US3674669A - Concentration of electrolyte from dilute washings by electrodialysis in a closed system - Google Patents

Concentration of electrolyte from dilute washings by electrodialysis in a closed system Download PDF

Info

Publication number
US3674669A
US3674669A US24602A US3674669DA US3674669A US 3674669 A US3674669 A US 3674669A US 24602 A US24602 A US 24602A US 3674669D A US3674669D A US 3674669DA US 3674669 A US3674669 A US 3674669A
Authority
US
United States
Prior art keywords
electrolyte
aqueous solution
solution
wash
bath
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
US24602A
Other languages
English (en)
Inventor
Sidney B Tuwiner
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.)
Rai Research Corp
Original Assignee
Rai Research 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 Rai Research Corp filed Critical Rai Research Corp
Application granted granted Critical
Publication of US3674669A publication Critical patent/US3674669A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/022—Reject series
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis

Definitions

  • This transfer of electrolyte is by electrodialysis in which a References Clled circulating stream of each wash solution acts as a diluting stream in relation to a circulating stream of a previous solution UNITED STATES PATENTS and as a concentratin stream in relation to a subsequent solu- 2 2,802,344 8/1957 Witherell ..204/180 P X 2,848,403 8/1958 Rosenberg ..204/l 80 P Extremely high ratios of concentration are achieved between 218601095 1 1/ Kan et a] ""204/180 P wash stages by operation of the electrodialysis stack under 2,863,813 12/1958 Juda et al.
  • the washing may be'bya flowing stream of water whenthe water is plentiful and inexpensive and'where the disposal of large volumes of dilute waste solution isnot a problem.
  • washingefiiciency whichis defined as the percentage ofdissolved material in the work going to' the fii'sfwash tank which is removed from the work by thesystemuThegreater the-amount of wash water and waste the greater istheefi'iciency.
  • washing efficiency isgreater, orthe'volume-of waste water is less, the greater the number of washing stages. However, beyond three'or four stages;the*gain is marginal in'relation to the increase in capital and operating costs.
  • Electrodialysis is also a 'method which'has been proposed. In this methodithe electrolyte components of the waste stream are removed and recovered in'a more concentrated stream for reuse or disposal.
  • Nickel plating solution waste is treated with a lime slurry to a predetermined pH to precipitate calcium sulfate and basic salts of nickel.
  • The'solids are removed in a clarifier from which the clear overflow is suitable for reuse while the underflow may be collected in lagoons or it may be removed after dewatering. Very little of the nickel values are recovered.
  • the dilute waste from the'chrome pickling of brass products contains hexavalent chromium, trivalent chromium, copper and'zinc sulfates and sulfuric acid. This is treated first with sulfur dioxide or sodium sulfite in an amount which is required stoichiometrically to reduce the hexavalent chromium to trivalent chromium sulfate. Lime is then added to raise the pH to 8-9 to precipitate basic salts of chromium, copper and zinc and calcium sulfate. The water is recovered in the overflow of a clarifier, the underflow going to a lagoon or dewatering filter.
  • Electrodialysis is a method which is known to accomplish'this concentration by the transfer of the component ions through ion-selective membranes under the driving forces resulting from an electric field.
  • An electrodialyzer consists of a stack of membranes separated by plastic spacers which enclose cells through which the streams are circulated.
  • the membranes are of two kinds: anionselective and cation-selective, which alternate in the stack.
  • the electric field is induced by electrodes, one at each end ofthe stack,- ananode and a cathode.
  • the force on the cations isin the direction of the field while that on the anions'isin the opposite direction.
  • Those cells which are bounded by membranes such that the field is in the direction from anion-selective to cation-selective are such that the electrolyte isdepleted.
  • the solution tends to become more concentrated.
  • the two types of cells alternate in order in the stack and the solution manifold openings are designed to feed each of the two streams to the appropriate group of cells.
  • One is the concentrating stream and the other is the diluting stream.
  • the two end cells which enclosethe electrodes are furnished with electrode rinse streams which are separate from the two principal process streams. These rinse streams are usually recycled.
  • the ratio of demineralization in the methods of the prior art is limited by the membrane transference nunibers'. To illustrate: if the transference number 'of the cations in the'cation selective membranes and that of the anions in the anion-selective membranes are both unity there is no limit to the ratio of concentration which can be achieved so long as there is provided an'amount of membrane area and electrical energy which is adequate in relation to the volume of solution and its concentration.
  • the complex cyanide ions such as Cu(CN) are adsorbed by the anion-selective membranes. These ions are strongly held and tend to neutralize the positively charged quarternary ammonium ions of the polymer and to produce a negative charge which tends to exclude mobile anions and promote the counter movement of sodium ions which carry most of the electric current in the membrane.
  • the current efficiencies are extremely poor when the concentrations are high.
  • a particular object is to maintain the effectiveness of wash solutions by the efficient use of electrodialyzers.
  • This invention is directed to a method and apparatus for washing adherred electrolyte from a workpiece, in which the efficiency of the wash solutions is maintained by continuously recirculating the wash solutions through a series of electrodialyzers.
  • the workpiece is removed from a treating bath and rinsed in a series of wash baths.
  • the solution from the first wash bath is passed through a first dialyzer which reduces the electrolyte content of the solution by transferring ions to a circulating stream from the treating bath.
  • the solution from the first wash bath is then passed through a second dialyzer which increases the electrolyte content of the solution by taking up ions from a circulating stream from the second wash bath.
  • Extremely high ratios of concentration are achieved between the wash stages by operation of the electrodialyzers under conditions of membrane polarization.
  • FIGURE represents schematically a system for the washing of work from a plating or metal finishing operation.
  • This work is removed from tank 1 which contains the plating or finishing solution. It then is immersed successively in wash tanks 2 and 3 with appropriate drainage after leaving each tank.
  • Streams 9, 10 and 14 represent solution which is dragged with the work at each stage. The volume of solution in these three streams is approximately the same but the concentration is lower in each successive stage. Additional stages beyond those illustrated may be used in which each additional stage between tank 2 and tank 3 is constructed and operated in the manner set forth below for tank 2.
  • Tank 1 may also represent a tank from which electrolyte is eventually recovered in accordance with known methods.
  • Pumps 4, 5 and 6 circulate streams 1 l, 12 and 13 out of, and back to the tanks 1, 2 and 3.
  • Stream 11 is the concentrating stream passed through dialyzer stack 7.
  • Stream 12 is the diluting stream passed through dialyzer stack 7 and also the concentrating stream passed through electrodialyzer stack 8.
  • Stream 13 is the diluting stream passed through stack 8.
  • stream 12 may be passed through dialyzer 7 and then back into tank 2, and a separate stream from tank 2 may be passed through dialyzer 8 and then back to tank 2.
  • the embodiment of the Figure as illustrated is preferred.
  • electrodialyzer stacks 7 and 8 mount the electrodialyzer stacks 7 and 8 on a single frame and to provide manifold connections for the flow of stream 12 from the one to the other.
  • Stream I2 flows in parallel relation with stream 11 through dialyzer 7 and similarly streams 12 and 13 flow in parallel relation through dialyzer 8.
  • the design of the electrodialyzer separators, electrodes, end compression heads and manifold connections are those which are well known and the membranes are those which are used in commercial electrolysis in the prior art. Note, for example, the construction and operation of such units as set forth in Diffusion and Membrane Technology, Reinhold Publishing Company, 1962.
  • the frames and separators of the electrodialyzer stacks should be of non-conductive plastic construction appropriate to the operating temperature.
  • the electrodes should be of a conductive materials, such as metal or graphite, appropriate to the solutions.
  • the anode may be of stainless steel or an expendable anode of copper.
  • the cathode may be of stainless steel or graphite.
  • the anode may be of lead and the cathode may be of stainless steel.
  • chloride nickel plating solutions the anode may be of platinized titanium or expendable nickel.
  • the cathode may be of graphite or of nickel. Selection of suitable materials of construction is in all cases in accordance with principles and practice which are well known.
  • electrode wash streams may be utilized to isolate the electrodes from the two principal streams.
  • the electrodialysis system is operated to avoid the concentration polarization which is an essential element of the present invention in its preferred em bodiment.
  • concentration polarization which is an essential element of the present invention in its preferred em bodiment.
  • the reason for avoidance of concentration polarization in the prior art is to avoid the use of excessive power but more important to avoid pH changes which lead to scale formation particularly on the anion selective membranes. Wash solutions used in the present invention are not subject to scale formation in the operation of the electrodialysis stacks under polarizing conditions.
  • the membranes may pass into a condition of lower counter-ion transference number. This leads to a lower current efficiency and consequently, a rise in concentration in the wash tanks, especially in tank 2, as the dragout continues. The increase in concentration in the wash solution leads to further deterioration in membrane transference number and the effect is cumulative leading to a much lower concentration ratio.
  • membrane polarization is most effective in enhancement of membrane performance when the rate of increase of voltage with current is greater than twice the resistance, i.e., when where I is the current in the stack and V is the stack voltage. This condition may be readily determined by measuring the voltages and currents in the system.
  • electrodialysis stacks 7 and 8 consist of Aquachem Model WD 6-2 electrodialyzers made by Aqua-Chem, Inc., Waukesha, Wisconsin, with nine cationselective membranes, Ionac MC 3470, and eight anion-selective membranes, Ionac MA 3475 each made by Ionac, Div. of Ritter Pfaulder, Birmingham, NJ.
  • the concentrating stream flowed through the cathode compartment and through alternate cells while the diluting stream flowed through the remaining cells and the anode compartment.
  • the efiective area of each membrane was 750 sq. cm and the flow rates were 225 gallons per hour for all streams.
  • the solution in tank 1 was initially made up with 8 oz/gall of copper cyanide, 9 oz/gall of sodium cyanide, 2.0 oz/gall of soda ash and 4.0 oz/gall of caustic soda. With a voltage of 50 volts for stack 7 and 30 volts for stack 8 the ratios of concentration in tanks 2 and 3 to that in tank 1 were as follows for varying rates of dragout.
  • This invention may be applied advantageously to the recovery of the components, including nickel chloride and nickel sulfate, of solutions dragged out of nickel plating baths; of copper sulfate and fluoborate from copper plating baths. It may be applied also to the recovery of complex fluorides of iron and chromium from the dragout of stainless steel pickle solutions and also to the recovery of gold, silver, and zinc values from cyanide bath dragout.
  • the electrolyte includes one or more complex cyanides of copper, zinc, gold, silver or cadmium.
  • a method of continuously recovering electrolyte from a metal finishing bath dragout on solids which comprises sequentially immersing said solids into and removing them from each of a series of vessels comprising a treating vessel and at least two wash vessels wherein each of said vessels contain an aqueous solution more concentrated in electrolyte than the aqueous solution in a subsequent vessel to which solids are transferred, continuously recycling a less concentrated solution from a first one of said vessels between said vessel and the diluting stream cells of an electrodialyzer, continuously recycling a more concentrated solution from a second vessel through the concentrating stream cells of said electrodialyzer, and operating said electrodialyzer to balance the electrolyte removed from the solids in said second vessel by the transfer of electrolyte to said first vessel to maintain the ratio of electrolyte between said vessels at a ratio of at least 5:1.

Landscapes

  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US24602A 1970-04-01 1970-04-01 Concentration of electrolyte from dilute washings by electrodialysis in a closed system Expired - Lifetime US3674669A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2460270A 1970-04-01 1970-04-01
US00265564A US3806436A (en) 1970-04-01 1972-06-23 Concentration of electrolyte from dilute washings

Publications (1)

Publication Number Publication Date
US3674669A true US3674669A (en) 1972-07-04

Family

ID=26698640

Family Applications (2)

Application Number Title Priority Date Filing Date
US24602A Expired - Lifetime US3674669A (en) 1970-04-01 1970-04-01 Concentration of electrolyte from dilute washings by electrodialysis in a closed system
US00265564A Expired - Lifetime US3806436A (en) 1970-04-01 1972-06-23 Concentration of electrolyte from dilute washings

Family Applications After (1)

Application Number Title Priority Date Filing Date
US00265564A Expired - Lifetime US3806436A (en) 1970-04-01 1972-06-23 Concentration of electrolyte from dilute washings

Country Status (6)

Country Link
US (2) US3674669A (enrdf_load_stackoverflow)
CA (1) CA946782A (enrdf_load_stackoverflow)
DE (1) DE2115687C3 (enrdf_load_stackoverflow)
FR (1) FR2085765B1 (enrdf_load_stackoverflow)
GB (1) GB1347896A (enrdf_load_stackoverflow)
NL (1) NL7104404A (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357220A (en) * 1980-02-01 1982-11-02 Eisenmann John L Method and apparatus for recovering charged ions from solution
US4880511A (en) * 1986-05-16 1989-11-14 Electroplating Engineers Of Japan, Limited Process and apparatus for recovery of precious metal compound
US5198117A (en) * 1991-12-02 1993-03-30 The Dow Chemical Company Method and apparatus for preparing an epoxide by anionic dialysis
US5622681A (en) * 1992-01-21 1997-04-22 The Dow Chemical Company Dialysis separation of heat stable organic amine salts in an acid gas absorption process
US6162361A (en) * 1996-02-14 2000-12-19 Adiga; Mahabala R. Plating waste water treatment and metals recovery system
US6284115B1 (en) 1999-09-21 2001-09-04 Agilent Technologies, Inc. In-line flow through micro-dialysis apparatus and method for high performance liquid phase separations
US20040156765A1 (en) * 2003-02-12 2004-08-12 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US20060266654A1 (en) * 2005-05-25 2006-11-30 Enthone Inc. Method for supplying a plating composition with deposition metal ion during a plating operation
US20150182914A1 (en) * 2002-08-21 2015-07-02 Exergy Technologies Corporation Apparatus and method for membrane electrolysis recycling of process chemicals

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS585997B2 (ja) 1979-01-25 1983-02-02 株式会社井上ジャパックス研究所 電鋳装置
DE3929121C1 (enrdf_load_stackoverflow) * 1989-09-01 1991-02-28 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
DE3929137C1 (enrdf_load_stackoverflow) * 1989-09-01 1991-02-28 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
US5230782A (en) * 1991-07-22 1993-07-27 International Business Machines Corporation Electrolytic process for reducing the organic content of an aqueous composition and apparatus therefore

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802344A (en) * 1953-07-08 1957-08-13 Eureka Williams Corp Electrodialysis of solutions in absorption refrigeration
US2848403A (en) * 1954-05-06 1958-08-19 Ionics Process for electrodialyzing liquids
US2860095A (en) * 1952-07-22 1958-11-11 Ionics Separation of electrolytic solutions into concentrated and dilute streams
US2863813A (en) * 1956-09-14 1958-12-09 Ionics Method of electrodialyzing aqueous solutions
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3459650A (en) * 1966-01-13 1969-08-05 Sumitomo Chemical Co Process for the purification of amino acids
US3481851A (en) * 1964-10-29 1969-12-02 Lancy Lab Apparatus and procedure for reconditioning metal treating solutions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2860095A (en) * 1952-07-22 1958-11-11 Ionics Separation of electrolytic solutions into concentrated and dilute streams
US2802344A (en) * 1953-07-08 1957-08-13 Eureka Williams Corp Electrodialysis of solutions in absorption refrigeration
US2848403A (en) * 1954-05-06 1958-08-19 Ionics Process for electrodialyzing liquids
US2863813A (en) * 1956-09-14 1958-12-09 Ionics Method of electrodialyzing aqueous solutions
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3481851A (en) * 1964-10-29 1969-12-02 Lancy Lab Apparatus and procedure for reconditioning metal treating solutions
US3459650A (en) * 1966-01-13 1969-08-05 Sumitomo Chemical Co Process for the purification of amino acids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Wilson, Deminerlization by Electrodialysis, pp. 12 18, TD433p7c12, 1960 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357220A (en) * 1980-02-01 1982-11-02 Eisenmann John L Method and apparatus for recovering charged ions from solution
US4880511A (en) * 1986-05-16 1989-11-14 Electroplating Engineers Of Japan, Limited Process and apparatus for recovery of precious metal compound
US5198117A (en) * 1991-12-02 1993-03-30 The Dow Chemical Company Method and apparatus for preparing an epoxide by anionic dialysis
US5622681A (en) * 1992-01-21 1997-04-22 The Dow Chemical Company Dialysis separation of heat stable organic amine salts in an acid gas absorption process
US6162361A (en) * 1996-02-14 2000-12-19 Adiga; Mahabala R. Plating waste water treatment and metals recovery system
US6284115B1 (en) 1999-09-21 2001-09-04 Agilent Technologies, Inc. In-line flow through micro-dialysis apparatus and method for high performance liquid phase separations
US20150182914A1 (en) * 2002-08-21 2015-07-02 Exergy Technologies Corporation Apparatus and method for membrane electrolysis recycling of process chemicals
US20040156765A1 (en) * 2003-02-12 2004-08-12 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US20080112864A1 (en) * 2003-02-12 2008-05-15 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US7537741B2 (en) 2003-02-12 2009-05-26 Nichromet Extraction Inc. Gold and silver recovery from polymetallic sulfides by treatment with halogens
US20060266654A1 (en) * 2005-05-25 2006-11-30 Enthone Inc. Method for supplying a plating composition with deposition metal ion during a plating operation
US7846316B2 (en) * 2005-05-25 2010-12-07 Enthone Inc. Method for supplying a plating composition with deposition metal ion during a plating operation

Also Published As

Publication number Publication date
DE2115687C3 (de) 1973-12-13
FR2085765A1 (enrdf_load_stackoverflow) 1971-12-31
GB1347896A (en) 1974-02-27
NL7104404A (enrdf_load_stackoverflow) 1971-10-05
US3806436A (en) 1974-04-23
FR2085765B1 (enrdf_load_stackoverflow) 1973-06-08
DE2115687B2 (de) 1973-05-24
CA946782A (en) 1974-05-07
DE2115687A1 (de) 1971-11-04

Similar Documents

Publication Publication Date Title
US3470044A (en) Electrolytic regeneration of spent ammonium persulfate etchants
Marder et al. Cadmium electroplating wastewater treatment using a laboratory-scale electrodialysis system
US3674669A (en) Concentration of electrolyte from dilute washings by electrodialysis in a closed system
EP0492612B1 (en) Electrolyzer and method of operating same
Yuzer et al. Optimal performance of electrodialysis process for the recovery of acid wastes in wastewater: Practicing circular economy in aluminum finishing industry
WO2006135188A1 (en) Electrodialysis reversal and electrochemical wastewater treatment method of compound containing nitrogen
Yan et al. An efficient Two-Chamber Electrodeposition-Electrodialysis combination craft for nickel recovery and phosphorus removal from spent electroless nickel plating bath
Strathmann Electrodialysis and its application in the chemical process industry
US5804057A (en) Method of removing metal salts from solution by electrolysis an electrode closely associated with an ion exchange resin
CN101830587A (zh) 一种处理重金属废水的工艺和装置
Rao et al. Electrodialysis in the recovery and reuse of chromium from industrial effluents
US4357220A (en) Method and apparatus for recovering charged ions from solution
Audinos Improvement of metal recovery by electrodialysis
Kruglikov Application of electromembrane processes in chromium electroplating technology
US3969207A (en) Method for the cyclic electrochemical processing of sulfuric acid-containing pickle waste liquors
CN108452681A (zh) 一种用于工业废水处理的电渗析装置
Bramer et al. Electrolytic Regeneration of Spent Pickling Solutions
US4179348A (en) Removal of cyanide from waste water
JPS5850153B2 (ja) 酸と金属塩の含有溶液から酸と金属を効率よく分離回収する方法
JPS5820289A (ja) 液体中の塩分濃度を変える装置
Revathi et al. Reclamation of hexavalent chromium from electroplating effluents by electroextraction
CN212151922U (zh) 一种利用电渗析资源化利用浓盐水的系统
Thampy et al. Concentration of sodium sulfate from pickle liquor of tannery effluent by electrodialysis
US20070256940A1 (en) Device and Method for Removing Foreign Matter from Process Solutions
CN119898924B (zh) 用于处理包含硝酸铝和硝酸的废水的方法和装置