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CN-122028981-A - Zirconia support for heterogeneous catalysts

CN122028981ACN 122028981 ACN122028981 ACN 122028981ACN-122028981-A

Abstract

The specification describes a zirconia support comprising ≡95 wt% zro 2 , wherein the support has a crush strength of 20N to 140N, a total pore volume of 0.10 mL/g to 0.40 mL/g when measured by N 2 physisorption, a density of 15 μl NH3 /m 2 to 30 μl NH3 /m 2 of acid sites, and a density of basic sites of 0.006 wt%/m 2 to 0.015 wt%/m 2 as measured by MBOH test. A method for producing a zirconia support starting from zirconia or zirconium hydroxide as a starting material is also described.

Inventors

  • Brian Blank
  • Haralambos Thomas
  • Ralph Dozer
  • Dana HATCH
  • PHILIP JOHN HUGHES
  • Martin Max Langbaiyin
  • Paul Andrew MCGUIRE
  • Hubert Xiedel
  • Stuart Michael. Smol
  • Edgar Steinwinker

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 zirconia support comprising ≡ 95 wt% ZrO 2 , wherein: the carrier has a crush strength of 20N to 140N; The support has a total pore volume of 0.10 mL/g to 0.40 mL/g when measured by N 2 physisorption; The carrier has an acidic site density of 15. Mu.L NH3 /m 2 to 30. Mu.L NH3 /m 2 , and The vector has a basic site density of 0.006 wt%/m 2 to 0.015 wt%/m 2 as measured by MBOH test.
  2. 2. The support of claim 1, wherein the support comprises ≡98 wt% ZrO 2 .
  3. 3. The support of claim 1, wherein the support comprises ≡99 wt% ZrO 2 .
  4. 4. A carrier according to any one of claims 1 to 3, wherein the carrier has a crush strength of 20N to 80N.
  5. 5. The vector of any one of claims 1 to 4, wherein the vector has an acid site density of 19 μl NH3 /m 2 to 28 μl NH3 /m 2 .
  6. 6. The vector of any one of claims 1 to 5, wherein the vector has a basic site density of 0.0075 wt%/m 2 to 0.014 wt%/m 2 .
  7. 7. The vector according to any one of claims 1 to 6, wherein the vector is in the form of a trilobal shape.
  8. 8. The carrier of claim 7, wherein the carrier is in the form of a trilobal shape having an average diameter of 1.0 mm to 4.0 mm.
  9. 9. The carrier according to any one of claims 1 to 8, wherein the carrier has: 20 Crush strength of N to 80N; 0.10 A total pore volume of from mL/g to 0.40 mL/g; 19. Acid site density of. Mu.L NH3 /m 2 to 28. Mu.L NH3 /m 2 , and 0.0075 Alkaline site density of wt%/m 2 to 0.014 wt%/m 2 .
  10. 10. A method of making a zirconia support comprising the steps of: (i) Combining a raw material selected from ZrO 2 or Zr (OH) 4 with a lubricant; (ii) Mixing the product of step (i) with an additive selected from an acid, base or zirconium salt and extruding the mixture to form a shaped body, or tabletting the product of step (i) to form a shaped body; (iii) Drying the shaped body, and (Iv) Calcining the shaped body.
  11. 11. The method of claim 10, wherein the raw material used in step (i) is ZrO 2 .
  12. 12. The method of claim 10 or claim 11, wherein the lubricant used in step (i) is microcrystalline cellulose, hydroxymethyl cellulose, or a metal stearate.
  13. 13. The method of any one of claims 10 to 12, wherein the additive is ammonia.
  14. 14. The method of any one of claims 10 to 12, wherein the additive is an acid.
  15. 15. The method of claim 14, wherein the additive is nitric acid.
  16. 16. The method of any one of claims 10 to 12, wherein the additive is a zirconium salt.
  17. 17. The method of claim 16, wherein the zirconium salt is zirconium nitrate.
  18. 18. The method of claim 16, wherein the zirconium salt is zirconium acetate.
  19. 19. The method of any one of claims 10 to 18, wherein in step (ii), the mixture is tableted to form a shaped body.
  20. 20. The method of any one of claims 10 to 18, wherein in step (ii), the mixture is extruded to form a shaped body.

Description

Zirconia support for heterogeneous catalysts Technical Field The present invention relates to the preparation of zirconia supports, methods of making zirconia supports, and supported catalysts (supported catalyst) made therefrom. Background Zirconia is a material with good stability and moderate acidity making it an interesting catalyst support (carrier). Zirconia can be used to produce shaped bodies such as spheres, particles or cylinders. Zirconia shaped bodies formed by extrusion generally have low crush strength, and various methods have been described to improve crush strength. WO2004/065002A1 (Shell) describes a process for preparing a calcined zirconia extrudate comprising the steps of preparing a formable mass (dough) comprising particulate zirconia having a total solids content of 50% to 85% by weight, extruding the formable mass to form a zirconia extrudate, and drying and calcining the zirconia extrudate. The particular zirconia comprises no more than 15% by weight of zirconia other than monoclinic zirconia. WO2010/101636A2 (Sud-CHEMIE INC) describes the incorporation of a polyacid/promoter material selected from the group consisting of polyacids, polyacids comprising oxides or acid forms of chromium, molybdenum or tungsten. Typical molar ratios of zirconium to promoter are between 2:1 and 20:1. WO2015/167978A1 (Clariant) describes a material comprising 50 wt% to 99 wt% zirconia and 1 wt% to 50 wt% metal oxide (based on metal) selected from nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide. The presence of the metal oxide is believed to stabilize the zirconia from undergoing undesirable phase transitions from tetragonal or amorphous phases to less desirable monoclinic phases. US5269990a describes shaped zirconia particles prepared by mixing zirconia powder and an aqueous colloidal zirconia solution or an aqueous acidic solution to obtain a shaped mixture comprising 4% wt% to 40% wt% water, shaping the mixture, and heating the shaped particles at a temperature in excess of about 90 ℃. US 2002/0123218 A1 and US20023/130117A1 describe a process for preparing a zirconia catalyst by mixing zirconium hydroxide with various additives to prepare a paste, then shaping the particles, drying and calcining the particles at a temperature of at least 400 ℃. US2011/0301021A1 describes a polyacid-promoted zirconia catalyst or catalyst support that can be prepared by combining a zirconium compound with a polyacid/promoter material, which can be Cr, mo or W, phosphoric acid, sulfuric acid, and a polyorganoacid. Zirconia supports have been commercially used in Hydrodeoxygenation (HDO) catalysts as described in US9314778B2 (Virent, inc) and references cited therein. The HDO reaction is a key reaction in the BioForming TM technology of VIRENT INC to convert biomass to fuel. In order to further facilitate the adoption of this technology, there is a need for a zirconia support that is simple and inexpensive to manufacture and desirably improves the performance of HDO catalysts comprising Pd, mo and Sn on zirconia supports. The present inventors have sought to provide alternative zirconia supports that (i) are simple and inexpensive to manufacture, and (ii) perform well when used as supports for HDO catalysts. Summary of The Invention Initial experiments by the present inventors have sought to produce zirconia shaped bodies having crush strength comparable to or better than commercially available zirconia supports. The shaped bodies were also converted to Hydrodeoxygenation (HDO) catalysts by impregnation with palladium, tin and molybdenum salts, as will be more fully described in the examples. The crush strength can be increased by increasing the calcination temperature, but it was found that increasing the calcination temperature eventually resulted in a negative impact on the performance of the support in the HDO reaction due to the variation in the concentration of the acidic and basic sites. Finally, it was found that in order to achieve good performance in HDO reactions, careful control of the concentration of acidic and basic sites within a certain range was required. The concentration of the acidic and basic sites is affected by several factors including the choice of raw materials, additives used in the process, and calcination conditions. In a first aspect, the invention relates to a zirconia support comprising ≡95 wt% ZrO 2, wherein: the carrier has a crush strength of 20N to 140N; The support has a total pore volume of 0.10 mL/g to 0.40 mL/g when measured by N 2 physisorption; The vector has an acidic site density of 15. Mu.L NH3/m2 to 30. Mu.L NH3/m2, and The vector had a basic site density of 0.006 wt%/m 2 to 0.015 wt%/m 2 as measured by MBOH test. The zirconia support according to the first aspect has a good balance between crush strength and performance in HDO reactions. In a second aspect, the present invention relates to a method of manufacturing a zirconia support, the method compris