Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Patent
1986-06-11
1988-04-26
Dees, Carl F.
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
502 74, B01J 2912, B01J 2922
Patent
active
047404876
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to catalyst materials containing a transition metal and a support material, to methods of making the catalysts and to processes for using the catalysts to produce useful fuel materials. In particular, the present invention relates to catalysts having ruthenium supported on a zeolite material, preferably an acidic material in combination with a Group VI or Group VIII metal on a refractory support, and to the use of the catalysts in treating hydrogen and carbon-containing material to produce a fuel material.
Although the present invention will be described with particular reference to treating shale oil to produce transport fuel and in particular middle distillate fuel, it is to be noted that the present invention is not so limited and is applicable to a variety of high-boiling feeds and processes.
One disadvantage of using alternative sources of fuel to, or substitute liquid fuels for, petroleum crude oil stocks, such as for example, using heavier fractions of crude oil, shale oil, coal and tar sands to derive the fuel, is that the product oils obtained from the alternatives can contain high levels of nitrogen, oxygen and sulphur. All of the high-boiling feed stocks concentrate heavy metal impurities, heterocyclic nitrogen, sulphur, and oxygen compounds and large polynuclear molecules. Nitrogen compounds are poisons to reforming and cracking catalysts, the combustion of sulphur- and nitrogen-containing material increases deleterious oxide emissions, and the presence of oxygen and nitrogen compounds in the final product causes poor storage stability. Therefore, in order to use these product oils as fuels or feedstock the amount of heteroatoms, in particular nitrogen, present in the product oils must be reduced. A commonly used method of heteroatom reduction is hydrotreatment of the oil using a suitable catalyst in the presence of hydrogen. In essence, the upgrading involves the removal of the organically bound N, S and O, and the breaking down of the high molecular weight components into a material having a desired boiling range. These processes are usually described as hydrodenitrogenation (HDN), hydrodesulphurisation (HDS), hydrodeoxygenation (HDO) and hydrocracking respectively.
Catalytic hydrotreating consists of the removal by hydrogenolysis of sulphur, oxygen and nitrogen as H.sub.2 S, H.sub.2 O and NH.sub.3, respectively, leaving heteroatom-free hydrocarbons. In addition some hydrocracking can occur, depending on the catalyst used. The conventional catalysts are based on transition metal sulphides and have been developed into relatively sophisticated systems by the petroleum industry. The catalysts normally employed are cobalt- and nickel-promoted molybdenum or tungsten supported on alumina or silica-alumina; the application of crystalline molecular sieve zeolites to catalytic hydrotreating has only recently attracted attention.
The production of middle distillates from heavy or "dirty" feedstock using conventional catalysts usually requires a two-stage process; one stage for the production of a suitable crude material and the other stage for the production of a useful fuel product. The present invention in one form is directed to a new catalyst system which is capable of simultaneously hydrotreating and hydrocracking heavy feeds for the direct production of middle distillates under commercially acceptable conditions.
The current generation of hydrocracking catalysts are bifunctional and provide both a hydrogenating and a cracking function. The hydrogenating component is normally provided by the noble metals, particularly palladium and platinum, except when the feed heteroatom content is high. In such circumstances, or in a two-stage process, the initial hydrotreating step usually employs sulphides of Group VI metals or of Group VI and Group VIII metal combinations; especially molybdenum or tungsten with cobalt or nickel to remove nitrogen and sulphur prior to the actual cracking of the feed stock which if not removed would poison the noble metal catalysts as indicated ea
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Harvey Timothy G.
Matheson Trevor W.
Pratt Kerry C.
Stanborough Mark S.
Commonwealth Scientific and Industrial Research Organization
Dees Carl F.
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