EP3385409B1 - Elektrolytisches schwefelsäurebad und verfahren zur zinn-elektroraffination - Google Patents

Elektrolytisches schwefelsäurebad und verfahren zur zinn-elektroraffination Download PDF

Info

Publication number
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
Authority
EP
European Patent Office
Prior art keywords
sulfone
sulphuric acid
tin
bis
acid 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.)
Active
Application number
EP18382212.1A
Other languages
English (en)
French (fr)
Other versions
EP3385409A1 (de
Inventor
Raúl FIGUEROA MARTÍNEZ
Xosé Ramón NÓVOA RODRÍGUEZ
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.)
Estanos Y Soldaduras Senra SLU
Original Assignee
Estanos Y Soldaduras Senra SLU
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 Estanos Y Soldaduras Senra SLU filed Critical Estanos Y Soldaduras Senra SLU
Publication of EP3385409A1 publication Critical patent/EP3385409A1/de
Application granted granted Critical
Publication of EP3385409B1 publication Critical patent/EP3385409B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/14Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin

Definitions

  • 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 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (14)

  1. Elektrolytisches Schwefelsäurebad, umfassend:
    - eine Schwefelsäurelösung,
    - eine Quelle an Sn(II)-Ionen,
    - eine Anode, umfassend das Ziel-Zinn, welches raffiniert werden soll,
    - eine Kathode,
    - Gelatine, und
    - eine Verbindung der allgemeinen Formel (I)
    Figure imgb0008
    wobei
    n 1 oder 2 ist,
    jedes R unabhängig für eine Halogen-, Alkyl-, Cycloalkyl-, Aryl-, Aralkyl-, Hydroxyl-, Alkoxy-, Allyloxy-, Carboxyl- oder Carboalkoxy-Gruppe steht; und
    wobei a und b unabhängig ausgewählt sind aus einer Ganzzahl von 0 bis 3, und benachbarte Rs kombiniert werden können, um einen Ring zu bilden.
  2. Das elektrolytische Schwefelsäurebad gemäß Anspruch 1, wobei die Schwefelsäurelösung einen pH von wenig oder gleich 1 aufweist.
  3. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 2, wobei die Konzentration an Sn(II)-Ionen zwischen 0,05 und 0,1 M beträgt.
  4. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 3, wobei die Quelle an Sn(II)-Ionen Zinnsulfat (SnSO4) ist.
  5. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 4, wobei die Anode, welche das zu raffinierende Ziel-Zinn umfasst, eine Anode ist, die aus einer reibungsvermindernden Legierung hergestellt ist.
  6. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 5, umfassend Gelatine in einer Konzentration von zwischen 0,05 und 3 g/L und eine Verbindung der allgemeinen Formel (I) in einer Konzentration von zwischen 0,05 und 1 g/L.
  7. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 6, wobei in der Verbindung der allgemeinen Formel (I) a und b 0, 1, 2 oder 3 sind und jedes R unabhängig für Halogen, Alkyl oder Hydroxyl steht.
  8. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 7, wobei die Verbindung der allgemeinen Formel (I) Bisphenylsulfon, eine Dialkyldiphenylsulfon, ein Dihalogendiphenylsulfon, ein Bisphenolsulfon, ein Alkyl-substituiertes Bisphenolsulfon, ein Halogen-substituiertes Bisphenolsulfon, ein Hydroxy-substituiertes Bisphenolsulfon oder die entsprechenden Sulfoxid-Homologen dieser Verbindungen ist.
  9. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 8, wobei die Verbindung der allgemeinen Formel (I) Bisphenylsulfon, Di-o-tolylsulfon, Di-p-tolylsulfon, Bis(2-chlorophenyl)sulfon, Bis(2-fluorophenyl)sulfon, Bis(4-chlorophenyl)sulfon, Bis(4-fluorophenyl)sulfon, 2,2'-Diphenolsulfon oder 4,4'-Diphenolsulfon oder die entsprechenden Sulfoxid-Homologen dieser Verbindungen ist.
  10. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 9, wobei die Verbindung der allgemeinen Formel (I) Di-p-tolylsulfoxid oder 4,4'-Sulfonylbisphenol ist.
  11. Das elektrolytische Schwefelsäurebad gemäß einem der Ansprüche 1 bis 10, wobei die Kathode aus reinem Zinn, Edelstahl oder Kupfer hergestellt ist.
  12. Verfahren zur Zinn-Elektroraffination, umfassend die Anwendung eines Stromes auf ein elektrolytisches Schwefelsäurebad gemäß einem der Ansprüche 1 bis 11.
  13. Das Verfahren gemäß Anspruch 12, wobei der angewendete Strom eine Dichte von zwischen 100 und 150 A/m2 aufweist.
  14. Verwendung von Gelatine und einer Verbindung der allgemeinen Formel (I) als eine Kombination von Additiven für ein elektrolytisches Schwefelsäurebad zur Zinn-Elektroraffination.
EP18382212.1A 2017-04-04 2018-03-27 Elektrolytisches schwefelsäurebad und verfahren zur zinn-elektroraffination Active EP3385409B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17382173 2017-04-04

Publications (2)

Publication Number Publication Date
EP3385409A1 EP3385409A1 (de) 2018-10-10
EP3385409B1 true EP3385409B1 (de) 2019-11-27

Family

ID=58501427

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18382212.1A Active EP3385409B1 (de) 2017-04-04 2018-03-27 Elektrolytisches schwefelsäurebad und verfahren zur zinn-elektroraffination

Country Status (1)

Country Link
EP (1) EP3385409B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111472021A (zh) * 2019-01-24 2020-07-31 升贸科技股份有限公司 电解液

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (de) * 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
TWI547595B (zh) * 2014-01-28 2016-09-01 新日鐵住金股份有限公司 表面處理鋼板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3385409A1 (de) 2018-10-10

Similar Documents

Publication Publication Date Title
Goh et al. Effects of hydroquinone and gelatin on the electrodeposition of Sn–Bi low temperature Pb-free solder
Lu et al. Manganese electrodeposition—A literature review
JP4298712B2 (ja) 銅の電解精製方法
US20140311896A1 (en) Electrorecovery of gold and silver from thiosulphate solutions
CN106435664A (zh) 一种填孔用可溶性阳极电镀铜溶液
JPWO2011102276A1 (ja) 高純度スルホン酸銅水溶液及びその製造方法
EP3385409B1 (de) Elektrolytisches schwefelsäurebad und verfahren zur zinn-elektroraffination
JP2021523298A (ja) 銅電解精製の改善
Illés et al. The recycling of pure metallic indium from waste LCD screens by a combined hydro-electrometallurgical method
US6187169B1 (en) Generation of organosulfonic acid from its salts
CN103966442B (zh) 一种废杂铜电积制备高纯铜的方法
US4083761A (en) Arsenic removal from electrolytes with application of periodic reverse current
JP2014214378A (ja) Snめっき剥離廃液からの銅回収方法
JP2008266766A (ja) ハロゲン系溶液からの板状電気銅の製造方法
Owais Effect of electrolyte characteristics on electrowinning of copper powder
JP3920983B2 (ja) 銀又は銀合金酸性電気めっき浴
AU735636B2 (en) Polyacrylic acid additives for copper electrorefining and electrowinning
JP2983548B2 (ja) スズービスマス合金の電気めっき法
US3915818A (en) Electrowinning process for the improved recovery of metal
Pradhan et al. Effect of zinc on the electrocrystallization of cobalt
US5837123A (en) Prevention of cathode corrosion during electrowinning
BE1030447B1 (nl) Additief-vrije Cu Elektrowinning
US2796394A (en) Separating and recovering nonferrous alloys from ferrous materials coated therewith
JPH05311484A (ja) リフロー錫または錫合金めっき浴
Hodjaoglu Electrochemical recovery of copper in the presence of contaminant ferrous ions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190306

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C25C 1/14 20060101AFI20190719BHEP

INTG Intention to grant announced

Effective date: 20190809

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1206745

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018001397

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20191127

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200227

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200227

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200327

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200419

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018001397

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1206745

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191127

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

26N No opposition filed

Effective date: 20200828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200327

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191127

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220327

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240327

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240325

Year of fee payment: 7