Phosphorus-modified MFI-structured molecular sieve, catalytic cracking auxiliary and catalytic cracking catalyst containing phosphorus-modified MFI-structured molecular sieve, and processes for preparing the same

Patent metadata

Field	Value
Publication number	US-12296323-B2
Application number	US-202117996187-A
Country	US
Kind code	B2
Filing date	Apr 13, 2021
Priority date	Apr 13, 2020
Publication date	May 13, 2025
Grant date	May 13, 2025

Abstract

A phosphorus-modified MFI-structured molecular sieve is characterized in that the molecular sieve has a K value, satisfying: 70%≤K≤90%; for example, 75%≤K≤90%; further for example, 78%≤K≤85%. The K value is as defined in the specification. A cracking auxiliary or cracking catalyst contains the phosphorus-modified MFI molecular sieve.

First claim

The invention claimed is:

1. A phosphorus-modified MFI-structured molecular sieve having a K value that satisfies 70%≤K≤90%;
wherein K=P1/P2×100%,
P1 is a mass content of phosphorus within a region having an area of 100 square nanometers and a vertical depth from 0 to 2 nm at any crystal surface of a crystal grain of the molecular sieve, as measured by an XPS method, and
P2 is a mass content of phosphorus within a region having an area of 100 square nanometers and a vertical depth from 5 to 10 nm at any crystal surface of the crystal grain of the molecular sieve, as measured by an EPMA method.

2. The molecular sieve according to claim 1 , wherein the molar ratio of the phosphorus content as P 2 O 5 to the alumina content is ≥0.01.

3. The molecular sieve according to claim 1 , wherein the phosphorus-modified MFI-structured molecular sieve is a micropore ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve.

4. The molecular sieve according to claim 1 , wherein the micropore ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000.

5. The molecular sieve according to claim 3 , wherein the hierarchical ZSM-5 molecular sieve has a proportion of the mesopore volume relative to the total pore volume of greater than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000.

6. A catalytic cracking auxiliary, based on the dry basis of the catalytic cracking auxiliary, containing 5-75 wt % of the phosphorus-modified MFI-structured molecular sieve according to claim 1 , 1-40 wt % of a binder and 0-65 wt % of a second clay.

7. A catalytic cracking catalyst containing phosphorus-modified MFI-structured molecular sieve, based on the dry basis of the catalyst, containing 1-25 wt % of Y zeolite, 5-50 wt % of the phosphorus-modified MFI-structured molecular sieve according to claim 1 , 1-60 wt % of an inorganic binder and optionally 0-60 wt % of a second clay.

8. A process of preparing the catalytic cracking auxiliary according to claim 6 , comprising mixing the phosphorus-modified MFI-structured molecular sieve, a binder, optionally a second clay and water, and spray-drying the mixture to produce the catalytic cracking auxiliary.

9. The process of preparing the catalytic cracking auxiliary according to claim 8 , wherein the binder comprises a phosphorus-aluminum inorganic binder.

10. The process of preparing the catalytic cracking auxiliary according to claim 8 , wherein based on the total weight of the catalytic cracking auxiliary, the binder, based on the dry weight, contains 3-39 wt % of the phosphorus-aluminum inorganic binder and 1-30 wt % of one or more additional inorganic binders.

11. The process of preparing the catalytic cracking auxiliary according to claim 10 , wherein the one or more additional inorganic binders is selected from pseudo-boehmite, alumina sol, silica-alumina sol, and water glass.

12. The process of preparing the catalytic cracking auxiliary according to claim 11 , further comprising: subjecting the spray-dried catalytic cracking auxiliary to a first calcining, and then washing, and optionally drying to produce the catalytic cracking auxiliary, wherein the first calcining is carried out at 300-650° C. for 0.5-8h; and the drying is carried out at 100-200° C. for 0.5-24h.

13. A process of preparing the catalytic cracking catalyst according to claim 7 , comprising mixing a Y zeolite, the phosphorus-modified MFI-structured molecular sieve, an inorganic binder, optionally a second clay, and water, and spray-drying the mixture to produce the catalytic cracking catalyst.

14. The process of preparing the catalytic cracking catalyst according to claim 13 , wherein the inorganic binder comprises a phosphorus-aluminum inorganic binder.

15. The process of preparing the catalytic cracking catalyst according to claim 13 , wherein based on the catalytic cracking catalyst, the inorganic binder comprises on the dry basis 3-39 wt % of the phosphorus-aluminum inorganic binder and on the dry basis 1-30 wt % of at least one additional inorganic binder selected from pseudo-boehmite, alumina sol, silica-alumina sol, and water glass.

16. The process of preparing the catalytic cracking catalyst according to claim 15 , further comprising subjecting the spray-dried catalytic cracking catalyst to a first calcining, and then washing, and optionally drying to produce the catalytic cracking catalyst, wherein the first calcining is carried out at 300-650° C. for 0.5-8h; and the drying is carried out at 100-200° C. for 0.5-24h.

17. A process for catalytically cracking a hydrocarbon oil, comprising: contacting a catalyst comprising the catalytic cracking auxiliary according to claim 6 with the hydrocarbon oil under a catalytic cracking condition.

18. The process for catalytically cracking the hydrocarbon oil according to claim 17 , wherein the catalyst further comprises a catalytic cracking catalyst, and the content of the catalytic cracking auxiliary is 0.1-30 wt %.

19. The process for catalytically cracking the hydrocarbon oil according to claim 17 , wherein the catalytic cracking condition includes: the reaction temperature is 500-800° C.; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight-run gas oil, propane light/heavy deasphalted oil, coker gas oil and coal liquefication product.

20. A process of preparing a phosphorus-modified MFI-structured molecular sieve having a K value that satisfies 70%≤K≤90%, comprising:
mixing an aqueous solution of the phosphorus-containing compound and an MFI-structured molecular sieve when they are at substantially the same temperature for at least 0.1 hours, drying, and calcining at 200-600° C. in air or steam for at least 0.1 hours, the substantially same temperature is in the range of 70-150° C.; or,
mixing and stirring a phosphorus-containing compound, an MFI-structured molecular sieve and water, adjusting the temperature to 70-150° C., 40-150° C., maintaining for at least 0.1 hours, drying, and calcining at 200-600° C. in air or steam for at least 0.1 hours,

wherein K=P1/P2×100%,
P1 is a mass content of phosphorus within a region having an area of 100 square nanometers and a vertical depth from 0 to 2 nm at a crystal surface of the crystal grain of a molecular sieve, as measured by an XPS method, and
P2 is a mass content of phosphorus within a region having an area of 100 square nanometers and a vertical depth from 5 to 10 nm at a crystal surface of the crystal grain of a molecular sieve, as measured by an EPMA method.

21. The process of preparing the phosphorus-modified MFI-structured molecular sieve according to claim 20 , wherein the phosphorus-containing compound is selected from organic phosphorous compounds and/or inorganic phosphorous compounds; the organic phosphorous compound is selected from trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric triamide, dibenzyl diethylphosphoramidite, 1,3-bis((triethyl-phosphaneyl)methyl)benzene, the inorganic phosphorous compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

22. The process of preparing the phosphorus-modified MFI-structured mole

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Luo Yibin
• Wang Chengqiang
• Ouyang Ying
• Xing Enhui
• Shu Xingtian

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/30

  characterised by their physical properties · CPC title

• B01J35/647

  2-50 nm · CPC title

• C10G2400/20

  C2-C4 olefins · CPC title

• C10G2300/308

  Gravity, density, e.g. API · CPC title