US3114687A - Electrorefining nickel - Google Patents

Electrorefining nickel Download PDF

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Publication number
US3114687A
US3114687A US117701A US11770161A US3114687A US 3114687 A US3114687 A US 3114687A US 117701 A US117701 A US 117701A US 11770161 A US11770161 A US 11770161A US 3114687 A US3114687 A US 3114687A
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United States
Prior art keywords
nickel
per liter
grams per
catholyte
cathode
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Expired - Lifetime
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US117701A
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English (en)
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Bernardus J Brandt
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt

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  • the present invention is directed to the electrorefining of nickel and, more particularly, to an improved method for producing electrolytic nickel or cathode nickel having improved surface quality.
  • the electrorefining cell employed is a compartmented cell divided into anode and cathode compartments by means of a permeable diaphragm and the electrolyte employed is a sulfate-chloride electrolyte.
  • the impure anode in the anode compartment is electrolytically corroded and substantially pure cathode nickel is deposited at a cathode in the cathode compartment as a result of electrolysis.
  • the impure anolyte is removed from the anode compartment at a steady rate and is subjected to purification treatments to remove therefrom impurities such as iron, copper, lead, arsenic, etc.
  • the purified electrolyte is then introduced at a steady rate into the cathode compartment and nickel of high purity is plated therefrom.
  • a slight hydrostatic head is maintained in the cathode compartment, allowing purified catholyte partly depleted in nickel to flow through the diaphragm into the anode compartment, thus preventing migration of unwanted ions from the impure anolyte in the anode compartment to the purified catholyte in the cathode compartment.
  • nickel and impurities are dissolved from the anode.
  • the impure anolyte is removed from the tanks, purified, and finally returned as purified catholyte to each cathode compartment for the deposition of pure nickel at each cathode.
  • the cathode nickel produced in accordance with commercial practice tends to have a surface which becomes progressively more rough and nodular as the thickness of the cathode increases or as the current density is increased.
  • This roughness and modularity effectively limits the current density at which nickel cathodes can be grown and the thickness of cathode nickel which can be produced by means of the electrorefining process.
  • electrolytic nickel cathodes having an improved surface smoothness and greater thickness as compared to prior nickel cathodes can be produced in an electrorefining operation by the addition of controlled amounts of a special organic compound to the purified electrolyte.
  • Another object of the invention is to provide a bath from which nickel cathodes having improved surface smoothness may be deposited by electrolysis.
  • Still another object of the invention is to provide a method for producing nickel cathodes which are thicker and smoother than nickel cathodes produced heretofore.
  • Yet another object of the invention is to provide a method for producing nickel cathodes which are thicker and smoother than conventional cathodes at current densities higher than those of conventional practice.
  • FIGURE 1 is a reproduction of a photograph taken at 1% diameters showing the cross section of the usual electrolytic nickel cathode presently available in commerce;
  • FIGURE 2 is a reproduction of a photograph taken at 1 /2 diameters of the cross section of an electrolytic nickel cathode produced in accordance with the present invention to a greater thickness than the cathode shown in FIGURE 1.
  • the present invention contemplates a process for the production of electrolytic nickel or cathode nickel having improved surface quality and ineluding improved surface smoothness which comprises electrolyzing an aqueous electrolyte having a pH of about 1 to 5 containing about 40 to about 60 or 70 grams per liter of nickel, about 12 to 30 grams per liter of sodium, from about 18 to 55 grams per liter or" chloride ions, from 65 to 120 grams per liter of sulfate ions, from about 10 to 25 grams per liter of boric acid and about 0.01 to about 0.10 gram per liter of a water-soluble organic cyanide (nitrile), i.e., a compound containing the --CEN group, attached to a C atom, dissolved therein to deposit sound electrolytic nickel at the cathode.
  • a water-soluble organic cyanide (nitrile) i.e., a compound containing the --CEN group, attached to a C atom, dissolved therein to deposit sound electrolytic nickel
  • the electrolysis is carried out while maintaining the electrolyte temperature between about F. and about 160 F. and while employing a current density between about 5 and about 25 amperes per square foot.
  • the catholyte may contain a total of up to about 0.004 gram per liter of such impurities as copper, iron, arsenic, lead, etc., without affecting the operating characteristics of the proc ess.
  • the catholyte may be saturated with respect to calcium ions. Thus, it may contain up to about 0.6 gram per liter of calcium, without affecting the op erating characteristics of said process.
  • the process utilizing the aforementioned electrolyte is applicable not only to the production of commercial cathode nickel but also to the production of the thin nickel cathode starting sheets employed in producing commercial cathode nickel.
  • an aqueous catholyte having a pH of about 4.0 to 5.0 and containing about 40 to about 70 grams per liter of nickel, about 20 to about 30 grams per liter of sodium, about 65 to about grams per liter of sulfate ions, about 20 to about 55 grams per liter of chloride ions, about 10 to about 25 grams per liter of boric acid and about 0.01 to about 0.05 gram per liter of ethylene cyanohydrin (hydracrylonitrile) dissolved therein and the balance essentially water to deposit nickel at the cathode.
  • the electrolysis is carried out by passing electric current through an anode (which, as explained before, may be either an impure nickel anode or a nickel matte anode), the electrolyte and the cathode (usually a nickel starting sheet) while maintaining the temperature between about F. and about F. and while employing a current density between about 10 to about 25 amperes per square foot.
  • anode which, as explained before, may be either an impure nickel anode or a nickel matte anode
  • the process is also operable when utilizing insoluble anodes.
  • concentration of the special organic cyanide compound contemplated in accordance with the present invention is governed largely by current density but should be at least about 0.01 gram per liter because at lower concentrations improvement in the surface quality of cathode nickel is negligible.
  • cathode nickel It should not exceed about 0.10 gram per liter as otherwise the purity of cathode nickel is detrimentally affected by carbon codeposition and the cathodes become highly stressed and/ or warped. Stresses set up in the nickel deposited on the stainless steel mother blanks to form the cathode starting sheets and due to excessive amounts of the aforementioned compounds are often so great that the cathode nickel separates from the mother blanks and the resulting starting sheets are badly warped. Attempts to straighten the warped starting sheets are defeated by their springy reaction due to the high stresses.
  • the production of the commercial cathode nickel is also adversely affected when excessive amounts of the additives are employed in that the cathodes become highly stressed and warped and diliiculty is encountered in extricating these warped cathodes from the cathode compartments and in thereafter straightening them.
  • organic cyanide (nitrile) compounds within the scope of the present invention include acetonitrile acrylonitrile (Cl-l :CHCN), acetaldehyde cyanohydrin (CH CHOHCN), cyanoacetic acid acetone cyanohydrin ((CH COHCN), propionitrile (CH CH CN), 2 cyanoacetamide (NH OCCH -CN) beta-chloropropionitrile (ClCH CH -CN), benzonitrile (C ll -ON) and para amino phenyl aceto nitrile (NH -C H CH CN).
  • organic cyanides suitable within the scope of the invention may be saturated or unsaturated, aliphatic or aromatic and may contain a substituted group such as a halogen, hydroxy, amino or carboxy group. Numerous additional examples could be given but the examples given above will suffice to illustrate the class of compounds suitable Within the scope of the invention.
  • Example I To a portion of a purified electrolyte having a pH of about 4.0 and containing about 55 grams per liter of nickel, about 28 grams per liter of sodium, about 46 grams per liter of chloride ion, about 87 grams per liter of sulfate ions, about 18 grams per liter of boric acid, about 0.3 gram per liter of calcium ion and less than about 0.004 gram per liter total of copper, lead, arsenic and iron, about 0.035 gram per liter of ethylene cyanohydrin was added. The electrolyte was then electrolyzed to deposit cathode nickel at a current density of about amperes per square foot and a temperature of about 140 F.
  • Nickel from the said electrolyte was deposited upon both faces of a nickel starting sheet in order to grow a cathode having a total thickness of about 0.4 inch.
  • the cathode was found to have a high degree of surface smoothness (such as illustrated in FIGURE 2) whereas a cathode grown from the same electrolyte without the addition of ethylene cyanohydrin was found to have a surface which was substantially more rough, nodular and berried (such as shown in FIGURE 1) when grown to the same thickness of about 0.4 inch.
  • Example II To another portion of the same electrolyte, an addition of about 0.035 gram per liter of ethylene cyanohydrin as a surface-smoothness promoting agent was made. The electrolyte was then electrolyzed to deposit cathode nickel upon both faces of a thin nickel starting sheet used as a cathode. The cathode was grown to the substantially greater thickness of about 0.8 inch. The surface ofthe resulting cathode was substantially smoother than the prior art cathode even though it had been grown to a thickness about twice as great as its customary for commercial electrolytic nickel.
  • cathode nickel produced in accordance with the invention from a purified sulfate-chloride nickel electrolyte is substantially indistinguishable chemically from cathode nickel produced heretofore. Furthermore, no difficulties are encountered in maintaining the required concentration of the organic cyanide compound in the plating bath and no diificulties are found in the purification cycle as a result of the addition to the bath of the organic cyanide compound.
  • sulfur-containing organic compounds which are reducible at the cathode should not be present in the electrolyte provided in accordance with the present invention as sulfur would be incorporated in the nickel deposit, thus impairing the high standard of purity of the cathode nickel.
  • the improvement for producing electrolytic nickel having substantial thickness, high purity and improved surface smoothness which comprises establishing an aqueous catholyte having a pH of about 1 to 5 and consisting of about 40 to about 70 grams per liter of nickel, about 12 to about 30 grams per liter of sodium, about 18 to 5 5 grams per liter of chloride ions, about 65 to grams per liter of sulfate ions, about 10 to 25 grams per liter of boric acid, about 0.01 to 0.10 gram per liter of a watersoluble organic cyanide compound selected from the group consisting of ethylene cyanohydrin, acetonitrile, acetaldehyde cyanohydrin, cyanoacetic acid, acrylonitrile, acetone cyanohydrin, propionitrile, 2 cyanoacetamide, beta-chloropropionitrile, para amino phenyl aceto nitrile and benzonitrile dissolved therein, the balance
  • the improvement for producing electrolytic nickel having substantial thickness, hi h purity and improved surface smoothness which comprises establishing an aqueous catholyte having a pH of about 4 to 5 and consisting of about 40 to 70 grams per liter of nickel, about about to grams per liter of sodium, about to grams per liter of sulfate ions, about 20 to 55 grams per liter of chloride ions, about 10 to 25 grams per liter of boric acid, about 0.01 to 0.05 gram per liter of a watersoluble organic cyanide compound selected from the group consisting of ethylene cyanohydrin, acetonitrile, acetaldehyde cyanohydrin, cyanoacetic acid, acrylonitrile, acetone cyanohydrin, propionitrile, 2 cyanoacetamide, beta-chloropropionitrile, para amino phenyl aceto nitrile and benzonitrile dissolved therein, the balance of said cat

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US117701A 1961-03-10 1961-06-16 Electrorefining nickel Expired - Lifetime US3114687A (en)

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CA818795 1961-03-10

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US (1) US3114687A (enrdf_load_stackoverflow)
BE (1) BE610023A (enrdf_load_stackoverflow)
GB (1) GB941103A (enrdf_load_stackoverflow)
NL (2) NL271807A (enrdf_load_stackoverflow)
SE (1) SE313927B (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1234999B (de) * 1964-07-20 1967-02-23 Internat Nickel Company Of Can Verfahren zur Herstellung von Elektrolytnickel
US3341433A (en) * 1964-05-01 1967-09-12 M & T Chemicals Inc Electrodeposition of nickel
US3432410A (en) * 1963-11-27 1969-03-11 Nickel Le Method of producing pure nickel by electrolytic refining
US3718549A (en) * 1971-06-14 1973-02-27 Kewanee Oil Co Alkaline nickel plating solutions
US3855089A (en) * 1972-11-27 1974-12-17 Deepsea Ventures Inc Process for the electrolytic refining of heavy metals
US3969399A (en) * 1970-07-17 1976-07-13 M & T Chemicals Inc. Electroplating processes and compositions
US4183789A (en) * 1977-03-30 1980-01-15 M&T Chemicals Inc. Anode bag benefaction

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394874A (en) * 1942-11-05 1946-02-12 Int Nickel Co Electrorefining of nickel
US2524010A (en) * 1946-07-12 1950-09-26 Harshaw Chem Corp Electrodeposition of nickel
US2623848A (en) * 1943-06-12 1952-12-30 Int Nickel Co Process for producing modified electronickel
US2802779A (en) * 1953-12-10 1957-08-13 Vickers Ltd Sa Electrodeposition of nickel and nickel alloys
US2882208A (en) * 1957-09-23 1959-04-14 Udylite Res Corp Electrodeposition of nickel
US2972571A (en) * 1960-02-10 1961-02-21 Harshaw Chem Corp Nickel plating solutions
US2978391A (en) * 1958-08-25 1961-04-04 Harshaw Chem Corp Nickel plating process and solution

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394874A (en) * 1942-11-05 1946-02-12 Int Nickel Co Electrorefining of nickel
US2623848A (en) * 1943-06-12 1952-12-30 Int Nickel Co Process for producing modified electronickel
US2524010A (en) * 1946-07-12 1950-09-26 Harshaw Chem Corp Electrodeposition of nickel
US2802779A (en) * 1953-12-10 1957-08-13 Vickers Ltd Sa Electrodeposition of nickel and nickel alloys
US2882208A (en) * 1957-09-23 1959-04-14 Udylite Res Corp Electrodeposition of nickel
US2978391A (en) * 1958-08-25 1961-04-04 Harshaw Chem Corp Nickel plating process and solution
US2972571A (en) * 1960-02-10 1961-02-21 Harshaw Chem Corp Nickel plating solutions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3432410A (en) * 1963-11-27 1969-03-11 Nickel Le Method of producing pure nickel by electrolytic refining
US3341433A (en) * 1964-05-01 1967-09-12 M & T Chemicals Inc Electrodeposition of nickel
DE1234999B (de) * 1964-07-20 1967-02-23 Internat Nickel Company Of Can Verfahren zur Herstellung von Elektrolytnickel
US3437571A (en) * 1964-07-20 1969-04-08 Int Nickel Co Production of electrolytic nickel
US3969399A (en) * 1970-07-17 1976-07-13 M & T Chemicals Inc. Electroplating processes and compositions
US3718549A (en) * 1971-06-14 1973-02-27 Kewanee Oil Co Alkaline nickel plating solutions
US3855089A (en) * 1972-11-27 1974-12-17 Deepsea Ventures Inc Process for the electrolytic refining of heavy metals
US4183789A (en) * 1977-03-30 1980-01-15 M&T Chemicals Inc. Anode bag benefaction

Also Published As

Publication number Publication date
BE610023A (fr) 1962-05-07
SE313927B (enrdf_load_stackoverflow) 1969-08-25
NL127165C (enrdf_load_stackoverflow)
GB941103A (en) 1963-11-06
NL271807A (enrdf_load_stackoverflow)

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