WO2007030029A1 - Procede de desilication de matieres premieres minerales - Google Patents

Procede de desilication de matieres premieres minerales Download PDF

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Publication number
WO2007030029A1
WO2007030029A1 PCT/RU2005/000452 RU2005000452W WO2007030029A1 WO 2007030029 A1 WO2007030029 A1 WO 2007030029A1 RU 2005000452 W RU2005000452 W RU 2005000452W WO 2007030029 A1 WO2007030029 A1 WO 2007030029A1
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WO
WIPO (PCT)
Prior art keywords
silicon dioxide
sio
raw material
ammonium
molar ratio
Prior art date
Application number
PCT/RU2005/000452
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English (en)
Russian (ru)
Inventor
Evgenija Ivanovna Melnichenko
Dantiy Grigor'evich Epov
Original Assignee
The Institute Of Chemistry, Far Eastern Branch, Russian Academy Of Sciences (Status Gosudarstvennogo Uchrezhdenija)
Laboratory For Innovation Tehnologies, Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by The Institute Of Chemistry, Far Eastern Branch, Russian Academy Of Sciences (Status Gosudarstvennogo Uchrezhdenija), Laboratory For Innovation Tehnologies, Ltd filed Critical The Institute Of Chemistry, Far Eastern Branch, Russian Academy Of Sciences (Status Gosudarstvennogo Uchrezhdenija)
Priority to PCT/RU2005/000452 priority Critical patent/WO2007030029A1/fr
Publication of WO2007030029A1 publication Critical patent/WO2007030029A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/10—Compounds containing silicon, fluorine, and other elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes

Definitions

  • the invention relates to the chemical industry and can be used in the field of processing various minerals and ores during their desiliconization to produce amorphous silicon dioxide.
  • a known method of desiliconization including autoclaving in a solution of concentrated sulfuric acid a mixture of solid silicon-containing materials and fluorine-containing compounds selected from the group: sodium fluoroaluminate, cryolite, aluminum fluorosilicate, ammonium hydrodifluoride, sodium aluminum silicon fluoride, sodium fluorosilicate, sodium aluminate and trihydrate om ammonium or sodium fluorosilicate or a mixture thereof.
  • Gaseous products released by this method silicon tetrafluoride, hydrogen fluoride and water vapor are heated to 600-1020 0 C in the presence of oxygen to form finely divided silica (US Pat. No. 6217840, publ. 04.17.2001).
  • Known methods of desiliconization based on the property of silicon dioxide to dissolve in alkali with the formation of silicates.
  • a method for desiliconizing clay ores including fine grinding and agglomeration of ores; the interaction of the obtained granules with NaOH at a temperature of 100 0 C to form a product containing sodium silicate; separating soluble silicates from the solid residue; carbonization of silicates by passing CO 2 into a liquid product to form SiO 2 .nH 2 O and sodium carbonate; washing the residual silica with separation of it from soluble sodium carbonate (US Pat. Na 5302364, publ. 04/12/1994; US Pat. No. 5445804, publ. 08/29/1995).
  • the disadvantages of the methods include pollution of the obtained silicon dioxide with sodium due to the use of alkali during processing .. alkali, which leads to a limitation of its scope; high, energy consumption for carbon dioxide thermal decomposition. calcium carbonate; the complexity of the method due to the disposal of the resulting. salt solutions; low yield (not more than 80%) and purity (not more than 90%) of the obtained silicon dioxide.
  • a known method for the separation of silica from its compounds including the interaction of the starting materials with fluoride, ammonium hydrodifluoride or a mixture thereof in an aqueous medium in the presence of hydrofluoric acid or a cation exchange resin to form ammonium silicofluoride, separating it from unreacted silica and impurities by settling, recrystallization of the formed silicon fluoride its subsequent 'with ammonia in an aqueous medium to precipitate silica (n. NQ US 5,458,864, publ. 17.10.1995).
  • the known method is time-consuming, based on the use of aggressive substances and requires high-purity silicon dioxide to obtain recrystallization of ammonium silicofluoride from siavic acid solutions.
  • a known method for the separation of silica from phosphorus-containing ores including the separation of silicon tetrafluoride during acidification of ores, absorption of the obtained gaseous product with water or a solution of ammonium fluoride to obtain silicofluoric acid or ammonium fluorosilicate, and subsequent separation of silica from them by known methods (p. EP Ns 337712, publ. .1989).
  • the method is characterized by a low yield and low purity of the resulting silicon dioxide.
  • Mechanical methods of desiliconization of ores include, as a rule, grinding, removal of clay components and subsequent flotation, but they are suitable for rock-forming minerals, such as carbonates, sulfates and clays (U.S. JVs 5334364, publ. 2.08.1994).
  • Dry heterophasic methods of desiliconization include the sublimation of silicon from ores in the form of tetrachloride at high temperature using oxygen and hydrogen to convert silicon tetrachloride to solid silicon dioxide (Chemistry and Technology of Rare and Scattered Elements, Vol. 2, ed. Higher School, M., 1976, 263-264).
  • the disadvantages of the chlorine method include high energy intensity, high cost, environmental insecurity of the use of gaseous chlorine, hydrolytic instability of silicon tetrachloride, which requires sealing equipment.
  • a known method of desiliconization of titanium-containing raw materials by two-stage heating of raw materials with ammonium hydrodifluoride, first at a temperature of 50-190 0 C for 2-72 hours, and then at 350-650 0 C for 0.5-10 hours.
  • the resulting condensate of fluoroammonium salts of titanium and silicon is then further heated to 500-800 0 C in the presence of water vapor and silicon is separated from titanium in the form of sublimate ammonium hexafluorosilicate (HFSA) (Cl. RF JVs 2058408, publ. 04/20/1996).
  • HFSA sublimate ammonium hexafluorosilicate
  • Closest to the claimed is a method of desiliconization of natural minerals and ores, including crushing the raw material, mixing it in a predetermined ratio with a fluorinating agent, which is used as fluoride - ammonium hydrodifluoride, which is a mixture of ammonium fluoride and hydrodifluoride, and subsequent heating at a speed of 5-10 ° C / min up to 500 0 C (p. RF ⁇ 2226500, publ. 2004.04.10).
  • the disadvantage of this method is the high energy intensity of the process, the applicability of the method for a limited range of raw materials, specifically shungite, and the low purity of the obtained silicon dioxide, which according to our data does not exceed 90%.
  • the objective of the invention is to reduce the energy consumption of the process and provide a high degree of desiliconization for a wide range of mineral objects, as well as to increase the purity and dispersion obtained by desilicon silicon dioxide.
  • the problem is solved by the method of desiliconization of mineral raw materials, including grinding of raw materials, fluorination during heating by mixing with ammonium hydrodifluoride in an amount that provides in the reaction mixture a molar ratio between ammonium hexafluorosilicate formed during fluorination and unreacted or additionally introduced silicon dioxide equal to (0.5-5-5 ): 1, and subsequent heating at a temperature of 220-320 0 C.
  • the mineral raw material and ammonium hydrodifluoride are mixed and heated to a temperature not exceeding 200 0 C in an amount that ensures that the reaction mixture after fluorination obtains a predetermined molar ratio of ammonium hexafluorosilicate (HFSA) and silicon dioxide formed during fluorination, equal to (0.5 - 5): 1.
  • HFSA ammonium hexafluorosilicate
  • silicon dioxide is additionally introduced to create a given molar ratio.
  • the fluorinated mixture is heated in the reactor at a temperature of 220 - 320 0 C and the resulting sublimation is collected in the form of a white finely divided mass.
  • Amorphous silicon dioxide is isolated from the resulting sublimation by known methods, based, for example, on the different solubility of the subliminal components, or by fractional condensation in water vapor and / or ammonia, followed by chemical decomposition of HPSA with ammonia.
  • the proposed method is based on the reaction of gas-phase chemical transport for the first time discovered by the applicant between HFSA and silicon dioxide, proceeding in a narrow temperature range of 220-320 0 C: (NH 4 ) 2 SiF 6 + SiO 2 schreib (NH 4 ⁇ Si 2 O 2 F 6 t, which is the technical result of the invention, which provides a reduction in the energy intensity of the process of desiliconization, a high degree of desiliconization, and the purity and dispersion of the resulting silicon dioxide.
  • the volatile compound formed (NBLOGgSiGOgF b is the fluoroammonium salt of metadisilicic acid - H 2 Si 2 O 5 and can be represented as doubled ammonium oxotrifluorosilicate 2NH 4 SiOF 3 , which is the carrier of silicon dioxide in the sublimation, which is confirmed by physical and chemical studies.
  • the derivatographic method established that the gas-phase transport reaction proceeds in the temperature range 220 - 320 0 C with a maximum speed at 245 0 C, which is recorded as a deep effect on the curves of differential mass loss (DTG) and differential thermal analysis (DTA).
  • TDG differential mass loss
  • DTA differential thermal analysis
  • the optimal molar ratio between HPSA and SiO 2 providing 100% extraction of SiO 2 in the gas phase, is (1-2): 1, which is confirmed by calculations based on the mass loss
  • Sublimated excess (NEL t ) 2 SiF 6 affects the chemical composition of the resulting sublimates, which are fine powders of gross composition and (NH 4 ) 2 SiF 6 -Si0 2 , where n takes values greater than or equal to 1.
  • the mechanism of HFSA evaporation changes: a volatile complex forms, as a result of which the crystalline form of SiO 2 becomes amorphous with additional purification, and the rate increases several times, which implies that the inventive method of desiliconization, as an important process for chemical technology, in the presence of SiO 2 can be carried out under mild conditions at significantly lower temperatures, and if necessary accelerated many times.
  • the method is carried out in the range of molar ratios of HFSA to silicon dioxide in a fluorinated feedstock equal to (0.5 - 5): 1, while
  • amorphous dioxide is the decomposition product of (NH 4 ) 2 Si 2 O 2 F 6 and is released from the gas phase in the condenser with decreasing temperature. Due to the difference in physicochemical properties with the carrier - HFSA, amorphous dioxide is easily separated from the carrier to obtain a white fine powder with a particle size of 5-10 ⁇ m, a low bulk density of 0.10 g / cm 3 or less, which is significantly lower than, for example, in soot or quartz, and the content of the main substance is 98.0-99.99 wt.%. 4.
  • Example 1 The invention is illustrated by the following examples. Example 1
  • quartz-containing zirconium ore of the Algaminsk deposit ( Russian) containing 52% ZrO 2 and 45% SiO 2 was used .
  • the latter is distributed between the gelcircon mineral
  • Example 3 As the source of ore using silicate ore kaolinite
  • Al 4 Si 4 O 10 (OH) 8 or Al 2 O 3 • 2SiO 2 • 2H 2 O (94.6%), which is a promising raw material for the aluminum industry. Fluorination is carried out with ammonium hydrodifluoride to produce HFSA. Reaction equation: Al 4 Si 4 O 10 (OH) 8 + 24NH 4 HF 2 4 (NH 4 ) 3 A1F 6 + 4 (NH 4 ) 2 SiF 6 + 18 H 2 O + 4NH 3
  • kaolinite ore does not contain free quartz, to carry out low-temperature desiliconization, the latter is introduced into the profiled mass in an amount of 220 g (with 1 kg of kaolinite) to provide a molar ratio of HPSA to SiO 2 equal to 2: 1, and heat to a temperature of 290-300 0 C for 12 hours. Obtained 1.4 kg of sublimation, consisting of amorphous silicon dioxide, HPSA and an admixture of ammonium hydrogen chloride. The silicon yield was 95%. The purity of the obtained silicon dioxide after its separation from the carrier is 99.8%.
  • the inventive method of desiliconization allows you to select with the degree of extraction of 90-99.9% from a wide range of silicon-containing minerals and ores amorphous finely divided silica of high purity with minimal energy and labor costs due to the implementation of the method based on the low-temperature gas-phase chemical transport reaction.
  • low temperatures (not higher than 320 0 C) of the process allow the use of technological equipment made of ordinary structural materials - stainless steel and fluoroplastic, which leads to a cheaper method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un procédé de désilication de matières premières minérales, qui permet d'extraire avec un degré d'extraction élevé, à partir d'un vaste groupe de minéraux et minerais silicés, le dioxyde de silicium amorphe finement dispersé à haut degré de pureté, avec une consommation minimale en termes d'énergie et de main d'oeuvre grâce à la réalisation de ce procédé sur la base d'une réaction en phase gazeuse de transport chimique. En outre, les basses températures du processus permettent d'utiliser un équipement technologique fabriqué à partir de matériaux de construction ordinaires tels que l'acier inoxydable et les fluoroplastes. Le procédé comprend la fluoration pendant le réchauffement des matières premières initiales avec de l'hydroflurure d'ammonium dans des quantités présentes dans le mélange de réaction et assurant un rapport entre l'hexafluorosilicate d'ammonium et le silicium supplémentaire n'ayant pas réagi ou introduit en supplément égal à (0,5 50) : 1 ainsi qu'un traitement thermique successif à une température de 220 320 °C, avec sublimation.
PCT/RU2005/000452 2005-09-06 2005-09-06 Procede de desilication de matieres premieres minerales WO2007030029A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU94021535A (ru) * 1994-06-15 1996-05-20 Институт химии Дальневосточного отделения РАН Способ переработки титансодержащего минерального сырья
RU2097321C1 (ru) * 1996-02-20 1997-11-27 Институт химии Дальневосточного отделения РАН Способ получения гексафторсиликата аммония
RU2226500C1 (ru) * 2002-09-10 2004-04-10 Рак Валентин Александрович Способ обескремнивания природных минералов и руд
RU2233694C1 (ru) * 2003-08-07 2004-08-10 Институт химии Дальневосточного отделения РАН (статус государственного учреждения) Устройство для переработки фтораммониевых кремнийсодержащих продуктов

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU94021535A (ru) * 1994-06-15 1996-05-20 Институт химии Дальневосточного отделения РАН Способ переработки титансодержащего минерального сырья
RU2097321C1 (ru) * 1996-02-20 1997-11-27 Институт химии Дальневосточного отделения РАН Способ получения гексафторсиликата аммония
RU2226500C1 (ru) * 2002-09-10 2004-04-10 Рак Валентин Александрович Способ обескремнивания природных минералов и руд
RU2233694C1 (ru) * 2003-08-07 2004-08-10 Институт химии Дальневосточного отделения РАН (статус государственного учреждения) Устройство для переработки фтораммониевых кремнийсодержащих продуктов

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