TW201622808A - Process for modification of particles - Google Patents

Abstract

The present invention relates to a process for modifying particles in an apparatus with two gaseous streams.

Description

Method for particle modification

The present invention relates to a method for modifying particles in an apparatus having two gaseous streams.

The characterization of particles used as solid process materials in industrial applications is a scientific and technical area of interest in many technical fields: manufacturing monolithic or composite parts, machinery, transportation (vehicle structures and motors), catalysis, energy generation, Microelectronics, optoelectronics, leisure industry, etc.

Suitable for such processes are particles (P1) which can be made of polymers, ceramics, metal semiconductors and metal oxides, and layered materials including, but not limited to, transition metal oxides or chalcogenides.

Also suitable for such methods are carbons of different forms (eg graphite (from natural and synthetic sources), expandable (eg intercalated) graphite, graphite oxide, expanded graphite, carbon black, activated carbon Particles (P1) made of carbon fiber, carbon nanotubes, fullerenes, graphene, nanoplatelets, coal and coke.

It is known that two types of particle modifications can be made in such methods: morphological modification, which can be manifested as a change in the size, aspect ratio, shape, optical appearance, or domain form of the material (eg, expansion of the layered material). And chemical modification that changes at least one of the chemical constituents of the material Capable of introducing a functional group (eg, a group containing O, N, S, P, Si, H, C) and/or a functional coating into a material or introducing a hetero atom into the atomic structure of the material (eg B or N). This can usually be carried out in the reaction zone of the apparatus used in the corresponding process. In the reaction zone, activation of the gas phase and/or starting materials can be achieved in different ways, such as heat, reactive plasma, chemical, radio frequency heating, laser heating, flame pyrolysis, microwave heating, combinations thereof Wait.

For some methods, morphological upgrading is required, while for other methods, chemical upgrading is required, and other methods require even continuous or combined morphological and chemical upgrading steps.

US 2012/0145041 A1 describes plasma treatment of small particles, such as carbon nanotubes suspended in a drum in a capacitive glow discharge.

US 2011/0300056 A1 describes a method for producing a nanostructure, which involves providing a graphite sheet comprising a graphene layer, sandwiching the graphite sheet to form a graphite interlayer compound, and exposing the graphite interlayer compound to about The temperature between 1600 ° C and about 2400 ° C is stripped to separate a plurality of individual graphene layers from the graphite interlayer compound.

US 2013/0022530 A1 describes a method for producing exfoliated graphite, which relates to providing a graphite interlayer compound and bringing the graphite interlayer compound between about 1600 ° C and about 3400 ° C via a plasma at at least 6000 ° C. The temperature is used to peel off the graphite interlayer compound.

The methods described in the state of the art are suitable for upgrading low energy plasma (e.g., capacitive glow discharge) at variable reaction times or for use with a plasma torch that lasts for a short reaction time (typically less than one second). High-energy plasma is upgraded. Although it is not possible to carry out a material modification requiring high excitation energy in the former case, in the latter case the material may be subjected to plasma treatment only during its natural flight time through the reaction zone.

For example, US 2013/0022530 A1 states that the residence time of the treated material in the reaction zone should not exceed 0.2 s. Once the material leaves the reaction zone, no further modification is possible. Therefore, the flexibility of such material processing methods is limited. In particular, in the case of US 2011/0300056 A1 and US 2013/0022530 A1, a multi-step method is not possible.

In principle, the fluidized bed system provides the possibility of processing the particles over the selected excitation energy and processing time. However, the material to be treated must be fluidizable, exhibiting high interparticle cohesion, coalescence tendency during the reaction, in the case of smaller particle sizes (microscale or submicron scale) or light mesoscale particles, Particles that are not suitable for aspect ratio or significant morphological changes (eg, producing extremely loose particles) that all result in poor fluidization or no fluidization at all can be a serious challenge. In this case, the particles no longer mix, resulting in extremely poor and uneven material handling. However, there is no option to combine a wide range of excitation energies, processing times, and chemical and morphological modifications (functionalizations) that can be used to treat such inadequately fluidizable materials.

It is not disclosed in the state of the art that the particles (P1) are allowed to be carried (fluidized) into the reaction zone and fixed in the reaction zone with a pulsed gas stream for chemical and/or morphological upgrading to provide a treatable A method of high flexibility and the possibility of a multi-step process for materials, processing times, activation methods (and thus also energy activation).

It is an object of the present invention to provide a novel process for modifying particles, particularly graphite, sandwich graphite and expandable graphite.

The object is carried out by a method for modifying particles (P1) in a device (A1) comprising at least two of gaseous streams (G1) and (G2) Inlet, gas inlet zone (IZ), reaction zone (RZ) located below the gas inlet zone (IZ), sample holder (SH) located below the reaction zone (RZ) And an outlet (O1) at the bottom of (A1), wherein the method comprises the following steps a) to e): a) feeding a gaseous stream (G1) comprising at least one inert gas and/or a reactive gas to the apparatus ( In A1), wherein (G1) flows through the reaction zone (RZ) from the top to the bottom in the apparatus (A1), and b) provides particles on the sample holder (SH) of the apparatus (A1) ( P1), c) feeding at least one pulse of a gaseous stream (G2) comprising at least one inert gas and/or a reactive gas to carry the particles (P1) into the reaction zone (RZ), and in the sample holder (G2) is fed into the device (A1) at the position below (SH), d) the particles (P1) are modified in the reaction zone (RZ), and e) the device is (O1) via the outlet (O1) (A1) discharging the gaseous stream (G1) and/or the gaseous stream (G2).

The main advantage is that morphological upgrading (eg continuous expansion) and chemical upgrading can be established in combination in the same device. Combining morphology and chemical modification in a continuous process allows for multifunctional material processing within a single device setup and produces a more uniform material treatment.

Another advantage is that since the gas flow in the device (A1) is no longer continuous due to the pulse of (G2), the particles (P1) are more uniformly exposed to the reaction gas phase in the reaction zone (RZ) under these conditions, The particles are prevented from forming a porous agglomerate as described above.

In addition to this, due to the pulse mode of the gaseous stream (G2), the mixing of the particles (P1) is ensured so that much more particles (P1) are exposed to the plasma and are therefore available Upgraded.

Another advantage is that during the pulse of at least one gaseous stream (G2), material elutriation is reduced due to different flow directions.

Another advantage is the spacing between pulses, the pulse frequency, the pulse length, the pulse intensity (which can be controlled by the pulsed gas flow rate and the pulsed gas pressure) and the experimental duration is freely adjustable. Moreover, the excitation energy can be varied at any time during the experiment, for example, different excitation energy profiles can be achieved, such as constant values, ramps, step profiles, and/or pulse profiles. In addition, the gases in the gaseous streams (G1) and (G2) can be varied at any time during the experiment.

The method of the invention for modifying the particles (P1) within the apparatus (A1) is defined in detail below.

The apparatus (A1) comprises at least two inlets of a gaseous stream (G1) and (G2), a gas inlet zone (IZ), a reaction zone (RZ) located below the gas inlet zone (IZ), and located in the reaction zone (RZ) ) The sample holder (SH) below and the outlet (O1) at the bottom of (A1).

The apparatus (A1) and optionally the apparatus (A2) according to the invention can be seen, for example, in Figures 1 and 3, and optionally with a pump at the outlet (O1) and/or the outlet (O2). All parts of the device (A1) and optionally the device (A2) are known to those skilled in the art. For completeness, reference is made to the presence of corresponding inlets and outlets at the locations of the arrows in Figures 1 and 3. Figures 1 and 3 only show schematic settings of the device (A1) and optionally the device (A2).

In the context of the present invention, the reaction zone (RZ) is the zone in which the interior of the apparatus (A1) undergoes a particle (P1) reaction. This area can occupy a large area inside the device (A1).

A gas inlet zone (IZ) above the reaction zone (RZ) is required as a vacuum reservoir to accommodate additional gases due to gas and/or gas pulses.

Furthermore, the sample holder in device (A1) is freely adjustable relative to the desired conditions and may be a frit or anything suitable in any sense known to those skilled in the art.

The particles (P1) according to the invention may contain, but are not limited to, polymers, ceramics (for example SiC, WC, TiN), metals, semiconductors (for example Si), metal oxides (for example Al ₂ O ₃ ), layered materials (eg transition metal oxides, transition metal chalcogenides), different forms of carbon (eg natural graphite, synthetic graphite, graphite oxide, expanded graphite, expandable graphite, sandwich graphite, carbon black, activated carbon, carbon fiber, carbon naphthalene) Rice tubes, fullerenes, graphene, coal or coke), wherein any mixtures and composites of the foregoing materials are possible, and wherein such particles (P1) can be used in a variety of forms and shapes, including (but not limited to) expandable and / or sandwich type materials, spherical particles, fibers or small pieces, such particles (P1) are preferably natural graphite, synthetic graphite, graphite oxide, expanded graphite, expandable graphite, sandwich graphite, Carbon black, activated carbon, carbon fiber, carbon nanotubes, fullerenes, graphene, coal or coke, and the particles (P1) are preferably natural graphite, synthetic graphite, expandable or sandwich graphite.

In the context of the present invention, sandwich graphite is obtained from graphite after the sandwiching step and may be, for example, graphite or graphite nitrate based sandwich compounds having different degrees of interlayer or graphite containing other interlayers to produce variable chemistry The compound being metered. This sandwich type graphite is then expandable.

Within the context of the present invention, a modification is defined as a morphological modification which can be embodied as a change in the size, aspect ratio, shape, optical appearance or phase form of the substance (eg expansion of the layered material) and is mainly regarded as The structural change of the particles (P1) is caused without substantially changing the chemical composition.

Chemical upgrading (functionalization) is at least one characteristic that alters the chemical composition of a material, including exchanging or introducing functional groups (eg, functional groups containing O, N, S, P, Si, H, C, and halogen) and/or Or a functional coating or the introduction of a hetero atom (for example O, C, S, B, halogen or N) on the surface of the material or into its atomic structure.

Within the context of the present invention, a gaseous stream (G2) can be simultaneously fed into the apparatus (A1) at several locations below the sample holder (SH).

In the context of the present invention, the gaseous streams (G1) and (G2) may be derived from the same tank or from different tanks.

In the context of the present invention, the gaseous streams (G1) and (G2) may be a gas mixture having the same composition. It can also be a gas mixture having a different composition. Furthermore, the flow rates of the gaseous streams (G1) and (G2) may have up to 50,000 sccm, preferably up to 2000 sccm, more preferably up to 500 sccm, and the pairs (G1) and (G2) may be in different ranges. In principle, there is no upper gas flow limit.

In the context of the present invention, in step a), a gaseous stream (G1) comprising at least one inert gas and/or a reaction gas is fed into the device (A1), wherein (G1) is in the device (A1) The internal flow direction is from the top to the bottom through the reaction zone (RZ). Here, the expression "feeding gaseous material stream" is understood to mean a continuous flow of inert gas and/or reaction gas through the reaction zone (RZ).

Within the context of the present invention, "continuous flow" as referred to above is understood to mean not a pulse and thus a continuous (gas) flow. However, it is still possible to shut off the gaseous stream (G1). This can help, for example, transport the particles into the device (A2). Preferably, the feed of the gaseous stream (G1) is continuously fed, more preferably continuously fed in steps a) to d). In step e), in which the gaseous material stream (G1) and/or the gaseous stream (G2) are discharged from the apparatus (A1), it is possible to shut off the gaseous stream (G1).

In the context of the present invention, the inert gas may contain, but is not limited to, Ar and He.

In the context of the present invention, the reaction gas may contain, but is not limited to, H ₂ , N ₂ , CO ₂ ; a functional group containing O, N, S, P, Si, H, C or halogen on the particle (P1) a gas of a base; a gas of B or N introduced into the particles (P1); or a mixture thereof, preferably H ₂ , N ₂ or CO ₂ .

Within the context of the present invention, the particles (P1) as defined above are provided on the sample holder (SH) of the device (A1) in step b).

In the context of the present invention, at least one pulse feeding a gaseous stream (G2) comprising at least one inert gas and/or a reactive gas in step c) is provided to carry the particles (P1) into the reaction zone (RZ) And (G2) feed at the position below the sample holder (SH) Go to the device (A1). Here, the expression "at least one pulse fed into the gaseous material stream" is understood to mean a gas flow pulse. Therefore, the pulse consists of a time-limited flow. Such pulses can be extremely short (<10 s) and up to a few minutes (<10 min) or longer in different settings. Preferably, the pulse is no longer than 30 minutes, more preferably no longer than 5 minutes, and most preferably no longer than 1 minute. The time between pulses can be as long as the pulse itself, as well as longer or shorter. The discontinuity between pulses is typically no longer than 60 min, preferably less than 10 min, more preferably less than 5 min, and most preferably less than 1 min.

In the context of the present invention, the expression "to carry particles (P1) into the reaction zone (RZ)" is understood to mean that the particles are moved upward into the reaction zone via one or more pulses of the gaseous stream (G2) ( RZ) and keep it here and mix it (see, eg, Example 3). Another way to describe this procedure would be to fluidize the particles (P1) and immerse them in the reaction zone (RZ).

Within the context of the present invention, it is provided that the particles (P1) are modified in the reaction zone (RZ) in step d). The modification is preferably carried out in the reaction zone (RZ). Therefore, it is important to keep the particles (P1) in this reaction zone long enough to achieve better and more complete results. Here, more than one upgrading step and different types of modifications (such as the morphologies and chemical modifications defined above) are possible, which can be, for example, in Examples 4-6. It is also possible to have continuous expansion and chemical upgrading, such as introducing heteroatoms such as, for example, N, O, C, S, B or halogen.

In a specific embodiment of the invention, the particles (P1) are modified in different ways in step d), such as thermal activation, plasma activation, plasma and electrical high frequency field activation, and reactive gases or The chemical reaction of the gas combination, radio frequency heating, laser heating, flame pyrolysis, microwave heating, and combinations thereof, preferably by combination with a reactive gas or gas, as appropriate The plasma reaction of the chemical reaction is carried out.

Within the context of the present invention, it is provided in step e) that the gaseous material stream (G1) and/or the gaseous material stream (G2) are discharged from the plant (A1) via the outlet (O1).

In the context of the present invention, the outlet (O1) is understood to mean the opening of the gaseous material streams (G1) and (G2). The outlet (O1) can be connected to the pump as appropriate. The pump is used to provide reduced pressure conditions in the apparatus (A1), wherein the process can be carried out at atmospheric pressure, preferably at less than 200 mbar, more preferably at less than 50 mbar, and most preferably at less than 10 mbar. This reduced pressure condition (compared to the conditions without the pump) makes it possible to operate the pump even at atmospheric pressure, since this pressure is less than the pressure present in the device (A1), which enables the discharge of the gaseous material flow (G1) And (G2).

In the context of the present invention, the outlet (O2) is an optionally used opening through which particles and gases (for example after the reaction of step d) can be transported (or for example blown out) into the device (A2), which The device (A2) contains, for example, a storage tank, a filter, a cyclone (for collecting the particles) and/or a pump.

Furthermore, after removal of the modified particles (P1) prior to method step d), the powder feeders known to those skilled in the art and located at the top of the apparatus (A1) may be new (for example) Fresh, raw, unmodified material (particles (P1)) is fed into the device (A1).

In a specific embodiment of the invention, step a) is carried out in the gas phase and the gas phase in the reaction zone (RZ) can be activated by means of a plasma. The necessary energy can be transferred to the gas phase by an electro-magnetic field by coupling or by coupling to a microwave discharge (2.45 GHz, 915 MHz or any other suitable frequency) in the reaction zone (by 27.12 MHz, 13.56 MHz) Or any other suitable Inductive or capacitive coupling generated at the reaction zone (RZ) is coupled to the plasma.

Suitable output power for generators used to provide energy for upgrading under plasma activation is known to those skilled in the art. Preferably, the generator is a microwave or radio frequency generator and the energy is not limited to the upper limit. If plasma activation is used, the generator power does not exceed 500 kW, the generator power preferably does not exceed 100 kW, the generator power is better than 30 kW, and the generator power is optimally less than 5 kW. The lower limit of the generator power is preferably not less than 1 W.

In a specific embodiment of the present invention, if plasma activation is used, the electromagnetic excitation frequency may be lower than 100 Hz, in a low frequency range between 100 Hz and 10 kHz, in a radio frequency range between 10 kHz and 300 MHz, at 300 MHz and 300 GHz. Between the microwave frequency range and / or higher than 300GHz.

Within the context of the present invention, the gaseous stream (G2) may have an angle a different with respect to the gaseous stream (G1) in its individual flow direction. The angle α cannot be higher than 180° because 180° means that the gaseous material flow (G2) is in the opposite direction to the gaseous material flow (G1) (see Figure 2). Thus, for example, an angle α of 200° will be equal to an angle α of 160°.

In a preferred embodiment of the present invention, at least one pulse of the gaseous material stream (G2) has an angle α within the apparatus (A1) that is at least 50° from the flow direction of (G1), preferably in a gaseous state. The flow direction of the material stream (G1) differs between 50° and 180°, and the better phase difference is between 80° and 120°, with an optimum phase difference of 90°.

However, in any of the mentioned angles, the pulse of the gaseous stream (G2) can be turbulent by means of the gaseous streams (G1) and (G2) in the apparatus (A1). It is easy to reach the particles (P1) on the sample holder (SH).

Example:

Starting material for all 6 examples (Particle (P1)): Sandwich type expandable graphite (Graphit Kropfmühl ES350 F5, lateral size: 80% > 300 μm)

Example 1-3: Method Comparison

The free settling/pour body density of the material is calculated by dividing the weight of the material filled in the apparatus (A1) by the volume filled.

Depending on the experiment below, the reaction product may consist of an expanded material as well as a non-expanded material.

The free settling/pour body density values of the materials are a combined measure for the degree of expansion (how much the particles (P1) expand) and for the amount of expanded material (how much the starting material expands). It is used in this context to evaluate the efficiency of three different methods (Examples 1 to 3) for the expansion of expandable sandwich graphite. The free settling/pour body density of the material was determined before and after treatment.

Example 1 (comparative)

This method is a standard fluidization method, which can be found in the literature (for example in "Principles and applications of CVD powder technology", C. Vahlas, B. Caussat, Ph. Serp, G. Angelopoulos, Mat. Sci. Eng. Reports, 2006. , 53, 1-72). In this method, a gaseous stream is used. The gaseous material stream is continuously supplied in the forward direction (which corresponds to the gaseous stream (G2) in the continuous flow mode in Figure 1), that is, the gas stream enters the system from below the sample holder (SH) and flows upwards, thereby The particles (P1) on the sample holder are fluidized into the reaction zone. Gas pumping is performed from the top, ie above the sample holder (SH) and the particles (P1).

Experimental parameters:

Argon flow rate (G2): 100-900ml/min

(The flow is gradually increased during the experiment to carry more starting material into the reaction zone); Reaction time: 20 min; Generator power: 1.5-2kW

(The generator power is increased according to the increased gas flow)

Example 2 (comparative)

This method exposes the unstirred particle standard to RF plasma, which can be found in the literature (eg, in "Plasma-assisted simultaneous reduction and nitrogen doping of graphene oxide nanosheets", NAKumar, H. Nolan, N. McEvoy, E. Rezvani, RL Doyle, MEGLyons and GS Duesberg, J. Mater. Chem. A, 2013, Vol. 1, pp. 4431-4435). In this method, only one gaseous stream is used. The gaseous stream enters the system at the top and flows downwards (which corresponds to the gaseous stream (G1) in the continuous flow mode in Figure 1) (for example, in "Formation of silicon carbide and silicon carbonitride by RF-plasma CVD", H .Sachdev, P. Schieid, Diamond and Related Materials, Vol. 10, Nos. 3-7, pp. 1160-1164), ie pressing down any particles (P1) in the system against the sample holder (SH) . Gas pumping is performed from below the sample holder (SH). Due to the reverse gas flow direction compared to Example 1, no particle mixing occurred, and only the surface of the particles directly exposed to the plasma was modified so that all particles and particle regions not directly exposed to the plasma were untreated. .

Experimental parameters:

Argon flow rate (G1): 100ml/min; Reaction time: 20 min; Generator power: 1.5 kW.

Example 3 (present invention)

The experimental arrangement is shown in Figure 1. The gaseous stream (G1) enters the apparatus (A1) at the top and flows downwards, ie the particles (P1) in the apparatus (A1) are pressed down against the sample holder (SH). Gas pumping is performed from below the sample holder (SH). The mixing of the particles (P1) is ensured by the continuous pressure/gas flow of the gaseous stream (G1) and the pulse of the gaseous stream (G2), which carries the particles (P1) to the reaction zone (RZ) Keep it here and mix it. The downward flow (G1) reduces the elution of the particles (P1). In the case where the number of pressure pulses of the gaseous stream (G2) is increased, the particles (P1) are expanded.

Experimental parameters:

Argon flow rate (G1): 100ml/min; Argon pulse (G2): 10; Reaction time: 10 minutes; Generator power: 1.5 kW.

Results of Examples 1-3

The free settler density of the starting material was about 570 mg/cm ³ .

Example 4-6: Multi-step experiment (continuous expansion and chemical upgrading)

The expandable sandwich type graphite is expanded in an argon plasma in the first step, and then reformed in the second step.

In Example 4, an inert gas argon gas was also used during the chemical upgrading step to supply a reference sample. In Example 5, nitrogen plasma reforming was performed after argon plasma expansion. In Example 6, carbon dioxide plasma reforming was performed after argon plasma expansion.

Using a chemical upgrading step, a hetero atom such as nitrogen is introduced at the surface of the material and/or a functional group such as oxygen or nitrogen is formed.

Example 4 (Invention): Continuous expansion of argon plasma and chemical modification of argon plasma, reference experiment

For both continuous expansion (morphological upgrading) and chemical upgrading, an inert gas of argon is used. No reactive gas is used for the upgrading step to provide a reference sample.

Experimental parameters for continuous expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW

Experimental parameters for upgrading (step 2): argon flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW

Example 5 (Invention): continuous expansion of argon plasma and reformation of CO ₂ plasma

Experimental parameters for continuous expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW.

Experimental parameters for continuous expansion (step 2): carbon dioxide flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW.

Example 6 (Invention): Argon plasma expansion and N ₂ plasma modification

Experimental parameters for expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW.

Experimental parameters for chemical upgrading (step 2): nitrogen flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW.

Results of Examples 4-6

The oxygen content of the treated material can be increased by performing an oxidative plasma upgrading step, such as by using a CO ₂ plasma (Example 5) (see Table 2). The nitrogen content of the material is increased by applying a upgrading step using a nitrogen-containing plasma, such as a nitrogen plasma (Example 6) (see Table 2). Further, according to XPS, a new nitrogen functional group which is not present in the starting material is formed (see Fig. 4).

In addition, the starting materials and the N 1s XPS detail spectra of Examples 4-6 are shown in FIG. The spectral display nitrogen plasma upgrading step (Example 6) not only increased the nitrogen content in the treated material, but also resulted in the formation of a new nitrogen species (which was not present in the material prior to the nitrogen plasma modification).

Claims (16)

A method for modifying a particle (P1) in a device (A1), the device (A1) comprising at least two inlets of a gaseous stream (G1) and (G2), a gas inlet zone (IZ), located a reaction zone (RZ) below the gas inlet zone (IZ), a sample holder (SH) located below the reaction zone (RZ), and an outlet (O1) at the bottom of the (A1), wherein the method comprises the following steps a ) to e): a) feeding a gaseous stream (G1) comprising at least one inert gas and/or a reactive gas into the apparatus (A1), wherein (G1) flows in the interior of the apparatus (A1) as self The top to bottom passes through the reaction zone (RZ), b) provides particles (P1) on the sample holder (SH) of the apparatus (A1), and c) feeds gaseous materials comprising at least one inert gas and/or reactive gas At least one pulse of stream (G2) to carry particles (P1) into the reaction zone (RZ), and (G2) is fed into the device (A1) at a position below the sample holder (SH), d) modifying the particles (P1) in the reaction zone (RZ), and e) discharging the gaseous stream (G1) and/or the gaseous stream (G2) from the apparatus (A1) via the outlet (O1) ). The method of claim 1, wherein the particles (P1) are selected from the group consisting of natural graphite, synthetic graphite, graphite oxide, expandable graphite, sandwich graphite, expanded graphite, carbon black, activated carbon, carbon fiber, carbon naphthalene. Rice pipe, fullerene, graphene, coal, coke, Al ₂ O ₃ , SiC, WC, TiN or Si, the particles (P1) are preferably natural graphite, synthetic graphite, graphite oxide, expanded graphite, expandable Graphite, sandwich graphite, carbon black, activated carbon, carbon fiber, carbon nanotubes, fullerenes, graphene, coal or coke. These particles (P1) are preferably natural graphite, synthetic graphite, sandwich graphite or Expanded graphite. The method of any one of claims 1 to 2, wherein at least one pulse of the gaseous stream (G2) has a flow direction inside the apparatus (A1) that differs from the flow direction of (G1) by at least 50°. The angle α is preferably between 50° and 180° from the flow direction of the gaseous material stream (G1), and the better phase difference is between 80° and 120°, and the optimum phase difference is 90°. The method of any one of claims 1 to 3, wherein in step d), thermal activation, plasma activation, plasma and electrical high frequency field activation, and chemical reaction with a reaction gas or gas are combined. Reaction, laser heating, microwave heating, radio frequency heating, and/or flame pyrolysis to modify the particles (P1), preferably by plasma activation of a chemical reaction, optionally in combination with a reactive gas or gas. get on. The method of claim 4, wherein if the plasma is activated, the generator power does not exceed 500 kW, the generator power preferably does not exceed 100 kW, the generator power is better than 30 kW, and the generator power The best is no more than 5kW. The method of any one of claims 4 and 5, wherein if the plasma is activated, the electromagnetic excitation frequency can be lower than 100 Hz, in a low frequency range between 100 Hz and 10 kHz, at 10 kHz and 300 MHz. In the inter-radio range, in the microwave frequency range between 300MHz and 300GHz and / or higher than 300GHz. The method of any one of claims 1 to 6, wherein the flow of the gaseous streams (G1) and (G2) may have up to 50,000 sccm, preferably up to 2000 sccm, more preferably up to 500 sccm, and (G1) and (G2) can be in different ranges. The method of any one of clauses 1 to 7, wherein the at least one pulse of the gaseous stream (G2) in step c) has a duration of no longer than 30 minutes, preferably Not longer than 5 minutes, optimally no longer than 1 minute. The method of any one of clauses 1 to 8, wherein the inert gas is Ar and/or He in a gaseous stream (G1) and/or a gaseous stream (G2); and/or The reaction gas is H ₂ , N ₂ , CO ₂ ; a gas containing a functional group of O, N, S, P, Si, H, C or halogen is formed on the particles (P1); in the particles (P1) a gas in which a B or N atom is introduced; or a mixture thereof, preferably H ₂ , N ₂ or CO ₂ . The method of any one of clauses 1 to 9, wherein the outlet (O1) of the apparatus (A1) is connected to a pump to provide a reduced pressure condition within the apparatus (A1), wherein the method It can be carried out at atmospheric pressure, preferably at less than 200 mbar, more preferably at less than 50 mbar, and most preferably at less than 20 mbar. The method of any one of claims 1 to 10, wherein the device (A1) is connected to the device (A2) via an outlet (O2), the device (A2) comprising a reservoir, a filter, a cyclone separation And / or pump. The method of claim 11, wherein the particles (P1) are transferred to the apparatus (A2) after being modified in step d). The method of any one of clauses 1 to 12, wherein after removing the modified particles (P1) in step d), via the powder feed at the top of the apparatus (A1) The fresh unmodified pellet (P1) is fed into the device (A1). The method of any one of claims 1 to 13, wherein the granule (P1) modification as in step d) of claim 1 of the patent application comprises morphological upgrading and/or chemical upgrading. The method of claim 12, wherein the chemical modification is carried out by reacting the particles (P1) with at least one reaction gas supplied from the gaseous stream (G1) and/or (G2). Row. The method of any one of clauses 1 to 15, wherein the feed of the gaseous stream (G1) is continuously fed, preferably continuously fed in steps a) to d).