Abstract: Improved methods and apparatus for manufacture of maleic anhydride by catalytic oxidation of n-butane or other hydrocarbon having four carbon atoms in a straight chain over a fixed catalyst bed comprising a phosphorus vanadium oxide catalyst. Movement of catalyst bodies with respect to each other and with respect to the walls of the reaction chamber is restrained so as to prevent the catalyst bodies from abrading against each other or the reactor chamber walls in a manner that would cause formation of catalyst fines. Methods and apparatus are also provided for removal of fines from a fixed catalyst bed. The methods of the invention are effective to prevent loss of catalyst from a tubular reactor, and to control degradation of solvent absorbent in a process in which maleic anhydride is separated from the reaction gas by absorption into such a solvent.

Abstract: An improved process for the manufacture of maleic anhydride by catalytic oxidation of a nonaromatic hydrocarbon having at least four carbon atoms in a straight chain, in which a gas containing oxygen and hydrocarbon is passed through a fixed catalyst bed in a tubular reactor. The activity of the catalyst bed is graded in such manner that the reactor can be operated at an initial (feed gas) hydrocarbon concentration of over 1.5% by volume, an integrated average temperature difference between gas and cooling fluid of at least about 15.degree. C. over that portion of the bed in which the gas temperature exceeds the cooling fluid temperature, and a productivity of at least about 5.0 lbs. maleic anhydride per hour, without the temperature difference between the gas and the cooling fluid exceeding 80.degree. C. at any point in the catalyst bed during the course of the reaction.

Abstract: An active catalyst having a crystal structure corresponding to that of a catalyst that has been prepared and activated by the following process. A substantially pentavalent vanadium-containing compound is reacted with a pentavalent phosphorus-containing compound in an alcohol medium capable of reducing the vanadium to an oxidation state of less than +5. Molybdenum is incorporated into the product of the reaction, thereby forming a solid molybdenum-modified precursor composition. The alcohol is removed to produce a dried solid molybdenum-modified precursor composition. Shaped bodies comprising said dried solid molybdenum-modified precursor composition are formed. The dried formed molybdenum-modified catalyst precursor composition is activated to transform it into the active catalyst.

Abstract: An active catalyst having a crystal structure corresponding to that of a catalyst that has been prepared and activated by the following process. A substantially pentavalent vanadium-containing compound is reacted with a pentavalent phosphorus-containing compound in an alcohol medium capable of reducing the vanadium to an oxidation state of less than +5. Molybdenum is incorporated into the product of the reaction, thereby forming a solid molybdenum-modified precursor composition. The alcohol is removed to produce a dried solid molybdenum-modified precursor composition. Shaped bodies comprising said dried solid molybdenum-modified precursor composition are formed. The dried formed molybdenum-modified catalyst precursor composition is activated to transform it into the active catalyst.

Abstract: Improved methods and apparatus for manufacture of maleic anhydride by catalytic oxidation of n-butane or other hydrocarbon having four carbon atoms in a straight chain over a fixed catalyst bed comprising a phosphorus vanadium oxide catalyst. Movement of catalyst bodies with respect to each other and with respect to the walls of the reaction chamber is restrained so as to prevent the catalyst bodies from abrading against each other or the reactor chamber walls in a manner that would cause formation of catalyst fines. Methods and apparatus are also provided for removal of fines from a fixed catalyst bed. The methods of the invention are effective to prevent loss of catalyst from a tubular reactor, and to control degradation of solvent absorbent in a process in which maleic anhydride is separated from the reaction gas by absorption into such a solvent.

Abstract: An activated porous phosphorus/vanadium oxide catalyst adapted for the catalytic oxidation of a hydrocarbon to produce a carboxylic acid anhydride. The catalyst comprises a shaped body having a volume of at least about 0.02 cc, a phosphorus content of between about 1.05 and about 1.20, a B.E.T. surface area of at least about 15 m.sup.2 /g, an average vanadium oxidation state of between about 4.06 and about 4.3, a total pore volume of at least about 0.15 cc/g, a normalized apparent shaped body density of between about 1.0 and about 2.0 g/cc, and a crush strength of at least about 4 pounds. At least about 20% of the pore volume of the catalyst is constituted of pores having a diameter between about 0.1 and about 3.3 .mu.M, and at least about 40% of the pore volume is constituted of pores having a diameter of less than about 0.1 .mu.M.

Abstract: An improved process for the manufacture of maleic anhydride by catalytic oxidation of n-butane in which the feed flow channel to the catalytic reactor contains an autoignition suppression agent containing acid sites or trivalent phosphorus as an ignition inhibiting component. The autoignition suppression agent may also be used in other gas/liquid containment envelopes for flammable mixtures of hydrocarbons and oxygen. A novel apparatus and method are disclosed for assessing the influence of system conditions on autoignition of hydrocarbon/oxygen mixtures.

Abstract: An activated porous phosphorus/vanadium oxide catalyst adapted for the catalytic oxidation of a hydrocarbon to produce a carboxylic acid anhydride. The catalyst comprises a shaped body having a volume of at least about 0.02 cc, a phosphorus content of between about 1.05 and about 1.20, a B.E.T. surface area of at least about 15 m.sup.2 /g, an average vanadium oxidation state of between about 4.06 and about 4.3, a total pore volume of at least about 0.15 cc/g, a normalized apparent shaped body density of between about 1.0 and about 2.0 g/cc, and a crush strength of at least about 4 pounds. At least about 20% of the pore volume of the catalyst is constituted of pores having a diameter between about 0.1 and about 3.3 .mu.M, and at least about 40% of the pore volume is constituted of pores having a diameter of less than about 0.1 .mu.M.

Abstract: Shaped oxidation catalyst structures containing catalytic material comprised of mixed oxides of vanadium and phosphorus which are useful for the production of maleic anhydride via the partial oxidation of nonaromatic hydrocarbons, particularly n-butane, in the vapor phase with molecular oxygen or a molecular oxygen-containing gas are provided. Such structures are characterized by exhibiting (a) a geometric volume of from about 30 percent to about 67 percent of that exhibited by the void space-free solid geometric form, (b) an external geometric surface area/geometric volume ratio of at least about 20 cm.sup.-1, (c) a bulk density of from about 0.4 g/cm.sup.3 to about 1.4 g/cm.sup.3, and (d) a mechanical resistance sufficient to maintain substantially the structural integrity of the shaped structure under handling and use conditions.

Abstract: Iron/lithium promoted phosphorus-vanadium-oxygen catalysts for the production of maleic anhydride are prepared by contacting a substantially tetravalent vanadium-containing compound and a phosphorus-containing compound and a promoter component containing each of iron and lithium in a substantially anhydrous alcohol medium in the presence of anhydrous hydrogen chloride to form an iron/lithium promoted phosphorus-vanadium-oxygen catalyst precursor. The catalyst precursor is recovered, dried, roasted, formed into structures if structures are desired, and calcined.

Abstract: Catalysts useful for the partial oxidation of nonaromatic hydrocarbons, particularly n-butane, with molecular oxygen or an oxygen-containing gas in the vapor phase to produce maleic anhydride are provided which comprise phosphorus, vanadium, and oxygen and a promoter component containing each of iron and lithium.

Abstract: Phosphorus-vanadium mixed oxide oxidation catalysts are prepared by introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an alcohol medium capable of reducing the vanadium to a valence state less than +5 in the presence of an alcohol-modifying agent to form a phosphorus-vanadium mixed oxide catalyst precursor. The catalyst precursor is recovered, dried, formed into desired structures, and calcined at temperatures from about 250.degree. C. to about 600.degree. C. The catalysts are highly effective in that they exhibit a weight/weight productivity of at least 70 grams of maleic anhydride per kilogram of catalyst per hour.

Abstract: Maleic anhydride is produced by the oxidation of a non-aromatic hydrocarbon having at least four carbon atoms in a straight chain with molecular oxygen or a molecular oxygen-containing gas in the vapor phase in the presence of a phosphorus-vanadium mixed oxide oxidation catalyst. Such catalysts are prepared by introducing a substantially pentavalent vanadium-containing compound and a pentavalent phosphorus-containing compound into an alcohol medium capable of reducing the vanadium to a valence state less than +5 in the presence of an alcohol-modifying agent to form a phosphorus-vanadium mixed oxide catalyst precursor. The catalyst precursor is recovered, dried, formed into desired structures, and calcined at temperatures from about 250.degree. C. to about 600.degree. C. The catalysts are highly effective in that they exhibit a weight/weight productivity of at least 70 grams of maleic anhydride per kilogram of catalyst per hour.

Abstract: Catalysts useful for the partial oxidation of non-aromatic hydrocarbons, particularly n-butane, with molecular oxygen or a molecular oxygen-containing gas in the vapor phase to produce maleic anhydride are provided which comprise mixed oxides of phosphorus and vanadium. The catalysts are highly effective in that they exhibit a weight/weight productivity of at least 70 grams of maleic anhydride per kilogram of catalyst per hour.

Abstract: Attrition resistant bismuth-containing metal/oxygen compositions comprising the infusion and reaction product of an alumina existing in a crystal form selected from the group consisting of .gamma., .delta., .eta., and .chi. crystal forms, and mixtures thereof or that can be transformed by heat to such crystal forms, and characterized by a mean particle size from about 10 .mu.m to about 200 .mu.m, a fractional porosity of at least 0.2, a surface area of at least 150 m.sup.2 /g, and a pore diameter such that at least 10 percent of the pores are less than 55 .ANG., and at least one bismuth oxide, or compound convertible by heat to such bismuth oxide, having a maximum mean particle size of about 100 .mu.m, with the proviso that the alumina/bismuth oxide mean particle size ratio is at least 2, which bismuth oxide is susceptible of undergoing infusion and reaction with the alumina upon being subjected to temperatures of at least 0.4 T.sub.

Abstract: Attrition resistant metal/oxygen compositions comprising the infusion and reaction product of an alumina existing in a crystal form selected from the group consisting of .gamma., .delta., .eta., and .chi. crystal forms, and mixtures thereof, or that can be transformed by heat to such crystal forms, and characterized by a mean particle size from about 10 .mu.m to about 200 .mu.m, a fractional porosity of at least 0.2, a surface area of at least 150 m.sup.2 /g, and a pore diameter such that at least 10 percent of the pores are less than 55 .ANG., and at least one metal oxide, or compound convertible by heat to such metal oxide, having a maximum mean particle size of about 100 .mu.m, with the proviso that the alumina/metal oxide mean particle size ratio is at least 2, which metal oxide is susceptible of undergoing infusion and reaction with the alumina upon being subjected to temperatures of at least 0.4 T.sub.

Abstract: Attrition resistant bismuth-containing metal/oxygen compositions comprising the infusion and reaction product of alumina and at least one bismuth oxide, or compound convertible by heat to such bismuth oxide, which bismuth oxide is susceptible of undergoing infusion and reaction with the alumina, are useful in metal oxide-catalyzed reactions. The compositions are especially useful in reactions which involve reaction conditions of high stress, for example, vapor phase oxidations under fluidized bed conditions.

Abstract: Attrition resistant metal/oxygen compositions comprising the infusion and reaction product of alumina and at least one metal oxide, or compound convertible by heat to such metal oxide, which metal oxide is susceptible of undergoing infusion and reaction with the alumina, are useful in a wide variety of metal oxide-catalyzed reactions. The compositions are especially useful in reactions which involve reaction conditions of high stress, for example, vapor phase oxidations under fluidized bed conditions.

Abstract: A process for the production of unsaturated primary amines which comprises reacting, in the substantial absence of molecular oxygen, an amine having the formula (R.sub.1 HC=CR.sub.2 CH.sub.2)m N H (3-m), wherein m is 2 or 3 and R.sub.1 and R.sub.2 are hydrogen or C.sub.1 - C.sub.3 alkyl groups, with ammonia in the presence of a catalyst comprising palladium or platinum atoms bearing phosphorus-containing ligands, the reaction being carried out at a temperature of from 0.degree. to 250.degree. C in the presence of a solvent for the amine and the catalyst.