WO1999008959A1 - Procede de production d'acide de silice - Google Patents

Procede de production d'acide de silice Download PDF

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Publication number
WO1999008959A1
WO1999008959A1 PCT/GB1997/002189 GB9702189W WO9908959A1 WO 1999008959 A1 WO1999008959 A1 WO 1999008959A1 GB 9702189 W GB9702189 W GB 9702189W WO 9908959 A1 WO9908959 A1 WO 9908959A1
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WO
WIPO (PCT)
Prior art keywords
silica
process according
containing material
acid
temperature
Prior art date
Application number
PCT/GB1997/002189
Other languages
English (en)
Inventor
Solomon Flax
Original Assignee
Goodanew, Martin, Eric
Promeks A/S
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.)
Filing date
Publication date
Application filed by Goodanew, Martin, Eric, Promeks A/S filed Critical Goodanew, Martin, Eric
Priority to PCT/GB1997/002189 priority Critical patent/WO1999008959A1/fr
Priority to AU39489/97A priority patent/AU3948997A/en
Publication of WO1999008959A1 publication Critical patent/WO1999008959A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
    • 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
    • C01B33/126—Preparation of silica of undetermined type

Definitions

  • the present invention relates to a process for producing silica acid.
  • the present invention relates to a process for processing silicates and aluminum silicates by hydrometallurgical techniques to produce silica acid and aluminum oxyhydrate, as well as to recover the metal impurities contained therein in oxyhydrate and hydrate form.
  • a hydrometallurgical method for extraction of aluminum (alumina) from bauxites with high silica content, as well as from nefelins by baking them with soda and limestone with subsequent leaching in caustic soda solution according to the reaction:
  • Another method known for production of active silica acid - silicagel - involves the treatment of sand (Si0 2 ) with caustic soda at a temperature of 800 - 900°C and subsequent leaching of sodium silicate and precipitation of silica acid with H 2 S0 4 , HCI or carbonic acid.
  • sand Si0 2
  • caustic soda at a temperature of 800 - 900°C
  • leaching of sodium silicate and precipitation of silica acid with H 2 S0 4 , HCI or carbonic acid.
  • a similar process has been described for the manufacture of amorphous silica from rocks (US Pat. no. 5,445,804) involving initial dissolution of the rock with an alkaline solution.
  • a method for production of silica acid, or white soot by treating silicon tetrachloride (SiCI 4 ) or silicon tetrafluoride (SiF 4 ) silica with water vapor at temperatures of 1000°C - 1100°C.
  • SiCI 4 silicon tetrachloride
  • SiF 4 silicon tetrafluoride
  • the caustic soda used for melting with Si0 2 is a relatively expensive material.
  • the sodium silicate, produced after melting, is treated with steam, after which solutions are obtained that are difficult to filter.
  • the sodium and hydrochloric acid present combine to form NaCI from which regeneration of NaOH and HCI is not economically viable.
  • silica In production of silica by gas-phase methods, expensive materials are used, such as silicon tetrachloride and silicon tetrafluoride. These materials are obtained by processes of chlorination and fluorination which are environmentally unfriendly.
  • Another disadvantage of the gas phase method is the necessity to perform hydrolysis of SiCI 4 at temperatures of 1000°C - 1100°C to achieve the reaction:
  • the object of the present invention is to provide a process for extraction of active silica acid from silica containing materials and both alumina and silica from aluminum silicate raw materials using reagents that are inexpensive and that may be completely regenerated.
  • the present invention provides a process for producing silica acid, by means of combining silica- containing materials with a calcium chloride solution, baking said mixture in an oven at a temperature of at least 800°C to produce a cake, processing said cake into particles, leaching the same with a strong inorganic acid selected from the group consisting of hydrochloric acid, nitric acid and mixtures thereof at a temperature of up to 110°C to produce a pulp, filtering said pulp to produce a silica acid sediment; and channeling said filtrate into a reactor for heating to evaporate HCI, for reuse in the above leaching step.
  • a strong inorganic acid selected from the group consisting of hydrochloric acid, nitric acid and mixtures thereof at a temperature of up to 110°C to produce a pulp, filtering said pulp to produce a silica acid sediment; and channeling said filtrate into a reactor for heating to evaporate HCI, for reuse in the above leaching step.
  • the present invention further provides a process wherein the silica containing material further contains alumina.
  • a metal chloride sediment is formed and said sediment is thermohydrolysed at a temperature of about 150°C - 350°C to hydrolyse metal chlorides contained therein.
  • a combustible carbon- containing material is added to the silica-containing material to improve the handling properties during calcination, wherein the combustible material is selected from the group consisting of wood, sawdust, charcoal, oil-shale and black oil, as will be exemplified hereinafter.
  • said silica containing component is microsilica, quartz, a spent SiO 2 -AI 2 O3 catalyst, ashes from coal, flint, clay and other silica or alumina-silicate containing materials.
  • the amount of calcium chloride added is preferably between stochiometric and 10% excess above the stochiometric amount for said reaction, and said baking is performed at a temperature of about 800°C - 1200°C.
  • said acid is at a concentration of at least 5% and said leaching is carried out at a temperature of at least 70 ⁇ C and preferably at least 100°C.
  • said leaching is carried out at a temperature of at least 70 ⁇ C and preferably at least 100°C.
  • hydrochloric acid of at least 5% concentration, and most preferred at least 15% concentration.
  • metal admixtures are precipitated by addition of calcium oxide, removed by filtration and the calcium chloride filtrate is reused in the initial mixing procedure.
  • the pulp obtained is filtered and the filtrate is channeled for production of aluminum, iron, calcium and other metals, while the silica acid is washed, dried and classified.
  • the silica product obtained form the process of the present invention contains > 99.5% of Si0 2 ; and has a well-developed surface up to 800 m 2 /l gr and high oil absorption capacity (D.B.P. test > 400 ml/100 gr).
  • Hydrochloric acid solution of metal chlorides (Al, Fe, Ca and others) are concentrated by evaporation and the precipitate undergoes thermohydrolysis. This enables almost complete regeneration of hydrochloric acid and calcium chloride. Metal admixtures are extracted in the form of concentrates containing hydroxides and oxihydrates of the corresponding metals.
  • FIGURES Fig. 1 Process flow diagram for production of silica acid, metal hydrates and oxyhydrates.
  • Fig. 2 Flow sheet of a plant for silica production.
  • Fig. 3 Process flow diagram for production of materials containing low metal content (e.g microsilica, quartz).
  • the amount of CaCI 2 and carbon-containing raw materials may vary both ways depending on the composition of the initial silica-containing raw materials.
  • the baking is performed at a temperature of 900°C for a period of about 3 hours (depending on the composition of the initial raw materials, the temperature may vary from 800°C to 1200°C, and baking time from 1 to 3 hours).
  • reactions take place between the catalyst components and calcium chloride, e.g.:
  • the cake is transferred from furnace 6 along line 7 into reactor 8, where quenching of the cake takes place. Water is transferred into the same reactor along line 9. In the reactor a rapid cooling of the cake down to 40 ⁇ - 60°C occurs. The cake is transformed by quenching into fine powder, which makes it usable without additional milling. Gas from baking furnace 6 is channeled along line 12 into scrubber 13. Water is also channeled to scrubber 13 along line 9 1 . In the scrubber, saturation of water with hydrochloride takes place until an azeothropic mixture is formed that contains ⁇ 20% of HCI used for the leaching process.
  • the finely divided cake is channeled from the quenching reactor along line 10 into leaching reactor 11 where 20% hydrochloric acid is channeled into the same reactor along line 14 from scrubber 13.
  • the leaching process is performed at a temperature of 90°-100°C with constant stirring for a period of about 2-3 hours.
  • the pulp after leaching is transferred to vacuum filter 16 along line 15; water is channeled into the same filter along line 9 11 to wash the silica.
  • the washed silica is transferred along line 18 for drying to dryer 19.
  • Silica drying is performed at a temperature of 120°-150°C.
  • the dried product is channeled for packing along line 26.
  • the filtrate from vacuum filter 16 is sent along line 17 into reactor 20, where evaporation of the solution and hydrolytic decomposition of metal chlorides takes place at the temperature > 150°C. Under these conditions chlorides of Fe, Al, Ti and other metals are hydrolyzed, while chlorides of calcium, magnesium, sodium and potassium are not and they are recycled to the calcium chloride solution of step a.
  • Gas from hydrolysis reactor 20 is transferred along line 12 1 into scrubber 13, where the gas is scrubbed and 20% hydrochloric acid is produced.
  • the hydrolyzed product is transferred along line 21 into reactor 22 where it is leached with water at room temperature, the water being transferred along line 9 111 .
  • CaCI 2 and MgCI 2 are transferred into solutions.
  • CaCI 2 concentration in the solution is ⁇ 1000 g/l.
  • the pulp from leaching reactor 22 is transferred by line 23 to a filter- press, where CaCI 2 solution is isolated from metal hydrates.
  • CaCI 2 solution is channeled along line 2 to the head of the process to be mixed with the initial silica-containing product and afterwards to baking; metal hydrates in the form of concentrates are channeled along line 27 for further processing.
  • the concentrates have the following composition: AI 2 0 3 -85.52%; Fe 2 0 3 -2.56%; Ln 2 0 3 -4.17% CuO-0.08%; NiO-1.16%; PbO-0.01 %; ZnO-0.11 %; Ti0 2 -4.72%; CaO-1.13%; MgO-0.51 %
  • Example 1 Processing of this raw material was performed under the conditions of Example 1. The process parameters were similar to those used in Examples 1 and 2. A slight difference was observed in the composition of metal concentrates due to the differences in the chemical composition of the initial raw materials.
  • Silica obtained from flint clay contained:
  • microsilica As a raw material, microsilica with the following composition was used: Si0 2 - 95.1 %; AI 2 O 3 - 0.026%; Na 2 0- 0.23%; Fe 2 0 3 - 0.83%; CaO - 0.15%; MgO - 0.13%; K 2 O - 0.3%; C - 2.5%; SO 4 '2 - 0.6%. Processing of this material was performed under the conditions of example 1.
  • microsilica contains a small amount of admixtures, its processing was simplified, the operations of hydrolysis and leaching were excluded.
  • Calcium chloride solution CaCI 2 - 700g/l; Mg, Al, Fe etc. - trace
  • Metal concentrate Fe 2 O 3 - 54.8%; K 2 O - 15.8%; Na 2 0- 14.1 %; CaO - 5.0%;
  • Quartzite with the following composition was used as a raw material: SiO2 - 99.5%; AI 2 O 3 - 0.02%; Na 2 O- 0.01%; Fe 2 O 3 - 0.25%; CaO - 0.11%; MgO - 0.10%; K 2 O - 0.01%.
  • Quartz contains a lower amount of admixtures than microsilica, therefore this product was processed according to the shortened scheme (see Fig.3): after evaporation the CaCI 2 solution was directed to the beginning ("head") of the process without purification for five cycles. Products analogous to those described in example 4 were obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Silicon Compounds (AREA)

Abstract

Cette invention concerne un procédé permettant de produire de l'acide de silice. Ce procédé consiste à combiner une matière renfermant de la silice à une solution de chlorure de calcium; à cuire ce mélange dans un four à une température d'au moins 800 °C en vue de produire un pain; à traiter ce pain en vue de former des particules; à opérer la lixiviation de ce pain, à une température pouvant atteindre 110 °C, au moyen d'un acide inorganique fort choisi parmi l'acide hydrochlorhydrique, l'acide nitrique et des mélanges de ces acides, et ce, en vue de produire une pâte; à filtrer cette pâte en vue de produire un dépôt d'acide de silice; puis à introduire le filtrat dans un réacteur, par écoulement, dans le but d'effectuer un chauffage destiné à provoquer l'évaporation du HCl en vue de sa réutilisation lors de la lixiviation décrite ci-dessus.
PCT/GB1997/002189 1997-08-14 1997-08-14 Procede de production d'acide de silice WO1999008959A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/GB1997/002189 WO1999008959A1 (fr) 1997-08-14 1997-08-14 Procede de production d'acide de silice
AU39489/97A AU3948997A (en) 1997-08-14 1997-08-14 A process for producing silica acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/GB1997/002189 WO1999008959A1 (fr) 1997-08-14 1997-08-14 Procede de production d'acide de silice

Publications (1)

Publication Number Publication Date
WO1999008959A1 true WO1999008959A1 (fr) 1999-02-25

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ID=10807012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/002189 WO1999008959A1 (fr) 1997-08-14 1997-08-14 Procede de production d'acide de silice

Country Status (2)

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AU (1) AU3948997A (fr)
WO (1) WO1999008959A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001058807A1 (fr) * 2000-02-10 2001-08-16 Promeks As Procede de preparation de silice amorphe
WO2005108292A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede ameliore de production de silice amorphe et hydrophobe pure a partir du quartz
WO2005108293A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede ameliore de production de silice mesoporeuse amorphe pure a partir de quartz
WO2005108291A1 (fr) * 2004-05-12 2005-11-17 Promeks As Processus ameliore de production de silice amorphe pure en particulier de xerogels destines a stabilisation de la biere et a d'autres fins d'isolation
WO2005108290A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede perfectionne pour produire de la silice amorphe pure a partir de quartz, de preference a utiliser en tant que matiere de charge
CN115057445A (zh) * 2022-07-22 2022-09-16 包头稀土研究院 硅氟氢酸的生产方法及混合稀土精矿的处理工艺
WO2023044537A1 (fr) * 2021-09-21 2023-03-30 Tianqi Lithium Kwinana Pty Ltd Procédé de production d'alumine

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1868499A (en) * 1929-06-07 1932-07-26 Electric Smelting & Aluminum C Process of recovering alumina from silicious materials containing it
GB479293A (en) * 1935-08-10 1938-02-03 Lucien Freling Process for the recovery of aluminium compounds
JPS4899097A (fr) * 1972-03-30 1973-12-15
GB2005240A (en) * 1977-10-07 1979-04-19 Alcan Res & Dev Production of hydrochloric acid
GB2205558A (en) * 1987-05-18 1988-12-14 Lonhro Plc Recovery of alumina from aluminosilicates
EP0549323A1 (fr) * 1991-12-25 1993-06-30 R & D SILICATE PRODUCTS LTD. Procédé de préparation de silice amorphe
EP0610136A1 (fr) * 1993-02-02 1994-08-10 Rotem Amfert Negev Ltd. Procédé de préparation de silice pure amorphe à partir de roches
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1868499A (en) * 1929-06-07 1932-07-26 Electric Smelting & Aluminum C Process of recovering alumina from silicious materials containing it
GB479293A (en) * 1935-08-10 1938-02-03 Lucien Freling Process for the recovery of aluminium compounds
JPS4899097A (fr) * 1972-03-30 1973-12-15
GB2005240A (en) * 1977-10-07 1979-04-19 Alcan Res & Dev Production of hydrochloric acid
GB2205558A (en) * 1987-05-18 1988-12-14 Lonhro Plc Recovery of alumina from aluminosilicates
EP0549323A1 (fr) * 1991-12-25 1993-06-30 R & D SILICATE PRODUCTS LTD. Procédé de préparation de silice amorphe
EP0610136A1 (fr) * 1993-02-02 1994-08-10 Rotem Amfert Negev Ltd. Procédé de préparation de silice pure amorphe à partir de roches
US5445804A (en) * 1993-02-02 1995-08-29 Rotem Fertilizers Ltd. Process for the manufacture of pure amorphous silica from rocks
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 100, no. 2, 9 January 1984, Columbus, Ohio, US; abstract no. 9432, ALMARIEI GEORGETA & AL.: "Continuous preparation of active silicon dioxide" XP002061886 *
CHEMICAL ABSTRACTS, vol. 81, no. 4, 29 July 1974, Columbus, Ohio, US; abstract no. 15220, MURAKAMI TADAMITSU: "Fine powder of silica" XP002061855 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001058807A1 (fr) * 2000-02-10 2001-08-16 Promeks As Procede de preparation de silice amorphe
US6797249B2 (en) 2000-02-10 2004-09-28 Promeks As Process for the preparation of amorphous silica
WO2005108292A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede ameliore de production de silice amorphe et hydrophobe pure a partir du quartz
WO2005108293A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede ameliore de production de silice mesoporeuse amorphe pure a partir de quartz
WO2005108291A1 (fr) * 2004-05-12 2005-11-17 Promeks As Processus ameliore de production de silice amorphe pure en particulier de xerogels destines a stabilisation de la biere et a d'autres fins d'isolation
WO2005108290A1 (fr) * 2004-05-12 2005-11-17 Promeks As Procede perfectionne pour produire de la silice amorphe pure a partir de quartz, de preference a utiliser en tant que matiere de charge
WO2023044537A1 (fr) * 2021-09-21 2023-03-30 Tianqi Lithium Kwinana Pty Ltd Procédé de production d'alumine
CN115057445A (zh) * 2022-07-22 2022-09-16 包头稀土研究院 硅氟氢酸的生产方法及混合稀土精矿的处理工艺
CN115057445B (zh) * 2022-07-22 2023-11-24 包头稀土研究院 硅氟氢酸的生产方法及混合稀土精矿的处理工艺

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Publication number Publication date
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