Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Reexamination Certificate
2002-04-08
2004-06-29
Bos, Steven (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
C502S330000
Reexamination Certificate
active
06756340
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to the conversion of hydrocarbons, especially the dehydrogenation of dehydrogenatable hydrocarbons, in the presence of a catalyst composite. This invention also pertains to a new catalyst composite.
The dehydrogenation of hydrocarbons is an important commercial process because of the great demand for dehydrogenated hydrocarbons for the manufacture of various chemical products such as detergents, high octane gasolines, pharmaceutical products, plastics, synthetic rubbers, and other products well known to those skilled in the art. One example of this process is dehydrogenating isobutane to produce isobutylene which can be polymerized to provide tackifying agents for adhesives, viscosity-index additives for motor oils, impact-resistant and anti-oxidant additives for plastics and a component for oligomerized gasoline.
INFORMATION DISCLOSURE
The prior art is cognizant of various catalytic composites which contain a Group VIII noble metal component, an alkali or alkaline earth metal component, and a component selected from the group consisting of tin, germanium, lead, indium, gallium, thallium, or mixtures thereof. However, the prior art has not yet known of a catalyst composite having a surface area of 120 m
2
/g or less, having an ABD of 0.5 g/cm
3
or greater and a mole ratio of the Group VIII noble metal component to the component selected from the group consisting of tin, germanium, lead, indium, gallium, thallium or mixtures thereof in the range from about 1.5 to about 1.7.
U.S. Pat. No. 4,070,413 describes a dehydrogenation process utilizing a catalyst comprising a Group VIII metal and lithium, both impregnated on an alumina support. The alumina support is further characterized in that it has been hydrothermally treated in steam at a temperature from about 800° to 1200° C. The catalyst of this invention is distinguished from that of the '413 patent in that the instant catalyst comprises, in addition to a Group VIII metal component and an alkali or alkaline earth metal component, a component selected from the group consisting of tin, germanium, lead, indium, gallium, thallium, or mixtures thereof. Additionally, the catalyst support of this invention has a higher ABD than that disclosed in the '413 patent. The '413 patent discloses a catalyst having a pre-hydrothermally treated ABD of from about 0.25 to about 0.45 g/cm
3
. From Example III, it is seen that the final catalyst composites of the catalyst of the U.S. Pat. No. '413 have an ABD of about 0.3. The catalyst of this invention must have a final ABD of at least 0.5 g/cm
3
.
U.S. Pat. No. 4,608,360 describes a catalytic composite comprising a Group VIII noble metal component, a co-formed IVA metal component, and an alkali or alkaline earth metal on an alumina support having a surface area of from 5 to 150 m
2
/g. Additionally, the alumina support of the '360 patent is characterized in that the mean pore diameter is about 300 angstroms or less and more than about 55% of the total pore volume of the support is associated with pores having a mean diameter of 600 angstroms or more. In distinction, the catalyst of this invention is characterized in that it has a surface area of 120 m
2
/g or less and an ABD of 0.5 g/cm
3
or more. The catalyst of the '360 patent from Example II has an ABD of about 0.3. Additionally, the catalyst of the present invention contains very little of its total pore volume in pores having a diameter of 600 angstroms or more while the '360 catalyst has over 50% of its total pore volume associated with pores having mean diameters of about 600 angstroms or more.
U.S. Pat. No. 4,717,779 discloses a process for dehydrogenating dehydrogenatable hydrocarbons using a selective oxidation catalyst comprising a Group VIII noble metal component, a Group IVA component, and if desired a Group IA or IIA component. The components are composited on an alumina support wherein an alumina precursor possesses an ABD less than about 0.6 g/cm
3
which, after calcination at a temperature of from about 900° to 1500° C., will result in an alumina possessing an ABD of from 0.3 to 1.1 g/cm
3
and where more than 40% of the pore volume is present in pores greater than 1500 angstroms. In contrast, the catalyst of the present invention comprises an ABD of 0.5 g/cm
3
or greater and preferably from 0.6 g/cm
3
or greater and a mole ratio of the Group VIII noble metal component to the Group IVA, Group IA or IIA component is in the range from about 1.5 to about 1.7. Additionally, very little of the total catalyst pore volume, that is, much less than 40% of the total catalyst pore volume, is comprised of pores of 1500 angstroms or greater.
U.S. Pat. No. 4,786,625, discloses a catalyst for the dehydrogenation of dehydrogenatable hydrocarbons comprising a platinum group metal component, a modifier metal component selected from the group consisting of tin, germanium, rhenium, and mixtures thereof, and optionally an alkali or alkaline earth metal component, all on a refractory oxide support, preferably alumina. The catalyst is characterized in that the platinum group metal component is surface impregnated. The catalyst of the present invention does not comprise any surface-impregnated components and, in addition, the alumina catalyst support of the '625 patent is not characterized as requiring a limited ABD or surface area.
U.S. Pat. No. 4,788,371, discloses a catalytic oxidative steam dehydrogenation process utilizing a single catalyst comprising a Group VIII noble metal component; one or more components selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and francium; and one or more components selected from the group consisting of boron, gallium, indium, thallium, germanium, tin, and lead, all on an inorganic oxide support, preferably alumina having a surface area of from 1 to 500 m
2
/g, but preferably from 5 to 120 m
2
/g. The catalyst does not disclose a specific range for the alumina support.
U.S. Pat. No. 4,914,075 discloses a catalytic composite comprising a Group VIII noble metal component, a Group IA or IIA metal component and a component selected from the group consisting of tin, germanium lead, indium, gallium, thallium or mixtures thereof, all on an alumina support having a low surface area of 120 m
2
/g or less and an ABD of 0.5 g/cm
3
or more. This reference discloses a catalyst which has a platinum to tin mole ratio of 0.914.
The present invention is a catalytic composite and process for its use with the catalyst having a support with a surface area of 120 m
2
/g or less in conjunction with an apparent bulk density (ABD) of at least 0.5 g/cm
3
. The support is utilized in conjunction with a platinum group metal component, an alkali or alkaline metal component and a third component selected from the group consisting of tin, germanium, lead, indium, gallium, thallium and mixtures thereof. It has surprisingly been discovered that a superior catalyst, which possesses an alkali or alkaline metal component in an amount from 0.9 to 1.1 weight percent based on the total composite weight and a mole ratio of the platinum group metal component to the third component from about 1.5 to about 1.7, demonstrates a higher initial maximum hydrocarbon dehydrogenation activity and a higher conversion from 5 to 20 hours on stream.
OBJECTS AND EMBODIMENTS
It is an object of the present invention to provide an improved catalytic composite and a process for the conversion of hydrocarbons and especially for the dehydrogenation of dehydrogenatable hydrocarbons utilizing the improved catalytic composite. Accordingly, in a broad embodiment, the present invention is a catalytic composite comprising a first component selected from Group VIII noble metal components or mixtures thereof, a second component in an amount from 0.9 to 1.1 weight percent, based on the total composite weight selected from the group consisting of alkali or alkaline earth metal components or mixtures thereof and a third component selected from the group consi
Adriaan Sachtler J. W.
Vora Bipin V.
Voskoboynikov Timur V.
Wei Daniel H.
Bos Steven
Cutts John G.
Nguyen Cam
Paschall James C.
Tolomei John G.
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