Mineral oils: processes and products – Refining – Metal contaminant removal
Patent
1997-12-05
1999-11-23
Griffin, Walter D.
Mineral oils: processes and products
Refining
Metal contaminant removal
502305, 502313, 502315, 502327, 502335, 50252712, 50252718, 50252715, 50252724, B01J 2300, B01J 2340, C10G 1700
Patent
active
059894121
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a hydrodemetallizing (hydrogenating and demetallizing) catalyst for a hydrocarbon oil and also relates to a process of hydrodemetallizing a hydrocarbon oil with the use of this catalyst. More particularly, the present invention is concerned with a hydrodemetallizing catalyst for a hydrocarbon oil which enables performing a continuous operation for a prolonged period of time in the hydrogenation of hydrocarbon oils, especially, a heavy oil and is also concerned with a process of hydrodemetallizing a hydrocarbon oil with the use of this catalyst.
BACKGROUND ART
The high boiling point hydrocarbon oils such as tar sand oil and petroleum distillation residue obtained by the atmospheric distillation or vacuum distillation of crude oil contain a large amount of impurities such as metals, sulfur compounds and nitrogen compounds. Thus, the hydrogenation technique as the most common purification means is now applied to the high boiling point hydrocarbon oils for utilizing them as various types of fuels and raw materials for chemical industry.
The trend toward a rapid shift of the stock oil to heavier oils is encountered especially in recent years. Accordingly, the demand for the resolution of technical problems of demetallization is increasing in addition to the problems of the conventional desulfurzation, denitrification and conversion to a light oil.
A problem of process technology in the hydrogenation of heavy oils is not only how to attain a high level of desulfurization degree but also how to remove metals as impurities and how to reduce the effect of metal deposition onto catalyst on the catalytic performance.
As different from sulfur compounds and nitrogen compounds, organometallic compounds and other metal components contained in the stock oil generally involve a phenomenon such that, except for unreacted part, substantially all of them deposit in the form of, for example, metal sulfides on the catalyst in accordance with the advance of the reaction and are not discharged outside the reaction system through the period of operation. This results in inviting problems such that the catalytic performance is lowered and that clogging of the catalyst bed increases the pressure drop in the reaction vessel.
Further, in the process of hydrogenation for heavy oil, carbonaceous substances (hereinafter may be referred to as "carbon") are deposited by the hydrocarbon decomposition reaction which is regarded as an inevitable side reaction.
The above deposited substance is the major cause of the pressure drop increase (hereinafter may be referred to as ".DELTA.P increase") experienced in the fixed bed reactor in which a particulate catalyst is packed.
In the process of heavy oil hydrogenation, generally, the type (for example, active metal species and amount of carried metals) of catalyst to be packed in the reactor and the amount of packed catalyst are determined on a condition that the catalyst would effectively function throughout the packed bed during the period of one cycle of continuous operation. However, in the actual operation, a rapid increase of .DELTA.P occurs before the planned volume of oil passage with the result that an arrival at the state of being no longer capable of continuing the operation is experienced.
That is, as long as the catalyst is appropriate for the stock oil, the activity of latter stage desulfurization catalyst is lowered in accordance with the predetermined schedule before the .DELTA.P increase of first direct desulfurization column (demetallizing reaction tower), and the operation is terminated. Unexpected deactivation of the desulfurization catalyst is caused by deterioration of the demetallizing catalyst at a latter period of the operation with the result that heavy metals contained in the stock oil acceleratingly deposit on the desulfurization catalyst. Moreover, at a latter period of the operation, the temperature of the catalyst bed is raised in accordance with the lowering of the activity of the demetallizing catalyst and desulfu
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Furuta Akio
Okagami Akio
Suhara Shinichiro
Tsuchiya Fujio
Catalysts & Chemicals Industries Co. Ltd.
Griffin Walter D.
Nguyen Tam M.
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