EP2828200A1 - Procédé de préparation de silice précipitée mettant en oeuvre un malaxeur ou une extrudeuse - Google Patents
Procédé de préparation de silice précipitée mettant en oeuvre un malaxeur ou une extrudeuseInfo
- Publication number
- EP2828200A1 EP2828200A1 EP13711378.3A EP13711378A EP2828200A1 EP 2828200 A1 EP2828200 A1 EP 2828200A1 EP 13711378 A EP13711378 A EP 13711378A EP 2828200 A1 EP2828200 A1 EP 2828200A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cake
- disintegration
- precipitated silica
- carried out
- bar
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
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
- C01B33/126—Preparation of silica of undetermined type
- C01B33/128—Preparation of silica of undetermined type by acidic treatment of aqueous silicate solutions
-
- 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
Definitions
- the present invention relates to an improved process for the preparation of precipitated silica.
- precipitated silicas as a catalyst support, as an absorbent of active substances (in particular liquid carriers, for example used in foodstuffs, such as vitamins (vitamin E in particular), choline chloride), as a viscosifying, texturizing or anti-caking agent, as an element for battery separators, as an additive for toothpaste, for paper.
- active substances in particular liquid carriers, for example used in foodstuffs, such as vitamins (vitamin E in particular), choline chloride
- a viscosifying, texturizing or anti-caking agent as an element for battery separators, as an additive for toothpaste, for paper.
- precipitated silicas as reinforcing filler in silicone matrices (for example for coating electrical cables) or in compositions based on polymer (s), natural or synthetic, in particular elastomer (s), especially diene, for example for shoe soles, floor coverings, gas barriers, fire-retardant materials and also technical parts such as ropeway rollers, appliance seals, liquid or gas line joints, brake system seals, ducts, cables and transmission belts.
- Precipitated silica has in particular been used for a long time as reinforcing white filler in elastomers, and in particular in tires.
- the precipitated silica preparation is generally carried out by precipitation reaction between a silicate, in particular an alkali metal silicate, and an acidifying agent, followed by a filtration separation step to obtain a filter cake and usually a step of washing said cake, then a possible step of disintegrating the filter cake and a drying step, for example by atomization, said cake.
- one of the aims of the present invention is to provide a process for the preparation of precipitated silica which makes it possible to limit energy expenditure, particularly in terms of drying.
- One of the aims of the present invention is to provide a method for preparing precipitated silica that can limit the drying times.
- One of the aims of the invention is in particular to provide an alternative to the known preparation processes of precipitated silica, which is economical and simple to implement.
- One of the aims of the present invention is thus to provide a method making it possible to reduce the energy consumption during drying, in particular with respect to the methods of the state of the art, and this, in general, of at least about 15%, in particular at least about 20%, for example at least about 25%, especially in the context of the very preferred variant of the invention.
- One of the aims of the present invention is preferably to provide a process for increasing the productivity of the precipitated silica preparation process, in particular at the level of the disintegration stage and / or the drying stage, in particular by means of to the processes of the state of the art, and this, in general, of at least about 20%, in particular at least about 25%, for example at least about 30%, especially in the context of the very preferred variant of the invention.
- the present invention therefore relates to a process for preparing precipitated silica comprising reacting a silicate with an acidifying agent to obtain a suspension of precipitated silica (S1), followed by a separation step to obtain a cake, a step disintegrating said cake to obtain a suspension of precipitated silica (S2) and a drying step of this suspension, and wherein the disintegrating step is carried out by mixing by means of a double-screw kneader or by extrusion.
- the method according to the present invention thus comprises the following steps:
- At least one silicate is reacted (precipitation reaction) with at least one acidifying agent, so as to obtain a suspension of precipitated silica (S1),
- a solid-liquid separation step is carried out, more particularly filtration, to obtain a solid product, also referred to as a "filter cake",
- said filter cake is subjected to a kneading disintegration operation by means of a double-screw (or twin-screw) kneader or by extrusion, to obtain a suspension of precipitated silica (S2), and the product thus obtained is dried, preferably by spray drying.
- the specific step of the process of the invention taken in combination with the other steps of said process, consists of a mixing disintegration step in a double screw mixer or by extrusion.
- This step consists in implementing a piston process.
- the use of a double-screw kneader or extrusion techniques for the disintegration step more particularly makes it possible to disintegrate filter cake having a very high content of dry matter.
- conventional disintegration techniques by chemical treatment in a continuous stirred tank
- the disintegration operation is a process of fluidification or liquefaction of the cake resulting from the filtration, in which the cake is made liquid, the precipitated silica being in suspension.
- this operation makes it possible in particular to lower the viscosity of the suspension to be dried later.
- This operation can conventionally be carried out by subjecting the cake to a chemical action, for example by adding an aluminum compound such as sodium aluminate, and / or acid, preferably coupled to an action mechanics (such as passing through a continuously stirred tank).
- the disintegration step of the process according to the invention therefore consists in a particular mechanical action, namely a mechanical action of the piston type, preferably coupled with a chemical treatment, such as for example one of the chemical treatments conventionally employed during the step of disintegrating the silica filter cake in the processes for preparing precipitated silicas.
- the particular mechanical action of the disintegration step of the process according to the invention is mixing by means of a double-screw kneader or extrusion.
- the implementation of the method according to the invention makes it possible to reduce the energy consumption and to increase the productivity, in particular at the level of the drying step and / or the disintegration step, compared with the processes of the invention. state of the art, advantageously while not degrading the properties of the precipitated silica obtained, in particular its dispersibility, in particular in the elastomers.
- the disintegration step is carried out by extrusion, use is made in particular of a single-screw extruder or, preferably, a double-screw (or twin-screw) extruder.
- a double-screw mixer or an extruder, in particular a twin-screw extruder makes it possible to distribute the energy to be supplied well.
- the disintegration implemented is more homogeneous than a traditional disintegration. Each portion of cake entering the kneader or extruder receives substantially the same energy.
- the chemical reagent (s) used in the chemical treatment generally coupled to the particular mechanical action of the disintegration step, in particular a compound of aluminum, such as sodium aluminate and / or an acid, is (are) introduced in line.
- a compound of aluminum such as sodium aluminate and / or an acid
- the use of a double-screw kneader or an extruder, in particular a double-screw extruder makes it possible to guarantee an identical residence time for all the cakes subjected to the disintegration step, contrary to the techniques traditional disintegration.
- the use of a double-screw kneader or an extruder, in particular a twin-screw extruder may also make it possible to reduce the residence time of the cake in the device used for the disintegration occurrence of said kneader or said extruder), with respect to the residence time of the cake in the devices conventionally used during disintegration (which are generally at least about 20 minutes in a stirring step continuously stirred tray for example).
- the residence time of the cake in the double-screw kneader or in the extruder is less than 10 minutes, advantageously between 20 seconds and 5 minutes.
- This residence time can be 1 minute. It may even be at most 1 minute, especially between 20 and 60 seconds, for example between 20 and 45 seconds.
- the double-screw kneader or the corresponding twin-screw extruder may comprise different feed zones and a plurality of feed zones. shear.
- the corresponding twin-screw mixer or twin-screw extruder used may comprise a first zone corresponding to the feed zone of the cake, a second zone corresponding to the zone of introduction of one or more chemical agents of the cake.
- disintegration in particular aluminate
- a third zone corresponding to the zone of introduction of a chemical disintegrating agent.
- This twin-screw mixer or twin-screw extruder may also comprise two distinct shear zones downstream of the feed and feed zones mentioned above.
- the disintegration step is carried out at a temperature of between 15 and 120 ° C. It can be carried out at a temperature of between 15 and 80 ° C., preferably between 40 and 70 ° C. It can also be used at a temperature of between 50 and 120 ° C., in particular between 60 and 100 ° C., especially by adding water vapor.
- the product (cake) subjected to the mixing disintegration step by means of a double-screw kneader or by extrusion, in particular by double-screw extrusion may have a dry matter content (or dryness or solids content) of at least 15% by weight, especially at least 18% by weight, in particular between 18 and 40%, for example between 20 and 35% by weight; .
- One of the advantages of the process according to the invention is that it makes it possible to treat by disintegration products (cakes) having a very high content of dry matter, in particular of at least 25% by weight, in particular between 25 and 40% by weight. %, for example between 25 and 35% by weight, especially without degradation of the properties of the final precipitated silica, such as dispersibility in the elastomers.
- the process according to the invention comprises a step of compacting at rather high pressure between the separation step and the disintegration step as described in the above discussion, allowing in general, obtaining a product (cake) having a very high content of dry materials such as those indicated above.
- This compaction step makes it possible to remove a large quantity of water from the cake obtained at the end of the precipitation and separation steps.
- the compacting step is carried out at a pressure greater than 10 bar, preferably at a pressure of at least 20 bar.
- the compacting step is carried out at a pressure greater than 10 bar and less than 60 bar, preferably between 15 and 45 bar, in particular between 20 and 45 bar, especially between 20 and 45 bar. 35 bars.
- This step can be carried out at a compacting pressure of between 20 and 30 bar.
- the pressure may be about 25 bar.
- the compaction step may optionally be performed on the same filter as that used during the filtration step.
- the filtration step, the optional washing step and the compaction step may in certain cases consist of a single separation step including filtration, a possible washing (with water for example) and a strong final compaction on a filter equipped with a compaction means, such as a filter press.
- the duration of the compacting step, at the indicated pressure, in this very preferred variant of the process of the invention is at least 200 seconds, preferably between 300 and 600 seconds.
- the product obtained at the end of the compacting step has a solids content of at least 28% by weight, in particular between 28 and 35% by weight, for example between 28 and 32%. in weight.
- This level of solids may be at least 29%, especially at least 30%, by weight, and in particular between 29 and 35% by weight, for example between 29 and 32% by weight.
- the process according to the invention relates to a process for the synthesis of precipitated silica, that is to say that a precipitation stage is first implemented in which at least one acidifying agent is reacted with at least one acidifying agent.
- silicate without limitation to a particular type of precipitated silica.
- the process according to the invention can be implemented in particular for the preparation of precipitated silicas as obtained according to the processes described for example in applications EP 0 520 862, EP 0 670 813 and EP 0 670 814, EP 0 917 519, WO 95/09127, WO 95/09128, WO 98/54090, WO 03/016215, WO 2009/1 12458 or WO 2012/010712.
- the precipitation reaction by reaction of a silicate with an acidifying agent can be carried out in the process according to the present invention according to any method of preparation, in particular by adding an acidifying agent to a silicate stockstock, or by simultaneous total or partial addition of acidifying agent and silicate on a base of water, or silicate or acidifying agent.
- acidifying agent and silicate is in a manner well known per se.
- a strong mineral acid such as sulfuric acid, nitric acid or hydrochloric acid or an organic acid such as acetic acid, formic acid or carbonic acid is generally used as the acidifying agent.
- the separation step mentioned above consists of a solid-liquid separation step.
- it consists of a filtration step at the end of which a filter cake is obtained, where appropriate followed by a washing step of said cake.
- the filtration may be carried out by any suitable method, for example by means of a filter press or a belt filter or a vacuum rotary filter.
- the product (cake) obtained is then subjected to the disintegration step as described above.
- the method of the invention may comprise a delustering step between the separation step and the disintegration step; in the context of the very preferred variant of the process according to the invention, this optional delustering step is carried out between the compaction step and the disintegration step.
- This optional step consists in crumbling the cake resulting from the separation step, or, in the context of the very preferred variant of the process according to the invention, the product (cake) resulting from the compaction step, and makes it possible to reduce the particle size of said cake.
- this step can be carried out with a Gericke thinner, wherein the cake is forced through a grid of diameter less than 20 mm, preferably of size between 2 and 14 mm.
- This delamination step can also be performed by Wyssmont tools such as the "Rotocage Lumpbreaker", the "Double Rotocage Lumpbreaker” or the "Triskelion Lumpbreaker”.
- the precipitated silica suspension S2 obtained at the end of the disintegration stage is then dried.
- This drying can be done by any means known per se.
- the drying is carried out by atomization.
- any type of suitable atomizer may be used, especially a turbine atomizer, preferably a nozzle atomizer, liquid pressure or two fluids.
- the precipitated silica that can then be obtained by the process according to the invention is advantageously in the form of substantially spherical beads (microbeads), preferably of medium size. at least 80 ⁇ .
- the precipitated silica then obtained is generally in the form of a powder, preferably of average size between 5 and 70 ⁇ .
- the precipitated silica that can then be obtained can be in the form of a powder, for example of average size between 5 and 70 ⁇ .
- the dried product especially when it is in powder form, or ground may optionally be subjected to an agglomeration step, which consists for example of a direct compression, wet granulation (ie with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction.
- agglomeration step which consists for example of a direct compression, wet granulation (ie with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction.
- agglomeration step which consists for example of a direct compression, wet granulation (ie with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction.
- the precipitated silica that can be obtained at the end of this agglomeration step is generally in the form of granules, in particular of at least 1 mm in size, in particular between 1 and 10 mm, in particular according to axis of their largest dimension.
- the precipitated silica suspension used (S1) is a slurry (slurry) of silica Z1 165MP resulting from a precipitation reaction, having the following characteristics:
- silica suspension S1 A portion of the silica suspension S1 is filtered and washed on a filter press and then compacted at a pressure of 8 bar.
- the resulting silica cake G1 has a solids content of 23.5%.
- the other part of the silica suspension S1 is filtered and washed on a filter press and is then compacted at a pressure of 25 bar.
- the resulting silica cake G2 has a solids content of 29%.
- the cake G1 is swept by a passage in a starter (Gericke) equipped with an 8 mm grid.
- the caked silica cake is then introduced by a metering screw at 5 kg / h in a twin-screw extruder Clextral BC21 rotating at 250 rpm.
- Sodium aluminate is introduced by a quilting at the extruder after the feed zone (10 cm from the inlet) so that the sodium aluminate flow rate is 0.33 ml / min.
- the product leaving the extruder is recovered in a tank in which the pH is regulated to 6 by addition of sulfuric acid.
- the slurry obtained is then spray-dried to give a precipitated silica in powder form P1.
- the cake G2 is moved by a passage in a starter (Gericke) equipped with an 8 mm grid.
- the caked silica cake is then introduced by a metering screw at 5 kg / h in a twin-screw extruder Clextral BC21 rotating at 250 rpm.
- Sodium aluminate is introduced by a quilting at the extruder after the feed zone (10 cm from the inlet) so that the flow rate of sodium aluminate is 0.4 ml / min.
- the product leaving the extruder is recovered in a tank in which the pH is regulated to 6 by addition of sulfuric acid.
- the slurry obtained is then spray-dried to give a precipitated silica in the form of powder P2.
- the process of the invention thus makes it possible to obtain very satisfactory results also for cakes with a high solids content.
- the precipitated silica suspension used (S1) is a slurry (slurry) of silica Z1 165MP resulting from a precipitation reaction, which has the following characteristics:
- Part of the silica suspension S1 is filtered and washed on a filter press, and then subjected to compacting at a pressure of 8 bar.
- the resulting silica cake G1 has a solids content of 23.5%.
- the other part of the silica suspension S1 is filtered and washed on a filter press and is then compacted at a pressure of 25 bar.
- the resulting silica cake G2 has a solids content of 29%.
- Part of the silica cake G1 is swept by a passage in a starter (Gericke) equipped with an 8 mm grid.
- the etched silica cake is then introduced by a metering screw at 76 kg / h (corresponding to a specific cake flow, that is to say at a flow rate reduced to the working volume of the kneader of 97.4 kg / h / L) in a UCP 2 " * 17" double screw mixer (RPA process) rotating at 105 rpm.
- Sodium aluminate is introduced by tapping at the kneader after the feed zone so that the flow of sodium aluminate is 4.65 ml / min.
- the kneaded product is recovered in a tank in which the pH is regulated at 6.2 by addition of sulfuric acid.
- the slurry obtained is then spray-dried in order to obtain a precipitated silica in the form of MP1 microbeads.
- the silica cake G2 is swept by a passage in a starter (Gericke) equipped with an 8 mm grid.
- the etched silica cake is then introduced by a metering screw at 127 kg / h in a UCP 2 " * 17" double-screw kneader (RPA process) rotating at 155 revolutions / min.
- Sodium aluminate is introduced by stitching at the kneader after the feed zone so that the sodium aluminate flow rate is 9.80 ml / min.
- the kneaded product is recovered in a tank in which the pH is regulated at 6.2 by addition of sulfuric acid.
- the slurry obtained is then spray-dried in order to obtain a precipitated silica in the form of MP2 microbeads.
- the process of the invention thus makes it possible to obtain very satisfactory results also for cakes with a high solids content.
- a portion of the silica cake G1 obtained in Example 2 is introduced into a continuous stirred tank in one hour at a specific cake rate, that is to say at a flow rate reduced to the useful volume of said tank of 1.78 kg / h / L, a much lower flow rate than that of Example 2 for the cake G1, sodium aluminate being also introduced at a rate of 14.75 g / min in said stirred tank.
- the product obtained is recovered in a tank in which the pH is adjusted to 6.7 by addition of sulfuric acid.
- the slurry obtained is then spray-dried to obtain precipitated silica in the form of MP3 microbeads.
- silica MP1 obtained in Example 2 has characteristics close to those of the MP3 silica, in particular a similar dispersibility.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1252585A FR2988383B1 (fr) | 2012-03-22 | 2012-03-22 | Procede de preparation de silice precipitee mettant en oeuvre un malaxeur ou une extrudeuse |
PCT/EP2013/055974 WO2013139933A1 (fr) | 2012-03-22 | 2013-03-21 | Procédé de préparation de silice précipitée mettant en oeuvre un malaxeur ou une extrudeuse |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2828200A1 true EP2828200A1 (fr) | 2015-01-28 |
Family
ID=47915228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13711378.3A Withdrawn EP2828200A1 (fr) | 2012-03-22 | 2013-03-21 | Procédé de préparation de silice précipitée mettant en oeuvre un malaxeur ou une extrudeuse |
Country Status (12)
Country | Link |
---|---|
US (1) | US10246338B2 (fr) |
EP (1) | EP2828200A1 (fr) |
JP (1) | JP5882531B2 (fr) |
KR (1) | KR102093347B1 (fr) |
CN (1) | CN104395238B (fr) |
BR (1) | BR112014023075B1 (fr) |
CA (1) | CA2867579C (fr) |
FR (1) | FR2988383B1 (fr) |
MX (1) | MX346937B (fr) |
RU (1) | RU2578302C1 (fr) |
TW (1) | TWI574917B (fr) |
WO (1) | WO2013139933A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2988386B1 (fr) | 2012-03-22 | 2014-05-09 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de delitage a chaud |
FR2988385B1 (fr) | 2012-03-22 | 2014-05-09 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de concentration membranaire |
FR2988384B1 (fr) | 2012-03-22 | 2015-09-11 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de fort compactage |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE527521C (de) | 1925-07-24 | 1931-06-18 | I G Farbenindustrie Akt Ges | Herstellung aktiver Kieselsaeure |
GB1511720A (en) * | 1974-10-05 | 1978-05-24 | Degussa | Sprayable precipitated-silica suspension |
US4094771A (en) * | 1976-01-13 | 1978-06-13 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for preparation of a sprayable precipitated silicic acid suspension |
FR2453880A1 (fr) * | 1979-04-13 | 1980-11-07 | Rhone Poulenc Ind | Nouveau pigment a base de silice sous forme de bille, procede pour l'obtenir et application, notamment comme charge renforcante dans les elastomeres |
FR2455619A1 (fr) * | 1979-05-04 | 1980-11-28 | Elf Aquitaine | Composition perfectionnee, a base de mercapto-etain, pour la stabilisation de resines vinyliques |
DE3144299A1 (de) * | 1981-11-07 | 1983-05-19 | Degussa Ag, 6000 Frankfurt | Faellungskieselsaeuren mit hoher struktur und verfahren zu ihrer herstellung |
FR2678259B1 (fr) | 1991-06-26 | 1993-11-05 | Rhone Poulenc Chimie | Nouvelles silices precipitees sous forme de granules ou de poudres, procedes de synthese et utilisation au renforcement des elastomeres. |
KR0158071B1 (ko) | 1993-09-29 | 1998-11-16 | 마르끄 델렌느 | 침강 실리카 |
FR2710630B1 (fr) | 1993-09-29 | 1995-12-29 | Rhone Poulenc Chimie | Nouvelles silices précipitées, leur procédé de préparation et leur utilisation au renforcement des élastomères. |
FR2732331B1 (fr) * | 1995-03-29 | 1997-06-20 | Rhone Poulenc Chimie | Nouveau procede de preparation de silice precipitee, nouvelles silices precipitees contenant du zinc et leur utilisation au renforcement des elastomeres |
FR2732328B1 (fr) * | 1995-03-29 | 1997-06-20 | Rhone Poulenc Chimie | Nouveau procede de preparation de silice precipitee, nouvelles silices precipitees contenant de l'aluminium et leur utilisation au renforcement des elastomeres |
FR2722185B1 (fr) | 1994-07-07 | 1996-09-27 | Rhone Poulenc Chimie | Suspension concentree de silice de precipitation, procedes pour sa preparation et utilisations de cette suspension |
FR2763581B1 (fr) * | 1997-05-26 | 1999-07-23 | Rhodia Chimie Sa | Silice precipitee utilisable comme charge renforcante pour elastomeres |
FR2769308B1 (fr) * | 1997-10-03 | 1999-12-24 | Rhodia Chimie Sa | Suspension aqueuse contenant des particules de silice |
DK1419106T3 (en) | 2001-08-13 | 2017-01-30 | Rhone Poulenc Chimie | PROCEDURE FOR MANUFACTURING SILICA WITH SPECIFIC PARTICLE SIZE DISTRIBUTION AND / OR POR SIZE DISTRIBUTION |
FR2910459B1 (fr) * | 2006-12-22 | 2010-09-17 | Rhodia Recherches & Tech | Nouveau procede de preparation de silices precipitees par mise en oeuvre d'un melangeur rapide |
FR2928363B1 (fr) | 2008-03-10 | 2012-08-31 | Rhodia Operations | Nouveau procede de preparation de silices precipitees, silices precipitees a morphologie, granulometrie et porosite particulieres et leurs utilisations, notamment pour le renforcement de polymeres |
FR2962996B1 (fr) | 2010-07-23 | 2012-07-27 | Rhodia Operations | Nouveau procede de preparation de silices precipitees |
FR2988385B1 (fr) | 2012-03-22 | 2014-05-09 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de concentration membranaire |
FR2988384B1 (fr) | 2012-03-22 | 2015-09-11 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de fort compactage |
FR2988386B1 (fr) | 2012-03-22 | 2014-05-09 | Rhodia Operations | Procede de preparation de silice precipitee comprenant une etape de delitage a chaud |
JP2014108315A (ja) * | 2012-12-04 | 2014-06-12 | Mitsubishi Electric Corp | 微生物不活化デバイス |
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2012
- 2012-03-22 FR FR1252585A patent/FR2988383B1/fr not_active Expired - Fee Related
-
2013
- 2013-03-21 JP JP2015500934A patent/JP5882531B2/ja not_active Expired - Fee Related
- 2013-03-21 RU RU2014142550/05A patent/RU2578302C1/ru active
- 2013-03-21 CN CN201380026830.5A patent/CN104395238B/zh not_active Expired - Fee Related
- 2013-03-21 WO PCT/EP2013/055974 patent/WO2013139933A1/fr active Application Filing
- 2013-03-21 BR BR112014023075-7A patent/BR112014023075B1/pt not_active IP Right Cessation
- 2013-03-21 KR KR1020147029144A patent/KR102093347B1/ko active IP Right Grant
- 2013-03-21 CA CA2867579A patent/CA2867579C/fr not_active Expired - Fee Related
- 2013-03-21 EP EP13711378.3A patent/EP2828200A1/fr not_active Withdrawn
- 2013-03-21 MX MX2014011210A patent/MX346937B/es active IP Right Grant
- 2013-03-21 US US14/386,093 patent/US10246338B2/en not_active Expired - Fee Related
- 2013-03-22 TW TW102110375A patent/TWI574917B/zh not_active IP Right Cessation
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2013139933A1 * |
Also Published As
Publication number | Publication date |
---|---|
US10246338B2 (en) | 2019-04-02 |
WO2013139933A1 (fr) | 2013-09-26 |
TW201400412A (zh) | 2014-01-01 |
TWI574917B (zh) | 2017-03-21 |
FR2988383A1 (fr) | 2013-09-27 |
CN104395238A (zh) | 2015-03-04 |
RU2578302C1 (ru) | 2016-03-27 |
KR102093347B1 (ko) | 2020-03-25 |
KR20140138304A (ko) | 2014-12-03 |
CN104395238B (zh) | 2018-08-28 |
US20150110700A1 (en) | 2015-04-23 |
MX2014011210A (es) | 2014-11-10 |
FR2988383B1 (fr) | 2017-06-09 |
CA2867579C (fr) | 2019-07-09 |
JP5882531B2 (ja) | 2016-03-09 |
BR112014023075B1 (pt) | 2021-03-30 |
MX346937B (es) | 2017-04-05 |
JP2015510866A (ja) | 2015-04-13 |
CA2867579A1 (fr) | 2013-09-26 |
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