Abstract: A process is provided for carrying out an oxidation on a sprayable feed including a furanic substrate to be oxidized and a catalytically effective combination of cobalt, manganese, and bromide components for catalyzing the oxidation of the furanic substrate, which process comprises spraying the feed into a reactor vessel as a mist, supplying an oxidant, reacting the furanic substrate and the oxidant, and managing the exothermic temperature rise due to the reaction through a selection and control of the operating pressure within the reactor vessel. A crude dehydration product from the dehydration of fructose, glucose or both, including 5-hydroxymethylfurfural, can be directly oxidized by the process to produce 2,5-furandicarboxylic acid in surprisingly increased yields.

Abstract: Oxidation process can include: introducing small droplets of liquid reaction mixture having oxidizable reactant, catalyst, and solvent into a reaction zone containing oxygen and diluent gas; and oxidizing the reactant with the oxygen at a suitable reaction temperature and a suitable reaction pressure to produce an oxidized product. The liquid reaction mixture can have an aromatic feedstock having an oxidizable substituent as the oxidizable reactant. The oxidized product can include an aromatic compound having at least one carboxylic acid. For example, the aromatic feedstock can include a benzene ring having at least one oxidizable alkyl substituent, furan hetero-ring having at least one oxidizable alkyl substituent, a naphthalene poly-ring having at least one oxidizable alkyl substituent, derivatives thereof, and mixtures thereof.

Abstract: A process is provided for carrying out an oxidation on a sprayable feed including a furanic substrate to be oxidized and a catalytically effective combination of cobalt, manganese, and bromide components for catalyzing the oxidation of the furanic substrate, which process comprises spraying the feed into a reactor vessel as a mist, supplying an oxidant, reacting the furanic substrate and the oxidant, and managing the exothermic temperature rise due to the reaction through a selection and control of the operating pressure within the reactor vessel. A crude dehydration product from the dehydration of fructose, glucose or both, including 5-hydroxymethylfurfural, can be directly oxidized by the process to produce 2,5-furandicarboxylic acid in surprisingly increased yields.

Abstract: A process is provided for carrying out an oxidation on a feed including levulinic acid and/or a levulinic acid oxidation precursor to succinic acid, one or more furanic oxidation precursors of 2,5-furandicarboxylic acid and a catalytically effective combination of cobalt, manganese, and bromide components for catalyzing the oxidation of the levulinic acid component and of the one or more furanic oxidation precursors to produce both succinic acid and 2,5-furandicarboxylic acid products, which process comprises supplying the feed to a reactor vessel, supplying an oxidant, reacting the levulinic acid component and the one or more furanic oxidation precursors with the oxidant to produce both succinic acid and 2,5-furandicarboxylic acid (FDCA) and then recovering the succinic acid and FDCA products. A crude dehydration product from the dehydration of fructose, glucose or both, including 5-hydroxymethylfurfural, can be directly oxidized by the process to produce 2,5-furandicarboxylic acid and succinic acid.

Abstract: Oxidations of hydrocarbons, cycloalkanes and alkenes, arylalkanes, and a variety of other organic substrates are accomplished by cobalt-N-hydroxysuccinimide co-catalyzed reactions with dioxygen under unusually mild, near ambient conditions of temperature and pressure. The improved safety of the oxidation method and the high yields of product obtained make use of a unique combination of cobalt (II) complexes with N-hydroxysuccinimide. These autoxidation reactions do not have prolonged initiation times. Many of these reactions can be safely performed under normal chemical laboratory conditions and do not require specialized equipment or reagents.

Abstract: Oxidation process can include: introducing small droplets of liquid reaction mixture having oxidizable reactant, catalyst, and solvent into a reaction zone containing oxygen and diluent gas; and oxidizing the reactant with the oxygen at a suitable reaction temperature and a suitable reaction pressure to produce an oxidized product. The liquid reaction mixture can have an aromatic feedstock having an oxidizable substituent as the oxidizable reactant. The oxidized product can include an aromatic compound having at least one carboxylic acid. For example, the aromatic feedstock can include a benzene ring having at least one oxidizable alkyl substituent, furan hetero-ring having at least one oxidizable alkyl substituent, a naphthalene poly-ring having at least one oxidizable alkyl substituent, derivatives thereof, and mixtures thereof.

Abstract: A process for the selective oxidation of olefins to epoxides comprising the step of contacting the olefin (propylene or ethylene) with an oxidant (hydrogen peroxide) in the presence of a Lewis acid oxidation catalyst (MTO), organic base (pyridine or its N-oxide), in a solvent system comprising an organic water-miscible solvent (methanol). The system is pressurized using either the olefin itself or by adding an inert pressurizing gas (nitrogen) to increase the pressure between 230 and 700 psi at a temperature between 0.7 and 1.3 times the critical temperature of the olefin. The resulting increased solubility of the olefin in the organic solvent system increases the selectivity and yield of the desired epoxide (propylene oxide or ethylene oxide).

Abstract: A process for the selective oxidation of olefins to epoxides comprising the step of contacting the olefin (propylene) with an oxidant (hydrogen peroxide) in the presence of a Lewis acid oxidation catalyst (MTO), organic base (pyridine or its N-oxide), in a solvent system comprising an organic water-miscible solvent (methanol); and adding a pressurizing gas (nitrogen) to increase the pressure, whereby olefin is further dissolved in organic solvent system to increase the selectivity and yield of the desired epoxide (propylene oxide).

Abstract: A process for the selective oxidation of olefins to epoxides comprising the step of contacting the olefin (propylene or ethylene) with an oxidant (hydrogen peroxide) in the presence of a Lewis acid oxidation catalyst (MTO), organic base (pyridine or its N-oxide), in a solvent system comprising an organic water-miscible solvent (methanol). The system is pressurized using either the olefin itself or by adding an inert pressurizing gas (nitrogen) to increase the pressure between 230 and 700 psi at a temperature between 0.7 and 1.3 times the critical temperature of the olefin. The resulting increased solubility of the olefin in the organic solvent system increases the selectivity and yield of the desired epoxide (propylene oxide or ethylene oxide).

Abstract: Oxidations of hydrocarbons, cycloalkanes and alkenes, arylalkanes, and a variety of other organic substrates are accomplished by cobalt-N-hydroxysuccinimide co-catalyzed reactions with dioxygen under unusually mild, near ambient conditions of temperature and pressure. The improved safety of the oxidation method and the high yields of product obtained make use of a unique combination of cobalt (II) complexes with N-hydroxysuccinimide. These autoxidation reactions do not have prolonged initiation times. Many of these reactions can be safely performed under normal chemical laboratory conditions and do not require specialized equipment or reagents.

Abstract: Improved oxidation methods are provided wherein a reaction mixture comprising a substrate to be oxidized (e.g., phenols, alkenes) and an oxidation catalyst (typically dispersed in an organic solvent system) is supplemented with a compressed gas which expands the reaction mixture, thus accelerating the oxidation reaction. In preferred practice pressurized subcritical or supercritical carbon dioxide is used as the expanding gas, which is introduced into the reaction mixture together with an oxidizing agent. The inventive methods improve the substrate conversion and product selectivity by increasing the solubility of the oxidizing agent in the reaction mixture.

Abstract: Improved oxidation methods are provided wherein a reaction mixture comprising a substrate to be oxidized (e.g., phenols, alkenes) and an oxidation catalyst (typically dispersed in an organic solvent system) is supplemented with a compressed gas which expands the reaction mixture, thus accelerating the oxidation reaction. In preferred practice pressurized subcritical or supercritical carbon dioxide is used as the expanding gas, which is introduced into the reaction mixture together with an oxidizing agent. The inventive methods improve the substrate conversion and product selectivity by increasing the solubility of the oxidizing agent in the reaction mixture.

Abstract: Improved oxidation methods are provided wherein a reaction mixture comprising a substrate to be oxidized (e.g., phenols, alkenes) and an oxidation catalyst (typically dispersed in an organic solvent system) is supplemented with a compressed gas which expands the reaction mixture, thus accelerating the oxidation reaction. In preferred practice pressurized subcritical or supercritical carbon dioxide is used as the expanding gas, which is introduced into the reaction mixture together with an oxidizing agent. The inventive methods improve the substrate conversion and product selectivity by increasing the solubility of the oxidizing agent in the reaction mixture.

Abstract: An electrochemical carbon monoxide detecting method and apparatus (10, 46) is disclosed which can detect carbon monoxide levels as low as about 500 ppm and which has excellent selectivity and a linear response over a broad range of carbon monoxide concentrations. The apparatus (10, 46) employs an electrical cell assembly (12, 54) having an electrolyte (20, 60) containing hydrated Cu(II) ions therein; upon creation of a constant magnitude potential difference between the cell electrodes (22, 24) ranging from about +0.03-+0.15 V, the Cu(II) ions are reduced to Cu(I) ions, and the latter react with carbon monoxide to form Cu(I)-carbonyl complexes. Detection of an electrical parameter indicative of the Cu(II)-Cu(I) reduction permits quantitative carbon monoxide determinations. Preferably, the detecting apparatus (14) is amperometric, employing a potentiostat (28) and output device (38). Alternately, detection can be accomplished potentiometrically.

Abstract: This invention concerns monosubstituted dithiooxamides, and a preferred class comprises those wherein the substituent is such that the resulting dithiooxamide derivative is substantially nonvolatile at about room temperature. Preferred materials are those for which when the monosubstituent dithiooxamide is complexed with a transition metal cation, the resulting polymer is substantially a dark, i.e., preferably blue or blue-black color. Carbonless paper constructions involving use of N-(monosubstituted)dithiooxamides to advantage are described.

Abstract: Salts containing cations of the formula: ##STR1## (in which M is Co, Fe, Cr or Mn, X, Y, R.sub.1,The Government has rights in this invention pursuant to Contract Number CHE-75-14837 awarded by the National Science Foundation.

Abstract: The present invention is a cobalt complex having the structural formula: ##STR1## wherein each R.sub.1 is independently, a phenyl or a C.sub.1 -C.sub.6 alkyl group; each R.sub.2 is independently hydrogen, a phenyl, or a C.sub.1 -C.sub.6 alkyl group; R.sub.3 is either N-succinimido substituted with a C.sub.3 or greater hydrocarbon functionality at the carbon atoms .alpha. to the imido carbonyl carbons, or a carbonyl functionality having a C.sub.1 greater hydrocarbon substituent with the proviso that if said substituent is methyl, R.sub.2 cannot be hydrogen; and Y is o-phenylene, --CH.sub.2 --.sub.a, wherein "a" is 2 or 3, --CH.sub.2 --.sub.b NR.sub.4 --CH.sub.2 --.sub.c, wherein "b" and "c" are independently 2 or 3 and R.sub.4 is hydrogen or a C.sub.1 -C.sub.12 alkyl group.These complexes have the ability to selectively and reversibly bind oxygen, thus making them useful components of oxygen separation membranes and absorbents.

Abstract: The present invention is a cobalt complex having the structural formula: ##STR1## wherein each R.sub.1 is independently hydrogen, a phenyl or a C.sub.1 -C.sub.6 alkyl group; each R.sub.2 is independently hydrogen or a C.sub.1 -C.sub.6 alkyl group; R.sub.3 is a C.sub.4 -C.sub.30 hydrocarbyl radical connecting the two carbonyl carbons; and Y is o-phenylene, --CH.sub.2).sub.a wherein "a" is 2 or 3, --CH.sub.2).sub.b NR.sub.4 --CH.sub.2).sub.c, wherein "b" and "c" are independently 2 or 3 and R.sub.4 is hydrogen or a C.sub.1 -C.sub.12 alkyl group.These complexes have the ability to selectively and reversibly bind oxygen, thus making them useful components of oxygen separation membranes and absorbents.