WO2005108292A1 - Procede ameliore de production de silice amorphe et hydrophobe pure a partir du quartz - Google Patents

Procede ameliore de production de silice amorphe et hydrophobe pure a partir du quartz Download PDF

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Publication number
WO2005108292A1
WO2005108292A1 PCT/NO2005/000156 NO2005000156W WO2005108292A1 WO 2005108292 A1 WO2005108292 A1 WO 2005108292A1 NO 2005000156 W NO2005000156 W NO 2005000156W WO 2005108292 A1 WO2005108292 A1 WO 2005108292A1
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WO
WIPO (PCT)
Prior art keywords
silica
accordance
hydrophobation
leaching
temperature
Prior art date
Application number
PCT/NO2005/000156
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English (en)
Inventor
Christian Rosenkilde
Natalia Loboda
Anton Stroh
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Promeks As
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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Publication of WO2005108292A1 publication Critical patent/WO2005108292A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to the production of pure amorphous silica from quartz or other SiO 2 based raw materials.
  • Several types of silica can be produced by using the techniques described in this application. Common for most of them is the purity of the silica, which is higher than commercial silicas on the market today.
  • the silica content in the product silica might be as high as 99.98%.
  • the various types of silica can be used for beer stabilization, insulation, catalysts and silicon rubber, and other applications that require pure silica. There are small differences during the production process for the various types of silica.
  • Amorphous silica is mainly produced by acidulation of a soluble silicate, commonly by addition of sulphuric or hydrochloric acid to a sodium silicate (water glass) solution.
  • the products are either precipitated silica or silica gel depending upon details in the production process.
  • other known processes silicon tetrachloride/alkoxide reacts with hydrogen and oxygen to form fumed silica are used commonly in the present silica industry.
  • US patent No. 1 ,868,499 relates to a process for recovering alumina from silicious materials where silica is considered as an unwanted by-product and no further processing of this product is carried out.
  • US patent No. 4689315 describes a method for the production of amorphous silica particles where the lime and the hydrochloric acid are consumed in the process.
  • European patent, EP 1265812 B1 relates to a process for the preparation amorphous silica where the raw materials are similar to the present invention, but where the process is limited with respect to the type of silica that can be produced, the purity of the silica product and that CaCI 2 is the only reagent used in the mixture with the raw materials.
  • the silica product according to the present invention is very pure, having an amorphous silica content of more than 90%, and it can be used for several applications.
  • the chemical impurities are at a much lower level than the commercial silica types, and the produced amorphous silica can have a very high surface area.
  • the silica is produced from quartz or other SiO 2 based materials and all other reagents, chemicals like mineral acid and chlorides from all elements in the group II of the periodic table (Be-Mg-Ca-Sr-Ba-Ra), used in the process are recycled. Only minor amounts for make-up of these chemicals are required.
  • the process according to the invention for production of amorphous silica from SiO 2 based raw materials includes the following steps:
  • MeCI 2 Heating the crushed ( ⁇ 100 ⁇ m) raw material together with MgCI 2 or CaCI 2 or other chlorides like BeCI 2 , SrCI 2 and BaCI 2 in the following referred to as MeCI 2 to a temperature in the range 800 - 1300 °C' preferably over a single or a two stage calcinations steps for a period of 0.5 to 3 hours, depending on the temperature, wherein the ratio of MeCI 2 to the SiO 2 is equal to or greater than 2 and in the presence of water vapour in excess of the stoichiometric amount (preferable at least 7%) needed for the reaction: x MeCI 2 + y SiO 2 + x H 2 0 - (MeO)x * (SiO 2 )y + 2x HCl wherein x is greater than y in order to obtain a conversion of quartz to Me-silicates in excess of 99.9%.
  • the HCl produced during calcination is absorbed in a scrubber and via step 4 reused
  • Silica application as a reinforcement filler in silicone rubber requires hydrophobation of silica and its easy dispersion in the polymer.
  • Silica hydrophobation can be made at any of three production stages: during leaching, Fig. 1 , or repulping, Fig. 2 or of the dried product, Fig. 3.
  • Hydrophobation can be made by addition of hydrophobation agent either as a liquid, or as a liquid in organic solvent, or as gas, or as gas diluted in another gas. The gas chosen for dilution should be dry.
  • 80g of calcium silicate produced in Step 1 with particle size ⁇ 200 micron was added to a beaker with 150 g water and stirred with a magnetic stirrer to avoid settling of the silicate.
  • the beaker was connected to a reactor through a peristaltic pump.
  • the glass reactor was equipped with a mechanical stirrer containing the device for gas blowing into the reaction mixture.
  • the reactor contained 650g of 16% hydrochloric acid.
  • the liquid hydrophobation agent was placed to a washing bottle with a glass sinter plate. The washing bottle was connected to the nitrogen flow regulator unit and with the mechanical stirrer of the reactor.
  • a water bath provided the temperature of 60°C in the reactor.
  • the addition of the silicate slurry started simultaneously with the addition of dichlorodimethylsilane by nitrogen blowing through the washing bottle.
  • the HCl concentration in the reactor was 13%, the solid/liquid ratio was 1/10 (w/w).
  • the amount of the hydrophobation agent (CHs) 2 CI 2 Si added was 23 g.
  • the silicate slurry flow through the peristaltic pump was 20ml/min and the dichlorodimethylsilane/nitrogen flow rate was 1.5g/min.
  • the reaction time was 15 min.
  • silica gel containing 93% water produced in steps1-4 and 118g water were placed to a glass reactor equipped with a mechanical stirrer and stirred to make homogeneous suspension.
  • the glass reactor was placed to a water bath to provide the temperature 45°C of the silica gel suspension.
  • 55ml of dichlorodimethylsilane was added dropwise to the suspension under vigorous stirring. When addition was over the reaction mixture was stirred additional 5 min and separated on a Buchnell funnel.
  • the silica was divided to two portions: one portion was washed with water to pH5 to get rid of acid formed during reaction of silanol groups with the hydrophobation agent, The other portion was washed with hexane. Then silica was dried at 140°C for 4 hours.
  • the silica had the following properties: Surface area 480m2/g, pore volume 1.0cm3/g, pore radius 4.1 nm, 99.92% SiO2, pH(5%) 5.1.
  • the particle size (D 50 ) was 2.9 micron.
  • Hydrophobation was made in a cylindrical glass reactor provided with a mechanical stirrer and a glass sinter plate, which separated the reactor volume in two parts, Gas inflow was below the sinter.
  • the glass reactor was placed to a water bath to provide the temperature 60°C in the reactor.
  • the upper part of the reactor was loaded with 100g of dry milled silica.
  • Gas (nitrogen) flow was controlled by a flow regulator. At first nitrogen passed through the powder under stirring. Then before entering the reactor nitrogen passed through a wash bottle with dichlorodimethylsilane.
  • the hydrophobation agent was thus fed to the reactor as a diluted gas.
  • the reaction mixture was heated to 60°C.
  • the amount of the hydrophobation agent (CH3) 2 CI 2 Si was 30ml.
  • the time of hydrophobation was 20 min.
  • the hydrophobic silica was first heated at 140°C for 30 min and then at 300°C for 30 min to get rid of the excess reagent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un procédé de production de silice amorphe à partir du quartz ou d'une autre matière première à base de SiO2. Le procédé consiste à: chauffer (étape de calcination) du quartz ou une autre matière première à base de SiO2 avec MgCl2 ou d'autres chlorures métalliques du groupe II de la table périodique, communément appelé MeCl2, à une température de 800 à 1300 °C, le rapport du MeCl2 au SiO2 étant égal ou supérieur à 2, en présence d'une vapeur d'eau excédant la quantité stoechiometrique requise; lixivier, à des températures préférables comprises entre 50 et 150 °C, le silicate produit avec HCI pour former une solution de MeCl2 avec de la silice insoluble; séparer la silice insoluble de la solution; recycler le MeCl2 jusqu'à l'étape de chauffage et la solution de HCI jusqu'à l'étape de lixiviation. L'hydrophobation de la silice est obtenue par adjonction de produits chimiques d'hydrophobation à un produit sec, soit au cours de l'étape de lixiviation précédant la séparation, soit pendant le repulpage consécutif à la séparation. Les autres chlorures métalliques utilisés dans le procédé peuvent être BeCl2, CaCl2, SrCl2 et BaCl2.
PCT/NO2005/000156 2004-05-12 2005-05-12 Procede ameliore de production de silice amorphe et hydrophobe pure a partir du quartz WO2005108292A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NO20041946 2004-05-12
NO20041946 2004-05-12
NO20042645A NO20042645D0 (no) 2004-05-12 2004-06-23 Forbedret prosess for fremstilling av ren amorf og hydrofobisk siliciumoksyd
NO20042645 2004-06-23

Publications (1)

Publication Number Publication Date
WO2005108292A1 true WO2005108292A1 (fr) 2005-11-17

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2437953A (en) * 2006-04-27 2007-11-14 Agilent Technologies Inc Silica-based chromatographic stationary phase
US7534352B2 (en) 2007-05-01 2009-05-19 Agilent Technologies, Inc. Reversed endcapping and bonding of chromatographic stationary phases using hydrosilanes
CN112624124A (zh) * 2020-12-16 2021-04-09 新沂市中大石英科技有限公司 一种高纯高疏水石英砂的制备工艺
CN114835129A (zh) * 2022-04-26 2022-08-02 连云港强邦石英制品有限公司 一种石英砂酸洗设备及酸洗工艺

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2786042A (en) * 1951-11-23 1957-03-19 Du Pont Process for preparing sols of colloidal particles of reacted amorphous silica and products thereof
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice
WO1999008959A1 (fr) * 1997-08-14 1999-02-25 Goodanew, Martin, Eric Procede de production d'acide de silice
US5908660A (en) * 1997-09-03 1999-06-01 Dow Corning Corporation Method of preparing hydrophobic precipitated silica
WO1999036356A2 (fr) * 1998-01-15 1999-07-22 Cabot Corporation Traitement de la silice au moyen d'organosilanes polyfonctionnels
RU2152967C1 (ru) * 1999-04-27 2000-07-20 Акционерное общество "Российская инновационная топливно-энергетическая компания" Способ получения гидрофобного, органофильного кремнезема
JP2001294775A (ja) * 2000-04-12 2001-10-23 Shin Etsu Chem Co Ltd 疎水性沈降シリカの製造方法
JP2002128516A (ja) * 2000-08-16 2002-05-09 Matsushita Electric Ind Co Ltd 疎水化された乾燥ゲルの製造方法およびそれを用いた断熱材
JP2002146232A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk シリカ微粉の表面改質法
JP2003020219A (ja) * 2001-07-09 2003-01-24 Matsushita Electric Ind Co Ltd 乾燥ゲルの製造方法とこの方法を用いて作られた断熱材
JP2003020218A (ja) * 2001-07-02 2003-01-24 Matsushita Electric Ind Co Ltd 疎水化乾燥ゲルの製造方法およびそれを用いた断熱材
EP1265812B1 (fr) * 2000-02-10 2003-11-19 Promeks AS Procede de preparation de silice amorphe
WO2004054927A1 (fr) * 2002-12-18 2004-07-01 Degussa Ag Silice structuree de type aerogel a surface modifiee

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2786042A (en) * 1951-11-23 1957-03-19 Du Pont Process for preparing sols of colloidal particles of reacted amorphous silica and products thereof
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice
WO1999008959A1 (fr) * 1997-08-14 1999-02-25 Goodanew, Martin, Eric Procede de production d'acide de silice
US5908660A (en) * 1997-09-03 1999-06-01 Dow Corning Corporation Method of preparing hydrophobic precipitated silica
WO1999036356A2 (fr) * 1998-01-15 1999-07-22 Cabot Corporation Traitement de la silice au moyen d'organosilanes polyfonctionnels
RU2152967C1 (ru) * 1999-04-27 2000-07-20 Акционерное общество "Российская инновационная топливно-энергетическая компания" Способ получения гидрофобного, органофильного кремнезема
EP1265812B1 (fr) * 2000-02-10 2003-11-19 Promeks AS Procede de preparation de silice amorphe
JP2001294775A (ja) * 2000-04-12 2001-10-23 Shin Etsu Chem Co Ltd 疎水性沈降シリカの製造方法
JP2002128516A (ja) * 2000-08-16 2002-05-09 Matsushita Electric Ind Co Ltd 疎水化された乾燥ゲルの製造方法およびそれを用いた断熱材
JP2002146232A (ja) * 2000-11-07 2002-05-22 Denki Kagaku Kogyo Kk シリカ微粉の表面改質法
JP2003020218A (ja) * 2001-07-02 2003-01-24 Matsushita Electric Ind Co Ltd 疎水化乾燥ゲルの製造方法およびそれを用いた断熱材
JP2003020219A (ja) * 2001-07-09 2003-01-24 Matsushita Electric Ind Co Ltd 乾燥ゲルの製造方法とこの方法を用いて作られた断熱材
WO2004054927A1 (fr) * 2002-12-18 2004-07-01 Degussa Ag Silice structuree de type aerogel a surface modifiee

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* Cited by examiner, † Cited by third party
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DATABASE WPI Derwent World Patents Index; AN 2002-181953 *
DATABASE WPI Week 200103, Derwent World Patents Index; AN 2001-022432 *
DATABASE WPI Week 200266, Derwent World Patents Index; AN 2002-611243 *
DATABASE WPI Week 200275, Derwent World Patents Index; AN 2002-693745 *
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DATABASE WPI Week 200352, Derwent World Patents Index; AN 2003-545663 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2437953A (en) * 2006-04-27 2007-11-14 Agilent Technologies Inc Silica-based chromatographic stationary phase
US8480889B2 (en) 2006-04-27 2013-07-09 Agilent Technologies, Inc. Chromatographic stationary phase
US7534352B2 (en) 2007-05-01 2009-05-19 Agilent Technologies, Inc. Reversed endcapping and bonding of chromatographic stationary phases using hydrosilanes
CN112624124A (zh) * 2020-12-16 2021-04-09 新沂市中大石英科技有限公司 一种高纯高疏水石英砂的制备工艺
CN112624124B (zh) * 2020-12-16 2022-05-13 新沂市中大石英科技有限公司 一种高纯高疏水石英砂的制备工艺
CN114835129A (zh) * 2022-04-26 2022-08-02 连云港强邦石英制品有限公司 一种石英砂酸洗设备及酸洗工艺

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