Process to conduct an endothermic catalytic cracking reaction in a fluidized bed reactor

Patent metadata

Field	Value
Publication number	US-11964934-B2
Application number	US-202118016843-A
Country	US
Kind code	B2
Filing date	Jul 27, 2021
Priority date	Jul 28, 2020
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

The disclosure relates to a process to perform a catalytic cracking reaction of hydrocarbons having at least four carbons, said process comprising the steps of providing a fluidized bed reactor comprising at least two electrodes and a bed comprising particles, wherein the particles are put in a fluidized state to obtain a fluidized bed; heating said bed to a temperature between 500° C. and 850° C. by passing an electric current through the fluidized bed to conduct the reaction. The process is remarkable 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 are electrically conductive particles and have a resistivity from 0.001 to 500 Ohm.cm at 500° C. and in that the step of heating the fluidized bed is performed by passing an electric current through the fluidized bed.

First claim

The invention claimed is:

1. A process to perform an endothermic catalytic cracking of one or more hydrocarbons having at least four carbons, comprising:
a) providing at least one fluidized bed reactor comprising at least two electrodes and a bed comprising particles, wherein:
i) the particles of the bed comprise electrically conductive particles and particles of a catalytic composition;
ii) the catalytic composition comprises from 5.0 to 90.0 wt. % of one or more zeolites based on the total weight of the catalyst composition, the zeolite comprises at least one 10-membered ring channel;
iii) 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.; and
iv) a void fraction of the bed ranges from 0.5 to 0.8;

b) injecting a fluid stream upwardly through the bed to putting the particles of the bed in a fluidized state thereby obtaining a fluidized bed;
c) heating the fluidized bed to a temperature ranging from 500° C. to 850° C. by passing an electric current through the fluidized bed and cracking the hydrocarbons by endothermic catalytic cracking reaction; and
d) optionally recovering the cracking products of the reaction.

2. The process according to claim 1 , characterized in that the at least one fluidized bed reactor comprising the at least two electrodes and the bed comprising particles is devoid of packing.

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 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 silicon carbide, molybdenum disilicide or 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 which are one or more oxides having a cubic fluorite structure being at least partially substituted with one or more lower-valent cations and wherein 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.

6. 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, and wherein said one or more lower-valent cations are selected from the group consisting of Ca, Sr, and 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 occurs or with a mixture of different B elements in the B position and wherein the one or more lower-valent cations are selected from magnesium, scandium, yttrium, neodymium or ytterbium; 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 cation and comprising at least one of Sn, Zr and Ti in B position and wherein the one or more lower-valent cations are selected from Ca or Mg.

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

8. 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.

9. The process according to claim 1 , characterized in that the one or more hydrocarbons having at least four carbons are selected from the group consisting of butenes, butanes, straight run naphtha, catalytic cracked naphtha, pyrolysis gasoline, coker and visbroken naphtha.

10. The process according to claim 1 , characterized in that the cracking products comprise one or more of ethylene, propylene and benzene, and optionally hydrogen, toluene, xylenes.

11. The process according to claim 1 , characterized in that said one or more zeolites are selected from the list comprising MFI, MEL, MTW, MTT and/or FER families and in that said one or more zeolites have a Si/A1 molar ratio comprised between 20 and 5000.

12. The process according to claim 1 , characterized in that said one or more zeolites further comprise one or more metal compounds which are one or more selected from the group consisting of group-2 elements, from group-4 elements, from group-11 elements, from one or more elements selected from the group consisting of Ce, Sn, Co, Mo, Mn, Ni, Fe, Cr, Pt, Pd, In, Ga, Re, W and V, and from rare earth elements.

13. The process according to claim 1 , characterized in that the catalytic composition comprises a catalytic support selected from the group comprising alumina, alumina sol, titania, zirconia, quartz, silica, silica sol, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, calcium-alumina, calcium-silicate, ceria-zirconia-alumina, ceria-titania-alumina, ceria-magnesia-alumina, calcium-silica-alumina, silica-alumina-zirconia, hafnia, lanthania, magnesia, ceria, zirconia stabilized with magnesia, zirconia stabilized with lanthania, zirconia stabilized with yttria, zirconia stabilized with ceria, alumina stabilized with lanthania, metal-aluminates, and mixture thereof.

14. The process according to claim 1 , characterized in that said process comprises a step of pre-heating with a gaseous stream of inert gas said fluidized bed reactor before conducting said endothermic catalytic cracking reaction in the fluidized bed reactor.

15. The process according to claim 1 , characterized in that, wherein the at least one fluidized bed reactor provided in step a) comprises a heating zone and a reaction zone and wherein the fluid stream provided in step b) is provided to the heating zone and comprises diluent gases, the step c) of heating the fluidized bed to a temperature ranging from 500° C. to 850° C. to conduct the catalytic cracking reaction of one or more hydrocarbons having at least four carbons comprises the following sub steps:
heating the fluidized bed to a temperature ranging from 500° C. to 850° C. by passing an electric current through the heating zone of the at least one fluidized bed,
transporting the heated particles from the heating zone to the reaction zone,
in the reaction zone, putting the heated particles in a fluidized state by passing upwardly through the said bed of the reaction zone a fluid stream comprising a hydrocarbon feedstock, and optional diluent gases to obtain

Assignees

• Totalenergies Onetech

Inventors

• Veryasov Gleb
• Nesterenko Nikolai
• Vermeiren Walter

Classifications

• C07C4/06 Primary

  Catalytic processes {(C07C4/025 takes precedence)} · 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

• B01J8/28

  the one above the other · 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