Catalytic oxidative conversion of hydrocarbons to aldehydes

Details Catalytic oxidative conversion of hydrocarbons to aldehydes Catalytic oxidative conversion of hydrocarbons to aldehydes

2001-04-30

2003-05-13

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S469900, C568S470000, C568S475000, C568S909500, C568S910500, C568S915000

Reexamination Certificate

active

06563006

ABSTRACT:

BACKGROUND—FIELD OF INVENTION
This invention relates to ambient air catalytic oxidation of saturated hydrocarbons, specifically to efficient catalytic oxidative conversion of hydrocarbons to aldehydes and unsaturated alcohols employing catalysts based on molecular strings of di-, tri- and/or poly-groups of bonded transition metal complexes.
BACKGROUND—DESCRIPTION OF PRIOR ART
A number of chemical reaction paths have previously been investigated for single step conversion of aliphatic hydrocarbons to aldehydes or alcohols but none teach high conversion efficiencies without employment of high temperature and pressure, aggressive chemical oxidizers or strong chemical agents. For example, controlled oxidation of methane, investigated under a wide range of conditions, has produced carbon dioxide, carbon monoxide, low concentrations of unsaturated hydrocarbons, oligomers, low levels of alcohols, aldehydes and water. None of these efforts have produced significant amounts of aldehydes or alcohols. As a result direct conversion of saturated hydrocarbons to aldehydes and/or alcohols has essentially been abandoned in favor of conversion of more labile hydrocarbons such as alkenes or other organic compounds with reactive groups. The invention disclosed in this application teaches catalytic air oxidative conversion of aliphatic hydrocarbons directly to aldehydes and unsaturated alcohols at room temperature and above using di-metal, tri-metal and/or poly-metal backbone or molecular string type transition metal catalysts without addition of aggressive chemical oxidizing agents and without addition of other strong chemicals. No labile or other reactive chemical groups are required for production of aldehydes and unsaturated alcohols from saturated hydrocarbons. Use of di-metal, tri-metal and/or poly-metal backbone or molecular string type transition metal catalysts described in this application produce a significantly higher yield of oxidized products than the relatively inactive mono-metal transition metal compounds.
Air oxidation of hydrocarbon vapors has been accomplished in pressurized reactions at elevated temperatures in the presence of selected transition metal salts or on the surface of shaped pore solid zeolites. Olefin or alkenyl type unsaturated hydrocarbons may be oxidized to aldehydes with air or oxygen at elevated temperatures in the presence of transition metal compounds as taught in the following patents. U.S. Pat. No. 6,143,928, issued Nov. 7, 2000, teaches of the catalytic oxidation of propylene with molecular oxygen containing gas at 100° C. to 450° C. and 1 to 50 bars pressure. U.S. Pat. No. 6,069,282, issued May 30, 2000, discloses preparation of vinyl, alkynyl or aryl aldehydes by reaction of vinyl, alkynyl or aryl-methanols with the aid of a mediator and an oxidant, wherein the mediator is selected from the group of aliphatic, cycloalphatic, heterocyclic or aromatic NO or NOH containing compounds. U.S. Pat. No. 5,426,238, issued Jun. 20, 1995, introduces a method for producing an aldehyde, which comprises reacting an olefin with carbon monoxide and hydrogen in a hydroformulation reaction in the presence of a rhodium catalyst with an organophosphorus ligand. U.S. Pat. No. 5,409,877, issued Apr. 25, 1995, demonstrates another method for production of an aldehyde and an alcohol using a heterogeneous transition metal catalyst for the hydroformylation of an olefin with H
2
and CO. These disclosures employ the labile olefinic double bond as a reaction site for selective oxidation but do not describe a method for convenient conversion of saturated hydrocarbons to aldehydes.
Strong chemical oxidizing agents have also been employed for controlled oxidative conversion of alcohols, alkenes and other labile compounds to aldehydes and other products under controlled conditions. U.S. Pat. No. 5,698,744, issued Dec. 16, 1997, shows a process for the selective oxidation employing ferromagnetic chromium dioxide. U.S. Pat. No. 5,602,280, issued Feb. 11, 1997, formed an unsaturated aldehyde and an unsaturated carboxylic acid by subjecting propylene, isobutylene or tertiary butanol to gas phase catalytic oxidation with molecular oxygen in the presence of transition metal oxides including tungsten oxides followed by re-oxidation of the transition metal oxide to its original oxidation state. Here the metal oxides may be considered to be co-reactants since they require re-oxidation by oxygen gas to be converted back to their beginning state. U.S. Pat. No. 4,885,412, issued Dec. 5, 1989, teaches a process for producing an aldehyde from alkylaromatics in the vapor phase in the presence of molten nitrate salt catalysts. Here the term catalyst has been used to indicate the necessity for a chemical oxidizer in the form of a molten nitrate. U.S. Pat. No. 4,859,799, issued Aug. 22, 1989, introduced a process for production of aldehydes or ketones by oxidative cleavage of olefinic double bonds by means of a coordination complex of a ligand and a peroxo derivative of a transition metal. Even electrochemical techniques have been employed to drive oxidative reactions of organic compounds as described in U.S. Pat. No. 4,387,007, issued Jun. 7, 1983, in which para-tertiary-butylbenzaldehyde was manufactured by the electrochemical oxidation of para-tertiary-butyltoluene. These chemical reactions required the oxidizing power of strong chemical oxidizing agents or electrochemistry to achieve product aldehydes.
Strong chemicals such as strong acids and strong base hydroxides have also been used to achieve conversion of labile compounds to aldehydes. U.S. Pat. No. 4,562,297, issued Dec. 31, 1985, teaches that 3,5-dihydrocarbyl-4-hydroxybenzaldehydes are prepared from 4-(1-alkyenyl)-2,5-dihydrocarbylphenol, such as 1,1-dimethyl-2-(3,5-di-ter-t-butyl-4-hydroxyphenyl)ethene, with at least a stoichiometric amount of an oxygen-containing gas at 50° C. to 250° C. in the presence of an alcohol solvent and a catalytic amount of an alkali or alkaline earth metal hydroxide. U.S. Pat. No. 4,240,985, issued Dec. 23, 1980, produced aldehydes by cleaving 2,2-dialkyltetrahydropyrans bearing two hydrogen atoms in the sixth position using a strong acid. Thus, it is apparent that there are three classes of existing processes for preparation of aldehydes with mono-transition metal compounds: one class converts labile groups, including unsaturated or olefinic compounds with or without hydrogen, alcohols and other labile groups to aldehydes by chemical conversion. A second process class employs strong chemical oxidizing agents, such as permanganates, chromates, perchlorates, peroxides, chromium oxides and other oxygen rich chemical agents at elevated temperature to produce aldehydes. A third class of processes uses strong acids or strong bases to affect chemical conversion in the production of selected aldehydes. None of these patents teach how to convert saturated hydrocarbons to aldehydes at ambient conditions.
Olefins or unsaturated hydrocarbons can also be oxidized to alcohols with oxygen or by strong chemical means, usually at elevated temperatures and pressures, in the presence or absence of transition metal compounds. U.S. Pat. No. 5,623,090 issued Apr. 22, 1997, U.S. Pat. No. 5,414,145 issued May 9, 1995 and U.S. Pat. No. 4,296,262 issued Oct. 20, 1981 oxidized olefins with oxygen to form alcohols, while U.S. patent issued Aug. 30, 1977 and U.S. Pat. No. 4,013,729 issued Mar. 22, 1977 oxidized olefins by strong chemical means. Olefins can also be hydrolyzed to produce alcohols as taught in U.S. Pat. No. 4,956,506 issued Sep. 11, 1990, U.S. Pat. No. 4,857,664 issued Aug. 15, 1989, U.S. Pat. No. 4,484,013 issued Nov. 20, 1984, U.S. Pat. No. 4,476,333 issued Oct. 9, 1984, U.S. Pat. No. 4,469,903 issued Sep. 4, 1984, U.S. Pat. No. 4,456,776 issued Jun. 26, 1984, U.S. Pat. No. 4,408,085 issued Oct. 4, 1983, U.S. Pat. No. 4,360,406 issued Nov. 23, 1982, U.S. Pat. No. 4,306,084 issued Dec. 15, 1981, U.S. Pat. No. 4,296,263 issued Oct. 20, 1981, U.S. Pat. No. 4,270,011 issued May 26, 1981 and U.S. Pat. No. 4,180,688 issued Dec

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