[go: up one dir, main page]

WO1993004980A1 - Recuperation du monoxyde de dichlore present dans des melanges gazeux - Google Patents

Recuperation du monoxyde de dichlore present dans des melanges gazeux Download PDF

Info

Publication number
WO1993004980A1
WO1993004980A1 PCT/US1992/006281 US9206281W WO9304980A1 WO 1993004980 A1 WO1993004980 A1 WO 1993004980A1 US 9206281 W US9206281 W US 9206281W WO 9304980 A1 WO9304980 A1 WO 9304980A1
Authority
WO
WIPO (PCT)
Prior art keywords
dichlorine monoxide
chlorine
gaseous mixture
monoxide
dichlorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1992/006281
Other languages
English (en)
Inventor
Ronald L. Dotson
John H. Hubbard
Budd L. Duncan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Olin Corp
Original Assignee
Olin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Olin Corp filed Critical Olin Corp
Publication of WO1993004980A1 publication Critical patent/WO1993004980A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/021—Chlorine hemioxide (Cl2O)

Definitions

  • This invention relates to a process for the production of dichlorine monoxide. More particularly, the invention is concerned with a process for recovering dichlorine monoxide from gaseous mixtures.
  • Dichlorine monoxide, Cl-O has been found to be an effective reagent for the bleaching of wood pulp and textiles.
  • Dichlorine monoxide has been made in the laboratory by the reaction of chlorine with mercury oxide, HgO.
  • dichlorine monoxide has been prepared by reacting chlorine with sodium carbonate (soda ash) or sodium bicarbonate in the presence of controlled amounts of water.
  • An example of this approach is found in U.S. Patent No. 3,914,397, issued October 21, 1975 to W.A. Mueller.
  • Gaseous dichlorine monoxide has also been prepared by treating concentrated solutions of hypochlorous acid with anhydrous calcium nitrate.
  • gaseous chlorine is passed rapidly across the surface of an agitated aqueous solution of sodium hydroxide at a reduced temperature.
  • a gaseous mixture of hypochlorous acid, dichlorine monoxide and unreacted chlorine is produced which, if dried over anhydrous calcium nitrate, produces dichlorine monoxide.
  • a process for producing dichlorine monoxide which comprises : a) drying a gaseous mixture of dichlorine monoxide and chlorine to form a drying gaseous mixture, b) liquefying the dry gaseous mixture at a temperature below about -20°C to produce a liquid containing dichlorine monoxide and chlorine, and c) separating the chlorine from the dichlorine monoxide.
  • gaseous mixtures containing high concentrations of hypochlorous acid vapor and dichlorine monoxide vapor have been produced in a process which reacts an aqueous solution of alkali metal hydroxide such as sodium hydroxide in droplet form with gaseous chlorine.
  • the process is preferably operated using an excess of chlorine gas above the stoichiometric amount required for the reaction with the alkali metal hydroxide.
  • the gaseous mixture produced contains hypochlorous acid vapor, water vapor, chlorine gas and dichlorine monoxide gas.
  • fine particles of an alkali metal chloride may be present.
  • the solids-free gaseous mixture is converted to an aqueous solution of hypochlorous acid containing at least 25 percent, and preferably having from about 35 to about 60 percent by weight of HOC1.
  • Suitable concentrations include those in the range of from about 40 to about 80, and preferably from about 45 to about 60 percent by weight of alkali metal hydroxide.
  • the alkali metal hydroxide solution is sprayed from at least one atomizer preferably positioned at or near the top of the reactor.
  • the gaseous mixture of hypochlorous acid vapor, water vapor, chlorine gas, and dichlorine monoxide gas produced in the reactor- is removed from the reactor and passed through a solids separator to remove any fine particles of alkali metal chloride which may be present.
  • the solids-free gaseous mixture is then converted to an aqueous solution of hypochlorous acid.
  • the conversion may be carried out, for example, by condensing the gaseous mixture at temperatures in the range of from about -5° to about +10°C.
  • the gaseous mixture of dichlorine monoxide and chlorine from the reactor or the condenser may be used as the starting material.
  • these gaseous mixtures may contain dichlorine monoxide vapor and hypochlorous acid vapor in amounts which provide concentrations of at least 2, for example, from about 5 to about 30, and preferably from about 10 to about 20 mole percent of C1-.0.
  • the gaseous mixture may also contain variable amounts of water vapor as well as variable amounts of inert gases such as oxygen or nitrogen.
  • drying methods include, for example, contacting the gaseous mixture with a drying agent or chilling the gaseous mixture and/or passing the gaseous mixture through a molecular sieve.
  • Drying agents which may be employed include calcium sulfate, calcium nitrate, sodium sulfate, magnesium perchlorate, perfluorosulfonic acid resins, molecular sieves and mixtures thereof.
  • the dried gaseous mixture . of chlorine and dichlorine monoxide is then liquefied, for example, by cooling to a temperature below about -20°C, and preferably in the range of from about -25° to about -80°C, for example, using a stripping and rectification unit.
  • the dichlorine monoxide in the liquefied mixture is separated from the chlorine by any suitable method including, for example, distillation, freezing or dissolution in selected solvents.
  • Suitable solvents include perfluoro and chlorofluoro substituted alkanes such as methane or ethane i.e. carbon tetrachloride.
  • the liquefied mixture is fed to a distillation column and the temperature of the mixture raised to a temperature below the boiling point of the dichlorine monoxide. Suitable temperatures include those in the range of from about -80° to about 0 C C, and preferably from about -20° to about 0°C. at about atmospheric pressure.
  • Chlorine gas is released from the liquid dichlorine monoxide. Following the separation of chlorine, the liquid dichlorine monoxide may be stored at low temperatures, converted to a solid using dry ice or dissolved in a solvent such as those listed above.
  • Dichlorine monoxide gas may be recovered by increasing the temperature of liquid dichlorine monoxide to above about 2°C. at atmospheric pressure.
  • Dichlorine monoxide gas produced is substantially free of impurities including chlorine and has a low percent of ionic activity.
  • a gaseous mixture of dichlorine monoxide (6.99 mole%), chlorine (4.79 mole%), water vapor (1.4 mole%) , and oxygen (2.68 mole%) at a temperature of about 0°C. was passed through a packed column of CaS0 4 at a temperature of 0°C.
  • the dried gaseous mixture was cooled in a condenser to a temperature of about -40°C. and liquefied.
  • the liquid was collected into a container partially filled with dry ice.
  • Dichlorine monoxide formed a stable solid phase with the dry ice while kept cold. The solid phase was allowed to warm until the dry ice had evaporated and the gas formed passed through a mass spectrometer.
  • the gas analysis was as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Procédé de production de monoxyde de dichlore dans lequel on sèche un mélange gazeux de monoxyde de dichlore et de chlore pour former un mélange gazeux sec, on liquéfie ce mélange gazeux sec à une température inférieure à environ -20 °C pour produire un liquide contenant du monoxyde de dichlore et du chlore, puis on sépare le chlore du monoxyde de dichlore. Le monoxyde de dichlore produit ne contient pratiquement pas d'impuretés, chlore y compris, et présente un faible pourcentage d'activité ionique.
PCT/US1992/006281 1991-09-03 1992-07-30 Recuperation du monoxyde de dichlore present dans des melanges gazeux Ceased WO1993004980A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75356191A 1991-09-03 1991-09-03
US753,561 1991-09-03

Publications (1)

Publication Number Publication Date
WO1993004980A1 true WO1993004980A1 (fr) 1993-03-18

Family

ID=25031174

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006281 Ceased WO1993004980A1 (fr) 1991-09-03 1992-07-30 Recuperation du monoxyde de dichlore present dans des melanges gazeux

Country Status (2)

Country Link
AU (1) AU2420992A (fr)
WO (1) WO1993004980A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115947442A (zh) * 2021-10-08 2023-04-11 香港科技大学 在高氯水环境中原位形成一氧化二氯的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1560614A (fr) * 1965-12-13 1969-03-21
US3914397A (en) * 1970-08-05 1975-10-21 Pulp Paper Res Inst Production of chlorine monoxide gas
US4321795A (en) * 1980-09-22 1982-03-30 Helmut Brandt Process for the purification of gaseous chlorine
USRE31348E (en) * 1978-03-09 1983-08-16 Olin Corporation Hypochlorous acid process using sweep reactor
WO1990005111A1 (fr) * 1988-10-31 1990-05-17 Olin Corporation Procede ameliore de production d'acide hypochloreux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1560614A (fr) * 1965-12-13 1969-03-21
US3914397A (en) * 1970-08-05 1975-10-21 Pulp Paper Res Inst Production of chlorine monoxide gas
USRE31348E (en) * 1978-03-09 1983-08-16 Olin Corporation Hypochlorous acid process using sweep reactor
US4321795A (en) * 1980-09-22 1982-03-30 Helmut Brandt Process for the purification of gaseous chlorine
WO1990005111A1 (fr) * 1988-10-31 1990-05-17 Olin Corporation Procede ameliore de production d'acide hypochloreux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Volume 8, 1979, by KIRK-OTHMER, (NEW YORK), see page 116, 117, 123, 124. *
JOURNAL OF AMERICAN CHEMICAL SOCIETY, Volume 44, 16 March 1922, NOYES et al., "The Ionization Constant of Hypochlorous Acid", see page 1635. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115947442A (zh) * 2021-10-08 2023-04-11 香港科技大学 在高氯水环境中原位形成一氧化二氯的方法

Also Published As

Publication number Publication date
AU2420992A (en) 1993-04-05

Similar Documents

Publication Publication Date Title
US5152915A (en) Recovery of dichlorine monoxide from hypochlorous acid solutions
CA1320120C (fr) Procede industriel de recuperation separative de chlore
US5124135A (en) Process for the selective absorption of chlorine and/or bromine from CO.sub. -containing off-gases with the aid of steam
US5895639A (en) Separation of hydrogen fluoride from a fluorocarbon/hydrogen fluoride azeotropic mixture by sulfuric acid
EP0213669A1 (fr) Procédé de préparation de l'urée
US5560899A (en) Process for separating HF from its mixtures with hydrochlorofluorocarbons 123 and/or 124
AU656223B2 (en) Process for producing concentrated hypochlorous acid solutions
NO874557L (no) Fremgangsmaate ved fremstilling av urea.
EP0025613B1 (fr) Procédé pour améliorer la qualité du chlore
JP3163831B2 (ja) １，１−ジフルオロエタンとフッ化水素の共沸混合物および１，１−ジフルオロエタンまたはフッ化水素の回収方法
WO1993004980A1 (fr) Recuperation du monoxyde de dichlore present dans des melanges gazeux
CA1332103C (fr) Procede pour la preparation d'acide hypochloreux
EP0517782B1 (fr) Procede pour la production d'hypochlorite de lithium
US4220609A (en) Process for the recovery of alkyl chlorides
US4137258A (en) Process for making pure salicylic acid
US5028408A (en) Process for the production of lithium hypochlorite
US3471558A (en) Method for the decomposition and evaporation of urea synthesis effluent
US2740690A (en) Process for manufacture of chlorine dioxide hydrate
KR100518672B1 (ko) 황산에 의한 플루오로카본/플루오르화수소 공비혼합물로부터의플루오르화수소 분리방법
EP1153885A1 (fr) Procédé de concentration de composés du fluor
CS276386B6 (en) Process for removing chlorine from a gaseous mixture

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MG MN MW NO PL RO RU SD

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE BF BJ CF CG CI CM GA GN ML MR SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA