Catalysts based on silicoaluminophosphate SAPO-11 and uses thereof

Patent metadata

Field	Value
Publication number	US-10399067-B2
Application number	US-201515109226-A
Country	US
Kind code	B2
Filing date	Jan 4, 2015
Priority date	Jan 5, 2014
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

The invention provides a process for preparing SAPO-11, that comprises combining in an aqueous solution alumina source, P 2 O source and a silica source in the presence of a crystallization template and a surfactant to form a gel, which is then subjected to hydrothermal crystallization and calcination. The so-formed SAPO-11, which possesses unique silicon distribution, high resistance to hydrothermal degradation (desilication) and high surface area, forms another aspect of the invention. Hydroprocessing of a vegetable oil in the presence of a catalyst comprising the Pt and SAPO-11 of the invention is also demonstrated.

First claim

The invention claimed is:

1. SAPO-11 possessing a silicon distribution, wherein the distribution of silicon atoms among the five silicon sites, indicated by the notation (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al), identifying the composition of the four nearest neighbor positions of a silicon atom in terms of the silicon and aluminum atoms filling said neighbor positions, is determined by a deconvoluted 29 Si-NMR spectrum of said SAPO-11, said spectrum exhibiting five peaks centered at −90 ppm (±2), −97 ppm(±2), −103 (±2) ppm, −108 (±2) ppm and −112 (±2) ppm, assigned to (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al) sites respectively, wherein said 29 Si-NMR spectrum indicates the predomination of aluminum-rich silicon sites (0Si,4Al) and (1Si,3Al), with the peaks assigned to (0Si,4Al) and (1Si,3Al) sites being the first and second most intense peaks, respectively, such that the major peak assigned to the (0Si,4Al) site indicates that the molar concentration of said site is not less than 60 molar % of the total number of silicon sites, wherein said SAPO-11 has an external surface area of above 200 m 2 /g, and wherein said SAPO-11 is hydrothermally stable in a hydrous environment formed in hydroprocessing of a lipid feedstock at 370° C.

2. SAPO-11 according to claim 1 , wherein the sum of the molar concentrations of the (0Si,4Al) and (1Si,3Al) sites constitutes not less than 75% of the total number of silicon sites, as indicated by the deconvulated results of the 29 Si-NMR spectrum of said SAPO-11.

3. SAPO-11 according to claim 1 , wherein the ratio of the concentration of the (0Si,4Al) site to the concentration of the (1Si,3Al) is greater than 3:1, as indicated by the deconvulated results of the 29 Si-NMR spectrum of said SAPO-11.

4. SAPO-11 of claim 1 , possessing silicon distribution, based on the deconvoluted results of 29 Si-NMR spectrum, as tabulated:

site
(0Si, 4Al)
(1Si, 3Al)
(2si, 2Al)
(3Si, 1Al)
(4Si, 0Al)

NMR peak
−90 ppm
−97 ppm
−103 ppm
−108 ppm
−112 ppm

centered at
(±2)
(±2)
(±2)
(±2)
(±2)

Molar %
60-75
10-20
7-12
6-8
4-6.

5. SAPO-11 according to claim 1 , wherein the external surface area is from 200 m 2 /g to 250 m 2 /g.

6. A catalyst Pt/(SAPO-11+Al 2 0 3 ), wherein the SAPO-11 component of said catalyst is as defined in claim 1 .

7. A process for producing a liquid fuel composition, comprising hydroprocessing a feedstock in the presence of a catalyst according to claim 6 , wherein said feedstock comprises oxygen-containing compounds.

8. A process according to claim 7 , comprising:
providing a feedstock oil selected from the group consisting of vegetable oil, animal oil, and mixtures thereof, and hydrodeoxygenating and hydroisomerizing the oil.

9. A process according to claim 8 , comprising:
(i) hydrodeoxygenating, hydroisomerizing and aromatizing the feedstock oil in the presence of the catalyst Pt/(SAP0-11+Al 2 0 3 ), wherein the SAPO-11 component of said catalyst posesses a silicon distribution, wherein the distribution of silicon atoms among the five possible silicon sites, indicated by the notation (nSi,(4-n)Al), 0≤n≤4, identifying the composition of the four nearest neighbor positions of a silicon atom in terms of the silicon and aluminum atoms filling said neighbor positions, is determined by a deconvoluted 29 Si-NMR spectrum of said SAPO-11, said spectrum exhibiting five peaks centered at −90 ppm (±2), −97 ppm(±2), −103 (±2) ppm, −108 (±2) ppm and −112 (±2) ppm, assigned to (0Si,4Al); (1Si,3Al), (2Si,2Al), (3Si,1Al) and (4Si,0Al) sites respectively, wherein said 29 Si-NMR spectrum indicates the predomination of aluminum-rich silicon sites (0Si,4Al) and (1Si,3Al), with the peaks assigned to (0Si,4Al) and (1Si,3Al) sites being the first and second most intense peaks, respectively, such that the major peak assigned to the (0Si,4Al) site indicates that the molar concentration of said site is not less than 60 molar % of the total number of silicon sites to obtain a gas-liquid mixture, wherein the gaseous component of said mixture comprises unreacted hydrogen and light hydrocarbons and the liquid component of said mixture comprises water and an organic liquid;
(ii) separating said gaseous component from said liquid component;
(iii) separating said liquid component into an organic and aqueous phases, and collecting at least said organic phase; and
(v) optionally subjecting said organic phase, or a portion thereof, to hydrocracking in the presence of hydrogen and one or more catalysts.

Assignees

• B G Negev Technologies And Applications Ltd At Ben Gurion Univ

Inventors

• Landau Miron
• Herskowitz Mordechai
• Rabaev Moshe
• Vidruk Roksana

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C10G45/68

  Aromatisation of hydrocarbon oil fractions · CPC title

• C10G45/58

  to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins (C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00) · CPC title

• C10G3/44

  characterised by the catalyst used · CPC title

• C01B37/08

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title