Catalytic silicoaluminophosphates having an AEL structure,...

Details Catalytic silicoaluminophosphates having an AEL structure,... Catalytic silicoaluminophosphates having an AEL structure,...

1999-05-20

2001-10-23

Griffin, Steven (Department: 1754)

Catalyst, solid sorbent, or support therefor: product or process

Zeolite or clay, including gallium analogs

And additional al or si containing component

C502S071000, C502S077000, C502S078000, C502S079000

Reexamination Certificate

active

06306790

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to using silicoaluminophosphates (“SAPO”s) having unique silicon distributions and their use as catalytic cracking catalysts for cracking hydrocarbon feedstocks. More particularly, the SAPOs have a high silica:alumina ratio, and are prepared from microemulsions containing surfactants.
BACKGROUND OF THE INVENTION
Conventional microporous crystalline silicoaluminophosphates such as SAPO-11 may be prepared by hydrothermal crystallization of silicoaluminophosphate gels containing a molecular structure forming template. SAPOs are members of a class known as non-zeolitic molecular sieves. SAPO molecular sieves have a framework of AlO
4
, SiO
4
and PO
4
tetrahedra linked by oxygen atoms. The negative charge in the network is balanced by the inclusion of exchangeable protons or cations such as protonated amines or alkylamonium. The interstitial spaces of channels formed by the crystalline network enables SAPOs to be used as molecular sieves in a manner similar to zeolites, which are crystalline aluminosilicates.
More recently a new silicoaluminophosphates have been prepared that are isostructural with conventional SAPO-11, but having a dramatically higher silicon:aluminum ratio and appropriate silicon distribution. Such materials are prepared from microemulsions.
Conventional SAPOs may be used as catalysts in petroleum processing. For example, SAPO catalysts may be used in lubricating oil hydroconversion procedures, hydrocracking, dewaxing, and combinations thereof. Conventional SAPO catalysts may also be used in catalytic cracking processes such as fluid catalytic cracking (“FCC”) processes.
There remains a need, though, for improved silicoaluminophosphates for use in hydrocarbon processing.
SUMMARY OF THE INVENTION
In one embodiment, the invention is a fluidized catalytic cracking method comprising injecting a feed into an FCC riser reactor having a reaction zone and catalytically cracking the feed in the reaction zone under catalytic cracking conditions in the presence of a cracking catalyst in order to form a cracked product, the cracking catalyst containing a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0.2 molar % to about 40 molar % total aluminum amount ranging from about 30 molar % to about 49.9 molar %, and a total phosphorus amount ranging from about 10 molar % to about 49 .9 molar %, the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being isostructural with a SAPO-11 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein
(a) the silicon present in the SAPO catalyst is distributed among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and
(b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions ( Si4Si), a second number of silicon sites having silicon atoms in three of the four nearest neighbor positions ( Si3Si), and a third number of silicon sites having silicon atoms in two of the four nearest neighbor positions (Si2Si), wherein
(i) the sum of the first, second, and third number of silicon sites ranges from about 10 to about 80 molar %, and
(ii) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0.7 to about 1.4, the molar % being based on the total number of silicon sites.
In another embodiment, the invention is a composition comprising a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0.2 molar % to about 40 molar %, a total aluminum amount ranging from about 30 molar % to about 49.9 molar %, and a total phosphorus amount ranging from about 10 molar % to about 49.9 molar %, the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being isostructural with a SAPO-11 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein
(a) the silicon present in the SAPO catalyst is distributed among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and
(b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions (Si4Si), a second number of silicon sites having silicon atoms in three of the four nearest neighbor positions (Si3 Si), and a third number of silicon sites having silicon atoms in two of the four nearest neighbor positions (Si2Si), wherein
(i) the sum of the first, second, and third number of silicon sites ranges from about 10 to about 80 molar %, and
(ii) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0.7 to about 1.4, the molar % being based on the total number of silicon sites.


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