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CN-122028982-A - Hydrodeoxygenation catalyst

CN122028982ACN 122028982 ACN122028982 ACN 122028982ACN-122028982-A

Abstract

The present specification describes a catalyst for hydrodeoxygenation of alcohols comprising 0.1 wt% to 1.5 wt% palladium, 1.0 wt% to 5.0 wt% molybdenum, and 0.05 wt% to 0.5 wt% tin on a zirconia support. A method for making the catalyst and a hydrodeoxygenation process using the catalyst are also described.

Inventors

  • Brian Blank
  • Dana HATCH
  • PHILIP JOHN HUGHES
  • Paul Andrew MCGUIRE
  • Maria Elena Rivas Velasco
  • Stuart Michael. Smol
  • Edgar Steinwinker
  • Stephen Gary Wayne Wright

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. A catalyst for hydrodeoxygenation of alcohols comprising, on a zirconia support 0.1 From wt% to 1.5 wt% palladium; 1.0 Molybdenum in an amount of from about 5.0 wt% by weight, and 0.05 Wt% to 0.5 wt% tin.
  2. 2. The catalyst of claim 1, wherein the catalyst comprises 0.1 wt% to 1.0 wt% palladium.
  3. 3. The catalyst of claim 1 or claim 2, wherein the catalyst comprises from 1.0 wt% to 3.0 wt% molybdenum.
  4. 4. A catalyst according to any one of claims 1 to 3, wherein the catalyst comprises from 0.05 wt% to 0.3 wt% tin.
  5. 5. The catalyst of any one of claims 1 to 4, wherein the catalyst has a metal surface area of ≡1.0 m 2 /g Catalyst when measured by CO chemisorption.
  6. 6. The catalyst of any one of claims 1 to 5, wherein the catalyst has a metal surface area of 1.0 m 2 /g Catalyst to 3.0 m 2 /g Catalyst when measured by CO chemisorption.
  7. 7. The catalyst of any one of claims 1-6, wherein the catalyst is in the form of a shaped body.
  8. 8. The catalyst of claim 7, wherein the shaped body has a spherical cross section.
  9. 9. The catalyst of claim 7, wherein the shaped body has a trilobal cross-section.
  10. 10. The catalyst of claim 9, wherein the shaped body has a trilobal cross-section with an average diameter of 1.0 mm to 4.0 mm.
  11. 11. The catalyst of any one of claims 1 to 10, wherein the content of metals other than palladium, molybdenum, tin and zirconium present in the catalyst is ∈0.1 wt% based on the total weight of the catalyst, if any such metals are present.
  12. 12. The catalyst of any one of claims 1 to 11, wherein the support has a total pore volume of 0.10 mL/g to 0.40 mL/g when measured by N 2 physisorption.
  13. 13. The catalyst of any one of claims 1 to 12, wherein the support has an acid site density of 15 μl NH3 /m 2 to 30 μl NH3 /m 2 .
  14. 14. The catalyst of any one of claims 1 to 13, wherein the support has an acid site density of 19 μl NH3 /m 2 to 28 μl NH3 /m 2 .
  15. 15. The catalyst of any one of claims 1 to 14, wherein the support has a basic site density of 0.006 wt%/m 2 to 0.015 wt%/m 2 as measured by MBOH test.
  16. 16. The catalyst of any one of claims 1 to 15, wherein the support has a basic site density of 0.0075 wt%/m 2 to 0.014 wt%/m 2 , measured by MBOH test.
  17. 17. A method of making a hydrodeoxygenation catalyst comprising the steps of: (i) Dissolving palladium, molybdenum, tin salts and chelating agents together to produce an impregnating solution; (ii) Adding the impregnating solution to a zirconia support to provide an impregnated support; (iii) Drying the impregnated support, and (Iv) Calcining the impregnated support to produce the hydrodeoxygenation catalyst; Wherein the hydrodeoxygenation catalyst is defined according to any of claims 1 to 16.
  18. 18. The method of claim 17, wherein the chelating agent is citric acid.
  19. 19. The method of claim 17 or claim 18, wherein the support has a total pore volume of 0.10 mL/g to 0.40 mL/g when measured by N 2 physisorption.
  20. 20. The method of any one of claims 17 to 19, wherein the vector has an acid site density of 15 μl NH3 /m 2 to 30 μl NH3 /m 2 .

Description

Hydrodeoxygenation catalyst Technical Field The present invention relates to catalysts for hydrodeoxygenation of feed streams, in particular catalysts for the conversion of sugars, sugar alcohols and other carbohydrates to lower molecular weight oxygenates. Background There is an urgent need for alternatives to fossil fuels. Biomass (material derived from living biological materials or recently living biological materials) is a possible class of renewable alternatives. A key challenge in promoting and maintaining biomass use is the need to develop efficient and environmentally friendly techniques for converting biomass into useful products. One such commercial process for converting biomass to fuel is sold under the name BioForming TM by VIRENT INC. The process involves extracting soluble carbohydrates from biomass, converting the biomass to reactive intermediates by a combination of Aqueous Phase Reforming (APR) and/or Hydrodeoxygenation (HDO), followed by further reactions to produce hydrocarbons. This process is described in US9314778B2 (Virent, inc) and references cited therein. The key requirement of the HDO process is to effectively remove oxygen from the carbohydrates without significantly damaging the corresponding carbon backbone. US9314778B2 compares the performance of single metal catalysts, bimetallic catalysts and trimetallic catalysts in HDO reactions. The trimetallic catalysts described comprise 2% Pd-2% Mo-0.5% Sn on tungstic zirconia (example 24, example 35) or 2% Pd-5% Mo-1% Sn on tungstic zirconia (example 26), in each case using tungstic zirconia from Norpro as support. These catalysts were tested for their performance in converting food grade corn syrup feedstock to mono-oxygenates (monooxygenate). These trimetallic catalysts give similar mono-oxygenate yields when compared to 3% pd on tungstated zirconia, but much lower yields of the undesired c7+ condensation products (see table 9 of the reference). Single-, bi-and tri-metal catalysts for HDO reactions are also described in US10131602B 2. Although the Pd-Mo-Sn catalyst on tungstic zirconia shows good performance in HDO reaction, there is room for further improvement. It would be advantageous if the amount of palladium could be reduced without sacrificing activity. The present invention solves these problems. Summary of The Invention By carefully selecting the amounts of Pd, mo and Sn, the inventors have surprisingly sought to provide a catalyst having comparable or better activity in HDO reactions while having a lower palladium content than previous HDO catalysts. Furthermore, the inventors have sought to simplify the catalyst preparation route so that it involves only a single impregnation step and is therefore easier to implement on a large scale. In a first aspect, the present invention relates to a catalyst for hydrodeoxygenation of alcohols comprising, on a zirconia support 0.1 From wt% to 1.5 wt% palladium; 1.0 Molybdenum in an amount of from about 5.0 wt% by weight, and 0.05 Wt% to 0.5 wt% tin. In a second aspect, the present invention relates to a method of making a hydrodeoxygenation catalyst, the method comprising the steps of: (i) Dissolving palladium, molybdenum, tin salts and chelating agents together to produce an impregnating solution; (ii) Adding an impregnating solution to the zirconia support to provide an impregnated support; (iii) Drying the impregnated support, and (Iv) Calcining the impregnated support to produce a hydrodeoxygenation catalyst; Wherein the hydrodeoxygenation catalyst is as defined in the first aspect. In a third aspect, the present invention relates to a hydrodeoxygenation process comprising the step of treating a feed stream comprising a carbohydrate feedstock with a catalyst to produce lower molecular weight oxygenates, wherein the catalyst is as defined in the first aspect. Description of the drawings FIG. 1 shows the relationship between basic site/BET surface area and activity. Fig. 2 shows the relationship between acid sites/BET surface area and activity. Fig. 3 shows how the average diameter of the trilobes (trilobe) are measured, the trilobes shown having an average diameter of 1.4 mm. Detailed description of the preferred embodiments Any sub-headings are included for convenience only and should not be construed as limiting the disclosure in any way. Catalyst The invention also relates to a catalyst for hydrodeoxygenation of alcohols comprising, on a zirconia support 0.1 From wt% to 1.5 wt% palladium; 1.0 Molybdenum in an amount of from wt% to 5.0 wt%; 0.05 wt% to 0.5 wt% tin. For the avoidance of doubt, wt% of metal refers to the amount of metal relative to the total weight of the catalyst. Studies by the inventors have shown that increasing the palladium and/or molybdenum content is associated with increasing the catalyst performance. Although some tin needs to be present to achieve adequate performance, increasing the tin content above 0.5 wt% can negatively impact performance. Thus, th