CARBON COATED PARTICLES

专利摘要:
A method for producing carbon-coated particles, the method comprising embedding core particles with a carbon layer in a carbon black reactor or a finishing section thereof, to form the coated particles of carbon carbon, the core particles being carbon free core particles, plasma carbon black cores particles or preformed core particles. The invention also relates to coated particles obtained by this process.
公开号:FR3035657A1
申请号:FR1653757
申请日:2016-04-27
公开日:2016-11-04
发明作者:David Matheu；Theis Clarke；David Scott Crocker；Frederick H Rumpf；David C Reynolds；Dhaval Doshi；Martin C Green
申请人:Cabot Corp；
IPC主号:

专利说明:

[0001] The invention relates to a process for producing carbon-coated particles, the process comprising the step of coating core particles with a carbon layer in a carbon black reactor or a finishing zone thereof. this. The invention also relates to carbon-coated particles obtained by such a method. BACKGROUND [2] Small particles, typically less than one micrometer in size, are blended into synthetic or natural rubber blends used for a wide variety of rubber products such as tires, pipes, belts, joints, rings etc. A wide variety of particles have been used or proposed for rubber mixtures, but the most common is carbon black (CB). These particles make it possible to design and improve the characteristics of the mixture particularly for the performance of the application. They make it possible, for example, to influence the stiffness, hardness, modulus and failure characteristics of the rubber. Rubber mixed with a reinforcing carbon black can have a drastic improvement in wear resistance and make the rubber usable for tire screeds or other demanding service applications. [3] An incidental effect of mixing rubber with reinforcing particles is that the rubber changes in nature from highly elastic to viscoelastic and that the charged rubber dissipates energy when the rubber is mechanically subjected to cycles. An important practical consequence of this viscoelastic behavior is that the tires dissipate mechanical energy when they flex during rotation, resulting in reduced fuel economy of the vehicle. Precipitated silica (PS) is usually used in combination with synthetic rubber for automotive tire screeds; the PS provides a rubber blend with slightly reduced wear, compared to a carbon black rubber compound, but with an attractive improvement in energy loss and thus in rolling resistance and vehicle fuel economy. [004] In general, carbon black exists in the form of aggregates which, on their part, are formed by primary particles of carbon black. In most cases, primary particles do not exist independently of the carbon black aggregate. While the primary particles may have a mean primary particle diameter in the range of about 10 nm to about 50 nm, for example from about 10 nm to about 15 nm, from about 10 nm to about 20 nm from about 10 nm to about 25 nm, from about 10 nm to about 30 nm, from about 10 nm to about 40 nm, the aggregates can be considerably larger. Carbon black aggregates have fractal geometries and, in the art, are often referred to as carbon black "particles" (not to be confused with the "primary particles" discussed above). Many types of carbon black are produced in a furnace type reactor by subjecting a hydrocarbon raw material (FS) to pyrolysis with hot combustion gases to produce combustion products containing carbon black. in particles. The characteristics of a given carbon black typically depend on the manufacturing conditions and can be changed, for example in temperature, pressure, raw material, quiescent time, quench temperature, flow rate and other parameters. [006] Equipment and techniques for producing carbon black are known in the art. An example is given in Provisional Application US-28974, a re-filing of U.S. Patent 3,619,140 issued to Morgan et al. The method involves generating a very hot flow of very high velocity combustion gas substantially in piston flow by combusting a fuel gas such as natural gas with oxygen, in a compact combustion zone and under conditions of a release of very great heat. Individual streams of liquid hydrocarbons (preheated carbon black produces oil or raw material) are injected in a direction transverse to the high velocity combustion stream under conditions under which the liquid hydrocarbon enters the flow of high velocity combustion at a linear velocity of greater than about 100 feet per second (about 30.48 m / s). [007] The fuel in the combustion zone is completely burned with excess oxygen: Carbon black cores are produced when the carbon black raw material is injected and then these nuclei coalesce and grow to become aggregates of carbon black of the product. [008] Techniques for in situ preparation of silicon-treated carbon black from carbon black raw material and silicon precursors in a carbon black reactor are disclosed in US-5,904,762 issued to Mahmud et al. and US-5,830,930 issued to Mahmud et al. In addition, US-5,830,930, 3035657 discloses elastomeric blends comprising silicon-treated carbon black. U.S. Patent No. 6,057,387 issued to Mahmud et al. discloses aggregate particles having a carbon phase and a species phase comprising silicon having certain characteristics relating to the particle surface and the size distribution. In such a silicon-treated CB, a silicon-containing species such as silicon oxide or carbide is distributed in at least a portion of the carbon black aggregate as an intrinsic part of the carbon black. Such carbon black aggregates may be modified by depositing a silicon-containing species, such as silica, on at least a portion of the surface of the carbon black aggregates during formation of carbon black aggregates in a reactor. to carbon black. The result can be described as CB coated with silicon. In a silicon-treated carbon black, the aggregates comprise two phases. One is carbon, present as graphitic crystallite and / or amorphous carbon, while the second phase, a discontinuous phase, is silica (and possibly other species with silicon). The silicon-containing phase may be present in amounts of 0.1 to 25% by weight of the carbon black aggregate. Thus, the silicon-containing species phase of the silicon-treated carbon black is an intrinsic part of the aggregate; it is distributed in at least a part of the aggregate or on the surface of the aggregate. U.S. Patent No. 6,017,980 issued to Wang et al. discloses elastomer composites having aggregates of a carbon phase and 0.1 to 25% by weight of a metal-containing species phase (eg Al or Zn) and the formation of such aggregates in situ in a carbon black reactor. As an option, a silicon-containing phase can be incorporated, together with the metal-containing species phase, into the carbon black phase. [9] US Patent No. 2,632,713 issued to Krejci discloses an in situ-treated carbon black material having 0.01 to 10% by weight of a species of silicon, boron or germanium. The additive material is introduced into a carbon black reactor with raw material or separately and can be added further downstream into the reactor to produce a surface coating on carbon black particles. Carbon black materials comprising silicon surface domains are disclosed in US Pat. No. 7,351,763 issued to Linster et al. and in US Pat. No. 6,071,995 issued to Labauze. [10] U.S. Patent No. 6,099,818 issued to Freund et al. discloses a method wherein the carbon black cores are formed by partially burning a fuel oil in a combustion chamber in an oxygen-containing gas. The carbon black cores are carried by the hot flue gas stream into the reaction zone and are immediately contacted with the carbon black raw material forming carbon black particles which coalesce and grow to become aggregates. According to U.S. Patent No. 6,056,933 issued to Vogler et al., Inversion CBs are produced in conventional carbon black reactors by controlling combustion in the combustion chamber to form carbon black cores which are immediately put in contact with the raw material of carbon black. U.S. Patent 6,391,274 issued to Vogler et al. discloses a process in which seeds (or cores) of carbon black formed in the combustion zone are carried along with the flow of combustion gases into the reaction zone where they initiate seed-induced carbon black formation with a carbon black raw material added. Silicon containing blends such as silanes or silicone oils are blended with the carbon black raw material to produce a carbon black containing 0.01 to 20 wt.% Of silicon. [11] Plasma techniques for preparing carbon black have also been developed. The Kvaerner process or the Kvaerner CB and hydrogen (CB & H) process, for example, is a process for producing carbon black and hydrogen gas from hydrocarbons such as methane, natural gas and biogas. . According to US Patent 5,527,518 issued to Lynum et al. on June 18, 1996, a method of manufacturing a carbon black material comprises a first step providing a raw material through a plasma torch feed line to a reaction zone to increase the temperature of the raw material. at about 1600 ° C, then passing the dehydrogenated carbon material to a second step to complete decomposition to carbon black and hydrogen. Additional raw material causes quenching and reaction with carbon black formed to increase the particle size density and the amount produced. [12] Published patent application US-2008/0289494 Al de Boutot et al., Published November 27, 2008 discloses a method and apparatus for cold arc discharge (CAD) used to decompose natural gas or methane. in its gaseous constituents (hydrogen and acetylene) and carbon particles. [013] According to US Pat. No. 7,452,514 B2 issued to Fabry et al. on November 18, 2008 and published patent application US-2009/0142250 Al de Fabry et al., published June 4, 2009, mixtures containing carbon black or carbon are formed by converting a carbon-containing raw material, using a process which comprises the following steps: generating a plasma gas with electrical energy, passing the plasma gas through a Venturi tube whose diameter narrows in the direction of the flow of the plasma gas, passing the plasma gas through a reaction zone in which, under the existing flow conditions generated by aerodynamic and electromagnetic forces, there is no significant recirculation of raw material in the plasma gas in the reaction zone, recovering the reaction products from the reaction zone; the reaction zone and separate mixtures containing carbon black or carbon from the other reaction products. [14] In the process described in US Pat. No. 4,101,639, issued July 18, 1978 to Surovikin et al., A hydrocarbon raw material is introduced into a reaction chamber and into a plasma stream saturated with steam. of water. [15] Published patent application US-2015/0210856 of Johnson et al., Published July 30, 2015, discloses a method and apparatus in which a plasma gas is introduced into a plasma forming zone and having at least one torch magnetically isolated plasma containing at least one electrode. The plasma is collected in a cooled head and fed to a carbon black forming zone which receives carbon black feedstock. A gas passage assembly connecting the areas forming the plasma and the CB is described by Hoermann et al. in the published patent application US-2015/0210858 published on July 30, 2015. 20 [016] The publication of the patent application US-2015/0210857 of Johnson et al, published on July 30, 2015 describes burning raw material ( typically methane) with plasma in an apparatus having a series of unit operations with individual capabilities. The individual capacities of unit operations are substantially balanced by replacing at least a portion of the feedstock with a feedstock having a higher molecular weight than methane. [017] Since a significant amount of carbon black material is used to reinforce the rubber components of tires, used tires and other carbon black-reinforced rubber products represent a significant waste stream. In order to dispose of such waste, used tires can be subjected to pyrolysis and attempts have been made to recover and reuse carbon-based components. [018] In general, the pyrolysis is done in a reactor having an oxygen-free atmosphere. As the process proceeds, the rubber becomes soft, then the rubber polymers are broken down into smaller molecules which are extracted from the reactor as vapors (which can be condensed subsequently for a liquid oil phase). and gas. It is likewise formed of a solid residue containing carbon which may further contain silica, alumina, zinc oxide and other components. See, for example, U.S. Patent 4,251,500 A issued to Morita et al., U.S. Patent No. 5,264,640 A issued to Platz and U.S. Patent No. 6,221,329 B1 issued to Faulkner et al. [019] With advances in equipment and techniques, the main products of a modern tire pyrolysis apparatus are oil, steel (required in the form of steel cables) and a coal component. artificial ("pyrolytic carbon"). Pyrolytic carbon characteristics are discussed, for example, by C. J. Norris et al. in Maney Online, Volume 43 (8), 2014, pages 245-256. Possible applications for carbon obtained by subjecting spent tires to pyrolysis are described, for example, by C. Roy et al. in the article "The vacuum pyrolysis of used tires - End-uses for oil and carbon black products", Journal of Analytical and Applied Pyrolysis , Volume 51, pages 201 to 221 (1999).
[0002] SUMMARY OF THE INVENTION [020] There is a continuing interest in developing particles or reinforcing agents that can provide beneficial tire performance features. Lowering costs, reducing manufacturing impacts to the environment and expanding the spectrum of available reinforcing agents are also goals. [021] Specific characteristics of a rubber blend can be optimized not only by the size, morphology and other physical characteristics of the reinforcing particles used, as known in the art, but also by the chemical composition of the body and particle surface. For example, the strongly reinforcing capacity of the carbon black may be attributed, at least in part, to the specificities of the interaction between the rubber molecules and the surface of the carbon black. [22] While it may be beneficial to use pyrolytically upgraded carbon by introducing it into new rubber blends, pyrolysis-beneficiated carbon particles generally provide reinforcement and other significantly lower characteristics compared to virgin carbon black. Between other deficiencies, it is assumed that a major problem of pyrolyzed carbon is that the particle surface has substantially changed and degraded, as compared to virgin carbon black, with respect to an interaction. with rubber molecules. [23] In some cases, fresh carbon black particles may also show inferior characteristics of rubber reinforcement. For example, the carbon black manufacturing process or the post-manufacturing treatment of carbon black particles can remove chemical groups from the surface of the carbon black particle or thermally anneal or graphite the black particle surface of carbon black. carbon, creating crystalline areas, or otherwise degrading the activity of the carbon black particle surface to generate lower rubber reinforcing characteristics. [24] In order to overcome this and other problems, the invention generally relates to a carbon-containing material, typically a particulate material, a process for making such a material and methods of using the same. [025] More particularly, the invention relates to a process for producing carbon-coated particles, the process comprising coating the core particles with a carbon layer in a carbon black reactor or a finishing section thereof. Here, to form the carbon-coated particles, the core particles being carbon-free core particles, plasma carbon black cores particles or preformed core particles. [026] The invention also relates to the following characteristics: the carbon layer is prepared from a liquid or gaseous raw material supplying carbon; carbon-free core particles or plasma carbon black cores are produced in situ; The method further comprises introducing the preformed core particles into the carbon black reactor; the preformed core particles are core particles of carbon black; the carbon-coated particles have an STSA in the range of about 30 to about 250 m2 / g and a COAN in the range of about 55 to about 110 cc / 100g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 to about 150 cc / 100 g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and an OAN index in the range of about 55 to about 400 cc / 100 g; A rubber composition or a rubber article comprises the carbon-coated particles described above; the method further comprises modifying the surface of the carbon-coated particles; the process for preparing carbon-coated particles comprises: generating nucleus particles in situ, the core particles being carbon-black plasma core particles or carbon-free core particles, and coating the core particles with a layer carbon in a carbon black process to form the carbon-coated particles; the carbon layer is prepared from a liquid or gaseous raw material supplying carbon; the plasma carbon black cores are formed in a carbon black process; the carbon-free core particles are generated in a reaction zone of a carbon black reactor; The carbon-free core particles are silica core particles; the carbon-free core particles are produced from a ring precursor; The core precursor is introduced upstream, at or downstream of a raw material injection point providing carbon; the core precursor is injected together with the raw material supplying carbon; The core precursor is introduced prior to the injection of a moderating liquid; the method further comprises collecting the carbon-coated particles from the reactor; the carbon layer has a thickness in the range of 0.5 nm to about 20 nm; the core particles are aggregates of primary particles; the coated particles have a particle size in the range of about 20 nm to about 500 nm; the carbon layer covers the core particles partially or completely; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 to about 110 cc / 100 g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and a COAN in the range of about 55 to about 150 cc / 100 g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and an OAN index in the range of about 55 to about 400 cc / 100 g; a rubber composition or a rubber article comprises the carbon-coated particles described above; The process comprises modifying the surface of the carbon-coated particles; the process for producing carbon-coated particles comprises: introducing preformed core particles into a carbon black reactor, and coating the core particles with a carbon layer obtained by pyrolysis of a liquid or gaseous raw material in the carbon black reactor, thereby forming the carbon-coated particles; The method further comprises dividing the preformed core particles before introducing preformed core particles into the carbon black reactor; the preformed core particles are introduced together with a gaseous reactor or vapor stream, dispersed in a liquid raw material, in a separate gas stream or in a separate aqueous stream; the method further comprises collecting the carbon-coated particles from the reactor; the preformed core particles are preformed carbon-free core particles, preformed carbon black particles or pyrolysis-enhanced carbon particles; The preformed core particles are nanoparticles of clay, rice husk silica, silica carbonate or precipitated calcium; the carbon-coated particles contain a core which is an aggregate or agglomerate of the same or different aggregates; the core has a size of about 50 nm to about 10 μm; The carbon layer has a thickness in the range of about 0.5 nm to about 20 nm; the carbon layer covers the core partially or completely; the carbon-coated particles have an STSA in the range of about 30 to about 250 m2 / g and a COAN in the range of about 55 to about 110 cd100g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m2 / g and a COAN in the range of about 55 to about 150 cc / 100g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2/9 and an OAN index in the range of about 55 to about 400 cc / 100 g. the method further comprises modifying the surface of the carbon-coated particles; A rubber composition or a rubber article comprises the carbon-coated particles described above; The process for producing carbon-coated particles comprises: introducing preformed core particles into a plasma carbon black reactor, and embedding the core particles with a carbon layer, characterized in that the carbon is generated from a gaseous raw material; the process for preparing carbon-coated particles, the process comprises: in situ preparation of the carbon black cores in a carbon black reactor, and coating the carbon black cores with a carbon layer obtained by the pyrolysis of a gaseous raw material in the carbon black reactor, thereby forming the carbon-coated particles; the process for preparing carbon-coated particles, the process comprises: preparing plasma carbon black particles, and coating the carbon black cores with a carbon layer to form the coated particles of carbon ; the carbon black nuclei particles are prepared by a process comprising: generating a plasma in a plasma zone of a reactor, and converting a core-providing raw material to carbon black core particles and hydrogen gas; the carbon-coated particles comprise a carbon-free core, a pyrolyzed carbon core, or a carbon-carbon plasma core coated with a carbon layer; the carbon-free core is formed from a material selected from the group consisting of precipitated silica, fumed silica, surface-modified silica and any combination thereof; the core is formed of clay nanoparticles, rice husk silica, calcium carbonate or any combination thereof; the carbon layer has a thickness of about 0.5 nm to about 20 nm; The carbon layer is amorphous carbon; The core has an aciniform structure; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 to about 110 cc / 100 g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and a COAN in the range of about 55 to about 150 cc / 100 g; the carbon-coated particles have an STSA in the range of about 30 to about 250 m 2 / g and an OAN index in the range of about 55 to about 400 cc / 100 g; a rubber composition or a rubber article comprises the carbon-coated particles described above; The surface of the coated particles is modified; equipment for preparing carbon-coated particles, the equipment comprises: a plasma zone, a reaction zone downstream of the plasma zone, a finishing zone downstream of the reaction zone, a conduit for introducing a plasma gas in the plasma zone, one or more inlets for introducing a first raw material into the reactor, one or more inlets for introducing a second raw material into the reactor, a convergence zone between the plasma zone and the zone; reaction, and, optionally, a zone of convergence between the reaction zone and the finishing zone. [0271] The particle disclosed herein comprises a core and a carbon-based outer zone, also referred to herein as "coating", "layer", "deposit" or "shell", and one aspect of the invention features particles coated with carbon and having a core (or core material) coated with a carbon layer. In some embodiments, the core is an aggregate or agglomerate completely or partially covered by the carbon coating. The carbon coating or the carbon-coated particles may be an aciniform material having a typical morphology and characteristics of a carbon black material. Illustrative examples of carbon-coated particles include a carbon-free core, a pyrolytically upgraded carbon core, or a carbon-carbon core coated with a carbon layer. [28] Other aspects of the invention relate to a process for making carbon-coated particles. In this process, core particles are coated with a carbon layer in a reactor, often a carbon black reactor, or a section thereof. Other suitable reactors such as, for example, a plasma reactor or another type of reactor, such as for example using methane, natural gas or the like, can also be used to carry out the operation of coating. In general, the carbon layer is prepared from a liquid or gaseous raw material supplying carbon. [29] In some embodiments, the core particles are particles already made or "preformed" that are introduced into a reactor and coated with a carbon layer to form carbon-coated particles. In other embodiments, the core particles are produced in situ, and in one embodiment, the core particles are generated and coated in an integrated step process carried out in a common reactor. [30] The core particles may consist or consist essentially of carbon or comprise carbon. Examples of suitable preformed carbon core particles include pyrolytically beneficiated carbon particles, plasma carbon black particles, preformed carbon black particles, especially carbon black particles having weak characteristics of reinforcement or corrosion. other lower surface properties and others. [31] Carbon-based core particles can also be generated in situ. For example, carbon black cores may be prepared by a plasma process or by another process in which a feedstock such as natural gas or methane, for example, is converted (fractionated) to form a feedstock. generate carbon and hydrogen, then coated with a layer of carbon to form carbon-coated particles. An example of equipment that can be used includes: a plasma zone, a reaction zone downstream of the plasma zone, a finishing zone downstream from the reaction zone, a conduit for introducing a plasma gas into the plasma zone, one or more inlets for introducing a first raw material into the reactor, one or more inlets for introducing a second raw material into the reactor, a convergence zone between the plasma zone and the reaction zone, and optionally an area of convergence between the reaction zone and the finishing zone. [32] Carbon-free particles can also be used. Examples include, but are not limited to, silica, rice husk silica, precipitated silica, clay, calcium carbonate, other carbon-free preformed core particles, and mixtures thereof. In one example, preformed, carbon-free core particles are introduced into a reactor such as, for example, a carbon black reactor and coated to produce carbon-coated particles. In another example, carbon-free core particles (eg, silica) are generated in situ (in a carbon black reactor, for example, using a core precursor) and coated with a carbon layer in the reactor. reactor to form carbon coated particles. [33] Some illustrative examples are given below. [34] In one embodiment, a method for producing carbon coated particles comprises: in situ generation of core particles, the core particles being carbon black plasma core particles or carbon free core particles, and coating the core particles with a carbon layer in a carbon black process to form the carbon-coated particles. [35] In another embodiment, a method for producing carbon coated particles comprises: introducing preformed core particles into a carbon black reactor and coating the core particles with a carbon layer obtained by pyrolysis of a liquid or gaseous raw material in the carbon black reactor, thereby forming the carbon-coated particles. [36] In yet another embodiment, a process for preparing carbon-coated particles comprises the in situ preparation of carbon black cores in a carbon black reactor, and coating the core particles with black carbon. of carbon with a carbon layer obtained by pyrolysis of a gaseous raw material in the carbon black reactor, thereby forming the carbon-coated particles. [037] In another embodiment, a method for producing carbon coated particles comprises: preparing carbon black cores particles in a plasma process, and coating the carbon black cores particles with a carbon layer to form the carbon-coated particles. In some cases, the carbon black cores are prepared by a process comprising the generation of a plasma in a plasma zone of a reactor, and the conversion of a nucleus feedstock introduced downstream of the reactor. the plasma zone of the reactor, carbon black cores particles and hydrogen gas. [38] In another embodiment, a method for producing carbon coated particles comprises coating: introducing preformed core particles into a carbon black reactor or into a plasma carbon black reactor, and coating the core particles with a carbon layer, the carbon layer being generated from a gaseous raw material. [39] In another embodiment, a process for producing carbon-coated particles comprises coating core particles such as carbon-free core particles, carbon-black plasma core particles, preformed particles such as for example, pyrolytically enhanced carbon particles (hereinafter referred to as "paralyzed carbon"), degraded carbon black particles (especially carbon black particles which have rubber-reinforcing properties) less than the morphologically expected reinforcing properties) or other types of carbon black particles, with a carbon layer in a carbon black reactor or a finishing zone thereof. [40] The invention has many advantages. In many embodiments, the carbon-based outer zone, alone or together with the core material, gives properties, for example, body or surface characteristics and / or chemistry, electrical properties, distribution, and the like. aggregates and / or primary sizes, performance properties, etc. which may be the same, similar or improved compared to a carbon black of a desired grade. [41] The properties of the particles can be adapted to a specific end use and in some examples the carbon-coated particles are used as reinforcements in tire components or other rubber components. In specific embodiments, the particles described herein provide rubber characteristics and application performance that may be the same, similar or improved over a comparative rubber composition prepared with a carbon black of one embodiment. given grade, such as an uncoated plasma carbon black of similar morphology, or a black standard ASTM furnace. [42] Having a carbon-based outer layer that can give desired carbon black properties adds significant flexibility when choosing a core material. For example, compared to traditional carbon black particles that exhibit good particle-polymer interactions and also strong particle-particle interactions, the latter interfering with ease of dispersion and increased rubber hysteresis or loss of energy, the use of A silica core can reduce particle-particle interactions while a carbon-based coating is designed to enhance particle-polymer interactions and high reinforcement. In combination, these two trends can provide the materials described herein with attractive properties for rubber applications, such as tires. [43] The techniques described herein may also be applied to change surface properties of pyrolyzed carbon or carbon black particles which exhibit weak reinforcing characteristics or other characteristics considered undesirable for rubber. [44] For example, while it may be beneficial to use pyrolytically upgraded carbon by blending it into a new rubber composition, the pyrolytically upgraded carbon typically provides reinforcement and other properties of the rubber substantially. lower compared to carbon black not yet used. Among other deficiencies, it is assumed that a major problem of pyrolyzed carbon is that, compared to unused carbon black, the particle surface has substantially changed and degraded for interaction with rubber molecules. Various aspects of the invention address these deficiencies, rendering pyrolyzed carbon or other compositions obtained from discarded articles more attractive for certain applications, for example for rubber reinforcement. This can have significant impacts on the environment, encourage recycling and reduce waste management and processing loads. [045] The implementation of the invention can also make it possible to use less expensive core particles such as clay, rice-shell silica, calcium carbonate, pyrolyzed carbon and the like. Since the core of the particles described herein may be formed not only from novel or upgraded compositions, but also from waste recovered from other processes, aspects of the invention may contribute to cost savings for the final product and / or the manufacture of certain grades of carbon black. Incorporation of such materials into the particles described herein also reduces the consumption of petroleum raw materials required in the manufacture of carbon black. Importantly, carbon-free core particles (i.e., composite or aggregate particles in which the continuous phase is formed of a carbon-free material) can even be formed in situ during the production of carbon-free materials. a material as described herein. [046] In the manufacture of carbon black, plasma based processes can provide significant economic benefits such as, for example, the use of materials that can be relatively inexpensive and often widely available, for example gas natural (NG). Other advantages relate to typically high productivity, the formation of useful products, especially carbon (C) and hydrogen gas (H2), and reduced emissions of carbon dioxide (CO2) or oxides of carbon dioxide. nitrogen (N0x). However, the resulting carbon black product may lack some properties associated with the higher performance currently required in tire components and other rubber components. Compared with conventional furnace black, plasma carbon black may have low levels of interaction with rubber molecules, resulting in lower reinforcing performance. Thus, in some cases, the invention has an influence on the benefits associated with plasma-based techniques for preparing carbon black, while at the same time generating carbon black surface properties which improve the performance of components of carbon black. [047] Specific embodiments of the invention relate to the separation of core materials which are introduced into the carbon black reactor; this is designed to stimulate a more efficient and effective coating. [048] When used in coating operations, the liquid hydrocarbons must first be vaporized and then mixed with core particles. In view of the very short time available, the resulting deposit may not be as fine and / or homogeneous as desired. Since the vaporization step is short-circuited when a gaseous hydrocarbon is used to generate the coating, the gaseous hydrocarbon can give a finer and / or more homogeneous deposit. Embodiments wherein the layer formed on the core particle is produced using natural gas or other gaseous hydrocarbons may also reduce or minimize SOUND and / or NO emissions. [49] The above features and other features of the invention, including various design details and combinations of components and other advantages, will be described hereinafter with reference to the accompanying drawings. It is understood that the particular method and the particular device embodying the invention are shown solely by way of example and in no way in a limiting manner. The principles and features of the present invention can be applied in various and many embodiments without departing from the scope of the present invention.
[0003] BRIEF DESCRIPTION OF THE DRAWINGS [50] In the accompanying drawings, the same reference numerals designate the same elements in all the figures. The drawings are not necessarily to scale; rather, it has been sought to illustrate the principles of the invention. In the drawings: [51] Fig. 1 is a cross-sectional view of a reactor adapted to prepare carbon-coated particles according to further embodiments of the invention. [52] Figure 2 is a schematic representation of an apparatus adapted to prepare carbon-coated particles according to embodiments of the invention. [53] Fig. 3 is a more detailed view of the upper part of the apparatus of Fig. 2. [54] Fig. 4 is a cross-sectional view of an apparatus for preparing coated particles using a finishing of a carbon black reactor. [55] Figure 5 is a transmission electron micrograph of a double-phase particle having a silica core coated with a carbon layer.
[0004] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [56] In general, the invention relates to coated particles and methods for producing and using them. A typical particle contains a core coated with a carbon layer. The core may consist of or consist essentially of or comprise a material that is different from the carbon coating. In general, the core and coating materials have different origins, chemical compositions and / or other properties. The coated particles can often be considered as composite particles having one or more attributes that are different from those of the core. By itself, the core may not have the necessary or desired properties for a specific end use, for example for better reinforcement of tire components. With external carbon deposition, the coated particles described herein may have different characteristics, thus finding important applications in rubber reinforcing compositions. [057] In order to obtain coated particles as described herein, the core is coated with a carbon layer. In some embodiments, the carbon layer has a morphology and properties typical of a carbon black material. [58] In some embodiments, the core material is provided as preformed or already produced particles. These may be obtained commercially or may be prepared in a process and / or apparatus different from the method or apparatus employed for carrying out the coating operation. Preformed cores can be composed of fresh materials (not yet used), recovered materials or recovered waste products or other products, or both. [59] The amounts of preformed core material to be provided can be determined by routine experiments, can be based on theoretical models, prior experiments or other techniques. Factors taken into account for determining loads may include equipment to be used, process parameters, type of core material, raw material used, and / or other streams used, downstream stages, properties envisaged and others. [060] In other embodiments, the core is produced in situ and embedded in a common process and / or reactor. In situ techniques may require one or more precursors, including a substance or substances that, under certain conditions, may be subjected to reactions to generate the core material. The core precursor can be provided in any suitable amount as determined by routine experimentation, model, desired properties in the coated particles, experiment, process and / or equipment parameters or other factors. In some cases, the preparation of preformed core particles and the coating operation are conducted in different stations or units which are part of a general production process or system, typically carried out in a single process. installation. [062] Different core materials may be employed. Carbon-free cores, for example, may be produced wholly or in part from a carbon-free material such as silica, alumina, other metal oxides such as titanium, zirconium, ceria, tin oxide, magnesium oxide, magnesium aluminum silicate, clay, for example bentonite, natural or synthetic zeolites, upgraded absorbents, electronic components, catalytic materials, ash, carbon-free nanoparticles, etc. . The core is defined as a "carbon-free core" if the continuous phase in the core is the carbon-free material. Likewise, a core particle, core aggregate or core agglomerate is respectively a "carbon-free core particle", "carbon-free core aggregate" or "carbon-free core agglomerate" if the phase continues in the particle. the aggregate or agglomerate is the carbon-free material. [063] In a specific example, the core consists or consists essentially of or comprises silica such as, for example, colloidal silica, PS, upgraded PS 20 (for example used tires), aggregates CB comprising silica zones (for example Ecoblack® particles), fumed fumed silica, unmodified pyrogenic silica, typically obtained by a pyrogenic process, hydrophobically modified, colloidal or other hydrophobically modified silica nanoparticles, mixtures containing one or more types of silica etc. [064] The silica core material may be provided in the form of silica nucleus particles already produced. Fresh material or upgraded waste can be used. [065] It is also possible to produce silica in situ. A suitable precursor may consist or consist essentially of or comprise one or more silicon-containing materials, for example, an organic silicon composition. Specific examples of compositions which can be used include silicones, for example volatile silicone polymers such as octamethylcyciotetrasiloxane (OMTS), silicates such as tetraethoxyorthosilicate (TEDS) and tetramethoxy-orthosilicate, silanes, siloxanes, silazanes etc. [66] Another illustrative embodiment uses a core which consists or consists essentially of or comprises a clay, rice-shell silica, calcium carbonate, nanoparticles of these materials, other nanoparticles or mixtures thereof In general, these core materials are provided as preformed particles. [67] Carbon cores can also be used. As defined above, a core, a core particle, a core aggregate or an agglomerate core is respectively a "carbon core", a "carbon core particle", a "carbon core aggregate" or a "carbon core agglomerate" if the core consists or consists essentially of or comprises a material in which the continuous phase is carbon or carbon black. [68] Certain aspects of the invention utilize a carbon black core produced wholly or partially in a process that employs electrical energy, typically a plasma based process. The plasma process converts a hydrocarbon raw material (eg methane) into its components, including carbon (hereinafter referred to as "CB plasma" or "CB plasma" core particles) and hydrogen. For example: CH4 (g) -> C (s) + H2 (g), [69] In addition to carbon and hydrogen, conversion of the hydrocarbon can generate small amounts of acetylene and / or or traces of other hydrocarbons. The reaction is often carried out in the absence of oxygen. In cases where oxygen-containing compositions are used, off-gasses may contain some CO and CO2, the latter typically being present in low amounts or traces. According to some techniques (see, for example, US Pat. No. 3,409,403), the reaction is carried out by an intermediate step in which the hydrocarbon raw material is first converted to acetylene, which in turn is decomposed into CB and H2. [071] Plasma carbon black cores may have properties such as, for example, an N2SA area of about 50 to about 250 m 2 / g (ASTM D6556), an STSA surface area of 50 to 220 m 2 / g (ASTM D5816), an OAN structure of 50 to 300 cm3 / 100g (ASTM D2414-16), a COAN structure of 40 to 150 cm3 / 100g (ASTM 303 565 7 22 D3493-16), toluene 70 to 87% (ASTM D1618-99, 2011), a pH value of 7 to 9, ash of 0.05 to 0.5% (ASTM D1506), a CB yield of 60 to 100%. [72] Different approaches for preparing plasma carbon black are known, as already seen, for example, in US Pat. No. 5,527,518 issued to Lynum et al. on June 18, 1996, US Pat. No. 4,101,639 issued to Surovikin et al. on July 18, 1978, the published patent application US-2008/0289494 Al de Boutot et al, published on November 27, 2008, the published patent application US-2009/0142250 Al de Fabry and published on June 4, 2009, the published patent applications US-2015/0210856 and US-2015/0210857 of Johnson et al, published July 30, 2015, and published patent application US-2015/0210858 of Hoermann et al. [73] Both hot arc and cold arc discharges can be used to prepare the plasma carbon black particles to be coated. While a hot arc discharge typically produces a continuous plasma arc that generates reactor temperatures in the range of about 1700 ° C to about 4000 ° C and higher, a cold arc discharge may be considered rather as an intermittent arc discharge which makes it possible for the reactor to operate at relatively low temperatures, typically below 200 ° C. Arrangements based on a cold arc discharge to produce solid carbon particles and gaseous components such as hydrogen and acetylene mixed with unreacted methane or natural gas are described, for example, in the US Pat. published patent US-2008/0289494 Al de Boutot et al., published November 27, 2008. [74] Other techniques for preparing plasma carbon black cores may be used as known in the art or as suitable or developed. For example, core particles may be prepared in a microwave plasma reactor. An illustration of such a reactor can be found in published patent application US-2007/0274893 Al de Wright et al, published November 29, 2007. US Patent No. 5,782,085 issued July 21, 1998 to Steinwandel et al. presents techniques for generating a plasma beam using microwaves (in the range 0.95 to 24 GHz, for example). These high frequencies employed may be generated by magnetron or traveling wave tube systems. The waves can be guided in waveguides of a geometry designed to allow only a few types of waves. Techniques Which Use Electromagnetic Energy in the Microwave Frequency Domain, the Radio Frequency Domain, the High Frequency Domain, the Ultra-High Frequency Domain or the Acoustic Frequency Domain, as Described for Example by J. Tranquille in published patent application US-2015/0174550 A1, published June 25, 2015, may also be used. [075] Plasma carbon black cores can be generated in situ or provided as plasma carbon black particles already produced (preformed). Suitable particulate carbon black solids in the form of particles may be obtained commercially or prepared in a method or apparatus other than the method or apparatus employed for carrying out the coating operation. [076] Other aspects of the invention utilize a core which consists or consists essentially of or comprises pyrolytically upgraded carbon. This type of material is obtained by pyrolysis of rubber waste products such as, for example, worn tires. In contrast to the above-described carbon coating, the pyrolytically beneficiated carbon typically contains not only carbon but also other components used in the manufacture of tire components such as alumina, silica, oxide and the like. zinc, etc. [077] The carbon recovered by pyrolysis can be characterized by properties such as, for example, a specific surface area (in m 2 / g), a structure or a DBP number (cm 3/100 g), an ash and / or sulfur content. . For illustrative purposes, the specific surface area, the DBP number, the ash and / or sulfur content reported by C. Roy (Journal of Analytical and Applied Pyrolysis, Vol 51, pp. 201-221 (1999)) for pyrolytically enhanced carbon from truck tires were 95 m2 / g, 102 cm3 / 100g, 0.7% and 0.5%, respectively. Typically, the carbon recovered by pyrolysis is supplied in the form of already made (preformed) core particles. [078] Other types of carbon core materials may be used. An illustrative example employs carbon black which is prepared or obtained by an independent or separate process and / or apparatus and is provided as preformed core particles. In specific embodiments, the carbon black particle has weak reinforcing characteristics or other undesirable surface or material qualities as compared to a typical carbon black having the same morphology or equivalent morphology (a black). degraded carbon). Such degraded carbon black may have been intentionally put in order to obtain a desirable property, but to the detriment of another desired property (eg, producing a very large surface particle, but having a high I2 / STSA ratio and an etched porous surface). Other examples include a quenched carbon black particle, a carbon black particle having a low polycyclic aromatic hydrocarbon (PAH) content, or a carbon black product resulting from a carbon black treatment after manufacture. which can remove chemical groups from the surface of the carbon black particle, or thermally treat or graphite the surface of the carbon black particle, creating crystalline areas, or otherwise degrade the surface activity of the carbon-black particle. carbon black to generate reduced reinforcing properties. Examples of reduced surface quality carbon black cores are described, for example, in U.S. Patent No. 4,138,471 issued February 6, 1979 to Lamont et al. and in published patent application US-2005/063892 Al de Tandon et al. [79] Core particles can be provided or generated in situ to have certain properties such as average particle size, average particle size distribution, microstructure, etc. In many cases, the core particles are aggregates of primary particles or small agglomerates (for example containing some aggregates). Often, core aggregates may have an average aggregate size in a range of from about 25 nanometers (nm) to about 500 nm, for example from about 25 nm to about 200 nm or from about 25 nm to about 100 nm. nm. In the case of carbon black materials, for example carbon black plasma, appropriate core particles, i.e. aggregates of primary carbon particles, may have a mean aggregate size in a range ranging from about 20 nanometers (nm) to about 500 nm, for example from about 25 nm to about 200 nm or from about 25 nm to about 100 nm. The core aggregates may have a characteristic microstructure, for example an aciniform morphology, found for example in aggregates of carbon black or silica. Core agglomerates may contain aggregates that are the same or different. [80] Some embodiments of the invention refer to the use of mixtures of core particles. Any combinations of preformed, in situ, fresh, upgraded or any other type of core material may be used as well as mixtures of core particles having different compositions and / or chemical properties. Whether formed in situ or preformed, a type of core particles can be combined with other carbon core materials or not and then coated. On the other hand, the other core material may be prepared in situ or provided as particles already made. As an illustration, examples of other materials that may be added to plasma carbon black cores include, but are not limited to, other types of carbon or carbon black, for example other grades. carbon black, double phase particles (eg carbon black and silica), acetylene black, carbon black, graphenes, carbon nanotubes, carbon-free material such as silica , alumina, other metal oxides such as titanate, zirconia and ceria, tin oxide, magnesium oxide, magnesium aluminum silicate, clays, for example bentonite, natural zeolites or synthetic, upgraded absorbents, electronic components, catalytic materials, ashes, carbon-free nanoparticles, etc. [081] To prepare carbon-coated particles, the core is coated with a carbon layer. The carbon layer is generated from a suitable source of carbon, often a liquid hydrocarbon such as, for example, by-products of coking operations and olefin manufacturing operations, for example, decanting oil. catalytic cracking operations, coal tar, other sources of petroleum refining etc. Specific examples of carbon-donating raw material compositions that can be used to coat core particles are given in US Pat. No. 5,190,739 issued to MacKay et al. [82] Liquid hydrocarbons may, however, contain sulfur (S) and / or nitrogen (N), and thus, generated gas offsets may require scrubbing or other emission clean-up measures. remove waste products such as SOx and / or NOx. Therefore, in some of the embodiments disclosed herein, the layer deposited on the core particle is generated from a source free or substantially free of S and / or N. Examples include, but are not limited to to, methane, natural gas, another gas source (one or more C1 to C4 hydrocarbons), for example. Not requiring a vaporization step, gaseous hydrocarbons can facilitate the formation of finer and / or more homogeneous coatings. [83] In an illustrative example, a silica core material is coated with carbon generated by the pyrolysis of natural gas, propane or butane. In some cases, the silica is premixed with a gaseous raw material (eg natural gas, propane or butane) and, optionally, with air. In another illustrative example, the core material is coated with a carbon layer generated by pyrolysis of a gaseous hydrocarbon raw material (eg, one or more C 1 to C 4 hydrocarbons) such as, for example , methane, natural gas and butane, consists or consists essentially of or comprises carbon black particles. For example, carbon black cores may be coated with a carbon layer generated by pyrolysis of natural gas in a carbon black reactor. These carbon black cores may be preformed or generated in situ. [084] The core particles are coated in a process carried out in a suitable apparatus. Optionally, the kernel itself is also produced during the same process and / or in the same device. According to an alternative or in addition, the core material 10 is provided to coat to obtain preformed particles. Several illustrative embodiments are described below. [085] In one embodiment, the coating of core particles, whether produced in situ or introduced as already made (preformed), is carried out in a process and / or using a reactor (furnace) adapted for the production of carbon black, or in a zone of such a reactor. Carbon black processes, reactors or furnaces are known in the art. examples include, but are not limited to, those described in RE 28974 which is a re-issued patent of US-3,619,140, both issued to Morgan et al., U.S. Patent No. 5,877,238 issued to Mahmud et al., US Pat. No. 5,190,739 issued to MacKay et al., WO-2014/140228 A1 to Schwaiger et al., U.S. Patent No. 6,277,350 B1 issued to Gerspacher, US-7 No. 5,072,821 B1 issued to Godai et al., U.S. Patent 4,582,695 A issued to Dilbert et al., U.S. Patent No. 6,099,818 to Freund et al., U.S. Patent No. 6,056,933 issued to Vogler and al., U.S. Patent 6,391,274 issued to Vogler et al., and others. A multi-stage reactor and a process for producing carbon black are disclosed in US Pat. No. 7,829,057 issued to Kutsovsky et al. November 9, 2010 and published patent application US-2007/0104636 Al Kutsovsky et al., published May 10, 2007. A multi-stage reactor and a process for producing carbon black and for producing aggregate particles Carbon black containing silicone or composite metal is disclosed in U.S. Patent No. 5,904,762 issued to Mahmud et al. Other reactors and / or carbon black processes can be used as known in the art. [086] In the example shown in Figure 1, hot combustion gases are generated in the combustion zone 1 by contacting a jet of liquid or gaseous fuel 9 with an oxidizing jet 5, for example air oxygen, or mixtures of air and oxygen (also known in the art as "oxygen-enriched air"). The fuel may be any jet of gas, vapor or liquid ready for combustion, such as hydrocarbons (eg methane, natural gas, acetylene), hydrogen, alcohols, kerosene, fuel blends etc. In many cases, the fuel chosen has a high content of carbon-containing components. [87] Thus, various gaseous or liquid fuels, for example hydrocarbons, can be used as combustion fuel. An equivalence ratio is a ratio of the fuel to the amount of oxidant required to carry the combustion fuel. Typical values for the equivalence ratio in the combustion zone range from 1.2 to 2.2. To facilitate the generation of hot combustion gases, the oxidant stream can be preheated. [88] Many embodiments of the invention relate to a combustion step that consumes the combustion fuel entirely. Excess, oxygen, fuel selection, burner design, jet speeds, conditions and mix-ups, air-to-air ratios, oxygen enriched air or pure oxygen, temperatures and other factors can be adjusted or optimized to ensure, for example, that combustion generates very little or no carbon seeds or nuclei. Instead, in a typical carbon black process, these cores are formed only after the introduction of the raw material yielding carbon black into the reactor. When carbon-free in situ core particles are used, offset formation of carbon cores relative to that of the core particles reduces or minimizes the inclusion of carbon in the cores. [89] The hot jet of combustion gas flows down zones 1 and 2 in zones 3 and 4. The raw material giving the coating (also called here the raw material of coating, the raw material giving carbon the carbon black raw material or the carbon black raw material) is introduced at one or more appropriate locations for other components and reactor streams. In the arrangement shown in FIG. 1, the coating raw material 6 is introduced into the reactor zone 3 at the injection point 7. [090] The raw material for coating can be injected into the jet of gas by nozzles designed for optimum distribution of oil in the jet of gas. Such nozzles can be either single flow or double flow. Dual flow nozzles may use, for example, steam, air, or nitrogen to vaporize the fuel. Single flow nozzles can be vaporized by pressure or the raw material can be injected directly into the gas jet. In the latter case, the vaporization is carried out by the force of the jet of gas. [091] The coating raw material may be, for example, a liquid or gaseous hydrocarbon capable of producing carbon black by pyrolysis or partial combustion. Suitable examples include, but are not limited to, sources of petroleum refineries such as decant oils from catalytic cracking operations, as well as ancillary products of coking operations and olefin manufacturing operations. . Specific examples of carbon-donating raw material compositions are given in US Pat. No. 5,190,739 issued to MacKay et al. Natural gas, methane, hydrocarbons, for example C2 to C8 hydrocarbons (propane, butane, ethylene, propylene, butadiene) and other sources of gaseous carbon or mixtures of liquid, gaseous or liquid and gaseous sources may also be used. [092] In a specific embodiment, a gaseous hydrocarbon, methane, natural gas or butane, for example, is used for in situ coating of carbon black core particles formed in a black process, reactor or furnace. carbon such as those disclosed, for example, in RE 28974 which is a re-issued US Patent 3,619,140, both issued to Morgan et al., U.S. Patent No. 5,877,238 issued to Mahmud et al. No. 5,190,739 issued to MacKay et al., WO2014 / 140228 A1 to Schwaiger et al., US Pat. No. 6,277,350 B1 issued to Gerspacher, US Pat. No. 7,097,822 B1 issued to Godai. et al., U.S. Patent 4,582,695 A issued to Dilbert et al., U.S. Patent No. 6,099,818 issued to Freund et al., U.S. Patent No. 6,056,933 issued to Vogler et al., US Pat. -6,391,274 issued to Vogler et al., US Pat. No. 7,829,057 issued to Kutsovsky et al. on November 9, 2010, US-5,904,762 issued to Mahmud et al., and published patent application US-2007/0104636 A1 of Kutsovsky et al., published May 10, 2007. [093] Carbon black can be generated in situ from a nucleus feedstock, often one or more hydrocarbon (s) or oil (s), for example a commercially available raw material having listed in US Pat. No. 5,190,739. Typically, the cores raw material is introduced into a reactor such as the reactor 50 of FIG. 1 upstream of the injection of the coating raw material. Suitable injection points or locations that can be used are described, for example, in US Pat. No. 7,829,057. The nucleus feedstock can be introduced in any conventional manner such as a jet. single or a plurality of jets, and the introduction of the raw material can be performed with different flow rates. For a plurality of jets, the flow rates may be different or the same for each jet. [94] In many cases, the injection of the nucleus feedstock is carried out in a manner which improves the penetration of the raw material into the interior regions of the hot combustion gas jet and / or a high degree of mixing and shearing the hot combustion gases and the nucleus raw material, to ensure that the raw material decomposes rapidly and completely and converts to a carbon black material. [95] With regard to the following introduction of a gaseous raw material for coating, this second raw material may be added downstream of the raw material giving cores in an amount and under conditions suitable for coating the particles. carbon black generated in situ with a carbon layer. Using a gaseous feedstock can cool the reactor, often to a greater degree than the cooling obtained by using an equivalent amount of an oil feedstock. Likewise, limitations on injector tips that are encountered with the oil raw materials are avoided.
[0005] In contrast to the use of a liquid raw material, for example oil or hydrocarbon, a gaseous raw material coating can provide environmental benefits and improvements in the quality of the coating. [96] Other embodiments relate to the introduction of one or more precursors to generate carbon free in situ core particles. Such a precursor may be premixed as a premix with the coating raw material and then fed together with the raw material into the reaction zone. In other embodiments, the precursor is introduced separately from the injection point of the coating raw material. [97] According to specific embodiments of the invention, the carbon-coating step follows the formation of core particles and the injection points of the nucleus precursor can be determined on the basis of temperatures, parameters and reactor, kinetic reaction data, time and mixing patterns, residence time, etc. Thus, depending on the case, the precursor may be introduced upstream or downstream of or at the same point as the point of injection of the coating raw material. Typically, the precursor is introduced upstream of the injection of the rinsing / damming liquid. In one embodiment, the reactions necessary to generate the core particles take place faster than those leading to the formation of the carbon material (carbon black precursor) necessary to effect the embedding of the cores. As a result, the core precursor can be injected together with the coating raw material or can be separately injected upstream at the same point along the reactor or downstream of the injection point of the coating raw material. According to FIG. 1, for example, the precursor, for example a precursor containing silicon which generates silica nuclei, can be injected together with the coating raw material 6. If desired, such a precursor can also be introduced upstream or slightly downstream of the raw material 6. [98] The amount of precursor to be used may be determined by routine experiments, calculations, models, experiment, etc. Factors to be considered include, but are not limited to, the type of materials to be employed, equipment and / or process parameters, e.g., speed and / or manufacturing production capability, various jets. input and output, kernel characteristics sought and others. [99] Conditions which enhance the formation of a carbon-free core (preferably over integration of a continuous carbon phase in the core) include, but are not limited to, relationships between the raw material yielding carbon black and a carbon-free precursor, the reactor temperature, especially in the reaction zones, and others. For example, increasing the amount of silicon precursor relative to the carbon black feedstock promotes formation of the carbon-free core followed by a carbon coating step. It is also possible to use a raw material giving less carbon black such as, for example, certain vegetable oils, for example soybean oil, thus lowering the amount of carbon material available in the zone of carbon. reaction. Alternatively or additionally, the reaction zone can be maintained at a temperature which is sufficiently high to promote the rapid conversion of a core precursor to a carbon-free core (i.e. wherein the continuous phase is a carbon-free material) compared to a slower conversion of raw material yielding carbon black to carbon black. In one example, the temperature of the reaction zone used to form silica cores from a silicon-containing composition is in the range of about 1680 ° C to about 1800 ° C, a temperature of about 40 ° C. at which the silica precursor reacts faster than the carbon black feedstock. [0100] Preformed cores particles (for example silica, rice shell silica, clay, precipitated silica, calcium carbonate, nanoparticles, pyrolyzed carbon, carbon black plasma, other types of black, already made carbon such as degraded carbon black - especially carbon black which has rubber reinforcing properties lower than the expected reinforcing properties according to its morphology - etc.) can be introduced into a reactor, as shown 10 on Figure 1, at a suitable injection point, for example at the injection point 7 or upstream or downstream thereof. More than one means and / or injection point can be used. Preformed core particles may be provided in one of the existing gaseous or vapor feed jets of the reactor or injected together with the coating raw material (jet 6 in FIG. 4). Alternatively, or in addition, preformed core particles may be dispersed in a liquid jet, for example in aqueous solutions, water, light hydrocarbons or the like, or may be introduced independently into a carrier gas. supplied to the reactor at a suitable location such as, for example, the jet 10 in FIG. 1. Inert gas, for example, upgraded flue gases and / or other carrier gases may be used. Preformed core particles may also be provided in a supercritical fluid such as, for example, supercritical CO2, or may be introduced with an existing jet, for example an air jet or even a jet of fuel (in FIG. respectively jet 5 and jet 9). At least a portion may be used as fuel in the combustion zone. The amount of preformed core material to be supplied may be determined by routine experiments, may be based on a theoretical model, experience or other techniques. Factors considered for determining the load may include the equipment used, process parameters, particulars of the material used, the type of feedstock and / or other jets used, downstream steps, desired characteristics and other. In certain situations, the formation of preformed particle blocks may be detrimental to the manufacture of a final product having desired properties, for example properties rendering the coated particles suitable for end use 303 56 5 7 32 for an integration in rubber compositions for tire applications. The problem can be addressed by different de-agglomeration techniques by introducing homogeneously preformed core particles into the coating raw material stream or by grinding them, for example, into a fluid energy mill, a jet mill, or the like. another powder mill equipment, just before the injection via a jet e gas carrier. In one embodiment, the preformed core material is dispersed into sufficiently fine particles for a coating which is made thereafter. For example, the core material may be mixed or homogenized with a liquid carbon feedstock, and injected as core material into the raw material for coating. Preformed core particles can also be transported into the reactor by a new jet (see for example jet 10 in FIG. 1) or an existing jet (of gas), including the combustion air jet or the natural gas (fuel). combustion). Inert gas, upgraded flue gas, and / or other carrier gases may also be used. The homogenization of preformed core particles may be carried out as known in the art and may include a homogenizer such as, for example, a colloid mill described in US Pat. No. 3,048,559 issued to Heller et al. on August 7, 1962. A moisture-operated micropulverizer may also be used as other means may be using a mechanical stress similar to the micro-spray or a milling action similar to the described colloid mill. Other examples of suitable homogenizers include, but are not limited to, the Microfluidizer® system commercially available from Microfluidics International Corporation (Newton, Mass., USA) and the MS 18, MS45 and MC 120 series models available from APV. Homogenizer Division of APV Gaulin Inc. (Wilmington, Mass., USA) as well as other commercially available or custom-made equipment. [0105] A different approach relates to techniques designed to coat nuclei that are relatively large (eg 200 nm to about 1, 5 or 30 micrometers). Such agglomerates, containing the same or different aggregates, may be coated with an "effective" carbon black layer, i.e., with sufficient carbon black coating to provide enhanced reinforcement and / or or an equivalence of performance properties compared to an appropriate reference. If agglomerates can be dispersed to smaller dimensions, preferably substantially less than 20 micrometers, then the coating of the agglomerate can be effective in a manner similar to that obtained by coating agglomerates of primary particles. Complete coating may not be necessary to achieve benefits with, for example, a carbon-coated silica core. It is believed that carbon black precursors may be able to penetrate and coat, if only partially, core aggregates in the agglomerate. When these coated agglomerates are incorporated into the rubber, they can be sufficiently divided and dispersed so that with incomplete coating of the core aggregates they provide a beneficial combination of performance and cost. Whether introduced as an already made material (preformed) or generated in situ, the core particles move in the flow direction in the reactor and are coated with carbon. Typically, with proper heating, the carbon-providing (coating) raw material is subjected to pyrolysis, generating carbon black precursors that deposit on the core particles. In a reactor such as that of FIG. 1, the coating may begin to be carried out at any point at or after the injection of the coating raw material and may continue during one or more subsequent steps. (s). The reaction is stopped in the rinsing zone / dam of the reactor. The barrier / rinse 8 is disposed downstream of the reaction zone and sprays a rinse / barrier liquid, such as water, into the newly formed carbon black particle jet. The dam / rinse serves to cool the carbon black particles and to reduce the temperature of the gas jet to reduce the rate of reaction. Q is the distance from the beginning of the reaction zone 4 to the rinsing / damming point 8 and 25 varies according to the position of the rinsing / damming. According to one option, the rinsing / dam may be staged or may take place at several points in the reactor. Pressurized spray, gas atomizer spray or other rinsing / damming techniques may be used. After rinsing / damming, the carbon-coated gases and particles, which have been cooled, flow towards the flow in any cooling and separation means 30 and the product is thus recovered. The separation of the carbon-coated particles from the gas jet is easily effected by conventional means such as a precipitator, a cyclone separator, a bag filter or any other means known to those skilled in the art.
[0006] When the carbon-coated particles have been separated from the gas jet, they may be subjected to a pelletizing step.  Another embodiment uses plasma carbon black particles which are produced in situ and then coated in a staging approach.  Methods and systems for performing both plasma carbon black cores and coating them with a carbon layer are hereinafter referred to as "integrated" and are described later with reference to FIGS. 2, 3 and 4.  As an example, Figure 2 shows a reactor 101 having a chamber 102 that is cylindrical or otherwise suitable.  In many cases, the inner walls of the reactor chamber are made of graphite.  The formation of core particles and their coating with a carbon layer are carried out in zones or regions of the reactor, as described below.  The reactor 101 is provided with conduits and injection means for supplying plasma gas (PG), a first raw material (HC in Figure 1) and a second raw material (coating) as indicated by the arrows.  If desired, one or more of these jets may be preheated, as is known in the art or as developed or adapted to fulfill specific process or apparatus design conditions.  The reactor may comprise additional inlets, one or more outlets for collecting the product, for example units for further processing of products, by-products or non-reaction materials, valves, flow meters, temperature controls, devices used to track or control process steps, computer interfaces, automation means, etc.  In the illustrative example described herein, the reactor 101 includes a head section 103 (shown in more detail in FIG. 3) which defines an upper end of the reactor.  On this end, are mounted three graphite electrodes 108 (Figure 3 shows only two).  The electrodes are connected to a power source 104 (shown in Figure 2) which is able to provide a three-phase alternating current.  The frequency of current can be the frequency of the network (50 to 60 Hz) or any other frequency, for example higher.  The plasma gas is introduced into the reaction chamber 102 at the center of the head section 103 (injection port 107 in FIG. 3) at a flow rate that can be adjusted according to the nature of the gas. plasma and electric power.  For example, it can be between about 0.001 normal cubic meters per hour (Nm3 / h) and 0.3 Nm3 / h per 3035657 kW of electrical power.  Other flow rates may be selected taking into account power requirements, production capacity, specific process parameters or equipment design, etc.  as known in the state of the art or obtained by calculations, models or routine experiments.  In some embodiments, the electrical power supplied to the electrodes 8 is of the order of 2.0 MW and hydrogen plasma gas is supplied to a reactor as described above with a flow rate of about 10 Nm3. at about 1000 Nm3M, for example in the range of about 100 to about 900, from about 200 to about 800, from about 300 to about 700, from about 400 to about 600, for example about 500 Nm3 / h.  Examples of gases other than hydrogen which may be employed as plasma gases include, but are not limited to, nitrogen, carbon monoxide (CO), inert or noble gases such as argon, helium and the like as well as other gases or mixtures of two or more gases, for example a mixture of 50% by volume of CO and H2.  The tips of the electrodes 108 are disposed on the flow path of the plasma gas stream and are arranged with a proximity sufficiently close to each other to trigger an arc of electrical composition (when sufficient power is available). provided by the source 4), generating a plasma in the arc or plasma zone 109.  The temperature of this plasma can be controlled, for example by the flow of plasma gas and the electrical power supplied to the electrodes 108.  In specific embodiments, the arc area 109 is optically followed through the aperture 115, allowing automatic control of the temperature and / or the amount of plasma gas flow.  From the arc zone, the flow or jet of plasma gas advances in the direction of the flow.  The flow rate of the plasma gas can be increased by providing a convergence zone such as a Venturi element 111, typically made of graphite, and a groove or contraction 120.  In some embodiments, the lower end of the Venturi element is formed as a cutting edge (rather than an increasing continuous section), facilitating rapid expansion as the plasma gas enters the reaction zone 110.  Other embodiments utilize a gas / throat assembly as disclosed in published US Patent Application No. 2015/0210858.  It is also introduced into the reaction zone 110, a carbon source for preparing the plasma carbon black cores particles (jet HC in Figure 2), also called here "raw material", a "raw material" giving 3035657 36 nuclei "or just" core material ".  In many aspects of the invention, the first raw material consists or consists essentially of or comprises methane or natural gas.  Examples of other suitable materials which could be used include, but are not limited to, hydrocarbons such as C2 to C8 hydrocarbons (propane, butane, ethylene, propylene, butadiene for example), light petroleum, heavy petroleum, smoke or pyrolysis oil, biogas, other fuels that contain carbon and hydrogen, combinations of these, etc.  The first raw material can be injected by one or a plurality of ports (2, 3, 4, 5 or more) or injectors at the location 113, arranged in the wall 112 of the reaction chamber 102.  Introducing the nucleating raw material below, and preferably just below, the Venturi element 111 is intended to enhance the mixing with the plasma gas.  The first raw material can be injected directly or radially towards the center of the reaction zone 110.  It can also be injected in a more tangential manner, thus entering the reaction zone 110 out of the center or at an angle with or against the flow.  Suitable rates for the introduction of the first raw material can be determined on the basis of calculations, models, experience, routine experiments etc. , taking into account the nature of the feedstock, reactor size, production capacity, electrical power, product output rate, other flow rates and / or other considerations.  In some embodiments, a first raw material, which is methane or natural gas, is introduced into a reactor such as that of Figures 2 and 3 at a flow rate in the range of about 100 Nm3 / h to about 1000 Nm3 / h, for example in the range of from about 200 to about 800, from about 300 to about 700, from about 400 to about 600 Nm3 / h.  In the case of a typical first liquid raw material, applied flow rates may be between about 10 and about 500 kg / h, such as from about 100 to about 400, from about 100 to about 300 or from about 100 to 200 kg / h.  Higher or lower rates can also be applied.  In some cases, the first raw material is introduced at a rate of at least 2, 5, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35 or more tonnes (1000 kg ) per hour.  The temperature in the reaction zone may be adjusted by manipulating one or more parameters such as, for example, the flow rate of the plasma gas flow, its temperature, the nature and / or the flow rate of the first raw material, the electrical power supplied to the electrodes 108, and / or process conditions.  In specific examples, the temperature in the reaction zone is in a range of from about 900 ° C to about 3000 ° C, such as in the range of about 1300 ° C to about 1900 ° C, by from about 1400 ° C to about 1800 ° C.  The pressure with which the raw material is injected can influence the surface of the core particles.  In many cases, the pressure in the reactor is kept slightly above atmospheric pressure, thus avoiding any oxygen uptake of the ambient air.  [0119] One or more process steps leading to the formation of carbon-black plasma core particles may be designed as unit operations with individual capabilities, as described, for example, in US patent application publication. 2015/0210857 Al [0120] The plasma carbon black cores particles generated in the reaction zone 110 are coated with a carbon layer in a finishing operation in which a second raw material (also called here "raw material giving a coating "or" coating raw material ") is pyrolyzed to deposit an active carbon surface on the plasma carbon black particles.  Suitable materials that can be used as a second raw material include, but are not limited to, petroleum refinery sources such as decant oils from catalytic cracking operations, by-products of coking operations and olefin manufacturing operations, ECR fuels (randomized controlled trial), etc.  Examples of coating raw material compositions can be found in US Pat. No. 5,190,739 issued to MacKay et al.  In many embodiments, the second raw material is different from the first raw material.  In other cases, the second raw material is the same as the first raw material.  Typically, the second raw material is supplied downstream of the injection point of the first raw material by one or more ports or injectors at the location 114.  In the example shown in FIG. 3, the second raw material is introduced at or below the convergence zone 116 and can be injected radially inwards from the circumference of the convergence zone.  The convergence zone 116 optionally includes the restriction or groove 122 and serves to accelerate the plasma carbon black particles and the H2 reaction product.  The design of the convergence zone 116 may be the same as or different from that of the first convergence zone (Venturi element 111 in FIG. 3).  Similarly, the configuration of the first and second grooves (respectively 120 and 122) may be the same or different.  Taper angles and / or diameters may be selected based on flow rates, capacity, design parameters and / or other considerations.  For example, the groove 122 may be wider than the groove 120 to accommodate additional gases that have evolved during the pyrolysis of the first raw material.  In other situations, the diameter of the groove 122 is less than or equal to that of the groove 120.  Cones or other arrangements resulting in a smaller ring may also be used.  In other embodiments, the finishing operation is carried out in the absence of a convergence zone, by only vaporizing the coating raw material in the jet carrying the plasma carbon black cores particles. the raw material of coating being introduced at one or more appropriate places.  Approaches in which the difference between the first step (core particle formation) and the second step (finishing step) are reduced or minimized, are also possible, the time that the core particles are substantially fully formed (ie that is, the time that the addition of mass to the core particle is substantially complete) before starting the coating operation.  Injection of the second raw material can be effected through nozzles designed for optimum distribution of the raw material in the gas jet.  Such nozzles may be a single fluid or two fluids.  Two-fluid (bi-fluid) nozzles can use, for example, steam, air or nitrogen to vaporize the fuel.  Single fluid nozzles vaporize by pressure.  In some cases, the second raw material can be injected directly into the jet comprising CH 4, H 2 and plasma gas.  The second raw material may be provided in sufficient amounts to produce a desired coating of the core material.  Typical ratios between the first raw material and the second raw material depend on different factors which can be determined by routine experiments, calculations, previous experience or other means.  The ratio of the first raw material to the second raw material may be from about 10: 1 to about 1:10, for example in the range of about 3: 1 to about 1: 1, or about 2: 1 to about 1: 1 by weight.  The temperatures which allow the pyrolysis of the coating raw material can be in the range of about 900 ° C to about 3000 ° C, such as in the range of about 1300 ° C to about 1900 ° C. ° C, for example from about 1400 ° C to about 1800 ° C.  The coating or finishing zone (disposed around and downstream of the injection point 114) may be heated, wholly or partially, by the jet of hot gases passing through the reactor.  In some embodiments, the plasma operations used to form the core particles are conducted at temperatures sufficiently high to provide all the thermal energy required to carry out the coating process.  For example, one or more additional plasma sources may be employed.  Additional or alternative heating may be provided by preheating the second raw material, recirculating hot combustion gases in an indirect heat exchange arrangement, or by other means.  Suitable temperatures that can be used to preheat the second raw material (or other sources employed for the method or apparatus described herein) may be the same or similar to those taught for disclosed preheating arrangements, for example in U.S. Patent No. 3,095,273 issued June 25, 1963 to Austin, U.S. Patent No. 3,288,696 issued November 29, 1966 to Orbach, U.S. Patent No. 3,984,528 issued Oct. 5, 1976 to Cheng et al. U.S. Patent No. 4,315,901 issued February 16, 1982 to Cheng et al. U.S. Patent 4,765,964 issued Aug. 23, 1988 to Gravley et al. U.S. Patent 5,997,837 issued Dec. 7, 1999 to Lynum et al. U.S. Patent No. 7,097,822 issued August 29, 2006 to Godai et al. U.S. Patent 8,871,173 B2 issued October 28, 2014 to Nester et al.  or CA-682,982.  A specific approach uses flue gas obtained from a reactor and heated, for example, by plasma heating, and dehydrated, as described, for example, in US Pat. No. 7,655,209 issued February 2, 2010 to Rumpf et al.  In certain aspects of the invention, the carbon-giving raw material used to coat plasma carbon black in situ is introduced into a finishing zone of a carbon black reactor, for example as described above. high.  FIG. 4 shows an apparatus 200 comprising an arc or plasma zone 109, a reaction zone 110, both essentially as described above, and a finishing zone 202 of a carbon black reactor, for example the reactor 50 in FIG.  The second raw material is introduced via feed line 214 and injection points 207 to groove 122.  The coating reaction is stopped in zone 4 by arranging, for example, a rinsing / dam downstream of the coating operation.  By introducing the second raw material after the preparation of the core particles has been completed, the carbon precursors (generated by the pyrolysis of the coating raw material to form dehydrogenated molecular fragments) are deposited (coated) on the surface of the core particles to form the carbon coating.  Various additional steps can be implemented.  With reference to FIG. 2, for example, the lower end of the chamber 102 is connected to the extraction means 105 through which the reaction products are extracted (removed) from the reactor.  These may be directed to standard separation means 106, for example cyclones and / or filters, where the coated particles are separated from hydrogen and other reaction products or products.  The hydrogen may be separated from other flue gas components and recycled as plasma gas or, for example, a component thereof.  It can be used in other operations in the facility or transported elsewhere for off-site use.  Unchanged HC, acetylene and / or other flue gas components may be directed to another use, removed or added to fresh HC in the production of carbon black particles. plasma carbon.  In some embodiments, a plasma reactor such as, for example, a conventional plasma reactor, may be used to coat core particles, typically preformed, using a coating material such as natural gas, methane, hydrocarbons, for example C2 to C8 hydrocarbons (for example propane, butane, ethylene, propylene, butadiene), light petroleum, heavy oil, waste or pyrolysis oil, biogas or other raw material compositions of coating which include carbon and hydrogen.  Gaseous raw materials do not require spraying and can thus give more uniform and / or thinner coatings.  In specific examples, the coating raw material contains very little or no sulfur or nitrogen, thus limiting SOx and / or NOx emissions and reducing flue gas cleaning requirements.  The amounts of preformed core material can be determined by routine experiments, can be based on theoretical models, previous experiments or other techniques.  Factors taken into account in determining charges may include the equipment used, process parameters, specifics of the plasma carbon black material used, the raw material used and / or other jets used, downstream steps, searched properties and others.  In one illustrative embodiment, dry or wet cake silica is passed through a fluid energy mill using natural gas as a fluid gas.  The mill mixture is mixed with a hot plasma jet, see Figures 2 and 3, where the natural gas is dehydrogenated and carbon is deposited on the silica.  The gas and the particles can then be separated, for example by conventional means.  The process can provide a homogeneous carbon coating on the silica core (as compared to a coating obtained from a liquid raw material which is to evaporate and be mixed), high performance particles from the core assembly of the invention. silica / carbon coating, little or no SO, NO, emission.  Since the total carbon load is less than that required to prepare regular carbon plasma black, this approach can prevent the formation of large carbon particles.  [0133] The coating raw material may be supplied together with H2, N2 or a suitable plasma gas, for example as described above.  In many cases, plasma gases and injection points of the gaseous feedstock (preferably downstream and in a manner that prevents recirculation back to the electrodes) are chosen because of reduced or minimized coking of the feedstocks. plasma electrodes.  Coking 20 can also be reduced or avoided using a microwave plasma process.  In some cases, the plasma carbon black particles are prepared at a station and then directed to a finishing station where the particles are coated with a carbon deposit.  This type of arrangement is hereinafter referred to as a "production line" system, arrangement or process and is composed of different stations or unit operations that can be implemented independently of one another.  In this approach, a station can be stopped, for example for repairs or maintenance while others can continue to operate.  The need for synchronization of different operations is reduced or minimized.  In other examples, two or more stations in a production line system work in a connected or concerted manner to increase throughput, minimize energy requirements, realize recycling benefits and / or other benefits.  A production line system or process may be configured for batch, semi-continuous or continuous operations.  Similar production line arrangements may be used for cores other than plasma carbon black cores.  The coated particles described herein can be generated together with the formation of carbon particles, for example traditional carbon black.  The mixture of composite particles and single-phase carbon particles can be used as blended.  The carbon-coated particles described herein may have a core that is wholly or partially (e.g., 99%, 98%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 15%, 10% or less) coated with carbon.  In specific examples, the coating is amorphous carbon.  In specific embodiments, the carbon or shell layer coats aggregates made of primary particles such as, for example, silica aggregates having a size in the range of about 20 nm to about 500 nm. such as from about 25 nm, 50 nm or 100 nm to about 200 nm, from about 200 nm to about 300 nm or from about 200 nm to about 400 nm.  The coating may be as thin as a few nm or less, for example from about 0.5 nm to about 5 nm.  In many cases, the coating may be as thick as about 20 nm.  For example, the coating may have a thickness of 0.5 nm to about 1 nm, 0.5 m to about 5 nm, 1 nm to about 10 nm, about 1 nm to about 15 nm, or about 1 nm to about 20 nm.  The resulting coated particles may have a particle size in the range of about 20 nm to about 500 nm.  The carbon layer may also be deposited on small agglomerates such as, for example, agglomerates made of aggregates and having an agglomerate or cluster size in the range of about 200 nm to about 5 microns. pm, for example from about 200 nm to about 1 I. JM, such as from about 200 nm to about 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm or 900 nm.  Wider agglomerates (including, for example, the same aggregates and / or agglomerates or different aggregates and / or agglomerates) having for example a characteristic size of 1 μm or more, often greater than 2, 3, 4 or 5 μm, can also be coated.  In some cases, the coated particles described herein retain at least some of the characteristic properties of the core material, for example in cases where the carbon coating is sufficiently fine and does not completely cover the core.  In other cases, the carbon coating will take precedence over the overall properties.  In rubber applications, fine coatings will retain the morphology and / or other properties of the core particle in the rubber composition.  Thicker coatings can be used to give mainly carbon black properties and rubber performance.  In some applications, the carbon-coated particles are intended to balance properties that are to be attributed to the core material and properties that are provided by the carbon coating.  The coated particles may be characterized by the same characteristics as those used to analyze the CB.  These include, but are not limited to, a specific surface size, structure, aggregate size, shape and distribution and chemical and physical characteristics of the surface.  The properties of the carbon black are determined analytically by tests known in the art.  For example, the size of the nitrogen adsorption surface and the Statistical Thickness Surface Area (STSA), another measure of surface size, are determined by adsorption. nitrogen according to a test procedure according to ASTM D6556-10.  The iodine number can be measured according to ASTM procedure D1510-13.  The "structure" of carbon black describes the size and complexity of carbon black aggregates formed by fusing primary carbon black particles together.  As used herein, the structure of the carbon black can be measured as the Oil Absorption Number (OAN) for the unmilled CB, expressed in milliliters of oil per 100 g. of carbon black, according to the procedure set forth in ASTM D-2414-13.  The oil absorption index of a Compressed Sample Oil Absorption Number (COAN) measures the part of the carbon black structure that is not easily changed by the application of mechanical stress.  The COAN index is measured according to the ATSM 30 D3493-13 standard.  Aggregate Size Distribution (ASD) is measured according to ISO 15825 using plate centrifuge photo-sedimentometry with a BI-DCP model manufactured by Brookhaven Instruments.  Carbon black materials having properties suitable for a specific application can be selected and determined according to ASTM standards (see 3035657 44 for example ASTM D 1765-03: standard classification system for carbon black used in products Rubber) by Cabot Corporation Specifications (see website www. pooch-corp. com) or other specifications of commercial qualities.  The coated particles described here may have a BET surface area, measured according to the Brunauer / EmmettfTeller (BET) technique according to the procedure of the ASTM D6556 standard, between 5 m 2 / g and 300 m 2 / g, for example between 50 m 2 and 300 m2 / g, for example between 100 m2 / g and 300 m2 / g.  In some cases, the BET area is in the range of about 100 m 2 / g to about 200 m 2 / g.  In other cases, the BET area is in the range of about 200 m 2 / g to about 300 m 2 / g.  The OAN index can be between 40 m / 100 g and 200 m / 100 g; for example between 60 m1 / 100g and 200 m1 / 100g, such as between 80 m1 / 100g and 200 m1 / 100g, for example between 100 m1 / 100g and 200 m1 / 100g or between 120 m1 / 100g and 200 m1 / 100g , 140 m1 / 100g and 200 m1 / 100g, 160 m1 / 100g and 200 m1 / 100g or such as between 40 m1 / 100g and 150 m1 / 100g.  The STSA may be in the range of about 5 m 2 / g to about 275 m 2 / g, for example from about 30 m 2 / g to about 250 m 2 / g, such as between 30 m 2 / g and 200 m2 / g.  The COAN number can be in the range of about 40 m1 / 100g to about 150 m1 / 100g, for example about 55 m1 / 100g to about 150 m1 / 100g, such as between 80 m1 / 100g and 120 m1 / 100g. 100g.  In specific embodiments, the carbon-coated particles have an STSA index in the range of about 30 to 250 m 2 / g and a COAN index in the range of about 55 to 110 cc / 100 g.  In other examples, the STSA number 20 is in the range of about 30 to about 250 m 2 / g, and the COAN value is in the range of about 55 to 110 cc / 100 g.  In other instances, the particles described herein may have an STSA in the range of about 30 to about 250 m 2 / g and an OAN in the range of about 55 to about 400 cc / 100 g.  In some examples, the carbon core and the carbon outer region exhibit different properties and different levels of interaction with elastomer molecules and performance in rubber composites.  In an integrated process such as, for example, the plasma method described above, the properties of the core particles can be determined by carrying out the entire process without adding the second raw material, thereby obtaining uncoated core particles which can be analyzed. according to one or more appropriate techniques.  Introducing the second raw material produces coated particles which can also be analyzed.  The results obtained for core particles and those obtained for coated particles can then be compared.  If desired, performance correlations can be established.  Other approaches may be employed.  For example, nuclei using pyrolytically upgraded carbon can be distinguished from the outer carbon layer on the basis of elements (eg, alumina, silica, zinc oxide, etc.). ) which are typically in the core but not found in the carbon coating.  The coated particles described herein may be subjected to further processing.  If desired, they may be surface-treated or surface-modified by techniques such as those known to, and practiced with, carbon black materials.  Thus, the coated particles may be prepared to contain small molecules and / or polymers, either ionic or nonionic, which are adsorbed on their surface.  In specific examples, the carbon-coated particles have functional groups (for example derived from smaller molecules or polymers, either ionic or non-ionic) which are directly attached to the carbon surface.  Examples of functional groups that can be directly attached (e.g., covalently) to the surface of carbon black particles and methods for effecting surface modification are described, for example, in US Pat. No. 5,554,739. issued to Belmont on September 10, 1996 and in US-5,922,118 issued to Johnson et al.  July 13, 1999.  As an illustration, a surface-modified carbon black which can be employed herein is obtained by treating carbon black with diazonium salts formed by the reaction of either sulfanilic acid or para-amino-benzoic acid ( PABA) with HC1 and NaNO2.  Modification of the surface by sulfanilic or para-aminobenzoic acid processes using, for example, diazonium salts, results in carbon black having effective amounts of hydrophilic moieties on the carbon coating.  Other techniques that can be used to provide functional groups attached to the surface of the carbon-coated particles are described in US Pat. No. 7,300,964 issued to Niedermeier et al.  November 27, 2007.  Oxide-coated and (modified) carbon-coated particles may be prepared in a manner similar to that used with carbon black, as described, for example, in US Pat. No. 7,922,805 to Kowalski et al.  on April 12, 2011 and in US Patent No. 6,471,763 issued to Karl on October 29, 2002.  An oxidized carbon-coated particle is one that has been oxidized using an oxidizing agent to introduce ionic and / or ionizable groups onto the surface.  Such particles may have a higher degree of oxygen-containing groups on the surface.  Oxidizing agents include, but are not limited to, oxygen gas, ozone, peroxides such as hydrogen peroxide, persulfates including sodium potassium persulfate, hypohalites such as hypohalite sodium, oxidizing acids such as permanganate salts, osmium tetroxide, chromium oxides or ceric ammonium nitrate.  Mixtures of oxidants can also be used, including mixtures of gaseous oxidants such as oxygen and ozone.  Other surface modification methods such as chlorination and sulfonylation may also be employed to introduce ionic or ionizable groups.  In a specific embodiment, the coated particles are surface-modified according to the teaching of US Pat. No. 8,975,316 issued to Belmont et al.  The coated particles may be used in different applications such as, for example, as reinforcement in rubber products, for example tire components.  Without wishing to be bound by a particular mechanism, it is believed that the activity of the interaction between carbon black and rubber is directly or indirectly related to the type of molecules whose carbon black surface is formed .  Other aspects of the invention relate to end-uses of the coated particles described herein, including, for example, unmodified or surface-modified carbon-coated particles.  For example, the particles may be incorporated into rubber articles being used, for example, in tire treads, especially in tire treads for cars, light vehicles, trucks and buses. off-the-road (OTR) tires, aircraft and similar tires, sub-belts, wire or cable ties, sidewalls, cushion rubber for escaped tires, and other uses.  In other applications, the particles may be used in industrial rubber articles such as engine mounts, hydraulic mounts, bridge supports and seismic isolators, chariot treads or treads, belts or belts. mining, pipes, gaskets, gaskets, sheets, weather-stripping articles, bumpers, anti-vibration parts and others.  The particles may be added as an alternative or in addition to traditional reinforcing agents for tire components and / or other industrial end uses of rubber.  In many cases, they are provided in a form that is the same or similar to known methods for introducing fresh carbon black into rubber products.  For example, the material described herein may be combined with natural and / or synthetic rubber in a dry blending process on the basis of an internal batch mixer, a continuous mixer or a roller mixer.  According to an alternative, the particles described herein can be mixed in rubber according to a liquid process known as Masterbatch® (masterbatch).  For example, a slurry containing the particles described herein can also be combined with a latex elastomer in a tray and then coagulated by adding a coagulant such as an acid, using the techniques described in US-6,841,606.  In specific embodiments, the particles are introduced according to the teachings of U.S. Patent No. 6,048,923 issued to Mabry et al.  April 11, 2000.  For example, a method for preparing an elastomeric masterbatch may include simultaneously feeding a particulate charge fluid and a latex elastomer fluid to the mixing zone of a coagulation reactor.  A coagulation zone extends from the mixing zone, preferably with a gradual increase in the cross section in the flow direction from an inlet to an extraction end.  The latex elastomer can be either natural or synthetic and the particulate fillers comprise, consist essentially of, or consist of material as described above.  The particulate fillers are conveyed to the mixing zone, preferably as a continuous high-velocity jet of the injected fluid, while the latex fluid is conveyed at low velocity.  The velocity, flow, and particulate concentration of the particulate load fluid are sufficient to initiate mixing with strong shear of the latex fluid and flow turbulence of the mixture at least in a rising portion of the coagulation zone to effect essentially coagulate the latex elastomer with the particulate fillers before the extraction end.
[0007] Essentially complete coagulation can be achieved without resorting to an acid or a salt as a coagulation agent. As disclosed in US Pat. No. 6,075,084, additional elastomer may be added to the material exiting the extraction end of the coagulation reactor. As disclosed in US-6,929,783, the coagulum can then be fed to a dewatering extruder. Other examples of suitable masterbatch methods are disclosed in US Pat. No. 6,929,783 to Chung et al., U.S. Patent Application Nos. 2012 / 0264875A1 to Berriot et al. and US-2003 / 0088006M to Yanagisawa et al. and EP-1,834,985 B1 issued to Yamada et al. Particles can be evaluated in a suitable rubber formulation using natural or synthetic rubber. Suitable amounts of coated particles to be used can be determined by routine experiments, calculations, taking into account factors such as typical ASTM standard furnace black charges in comparable manufacturing processes, parameters specific to the techniques and equipment used, the presence or absence of other additives, the desired properties of the end product, etc. The performance of the coated particles described herein as reinforcing agents for rubber compositions can be established by determining, for example, the performance of a rubber composition which is similar in all respects except for the use of a type of carbon black suitable for the given application. In other approaches, values obtained for compositions prepared according to the invention can be compared with values known to the art together with desired parameters in a given application. Suitable tests include green rubber tests, polymerization tests, and polymerized rubber tests. Among the appropriate green rubber tests, ASTM D4483 establishes a test method for the Mooney Viscosity ML1 + 4 test at 100 ° C. The mixing time (scorch time) is measured according to ASTM D4818. The polymerization curve is obtained with a Rubber Process Analyzer (RPA2000) analyzer at 0.5 °, 100 cpm, and 150C (NR) - 160C (SBR) according to ASTM D5289. The performance characteristics of polymerized samples can be determined by a series of suitable tests. The tensile strength, the elongation of rupture and the impact of various forces (for example at 100% and at 300% are obtained by ASTM D412, method A. Dynamic mechanical properties including the storage module, the modulus of The loss, and the tan 6, are obtained by a stress scan test at 10 Hz, 60 C and different stress amplitudes from 0.1% to 63% Shore A hardness is measured according to ASTM D2240. The shear rate of a type C cube of polymerized rubber samples is measured according to ASTM D624. [0162] A non-dispersed area is calculated by analyzing images obtained by reflection mode optical microscopy for polymerized rubber compositions. The dispersion can also be represented by the Z value (measured, after crosslinking, according to the method described by S. Otto et al., in Kautschuk Gummi Kunststoffe, 58th year, No. 7-8 / 2005, the article being entitled New Reference value for the description of Filler Dispersion with the 1000NT Dispergrader. The ISO 11345 standard describes visual methods for rapid and comparative determination of the degree of macro-dispersion of carbon black and carbon black / silica in rubber. The abrasion resistance is quantified as an index based on an abrasion loss of polymerized rubber using a Cabot Abrader (Lambourn type). Attractive abrasion resistance results may be indicative of advantageous wear properties. Good hysteresis results can be associated with low rolling resistance (and corresponding higher fuel economy) for automotive tire applications, reduced temperature rise, tire life, fatigue life, fatigue life, fatigue life, tire life, tire performance, and the like. life time of the tread and the carcass, fuel economy characteristics for the motor vehicle ect. The invention is also described hereinafter by the following nonlimiting examples.
[0008] Example I [0165] Experiments were conducted in a pilot plant using a carbon black reactor such as that shown in Figure 1. The conditions for test series A, B and C are shown in Table 1. In each case, a combustion zone equivalence ratio of 1.43 to 1.67 was used, which amounts to 30 to 40% of a fuel-rich combustion reaction. The primary fuel for the combustion reaction was natural gas and was fed to the reactor through the jet 9. The natural gas fed to the carbon black process had an ambient temperature of about 77 ° F (25 ° C). ° C). The liquid carbon feedstock used was a commercially available raw material and having the properties listed in MacKay et al US Pat. No. 5,190,739. The precursor for forming silica cores was oxymethylcyclotetrasilane [D4] supplied by Dow Coming Corporation, Ividland, Minnesota (Xiametee). The two raw materials yielding carbon black and the precursor were injected together in the presence of a jet of hot gases formed in the combustion zone in zone 3 by the jet 6. The silicon-containing liquid precursor and the material The first liquid giving carbon black was introduced into the process in various amounts as shown in Table 1. The reaction was stopped using a water spraying in zone 8. Table 1 Parameter Series A Series B Series C Air flow, Nm3 / h 1600 1600 1600 Temp. air preheating, ° C 500 500 500 Natural gas flow, Nm3 / h 239.5 279.5 239.5 Raw material flow rate to carbon black, 98.7 49.9 65.1 kg / h Silicon precursor flow rate, kg / hr 150 200 150 STSA, m2 / 95.1 95.2 95.8 Ash content of the particles,% 65.4 72.3 62.6 [0167] The resulting particles have a silica core and a carbon coating, prepared as described above and having properties shown in Table 1, were observed by electron transmission microscopy (TEM). Samples were prepared by sonicating them in alcohol and chloroform and placing them on pierced carbon grids. As can be seen in FIG. 5, the dominant microstructure was aciniform silica coated with a carbon layer 1 to 5 mm thick. This was determined by the amorphous contrast of the silica cores and the turbostatic edges of the carbon coating. The carbon has coated the entire silica aggregates rather than individual primary particles. Some single-phase carbon black particles have also been observed. Example 2 Ground particles of rice husks, which can contain about 20% naturally occurring nano-silica domains, are added to the jet of Figure 1 to the preheated air supplied to the combustion zone. using a weight loss type loader (Schenck AccuRate Mechatron ™ Loader manufactured by Schenck Process, Chagrin, Ohio). The air is enriched with 25% oxygen. The process is carried out in a reactor such as that shown in FIG. 1. Particles are transported by the combustion zone 10, and thanks to the high temperature and the presence of excess oxygen both in the feed pipe In particular, in the combustion zone, a significant portion of the outer carbon material in the rice husk is gasified, leaving behind small areas of silica. These particles are carried with the combustion gases in the reaction zone (zone 3 in FIG. 1). From the raw material to carbon black is vaporized in the jet of combustion gas, the deposition being favored with respect to nucleation, and the majority of carbon black formed is deposited as a coating on the existing silica particles. The reaction mixture is stopped downstream (zone 8) with water to cool the coated particles and to stop the pyrolysis reaction. The result is a particle with an interior that is composed essentially of silica, and an outer coating of carbon black. Table 2 shows the flow rates of the various inputs to the reactor.
[0009] Table 2 Parameter Air flow, Nm3 / h 1600 Additional oxygen flow, 86.5 Nm3 / h Temp. air preheating, ° C 500 Flow rate of natural gas, Nm3 / h 83.7 Flow of crushed rice husks, 150 kg / h Feed rate of raw material to 188.5 carbon black, kg / h Example 3 5 [0170] the precipitated silica having an area of 160 m 2 / g is mixed with carbon black raw material in a shear mixer tank together with a suitable surfactant to produce a slurry of 30% by weight of precipitated silica. The process is carried out in a reactor as shown in FIG. 1. A combustion fuel is burned with excess air in a combustion zone 1, the hot product gases being transported downstream in the zone. 3. The carbon black / precipitated silica raw material slurry is injected transversely to the flow of the combustion gas under pressure in the reactor by the jet 6. The raw material is first vaporized, leaving behind silica in the form of porous drops. When the carbon black raw material begins to pyrolyze and condense, the particle deposition dominates over nucleation, and most of the carbon black formed is a coating on the existing silica particles. The reaction mixture is stopped downstream (zone 8) with water to cool the coated particles and to stop the pyrolysis reaction. Table 3 shows the flow rates of the various inputs into the reactor. Table 3 Parameter Airflow, Nm3 / h 1600 Temp. Preheating air, ° C 500 Primary combustion,% 200 Natural gas flow, Nm3 / h 83.7 Flow rate of raw material slurry to 560 carbon black and precipitated silica, kg / h Example 4 [0171] Particles of carbon upgraded by pyrolysis are added upstream of the reactor to the jet of preheated air (jet 5 in FIG. 1) supplied to the combustion zone by means of a weight loss type feeder (Schenck AccuRate Mechatron TM charger manufactured by Schenck Process, Chagrin, Ohio). The air is enriched with 25% oxygen. Particles are carried by the combustion zone, and due to the high temperature and the presence of excess oxygen both in the air duct and in particular in the combustion zone, a significant portion of the outside carbonaceous material The rice husk is gasified, leaving a portion of the particles in the jet of combustion gas. The carbon that is consumed in the area replaces natural gas as a combustion fuel. The particles are carried with the combustion gases in the reaction zone (zone 3 in FIG. 1). From the raw material to carbon black is vaporized in the jet of combustion gas by jet 6 transversely to the flow and is vaporized, then nucleation and pyrolysis begin to take place. A carbon coating is deposited on the carbon core upgraded by pyrolysis. The reaction mixture is stopped downstream (zone 8) with water to cool the coated particles and to stop the pyrolysis reaction. The result is a particle with an interior that is composed essentially of pyrolyzed carbon, and an outer coating of carbon black. Table 4 shows the flow rates of the various inputs in the reactor. Table 4 Parameter Airflow, Nm3 / h 1600 Additional oxygen flow, Nm3 / h 86.5 Temp. air preheating rate, ° C 500 Natural gas flow rate, Nm3 / h 83.7 Volatile carbon flow rate, pyrolysis, kg / h 150 Raw material flow rate to 188.5 carbon, kg / h 5 Example 5 [0172] From Precipitated silica with an area (SA) of about 160 m 2 / g as a wet cake is milled using a fluid energy mill. The milled material is transported into the combustion zone by the jet 10 which may be a gas such as air or nitrogen. The water is removed by heat from the combustion reaction, and the silica particles are entrained in the flue gas stream. From the raw material to carbon black is vaporized in the jet of combustion gas via jet 6 transversely to the combustion stream and vaporized, then nucleation and pyrolysis begin to appear. A coating of carbon is deposited on the precipitated silica core. The reaction mixture is stopped downstream (zone 8) with water to cool the coated particles and to stop the pyrolysis reaction. The result is a particle with an interior that is composed essentially of silica, and an outer coating of carbon black. Table 5 shows the flow rates of the various inputs to the reactor.
[0010] 3035657 Table 5 Parameter Air flow, Nm3 / h 1600 Temp. air preheating temperature, ° C 500 Natural gas flow rate, Nm3 / h 175.6 Moist precipitated silica flow rate, kg / h, dry basis 120 Carrier gas flow rate, Nm3 / h 120 Raw material flow rate to 344.5 carbon black Example 6 [0173] In a plasma reactor as shown in Figure 3, a hydrogen flow of 500 Nm3 / hr is added via port 107. Electrodes (108) are fed with 2.0 MW of electrical power, generating a hot plasma gas. The hot plasma gas is passed through the strangely (throat) 120 which has a diameter of 2.5 inches (about 6.35 mm), increasing the speed. At the injection site 113, 150 kg / h of liquid hydrocarbon raw material is added to the hot sliding plasma gas by three pressurized nozzles 10 arranged radially (with a hole of 0.5 mm each, at 700 psig). The liquid carbon raw material used is a settling oil, a commercially available carbon black raw material. By mixing it with the hot plasma gas, the hydrocarbon liquid raw material is pyrolyzed to form carbon black and hydrogen gas. The mixture of hot H2, other gases and carbon black is then accelerated by the convergence zone 116 and the restriction (groove) 122, the latter having a diameter of 3 inches (about 7.62 mm). where a second injection at the location 114 of 75 kg / h of a liquid carbon raw material (also of the settling oil) is added to the mixture by three pressurized tips arranged radially (with a hole of 0.4 mm each, at 400 psig). This second raw material is divided by pyrolysis into carbon black and H2 and preferably coats the plasma core particles which are formed in zone 110, increasing their mass, decreasing their area and increasing their structure. Example 7 [0174] In a plasma reactor as shown in FIG. 3, a hydrogen flow of 500 Nm3 / h is added via port 107. Electrodes (108) are supplied with 2.0 MW of electrical power. generating a hot plasma gas. The hot plasma gas is passed through the strangely (throat) 120 which has a diameter of 2.5 inches (about 6.35 mm), increasing the speed. At the injection point 113, 440 Nm 3 / h of methane 10 is injected into the plasma gas by three injection ports with a diameter of 6.5 mm each and arranged radially. Next impact and mixing with plasma gas; the methane is pyrolyzed to form carbon black and hydrogen gas. The mixture of hot H2, other flue gases and carbon black is then accelerated by the convergence zone 116 and the restriction (groove) 122, the latter having a diameter of 3 inches (about 7.62 mm). ), where an injection at the location 114 of 75 kg / h of a liquid carbon raw material (also of the settling oil) is added to the mixture by three pressurized tips arranged radially (with a hole of 0.4 mm each, at 400 psig). This second raw material is pyrolytically divided into carbon black and H2 and preferably coats the plasma core particles which are formed in zone 110, increasing their mass, decreasing their area and increasing their structure. While the invention has been shown and described particularly with reference to preferred embodiments thereof, it is understood by those skilled in the art that various changes in shape and detail may be made without departing from the scope of the invention. principle of the invention encompassed by the appended claims.

权利要求:
Claims (60)
[0001]
REVENDICATIONS1. A process for producing carbon-coated particles, the method comprising coating the core particles with a carbon layer in a carbon black reactor or a finishing section thereof, to form the carbon-coated particles, characterized in that the core particles are carbon-free core particles, carbon-black plasma core particles or preformed core particles.
[0002]
2. Method according to claim 1, characterized in that the carbon layer is prepared from a liquid or gaseous raw material supplying carbon.
[0003]
3. Method according to claim 1, characterized in that the carbon-free core particles or the carbon-black plasma core particles are produced in situ.
[0004]
The method of claim 1, further comprising introducing the preformed core particles into the carbon black reactor.
[0005]
5. Method according to claim 4, characterized in that the preformed core particles are core particles of carbon black.
[0006]
6. A process according to claim 1, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 to about 110 cc / 100g.
[0007]
7. A process according to claim 1, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m2 / g and a COAN index in the range of about 55 to about 150 cc / 100g.
[0008]
Process according to claim 1, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and an OAN value in the range of about 55 to about 400 cc / 100g.
[0009]
A rubber composition or rubber article comprising the carbon-coated particles prepared by the process of claim 1.
[0010]
The method of claim 1, further comprising modifying the surface of the carbon coated particles. 3035657 58
[0011]
A process for preparing carbon-coated particles, the process comprising: generating the core particles in situ, the core particles being carbon-black plasma core particles or carbon-free core particles, and coating the core particles with a carbon layer in a carbon black process to form the carbon-coated particles.
[0012]
12. The method of claim 11, characterized in that the carbon layer is prepared from a liquid or gaseous raw material supplying carbon.
[0013]
13. Process according to claim 11, characterized in that the plasma carbon black cores are formed in a carbon black process. 10
[0014]
14. The method of claim 11, characterized in that the carbon-free core particles are generated in a reaction zone of a carbon black reactor.
[0015]
15. The method of claim 11, characterized in that the carbon-free core particles are silica core particles. 15
[0016]
16. The method of claim 11, characterized in that the carbon-free core particles are produced from a core precursor.
[0017]
17. The method of claim 16, characterized in that the nucleus precursor is introduced upstream, at the place or downstream of a raw material injection point providing carbon. 20
[0018]
18. The method of claim 16, characterized in that the core precursor is injected together with the raw material providing carbon.
[0019]
19. The method of claim 16, characterized in that the core precursor is introduced before the injection of a moderating liquid.
[0020]
20. The process of claim 11, further comprising collecting the carbon-coated particles from the reactor.
[0021]
21. The method of claim 11, characterized in that the carbon layer has a thickness in the range of 0.5 nm to about 20 nm. 3035657 59
[0022]
22. The method of claim 11, characterized in that the core particles are aggregates of primary particles.
[0023]
23. The method of claim 11, characterized in that the coated particles have a particle size in the range of about 20 nm to about 500 nm. 5
[0024]
24. The method of claim 11, characterized in that the carbon layer covers the core particles partially or completely.
[0025]
25. The process according to claim 11, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m2 / g and a COAN index in the range of about 55 to about 110 cc / 100g. 10
[0026]
26. A process according to claim 11, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m2 / g and a COAN index in the range of about 55 to about 150 cc / 100g.
[0027]
27. A process according to claim 11, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m2 / g and an OAN value in the range of about 55 to about 400 cc / 100g.
[0028]
28. A rubber composition or rubber article comprising the carbon-coated particles prepared by the process of claim 11.
[0029]
The method of claim 11, further comprising modifying the surface of the carbon coated particles. 20
[0030]
A process for producing carbon-coated particles, the method comprising introducing preformed core particles into a carbon black reactor, and coating the core particles with a carbon layer obtained by pyrolysis of a raw material liquid or gaseous in the carbon black reactor, thereby forming the carbon-coated particles.
[0031]
The method of claim 30, further comprising dividing the preformed core particles before introducing preformed core particles into the carbon black reactor.
[0032]
32. The method of claim 30, characterized in that the preformed core particles are introduced together with a gaseous reactor or vapor stream, dispersed in a liquid raw material, in a separate gas stream or in an aqueous stream. separate.
[0033]
The method of claim 30, further comprising collecting the carbon-coated particles from the reactor. 5
[0034]
34. The method of claim 30, characterized in that the preformed core particles are preformed carbon-free core particles, preformed carbon black particles or carbon particles recovered by pyrolysis.
[0035]
35. The method of claim 30, characterized in that the preformed core particles are nanoparticles of clay, rice husk silica, silica carbonate or precipitated calcium.
[0036]
36. Process according to claim 30, characterized in that the particles coated with carbon contain a core which is an aggregate or an agglomerate of the same or of different aggregates.
[0037]
37. The method of claim 36, characterized in that the core has a size of from about 50 nm to about 10 μm.
[0038]
38. The method of claim 30, characterized in that the carbon layer has a thickness in the range of about 0.5 nm to about 20 nm.
[0039]
39. The method of claim 30, characterized in that the carbon layer covers the core partially or completely. 20
[0040]
40. A process according to claim 30, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m2 / g and a COAN index in the range of about 55 to about 110 cc / 100g.
[0041]
41. A process according to claim 30, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 to about 150 cc / 100g.
[0042]
42. A process according to claim 30, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and an OAN index in the range of about 55 to about 400 cc / 100g. 303 565 7 61
[0043]
The method of claim 30, further comprising modifying the surface of the carbon coated particles.
[0044]
44. A rubber composition or rubber article comprising the carbon-coated particles prepared by the process according to claim 30.
[0045]
A process for producing carbon-coated particles, the process comprising: introducing preformed core particles into a plasma carbon black reactor, and coating the core particles with a carbon layer, characterized in that the layer carbon is generated from a gaseous raw material.
[0046]
A process for preparing carbon-coated particles, the process comprising: in situ preparation of the carbon black cores in a carbon black reactor, and coating of the carbon black cores with a carbon layer Obtained by pyrolysis of a gaseous raw material in the carbon black reactor, thereby forming the carbon-coated particles.
[0047]
47. A process for preparing carbon-coated particles, the process comprising: preparing carbon-black cores particles by a plasma method, and coating the carbon-black cores particles with a carbon layer to form the particles coated with carbon.
[0048]
48. Process according to claim 47, characterized in that the carbon black cores particles are prepared according to a process comprising: the generation of a plasma in a plasma zone of a reactor, and the conversion of a raw material providing a core of carbon black core particles and hydrogen gas.
[0049]
49. Carbon-coated particles comprising a carbon-free core, a pyrolytically beneficiated carbon core or a carbon-carbon plasma core coated with a carbon layer.
[0050]
Carbon-coated particles according to claim 49, characterized in that the carbon-free core is formed from a selected material of the group consisting of precipitated silica, fumed silica, surface-modified silica, and any combination of these.
[0051]
51. Carbon-coated particles according to claim 49, characterized in that the core is formed of clay nanoparticles, rice husk silica, calcium carbonate or any combination thereof.
[0052]
52. Carbon-coated particles according to claim 49, characterized in that the carbon layer has a thickness of about 0.5 nm to about 20 nm.
[0053]
53. Particles coated with carbon according to claim 49, characterized in that the carbon layer is amorphous carbon. 10
[0054]
54. Particles coated with carbon according to claim 49, characterized in that the core has an aciniform structure.
[0055]
55. Carbon-coated particles according to claim 49, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 at about 110 cc / 100g. 15
[0056]
56. Carbon-coated particles according to claim 49, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and a COAN index in the range of about 55 at about 150 cc / 100g.
[0057]
57. The carbon-coated particles according to claim 49, characterized in that the carbon-coated particles have an STSA index in the range of about 30 to about 250 m 2 / g and an OAN index in the range of about 55 to about 400 cc / 100g.
[0058]
58. A rubber composition or rubber article comprising the carbon-coated particles prepared by the process of claim 49.
[0059]
59. Particles coated with carbon according to claim 49, characterized in that the surface of the coated particles is modified. 25
[0060]
60. Equipment for preparing carbon-coated particles, the equipment comprising: a plasma zone, a reaction zone downstream of the plasma zone, a finishing zone downstream of the reaction zone, 63 a conduit for introducing a plasma gas into the plasma zone, one or more inlets for introducing a first raw material into the reactor, one or more inlets for introducing a second raw material into the reactor, a zone of convergence between the zone; of plasma and the reaction zone, and, optionally, a zone of convergence between the reaction zone and the finishing zone.

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同族专利:

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公开号 | 公开日

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CN107709472B|2021-05-18|

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US11198774B2|2021-12-14|

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JP2020128548A|2020-08-27|

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DE112016001963T5|2018-01-18|

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CA2983470A1|2016-11-03|

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US10519298B2|2019-12-31|

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CA2983470C|2021-07-06|

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US20160319110A1|2016-11-03|

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CN107709472A|2018-02-16|

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JP2018522996A|2018-08-16|

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BR112017023407A2|2018-07-24|

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US20220056241A1|2022-02-24|

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WO2016176237A1|2016-11-03|

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US20200190288A1|2020-06-18|

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WO2016176237A9|2017-08-24|

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FR3035657B1|2021-12-03|

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优先权:

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申请号 | 申请日 | 专利标题

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US201562155142P| true| 2015-04-30|2015-04-30|

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US201662304694P| true| 2016-03-07|2016-03-07|

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