US3652417A - Stabilization of alkali metal permanganate in alkaline solution - Google Patents

Stabilization of alkali metal permanganate in alkaline solution Download PDF

Info

Publication number
US3652417A
US3652417A US709816A US3652417DA US3652417A US 3652417 A US3652417 A US 3652417A US 709816 A US709816 A US 709816A US 3652417D A US3652417D A US 3652417DA US 3652417 A US3652417 A US 3652417A
Authority
US
United States
Prior art keywords
permanganate
alkali metal
solution
alkaline
per liter
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.)
Expired - Lifetime
Application number
US709816A
Inventor
Hans S Posselt
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.)
Carus LLC
Original Assignee
Carus LLC
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 Carus LLC filed Critical Carus LLC
Application granted granted Critical
Publication of US3652417A publication Critical patent/US3652417A/en
Assigned to TREFOIL CAPITAL CORPORATION reassignment TREFOIL CAPITAL CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CARUS CORPORATION A DE CORP
Assigned to GLENFED FINANCIAL CORPORATION reassignment GLENFED FINANCIAL CORPORATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CARUS CORPORATION
Anticipated expiration legal-status Critical
Assigned to CARUS CORPORATION, A DE CORP. reassignment CARUS CORPORATION, A DE CORP. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). REEL 424, FRAMES 261-276 - 1-18-84 Assignors: FIDELCOR BUSINESS CREDIT CORPORATION, FORMERLY TREFOIL CAPITAL CORPORATION
Assigned to CARUS CORPORATION, A DE CORP. reassignment CARUS CORPORATION, A DE CORP. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GLENFED FINANCIAL CORPORATION
Assigned to GLENFED CAPITAL CORP. reassignment GLENFED CAPITAL CORP. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: CARUS CORPORATION
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
    • C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals

Definitions

  • the useful life of a permanganate bath is not only determined by the rate of consumption, e.g., due to oxidation of lower oxides (as applies to metal descaling), but also by parasitic side reactions which result in the useless evolution of molecular oxygen from the bath. It is the principal subject of this invention to have devised measures to suppress said side reactions and thus to substantially lengthen the useful life of an alkaline permanganate bath. In view of the relatively high cost of replenishing KMnO the invention represents a significant economic improvement in this area of technology.
  • permanganate in alkaline solution will also undergo self-decomposition to manganate, in a reaction generally referred to as deoxidation.
  • reaction (II) represents a quasi-equilibrium (not a true equilibrium because the O continuously escapes from the system).
  • the quasi-equilibrium state is characterized by the fact that reaction (II) will come to a virtual standstill when a certain concentration of manganate is present in the system.
  • reaction (II) there are still other reactions occurring in the system.
  • a very significant one in this context is the hydrolysis (or disproportionation) of K MnO
  • This reaction is important because it can disturb the (quasi) equilibrium in reaction (II), causing more KMnO to be decomposed into K MnO and 0 Reaction (III) has been said to occur in both directions, but many investigators were unable to confirm the hypothesis that KMnO will consistently react with MnO to any significant extent to give K MnO Thus to the present date it remained a question whether and under what conditions reaction (III) can attain the state of equilibrium.
  • K MnO can be regarded as a deoxidation inhibitor.
  • Equation III wherein alkali metal manganate is a component
  • Equation V the horizontal equation represents the deoxidation reaction and the vertical equation represents the disproportionation (hydrolysis) reaction.
  • the latter is obtained by addition of compounds acting as anti-coagulating agents or protective colloids for ultrafine or colloidal MnO in the solution.
  • These compounds are anionic and comprise, as a general class, surfactants, polyelectrolytes or protective colloids. They must be stable toward both alkali and the powerful oxidative properties of the alkali metal per manganate in aqueous solution, especially at elevated temperatures.
  • the group of compounds best suited for the above purposes are anionic, saturated fluorocarbon surfactants, particularly saturated fluor ocarbon sulfonic acids ant l 55k? thereof, par ticularly alkali metal salts, and saturated fluorocarbon carboxylic acids and salts thereof, particularly alkali metal salts.
  • These sulfonic or carboxylic acids have the general formula RSO H or RCOOl-l wherein R is a saturated fluorocarbon group having 1-18 carbons and particularly as described in- U.S. Pat. No. 2,732,398.
  • the group R is a saturated fluorocarbon structure containing l-l8 carbon atoms, each of which is perfluoroalkyl and perfluorocycloalkyl (perfluorocyclohexyl).
  • the group R preferably has at least three carbons.
  • the invention embraces a dry mixture of said alkali metal (i.e., sodium and/or potassium) permanganate and 0.01 to 1 percent by weight, based on said permanganate, of the aforedescribed anionic surfactants or MnO anti-coagulating agents.
  • alkali metal i.e., sodium and/or potassium
  • the dry mixture may contain alkali metal hydroxide or alkali metal hydroxide and alkali metal carbonate to provide the desired alkalinity of a metal descaling bath.
  • dry mixtures may thus comprise:
  • the preferred perfluoroalkyl sulfonic acid has at least four carbons and may be, for example, perfluoroheptane sulfonic acid or perfluorooctane sulfonic acid.
  • the alkali metal salts thereof may be used, e.g., the sodium or potassium salts.
  • the acid will be neutralized to the alkali metal salt, in any case, in the ultimate alkaline permanganate solution.
  • the anionic sur- 1 factant may be a perfluoroalkyl carboxylic acid with at least four carbons or the alkali metal salt thereof, e.g., peri fluoroheptanoic acid, perfluorooctanoic acid or their sodium 1 or potassium salts.
  • the anhydrides of the aforesaid perfiuoroalkyl carboxylic acids are other alternatives for the surfactant of the dry mixtures recognizing, .of course, that such anhydrides will be hydrolyzed into the corresponding acids in the form of their alkali metal salts in the aqueous, alkaline permanganate solutions.
  • the above described dry mixtures may be dissolved in water in the proportions of about -250 grams dry mixture per liter of water.
  • An optimum balance between useful bath life and oxidative efficiency, particularly for metal descaling, for the mixtures substantially corresponding to the proportions of Example 1 is achieved at a solution strength of 160-180 grams dry mixture NaOl-l liter of water, corresponding to an alkalinity in the order of about 93 to 107 grams NaOl-l.
  • the alkali metal permanganate (preferably KMnO may constitute 5-95 percent by weight of the mixture; the alkali hydroxide (preferably NaOl-l), 5-95 percent by weight; ,the optional alkali metal carbonate (preferably Na CO 0-60 percent by weight; and the anionic surfactant ,(preferably the aforedescribed perfiuorocarbon compounds), 0.01-1 percent by weight.
  • aqueous solutions may comprise in the preferred concentration ranges: 20-150 grams per liter of alkali metal hydroxide, preferably NaOl-l; 5-100 grams per liter of alkali metal permanganate,
  • solute ingredients may be added together in the form of the above described dry mixtures or separately as individual components thereof.
  • the baths preferably are arranged in the sequence of a permanganate, alkaline, scaleconditioning bath, a water rinse, an acid pickling bath, and a water rinse.
  • Exemplary scale conditioning baths have a KMnQ, concentration of 2-10 percent, an NaOH concentration of 5-10 percent; an anionic surfactant concentration of 25-100 mg. per liter; and an elevated bath temperature of 190-230 F. During use, the bath is replenished as required to maintain the above optimum concentrations.
  • the above described perfluorocarbon anionic surfactants also serve in suppressing evolution of caustic mist from the bath and in reducing drag out loss of the bath on treated metal parts removed therefrom.
  • Mn04 Ba BaMnO, (insoluble) as opposed to the usual 3-electron exchange in the absence of barium ion:
  • a substantial amount of barium ion in the permanganate solutions is not considered to be desirable.
  • the presence in said solutions of substantial amounts of other alkaline earth metal ions such as Ca and Mg ions (and also heavy metal ions) has an overall detrimental effect by promotion of MnO precipitation, thus increasing permanganate loss through the above described permanganate self-decomposition.
  • a composition consisting essentially of alkali metal permanganate, and, as a stabilizer against self-decomposition of said permanganate in aqueous, alkaline solution, about 0.01 to 1 percent by weight, based on said permanganate, of a perfluoro alkyl compound selected from the group consisting of perfiuoro alkylsulfonic and carboxylic acids having 1 -l8 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline alkali metal permanganate solu tion and acts as an anticoagulant for colloidal MnO in said solution.
  • perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms or alkali metal salt thereof and said permanganate is potassium permanganate or sodium permanganate.
  • An aqueous, alkaline, alkali metal permanganate solution 7 having a permanganate concentration of about 5-100 grains per liter and an alkalinity equivalent to about 20-150 grams per liter of NaOH, said permanganate being stabilized against self-decomposition in said solution by about 0.01 to 1 percent by weight based on said permanganate, of a perfluoro alkyl compound selected from the group consisting of perfluoro alkylsulfonic and carboxylic acids having 1-18 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline, alkali metal permanganate solution and acts as an anticoagulant for colloidal MnO in said solution.
  • a perfluoro alkyl compound selected from the group consisting of perfluoro alkylsulfonic and carboxylic acids having 1-18 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline,
  • a composition as claimed in claim 3 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.
  • a method for improving stability of alkali metal permanganate against self-decomposition in aqueous, alkaline soluanti-agglomerating agent on said ultrafine manganese dioxide 6.
  • said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.

Abstract

Stabilization of alkali metal permanganate against deoxidative, self-decomposition in aqueous, alkaline solution by preventing ultrafine (colloidal) MnO2 dispersed in said solution from agglomerating by providing therein small amounts of anionic anticoagulating agent for dispersed MnO2, preferably perfluorocarbon surfactant.

Description

nie :11 States Patent Posselt 1 Mar. 28, 1972 STABILIZATION OF ALKALI METAL IPERMANGANATE IN ALKALINE SOLUTION Inventor: lllans S. Posselt, La Salle, Ill.
Assignee: Carus Corporation Filed: Mar. 1, 1968 Appl. No.: 709,816
252/186, 252/313 Int. Cl. ..C02b 5/02, Cl 1d 1/28 Field 01' Search ..252/156, 80, 103, 186; 23/58 References Cited UNITED STATES PATENTS l/l956 Brice et a1 ..252/71 X 2,750,334 6/1956 Brown ..204/32 X 3,000,829 9/1961 3,210,284 10/1965 Duvall ..252/80 Primary Examiner-Herbert B. Guynn Assistant Examiner-Arnold I. Rady Attorney-Marzall, Johnston, Cook & Root [5 7] ABSTRACT 7 Claims, No Drawings STABILIZATION OF ALKALI METAL PERMANGANATE IN ALKALINE SOLUTION BACKGROUND OF THE INVENTION AND PERMANGANATE CHEMISTRY Alkaline solutions of potassium permanganate are used in a variety of industrial applications such as metal cleaning, radioactive decontamination, metal descaling, gas scrubbing, etc. In all these applications the longevity of the KMnO, is of high economic importance.
The useful life of a permanganate bath is not only determined by the rate of consumption, e.g., due to oxidation of lower oxides (as applies to metal descaling), but also by parasitic side reactions which result in the useless evolution of molecular oxygen from the bath. It is the principal subject of this invention to have devised measures to suppress said side reactions and thus to substantially lengthen the useful life of an alkaline permanganate bath. In view of the relatively high cost of replenishing KMnO the invention represents a significant economic improvement in this area of technology.
To understand the principles of this invention, it is necessary to appreciate the pertinent chemistry:
To illustrate the useful chemical action of KMnO. let us look at how it typically works in scale removal from a metal surface. A typical oxide scale will consist of higher oxides in its outer layers and of lower oxides in its inner layers (i.e., at and close to the interface metal-metal oxide). The action of MnO in scale removal has been shown to consist of an oxidative attack upon the lower oxide layers of the scale, causing a change in its physical and chemical properties which will lead to either partial dissolution of the scale or more susceptibility to pickling in a subsequent acid treatment step.
Thus, the useful chemical action exerted by KMnO, in this alkaline system can be expressed in a simplified manner in the following equation (using steel as the metal under treatment):
2Fe0 ZKMnO, ZKOH Fe 2K MnO H Ou Under the conditions of this type of a bath (alkali concentration in the range from g./l. to 150 g./l. NaOH and temperature up to 220 F.) permanganate ion (MnOf) is the only effective species in metal descaling, while manganate ion (M- nOf') is without effect.
Aside from the useful chemical reduction of KMnO, as exemplified by equation (I), permanganate in alkaline solution will also undergo self-decomposition to manganate, in a reaction generally referred to as deoxidation.
4KMnO 4KOH I. 4K MnO, 0 2I-I,O (II) The significance of this reaction is that molecular oxygen is generated from permanganate without any economic benefit. To prevent or curb this self-decomposition is of high interest to the economics of the process.
The reaction mechanisms proposed for the above mentioned deoxidation reaction are quite complex and up to this date none of them is fully satisfactory. Nevertheless, it has been established that reaction (II) represents a quasi-equilibrium (not a true equilibrium because the O continuously escapes from the system). The quasi-equilibrium state is characterized by the fact that reaction (II) will come to a virtual standstill when a certain concentration of manganate is present in the system. Accounts of results of investigations into this reaction have been published by Landsberg et al.
In addition to reaction (II) there are still other reactions occurring in the system. A very significant one in this context is the hydrolysis (or disproportionation) of K MnO This reaction is important because it can disturb the (quasi) equilibrium in reaction (II), causing more KMnO to be decomposed into K MnO and 0 Reaction (III) has been said to occur in both directions, but many investigators were unable to confirm the hypothesis that KMnO will consistently react with MnO to any significant extent to give K MnO Thus to the present date it remained a question whether and under what conditions reaction (III) can attain the state of equilibrium.
Tomicek et al. (Collection Czech. Chem. Commun. 11, 44958(l939) have described the usefulness of telluric acid for stabilizing quadrivalent manganese in analytical applications of permanganate. The stabilizing action of telluric acid is explained in terms of a complexing power of tellurate ion on quadrivalent manganese. This approach, however, does not appear very feasible for industrial purposes since tellurium compounds are rather expensive and furthermore toxic.
In applications where KMnO is the only active species, e.g., metal descaling, the removal (and deposition) of MnO is highly undesirable since it lowers the concentration of K M- n0. which in turn induces further deoxidation (loss of active oxygen). In the light of this theory, K MnO can be regarded as a deoxidation inhibitor.
DESCRIPTION OF INVENTION The overall process of such caustic permanganate solutions can be visualized by the following reaction scheme:
(Ill) loss of O2; deoxidation KMn0-----+ repeat itself.
From the net reaction of such systems:
4KMnO, 2I-I O 30 4Mn0 4KOI-I (IV) and the fact that molecular oxygen is produced by deoxidation, one can easily deduce that deoxidation is a useless and wasteful process. Further, it is very desirable to prevent or suppress the deposition of MnO, on solid reactant surfaces since rates of oxidation slow down by physically masking attack on the reactant.
The two reversible reactions of Equation III, wherein alkali metal manganate is a component, are expressed more fully in Equation V, below, wherein the horizontal equation represents the deoxidation reaction and the vertical equation represents the disproportionation (hydrolysis) reaction. Hi0 KMI'IO KOH If: M1104 E20 OzT KOH KMnOc MnOz M) (Colloidal) (Coagulated) Having developed the above overall reaction scheme of the interrelated deoxydation reaction and disproportionation reaction and having deduced therefrom that coagulation of MnO consumes alkali metal manganate in the disproportionation reaction, which in turn results in wasted alkali metal permanganate consumption in the deoxidation reaction, my discoveries are put into practical application by providing in alkaline, alkali metal permanganate solutions chemical means for inhibiting the disadvantageous, irreversible coagulation of colloidal MnO into insoluble MnO macrosize aggregates.
The latter is obtained by addition of compounds acting as anti-coagulating agents or protective colloids for ultrafine or colloidal MnO in the solution. These compounds are anionic and comprise, as a general class, surfactants, polyelectrolytes or protective colloids. They must be stable toward both alkali and the powerful oxidative properties of the alkali metal per manganate in aqueous solution, especially at elevated temperatures.
The group of compounds best suited for the above purposes are anionic, saturated fluorocarbon surfactants, particularly saturated fluor ocarbon sulfonic acids ant l 55k? thereof, par ticularly alkali metal salts, and saturated fluorocarbon carboxylic acids and salts thereof, particularly alkali metal salts. These sulfonic or carboxylic acids have the general formula RSO H or RCOOl-l wherein R is a saturated fluorocarbon group having 1-18 carbons and particularly as described in- U.S. Pat. No. 2,732,398. As therein described, the group R is a saturated fluorocarbon structure containing l-l8 carbon atoms, each of which is perfluoroalkyl and perfluorocycloalkyl (perfluorocyclohexyl). For the purposes herein, the group R preferably has at least three carbons.
The invention embraces a dry mixture of said alkali metal (i.e., sodium and/or potassium) permanganate and 0.01 to 1 percent by weight, based on said permanganate, of the aforedescribed anionic surfactants or MnO anti-coagulating agents. Other compounds may be mixed therewith if desired. For example, the dry mixture may contain alkali metal hydroxide or alkali metal hydroxide and alkali metal carbonate to provide the desired alkalinity of a metal descaling bath.
These dry mixtures may thus comprise:
a. KMnO, or NaMnO, and 0.01 to 1 percent of the anionic surfactant.
b. KMnO, or NaMnO.,, and in percentages based on the permanganate, NaOH or KOH- 50 250%; Na CO -O-250%; anionic surfactant 0.01 to 1 percent.
EXAMPLE 1 An example of such dry mixture is:
Present by weight KMnO. 30 1 NaOl-l 60 Na CO, (optional) Perfluoroalkyl sulfonic acid or its alkali metal salt 0.03%
The preferred perfluoroalkyl sulfonic acid has at least four carbons and may be, for example, perfluoroheptane sulfonic acid or perfluorooctane sulfonic acid. The alkali metal salts thereof may be used, e.g., the sodium or potassium salts. The acid will be neutralized to the alkali metal salt, in any case, in the ultimate alkaline permanganate solution. Instead of the ;perfluorosulfonic acid in the above example, the anionic sur- 1 factant may be a perfluoroalkyl carboxylic acid with at least four carbons or the alkali metal salt thereof, e.g., peri fluoroheptanoic acid, perfluorooctanoic acid or their sodium 1 or potassium salts. The anhydrides of the aforesaid perfiuoroalkyl carboxylic acids are other alternatives for the surfactant of the dry mixtures recognizing, .of course, that such anhydrides will be hydrolyzed into the corresponding acids in the form of their alkali metal salts in the aqueous, alkaline permanganate solutions.
The above described dry mixtures may be dissolved in water in the proportions of about -250 grams dry mixture per liter of water. An optimum balance between useful bath life and oxidative efficiency, particularly for metal descaling, for the mixtures substantially corresponding to the proportions of Example 1 is achieved at a solution strength of 160-180 grams dry mixture NaOl-l liter of water, corresponding to an alkalinity in the order of about 93 to 107 grams NaOl-l.
In terms of ranges of proportions of these dry mixtures, particularly those ultimately to be used inaqueous metal descaling baths, the alkali metal permanganate (preferably KMnO may constitute 5-95 percent by weight of the mixture; the alkali hydroxide (preferably NaOl-l), 5-95 percent by weight; ,the optional alkali metal carbonate (preferably Na CO 0-60 percent by weight; and the anionic surfactant ,(preferably the aforedescribed perfiuorocarbon compounds), 0.01-1 percent by weight.
The aqueous solutions, particularly those for metal descaling, may comprise in the preferred concentration ranges: 20-150 grams per liter of alkali metal hydroxide, preferably NaOl-l; 5-100 grams per liter of alkali metal permanganate,
preferably KMnO 0-100 grams per liter of alkali metal carbonate, preferably Na CO and 25-100 milligrams per liter of the above described anionic surfactant. in the initial makeup of such solutions or the replenishment thereof in use such as metal descaling, the solute ingredients may be added together in the form of the above described dry mixtures or separately as individual components thereof.
In metal descaling of ferrous metals, e.g., steel plates, wires or the like, made from mild steel, tool steel, carbon steel, stainless steel or other ferrous alloys, the baths preferably are arranged in the sequence of a permanganate, alkaline, scaleconditioning bath, a water rinse, an acid pickling bath, and a water rinse. Exemplary scale conditioning baths have a KMnQ, concentration of 2-10 percent, an NaOH concentration of 5-10 percent; an anionic surfactant concentration of 25-100 mg. per liter; and an elevated bath temperature of 190-230 F. During use, the bath is replenished as required to maintain the above optimum concentrations. In addition to stabilizing the bath against deoxidation loss of KMnO via maintaining the colloidal state of MnO in the bath, the above described perfluorocarbon anionic surfactants also serve in suppressing evolution of caustic mist from the bath and in reducing drag out loss of the bath on treated metal parts removed therefrom.
Duvall US. Pat. No. 3,210,284 states that KMnO can be stabilized in caustic solutions by addition of Ba ion which precipitates all manganate (VI) as the insoluble barium salt. Since manganate (V1) is inevitably the first state of KMnO reduction in caustic solution (p1-1 11) one can-if Ba is present-utilize the exchange of one electron only IMHOF 8 v M:
Mn04= Ba BaMnO, (insoluble) as opposed to the usual 3-electron exchange in the absence of barium ion:
MnO,,-+ 3e 411* MnO 2H O Thus, KMnO, oxidations carried out under caustic conditions and in the presence of barium ion have a profound economic disadvantage which entirely overshadows other possible benefits gained from barium ion addition.
Accordingly, in the practice of the invention herein, a substantial amount of barium ion in the permanganate solutions is not considered to be desirable. Also, the presence in said solutions of substantial amounts of other alkaline earth metal ions :such as Ca and Mg ions (and also heavy metal ions) has an overall detrimental effect by promotion of MnO precipitation, thus increasing permanganate loss through the above described permanganate self-decomposition.
It is thought that the invention and its numerous attendant advantages will be fully understood from the foregoing description, and it is obvious that numerous changes may be made in the form, construction and arrangement of the several parts without departing from the spirit or scope of the invention, or sacrificing any of its attendant advantages, the forms herein disclosed being preferred embodiments for the purpose of illustrating the invention.
The invention is hereby claimed as follows:
1. A composition consisting essentially of alkali metal permanganate, and, as a stabilizer against self-decomposition of said permanganate in aqueous, alkaline solution, about 0.01 to 1 percent by weight, based on said permanganate, of a perfluoro alkyl compound selected from the group consisting of perfiuoro alkylsulfonic and carboxylic acids having 1 -l8 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline alkali metal permanganate solu tion and acts as an anticoagulant for colloidal MnO in said solution.
2. A composition as claimed in claim 1 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms or alkali metal salt thereof and said permanganate is potassium permanganate or sodium permanganate.
3. An aqueous, alkaline, alkali metal permanganate solution 7 having a permanganate concentration of about 5-100 grains per liter and an alkalinity equivalent to about 20-150 grams per liter of NaOH, said permanganate being stabilized against self-decomposition in said solution by about 0.01 to 1 percent by weight based on said permanganate, of a perfluoro alkyl compound selected from the group consisting of perfluoro alkylsulfonic and carboxylic acids having 1-18 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline, alkali metal permanganate solution and acts as an anticoagulant for colloidal MnO in said solution.
4. A composition as claimed in claim 3 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.
5. A method for improving stability of alkali metal permanganate against self-decomposition in aqueous, alkaline soluanti-agglomerating agent on said ultrafine manganese dioxide. 6. A method as claimed in claim -5 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.
7. A process as claimed in claim 5 wherein said aqueous, alkaline, alkali metal permanganate solution has a permanganate concentration of about 5-100 grams per liter and'an alkalinity equivalent to about 20-150 grams per liter of NaOl-l.

Claims (6)

  1. 2. A composition as claimed in claim 1 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms or alkali metal salt thereof and said permanganate is potassium permanganate or sodium permanganate.
  2. 3. An aqueous, alkaline, alkali metal permanganate solution having a permanganate concentration of about 5-100 grams per liter and an alkalinity equivalent to about 20-150 grams per liter of NaOH, said permanganate being stabilized against self-decomposition in said solution by about 0.01 to 1 percent by weight based on said permanganate, of a perfluoro alkyl compound selected from the group consisting of perfluoro alkylsulfonic and carboxylic acids having 1-18 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in said alkaline, alkali metal permanganate solution and acts as an anticoagulant for colloidal MnO2 in said solution.
  3. 4. A composition as claimed in claim 3 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.
  4. 5. A method for improving stability of alkali metal permanganate against self-decomposition in aqueous, alkaline solution which comprises preventing ultrafine manganese dioxide dispersed in said solution from aggregating by providing in said solution a small but sufficient amount of a perfluoro alkyl compound selected from the group consisting of perfluoro alkylsulfonic and carboxylic acids having 1-18 carbons and perfluorocyclohexylsulfonic and carboxylic acids which is stable in the alkaline, alkali metal permanganate solution and acts as anti-agglomerating agent on said ultrafine manganese dioxide.
  5. 6. A method as claimed in claim 5 wherein said perfluoroalkyl compound is a perfluoroalkyl sulfonic or carboxylic acid having 4-18 carbon atoms alkali metal salt and said permanganate is potassium permanganate or sodium permanganate.
  6. 7. A process as claimed in claim 5 wherein said aqueous, alkaline, alkali metal permanganate solution has a permanganate concentration of about 5-100 grams per liter and an alkalinity equivalent to about 20-150 grams per liter of NaOH.
US709816A 1968-03-01 1968-03-01 Stabilization of alkali metal permanganate in alkaline solution Expired - Lifetime US3652417A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US70981668A 1968-03-01 1968-03-01

Publications (1)

Publication Number Publication Date
US3652417A true US3652417A (en) 1972-03-28

Family

ID=24851406

Family Applications (1)

Application Number Title Priority Date Filing Date
US709816A Expired - Lifetime US3652417A (en) 1968-03-01 1968-03-01 Stabilization of alkali metal permanganate in alkaline solution

Country Status (1)

Country Link
US (1) US3652417A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425380A (en) 1982-11-19 1984-01-10 Kollmorgen Technologies Corporation Hole cleaning process for printed circuit boards using permanganate and caustic treating solutions
EP0207586A1 (en) * 1985-05-31 1987-01-07 Macdermid Incorporated Sodium permanganate etch baths and their use in cleaning, desmearing and/or etching resinous substrates
FR2710071A1 (en) * 1993-09-16 1995-03-24 Aix Marseille Iii Universite Formulation and device which make it possible to prolong and improve the efficiency of degreasing solvents

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732398A (en) * 1953-01-29 1956-01-24 cafiicfzsojk
US2750334A (en) * 1953-01-29 1956-06-12 Udylite Res Corp Electrodeposition of chromium
US3000829A (en) * 1958-06-12 1961-09-19 Purex Corp Ltd Composition and process for descaling metal parts
US3080323A (en) * 1959-04-07 1963-03-05 Purex Corp Ltd Composition for radioactive decontamination and descaling of cobalt alloys
US3210284A (en) * 1962-03-23 1965-10-05 Wyandotte Chemicals Corp Stabilization of alkaline potassium permanganate solutions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732398A (en) * 1953-01-29 1956-01-24 cafiicfzsojk
US2750334A (en) * 1953-01-29 1956-06-12 Udylite Res Corp Electrodeposition of chromium
US3000829A (en) * 1958-06-12 1961-09-19 Purex Corp Ltd Composition and process for descaling metal parts
US3080323A (en) * 1959-04-07 1963-03-05 Purex Corp Ltd Composition for radioactive decontamination and descaling of cobalt alloys
US3210284A (en) * 1962-03-23 1965-10-05 Wyandotte Chemicals Corp Stabilization of alkaline potassium permanganate solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425380A (en) 1982-11-19 1984-01-10 Kollmorgen Technologies Corporation Hole cleaning process for printed circuit boards using permanganate and caustic treating solutions
EP0207586A1 (en) * 1985-05-31 1987-01-07 Macdermid Incorporated Sodium permanganate etch baths and their use in cleaning, desmearing and/or etching resinous substrates
AU580146B2 (en) * 1985-05-31 1989-01-05 Macdermid, Inc. Sodium permanganate etch baths containing a co-ion for permanganate and their use in desmearing and/or etching printed circuit boards
FR2710071A1 (en) * 1993-09-16 1995-03-24 Aix Marseille Iii Universite Formulation and device which make it possible to prolong and improve the efficiency of degreasing solvents

Similar Documents

Publication Publication Date Title
US3668131A (en) Dissolution of metal with acidified hydrogen peroxide solutions
US3407141A (en) Dissolution of metal with acidified hydrogen peroxide solutions
US4455287A (en) Method of stabilizing chelated polyvalent metal solutions
US3537895A (en) Copper and aluminum pickling
US5411607A (en) Process and composition for sealing anodized aluminum surfaces
FI100727B (en) Composition for stabilizing inorganic peroxide solutions
JPH0365436B2 (en)
CN103757633B (en) A kind of magnesium alloy nickel strip method
CN107502894B (en) A kind of environment-friendly type brightening solution for stainless steel and preparation method thereof and polishing process
CN107299348B (en) A kind of environment-friendly type brightening solution for stainless steel and preparation method thereof and polishing process
JPS6347375A (en) Room temperature black dyeing liquid
JPH08274057A (en) Semiconductor substrate cleaning device, cleaning method and formation of cleaning liquid
US3537926A (en) Chemical brightening of iron-containing surfaces of workpieces
US3652417A (en) Stabilization of alkali metal permanganate in alkaline solution
EP0353084A2 (en) Stabilized hydrogen peroxide compositions
CN105819594A (en) Recirculated cooling water processing method
JPS601600B2 (en) Method of chemical decontamination of nuclear reactor structural parts
US3507795A (en) Composition for removal of copper and copper oxide scales from boilers
JPH04362183A (en) Method for regenerating aluminum surface cleaning bath
EP0353083A2 (en) Hydrogen peroxide compositions containing a substituted oxybenzene compound
JP3034796B2 (en) Chemical cleaning method
US3483050A (en) Acid-peroxide dissolution of metals in the presence of titanium
JP4580085B2 (en) Method for etching metal tin or tin alloy and metal tin or tin alloy etchant
US1305213A (en) Pickling ferrous articles and electrically regenerating the pickling
KR100549864B1 (en) Composition of nitric acid free pickling solution for stainless steel

Legal Events

Date Code Title Description
AS Assignment

Owner name: TREFOIL CAPITAL CORPORATION 332 SOUTH MICHIGAN AVE

Free format text: SECURITY INTEREST;ASSIGNOR:CARUS CORPORATION A DE CORP;REEL/FRAME:004214/0261

Effective date: 19840113

AS Assignment

Owner name: GLENFED FINANCIAL CORPORATION,NEW JERSEY

Free format text: SECURITY INTEREST;ASSIGNOR:CARUS CORPORATION;REEL/FRAME:004910/0193

Effective date: 19880629

Owner name: GLENFED FINANCIAL CORPORATION, 104 CARNEGIE CENTER

Free format text: SECURITY INTEREST;ASSIGNOR:CARUS CORPORATION;REEL/FRAME:004910/0193

Effective date: 19880629

AS Assignment

Owner name: CARUS CORPORATION, A DE CORP.

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:FIDELCOR BUSINESS CREDIT CORPORATION, FORMERLY TREFOIL CAPITAL CORPORATION;REEL/FRAME:005255/0001

Effective date: 19891023

AS Assignment

Owner name: CARUS CORPORATION, A DE CORP., ILLINOIS

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:GLENFED FINANCIAL CORPORATION;REEL/FRAME:005237/0900

Effective date: 19891212

AS Assignment

Owner name: GLENFED CAPITAL CORP., ILLINOIS

Free format text: MORTGAGE;ASSIGNOR:CARUS CORPORATION;REEL/FRAME:005293/0081

Effective date: 19891103