Phosphorus-containing molecular sieve, its preparation and application thereof

Patent metadata

Field	Value
Publication number	US-11524281-B2
Application number	US-201816760562-A
Country	US
Kind code	B2
Filing date	Oct 22, 2018
Priority date	Oct 31, 2017
Publication date	Dec 13, 2022
Grant date	Dec 13, 2022

Abstract

A phosphorus-containing molecular sieve has a phosphorus content of about 0.3-5 wt %, a pore volume of about 0.2-0.95 ml/g, and a ratio of B acid content to L acid content of about 2-10. The molecular sieve has a specific combination of characteristics, including a high ratio of B acid content to L acid content, thereby exhibiting higher hydrocracking activity and ring-opening selectivity when used in the preparation of a hydrocracking catalyst.

First claim

The invention claimed is:

1. A phosphorus-containing Y molecular sieve, having a phosphorus content of about 0.3 wt % to about 5 wt %, calculated as oxide, a pore volume of about 0.2 ml/g to about 0.95 ml/g, and a ratio of Bronsted acid content to Lewis acid content of about 3.4 to about 9.5,
wherein the phosphorus-containing Y molecular sieve is produced using a method comprising hydrothermally treating a phosphorus-containing molecular sieve starting material; mixing the hydrothermally treated phosphorus-containing molecular sieve starting material with water to form a slurry; and acid leaching by adding an acid solution to the slurry at a temperature of about 40° C. to about 95° C. at a substantially constant rate in a range of about 0.05 mol/hr to about 10 mol/hr, calculated on the basis of H + relative to 1L of the slurry; subjecting the slurry to an isothermal reaction for about 0.5 h to about 20 h, wherein a ratio of a weight of an acid in the acid solution to a dry weight of the phosphorus-containing molecular sieve starting material is in a range of about 0.01:1 to about 0.6:1, and
the phosphorus-containing Y molecular sieve has a 27Al-NMR structural spectrum showing an I 60ppm /I −1ppm of about 5 to about 40, and an I −1ppm /I ±6ppm of about 0.4 to about 2.

2. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing Y molecular sieve has a lattice constant of 2.425-2.470 nm and a specific surface area of about 250-850 m 2 /g.

3. The phosphorous-containing Y molecular sieve of claim 1 , wherein the ratio of the weight of water in the slurry to a dry weight of the phosphorus-containing molecular sieve starting material is in a range of about 14:1 to about 5:1.

4. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing molecular sieve starting material has a phosphorus content of about 0.1 wt % to about 15 wt %, and a sodium content of about 0.5 wt % to about 4.5 wt %, calculated as oxides and based on the dry weight of the phosphorus-containing molecular sieve starting material.

5. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing molecular sieve starting material is a phosphorus-containing molecular sieve having a lattice constant of 2.425-2.470 nm, a specific surface area of about 250 m 2 /g to about 750 m 2 /g, and a pore volume of about 0.2 ml/g to about 0.95 ml/g.

6. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing molecular sieve starting material is in the form of particles, and particles having a particle size of about 1 mm to about 500 mm accounts for about 10 wt % to about 100 wt % of a total weight of the phosphorus-containing molecular sieve starting material, and the particle size is a diameter of a circumscribed circle of the particle.

7. The phosphorus-containing Y molecular sieve of claim 1 , wherein the hydrothermal treatment is carried out in the presence of steam at a temperature of about 350° C. to about 700° C. and a pressure of about 0.1 MPa to about 2 MPa for a hydrothermal treatment time of about 0.5 h to about 10 h.

8. The phosphorus-containing Y molecular sieve of claim 1 , wherein in the acid leaching comprises adding the acid solution into the slurry a plurality of times, and
wherein, in each of the plurality of times, the acid solution is added at a substantially constant rate in a range of about 0.05 mol/h to about 10 mol/h, calculated on the basis of H + relative to 1L of the molecular sieve slurry, and, after each of the plurality of times, the slurry is subject to an isothermal reaction for a period of time such that the isothermal reaction time is about 0.5 hours to about 20 hours in total.

9. A hydrocracking catalyst, comprising: on a dry basis and based on the weight of the catalyst, about 45 wt % to about 90 wt % of a first metal component, calculated as metal oxide, and about 1 wt % to about 15 wt % of a second metal component, calculated as metal oxide; and
a support comprising the phosphorus-containing Y molecular sieve of claim 1 and a refractory inorganic oxide, wherein a weight ratio of the phosphorus-containing molecular sieve to the refractory inorganic oxide is about 0.03:1 to about 20:1,
wherein the first metal is a metal of Group VIB and the second metal is a metal of Group VIII.

10. The catalyst of claim 9 , wherein the refractory inorganic oxide is selected from alumina, silica, amorphous silica-alumina compounds, zirconia, magnesia, thoria, beryllia, boric oxide, cadmium oxide, and combinations thereof, the first metal is molybdenum and/or tungsten, and
the second metal is selected from iron, nickel, cobalt, and combinations thereof.

11. A method for hydrocracking of a hydrocarbon feedstock, comprising a step of contacting the hydrocarbon feedstock with the hydrocracking catalyst of claim 9 under hydrocracking reaction conditions.

12. The method of claim 11 , wherein the hydrocarbon feedstock is selected from straight run gas oils, vacuum gas oils, demetallized oils, atmospheric residues, deasphalted vacuum residues, coker distillates, catalytic cracker distillates, shale oils, tar sand oils, coal liquefied oils, and combinations thereof.

13. The method of claim 11 , wherein the hydrocracking reaction conditions comprise a reaction temperature of about 200-650° C., a reaction pressure of about 3-24 MPa, a liquid hourly space velocity of about 0.1-10 h −1 , and a hydrogen-to-oil ratio by volume of about 100-5000 Nm 3 /m 3 .

14. The phosphorus-containing Y molecular sieve of claim 2 , wherein the phosphorus-containing Y molecular sieve is selected from NaY, HNaY, REY, USY molecular sieves, and combinations thereof.

15. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing molecular sieve starting material has a water content of about 10 wt % to about 40 wt %.

16. The phosphorus-containing Y molecular sieve of claim 1 , wherein a ratio of a weight of an acid in the acid solution to a dry weight of the phosphorus-containing molecular sieve starting material is in a range of about 0.01:1 to about 0.3:1.

17. The phosphorus-containing Y molecular sieve of claim 6 , wherein the phosphorus-containing molecular sieve starting material having a particle size of about 5-100 mm accounts for about 30 wt % to about 100 wt % of the total weight of the phosphorus-containing molecular sieve starting material.

18. The phosphorus-containing Y molecular sieve of claim 7 , wherein the acid solution used in the acid leaching has an acid concentration of about 0.01 mol/L to about 15.0 mol/L, and the acid is selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, acetic acid, and combinations thereof.

19. The phosphorus-containing Y molecular sieve of claim 1 , wherein the phosphorus-containing Y molecular sieve has a phosphorus content of 0.4 wt % to 2.0 wt %, calculated as oxide, a pore volume of 0.25 ml/g to 0.60 ml/g, and a ratio of Bronsted acid content to Lewis acid content of 3.4 to 9.5, and wherein the phosphorus-containing Y molecular sieve has a 27Al-NMR structural spectrum showing an I 60ppm /I −1ppm of 10.0 to 39, and an I −1ppm /I ±6ppm of 0.4 to 2.

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Mao Yichao
• Li Mingfeng
• Long Xiangyun
• Zhang Runqiang
• Zhao Yang

Classifications

• C10G2300/107

  Atmospheric residues having a boiling point of at least about 538 °C · CPC title

• B01J29/084

  Y-type faujasite · CPC title

• C10G47/20 Primary

  the catalyst containing other metals or compounds thereof · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C01P2002/70

  defined by measured X-ray, neutron or electron diffraction data · CPC title