EP1417357B1 - Hydrogen evolution inhibiting additives for zinc electrowinning - Google Patents

Hydrogen evolution inhibiting additives for zinc electrowinning Download PDF

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Publication number
EP1417357B1
EP1417357B1 EP02754027A EP02754027A EP1417357B1 EP 1417357 B1 EP1417357 B1 EP 1417357B1 EP 02754027 A EP02754027 A EP 02754027A EP 02754027 A EP02754027 A EP 02754027A EP 1417357 B1 EP1417357 B1 EP 1417357B1
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EP
European Patent Office
Prior art keywords
cpc
zinc
zinc electrowinning
current efficiency
electrowinning
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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
EP02754027A
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German (de)
French (fr)
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EP1417357A2 (en
Inventor
Elod Lajos Gyenge
Joey Chung-Yen Jung
Klaus Heinrich Oehr
Steven Splinter
Colin W. Oloman
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MagPower Systems Inc
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MagPower Systems 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
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury

Definitions

  • the invention is related to additives for zinc electrowinning that inhibit hydrogen evolution and/or improve current efficiency for zinc electrodeposition, specifically cetylpyridinium-based additives.
  • Cetylpyridinium chloride (CPC), a cetylpyridinium salt, was tested as an additive in a zinc electrowinning process in two separate zinc electrowinning electrolyte compositions: 1) with antimony and 2) with both antimony and glue.
  • the CPC additive had the most significant influence in the presence of antimony or antimony + glue combination, where it increased the current efficiency by 23.2% and 7.6%, respectively. Moreover, the presence of 0.05 mM CPC did not increase the overall cell voltage.
  • a constant current of 0.045 A representing an electrowinning current density of 450 amperes/meter 2 , was applied for either 4 or 20 hours to a non-agitated electrolyte.
  • the electrode assembly was removed from the glass beaker, rinsed with distilled water and the cathode deposit carefully scraped off and weighed with four digits precision using a digital Mettler AE 100 analytical balance.
  • the test cells were rinsed between experiments with distilled water and acetone in order to remove traces of the organic additives. Replicates were also performed and the standard deviation was estimated.
  • CPC cetylpyridinium chloride
  • Antimony (Sb) in 0.04 mg/l (milligrams/litre) concentration was added as antimony - potassium tartrate to the zinc electrowinning electrolyte. Both four and twenty hour runs were performed. The experimental results of the four-hour runs are summarized in Table 1.
  • Example 2 Similar experiments to those in Example 1 were performed with an electrolyte containing 0.04 mg/l of Sb and 10 mg/l of glue (e.g. "pearl glue” supplied by Hudson Industries, Johnstown, New York). Both 4 and 20 hour runs were carried out. The effect of the CPC additive on the zinc electrowinning current efficiency in the 4 hour runs is shown in Table 3 .
  • glue e.g. "pearl glue” supplied by Hudson Industries, Johnstown, New York.
  • the cell voltage is another important figure of merit of the electrowinning process.
  • An increase in the cell voltage represents an increase in the amount of energy required and, therefore, a less efficient electrowinning process.
  • Table 5 shows that using 0.05 mM CPC in conjunction with Sb and glue did not induce an increase of the cell voltage. Effect of CPC on the average cell voltage in 4 hour experiments with 0.04 mg/l Sb and 10 mg/l glue in the electrolyte. Conditions: Temperature: 37 °C Time: 4 hours Average cell voltage (V) No additive 2.83 CPC 0.05 mM 2.83

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Primary Cells (AREA)

Description

    FIELD
  • The invention is related to additives for zinc electrowinning that inhibit hydrogen evolution and/or improve current efficiency for zinc electrodeposition, specifically cetylpyridinium-based additives.
    • BACKGROUND
  • Improving the energy efficiency of the zinc electrowinning process by inhibition of the parasitic hydrogen evolution reaction, which occurs in parallel with zinc deposition, is of major technological and commercial interest. One way of minimizing the cathodic hydrogen evolution is by the use of additives, generally organic compounds, which selectively increase the hydrogen evolution overpotential. Mackinnon et al. (Journal of Applied Electrochemistry, Volume 20, pages 728-736, 1990) and Scott et al. (Journal of Applied Electrochemistry, Volume 18, pages 120-127, 1988) describe the use of animal glue in combination with antimony to improve the current efficiency for zinc electrowinning when compared to additive-free electrolytes.
  • There is a need for improved additives that minimize hydrogen evolution during zinc electrowinning while providing the same or improved performance over traditional additives.
  • Therefore, it is an object of this invention to provide improved additives for zinc electrowinning that minimize hydrogen evolution while providing similar or improved performance over traditional additives.
    • SUMMARY
  • Cetylpyridinium chloride (CPC), a cetylpyridinium salt, was tested as an additive in a zinc electrowinning process in two separate zinc electrowinning electrolyte compositions: 1) with antimony and 2) with both antimony and glue.
  • The CPC additive had the most significant influence in the presence of antimony or antimony + glue combination, where it increased the current efficiency by 23.2% and 7.6%, respectively. Moreover, the presence of 0.05 mM CPC did not increase the overall cell voltage.
    • DETAILED DESCRIPTION Methods And Apparatus
  • Commercial beaker test cells containing a commercial electrowinning electrolyte (liquor) were connected to a power supply and placed in a 37 °C water bath. The anodes and cathodes were made of lead and aluminium, respectively. The laboratory supplied MSDS sheet indicated for the electrolyte the following composition: zinc sulfate 28 - 34% by weight, magnesium sulfate 9 - 15 g/l (grams/litre) and manganese 1.5 - 2.5 g/l.
  • After allowing the temperature inside the test cells to reach the desired value of 37 °C, a constant current of 0.045 A, representing an electrowinning current density of 450 amperes/meter2, was applied for either 4 or 20 hours to a non-agitated electrolyte. After completion of the experiment the electrode assembly was removed from the glass beaker, rinsed with distilled water and the cathode deposit carefully scraped off and weighed with four digits precision using a digital Mettler AE 100 analytical balance. The test cells were rinsed between experiments with distilled water and acetone in order to remove traces of the organic additives. Replicates were also performed and the standard deviation was estimated.
  • The zinc electrodeposition current efficiency was calculated based on Faraday's law: CE(%) = z · F · m d I · t · A Zn · 100 where
    • CE-
    current efficiency for Zn electrodeposition (%)
    z -
    no. of electrons exchanged [=2]
    F -
    Faraday's number [=96485.3 C mol-1]
    m d -
    amount of zinc deposit (g)
    l -
    applied current [=0.045 A]
    t -
    time (s)
    A Zn -
    atomic weight of zinc [=65.39].
  • The cetylpyridinium chloride (CPC) (e.g. Sigma-Aldrich, U.S.) had the following structure: C21H38N+Cl-
    Figure 00040001
    • Example 1 Zinc Electrowinning Liquor with antimony present
  • Antimony (Sb) in 0.04 mg/l (milligrams/litre) concentration was added as antimony - potassium tartrate to the zinc electrowinning electrolyte. Both four and twenty hour runs were performed. The experimental results of the four-hour runs are summarized in Table 1.
  • Without the CPC additive present in the electrolyte, Sb had a detrimental effect on the current efficiency, i.e. between 65.1% (cell no. 15) and 74.7% (cell no. 14). On average, the current efficiency without the CPC additive present was 69.9%. Adding CPC improved the current efficiency on average by 23.2%, i.e. from 69.9% to 93.1%.
    Effect of CPC on the current efficiency of zinc electrowinning in the electrolyte containing 0.04 mg/l Sb (as Sb-tartrate).
    Conditions:
    Temperature: 37 °C
    Time: 4 hours    		 Current efficiency (%) per cell No. Average CE (%)
    14 15
    No additive 74.7 65.1 69.9
    ±1.0 ±6.8
    CPC 0.05 mM (mM = millimolar) 93.7 92.7 93.1
    ±2.9 ±0.9
  • The effect of CPC in a longer-term (20 hours) experiment is shown in Table 2. Without the CPC additive, the current efficiency of cell no. 15 was only 36.6%, whilst with 0.05 mM CPC present the zinc electrowinning current efficiency was 58.9%. Thus, with the CPC additive the current efficiency was higher by 22.3%.
    Effect of CPC on the zinc electrowinning current efficiency in 20 hour experiment with 0.04 mg/l Sb in the electrolyte.
    Conditions:
    Temperature: 37 °C
    Time: 20 hours    		 Current efficiency (%) per Cell No.
    15
    No additive 36.6
    CPC 0.05 mM 58.9
    • Example 2 Zinc Electrowinning Liquor with both antimony and glue
  • Similar experiments to those in Example 1 were performed with an electrolyte containing 0.04 mg/l of Sb and 10 mg/l of glue (e.g. "pearl glue" supplied by Hudson Industries, Johnstown, New York). Both 4 and 20 hour runs were carried out. The effect of the CPC additive on the zinc electrowinning current efficiency in the 4 hour runs is shown in Table 3.
  • The presence of glue minimizes to a certain extent the negative effect of antimony, yielding current efficiencies between 88.9% and 90%. However, adding 0.05 mM CPC brought about additional increases of current efficiency, i.e. from 89.4% on average in the absence to 97% in the presence of CPC (Table 3).
    Effect of CPC on the current efficiency of zinc electrowinning in the electrolyte containing 0.04 mg/l Sb (as Sb-tartrate) + 10 mg/l glue.
    Conditions:
    Temperature: 37 °C
    Time: 4 hours    		 Current efficiency (%) per Cell No. Average CE (%)
    13 16
    No additive 88.9 90.0 89.4
    ±0.9 ±0.8
    CPC 0.05 mM 98.3 95.8 97.0
    ±1.8
  • The 20 hour experiments (Table 4) showed that CPC in 0.05 mM concentration increased the current efficiency of cell no. 16 from 77.2% to 87.3%.
    Effect of CPC on the zinc electrowinning current efficiency in 20 hour experiment with 0.04 mg/l Sb and 10 mg/l glue in the electrolyte.
    Conditions:
    Temperature: 37 °C
    Time: 20 hours    		 Current efficiency (%) per Cell No.
    16
    No additive 77.2
    CPC 0.05 mM 87.3
  • The cell voltage is another important figure of merit of the electrowinning process. An increase in the cell voltage represents an increase in the amount of energy required and, therefore, a less efficient electrowinning process. Table 5 shows that using 0.05 mM CPC in conjunction with Sb and glue did not induce an increase of the cell voltage.
    Effect of CPC on the average cell voltage in 4 hour experiments with 0.04 mg/l Sb and 10 mg/l glue in the electrolyte.
    Conditions:
    Temperature: 37 °C
    Time: 4 hours    		 Average cell voltage (V)
    No additive 2.83
    CPC 0.05 mM 2.83
  • Accordingly, while this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the scope of the invention.

Claims (9)

  1. A method of improved zinc electrowinning, comprising: adding a cetylpyridinium salt additive to a zinc electrowinning electrolyte.
  2. A method according to claim 1, wherein said cetylpyridinium salt is a cetylpyridinium halide.
  3. A method according to claim 2, wherein said cetylpyridinium halide is cetylpyridinium chloride.
  4. A method according to claim 3, wherein said cetylpyridinium chloride is at 0.05 millimolar (mM) concentration in said zinc electrowinning liquor.
  5. A method according to claim 1, wherein said zinc electrowinning electrolyte contains zinc sulfate.
  6. A method according to claim 1, wherein said zinc electrowinning electrolyte contains antimony.
  7. A method according to claim 1, wherein said zinc electrowinning electrolyte contains glue.
  8. A method according to claim 7, wherein said glue is animal glue.
  9. A method according to claim 8, wherein said animal glue is gelatin.
EP02754027A 2001-08-14 2002-08-13 Hydrogen evolution inhibiting additives for zinc electrowinning Expired - Lifetime EP1417357B1 (en)

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US31182501P 2001-08-14 2001-08-14
US311825P 2001-08-14
PCT/CA2002/001250 WO2003016593A2 (en) 2001-08-14 2002-08-13 Hydrogen evolution inhibiting additives for zinc electrowinning

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EP1417357A2 EP1417357A2 (en) 2004-05-12
EP1417357B1 true EP1417357B1 (en) 2005-03-16

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EP (1) EP1417357B1 (en)
JP (1) JP2004537653A (en)
KR (1) KR100599993B1 (en)
CN (1) CN100342061C (en)
AU (1) AU2002322888B2 (en)
BR (1) BR0211933A (en)
CA (1) CA2457071C (en)
DE (1) DE60203301T2 (en)
ES (1) ES2238586T3 (en)
HK (1) HK1075920A1 (en)
MX (1) MXPA04001459A (en)
NO (1) NO20040651L (en)
RU (1) RU2288299C2 (en)
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ZA (1) ZA200405167B (en)

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CN100540748C (en) * 2006-06-15 2009-09-16 云南冶金集团总公司 Assembled gelatin additive
CN103993330A (en) * 2014-05-07 2014-08-20 成都理工大学 Zinc electrolysis technology of zinc ammonia complex aqueous solution
CN106676578B (en) * 2015-11-11 2018-09-28 沈阳有色金属研究院 A kind of new and effective joint additive of Zinc electrolysis
CN110512236B (en) * 2019-09-27 2021-05-04 中国科学院长春应用化学研究所 Combined additive and application thereof in zinc electrodeposition
CN115133159A (en) * 2022-09-01 2022-09-30 河南师范大学 Functional aqueous zinc ion battery electrolyte and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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US4028199A (en) * 1974-08-05 1977-06-07 National Development Research Corporation Method of producing metal powder
CA1064852A (en) * 1975-12-31 1979-10-23 Cominco Ltd. Method for evaluating a system for electrodeposition of metals
CA1111125A (en) * 1978-07-05 1981-10-20 Robert C. Kerby Method and apparatus for control of electrowinning of zinc
US4699696A (en) * 1986-04-15 1987-10-13 Omi International Corporation Zinc-nickel alloy electrolyte and process
US4717458A (en) * 1986-10-20 1988-01-05 Omi International Corporation Zinc and zinc alloy electrolyte and process
CN1023818C (en) * 1991-03-19 1994-02-16 昆明工学院 Vacuum distillation zinc extraction method of hot galvanizing residue
US5635051A (en) * 1995-08-30 1997-06-03 The Regents Of The University Of California Intense yet energy-efficient process for electrowinning of zinc in mobile particle beds
US6086691A (en) * 1997-08-04 2000-07-11 Lehockey; Edward M. Metallurgical process for manufacturing electrowinning lead alloy electrodes
CN1065919C (en) * 1998-04-24 2001-05-16 昆明理工大学 Vacuum distillation of hard zinc to extract zinc and to concentrate germanium, indium and silver
US6238542B1 (en) * 1998-09-15 2001-05-29 Thomas Helden Water soluble brighteners for zinc and zinc alloy electrolytes
EP1013799A1 (en) * 1998-12-23 2000-06-28 Half Tone Ltd. Solution and process for the electrodeposition of gold and gold alloys

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RU2288299C2 (en) 2006-11-27
KR20040044443A (en) 2004-05-28
CA2457071C (en) 2007-05-29
CN100342061C (en) 2007-10-10
RU2004107493A (en) 2005-06-10
WO2003016593A3 (en) 2003-10-09
CN1653209A (en) 2005-08-10
EP1417357A2 (en) 2004-05-12
ES2238586T3 (en) 2005-09-01
DE60203301T2 (en) 2006-04-13
JP2004537653A (en) 2004-12-16
KR100599993B1 (en) 2006-07-13
AU2002322888B2 (en) 2007-06-21
ZA200405167B (en) 2005-06-27
DE60203301D1 (en) 2005-04-21
NO20040651L (en) 2004-04-16
MXPA04001459A (en) 2005-02-17
WO2003016593A2 (en) 2003-02-27
US20050011769A1 (en) 2005-01-20
CA2457071A1 (en) 2003-02-27
HK1075920A1 (en) 2005-12-30
BR0211933A (en) 2004-10-26

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