EP0452679A1 - Electrochemical preparation of tin(II)-chloride aqueous solutions - Google Patents
Electrochemical preparation of tin(II)-chloride aqueous solutions Download PDFInfo
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- EP0452679A1 EP0452679A1 EP91104097A EP91104097A EP0452679A1 EP 0452679 A1 EP0452679 A1 EP 0452679A1 EP 91104097 A EP91104097 A EP 91104097A EP 91104097 A EP91104097 A EP 91104097A EP 0452679 A1 EP0452679 A1 EP 0452679A1
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- Prior art keywords
- tin
- anode
- hydrochloric acid
- aqueous solutions
- diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Definitions
- the invention relates to an electrochemical process for the preparation of aqueous tin (II) chloride solutions.
- the invention has for its object to develop a method for producing tin (II) chloride solutions which avoids the aforementioned disadvantages of chemical dissolution.
- the object on which the invention is based is achieved in that metallic tin is anodically dissolved in aqueous hydrochloric acid by applying a DC voltage, the anode and cathode spaces being separated from one another by diaphragms or organic membranes.
- the diaphragms used are preferably inorganic, in particular ceramic, diaphragms densely sintered above 1000 ° C. with a thickness of about 6 to 10 mm.
- Anion-permeable organic membranes with a thickness of about 0.2 to 0.6 mm are preferably used as organic membranes.
- the method is preferably carried out in a plastic cell, the walls of which are made of polyethylene and which is divided by the diaphragms or the organic membranes into two rooms of approximately the same size.
- metallic tin e.g. B. in the form of inexpensive ingots used.
- Aqueous hydrochloric acid is used as the electrolyte liquid both in the cathode and in the anode compartment.
- some hydrogen develops at the anode.
- This initial evolution of hydrogen at the anode practically comes to a standstill after a few hours and is due to an additional chemical dissolution.
- the process according to the invention for the electrochemical production of tin (II) chloride solutions makes it possible to produce tin (II) chloride solutions with a higher concentration than is possible with chemical dissolving processes.
- the HCl concentration in the anode compartment decreases during the anodic dissolution of metallic tin.
- Hydrogen ions are hydrated Form transferred from the anode space into the cathode space and released as hydrogen after electron uptake at the cathode.
- chloride ions are transferred from the cathode compartment to the anode compartment, which results in a decrease in the HCl concentration in the cathode compartment.
- tin (II) chloride solutions with low levels of free HCl can be prepared using the process according to the invention.
- a polyethylene rectangular electrolysis cell with the dimensions 350 mm x 360 mm x 360 mm is a polyethylene inner cell with the dimensions 300 mm x 200 mm x 180 mm, on the two opposite sides 0.4 mm thick, preferably anion-permeable membranes of 1 dm2 Surface screwed liquid-tight and which represents the anode compartment, while the adjacent space in the outer cell forms the cathode compartment, aqueous hydrochloric acid, namely in the anode compartment 10 l with 153 g HCl / l and in the cathode compartment 18 l with 197 g HCl / l given.
- a tin electrode in ingot form (11.36 kg) with an effective surface area of 8 dm 2 is introduced into the center of the anode space and two analog tin electrodes in ingot form are placed directly opposite the membrane surfaces in the cathode space.
- Example 2 the same cell device as described in Example 1 is used, except that the inner cell is used instead of membranes with inorganic diaphragms based on aluminum silicate, which were densely sintered above 1000 ° C.
- a tin electrode (7 kg) with an effective surface area of 6 dm2 is placed in the center of the anode space and two analog tin electrodes in ingot form are placed directly opposite the diaphragm surfaces in the cathode space.
- the tin (II) chloride solution is produced electrochemically under the following working conditions: In Examples 1 to 3, stirring was carried out in the anode compartment during the preparation of the tin (II) chloride solution.
- the electrolyte solutions heat up to approx. 30 to 40 ° C during the manufacturing process.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Die Erfindung betrifft ein elektrochemisches Verfahren zur Herstellung von wäßrigen Zinn-(II)-chloridlösungen.The invention relates to an electrochemical process for the preparation of aqueous tin (II) chloride solutions.
Es ist bekannt, Zinn-(11)-chloridlösungen durch Auflösen von metallischem Zinn mit Salzsäure herzustellen. Die chemische Auflösung von Zinn in Salzsäure weist Nachteile auf.It is known to prepare tin (11) chloride solutions by dissolving metallic tin with hydrochloric acid. The chemical dissolution of tin in hydrochloric acid has disadvantages.
So ist es nicht möglich, durch chemisches Auflösen von Zinn in Salzsäure sehr hoch konzentrierte Lösungen herzustellen. Darüber hinaus ist es bei der chemischen Herstellung von Zinn-(II)-chloridlösungen nicht möglich, höher konzentrierte Lösungen bei gleichzeitig niederen Gehalten an freier HCl herzustellen. Ferner sind die Reaktionszeiten bei der chemischen Auflösung von Zinn in Salzsäure relativ lang.It is therefore not possible to produce very highly concentrated solutions by chemically dissolving tin in hydrochloric acid. In addition, it is not possible in the chemical production of tin (II) chloride solutions to produce more concentrated solutions with lower levels of free HCl at the same time. Furthermore, the reaction times for the chemical dissolution of tin in hydrochloric acid are relatively long.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Zinn-(II)-chloridlösungen zu entwickeln, das die vorerwähnten Nachteile der chemischen Auflösung vermeidet.The invention has for its object to develop a method for producing tin (II) chloride solutions which avoids the aforementioned disadvantages of chemical dissolution.
Die der Erfindung zugrunde liegende Aufgabe wird dadurch gelöst, daß man metallisches Zinn unter Anlegen einer Gleichspannung anodisch in wäßriger Salzsäure auflöst, wobei man den Anoden- und den Kathodenraum voneinander durch Diaphragmen oder organische Membranen trennt.The object on which the invention is based is achieved in that metallic tin is anodically dissolved in aqueous hydrochloric acid by applying a DC voltage, the anode and cathode spaces being separated from one another by diaphragms or organic membranes.
Als Diaphragmen verwendet man vorzugsweise anorganische, insbesondere keramische, oberhalb 1000° C dichtgesinterte Diaphragmen einer Stärke von etwa 6 bis 10 mm.The diaphragms used are preferably inorganic, in particular ceramic, diaphragms densely sintered above 1000 ° C. with a thickness of about 6 to 10 mm.
Vorzugsweise verwendet man als organische Membranen aniondurchlässige organische Membranen einer Stärke von etwa 0,2 bis 0,6 mm.Anion-permeable organic membranes with a thickness of about 0.2 to 0.6 mm are preferably used as organic membranes.
Das Verfahren wird vorzugsweise in einer Kunststoffzelle durchgeführt, deren Wände aus Polyethylen bestehen und welche durch die Diaphragmen oder die organischen Membranen in zwei etwa gleich große Räume unterteilt ist.The method is preferably carried out in a plastic cell, the walls of which are made of polyethylene and which is divided by the diaphragms or the organic membranes into two rooms of approximately the same size.
Bei der anodischen Auflösung des metallischen Zinns entwickelt sich gleichzeitig kathodisch Wasserstoff. Als Anoden- und als Kathodenmaterial wird metallisches Zinn, z. B. in Form preisgünstiger Ingots, verwendet.During the anodic dissolution of the metallic tin, hydrogen develops cathodically at the same time. As an anode and as a cathode material, metallic tin, e.g. B. in the form of inexpensive ingots used.
Als Elektrolytflüssigkeit wird sowohl im Kathoden- als auch im Anodenraum wäßrige Salzsäure verwendet. Zu Beginn der anodischen Auflösung des metallischen Zinns entwickelt sich an der Anode etwas Wasserstoff. Diese anfängliche Wasserstoffentwicklung an der Anode kommt nach wenigen Stunden praktisch zum Stillstand und ist auf ein zusätzliches chemisches Auflösen zurückzuführen.Aqueous hydrochloric acid is used as the electrolyte liquid both in the cathode and in the anode compartment. At the beginning of the anodic dissolution of the metallic tin, some hydrogen develops at the anode. This initial evolution of hydrogen at the anode practically comes to a standstill after a few hours and is due to an additional chemical dissolution.
Bei dem erfindungsgemäßen Verfahren wird im Anodenraum praktisch weitestgehend nur Zinn-(II)-chlorid gebildet; lediglich bei höheren Zinn-(II)-konzentrationen (> 250 g gelöstem zweiwertigen Zinn/l) wird in geringem Maße vierwertiges Zinn gebildet. Dies ist insbesondere bei niederen Konzentrationen an freier HCl und gleichzeitig hohen Stromdichten zu beobachten.In the method according to the invention, practically only tin (II) chloride is practically formed in the anode compartment; only at higher tin (II) concentrations (> 250 g dissolved divalent tin / l) does tetravalent tin form to a small extent. This can be observed in particular at low concentrations of free HCl and at the same time high current densities.
Das erfindungsgemäße Verfahren zur elektrochemischen Herstellung von Zinn-(II)-chloridlösungen, bei dem sich die Elektrolytlösungen leicht erwärmen, erlaubt es, höher konzentrierte Zinn-(II)-chloridlösungen herzustellen, als dies bei chemischen Löseverfahren möglich ist. Hierbei nimmt die HCl-Konzentration im Anodenraum während des anodischen Auflösens von metallischem Zinn ab. Wasserstoffionen werden in hydratisierter Form aus dem Anodenraum in den Kathodenraum überführt und nach Elektronenaufnahme an der Kathode als Wasserstoff freigesetzt. Ferner werden Chloridionen aus dem Kathodenraum in den Anodenraum überführt, was eine Abnahme der HCl-Konzentration im Kathodenraum zur Folge hat.The process according to the invention for the electrochemical production of tin (II) chloride solutions, in which the electrolyte solutions heat up slightly, makes it possible to produce tin (II) chloride solutions with a higher concentration than is possible with chemical dissolving processes. The HCl concentration in the anode compartment decreases during the anodic dissolution of metallic tin. Hydrogen ions are hydrated Form transferred from the anode space into the cathode space and released as hydrogen after electron uptake at the cathode. Furthermore, chloride ions are transferred from the cathode compartment to the anode compartment, which results in a decrease in the HCl concentration in the cathode compartment.
Darüber hinaus kann man mit dem erfindungsgemäßen Verfahren Zinn-(II)-chloridlösungen mit niederen Gehalten an freier HCl herstellen.In addition, tin (II) chloride solutions with low levels of free HCl can be prepared using the process according to the invention.
Hinzu kommt ferner, daß die Herstellung von Zinn-(II)-chloridlösungen auf elektrochemischem Wege entsprechend dem erfindungsgemäßen Verfahren wesentlich schneller vor sich geht als auf chemischem Wege.In addition, there is the fact that the preparation of tin (II) chloride solutions by electrochemical means in accordance with the method according to the invention proceeds much faster than by chemical means.
Das erfindungsgemäße Verfahren wird durch nachstehende Beispiele näher erläutert.The process according to the invention is explained in more detail by the following examples.
In eine Polyethylenrechteck-Elektrolysezelle mit den Abmessungen 350 mm x 360 mm x 360 mm wird eine Polyethyleninnenzelle mit den Abmessungen 300 mm x 200 mm x 180 mm, an der auf zwei gegenüberliegenden Seiten 0,4 mm dicke, bevorzugt aniondurchlässige Membranen von jeweils 1 dm² Fläche flüssigkeitsdicht aufgeschraubt sind und die den Anodenraum darstellt, während der angrenzende Raum in der Außenzelle den Kathodenraum bildet, wird wäßrige Salzsäure, und zwar in den Anodenraum 10 l mit 153 g HCl/l und in den Kathodenraum 18 l mit 197 g HCl/l gegeben.In a polyethylene rectangular electrolysis cell with the dimensions 350 mm x 360 mm x 360 mm is a polyethylene inner cell with the dimensions 300 mm x 200 mm x 180 mm, on the two opposite sides 0.4 mm thick, preferably anion-permeable membranes of 1 dm² Surface screwed liquid-tight and which represents the anode compartment, while the adjacent space in the outer cell forms the cathode compartment, aqueous hydrochloric acid, namely in the anode compartment 10 l with 153 g HCl / l and in the cathode compartment 18 l with 197 g HCl / l given.
Ferner werden in den Anodenraum raummittig eine Zinnelektrode in Ingotform (11,36 kg) mit einer wirksamen Oberfläche von 8 dm² und in den Kathodenraum zwei analoge Zinnelektroden in Ingotform jeweils unmittelbar gegenüber den Membranflächen eingebracht.Furthermore, a tin electrode in ingot form (11.36 kg) with an effective surface area of 8 dm 2 is introduced into the center of the anode space and two analog tin electrodes in ingot form are placed directly opposite the membrane surfaces in the cathode space.
Nach Anlegen von Gleichspannung wird die Herstellung der Zinn-(II)-chloridlösung auf elektrochemischem Wege unter folgenden Arbeitsbedingungen durchgeführt:
In der gleichen Zellenvorrichtung und mit gleichen Elektroden, wie in Beispiel 1, wurde nach Anlegen einer Gleichspannung die Herstellung einer Zinn-(II)-chloridlösung auf elektrochemischem Wege unter folgenden Arbeitsbedingungen durchgeführt:
Hierbei wurden Flüssigkeitsverdampfungsverluste durch Wasserzugabe ergänzt.In the same cell device and with the same electrodes as in Example 1, the preparation of a tin (II) chloride solution was carried out electrochemically after the application of a DC voltage under the following working conditions:
Here, liquid evaporation losses were supplemented by adding water.
Es wird wiederum die gleiche Zellenvorrichtung wie in Beispiel 1 beschrieben benutzt, lediglich mit der Ausnahme, daß die Innenzelle anstelle von Membranen mit anorganischen Diaphragmen auf Basis von Aluminiumsilikat, die oberhalb 1000° C dichtgesintert wurden, versehen ist. In den Anodenraum werden raummittig eine Zinnelektrode (7 kg) mit einer wirksamen Oberfläche von 6 dm² und in den Kathodenraum zwei analoge Zinnelektroden in Ingotform jeweils unmittelbar gegenüber den Diaphragmenflächen eingebracht.Again, the same cell device as described in Example 1 is used, except that the inner cell is used instead of membranes with inorganic diaphragms based on aluminum silicate, which were densely sintered above 1000 ° C. A tin electrode (7 kg) with an effective surface area of 6 dm² is placed in the center of the anode space and two analog tin electrodes in ingot form are placed directly opposite the diaphragm surfaces in the cathode space.
Nach Anlegen von Gleichspannung wird die Herstellung der Zinn-(II)-chloridlösung auf elektrochemischem Wege unter folgenden Arbeitsbedingungen durchgeführt:
Bei den Beispielen 1 bis 3 wurde jeweils im Anodenraum während der Herstellung der Zinn-(II)-chloridlösung gerührt. Die Elektrolytlösungen erwärmen sich während des Herstellungsverfahrens auf ca. 30 bis 40° C.After applying DC voltage, the tin (II) chloride solution is produced electrochemically under the following working conditions:
In Examples 1 to 3, stirring was carried out in the anode compartment during the preparation of the tin (II) chloride solution. The electrolyte solutions heat up to approx. 30 to 40 ° C during the manufacturing process.
Im Vergleich zu den elektrochemischen Versuchen wurde ein rein chemisches Auflösen von metallischem Zinn (518,4 g Sn) in Ingotform mit einer wirksamen Oberfläche von 1,3 dm² unter ständigem Rühren in 1 l wäßriger Salzsäure wie folgt vorgenommen:
Hiermit wird deutlich, daß die rein chemische Auflösung von metallischem Zinn in Salzsäure wesentlich langsamer vor sich geht und auch nicht so hohe Zinn-(II)-chloridkonzentrationen erbringt, als dies bei der elektrochemischen Auflösung der Fall ist.In comparison to the electrochemical experiments, a purely chemical dissolution of metallic tin (518.4 g Sn) in ingot form with an effective surface area of 1.3 dm² was carried out with constant stirring in 1 l of aqueous hydrochloric acid as follows:
This makes it clear that the purely chemical dissolution of metallic tin in hydrochloric acid proceeds much more slowly and also does not produce as high tin (II) chloride concentrations as is the case with electrochemical dissolution.
Die Ausbeuten bei dem erfindungsgemäßen Verfahren zur elektrochemischen Herstellung von Zinn-(II)-chloridlösungen liegen rein rechnerisch, bezogen auf in Lösung gegangenes zweiwertiges Zinn, etwas über 100 %, da zu Beginn der Reaktion auch ein chemisches Lösen zusätzlich eintritt.The yields in the process according to the invention for the electrochemical production of tin (II) chloride solutions are purely arithmetically above 100%, based on the divalent tin that has gone into solution, since chemical dissolution also occurs at the start of the reaction.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904010052 DE4010052A1 (en) | 1990-03-29 | 1990-03-29 | METHOD FOR THE ELECTROCHEMICAL PRODUCTION OF AQUEOUS TIN (II) CHLORIDE SOLUTIONS |
| DE4010052 | 1990-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0452679A1 true EP0452679A1 (en) | 1991-10-23 |
Family
ID=6403303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91104097A Withdrawn EP0452679A1 (en) | 1990-03-29 | 1991-03-16 | Electrochemical preparation of tin(II)-chloride aqueous solutions |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0452679A1 (en) |
| DE (1) | DE4010052A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862068B (en) * | 2016-05-30 | 2018-02-16 | 云南锡业股份有限公司 | A kind of synthetic method of stannous chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU202904A1 (en) * | METHOD OF ELECTROCHEMICAL PREPARATION OF CHLORISTOOLOVA | |||
| DE2602031B1 (en) * | 1976-01-21 | 1977-04-21 | Goldschmidt Ag Th | METHOD FOR MANUFACTURING TINNII SULPHATE |
| US4330377A (en) * | 1980-07-10 | 1982-05-18 | Vulcan Materials Company | Electrolytic process for the production of tin and tin products |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD128687A5 (en) * | 1977-01-21 | 1977-12-07 | Goldschmidt Ag Th | METHOD FOR PRODUCING ZINNII-SULFATE |
-
1990
- 1990-03-29 DE DE19904010052 patent/DE4010052A1/en not_active Withdrawn
-
1991
- 1991-03-16 EP EP91104097A patent/EP0452679A1/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU202904A1 (en) * | METHOD OF ELECTROCHEMICAL PREPARATION OF CHLORISTOOLOVA | |||
| DE2602031B1 (en) * | 1976-01-21 | 1977-04-21 | Goldschmidt Ag Th | METHOD FOR MANUFACTURING TINNII SULPHATE |
| US4330377A (en) * | 1980-07-10 | 1982-05-18 | Vulcan Materials Company | Electrolytic process for the production of tin and tin products |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4010052A1 (en) | 1991-10-02 |
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