The present invention relates to the field of heterogeneous catalysis, notably a gas-solid heterogeneous catalysis process comprising the contacting of at least one gaseous reactant with a catalytic solid compound positioned on a support. The present invention also relates to the support for said catalyst.
Very many processes require heterogeneous catalysis. These catalysis processes require a step of heating, sometimes at high temperature, for the implementation of the reaction, and are therefore expensive and highly energy-consuming. Research has therefore focused on more economical solutions and notably on reactions that are less energy intensive.
Among these solutions, international application WO 2014/162099 has proposed a heterogeneous catalysis process in which the heating is carried out by magnetic induction in order to reach the temperature necessary for the reaction. More particularly in this process, the reactant is contacted with a catalytic composition which comprises a ferromagnetic nanoparticulate component, the surface of which consists at least partially of a compound that is a catalyst for said reaction, said nanoparticulate component being heated by magnetic induction in order to reach the desired temperature range. This heating may be carried out by means of a field inductor external to the reactor. In this system, the nanoparticles are heated by their own magnetic moment, enabling the startup of the catalytic reaction. The heating is therefore initiated within the very heart of the reactor, rapidly with minimal energy input. This results in substantial savings.
However, the cost of these reactions still remains high, due in particular the cost of the catalytic particles in nanometric form and more particularly the magnetic nanoparticles. Moreover, these nanomaterials must, in general, be handled with caution.
Another problem linked to the use of nanoparticles is the modification of their heating properties due, on the one hand, to their tendency toward sintering during high-temperature reactions, and, on the other hand, to aging resulting from a change in the chemical order in said nanoparticles (modification of the structure and of the local chemical composition).
A first objective of the invention is therefore to overcome the aforementioned drawbacks by further reducing the cost of these heterogeneous catalysis reactions, while maintaining the reaction performance thereof.
Another objective of the invention is to propose a process that makes it possible to reduce the proportion of the components in the form of nanometric particles in the reactor.
Another objective of the invention is to propose a heterogeneous catalysis process that exhibits a maintenance of the heating properties and of the catalytic properties over very long periods of time, while being suitable for intermittent operation.
Another objective of the invention is to propose a process for catalysis of a gas-solid chemical reaction, more particularly of a hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction.
In the search for new savings, the inventors discovered, surprisingly, that the heating agent may not necessarily be in nanometric form, but may be present in the reactor in the form of micrometric powder or of wires.
For this purpose, the present invention proposes a process for heterogeneous catalysis of a hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction using, in a reactor, carbon dioxide and gaseous dihydrogen and at least one catalytic solid compound capable of catalyzing said reaction in a given temperature range T, comprising the contacting of said gaseous reactant and of said catalytic compound in the presence of a heating agent, and the heating of the heating agent to a temperature within said temperature range T, the process is characterized in that the heating agent comprises a ferromagnetic material in the form of micrometric powder composed of micrometric ferromagnetic particles having sizes of between 1 μm and 1000 μm and/or of wires based on iron or on an iron alloy, preferably having a wire diameter of between 10 micrometers and 1 millimeter, said ferromagnetic material being heated by magnetic induction by means of a field inductor external to the reactor, the magnetic field generated by the field inductor external to the reactor having an amplitude of between 1 mT and 80 mT and a frequency of between 30 kHz and 500 kHz. The results obtained with such a heating agent which is no longer nanometric, but of much greater size, are equivalent to those obtained in the process of WO 2014/162099 with a ferromagnetic nanoparticulate component.
According to a first embodiment of the invention, when it is present in powder form, the ferromagnetic material is advantageously composed of micrometric ferromagnetic particles having sizes of between 1 μm and 100 μm, preferably between 1 μm and 50 μm, more preferably between 1 μm and 10 μm.
With such micrometric ferromagnetic particles, which admittedly sometimes have a tendency toward agglomeration, no sintering is observed and the effectiveness of the heating is thus maintained.
As regards the catalytic compound used in the process according to the invention, said catalytic compound comprises a catalyst for the heterogeneous catalysis reaction that is in the form of metallic particles positioned on a support.
Said metallic catalyst particles are advantageously chosen from manganese, iron, nickel, cobalt, copper, zinc, ruthenium, rhodium, palladium, iridium, platinum, tin, or an alloy comprising one or more of these metals.
Said metallic catalyst particles are positioned at the surface of an oxide forming a support for the catalyst, such as an oxide of at least one of the following elements: silicon, cerium, aluminum, titanium or zirconium, (for example Al2O3, SiO2, TiO2, ZrO2, CeO2) constituting a catalyst-oxide assembly that is in the form of a powder of micrometric or nanometric size which is mixed with the ferromagnetic material in the form of micrometric powder. The mixing of these powders (catalyst-oxide assembly with the microparticulate ferromagnetic material) thus creates intimate contact between the heating agent and the catalyst, making it possible to rapidly start the catalysis reaction at the surface of the catalyst.
According to a second embodiment of the invention, the support for the catalyst is said ferromagnetic material that is in the form of wires.
Advantageously, the ferromagnetic material that is in the form of wires, which are supports for the catalyst, may comprise, or predominantly consist of, steel wool, containing wires based on iron or on an iron alloy, preferably having a wire diameter of between 20 μm and 500 μm, more preferably between 50 μm and 200 μm.
Indeed, quite surprisingly, steel wool, a cheap and readily available material that can be purchased in home improvement stores, has proved to be an excellent heating agent. More particularly, very fine (superfine) steel wool, having a wire diameter of less than a millimeter, is both a good catalyst support and effective for enabling the heating of said catalyst by magnetic induction.
This material is very easy to use and has a very long service life. Furthermore, it is easily recyclable and is non-polluting.
The process according to the invention is advantageously a hydrocarbon synthesis reaction, more particularly the heterogeneous catalysis reaction is.
The heterogeneous catalysis process according to the invention, hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction starting from carbon dioxide and dihydrogen, may in particular be carried out with a magnetic field generated by the field inductor external to the reactor having an amplitude of between 1 mT and 50 mT and a frequency of between 50 kHz and 400 kHz, preferably between 100 kHz and 300 kHz.
The present invention also relates to a catalyst support for the implementation of the heterogeneous catalysis process described above, characterized in that it comprises a ferromagnetic material in the form of wires of micrometric diameters, deposited at the surface of which are metallic catalyst particles.
Advantageously, the ferromagnetic material is based on iron, or on an iron alloy, preferably comprising at least 50 wt % iron, more preferably at least 80 wt % iron.
This ferromagnetic material may in particular be composed of superfine steel wool, comprising an entanglement of wires composed of at least 90 wt % iron, and of which the diameter of the wires is between 10 μm and 1 mm, preferably between 20 μm and 500 μm, more preferably between 50 μm and 200 μm.
The invention will be clearly understood on reading the following description of non-limiting exemplary embodiments with reference to the appended drawings in which:
Preparation of the Catalyst on Cerium Oxide Support
Nickel at 10 wt % on cerium oxide (abbreviated to Ni(10 wt %)/CeO2) is prepared by decomposition of Ni(COD)2 in the presence of CeO2 in mesitylene.
According to a conventional preparation process, 1560 mg of Ni(COD)2 are dissolved in 20 mL of mesitylene then 3 g of CeO2 are added. The mixture obtained is heated at 150° C. under an argon atmosphere for 1 hour with vigorous stirring. This mixture, initially milky white, is black at the end of the reaction. After decantation, the translucent supernatant is removed and the particles obtained are washed three times with 10 mL of toluene. The toluene is then removed under vacuum, making it possible to obtain a thick powder of Ni10 wt %/CeO2 (3.5 g) which is collected and stored in a glove box. Analysis by inductively coupled plasma mass spectrometry (ICP-MS) confirms the loading of 9 wt % of nickel (10% targeted) of the cerium oxide. Observation by transmission electron microscopy (TEM) and EDS analysis show the presence of small monodisperse particles of nickel (with a size of 2-4 nm).
Process for Preparing Ni on SiRAIOx®
In a Fischer-Porter bottle and under an inert atmosphere, 0.261 g of Ni(COD)2 is dissolved in 20 mL of mesitylene and 0.500 g of SiRAIOx® is added. The mixture is heated at 150° C. for one hour with stirring. After returning to ambient temperature, the powder is left to precipitate, then the supernatant is removed and the powder is washed three times with 10 mL of THF. The powder is then dried under vacuum and stored under an inert atmosphere.
Mixture of Iron Powder+Ni/CeO2
2 g of iron powder are mixed with 1 g of nickel catalyst deposited on cerium oxide prepared previously. Observation with a scanning electron microscope and also EDS mapping make it possible to visualize grains of iron powder having a size of the order of 3-5 μm and to confirm that the nickel is indeed present on the cerium oxide CeO2.
Superfine steel wool (Gerlon, purchased from Castorama). ICP-MS analysis of the superfine steel wool gives a composition of 94.7 wt % of iron. EDS mapping shows the presence of numerous impurities on the surface of the wool (mainly potassium, manganese, silicon). SEM observation makes it possible to determine the diameter of the wires of the superfine steel wool used, which is around 100 μm and has a rough and uneven surface.
The experimental protocol for depositing nickel metal on superfine steel wool (entanglement of wires of around 100 μm in diameter, containing 94.7 wt % of iron) is substantially the same as on CeO2. 1560 mg of Ni(COD)2 are dissolved in 100 mL of mesitylene in order to completely submerge the steel wool (3 g). After one hour under rapid stirring at 150° C. under argon, the mixture is placed in a glove box and the solution (of black color) is drained off. The steel wool has itself also turned black. The steel wool is then rinsed with toluene, and then dried under vacuum for 30 minutes and stored in a glove box. Observation by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy show the deposition of polydisperse particles of nickel (100 nm-1000 nm) on the surface of the wires of the steel wool.
ICP-MS analysis over three different zones shows different nickel loadings: 1.23%, 1.44% and 1.33% (weight percentages). These differences between these loadings are quite small, the surface of the wool appears homogeneous. Despite everything, the amount of nickel deposited is below the targeted percentage of 10 wt % of Ni.
The methanation reaction
CO2.+.4.H2.→.CH4.+.2.H2O. [Chem. 1]
which is a combination of
.CO2+.H2. ↔CO+.H2O. [Chem. 2]
and of
CO.+3.H2.→.CH4.+.H2O. [Chem. 3]
is carried out in a quartz fixed-bed tubular continuous reactor 1 (Avitec) (internal diameter: 1 cm with a height of catalyst bed 4, dependent on the heating element, of around 2 cm, resting on sintered glass 3) (cf.
The measurements of the conversion rates and selectivity as a function of the temperature are carried out with temperature servocontrol of the generator associated with the coil 2. For this purpose, a temperature probe 5 connected to the generator is submerged in the catalyst bed (heating agent+catalyst assembly). The generator sends a magnetic field in order to reach the fixed temperature and then only sends pulses to maintain this temperature. The reaction is carried out at atmospheric pressure and at a temperature that varies between 200° C. and 400° C. The reactor 1 is supplied with H2 and CO2, the flow rate of which is controlled by a flowmeter (Brooks flowmeter) and controlled by Lab View software. The proportions are the following: an overall constant flow rate of 25 mL/min comprises 20 mL/min of H2 and 5 mL/min of CO2. The supplying is carried out at the top of the reactor, the water formed is condensed at the bottom of the reactor (without condenser) and is recovered in a round-bottomed flask. The methane formed and the remaining gases (CO2 and H2) and also the CO are sent to a gas chromatography column (Perkin Elmer, Clarus 580 GC column). The conversion of the CO2, the selectivity of the CH4 and the yield of CO and of CH4 are calculated according to the following equations:
FC is the response factor for each reactant according to reaction monitoring by gas chromatography,
A is the area of the peak measured in chromatography.
Measurements of the energy efficiency:
Energy efficiency measurements are carried out at the same time as the conversion and selectivity measurements of the methanation reaction. The electricity consumption data for the coil 2 are recovered by means of software developed in the laboratory. The energy efficiency is then calculated according to the following method
PCS (gross calorific value) represents the amount of energy released by the combustion of 1 mg of gas.
The energy efficiency is expressed in % in
These results differ notably from those obtained in the recent publication by Kale et al., Iron carbide or iron carbide/cobalt nanoparticles for magnetically-induced CO2 hydrogenation over Ni/SiRAIOx catalysts, Catal. Sci. Technol., 2019, 9, 2601., which reports, for the FeC nanoparticles, SAR values of between 1100 and 2100 W/g at 100 kHz.
It might then be expected to have to provide the microparticulate iron powder and the steel wool with a higher field than for the nanoparticles. But the results from
The micrometric iron powder and the micrometric steel wool therefore constitute advantageous ferromagnetic materials for in situ heating, by magnetic induction, of the reactors carrying out gas-solid catalytic reactions such as methanation reactions starting from carbon dioxide and dihydrogen, which is presented in the following examples.
The catalyst bed consists of nickel particles on cerium oxide: Ni: 0.09 g/CeO2: 0.91 g, mixed with 2 g of iron powder. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of CO2.
The results of the conversion rates of CO2 and of CH4 are presented in
The catalyst bed consists of nickel particles deposited on cerium oxide: Ni: 0.09 g/CeO2: 0.91 g and of 0.35 g of (superfine) steel wool. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of CO2.
The results of the conversion rates of CO2 and of CH4 are presented in
The catalyst bed consists of nickel particles: Ni: 0.03 g deposited on 2.27 g of (superfine) steel wool. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of CO2.
The results of the conversion rates of CO2 and of CH4 are presented in
The energy efficiency calculations of the preceding three examples (examples 5, 6 and 7) grouped together in
Number | Date | Country | Kind |
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19 10345 | Sep 2019 | FR | national |
Filing Document | Filing Date | Country | Kind |
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PCT/FR2020/051625 | 9/18/2020 | WO |