US3535215A - Method for operating electrolytic cells - Google Patents

Method for operating electrolytic cells Download PDF

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Publication number
US3535215A
US3535215A US687831A US3535215DA US3535215A US 3535215 A US3535215 A US 3535215A US 687831 A US687831 A US 687831A US 3535215D A US3535215D A US 3535215DA US 3535215 A US3535215 A US 3535215A
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United States
Prior art keywords
cell
hypochlorite
chlorate
anode
glycol
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Expired - Lifetime
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US687831A
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English (en)
Inventor
Morris P Grotheer
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Occidental Chemical Corp
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Hooker Chemical Corp
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Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C25B1/265—Chlorates

Definitions

  • Alkali metal chlorates may be produced by the electrolysis of aqueous solutions of alkali metal chlorides. The chlorine generated at the anode is reacted with the hydroxide ions generated at the cathode to produce the chlorates. Under ideal conditions, the production of sodium chlorate would consume all of the chlorine in the reaction:
  • hypochlorite (31- +OH :OCl-- C
  • concentration of hypochlorite decreases
  • conversion to chlorate is slower.
  • hypochlorite should be recycled to the electrolytic cell only in low concentrations, conversion to chlorate or destruction of the hypochlorite is necessary.
  • the hypochlorite content remaining in a chlorate cell liquor is reduced via its decomposition in a retention tank, or by application of heat.
  • an effective method for hypochlorite removal from diaphragm chlorate cell liquors containing small amounts of the same is to contact the solution with an olefinic compound to effect the reaction:
  • halohydrin in the presence of an alkaline reagent such as sodium hydroxide, may be converted to the corresponding glycol or polyol.
  • an alkaline reagent such as sodium hydroxide
  • the formation of a specific isomer of the glycol, polyol or halohydrin forms no critical feature for the purposes of this invention.
  • the reaction between an olefinic compound with the hypochlorite present in chlorate cell liquors may be conducted batchwise in a holding tank, or by cocurrent or countercurrent flow through a column. This reaction proceeds rapidly at a temperature between room temperature and about degrees centigrade.
  • the reaction between hypochlorite and an unsaturated compound may be continued until the hypochlorite content is reduced to zero or the reaction may be controlled to afford a recycle liquor containing an acceptably low hypochlorite content compatible with the specific operating conditions and apparatus.
  • Gaseous olefinically unsaturated compounds are preferred reactants of this invention because they are most easily handled.
  • the gaseous unsaturated organic compound may be bubbled through the chlorate cell liquor by any applicable means.
  • liquid olefinically unsaturated compounds are also applicable and they may be employed in conjunction with a mixing tank or they may be allowed to react with the hypochlorite by allowing them to rise through the chlorate cell liquor (based on their specific gravity). It is most advantageous to employ an unsaturated reactant which is soluble in the recycled cell liquor, but the product halohydrin, polyol or glycol may be removed as such if desired.
  • the unsaturated organic reactants employed in this invention are olefinically unsaturated hydrocarbons containing 28 carbon atoms.
  • the straight and branched chain aliphatic unsaturated hydrocarbons are applicable as well as cyclo aliphatic hydrocarbons such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene and the like.
  • the most preferred olefinic compounds are ethylene, propylene, 2- methyl propene, l-butene, 2-butene, 1,3-butadiene, pentadienes such as 1,3- or 1,4-pentadiene and the like.
  • the advantages of this process are two-fold.
  • Second, the products, glycols, polyols, and halohydrins remaining in the mother liquor may be cycled into the electrolytic cell where they perform a heretofore unknown function of reducting oxidative attack on the carbon or graphite anodes.
  • the more easily oxidized glycols, polyols or halohydrins are sacrificially oxdized at the anode in preference to carbon.
  • the instant invention contemplates neutralizing a depleted mercury cell brine and reacting it with an unsaturated aliphatic hydrocarbon to remove the remaining hypochlorite.
  • the halohydrin, glycol and/or polyol product is more desirable than a haloalkane or haloalkene of the prior art because of the improved benefit in the use of the halohydrin, glycol or polyol as an additive to the mercury cell feed brine.
  • the halohydrin, glycol and/or polyol product, when added to mercury cells acts to reduce graphite consumption and in addition, the additives tend to reduce the hydrogen content in the chlorine produced in a mercury cell.
  • the drawing represents a fiow diagram of a typical process involving the use of a diaphragm chlorate cell in the production of an alkali metal chlorate.
  • Example 1 To demonstrate the retardation of graphite anode consumption through the addition of an organic compound, such as ethylene glycol, the following example was performed.
  • Ethylene glycol is an example of a product which may be produced by the reaction of ethylene with hypochlorite present in chlorate cell liquors. This example represents an accelerated test.
  • Two electrolytic cells containing graphite anodes and cathodes were operated without diaphragms at a temperature of 60 degress centigrade at a current density of 1.5 amperes per square inch.
  • the electrolyte contained 100 grams per liter sodium chloride and 200 grams per liter sodium chlorate.
  • Ethylene glycol was added to one of the cells at a concentration of 1 gram per liter.
  • the electrolytic solutions were discarded once a day and fresh electrolyte was added to each cell.
  • the ethylene glycol was also replenished daily.
  • the cells operated for a total of 100 hours.
  • Example 2 The depleted brine from a mercury type chlor-alkali cell was subjected to a light vacuum to partially remove dissolved chlorine. The resulting brine was treated to afford a neutral solution. Then, the solution was contacted with ethylene at about 70 degress centigrade to produce the corresponding chlorohydrin and/ or glycol with partial or complete removal of hypochlorite. To this chlorohydrin-containing solution, sodium chloride was added. The solution was recycled to the mercury cell for electrolysis with a resultant reduction in graphite anode consumption and diminished quantities of hydrogen in the chlorine gas produced in the cell.
  • step (c) electrolyzing the feed brine of step (b) in said electrolytic cell.
  • said unsaturated compound is a member of the group consisting of ethylene, propylene, 2-methylpropene, l-butene, 2-butene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene and mixtures thereof.
  • a process for reducing oxidation of carbon anode in a diaphragm type electrolytic chlorate cell which comprises reacting the chlorate cell liquor containing residual amounts of hypochlorite with an olefinically unsaturated hyrdocarbon compound to produce a product selected from the group consisting of a chlorohydrin, a glycol, a polyol, and mixtures thereof, passing the treated solution to a crystallizer, and recycling the mother liquor containing the products of reaction between said hypochlorite and said hydrocarbon compound plus make up brine to the anode compartment of said diaphragm type electrolytic chlorate cell.
  • said unsaturated compound is a member of the group consisting of ethylene, propylene, Z-methyl-propene, l-butene, Z-butene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene and mixtures thereof.
  • a process for removing hypochlorite from the depleted brine of a mercury cell containing a carbon anode comprising bringing the depleted brine to near neutrality by treatment with a base, then contacting said depleted brine with an unsaturated hydrocarbon compound to produce a product selected from the group consisting of a chlorohydrin, a glycol, a polyol and mixtures thereof, reconstituting said depleted brine with alkali metal chloride to afford an acceptable mercury cell feed brine, recycling said reconstituted feed brine to said mercury cell for electrolysis, said chlorohydrin, glycol, polyol and mixtures thereof serving to decrease carbon anode oxidation and reduce the amount of hydrogen evolved with chlorine in the mercury cell.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US687831A 1967-12-04 1967-12-04 Method for operating electrolytic cells Expired - Lifetime US3535215A (en)

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US68783167A 1967-12-04 1967-12-04

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US3535215A true US3535215A (en) 1970-10-20

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US (1) US3535215A (xx)
BE (1) BE724808A (xx)
DE (1) DE1812723A1 (xx)
FR (1) FR1595922A (xx)
GB (1) GB1247563A (xx)
NL (1) NL6817308A (xx)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878072A (en) * 1973-11-01 1975-04-15 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of chlorates
US3897320A (en) * 1973-11-01 1975-07-29 Hooker Chemicals Plastics Corp Electrolytic manufacture of chlorates, using a plurality of electrolytic cells
US4391681A (en) * 1981-05-14 1983-07-05 The British Petroleum Company P.L.C. Method of inhibiting formation of and breaking of mercury butter in chlor-alkali cells
US20150219583A1 (en) * 2014-02-06 2015-08-06 Honeywell International Inc. Lead-free galvanic oxygen sensor
CN111074293A (zh) * 2020-01-14 2020-04-28 石河子天域新实化工有限公司 离子膜法烧碱生产中氯酸盐分解工艺方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1257560A (en) * 1986-10-29 1989-07-18 Tenneco Canada Inc. (Erco Division) Electrochemical removal of hypochlorites from chlorate cell liquors

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US536848A (en) * 1895-04-02 Electrolysis
US1253617A (en) * 1916-03-18 1918-01-15 Chemical Dev Company Process of and apparatus for oxidizing hydrocarbons.
US1253615A (en) * 1915-06-22 1918-01-15 Chemical Dev Company Manufacture of chlorhydrins.
US1264535A (en) * 1915-12-09 1918-04-30 Chemical Dev Company Electrolysis of chlorids.
US2949412A (en) * 1948-11-24 1960-08-16 Dow Chemical Co Mercury-cell electrolysis of sodium chloride brine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US536848A (en) * 1895-04-02 Electrolysis
US1253615A (en) * 1915-06-22 1918-01-15 Chemical Dev Company Manufacture of chlorhydrins.
US1264535A (en) * 1915-12-09 1918-04-30 Chemical Dev Company Electrolysis of chlorids.
US1253617A (en) * 1916-03-18 1918-01-15 Chemical Dev Company Process of and apparatus for oxidizing hydrocarbons.
US2949412A (en) * 1948-11-24 1960-08-16 Dow Chemical Co Mercury-cell electrolysis of sodium chloride brine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878072A (en) * 1973-11-01 1975-04-15 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of chlorates
US3897320A (en) * 1973-11-01 1975-07-29 Hooker Chemicals Plastics Corp Electrolytic manufacture of chlorates, using a plurality of electrolytic cells
US4391681A (en) * 1981-05-14 1983-07-05 The British Petroleum Company P.L.C. Method of inhibiting formation of and breaking of mercury butter in chlor-alkali cells
US20150219583A1 (en) * 2014-02-06 2015-08-06 Honeywell International Inc. Lead-free galvanic oxygen sensor
US12055514B2 (en) 2014-02-06 2024-08-06 Life Safety Distribution Ag Lead-free galvanic oxygen sensor
CN111074293A (zh) * 2020-01-14 2020-04-28 石河子天域新实化工有限公司 离子膜法烧碱生产中氯酸盐分解工艺方法
CN111074293B (zh) * 2020-01-14 2022-05-10 石河子天域新实化工有限公司 离子膜法烧碱生产中氯酸盐分解工艺方法

Also Published As

Publication number Publication date
NL6817308A (xx) 1969-06-06
FR1595922A (xx) 1970-06-15
BE724808A (xx) 1969-06-02
GB1247563A (en) 1971-09-22
DE1812723A1 (de) 1969-07-03

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