CA1225242A - High temperature softening of lead bullion - Google Patents
High temperature softening of lead bullionInfo
- Publication number
- CA1225242A CA1225242A CA000465820A CA465820A CA1225242A CA 1225242 A CA1225242 A CA 1225242A CA 000465820 A CA000465820 A CA 000465820A CA 465820 A CA465820 A CA 465820A CA 1225242 A CA1225242 A CA 1225242A
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- Prior art keywords
- bullion
- copper
- lead
- furnace
- softening
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- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
-
- 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
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A process for the refining of lead bullion containing lead and copper, plus one or more of the elements sulphur, arsenic, antimony, tin, silver, bismuth and other elements known to be contained in lead bullion is disclosed. The process comprises first desulphurizing and softening the lead bullion in a furnace at a temperature sufficiently high to prevent the formation of a separate copper contain-ing phase, and then cooling of the softened bullion in a kettle or furnace to a temperature near 330 C to form a dross or matte containing substantially all the copper originally contained in the bullion.
A process for the refining of lead bullion containing lead and copper, plus one or more of the elements sulphur, arsenic, antimony, tin, silver, bismuth and other elements known to be contained in lead bullion is disclosed. The process comprises first desulphurizing and softening the lead bullion in a furnace at a temperature sufficiently high to prevent the formation of a separate copper contain-ing phase, and then cooling of the softened bullion in a kettle or furnace to a temperature near 330 C to form a dross or matte containing substantially all the copper originally contained in the bullion.
Description
~:25i~4i~
HIGH TE~ER~TUPE SOFTENING Ox LEAD MULLION
This invention relates to the pyrometallur~ical refining of copper containing hard lead bullion, especially lead bullion, but not limited to bullion arising in the primary smelting of lead. This includes lead bullion derived from such primary processes such as fullest furnace process, flash furnace process, electric furnace smelting, or other primary or secondary lead bullion derived from such furnaces as the reverberatory furnace, short rotary furnace or the Top Blown Rotary Converter. Such lead bullion typically contains in addition to the elements lead and copper one or more of the elements Selfware, arsenic, antimony tin, silver, bismuth and other elements known to be contained in lead bullion.
The usual order to pyrometallurgical refining the above impure lead bullion so as to produce marketable refined lead and byproduct comprises the following major steps:
(a) Separation of elements or components which have limited sealability at the frying temperature ox the impure lead bullion. These operations are known as the dry drowsing and copper drowsing aerations, and quantitatively separate the copper and Selfware contained in the bullion, and depending on the bullion Z5 composition, a significant fraction of Thea arsenic, antimony and tin contained therein.
' I
HIGH TE~ER~TUPE SOFTENING Ox LEAD MULLION
This invention relates to the pyrometallur~ical refining of copper containing hard lead bullion, especially lead bullion, but not limited to bullion arising in the primary smelting of lead. This includes lead bullion derived from such primary processes such as fullest furnace process, flash furnace process, electric furnace smelting, or other primary or secondary lead bullion derived from such furnaces as the reverberatory furnace, short rotary furnace or the Top Blown Rotary Converter. Such lead bullion typically contains in addition to the elements lead and copper one or more of the elements Selfware, arsenic, antimony tin, silver, bismuth and other elements known to be contained in lead bullion.
The usual order to pyrometallurgical refining the above impure lead bullion so as to produce marketable refined lead and byproduct comprises the following major steps:
(a) Separation of elements or components which have limited sealability at the frying temperature ox the impure lead bullion. These operations are known as the dry drowsing and copper drowsing aerations, and quantitatively separate the copper and Selfware contained in the bullion, and depending on the bullion Z5 composition, a significant fraction of Thea arsenic, antimony and tin contained therein.
' I
2 -(b) Separation of elements less noble than the element lead. This operation is commonly known as softening, and quantitatively through oxidation by various means, removes the elements arsenic, antimony and tin.
(c) Separation of elements more noble than lead.
This usually comprises two distinct operations, the Parses des-lverl~ing process, and the Kroll-Betterton debismuthizing process.
When arsenic, Selfware, or antimony are present in the lead bullion, as is universally the case in bullion origin noting from a primary source, there is contamination of the dry and copper drowses with these elements when the conventional flow sheet is followed, Furthermore, in situations where the amount of copper in the bullion is low compared to the amount of Selfware arsenic and antimony, smelting of the dry and copper drowses to upgrade the copper content thereof will produce a copper product having a low Curb ratio and being high in arsenic. The lead smelter, on selling this copper product to a copper processor, receives a greatly reduced return on this copper due to penalties imposed on the lead and arsenic contained in the copper product, as well as losing the lead in the copper product for which little return is paid.
The inventors have discovered a process which reduces contamination of the dry and copper drowses with arsenic, Selfware or antimony resulting in a greatly improved Curb ratio in the copper matte, and in significant :~22~i~42 reductions in the arsenic contained therein. This marked improvement is achieved reversing the order of the drowsing and softening operations, that is, to soften the bullion as the first refining step, followed my the dry and copper drowsing.
The process in accordance with the present invention comprises the steps of first desulphurizing and softening the lead bullion in a furnace at a temperature sufficient high to prevent the formation of a separate copper lo containing phase, and then cooling the softened bullion in a kettle or furnace to a temperature near 330~C to form a dross or matte containing substantially all the copper originally contained in the bullion.
In softening the lead mullion prior to drowsing, a major fraction of the Selfware, arsenic, antimony, and tin contained in the bullion is removed, thus a relatively small amount of the initial Selfware, arsenic, antimony, or tin originally contained in the bullion will report to the dry and copper drowses in the subsequent drowsing operation.
To upgrade the copper tenor of these drowses and to recover much of the lead and silver container therein for return to the lead refining circuit, the copper drowses are preferably smelted with additions of soda ash and coke in a reverberatory furnace. The copper matte so produced has a Curb ratio which is higher than the conventional repining technique and-contains a lower amount of arsenic thus making this copper matte more attractive for treatment in a copper sr,lelterO
I
The smelter bullion is desulphurized and softened by the injection of an oxygen containing yes mixture containing between 5 and 100% oxygen. Lethargy or a high lead oxide containing slag may also be used.
In addition to maintaining the bulk of the softening furnace bath low in Selfware, arsenic and antimony, it is preferable that the bullion be well mixed and that it be operated in a continuous mode. By the use of the term continuous mode of operation", it is understood that both toe inflow of smelter bullion, and the outflow of softened bullion and slag can be continuous or semi continuous (interrupted) as required my practical operating procedures. The term continuous mode of oration" also includes watch additions of lead bullion to the furnace where the size of the batch addition is less than one fifth of the size of the - furnace bath.
Materials containing copper and/or lead, and containing one or more of the following: Selfware, 20 arsenic, antimony or tin, can also be added to the softening furnace in addition to the smelter bullion.
The invention will now be disclosed, by way of example, with reference to the accompanying drawings in which:
Figure 1 shows the conventional flow sheet for the refining of smelter bullion;
Figure 2 is the three component phase digger illustrating the miscibility gap of the Cut Phi 122~
S system at 1200qC;
Figure 3 IS the three component phase diagram illustrating the miscibility gap of the Cut Pub, As system at 1200 Q C i Figure 4 is a flow sheet of a high temperature softening process for the refining of smelter bullion in accordance with the present invention, and Figure 5 is a diagram illustrating the lead corner of the Cut Pub, S system and showing the Ihinimum temperature which must be maintained with the sigh temperature softening furnace in order to prevent the formation of metallic copper, copper sulfide, or copper matte for a range of copper and Selfware compositions.
Referring to Figure l which shows the conventional flow sheet for the refining of smelter bullion, the first step in the operation is step 10 known as the dry drowsing and copper drowsing which is normally done in kettles or other suitable furnaces. In the dry drowsing step, copper, Selfware, arsenic and lead are precipitate from the lead bullion through the following reactions:
2 Cut US > Cut S I
(c) Separation of elements more noble than lead.
This usually comprises two distinct operations, the Parses des-lverl~ing process, and the Kroll-Betterton debismuthizing process.
When arsenic, Selfware, or antimony are present in the lead bullion, as is universally the case in bullion origin noting from a primary source, there is contamination of the dry and copper drowses with these elements when the conventional flow sheet is followed, Furthermore, in situations where the amount of copper in the bullion is low compared to the amount of Selfware arsenic and antimony, smelting of the dry and copper drowses to upgrade the copper content thereof will produce a copper product having a low Curb ratio and being high in arsenic. The lead smelter, on selling this copper product to a copper processor, receives a greatly reduced return on this copper due to penalties imposed on the lead and arsenic contained in the copper product, as well as losing the lead in the copper product for which little return is paid.
The inventors have discovered a process which reduces contamination of the dry and copper drowses with arsenic, Selfware or antimony resulting in a greatly improved Curb ratio in the copper matte, and in significant :~22~i~42 reductions in the arsenic contained therein. This marked improvement is achieved reversing the order of the drowsing and softening operations, that is, to soften the bullion as the first refining step, followed my the dry and copper drowsing.
The process in accordance with the present invention comprises the steps of first desulphurizing and softening the lead bullion in a furnace at a temperature sufficient high to prevent the formation of a separate copper lo containing phase, and then cooling the softened bullion in a kettle or furnace to a temperature near 330~C to form a dross or matte containing substantially all the copper originally contained in the bullion.
In softening the lead mullion prior to drowsing, a major fraction of the Selfware, arsenic, antimony, and tin contained in the bullion is removed, thus a relatively small amount of the initial Selfware, arsenic, antimony, or tin originally contained in the bullion will report to the dry and copper drowses in the subsequent drowsing operation.
To upgrade the copper tenor of these drowses and to recover much of the lead and silver container therein for return to the lead refining circuit, the copper drowses are preferably smelted with additions of soda ash and coke in a reverberatory furnace. The copper matte so produced has a Curb ratio which is higher than the conventional repining technique and-contains a lower amount of arsenic thus making this copper matte more attractive for treatment in a copper sr,lelterO
I
The smelter bullion is desulphurized and softened by the injection of an oxygen containing yes mixture containing between 5 and 100% oxygen. Lethargy or a high lead oxide containing slag may also be used.
In addition to maintaining the bulk of the softening furnace bath low in Selfware, arsenic and antimony, it is preferable that the bullion be well mixed and that it be operated in a continuous mode. By the use of the term continuous mode of operation", it is understood that both toe inflow of smelter bullion, and the outflow of softened bullion and slag can be continuous or semi continuous (interrupted) as required my practical operating procedures. The term continuous mode of oration" also includes watch additions of lead bullion to the furnace where the size of the batch addition is less than one fifth of the size of the - furnace bath.
Materials containing copper and/or lead, and containing one or more of the following: Selfware, 20 arsenic, antimony or tin, can also be added to the softening furnace in addition to the smelter bullion.
The invention will now be disclosed, by way of example, with reference to the accompanying drawings in which:
Figure 1 shows the conventional flow sheet for the refining of smelter bullion;
Figure 2 is the three component phase digger illustrating the miscibility gap of the Cut Phi 122~
S system at 1200qC;
Figure 3 IS the three component phase diagram illustrating the miscibility gap of the Cut Pub, As system at 1200 Q C i Figure 4 is a flow sheet of a high temperature softening process for the refining of smelter bullion in accordance with the present invention, and Figure 5 is a diagram illustrating the lead corner of the Cut Pub, S system and showing the Ihinimum temperature which must be maintained with the sigh temperature softening furnace in order to prevent the formation of metallic copper, copper sulfide, or copper matte for a range of copper and Selfware compositions.
Referring to Figure l which shows the conventional flow sheet for the refining of smelter bullion, the first step in the operation is step 10 known as the dry drowsing and copper drowsing which is normally done in kettles or other suitable furnaces. In the dry drowsing step, copper, Selfware, arsenic and lead are precipitate from the lead bullion through the following reactions:
2 Cut US > Cut S I
3 Cut was Cut us I
Pub US Pus (3) The above reactions occur simultaneously as the smelter bullion is cooled from temperatures above Luke to a temperature near 33QC. The lead Balinese vigorously stirred during cooling, forming a dry dross which contains the compounds Cut S, Cut As, ail Pus, minor amounts of antimony compounds, oxide compounds Lowe in501uable in the lead mullion, as well as large amounts of entangled lead, and significant amounts, in terms of value, of silver after dry drowsing, the lead mullion retains a . 05% copper, which. is removed through the copper drowsing operation in which Selfware is stirred into the hellion at a rate of lo Cooper tone ox lead, reducing the copper level to under 0.01~. This second copper dross contains Pus, Cut S and large amounts of entangled lead.
Typical compositions of dry and copper drowses in tot% are:
Cut Pi S As Sub A
Dry Dross 11 73 5 508 0.3 0.1 Copper Dross 3 88 1.0 0.5 0.3 To upgrade the copper tenor of these drowses, and to recover much of the lead and silver contained therein for return to the lead refining circuit, the copper drowses are smelted with additions of soda ash and coke in a reverberatory furnace lo. Up to four phases may coexist within the. copper furnace, a slag phase in which oxide compounds not reduced during smelting report, a matte phase in which the copper and lead sulfides compounds report, a spouse phase in which the lead and-copper arsenide report, and the mullion phase in which the liberated lead and silver report. The matte and spouse are the major copper bearing phases which are recovered in the form of a granulated copper matte.
~L;2252~
The smelter hellion can alternatively ye drowsed and the copper removed as a matte phase in a continuous drowsing furnace, which combines the dry drowsing and dross smelting steps into a single unit, as is described my Ho Peck and JO McNicol in the Journal of Metals.
Sol. 18, page lQ27 to 1032.
The decopperized bullion is then subjected to a so-called softening operation 14 wherein, through oxidation by various means, arsenic, antimony and tin are removed. The softening slag is sent to an antimony reverberatory furnace 16 for the recovery of a high antimony slag. The antimony furnace bullion is returned to the lead refining circuit.
The softened lead bullion is subsequently subjected to two distinct known operations, the Parses dissolvers-in operation 18 followed by the Kroll-Betterton debismuthizing operation 20. A dezincing operation (not shown) is requited between the Parses and ~roll-Betterton process to remove the zinc introduced during desilveri~in~.
Finally, a final clean-up operation is necessary to remove the calcium and magnesium introduced during de~ismuthizing prior to casting of the lea, as shown as step 22 in Figure I
The trade of the copper matte phase produce in furnace 12, that is the Curb ratio, is dependent upon the amount of Selfware contained in the dross, as is predicted by the copper, lead, Selfware pus diagram shown in Figure 2. Because of the direction of the tie-lines between the matte and bullion compositions which are in equilibrium with each other, those skilled in the field of metallurgy will understand that the Curb ratio, or grade of copper matte, will decrease with increasing amounts of Selfware in the dross Thus to maximize the Curb ratio of the matte, the Selfware content of the dross must be minimized.
A similar situation exists in the copper, lead, arsenic system, shown in the phase diagram, Figure 3.
Those skilled in the field of metallurgy will recognize that the Cu/Pb-ratio of the spouse will decrease as the arsenic content of the dross increases. Thus it is essential to limit the arsenic contained in the dross in order to produce a spouse of high Curb ratio.
When arsenic, Selfware, or antimony are present in the smelter bullion, as is universally the case in bullion originating from a primary source,- there will be contamination of the dry and copper drowses with these elements when the conventional flow sheet, as outlined in Figure 1, is followed. In situations where the amount of copper in the bullion is low compared to the amount of Selfware arsenic and antimony, smelting of the dry and copper drowses will produce a copper product, that is a matte plus spouse mixture having a low-Cu/Pb ratio and being high in arsenic. The lead smelter, on selling this copper product to a copper processor, receives a greatly reduced return on this copper due to penalties imposed on the lead and arsellic contained in the copper product, as well as losing the lead in the copper product for jowl i Oil little return is paid.
~225i~
g The inventors have discovered a process resulting in a greatly improved Curb ratio in the copper matte, and Lo significant reductions in toe arsenic contained therein. This marked improvement is achieved by reversing the order of the drowsing and softening operations, that is, to soften the mullion as the first refining step, followed by the dry and copper drowsing, as is outlined in the flow sheet in Figure 4. In softening the smelter mullion prior to drowsing as shown in step 30 of the flyweight, a major fraction of the Selfware, arsenic, antimony and tin contained-in the bullion is removed, thus a relatively small amount of the initial Selfware, arsenic, antimony or tin originally contained in the mullion will report to the dry and copper drowses in the subsequent drowsing operation.
The term "sigh Temperature Softening" will ye used heron to describe the process of softening prior to copper drowsing as is outlined in Figure 4.
In High Temperature Softening it is necessary to maintain the lead bullion sufficiently hot to prevent the precipitation of copper compounds, specifically metallic copper, Cut S anger copper containing matte, and Cut As and/or copper containing spouse. The temperature required to maintain these compounds in solution within the lead bullion will depend on the copper, Selfware and arsenic content of the bulk bullion within the softening furnace. A so_tenlng temperature of 800C will ye sufficient to maintain in solution 2 wit% Cut at all levels . , ~225~
of arsenic, up to and including 4 White As in bullion.
The presence of Selfware on the bullion however severely restricts the volubility of copper by the formation of insoluble Cut S and copper lead mattes. The limits of copper volubility in Selfware containing bullion at various temperatures can be determined with the aid of Figure 5, which describes the lead corner of the Pb-Cu-S
system This figure demonstrates that to maintain 2 White Cut dissolved in the bullion at 80QC far example, the lead bullion must contain less than 0.10 wit% Selfware while within the softening process.
Because of the higher softening temperatures required to maintain the copper in solution, High Temperature Softening is preferability conducted in a refractory - 15 lined or water jacketed furnace; Such furnaces may be of the type where the process air is introduced through a single or plurality of lances, such as a reverberatory type furnace as is described in USE Patent no. 2,043,524, or a Top Blown Rotary Converter, or a type of furnace where air is introduced through Tories set below the bullion lines such as a Peirce~Smith converter, or any of a variety of bottom blown vessels.
Further, due to the necessity of maintaining the bulk of the furnace bethel in Selfware, arsenic and antimony, it is preferable but not necessary that the High Temperature Softening furnace be well mixed and that it be operated in a Continuous mode. By the use of the term "continuous mode of operation", it is understood that both the inflow of smelter hellion, and the outflow a softened bullion and slag can be continuous or semi-continuous Interrupted as required by practical operating procedures. The term Continuous mode of operation" also includes batch additions of smelter bullion to the furnace, where, the size of the batch addition is less than one fifth of the size of the furnace bath.
In a well mixed furnace, operated in a continuous mode, the composition of the bulk of the bullion bath is the same as the output softened bullion composition, which is low in Selfware, arsenic, antimony and tin.
- Only in the area adjacent to the point of smelter bullion input will the bullion composition be elevated in Selfware, arsenic, antimony and tin content. It is therefore possible to maintain up to 2 wit% copper dissolved in the bullion at temperature as low as 8Q0C, independent ox the Selfware arsenic, antimony and tin content of the input smelter bullion.
It is preferable, jut not necessary, that the temperature of the smelter bullion being charged into the High Temperature Softening furnace, ye above the temperature at which the copper precipitates from the bullion as a matte an spouse phase. However, should the input felon contain some copper matte or spouse, the I softening reactions can consume this matte or spouse, returning tune copper to the bullion phase.
~225i2~
The smelter bullion it softened through oxidation by an oxygen containing gas which may vary from between 5 and 100~ oxen. Toe reactions which occur during the oxidation process are listed below:
Pow Qn~l/2 2 Pbslag (4) ZPbOsla~ * mullion 2Pbbullion S2sa 3PbOslag+ mullion Boolean As203slag I
.3æb0slag~2 Jo ion 3PbbUllion 5b203slag I
ZPbOslag~ Sty 2 mullion 2P~bullion+ S2gas (8) 2Pboslag+pbsmatte 3P~bullion + S2gas Lo) In a continuous High Temperature Softening furnace, with a well mixed bath, the lead bullion within the furnace is low in sulphur,arsenic) antimony and tin and therefore there is a very low probability for these elements to react directly with-the introduced oxygen. The introduced oxygen instead reacts with the lead, as per reaction I
forming lead oxide which enters the slag. This lead oxide acts as the oxygen transfer medium through which the bullion is softened by reactions (5), (6), and I Should any matte be introduced to the sigh Temperature Softening furnace through the addition of cool smelter bullion, this matte would also be consumed by reaction between the lead oxide in the slag as described in reactions (8) and I
The smelter bullion may also be softened by the addition of lethargy or a high lead oxide containing slag to the high temperature softening furnace.
issue The softening slag is transferred to a conventional slag reduction furnace 32 where the slag is reduced to produce a high antimony slag product and a hard bullion for recycle to the high temperature softening furnace.
The softened bullion is then subjected to a dry drowsing and copper drowsing operation 34 identical to the corresponding operation in the flow sheet of Figure 1 and the copper drowses treated in a copper reverberatory furnace 36 also identical to the one used in the flow-sheet of Figure 1 to produce a granulated copper matte and a bullion which is returned Jo the dry and copper drowsing furnace.
The last two steps 38 and 40 in the flow sheet of Figure 4 are identical to the corresponding steps in Figure 1 of the drawings.
The object of this invention will be illustrated - through the following example. At the Smelting Division of Brunswick lining and Smelting Corporation Limited, Baldwin, New Brunswick, a 15 day pilot High Temperature Softening test was conducted in which 3118 tones Of blast furnace bullion were treated. The softening was conducted in rectangular refractory lined reverberatory furnace of internal dimension 5.2 m x 2.1 m. The furnace lead capacity was approximately 50 tones. Air was introduced into the bullion through five 3~4" nominal schedule 40 steel lances passing through the roof of the reverberatory furnace, and immersed 5 cm beneath the bullion surface.
14 - ~.22~2 e blowing rate was adjusted to maintain a target level ox 0~05 to 0,06 wit%. Sub in the softened bullion, - and ranged between 340 and aye Nm3/hr. The temperature of the bullion within the High Temperature Softening furnace was maintained between 830 to 880~C, through the use of draught control or a supplementary neat burner.
The blast furnace bullion was transferred from the blast furnace to the High Temperature Softening furnace lo in pots of approximately 7 tones capacity at intervals of approximately 45 minutes. The blast furnace bullion was charged through a charge cone located centrally in the High Temperature Softening furnace. The. in flowing bullion displaced the softened bullion through a bullion under flow, and at the same time the softening slag was displaced through a slag overflow slot.
The operation of the High Temperature Softening furnace is considered as continuous as the weight of the incoming bullion pots wassail in comparison to the weight of bullion in the furnace, and the composition of toe lead in the High Temperature Softening furnace .
did not charge significantly after addition of a pot of lead Due to the large distance between the blast furnace and the High Temperature Softening furnace, there was a significant time delay in transferring the blast furnace bullion to the High Temperature Softening furnace, allowing the blast furnace bullion to cool to under 800~C, and resulting in a matte crust formation 12~
on the transfer pots. On addition ox this matte crust to the sigh Temperature Softening furnace, the matte was quickly consumed through reactions (,8) and (9).
Had the High Temperature Softening furnace been in close proximity to the blast furnace, the blast furnace bullion Gould have entered the softening furnace at a temperature above the matte formation temperature, thus desulphurization of the bullion would have occurred exclusively through reaction I
'The analyses of the in flowing and outflowing streams, as well as the element distributions are shown in Table I.
TAO I
IiIGIi TEMPERATURE S~FTE2iING'~SS BALANCE
Input - to = _ _ S --Sub ¦ A ¦
Blast Howe mullion 3118 wit % 1.61 95.6 0.42 1.53 0.39 1 ~.146 owe .
Bullion 2641 it % 1.50 97.7 0.15 0.086 0.059 0.17 % dust. 78.6 86.6 30.3 4.5 13.4 99.6 Song Slag 502 wit % 2.15 76.8 0.84 9.42 1.99 0.0~3 dust. 21.4 13.0 32.2 93./ 85.7 0.3 Fume 17 -it % ~'.QZ 73.5 5.3 0.65 0.005 dust. 0.0 0.4 37.6 1.8 I 0.0 _ issue The softened bullion produced in the above described pilot High Temperature Softening test tray drowsed as per conventional kettle drowsing practice. The dry drowsing was conducted in kettles of 2~0 short ton nominal capacity, in which was maintained a minimum of a 90 tone decopperized bullion heel. For each 90 tone of softened mullion decopperized, 500 kg of soda ash was added to the drowsing kettles. The drowsing kettles were continuously stirred during the addition of softened bullion.
lo The drowsing of the softened bullion resulted in - several advantages over the direct drowsing of blast furnace bullion. These included: I) the formation of a powdery, free flowing dry dross, completely free of large matte and spouse lumps, and suitable for vacuum dross pick-up; it the absence of rim build-up in the kettles; and lit a large reduction in arsenic fume during transfer and pouring of the softened bullion into the drowsing kettles.
Following the dry drowsing, tlhich reduced the copper content of the bullion to 0.05%, the bullion was subjected to a conventional copper drowsing, reducing the copper content of the bullion to under Us through Selfware additions.
The dry drowsing of the softened bullion reduced the residual Selfware, arsenic and antimony contents of the High Temperature Softened bullion to sufficiently low levels so that no problems with mushy or difficult to separate crust formation occurred during desilverizing ,. . . .
~L225.~L2 with the Parses process, or debismuthizing with -the Kroll-Betterton process.
The mass balance for the dry and copper drowsing of the High Temperature Softened mullion is shown in Table II below:
TABLE II
-COPPER DROWSING OF SOFTENED BULLION
Texas 01 ,5 __ _ _. . _ Input Softened mullion 2641 wit % 1.50 97~7 0.15 0.086 0.059 0.176 output Al ~cmæosite 360 wit 11.0 77.7 3.3 0.96 Q.45 0.12 % dust. 99.5 10.8 79.0 89.9 7.9 Drowsed Bullion 2314 wit % 0.009 99.4 0.04 0.008 0.22 _ % dust. 0.5 a . 2 _ 21.0 10.1 92.1 The copper dross obtained from the softened bullion was smelted in a conventional dross smelting reverberatory .
furnace, producing a copper product high in Curb ratio and low in arsenic. This copper product consisted of primarily matte with a small amount of copper furnace slag and a trace amount of spouse. The copper dross was smelted with approximately 5% Lye weight of lump coke, and no soda ash other than that added during the drowsing operation. The copper dross produced from crossing the softened bullion smelted rapidly, producing a fluid matte and slag, and producing no build-ups within the dross smelting furnace, , ~Z~5~
as is frequently the case in smelting the dross from blast furnace mullion.
The mass balance for the dross smelting operation is shown in Table IT below:
TABLE III
Smelting OF COPPE~;DR3SS PLED FRY SOWED BULLION
no tcnnes = Cut by 5 _ 5 A
Copper Dross . .
Compost wit % 11.~0 77.7 3.3 0.36 Owe 0.12 Outputs Gcroa~rted , .
Product 65 wit % 57.7 14.3 18.5 1.00 0.039 Copper % dust. 95.6 3.3 34.6 6.3 Furnace Boolean. tot % 0.63 98.3 0.06 0 14 Guy % dust. 4.3 99.7 8.6 93 5 Fume 17 wit % 0.18 32.5 6.3 0.12 0 003 _ dust. 0.1 2.0 _ 56.9 _ 0.1 ~5~4~
The copper matte obtained through the High Temperature Softening flow sheet, as outlined in Figure 4, has a Curb ratio of over 4, and only 1% arsenic in the matte.
Following the conventional flow sheet, as outlined in Figure 1, the Smelting Division of Brunswick Mining and Smelting, produced from blast furnace bullion of similar composition as used in the above example, a copper product having a Curb ratio of OWE to 1.75, and containing 7.5% As, with 0.11~ Ago Per unit weight of lo copper produced, the Sigh Temperature Softening flow sheet, Figure 4, reduces the lead contained in the copper product by a factor of 2, the arsenic contained by a factor of 10 and the silver contained by a factor of 3. These lower lead and arsenic contents, per unit of copper, make this copper matte more -attractive for treatment in a copper smelter, thus- reduced penalties are imposed on this material, increasing the return to the -lead smelter.
Those familiar with the field of metallurgy will understand that the High Temperature Softening process can also be used to upgrade copper materials containing lead, Selfware, arsenic, antimony or tin by adding such materials into the High Temperature Softening furnace in either a solid or liquid form along with the smelter bullion.
Pub US Pus (3) The above reactions occur simultaneously as the smelter bullion is cooled from temperatures above Luke to a temperature near 33QC. The lead Balinese vigorously stirred during cooling, forming a dry dross which contains the compounds Cut S, Cut As, ail Pus, minor amounts of antimony compounds, oxide compounds Lowe in501uable in the lead mullion, as well as large amounts of entangled lead, and significant amounts, in terms of value, of silver after dry drowsing, the lead mullion retains a . 05% copper, which. is removed through the copper drowsing operation in which Selfware is stirred into the hellion at a rate of lo Cooper tone ox lead, reducing the copper level to under 0.01~. This second copper dross contains Pus, Cut S and large amounts of entangled lead.
Typical compositions of dry and copper drowses in tot% are:
Cut Pi S As Sub A
Dry Dross 11 73 5 508 0.3 0.1 Copper Dross 3 88 1.0 0.5 0.3 To upgrade the copper tenor of these drowses, and to recover much of the lead and silver contained therein for return to the lead refining circuit, the copper drowses are smelted with additions of soda ash and coke in a reverberatory furnace lo. Up to four phases may coexist within the. copper furnace, a slag phase in which oxide compounds not reduced during smelting report, a matte phase in which the copper and lead sulfides compounds report, a spouse phase in which the lead and-copper arsenide report, and the mullion phase in which the liberated lead and silver report. The matte and spouse are the major copper bearing phases which are recovered in the form of a granulated copper matte.
~L;2252~
The smelter hellion can alternatively ye drowsed and the copper removed as a matte phase in a continuous drowsing furnace, which combines the dry drowsing and dross smelting steps into a single unit, as is described my Ho Peck and JO McNicol in the Journal of Metals.
Sol. 18, page lQ27 to 1032.
The decopperized bullion is then subjected to a so-called softening operation 14 wherein, through oxidation by various means, arsenic, antimony and tin are removed. The softening slag is sent to an antimony reverberatory furnace 16 for the recovery of a high antimony slag. The antimony furnace bullion is returned to the lead refining circuit.
The softened lead bullion is subsequently subjected to two distinct known operations, the Parses dissolvers-in operation 18 followed by the Kroll-Betterton debismuthizing operation 20. A dezincing operation (not shown) is requited between the Parses and ~roll-Betterton process to remove the zinc introduced during desilveri~in~.
Finally, a final clean-up operation is necessary to remove the calcium and magnesium introduced during de~ismuthizing prior to casting of the lea, as shown as step 22 in Figure I
The trade of the copper matte phase produce in furnace 12, that is the Curb ratio, is dependent upon the amount of Selfware contained in the dross, as is predicted by the copper, lead, Selfware pus diagram shown in Figure 2. Because of the direction of the tie-lines between the matte and bullion compositions which are in equilibrium with each other, those skilled in the field of metallurgy will understand that the Curb ratio, or grade of copper matte, will decrease with increasing amounts of Selfware in the dross Thus to maximize the Curb ratio of the matte, the Selfware content of the dross must be minimized.
A similar situation exists in the copper, lead, arsenic system, shown in the phase diagram, Figure 3.
Those skilled in the field of metallurgy will recognize that the Cu/Pb-ratio of the spouse will decrease as the arsenic content of the dross increases. Thus it is essential to limit the arsenic contained in the dross in order to produce a spouse of high Curb ratio.
When arsenic, Selfware, or antimony are present in the smelter bullion, as is universally the case in bullion originating from a primary source,- there will be contamination of the dry and copper drowses with these elements when the conventional flow sheet, as outlined in Figure 1, is followed. In situations where the amount of copper in the bullion is low compared to the amount of Selfware arsenic and antimony, smelting of the dry and copper drowses will produce a copper product, that is a matte plus spouse mixture having a low-Cu/Pb ratio and being high in arsenic. The lead smelter, on selling this copper product to a copper processor, receives a greatly reduced return on this copper due to penalties imposed on the lead and arsellic contained in the copper product, as well as losing the lead in the copper product for jowl i Oil little return is paid.
~225i~
g The inventors have discovered a process resulting in a greatly improved Curb ratio in the copper matte, and Lo significant reductions in toe arsenic contained therein. This marked improvement is achieved by reversing the order of the drowsing and softening operations, that is, to soften the mullion as the first refining step, followed by the dry and copper drowsing, as is outlined in the flow sheet in Figure 4. In softening the smelter mullion prior to drowsing as shown in step 30 of the flyweight, a major fraction of the Selfware, arsenic, antimony and tin contained-in the bullion is removed, thus a relatively small amount of the initial Selfware, arsenic, antimony or tin originally contained in the mullion will report to the dry and copper drowses in the subsequent drowsing operation.
The term "sigh Temperature Softening" will ye used heron to describe the process of softening prior to copper drowsing as is outlined in Figure 4.
In High Temperature Softening it is necessary to maintain the lead bullion sufficiently hot to prevent the precipitation of copper compounds, specifically metallic copper, Cut S anger copper containing matte, and Cut As and/or copper containing spouse. The temperature required to maintain these compounds in solution within the lead bullion will depend on the copper, Selfware and arsenic content of the bulk bullion within the softening furnace. A so_tenlng temperature of 800C will ye sufficient to maintain in solution 2 wit% Cut at all levels . , ~225~
of arsenic, up to and including 4 White As in bullion.
The presence of Selfware on the bullion however severely restricts the volubility of copper by the formation of insoluble Cut S and copper lead mattes. The limits of copper volubility in Selfware containing bullion at various temperatures can be determined with the aid of Figure 5, which describes the lead corner of the Pb-Cu-S
system This figure demonstrates that to maintain 2 White Cut dissolved in the bullion at 80QC far example, the lead bullion must contain less than 0.10 wit% Selfware while within the softening process.
Because of the higher softening temperatures required to maintain the copper in solution, High Temperature Softening is preferability conducted in a refractory - 15 lined or water jacketed furnace; Such furnaces may be of the type where the process air is introduced through a single or plurality of lances, such as a reverberatory type furnace as is described in USE Patent no. 2,043,524, or a Top Blown Rotary Converter, or a type of furnace where air is introduced through Tories set below the bullion lines such as a Peirce~Smith converter, or any of a variety of bottom blown vessels.
Further, due to the necessity of maintaining the bulk of the furnace bethel in Selfware, arsenic and antimony, it is preferable but not necessary that the High Temperature Softening furnace be well mixed and that it be operated in a Continuous mode. By the use of the term "continuous mode of operation", it is understood that both the inflow of smelter hellion, and the outflow a softened bullion and slag can be continuous or semi-continuous Interrupted as required by practical operating procedures. The term Continuous mode of operation" also includes batch additions of smelter bullion to the furnace, where, the size of the batch addition is less than one fifth of the size of the furnace bath.
In a well mixed furnace, operated in a continuous mode, the composition of the bulk of the bullion bath is the same as the output softened bullion composition, which is low in Selfware, arsenic, antimony and tin.
- Only in the area adjacent to the point of smelter bullion input will the bullion composition be elevated in Selfware, arsenic, antimony and tin content. It is therefore possible to maintain up to 2 wit% copper dissolved in the bullion at temperature as low as 8Q0C, independent ox the Selfware arsenic, antimony and tin content of the input smelter bullion.
It is preferable, jut not necessary, that the temperature of the smelter bullion being charged into the High Temperature Softening furnace, ye above the temperature at which the copper precipitates from the bullion as a matte an spouse phase. However, should the input felon contain some copper matte or spouse, the I softening reactions can consume this matte or spouse, returning tune copper to the bullion phase.
~225i2~
The smelter bullion it softened through oxidation by an oxygen containing gas which may vary from between 5 and 100~ oxen. Toe reactions which occur during the oxidation process are listed below:
Pow Qn~l/2 2 Pbslag (4) ZPbOsla~ * mullion 2Pbbullion S2sa 3PbOslag+ mullion Boolean As203slag I
.3æb0slag~2 Jo ion 3PbbUllion 5b203slag I
ZPbOslag~ Sty 2 mullion 2P~bullion+ S2gas (8) 2Pboslag+pbsmatte 3P~bullion + S2gas Lo) In a continuous High Temperature Softening furnace, with a well mixed bath, the lead bullion within the furnace is low in sulphur,arsenic) antimony and tin and therefore there is a very low probability for these elements to react directly with-the introduced oxygen. The introduced oxygen instead reacts with the lead, as per reaction I
forming lead oxide which enters the slag. This lead oxide acts as the oxygen transfer medium through which the bullion is softened by reactions (5), (6), and I Should any matte be introduced to the sigh Temperature Softening furnace through the addition of cool smelter bullion, this matte would also be consumed by reaction between the lead oxide in the slag as described in reactions (8) and I
The smelter bullion may also be softened by the addition of lethargy or a high lead oxide containing slag to the high temperature softening furnace.
issue The softening slag is transferred to a conventional slag reduction furnace 32 where the slag is reduced to produce a high antimony slag product and a hard bullion for recycle to the high temperature softening furnace.
The softened bullion is then subjected to a dry drowsing and copper drowsing operation 34 identical to the corresponding operation in the flow sheet of Figure 1 and the copper drowses treated in a copper reverberatory furnace 36 also identical to the one used in the flow-sheet of Figure 1 to produce a granulated copper matte and a bullion which is returned Jo the dry and copper drowsing furnace.
The last two steps 38 and 40 in the flow sheet of Figure 4 are identical to the corresponding steps in Figure 1 of the drawings.
The object of this invention will be illustrated - through the following example. At the Smelting Division of Brunswick lining and Smelting Corporation Limited, Baldwin, New Brunswick, a 15 day pilot High Temperature Softening test was conducted in which 3118 tones Of blast furnace bullion were treated. The softening was conducted in rectangular refractory lined reverberatory furnace of internal dimension 5.2 m x 2.1 m. The furnace lead capacity was approximately 50 tones. Air was introduced into the bullion through five 3~4" nominal schedule 40 steel lances passing through the roof of the reverberatory furnace, and immersed 5 cm beneath the bullion surface.
14 - ~.22~2 e blowing rate was adjusted to maintain a target level ox 0~05 to 0,06 wit%. Sub in the softened bullion, - and ranged between 340 and aye Nm3/hr. The temperature of the bullion within the High Temperature Softening furnace was maintained between 830 to 880~C, through the use of draught control or a supplementary neat burner.
The blast furnace bullion was transferred from the blast furnace to the High Temperature Softening furnace lo in pots of approximately 7 tones capacity at intervals of approximately 45 minutes. The blast furnace bullion was charged through a charge cone located centrally in the High Temperature Softening furnace. The. in flowing bullion displaced the softened bullion through a bullion under flow, and at the same time the softening slag was displaced through a slag overflow slot.
The operation of the High Temperature Softening furnace is considered as continuous as the weight of the incoming bullion pots wassail in comparison to the weight of bullion in the furnace, and the composition of toe lead in the High Temperature Softening furnace .
did not charge significantly after addition of a pot of lead Due to the large distance between the blast furnace and the High Temperature Softening furnace, there was a significant time delay in transferring the blast furnace bullion to the High Temperature Softening furnace, allowing the blast furnace bullion to cool to under 800~C, and resulting in a matte crust formation 12~
on the transfer pots. On addition ox this matte crust to the sigh Temperature Softening furnace, the matte was quickly consumed through reactions (,8) and (9).
Had the High Temperature Softening furnace been in close proximity to the blast furnace, the blast furnace bullion Gould have entered the softening furnace at a temperature above the matte formation temperature, thus desulphurization of the bullion would have occurred exclusively through reaction I
'The analyses of the in flowing and outflowing streams, as well as the element distributions are shown in Table I.
TAO I
IiIGIi TEMPERATURE S~FTE2iING'~SS BALANCE
Input - to = _ _ S --Sub ¦ A ¦
Blast Howe mullion 3118 wit % 1.61 95.6 0.42 1.53 0.39 1 ~.146 owe .
Bullion 2641 it % 1.50 97.7 0.15 0.086 0.059 0.17 % dust. 78.6 86.6 30.3 4.5 13.4 99.6 Song Slag 502 wit % 2.15 76.8 0.84 9.42 1.99 0.0~3 dust. 21.4 13.0 32.2 93./ 85.7 0.3 Fume 17 -it % ~'.QZ 73.5 5.3 0.65 0.005 dust. 0.0 0.4 37.6 1.8 I 0.0 _ issue The softened bullion produced in the above described pilot High Temperature Softening test tray drowsed as per conventional kettle drowsing practice. The dry drowsing was conducted in kettles of 2~0 short ton nominal capacity, in which was maintained a minimum of a 90 tone decopperized bullion heel. For each 90 tone of softened mullion decopperized, 500 kg of soda ash was added to the drowsing kettles. The drowsing kettles were continuously stirred during the addition of softened bullion.
lo The drowsing of the softened bullion resulted in - several advantages over the direct drowsing of blast furnace bullion. These included: I) the formation of a powdery, free flowing dry dross, completely free of large matte and spouse lumps, and suitable for vacuum dross pick-up; it the absence of rim build-up in the kettles; and lit a large reduction in arsenic fume during transfer and pouring of the softened bullion into the drowsing kettles.
Following the dry drowsing, tlhich reduced the copper content of the bullion to 0.05%, the bullion was subjected to a conventional copper drowsing, reducing the copper content of the bullion to under Us through Selfware additions.
The dry drowsing of the softened bullion reduced the residual Selfware, arsenic and antimony contents of the High Temperature Softened bullion to sufficiently low levels so that no problems with mushy or difficult to separate crust formation occurred during desilverizing ,. . . .
~L225.~L2 with the Parses process, or debismuthizing with -the Kroll-Betterton process.
The mass balance for the dry and copper drowsing of the High Temperature Softened mullion is shown in Table II below:
TABLE II
-COPPER DROWSING OF SOFTENED BULLION
Texas 01 ,5 __ _ _. . _ Input Softened mullion 2641 wit % 1.50 97~7 0.15 0.086 0.059 0.176 output Al ~cmæosite 360 wit 11.0 77.7 3.3 0.96 Q.45 0.12 % dust. 99.5 10.8 79.0 89.9 7.9 Drowsed Bullion 2314 wit % 0.009 99.4 0.04 0.008 0.22 _ % dust. 0.5 a . 2 _ 21.0 10.1 92.1 The copper dross obtained from the softened bullion was smelted in a conventional dross smelting reverberatory .
furnace, producing a copper product high in Curb ratio and low in arsenic. This copper product consisted of primarily matte with a small amount of copper furnace slag and a trace amount of spouse. The copper dross was smelted with approximately 5% Lye weight of lump coke, and no soda ash other than that added during the drowsing operation. The copper dross produced from crossing the softened bullion smelted rapidly, producing a fluid matte and slag, and producing no build-ups within the dross smelting furnace, , ~Z~5~
as is frequently the case in smelting the dross from blast furnace mullion.
The mass balance for the dross smelting operation is shown in Table IT below:
TABLE III
Smelting OF COPPE~;DR3SS PLED FRY SOWED BULLION
no tcnnes = Cut by 5 _ 5 A
Copper Dross . .
Compost wit % 11.~0 77.7 3.3 0.36 Owe 0.12 Outputs Gcroa~rted , .
Product 65 wit % 57.7 14.3 18.5 1.00 0.039 Copper % dust. 95.6 3.3 34.6 6.3 Furnace Boolean. tot % 0.63 98.3 0.06 0 14 Guy % dust. 4.3 99.7 8.6 93 5 Fume 17 wit % 0.18 32.5 6.3 0.12 0 003 _ dust. 0.1 2.0 _ 56.9 _ 0.1 ~5~4~
The copper matte obtained through the High Temperature Softening flow sheet, as outlined in Figure 4, has a Curb ratio of over 4, and only 1% arsenic in the matte.
Following the conventional flow sheet, as outlined in Figure 1, the Smelting Division of Brunswick Mining and Smelting, produced from blast furnace bullion of similar composition as used in the above example, a copper product having a Curb ratio of OWE to 1.75, and containing 7.5% As, with 0.11~ Ago Per unit weight of lo copper produced, the Sigh Temperature Softening flow sheet, Figure 4, reduces the lead contained in the copper product by a factor of 2, the arsenic contained by a factor of 10 and the silver contained by a factor of 3. These lower lead and arsenic contents, per unit of copper, make this copper matte more -attractive for treatment in a copper smelter, thus- reduced penalties are imposed on this material, increasing the return to the -lead smelter.
Those familiar with the field of metallurgy will understand that the High Temperature Softening process can also be used to upgrade copper materials containing lead, Selfware, arsenic, antimony or tin by adding such materials into the High Temperature Softening furnace in either a solid or liquid form along with the smelter bullion.
Claims (9)
1. A process for the refining of lead bullion containing lead and copper, plus one or more of the elements sulphur, arsenic, antimony, tin, silver, bismuth and other elements known to be contained in lead bullion, comprising:
a) first desulphurizing and softening the lead bullion in a furnace at a temperature sufficiently high to prevent the formation of a separate copper containing phase; and b) then cooling of the softened bullion in a kettle or furnace to a temperature near 330°C to form a dross or matte containing substantially all the copper originally contained in the bullion.
a) first desulphurizing and softening the lead bullion in a furnace at a temperature sufficiently high to prevent the formation of a separate copper containing phase; and b) then cooling of the softened bullion in a kettle or furnace to a temperature near 330°C to form a dross or matte containing substantially all the copper originally contained in the bullion.
2. A process as defined in claim 1, wherein softening is done in kettles and further comprising the step of smelting of the copper containing dross to form a matte of high Cu/Pb ratio and a lead bullion containing the lead recovered from the dross.
3. A process as defined in claim 1, wherein the lead bullion is desulphurized and softened by the injection of a oxygen containing gas mixture containing between 5 to 100% oxygen.
4. A proces as defined in claim 3 wherein the lead bullion is desulphurized and softened by feeding the bullion continuously or semi-continuously into the softening furnace, and wherein the desulphurized and softened bullion and slag are continuously or semi-continuously removed from the softening furnace.
5. A process as defined in claim 3, wherein feeding of the bullion Into the. softening furnace is also done in a batch mode where the size of the batch additions is less than one fifth of the size of the furnace bath.
6. A process as defined in claim 4 or 5, wherein the bullion is well mixed within the softening furnace.
7. A process as defined in claim 1, 2 or 3, wherein the temperature of the bullion inside the softening furnace is maintained above the temperature at which metallic copper, or a copper containing matte or sulphide, or a copper containing speiss or arsenide or antimonide will be exsolved from the bullion.
8. A process as defined in claim 1, 2 or 3, wherein materials containing copper and/or lead, and containing one or more of the following sulphur, arsenic, antimony or tin elements are added to the softening furnace in addition to the lead bullion.
9. A process as defined in claim 1, 2 or 3, wherein the lead bullion is desulphurized and softened by the addition of litharge or a high lead oxide containing slag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000465820A CA1225242A (en) | 1984-10-18 | 1984-10-18 | High temperature softening of lead bullion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000465820A CA1225242A (en) | 1984-10-18 | 1984-10-18 | High temperature softening of lead bullion |
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| Publication Number | Publication Date |
|---|---|
| CA1225242A true CA1225242A (en) | 1987-08-11 |
Family
ID=4128950
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465820A Expired CA1225242A (en) | 1984-10-18 | 1984-10-18 | High temperature softening of lead bullion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2813614A1 (en) * | 2000-09-07 | 2002-03-08 | Metaleurop Sa | PROCESS FOR RECOVERING METALLIC ELEMENTS FROM ZINCIFEROUS RAW MATERIALS |
| EP2459761A4 (en) * | 2009-07-31 | 2016-06-15 | Stannum Group LLC | Process for refining lead bullion |
| WO2024255008A1 (en) * | 2023-06-12 | 2024-12-19 | 昆明理工大学 | Fire refining method for complex lead bullion |
-
1984
- 1984-10-18 CA CA000465820A patent/CA1225242A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2813614A1 (en) * | 2000-09-07 | 2002-03-08 | Metaleurop Sa | PROCESS FOR RECOVERING METALLIC ELEMENTS FROM ZINCIFEROUS RAW MATERIALS |
| WO2002020858A1 (en) * | 2000-09-07 | 2002-03-14 | Metaleurop S.A. | Method for recuperating metal elements from zinc-bearing raw materials using molten lead |
| EP2459761A4 (en) * | 2009-07-31 | 2016-06-15 | Stannum Group LLC | Process for refining lead bullion |
| WO2024255008A1 (en) * | 2023-06-12 | 2024-12-19 | 昆明理工大学 | Fire refining method for complex lead bullion |
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