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EP-4739427-A1 - REACTOR SYSTEM FOR SORPTION-ENHANCED CATALYTIC REACTIONS WITH CONTINUOUS REGENERATION OF ADSORBENT, AND RELATED METHODS

EP4739427A1EP 4739427 A1EP4739427 A1EP 4739427A1EP-4739427-A1

Abstract

The present invention relates to a circulating, fluidized bed, catalytic reactor, wherein the circulating, fluidized bed, catalytic reactor comprises a plurality of catalyst particles and a plurality of adsorbent particles, wherein the plurality of catalyst particles and the plurality of adsorbent particles have different size and/or different density, such that the plurality of catalyst particles and the plurality of adsorbent particles are capable of separating by means of particle segregation; and means for recirculating a solid stream of the plurality of adsorbent particles. The invention also relates to a reactor system that comprises said catalytic reactor, connected to an adsorbent regeneration reactor. Finally, the invention relates to a method for the continuous, selective regeneration of adsorbent particles in a Sorption Enhanced Reaction (SER), and to uses of the reactor system of the invention in the context of specific reactions.

Inventors

  • MENÉNDEZ SASTRE, Miguel
  • HERGUIDO HUERTA, JAVIER
  • SOLER HERRERO, JAIME
  • LASOBRAS LAGUNA, Javier

Assignees

  • Universidad De Zaragoza

Dates

Publication Date
20260513
Application Date
20240702

Claims (13)

  1. 1. A circulating, fluidized bed, catalytic reactor, wherein the circulating, fluidized bed, catalytic reactor comprises: - a plurality of catalyst particles and a plurality of adsorbent particles, wherein the plurality of catalyst particles and the plurality of adsorbent particles have different size and/or different density, such that the plurality of catalyst particles and the plurality of adsorbent particles are capable of separating by means of particle segregation; and - means for recirculating a solid stream of the plurality of adsorbent particles.
  2. 2. The circulating, fluidized bed, catalytic reactor according to claim 1 , wherein the plurality of catalyst particles and the plurality of adsorbent particles correspond to Geldart classification types A and/or B.
  3. 3. The circulating, fluidized bed, catalytic reactor according to any one of claims 1 or 2, wherein the plurality of catalyst particles and the plurality of adsorbent particles have a particle size in the range 30pm-1 mm, and/or wherein the particle diameter ratio is equal to or higher than 1.5.
  4. 4. The circulating, fluidized bed, catalytic reactor according to claim 1 , wherein the plurality of catalyst particles corresponds to Geldart classification type D, and wherein the plurality of adsorbent particles corresponds to Geldart classification types A or B.
  5. 5. The circulating, fluidized bed, catalytic reactor according to any one of claims 1 to 4, wherein the plurality of catalyst particles is capable of separating as jetsam and wherein the plurality of adsorbent particles is capable of separating as flotsam.
  6. 6. The circulating, fluidized bed, catalytic reactor according to any one of claims 1 to 5, wherein the plurality of catalyst particles is capable of separating as flotsam and wherein the plurality of adsorbent particles is capable of separating as jetsam.
  7. 7. The circulating, fluidized bed, catalytic reactor according to any one of claims 1 to 6, wherein the reactor comprises a reactor vessel, and wherein the reaction vessel has different diameters in at least two different sections.
  8. 8. The circulating, fluidized bed, catalytic reactor according to any one of claims 1 to 7, wherein the reactor further comprises an inlet stream of an oxidizing agent.
  9. 9. A reactor system, wherein the reactor system comprises: a circulating, fluidized bed, catalytic reactor according to any one of claims 1 to 8; and an adsorbent regeneration reactor; wherein the means for recirculating a solid stream of the plurality of adsorbent particles in the circulating, fluidized bed, catalytic reactor are connected to the adsorbent regeneration reactor.
  10. 10. The reactor system according to claim 9, wherein the adsorbent regeneration reactor is a fluidized bed reactor or a pneumatic transport reactor.
  11. 11 . A method for the continuous, selective regeneration of adsorbent particles in a Sorption Enhanced Reaction (SER), wherein the method comprises: providing a reactor system according to any one of claims 9 or 10; carrying out the SER in the circulating, fluidized bed, catalytic reactor under conditions that separate the plurality of catalyst particles from the plurality of adsorbent particles by means of particle segregation; continuously extracting adsorbent particles using the means for recirculating a solid stream of adsorbent particles in the circulating, fluidized bed, catalytic reactor; regenerating the adsorbent particles in the adsorbent regeneration reactor; returning the regenerated adsorbent particles to the fluidized bed catalytic reactor.
  12. 12. Use of the fluidized bed catalytic reactor according to any one of claims 1 to 8, or use of a reactor system according to any one of claims 9 or 10 for carrying out a reaction selected from the group comprising: Methanol synthesis from CO2, CO, or mixtures of CO2-CO; and hydrogen; Dimethyl ether production from CO2, CO, or mixtures of CO2-CO; and hydrogen; Synthesis of synthetic natural gas by CO2 hydrogenation, by CO hydrogenation, or by hydrogenation of mixtures containing CO and CO2; Fischer-Tropsch hydrocarbon production from syngas; Hydrogen production from CO + H2O mixtures by water gas shift reaction; CO production from CO2 + H2 mixtures by reverse water gas shift reaction; Hydrogen production from natural gas or hydrocarbons by steam reforming (CH4 + H 2 O CO 2 + 3H 2 , CH 4 + 2H 2 O CO 2 + 4H 2 , C n H m + n H 2 O n CO 2 + (m/2+n) H2or CnH m + 2n H2O n CO2 + (m/2+2n) H2); and Desulfurization of organic compounds such as naphtha, liquefied petroleum gases and, in general, petroleum derivatives that can be hydrogenated in the gas phase.
  13. 13. The use according to claim 12, wherein the reaction is selected from the group consisting of: Methanol synthesis from CO2, CO, or mixtures of CO2-CO; and hydrogen; - Dimethyl ether production from CO2, CO, or mixtures of CO2-CO; and hydrogen; Synthesis of synthetic natural gas by CO2 hydrogenation; Fischer-Tropsch hydrocarbon production from syngas; and CO production from CO2 + H2 mixtures by reverse water gas shift reaction.

Description

DESCRIPTION REACTOR SYSTEM FOR SORPTION-ENHANCED CATALYTIC REACTIONS WITH CONTINUOUS REGENERATION OF ADSORBENT, AND RELATED METHODS FIELD OF THE INVENTION The present invention relates to the field of catalyst-mediated reactions, more specifically to the field of Sorption-Enhanced Reactions (SER), wherein adsorbent particles are capable of removing a reaction product from the medium, thereby providing a yield larger than the corresponding to the thermodynamic equilibrium in a conventional reactor. BACKGROUND ART The instant invention relates to the field of catalyst-mediated reactions, wherein the yield of the catalyst-mediated reaction is limited by the thermodynamic equilibrium. This limitation often results in low yields when the reaction is carried out in a conventional reactor. Low yields make it necessary to separate and recirculate unconverted reactants, which increases operational costs. To solve this issue, several types of reactors may be used, wherein the thermodynamic equilibrium is displaced by the specific separation of a reaction product, either using membrane reactors or though Sorption Enhanced Reaction (SER). Sorption Enhanced Reactions (SER) are catalyst-aided processes which involve, in addition to the catalyst, the use of an adsorbent in order to modify the thermodynamic equilibrium in a chemical reaction, such that the reaction rate is increased. Fixed bed reactors have been typically used for SER purposes, wherein catalyst solid particles are intimately mixed with adsorbent solid particles. In this type of reactors, the adsorbent becomes saturated with one of the reaction by-products after a certain amount of time and needs to be regenerated. Since the catalyst and adsorbent solid particles are intimately mixed, both catalyst and adsorbent particles are subjected to the same regeneration conditions. This mode of operation has several drawbacks, such as operating in a non-stationary state, which is not industrially desirable, or needing several beds, so that some beds can be in operation while others are undergoing the regeneration process. Importantly, in these reactors, catalyst particles are subjected to the same processes of heating, environmental changes, etc; which are required for the regeneration of the adsorbent. These process conditions can damage the catalyst (deactivation, sintering, etc.). The problem of operating in a non-stationary state is solved by using circulating fluidized bed reactors, wherein the mixture of catalyst and adsorbent solid particles is continuously directed to a second, separate reactor for regeneration of the adsorbent. As in the case of fixed bed reactors, this mode of operation involves that catalyst particles undergo the relatively harsh conditions of the regeneration process and, as a consequence, the risk also exists that the catalyst may be damaged. Bjornar Arstad et al. (“Continuous hydrogen production by sorption enhanced steam methane reforming (SE-SMR) in a circulating fluidized bed reactor: Sorbent to catalyst ratio dependencies”, Chemical Engineering Journal 189- 190 (2012) 413-421) disclose continuous hydrogen production, which is attained by sorption enhanced steam methane reforming (SE-SMR) using a circulating fluidized bed reactor system that comprises a catalyst (Ni/NiAhOt) and a CO2 adsorbent (calcined natural dolomite). Bjornar Arstad et al. mention catalyst deactivation issues, mainly due to sintering (active surface loss) and/or oxidation. As a solution, they suggest the addition of an active component to the catalyst to prevent catalyst oxidation, and/or the introduction of H2 into the regenerator. Isabel Martinez et al. (“Performance and operating limits of a sorbent-catalyst system for sorption-enhanced reforming (SER) in a fluidized bed reactor”, Chemical Engineering Science, Volume 205, pp. 94-105, 2019) compare different types of catalyst-sorbent combinations in the context of sorption-enhanced reforming (SER) processes. The authors acknowledge that where the SER process is operated in steady state in a dual fluidized bed system by circulating the solids between two reactors (i.e. , continuous process operation), the sorbent requires regeneration in a highly oxidizing and steam-rich atmosphere. This document addresses the issue of catalyst deactivation due to oxidation while sorbent regeneration takes place but suggests that the problem may be solved by ensuring a minimum presence of H2 in the regenerator. As shown, catalyst deactivation during the regeneration of adsorbent particles in the context of sorption-enhanced catalytic reactions is a problematic issue in this technical field and the provision of alternative, effective solutions is highly desired. SUMMARY OF THE INVENTION The instant invention solves the issue of catalyst deactivation by attaining the selective regeneration of adsorbent particles (i.e., independently from catalyst particles) in a reactor set-up that comprises a circulating, fluidized bed, catal