EP3385409B1 - Bain d'acide sulfurique électrolytique et procédé d'électroaffinage d'étain - Google Patents

Bain d'acide sulfurique électrolytique et procédé d'électroaffinage d'étain Download PDF

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EP3385409B1
EP3385409B1 EP18382212.1A EP18382212A EP3385409B1 EP 3385409 B1 EP3385409 B1 EP 3385409B1 EP 18382212 A EP18382212 A EP 18382212A EP 3385409 B1 EP3385409 B1 EP 3385409B1
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Prior art keywords
sulfone
sulphuric acid
tin
bis
acid bath
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EP3385409A1 (fr
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Raúl FIGUEROA MARTÍNEZ
Xosé Ramón NÓVOA RODRÍGUEZ
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Estanos Y Soldaduras Senra SLU
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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
    • C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin

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  • the present invention relates to the field of hydrometallurgical processes. More particularly, the present invention relates to the field of tin electrorefining.
  • pyrometallurgical and hydrometallurgical treatments Two processes are used to recover tin metal from electronic waste: pyrometallurgical and hydrometallurgical treatments.
  • the pyrometallurgical treatment consists on melting the tin-containing scrap and suffers from the main disadvantages of low efficiency and the high prime costs due to high amounts of energy needed to keep high temperature.
  • hydrometallurgical treatment consists of the use of aqueous chemistry for the recovery of metals from the residual materials by electrodeposition and includes electrowining and electrorefining processes. Electrowinning is the primary extraction of a metal from a residual material that has been put in solution via a process commonly referred to as leaching. Electrorefining is the subsequent refining of tin to high purity.
  • Both operations are accomplished in an electrolytic cell which comprises two electrodes immersed in an ionically conducting liquid (aqueous electrolyte) containing tin metal dissolved as positive ions. At the negative charged cathode, the tin cations are reduced and deposit as neutral tin atoms.
  • aqueous electrolyte ionically conducting liquid
  • Tin can be electrodeposited from various electrolytes.
  • acid solutions are usually preferred since alkaline solutions require higher temperatures and double specific charge.
  • the sulfonic acid was favoured as electrolyte solution because of the low corrosivity and nice ability to dissolve metallic impurities that are insoluble in other organic or mineral acids, such as lead.
  • FERROSTAN® process which is based in phenolsulfonic acid as electrolyte
  • RONASTAN® process which is based in methanesulfonic acid as electrolyte.
  • sulphuric acid has many advantages, including its environmental friendliness and relatively low cost. Therefore, sulphuric acid-based electrolytes for tin electrodeposition have attracted growing interest.
  • tin electrodeposition using sulphuric acid suffer from deposition of tin species in the shape of needles, whiskers and dendrites on the surface of the anode, which is commonly known as "dendritic growth" (see Figure 1(a), Figure 2 and Figure 4(c) and 4(d) ), and which lead to decrease of tin electrodeposition efficiency. Consequently, organic additives are necessary if smooth, shiny and dense films of tin metal are desired.
  • Additive examples may include surfactants to promote the electrode reaction, oxidation inhibitors to reduce the formation rate of stannic ions ( Xiao et al. Inter. J. Minerals, Metallurgy and Materials, 2013, 20(5), 472 ), grain refiners such as tartrate ( Rockwell et al. Thin Solid Films, 2008, 516 (21), 7361 ) or formaldehyde and polyoxyethylene octylphenol ether ( Xiao et al. Mater. Prot., 2011, 44(1), 1 ) to avoid dendritic growth and brighteners such as pyridine and quinoline compounds ( US 4,000,047 A1 ) to obtain matte or bright deposits.
  • surfactants to promote the electrode reaction
  • oxidation inhibitors to reduce the formation rate of stannic ions
  • grain refiners such as tartrate ( Rockwell et al. Thin Solid Films, 2008, 516 (21), 7361 ) or formaldehyde and poly
  • the object of the present invention is the provision of an electrolytic sulphuric acid bath which provide enhanced tin electrorefining performance.
  • the sulphuric acid bath of the present invention is characterized by a combination of additives comprising gelatine and a compound of general formula (I) such as bisphenol sulfone, di-tolyl sulfoxide, or a derivate thereof.
  • a compound of general formula (I) such as bisphenol sulfone, di-tolyl sulfoxide, or a derivate thereof.
  • the present invention relates to an electrolytic sulphuric acid bath for tin electrorefining which comprises:
  • the present invention is directed to a method for tin electrorefining comprising the application of a current to the electrolytic sulphuric acid bath as defined above.
  • the present invention is directed to the use of gelatine and a compound of general formula (I) as a combination of additives for an electrolytic sulphuric acid bath for tin electrorefining.
  • the present invention allows a good electrical efficiency of tin deposition, keeping impurities in the tin deposit in the ppm range and thus, obtaining an electrorefined tin having high purity reaching or being greater than 99.9%, which fulfils the requirements for electronic applications.
  • the resulting deposited tin shows a lower porosity than that obtained without additives, which limits its oxidation in the atmosphere.
  • a first aspect of the invention is directed to an electrolytic sulphuric acid bath suitable for tin electrorefining which comprises:
  • electrolytic bath refers to a chamber (for example, a cell) comprising an electrically conducting solution (electrolyte) that generally contains ions, atoms or molecules that have lost or gained electrons when they are dissolved in a polar solvent, such as water, and two electrodes (anode and cathode) immersed in the conducting solution.
  • the electrically conducting solution is an aqueous solution of sulphuric acid.
  • the electrolytic sulphuric acid bath of the present invention is suitable for tin electrorefining.
  • electrolytic refining or “electrolytic refining” refers to refining of a metal (tin, in the context of the present invention) by electrolysis where the target material containing the metal is used as the anode going into an electrically conducting solution and the refined metal being deposited upon the cathode.
  • the electrolytic sulphuric acid bath of the present invention comprises a sulphuric acid solution which comprises an aqueous solution of sulphuric acid to produce a sufficiently high acidity to avoid Sn 2+ hydrolysis to Sn 4+ which, otherwise precipitates, lowering the process yield.
  • a sulphuric acid solution which comprises an aqueous solution of sulphuric acid to produce a sufficiently high acidity to avoid Sn 2+ hydrolysis to Sn 4+ which, otherwise precipitates, lowering the process yield.
  • the presence of sulphate ions in the electrolytic sulphuric acid bath helps the removal of impurities, such as Pb and Sb, by precipitation at the anode or at the bottom of the bath, as insoluble salts. As a consequence, an excess of the acid improves the elimination of certain impurities.
  • the sulphuric acid solution has a pH below or equal to 1.
  • a non-limitative example of a sulphuric acid solution suitable for the electrolytic bath of the present invention can be obtained by dissolving between about 30 g and about 200 g of 96% H 2 SO 4 in 1 L of water, preferably about 100 g in 1 L.
  • the electrolytic sulphuric acid bath of the present invention further comprises a source of Sn(II) ions.
  • the Sn(II) ions are in a concentration between about 0.05 M and about 0.1 M.
  • a non-limitative example of a source of Sn(II) ions suitable for the electrolytic sulphuric acid bath of the present invention is a tin salt, such as tin sulphate, directly dissolved in the sulphuric acid solution to produce Sn 2+ positive ions.
  • the source of Sn(II) ions is tin sulphate (SnSO 4 ), since it contributes simultaneously to increase the concentration of Sn(II) ions as well as of sulphate ions, thus favouring the precipitation of impurities such as Pb.
  • the electrolytic sulphuric acid bath of the present invention further comprises an anode comprising the target tin to be refined.
  • Non-limitative examples of anodes suitable in the electrolytic sulphuric acid bath of the present invention include anodes made of tin-based alloys like antifriction alloys (also known as white metal or Babbitt metal), pewter alloys, soft solder alloys or combinations thereof.
  • titanium-based alloy refers to alloys containing high percentages of Sn as well as minor percentages of Fe, Ni, Cd, Bi, Zn, As, Ge and In, among others.
  • the term “pewter alloy” refers to alloys preferably containing between about 90% and about 95% of tin, as well as between about 1% and about 3% Cu with Sb as balance.
  • soft solder alloy refers to alloys preferably containing more than 50% of tin in the form of binary or ternary alloys such as Sn-Pb, Sn-Cu, Sn-Ag, Sn-Bi or Sn-Ag-Cu.
  • the electrolytic sulphuric acid bath of the present invention further comprises, gelatine and a compound according to the general formula (I) as defined above as additives. These additives may be added to the bath either previously premixed or not.
  • gelatine refers to a mixture of peptides and proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and connective tissues of animals such as domesticated cattle, chicken, pigs, and fish.
  • gelatine suitable in the electrolytic sulphuric acid bath of the present invention is gelatine with high-protein polymers of amino acids linked by peptide chains (--CO--NH--), and having molecular weights in the range of 10,000 to 300,000.
  • animal glue is used as gelatine additive since it is relatively inexpensive, commercially available and convenient to handle.
  • the electrolytic sulphuric acid bath of the present invention further comprises compounds represented by the general formula (I) wherein
  • each R group must be bound to a different carbon atom of the benzene ring.
  • halogen refers to bromine, chlorine, iodine or fluorine.
  • alkyl refers to a linear or branched alkane derivative containing from 1 to 12, preferably from 1 to 6, carbon atoms and which is bound to the rest of the molecule through a single bond.
  • alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, etc.
  • cycloalkyl refers to a radical derived from cycloalkane containing from 3 to 7, preferably from 3 to 6 carbon atoms.
  • Illustrative examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • aryl refers to an aromatic group having between 6 and 10, preferably 6 or 10 carbon atoms, comprising 1 or 2 aromatic nuclei fused to one another.
  • aryl groups include phenyl, naphthyl, indenyl, phenanthryl, etc. Preferably, it is phenyl.
  • aralkyl refers to an alkyl group as defined above substituted with an aryl group as defined above. Examples of such groups include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, etc. Preferably, it is benzyl.
  • alkoxy refers to a radical of the formula -O-alkyl, where alkyl has been previously defined, e. g., methoxy, ethoxy, propoxy, etc.
  • Suitable carboalkoxy groups include groups such as methyl carboxylate, ethyl carboxylate, propyl carboxylate, butyl carboxylate, etc.
  • General formula (I) comprises both symmetric and non-symmetric sulfones and sulfoxides.
  • the compound of general formula (I) is symmetric.
  • the compound of general formula (I) is selected from the group consisting of:
  • Non-limitative examples of bisphenol sulfones of general formula (I) suitable for the electrolytic sulphuric acid bath of the present invention also include:
  • Non-limitative examples of compounds of general formula (I) suitable for the electrolytic sulphuric acid bath of the present invention also include the sulfoxide homologues of the compounds defined above such as bisphenyl sulfoxide, di-o-tolyl sulfoxide, di-p-tolyl sulfoxide, bis(2-chlorophenyl) sulfoxide, bis(2-fluorophenyl) sulfoxide), bis(4-chlorophenyl) sulfoxide, bis(4-fluorophenyl) sulfoxide, 2,2'-diphenol sulfoxide and 4,4'-diphenol sulfoxide.
  • the sulfoxide homologues of the compounds defined above such as bisphenyl sulfoxide, di-o-tolyl sulfoxide, di-p-tolyl sulfoxide, bis(2-chlorophenyl) sulfoxide, bis(2-fluorophenyl
  • a and b are independently selected from 0, 1 or 2. In a more preferred embodiment, in the compound of general formula (I) a and b are 0, 1 or 2 wherein each R independently stands for halogen, alkyl or hydroxyl.
  • the compound of general formula (I) is selected from the group consisting of bisphenyl sulfone (diphenyl sulfone); dialkyldiphenyl sulfones including but not limited to 2,2'- and 4,4'-dialkyldiphenyl sulfones (such as di-o-tolyl sulfone and di-p-tolyl sulfone); dihalogendiphenyl sulfones including but not limited to 2,2'- and 4,4'-dihalogendiphenyl sulfones (such as bis(2-chlorophenyl) sulfone, bis(2-fluorophenyl) sulfone, bis(4-chlorophenyl) sulfone and bis(4-fluorophenyl) sulfone); bisphenol sulfones including but not limited to 2,2'- and 4,4'-bisphenol sulfones (such as 2,2'- and 4,
  • alkyl is preferably selected from methyl, ethyl, propyl and butyl and halogen is preferably selected from Br, Cl and F.
  • the compound of general formula (I) is di-p-tolyl sulfoxide or 4,4'-diphenol sulfone (also known as 4,4'-sulfonylbisphenol, bisphenol S or BPS). In the present application, this latter compound is sometimes simply referred to as bisphenol sulfone.
  • the mixture of additives of the electrolytic sulphuric acid bath of the present invention comprises gelatine in a concentration between about 0.05 g/L and about 3 g/L and a compound of general formula (I) in a concentration between about 0.05 g/L and about 1 g/L, preferably it comprises gelatine in a concentration between about 0.1 g/L and about 3 g/L and a compound of general formula (I) in a concentration between about 0.1 g/L and about 1 g/L, more preferably it comprises gelatine in a concentration between about 0.1 g/L and about 1 g/L and a compound of general formula (I) in a concentration between about 0.2 g/L and about 0.4 g/L, even more preferably it comprises gelatine in a concentration between about 0.1 g/L to about 0.2 g/L and a compound of general formula (I) in a concentration between about 0.2 g/L and about 0.4 g/L.
  • the electrolytic sulphuric acid bath of the present invention further comprises a cathode where the deposition of tin takes place.
  • Non-limitative examples of cathodes suitable in the electrolytic sulphuric acid bath of the present invention include cathodes made of raw tin or, in order to reduce costs, a material as copper or stainless steel that resists the aggressiveness of the electrolytic acid medium. For example, it has been observed that a sheet of commercial stainless steel "AISI 316" produces good results without being attacked by the sulphuric acid solution.
  • Another aspect of the present invention is directed to a method for electrorefining of tin comprising the application of a current to the electrolytic sulphuric acid bath as defined above.
  • the operating current must be adjusted to carry out the selective oxidation of tin at the anode and its deposition at the cathode and without contamination of the tin deposit by other elements present in the anode.
  • the current to be applied depends on the geometry of the electrolysis cell.
  • the term "current density” refers to the electric current per unit area of a cross section. In SI units, the electric current density is measured in amperes per square metre.
  • the current applied in the method of the present invention has a density between about 100 A/m 2 and about 150 A/m 2 . Nevertheless, the selection of the most appropriate current in each individual case may be determined by one of ordinary skill in the art using routine experimentation.
  • the tin at the anode is selectively oxidized and deposited onto the surface of the cathode as a tin layer.
  • the resulting tin layer can be typically peeled off easily from that surface.
  • the combined use of gelatine and a compound of general formula (I) as additives in an electrolytic sulphuric acid bath for tin electrorefining according to the present invention provides a synergistic effect allowing a good electrical efficiency of tin deposition, keeping impurities in the tin deposit in the ppm range and thus, obtaining an electrorefined tin having a purity equal or greater than 99.9%, even 99.99% or even 99.999%. This purity fulfils requirements for electronic applications.
  • the term "about” means a slight variation of the value specified, preferably within 10 percent of the value specified. Nevertheless, the term “about” can mean a higher tolerance of variation depending on for instance the experimental technique used. Said variations of a specified value are understood by the skilled person and are within the context of the present invention. Further, to provide a more concise description, some of the quantitative expressions given herein are not qualified with the term "about”.
  • Example 1 Tin electrorefining with sulphuric acid electrolytic solutions comprising gelatine and 4,4'-sulfonylbisphenol (BPS).
  • electrolytic solutions including sulphuric acid and a mixture of gelatin and BPS as additives.
  • the electrolytic solution included 5.4% volume percent sulphuric acid in deionized water.
  • the tin sulfate was dissolved into the sulphuric acid electrolyte to a concentration of 20 g/L which acts as starting electrodeposition bath.
  • the two additives, gelatine and BPS were added to this electrolytic solution.
  • the gelatine had a concentration of 0.2 g/L in the electrolytic solution.
  • BPS had a concentration of 0.4 g/L in the electrolytic solution.
  • the electrolysis system included a 1000 L polypropylene tank equipped with a vertical pump for solution agitation and filtration.
  • the system also included a stainless steel cathode, and two anodes of tin alloy placed alternatively, and a DC power supply connected to the cathode and anodes. Electrolysis was performed at room temperature.
  • the electrorefining parameters were adjusted in this experiment as follows: sulphate ions (SO 4 2- ) concentration in the electrolytic solution (107 g/L); Sn(II) ions concentration in the electrolytic solution (12 g/L); current density 150 A/m 2 .
  • the composition of the tin alloy used as anode was a Babbitt alloy and it was analysed using SPECTROMAXx Arc Spark Optical Emission Spectrometry (Spark OES) is shown in Table 1.
  • Table 1 Spark OES analysis of the tin alloy used as anode (Babbitt alloy) Element Percentage (%) Sn 80.29 Sb 11.19 Cu 5.92 Pb 2.16 Ag 0.127 Fe 0.083 Ni 0.06 Cd 0.016 Bi 0.022 Zn 0.002 As 0.128 In 0.002
  • the electrolysis was performed for 7 days. After electrorefining, the refined tin was harvested from the cathodes and cast to produce refined tin samples. The refined tin samples were analyzed after casting using Spark OES and for trace elements using Varian's Vista Pro ICP-AES. The results are presented in Table 2 below.
  • Table 2 Analysis of electrodeposited tin in the cathode Element Percentage ( % ) * Sn 99.9991 Ag ⁇ 0.0002 Al ⁇ 0.0001 As ⁇ 0.0007 Au ⁇ 0.0001 Bi 0.0002 Cd ⁇ 0.0002 Co ⁇ 0.0003 Cu 0.0005 Fe 0.0002 Ge 0.0002 In ⁇ 0.0001 Ni 0.0003 P ⁇ 0.0005 Pb ⁇ 0.0003 Pd 0.0001 Sb 0.0001 Zn ⁇ 0.0001 *The values that fall below the limit of detection are preceded by " ⁇ " symbol.
  • the present inventors were able to achieve impurities removal and good morphology as shown in Figure 1(c) and Figure 3 .
  • the electrorefined tin has high purity and can be melted open to air without significant oxidation.
  • Example 2 Tin electrorefining with sulphuric acid electrolytic solutions comprising gelatine and di-p-tolyl sulfoxide.
  • the electrolysis system included a 1000 L polypropylene tank equipped with a vertical pump for solution agitation and filtration, a stainless steel cathode, and two tin anodes for homogeneous current distribution and tin(II) supply. A DC power supply provided the required current. Electrolysis was performed at room temperature.
  • Table 4 Analysis of electrodeposited tin in the cathode Element Percentage (%) * Sn 99.9985 Ag ⁇ 0.0002 Al ⁇ 0.0001 As ⁇ 0.0007 Au ⁇ 0.0001 Bi 0.0003 Cd ⁇ 0.0002 Co ⁇ 0.0003 Cu 0.0005 Fe 0.0002 Ge 0.0002 In ⁇ 0.0001 Ni 0.0001 P ⁇ 0.0005 Pb ⁇ 0.0003 Pd 0.0001 Sb 0.0001 Zn ⁇ 0.0001 *The values that fall below the limit of detection are preceded by " ⁇ " symbol
  • the tin deposits obtained using a mixture of gelatine and di-p-tolyl sulfoxide can be melt open to air without significant oxidation.
  • E E e + ⁇
  • ⁇ the overpotential
  • E e the equilibrium potential at which no current flows through the cell or there is no electrodeposition.
  • the overpotential ⁇ is the extra potential necessary for current circulation through the electrochemical cell.
  • the value of ⁇ is influenced by solution and interfacial processes that are involved in the three parameters outlined above.
  • the conductivity of the solution, ⁇ represents the Ohm's type opposition to current circulation according to Eq. 2, where ⁇ R represents the resistance overpotential and I the current circulating through the electrochemical cell.
  • ⁇ R l / ⁇
  • step (C) above represents the concentration polarisation due to Fick's law controlled transport of reactant, according to Eq. 4.
  • ⁇ C RT zF Ln 1 ⁇ I I L
  • R,T and F have the usual meaning, and z represents the electron number involved in the redox cathodic process.
  • I L holds for the limiting current given by Fick's law.
  • ⁇ C represents the overpotential due to transport.
  • step (C), ⁇ C is usually the rate-limiting step.
  • the electron transfer rates (step B) are usually much faster than step (C).
  • step (C) is the rate-limiting step (i.e. ⁇ ⁇ C .
  • Dendritic deposits will result from the lack of metal ions transported to the electrode interface to support further cathodic reduction. Under such circumstances, the incipient fine crystals recrystallize and grow larger to lower the total energy of the system.
  • the dimension that has more degrees of freedom is the direction perpendicular to the electrode surface. This is normally how dendrites are formed.
  • step B the rate-limiting step 2 (i.e. ⁇ ⁇ A ). This can be achieved either by lowering current density, (i.e. smaller ⁇ ), or using organic molecules to inhibit the electron transfer process by blocking the high-energy sites of the electrode surface, thus increasing the activation energy for step B, which increases ⁇ A .
  • Organic molecules adsorb at the metallic surface (thus blocking active sites) depending on their functional group. It is thus expected that molecules of the same family behave similarly in terms of providing ⁇ ⁇ A .

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Claims (14)

  1. Bain d'acide sulfurique électrolytique comprenant :
    - une solution d'acide sulfurique,
    - une source d'ions Sn(II),
    - une anode comprenant l'étain cible à raffiner,
    - une cathode,
    - de la gélatine, et
    - un composé de formule générale (I)
    Figure imgb0009
     dans laquelle
    n vaut 1 ou 2,
    chaque R représente indépendamment un groupe halogène, alkyle, cycloalkyle, aryle, aralkyle, hydroxyle, alcoxy, allyloxy, carboxyle ou carboalcoxy ; et
    dans laquelle a et b sont indépendamment choisis parmi un nombre entier allant de 0 à 3, et des R adjacents peuvent être combinés pour former un cycle.
  2. Bain d'acide sulfurique électrolytique selon la revendication 1, dans lequel la solution d'acide sulfurique a un pH inférieur ou égal à 1.
  3. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 2, dans lequel la concentration en ions Sn(II) est comprise entre 0,05 et 0,1 M.
  4. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 3, dans lequel la source d'ions Sn(II) est le sulfate d'étain (SnSO4).
  5. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 4, dans lequel l'anode comprenant l'étain cible à raffiner est une anode faite d'un alliage antifriction.
  6. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 5, comprenant de la gélatine à une concentration comprise entre 0,05 et 3 g/L et un composé de formule générale (I) à une concentration comprise entre 0,05 et 1 g/L.
  7. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 6, dans lequel, dans le composé de formule générale (I), a et b valent 0, 1, 2 ou 3 et chaque R représente indépendamment halogène, alkyle ou hydroxyle.
  8. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 7, dans lequel le composé de formule générale (I) est la bisphényl sulfone, une dialkyldiphényl sulfone, une dihalogénodiphényl sulfone, une bisphénol sulfone, une bisphénol sulfone substituée par alkyle, une bisphénol sulfone substituée par halogène, une bisphénol sulfone substituée par hydroxy ou les homologues sulfoxyde correspondants de ces composés.
  9. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 8, dans lequel le composé de formule générale (I) est la bisphényl sulfone, la di-o-tolyl sulfone, la di-p-tolyl sulfone, la bis(2-chlorophényl) sulfone, la bis(2-fluorophényl) sulfone, la bis(4-chlorophényl) sulfone, la bis(4-fluorophényl) sulfone, la 2,2'-diphénol sulfone, ou la 4,4'-diphénol sulfone ou les homologues sulfoxyde correspondants de ces composés.
  10. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 9, dans lequel le composé de formule générale (I) est le di-p-tolyl sulfoxyde ou le 4,4'-sulfonylbisphénol.
  11. Bain d'acide sulfurique électrolytique selon l'une quelconque des revendications 1 à 10, dans lequel la cathode est faite d'étain pur, d'acier inoxydable ou de cuivre.
  12. Procédé d'électroraffinage d'étain comprenant l'application d'un courant au bain électrolytique d'acide sulfurique selon l'une quelconque des revendications 1 à 11.
  13. Procédé selon la revendication 12, dans lequel le courant appliqué a une densité comprise entre 100 et 150 A/m2.
  14. Utilisation de gélatine et d'un composé de formule générale (I) comme combinaison d'additifs pour un bain d'acide sulfurique électrolytique d'électroraffinage d'étain.
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US1466126A (en) * 1922-02-01 1923-08-28 Guggenheim Brothers Electrolytic refining or depositing of tin
US2313371A (en) * 1940-06-28 1943-03-09 Carnegie Illinois Steel Corp Electrodeposition of tin and its alloys
CH224001A (fr) * 1941-03-29 1942-10-31 Jacob Henri Procédé d'obtention d'étain fin.
US2633450A (en) * 1949-04-27 1953-03-31 United States Steel Corp Tin and tin alloy plating bath
BE671254A (fr) * 1964-08-20 1966-02-14
US4000047A (en) 1972-11-17 1976-12-28 Lea-Ronal, Inc. Electrodeposition of tin, lead and tin-lead alloys
JP6052430B2 (ja) * 2014-01-28 2016-12-27 新日鐵住金株式会社 表面処理鋼板

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