EP0343012B1 - Alliages de magnésium-calcium pour la débismuthation du plomb - Google Patents
Alliages de magnésium-calcium pour la débismuthation du plomb Download PDFInfo
- Publication number
- EP0343012B1 EP0343012B1 EP89305122A EP89305122A EP0343012B1 EP 0343012 B1 EP0343012 B1 EP 0343012B1 EP 89305122 A EP89305122 A EP 89305122A EP 89305122 A EP89305122 A EP 89305122A EP 0343012 B1 EP0343012 B1 EP 0343012B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- calcium
- alloy
- magnesium
- lead
- bismuth
- 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.)
- Expired - Lifetime
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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
- C22B13/00—Obtaining lead
- C22B13/06—Refining
Definitions
- the present invention relates to calcium-magnesium alloys for use in the removal of bismuth from lead by the Kroll-Betterton process, or for similar lead refining processes which require alkaline-earth metals.
- alkaline earth metals are added to the lead melt in order to react with the bismuth therein.
- One or more alkaline earth metals usually magnesium and calcium, are added in either a continuous or batch fashion to the unrefined lead.
- the preferred temperature range for making the addition is between 380 ° C to 500 ° C. Below this temperature range, the reaction is sluggish while above the range excessive oxidation of reactive alkaline earth metals, particularly calcium, occurs. Oxidation gives rise to bright flaring, excessive fume generation and an overall loss of reagent leading to lower reagent recoveries, excessive processing costs, unpredictable final bismuth levels and environmental concerns.
- the addition of calcium metal to the lead bath is often accompanied by an increase in the bulk temperature of the lead either due to an exothermic release of heat during the reaction and/or the heat generated by the oxidation of calcium metal.
- This increase in bath temperature may result in additional calcium oxidation as well as lengthening the overall processing time since the melt must be cooled to just above its solidification point prior to removing the bismuth rich dross.
- calcium metal is highly reactive with atmospheric oxygen and humidity. Hence, calcium metal must be packaged, shipped and stored in such a way as to eliminate contact with air and moisture. Excessive contact with water will result in heat and hydrogen evolution which can cause fire and explosion. Mild contamination of the calcium prior to the lead treatment will result in lower than expected reagent recoveries and unpredictable final bismuth levels.
- the melt is then cooled to a temperature near its solidification point which causes the alkaline-earth bismuth compounds to float up as a solid dross which may be skimmed from the surface of the melt.
- debismuthizing is carried out by the use of an alloy which consists essentially of magnesium and calcium, the magnesium being present in the proportion of from 65% to 75% on a weight basis.
- lead is the principal alloying constituent and is present to lower the melting point of the reagent thus promoting dissolution of magnesium, and in particular calcium, both of which have melting points substantially higher than the lead bath temperature.
- Zeitschrift fur Erzbergbau und Metall prisencher, Part 5, Volume II, of May 1949 Evers reported the results of investigations into the Kroll-Betterton process, in which the magnesium and calcium were added separately, the calcium in the form of a lead calcium alloy. The concentration of bismuth remaining in the lead was further reduced by the addition of antimony.
- phase diagram shows that the 79.4% magnesium, 20.6% calcium alloy suggested by Rehns begins to melt at 516.5 ° C and is fully molten by about 575 °C.
- a lead bath temperature of 593 ° C Rehns ensures that this alloy will be fully molten and hence its dissolution and the resulting reagent recovery will not be impeded by the presence of any unmelted, highly stable Mg 2 Ca intermetallic compound.
- Kroll-Betterton type debismuthizing processes usually operate in the 380 ° C to 500 ° C range. Rehns specified temperature, 593 °C, is thus substantially higher than reported commercial debismuthizing practices.
- magnesium-calcium alloys with magnesium to calcium ratios on a weight basis between 1.2 and 5.2, and preferably between 1.9 and 3.0 are added to lead in the commercial temperature range, that is between 380 ° C to 500 ° C.
- all of these alloys have melting points in excess of 516.5°C and, in the range of the preferred embodiment, the alloys do not fully melt until temperatures exceed between 610°C to 685 ° C which is substantially above the temperature of the lead bath.
- the alloys do not completely melt and hence the reaction must proceed by dissolving (not melting) a solid into liquid lead.
- this solid phase is essentially the stable, high melting point Mg 2 Ca intermetallic compound.
- the rate of reaction depends only on how fast the alloy melts which in turn depends on the rate of heat transfer from the bath to the reagent. Once melted, any Mg 2 Ca compound present in the alloy is completely dissociated and hence available for debismuthizing.
- the rate at which the solid Mg 2 Ca phase in the alloys eutectic dissolves into the liquid lead depends on thermodynamic and kinetic considerations which are related to the chemical stability of Mg 2 Ca relative to magnesium-calcium-bismuth compounds which form during debismuthizing.
- the rate of dissolution and hence the degree of dissociation of Mg 2 Ca in the alloy has significant commercial significance as it will determine processing time and reagent recoveries.
- French Patent Application No. 81 19673 assigned to Extramet discloses a process for debismuthizing lead by using a mixture of two types of alloy granules.
- the first type of granule comprises a calcium-magnesium alloy near the calcium-rich eutectic point (approximately 82 weight % calcium) and the second alloy comprises a magnesium-calcium alloy near the magnesium-rich eutectic point (approximately 16.2 weight % calcium).
- These two types of granules are mixed together in the appropriate amounts to give the ratio of the metals for the best result and are injected into the lead melt to react with the bismuth therein.
- composition of the individual alloys are chosen to be near the eutectic points so that they have relatively lower melting points compared to pure magnesium and calcium metals. It is claimed that this speeds up the rate of the reaction at a given processing temperature.
- the mixture is injected into the lead bath with an inert gas. The temperature of the lead bath is maintained high enough to melt and not simply dissolve the lead granules.
- This heterogeneous mixture of magnesium-rich calcium-rich alloy granules is still susceptible to poor reagent recovery because the calcium-rich alloy granules will behave in much the same way as pure calcium metal.
- the eutectic may contain up to almost 2/3 of finely divided calcium metal with the remainder being the Mg 2 Ca intermetallic compound.
- the high proportion of calcium metal in the eutectic causes the calcium-rich alloy granules to react with atmospheric oxygen and humidity in much the same way as calcium metal. Tests with ingots cast at the calcium-rich eutectic composition have shown that this alloy reacts with atmospheric oxygen and humidity and, hence, is not stable in air.
- the heterogeneous granule mixture of magnesium-rich granules and calcium-rich granules must be packaged under dry, inert gas in a similar fashion to calcium metal. Contamination of the calcium-rich granules with oxygen or moisture prior to treatment will result in lower reagent recoveries and unpredictable final bismuth levels.
- the calcium-rich granules are also susceptible to oxidation during treatment with the lead in much the same way as calcium metal, especially if they float to the surface before they have completely reacted due to large differences in density between lead and calcium.
- the injection of the granules into the lead bath with an inert gas carrier adds additional turbulence to the melt, increasing the amount of oxidation and emissions from the lead bath.
- the difficulties associated with the use of calcium metal or granular mixtures containing calcium-rich alloy granules are avoided by using a single magnesium-calcium alloy of the desired composition.
- the alloy is primarily made up of magnesium and calcium but may contain one or more minor amounts of other alloying elements.
- an alloy for use in lead refining which is rich in magnesium and has magnesium to calcium ratios on a weight basis between 1.2 and 5.2; the lower ratio corresponding to the intermetallic compound Mg 2 Ca.
- the alloy has a magnesium to calcium ratio between about 1.9 to 3.0.
- Figure 1 illustrates the binary magnesium-calcium phase diagram and shows that the addition of calcium to magnesium will initially lower the melting point of the alloy compared to metallic magnesium. However, once the alloy exceeds 16.2% calcium (i.e. a Mg to Ca ratio of 5.17), its melting point begins to rise due to an increasing concentration in the eutectic of the highly stable intermetallic compound, Mg 2 Ca. This stable compound has a meting point of 715 ° C which is between about 200 - 300 ° C above commercial debismuthizing temperatures.
- magnesium and calcium are first dissolved in liquid lead at temperatures usually between 415°C to 500 °C. Subsequent cooling of the lead precipitates a solid compound, CaMg 2 Bi 2 , which is separated out in the dross. The lead is eventually cooled to just above its liquidus temperature; however, some calcium, magnesium and bismuth will still be retained in solution in the lead.
- the inventors have calculated the theoretical alloy requirements to chemically remove bismuth, based on the stoichiometry of the bismuth containing intermetallic, CaMg 2 Bi 2 , and the solubility relationship given in equation (1).
- Figure 2 illustrates the effects of alloy composition on the quantity of alloy needed to remove bismuth to 0.005% and 0.020% which represents the range of final bismuths in most commercial treatments.
- Figure 3 illustrates the effects of alloy composition on the percentage change in the lead refiners' cost relative to an alloy containing 60% calcium. These data are based on the amount of alloy required to chemically remove bismuth and the cost of the magnesium and calcium components in the alloy. It can be seen that, depending on the final bismuth level, the lead refiners' costs are lowest for alloys containing between 25% to 35% calcium (a Mg to Ca weight ratio between 3.0 to 1.9).
- alloys containing between 35% to 25% calcium are optimum.
- the dissolving rate of the alloy at conventional debismuthizing temperatures has significant commercial implications since it will determine the amount of alloy that can be recovered during the allotted processing time.
- the alloys do not completely melt and hence the reaction proceeds by dissolving (not melting) a solid into liquid lead.
- this solid phase is essentially the stable, high melting point Mg 2 Ca intermetallic compound.
- the time required for the alloys to react depends on the dissolving rate of the stable, high melting point of Mg 2 Ca which in turn depends on thermodynamic and kinetic considerations related to the stability of Mg 2 Ca relative to the CaMg 2 Bi 2 dross.
- Table I summarizes the results of laboratory tests to determine the effects of composition, temperature and agitation on the dissolving rate of these alloys:
- the 15% calcium alloy is fully molten at 530 °C which is 120 ° C below the melting point for the 30% calcium alloy.
- this lower melting point and hence faster dissolving time can be attributed to the fact that the 15% calcium alloy contains only 33% of the high melting point Mg 2 Ca intermetallic in its eutectic compared to 66% Mg 2 Ca for the 30% calcium alloy.
- the alloy's dissolving rate is also dependent on the temperature of the lead bath.
- the results shown in Table I indicate that the dissolving rate of a 30% calcium alloy (a Mg to Ca weight ratio of 2.3) increases by about 4 times when the lead temperature is increased from 415 ° C to 500 °C which covers the range of processing temperatures for most commercial debismuthizing operations. Agitating the lead will also increase the alloy's dissolving rate.
- magnesium rich-calcium alloys with Mg to Ca weight ratios between 1.9 to 3.0 are superior to other alloy compositions since they combine the optimum chemical reactivity and dissolving characteristics.
- Alloys containing about 35% calcium are the most chemically effective since they minimize the amount of alloy needed to remove bismuth from lead. However, the slow dissolving rate of this alloy limits its use commercially to practices which operate at high temperatures (about 500 ° C) with aggressive agitation.
- alloys containing as low as 25% calcium are more commercially attractive since they offer significantly faster dissolving rates at an acceptable chemical reactivity with bismuth (see Figures 2 and 3).
- Magnesium rich-calcium alloys with Mg to Ca weight ratios outside the 1.9 to 3.0 range are inferior for removing bismuth because they are either too rich in calcium leading to inordinately long processing times and high processing costs or too rich in magnesium to be sufficiently reactive with bismuth.
- the alloys of the present invention are prepared by melting the appropriate proportions of calcium and magnesium metals under a protective atmosphere and pouring and solidifying the alloy in the same or similar protective atmospheres.
- the protective atmosphere may comprise nitrogen, argon or any other gases which are protective or non-reactive when in contact with magnesium and calcium.
- the temperature used to melt the metals and prepare the alloy is preferably but not necessarily in the range of 680 - 750 ° C.
- a method for achieving the solution of calcium in lead resulting in high recoveries comprises the steps of providing a magnesium and calcium alloy which has a magnesium to calcium ratio between 1.2 and 5.2, and adding this alloy to a lead bath.
- magnesium-rich alloys consist of eutectic structures which contain mostly finely divided magnesium metal and Mg 2 Ca intermetallic with the complete absence or only minor quantities of finely divided calcium metal, they are not subject to the aforementioned difficulties associated with calcium metal or calcium-rich alloy granules.
- these alloys are stable in air. Since the alloy does not oxidize or hydroxylize in air, it does not require special packaging or protective atmospheres. There is no danger of fire or explosion if these alloys come in contact with moisture. When added to liquid lead, these alloys react with minimal or no oxidation. The reaction is often accompanied by a minor degree of bubbling; however, there is essentially little or no flaring or fume generation. Since the alloys are not prone to contamination from contact with air prior to treatment, reagent recoveries are higher and more predictable than with other reagents. Further, since the alloys do not oxidize readily even if they float to the surface, provided the bath is being agitated no excessive flaring or fuming occurs, which would lead to lower recoveries. This substantially increases the predictability of achieving the desired final bismuth level which is particularly important when aiming at low bismuth levels of less than 0.01%.
- the alloy is preferably added to the lead bath in the form of large ingots. Under some circumstances, smaller ingots, large chunks, granules or powder may also be used.
- the alloys can be added either by plunging or supplied to the surface of an agitated lead bath.
- the alloys can be added at commercial debismuthizing temperatures that are between about 380 ° C to 500 ° C and are not restricted to the higher temperatures needed to fully melt the alloy as in the case of the prior art discussed.
- the dissolution rate of these alloys increases with increasing temperature and by agitation. Since there is virtually no flaring and related fume generation with this alloy, even at temperatures as high as 530 ° C and with agitation, no special fume collection system is required to contain emissions. Agitation is sometimes avoided when calcium metal is utilized as it increases oxidation and flaring.
- the lead melt is allowed to cool in the customary fashion of the Kroll-Betterton process to separate out the solid bismuth-rich dross.
- this application has disclosed an invention which improves the dissolution characteristics of magnesium and calcium in lead at commercial debismuthizing temperatures thereby improving the efficiency of bismuth removal from lead.
- This alloy is stable in atmospheric air and humidity and requires no special protective packaging as does calcium metal.
- the alloy dissolves with essentially no oxidation, flaring and fume generation. This results in higher and more consistent reagent recoveries and more predictable final bismuth levels which are particularly important when aiming for final bismuth levels less than about 0.01 %.
- the virtual absence of fume precludes the need for special fume collection systems.
- the absence of flaring and oxidation enables the alloy to be added with agitation and, if desired, at higher processing temperatures than is customary with calcium metal.
- the present application describes the use of certain magnesium-calcium alloys in Kroll-Betterton type processes for the removal of bismuth impurities from lead.
- the inventors have found that the use of certain magnesium rich-calcium alloys at commercial debismuthizing temperatures results in a more efficient process since;
- magnesium-calcium alloys are superior to other alloy compositions since this preferred range minimizes the amount of alloy required to remove bismuth and gives alloy dissolving rates which are acceptable at commercial debismuthizing temperatures.
- the alloy may contain other constituents, such as different alkali earth metal, which do not affect the essential nature of the metallurgical process herein disclosed.
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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)
- Cell Electrode Carriers And Collectors (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Lead Frames For Integrated Circuits (AREA)
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA567408 | 1988-05-20 | ||
CA567408 | 1988-05-20 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0343012A2 EP0343012A2 (fr) | 1989-11-23 |
EP0343012A3 EP0343012A3 (fr) | 1991-01-09 |
EP0343012B1 true EP0343012B1 (fr) | 1995-09-13 |
EP0343012B2 EP0343012B2 (fr) | 2002-09-18 |
Family
ID=4138064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89305122A Expired - Lifetime EP0343012B2 (fr) | 1988-05-20 | 1989-05-19 | Alliages de magnésium-calcium pour la débismuthation du plomb |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0343012B2 (fr) |
JP (1) | JP2714984B2 (fr) |
AT (1) | ATE127859T1 (fr) |
AU (1) | AU620822B2 (fr) |
DE (1) | DE68924194T3 (fr) |
ES (1) | ES2076961T3 (fr) |
GR (1) | GR3018160T3 (fr) |
YU (1) | YU102489A (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041160A (en) * | 1988-05-20 | 1991-08-20 | Timminco Limited | Magnesium-calcium alloys for debismuthizing lead |
FR2807768A1 (fr) * | 2000-04-13 | 2001-10-19 | Pechiney Electrometallurgie | Procede de debismuthage du plomb fondu par le calcium et le magnesium |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5234492A (en) * | 1992-04-14 | 1993-08-10 | Asarco Incorporated | Refining of bismuth |
CN114410982B (zh) * | 2021-12-23 | 2023-08-25 | 邢台松赫环保科技有限公司 | 一种铅火法精炼深度除铋方法 |
JP2023125624A (ja) * | 2022-02-28 | 2023-09-07 | 国立大学法人東北大学 | 水素発生合金、実験教材、マグネシウム電池用負極材、及び発電用水素発生剤 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1428041A (en) * | 1920-09-21 | 1922-09-05 | Kroll Guillaume Justine | Process for the separation and recovery of metals from metal alloys |
US1853540A (en) * | 1930-03-29 | 1932-04-12 | American Smelting Refining | Process of debismuthizing lead |
US2129445A (en) * | 1937-07-08 | 1938-09-06 | American Metal Co Ltd | Treating impure lead and/or tin metal |
CA1079979A (fr) * | 1975-08-19 | 1980-06-24 | Denby H. Ward | Elimination du bismuth contenu dans le plomb |
NL7903764A (nl) * | 1979-05-14 | 1980-11-18 | Shell Int Research | Werkwijze ter bereiding van calcium-houdend lood, daarmee verkregen lood en daaruit verkregen accuplaten of -roosters. |
FR2514786A1 (fr) * | 1981-10-20 | 1983-04-22 | Extramet Sa | Procede de debismuthage du plomb |
-
1988
- 1988-10-28 AU AU24515/88A patent/AU620822B2/en not_active Ceased
-
1989
- 1989-05-18 YU YU01024/89A patent/YU102489A/xx unknown
- 1989-05-19 ES ES89305122T patent/ES2076961T3/es not_active Expired - Lifetime
- 1989-05-19 DE DE68924194T patent/DE68924194T3/de not_active Expired - Lifetime
- 1989-05-19 AT AT89305122T patent/ATE127859T1/de not_active IP Right Cessation
- 1989-05-19 JP JP1124657A patent/JP2714984B2/ja not_active Expired - Fee Related
- 1989-05-19 EP EP89305122A patent/EP0343012B2/fr not_active Expired - Lifetime
-
1995
- 1995-11-22 GR GR950403278T patent/GR3018160T3/el unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041160A (en) * | 1988-05-20 | 1991-08-20 | Timminco Limited | Magnesium-calcium alloys for debismuthizing lead |
FR2807768A1 (fr) * | 2000-04-13 | 2001-10-19 | Pechiney Electrometallurgie | Procede de debismuthage du plomb fondu par le calcium et le magnesium |
WO2001079570A1 (fr) * | 2000-04-13 | 2001-10-25 | Skw La Roche De Rame Sas | Procede de debismuthage du plomb fondu par addition d'alliages ca lcium-magnesium |
Also Published As
Publication number | Publication date |
---|---|
ATE127859T1 (de) | 1995-09-15 |
AU620822B2 (en) | 1992-02-27 |
AU2451588A (en) | 1989-11-23 |
ES2076961T3 (es) | 1995-11-16 |
DE68924194T3 (de) | 2003-01-30 |
GR3018160T3 (en) | 1996-02-29 |
DE68924194D1 (de) | 1995-10-19 |
JPH0270038A (ja) | 1990-03-08 |
EP0343012B2 (fr) | 2002-09-18 |
JP2714984B2 (ja) | 1998-02-16 |
YU102489A (en) | 1991-10-31 |
EP0343012A2 (fr) | 1989-11-23 |
DE68924194T2 (de) | 1996-11-28 |
EP0343012A3 (fr) | 1991-01-09 |
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