The Lummus Company

Lummus Crest, Inc.

Beijing Research Institute of Chemical Industry

Beijing Research Institute of Chemical Industry He Ping Li

Herbert D Riegel

Morgan C Sze

Harvey D Schindler

Vincent A Strangio

Chiung-Yuan Huang

Jo-Lung Chien

Bing Y Zhao

Xin X Liu

Maurice E Brooks

Dienes and/or acetylene impurities in an olefin feed; in particular a propylene feed, may be selectively hydrogenated in a single stage by use of a catalyst of palladium supported on alumina which is substantially crystalline alpha alumina, wherein the average pore radius is 200-2000 .ANG., with at least 80% of the pores having a pore radius within the range of 100 to 3000 .ANG.. The surface acidity of the catalyst is generally from 0.002 to 0.05 millimole of pyridine absorbed per gram of catalyst. The active palladium surface area is from 20 to 200 m.sup.2 /g. The palladium is in the form of crystallines having an average size of at least 25 .ANG..

Catalyst and process for hydrogenation of unsaturated hydrocarbons

Dienes and/or acetylene impurities in an olefin feed; in particular a propylene feed, may be selectively hydrogenated in a single stage by use of a catalyst of palladium supported on alumina which is substantially crystalline alpha alumina, wherein the average pore radius is 200-2000 .ANG., with a least 80% of the pores having a pore radius within the range of 100 to 3000 .ANG.. The surface acidity of the catalyst is generally from 0.002 to 0.05 millimole of pyridine absorbed per gram of catalyst. The active palladium surface area is from 20 to 200 m.sup.2 /g. The palladium is in the form of crystallines having an average size of at least 25 .ANG..

Novel catalyst and process for hydrogenation of unsaturated hydrocarbons

Hydrogen chloride is recovered from a mixture with propylene by extractive distillation with an inert extraction solvent to minimize reaction between hydrogen chloride and propylene during such distillation. The temperature and pressure conditions are coordinated with the extraction solvent and amount thereof to prevent the presence of hydrogen chloride in a liquid state. The process is particularly suitable for recovering hydrogen chloride in the production of allyl chloride by thermal chlorination of propylene.

Hydrogen chloride-propylene separation

In an integrated process for oxychlorination and combustion of chlorinated hydrocarbons, chlorinated hydrocarbon is burned to recover chlorine values essentially as hydrogen chloride. Hydrogen chloride is recovered from the effluent from the combustion by absorption with aqueous hydrogen chloride. Hydrogen chloride recovered by the absorption is subsequently recovered and employed in an oxychlorination reaction. A gas containing hydrogen chloride, water vapor and some oxygen recovered from the oxychlorination is cooled to condense aqueous hydrogen chloride which is employed in the absorption for recovering hydrogen chloride. The remaining gas is employed in the combustion of chlorinated hydrocarbons. The process has particular applicability to an oxychlorination reaction of the type wherein a molten salt containing the higher and lower valent chlorides of a multivalent metal is contacted with hydrogen chloride and oxygen to recover hydrogen chloride by enriching the higher valent metal chloride content of the molten salt.

Recovery of chlorine values in integrated process for oxychlorination

A molten salt containing the higher and lower valent chlorides, such as mixture of cuprous and cupric chloride, is contacted with oxygen and hydrogen chloride to enrich the salt in the higher valent metal chloride. The salt enriched in the higher valent metal chloride is contacted with carbon monoxide to both strip gaseous chlorine from the salt and produce phosgene by reaction with carbon monoxide and thereby recover essentially all chlorine values added to the salt. The reaction can be effected to provide stoichiometric quantities of carbon monoxide and chlorine in the effluent for producing additional phosgene.

Production of phosgene

In an integrated process for oxychlorination and combustion of chlorinated hydrocarbons, chlorinated hydrocarbons is burned to recover chlorine values essentially as hydrogen chloride. Combustion effluent and off-gas from an oxychlorination reaction are simultaneously treated to recover anhydrous hydrogen chloride for use in the oxychlorination reaction. In accordance with one embodiment, off-gas from the oxychlorination is employed in the combustion, prior to hydrogen chloride recovery in order to utilize any oxygen values therein. The process has particular applicability to an oxychlorination reaction of the type wherein a molten salt containing the higher and lower valent chlorides of a multivalent metal is contacted with hydrogen chloride and oxygen to recover hydrogen chloride by enriching the higher valent metal chloride content of the molten salt.

A compound is chlorinated with chlorine to produce chlorinated product and hydrogen chloride byproduct. Recovered hydrogen chloride byproduct is contacted with oxygen and a molten salt mixture containing the higher and lower valent chlorides of a multivalent metal, such as cuprous and cupric chloride, to effect recovery of the hydrogen chloride by enriching the molten salt content of the higher valent chloride. The molten salt, enriched in higher valent chloride, is then dechlorinated by use of a stripping gas, preferably hydrogen chloride, to produce a gaseous effluent containing stripped chlorine and the stripping gas, which is then recycled to the chlorination step. The presence of stripping gas, as a diluent, improves the chlorination operation.

Production of chlorinated compounds by use of molten salts

Hexachlorocyclopentadiene is produced by the use of a molten salt mixture of cuprous and cupric chloride, with the reaction effluent including the product, chlorine, hydrogen chloride, unreacted feed and organic byproduct, as well as entrained molten salt. The effluent is cooled at a temperature and pressure to effect condensation of organics, with the salt being present in the condensate. The salt is then separated from the organics for re-use in the process. Hydrogen chloride and chlorine present in the effluent are also recovered for re-use in the process.

Production of hexachlorocyclopentadiene

Methane is oxychlorinated to one or more chlorinated methanes, without net production of carbon tetrachloride, by contacting methane and chlorine and/or hydrogen chloride with a molten mixture of cuprous chloride, cupric chloride, and copper oxychloride, in the presence of an amount of carbon tetrachloride which inhibits net production thereof.

Oxychlorination of methane

Hydrogen chloride and oxygen are contacted with a molten mixture of cuprous and cupric chloride in a oxidation reaction zone to enrich the cupric chloride content of the melt, and the melt introduced into a dechlorination zone wherein gaseous chlorine is removed from the melt. The oxidation reactor is operated at a pressure higher than the dechlorination reactor, and molten salt circulation rates are controlled in a manner such that the cupric chloride content and temperature of the salt introduced into the dechlorination reaction zone are higher than the cupric chloride concentration and temperature of the melt introduced into the oxidation reactor.

Production of chlorine

Process for coupling an alkane to either an alkane, alkene, aliphatic carboxylic acid, or aromatic hydrocarbon by effecting contacting thereof and a melt containing a multivalent metal halide in both its higher and lower valance state. In accordance with a preferred embodiment, the contacting is effected in the presence of an oxygen containing gas or the melt is previously contacted with an oxygen containing gas to produce the corresponding oxyhalide of the metal, whereby the reaction may be effected on a continuous basis.

Coupling process

Hexachlorocyclopentadiene is produced by contacting pentane, pentene, cyclopentane or cyclopentene or chlorinated derivatives thereof with a molten salt mixture of cuprous and cupric chloride. Cyclopentadiene can also be employed as an initial feed, in which case the cyclopentadiene is initially chlorinated to effect saturation thereof, followed by contacting of the chloro substituted cyclopentane with a molten salt mixture of cuprous and cupric chloride to produce hexachlorocyclopentadiene.

A molten mixture containing the higher and lower valent forms of a multivalent metal chloride; in particular, cuprous and cupric chloride, is contacted with oxygen, and aqueous hydrogen chloride recycle, to recover the chlorine values by generation of the higher valent metal chloride and also effect oxidation of the melt by production of the oxychloride. The gas withdrawn from the oxidation contains hydrogen chloride, chlorine and water vapor, with the hydrogen chloride being separate from the gas as aqueous hydrogen chloride and recycle to the oxidation. The chlorine and water vapor in the gas are contacted with activated carbon to produce hydrogen chloride, which is separated as aqueous hydrogen chloride and recycled to the oxidation.

Recovery of chlorine values from a melt oxidation gas

In the production of chlorinated hydrocarbons, a gas stream, containing hydrocarbon and carbon monoxide and/or nitrogen, as inerts, is separated from the effluent, and contacted with chlorinated hydrocarbon, as an absorption liquid, to absorb unreacted hydrocarbon. The absorbed hydrocarbon is stripped from the solution and recycled to the chlorinated hydrocarbon production. The process is particularly applicable to the production of chlorinated methanes and vinyl chloride.

Growing community of inventors

Maplewood, NJ, United States of America

Herbert D Riegel