WO1982001198A1 - Electrolytic process for the production of stannous chloride - Google Patents

Electrolytic process for the production of stannous chloride Download PDF

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Publication number
WO1982001198A1
WO1982001198A1 PCT/US1980/001307 US8001307W WO8201198A1 WO 1982001198 A1 WO1982001198 A1 WO 1982001198A1 US 8001307 W US8001307 W US 8001307W WO 8201198 A1 WO8201198 A1 WO 8201198A1
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WO
WIPO (PCT)
Prior art keywords
anode
cathode
stannous
compartment
chloride
Prior art date
Application number
PCT/US1980/001307
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English (en)
French (fr)
Inventor
Materials Co Vulcan
J Franks
Original Assignee
Materials Co Vulcan
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 Materials Co Vulcan filed Critical Materials Co Vulcan
Priority to EP81901190A priority Critical patent/EP0061449B1/en
Priority to GB8213800A priority patent/GB2094352A/en
Priority to DE8181901190T priority patent/DE3071064D1/de
Priority to PCT/US1980/001307 priority patent/WO1982001198A1/en
Publication of WO1982001198A1 publication Critical patent/WO1982001198A1/en

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Classifications

    • 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

Definitions

  • ion permselective membranes In contrast to known fluid permeable membranes, ion permselective membranes, also referred to as ion exchange membranes, have been found useful in a variety of fluid purification applications.
  • One specific use is the demineralization of water.
  • Other specific uses include the treatment of pickling liquors to produce sulfuri ⁇ acid and electrolytic iron, the treatment of copper or leaching solutions to produce hydrochloric acid and copper and the purification of aluminum sulfate solutions by electrolytically depositing iron therefrom. See, Industrial & Engineering Chemistry, Vol. 54, No. 6, page 29 (June 1962) and U.S. Patents 3,537,961 and 3,347,761.
  • cationic permselective membranes have been disclosed for use in processes to produce stannic oxide sol products (see U.S. Patent 3,723,273), anionic permselective membranes have been disclosed for use in a process to form tin and lead salts, e.g., stannous sulfate (see U.S. Patent 3,795,595) and cationic permselective membranes have been suggested for use in the regeneration and recycling of chromium etching solutions. See Chemical Engineering, June 4, 1979, page 77.
  • Stannous chloride in more recent years has been conventionally prepared by dissolving metallic tin in aqueous hydrochloric acid and evaporating the solution until crystals of the dihydrate SnCl 2 : 2H 2 O, commonly known as tin salt, separate.
  • the anhydrous salt can also be made by heating metallic tin in a stream of gaseous hydrogen chloride or by reacting tin metal with chlorine gas in the presence of liquid stannic chloride.
  • Patent 3,816,602 in which about 1 mol of tin metal, about 1 mol of ftiming or essentially anhydrous stannic chloride and at least 4 mols of free water are reacted to produce stannous chloride.
  • One of the problems with presently available processes for producing stannous chloride is the requirement for the addition of tin metal to reduce the stannic chloride to the stannous chloride form. As tin prices increase, the utilization of such processes results in an increasing cost of the stannous chloride.
  • the tin metal may contain various metallic impurities (for example, copper, iron, arsenic, antimony or lead) which may deleteriously affect the final product and prevent its utilization in certain end use products and applications.
  • the use of stannous chloride in connection with food additives requires very low tolerences of copper and arsenic. These metal impurities also pose problems in electrotinplating applications.
  • Still another object of the present invention is to provide an electrolytic process which may be used in a recycle process to provide a stannous salt containing solution from a stannic salt containing solution.
  • an electrolytic process for the production of stannous salts in an electrolytic cell comprising an anode compartment and a cathode compartment and a cationic permselective barrier between the anode and cathode compartments comprising introducing stannic anions into the cathode compartment of the electrolytic cell, providing an electrolyte in the anode compartment, applying direct current to the anode and cathode to produce stannous anions in the cathode compartment while substantially simultaneously preventing migration of stannous anions between the cathode and anode compartments by maintaining an electrolyte fluid impermeable cationic permselective barrier between the anode and cathode, removing produced gas from the anode compartment and removing the stannous anions from
  • an electrolytic process for the production of stannous chloride utilizing an electrolytic cell comprising a cathode and an anode and an ion permselective barrier dividing the electrolytic cell into anode and cathode compartments
  • process comprises providing a mixture of stannic and chloride ions having a chloride to tin ratio of at least about 4:1 in the cathode compartment, providing an anolyte solution in the cathode compartment of a mineral acid or tin salt thereof, applying direct current to the anode and cathode to form stannous anions and substantially preventing migration of the stannous anions from the cathode compartment to the anode compartment by maintaining a cationic permselective barrier between the anode and cathode to form a product solution of stannous and chloride ions having a chloride to tin ratio of at least about 2:1 and being substantially free of stannic anions in the cathode compartment,
  • stannic ion solutions containing an excess of acid moieties form stannic anions in solution which are substantially prevented from passing from the cathode compartment to the anode compartment in the electrolytic cell by the cationic permselective membrane.
  • As the stannous ion is produced in the cathode compartment further acid moieties are also produced which increase the formation of stannous anion complexes because of the equilibrium constants of the various ions which are produced in the cathode compartment.
  • the equilibrium constants of the various cationic, neutral and anionic complexes which could be present under these circumstances are such as to favor the anionic complexes.
  • the operation of the present process forms further free acid and thus more strongly shifts the equilibrium in favor of the formation of the anionic complexes.
  • the catholyte solution containing stannous anions can be easily treated to remove the desired stannous salt product
  • stannous chloride which can be in the ultimate recovered form of stannous chloride dihydrate, anhydrous stannous chloride or a stannous chloride solution containing some excess acid - the latter being apparently in the form of a complexed chlorostannous acid such as HSnCl 3 , H 2 SnCl 4 or mixtures thereof.
  • the process of the present invention can be used to convert at least 90, preferably at least 95, most preferably at least 98, percent of the stannic anions to stannous anions.
  • the FIGURE is a schematic representation of an electrolytic cell used in the process of the present invention.
  • the FIGURE shows a representation of an electrolytic cell which may be utilized in the process of the present invention.
  • This cell comprises an anode 10 and a cathode 11 within an electrolytic cell 12.
  • a cationic permselective membrane 13 is disposed about the anode 10 to separate the anode and cathode compartments of the electrolytic cell 12.
  • the cationic permselective membrane 13 extends generally along the length of the anode 10.
  • a closure 14 seals the bottom of the anode compartment.
  • the cathode compartment of the electrolytic cell 12 contains a catholyte solution 15 which initially contains the stannic anion solution as further described hereinafter.
  • the anode compartment of the electrolytic cell 12 contains an anolyte solution 16 which can be of any suitable, non-deleterious acid or acid salt electrolyte solution as also further described hereinafter.
  • the anode compartment further contains a vacuum tube 17 or other means for removing gases which are produced within the anolyte compartment during the operation thereof.
  • the electrolytic cell 12 can also contain a stirrer or other means for agitating the solution (not shown) and a thermocouple for obtaining the temperature of the solution (not shown).
  • the electrolytic cell also contains suitable connections 18 and 19 for the addition of and removal of the catholyte solution 15 from the electrolytic cell 12.
  • the anode 10 and cathode 11 are connected to a suitable source of direct current power source at their terminals. Heating or cooling means may also be provided to maintain the anolyte and the catholyte at the desired operating temperatures.
  • the anode and cathode may be of any convenient shape such as a sheet or rod and the overall size of the anode, the cathode and the respective compartments may be varied according to the particular style of operation although it may be advantageous in certain instances to have the cathode larger, e.g., up to about 3 or more times the size, of the anode.
  • Any type of anode and cathode material that is electrically conductive and has low reactivity in electrolyte solution, i.e., is substantially inert to the electrolyte may be used.
  • carbon has been found to be suitable.
  • Other suitable materials may also be utilized.
  • anode compartments interposed between cathode compartments may also be utilized.
  • the electrolytic cell may be operated at anode current densities at from about 5 to 200 or more amperes per square foot of anode area (the upper limit being determined generally by the upper limit of the value of the current density permitted by the particular cationic permselective membrane utilized) and at cell voltages ranging from about 1 to 20, preferably from about 1 to about 10, volts.
  • the temperature of the anolyte may be from about 5°C up to about 75 °C but more typically is about 10°C to about 60°C, preferably from about 15 °C to 55°C. Again, the maximum permissable temperature may vary according to the particular cationic permselective membrane utilized.
  • the temperature of the catholyte may fall within the same range as given for the anolyte and preferably is within about 5°C of the anolyte temperature.
  • the anolyte i.e., the electrolyte in the anode compartment, may be any aqueous solution of acompatible electrolyte material.
  • the anolyte will be a mineral acid solution or a tin salt thereof.
  • a limitation on the utilization of a material as the anolyte arises from two factors. That is, as described hereinbelow, the utilization of a particular material generally results in the production of an oxidizing gas which must be removed from the electrolytic cell during processing in order to achieve the desired results.
  • the toxicity of the produced gas and/or economics of the overall process may dictate the utilization of a particular material as the anolyte.
  • the use of nitric acid may result in the production of gaseous nitrous oxides in the anode compartment which are toxic and difficult to control.
  • the utilization of nitric acid is not normally preferred unless such gaseous by-products are desired for other purposes.
  • the utilization of hydrochloric acid as the electrolyte will result in the production of chlorine gas in the anode compartment which gas while also toxic may be useful in certain processes for other purposes.
  • hydrochloric acid may be more acceptable economically as the anolyte material.
  • Hydrohalous acids are one of the preferred groups of anolyte electrolyte materials.
  • Sulphuric acid may also be utilized as the anolyte and in such case oxygen will be the produced gas. Since oxygen presents no toxicity problems, sulphuric acid is one of the other preferred embodiments of the presently claimed invention.
  • Tin salts of any suitable acid may also be used. While other metallic salts of these acids are theoretically utilizable, the presence of other metallic cations in the anode compartment could result in the transference of these other metal cations into the cathode compartment and thus into the stannous salt solutions being produced therein. Ordinarily, these other metal cations are not desired in the stannous salt solutions. It is thus preferred that when metal salts are used in the anolyte, that the stannous salts of these particular acids be utilized. Typically, the concentration of the acid or salt solution ranges from about 2 to about 50% free acid or salt by weight of the anolyte solution.
  • the catholyte i.e., the electrolyte in the cathode compartment, may be any aqueous solution containing stannic anions.
  • stannic anioncontaining solutions which are available from various commercial processes (e.g., acid plating baths or the like) the solution contains an excess of acid relative to the amount necessary to form the stannic acid salt.
  • stannic chloride has the typical formula SnCl 4 .
  • stannic chloride manufacturing processes other than those for the production of anhydrous stannic chloride
  • a small amount of excess hydrochloric acid is generally added to stabilize stannic chloride such that the ratio of chlorine to tin in the stannic chloride solution is greater than 4, generally about 4.5 to 1.
  • the anolyte feed stocks which may be utilized in the electrolysis process of the present invention are those which have been produced in various other chemical processes and which may contain minor and/or substantial amounts of various impurities.
  • any type of cation permselective membrane may be used which will substantially exclude or prevent tin anions from passing from the anode compartment to the cathode compartment of the electrolytic cell, but which will allow passage of cations therethrough.
  • the cation permselective membrane is a cation exchange membrane or sheet which is substantially impermeable to the aqueous electrolyte.
  • cation exchange membranes are well known per se and include both membranes where ion exchange groups or material are impregnated in or distributed throughout a polymeric matrix or binder, as well as those where such groups are associated only with the outer surface of a membrane backing or reinforcing fabric.
  • Continuous ion exchange membranes in which the entire membrane structure has ion-exchange characteristics and which may be formed by molding or casting a partially polymerized ion exchange resin into sheet form, may also be used.
  • the ion exchange material may include material to which acid groups such as —SO-3H or —COOH are added to a polystyrene resin by conventional procedures.
  • the groups may be added by contacting the surface to be coated with a rea ⁇ tant, the molecular structure of which leaves exposed to the surface thereof ion exchange groups of the same type as those found upon the surfaces of cation exchange membranes, e.g., —S0 3 H or —COOH moieties.
  • Widely known cation exchange membranes may be prepared by copolymerizing a mixture of ingredients, one of which contains a substituent or group which is acid in nature and which may comprise the sulfonic acid group or the carboxylic acid group.
  • this ionizable group may be attached to a polymeric compound such as copolymers of styrene and divinyl benzene, polystyrene phenolaldehyde resins, resorcinol-aldehyde polymers, copolymers of divinyl benzene with acrylic acid, copolymers of divinyl benzene with maleic anhydride, copolymers of divinyl benzene with acrylonitrile, copolymers of divinyl benzene and methacrylic acid, cellulose derivatives such as regenerated cellulose, ethyl cellulose and polyvinyl alcohol, and like polymers containing free hydroxyl groups, which are reacted with sulfonating agents
  • these ion exchange membranes are reinforced, i.e., have a backing consisting of a sheet of a relatively inert material, as for example, glass having a woven or mesh structure.
  • a backing consisting of a sheet of a relatively inert material, as for example, glass having a woven or mesh structure.
  • Other known backings include woven and non-woven fabrics of materials such as asbestos, polyesters, polyamides, acrylics, modacry lies, ceramic or glass fibers, vinylidene chloride, rayons, polypropylene, polytetrafluoroethylene and the like. Fabrics or backings made of mixtures of two or more of these materials may also be used in the present invention.
  • the thickness of the cation permselective membrane is not particularly critical, but will of course depend on the particular operating conditions.
  • suitable membranes may be as thin as 20,000th of an inch to as much as 1/2 inch thick.
  • the minimum thickness of a membrane will also depend on the total thickness of the supporting structure. Although the thicker membranes have a longer useful life, their electrical resistances increase proportionally to their thickness, so that if the membrane is made increasingly thicker, a value will be obtained for which the resistance is too great for practical use.
  • Typical commercially available cation exchange membranes include those available from Ionics Incorporated, Watertown, Mass.; from Ionac Chemical Company, Birmingham, N.J., under the trade name “Ionac”; from AMF Incorporated of New York, N.Y., under the trade name “AMFion” and from E.I. duPont de Nemours & Co. (Inc.) under the trade name "Nafion”.
  • the present process may be conducted on a batch, semi-continuous or continuous basis and at atmospheric, super-atmospheric or sub-atmospheric pressures but typically is run at atmospheric pressure.
  • the present invention is particularly useful in the recycling of stannous chloride streams used in commercial processes which produce stannic chloride streams as a result of a particular treatment. In this manner, a regeneration or replenishment of the stannous chloride streams may be affected with a minimum addition of tin (although tin or stannous chloride may be added to the stream as make up in appropriate situations ) .
  • the particular gas which is evolved will depend on the particular electrolyte material which is used in the anolyte and the choice of the electrolyte material will depend upon the utilization of the process and the type of by-product gas which is desired or which poses the least amount of problems for collection and disposal. Different anolyte materials may be used to effectuate the production of different gases.
  • anolyte compartment to manufacture a tin chemical other than that being produced in the cathode compartment. That is, when stannous chloride-hydrochloric acid anionic complexes are being formed in the cathode compartment, it is possible to produce stannous sulfate in the anode compartment using sulfuric acid as the anolyte and a soluble tin electrode.
  • means to remove the anolyte material and replenish the soluble electrode during operation may be provided or the process may be conducted as a batch process with removal of the anolyte and catholyte solutions after the anode has been completely dissolved.
  • Other tin chemicals may be manufactured in the anolyte solution in the same manner by the appropriate selection of the electrolyte of the anode compartment.
  • tin crystals may be formed on the cathode.
  • these tin crystals should be completely redissolved in the catholyte solution.
  • the solution may be left in the electrolysis cell after the current has been terminated to dissolve the tin crystals in the solution.
  • this dissolution period (or "steep") period is of a relatively short (e.g . , a few hours or less) duration.
  • a solution having the following parameters was electrolytically reduced at three different amperages, each amperage being held constant during the indicated time interval to establish an overall reduction rate for each respective current value.
  • Carbon electrode rods were employed for the cathode and anode. The submerged area of each was 14cm 2 .
  • the cathode to anode ratio was 1 and the membrane to cathode ratio was 3.
  • the anolyte used was 2N HC1.
  • the catholyte contained 150 milliliters tin (stannic) chloride solution.
  • Run Interval A electrolysis at 0.3 amps for 1 hour
  • the solution is allowed to remain with agitation (or steep) for about 5 to 10 minutes. There is no visual observation of any tin crystals on the cathode before or after the steep.
  • a similar agitation (or steep) time is provided, after Run Interval B (2.0 amps at 1 hour electrolysis).
  • Run Interval C (3.0 amps for 1 1/2 hours at the 100-115°F
  • Example I A similar but more dilute solution as used in Example I is utilized using the same sample volumes, electrodes, membrane and anolyte solution as in Example I.
  • the solution is electrolytically reduced for 1 hour at 3 amps (200 amps/ft 2 cathode current density and 3.2 volts cell potential) at 100-110°F (38-43°C) followed by a steep for 1 hour at 100°F (38 °C) to dissolve observed tin crystals.
  • the total tin in grams per liter at that point is measured at 147.7 g/1 and the production of Sn +2 from Sn +4 in this first interval is 42.1 g/l/hr.
  • the solution is then further electrolytically reduced at the same electrical values at a temperature of 100-105°F (38-41°C) and is also held for the same steep time and temperature.
  • the total tin is measured as 143.9 g/1 and the production of Sn +2 is 39.4 g/l/hr.
  • the catholyte starting solution contains about 193 g/1 of total tin, all of which is in the stannic form.
  • the electrolysis data is shown in Table 2 and the production and rate data (in terms of total tin, total stannous tin, and rate of production of stannous tin) is shown in Table 3. In each instance, a steep is performed as indicated in Table 3 to completely dissolve any tin crystals which are observed on the cathode. If no tin crystals are observed, no steep is performed.
  • the catholyte solution from the above electrolytic process is conveyed to a concentrator which is a conventional vacuum concentration apparatus in which both the water and hydrochloric acid content are reduced to obtain a stannous chloride solution which contains a slight excess of hydrochloric acid (about 20% in excess of the chlorine necessary for stoichiometric stannous chloride).
  • the final solution contains sufficient excess acid to theoretically form the compound SnCl 2 :KCl.
  • This product may be then utilized in various commercial processes in which stannous chloride is normally employed with particularly efficacious results.
  • the overall current efficiency for the process of this Example was 90%.
  • a feed solution containing 368.7 g/1 of total tin with a mole ratio of Cl/Sn of 5.02 (and zero measured amount of Sn +2 ) is introduced into an electrolytic cell having two carbon electrodes and no cationic permselective membrane.
  • the anode cathode areas submerged in solution is 32.5 cm 2 .
  • the solution is subjected to electrolysis at a constant 4 amps and a voltage varying from 4.5 to 3.2 volts and a temperature of 75 to 110°F (24-43 °C) for one hour.
  • the solution is then steeped for 15 minutes at about 100°F (38°C). Analysis of the resulting solution shows the production of 3.25 gm/1 of stanr.ous tin which is a current efficienty of 36.8%.
  • This solution is then subjected to one hour further electrolysis time at a constant 2 amps, tempera ture of between 75 to 85°F (24 to 29.5°C) and 2.34 volts. Again, the solution is steeped for 15 minutes at about 80°F (27 °C) after electrolysis. Analysis of the solution showed that 3.37 gm/1 of stannous tin forms which is a difference of 0.12 gms from that in the solution which was used at the starting of this portion of the electrolysis. The percent current efficiency for this portion of the electrolysis is 2.8%.
  • the resulting solution is then subjected to a further electrolysis at a constant 7 amps, 4.35 to 3.9 volts at 85 to 115 °F (29.5 to 46 °C) for one hour with 30 minutes steep time. Analysis of the resulting solution shows 3.76 gm/1 of stannous tin which is an increase of 0.39 gm/1 which converts to a process efficiency of 2.5%.

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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)
PCT/US1980/001307 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride WO1982001198A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP81901190A EP0061449B1 (en) 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride
GB8213800A GB2094352A (en) 1980-10-03 1980-10-03 Electrolytic process for production of stannous chloride
DE8181901190T DE3071064D1 (en) 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride
PCT/US1980/001307 WO1982001198A1 (en) 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOUS80/01307801003 1980-10-03
PCT/US1980/001307 WO1982001198A1 (en) 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride

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WO1982001198A1 true WO1982001198A1 (en) 1982-04-15

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PCT/US1980/001307 WO1982001198A1 (en) 1980-10-03 1980-10-03 Electrolytic process for the production of stannous chloride

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EP (1) EP0061449B1 (en, 2012)
DE (1) DE3071064D1 (en, 2012)
GB (1) GB2094352A (en, 2012)
WO (1) WO1982001198A1 (en, 2012)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8992759B1 (en) 2014-02-20 2015-03-31 Honeywell International Inc. Metal refining process using mixed electrolyte

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2175996C1 (ru) * 2000-08-09 2001-11-20 Южно-Российский государственный технический университет (Новочеркасский политехнический институт) Станнитный электролит-коллоид с добавкой пав "нпи-89"
RU2175997C1 (ru) * 2000-08-09 2001-11-20 Южно-Российский государственный технический университет (Новочеркасский политехнический институт) Станнитный электролит-коллоид с продуктом конденсации этилендиамина и октила бромистого
RU2290455C1 (ru) * 2005-07-18 2006-12-27 Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)", ГОУ ВПО ЮРГТУ (НПИ) Станнитный электролит-коллоид для регенерации и утилизации олова
RU2294401C1 (ru) * 2005-08-10 2007-02-27 Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" ГОУ ВПО ЮРГТУ (НПИ) Способ регенерации олова из отходов белой жести

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US3394061A (en) * 1964-11-23 1968-07-23 Vulcan Detinning Division Tin recovery
US3907653A (en) * 1975-02-06 1975-09-23 Pitt Metals And Chemicals Inc Process for recovering tin salts from a halogen tin plate sludge
US3926759A (en) * 1975-02-06 1975-12-16 Pitt Metals And Chemicals Inc Process for recovering tin salts from the waste rinse water of a halogen tin plating process
US4066518A (en) * 1976-08-20 1978-01-03 Pitt Metals And Chemicals, Inc. Production of potassium or sodium stannate
US4147605A (en) * 1976-03-22 1979-04-03 Diamond Shamrock Corporation Method of producing sols by electrodialysis

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234403A (en) * 1979-06-15 1980-11-18 Vulcan Materials Company Electrolytic process for the production of stannous chloride products

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3394061A (en) * 1964-11-23 1968-07-23 Vulcan Detinning Division Tin recovery
US3907653A (en) * 1975-02-06 1975-09-23 Pitt Metals And Chemicals Inc Process for recovering tin salts from a halogen tin plate sludge
US3926759A (en) * 1975-02-06 1975-12-16 Pitt Metals And Chemicals Inc Process for recovering tin salts from the waste rinse water of a halogen tin plating process
US4147605A (en) * 1976-03-22 1979-04-03 Diamond Shamrock Corporation Method of producing sols by electrodialysis
US4066518A (en) * 1976-08-20 1978-01-03 Pitt Metals And Chemicals, Inc. Production of potassium or sodium stannate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0061449A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8992759B1 (en) 2014-02-20 2015-03-31 Honeywell International Inc. Metal refining process using mixed electrolyte

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GB2094352B (en, 2012)
EP0061449B1 (en) 1985-09-04
EP0061449A1 (en) 1982-10-06
EP0061449A4 (en) 1983-03-04
DE3071064D1 (en) 1985-10-10
GB2094352A (en) 1982-09-15

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