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US 4,052,467 AGranted
Catalytic reduction of aldehydes to alcohols
AssigneePhillips Petroleum Company
InventorsKing L. Mills, Roy V. Denton
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AssigneePhillips Petroleum Company
InventorsKing L. Mills, Roy V. Denton
Estimating the term…
Aldehydes in a feed containing sulfur in the range of about 10 ppm to 1 weight percent in the form of thiophene or other heterocyclic ring compounds are hydrogenated in admixture with H.sub.2 to the corresponding alcohols with a catalyst comprising a reduced mixture of the oxides of Zn and Cu, without decomposing the ring sulfur compounds to a form of sulfur which deactivates the catalyst by using critical reaction conditions.
A process for reducing an aldehyde to the corresponding alcohol in a hydroformylation process derived liquid feed containing at least 1 weight percent of said aldehyde and further containing at least 10 ppm and up to 1 weight percent of sulfur in the form of ring-type sulfur compounds, said aldehyde containing up to 30 carbon atoms per molecule, which comprises contacting said liquid feed under substantially liquid conditions in admixture with H.sub.2 in an amount sufficient to hydrogenate said aldehyde at a temperature in the range of 450.degree. to 550.degree. F., a pressure in the range of 800 to 1200 psig sufficient to maintain substantially a liquid phase, and a liquid hourly space rate in the range of 1.0 to 1.5, with a catalyst comprising a mixture of the oxides or hydroxides of Zn and Cu reduced by treatment with CO, H.sub.2, or mixture, wherein said catalyst initially contains 40 to 90 weight percent ZnO and 60 to 10 weight percent CuO exclusive of support, if any, prior to said reduction, and wherein said treatment with CO, H.sub.2, or mixture is conducted at about 400.degree. F. to 800.degree. F.
Dependencies are inferred from the claim text.
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By reaction with carbon monoxide: by oxo-reactions
Of a —CHO group: with hydrogen or hydrogen-containing gases
Acyclic or carbocyclic compounds
Term ended 4 Oct 1994 (estimated)
USPTO file history isn’t available for this patent, so only indexed dates are shown.
The invention relates to a process for the catalytic reduction of aldehydes to alcohols, using feeds which contain thiophene or other ring-type sulfur compounds in a concentration in the range of about 10 parts per million (ppm) to about 1 weight percent of the feed (calculated as S).
In the oxo process for the formation of aldehydes and alcohols by the reaction of CO and H.sub.2 with olefins, it is desirable to catalytically reduce the aldehydes to the corresponding alcohols. There are a number of catalysts which function in this reduction successfully, providing the feed material is relatively sulfur-free, i.e., containing less than 10 ppm of sulfur. However, there are relatively few sulfactive catalysts for this reduction and these are relatively inefficient for the reduction process and also nonselective in the presence of olefins and aromatics.
The instant invention is concerned with a process which efficiently reduces aldehydes to the corresponding alcohols in the presence of thiphene and other ring-type sulfur compounds without decomposing the sulfur compounds to free sulfur and/or sulfur compounds which deleteriously affect the reduction catalyst.
The following examples are presented to illustrate the invention without unduly restricting the same.
A 77-hour test was made to reduce a synthetic blend of heptaldehyde in light cycle oil (boiling in the range of 420.degree.-650.degree. F), utilizing a reduced mixture of copper and zinc oxides containing 55.9 percent zinc and 38.7 percent (by weight) copper. The feed inlet temperature was maintained at 500.degree. F, the pressure at 1000 psig, and the hydrogen concentration at 2000 cubic feet per barrel of charge. The heptaldehyde in the feed amounted to 30 weight percent thereof. The sulfur content in the form of thiophene amounted to 0.20 weight percent of the feed. A liquid hourly space rate of 1 was utilized. The catalyst was reduced for 8 hours at 800.degree. F. Data obtained in the runs are presented in Table I below.
Table I ______________________________________ Hours on Stream 12 24 36 48 66 72 77 ______________________________________ Aldehyde conv. 99.5 99.4 99.1 99.2 99.0 98.7 99.3 mol % Alcohol yield, -- 90.2 94.1 95.0 90.0 89.6 93.1 mol % Efficiency -- 90.0 93 94 89 88.5 92 ______________________________________