WO2005108291A1 - Improved process for production of pure amorphous silica in particular xerogels for beer stabilization and for insulation purposes - Google Patents
Improved process for production of pure amorphous silica in particular xerogels for beer stabilization and for insulation purposes Download PDFInfo
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- WO2005108291A1 WO2005108291A1 PCT/NO2005/000155 NO2005000155W WO2005108291A1 WO 2005108291 A1 WO2005108291 A1 WO 2005108291A1 NO 2005000155 W NO2005000155 W NO 2005000155W WO 2005108291 A1 WO2005108291 A1 WO 2005108291A1
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- silica
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- 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
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- 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
- C01B33/16—Preparation of silica xerogels
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 silica 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. Further, 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 that never have been investigated before.
- 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 quartz includes the following steps:
- MeCI 2l Heating the crushed ( ⁇ 100 ⁇ m) quartz or other SiO 2 based 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 2l to a temperature in the range 800 - 1300 ° C preferably over a single or a two stage calcination 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 O -» (MeO)x * (SiO 2 )y + 2x HCI wherein x is greater than y in order to obtain a conversion of SiO 2 to magnesium (or calcium) silicates in excess of 99.9%.
- Step 3 Separating insoluble silica from the solution using filters (belt filter, press filter, filter press etc.) or another separation method.
- the solution contains excess of HCI, MeCI 2 and impurities.
- Step 4 Recycling of the chloride solution to step 1 and the HCI solution to step 2 using a recovery system in order to separate the solutions.
- the impurities are removed prior to the reuse of the solutions in order to avoid build-up of impurities.
- Several techniques can be used to remove impurities depending on the amount of impurities in the raw materials, but one way is to precipitate impurities as hydroxides at elevated pH.
- the purity of acid-set silica gels A and B is very high, typically 99.96-99.98%SiO 2 , which makes them extremely useful in such applications as Zeolite production, insulation, in food industry etc.
- Example 1 Silica A. Calcium silicate/water mixing. Calcium silicate produced in Step 1 with particle size ⁇ 200micron (200kg) was fed to a tank containing 360 litre of water under continuous agitation. Samples of the slurry were taken to test the homogeneity of the silicate distribution in water. Leaching. The slurry of calcium silicate and water was fed to the reactor filled with
- Washing at the filter press was made in three steps: washing from diagonal 1 , washing from diagonal 2 and central washing. To get silica with purity >99.95% SiO 2 the repulping stage was repeated twice. The washing procedure was controlled by the chloride content in the wash water and in wet cake ( ⁇ 30ppm). The wet cake contained about 90%) water. Drying. The wet cake was dried in a Barr-Rosin ring drier, and the dried silica was jet milled.
- Example 2 Silica B Calcium silicate/water mixing was made as in Example 1. Leaching. The slurry of calcium silicate and water was fed to the reactor filled with 15.85%) hydrochloric acid (1520 litre). Slurry feeding took about 30 min under agitation. After the slurry addition the final acid concentration in the reactor was 13%. The temperature in the reactor was 45°C and the agitator was operated with 100%) speed. The reactor was heated to 150°C. The leaching proceeded at this temperature for 60 minutes. After cooling of the leaching slurry to 40°C-45°C the reactor was emptied to an intermediate tank from which the leaching slurry passed to a filter press. Filtration and washing was made as in Example 1. The wet cake contained about 80%- 84%) water. Drying.
- This type of silica had the following characteristics: Surface area, 480 m2/g; pore volume, 1.05 ml/g, pore radius, 4,2 nm; bulk density 0,25 g/ml; absorption, 180 ml oil/1 OOg; % of SiO 2 99,97; and pH 5,0.
- Average particle size was 70 micron.
- the particle size (D 5 n) was 20micron.
- Spray dried silica A and B can be used for filtration purposes, as catalyst carriers, beer stabilizer or for other purposes that require very pure silica, e.g. zeolite production.
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Abstract
A process for production of amorphous silica from quartz or other SiO2 based raw material, includes the following steps: heating (calcinations step) of quartz or other SiO2 based raw material with MgCl2 , CaCl2 or other chlorides like BeCl2, SrCl2 and BaCl2 (commonly referred to as MeCl 2) at a temperature of 800 - 1300 °C wherein the weight ratio of MeCl2 to SiO2 is equal or greater than 2 and the presence of water vapour in excess of the stoichiometric amount needed; leaching at temperatures preferable between 50 - 95 or between 110 and 170 °C of the produced silicate with HCl to form a solution of MeCl2 with insoluble silica; separation of insoluble silica from the solution; recycling of MeCl2 to the heating step and the remaining HCl solution to the leaching step.
Description
IMPROVED PROCESS FOR PRODUCTION OF PURE AMORPHOUS SILICA IN PARTICULAR XEROGELS FOR BEER STABILIZATION AND FOR INSULATION PURPOSES
The present invention relates to the production of pure amorphous silica from quartz or other SiO2 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 silica 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. Also other known processes (silicon tetrachloride/alkoxide reacts with hydrogen and oxygen to form fumed silica) are used commonly in the present silica industry.
Methods for preparation of amorphous silica from soluble silicates are well established, but suffer from the disadvantage that soluble alkali silicate and mineral acid are consumed in the production process. Furthermore, these silica products often contain rather high amounts of alkali metals, which is unwanted for many applications.
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.
Further, 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 CaCI2 is the only reagent used in the mixture with the raw materials.
Common for all prior art solutions is that no provisions are made with regard to the possibilities for the silica product, no description of the silica product is given and nothing is stated about the applications for the various types of pure silica products.
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 that never have been investigated before. 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 SiO2 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 invention according to the present invention will be further described in the following with reference to the attached drawing showing, Fig.1 , the main steps of the process. The process according to the invention for production of amorphous silica from quartz includes the following steps:
Step l.
Heating the crushed (< 100 μm) quartz or other SiO2 based raw material together with MgCI2 or CaCI2, or other chlorides like BeCI2, SrCI2 and BaCI2, in the following referred to as MeCI2l to a temperature in the range 800 - 1300 °C preferably over a single or a two stage calcination steps for a period of 0.5 to 3 hours, depending on the temperature,
wherein the ratio of MeCI2 to the SiO2 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 MeCI2 + y SiO2 + x H2O -» (MeO)x * (SiO2)y + 2x HCI wherein x is greater than y in order to obtain a conversion of SiO2 to magnesium (or calcium) silicates in excess of 99.9%. The HCI produced during calcination is absorbed in a scrubber and via step 4 reused in step 2.
Step 2.
Leaching of the metal silicate with HCI at a temperature between 50 - 95 °C,or between 110 -170 °C, to form a solution of MeCI2 with insoluble silica.
Step 3. Separating insoluble silica from the solution using filters (belt filter, press filter, filter press etc.) or another separation method. The solution contains excess of HCI, MeCI2 and impurities.
Step 4. Recycling of the chloride solution to step 1 and the HCI solution to step 2 using a recovery system in order to separate the solutions. The impurities are removed prior to the reuse of the solutions in order to avoid build-up of impurities. Several techniques can be used to remove impurities depending on the amount of impurities in the raw materials, but one way is to precipitate impurities as hydroxides at elevated pH. The purity of acid-set silica gels A and B is very high, typically 99.96-99.98%SiO2, which makes them extremely useful in such applications as Zeolite production, insulation, in food industry etc.
Example 1. Silica A.
Calcium silicate/water mixing. Calcium silicate produced in Step 1 with particle size <200micron (200kg) was fed to a tank containing 360 litre of water under continuous agitation. Samples of the slurry were taken to test the homogeneity of the silicate distribution in water. Leaching. The slurry of calcium silicate and water was fed to the reactor filled with
15.85% hydrochloric acid (1520 litre). Slurry feeding took about 30 min under agitation. After the slurry addition the final acid concentration in the reactor was 13%. The temperature in the reactor was 45°C and the agitator operated with 100% speed. The reactor was heated to 104°C for about 30 minutes. At the temperature 70°C-80°C the speed of agitator decreased to 30%. The leaching proceeded at this temperature for 30 minutes. After cooling of the leaching slurry to 40°C-45°C the reactor was emptied to an intermediate tank from which the leaching slurry passed to a filter press. Filtration. After the first filtration and washing the silica was repulped and again filtered and washed. Washing at the filter press was made in three steps: washing from diagonal 1 , washing from diagonal 2 and central washing. To get silica with purity >99.95% SiO2 the repulping stage was repeated twice. The washing procedure was controlled by the chloride content in the wash water and in wet cake (<30ppm). The wet cake contained about 90%) water. Drying. The wet cake was dried in a Barr-Rosin ring drier, and the dried silica was jet milled.
The silica had the following characteristics. Surface area 750m2/g, pore volume 0.61cm3/g, oil absorption 108ml oil/1 OOg silica, bulk density 0.48 g/cm3, pH5.3, 99.98%SiO2, 4.0% water. This type of silica, type A, had D50=3.8 micron, the bulk density was 0.22 g/ml and the oil absorption 170ml oil/1 OOg silica.
Example 2. Silica B Calcium silicate/water mixing was made as in Example 1.
Leaching. The slurry of calcium silicate and water was fed to the reactor filled with 15.85%) hydrochloric acid (1520 litre). Slurry feeding took about 30 min under agitation. After the slurry addition the final acid concentration in the reactor was 13%. The temperature in the reactor was 45°C and the agitator was operated with 100%) speed. The reactor was heated to 150°C. The leaching proceeded at this temperature for 60 minutes. After cooling of the leaching slurry to 40°C-45°C the reactor was emptied to an intermediate tank from which the leaching slurry passed to a filter press. Filtration and washing was made as in Example 1. The wet cake contained about 80%- 84%) water. Drying. The wet cake dried in a Barr-Rosin ring drier resulted in silica with the following properties: chloride content <100ppm, Al<30ppm, Ca=90ppm, Fe<50ppm, Ca, Mg, Ti= 20ppm, Na<90ppm, Ni, V, Zr<10ppm.
This type of silica had the following characteristics: Surface area, 480 m2/g; pore volume, 1.05 ml/g, pore radius, 4,2 nm; bulk density 0,25 g/ml; absorption, 180 ml oil/1 OOg; % of SiO299,97; and pH 5,0.
Average particle size was 70 micron.
A portion of the filter cake was repulped and spray dried. The properties of the silica B was:
Surface area, 480 m2/g; pore volume, 1.2 ml/g, pore radius, 4,7 nm; bulk density 0,28 g/ml; oil absorption, 290 ml oil/100g; % of SiO299,97; and pH 5,2.
The particle size (D5n) was 20micron.
Spray dried silica A and B can be used for filtration purposes, as catalyst carriers, beer stabilizer or for other purposes that require very pure silica, e.g. zeolite production.
Claims
1. Process for production of amorphous silica from quartz or other SiO2 based raw material, characterised by the following steps:
• heating (calcinations step) of the SiO2 based material with MgCI2 , CaCI2 or other chlorides like BeCI2, SrCI2 and BaCI2 (commonly referred to as MeCl 2) at a temperature of 800 - 1300 °C wherein the weight ratio of MeCI2 to SiO2 is greater than 2 and the presence of water vapour in excess of the stoichiometric amount needed • leaching at temperatures preferable between 50 and 95 or between 110 and 170 °C of the produced calcium silicate with HCI to form a solution of MeCI2 with insoluble silica, • separation of insoluble silica from the solution, whereby, after first filtration and washing, the silica is repulped and again filtered and washed, • recycling of MeCI2 to the heating step and the remaining HCI solution to the leaching step,
2. Process in accordance with claims 1 , characterised in that the calcination step is carried out at the temperature 1150-1250°C if the raw material is quartz.
3. Process in accordance with claims 1 ,2 characterised in that the calcination step is carried out in two steps where the first step is kept below 1000 °C and the second step can have temperature as high as 1300 °C.
Process in accordance with claims 1 - 3, characterised in that metal impurities such as Fe,AI and Ti are removed prior to reuse of the chlorine and acid solutions.
Process in accordance with claims 1 -3 characterised in that to obtain silica with purity >99.95%> SiO2 the repulping stage is repeated at least twice
6 Process in accordance with claim 1,2 characterised in that silica type A is produced by addition of slurry of bake to acid, the leaching is made at a temperature between 60 - 95 °C and after filtration and washing the wet filter cake is dried in a suitable oven or spray dried
7 Process in accordance with claim 1,2 characterised in that a silica type B is produced by leaching at 140 - 160 °C and for the rest as for type A.
8. Use of silica products produced according to the preceding claims for filtration purposes, as catalyst carriers, beer stabilizer or as raw material for zeolites.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO20041960 | 2004-05-12 | ||
| NO20041960 | 2004-05-12 | ||
| NO20042646 | 2004-06-23 | ||
| NO20042646A NO20042646D0 (en) | 2004-05-12 | 2004-06-23 | Improved process for the production of pure amorphous silica especially zerogel for stabilization of ol, as well as for insulation formula |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005108291A1 true WO2005108291A1 (en) | 2005-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NO2005/000155 Ceased WO2005108291A1 (en) | 2004-05-12 | 2005-05-12 | Improved process for production of pure amorphous silica in particular xerogels for beer stabilization and for insulation purposes |
Country Status (2)
| Country | Link |
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| NO (1) | NO20042646D0 (en) |
| WO (1) | WO2005108291A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9205375B2 (en) | 2007-09-20 | 2015-12-08 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
| US9359221B2 (en) | 2010-07-08 | 2016-06-07 | Skyonic Corporation | Carbon dioxide sequestration involving two-salt-based thermolytic processes |
| US9968883B2 (en) | 2014-01-17 | 2018-05-15 | Carbonfree Chemicals Holdings, Llc | Systems and methods for acid gas removal from a gaseous stream |
| US10583394B2 (en) | 2015-02-23 | 2020-03-10 | Carbonfree Chemicals Holdings, Llc | Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide |
Citations (4)
| 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 |
| WO1997022554A1 (en) * | 1995-12-15 | 1997-06-26 | Mashal Alumina Industries Ltd. | Process for recovery of alumina and silica |
| WO1999008959A1 (en) * | 1997-08-14 | 1999-02-25 | Goodanew, Martin, Eric | A process for producing silica acid |
| EP1265812B1 (en) * | 2000-02-10 | 2003-11-19 | Promeks AS | A process for the preparation of amorphous silica |
-
2004
- 2004-06-23 NO NO20042646A patent/NO20042646D0/en unknown
-
2005
- 2005-05-12 WO PCT/NO2005/000155 patent/WO2005108291A1/en not_active Ceased
Patent Citations (4)
| 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 |
| WO1997022554A1 (en) * | 1995-12-15 | 1997-06-26 | Mashal Alumina Industries Ltd. | Process for recovery of alumina and silica |
| WO1999008959A1 (en) * | 1997-08-14 | 1999-02-25 | Goodanew, Martin, Eric | A process for producing silica acid |
| EP1265812B1 (en) * | 2000-02-10 | 2003-11-19 | Promeks AS | A process for the preparation of amorphous silica |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9205375B2 (en) | 2007-09-20 | 2015-12-08 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
| US9359221B2 (en) | 2010-07-08 | 2016-06-07 | Skyonic Corporation | Carbon dioxide sequestration involving two-salt-based thermolytic processes |
| US9968883B2 (en) | 2014-01-17 | 2018-05-15 | Carbonfree Chemicals Holdings, Llc | Systems and methods for acid gas removal from a gaseous stream |
| US10583394B2 (en) | 2015-02-23 | 2020-03-10 | Carbonfree Chemicals Holdings, Llc | Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide |
| US11498029B2 (en) | 2015-02-23 | 2022-11-15 | Carbonfree Chemicals Holdings, Llc | Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide |
| US11772046B2 (en) | 2015-02-23 | 2023-10-03 | Carbonfree Chemicals Holdings, Llc | Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide |
| US12179148B2 (en) | 2015-02-23 | 2024-12-31 | Carbonfree Chemicals Holdings, Llc | Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20042646D0 (en) | 2004-06-23 |
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