Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Reexamination Certificate
2000-01-03
2002-03-12
Griffin, Steven P. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
C502S064000, C502S071000, C502S077000, C502S078000
Reexamination Certificate
active
06355591
ABSTRACT:
The subject invention relates to a fluid catalytic cracking catalyst additive composition and a process for the preparation of the same.
More specifically, the subject invention relates to a fluid catalytic cracking catalyst additive composition comprising molecular sieve zeolites, aluminum Phosphate composite derived from aluminum metal, Phosphoric acid and clay.
The object of the invention is to obtain the enhanced yield of Liquefied Petroleum Gas (LPG) by catalytic cracking of high boiling petroleum feedstocks.
The other object of the invention is to provide a fluid catalytic cracking additive which is resistant to attrition.
Catalytic cracking processes in which a hydrocarbonaceous oil is converted to lower boiling hydrocarbon products in the presence of cracking catalysts are well known. Catalyst comprising a zeolite and a silica alumina residue made from calcined clay starting material in which the zeolite is produced in the clay are claimed in U.S. Pat. No. 3,663,165.
British Patent No. 1,524,123 discloses the preparation of clay derived zeolite where the sodium content of the catalyst is reduced to less than 1 weight percent.
U.S. Pat. No. 4,454,241 claims a catalyst comprising a crystalline aluminosilicate zeolite prepared form a clay starting material , a residue derived from said clay and an effective amount of phosphorous
Further, U.S. Pat. No. 4,873,211 discloses the cracking catalyst composition comprising zeolite and a matrix material comprising aluminum phosphate which is substantially free from alumina and magnesia, where slurry of a zeolite is mixed with a slurry of aluminum phosphate.
Zeolitic materials both natural and synthetic have been demonstrated in the past to have catalytic capabilities for various types of hydrocarbon conversion. Certain zeolites are ordered, porous crystalline structures within which there are a large number of small cavities which are interconnected by a number of still smaller channels. These cavities and channels are precisely uniform in size. Since the dimensions of these pores are such so as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions., these materials have come to be known as “molecular sieves” and are utilized in a variety of ways to take advantage of these properties. Prior art techniques have resulted in the formation of great variety of synthetic crystalline aluminosilicates. These aluminosilicates have come to be designated by letter or other convenient symbols, to name the few the same are illustrated as “Zeolite A” claimed in U.S. Pat. No. 2,882,243, “Zeolite X” claimed in U.S. Pat. No. 2,882,244, “Zeolite Y” claimed in U.S. Pat. No. 3,130,007, “Zeolite K-G” claimed in U.S. Pat. No. 3,055,654, Zeolite ZK-5 claimed in U.S. Pat. No. 3,247,195, “Zeolite Beta” claimed in U.S. Pat. No. 3,308,069, “Zeolite ZK-4” claimed in U.S. Pat. No. 3,314,752 and “Zeolite ZSM-5” claimed in U.S. Pat. No. 3,702,886.
Members of family of zeolites designated as ZSM-5 have an exceptionally high degree of thermal stability thereby rendering them particularly effective for use in process involving elevated temperatures. Zeolite ZSM-5 have found to be one of the most stable families of zeolites. Zeolites ZSM-5 are useful in cracking and hydrocracking, they are outstandingly useful in other petroleum refining processes as claimed in U.S. Pat. No. 3,702,886.
The catalytic composition comprising (1) a metal from Group VI-A of the Periodic Table of Elements and a metal from Group VIII of the Periodic Table of Elements, (2) their Oxides, (3) their Sulfides and (4) mixtures thereof and a co-catalytic acidic support comprising a large pore crystalline aluminosilicate material and a porous support material selected from the group consisting of alumina, aluminum phosphate and silica have been claimed in U.S. Pat. No. 3,649, 523.
U.S. Pat. No. 5,190,902 has described the use of aluminum phosphate binder material in formulating cracking catalyst where as aluminum phosphate as catalyst support material is described in U.S. Pat. No. 5,55,2361 wherein high surface area aluminum phosphate has been prepared from aluminum nitrate and phosphoric acid.
Further, U.S. Pat. No. 5,380,690 discloses a process for in-situ phosphorous addition into the zeolite framework and subsequent use in cracking catalyst formulation.
The available prior art compositions though possess catalytic properties but there is always a need to produce improved catalyst additives that are capable of producing enhanced yields of liquefied petroleum gas as compared to the available conventional catalyst compositions.
The embodiment of the invention resides in developing a process for preparing a aluminum phosphate composite using aluminum metal and phosphoric acid and the composition thereof.
In the process for preparing the FCC catalyst additive, the aluminum metal powder is mixed with phosphoric acid solution containing 20-86 wt % H
3
PO
4
to obtain a aluminum phosphate having a pH of from 0.5 to 0.9 and Al to PO
4
molar ratio of from 1-3, the aluminum phosphate so obtained is mixed with clay (Kaolin) to get a resultant mixture, the said resultant mixture is then combined with aqueous slurries of zeolite as ZSM-5 under high sheer mixing condition to obtain a spray drier feed slurry that contains 20 to 45 wt % solids preferably comprising 4 to 20 wt % aluminum phosphate, 1-40 wt % ZSM-5 and 40-90 wt % Kaolin.
The catalyst additive slurry is held in a spray dryer feed storage tank under mixing conditions until spray dried and calcined for one hour at a temperature of 450-600° C. During the drying process the aluminum phosphate solution is converted into a binder.
The spray dried FCC catalyst additive of the subject invention has a particle size of 20-150 microns. The subject additives are used in the conventional fluid cracking catalyst unit wherein the FCC catalyst are reacted with hydrocarbon feedstock at 400-700° C. and regenerated at 500-850° C. to remove coke. The subject additives are having the attrition index of 3-15, preferably 5-10.
Accordingly, the subject invention relates to a fluid catalytic cracking additive composition to obtain enhanced yield of Liquefied Petroleum Gas in catalytic cracking of high boiling petroleum feed stocks comprising 4 to 20 wt % aluminum phosphate composite, 1-40 wt % crystalline molecular sieve zeolites from the group selected from mordenite ZSM-5, Beta and mixtures thereof and 40-90 wt % clay.
More specifically, the invention relates to a fluid catalytic cracking additive composition to obtain enhanced yield of Liquefied Petroleum Gas in catalytic cracking of high boiling petroleum feed stocks comprising 4 to 20 wt % aluminum phosphate composite, 1-40 wt % ZSM-5 and 40-90 wt % Kaolin.
The subject invention also relates to a process for the preparation of fluid catalytic cracking additive composition to obtain enhanced yield of Liquefied Petroleum Gas in catalytic cracking of high boiling petroleum feed stocks comprising:
i) reacting the aluminum metal powder with phosphoric acid solution containing 20-86 wt % H
3
PO
4
to obtain aluminum phosphate composite,
ii) mixing aluminum phosphate composite with clay to get a resultant mixture,
(iii) adding the said resultant mixture to aqueous slurries of crystalline molecular sieve zeolites selected from the group consisting of mordenite ZSM-5, Beta and mixtures thereof, under high sheer mixing condition to obtain a spray drier feed slurry containing 20 to 45 wt % solids,
(iv) spray drying the above feed to get the micropore of 20-150 micron size and
(v) calcining the sample for one hour at a temperature of 450-600° C.
More specifically the invention relates to a process for the preparation of fluid catalytic cracking additive composition to obtain enhanced yield of Liquefied Petroleum Gas in catalytic cracking of high boiling petroleum feed stocks comprising:
i) reacting the aluminum metal powder with phosphoric acid solution containing 20-86 wt % H
3
PO
4
to obtain aluminum phosphate composite;
ii) mixing aluminum phosphate composite with Kaolin clay
Chandran Gopal Ravi
Ghosh Sobhan
Gupta Kamlesh
Krishnan Venkatachalam
Kuvettu Mohan Prabhu
Griffin Steven P.
Ildebrando Christina
Indian Oil Corporation Limited
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