Tenneco Canada Inc.

Sterling Canada, Inc.

Tenneco Canada Inc. (erco Division)

Erco Industries Limited

Zbigniew Twardowski

Marek Lipsztajn

Gerald Cowley

Maurice C Fredette

Edward J Bechberger

James D McGilvery

Richard Swindells

Chlorine dioxide, useful as a pulp mill chemical, is produced without producing sodium sulfate effluent for disposal, by effecting reduction of chloric acid in an aqueous reaction medium in a reaction zone at a total acid normality of up to about 7 normal in the substantial absence of sulfate ion and in the promence of a dead load of sodium chlorate added to and subsequently removed from the reaction medium. Chloric acid for the process is produced electrolytically from an aqueous solution of the deadload sodium chlorate and make-up quantities of sodium chlorate. The chloric acid reduction to produce chlorine dioxide may be effected using methanol or electrolytically.

Chlorine dioxide generation from chloric acid

Scale is removed from within cation-exchange membranes by operating the cathode compartment of a cell divided by the cation-exchange membrane with a mildly-acid catholyte while effecting transfer of cationic species from the anode compartment to the cathode compartment.

Membrane cell washing

The formation of sodium sulfate by-product in sulfuric acid-based chlorine dioxide generating processes is decreased and preferably eliminated entirely, by effecting electrochemical treatment of sodium ion-containing feed materials for the generator to remove sodium ions and to add hydrogen ions. Sodium hydroxide may be produced as a by-product. The process is generally applicable to the electrochemical treatment of alkali metal chlorates, alkali metal sulfates and mixtures thereof to produce acidified solutions useful in providing chlorate ion-containing feeds to such chlorine dioxide generating processes or for other purposes.

Electrochemical processing of aqueous solutions

Chlorine dioxide, useful as a pulp mill chemical, is produced without producing sodium sulfate effluent for disposal, by effecting reduction of chloric acid in an aqueous reaction medium in a reaction zone at a total acid normality of up to about 7 normal in the substantial absence of sulfate ion and in the presence of a dead load of sodium chlorate added to and subsequently removed from the reaction medium. Chloric acid for the process is produced electrolytically from an aqueous solution of the deadload sodium chlorate and make-up quantities of sodium chlorate. The chloric acid reduction to produce chlorine dioxide may be effected using methanol or electrolytically.

The formation of sodium sulfate by-product in sulfuric acid-based chlorine dioxide generating processes is decreased and preferably eliminated entirely, by effecting electrochemical treatment of sodium ion-containing feed materials for the generator to remove sodium ions and add hydrogen ions. Sodium hydroxide is produced as a by-product. The process is generally applicable to the electrochemical treatment of alkali metal chlorates, alkali metal sulfates and mixtures thereof to produce acidified solutions useful in providing chlorate ion-containing feeds to such chlorine dioxide generating processes.

Chloric acid is produced in an electrolytic-electrodialytic process in which chlorate ions from a sodium chlorate solution are transferred through an anion-exchange membrane to combine with electrolytically-produced hydrogen ions in a compartment of a cell, from which the resulting chloric acid is recovered. The sodium ions are transferred through a cation-exchange membrane to combine with electrolytically-produced hydroxyl ions in another compartment of the cell, from which the resulting sodium hydroxide is recovered.

Production of chloric acid

Chlorine dioxide is produced electrolytically in the cathode compartment of an electrolytic cell using a three-dimensional high surface-area cathode. The cathode compartment is separated from an anode compartment by a cation-exchange membrane. Sodium chlorate is reacted with hydrogen ions and chloride ions in the cathode compartment and chlorine dioxide is vented from the cathode compartments. Chlorine co-produced with the chlorine dioxide is reduced at the cathode to provide chloride ions for the reaction while electrolytically-produced hydrogen ions are transferred across the membrane from the anode compartment to the cathode compartment to provide hydrogen ions for the reaction.

Production of chlorine dioxide in an electrolytic cell

A hydrochloric acid-based chlorine dioxide generating process is integrated with an electrolytic process for sodium hydroxide production. Generator liquor in the form of a sodium chloride-enriched solution from the chlorine dioxide generator is passed to the central compartment of a three-compartment cell. Hydrogen ions formed in the anode compartment of the three-compartment cell migrate through a cation-exchange membrane to the central compartment to form hydrochloric acid with the sodium chloride solution while sodium ions migrate through a further cation-exchange membrane to form sodium hydroxide with hydroxyl ions produced in the cathode compartment of the three-compartment cell. The acidified generator liquor containing the hydrochloric acid formed in the central compartment is forwarded to the chlorine dioxide generator to provide half the acid requirement therefor.

Combined process for production of chlorine dioxide and sodium hydroxide

Dissolved arsenic (III) contaminant is removed from mineral acids, such as hydrochloric acid, by electrolysis using a high surface area cathode having a three-dimensional electrolyte-contacting surface which exposes the electrolyte to electrolysis for a relatively long period of time. The dissolved arsenic is reduced to arsenic metal, which then plates out on the cathode. Dissolved concentrations of arsenic of less than 1 ppm can be achieved using the invention.

Removal of arsenic from acids

Chlorine dioxide is transferred by membrane pervaporation from one chamber filled with aqueous chlorine dioxide-generating reactants or other chlorine dioxide donor medium across a gas-permeable hydrophobic membrane to a recipient aqueous medium filling a second chamber. The recipient medium may be water, pulp suspension or sodium chlorite solution. The membrane typically is expanded polytetrafluoroethylene.

Membrane pervaporation process

Effluent acid from a non-evaporating chlorine dioxide-generating process is subjected to diffusion-dialysis across an anion-exchange membrane to preferentially transfer sulphuric acid from the effluent acid stream to a recipient aqueous medium while sodium sulphate remains in a waste stream. The sulphuric acid extracted from the effluent acid stream on this way may be recycled to the chlorine dioxide generator, after concentration, if desired.

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Mississauga, Canada

Zbigniew Twardowski