Method of processing zirconium tetrachloride to obtain zirconium dioxide and hydrochloric acid. RU patent 2466095.
 Zircon concentrate processing method / 2450974Method 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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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. |
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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: chemistry.
SUBSTANCE: invention relates to methods of processing zirconium tetrachloride and can be used in chlorine metallurgy when producing zirconium dioxide and hydrochloric acid. The method involves mixing zirconium tetrachloride with water in molar ratio ZrCL4:H2O=1:(1.0-1.2), obtaining zirconium oxychloride and hydrogen chloride gas, dissolving zirconium oxychloride in water, adding sulphuric acid with distillation of the HCl-H2O azeotropic mixture and precipitation of basic zirconium sulphate, filtering the suspension, washing and calcining the residue to obtain zirconium dioxide. Hydrogen chloride gas formed when producing zirconium oxychloride is taken for absorption, where the absorbent used is the HCl-H2O azeotropic mixture obtained during precipitation of basic zirconium sulphate. Concentrated hydrochloric obtained from absorption can be used in non-ferrous metallurgy when leaching concentrates and ores, etching metal surfaces of equipment, metal-roll and for other purposes.
EFFECT: invention simplifies the technique of producing zirconium dioxide and concentrated hydrochloric acid.
1 dwg, 1 ex
The invention relates to methods of processing of zirconium tetrachloride in the field of chlorine metallurgy in the production of zirconium dioxide and hydrochloric acid.
A method of obtaining zirconium dioxide processing of zirconium tetrachloride with water vapor at a temperature below 150°C and a molar ratio of water vapor to the zirconium tetrachloride < 2. The resulting product is zirconium oxychloride with respect to Cl:Zr=2.2 and About:Zr=1,9 calcined in a muffle furnace for 2 hours at 300°C. the Emitted during combustion of hydrogen chloride and a pair of zirconium tetrachloride sent to the recovery system [1]. The disadvantages of this method are the lack of utilization of hydrogen chloride and incomplete use of zirconium tetrachloride.
The closest known analogues to the technical essence and the achieved results is the method of processing of zirconium tetrachloride with the production of zirconium dioxide and hydrochloric acid [2] (the PROTOTYPE).
According to the prototype of the zirconium tetrachloride is dissolved in water, when thermohydrolysis hydrochloric acid solution of zirconium oxychloride precipitate zirconium hydroxide or the introduction of sulphuric acid precipitated basic zirconium sulfate and evaporated vapour-gas mixture of Hcl-H2O. the Suspension is filtered, the precipitate is dried and calcined production of zirconium dioxide. Vapour-gas mixture of Hcl-H2O absorb in the Oh, the resulting hydrochloric acid solution fortify salt by distillation using as the separating agent of the chlorides of alkaline earth metals to produce salable 31%Hcl hydrochloric acid.
The disadvantages of this method are the complexity of the process, due to the use of salt rectification using a separating agent and the need regenerationists agentwebranking that due to the additional energy costs.
An object of the invention is to simplify the technology of Zirconia and concentration of hydrochloric acid.
The achievement of the technical result is ensured by the sequence of actions and technological parameters of the proposed method, the essence of which is expressed by the following set of essential features:
a mixture of zirconium tetrachloride with water at a molar ratio of ZrCl4:H2O=1:(1,0-1,2) and heating up to 160-180°C To produce a powder of zirconium oxychloride and gaseous hydrogen chloride;
- dissolving powder of zirconium oxychloride in water, the introduction of sulfuric acid at a molar ratio of ZrOCl2:H2SO4=1:(0.5 to 0.6), heating the reaction mass to 110-115°C., the distillation of the azeotropic mixture of Hcl-H2O (~20 wt.% HCl) is the deposition of a basic sulfate of zirconium;
- absorption of emitted mixture of zirconium tetrachloride with water to gaseous hydrogen chloride using as the adsorbent obtained by the selection of the basic sulfate of zirconium azeotropic mixture of Hcl-H2O (~20 wt.% HCl) and receiving 31-35 wt.% HCl hydrochloric acid;
filtering, washing, purified (e.g., demineralized water, and calcining the basic zirconium sulfate with the production of zirconium dioxide and exhaust gases.
Salient features of the proposed method of obtaining Zirconia are:
- use as a reagent in obtaining zirconium oxychloride water at a molar ratio ZrCl4:H2O=1:(1,0-1,2) and the subsequent increase in the process temperature up to 160-180°C To produce the result of the interaction of gaseous hydrogen chloride and powdered zirconium oxychloride;
- use as an absorbent for absorption of emitted mixture of zirconium tetrachloride with water-hydrogen chloride azeotrope mixture of Hcl-H2O (~20 wt.% HCl), formed by deposition of a basic sulfate of zirconium to produce commodity (31-35 wt.% HCl) hydrochloric acid.
It should be noted that in comparison with the prototype excluded salt rectification and regeneration by evaporation of the diluted exhaust R is the target of the chlorides of alkaline earth metals or other separating agent.
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 the technological scheme of production of Zirconia.
When the mixture of zirconium tetrachloride with water and observing the molar ratio of ZrCl4:H2O=1:(1,0-1,2) mixture is heated to 65-70°C and the release of gaseous hydrogen chloride, to complete the removal of which 85-90% of the reaction mass is heated to 160-180°C. as a result of such processing are obtained poroshkoobraznyj zirconium oxychloride and hydrogen chloride.
Powdered zirconium oxychloride is dissolved in water and the resulting solution was added sulfuric acid to precipitate the basic zirconium sulfate. The process is carried out when heated with distillation from the reaction mass azeotropic mixture of Hcl - H2O (~20 wt.% HCl). The resulting suspension of the basic zirconium sulfate is diluted with water, filtered, washed with purified water sludge is sent for drying and calcining to obtain Zirconia.
Gaseous hydrogen chloride obtained in the mixture of zirconium tetrachloride with water, is directed to the absorption of hydrogen chloride using as absorbastone mixture of HCl-H2O (~20 is AC.% HCl) and receiving 31-35 wt.% HCl hydrochloric acid. Obtained for the absorption of concentrated hydrochloric acid can be used in non-ferrous metals in the leaching of concentrates and ores, etching of the metal surfaces of the equipment, steel and other purposes.
The off-gases from the calcination of the basic sulfate of zirconium, as well as absorption and plumbing neutralized by known methods.
An example of the method.
233 g of zirconium tetrachloride was mixed with 18 ml of water, the resulting mixture was warmed to 170°C. and kept under stirring for 2 hours. In the process of giving water, heating and aging the obtained 65.8 g of hydrogen chloride. The obtained powder of zirconium oxychloride in an amount of <185,2 g was dissolved in 430 cm3the water in the solution has downloaded and 63.9 g of 92 wt.% sulfuric acid, at a temperature of 110-115°C drove 360 g azeotropic mixture of Hcl-H2O (containing 72 g of Hcl). One stripped off zirconium bearing solution was diluted with water, the mixture was heated to 95°C, held for the deposition of the basic zirconium sulfate, the resulting suspension was filtered, the precipitate washed with demineralised water, dried, and the dry product was probalily at 900°C and received 120,8 g of Zirconia.
Hydrogen chloride in the amount of 65.8 g, obtained by mixing the zirconium tetrachloride with water, absorb 360 g azeotropic mixture of Hcl-H2O (the content is overall 72 g Hcl), obtained by precipitation of zirconium sulfate. As a result of absorption obtained 425,8 g of hydrochloric acid with a concentration 32,4 wt.% HCl. This acid is a commodity product and can be used in ferrous and nonferrous metallurgy, chemical and other industries.
List of used sources
1. A.S. No. 272, 293, IPC 01G 25/02. The method of obtaining zirconium dioxide // Appl. 18.12.68. No. 1290771/23-26. Publ. 03.06.70. BI No. 19.
2. Kozhemyakin B.A., Elfimov I.I. Low-waste production of compounds of zirconium. Non-ferrous metals, 1981, No. 10, p.75-77.
The method of processing of zirconium tetrachloride with the production of zirconium dioxide and hydrochloric acid, including the interaction of zirconium tetrachloride with water, obtaining zirconium oxychloride and gaseous hydrogen chloride, dissolving zirconium oxychloride in water, the introduction of sulfuric acid with azeotropic distillation of a mixture of Hcl-H2O and by the precipitation of a basic sulfate of zirconium, the absorption of hydrogen chloride, filtering the suspension, washing and calcining the precipitate, characterized in that the zirconium tetrachloride is mixed with water at a molar ratio of ZrCl4:H2O=1:(1,0-1,2), is heated to a temperature of 160-180°C To produce a powder of zirconium oxychloride and gaseous hydrogen chloride used for absorption, where the absorbent is applied distillate who will be with the introduction of sulphuric acid and precipitation of the basic sulfate of zirconium azeotropic mixture of Hcl-H 2O.