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
AssigneesChina Petroleum & Chemical Corporation, Research Institute of Petroleum Processing, Sinopec
InventorsYibin Luo, Chengqiang Wang, Ying Ouyang, Enhui Xing, Xingtian Shu
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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.
Claims27
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.
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.
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.
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.
A process of preparing a phosphorus-modified MFI-structured molecular sieve, comprising:
- mixing an aqueous solution of the phosphorus-containing compound at a temperature of 40-150° C., 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 40-150° C.;
- or,
- mixing and stirring a phosphorus-containing compound, an MFI-structured molecular sieve and water, adjusting the temperature to 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 the phosphorus-containing compound is a mixture of boron phosphate and one or more selected from trimethyl phosphate, triphenylphosphine, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate, in the mixture, boron phosphate comprises 10%-80% by weight.
Dependencies are inferred from the claim text.