Process to conduct an endothermic dehydrogenation and/or aromatisation reaction in a fluidized bed reactor

Patent metadata

Field	Value
Publication number	US-11840509-B2
Application number	US-202118017070-A
Country	US
Kind code	B2
Filing date	Jul 27, 2021
Priority date	Jul 28, 2020
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

The disclosure relates to a process to perform an endothermic dehydrogenation and/or aromatization reaction of hydrocarbons, said process comprising the steps of providing at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles; putting the particles in a fluidized state to obtain a fluidized bed; heating the fluidized bed to a temperature ranging from 480° C. to 700° C. to conduct the reaction; and obtaining a reactor effluent containing hydrogen, unconverted hydrocarbons, and olefins and/or aromatics; wherein the particles of the bed comprise electrically conductive particles and particles of a catalytic composition, wherein at least 10 wt. % of the particles are electrically conductive particles and have a resistivity ranging from 0.001 Ohm·cm to 500 Ohm·cm at 500° C. and wherein the step of heating the fluidized bed is performed by passing an electric current of through the fluidized bed.

First claim

The invention claimed is:

1. A process to perform an endothermic dehydrogenation and/or aromatization of hydrocarbons having at least two carbons to produce olefins and/or aromatics said process comprising the steps of:
a) providing at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles;
b) putting the particles of the bed in a fluidized state by passing upwardly through the said bed a vaporized fluid stream to obtain a fluidized bed;
c) heating the fluidized bed to a temperature ranging from 480° C. to 700° C. to conduct the endothermic dehydrogenation and/or aromatisation reaction; and
d) obtaining a reactor effluent containing hydrogen, unconverted hydrocarbons, and olefins and/or aromatics;
characterized in that the particles of the bed comprise electrically conductive particles and particles of a catalytic composition, wherein at least 10 wt. % of the particles based on the total weight of the particles of the bed are electrically conductive particles and have a resistivity ranging from 0.001 Ohm·cm to 500 Ohm·cm at 500° C., wherein the catalytic composition comprises one or more metallic compounds;
in that the void fraction of the bed is ranging from 0.5 to 0.8; in that the particles of the bed have an average particle size ranging from 5 to 300 μm as determined by sieving according to ASTM D4513-11; and in that the step (c) of heating the fluidized bed is performed by passing an electric current through the fluidized bed;
further wherein:
the process is a paraffin dehydrogenation process and the catalyst composition comprises one or more catalyst materials selected from gallium, zinc, chromium, iron, metal of the group VIII or mixtures thereof; and one or more catalytic supports; or
that said process is an alkyl-aromatic dehydrogenation process and the catalyst composition comprises from 50 to 85 wt. % of Fe 2 O 3 based on the total weight of the catalyst composition; from 3 to 25 wt. % of K 2 O; from 3 to 30 wt. % of CeO 2 ; from 0.1 to 5 wt. % of CaO; from 0.1 to 5 wt. % of Na 2 O and from 0.1 to 150 ppm of at least one element selected from Pb, Pt, Os, Jr, Ru, Re, Pd, Ag, Au, Sn or any mixture thereof; or
said process is a naphtha reforming process and the catalyst composition comprises from 0.01 to 3.0 wt. % of one or more metals of the group VIII based on the total weight of the catalyst composition; from 0.1 to 3.5 wt. % of a halide; and from 0.01 to 5.0 wt. % of one or more metals selected from groups IIIA, IVA, IB, VIB and/or VIIB; or
said process is a paraffin aromatisation process and the catalyst composition comprises from 5.0 to 90.0 wt. % of one or more zeolites comprising at least one 10-membered ring channel and based on the total weight of the catalyst composition; from 0.1 to 5.0 wt. % of a halide; and from 0.05 to 10.0 wt. % of one or more catalyst materials selected from Ga, In, Zn, Cu, Re, Mo, W; or from 0.005 to 1.0 wt. % of one or more metals of the group VIII or mixtures thereof based on the total weight of the catalyst composition.

2. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are or comprise one or more particles selected from the group consisting of one or more metallic alloys, one or more non-metallic resistors, one or more metallic carbides, one or more transition metal nitrides, one or more metallic phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, one or more mixed oxides being doped with one or more lower-valent cations, one or more mixed sulphides being doped with one or more lower-valent cations and/or any mixture thereof.

3. The process according to claim 1 , characterized in that from 50 wt. % to 100 wt. % of the electrically conductive particles of the bed based on the total weight of the electrically conductive particles of the bed are one or more particles selected from the group consisting of one or more metallic alloys, one or more non-metallic resistors, one or more metallic carbides, one or more transition metal nitrides, one or more metallic phosphides, one or more carbon-containing particles, one or more superionic conductors, one or more phosphate electrolytes, one or more mixed oxides being doped with one or more lower-valent cations, one or more mixed sulphides being doped with one or more lower-valent cations, and any mixture thereof.

4. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are or comprise one or more non-metallic resistors selected from the group consisting of silicon carbide, molybdenum disilicide and a mixture thereof.

5. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are or comprise one or more mixed oxides being doped with one or more lower-valent cations that are one or more oxides having a cubic fluorite structure being at least partially substituted with one or more lower-valent cations.

6. The process according to claim 5 , characterized in that said one or more lower-valent cations are selected from the group consisting of Sm, Gd, Y, Sc, Yb, Mg, Ca, La, Dy, Er, and Eu.

7. The process according to claim 5 , characterized in that the mixed oxides being doped with one or more lower-valent cations are selected from the group consisting of:
one or more ABO 3 -perovskites with A and B tri-valent cations being at least partially substituted in A position with one or more lower-valent cations and comprising at least one of Ni, Ga, Co, Cr, Mn, Sc, Fe and/or a mixture thereof in B position, characterized in that said one or more lower-valent cations are selected from Ca, Sr, or Mg;
one or more ABO 3 -perovskites with A bi-valent cation and B tetra-valent cation, being at least partially substituted with one or more lower-valent cations in the B position or with a mixture of different B elements in the B position, characterized in that said one or more lower-valent cations are selected from Mg, Sc, Y, Nd or Yb; and
one or more A 2 B 2 O 7 -pyrochlores with A tri-valent cation and B tetra-valent cation being at least partially substituted in A position with one or more lower-valent cations and comprising at least one of Sn, Zr and Ti in B position, characterized in that said one or more lower-valent cations are selected from Ca or Mg.

8. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are or comprise one or more metallic alloys.

9. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are or comprise one or more superionic conductors selected from the group consisting of LiAlSiO 4 , Li 10 GeP 2 S 12 , Li 3.6 Si 0.6 P 0.4 O 4 , sodium superionic conductors, and sodium beta alumina.

10. The process according to claim 1 , characterized in that the process is selected from a paraffin dehydrogenation process, an alkyl-aromatic dehydrogenation process, a naphtha reforming process and a paraffin aromatization process.

11. The process according to claim 1 , characterized in that said process is a paraffin dehydrogenation process and in that said one or more catalytic support is one or more refractory materials.

12. The process according to claim 11 , characterized in that the step c) of heating the fluidized bed to a temperature ranging from 480° C. to 700° C. to conduct the endothermic dehydrogenation and/or aromatization of hydrocarbons further comprises the sub step of recovering the particles from the reaction zone and recycling them to the heating zone.

13. The installation according to claim 1

Assignees

• Totalenergies Onetech

Inventors

• Veryasov Gleb
• Nesterenko Nikolai
• Vermeiren Walter

Classifications

• C07C5/3337 Primary

  of the platinum group · CPC title

• B01J8/1827

  the fluidising gas being a reactant · CPC title

• B01J8/1836

  Heating and cooling the reactor (B01J8/42 takes precedence) · CPC title

• B01J8/42

  with fluidised bed subjected to electric current or to radiations {this sub-group includes the fluidised bed subjected to electric or magnetic fields} · CPC title

• B01J2208/00398

  inside the reactor bed · CPC title