Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By dehydrogenation
Reexamination Certificate
1999-11-29
2001-01-16
Wood, Elizabeth D. (Department: 1755)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By dehydrogenation
C585S654000, C585S661000, C585S671000
Reexamination Certificate
active
06175048
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a catalyst composition useful for converting a saturated hydrocarbon to olefins, a process for producing the composition, and a process for using the composition in a hydrocarbon conversion process.
BACKGROUND OF THE INVENTION
It is well known to those skilled in the art that olefins are a class of very important industrial chemicals which find a variety of uses in petrochemical industry such as, for example, in production of various organic compounds and polymers. Olefins can be produced by several different methods such as, for example, thermal cracking of saturated hydrocarbons and catalytic dehydrogenation of saturated hydrocarbons.
It is conventional in the dehydrogenation of saturated hydrocarbons to utilize catalysts such as platinum, nickel-kieselguhr, chromium oxide-alumina, zinc oxide-alumina, and platinum-alumina. Additionally, a platinum catalyst on a support, with or without oxygen present, is known to be one possible system for the dehydrogenation of paraffin hydrocarbons in the presence of steam.
A process for the dehydrogenation of alkanes, cycloalkanes and arylalkanes can also be carried out over a catalyst composition comprising a Group VIII metal, such as platinum, or a mixture of a Group VIII metal and a Group IVA metal, such as tin. Such catalyst is generally deposited on a support selected from the group consisting of alumina, HF-treated alumina, silica, zinc oxide, magnesia, zirconia, aluminosilicate, and Group IIA and Group IIB aluminate spinels. A dehydrogenation process can be materially improved when the process is conducted in the presence of gaseous hydrogen or mixtures of gaseous hydrogen and gaseous oxygen.
However, in the known processes, the conversion of a saturated hydrocarbon to an olefin and the selectivity thereto are generally not as high as one skilled in the art would desire. Generally, to produce branched olefins, an isomerization process is required thereby increasing the cost for producing branched olefins. Accordingly, there is an ever-increasing need to develop a catalyst and a process for converting a saturated hydrocarbon to the more valuable olefins, specially branched olefins, (hereinafter referred to as hydrocarbon conversion process). Such development would also be a significant contribution to the art and to the economy.
SUMMARY OF THE INVENTION
An object of this invention is to provide a catalyst composition which can be used to convert a saturated hydrocarbon to an olefin. Also an object of this invention is to provide a process for producing the catalyst composition. Another object of this invention is to provide a process which can employ the catalyst composition to convert a saturated hydrocarbon to olefins. An advantage of the catalyst composition is that, when compared with a commercially available dehydrogenation catalyst, it exhibits high hydrocarbon conversion activity, satisfactory yield of olefins, and good selectivity to branched olefins. Other objects and advantages will become more apparent as this invention is more fully disclosed hereinbelow.
According to a first embodiment of the present invention, a composition which can be used as catalyst for converting a saturated hydrocarbon or a mixture of hydrocarbons containing at least one saturated hydrocarbon to an olefin or a mixture of olefins is provided. The composition comprises at least one metal or metal oxide selected from Group VA metals, an inorganic support, optionally at least one metal or metal oxide selected from Group IVA metals, and further optionally at least one metal or metal oxide selected from Group VIII metals. The terms “Group IVA”, “Group VA”, and “Group VIII” refer to the Periodic Table of the Elements, CRC Handbook of Chemistry and Physics, 67 th edition, 1986-1987, CRC Press, Boca Raton, Fla.
According to a second embodiment of the invention, a process for producing a composition which can be used as catalyst in a hydrocarbon conversion process is provided. The process can comprise, consist essentially of, or consist of the steps: (1) combining a Group VA metal compound, an inorganic support, and optionally a Group IVA metal compound and/or a Group VIII metal compound to form a mixture, and (2) calcining the mixture under a condition sufficient to convert each metal compound to its oxide form.
According to a third embodiment of the present invention, a process which can be used for converting a saturated hydrocarbon or mixture of hydrocarbons containing at least one saturated hydrocarbon to an olefin or a mixture of olefins containing at least one branched olefin is provided which comprises, consists essentially of, or consists of, contacting a fluid which comprises a saturated hydrocarbon or mixture of hydrocarbons, optionally in the presence of an inert fluid, with a catalyst composition which can be the same as disclosed above in the first embodiment of the invention under a condition effective to convert a saturated hydrocarbon to an olefin or a mixture of olefins.
DETAILED DESCRIPTION OF THE INVENTION
According to the first embodiment of the invention, a composition which can be used as catalyst in a hydrocarbon conversion process for converting a saturated hydrocarbon to an olefin is provided. As used herein, the term “hydrocarbon” is generally referred to, unless otherwise indicated, as one or more hydrocarbons, saturated or unsaturated, having 1 to about 30 carbon atoms, preferably 2 to about 20 carbon atoms, more preferably 2 to about 16, and most preferably 2 to 10 carbon atoms per molecule. Also preferably, the hydrocarbon is an aliphatic saturated hydrocarbon, a mixture of saturated aliphatic hydrocarbons, or a mixture of saturated aliphatic hydrocarbons and unsaturated hydrocarbons. An example of hydrocarbons include, but are not limited to, ethane, propanes, butanes, pentanes, heptanes, octanes, nonanes, dodecanes, gasoline, or combinations of two or more thereof. The composition can comprise, consist essentially of, or consist of, an inorganic support having incorporated therein, or impregnated thereon, a selectivity-improving amount of a promoter to improve the yield of or selectivity to an olefin when the composition is used in a hydrocarbon conversion process. The term “improving” or “improve” is referred to, unless otherwise indicated, as an increased weight percent of, or percent selectivity to, olefin in the product stream of a hydrocarbon conversion process using a promoted catalyst such as Bi
2
O
3
-promoted silicoaluminophosphate (SAPO), as compared to using a nonpromoted catalyst.
The term “metal” used herein refers to, unless otherwise indicated, both “metal” and “element” of the Periodic Table of the Elements because some elements in the Periodic Table of the Elements may not be considered as metals by those skilled in the art.
According to the first embodiment of the invention, the weight percent of the Group IVA, Group VA, or Group VIII metal or element in the composition of the invention can be any weight % so long as the weight % can improve the yield of or selectivity to an olefin in a hydrocarbon conversion process for converting of a hydrocarbon to a an olefin. Generally, the weight % of Group IVA or Group VIII metal can be in the range of from about 0.0001 to about 5%, preferably about 0.005 to about 3%, more preferably about 0.05 to about 2%, and most preferably from 0.1 to 1.5% for an effective hydrocarbon conversion. Generally, the weight % of Group VA metal in the composition of the invention can be in the range of from about 0.1 to about 50%, preferably about 0.5 to about 40%, more preferably about 1 to about 30%, and most preferably 1 to 20%.
Any metal that, when incorporated into an inorganic material such as silicoaluminophosphate or a nonzeolitic molecular sieve, is capable of improving a hydrocarbon conversion process to an olefin can be employed in the invention. Presently, it is preferred that the promoter comprises at least one Group VA metal, optionally at least one Group VIII metal, and further optionally at least one Group IVA metal. The
Drake Charles A.
Wu An-hsiang
Kelly Kameron D.
Phillips Petroleum Company
Wood Elizabeth D.
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