METHOD FOR THE HETEROGENEOUS CATALYSIS USING A FERROMAGNETIC MATERIAL HEATED BY MAGNETIC INDUCTION AND CATALYST SUPPORT USED FOR SAID METHOD

Abstract

The invention relates to a method for the heterogeneous catalysis of a reaction for the hydrogenation of a carbon oxide in the gaseous state, such as a methanation reaction, using, in a reactor (1), carbon dioxide and gaseous dihydrogen and at least one solid catalytic compound capable of catalyzing said reaction in a given temperature range T, comprising contacting said gaseous reactant and said catalytic compound in the presence of a heating agent, and heating the heating agent to a temperature within said temperature range T. The method is characterized in that the heating agent comprises a ferromagnetic material in the form of micrometric powder and/or wires, said ferromagnetic material being heated by magnetic induction by means of a field inductor, such as a coil (2) external to the reactor (1). According to one embodiment, the catalyst support for implementing said method comprises a ferromagnetic material in the form of wires of micrometric diameters, on the surface of which metal catalyst particles are deposited.

Claims

1. A process for heterogeneous catalysis of a hydrogenation reaction of a carbon oxide in the gaseous state, 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, said method comprising: contacting of said gaseous reactant and of said catalytic compound in the presence of a heating agent, and heating of the heating agent to a temperature within said temperature range T, wherein the heating agent has 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, 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.

2. The process as claimed in claim 1, wherein the ferromagnetic material in powder form is composed of micrometric ferromagnetic particles having sizes of between 1 μm and 100 μm.

3. The process as claimed in claim 1, wherein the ferromagnetic material in powder form is composed of ferromagnetic particles, having sizes of between 1 μm and 50 μm.

4. The process as claimed in claim 1, wherein the catalytic compound comprises a catalyst for the heterogeneous catalysis reaction that is in the form of metallic particles positioned on a support.

5. The process as claimed in claim 4, wherein said metallic catalyst particles are chosen from the group consisting of manganese, iron, nickel, cobalt, copper, zinc, ruthenium, rhodium, palladium, iridium, platinum, tin, and an alloy comprising one or more of these metals.

6. The process as claimed in claim 4, wherein the metallic catalyst particles are positioned at the surface of an oxide forming a support for the catalyst, constituting a catalyst-oxide assembly that is in the form of a powder which is mixed with the ferromagnetic material in powder form.

7. The process as claimed in claim 4, wherein the support for the catalyst is said ferromagnetic material that is in the form of wires.

8. The process as claimed in claim 7, wherein the ferromagnetic material that is in the form of wires, which are the supports for the catalyst, comprises steel wool, containing wires based on iron or on an iron alloy.

9. The process as claimed in claim 1, wherein the magnetic field generated by the field inductor external to the reactor has an amplitude of between 1 mT and 50 mT.

10. The process as claimed in claim 1, wherein the magnetic field generated by the field inductor external to the reactor has a frequency of between 50 kHz and 400 kHz.

11. A catalyst support for the implementation of the process as claimed in claim 7, wherein said catalyst comprises a ferromagnetic material in the form of wires of micrometric diameters, deposited at the surface of which are metallic catalyst particles.

12. The catalyst support as claimed in claim 11, wherein the ferromagnetic material is based on iron or on an iron alloy.

13. The support as claimed in claim 11, wherein the ferromagnetic material is 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.

14. The process as claimed in claim 1, wherein said wires based on iron or on an iron alloy have a wire diameter of between 10 micrometers and 1 millimeter.

15. The process as claimed in claim 3, wherein the ferromagnetic material in powder form is composed of ferromagnetic particles, having sizes of between 1 μm and 10 μm.

16. The process as claimed in claim 6, wherein said oxide is an oxide selected from the group of following elements consisting of: silicon, cerium, aluminum, titanium or zirconium.

17. The process as claimed in claim 8, wherein said wires based on iron or on an iron alloy have a wire diameter of between 20 μm and 500 μm.

18. The process as claimed in claim 8, wherein said wires based on iron or on an iron alloy have a wire diameter of between 50 μm and 200 μm.

19. The process as claimed in claim 10, wherein the magnetic field generated by the field inductor external to the reactor has a frequency of between 100 kHz and 300 kHz.

20. The catalyst support as claimed in claim 12, wherein the ferromagnetic material is based on iron or on an iron alloy comprising at least 50 wt % iron.

21. The catalyst support as claimed in claim 12, wherein the ferromagnetic material is based on iron or on an iron alloy comprising at least 80 wt % iron.

22. The support as claimed in claim 13, wherein the ferromagnetic material is 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 20 μm and 500 μm.

23. The support as claimed in claim 13, wherein the ferromagnetic material is 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 50 μm and 200 μm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The invention will be clearly understood on reading the following description of non-limiting exemplary embodiments with reference to the appended drawings in which:

[0027] FIG. 1A is a simplified partial diagram of a reactor for the implementation of the gas-solid heterogeneous catalysis process according to the invention, under an upward gas flow, showing the positioning of the catalyst+heating agent assembly in the part of the tubular reactor encircled by the external magnetic field inductor,

[0028] FIG. 1B is a simplified partial diagram of a reactor for the implementation of the gas-solid heterogeneous catalysis process according to the invention, under a downward gas flow, showing the positioning of the catalyst+heating agent assembly in the part of the tubular reactor encircled by the external magnetic field inductor,

[0029] FIG. 2 is a graph comparing the performance of various heating agents according to the invention, carried out under argon at 100 kHz (specific absorption rate, SAR, corresponding to the amount of energy absorbed per unit mass, expressed in watts per gram of material, as a function of the alternating magnetic field intensity applied, expressed in mT): iron powder having microparticles with a size of the order of 3-5 μm, fine steel wool (wire diameter of greater than 1 mm) and superfine steel wool (wire diameter of less than 1 mm, of the order of 100 μm),

[0030] FIG. 3 is a graph presenting results of a methanation process according to the invention using iron powder as heating agent and an Ni on SiRAIOx® ((silicon aluminum oxide from SESAL) catalyst,

[0031] FIG. 4 is a histogram showing the conversion rates (in %) of CO.sub.2 and of CH.sub.4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of a mixture of iron powder and Ni/CeO.sub.2,

[0032] FIG. 5 is a histogram showing the conversion rates (in %) of CO.sub.2 and of CH.sub.4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of a mixture of steel wool and Ni/CeO.sub.2,

[0033] FIG. 6 is a histogram showing the conversion rates (in %) of CO.sub.2 and of CH.sub.4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of nickel on steel wool,

[0034] FIG. 7 is a graph comparing the energy efficiency (expressed in %) as a function of temperature for the three types of catalyst beds (catalyst+heating agent) tested in the examples presented in FIGS. 4, 5 and 6.

EXAMPLES

Example 1: Preparation of the Catalyst

[0035] Preparation of the Catalyst on Cerium Oxide Support

[0036] Nickel at 10 wt % on cerium oxide (abbreviated to Ni(10 wt %)/CeO.sub.2) is prepared by decomposition of Ni(COD).sub.2 in the presence of CeO.sub.2 in mesitylene.

[0037] According to a conventional preparation process, 1560 mg of Ni(COD).sub.2 are dissolved in 20 mL of mesitylene then 3 g of CeO.sub.2 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 %/CeO.sub.2 (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).

[0038] Process for Preparing Ni on SiRAIOx®

[0039] In a Fischer-Porter bottle and under an inert atmosphere, 0.261 g of Ni(COD).sub.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.

[0040] Mixture of Iron Powder+Ni/CeO.sub.2

[0041] 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 CeO.sub.2.

Example 2: Preparation of the Catalyst on Steel Wool Support

[0042] 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.

[0043] 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 CeO.sub.2. 1560 mg of Ni(COD).sub.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.

[0044] 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.

Example 3: Methanation Reaction: Measurements of Conversion and Calculation of the Selectivity

[0045] The methanation reaction

CO.sub.2.+.4.H.sub.2..fwdarw..CH.sub.4.+.2.H.sub.2O.  [Chem. 1]

which is a combination of

.CO.sub.2+.H.sub.2. .Math.CO+.H.sub.2O.  [Chem. 2]

and of

CO.+3.H.sub.2..fwdarw..CH.sub.4.+.H.sub.2O.  [Chem. 3]

[0046] 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. FIG. 1); the gaseous stream may be in upward flow 6 (FIG. 1A) or in downward flow 7 (FIG. 1B)). The coil 2 (from the company Five Celes) used is a solenoid with an internal diameter of 40 mm and a height of 40 mm that constitutes the external magnetic field inductor connected to a generator. Its resonance frequency is 300 kHz with a magnetic field varying between 10 and 60 mT. The coil 2 is water cooled.

[0047] 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 H.sub.2 and CO.sub.2, 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 H.sub.2 and 5 mL/min of CO.sub.2. 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 (CO.sub.2 and H.sub.2) and also the CO are sent to a gas chromatography column (Perkin Elmer, Clarus 580 GC column). The conversion of the CO.sub.2, the selectivity of the CH.sub.4 and the yield of CO and of CH.sub.4 are calculated according to the following equations:

[00001]$\left[\mathrm{Math}.2\right]$$X\left({\mathrm{CO}}_2\right)={\mathrm{CO}}_2\mathrm{conversion}=\frac{\begin{array}{c}(\mathrm{FC}\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)+\\ \mathrm{FC}\left(C{H}_4\right)\times A\left(C{H}_4\right)\end{array}}{\begin{array}{c}(\mathrm{FC}\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)+\\ \mathrm{FC}\left(C{H}_4\right)\times A\left(C{H}_4\right)+A\left({\mathrm{CO}}_2\right)\end{array}}$$Y\left(\mathrm{CO}\right)=\mathrm{CO}\mathrm{yield}=\frac{(FC\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)}{\begin{array}{c}(\mathrm{FC}\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)+\\ \mathrm{FC}\left(C{H}_4\right)\times A\left(C{H}_4\right)+A\left({\mathrm{CO}}_2\right)\end{array}}$$Y({\mathrm{CH}}_4)={\mathrm{CH}}_4\mathrm{yield}=\frac{FC\left(C{H}_4\right)\times A\left(C{H}_4\right)}{\begin{array}{c}(\mathrm{FC}\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)+\\ \mathrm{FC}\left(C{H}_4\right)\times A\left(C{H}_4\right)+A\left({\mathrm{CO}}_2\right)\end{array}}$$\begin{array}{cc}S({\mathrm{CH}}_4)={\mathrm{CH}}_4\mathrm{selectivity}=\frac{FC\left(C{H}_4\right)\times A\left(C{H}_4\right)}{\begin{array}{c}(\mathrm{FC}\left(\mathrm{CO}\right)\times A\left(\mathrm{CO}\right)+\\ \mathrm{FC}\left(C{H}_4\right)\times A\left(C{H}_4\right)\end{array}}& \end{array}$$\mathrm{With}\mathrm{FC}\left(\mathrm{CO}\right)=1.61\mathrm{and}\mathrm{FC}\left(C{H}_4\right)=1.71.$

[0048] 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.

[0049] 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

[00002]$\begin{array}{cc}\begin{array}{cc}{n}_{\mathrm{therm}-\mathrm{NRJ}}=\frac{Y_{\mathrm{CH}4}.D_{m,\mathrm{CH4}}.{\mathrm{PCS}}_{\mathrm{CH}4}}{D_{m.H2}.{\mathrm{PCS}}_{H2}+E_{\mathrm{bobine}}}& \end{array}& \left[\mathrm{Math}.2\right]\end{array}$

[0050] PCS (gross calorific value) represents the amount of energy released by the combustion of 1 mg of gas. [0051] The values given by the literature are PCS.sub.H2=141.9 MJ/kg and PCS.sub.CH4=55.5 MJ/kg, [0052] Y.sub.CH4 being the CH.sub.4 yield of the reaction, [0053] D.sub.mi being the mass flow rate of the product i, [0054] E.sub.bobine corresponds to the energy consumed by the inductor in order to operate (namely, to generate the magnetic field and cool the system).

[0055] The energy efficiency is expressed in % in FIG. 7.

Example 4: Comparison of Various Heating Agents

[0056] 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 CO.sub.2 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. FIG. 2 shows that for a microparticulate ferromagnetic material such as iron powder or steel wool, these values are 10 to 20 times lower.

[0057] 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 FIG. 3 show that this is not the case. For the iron carbide nanoparticles, it is necessary to provide a field of around 48 mT to achieve a yield close to 90%. With the iron powder, after launching the reaction, a field of only 8 mT is necessary. The distinctive feature of the iron powder and of the steel wool lies in the eddy currents that come into play and lead to a reduction of the magnetic field for heating the material.

[0058] 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.

Example 5: Mixture of Iron Powders and of Catalyst

[0059] 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 H.sub.2 and 5 mL/min of CO.sub.2.

[0060] The results of the conversion rates of CO.sub.2 and of CH.sub.4 are presented in FIG. 4. This assembly of powders (iron powder+Ni/CeO.sub.2) makes it possible to obtain very satisfactory yields (Y(CH.sub.4)), reaching 100% at temperatures of 300-350° C.

Example 6: Mixture of Steel Wool and Ni/CeO.SUB.2 .Catalyst

[0061] 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 H.sub.2 and 5 mL/min of CO.sub.2.

[0062] The results of the conversion rates of CO.sub.2 and of CH.sub.4 are presented in FIG. 5. This steel wool+Ni/CeO.sub.2 assembly also makes it possible to obtain very satisfactory yields (Y(CH.sub.4)), reaching 100% at temperatures of 300-350° C.

Example 7: Ni Catalyst Deposited on Steel Wool

[0063] 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 H.sub.2 and 5 mL/min of CO.sub.2.

[0064] The results of the conversion rates of CO.sub.2 and of CH.sub.4 are presented in FIG. 6. The maximum yield (Y(CH.sub.4)) is 90% at 400° C. This result is very encouraging, knowing that this system is simpler to implement.

Example 8: Energy Efficiency

[0065] The energy efficiency calculations of the preceding three examples (examples 5, 6 and 7) grouped together in FIG. 7 show that it is necessary to provide less energy to the steel wool system than to the iron powder system in order to reach the same temperature. This difference between powder and wool is observed particularly with the steel wool+Ni/CeO.sub.2 system. The energy efficiency of the steel wool+Ni is not as good since there is more wool to heat and therefore more energy to provide for a same amount of methane produced. In the example presented, it was necessary to introduce a large amount of steel wool, since very little nickel had been deposited thereon, in order to achieve an advantageous yield (90%).