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  Hydrogenation catalyst with improved textural propertiesUSPTO Application #: 20070105713Title: Hydrogenation catalyst with improved textural properties Abstract: A method is provided for making a catalyst support, and includes the steps of providing an aqueous suspension of refractory inorganic oxide and refractory inorganic carbide; forming the suspension into droplets; exposing the droplets to a gelling agent whereby the droplets are at least partially solidified so as to provide substantially sphere-shaped portions of refractory inorganic oxide and refractory inorganic carbide; and drying and calcining the sphere-shaped portions so as to provide substantially spherical particles of catalyst support containing refractory inorganic oxide and refractory inorganic carbide. Catalytically active metal phases and hydrogenation processes using the catalyst are also described. (end of abstract) Agent: Bachman & Lapointe, P.C. - New Haven, CT, US Inventors: Jorge M. Martinis, Maria E. Valera, Jose R. Velasquez, Angel R. Carrasquel USPTO Applicaton #: 20070105713 - Class: 502240000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Silicon Containing Or Process Of Making, With Metal, Metal Oxide, Or Metal Hydroxide The Patent Description & Claims data below is from USPTO Patent Application 20070105713. Brief Patent Description - Full Patent Description - Patent Application Claims
BACKGROUND OF THE INVENTION [0001] The invention relates to a hydrogenation catalyst, a method for making the catalyst, and a hydrogenation process utilizing the catalyst, wherein the catalyst has desirable physical characteristics. [0002] Hydrogenation processes are used for processing various hydrocarbon feedstocks to obtain desirable products. Such processes utilize a catalyst to direct the reaction toward the desired products. The catalyst must be capable of withstanding the operating conditions of the process without rapidly losing effectiveness. [0003] Numerous types of reactors can be used for carrying out the hydrogenation reaction. One type is known as an ebulliating bed reactor. An ebulliating bed reactor is characterized by a vessel containing a bed of the catalyst through which the feedstock is passed, typically from the bottom toward the top of the reactor. This results in a bed of the catalyst suspended in the medium and subjected to continuous collisions. The catalyst itself remains inside the reactor. [0004] One problem encountered in the art with ebulliating reactors is the attrition rate of the catalyst contained in the reactor. That is, the catalyst tends to break down to smaller particles or fines after any significant amount of use. [0005] U.S. Pat. No. 5,710,093 to Rivas et al. is drawn to a hydrogenation catalyst, and utilizes a process which produces spherical catalyst bodies that have good process properties and are resistant to attrition. Even greater improvements in the activity, heat dissipation and attrition resistance of the catalyst are of course desirable. [0006] It is therefore a primary object of the present invention to provide a catalyst system wherein the catalyst particles are resistant to attrition. [0007] It is a further object of the present invention to provide a catalyst having good heat dissipation properties so as to assist in dissipating heat generated by the exothermic hydrogenation reaction. [0008] It is a still further object of the present invention to provide a catalyst system which has excellent activity and selectivity toward desirable hydrogenation reactions for converting a carbon monoxide feedstock to C.sub.2+hydrocarbons. [0009] Other objects and advantages of the present invention will appear hereinbelow. SUMMARY OF THE INVENTION [0010] According to the present invention, the foregoing objects and advantages have been readily attained. [0011] According to the invention, a method is provided for making a catalyst support, wherein the method comprises the steps of providing an aqueous suspension of refractory inorganic oxide and refractory inorganic carbide; forming the suspension into droplets; exposing the droplets to a gelling agent whereby the droplets are at least partially solidified so as to provide substantially sphere-shaped portions of refractory inorganic oxide and refractory inorganic carbide; and drying and calcining the sphere-shaped portions so as to provide substantially spherical particles of catalyst support containing refractory inorganic oxide and refractory inorganic carbide. [0012] Still further according to the invention, catalyst support is provided which comprises substantially spherical particles of a substantially homogenous mixture of refractory inorganic oxide and refractory inorganic carbide, the support having a solid surface area of at least about 65 m.sup.2/g, a particle size of at least about 0.1 mm and preferably between about 0.1 and about 3 mm, a pore volume of at least about 0.2 cc/g, and an average pore diameter of at least about 150 .ANG.. [0013] In further accordance with the invention, a process is provided for hydrogenation of a carbon monoxide feed which method comprises the steps of providing a catalyst system comprising a catalyst support and a catalytically active metal phase on the catalyst support, wherein the catalyst support comprises substantially spherical particles of a substantially homogenous mixture of refractory inorganic oxide and refractory inorganic carbide, the support having a solid surface area of at least about 65 m.sup.2/g, a particle size of at least about 0.1 mm and preferably between about 0.1 and about 3 mm, a pore volume of at least bout 0.2 cc/g, and an average pore diameter of at least about 150 .ANG., and the catalytically active metal phase comprising at least one first metal selected from Group 4 of the periodic table of elements, and at least one second metal selected from the group consisting of Groups 8, 9 and 10 of the periodic table of elements; providing a carbon monoxide feed; and exposing the feed to the catalyst at hydrogenation conditions so as to convert the feed into a product comprising CH.sub.4, CO.sub.2 and C.sub.2.sup.+. The process of the present invention advantageously produces a conversion rate of at least about 60% vol. of the feed. DETAILED DESCRIPTION [0014] The invention relates to a hydrogenation catalyst, a method for making the catalyst, and a hydrogenation process utilizing the catalyst wherein the catalyst has excellent activity toward desired hydrogenation products and good properties in connection with the dissipation of heat. The hydrogenation catalyst of the present invention includes a catalyst support having desirable properties, and a catalytically active metal phase on the support which further provides the desired hydrogenation activity. According to the invention, the catalyst support is produced in the form of substantially spherical particles of a substantially homogenous mixture of refractory inorganic oxide, preferably silica, and refractory inorganic carbide, preferably silicon carbide. [0015] The support advantageously has a solid surface area of at least about 65 m.sup.2/g, a particle size of at least about 0.1 mm and preferably between about 0.1 and about 3 mm, a pore volume of at least bout 0.2 cc/g, and an average pore diameter of at least about 150 .ANG.. [0016] According to the invention, a method is also provided for making the catalyst and catalyst support of the present invention. [0017] The present method starts with provision of a suspension or slurry of silica, preferably colloidal or amorphous silica in water. Such a suspension or slurry can be readily prepared in many ways well known to a person of ordinary skill in the art. One preferred method for preparing the suspension is to mix a water soluble refractory inorganic salt, for example sodium silicate, with water to provide the desired suspension. [0018] It is preferable to keep the viscosity of the suspension at a level high enough to keep the silica in suspension, preferably at a viscosity of at least about 10 cp at 25.degree. C. To this end, it may be desirable to add a viscosity agent to the suspension. One example of a suitable viscosity agent is ethylene oxide polymer. According to the invention, this agent in concentration within the suspension of about 250 ppm, has been found to provide the desired viscosity. Of course, other viscosity agents would be well known to the person of ordinary skill in the art and are well within the broad scope of the present invention. The suspension at this point typically has a pH of between about 8 and about 10. [0019] According to the invention, refractory inorganic carbide particles, preferably silicon carbide particles, are now mixed with the suspension. These particles preferably have an average particle size which is less than or equal to about 150 .mu.m. This particle size has been found to help provide desirable surface area and pore volume properties in the end product. This mixture is mixed sufficiently to provide a substantially homogenously mixed aqueous suspension of silica and silicon carbide. This material is now ready for forming into the desired shapes or portions in accordance with the present invention. [0020] In order to form the aqueous suspension into the desired spherical shape, the suspension is preferably formed into droplets by exposing the suspension to an inert organic phase, preferably in the presence of a non-ionic surfactant. The difference in surface tension causes the aqueous suspension to form droplets, the size of which can be controlled through the application of different mixing intensity. This mixing is carried out at least sufficiently to produce substantially uniform droplet sizes within a suitable droplet size distribution, for example, between about 0.1 and about 3 mm, and preferably until at least about 80% of the aqueous suspension is contained within a droplet size distribution between about 0.1 and about 0.4 mm in size. Of course, other methods known to a skilled artisan could be used to form the droplets well within the broad scope of the present invention. [0021] In accordance with one embodiment of the invention, this mixing step is carried out sufficiently to produce an emulsion of the aqueous suspension in the organic phase. Continue reading... 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