EP0406929B1 - Process for removing thallium from lead - Google Patents
Process for removing thallium from lead Download PDFInfo
- Publication number
- EP0406929B1 EP0406929B1 EP90201550A EP90201550A EP0406929B1 EP 0406929 B1 EP0406929 B1 EP 0406929B1 EP 90201550 A EP90201550 A EP 90201550A EP 90201550 A EP90201550 A EP 90201550A EP 0406929 B1 EP0406929 B1 EP 0406929B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lead
- thallium
- chloride
- stirred
- iron
- 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.)
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- 229910052716 thallium Inorganic materials 0.000 title claims description 42
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 17
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 238000003756 stirring Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 5
- 238000007670 refining Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/06—Refining
- C22B13/08—Separating metals from lead by precipitating, e.g. Parkes process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/06—Refining
Definitions
- the invention relates to a method for removing thallium from lead by stirring in chlorides and withdrawing a salt slag containing thallium.
- Pyrometallurgically produced lead contains thallium in an amount which is dependent on the thallium content of the starting materials and the method of smelting.
- a large part of the thallium contained in the starting materials is volatilized and removed from the process with the fly dust.
- a part of the thallium then goes into the slag again in the shaft furnace, so that the lead contains only small amounts of thallium.
- the fly dusts are recirculated and the volatilized thallium is not discharged into the fly dusts.
- the lead produced in this process can contain up to about 250 ppm.
- Such a method of direct lead extraction is described for example in EP-PS 003 853.
- the thallium content of the lead has to be reduced to certain values.
- the object of the invention is to avoid the disadvantages of the known methods and to allow thallium to be largely removed from the lead in the most economical and technically simple manner possible.
- iron chloride is present in one stage in the lead at a temperature of about 460 to 510 ° C. in an amount of at least about 131.4 times the equivalent, based on the thallium, and in an amount of 0.1 up to 0.5% by weight - calculated as anhydrous FeCl2 and, based on the lead, is stirred into the lead and a salt slag containing thallium is drawn off.
- the iron chloride can consist of iron (II) chloride or a mixture of iron (II) chloride and iron (III) chloride. With higher thallium contents in the lead and when refining to very low thallium contents, the addition is made in the upper range.
- the iron chloride can be used in dry form or containing water of crystallization.
- the iron chloride is stirred into the molten lead and the lead is stirred according to the following the lead refining methods which are customary and known.
- the stirring time required to achieve the desired residual thallium content in the lead is determined empirically. It depends on the initial thallium content in the lead, the size of the refining vessel and the agitator.
- the salt slag formed can be removed liquid from the surface of the work lead or it can be stirred dry beforehand. A two-stage mode of operation is also possible.
- a preferred embodiment consists in that iron (II) chloride is stirred in.
- Iron II chloride has a higher decomposition temperature than iron III chloride and is less hygroscopic and has a much lower vapor pressure.
- FeCl2 is stirred in from the processing of waste acid from pickling baths.
- This iron chloride is largely available as FeCl2 x 4 H2O. This iron chloride is very suitable for removing the thallium and is an inexpensive waste product.
- a preferred embodiment is that after the iron chloride has been introduced, the working lead is stirred at a falling temperature.
- the iron chloride is first stirred in at a higher temperature of the work lead and then stirring is continued with a falling temperature of the work lead until the reaction has ended. This gives particularly good results.
- a preferred embodiment is that the iron chloride is used after vacuum dezincification of the lead. After vacuum dezincification, the lead has a very favorable temperature for the use of iron chloride. A low residual zinc content of the lead after vacuum dezincification to 0.1% Zn is advantageous for the reaction.
- a preferred embodiment consists in the fact that the salt slag which has been removed and contains iron chloride is used from the previous one-stage removal of thallium into a subsequent one-stage removal of thalium. This results in a salt slag with a relatively high thallium content, which makes processing for the production of thallium easier.
- the thallium can be obtained from the salt slags by known methods.
- the advantages of the invention are that extensive removal of the thallium is possible using a relatively cheap and easy-to-use additive, which also does not result in contamination of the lead.
- the addition amount leads to a good removal of the thallium from the lead, without using an unnecessarily large excess.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Entfernen von Thallium aus Werkblei durch Einrühren von Chloriden und Abzug einer Thallium enthaltenden Salzschlacke.The invention relates to a method for removing thallium from lead by stirring in chlorides and withdrawing a salt slag containing thallium.
Pyrometallurgisch erzeugtes Werkblei enthält Thallium in einer Menge, die vom Thallium-Gehalt der Einsatzstoffe und dem Verfahren der Verhüttung abhängig ist. Beim Schachtofen-Verfahren mit vorgeschalteter Sinter-Röstung wird ein großer Teil des in den Ausgangsmaterialien enthaltenen Thalliums Verflüchtigt und mit dem Flugstaub aus dem Verfahren entfernt. Im Schachtofen geht dann nochmals ein Teil des Thalliums in die Schlacke, so daß das Werkblei nur geringe Mengen an Thallium enthält. Bei den neueren Verfahren der direkten Bleigewinnung aus sulfidischen Erzen ohne vorhergehende separate Röstung werden die Flugstäube rezirkuliert, und die Ausschleusung von verflüchtigtem Thallium in den Flugstäuben entfällt. Das in diesen Verfahren erzeugte Werkblei kann bis zu etwa 250 ppm enthalten. Ein solches Verfahren der direkten Bleigewinnung ist zum Beispiel in der EP-PS 003 853 beschrieben. Je nach Anforderung an die Qualität des Feinbleis muß der Thallium-Gehalt des Werkbleis auf bestimmte Werte gesenkt werden.Pyrometallurgically produced lead contains thallium in an amount which is dependent on the thallium content of the starting materials and the method of smelting. In the shaft furnace process with upstream sintering roasting, a large part of the thallium contained in the starting materials is volatilized and removed from the process with the fly dust. A part of the thallium then goes into the slag again in the shaft furnace, so that the lead contains only small amounts of thallium. In the newer methods of direct lead extraction from sulfidic ores without prior separate roasting, the fly dusts are recirculated and the volatilized thallium is not discharged into the fly dusts. The lead produced in this process can contain up to about 250 ppm. Such a method of direct lead extraction is described for example in EP-PS 003 853. Depending on the requirements for the quality of the fine lead, the thallium content of the lead has to be reduced to certain values.
Aus V. Tafel "Lehrbuch der Metallhüttenkunde", 2. Auflage, 1953, Band 2, Seite 649, ist es bekannt, daß der Thallium-Gehalt von Werkblei durch Einrühren von Zinkchlorid gesenkt werden kann, wobei eine etwa 5 % T1, 11 % Zn, 1,4 % As und 7 % Cl enthaltende Chloridschmelze erzeugt wird, die stark mit metallischem Blei (50 %) vermischt ist.From V. Tafel "Textbook of Metallurgy", 2nd edition, 1953, Volume 2, page 649, it is known that the thallium content of lead can be reduced by stirring in zinc chloride, an approximately 5% T1, 11% Chloride melt containing Zn, 1.4% As and 7% Cl is produced, which is strongly mixed with metallic lead (50%).
Aus der JP-B-81/50 788 ist es ebenfalls bekannt, Thallium durch Einrühren von Zinkchlorid aus dem Werkblei zu entfernen. Zinkchlorid ist sehr hygroskopisch, stellt deshalb hohe Anforderungen an die Lagerung, und die Gefahr von Explosionen bei der Zugabe in das Werkblei ist groß. Außerdem wird der Zinkgehalt vom Werkblei aufgenommen und dieses dadurch verunreinigt bzw. ist nach der Thalliumentfernung eine Nachraffination erforderlich.From JP-B-81/50 788 it is also known to remove thallium from the lead by stirring in zinc chloride. Zinc chloride is very hygroscopic and therefore places high demands on storage, and there is a high risk of explosions when added to the lead. In addition, the zinc content is absorbed by the lead and contaminates it, or post-refining is necessary after the thallium removal.
Aus der JP-B-86/6134 ist es bekannt, Thallium durch Einrühren von Bleichlorid, Ammoniumchlorid oder einer Mischung beider Salze aus dem Werkblei zu entfernen. Ammoniumchlorid verflüchtigt sich jedoch schon bei relativ niedrigen Temperaturen. Bleichlorid ist sehr teuer, verdampft leicht und enthält nur einen geringen Cl-Anteil.From JP-B-86/6134 it is known to remove thallium from the lead by stirring in lead chloride, ammonium chloride or a mixture of both salts. However, ammonium chloride evaporates at relatively low temperatures. Lead chloride is very expensive, evaporates easily and contains only a small amount of Cl.
Der Erfindung liegt die Aufgabe zugrunde, die Nachteile der bekannten Verfahren zu vermeiden und eine weitgehende Entfernung von Thallium aus dem Werkblei in möglichst wirtschaftlicher und technisch einfacher Weise zu ermöglichen.The object of the invention is to avoid the disadvantages of the known methods and to allow thallium to be largely removed from the lead in the most economical and technically simple manner possible.
Die Lösung dieser Aufgabe erfolgt erfindungsgemäß dadurch, daß Eisenchlorid einstufig in das bei einer Temperatur von etwa 460 bis 510°C befindliche Werkblei in einer mindestens etwa 131,4- fachen Äquivalentmenge, bezogen auf den Thallium gehalt, und in einer Menge von 0,1 bis 0,5 Gew.-% - gerechnet als wasserfreies FeCl₂ und, bezogen auf das Werkblei - in das Werkblei eingerührt und eine Thallium enthaltende Salzschlacke abgezogen wird. Das Eisenchlorid kann aus Eisen-II-Chlorid oder einer Mischung aus Eisen-II-Chlorid und Eisen-III-Chlorid bestehen. Bei höheren Thallium-Gehalten des Werkbleis und bei einer Raffination auf sehr niedrige Thallium-Gehalte erfolgt die Zugabe im oberen Bereich. Geringe Gehalte an oder Zusätze von Bleichlorid, Zinkchlorid, Ammoniumchlorid oder Kupferchlorid sind möglich. Das Eisenchlorid kann in trockener Form oder Kristallwasser-haltig eingesetzt werden. Das Einrühren des Eisenchlorids in das geschmolzene Werkblei und das Rühren des Werkbleis erfolgt nach den bei der Blei-Raffination üblichen und bekannten Methoden. Die zur Erzielung des gewünschten Restgehaltes an Thallium im Werkblei erforderliche Rührzeit wird empirisch ermittelt. Sie ist abhängig vom Ausgangsgehalt an Thallium im Werkblei, von der Größe des Raffinierkessels und vom Rührwerk. Die gebildete Salzschlacke kann flüssig von der Oberfläche des Werkbleis entfernt werden oder sie kann vorher trocken gerührt werden. Es ist auch eine zweistufige Arbeitsweise möglich.This object is achieved in accordance with the invention in that iron chloride is present in one stage in the lead at a temperature of about 460 to 510 ° C. in an amount of at least about 131.4 times the equivalent, based on the thallium, and in an amount of 0.1 up to 0.5% by weight - calculated as anhydrous FeCl₂ and, based on the lead, is stirred into the lead and a salt slag containing thallium is drawn off. The iron chloride can consist of iron (II) chloride or a mixture of iron (II) chloride and iron (III) chloride. With higher thallium contents in the lead and when refining to very low thallium contents, the addition is made in the upper range. Low levels or additions of lead chloride, zinc chloride, ammonium chloride or copper chloride are possible. The iron chloride can be used in dry form or containing water of crystallization. The iron chloride is stirred into the molten lead and the lead is stirred according to the following the lead refining methods which are customary and known. The stirring time required to achieve the desired residual thallium content in the lead is determined empirically. It depends on the initial thallium content in the lead, the size of the refining vessel and the agitator. The salt slag formed can be removed liquid from the surface of the work lead or it can be stirred dry beforehand. A two-stage mode of operation is also possible.
Eine vorzugsweise Ausgestaltung besteht darin, daß Eisen-II-Chlorid eingerührt wird. Eisen-II-Chlorid hat gegenüber Eisen-III-Chlorid eine höhere Zersetzungstemperatur und ist weniger hygroskopisch und besitzt einen sehr viel niedrigeren Dampfdruck.A preferred embodiment consists in that iron (II) chloride is stirred in. Iron II chloride has a higher decomposition temperature than iron III chloride and is less hygroscopic and has a much lower vapor pressure.
Eine vorzugsweise Ausgestaltung besteht darin, daß FeCl₂ aus der Aufarbeitung von Abfallsäure aus Beizbädern eingerührt wird. Dieses Eisenchlorid liegt weitgehend als FeCl₂ x 4 H₂O vor. Dieses Eisenchlorid ist zur Entfernung des Thalliums sehr gut geeignet und stellt ein billiges Abfallprodukt dar.A preferred embodiment is that FeCl₂ is stirred in from the processing of waste acid from pickling baths. This iron chloride is largely available as FeCl₂ x 4 H₂O. This iron chloride is very suitable for removing the thallium and is an inexpensive waste product.
Eine vorzugsweise Ausgestaltung besteht darin, daß nach dem Einsetzen des Eisenchlorids das Rühren des Werkbleis mit fallender Temperatur erfolgt. Das Eisenchlorid wird zunächst bei höherer Temperatur des Werkbleis eingerührt und dann wird mit fallender Temperatur des Werkbleis bis zur Beendigung der Reaktion weitergerührt. Dadurch werden besonders gute Ergebnisse erzielt.A preferred embodiment is that after the iron chloride has been introduced, the working lead is stirred at a falling temperature. The iron chloride is first stirred in at a higher temperature of the work lead and then stirring is continued with a falling temperature of the work lead until the reaction has ended. This gives particularly good results.
Eine vorzugsweise Ausgestaltung besteht darin, daß das Eisenchlorid nach der Vakuum-Entzinkung des Werkbleis eingesetzt wird. Das Werkblei hat nach der Vakuum-Entzinkung eine sehr günstige Temperatur für den Einsatz des Eisenchlorids. Ein geringer Rest-Zinkgehalt des Werkbleis nach der Vakuum-Entzinkung bis 0,1 % Zn ist für die Reaktion vorteilhaft.A preferred embodiment is that the iron chloride is used after vacuum dezincification of the lead. After vacuum dezincification, the lead has a very favorable temperature for the use of iron chloride. A low residual zinc content of the lead after vacuum dezincification to 0.1% Zn is advantageous for the reaction.
Eine vorzugsweise Ausgestaltung besteht darin, daß die abgezogene, Eisenchlorid enthaltende Salzschlacke aus der vorhergehenden einstufigen Entfernung von Thallium in eine nachfolgende einstufige Entfernung von Thalium eingesetzt wird. Dadurch wird eine Salzschlacke mit relativ hohem Thallium-Gehalt erhalten, wodurch eine Aufarbeitung zur Gewinnung von Thallium erleichtert wird.A preferred embodiment consists in the fact that the salt slag which has been removed and contains iron chloride is used from the previous one-stage removal of thallium into a subsequent one-stage removal of thalium. This results in a salt slag with a relatively high thallium content, which makes processing for the production of thallium easier.
Das Thallium kann aus den Salzschlacken nach bekannten Verfahren gewonnen werden.The thallium can be obtained from the salt slags by known methods.
Aus der DE-OS 36 31 196 ist es bekannt, Thallium durch Zugabe von Metallchloriden bzw. Chlorgas in mehreren Stufen bei Temperaturen zwischen 350 und 450°C unter Anwendung eines geringen Gesamtüberschusses, bezogen auf den Thalliumgehalt, zu entfernen, wobei nach jeder Stufe die Metallschmelze von den entstandenen Thallium-haltigen Chloridschmelzen vollständig befreit wird. Für einen Endgehalt an Thallium von unter 10 ppm wird eine zwei- bis vierfache Äquivalentmenge an Chlorid, bezogen auf den stöchiometrischen Bedarf, zugesetzt. Als Metallchloride sollen viele Chloride zweiwertiger Metalle zugesetzt werden können, wie z.B. die des Magnesiums, Mangans, Eisens, Kobalts und Nickels. Diesen Chloriden wird jedoch keine wesentliche Bedeutung zugemessen, da vorzugsweise Zinkchlorid und Chlorgas eingesetzt werden - wobei sich mit dem Chlorgas dann Bleichlorid bildet - und da in den Beispielen nur Zinkchlorid bzw. eine Mischung von Zinkchlorid und Bleichlorid eingesetzt werden.From DE-OS 36 31 196 it is known to remove thallium by adding metal chlorides or chlorine gas in several stages at temperatures between 350 and 450 ° C using a small total excess, based on the thallium content, the after each stage Metal melt is completely freed from the resulting thallium-containing chloride melts. For one Final thallium content of less than 10 ppm, a two to four times the equivalent amount of chloride, based on the stoichiometric requirement, is added. Many chlorides of divalent metals, such as those of magnesium, manganese, iron, cobalt and nickel, are said to be able to be added as metal chlorides. However, no significant importance is attached to these chlorides, since zinc chloride and chlorine gas are preferably used - with lead chloride then forming with the chlorine gas - and since only zinc chloride or a mixture of zinc chloride and lead chloride are used in the examples.
Die Erfindung wird anhand von Ausführungsbeispielen näher erläutert.The invention is explained in more detail using exemplary embodiments.
147 kg Werkblei wurden in einem mit Rührwerk ausgerüsteten Versuchskessel eingeschmolzen und auf 460°C aufgeheizt. Das Blei enthielt 96 ppm Thallium und 380 ppm Zink. 900 g FeCl₂ x 4 H₂O wurden eingerührt. Nach 30 min. Rühren wurden 1,3 kg bleihaltige Salzschlacke mit 0,85 % Thallium abgezogen. Das Blei enthielt noch 3,2 ppm Thallium und <5 ppm Zink.147 kg of lead were melted in a test kettle equipped with an agitator and heated to 460 ° C. The lead contained 96 ppm thallium and 380 ppm zinc. 900 g FeCl₂ x 4 H₂O were stirred in. After 30 min. 1.3 kg of lead-containing salt slag with 0.85% thallium were drawn off while stirring. The lead still contained 3.2 ppm thallium and <5 ppm zinc.
140 kg Werkblei wurden in einem mit einem Rührwerk ausgerüsteten Versuchskessel eingeschmolzen und auf 470°C aufgeheizt. Das Blei enthielt 77 ppm Thallium und 320 ppm Zink. 920 g der Salzschlacke aus Beispiel 3 wurden eingerührt. Nach 30 min. Rühren wurden 950 g Salzschlacke mit 1,66 % Tl abgezogen. Das Blei enthielt 10 ppm Tl und <5 ppm Zink.140 kg of lead were melted in a test kettle equipped with an agitator and heated to 470 ° C. The lead contained 77 ppm thallium and 320 ppm zinc. 920 g of the salt slag from Example 3 were stirred in. After 30 min. 950 g of salt slag with 1.66% Tl were drawn off while stirring. The lead contained 10 ppm Tl and <5 ppm zinc.
Die Vorteile der Erfindung bestehen darin, daß eine weitgehende Entfernung des Thalliums möglich ist unter Verwendung eines relativ billigen und einfach zu handhabenden Zusatzstoffes, der außerdem keine Verunreinigung des Bleis ergibt. Die Zugabemenge führt zu einer guten Entfernung des Thalliums aus dem Werkblei, ohne daß ein unnötig großer Überschuß eingesetzt wird.The advantages of the invention are that extensive removal of the thallium is possible using a relatively cheap and easy-to-use additive, which also does not result in contamination of the lead. The addition amount leads to a good removal of the thallium from the lead, without using an unnecessarily large excess.
Claims (6)
- A process of removing thallium from lead bullion, wherein iron chloride in one stage at a temperature of about 460 to 510°C, in a quantity of at least about 131,4 equivalents, based on the quantity of thallium, and in a quantity of 0.1 to 0.5 % by weight, calculated as anhydrous FeCl₂, based on the lead bullion, is stirred into the lead bullion and the thallium-containing salt slag is skimmed off.
- A process according to claim 1, wherein iron (II) chloride is stirred into the lead bullion.
- A process according to claims 1 or 2, wherein FeCl₂ obtained by a processing of waste acids from pickling baths is stirred into the lead bullion.
- A process according to any of claims 1 to 3, wherein the lead bullion is stirred at a decreasing temperature when the iron chloride has been added.
- A process according to any of claims 1 to 4, wherein the iron chloride is added to the lead bullion after the latter has been dezinced in a vacuum.
- A process according to any of claims 1 to 5, wherein the iron chloride-containing salt slag which has been skimmed off in the previous removing of thallium in one stage is added in a following removing of thallium in one stage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3922073 | 1989-07-05 | ||
| DE3922073A DE3922073A1 (en) | 1989-07-05 | 1989-07-05 | METHOD FOR REMOVING THALLIUM FROM WORK LEAD |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0406929A1 EP0406929A1 (en) | 1991-01-09 |
| EP0406929B1 true EP0406929B1 (en) | 1995-03-22 |
Family
ID=6384337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90201550A Expired - Lifetime EP0406929B1 (en) | 1989-07-05 | 1990-06-15 | Process for removing thallium from lead |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0406929B1 (en) |
| KR (1) | KR910003127A (en) |
| CN (1) | CN1026800C (en) |
| BR (1) | BR9003188A (en) |
| CA (1) | CA2020412A1 (en) |
| DE (2) | DE3922073A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI115537B (en) * | 2003-03-14 | 2005-05-31 | Outokumpu Oy | Method for the removal of thallium from a solution containing zinc |
| CN104894373A (en) * | 2015-05-15 | 2015-09-09 | 株洲冶炼集团股份有限公司 | Method for removing thallium in zinc hydrometallurgy solution purification process |
| CN119663026B (en) * | 2025-02-24 | 2025-06-13 | 山西建邦集团铸造有限公司 | Method for efficiently recovering thallium in complex solution |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2956871A (en) * | 1958-02-10 | 1960-10-18 | American Smelting Refining | Vacuum dezincing of lead |
| SE412766B (en) * | 1978-06-29 | 1980-03-17 | Boliden Ab | PROCEDURE FOR THE MANUFACTURING AND REFINING OF RABLY FROM ARSENIC CONTRIBUTION |
| EP0099096A1 (en) * | 1982-07-14 | 1984-01-25 | Hoechst Aktiengesellschaft | Method of separating heavy metal ions from raw phosphate |
| IN159763B (en) * | 1982-07-16 | 1987-06-06 | Bnf Metals Tech Centre | |
| DE3631196A1 (en) * | 1986-09-13 | 1988-03-24 | Preussag Ag Metall | Process for removing thallium from crude lead and high-purity lead |
-
1989
- 1989-07-05 DE DE3922073A patent/DE3922073A1/en not_active Withdrawn
-
1990
- 1990-06-15 DE DE59008744T patent/DE59008744D1/en not_active Expired - Fee Related
- 1990-06-15 EP EP90201550A patent/EP0406929B1/en not_active Expired - Lifetime
- 1990-07-04 CN CN90106527A patent/CN1026800C/en not_active Expired - Fee Related
- 1990-07-04 CA CA002020412A patent/CA2020412A1/en not_active Abandoned
- 1990-07-04 KR KR1019900010084A patent/KR910003127A/en not_active Ceased
- 1990-07-05 BR BR909003188A patent/BR9003188A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1049380A (en) | 1991-02-20 |
| CN1026800C (en) | 1994-11-30 |
| CA2020412A1 (en) | 1991-01-06 |
| EP0406929A1 (en) | 1991-01-09 |
| DE3922073A1 (en) | 1991-01-17 |
| BR9003188A (en) | 1991-08-27 |
| DE59008744D1 (en) | 1995-04-27 |
| KR910003127A (en) | 1991-02-26 |
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