An electrochemical process for converting alcohols to the corresponding olefins in a fluidized bed reactor.

Abstract

The present invention relates to a process for catalytic dehydration of alcohols having at least two carbon atoms to olefins, comprising the steps of: a) providing a fluidized bed reactor and a bed comprising particles; b) fluidizing the particles to form a fluidized bed; and c) heating the fluidized bed to a temperature between 200°C and 500°C, wherein the particles of the bed comprise electrically conductive particles and particles of a solid acid catalyst or particles, at least 10% by weight of the particles based on the total weight of the particles of the bed are electrically conductive particles having a resistivity at 400°C between 0.001 ohm·cm and 500 ohm·cm, and the step c) of heating the fluidized bed is performed by passing an electric current through the fluidized bed.

Description

[Technical field]

[0001] The present invention relates to a process for the catalytic dehydration of alcohols having at least two carbon atoms to the corresponding olefins in a fluidized bed reactor, the reaction being carried out in the fluidized bed reactor without the need for an external heating device. It is an object of the present invention to contribute to replacing the use of fossil carbon-based fuel heating systems. The present invention relates to the electrification of the chemical industry. [Background technology]

[0002] Replacing fossil carbon-based fuels in chemical production and recycling processes with greener, decarbonized energy sources is essential in light of climate change and the ongoing energy transition.

[0003] In this respect, alcohols appear to be promising platform molecules, since their dehydration to the corresponding olefins can provide the same monomers as those obtained via the conventional petroleum route, while at the same time reducing carbon emissions. Therefore, the conversion of alcohols to olefins is an important process that contributes to carbon neutrality.

[0004] Most of the technologies for converting alcohol to olefins use conventional fixed-bed reactors. The fluidized bed process for dehydrating ethanol described in U.S. Pat. No. 4,134,926 cannot avoid the use of burners, ovens or other conventional heating means, which leads to greenhouse gas emissions. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] US Pat. No. 4,134,926 Summary of the Invention [Problem to be solved by the invention]

[0006] It is an object of the present invention to provide a large scale solution to one or more problems encountered in the prior art, suitable for application in industries such as the chemical industry. Another object of the present invention is to contribute to replacing the use of fossil carbon-based fuel heating devices in fluidized bed reactors. The present invention provides a solution for the catalytic dehydration of alcohols to olefins using electricity as the sole energy source. [Means for solving the problem]

[0007] In a first embodiment, the present invention provides a process for the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins, the process comprising the steps of: a) providing at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles; b) fluidizing the particles in the bed by passing a fluid stream upwardly through the bed to form a fluidized bed; c) heating the fluidized bed to a temperature in the range of 200° C. to 500° C. to catalytically dehydrate the alcohol-containing feedstock, including one or more alcohols having at least two carbon atoms, to one or more olefins; the bed particles comprise electrically conductive particles and particles of a catalyst composition, at least 10% by weight of the particles are electrically conductive particles based on the total weight of the particles of the bed and have a resistivity in the range of 0.001 ohm·cm to 500 ohm·cm at 400°C, the catalyst composition comprises one or more solid acid catalysts, and the step c) of heating the fluidized bed is carried out by passing an electric current through the fluidized bed.

[0008] Surprisingly, it has been found that by using conductive particles, such as silicon carbide or graphite, in one or more fluidized bed reactors and passing electricity through them, it is possible to maintain a temperature sufficient for the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins having the same number of carbons as the alcohol, which requires conditions such as temperature reactions in the range of 200°C to 500°C, without the need for external heating equipment.

[0009] The use of at least 10% by weight of conductive particles within the bed particles minimizes heat loss when a voltage is applied. Most, if not all, of the electrical energy is converted to heat by the Joule effect and used to heat the reactor medium. For example, the conductive particles are or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and / or any mixture thereof.

[0010] In a preferred embodiment, the conductive particles are or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, and any mixtures thereof.

[0011] Advantageously, the process of the invention further comprises a step (d) of recovering one or more olefins, said step (d) being carried out after step (c).

[0012] In one embodiment, the process of the present invention comprises carrying out step (d) and further comprising a step (e) of oligomerizing one or more olefins recovered in step (d).

[0013] In another embodiment, the process of the present invention performs step (d) above and further comprises a step (f) of providing one or more aromatic compounds, and a step (g) of alkylating another portion of the aromatic compounds recovered in step (d) with one or more olefins.

[0014] In another alternative embodiment, step (d) above is performed, the process further comprises a step (e) of oligomerizing a portion of the olefin(s) recovered in step (d), the process further comprises a step (f) of providing one or more aromatic compounds, and a step (g) of alkylating the one or more aromatic compounds with another portion of the olefin(s) recovered in step (d), the step (g) being performed simultaneously with step (e). Regardless of which embodiment is selected, the inventive process further comprises an optional step (h) of hydrogenating the olefins after steps (e) and / or (g) have been performed.

[0015] An oligomerization step (e) and / or an alkylation step (g) and an optional hydrogenation step (h) on the aromatic compounds provided in step (f) are carried out after step (d) of recovering one or more olefins, which makes it possible to produce jet fuel and decarbonize the aviation industry.

[0016] In a preferred embodiment, the volumetric heat generation rate is 0.1 MW / m 3 Greater than 1MW / m 3 Larger, especially 3MW / m 3 Greater than.

[0017] In a preferred embodiment, at least one fluidized bed reactor is free of heating means. For example, at least one fluidized bed reactor includes a vessel and no heating means are disposed around or within the vessel. For example, at least one fluidized bed reactor is free of heating means selected from an oven, a gas burner, a hot plate, or any combination thereof. For example, all fluidized bed reactors are free of heating means selected from an oven, a gas burner, a hot plate, or any combination thereof.

[0018] For example, the content of the conductive particles is in the range of 15% by weight to 95% by weight, more preferably 20% by weight to 90% by weight, even more preferably 25% by weight to 80% by weight, and most preferably 30% by weight to 75% by weight.

[0019] For example, the content of conductive particles relative to the total weight of the bed is at least 12% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, even more preferably at least 25% by weight, and most preferably at least 30% by weight or at least 40% by weight or at least 50% by weight or at least 60% by weight, relative to the total weight of the particles in the bed.

[0020] For example, the conductive particles have a resistivity in the range of 0.005 to 400 ohm·cm at 400°C, preferably in the range of 0.01 to 300 ohm·cm at 400°C, more preferably in the range of 0.05 to 150 ohm·cm at 400°C, and most preferably in the range of 0.1 to 100 ohm·cm at 400°C.

[0021] For example, the conductive particles have a resistivity of at least 0.005 ohm-cm at 400°C, preferably at least 0.01 ohm-cm at 400°C, more preferably at least 0.05 ohm-cm at 400°C, even more preferably at least 0.1 ohm-cm at 400°C, and most preferably at least 0.5 ohm-cm at 400°C.

[0022] For example, the conductive particles have a resistivity of at most 400 ohm·cm at 400°C, preferably at most 300 ohm·cm at 400°C, more preferably at most 200 ohm·cm at 400°C, even more preferably at most 150 ohm·cm at 400°C, and most preferably at most 100 ohm·cm at 400°C. The content of conductive particles relative to the total weight of particles in the bed and the selection of conductive particles with a given resistivity influence the temperature reached by the fluidized bed. Thus, the skilled person can increase the density of the particle bed, the content of conductive particles relative to the total weight of particles in the bed, and / or select conductive particles with a lower resistivity in order to increase the temperature reached by the fluidized bed if the target temperature is not reached.

[0023] For example, the content of the particles in the catalyst composition is in the range of 15% by weight to 95% by weight, more preferably 20% by weight to 90% by weight, even more preferably 25% by weight to 80% by weight, and most preferably 30% by weight to 75% by weight.

[0024] For example, the density of a bed of particles is expressed as the void fraction. This void fraction, or bed porosity, is the volume of voids between the particles divided by the total volume of the bed. At the initiation velocity of fluidization, the void fraction is usually 0.4-0.5. The void fraction increases up to 0.98 in fast fluidized beds, ranging from a low of about 0.5 at the bottom to higher than 0.9 at the top of the bed. The void fraction can be controlled by the linear velocity of the fluidizing gas and can be reduced by recycling the solid particles recovered at the top and returned to the bottom of the bed, thereby compensating for the entrainment of solid particles out of the bed.

[0025] The void fraction VF is defined as the volume fraction of voids in a particle bed and is determined according to the following formula: VF = (Vt - Vp) / Vt (1) (where Vt is the total bed volume, given by: Vt=AH (2) where A is the cross-sectional area of ​​the fluidized bed, H is the height of the fluidized bed, Vp is the total volume of particles in the fluidized bed)

[0026] For example, the porosity of the bed is in the range of 0.5 to 0.8, preferably in the range of 0.5 to 0.7, and more preferably in the range of 0.5 to 0.6. In order to increase the density of the particle bed, it is necessary to decrease the porosity.

[0027] For example, the particles of the bed have an average particle size, as measured by sieving according to ASTM D4513-11, in the range of 5 to 300 μm, preferably in the range of 10 to 200 μm, more preferably in the range of 20 to 200 μm or 30 to 150 μm.

[0028] Preferably, the average size is measured by sieving according to ASTM D4513-11, but if the average size of the particles is less than 20 μm, the average size can also be measured by laser light scattering according to ASTM D4464-15.

[0029] For example, the conductive particles of the bed have an average particle size, as measured by sieving according to ASTM D4513-11, in the range of 5 to 300 μm, preferably in the range of 10 to 200 μm, and more preferably in the range of 30 to 150 μm.

[0030] In one embodiment, the conductive particles of the bed are 50% to 100% by weight, preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight, based on the total weight of the conductive particles of the bed, of one or more selected from metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes.

[0031] Preferably, the conductive particles of the bed are or comprise one or more selected from metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, and preferably have a content of 50% to 100% by weight, preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight, based on the total weight of the conductive particles of the bed.

[0032] Preferably, the conductive particles of the bed are or include one or more selected from a non-metallic resistor, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, and preferably have a content of 50% to 100% by weight, preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight, based on the total weight of the conductive particles of the bed.

[0033] Alternatively, the conductive particles of the bed preferably have a content of 50% to 100% by weight, preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight, based on the total weight of the conductive particles of the bed, of one or more particles selected from one or more metal alloys, one or more non-metallic resistors (provided that the non-metallic resistor is not silicon carbide), one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof. For example, the conductive particles of the bed are or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more carbon-containing particles, and any mixture thereof.

[0034] For example, the conductive particles of the bed are or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more carbon-containing particles, and any mixture thereof, and are preferably present in an amount of 50% to 100% by weight, more preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight, based on the total weight of the conductive particles of the bed.

[0035] For example, the conductive particles of the bed are or contain one or more selected from one or more nonmetallic resistors, one or more carbon-containing particles, and any mixture thereof, and the content thereof is preferably 50% by weight to 100% by weight, preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, and most preferably 90% by weight to 100% by weight, based on the total weight of the conductive particles of the bed.

[0036] For example, said metal alloy or alloys are selected from Ni-Cr, Fe-Ni-Cr, Fe-Ni-Al or mixtures thereof. Preferably, when said metal alloy contains at least chromium, the chromium content is at least 15 mol%, more preferably at least 20 mol%, even more preferably at least 25 mol%, most preferably at least 30 mol% of the total molar content of said metal alloy containing at least chromium. Advantageously, furthermore, the iron content in the metal alloy is at most 2.0%, preferably at most 1.5 mol%, more preferably at most 1.0 mol%, even more preferably at most 0.5 mol% relative to the total molar content of the metal alloy.

[0037] For example, the non-metallic resistor may be silicon carbide (SiC), molybdenum disilicide (MoSi2), nickel silicide (NiSi), sodium silicide (Na2Si), magnesium silicide (Mg2Si), platinum silicide (PtSi), titanium silicide (TiSi2), tungsten silicide (WSi2) or mixtures thereof, preferably silicon carbide.

[0038] For example, the metal carbide or metal carbides are selected from iron carbide (Fe3C) and / or molybdenum carbide (such as a mixture of MoC and Mo2C).

[0039] For example, the metal nitride or nitrides are selected from zirconium nitride (ZrN), tungsten nitride (WN, mixtures of WN and WN, etc.), vanadium nitride (VN), tantalum nitride (TaN), and / or niobium nitride (NbN).

[0040] For example, the one or more metallic phosphides are selected from copper phosphide (Cu3P), indium phosphide (InP), gallium phosphide (GaP), sodium phosphide (Na3P), aluminum phosphide (AlP), zinc phosphide (Zn3P2) and / or calcium phosphide (Ca3P2).

[0041] For example, the one or more carbon-containing particles may be selected from graphite, carbon black, petroleum coke, coke, or any combination thereof.

[0042] For example, one or more of the superionic conductors mentioned above may be LiAlSiO4, Li10GeP2S 12 , Li 3.6 S 0.6 P 0.4 O4, Na3Zr2PSi2O 12 Sodium superionic conductors (NaSICON) such as NaAl 11 O 17 , Na 1.6 Al 11 0 17.3 and / or Na 1.76 Li 0.38 Al 10.62 0 17 and the like.

[0043] For example, the one or more phosphate electrolytes are selected from LiPO4 or LaPO4.

[0044] For example, the conductive particles of the bed are or include a non-metallic resistive material such as silicon carbide.

[0045] For example, the conductive particles of the bed are or include a mixture of a non-metallic resistive material that is silicon carbide and conductive particles other than silicon carbide. The presence of conductive particles other than silicon carbide in the bed is optional. Silicon carbide can be present as a heating initiator material for the bed, since it was found that its resistivity at room temperature is too high to initiate heating of the bed. Instead of the presence of conductive particles other than silicon carbide, heat can also be supplied to the reactor for a certain period of time to initiate the reaction.

[0046] For example, the silicon carbide is selected from sintered silicon carbide, nitride-bonded silicon carbide, recrystallized silicon carbide, reaction-bonded silicon carbide, and mixtures thereof. The type of silicon carbide material is selected according to the heating power required to provide the reaction heat for the catalytic dehydration of alcohol to one or more olefins.

[0047] For example, the conductive particles of the bed are or include a mixture of a non-metallic resistor that is silicon carbide and conductive particles other than silicon carbide, and the conductive particles of the bed include 10% to 99% by weight of silicon carbide, preferably 15% to 95% by weight, more preferably 20% to 90% by weight, even more preferably 25% to 80% by weight, and most preferably 30% to 75% by weight of silicon carbide, based on the total weight of the conductive particles of the bed.

[0048] For example, the conductive particles of the bed are or include one or more metal alloys. Preferably, the one or more metal alloys are selected from Ni-Cr, Fe-Ni-Cr, Fe-Ni-Al or mixtures thereof.

[0049] Preferably, when said metal alloy comprises at least chromium, the chromium content is at least 15 mol%, more preferably at least 20 mol%, even more preferably at least 25 mol%, most preferably at least 30 mol% of the total molar content of the metal alloy comprising at least chromium. Advantageously, furthermore, the iron content in the metal alloy is at most 2.0%, preferably at most 1.5 mol%, more preferably at most 1.0 mol%, even more preferably at most 0.5 mol% relative to the total molar content of said metal alloy.

[0050] For example, the conductive particles of the bed are or include a mixture of a non-metallic resistive material which is silicon carbide and particles other than silicon carbide, and the particles other than silicon carbide are or include molybdenum disilicide. Preferably, the molybdenum disilicide particles have an average particle size in the range of 5 to 300 μm, more preferably in the range of 10 to 200 μm, and most preferably in the range of 30 to 150 μm, as measured by sieving according to ASTM D4513-11.

[0051] For example, the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out at a temperature in the range of 200°C to 500°C, preferably in the range of 240°C to 490°C, and more preferably in the range of 260°C to 480°C.

[0052] For example, the catalytic dehydration of one or more alcohols having at least two carbon atoms to olefins is carried out at a pressure ranging from 0.05 MPa to 3 MPa, preferably from 0.05 MPa to 1.5 MPa, more preferably from 0.12 MPa to 0.8 MPa, or from 0.12 MPa to 0.5 MPa, which are considered to be moderate pressures.

[0053] For example, the partial pressure of the alcohol-containing raw material is in the range of 0.12 MPa to 0.7 MPa.

[0054] In one embodiment, the process of the present invention includes preheating the fluidized bed reactor with a gas stream prior to catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins in the fluidized bed reactor. Preferably, the gas stream is a stream of one or more inert gases and / or has a temperature between 100° C. and 300° C. This embodiment is important when energizing the system and / or when the bed particles are too resistive at room temperature to initiate electrical heating of the bed. For example, the one or more inert gases are gases that do not adversely affect the catalyst. For example, the one or more inert gases are selected from nitrogen, argon, helium, saturated hydrocarbons having up to 10 carbon atoms, or any combination thereof. More preferably, the one or more inert gases are or include saturated hydrocarbons having up to 10 carbon atoms, and even more preferably saturated hydrocarbons having 3 to 7 carbon atoms, or 4 to 6 carbon atoms. For example, the one or more inert gases are or include butane, pentane, naphtha, or any combination thereof.

[0055] In one embodiment, the process of the present invention includes diluting the alcohol-containing feedstock with one or more diluents, for example, the one or more diluents selected from steam, hydrogen, methane, carbon dioxide, or any combination thereof, and the one or more diluents can control the selectivity of the reaction.

[0056] The alcohol-containing feedstock comprises one or more alcohols having at least two carbon atoms, and optionally one or more inert gases and / or one or more diluents. By specifying that the alcohol-containing feedstock comprises one or more alcohols having at least two carbon atoms, it is meant that if methanol is present in the alcohol-containing feedstock, the methanol cannot be converted to olefins. Preferably, the alcohol-containing feedstock does not comprise methanol. For example, the amount of one or more alcohols having at least two carbon atoms in the alcohol-containing feedstock ranges from 5% to 100% by weight based on the total weight of the alcohol-containing feedstock. For example, the one or more alcohols of the alcohol-containing feedstock are or comprise one or more alcohols having 2 to 10 carbon atoms. For example, the one or more alcohols of the alcohol-containing feedstock can be ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, hexane-1-ol, hexane-2-ol, hexane-3-ol, 2-methylpentan-1-ol, 3-methylpentan-1-ol, 4-methylpentan-1-ol, 2-methylpentan-2-ol, 3-methylpentan-4-ol, 4-methylpentan-5-ol, 5-methylpentan-6-ol, 6-methylpentan-7-ol, 7-methylpentan-8-ol, 8-methylpentan-9-ol, 9-methylpentan-10-ol, 10-methylpentan-11-ol, 11-methylpentan-12-ol, 12-methylpentan-13-ol, 13-methylpentan-14-ol, 14-methylpentan-15-ol, 15-methylpentan-16-ol, 16-methylpentan-17-ol, 17-methylpentan-18-ol, 18-methylpentan-19-ol, 19-methylpentan-20-ol, 20-methylpentan-21-ol, 20-methylpentan-22-ol, 20-methylpentan-23-ol, 20-methylpentan-24-ol, 20-methylpentan-25-ol, 20-methylpentan-26-ol, 20-methylpentan-27-ol, 20-methylpentan-28-ol, 20-methylpentan-29-ol, 20-methylpentan-30-ol, 20-methylpentan-31-ol, 20-methylpentan-32-ol, 20-methylpentan-33-ol, 20-methylpentan-3 The alcohol-containing feedstock may be or include, for example, pentane-2-ol, 4-methylpentane-2-ol, 2-methylpentane-3-ol, 3-methylpentane-3-ol, 2,2-dimethylbutane-1-ol, 2-3-dimethylbutane-1-ol, 3,3-dimethylbutane-1-ol, 2,3-dimethylbutane-2-ol, 3,3-dimethylbutane-2-ol, 2-ethylbutane-1-ol, or any combination thereof. For example, the amount of one or more inert gases in the alcohol-containing feedstock ranges from 0% to 95% by weight based on the total weight of the alcohol-containing feedstock. For example, the amount of one or more diluents in the alcohol-containing feedstock ranges from 0% to 95% by weight based on the total weight of the alcohol-containing feedstock.

[0057] For example, the weight hourly space velocity of the reaction stream of the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is 0.1 h -1 ~100h -1 , preferably 1.0h -1 ~50h -1 , more preferably 1.5 h - 1~10h -1 , more preferably 2.0h -1 ~6.0h -1 Weight hourly space velocity is defined as the ratio of the mass flow rate of the reacting stream to the mass of solid particulate matter in the fluidized bed.

[0058] In particular, the product(s) obtained in the process of the present invention may include one or more olefins, water, unconverted alcohol (if present), one or more inert gases (if present) and one or more diluents (if present). For example, the one or more olefins are recovered by fractional distillation means and / or the one or more inert gases (if present) are recycled to the reactor inlet. For example, the unconverted alcohol is recycled to the reactor inlet.

[0059] In a preferred embodiment, the residence time of the alcohol-containing feedstock in the fluidized bed section of the reactor may range from 0.1 to 10 seconds at a temperature of 260 to 500°C.

[0060] For example, where the alcohol-containing feedstock comprises one or more alcohols having at least two carbon atoms, the at least one fluidized bed reactor provided in step a) comprises a heating zone and a reaction zone, the fluid stream provided in step b) is provided to the heating zone and optionally comprises one or more inert gases and / or one or more diluent gases, and step c) heats the fluidized bed to a temperature between 200° C. and 500° C. for endothermic catalytic dehydration of the alcohol-containing feedstock to one or more olefins, the method comprises the following substeps: - heating the fluidized bed to a temperature between 200°C and 500°C by passing an electric current through at least one heating zone of the fluidized bed; - transporting the heated particles from the heating zone to a reaction zone; - fluidizing the heated particles to form a fluidized bed in a reaction zone by flowing a fluid stream comprising an alcohol-containing feedstock, optionally mixed with one or more inert gases and / or one or more diluent gases, upwardly through said bed in the reaction zone to effect endothermic catalytic dehydration of the alcohol-containing feedstock to one or more olefins; - Optionally recovering the particles from the reaction zone and recycling them to the heating zone.

[0061] For example, the step of heating the fluidized bed is carried out by passing a current through the fluidized bed at a voltage of 300V or less, preferably 200V or less, more preferably 150V or less, even more preferably 120V or less, most preferably 100V or less, and even most preferably 90V or less.

[0062] The fluid stream may be a gas stream and / or a vapor stream.

[0063] In step c) the alcohol-containing feedstock is subjected to a step of catalytic dehydration of the alcohol-containing feedstock to one or more olefins, which means that an alcohol-containing feedstock is provided.

[0064] For example, when the heating zone and the reaction zone are intermixed (ie, are the same zone), the fluid stream provided in step b) comprises an alcohol-containing feedstock.

[0065] For example, if the heating zone and the reaction zone are separate zones, the fluid stream fed to the heating zone in step b) does not comprise the alcohol-containing feedstock. For example, if the inventive process provides at least one fluidized bed reactor as the heating zone and at least one fluidized bed reactor as the reaction zone, the fluid stream fed to the heating zone in step b) does not comprise the alcohol-containing feedstock and the fluid stream fed to the reaction zone in step b) comprises the alcohol-containing feedstock.

[0066] It will be understood that an alcohol-containing feedstock is fed to the reaction zone, and that if the heating zone is separate from the reaction zone, then the alcohol-containing feedstock is not fed to the heating zone. It will be understood that in addition to the alcohol-containing feedstock being fed to the reaction zone, steam, as described above, can be fed to the reaction zone to achieve the recommended steam to hydrocarbon ratio in the reaction zone.

[0067] For example, the at least one fluidized bed reactor provided in step a) comprises a heating zone and a reaction zone, and the step c) of heating the fluidized bed comprises the following substeps: - A gas stream having a temperature in the range of 100°C to 300°C is passed upwardly through the particles in the fluidized bed to preheat the fluidized bed to a temperature in the range of 100°C to 300°C. - Heating the particles in the fluidized bed to a temperature in the range of 200°C to 500°C by passing an electric current through a heating zone of at least one fluidized bed reactor. - Transporting the heated particles from the heating zone to the reaction zone. - fluidizing the heated particles in a reaction zone by passing a fluid stream comprising an alcohol-containing feedstock upwardly through the bed in the reaction zone to form a fluidized bed, and endothermic catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins. Optionally, the particles are recovered from the reaction zone and recycled to the heating zone.

[0068] To carry out the catalytic reaction, the bed particles further comprise a catalyst, which is one or more solid acid catalysts. For example, the content of the catalyst composition particles is in the range of 15% to 90% by weight of the bed particles, more preferably 20% to 85% by weight, even more preferably 25% to 80% by weight, and most preferably 30% to 75% by weight.

[0069] For example, the solid acid catalyst or catalysts may have a surface area of ​​50 m2 as measured by N2 adsorption measurements. 2 / g~800m 2 / g, preferably 100m 2 / g to 750m 2 / g, more preferably 150m 2 / g to 700m 2 / g range.

[0070] For example, the one or more solid acid catalysts are one or more oxides, preferably one or more oxides selected from γ-Al2O3, β-Al2O3, η-Al2O3, δ-Al2O3, amorphous Al2O3, chlorine-containing alumina, fluorine-containing alumina, phosphorus-containing alumina, ZrO2, acid-treated zirconia, acid-treated titania, niobium oxide, tungsten oxide, or any combination thereof.

[0071] For example, the one or more solid acid catalysts are one or more mixed oxides. Preferably, the one or more mixed oxides are SiO2-Al2O3, SiO2-TiO2, SiO2-SnO2, SiO2-ZrO2, SiO2-BeO, SiO2-MgO, SiO2-CaO, SiO2-SrO, SiO2-ZnO, SiO2-Ga2O3, SiO2-Y2O3, SiO2-La2O3, SiO2-WO3, SiO2-ThO2, Al2O3-MgO, Al2O3-ZnO, Al2O3-ThO2, Al2O3-TiO2, Al2O3-ZrO2, Al2O3-MoO3, Al2O3-WO3, A The inorganic filler is selected from among l2O3-Cr2O3, Al2O3-Mn2O3, Al2O3-Fe2O3, TiO2-MgO, TiO2-ZnO, TiO2-ZrO2, TiO2-SnO2, TiO2-Sb2O5, TiO2-V2O5, TiO2-Cr2O3, TiO2-MoO3, TiO2-WO3, WO3-son2, WO3-ZrO2, Nb2O5-Al2O3, Nb2O5-WO3, Nb2O5-MoO3, Nb2O5-ZrO2, Nb2O5-TiO2, TiO2-Fe2O3, and any combination thereof.

[0072] For example, the one or more solid acid catalysts are one or more phosphates. Preferably, the one or more phosphates are one or more phosphates selected from titanium phosphate, zirconium phosphate, iron phosphate, or any combination thereof.

[0073] For example, the one or more solid acid catalysts are one or more zeolites selected from the group of the MFI, MEL, MOR, FER, MTT, MWW, TON, EUO, HEU, MFS and MRE families, and any combination thereof.

[0074] For example, the one or more solid acid catalysts are one or more zeolites having a Si / Al ratio of at least 10 as determined by X-ray fluorescence spectroscopy.

[0075] For example, the one or more solid acid catalysts are one or more silica aluminophosphate molecular sieves selected from the AEI, CHA and AEL family groups and any combination thereof.

[0076] The measurement of catalytic acid sites can be defined as the ability to donate a proton as defined by Brønsted, or the ability to accept an electron pair as defined by Lewis. The measurement of acidity is performed by temperature programmed desorption of ammonia or infrared spectroscopy. These methods are described in the following [Non-Patent Document 1] and [Non-Patent Document 2]. [Non-Patent Document 1] "Studies in Surface Science and Catalysis", Kozo TANABE, Makoto MISONO, Yoshio ON0, Hideshi HATTORI, Vol. 51, NEW SOLID ACIDS AND BASES - THEIR CATALYTIC PROPERTIES, by KODANSHA LTD. and ELSEVIER SCIENCE PUBLISHERS, 1989 [Non-Patent Document 2] “Solid Acid Catalysis - From Fundamentals to Applications”, Hideshi Hattori & Yoshio Ono, by Taylor & Francis Group, 2015.

[0077] For example, the zeolite or zeolites may be steamed prior to use in step (c) and then optionally leached to dealuminate the zeolite or zeolites, in other words, the zeolite or zeolites contain less than 10% by weight aluminium based on the undealuminated zeolite or zeolites.

[0078] For example, the zeolite or zeolites include a structure having at least one 10-membered ring.

[0079] For example, the one or more zeolites are selected from the group of the MFI, MEL, MOR, FER, MTT, MWW, TON, EUO, HEU, MFS and MRE families and any combination thereof. Preferably, the one or more zeolites are selected from the group of the MFI, MEL families and any combination thereof.

[0080] For example, the one or more zeolites further include boron.

[0081] For example, the one or more zeolites are one or more phosphorus-modified zeolites.

[0082] Advantageously, the zeolite or zeolites are in H type, in other words, less than 50% by weight, preferably less than 45% by weight or less than 40% by weight, relative to the total weight of the zeolite or zeolites, comprises one or more metal ions, preferably chosen from Na, Mg, Ca, La, Ni, Ce, Zn, Co or any combination thereof.

[0083] According to a second aspect of the present invention, there is provided an apparatus for the endothermic catalytic dehydration of one or more alcohols having at least two carbon atoms according to the first aspect to one or more olefins, the apparatus comprising: i) a current-carrying fluidized bed unit comprising at least one fluidized bed reactor comprising: - at least two electrodes, - a reaction vessel, - one or more fluid nozzles for introducing into at least one fluidized bed reactor an alcohol-containing feedstock comprising one or more alcohols having at least two carbon atoms and, optionally, one or more inert gases and / or one or more diluent gases; and - bed containing particles, ii) a product recovery unit; iii) an olefin conversion unit selected from an olefin oligomerization unit or an aromatic alkylation unit or an olefin oligomerization and aromatic alkylation unit, with product recovery occurring downstream of the current-flowing moving bed unit and upstream of the olefin conversion unit; iv) an optional hydrogenation unit, which, if present, is downstream of the olefin conversion unit; the bed particles include conductive particles and particles of a catalyst composition, at least 10 wt % of the bed particles based on the total weight of the bed particles are conductive and have a resistivity in the range of 0.001 Ohm cm to 500 Ohm cm at a temperature of 400°C, and the catalyst composition includes one or more solid acid catalysts.

[0084] Preferably, at least two of the electrodes include or are made of tantalum.

[0085] For example, the conductive particles may be one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof.

[0086] Advantageously, at least one fluidized bed reactor is devoid of heating means. For example, at least one fluidized bed reactor is devoid of heating means arranged around or inside the reaction vessel. For example, all fluidized bed reactors are devoid of heating means. By "heating means" at least one fluidized bed reactor is meant that there are no "classical" heating means such as ovens, gas burners, hot plates, etc., i.e., there are no heating means other than at least two electrodes on the fluidized bed reactor itself. For example, at least one fluidized bed reactor is devoid of heating means selected from ovens, gas burners, hot plates, or any combination thereof. For example, all fluidized bed reactors are devoid of heating means selected from ovens, gas burners, hot plates, or any combination thereof.

[0087] In a preferred embodiment, at least one fluidized bed reactor containing at least two electrodes and a bed containing particles is free of packing.

[0088] For example, the fluidizing gas may be one or more diluent gases.

[0089] For example, at least one reaction vessel has an internal diameter of at least 100 cm, preferably at least 200 cm, more preferably at least 300 cm.

[0090] Preferably, the reactor vessel comprises a reactor vessel wall made of a corrosion resistant material, advantageously the reactor vessel wall material comprises nickel (Ni), SiAlON ceramic, yttria stabilized zirconia (YSZ), tetragonal polycrystalline zirconia (TZP) and / or tetragonal polycrystalline zirconia (TPZ).

[0091] Preferably, one of the electrodes is a reaction vessel or a gas distributor and / or at least two of the electrodes are made of stainless steel or a nickel-chromium alloy or a nickel-chromium-iron alloy.

[0092] For example, at least one fluidized bed reactor vessel may include a heating zone, a reaction zone, one or more fluid nozzles for supplying an alcohol-containing feedstock to the reaction zone, and, optionally, a means for transporting bed particles from the reaction zone to the heating zone.

[0093] For example, the inventive installation comprises at least two fluidized bed reactors connected to each other, at least one reactor of the at least two fluidized bed reactors being a heating zone and at least another reactor of the at least two fluidized bed reactors being a reaction zone. Preferably, the inventive installation comprises one or more fluid nozzles arranged to inject an alcohol-containing feedstock into at least one fluidized bed reactor that is a reaction zone, and optionally means for transporting particles in the bed from the heating zone to the reaction zone and means for returning particles from the reaction zone to the heating zone (optional). This configuration is important in that a given particle bed is common to at least two fluidized bed reactors.

[0094] For example, at least one of the fluidized bed reactors is a single fluidized bed reactor with the heating zone at the bottom of the fluidized bed reactor and the reaction zone at the top of the fluidized bed reactor. Preferably, the inventive installation comprises one or more fluid nozzles for injecting the alcohol-containing feedstock between the two zones. The diameters of the heating zone and the reaction zone may be different to achieve optimal conditions for heating in the lower zone and optimal conditions for the dehydration reaction in the upper zone. The particles can be transferred from the heating zone to the reaction zone by entrainment and vice versa by gravity back from the reaction zone to the heating zone. Optionally, the particles can be collected from the upper heating zone and transferred to the lower heating zone by a separate transfer line.

[0095] For example, at least one fluidized bed comprises at least two lateral zones, an outer zone and an inner zone, the outer zone surrounding the inner zone, the outer zone being the heating zone and the inner zone being the reaction zone. In a less preferred configuration, the outer zone is the reaction zone and the inner zone is the heating zone. Preferably, the inventive system comprises one or more fluid nozzles for injecting the alcohol-containing feedstock into the reaction zone.

[0096] In one embodiment, 50% to 100% by weight of the conductive particles of the bed are one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes and any mixtures thereof, based on the total weight of the conductive particles of the bed; preferably, the proportion of the conductive particles of the bed is 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

[0097] From a third aspect, the present invention provides the use of a bed comprising particles in at least one fluidized bed reactor for the catalytic dehydration of one or more alcohols having at least 2 carbon atoms to one or more olefins according to the first aspect, characterized in that the particles of the bed comprise electrically conductive particles and particles of a catalytic composition, at least 10% by weight of the particles of the bed relative to the total weight of the particles of the bed being electrically conductive and having a resistivity in the range of 0.001 ohm·cm to 500 ohm·cm at a temperature of 400° C., and the catalytic composition comprises one or more solid acid catalysts.

[0098] For example, the conductive particles are or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof.

[0099] For example, the use of the present invention includes heating a bed containing particles in a first reactor to a temperature in the range of 200°C to 500°C, transferring the heated particle bed from the first reactor to a second reactor, and feeding the alcohol-containing feedstock to the second reactor. Preferably, at least the second reactor is a fluidized bed reactor and / or at least the second reactor lacks a heating means. More preferably, the first reactor and the second reactor are fluidized bed reactors and / or the first and second reactors lack a heating means. For example, the second reactor lacks an electrode. In one embodiment, 50% to 100% by weight of the conductive particles of the bed are one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes and any mixtures thereof, based on the total weight of the conductive particles of the bed; preferably, the proportion of the conductive particles of the bed is 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

[0100] From a fourth aspect, the present invention provides the use of an installation comprising at least one fluidized bed reactor for the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins, characterized in that the installation is according to the second aspect. Preferably, the use of this installation is such that the reaction in the at least one fluidized bed reactor for the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out in a process according to the first aspect.

[0101] It will be apparent to one skilled in the art that the particular features, structures, characteristics or embodiments of the present invention may be combined in any suitable manner in one or more embodiments. [Brief description of the drawings]

[0102] [Figure 1] FIG. 1 shows a prior art installation. [Diagram 2] FIG. 1 shows an installation of the present invention with one reactor in which the heating zone and the reaction zone are the same. [Diagram 3] FIG. 1 is a diagram showing an equipment of the present invention having one reactor in which a heating zone and a reaction zone are arranged one above the other. [Figure 4] FIG. 1 shows an installation according to the invention with one reactor in which the heating zone and the reaction zone are arranged side by side with each other. [Diagram 5] FIG. 1 shows an installation of the present invention having two reactors. [Figure 6] FIG. 1 shows an example of a temperature programmed desorption (TPD) method setup. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0103] The definitions in the present invention are shown below. As used herein, the terms "comprising," "having," and "consisting of" are synonymous with "comprising," and are inclusive or open-ended and do not exclude additional, unrecited features, elements, or method steps. The terms "comprising," "having," and "consisting of" also include the term "consisting only of."

[0104] Recitation of numerical ranges by endpoints includes all integers and, where appropriate, fractions subsumed within the range (e.g., 1 to 5 includes 1, 2, 3, 4, 5 when, e.g., referring to the number of elements, and also includes 1.5, 2, 2.75, 3.80 when, e.g., referring to measurements). Recitation of endpoints also includes the recited endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Numerical ranges recited herein include all subranges subsumed therein.

[0105] Zeolite codes (e.g., CHA) are defined according to the following [Non-Patent Document 3], which is incorporated herein by reference. [Non-Patent Document 3] "Atlas of Zeolite Framework Types", 6th revised edition, 2007, Elsevier

[0106] The Si / Al atomic ratio of a zeolite corresponds to the amount of SiO2 divided by the amount of Al2O3 due to the fact that there are two aluminum atoms for every one silicon atom. The silicon-to-aluminum ratio (also written SAR) corresponds to the amount of SiO2 divided by the amount of Al2O3, not the ratio of Si and Al atoms in the zeolite formula. Therefore, the SAR value always corresponds to twice the value of the Si / Al atomic ratio.

[0107] The present invention provides a process for catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins, comprising the steps of: a) providing at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles; b) fluidizing the particles in the bed by passing a fluid stream upwardly through the bed to form a fluidized bed; c) heating the fluidized bed to a temperature between 200° C. and 500° C. to catalytically dehydrate the alcohol-containing feedstock, which includes one or more alcohols having at least two carbon atoms, to one or more olefins; d) optionally recovering one or more olefins. The process of the invention is characterized in that the bed particles comprise electrically conductive particles and particles of a catalyst composition, at least 10% by weight of the particles relative to the total weight of the bed particles are electrically conductive and have a resistivity in the range of 0.001·Ohm·cm to 500 Ohm·cm at 400°C, the catalyst composition comprises one or more solid acid catalysts, and the step c) of heating the fluidized bed is carried out by passing an electric current through the fluidized bed.

[0108] For example, the olefin(s) have the same number of carbons as the alcohol(s), which is why methanol cannot be converted to olefins if present in the alcohol-containing feedstock. Preferably, the alcohol-containing feedstock is free of methanol.

[0109] For example, the conductive particles of the bed may be or include one or more selected from one or more carbon-containing particles, one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof.

[0110] In one embodiment, 50% to 100% by weight of the conductive particles of the bed are one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixtures thereof, based on the total weight of the conductive particles of the bed, and the content is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

[0111] The fluid stream may be a gaseous and / or vaporized stream.

[0112] For example, the step of heating the fluidized bed is carried out by passing a current through the fluidized bed at a voltage of 300 V or less, preferably 200 V or less, more preferably 150 V or less, even more preferably 120 V or less, most preferably 100 V or less, and even most preferably 90 V or less.

[0113] The solid particulate material in a fluidized bed reactor is usually supported by a perforated plate, called a distributor, or a plate with nozzles or chimneys. The fluid is forced up through the distributor and passes through the voids between the solid particulate material. At low fluid velocities, the solids remain settled while the fluid passes through the voids in the material. This is called a packed bed reactor. As the fluid velocity increases, the particulate solids reach a stage where the force of the fluid on the solids is sufficient to counterbalance the weight of the solid particulate material. This stage is called incipient fluidization and occurs at this minimum fluidization velocity. Above this minimum velocity, the contents of the reactor bed begin to expand and become fluidized. Different flow regimes are observed in the reactor depending on the operating conditions and the properties of the solid phase. The minimum fluidization velocity required for bed expansion varies with the size, shape, porosity, and density of the particles and the density and viscosity of the rising fluid.

[0114] In the following [Non-Patent Document 4], Geldart distinguishes between four different fluidization categories for average particles, determining the following fluidization regimes: - Type A, aerable fluidized (medium size, medium density particles that are easy to fluidize. Usually 30-100μm particles, density about 1500kg / m 3 ) - Type B, fluidized like sand (heavy particles that are difficult to fluidize. Usually 100-800μm particles, density 1500-4000kg / m 3 ) - Type C, agglomerated fluidization (fluidization of solid particles, typically powder-like, fine particles (approximately 20 μm) where intraparticle or cohesive forces predominate); and - Type D, jettable fluidization (high density, large particles of about 1-4 mm, dense, jettable). [Non-Patent Document 4] PR Gunjal, VV Ranade, in Industrial Catalytic Processes for Fine and Specialty Chemicals, (2016)

[0115] Fluidization can be broadly classified into two regimes: homogeneous and heterogeneous (Non-Patent Document 5). In homogeneous or particulate fluidization, the particles are uniformly fluidized without any distinct voids. In heterogeneous or bubbling fluidization, gas bubbles without solids are clearly observed. These voids behave like bubbles in a gas-liquid stream, changing size and shape as they rise through the medium and exchange gas with the surrounding homogeneous medium. In particulate fluidization, the particles move significantly, the bed expands smoothly, and the bed surface is clearly defined. Particulate fluidization is observed only with Geldart-A type particles. The bubbling fluidization regime is observed at much higher velocities than homogeneous fluidization, where identifiable gas bubbles grow from the distributor, coalesce with other bubbles, and finally burst at the bed surface. These bubbles enhance the mixing of the solids and gas, and the size of the bubbles tends to become larger as the fluidization rate increases. Slugation conditions are observed when the bubble diameter increases to that of the reactor. Under turbulent conditions, the bubbles grow and begin to break up as the bed expands. Under this condition the upper surface of the bed is no longer distinct. With fast or air fluidization no distinct bed surface is observed and the particles are carried out of the bed and must be recycled back to the reactor. [Non-Patent Document 5] Fluid Bed Technology in Materials Processing, 1999 by CRC Press

[0116] Fluidized bed reactors have the following advantages: Uniform particle mix: Because solid particulate materials inherently behave like a fluid, fluidized beds do not suffer from the poor mixing that occurs in packed beds. The elimination of radial and axial concentration gradients allows for better fluid-solid contact, which is essential for reaction efficiency and quality. Uniform temperature gradient: Many chemical reactions require the addition or removal of heat, but under fluidized conditions localized hot or cold spots within the reaction bed are avoided. Ability to operate reactor continuously: The fluidized bed characteristic of the reactor allows the product to be continuously removed and new reactants to be introduced into the reaction vessel. In addition to the continuous operation of the chemical reaction, being a fluidizable solid particulate material, the fluidized bed also allows the solid material to be removed continuously or at a specific frequency, and new fresh solid material to be added continuously or at a specific frequency.

[0117] Heat can be generated by passing an electric current through a conductive material that has a resistivity (resistance) high enough to convert the electricity into heat. Electrical resistivity (also called specific electrical resistance or volume resistivity, which is an intrinsic property independent of shape or size) and its inverse, electrical conductivity, are fundamental properties of materials that quantify how well they resist or conduct electric current (the SI units of electrical resistivity are the ohm-meter (Ω·m) and conductivity is the siemens per meter (S / m)).

[0118] When an electric current is passed through a fixed bed of electrically conductive particulate solids of sufficient resistivity, the bed offers resistance to the flow of electric current. This resistance depends on many parameters, such as the nature of the solid, the nature of the bonds between the particles in the bed, the porosity of the bed, the height of the bed, and the geometry of the electrodes. Fluidizing the fixed bed by passing a gas through it increases the resistance of the bed. The resistance offered by the conductive particles generates heat in the bed, which keeps it isothermal (called an electrothermal fluidized bed or electrofluid reactor). Electrofluidic reactors are advantageous for in situ heating during many high temperature reactions, particularly in the operation of endothermic reactors, and save energy since no external heating or heat transfer is required. A prerequisite is that at least a portion of the solid particle material is electrically conductive, but sufficient heat can be generated even when non-conductive solid particles are mixed in. Such non-conductive or very highly resistive solids can act as catalysts in chemical transformations. Since the heating is of the charge-resistance type, the inherent resistivity of the particles affects the bed resistance, which in turn determines the resistance of the electrothermal fluidized bed furnace, depending on the characteristics of the bed material. The size, shape, composition and size distribution of the particles also affect the magnitude of the bed resistance. Also, when the bed is fluidized, voids appear between the particles, which increases the bed resistance. The total bed resistance is the sum of two components: the electrode contact resistance (i.e. the resistance between the electrode and the bed) and the bed resistance. A high contact resistance results in widespread localized heating near the electrode, while the rest of the bed remains rather cool. The contact resistance is determined by factors such as the current density, the fluidization rate, the type of bed material, the electrode size and the type of material used for the electrode. The electrode composition can advantageously be metals such as iron, cast iron, other steel alloys, copper, copper-based alloys, nickel, nickel-based alloys or refractory metals, intermetallic compounds or carbides, nitrides such as alloys of Zr, Hf, V, Nb, Ta, Cr, Mo, W or ceramics. The contact area between the fluidized bed material and the electrode can be adjusted depending on the degree of immersion of the electrode and the amount of particulate material in the fluidized bed. Thus, the electrical resistance and power levels can be manipulated by adjusting these variables.Advantageously, the electrode should have a lower resistivity (and therefore lower Joule heating) than the particulate material of the fluidized bed to prevent overheating of the electrode compared to the fluidized bed. In a preferred embodiment, the electrode can be cooled by passing a cooler fluid inside or outside the electrode. This fluid can be any liquid that is evaporated by the heated gas flow, or it can be part of a cold feedstock that initially cools the electrode before entering the fluidized bed.

[0119] Bed resistance can be predicted by Ohm's law. The mechanism of current transfer in a fluidized bed is believed to occur by current flow along the continuous chains of conductive particles at low operating voltages. At higher voltages, current transfer occurs by a combination of arcing between the conductive particle chains and the electrode and bed, and arcing between the particles (which can ionize the gas and reduce the bed resistance). Arcing inside the bed is generally undesirable as it reduces electrical and thermal efficiency. Gas velocity has a large effect on bed resistance, with increasing gas flow causing a rapid increase in resistance beyond the settled bed. A maximum occurs near the initial fluidization velocity and then decreases with increasing velocity. Resistance increases again at sufficient gas flow to initiate slugging. Average particle size and shape affect the resistance because they affect the contact points between particles. Generally, the resistivity of the bed increases 2-5 times from a settled bed (e.g., 20 Ohm·cm for graphite) to the initial fluidization (60 Ohm·cm for graphite), and 10-40 times from a settled bed to twice the initial fluidization velocity (300 Ohm·cm for graphite). Non-conductive or less conductive particles can also be added to the conductive particles. If the conductive solid fraction is small, the bed resistivity increases because the bonds of the conductive solid chains between the electrodes are broken. If the non-conductive solid fraction is finer in size, the bed resistance increases because it fills the gaps or voids of the larger conductive solids.

[0120] In general it is desirable to obtain the required high heating power with a low voltage and high current. The power supply can be either AC or DC. The voltage applied to an electrothermal fluidized bed to achieve sufficient heating power is usually less than 100V. An electrothermal fluidized bed can be controlled in three ways: 1. Adjust the gas flow: Since the conductivity of the bed depends on the degree of voids or gas bubbles in the bed, changing the gas flow rate will change the power level. Therefore, the temperature can be controlled by adjusting the fluidization gas flow rate. The flow rate required for optimal performance corresponds to a velocity equal to or slightly above the minimum fluidization velocity. 2. Adjusting electrode immersion depth: The power level can also be controlled by varying the immersion level of the electrodes in the bed, since the conductivity of the bed depends on the contact area between the conductive particles and the electrodes: the surface area of ​​the electrode through which current flows increases with the degree of immersion of the electrode, decreasing the overall resistance. 3. Adjustment of applied voltage: Although it is often more affordable or economical to vary the power level using the first two methods above rather than increasing the applied voltage, in an electrically heated fluidized bed three variables can be used to control the heating power produced.

[0121] The reactor walls are typically made of ceramics (e.g. SiC), refractory metals or alloys. They are versatile and compatible with many high temperature industrial reactions. The reaction atmosphere is often restricted to neutral or reducing, as oxidizing atmospheres may burn carbon materials or form non-conductive metal oxide layers on the metals or alloys. The walls and / or distribution plate themselves act as the reactor electrodes. The fluidizing solids can be molybdenum disilicide, silicon carbide or other high melting conductive particles. The other electrodes, usually immersed in the bed, are also refractory metals, intermetallics or alloys.

[0122] It may be advantageous to heat the conductive particles and / or catalyst particles in a separate zone of the reactor where little or substantially no feed hydrocarbon is present and only diluent gas is present to generate the required heat of reaction. The advantage is that suitable fluidization conditions for generating heat by passing an electric current through a bed of conductive particles can be optimized while optimal reaction conditions during hydrocarbon conversion can be selected for other zones of the reactor. Such conditions of optimal void fraction and linear velocity may be different for heating purposes and for chemical conversion purposes.

[0123] In one embodiment of the invention, the system comprises two zones arranged in series, the first being a heating zone and the second being a reaction zone, and the conductive particles and catalyst particles are continuously moved or transported from the first zone to the second zone and vice versa. The first and second zones may be different parts of a fluidized bed or may be located in separate fluidized bed reactors connected to each other.

[0124] In the above embodiment, the process for catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins comprises the steps of: a) providing at least one fluidized bed reactor having at least two electrodes and a bed containing particles; b) fluidizing the particles by passing a fluidized stream upward through the bed to form a fluidized bed; c) heating the fluidized bed to a temperature in the range of 200° C. to 500° C. to catalytically dehydrate the alcohol-containing feedstock, which includes one or more alcohols having at least two carbon atoms, to one or more olefins; d) optionally recovering one or more of said olefins; at least 10% by weight of the particles are electrically conductive particles based on the total weight of the particles in the bed and have a resistivity in the range of 0.001 Ohm·cm to 500 Ohm·cm at 400° C., providing in step a) at least one fluidized bed reactor comprising a heating zone and a reaction zone, the fluid stream provided in step b) being fed to the heating zone and optionally comprising one or more diluent gases and / or one or more inert gases, and in step c) heating the fluidized bed to a temperature of 200° C. to 500° C. for catalytic dehydration of the alcohol-containing feedstock to one or more olefins comprising the following sub-steps: - heating the fluidized bed to a temperature between 200 ° C and 500 ° C by passing an electric current through at least one heating zone of the fluidized bed; - transporting the heated particles from the heating zone to the reaction zone; - fluidizing the heated particles in a reaction zone to form a fluidized bed by passing a fluid stream comprising the alcohol-containing feedstock and an optional diluent gas upwardly through the bed in said reaction zone to effect endothermic catalytic dehydration of the alcohol-containing feedstock to convert the alcohol-containing feedstock into one or more olefins; Optionally, particles are recovered from the reaction zone and recycled to the heating zone.

[0125] For example, the conductive particles may be or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and / or mixtures thereof.

[0126] For example, the one or more inert gases are selected from nitrogen, carbon dioxide, argon, helium, saturated hydrocarbons having up to 10 carbon atoms, or any combination thereof. More preferably, the one or more inert gases are or include saturated hydrocarbons having up to 10 carbon atoms. Even more preferably, they are saturated hydrocarbons having 3 to 7 carbon atoms, or 4 to 6 carbon atoms. For example, the one or more inert gases are or include butane, pentane, naphtha, or combinations thereof.

[0127] For example, the one or more diluents may be selected from steam, hydrogen, methane, or any combination thereof.

[0128] The fluid stream may be a gas stream and / or a vapor stream.

[0129] For example, the at least one fluidized bed reactor is at least two fluidized bed reactors connected to each other, at least one of the at least two fluidized bed reactors being a heating zone and at least another of the at least two fluidized bed reactors being a reaction zone. Preferably, the at least one fluidized bed reactor being a heating zone is provided with a gravity or pneumatic transport means for transporting particles from the heating zone to the reaction zone, and / or the inventive installation is provided with a means configured to inject an alcohol-containing feedstock into the at least one fluidized bed reactor being a reaction zone. The installation does not have a means for injecting an alcohol-containing feedstock into the at least one fluidized bed reactor being a heating zone.

[0130] For example, at least one of the fluidized bed reactors is a single fluidized bed reactor with a heating zone at the bottom of the fluidized bed reactor and a reaction zone at the top of the fluidized bed reactor. Preferably, the system includes a means for injecting alcohol-containing feedstock and / or diluent between the two zones. The diameters of the heating and reaction zones may be different to achieve optimal conditions for heating in the bottom zone and optimal conditions for hydrocarbon conversion in the upper zone. Particles can be transferred from the heating zone to the reaction zone by entrainment and vice versa from the reaction zone back to the heating zone by gravity. Optionally, particles can be collected from the upper heating zone and transferred back to the lower heating zone by another transfer line.

[0131] In step c) catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out on an alcohol-containing feedstock. This means that an alcohol-containing feedstock is provided. It will be understood that the alcohol-containing feedstock is fed to a reaction zone and, if the heating zone is separate from the reaction zone, preferably the alcohol-containing feedstock is not fed to the heating zone. If the heating zone and the reaction zone are mixed (i.e., are the same zone), the fluid stream provided in step b) comprises the alcohol-containing feedstock.

[0132] Particles - Bed containing catalyst particles The bed particles further contain one or more solid acid catalysts for catalytic reaction. For example, the content of the catalyst particles is in the range of 15% to 90% by weight, more preferably 20% to 85% by weight, even more preferably 25% to 80% by weight, and most preferably 30% to 75% by weight, based on the total weight of the bed particles.

[0133] For example, the solid acid catalyst or catalysts may be N 2 The surface area measured by adsorption measurements is 50 m 2 / g~800m 2 / g, preferably 100m 2 / g~750m2 / g, more preferably 150m 2 / g~700m 2 / g range.

[0134] The catalyst used in the bed can be any one of a wide variety of dehydration catalysts. Such catalysts are generally known in the art and details in this regard are not believed to be necessary for a complete understanding of the invention. Exemplary dehydration catalysts include alumina, silica-alumina, activated clays, zeolites, and modified zeolites.

[0135] More specifically, the catalyst composition comprises one or more zeolites and / or one or more silicoaluminophosphate molecular sieves. Preferably, the one or more zeolites have a Si / Al ratio as measured by XRF spectroscopy of at least 10, more preferably at least 15, even more preferably at least 50, most preferably at least 100, even most preferably at least 150, or at least 180, or at least 200. Preferably, the one or more zeolites have a Si / Al ratio as measured by XRF spectroscopy of up to 1000. For example, the one or more zeolites have a Si / Al ratio as measured by XRF spectroscopy in the range of 10-1000, or 15-1000, or 50-1000, or 100-1000, or 180-1000, or 200-1000. As used herein, the term "Si / Al ratio" or "silicon / aluminum atomic ratio" or "silicon / aluminum ratio" refers to the Si / Al atomic ratio of the whole material, which can be measured by elemental analysis or by X-ray fluorescence (XRF) spectroscopy upon dissolution of the material. In particular, in the case of crystalline silicate materials, the stated Si / Al ratio applies to the whole material, not just the Si / Al framework of the crystalline silicate.

[0136] Preferably, the zeolite(s) have a relatively low acidity. The acidity of the catalytic zeolite(s) can be determined by temperature programmed desorption (TPD) of ammonia by measuring the amount of ammonia that adsorbs onto acid sites on the catalyst and the amount of ammonia remaining on the catalyst after contact with the catalyst by differential thermogravimetry.

[0137] For example, the zeolite or zeolites may be steamed prior to use in step (c), and then leached, if necessary, to dealuminate the zeolite or zeolites. In other words, the zeolite or zeolites contain at least less than 10% aluminum based on the non-dealuminized zeolite or zeolites. Preferably, the zeolite or zeolites are steamed at a temperature between 425°C and 870°C, more preferably between 540°C and 815°C, and / or at atmospheric pressure (i.e., about 0.1 MPa) and / or at a water pressure between 13 kPa and 200 kPa. Preferably, the steaming is carried out in an atmosphere containing 5-100% by volume steam based on the total volume of the atmosphere. The steaming preferably contains 5-100% by volume steam and 0-95% by volume inert gas based on the total volume of the steam. For example, the inert gas is nitrogen. A more preferred atmosphere comprises 72% by volume steam and 28% by volume nitrogen based on the total volume of the atmosphere, i.e., 72 kPa steam at 1 atmosphere pressure. The steaming is preferably carried out for a time in the range of 1 to 200 hours, more preferably 20 to 100 hours. As noted above, the steaming reduces the amount of tetrahedral aluminum in the crystalline silicate framework by forming alumina.

[0138] For example, the zeolite or zeolites include a structure having at least one 10-membered ring.

[0139] For example, the one or more zeolites are selected from the group of MFI, MEL, MOR, FER, MTT, MWW, TON, EUO, HEU, MFS and MRE families, and any combination thereof. Preferably, the one or more zeolites are selected from the group of MFI, MEL, FER, MTT, MWW, TON, EUO, MFS and MRE families, and any combination thereof. More preferably, the one or more zeolites are selected from the group of MFI, MEL and any combination thereof.

[0140] For example, when the zeolite is an MFI, the MFI zeolite preferably has a Si / Al ratio of at least 100 as measured by X-ray fluorescence spectroscopy of the zeolite or zeolites in solid form.

[0141] For example, when the zeolite is FER, it is preferred that the FER zeolite has a Si / Al ratio of at least 10, more preferably at least 15, as measured by X-ray fluorescence spectroscopy of the zeolite or zeolites in the solid state.

[0142] At Si / Al ratios above these values, alcohols are dehydrated to olefins with little side reactions leading to aldehydes, saturated hydrocarbons or undesirable components.

[0143] Preferably, the zeolite of the MFI family is one or more selected from ZSM-5, silicalite-1, boralite C or TS-1. More preferably, the zeolite of the MFI family is one or more selected from ZSM-5 or silicalite-1. Even more preferably, the zeolite of the MFI family is ZSM-5.

[0144] Preferably, the zeolite of the MEL family is one or more selected from ZSM-11, silicalite-2, boralite D, TS-2 or SSZ-46, more preferably the zeolite of the MEL family is ZSM-11.

[0145] Preferably, the MOR family zeolite is UZM-14.

[0146] Preferably, the zeolite of the FER family is one or more selected from ferrierite, FU-9 or ZSM-35.

[0147] Preferably, the MTT family zeolite is ZSM-23.

[0148] Preferably, the zeolite of the MWW family is one or more selected from MCM-22, PSH-3, ITQ-1 or MCM-49.

[0149] Preferably, the TON family zeolite is one or more selected from ZSM-22, Theta-1, or NU-10.

[0150] Preferably, the zeolite of the EUO family is selected from ZSM-50 or EU-1.

[0151] Preferably, the HEU family zeolite is clinopyrotite.

[0152] Preferably, the MFS family zeolite is ZSM-57.

[0153] Preferably, the MRE family zeolite is ZSM-48.

[0154] For example, the zeolite or zeolites further include boron.

[0155] For example, the one or more zeolites are one or more phosphorus-modified zeolites.

[0156] For example, the one or more zeolites is a dealuminated zeolite.

[0157] Advantageously, the zeolite or zeolites are in H type. In other words, less than 50% by weight, preferably less than 45% by weight or less than 40% by weight, relative to the total weight of the zeolite or zeolites, comprises one or more metal ions, preferably chosen from Na, Mg, Ca, La, Ni, Ce, Zn, Co or any combination thereof.

[0158] The following describes the zeolite(s) (i.e., crystalline silicate(s)) in more detail.

[0159] Zeolites (or zeolites) are microporous crystalline inorganic polymers based on a framework of XO4 tetrahedra bonded together by sharing oxygen ions, where X is trivalent (e.g. Al, B, ...) or tetravalent (e.g. Ge, Si, ...). The crystal structure of crystalline silicates is defined by the specific order in which the network of tetrahedral units are bonded together. The size of the pore openings of crystalline silicates is determined by the number of tetrahedral units or oxygen atoms required to form the pores and the nature of the cations present within the pores. Zeolites have a unique combination of properties: high internal surface area, uniform pores of one or more discrete sizes, ion exchange properties, good thermal stability and the ability to adsorb organic compounds. The pores of these crystalline silicates are similar in size to many organic molecules of practical importance, allowing them to control the ingress and egress of reactants and products, making them particularly selective in catalytic reactions. Crystalline silicates of MFI structure have a bidirectional intersecting pore system with the following pore sizes: linear channels along

[0010] : 0.53-0.56 nm, sinusoidal channels along

[0100] : 0.51-0.55 nm. Crystalline silicates of MEL structure have a bidirectional intersecting linear pore system with linear channels along

[0100] with pore sizes of 0.53-0.54 nm.

[0160] In a more specific embodiment, the dealumination of the crystalline silicate catalyst is carried out by heating the catalyst in steam to remove the aluminum from the crystalline silicate framework and contacting the catalyst with an aluminum complexing agent to extract the aluminum from the catalyst by removing it from the pores of the framework alumina deposited during the steaming step, thereby increasing the silicon / aluminum atomic ratio of the catalyst. Catalysts having high silicon / aluminum atomic ratios for use in the catalytic process of the present invention are produced by removing aluminum from commercially available crystalline silicates. As an example, a typical commercially available silicalite has a silicon / aluminum atomic ratio of about 120. In the present invention, commercially available crystalline silicates are modified by steaming to reduce the tetrahedral aluminum in the crystalline silicate framework and convert the aluminum atoms to octahedral aluminum in the form of amorphous alumina. In the cooking step, aluminum atoms are chemically removed from the crystalline silicate framework structure to form alumina particles. These particles may partially block the pores or channels in the framework, which may inhibit the dehydration process of the present invention. Thus, following the cooking step, the crystalline silicate can be leached or extracted to remove the amorphous alumina from the pores and at least partially restore the micropore volume. The overall effect of dealumination of the crystalline silicate is achieved by physical removal by the leaching step which forms a water-soluble aluminum complex and removes the amorphous alumina from the pores. Thus, the process of the present invention achieves substantially uniform dealumination over the entire pore surface of the catalyst by removing aluminum from the crystalline silicate framework and removing the formed alumina from the pores. This reduces the acidity of the catalyst. The reduction in acidity ideally occurs substantially uniformly over the entire pores bounded within the crystalline silicate framework. The steaming is followed by an extraction process to dealuminate the catalyst by leaching. Preferably, the aluminum is extracted from the crystalline silicate by a complexing agent which forms a soluble complex with alumina. The complexing agent is preferably an aqueous solution thereof.The complexing agent may comprise an organic acid such as citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, fumaric acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, trichloroacetic acid, trifluoroacetic acid, or a salt of these acids (e.g., the sodium salt), or a mixture of two or more of these acids or salts. The complexing agent may comprise an inorganic acid such as nitric acid, halogen acid, sulfuric acid, phosphoric acid, or a salt of these acids or a mixture of these acids. The complexing agent may also comprise a mixture of these organic and inorganic acids or their corresponding salts. The complexing agent for aluminum preferably forms a water-soluble complex with aluminum, in particular to remove alumina formed from crystalline silicates during the steaming step. A particularly preferred complexing agent may comprise an amine, preferably ethylenediaminetetraacetic acid (EDTA) or a salt thereof, in particular the sodium salt thereof. In a preferred embodiment, the silicon / aluminum ratio of the framework is increased in this manner to a value of about 150-1000, more preferably at least 200-1000.

[0161] After the aluminium leaching step, the crystalline silicate may be washed, for example with distilled water, and then preferably dried at elevated temperature, for example at about 110°C.

[0162] Additionally, if an alkali metal or alkaline earth metal has been used in the preparation of the catalyst of the present invention, the molecular sieve may be subjected to an ion-exchange step, conventionally carried out in aqueous solution using ammonium salts or inorganic acids.

[0163] After the dealumination step, the catalyst may be calcined, for example, at a temperature of from 400 to 800° C. and / or at atmospheric pressure and / or for a time in the range of from 1 to 10 hours.

[0164] Prior to use in dehydration, the crystalline silicates may be subjected to a variety of treatments including ion exchange, modification with metals (including but not limited to alkali, alkaline earth, transition, or rare earth elements), passivation of the exterior surface, modification with phosphorus compounds, steam treatment, acid treatment or other dealumination methods or combinations thereof.

[0165] For example, the one or more silica aluminophosphate molecular sieves are selected from the AEI, CHA, and AEL family groups and any combination thereof. Preferably, one silica aluminophosphate molecular sieve selected from the AEI family is SAPO-18. Preferably, one silica aluminophosphate molecular sieve selected from the CHA family is SAPO-34. Preferably, one silica aluminophosphate molecular sieve selected from the AEL family is SAPO-11.

[0166] SAPO molecular sieves are based on ALPO and have an Al / P ratio of essentially 1 atom / atom. During the synthesis, silicon precursors are added to intercalate silicon into the ALPO framework and form acidic sites on the surface of the pores of the 10-ring sieve. The silicon content ranges from 0.1 to 10 atomic % (Al+P+Si is 100).

[0167] In another particular embodiment, the one or more solid acid catalysts are formed, for example, into pellets. The one or more zeolites are preferably mixed with a binder, preferably an inorganic binder, and formed into a desired shape, for example, into pellets. The binder is selected to withstand the temperature and other conditions used in the dehydration process of the present invention. The binder is an inorganic material selected from clay, silica, metal silicates, gels containing metal oxides such as ZrO2 and / or metals or mixtures of silica and metal oxides. If the binder used in combination with the crystalline silicate is itself catalytically active, this may alter the conversion and / or selectivity of the catalyst. When an inert material is used as a binder, it functions well as a diluent to control the amount of conversion, and the product can be obtained economically and orderly without using other means to control the reaction rate. It is desirable to provide a catalyst with good crush strength. This is because it is desirable to prevent the catalyst from breaking down into powdery materials in commercial use. Clay or oxide binders are usually used only for the purpose of improving the crush strength of the catalyst. A particularly preferred binder for the catalyst of the present invention comprises silica. The relative proportions of the fine crystalline silicate material and the inorganic oxide matrix of the binder can vary widely. Typically, the binder content ranges from 5 to 95% by weight based on the total weight of the composite catalyst (the composite catalyst being a mixture of one or more solid acid materials and a binder), more typically from 20 to 50% by weight based on the weight of the composite catalyst. Such mixtures of crystalline silicate and inorganic oxide binder are also called formulated crystalline silicates. When the catalyst is mixed with the binder, the catalyst can be formulated into spheres or spray-dried powders.

[0168] Spherical shapes can be produced by rotary granulators or oil drop techniques. Additionally, small spheres can be produced by spray drying the catalyst-binder suspension. The compounded crystalline silicate is calcined in air or inert gas, typically at temperatures between 200 and 900 °C for 1 to 48 hours.

[0169] The binder is preferably free of aluminum compounds such as alumina because, as noted above, the preferred catalysts for use in the present invention are dealuminated to increase the silicon / aluminum ratio of the crystalline silicate. The presence of alumina in the binder would result in additional excess alumina if the binding step is carried out before the aluminum extraction step. Mixing the aluminum-containing binder with the crystalline silicate catalyst after aluminum extraction would result in the catalyst being realuminated.

[0170] Additionally, mixing of the catalyst and binder can occur either before or after the cooking and extraction steps.

[0171] In another embodiment, the catalyst is a crystalline silicate catalyst having a monoclinic structure, for example prepared by a process comprising the steps of providing a crystalline silicate of MFI type having a silicon / aluminium atomic ratio of less than 80, steaming the crystalline silicate, and then leaching the aluminium from the zeolite by contacting it with an aqueous solution of a leaching agent to provide a silicon / aluminium atomic ratio in the catalyst of at least 180, whereby the catalyst has a monoclinic structure. Preferably, in the steaming step, the temperature is between 425 and 870°C, more preferably between 540 and 815°C, and / or the water pressure is between 13 and 200 kPa. Preferably, the aluminium is removed by leaching by contacting the zeolite with an aqueous solution of an aluminium complexing agent which tends to form a soluble complex with alumina to form a water soluble compound.

[0172] In this preferred method for producing monoclinic crystalline silicate, the starting crystalline silicate catalyst is of MFI type with orthorhombic symmetry and has a relatively low silicon / aluminum atomic ratio that can be synthesized without organic template molecules, and the crystalline silicate catalyst obtained after steaming and aluminum removal has a relatively high silicon / aluminum atomic ratio and monoclinic symmetry. The crystalline silicate can be ion-exchanged with ammonium ions after the aluminum removal step. The MFI type crystalline silicate exhibits orthorhombic symmetry and is known in the art to be in the space group Pnma. The X-ray diffraction diagram of this orthorhombic structure has one peak at d = about 0.365 nm, d = about 0.305 nm, and d = about 0.300 nm (see EP 0146524).

[0173] The starting crystalline silicate has a silicon / aluminum atomic ratio of less than 80. A typical ZSM-5 catalyst has 3.08 wt% Al2O3, 0.062 wt% Na2O, and is 100% orthorhombic, based on the total weight of the ZSM-5 catalyst. The silicon / aluminum atomic ratio of this catalyst is 26.9.

[0174] The steaming step is carried out in the manner already described. The steaming step results in the formation of alumina and reduces the amount of tetrahedral aluminium in the crystalline silicate framework. The aluminium leaching or extraction step is also carried out as described above. In the aluminium leaching step, the crystalline silicate is immersed in an acidic solution or in a solution containing a complexing agent, followed by heating, preferably for a long period of time, for example 18 hours, at reflux conditions (boiling temperature at which the condensed vapours return completely). After the aluminium leaching step, the crystalline silicate is washed, for example with distilled water, and then preferably dried at elevated temperature, for example around 110°C. Optionally, the crystalline silicate is ion-exchanged with ammonium ions, for example by immersing the crystalline silicate in an aqueous solution of NH4Cl.

[0175] The catalyst is finally calcined at an elevated temperature, for example at least 400° C. Calcination times are typically around 3 hours.

[0176] The resulting crystalline silicate has monoclinic symmetry and belongs to the space group P21 / n. The X-ray diffraction diagram of the monoclinic structure shows three doublets at approximately d = 0.36, 0.31 and 0.19 nm. The presence of these doublets is characteristic of monoclinic symmetry. More specifically, the doublet around d = 0.36 consists of two peaks at d = 0.362 nm and d = 0.365 nm. In contrast, the orthorhombic structure has a single peak at d = 0.365 nm.

[0177] The presence of monoclinic structure can be quantified by comparing the X-ray diffraction line intensity around d=0.36 nm. When a mixture of MFI crystalline silicates with pure orthorhombic and pure monoclinic structures is prepared, the composition of the mixture can be expressed as the monoclinicity index (%). The X-ray diffraction pattern is recorded and the peak heights at d=0.362 nm for monoclinic and d=0.365 nm for orthorhombic are measured and denoted Im and Io, respectively. The relationship required to determine the monoclinicity of an unknown sample is given by the linear regression line between the monoclinicity index and Im / Io: Monoclinicity Index %=(axIm / Io-b)x100, where a and b are the regression parameters.

[0178] Such monoclinic crystalline silicates can be prepared without the use of organic template molecules during the crystallization step, with a relatively high silicon / aluminum atomic ratio, at least 100, preferably greater than about 200. Furthermore, the crystallite size of the monoclinic crystalline silicate can be maintained relatively small, typically less than 1 micron, more typically about 0.5 microns. This is because the crystallite size of the starting crystalline silicate is small and is not enlarged by subsequent process steps. Because the crystallite size can be maintained relatively small, the catalytic activity is correspondingly increased. This is more advantageous than known monoclinic crystalline silicate catalysts. The present monoclinic crystalline silicate catalyst is more advantageous than known monoclinic crystalline silicate catalysts, since known monoclinic crystalline silicate catalysts are prepared in the presence of organic template molecules, have inherently large crystallite sizes, typically greater than 1 micron, and have high Si / Al ratios.

[0179] The phosphorus-modified zeolite or zeolites as catalysts can be prepared based on MFI, MOR, MEL, HEU or FER crystalline aluminosilicate molecular sieves with an initial Si / Al ratio advantageously between 4 and 500. The P-modified zeolites of this recipe can be obtained based on inexpensive crystalline silicates with low Si / Al ratios (less than 30).

[0180] As an example, the above P-modified zeolites can be produced by a process having the following sequence: - MFI, MEL, FER, MOR, HEU + or NH4 + Selecting a zeolite of the type (advantageously with a Si / Al ratio between 4 and 500), - introducing P under conditions effective to advantageously incorporate at least 0.05 wt. % P based on the total weight of the selected zeolite; - If liquid is present, separate the solids from the liquid, - an optional washing step, a drying step or an optional drying step followed by a washing step, - The firing process is carried out.

[0181] The above low Si / Al ratio zeolites are pre-prepared with or without the direct addition of organic templates.

[0182] Optionally, the process for producing the P-modified zeolite described above includes a steaming step, preferably followed by a leaching step. In this process, the steaming step is followed by leaching. It is generally known to those skilled in the art that when a zeolite is steamed, aluminum leaves the zeolite framework and remains as aluminum oxide inside and outside the zeolite pores. This transformation is known as dealumination of the zeolite. Treating the steamed zeolite with an acid solution dissolves the aluminum oxide outside the framework. This transformation is known as leaching. The zeolite is then advantageously separated by filtration and optionally washed. A drying step can also be performed between the filtration and washing steps. The washing solution can be separated from the solids, for example by filtration, or evaporated.

[0183] Phosphorus can be introduced by any means, for example, according to the recipes described in the following Patent Documents 2 and 3. [Patent Document 2] US Patent No. US3911041 [Patent Document 3] US Patent No. US5573990 [Patent Document 4] US Patent No. US6797851

[0184] Catalysts made with P-modified zeolite may be the P-modified zeolite itself, or may be P-modified zeolite blended catalysts in combination with other materials that impart additional hardness or catalytic activity to the finished catalyst product.

[0185] The separation of the liquid and solid is advantageously carried out by filtration at a temperature between 0 and 90° C., by centrifugation at a temperature between 0 and 90° C., by evaporation or by an equivalent method.

[0186] Optionally, the zeolite can be dried after separation and before washing. Advantageously, drying is carried out at a temperature between 40 and 600° C. and / or for a time advantageously between 1 and 10 hours. This drying can be carried out either under static conditions or with a gas stream. Air, nitrogen or any inert gas can be used.

[0187] The washing step can be performed with cold water (<40°C) during the filtration (separation step), with hot water (>40°C, <90°C), or by treating the solids with an aqueous solution (1 kg solids / 4 liters of aqueous solution) under reflux conditions for 0.5-10 hours, followed by evaporation or filtration.

[0188] The final calcination step is advantageously carried out at a temperature between 400 and 700 ° C, either in static conditions or in a gas stream. Air, nitrogen or any inert gas can be used.

[0189] In one particular embodiment, the phosphorus-modified zeolite is prepared by a process comprising the steps of: - MFI, MEL, FER, MOR, HEU + or NH4 + Selecting a zeolite based on its morphology (advantageously having a Si / Al ratio between 4 and 500, in a particular embodiment between 4 and 30); - steam treatment at a temperature between 400 and 870 °C and / or for a period between 0.01 and 200 hours, - leaching with an aqueous acid solution under conditions effective to remove most of the Al from the zeolite; - introducing P using an aqueous solution containing a P source under conditions effective to advantageously introduce at least 0.05 wt. % P based on the total weight of the selected zeolite; - Separating solids from liquids, - carrying out an optional cleaning step or an optional drying step or an optional cleaning step after the drying step, - Bake.

[0190] There may be optional intermediate steps between the steaming and leaching steps, such as contact with silica powder and drying.

[0191] Advantageously, the selected MFI, MEL, FER, MOR, HEU (or H + or NH4 +The forms MFI, MEL, FER, MOR, HEU) have an initial atomic ratio Si / Al of 100 or less, and in a particular embodiment, 4 to 30. + or NH4 + The conversion into the above-mentioned form is known per se and is described in [Patent Document 5] and [Patent Document 6]. [Patent Document 5] US Patent No. US3911041 [Patent Document 6] US Patent No. US5573990

[0192] Advantageously, the final P content is at least 0.05 wt.%, preferably between 0.3 wt.% and 7 wt.%, relative to the total weight of the phosphorus modified zeolite. Advantageously, the phosphorus modified zeolite contains at least 10% less Al relative to the parent zeolites MFI, MEL, FER, MOR and HEU, since it has been extracted and removed from the zeolite by leaching.

[0193] The zeolite is then separated from the washing solution or dried without being separated from the washing solution, preferably by filtration, and then calcined, for example at 400° C. for 2 to 10 hours.

[0194] The temperature of the steaming step is preferably between 420 and 870°C, more preferably between 480 and 760°C. The pressure is preferably atmospheric and / or the water pressure can be in the range of 13 to 100 kPa. The steam atmosphere preferably comprises 5 to 100% by volume of steam and 0 to 95% by volume of an inert gas, based on the total volume of the steam atmosphere. For example, the inert gas is nitrogen. The steaming is preferably carried out for 0.01 to 200 hours, advantageously 0.05 to 200 hours, more preferably 0.05 to 50 hours. The steaming reduces the amount of tetrahedral aluminum in the crystalline silicate framework by forming alumina.

[0195] Leaching can be carried out with organic acids such as citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, fumaric acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, trichloroacetic acid, trifluoroacetic acid, or salts of these acids (e.g., sodium salts), or mixtures of two or more of these acids or salts. Other inorganic acids can include inorganic acids such as nitric acid, hydrochloric acid, methanesulfuric acid, phosphoric acid, phosphonic acid, sulfuric acid, or salts of these acids (e.g., sodium or ammonium salts), or mixtures of two or more of these acids or salts.

[0196] The residual phosphorus content can be adjusted by the phosphorus concentration in the aqueous acid solution containing the phosphorus source, the drying conditions and the washing procedure (if any). A drying step can also be performed between the filtration and washing steps.

[0197] The above phosphorus modified zeolite can be used as a catalyst by itself. In another embodiment, it can be combined and formulated into a catalyst with other materials that provide additional hardness or catalytic activity to the finished catalyst product. The materials that can be mixed with the phosphorus modified zeolite can be various inert or catalytically active materials or various binder materials. These materials include compositions such as kaolin and other clays, various forms of rare earth metals, phosphates, alumina or alumina sol, titania, zirconia, quartz, silica or silica sol, and mixtures thereof. These components are effective in densifying the catalyst and increasing the strength of the formulated catalyst. The catalyst can also be formed into spheres or spray dried particles. The amount of P modified zeolite in the final catalyst product is 10-90 weight percent of the total catalyst, preferably 20-70 weight percent of the total catalyst.

[0198] Bed containing particles - conductive particles To achieve the temperatures necessary for catalytic dehydration of one or more alcohols to one or more olefins, at least 10 wt. % of the particles, based on the total weight of the particles in the bed, are electrically conductive and have a resistivity in the range of 0.001 Ohm·cm to 500 Ohm·cm at 400°C.

[0199] For example, the conductive particles of the bed may be or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof.

[0200] For example, 50% by weight to 100% by weight of the conductive particles of the bed is one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixtures thereof, based on the total weight of the conductive particles of the bed, and the content thereof is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, and most preferably 90% by weight to 100% by weight.

[0201] In one embodiment, 50% to 100% by weight of the conductive particles in the bed are free of graphite and / or carbon black, preferably 60% to 95% by weight, more preferably 70% to 90% by weight, and even more preferably 75% to 85% by weight are free of graphite and / or carbon black, based on the total weight of the conductive particles in the bed.

[0202] For example, the content of the conductive particles is in the range of 10% by weight to 100% by weight, preferably 15% by weight to 95% by weight, more preferably 20% by weight to 90% by weight, even more preferably 25% by weight to 80% by weight, and most preferably 30% by weight to 75% by weight, based on the total weight of the particles in the bed.

[0203] For example, the content of conductive particles relative to the total weight of the bed is at least 12% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, even more preferably at least 25% by weight, and most preferably at least 30% by weight or at least 40% by weight or at least 50% by weight or at least 60% by weight, relative to the total weight of the particles in the bed.

[0204] For example, the conductive particles have a resistivity in the range of 0.005 to 400 ohm·cm at 400°C, preferably in the range of 0.01 to 300 ohm·cm at 400°C, more preferably in the range of 0.05 to 150 ohm·cm at 400°C, and most preferably in the range of 0.1 to 100 ohm·cm at 400°C.

[0205] For example, the conductive particles have a resistivity of at least 0.005 ohm-cm at 400°C, preferably at least 0.01 ohm-cm at 400°C, more preferably at least 0.05 ohm-cm at 400°C, even more preferably at least 0.1 ohm-cm at 400°C, and most preferably at least 0.5 ohm-cm at 400°C.

[0206] For example, the conductive particles have a resistivity of at most 400 ohm-cm at 400° C. Preferably, the resistivity is at most 300 ohm-cm at 400° C., more preferably at most 200 ohm-cm at 400° C., even more preferably at most 150 ohm-cm at 400° C., and most preferably at most 100 ohm-cm at 400° C.

[0207] For example, the particles of the bed have an average particle size of 5 to 300 μm, preferably 10 to 200 μm, more preferably 30 to 150 μm, as measured by sieving according to ASTM D4513-11.

[0208] For example, the conductive particles of the bed have an average particle size, as measured by sieving according to ASTM D4513-11, in the range of 5 to 300 μm, preferably in the range of 10 to 200 μm, and more preferably in the range of 30 to 150 μm.

[0209] Electrical resistance is measured by a four-probe DC method using an ohmmeter. A dense powder sample formed into a cylindrical pellet is placed between the probe electrodes. The resistivity is determined from the measured resistance R by applying the known formula ρ=RxA / L, where L is the distance between the probe electrodes (usually a few millimeters) and A is the electrode area.

[0210] The conductive particles of the bed exhibit electronic, ionic or mixed electronic-ionic conductivity. The ionic bonds in many refractory compounds allow ionic diffusion and, accordingly, ionic conduction under the influence of an electric field and suitable temperature conditions.

[0211] The electrical conductivity σ is the proportional constant between the current density j and the electric field E, and is expressed by the following equation: σ=j / E=Σc i x Z i qxμ (where ci is the carrier density (number / cm 3 ), i is the mobility (cm 2 / Vs), Z i q is the charge of the i-th charge carrier (q=1.6x10 -19 C) is

[0212] The large order of magnitude differences between metals, semiconductors, and insulators are usually due to differences in c, not μ, while the high conductivity of electronic and ionic conductors is usually due to the much higher mobility of electronic species than of ionic species.

[0213] The most common materials available for resistance heating can be divided into nine groups: (1) Metal alloys suitable for temperatures up to 1200-1400°C; (2) Non-metallic resistors such as silicon carbide (SiC), molybdenum disilicide (MoSi2), nickel disilicide (NiSi), sodium disilicide (Na2Si), magnesium disilicide (Mg2Si), platinum disilicide (PtSi), titanium disilicide (TiSi2), and tungsten disilicide (WSi2) up to 1600-1900°C; (3) carbon-containing materials; (4) Metal carbides, (5) metal nitrides, (6) metal phosphides, (7) superionic conductors, (8) Phosphate electrolyte.

[0214] The first group of metal alloys used at temperatures up to 1150 - 1250 °C can consist of Ni - Cr alloys with low Fe content (0.5 - 2.0%), preferably Ni - Cr alloys (80% Ni, 20% Cr) and (70% Ni, 30% Cr). Increasing the Cr content improves the oxidation resistance of the material at high temperatures. The second group of metal alloys with three components is Fe - Ni - Cr alloys, which have a maximum operating temperature of 1050 - 1150 °C in an oxidizing atmosphere but can also be used in a reducing atmosphere. Fe - Cr - Al (chemical composition 15 - 30% Cr, 2 - 6% Al, the rest Fe) is protected from corrosion by the surface layer of oxides of Cr and Al and can be used at 1300 - 1400 °C in an oxidizing atmosphere. Silicon carbide as a non - metallic resistor shows a wide range of resistivity, and its resistivity can be controlled by the synthesis method and the presence of impurities such as aluminum, iron, oxides, nitrogen, excess carbon, and silicon, becoming non - stoichiometric silicon carbide. Generally, silicon carbide shows high resistivity at low temperatures and good resistivity in the range of 500 - 1200 °C. In another embodiment, the non - metallic resistor does not contain silicon carbide and / or can include molybdenum disilicide (MoSi2), nickel silicide (NiSi), sodium silicide (Na2Si), magnesium silicide (Mg2Si), platinum silicide (PtSi), titanium silicide (TiSi2), tungsten silicide (WSi2) or mixtures thereof.

[0215] Some sublattice disordered oxides or sulfides show high ionic transport ability with increasing temperature. These are LiAlSiO4, Li 10 GeP2S 12 , Li 3.6 Si 0.6 P 0.4 O4, NaSICON (sodium (Na) superionic conductor) (general formula Na1 + xZr2P3 - xSixO 12 , 0 < x < 3, for example Na3Zr2PSi2O 12 (x = 2) or sodium beta - alumina (NaAl 11 O 17 , Na 1.6 Al11 O 17.3 and / or Na 1.76 Li 0.38 Al 10.62 O 17 ) and other superionic conductors.

[0216] Phosphate electrolytes such as LiPO4 or LaPO4 can also be used as conductive particles.

[0217] Metal carbides, metal nitrides and metal phosphides can also be selected as conductive particles. For example, the metal carbide is selected from iron carbide (Fe3C), molybdenum carbide (such as a mixture of MoC and Mo2C). For example, the one or more transition metal nitrides are selected from zirconium nitride (ZrN), tungsten nitride (such as a mixture of W2N, WN and WN2), vanadium nitride (VN), tantalum nitride (TaN) and / or niobium nitride (NbN). For example, the one or more metal phosphides are selected from copper phosphide (Cu3P), indium phosphide (InP), gallium phosphide (GaP), sodium phosphide (Na3P), aluminum phosphide (AlP), zinc phosphide (Zn3P2) and / or calcium phosphide (Ca3P2).

[0218] In one preferred embodiment of the invention, conductive particles that exhibit low resistivity at high temperatures can be heated by external means before reaching a high enough temperature to replace electrical resistive heating, or mixed with a solid that has a low enough resistivity at low temperatures that the resistivity of the mixture can heat the fluidized bed to the desired reaction temperature.

[0219] For example, the conductive particles of the bed are or include silicon carbide, for example, at least 10% by weight of the conductive particles of the bed are silicon carbide particles and have a resistivity in the range of 0.001 ohm·cm to 500 ohm·cm at 400° C., based on the total weight of the conductive particles of the bed.

[0220] In an embodiment in which the conductive particles of the bed are or comprise silicon carbide, it will be advantageous for the skilled person to carry out a step of preheating the fluidized bed reactor with a gas stream before carrying out the endothermic reaction in the fluidized bed reactor. Advantageously, this gas stream is a stream of an inert gas, i.e. nitrogen, argon, helium, methane, hydrogen or steam. The temperature of the gas stream can be at least 300°C, or at least 350°C, or at least 400°C, or at least 450°C, and / or up to 500°C. Advantageously, the temperature of the gas stream is between 300°C and 500°C. Said gas stream of inert gas can also be used as a fluidizing gas. Preheating of said gas stream of inert gas is carried out by conventional means, including the use of electrical energy. The temperature of the gas stream used for preheating the bed does not have to reach the reaction temperature.

[0221] In fact, because of the high resistivity of silicon carbide at room temperature, it is useful to heat the fluidized bed by external means to facilitate initiation of the reaction. Preferably, the fluidized bed reactor does not have a heating means. Once the bed has been heated to the desired temperature, the use of a hot gas stream is no longer necessary.

[0222] However, in one embodiment, the conductive particles of the bed are or include a mixture of silicon carbide particles and conductive particles different from the silicon carbide particles.

[0223] The preheating step can also be used when conductive particles other than silicon carbide particles are present in the bed. For example, the preheating step can be used when the content of silicon carbide in the conductive particles of the bed is 80% by weight or more, such as 85% by weight or more, such as 90% by weight or more, such as 95% by weight or more, such as 98% by weight or more, such as 99% by weight or more, based on the total weight of the particles of the bed. However, the preheating step can be used whatever the content of silicon carbide particles in the bed is. In an embodiment in which the conductive particles of the bed are or include a mixture of silicon carbide particles and conductive particles other than silicon carbide particles, the conductive particles of the bed can comprise 10% by weight to 99% by weight of silicon carbide particles based on the total weight of the conductive particles of the bed. The content is preferably 15% by weight to 95% by weight, more preferably 20% by weight to 90% by weight, even more preferably 25% by weight to 80% by weight, and most preferably 30% by weight to 75% by weight.

[0224] For example, the conductive particles of the bed may be or include a mixture of silicon carbide particles and conductive particles different from silicon carbide particles, and the conductive particles of the bed may include at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, and most preferably at least 80% by weight of silicon carbide particles based on the total weight of the conductive particles of the bed.

[0225] In one embodiment, the conductive particles of the bed comprise from 10% to 90% by weight, preferably from 15% to 95% by weight, more preferably from 20% to 90% by weight, even more preferably from 25% to 80% by weight, and most preferably from 30% to 75% by weight of conductive particles different from silicon carbide particles, based on the total weight of the conductive particles of the bed.

[0226] However, it would be important to keep the content of conductive particles other than silicon carbide particles in the mixture very low.Thus, in one embodiment, the conductive particles of the bed are or comprise a mixture of silicon carbide particles and conductive particles other than silicon carbide particles, and the conductive particles of the bed comprise 1% to 20% by weight of conductive particles other than silicon carbide, preferably 2% to 15% by weight, more preferably 3% to 10% by weight, even more preferably 4% to 8% by weight of conductive particles other than silicon carbide, based on the total weight of the conductive particles of the bed.

[0227] For example, the conductive particles of the bed may be or include a mixture of silicon carbide particles and particles other than silicon carbide particles, and the particles other than silicon carbide particles may be or include molybdenum disilicide particles.

[0228] Thus, in one embodiment, the conductive particles are a combination of silicon carbide particles and molybdenum disilicide particles. The conductive particles heat up when an electric current is applied to the fluidized bed reactor, and contribute to increasing and / or maintaining the temperature within the reactor by fluidization. The Joule heat of the molybdenum disilicide can accelerate the heating of the reactants and / or other particles present in the fluidized bed reactor.

[0229] The average particle size of the molybdenum disilicide is preferably in the range of 1 to 400 μm, preferably in the range of 5 to 300 μm, more preferably in the range of 10 to 200 μm, and most preferably in the range of 30 to 150 μm, as measured by sieving according to ASTM D4513-11.

[0230] The presence of molybdenum disilicide particles in the bed allows the process of the present invention to be applied with or without a preheating step, preferably without a preheating step. Indeed, when electricity is applied to the fluidized bed reactor, the molybdenum disilicide particles heat up and contribute to increasing and / or maintaining the desired temperature in the reactor by fluidization.

[0231] Silicon Carbide Particles For example, the silicon carbide may be selected from sintered silicon carbide, nitride bonded silicon carbide, recrystallized silicon carbide, reaction bonded silicon carbide, and mixtures thereof.

[0232] Sintered SiC (SSiC) is a self-bonding material that contains less than 1% by weight of a sintering aid, usually boron.

[0233] Recrystallized silicon carbide (RSiC) is a high-purity SiC material sintered by an evaporation-condensation process without any additives.

[0234] Nitride-bonded silicon carbide (NBSC) is made by adding fine silicon powder along with silicon carbide particles, and finally sintering in a nitrogen furnace in the presence of mineral additives. The silicon carbide is bonded by the silicon nitride phase (Si3N4) that forms during nitridation.

[0235] Reaction bonded silicon carbide (RBSC), also known as siliconized silicon carbide or SiSiC, is a type of silicon carbide produced by the chemical reaction of porous carbon or graphite with molten silicon. The silicon reacts with the carbon to form silicon carbide, bonding the silicon carbide particles together. The excess silicon fills the remaining pores in the body, producing a dense SiC-Si composite. Because traces of silicon remain, reaction bonded silicon carbide is often referred to as siliconized silicon carbide. This process is known by various names, including reaction bonding, reaction sintering, autogenous bonding, or melt infiltration.

[0236] Generally, the resistivity of high-purity SiC particles exceeds 1000 Ohm.cm, while sintered, reaction-bonded, and nitride-bonded ones show resistivities of about 100-1000 depending on the impurities in the SiC phase. The electrical resistivity of bulk polycrystalline SiC ceramics shows a wide range of resistivities depending on the sintering additives and heat treatment conditions (Non-Patent Document 6, Non-Patent Document 7). High-purity SiC polytypes have high electrical resistivities (>106 Ω·cm) due to their large band gap energy, but the electrical resistivity of SiC is affected by doping impurities. N and P act as n-type dopants and reduce the resistivity of SiC, while Al, B, Ga, and Sc act as p-type dopants. SiC doped with Be, O, and V has very high insulating properties. N is considered the most efficient dopant to improve the electrical conductivity of SiC. For N-doping of SiC (to reduce resistivity), Y2O3 and Y2O3-REM2O3 (REM, rare earth metals = Sm, Gd, Lu) are used as sintering additives to efficiently grow conductive SiC grains containing N donors. N-doping of SiC grains is promoted by the addition of nitrides (AlN, BN, Si3N4, TiN, ZrN) or combinations of nitrides and Re2O3 (AlN_REM2O3 (REM = Sc, Nd, Eu, Gd, Ho, Er) or TiN_Y2O3). [Non-Patent Document 6] Journal of the European Ceramic Society, Volume 35, Issue 15, December 2015, Pages 4137; [Non-Patent Document 7] Ceramics International, Volume 46, Issue 4, March 2020, Pages 5454

[0237] equipment The terms "bottom" and "top" are understood with respect to the general orientation of the installation or fluidized bed reactor. Thus, "bottom" means closer to the ground than "top" along the vertical axis. The same references in different figures indicate identical or similar elements.

[0238] FIG. 1 shows a conventional fluidized bed reactor 1, which includes a reaction vessel 3, a bottom fluid nozzle 5 for introducing an alcohol-containing feedstock, an optional inlet 7 for feeding the material, an optional outlet 9 for discharging the material, a gas outlet 11 and a bed 15. In the fluidized bed reactor 1 of FIG. 1, heat is provided by preheating the feedstock, for example by combustion of a fossil fuel, using heating means 17 located at the level of the lines supplying the fluidizing gas and the alcohol-containing feedstock to the reactor.

[0239] The equipment of the present invention will now be described with reference to Figures 2 to 5. For simplicity, internal devices used in fluidized bed reactors known to those skilled in the art, such as bubble breakers, deflectors, particle termination devices, cyclones, ceramic wall coatings, thermocouples, etc., are not shown.

[0240] FIG. 2 shows a first installation with a fluidized bed reactor 19 with the same heating and reaction zones, which has a reaction vessel 3, a bottom fluid nozzle 21 for introducing a fluidizing gas and an alcohol-containing feedstock, an optional inlet 7 for the input of materials, an optional outlet 9 for the discharge of materials and a gas outlet 11. The fluidized bed reactor 19 in FIG. 2 shows two electrodes 13 submerged in the bed 25.

[0241] FIG. 3 illustrates an embodiment in which at least one fluidized bed reactor 19 includes a heating zone 27 and a reaction zone 29, with the heating zone 27 being the bottom zone and the reaction zone 29 being on top of the heating zone 27. One or more fluid nozzles 23 feed the alcohol-containing feedstock to the reaction zone from a distributor 33. As can be seen in FIG. 3, the one or more fluid nozzles 23 can be connected to the distributor 33 to distribute the ammonia-containing feedstock within the bed 25.

[0242] FIG. 4 shows an installation with at least one fluidized bed reactor 18 with at least two zones, an outer zone being a heating zone 27 and an inner zone being a reaction zone 29. Heated particles in bed 25 are passed from the outer zone to the inner zone by one or more openings 41 and mixed with alcohol-containing feed and / or steam. At the end of the reaction zone, the particles are separated from the reaction products and transferred to the heating zone.

[0243] FIG. 5 shows an installation in which at least two fluidized bed reactors (37, 39) are connected to each other, where at least one fluidized bed reactor is a heating zone 27 and at least one fluidized bed reactor is a reaction zone 29.

[0244] The present invention provides an equipment for use in a process for endothermic catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins. The equipment of the present invention comprises the following i) to iii): i) a current-carrying fluidized bed unit with at least one fluidized bed reactor (18, 19, 37, 39), which unit comprises: - at least two electrodes 13, - reaction vessel 3, - one or more fluid nozzles (21, 23) for introducing into at least one fluidized bed reactor (18, 19, 37, 39) an alcohol-containing feedstock comprising one or more alcohols having at least two carbon atoms and, optionally, one or more inert gases and / or one or more diluent gases; and - 25 beds with particles, the particles of bed 25 include conductive particles and particles of a catalyst composition, at least 10% by weight of the particles of the bed based on the total weight of the particles of bed 25 are conductive and have a resistivity in the range of 0.001 Ohm·cm to 500 Ohm·cm at 400° C., and the catalyst composition includes one or more solid acid catalysts.

[0245] In particular, the present invention provides an apparatus for the endothermic catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins, the apparatus comprising: i) A current-carrying fluidized bed unit comprising at least one fluidized bed reactor (18, 19, 37, 39) having: - at least two electrodes (13), - reaction vessel (3), - one or more fluid nozzles (21, 23) for introducing into at least one fluidized bed reactor (18, 19, 37, 39) an alcohol-containing feedstock comprising one or more alcohols having at least two carbon atoms and, optionally, one or more inert gases and / or one or more diluent gases, - bed containing particles (25), ii) a product recovery unit; iii) an olefin conversion unit selected from an olefin oligomerization unit, an aromatic alkylation unit or an olefin oligomerization and aromatic alkylation unit; Including, The above product recovery is downstream of the current-flow moving bed unit and upstream of the olefin conversion unit; The bed particles include conductive particles and particles of a catalyst composition, at least 10 wt. % of the bed particles based on the total weight of the bed particles are conductive and have a resistivity in the range of 0.001 ohm·cm to 500 ohm·cm at a temperature of 400°C, and the catalyst composition includes one or more solid acid catalysts.

[0246] Preferably, at least two of the electrodes include or are made of tantalum.

[0247] Details regarding the oligomerization step (e), i.e. the olefin oligomerization unit, which is an olefin conversion unit, that can be carried out on one or more olefins recovered in step (d) are described in [Non-Patent Document 8] and [Non-Patent Document 9] below. [Non-Patent Document 8] “Applications of light olefin oligomerization to the production of fuels and chemicals” (Nicholas CP, Applied Catal. A: General, 2017, 543, 82-97) [Non-Patent Document 9] "Hydrocarbon Biorefinery" (ISBN 978-0-12-823306-1).

[0248] Details of the aromatic alkylation step (f), i.e., the aromatic alkylation unit, which may be carried out on one or more olefins recovered in step (d), are described in the following non-patent literature 10 and 11. [Non-Patent Document 10] "Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes" (Degnan Jr. TF, et al., Applied Catal. A: General, 2001, 221, 283-294) [Non-Patent Document 11] “Recent advances in the industrial alkylation of aromatics: new catalysts and new processes” (Perego C., et al., Catal. Today, 2002, 73, 3-22).

[0249] The aromatic alkylation unit is designed to receive, in addition to the olefin(s) recovered in step (d), a source of one or more aromatic compounds provided in step (f). Advantageously, the oligomerization step (e) of the olefin(s) recovered in step (d) and the alkylation step (g) of the aromatic compounds provided in step (f) can be carried out simultaneously in the same olefin conversion unit, e.g. an olefin oligomerization unit and an aromatic alkylation unit.

[0250] It may be useful to hydrogenate any olefinic bonds remaining after the olefins have been converted in the olefin oligomerization unit or aromatic alkylation unit or olefin oligomerization and aromatic alkylation unit, especially after the oligomerization step (e) to produce compounds having olefinic moieties, which is why the optional hydrogenation unit is located downstream of the olefin conversion unit.

[0251] For example, the conductive particles of the bed may be or include one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixture thereof.

[0252] In one embodiment, 50% to 100% by weight of the conductive particles of the bed are one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and any mixtures thereof, based on the total weight of the conductive particles of the bed, and this content is preferably 60% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

[0253] For example, one electrode may be a submerged central electrode or two submerged electrodes 13 in the reaction vessel 3 of at least one reactor (18, 19, 37).

[0254] For example, the fluidizing gas may be one or more diluent gases.

[0255] In a preferred embodiment, at least one fluidized bed reactor (18, 19, 37, 39) is devoid of heating means. For example, at least one fluidized bed reactor is devoid of heating means selected from an oven, a gas burner, a hot plate, or any combination thereof. For example, all fluidized bed reactors are devoid of heating means selected from an oven, a gas burner, a hot plate, or any combination thereof. In a preferred embodiment, at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles is devoid of packing.

[0256] For example, the reaction vessel 3 has an inner diameter of at least 100 cm, or at least 200 cm, or at least 400 cm. Such a large diameter allows, for example, a weight hourly space velocity of the reaction flow of 0.1 h -1 ~100h -1 , preferably 1.0 h- 1~50h -1 , more preferably 1.5 h -1 ~10h -1 , more preferably 2.0h -1 ~6.0h -1 Chemical reactions can be carried out on an industrial scale using a fluidized bed. Weight hourly space velocity is defined as the ratio of the mass flow rate of the reacting stream to the mass of solid particulate matter in the fluidized bed.

[0257] At least one fluidized bed reactor (18, 19, 37) comprises at least two electrodes 13. For example, one electrode is electrically connected to the outer wall of the fluidized bed reactor and another electrode is submerged within the fluidized bed 25. Alternatively, both electrodes 13 are submerged within the fluidized bed 25. The at least two electrodes 13 are electrically connected and can be connected to a power source (not shown).

[0258] For example, at least one fluidized bed reactor comprises at least one cooling device arranged to cool at least one electrode.

[0259] When using a fluidized bed reactor, a potential of up to 300V, preferably up to 250V, more preferably up to 200V, even more preferably up to 150V, most preferably up to 100V, and even most preferably up to 90V or up to 80V is applied.

[0260] The power of the current is adjustable so that the temperature in the reactor bed can be easily regulated.

[0261] Preferably, the reactor vessel 3 comprises a reactor wall made of a corrosion resistant material, advantageously the reactor wall material comprises nickel (Ni), SiAlON ceramic, yttria stabilized zirconia (YSZ), tetragonal polycrystalline zirconia (TZP) and / or tetragonal polycrystalline zirconia (TPZ). SiAlON ceramic is a ceramic based on the elements silicon (Si), aluminum (Al), oxygen (O) and nitrogen (N). It is a solid solution of silicon nitride (Si3N4) in which the Si-N bonds are partially replaced by Al-N and Al-O bonds.

[0262] For example, the reaction vessel 3 is made of an electrically resistive material which is a mixture of silicon carbide and molybdenum disilicide, and the electrically resistive material of this reaction vessel 3 contains 10% to 99% by weight of silicon carbide relative to the total weight of the electrically resistive material, and the content is preferably 15% to 95% by weight, more preferably 20% to 90% by weight, even more preferably 25% to 80% by weight, and most preferably 30% to 75% by weight.

[0263] For example, the reaction vessel 3 is made of an electrically resistive material that is a mixture of silicon carbide and molybdenum disilicide.

[0264] For example, the reaction vessel 3 is not electrically conductive, for example, the reaction vessel 3 is made of ceramic.

[0265] For example, at least one fluidized bed reactor (18, 19, 37, 39) includes a heating zone 27 and a reaction zone 29, one or more fluid nozzles 21 supplying a fluidizing gas from a distributor 31 to at least the heating zone, one or more fluid nozzles 23 supplying an alcohol-containing feedstock from a distributor 33 to the reaction zone, and an optional means 41 for transporting particles from the heating zone 27 to the reaction zone 29 and an optional means 35 for transporting particles from the reaction zone 29 to the heating zone 27.

[0266] For example, as shown in FIG. 3, at least one fluidized bed reactor is a single fluidized bed reactor 19 with a heating zone 27 at the bottom of the fluidized bed reactor 19 and a reaction zone 29 at the top of the fluidized bed reactor 19. Preferably, the installation comprises one or more fluid nozzles 23 for injecting the alcohol-containing feedstock between the two zones (27, 29) or into the reaction zone 29. The fluidized bed reactor 19 further comprises an inlet 7 for an optional feed material, an outlet 9 for an optional feed material discharge and a gas outlet 11. Preferably, the fluidized bed reactor 19 does not comprise a heating means. For example, the electrode 13 is located at the bottom of the fluidized bed reactor 19, i.e., in the heating zone 27. For example, there is no electrode at the top of the fluidized bed reactor 19, i.e., in the reaction zone 29. The fluidized bed reactor 19 optionally comprises a means 35 for transporting particles from the reaction zone 29 to the heating zone 27, for example by a line located between the top and the bottom of the fluidized bed reactor 19.

[0267] For example, as shown in FIG. 4, the inventive installation comprises at least two fluidized bed zones (27, 29) connected laterally to each other, of which at least one fluidized bed zone 27 is a heating zone and at least one fluidized bed zone 29 is a reaction zone. For example, the heating zone 27 surrounds the reaction zone 29. Preferably, the inventive installation comprises one or more fluid nozzles 23 arranged to inject alcohol-containing feedstock and / or steam into the at least one reaction zone 29 by means of a distributor 33. The fluidized bed zones (27, 29) further comprise an inlet 7 for optional material input and a gas outlet 11. Preferably, at least one fluidized bed zone, which is the heating zone 27, and / or at least one fluidized bed zone, which is the reaction zone 29, is devoid of heating means. For example, at least one fluidized bed zone, which is the reaction zone 29, is shown to have an optional outlet 9 for material discharge. The one or more fluid nozzles 21 feed fluidizing gas from the distributor 31 to at least the heating zone. The heated particles are transported from the heating zone 27 to the reaction zone 29 by one or more inlet devices 41, and the separated particles are returned from the reaction zone 29 to the heating zone 27 by one or more means 35 including a downcomer. The fluidizing gas in the heating zone 27 can be one or more inert diluents selected from steam, hydrogen, carbon dioxide, methane, argon, helium, and nitrogen. In this configuration, the fluidizing gas in the heating zone can also include air or oxygen for burning the coke deposits from the particles. For example, as shown in FIG. 5, the installation comprises at least two fluidized bed reactors (37, 39) connected to each other, at least one fluidized bed reactor 37 being the heating zone 27 and at least one fluidized bed reactor 39 being the reaction zone 29. Preferably, the installation comprises one or more fluid nozzles 23 arranged to inject the alcohol-containing feedstock and / or steam into at least one fluidized bed reactor 39 being the reaction zone 29. The fluidized bed reactor (37, 39) further comprises an optional inlet 7 for the input of materials and a gas outlet 11.Preferably, at least one fluidized bed reactor 37 of the heating zone 27 and / or at least one fluidized bed reactor 39 of the reaction zone 29 are not equipped with heating means. For example, at least one fluidized bed reactor 39 of the reaction zone 29 shows an optional outlet 9 for discharging materials. Heated particles are transported from the heating zone 27 to the reaction zone 29 as required by inlet device 41, and particles separated after the reaction zone are returned from the reaction zone to the heating zone by device 35. The fluidizing gas of the heating zone can be one or more inert diluents selected from steam, hydrogen, carbon dioxide, methane, argon, helium, nitrogen. In this configuration, the fluidizing gas of the heating zone can also contain air or oxygen for burning the coke deposits from the particles.

[0268] For example, at least one fluidized bed reactor 37 that is a heating zone 27 contains at least two electrodes 13, and at least one fluidized bed reactor 39 that is a reaction zone 29 is devoid of electrodes.

[0269] For example, at least two fluidized bed reactors (37, 39) are connected to each other by means 41, such as one or more lines suitable for transporting particles from the heating zone 27 to the reaction zone 29.

[0270] For example, at least two fluidized bed reactors ( 37 , 39 ) are connected to each other by means 35 , such as one or more lines suitable for returning particles from the reaction zone 29 to the heating zone 27 .

[0271] Catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins For example, the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out at a temperature between 200°C and 500°C, preferably between 240°C and 490°C, more preferably between 260°C and 480°C.

[0272] For example, the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out at pressures in the range of 0.05 MPa to 3 MPa, preferably 0.05 MPa to 1.5 MPa, more preferably 0.12 MPa to 0.8 MPa, or 0.12 MPa to 0.5 MPa, which are considered to be moderate pressures that are easy and economical to achieve.

[0273] For example, the partial pressure of the alcohol-containing feedstock ranges from 0.12 MPa to 0.7 MPa.

[0274] For example, the catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins is carried out in the presence of a reaction stream, the weight hourly space velocity of the reaction stream being 0.1 h -1 ~100h -1 , preferably 1.0h -1 ~50h -1 , more preferably 1.5 h -1 ~10h -1 , more preferably 2.0h -1 ~6.0h -1 It is.

[0275] For example, the residence time of the alcohol-containing feedstock in the fluidized bed section of the reactor can range from 0.1 to 10 seconds, or from 1 to 10 seconds, at temperatures between 260° C. and 500° C.

[0276] Testing and Evaluation Methods X-ray diffraction (XRD) was used to determine the crystal structure of the catalysts. This was performed on powder samples of the synthesized zeolite or zeolites and was carried out using a PANalytical X'Pert Pro diffractometer equipped with CuKα monochromatic radiation (λ = 1.5418 nm, 45 kV, 40 mA). Samples were scanned in the range 5-50°2θ with a step size of 0.02°. The unit cell parameters of the zeolite particles were determined from the X-ray diffraction data by calculations based on Bail profile refinement and pseudo-Voigt profile functions using JANA2006 software. Furthermore, the framework and extraframework structures (structure types and atomic positions) were determined and quantified using JANA2006 software to minimize the difference between the observed patterns and the calculated patterns of the structural models.

[0277] Temperature Programmed Desorption (TPD) is a method to observe the molecules desorbed from the surface as the surface temperature increases, which was performed according to heating sequences I, II, and III shown in Figure 6. Each heating sequence corresponds to activation, saturation, and analysis, respectively. Briefly, in the first step (marked I in Figure 6), starting from room temperature (25 °C) under helium flow (rate 50 cc / min), the temperature is gradually increased to 600 °C at a rate of 20 °C / min. After 1 h at 600 °C, the solid acid sample is considered activated, and the temperature is gradually decreased to 100 °C at a rate of 10 °C / min. Then, in the second step (marked II in Figure 6), the temperature is maintained at 100 °C for 3 h, and 10% ammonia (NH3) is added to the helium flow (reduced to 30 cc / min) during the first hour. This causes the solid acid surface to be saturated with ammonia molecules adsorbed on the surface. The initial flow of helium is resumed for the last 2 hours above the temperature threshold of 100°C. Then, in the third step (marked III in Fig. 6), the temperature is increased again to 600°C at a rate of 10°C / min in order to desorb the ammonia. The sample is kept at 600°C for another hour. Those skilled in the art will understand that different parameters (time, temperature, flow rate, carrier gas) can be used to carry out this method. The respective adsorption conditions of ammonia on the solid acid can be recognized by measuring the amount of ammonia using a thermal conductivity detector, and the surface details of the solid acid, such as the number of acid sites, can be obtained.

[0278] X-ray Fluorescence Spectroscopy (XRF) X-ray fluorescence spectroscopy (XRF) measurements were performed using an Orbis Micro-EDXRF spectrometer equipped with a Rh source (15 kV, 500 μA) and a silicon drift detector. XRF measurements were performed on the materials themselves (undissolved). This was used to determine the amount of SiO2 and Al2O3 and the subsequent Si / Al atomic ratio.

[0279] N 2 Adsorption measurement N 2Adsorption analysis was performed using a Micrometrics ASAP 2020 volumetric adsorption analyzer to determine the nitrogen adsorption / desorption isotherms. The samples were degassed overnight at 350 °C under vacuum prior to the measurements. From this measurement, the specific surface area of ​​the solid acid catalyst was determined.

Claims

1. The following steps: a) providing at least one fluidized bed reactor having at least two electrodes and a bed containing particles; b) fluidizing the particles in the bed by passing a fluid stream upward through the bed to form a fluidized bed; c) heating the fluidized bed to a temperature in the range of 200°C to 500°C to catalytically dehydrate an alcohol-containing feedstock comprising one or more alcohols having at least two carbon atoms to one or more olefins; d) recovering one or more of the olefins; 1. A process for catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins, comprising: the particles of the bed comprise electrically conductive particles and particles of a catalyst composition, at least 10 wt. % of the particles are electrically conductive particles based on the total weight of the particles of the bed and have a resistivity at 400°C in the range of 0.001 ohm-cm to 500 ohm-cm, the catalyst composition comprises one or more solid acid catalysts, and the step c) of heating the fluidized bed is carried out by passing an electric current through the fluidized bed.

2. 2. The method of claim 1, wherein the conductive particles of the bed comprise one or more selected from one or more metal alloys, one or more non-metallic resistors, one or more metal carbides, one or more metal nitrides, one or more metal phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, and / or any mixture thereof.

3. 2. The method of claim 1, wherein the conductive particles of the bed comprise a mixture of non-metallic resistive silicon carbide particles and conductive particles other than silicon carbide.

4. the conductive particles of the bed comprise 10% to 99% by weight of silicon carbide relative to the total weight of the conductive particles of the bed; and / or - the conductive particles different from silicon carbide are one or more carbon-containing particles; 4. The method of claim 3.

5. 4. The method of claim 3, wherein said conductive particles other than silicon carbide are one or more carbon-containing particles.

6. 2. The method of claim 1, wherein the conductive particles of the bed comprise one or more metal alloys and / or one or more superionic conductors.

7. The conductive particles in the bed are LiAlSiO 4 , Li 10 GeP 2 S 12 , Li 3.6 Si 0.6 P 0.4 O 4 10. The method of claim 1, wherein the superionic conductor comprises one or more superionic conductors selected from sodium beta alumina, sodium superionic conductor, or sodium beta alumina.

8. The one or more alcohols having at least two carbon atoms are ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, hexane-1-ol, hexane-2-ol, hexane-3-ol, 2-methylpentan-1-ol, 3-methylpentan-1-ol, 4-methylpentan-1-ol, 2-methylpentan-2-ol, 3-methylpentan-2-ol, 2. The method of claim 1, wherein the methylbutan-1-ol is selected from the group consisting of 4-methylpentan-2-ol, 2-methylpentan-3-ol, 3-methylpentan-3-ol, 2,2-dimethylbutan-1-ol, 2,3-dimethylbutan-1-ol, 3,3-dimethylbutan-1-ol, 2,3-dimethylbutan-2-ol, 3,3-dimethylbutan-2-ol, 2-ethylbutan-1-ol, and any combination thereof.

9. 2. The process of claim 1, comprising, prior to catalytic dehydration of one or more alcohols having at least 2 carbon atoms to one or more olefins in the fluidized bed reactor, preheating the fluidized bed reactor with a gas stream, wherein the gas stream is a stream of one or more inert gases selected from nitrogen, argon, helium, saturated hydrocarbons having up to 10 carbon atoms or any combination thereof, and / or has a temperature of from 100°C to 300°C.

10. 2. The method of claim 1, wherein the at least one fluidized bed reactor provided in step a) has a heating zone and a reaction zone, the fluid stream provided in step b) is provided to the heating zone, and the step of heating the fluidized bed to a temperature of 200° C. to 500° C. to perform the endothermic catalytic dehydration of an alcohol-containing feedstock comprising one or more alcohols having at least two carbon atoms to one or more olefins in step c) comprises the following substeps: - heating the fluidized bed to a temperature of between 200°C and 500°C by passing an electric current through at least one heating zone of the fluidized bed; - transporting the heated particles from the heating zone to the reaction zone; in the reaction zone, a fluid stream comprising the alcohol-containing feedstock and, optionally, one or more inert gases and / or one or more diluent gases is flowed upwardly through the bed in the reaction zone, thereby fluidizing the heated particles to form a fluidized bed and effecting endothermic catalytic dehydration of the alcohol-containing feedstock to one or more olefins.

11. 2. The method according to claim 1, wherein the at least one fluidized bed reactor (18, 19, 37, 39) provided in step a) comprises a heating zone (27) and a reaction zone (29), and wherein step c) of heating the fluidized bed (25) comprises the following substeps: - Preheating the fluidizing stream (gas stream having a temperature between 100°C and 300°C) to the temperature of the fluidized bed (25) by passing it upward through the particles (25) of the fluidized bed (25), between 100°C and 300°C; - heating the fluidized bed (25) to a temperature in the range of 200°C to 500°C by passing an electric current through the heating zone (27) of at least one fluidized bed reactor (18, 19, 37, 39); - transporting the heated particles from the heating zone (27) to the reaction zone (29); - passing a fluid stream comprising an alcohol-containing feedstock upwardly through the bed (25) in the reaction zone (29) to fluidize the heated particles to form a fluidized bed (25) for endothermic catalytic dehydration of one or more alcohols having at least two carbon atoms to one or more olefins; - The particles are recovered from the reaction zone (29) and recycled to the heating zone (27).

12. One or more solid acid catalysts are N 2 The surface area measured by adsorption measurement is 50 m 2 / g~800m 2 / g and / or the content of the particles of the catalyst composition is in the range of 15% by weight to 90% by weight relative to the total weight of the particles of the bed.

13. 10. The method of claim 1, wherein the one or more solid acid catalysts are selected from one or more oxides, one or more mixed oxides, one or more phosphates, one or more zeolites, one or more silicoaluminophosphate molecular sieves, or combinations thereof.

14. 10. The method of claim 1, wherein the one or more solid acid catalysts are mixed with a binder.

15. 15. The method of claim 14, wherein the binder is an inorganic material selected from one or more clays, silica, one or more metal silicates, one or more metal oxides, one or more gels, or combinations thereof.

16. step (d) is carried out, and further comprising a step (e) of oligomerizing a portion of the one or more olefins recovered in step (d); 10. The process of claim 1, further comprising a step (f) of providing one or more aromatic compounds and a step (g) of alkylating the one or more aromatic compounds with another portion of the one or more olefins recovered in step (d), wherein step (g) is carried out simultaneously with step (e).

17. 10. Use of a bed (25) comprising particles in at least one fluidized bed reactor (18, 19, 37, 39) for carrying out the process of claim 1 for catalytic dehydration of one or more alcohols having at least two carbon atoms to olefins, characterized in that at least 10% by weight of the particles, based on the total weight of the particles in the bed, are electrically conductive particles and have a resistivity at 400° C. in the range of 0.001 ohm-cm to 500 ohm-cm.

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