mix containing zirconium and cesium and one of lanthanides, ether than cerium, and yttrium is obtained. Obtained mix is heated to 100 °C to produce precipitate in the form of suspension in reaction medium which is brought up to the level of alkaline pH. First, added is additive selected from anion surfactants, nonionic surfactants, polyethylene glycols, carbonic acids and their salts, and surfactants of the type of carboxymethylated oxethylates of fat alcohols is added to produced medium and, then precipitate is separated. In compliance with another version, first, precipitate is liberated from reaction medium and, thereafter, aforesaid additive is added to precipitate. Precipitate is calcinated in atmosphere of inert gas or in vacuum at 900 °C and, then in oxidising atmosphere at 600 °C. Produced composition contains cerium oxide in amount of not over 50 wt %. Reduction degree after calcination in atmosphere of air at 600 °C makes at least 95 %, while specific surface after calcination at 1100 °C for 4 h makes at least 15 m2/g. |
|
Composition for making thin film based on system of double oxides of zirconium and titanium / 2404923 Invention can be used in electronic engineering, lighting and construction industry. The composition is obtained by preparing a film-forming solution based on 96 wt % ethyl alcohol, 6.68-10.02 wt % crystalline hydrate of zirconium oxochloride and 3.34-5.01 wt % tetraethoxytitanium. The obtained solution is deposited onto a substrate and thermally treated. |
|
Heat-resistant coating (options) and article containing it / 2266352 Invention relates to heat-resistant coatings made of ceramic materials and to metallic articles having such type coatings, said articles being effectively applicable in gas-turbine engines. Coatings contain at least one oxide and another oxide selected from zirconium dioxide, cerium oxide, and hafnium oxide, said at least one oxide having general formula A2O3 wherein A is selected from group consisting of La, Pr, Nd, Sm, Eu, Tb, In, Sc, Y, Dy. Ho, Er, Tm, Yb, Lu, and mixtures thereof. Metallic articles are therefore constituted by metal substrate and above defined coating. |
 Zirconium oxide-based mesoporous material and a method for preparation thereof / 2280504Invention provides zirconium oxide-based mesoporous material with following composition: SO42-/ZrO2-EOx, where E represents group III or IV element, x = 1.5 or 2, content of sulfate ions 0.1-10 wt %, and molar ratio ZrO2/EOx = 1:(0.4-1.0), said material having specific surface 300-800 m2/g with total pore volume 0.3 to 0.8 cm3/g. Method involves preparation of composition consisted of hydrated zirconium sulfate, sulfate ions, and water via precipitation of hydrated oxide phase from soluble zirconium or zirconyl salts followed by hydrothermal reprecipitation in presence of cationic surfactants to form mesoporous structure, which is then stabilized by treatment with group III or IV element compounds taken is additive proportions to mesoporous crystalline structure. |
 Material for production of the catalyst carrier with the high oxygen capacity (versions)and the method of its manufacture / 2286209The invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures. |
 Method of preparing mixed zirconium-cerium-based oxides / 2311956Invention provides mixed zirconium-cerium-based oxides characterized by thermal resistance and are suitable as promoters or catalyst supports in exhausted gas treatment system of automobiles. Preparation protein comprises reacting alkali with aqueous solution of soluble zirconium salt containing 0.42-07 mole sulfate anions per one mole zirconium cations. Reaction is conducted at temperature not higher than 50°C in presence of soluble cerium salt to form mixed cerium/zirconium hydroxide, which is then calcined to produce mixed oxide. |
|
Method of brazilite concentrate purification / 2343117 Mixing of brazilite concentrate with concentrated sulphuric acid, its sulphatisation with heating, formation of pulp by processing sulphatisation product with liquid reagent, separating of brazilite from pulp are carried out; mixing of brazilite concentrate and suphuric acid is carried out with weight ratio of concentrate and acid respectively 1:(0.165-0.195) and concentration of sulphuric acid not less than 81 wt %, before sulphatisation mixture of brazilite concentrate and sulpuric acid is pressed into briquettes or subjected to extrusion with further division of extrusion product into briquettes, pressing or extrusion of mixture is carried out at pressure 49·105÷7843·104 N/m2, and sulphatisation of briquettes is carried out at temperature 180-200°C. |
|
Composition for obtaining thin film based on system of double zirconium and germanium oxides / 2343118 Composition for obtaining thin film based on system of double zirconium and germanium oxides includes following components, wt %: crystallohydrate of zirconium oxochloride ZrOCl2-8H2O - 3.8-9.0; germanium tetrachloride - 3.0-7.1; 96% ethyl alcohol - remaining part. |
|
Method of brazilite concentrate extraction / 2344080 Invention refers to brazilite concentrate technology from zirconium waste with simultaneous liberation of rare-metal concentrate. Invention refers to method of brazilite concentrate extraction. Herewith raw materials are magnetic finish fraction of brazilite concentrate. Magnetic fraction is processed with 7-10% hydrochloric acid or 10-30% sulphuric acid at 60-90°C. Brazilite deposition is separated, washed, dried and followed with two-phase magnetic separation. The first stage includes magnetic separation in magnetic field of average intensity equal to 10000-14000 E and liberation of crude brazilite concentrate and average-magnetic delivered to spoil bank. The second stage includes separation of crude brazilite concentrate in high-intensity magnetic field 20000-24000 E and liberation of base of brazilite concentrate and low-magnetic fraction processed in high-temperature sulphuric acid medium. Low-magnetic fraction is processed with 85-93% sulphuric acid at 200-250°C in mass relation S:L=1:0.4-0.6. Produced sulphatisation product is pulped in water with derived pulp from which residue of brazilite concentrate is separated and sulphate suspension containing rare elements is produced. |
|
Method of preparing zirconium oxides and zirconium based mixed oxides / 2349550 Present invention is meant for chemical and automobile industry and can be used in making promoters and catalyst carriers for automobile systems of releasing exhaust gases. Zirconium hydroxide is precipitated from an aqueous solution of a zirconium salt by an alkali in the presence of a controlled amount of sulphate anions at ratio SO4 2-/Zr4+ ranging from 0.3/1 to 1.5/1 and temperature not above 50°C. Sodium hydroxide can be used as the alkali. The aqueous solution can contain a salt of an alkaline, rare earth, transition metal, silicon, tin or lead, as well as their mixture. The hydroxide is calcinated, forming oxide, which practically does not contain sulphate. Specific surface area of the oxide after sintering at 1000°C is not less than 40 m2/g, and not less than 10 m2/g after sintering at 1100°C. |
|
Method of purifying baddeleyite concentrate / 2356839 Present invention relates to the method of purifying baddeleyite concentrate. The method involves treatment of baddeleyite with concentrated sulphuric acid while heating, obtaining a solid sulphatisation product, which is turned into pulp using water. Purified baddeleyite concentrate is gravitationally separated from the pulp. A hydrated residue is also separated from the sulphuric acid solution, containing rare elements and impurity components. The method is distinguished by that, the baddeleyite concentrate is subjected to pre-treatment with dilute 2-7% sulphuric or hydrochloric acid at temperature 40-60°C with transfer of part of impurity components into the solution and formation of a residue of baddeleyite concentrate, which is separated from the sulphuric acid or hydrochloric acid solution, washed with water and subjected to magnetic separation, obtaining pre-purified baddelyite concentrate. The concentrate is then treated with concentrated 93-96% sulphuric acid at temperature 180-200°C. After separation of the baddeleyite concentrate, the sulphuric acid solution is neutralised with lime milk. |
|
Method of producing hydrate of metal oxide / 2375306 Method of producing a hydrate of a metal oxide involves treatment of a metal salt with ammonia gas, separation of hydrate residue from the suspension with formation of a solution which contains an ammonium salt, washing the hydrate residue and drying. The metal salt used is an aluminium, titanium or zirconium salt in form of crystalline hydrates with particle size of 0.1 to 3.0 mm. Metal salts are treated with ammonia gas by passing ammonia gas through a layer of particles of crystalline hydrates until pH of aqueous extraction of the reaction mass of not less than 7. The obtained reaction mass is leached with water or a solution from washing the hydrate residue with formation of a suspension, from which the hydrate residue is separated. |
FIELD: metallurgy.
SUBSTANCE: method involves chlorination of zircon concentrate, separate condensation of chlorinates, cleaning of silicon and zirconium tetrachlorides, aqueous hydrolysis of zirconium tetrachloride and deposition of zirconyl sulphate with distillation of azeotropic HCl-H2O mixture, filtration, washing and calcination of deposition so that zirconium dioxide is obtained, high-temperature vapour-phase hydrolysis of silicon tetrachloride in hydrogen-air flame so that pyrogenic silicon dioxide and HCl-bearing exhaust gases are obtained; absorption of hydrogen chloride by using azeotropic HCl-H2O mixture as absorbent, which is formed during hydrolytic separation of zirconyl sulphate.
EFFECT: invention allows multipurpose use of raw material.
1 cl, 1 dwg, 1 ex
The invention relates to the field of metallurgy of rare metals and technology of inorganic substances, in particular to the processing of zirconium concentrate with the production of zirconium dioxide and silicon dioxide.
A method of refining of zirconium concentrate to produce Zirconia sintering of zirconium concentrate with carbonate and calcium chloride at 1100-1200°C, leaching SPECA 5-10 wt.% HCl hydrochloric acid, removing the excess of calcium oxide and decomposition of orthosilicate calcium. The resulting colloidal silicic acid is removed together with the solution in reset. Containing lead zirconate calcium insoluble residue is leached with sulfuric acid, filtering and washing the separated directed to dump calcium sulfate (CaSO4·0,5H2About), the filtrate is hydrolyzed with the formation of sulfate Zirconia, the resulting suspension is filtered, the precipitate washed and calcined at 850 to 900°C with the production of zirconium dioxide. The disadvantage of this method is the formation of large quantities of waste (~6 t 1 t ZrO2) calcium sulphate, acid wastewater and silicic acid [1].
A method of refining of zirconium concentrate interaction with ammonium fluoride in an autoclave at a temperature of 250-400°C, sulfatization of the reaction mixture with sulfuric acid, water leaching to produce in the region is the target of zirconyl ion. The disadvantage of this method is the formation of toxic fluoride of silicon compounds, ammonia and frequency of process [2].
A method of refining of zirconium concentrate interaction with fluorine at a temperature of 350-500°C and a pressure of 0.12 MPa in an autoclave to obtain Tetra zirconium and silicon. The pyrolysis of silicon tetrafluoride in the hydrogen-oxygen flame get pyrogenic silicon dioxide and hydrogen fluoride. The disadvantage of this method is the increased risk of fluoride and its compounds, as well as the periodicity of the process [3].
The closest known analogues to the technical essence and the achieved results is the method of processing of zirconium concentrate chloride method [4] (PROTOTYPE).
According to the method prototype, zircon concentrate glorious chlorine in the presence of a carbonaceous reductant with getting gas mixture of chlorides of zirconium, silicon, impurities of iron, aluminum, etc. and oxides of carbon. When separate condensation products of chlorination produce zirconium tetrachloride and silicon. The purified zirconium tetrachloride dissolved to obtain a solution of zirconium oxychloride, from a solution by sulfuric acid hydrolysis of precipitated sulfate Zirconia (ZrO2·xSO3·yH2O). The suspension is filtered, the precipitate washed and calcined to obtain dioxide circus is tion. Obtained in the wet exhaust gas cleaning calcining the slurry ZrO2in sulfuric acid return to the stage sulfuric acid hydrolysis. Purified from impurities by distillation on a three-stage cascade silicon tetrachloride is used in the chemical industry in the production of ethyl silicate-40. The disadvantage of this method is the formation of a large amount of waste, since the dissolution and acid hydrolysis of zirconium tetrachloride hydrogen chloride (~1.2 t 1 t ZrO2) is sent together with the filtrate and the washing water in the drains.
An object of the invention is to increase the complexity of use of raw materials.
The technical result obtained by carrying out the invention, is to reduce waste production in the processing of zircon concentrate.
This technical result is achieved in the implementation of the proposed method of processing of zirconium concentrate, the essence of which is expressed by the following set of essential features:
the chlorination of zirconium concentrate in the presence of carbon at a temperature of 900-950°C;
- separate condensation products of chlorination with the separation of zirconium tetrachloride and silicon;
- distillation and distillation purification of silicon tetrachloride;
cleanup tetrachloride C is rcone from non-volatiles by sublimation;
aqueous hydrolysis of zirconium tetrachloride, deposition from a solution of sulphate of Zirconia and distillation of the azeotropic mixture of HCl-H2O (~20 wt.% HCl);
filtering, washing and calcining sulfate Zirconia with the production of zirconium dioxide and flue gas;
- cooling and condensation of the components of exhaust gases, obtained by calcining sulfate Zirconia, emitting suspension ZrO2sulfuric acid is directed to the deposition of sulfate Zirconia;
- high-temperature vapor-phase hydrolysis of silicon tetrachloride in hydrogen-air flame with getting fumed silicon dioxide and containing HCl gases;
- absorption of hydrogen chloride from gases containing gaseous hydrogen chloride, using as the absorbent azeotropic mixture of HCl-H2O (~20 wt.% HCl) and receiving 31-35 wt.% HCl hydrochloric acid;
- electrolysis 31-35 wt.% hydrochloric acid, with the resulting chlorine is sent to the chlorination of zirconium concentrate, and hydrogen at high temperature vapor-phase hydrolysis of silicon tetrachloride in hydrogen-air flame;
the concentration of the spent electrolyte containing 20 wt.% HCl, up 31-35 wt.% HCl.
The main feature of the proposed method of processing of zirconium concentrate is used as absorbent in absorb the AI hydrogen chloride gases from the high-temperature vapor-phase hydrolysis of silicon tetrachloride azeotropic mixture of HCl-H 2O (~20 wt.% HCl) with stage sulfuric acid hydrolysis of zirconium tetrachloride to produce commodity (31-35 wt.% HCl) hydrochloric acid. For the purpose of recycling hydrogen chloride obtained concentrated acid is sent to the electrolysis, where chlorine is sent to the chlorination of zirconium concentrate, and hydrogen at high temperature vapor-phase hydrolysis of silicon tetrachloride.
It should be noted that the amount of hydrogen produced during the electrolysis, exceeds the requirements of the process of high-temperature vapor-phase hydrolysis of silicon tetrachloride and therefore the excess hydrogen can be used as a reagent or fuel for production needs. It should also be noted that due to the chlorination of zirconium impurities concentrate and technological losses of hydrogen chloride deficit chlorine, which can be compensated by applying an additional amount of chlorine in the chlorination or gaseous hydrogen chloride absorption, where the absorbent can be used part of the spent electrolyte.
From a comparison of the techniques discussed here should be that the new methods perform actions and a new order of execution of actions provides the achievement of the technical result in the implementation of the invention.
The drawing shows a process with the EMA processing of zirconium concentrate with the production of zirconium dioxide and silicon dioxide.
Crushed zircon concentrate 1 and carbon 2 is dosed in charator 4, where the tuyeres served chlorine 3. At a temperature of 900-950°C and stirring in chloretone 4 processes chlorination of raw components with the formation of zirconium tetrachloride and silicon chloride compounds impurities, oxides of carbon reactions (1-4):
Gases and vapors of chlorides, forming a gas-vapor mixture 5, arrive at separate condensation products of chlorination in the capacitors 6 and 8. At the first stage 6 is condensed technical zirconium tetrachloride 10, and then at the second stage 8 of the gas mixture 7 is condensed silicon tetrachloride 9.
Technical zirconium tetrachloride 10 is directed to freeze installation 11 for treatment of non-volatiles. The purified zirconium tetrachloride 12 is directed to the hydrolysis cascade 13.
Hydrolysis of 13 zirconium tetrachloride is carried out in two stages. In the first stage of hydrolysis of the zirconium tetrachloride 12 communicates with the water 14 to obtain a solution of chloride of Zirconia by the reaction:
In the second stage the solution is dosed sulfuric acid 15 for the deposition of sulfate Zirconia on the total reaction:
</>
Both stages are conducted when heated with distillation from the reaction mass azeotropic mixture of HCl-H2About 20 wt.% HCl) 16. The resulting suspension sulfate Zirconia filtered, washed with purified water sludge 17 sent for calcining 18, where receiving the Zirconia 19 and the exhaust gases 20 containing products pylones, sulfur trioxide, water vapor and noncondensable gases from the reaction:
Exhaust gases 20 are washed in the scrubber 21 to highlight sulfuric acid and products of pylones with getting the suspension ZrO2in sulfuric acid 22 directed to the deposition of sulfate Zirconia on hydrolysis step 13.
Silicon tetrachloride 9 is directed to the distillation and distillation purification 23, where the separated high-boiling solid chlorides, dissolved gases, low-boiling impurities and titanium tetrachloride. Purified silicon tetrachloride 24 is directed to a high-temperature vapor-phase hydrolysis of 25.
Silicon tetrachloride 24, 26 air and hydrogen 32 is directed to the combustion in the burner, the flame of which is at a temperature of 1000-1200°C process temperature vapor-phase hydrolysis of 25 silicon tetrachloride with getting pyrogenic silicon dioxide 27 and containing HCl gases 28 to reactions (8-9):
The cooled exhaust gases 28 containing gazoo the different hydrogen chloride, nitrogen and water vapor, is sent to the scrubber 29 on the absorption of hydrogen chloride using as the absorbent azeotropic mixture of HCl-H2O (20 wt.% HCl) 16 and receiving 31-35 wt.% HCl hydrochloric acid 30. Hydrochloric acid 30 with stage absorption filter and sent to electrolysis 31. Obtained by electrolysis chlorine 3 is used in the chlorination of zirconium concentrate, and hydrogen 32 is used in the process of high-temperature vapor-phase hydrolysis of silicon tetrachloride 25.
During electrolysis 31-35 wt.% HCl hydrochloric acid in addition to the target 3 chlorine and hydrogen 32 receive the spent electrolyte 33, containing ~20 wt.% HCl. Extractive rectification 34 the concentration of HCl in spent electrolyte to increase 31-35 wt.% HCl, concentrated acid 35 is used in the electrolysis 31. Auxiliary reagent extractive distillation regenerate, and acid distillate 36 is sent to the effluent. Exhaust gases and effluents are neutralized by known methods.
An example of the method
1000 g of zirconium concentrate to grind to a particle size of less than 160 microns, mixed with carbon and received 1130 blend containing wt.%: Zr(Hf)O258,3; SiO229,1; TiO20,09; 11,6; admixtures of compounds of iron, aluminum and other - other. The resulting mixture was prokaryotae at a temperature of 930-950°C chlorine (99,5% vol. Cl2in molten chloride salts.</>
Separate components condensation of vapor-gas mixture received zirconium tetrachloride containing impurities of solid chlorides of iron, aluminum, etc. and silicon tetrachloride containing impurities boiling and high-boiling liquid chlorides.
Received technical zirconium tetrachloride was purified from impurities by sublimation and condensation received 1152 g of peeled ZrCl4that used for the synthesis of zirconium dioxide by the method of water hydrolysis of zirconium tetrachloride in the presence of sulfuric acid.
The zirconium tetrachloride dissolved in 3100 ml of water, downloaded 144 ml of 93 wt.% sulfuric acid, at a temperature 108-109°C drove 2440 ml of azeotropic mixtures of HCl-H2About 20 wt.% HCl). One stripped off zirconium bearing solution was diluted with water, the mixture was heated to 95°C, held for 1 hour to precipitate sulfate Zirconia, was filtered, washed, dried at 105°C, received 1050 g of sulfate Zirconia. Product probalily at 900°C and received 584 g of Zirconia, in which the concentration of ZrO2is to 99.7 wt.%. This product can be used for calcium thermal production of powdered zirconium, for the production of refractory materials, ceramic pigments, enamels and other purposes.
Technical silicon tetrachloride was purified by distillation and rectification from suspended solids, boiling and high-boiling PR is Mesa and got 710 g of peeled SiCl 4.
The obtained silicon tetrachloride was evaporated, mixed with a stream of conveying air. Gas-vapor mixture and hydrogen filed in the burner, where he spent a vapor-phase hydrolysis of SiCl4in the hydrogen-air flame at a temperature of 1000-1150°C. From palaeohistology mixture allocated silicon dioxide, which was purified from the adsorbed impurities. Received 236 g of the product in which the concentration of SiO2on calcined substance is 99.9 wt.%, the value of specific surface area of the product was 250 m2/g which corresponds to "Aerosil". This product can be used as a filler in the manufacture of rubber products, plastics, as thickener paints, lubricants and other purposes.
The obtained gas mixture (1100 l) after selecting "Aerosil" contains (vol.%): HCl 31,0; N2About 9,4; nitrogen, air, etc. the rest. The gas mixture was absorbed azeotropic mixture of HCl-H2About 20 wt.% HCl)obtained at the stage of hydrolytic precipitation of sulfate Zirconia. Formed of 2.8 liters of hydrochloric acid solution with a concentration 32,8 wt.% HCl. This acid is a commodity product and can be used in ferrous and nonferrous metallurgy, chemical and other industries.
In the electrolysis of concentrated hydrochloric acid obtained at the anode 159 l of chlorine in which the chlorine content2the leaves of 99.5 vol.%, and on the cathode obtained 162 liters of hydrogen, in which, after washing, the concentration of H299.5 vol.%, and 2,53 l of spent electrolyte containing 20 wt.% HCl.
The dried chlorine and hydrogen are used in the chlorination of zirconium concentrate and high-temperature vapor-phase hydrolysis of silicon tetrachloride, respectively.
LIST of USED SOURCES
1. Zelikman A.N., Kites astray freight / metallurgy of rare metals. // M: metallurgy, 1991, p.184-186.
2. RF patent №2211804, IPC C01G 25/00. Torontonians way decomposition of zircon. / Appl. 01.04.2002. No. 2002108245/12. Publ. 10.09.2003. Bull. No. 25.
3. RF patent №2311345, IPC C01G 25/04, SW 33/18. The method of processing of zircon concentrate. / Appl. 20.02.2006. No. 2006105300/15. Publ. 27.11.2007. Bull. No. 33.
4. Speak N.D., Nuts VP, Titov A.A. / Method for processing zirconium concentrate chlorine method. // M: Central Institute of Economics and information nonferrous metallurgy, 1979, pp.5-20, 23-30.
1. The method of processing of zirconium concentrate, including chlorination of zirconium concentrate in the presence of carbon, separate condensation products of chlorination with the separation of zirconium tetrachloride and silicon, distillation and distillation purification of silicon tetrachloride purification of zirconium tetrachloride from non-volatiles sublimation, water hydrolysis of zirconium tetrachloride, deposition from a solution of Sul the veil of Zirconia and distillation of the azeotropic mixture of HCl-H 2O, filtering, washing and calcining sulfate Zirconia with the production of zirconium dioxide, wherein the silicon tetrachloride is directed to a high-temperature vapor-phase hydrolysis in the hydrogen-air flame with getting fumed silicon dioxide and containing HCl gases, and the subsequent absorption of hydrogen chloride from gases is performed using as the absorbent azeotropic mixture of HCl-H2O.
2. The method according to claim 1, characterized in that the resulting absorption of concentrated hydrochloric acid is electrolyzed, with the resulting chlorine is sent to the chlorination of zirconium concentrate, and hydrogen at high temperature vapor-phase hydrolysis of silicon tetrachloride in hydrogen-air flame.