Process to conduct an alkane transformation into olefins in an electrified fluidized bed reactor

Patent metadata

Field	Value
Publication number	US-12187675-B2
Application number	US-202218710414-A
Country	US
Kind code	B2
Filing date	Nov 14, 2022
Priority date	Nov 25, 2021
Publication date	Jan 7, 2025
Grant date	Jan 7, 2025

Abstract

The disclosure concerns a process to perform a reaction of alkane transformation into olefins, said process comprising the steps of (a) providing a stream of light alkane-comprising feedstock with one or more alkanes and one or more oxidants selected from CO 2 and/or COS; and 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 to obtain a fluidized bed; and (c) heating the fluidized bed to a temperature ranging from 600° C. to 1500° C. to conduct the reaction; the process is remarkable in that the step c) is performed by passing an electric current through the fluidized bed; the particles of the bed comprise electrically conductive particles, and in that, at least 10 wt. % of the particles are electrically conductive particles and have a resistivity ranging from 0.001 to 500 Ohm·cm at 800° C.

First claim

The invention claimed is:

1. A process to perform an alkane transformation into olefin; said process comprising the steps of:
a) providing a stream of light alkane-comprising feedstock comprising one or more alkanes selected from methane, ethane, propane, butane, isobutane and any mixture thereof and one or more oxidants selected from carbon dioxide, carbonyl sulphide and any mixture thereof, wherein oxidant content amounts least 15 vol. % based on the total volume of the light alkane-comprising feedstock; and further 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 to obtain a fluidized bed;
c) heating the fluidized bed to a temperature ranging from 600° C. to 1500° C. to conduct the transformation into olefin on the light alkane-comprising feedstock; and
d) optionally, recovering the products of the reaction;

characterized in that the step c) of heating the fluidized bed is performed by passing an electric current through the fluidized bed; in that the particles of the bed comprise electrically conductive particles and particles of a catalytic composition; in that, 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 800° C.; in that the void fraction of the bed is ranging from 0.5 to 0.8 and 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 catalyst composition comprises one or more selected from rare earth oxides, rare earth sulphides, transition metal oxides, and any mixture thereof and/or one or more selected from Na—W—Mn/SiO 2 , NaCl—MnNa 2 WO 4 /SiO 2 , La 2 O 3 —CeO 2 , Li/MgO, CaO—Sm 2 O 3 , KCl—SmCl 3 , CaO—NaCl/Na 2 CO 3 , CeO 2 /ZnO, La 2 O 3 /Al 2 O 3 and FeS x , the catalyst composition further comprising one or more dopants when one oxidant of the light alkane-comprising feedstock is carbon dioxide.

2. The process according to claim 1 , characterized in that the electrically conductive particles of the bed are one or more selected from 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.

3. The process according to claim 1 , characterized in that the electrically conductive particles of the bed comprise one or more carbon-containing particles being graphite and/or in that the electrically conductive particles of the bed comprise one or more non-metallic resistors selected from silicon carbide, molybdenum disilicide or a mixture thereof.

4. The process according to claim 1 , characterized in that the electrically conductive particles of the bed comprise a mixture of a non-metallic resistor being silicon carbide and electrically conductive particles different from silicon carbide; with preference:
the electrically conductive particles of the bed comprise from 10 wt. % to 99 wt. % of silicon carbide based on the total weight of the electrically conductive particles of the bed; and/or
the said electrically conductive particles different from silicon carbide are one or more carbon-containing particles and/or one or more mixed oxides being doped with one or more lower-valent cations and/or one or more mixed sulphides being doped with one or more lower-valent cations.

5. The process according to claim 1 , characterized in that the electrically conductive particles of the bed comprise one or more mixed oxides being doped with one or more lower-valent cations, the mixed oxides are selected from:
one or more oxides having a cubic fluorite structure being at least partially substituted with one or more lower-valent cations selected from Sm, Gd, Y, Sc, Yb, Mg, Ca, La, Dy, Er, Eu; and/or
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, preferentially selected from Ca, Sr, or Mg, and comprising at least one of Ni, Ga, Co, Cr, Mn, Sc, Fe and/or a mixture thereof in B position; and/or
one or more ABO 3 -perovskites with A bivalent cation and B tetra-valent cation, being at least partially substituted with one or more lower-valent cations selected from Mg, Sc, Y, Nd or Yb in the B position or with a mixture of different B elements in the B position; and/or
one or more A 2 B 2 O 7 -pyrochlores with A trivalent cation and B tetra-valent cation being at least partially substituted in A position with one or more lower-valent cations selected from Ca or Mg, and comprising at least one of Sn, Zr and Ti in B position.

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

7. The process according to claim 1 , characterized in that the catalyst composition comprises one or more selected from rare earth oxides, rare earth sulphides, transition metal oxides transition metal sulphides and any mixture thereof and in that the catalyst composition comprises one or more dopants, the one or more dopants comprise at least one alkali, alkali-earth, transition metal, post-transition metal or rare earth metal carbonate or thiocarbonate, or any mixture thereof.

8. The process according to claim 1 , characterized in that the void fraction of the bed is ranging from 0.5 to 0.7.

9. The process according to claim 1 , characterized in that the particles of the bed have an average particle size ranging from 10 to 200 μm as determined by sieving according to ASTM D4513-11.

10. The process according to claim 1 , characterized in that in step b) the particles of the bed are put in a fluidized state by passing upwardly through the said bed a gaseous stream comprising methane; and/or in that it comprises a step of pre-heating with a gaseous stream the one or more fluidized bed reactors before conducting said alkane partial oxidation reaction and/or oxidative coupling reaction in the fluidized bed reactor, wherein the gaseous stream has a temperature comprised between 400° C. and 1000° C.

11. The process according to claim 1 , characterized in that the at least one fluidized bed reactor provided in step a) comprises a heating zone and a reaction zone and wherein the step c) of heating the fluidized bed to a temperature ranging from 600° C. to 1500° C. to conduct the alkane partial oxidation reaction and/or oxidative coupling reaction comprises the following sub-steps:
heating the fluidized bed to a temperature ranging from 600° C. to 1500° 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 stream comprising a light alkane-comprising feedstock and optional diluent gases to obtain a fluidized bed to conduct the alkane transformation into olefin on the light alkane-comprising feedstock,
optionally, recovering t

Assignees

• Totalenergies Onetech

Inventors

• Veryasov Gleb
• Vermeiren Walter
• Nesterenko Nikolai

Classifications

• C07C2523/14

  of germanium, tin or lead · CPC title

• C07C2523/04

  Alkali metals · CPC title

• C07C2521/12

  Silica and alumina · CPC title

• C07C5/42

  by dehydrogenation with a hydrogen acceptor · CPC title

• B01J2208/00398

  inside the reactor bed · CPC title