WO2002051749A1 - Procede de preparation d'une silice precipitee comprenant deux familles d'agregats et a distribution de tailles de pores monomodale - Google Patents
Procede de preparation d'une silice precipitee comprenant deux familles d'agregats et a distribution de tailles de pores monomodale Download PDFInfo
- Publication number
- WO2002051749A1 WO2002051749A1 PCT/FR2001/004162 FR0104162W WO02051749A1 WO 2002051749 A1 WO2002051749 A1 WO 2002051749A1 FR 0104162 W FR0104162 W FR 0104162W WO 02051749 A1 WO02051749 A1 WO 02051749A1
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- WIPO (PCT)
- Prior art keywords
- silica
- aggregates
- equal
- minutes
- reaction
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/80—Compositional purity
-
- 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
- C01P2006/90—Other properties not specified above
Definitions
- the present invention relates to a new process for the preparation of a precipitated silica, formed of two populations of aggregates while having a size distribution of the monomodal pores.
- the main object of the invention is therefore a process for preparing a precipitated silica which, on the one hand, comprises two families of aggregates, the aggregates of the first family consisting of (individual) particles of silica of sizes between 4 and 15 nm, preferably between 10 and 15 nm, the aggregates of the second family consisting of (individual) silica particles of sizes between 16 and 35 nm, preferably between 17 and 30 nm, in particular between 20 and 25 nm, and, on the other hand, presents a distribution of monomodal pore sizes (a single peak is observed in the graphic representation of this distribution).
- the size of the particles can be measured in particular by Transmission Electron Microscopy; the pore size distribution is determined by mercury porosimetry (standard DIN 66133).
- the mixture obtained is filtered so as to obtain a filtration cake, advantageously pumpable,
- the precipitated silica obtained advantageously consists of an intimate mixture of two families (populations) of aggregates, the aggregates of the first family generally representing 15 to 85%, preferably 20 to 50%, by weight of the silica, and the aggregates of the second family generally representing 15 to 85%, preferably 50 to 80%, by weight of the silica.
- Each (aqueous) silica suspension used in the process of the invention results from a precipitation reaction of a silica, before the filtration step, in particular by reaction between an alkali metal silicate (sodium silicate for example) and an acid (sulfuric acid for example).
- an alkali metal silicate sodium silicate for example
- an acid sulfuric acid for example
- Silica suspensions can for example be used as obtained during the precipitation reactions described in applications EP 0520862, WO 95/09127, WO 95/09128 and WO 98/54090.
- the two silica suspensions used can be derived from the precipitation reactions of silica having between them a difference in BET specific surface area values and / or a difference in CTAB specific surface area values of at least 30 m 2 / g, in particular d '' at least 40 m 2 / g, for example at least 60 m 2 / g. According to a variant of the invention, this difference is even at least
- the BET specific surface is determined according to the BRUNAUER - EMMET - TELLER method described in "The Journal of the American Chemical Society", Vol. 60, page 309, February 1938 and corresponding to standard NF T 45007 (November 1987).
- the CTAB specific surface is the external surface determined according to standard NF T 45007 (November 1987) (5.12).
- the mass ratio between the two suspensions to be mixed is generally between 25:75 and 75:25, in particular between 40:60 and 60:40. Most often this ratio is around 50:50.
- the filtration of the mixture of the two suspensions (slurries) can be carried out by means of any suitable filter making it possible to advantageously obtain a pumpable filter cake, in particular a press filter or a vacuum filter . Filtration can be accompanied by washing.
- the drying can be carried out using a turbine atomizer; the precipitated silica obtained is then generally in the form of powder, preferably of average size of at least 15 ⁇ m, in particular between 30 and 120 ⁇ m.
- the precipitated silica obtained is then rather in the form of substantially spherical beads, preferably of average size of at least 80 ⁇ m, for example of at least 150 ⁇ m and generally of at most 300 ⁇ m (standard NF X 11507).
- the drying can be preceded by a fluidification operation (disintegration) of the cake, by a mechanical action, for example by passing the cake through a grinder of the colloidal or ball type; this mechanical action can be carried out in the presence of an aluminum compound, in particular sodium aluminate and, preferably, in the presence of an acidifying agent.
- the fluidification operation notably makes it possible to lower, if necessary, the viscosity of the cake to be dried.
- a grinding step can optionally be carried out on the silica obtained; this grinding generally leads to a powder.
- the dried (in particular by a turbine atomizer) or ground product can be subjected to an agglomeration operation (in particular direct compression, wet granulation, extrusion, and preferably dry compaction); the precipitated silica obtained is then usually in the form of granules, preferably of size at least 1 mm, in particular between 1 and 10 mm.
- an agglomeration operation in particular direct compression, wet granulation, extrusion, and preferably dry compaction
- the precipitated silica capable of being obtained by the process according to the invention generally has a DOP oil intake of between 180 and
- the DOP oil intake is determined according to standard NFT 30-022 (March 1953) using dioctylphthalate.
- It usually has: - a BET specific surface area of between 110 and 260 m 2 / g, in particular between 140 and 230 m 2 / g,
- CTAB specific surface of between 100 and 250 m 2 / g, for example between 140 and 230 m 2 / g.
- pH is for example between 6.0 and 7.5, in particular between 6.4 and 7.0.
- a subject of the present invention is also the silica capable of being obtained by the process according to the invention.
- the silicas (capable of being) obtained by the process according to the invention preferably have a good ability to disperse / disagglomerate; this ability can be quantified by means of the test described in application WO 98/54090; thus, they may have a median diameter (0 50 ), after deagglomeration with ultrasound, less than 5 ⁇ m; they can also have an ultrasound disaggregation factor (F D ) of at least 5.5 ml. They find a particularly advantageous application as a reinforcing filler in polymer compositions.
- polystyrene resins are generally based on one or more polymers or copolymers, in particular on one or more elastomers
- hermoplastic elastomers preferably having a glass transition temperature of between -150 and +300 ° C, for example between -150 and +20 ° C.
- polystyrene polystyrene
- silicone elastomers and halogenated polymers Said polymer compositions can be vulcanized with sulfur. In general, they further comprise at least one coupling agent and / or at least one recovery agent; they can also comprise, inter alia, an oxidizing agent.
- the proportion by weight of silica in the polymer composition can vary within a fairly wide range. In general, it represents 20 to 70%, for example 25 to 60%, of the amount of the polymer (s).
- the present invention also relates to the finished articles based on the polymer compositions described above. Mention may be made, as finished articles, of floor coverings, shoe soles, parts of vehicle tracks, tire casings (in particular the sidewalls and tire tread), cable car rollers, seals for household appliances, sheaths, cables, transmission belts.
- the following examples illustrate the invention without, however, limiting its scope.
- the mixture obtained has an SiO 2 concentration equal to 74 g / l. Maintained with stirring, it is brought to 90 ° C. by double jacket heating. When this temperature is reached, a diluted sulfuric acid with a density of 20 ° C. equal to 1050 kg / m 3 is introduced at a flow rate of 4.91 l / h until a value is obtained in the reaction medium. pH 8 (after 60 minutes of introduction of acid). The temperature is equal to 90 ° C during the first 40 minutes of the reaction, it is then brought from 90 ° C to 95 ° C in about 5 minutes by heating by double jacket, then maintained at 95 ° C until the end. of the reaction.
- silicate is introduced jointly into the reaction medium.
- the introduction of the silicate is stopped and the introduction of diluted acid is then continued, so that the pH value of the reaction medium reaches 5.2 in approximately 7 minutes.
- the reaction suspension is then kept at this pH for 5 minutes.
- the mixture obtained has an Si0 2 concentration equal to 75 g / l. Maintained with stirring, it is brought to 73 ° C. by double jacket heating. When this temperature is reached, a dilute sulfuric acid with a density of 20 ° C. equal to 1050 kg / m 3 is introduced at a flow rate of 5.2 l / h until a value is obtained in the reaction medium. of pH equal to 8. The temperature is equal to 73 ° C during the first 25 minutes of the reaction, it is then brought from 73 ° C to 95 ° C in about 20 minutes by heating by double jacket, then maintained at 92 ° C until the end of the reaction.
- aqueous sodium silicate of the type described above is introduced jointly into the reaction medium at a flow rate of 1.76 l / h and sulfuric acid, also of the type described above at a controlled rate so as to maintain the pH value of the reaction medium equal to 8 +/- 0.1.
- the introduction of the silicate is stopped and then the introduction of dilute acid is continued so that the pH value of the reaction medium reaches 5.2 in approximately 7 minutes.
- the reaction suspension is then kept at this pH for 5 minutes.
- the 2 reaction slurries N ° 1 and 2 are then mixed up to 50/50 by mass of slurry, the resulting mixture being filtered under vacuum and washed using a flat filter.
- the cake obtained is then fluidized by mechanical action. After this disintegration operation, a pumpable cake is obtained having a dry matter content of 15%; this cake is dried by means of a turbine atomizer.
- the characteristics of the silica obtained (in powder form) are as follows:
- the pore size distribution of this silica is monomodal.
- the mixture obtained has an Si0 2 concentration equal to 75 g / l. Maintained with stirring, it is brought to 91 ° C. by double jacket heating. When this temperature is reached, at a flow rate of 5 l / h, dilute sulfuric acid with a density at 20 ° C equal to 1050 kg / m 3 is introduced until the medium is obtained. reaction with a pH value equal to 8. The temperature is equal to 91 ° C. for the first 25 minutes of the reaction, it is then brought from 91 ° C. to 95 ° C. in approximately 5 minutes by heating by double jacket, then maintained at 95 ° C until the end of the reaction.
- aqueous sodium silicate of the type described above is introduced jointly at a flow rate of 2.59 l / h and sulfuric acid, also of the type described above at a controlled rate so as to maintain the pH value of the reaction medium equal to 8 +/- 0.1.
- the introduction of the silicate is stopped and the introduction of diluted acid is then continued, so that the pH value of the reaction medium reaches 5.2 in approximately 8 minutes.
- the reaction suspension is then kept at this pH for 5 minutes.
- the mixture obtained has an Si0 2 concentration equal to 60 g / l. Maintained with stirring, it is brought to 74 ° C. by double jacket heating. When this temperature is reached, a diluted sulfuric acid with a density at 20 ° C. equal to 1050 kg / m 3 is introduced at a flow rate of 5.94 l / h until a value is obtained in the reaction medium. of pH equal to 8. The temperature is equal to 91 ° C during the first 25 minutes of the reaction, it is then brought from 74 ° C to 94 ° C in about 20 minutes by heating by double jacket, then maintained at 94 ° C until the end of the reaction.
- aqueous sodium silicate of the type described above is introduced jointly into the reaction medium at a flow rate of 153 l / h and of sulfuric acid, also of the type described above at a controlled rate so as to maintain the pH value of the reaction medium equal to 8 +/- 0.1.
- the introduction of the silicate is stopped and the introduction of diluted acid is then continued, so that the pH value of the reaction medium reaches 5.2 in approximately 7 minutes.
- the reaction suspension is then kept at this pH for 5 minutes.
- the mixture obtained has an Si0 2 concentration equal to 76 g / l. Maintained with stirring, it is brought to 66 ° C. by double jacket heating. When this temperature is reached, a dilute sulfuric acid with a density at 20 ° C. equal to 1050 kg / m 3 is introduced at a flow rate of 520 l / h until a pH value is obtained in the reaction medium. equal to 8. The temperature is 66 ° C during the first 30 minutes of the reaction, it is then brought from 66 ° C to 95 ° C in about 11 minutes by introduction of live steam, then maintained at 95 ° C until 'at the end of the reaction.
- aqueous sodium silicate of the type described above is introduced jointly into the reaction medium at a flow rate of 167 l / h and of sulfuric acid, also of the type described above at a controlled rate so as to maintain the pH value of the reaction medium equal to 8 +/- 0.1.
- the introduction of the silicate is stopped and the introduction of diluted acid is then continued, so that the pH value of the reaction medium reaches 5.2 in approximately 10 minutes.
- the reaction suspension is then kept at this pH for 5 minutes.
- the resulting mixture being filtered and washed by means of a vertical filter press, the filter plates being equipped with a deformable membrane making it possible to compress the cake by introduction of air under pressure.
- the cake formed is then washed with water; after washing, the cake is compacted by the introduction of air.
- the silica cake recovered after deburring the filter has a dry matter content of 22%.
- a silica is obtained which is in the form of substantially spherical beads (average size: 250 ⁇ m), the characteristics of which are as follows: - aluminum content 0.3%
- the pore size distribution of this silica is monomodal.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01995762A EP1343724A1 (fr) | 2000-12-22 | 2001-12-21 | Procede de preparation d'une silice precipitee comprenant deux familles d'agregats et a distribution de tailles de pores monomodale |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0017363A FR2818631B1 (fr) | 2000-12-22 | 2000-12-22 | Procede de preparation d'une silice precipitee comprenant deux familles d'agregats et a distribution de tailles de pores monomodale |
FR00/17363 | 2000-12-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002051749A1 true WO2002051749A1 (fr) | 2002-07-04 |
Family
ID=8858454
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2001/004162 WO2002051749A1 (fr) | 2000-12-22 | 2001-12-21 | Procede de preparation d'une silice precipitee comprenant deux familles d'agregats et a distribution de tailles de pores monomodale |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1343724A1 (fr) |
FR (1) | FR2818631B1 (fr) |
WO (1) | WO2002051749A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003106339A1 (fr) * | 2002-06-14 | 2003-12-24 | Degussa Ag | Acide silicique obtenu par precipitation contenant de l'aluminium presentant un rapport bet/ctab ajustable |
FR2930538A1 (fr) * | 2008-04-25 | 2009-10-30 | Rhodia Operations Sas | Nouveau procede de preparation de silice precipitee |
US20110178227A1 (en) * | 2008-03-10 | 2011-07-21 | Rhodia Operations | Novel precipitated silica having particular morphology, grading and porosity, preparation thereof and reinforcing of polymers therewith |
CN107636058A (zh) * | 2015-06-12 | 2018-01-26 | 株式会社普利司通 | 橡胶组合物和轮胎 |
EP2767558B1 (fr) * | 2011-08-31 | 2019-12-11 | Bridgestone Corporation | Composition de caoutchouc, composition de caoutchouc réticulée et pneus |
CN111372791A (zh) * | 2017-11-29 | 2020-07-03 | 倍耐力轮胎股份公司 | 含纳米尺寸的具有针状形貌的硅酸盐纤维的微珠,其制备,包括它们的弹性体组合物和车辆用轮胎 |
US20220021077A1 (en) * | 2018-12-11 | 2022-01-20 | Rhodia Operations | Precipitated silica for battery separator |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117361547B (zh) * | 2023-09-11 | 2024-04-30 | 金三江(肇庆)硅材料股份有限公司 | 一种二氧化硅颗粒及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0217701A1 (fr) * | 1985-09-13 | 1987-04-08 | Rhone-Poulenc Chimie | Procédé de renforcement d'élastomères par une charge siliceuse |
WO1998054090A1 (fr) * | 1997-05-26 | 1998-12-03 | Rhodia Chimie | Silice precipitee utilisable comme charge renforçante pour elastomeres |
EP0942029A2 (fr) * | 1998-03-09 | 1999-09-15 | The Goodyear Tire & Rubber Company | Composition du caoutchouc contenant de silice, qui a premiers et seconds agrégats, chaque contenant des dimensions des particules différentes |
-
2000
- 2000-12-22 FR FR0017363A patent/FR2818631B1/fr not_active Expired - Lifetime
-
2001
- 2001-12-21 EP EP01995762A patent/EP1343724A1/fr not_active Withdrawn
- 2001-12-21 WO PCT/FR2001/004162 patent/WO2002051749A1/fr not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0217701A1 (fr) * | 1985-09-13 | 1987-04-08 | Rhone-Poulenc Chimie | Procédé de renforcement d'élastomères par une charge siliceuse |
WO1998054090A1 (fr) * | 1997-05-26 | 1998-12-03 | Rhodia Chimie | Silice precipitee utilisable comme charge renforçante pour elastomeres |
EP0942029A2 (fr) * | 1998-03-09 | 1999-09-15 | The Goodyear Tire & Rubber Company | Composition du caoutchouc contenant de silice, qui a premiers et seconds agrégats, chaque contenant des dimensions des particules différentes |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8017098B2 (en) | 2002-06-14 | 2011-09-13 | Evonik Degussa Gmbh | Aluminum-containing precipitated silicic acid having an adjustable BET/CTAB ratio |
WO2003106339A1 (fr) * | 2002-06-14 | 2003-12-24 | Degussa Ag | Acide silicique obtenu par precipitation contenant de l'aluminium presentant un rapport bet/ctab ajustable |
US9359215B2 (en) * | 2008-03-10 | 2016-06-07 | Rhodia Operations | Precipitated silica having particular morphology, grading and porosity, preparation thereof and reinforcing of polymers therewith |
US20110178227A1 (en) * | 2008-03-10 | 2011-07-21 | Rhodia Operations | Novel precipitated silica having particular morphology, grading and porosity, preparation thereof and reinforcing of polymers therewith |
KR20110008192A (ko) * | 2008-04-25 | 2011-01-26 | 로디아 오퍼레이션스 | 침강 실리카의 신규 제조 방법 |
CN102066253A (zh) * | 2008-04-25 | 2011-05-18 | 罗地亚管理公司 | 沉淀二氧化硅的新的制备方法 |
WO2009138678A1 (fr) * | 2008-04-25 | 2009-11-19 | Rhodia Operations | Nouveau procédé de préparation de silice précipitée |
US8454919B2 (en) | 2008-04-25 | 2013-06-04 | Rhodia Operations | Production of precipitated silica |
KR101589771B1 (ko) | 2008-04-25 | 2016-01-28 | 로디아 오퍼레이션스 | 침강 실리카의 신규 제조 방법 |
FR2930538A1 (fr) * | 2008-04-25 | 2009-10-30 | Rhodia Operations Sas | Nouveau procede de preparation de silice precipitee |
EP2767558B1 (fr) * | 2011-08-31 | 2019-12-11 | Bridgestone Corporation | Composition de caoutchouc, composition de caoutchouc réticulée et pneus |
CN107636058A (zh) * | 2015-06-12 | 2018-01-26 | 株式会社普利司通 | 橡胶组合物和轮胎 |
CN111372791A (zh) * | 2017-11-29 | 2020-07-03 | 倍耐力轮胎股份公司 | 含纳米尺寸的具有针状形貌的硅酸盐纤维的微珠,其制备,包括它们的弹性体组合物和车辆用轮胎 |
US11365306B2 (en) | 2017-11-29 | 2022-06-21 | Pirelli Tyre S.P.A. | Microbeads comprising silicate fibres with needle-shaped morphology of nanometric size, preparation thereof, elastomeric compositions and tyres for vehicles comprising them |
US20220021077A1 (en) * | 2018-12-11 | 2022-01-20 | Rhodia Operations | Precipitated silica for battery separator |
Also Published As
Publication number | Publication date |
---|---|
FR2818631B1 (fr) | 2003-09-26 |
EP1343724A1 (fr) | 2003-09-17 |
FR2818631A1 (fr) | 2002-06-28 |
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