Sulfur removal from hydrocarbons with nickel containing catalyst

Mineral oils: processes and products – Chemical conversion of hydrocarbons – Cracking

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208 91, 208 58, 208 64, C10G 1102, C10G 2505

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active

053244206

DESCRIPTION:

BRIEF SUMMARY
This invention relates to the treatment of sulphur-bearing hydrocarbon feedstocks, and especially to the removal of sulphur from the feedstock. In particular, the invention relates to treatment of olefin feedstocks, especially those to be hydroformylated by the oxo process to produce alcohols used in esterification.
Olefins, in hydroformylation feedstocks for example, frequently have sulphur-containing impurities. Thiols, thiophenes, hydrogen sulphide, and other sulphur-containing compounds may make the feed unacceptable because of the tendency for the sulphur rapidly to poison the catalyst used, either in the hydroformylation or, especially, if the resulting aldehyde is to be reduced over a catalyst, e.g. copper chromite, nickel or cobalt, either supported or unsupported, to an alcohol. In particular, the selectivity and activity of a copper chromite catalyst are both adversely affected by sulphur, and cobalt or nickel catalysts suffer a loss in activity.
That such feedstocks may be desulphurized has been disclosed, without details of the procedure, in a brochure entitled "Oxo-alcohols and Plasticizers" published by Exxon Chemical Holland Inc.
It has been proposed, in British Specification No. 1142339, to remove carbon oxysulphide from C.sub.3 feedstocks by their passage in the liquid phase over an oxide of cadmium, zinc, nickel or cobalt on a carrier.
In U.S. Pat. No. 4,592,829, it is proposed to hydrofine a reformer feedstock containing a preponderance of aromatics and lesser amounts of paraffins and olefins, and to complete the desulphurization of the hydrofined feedstock by passing it over a supported nickel/iron catalyst. In U.S. Pat. No. 4,634,515 desulphurization of a hydrofined naphtha feedstock is completed over a nickel catalyst of greater than normal average crystallite size, having at least 50% of the nickel in the reduced state. Desulphurization of aromatic hydrocarbon feedstocks and of feedstocks composed of paraffinic and unsaturated heavier hydrocarbons over the nickel-containing catalyst designated "Girdler G-134 A RS" is advocated in a brochure entitled "Katalysatoren der SUD-Chemie AG" published by that company.
The present invention provides a process for the manufacture of an aldehyde, and optionally of an alcohol or an acid, by hydroformylation of an olefin-containing feedstock and optional subsequent hydrogenation using a catalyst, e.g. copper chromite, nickel or cobalt, either supported or unsupported, susceptible to sulphur poisoning, wherein a sulphur-bearing olefin-containing feedstock is contacted under substantially non-hydrogenating conditions with a nickel-containing catalyst, whereby the sulphur content of the feedstock is lowered, the resulting reduced-sulphur feedstock is hydroformylated, and optionally the resulting aldehyde reduced to form an alcohol or oxidized to form an acid.
The invention also provides the use of a nickel-containing catalyst in desulphurization of an olefin feedstock to a hydroformylation process, especially to a hydroformylation process followed by reduction to an alcohol or oxidation to an acid.
The olefin feedstock may contain C.sub.3 to C.sub.18, advantageously C.sub.4 to C.sub.12, more advantageously C.sub.4 to C.sub.6, olefins, and preferably comprises pentene or hexene.
The feedstock is advantageously contacted with the nickel-containing catalyst at a temperature and under a pressure such that the feedstock is liquid. Although precise conditions depend on the feedstock, for hexene and similar olefins a pressure within the range of 20 to 40 bar and a temperature within the range of from 150.degree. to 200.degree. C., advantageously 165.degree. to 190.degree. C., are generally preferred, the precise temperature range depending also on the catalyst. Temperatures above the range indicated above are to be avoided if formation of oligomeric compounds is to be avoided; at lower temperatures the effectiveness of sulphur removal is reduced. Within the effective range, optimum temperature will depend also on the catalyst and, during operation, its sulp

REFERENCES:
patent: 4634515 (1987-01-01), Bailey et al.
patent: 5030774 (1991-07-01), Oswald et al.
patent: 5082977 (1992-01-01), Chaung

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