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CN-122028983-A - Acid condensation catalyst

CN122028983ACN 122028983 ACN122028983 ACN 122028983ACN-122028983-A

Abstract

The present specification describes an acid condensation catalyst comprising a zeolite having a pore size of 10 tetrahedral atoms, a porosity of ≡0.05 mL/g in the range of 20 a-100 a and a silica to alumina ratio (SAR) of 10 to 50, an alumina binder in which the zeolite is dispersed, and at least one metal, wherein the acid condensation catalyst has a porosity of ≡0.06 mL/g in the range of 20 a-100 a as measured by physical adsorption using the BJH method. Also described is a process for preparing the catalyst, and a process for acid condensing a feed stream comprising one or more oxygenates, the process being carried out in the presence of a catalyst as described.

Inventors

  • Leta Johnson
  • Edgar Steinwinker
  • STEPHEN JOHN SCHUYTEN

Assignees

  • 庄信万丰戴维科技有限公司
  • 维仁特公司

Dates

Publication Date
20260512
Application Date
20241024
Priority Date
20231206

Claims (20)

  1. 1. An acid condensation catalyst comprising: a zeolite having a pore size of 10 tetrahedral atoms, a porosity of ≡0.05 mL/g Zeolite in the range of 20 a-100 a, and a silica to alumina ratio (SAR) of 10 to 50; an alumina binder in which the zeolite is dispersed, and At least one metal; Wherein the acid condensation catalyst has a porosity of ≡0.06 mL/g Catalyst within the range of 20 a-100 a as measured by physical adsorption using the BJH method.
  2. 2. The catalyst of claim 1, wherein the catalyst has a porosity in the range of 20 a-100 a of 0.06 mL/g Catalyst to 0.30 mL/g Catalyst .
  3. 3. The catalyst of claim 1, wherein the catalyst has a porosity of ≡0.09 mL/g Catalyst in the range of 20 a-100 a as measured by physical adsorption using the BJH method.
  4. 4. The catalyst of claim 3, wherein the catalyst has a porosity in the range of 0.09 mL/g Catalyst to 0.30 mL/g Catalyst as measured by physical adsorption of 20 a-100 a using the BJH method.
  5. 5. The catalyst of any one of claims 1 to 4, wherein the catalyst has a porosity in the range of 100 a-1000 a of 0.05 mL/g Catalyst to 1.0 mL/g Catalyst .
  6. 6. The catalyst of any one of claims 1 to 4, wherein the catalyst has a porosity in the range of 100 a-1000 a of 0.20 mL/g Catalyst to 0.50 mL/g Catalyst .
  7. 7. The catalyst of any one of claims 1 to 6, wherein the catalyst is in the form of pellets, microparticles or extrudates.
  8. 8. The catalyst of any one of claims 1 to 7, wherein the zeolite has a SAR in the range of 20 to 40.
  9. 9. The catalyst of any one of claims 1 to 8, wherein the zeolite has a ZSM-5 framework.
  10. 10. The catalyst of any one of claims 1 to 9, wherein the content of alumina is 5 wt% to 40 wt% based on the total weight of the catalyst.
  11. 11. The catalyst of any one of claims 1 to 10, wherein the zeolite is present in an amount of 60 wt% to 95 wt% based on the total weight of the catalyst.
  12. 12. The catalyst of any one of claims 1 to 11, wherein the metal is nickel.
  13. 13. The catalyst of claim 10, wherein the nickel content is 0.1 wt% -5 wt% based on the total weight of the catalyst.
  14. 14. The catalyst of claim 10, wherein the nickel content is 0.5 wt% -2 wt% based on the total weight of the catalyst.
  15. 15. The catalyst of any one of claims 1 to 14, wherein the metal is not present as a metal phosphide.
  16. 16. The catalyst of any one of claims 1 to 15, wherein the catalyst comprises: A zeolite having a ZSM-5 framework, a porosity of ≡0.05 mL/g Zeolite in the range of 20 a-100 a and a silica to alumina ratio (SAR) of 10 to 50, the amount of zeolite corresponding to 60 wt% -95 wt% based on the total weight of the catalyst; an alumina binder in which the zeolite is dispersed in an amount corresponding to 5 wt% -40% wt% based on the total weight of the catalyst, and 0.1 Wt% -5: 5 wt% nickel based on the total weight of the catalyst, and wherein the acid condensation catalyst has a porosity within the range of 20 a-100 a of ≡0.06 mL/g Catalyst as measured by physical adsorption using a BJH method.
  17. 17. A method of making an acid condensation catalyst comprising the steps of: (i) Combining a zeolite with an alumina binder precursor, the zeolite having a pore size of 10 tetrahedral atoms, a silica to alumina ratio (SAR) of 10 to 50 and having a porosity in the range of 20 a-100 a of ≡0.05 mL/g measured by physical adsorption using the BJH method; wherein the alumina binder precursor is peptized with an acid before or after combination with the zeolite; (ii) Forming the mixture into particles suitable for a fixed bed process; (iii) Calcining to convert the alumina binder precursor to alumina, and (Iv) Impregnating the product of step (iii) with a metal salt; Wherein the catalyst is as defined in any one of claims 1 to 16.
  18. 18. The method of claim 17, wherein the zeolite has a porosity ranging from 0.05 mL/g to 0.15 mL/g in the range of 20 a-100 a.
  19. 19. The method of claim 17 or claim 18, wherein the alumina binder is peptized using a monobasic acid.
  20. 20. The method of any one of claims 17 to 19, wherein the metal salt is a transition metal salt or a lanthanide metal salt.

Description

Acid condensation catalyst Technical Field The present invention relates to catalysts for conducting acid-catalyzed condensation of an oxygen-containing feedstock to produce aromatic products. Background Because of the negative environmental impact of fossil fuels, there is an urgent need to find alternatives to fossil fuels. One approach is to produce fuel from biomass, which is renewable, unlike fossil fuels. To this end VIRENT ENERGY SYSTEMS inc. A process for converting biomass to fuel grade materials has been developed (BioForming TM technology). BioForming TM techniques have been described extensively in, for example, U.S. patent No. 7 977 517 (VIRENT ENERGY SYSTEMS, inc.) and U.S. 2016/108330A1 (Virent, inc.). The process comprises three steps. First, a feedstock comprising sugar and/or cellulosic biomass is hydrogenated to provide a polyol-containing material. Second, the polyol-containing material is subjected to hydrodeoxygenation to provide a stream containing unsaturated compounds. Third, materials comprising unsaturated compounds are subjected to an acid condensation step to produce a variety of products comprising aromatic compounds. In US7977517B2 and US2016/108330A1, the acid condensation step (AC step) is carried out in the presence of a catalyst having an acidic site (AC catalyst). Various catalysts have been proposed including zeolites, silica-alumina phosphates, aluminum phosphates, amorphous silica alumina, zirconia, sulfated zirconia. Exemplary zeolite catalysts include La doped H-mordenite, ni doped H-mordenite, eu doped H-mordenite, ga doped beta zeolite, phosphoric acid doped SiO 2/Al2O3, ni doped Al 2O3 bound ZSM-5, and Ga doped Al 2O3 bound ZSM-5 (examples 38-44, all references). The catalysts were tested in the vapor phase condensation of various oxygenate feeds. Further examples of catalysts for the acid condensation step are described in US9878966B 2. In one example, the catalyst comprises 1 wt% Ni (1/16 "extrudate, 20% Al 2O3 binder, ZSM-5 SAT 30, zeolyst) on a commercially available Al 2O3 bound ZSM-5 support. Another example of a process for converting olefins or alkanes to aromatics is described in US2022/0203343a 11. The catalyst comprises a microporous zeolite-type material (microporous zeotype), a binder, and a metal phosphide. The examples in this reference were prepared using a commercial zeolite CBV3024 from Zeolyst, the commercial zeolite CBV3024 having a SAR of 30. An unwanted by-product of the acid condensation step is carbon deposits (also known as coke). The presence of coke prevents the feed molecules from entering the acidic sites of the zeolite, thereby reducing the activity of the catalyst. Some degree of coke formation is unavoidable and coke yield is generally related to catalyst productivity. In operation, it is necessary to perform catalyst regeneration, wherein the accumulated carbon in the catalyst is burned off, which requires reactor shut down. It would be advantageous to provide a catalyst having a reduced coke yield and/or higher activity at a given coke yield, which contributes to higher product yields and less regeneration time. The present invention provides a solution to this problem. Summary of The Invention The inventors have now determined that AC catalysts comprising a zeolite having a pore size of 10 tetrahedral atoms and an alumina binder are particularly suitable for the AC step. In particular, the inventors have determined that the activity and coke yield of the catalyst can be controlled by selecting the alumina and zeolite to achieve a specific pore size distribution in the catalyst. The following theory, which has been constructed afterwards, explains how the porosity of alumina and zeolite affects the coking performance of the catalyst. The catalyst of the present invention comprises a zeolite and a binder matrix. The function of the binder is to impart strength to the catalyst and to prevent cracking of the catalyst in the reactor. Alumina particles constituting the binder surround the zeolite particles and hold the mixture together. Small alumina crystals are desirable compared to the size of the zeolite particles to impart strength to the catalyst because small alumina particles can be best packed around larger zeolite particles. Commercial alumina is typically an agglomerate of smaller crystals of alumina hydroxide called boehmite or pseudoboehmite (referred to herein as an "alumina binder precursor"). Individual crystals of the alumina binder precursor have an order of magnitude of 2nm to several tens of nm. The agglomerates comprise micropores and/or mesopores which contribute to the overall microporosity and mesoporosity of the final catalyst. The alumina binder precursor is peptized with an acid either before or after combination with the zeolite in order to disperse the individual crystals of the alumina binder precursor and thereby allow them to better fill around the zeolite particles. The peptization and bonding processes