EP0788558B1 - Method and apparatus for adding aluminum and calcium to molten lead - Google Patents

Method and apparatus for adding aluminum and calcium to molten lead Download PDF

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Publication number
EP0788558B1
EP0788558B1 EP95931106A EP95931106A EP0788558B1 EP 0788558 B1 EP0788558 B1 EP 0788558B1 EP 95931106 A EP95931106 A EP 95931106A EP 95931106 A EP95931106 A EP 95931106A EP 0788558 B1 EP0788558 B1 EP 0788558B1
Authority
EP
European Patent Office
Prior art keywords
housing
lead
calcium
impeller
aluminum
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
Application number
EP95931106A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0788558A1 (en
Inventor
Stephen George Hibbins
Fernando Anthony Timpano
Douglas John Zuliani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Timminco Ltd
Original Assignee
Timminco Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CA002132485A external-priority patent/CA2132485A1/en
Application filed by Timminco Ltd filed Critical Timminco Ltd
Publication of EP0788558A1 publication Critical patent/EP0788558A1/en
Application granted granted Critical
Publication of EP0788558B1 publication Critical patent/EP0788558B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/51—Methods thereof
    • B01F23/511—Methods thereof characterised by the composition of the liquids or solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/91—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with propellers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/15—Stirrers with tubes for guiding the material

Definitions

  • This invention relates to a method for simultaneous addition of aluminum and calcium and alloys thereof to molten lead for the production of lead-calcium alloys.
  • lead-calcium alloy grids were developed since these alloys greatly reduce the amount of hydrogen gas generated by the electrochemical reaction. As little as 0.1% calcium in the lead alloy is sufficient to reduce gassing to a level where the battery can virtually be sealed and no water additions are required.
  • calcium may be introduced by adding calcium carbide as in U.S. Patent No. 1,941,534 to Betterton, which issued January 2, 1934.
  • the metallurgical difficulty with producing lead-calcium alloys is not in general related to the addition of calcium to molten lead since, as discussed above, there are several alternative alloying methods.
  • the major problems relate to the fade of calcium once it has been dissolved in the liquid lead pool.
  • Lead-calcium alloys are very prone to the loss of calcium due to oxidation at the melt surface where reactive calcium dissolved in the molten lead comes in contact with oxygen in atmospheric air.
  • a solution to the problems associated with calcium fade is given by the addition of minor amounts of aluminum (0.005% to 0.05%) to the lead-calcium alloy.
  • Aluminum forms a tenacious oxide layer on the surface of the lead alloy melt thereby minimizing the oxidation of calcium.
  • the molten lead temperature has to be raised above aluminum's melting point (660°C) which is considerably higher than the normal range for lead processing. Due to its reactive nature, calcium metal is usually added at about 420°C. Hence there is an incompatibility between the melt temperatures at which solid aluminum and calcium metals can be added. Alternatively, pre-melted liquid aluminum can be poured and stirred into the lead bath; however, this requires a second furnace to melt the aluminum.
  • the eutectic alloy allows for simultaneous addition of calcium and aluminum in a ratio of approximately 3 Ca:1 Al at molten lead temperatures of about 570°C.
  • reagent recoveries with this alloy are higher than for the pure calcium and aluminum metal addition practices outlined above; calcium and aluminum recoveries of 90% and 70% respectively can be expected with the alloy.
  • the major difficulty arising with the use of this alloy is, however, that the addition ratio is 3 Ca:1 Al which often does not correspond to the proportion of calcium and aluminum required by the lead alloy specifications.
  • the desired Ca:Al ratio in the final lead alloy can be as high as 10:1.
  • U.S. Patent 4,627,961 issued December 9, 1986 to Dudek, calls for the simultaneous addition of calcium and aluminum by compressing a mechanical mixture of the respective metal granules into a briquette. The briquettes are then added into a vortex created by stirring molten lead at temperatures between 550 and 600°C. The major difficulty with this method is unpredictability in the amount of calcium and aluminum recovered in the melt. Trials with calcium/aluminum briquettes, described in column 1 of aforesaid U.S. Patent No. 4,808,376, show highly variable results with calcium recoveries varying by up to 10% and aluminum recoveries varying by over 34%.
  • the present invention utilizes a simple system for simultaneous addition of calcium and aluminum metals at normal lead processing temperatures (typically 560°C and in any event below 660°C) with high and predictable recoveries and minimal oxidation and fume emissions.
  • the present invention makes use of the exothermic release of heat provided when calcium metal dissolves in molten lead.
  • the heat release associated with calcium dissolution will cause a sharp local increase in the temperature of the lead surrounding the dissolving calcium particles. Since high melt temperatures are required to dissolve aluminum in lead, any aluminum particles coming in contact with the locally superheated lead adjacent to a calcium particle will dissolve rapidly.
  • the temperature of the lead bath will normally be less than 660°C.
  • a further aspect of the invention is an apparatus for introducing calcium and aluminum into a bath of molten lead as specified in claim 5 or 8.
  • proper swirling of the lead is partially dependent on the shape of the housing and partially dependent on the nature and position of the impeller.
  • the housing is constricted to impede flow of lead through the bottom opening and to assist in recirculation.
  • the lower portion of the tubular housing converges downwardly, providing a conical constriction leading to an outlet opening which may be about one half the maximum diameter of the housing and may be less than the impeller diameter. This helps to promote radial liquid flow to ensure that the calcium and aluminum particles are held in the tubular housing for an adequate length of time.
  • the design and location of the impeller is critical to establishing optimum liquid flow patterns inside the tubular housing.
  • the impeller is located inside the housing just above the bottom opening, or at least closer to the bottom outlet than to a mid point of the downwardly converging portion.
  • the conical constriction in the bottom portion of the tubular housing is extremely important since it restricts the flow of lead through the bottom opening and thereby promotes radial flow. Without this constriction in the diameter of the tubular housing, the vortex would favour more axial flow thereby enabling calcium and particularly aluminum solid particles to escape the housing before being completely dissolved into the lead.
  • the impeller is located near the point of constriction inside the tubular housing.
  • flow inside the housing reverses with liquid lead from the bulk melt being drawn in through the bottom opening and passing out of the top openings.
  • the canopy above the top openings ensures that any unreacted calcium and aluminum particles which may be inadvertently discharged through the top openings are caught in the canopy because of their high buoyancy relative to lead and are thereby prevented from floating to the surface of the lead bath where they would be lost as unreacted reagent.
  • the rotary impeller used in both embodiments herein is preferably at least partially of the centrifugal type, so that the lead in the region of the impeller is caused to move both radially and axially and to strike the walls of the tubular housing, and to swirl around adjacent to the wall before leaving the outlet.
  • the tubular housing is constricted in diameter so as to decrease axial flow and promote more radial flow within the housing. This is an important aspect of the present invention since it increases residence time of the aluminum and calcium particles inside the tubular housing.
  • Fig. 1 shows the essential elements of prior art U.S. Patent No. 3,741,754 used for adding reactive metal, such as calcium, to molten lead while using a protective gas covering provided by an inert gas.
  • a supply chute 12 forming the lower end of a feed hopper is used to deliver a supply of the reactive material.
  • a cylindrical housing 16 which is closed at its top end 17 and open at its bottom end 18 is supported by support arm 20 from a movable frame 24.
  • An inner chamber 26 is centrally disposed within housing 16. Within chamber 26 is located an impeller 28 of the marine or axial flow type attached to rotary shaft 29, which shaft extends up through gland 30 and has its upper end driven by a motor/gear box combination also mounted on frame 24.
  • a vibrator 31 is connected to the base of chute 12 to assist flow of the reactive metal into the lead bath 32.
  • An inert gas stream is provided through supply conduit 33; this assists movement of reactive particles into the top of housing 16.
  • Frame 24 is arranged to be movable over a molten metal bath to be treated.
  • the frame 24 is positioned to insert part of housing 16 and all of inner chamber 26 below the surface 32 of the molten lead.
  • Inert gas is supplied through conduit 33, and the lead temperature adjusted to 900 to 950°F (i.e. 482 to 510°C).
  • Calcium particles are supplied at a rate of about 115 grams per second (about 15 pounds per minute), while the impeller 28 is rotated at about 280 rpm to produce a deep vortex in the bath.
  • the impeller tends to pull liquid lead upwardly through the annular space between the housing 16 and the inner chamber 26 and then downwardly through the chamber and out through its bottom outlet into the bath.
  • the calcium particles are mixed with the molten lead during this movement.
  • calcium-lead alloys were reportedly made ranging in calcium content from about 0.025% to 1.5% by weight calcium, based on the combined weight of calcium and lead in the alloy.
  • the prior patent also reported that the addition of 6 mesh calcium nodules at a rate of about 115 grams per second (about 15 pounds per minute) to a lead bath at 480-510°C produced calcium recovery of about 88% by weight, i.e. about 88% of all calcium input became a part of the calcium-lead alloy.
  • Fig. 2 shows the preferred embodiment of apparatus in accordance with the invention which has been found to overcome the shortcomings of the prior art apparatus of Fig. 1.
  • two supply chutes 111 and 112 are provided from two separate hoppers 111a and 112a for calcium and aluminum particles or for calcium/aluminum alloy particles. These chutes pass into the otherwise closed top 113 of tubular housing 116 having an open bottom end outlet 117.
  • the chutes can, if required, also be used for the introduction of a protective inert gas into the top of the housing.
  • the housing and chutes are carried by a frame part 124 which can be moved into place as required over a vessel 125 containing the molten lead, the upper surface of which is indicated at 132.
  • the closed top 113 accommodates drive shaft 129 of motor 130 which carries impeller 128 at its lower end.
  • the housing 116 has a series of slots 118 around its periphery, which provide inlet means located at relatively small depth below the surface 132 of the lead; i.e. a depth which is small relative to that of the bottom outlet 117.
  • a downwardly diverging frusto-conical deflector or canopy 119 is fixed to the outer surface of the housing 116 just above the slots 118; this ensures that melt entering the slots is not contaminated with surface dross or the like.
  • the impeller 128 and the design of the housing 116 lie in the nature of the impeller 128 and the design of the housing 116.
  • the impeller instead of being a marine or axial flow type propeller, as shown in the '754 patent, is at least partially of the centrifugal flow type.
  • the blades of the impeller are set at an angle of between 40° and 50° to the horizontal impeller plane, preferably about 45°; rather than the shallower angle usual with axial flow type impellers.
  • Applicants' impeller provides both substantial radial flow as well as axial flow; axial flow ensures that lead is moved through the housing while centrifugal flow ensures that it is swirled around in the housing long enough to become alloyed with the calcium and aluminum.
  • an impeller of this kind may be termed a modified turbine impeller.
  • the axial flow impeller in the '754 patent was more than two thirds the internal diameter of the housing, in the present invention the impeller diameter is less than one-half the diameter of the cylindrical portion of the housing 116 and is preferably slightly smaller than the diameter of the bottom outlet.
  • the housing is wholly cylindrical in shape, applicants' housing 116 is cylindrical in the upper portion and constricted by a frusto-conical lower section 116a.
  • the turbine impeller in combination with the frusto-conical constriction create a vortex with sufficient radial flow such that particles of the feed metals are caused to swirl around within the housing between the wall and the impeller, and above the impeller, and this ensures close proximity of the calcium and aluminum particles and maximizes their retention time within the housing.
  • the exothermic reaction between the calcium and the lead heats the lead within the housing and adjacent to the particles and this causes dissolving of the aluminum.
  • protective gas if desired can be introduced into the housing through chutes 111 and 112 or by a separate inlet port. While the use of a protective gas is not essential, tests show that use of an inert gas such as argon will improve calcium recovery by as much as 15 to 20%.
  • a conical housing similar to that shown in Fig. 2 was inserted into a 1250 kg molten lead bath.
  • the lead melt was initially maintained at 560°C. 1.45 kg of calcium metal particles and 0.21 kg of aluminum metal particles were added simultaneously to the lead vortex generated with the impeller operating at 600 rpm inside the conical reaction housing.
  • the reagents were introduced into the melt over a 7 to 8 minute time interval. Stirring inside the housing continued for up to 20 minutes from the start of reagent feeding. Samples were taken for chemical spectrographic analysis from the bulk lead pool outside the housing at 0, 5, 10 and 20 minute intervals from the start of reagent feeding. The results below indicate that, with the housing and impeller combination with this preferred embodiment, calcium recovery reached 92.7% by 10 minutes and 96.1% after 20 minutes. Aluminum recovery is exceptionally high reaching 81.6% at 10 minutes and increased to 82.7% after 20 minutes.
  • Example 2 The exact same experiment as described in Example 1 was repeated to confirm calcium and aluminum particle dissolution and recovery with the apparatus of this invention as described. Once again, dissolution was complete at the 10 minute mark, that is within 2 to 3 minutes after the end of reagent feeding. Final calcium analyzed at 1050 ppm (92.3% recovery) and the aluminum analyzed at 165 ppm (98.2% recovery).
  • FIG. 3 A second embodiment of this invention as shown in Fig. 3, in which the same reference numerals are used for parts which are the same as those of Fig. 2.
  • the Fig. 3 arrangement allows for the turbine impeller 228 to be located approximately at the elevation where the cylindrical portion of the housing meets the constricted portion 216a.
  • the impeller design and the frusto-conical lower section of the housing promote combined axial and radial flow patterns as shown by the arrows in Fig. 3. In this case, however, it has been found that raising the position of the impeller results in a reversal of the metal flow with liquid lead flowing in through the bottom opening and out the top openings.
  • rotating impeller 228 at sufficient speed e.g.
  • a conical housing similar to that shown in Fig. 3 was inserted into a 1250 kg molten lead bath.
  • the lead melt was initially maintained at 560°C. 1.48 kg of calcium metal particles and 0.21 kg of aluminum metal particles were added simultaneously to the lead vortex generated with the impeller operating at 600 rpm inside the conical reaction housing.
  • the reagents were introduced into the melt over a 7 to 8 minute time interval. Stirring inside the housing continued for up to 20 minutes from the start of reagent feeding. Samples were taken for chemical spectrographic analysis from the bulk lead pool outside the housing at 0, 5, 10 and 20 minute intervals from the start of reagent feeding.
  • the 40 ppm increase in calcium levels between 10 and 20 minutes is considered insignificant; hence dissolution with the housing was complete at 10 minutes, that is within 2 to 3 minutes after end of reagent feeding.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)
EP95931106A 1994-09-20 1995-09-19 Method and apparatus for adding aluminum and calcium to molten lead Expired - Lifetime EP0788558B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA002132485A CA2132485A1 (en) 1994-05-09 1994-09-20 Method and apparatus for adding aluminum and calcium to molten lead
CA2132485 1994-09-20
PCT/CA1995/000525 WO1996009418A1 (en) 1994-09-20 1995-09-19 Method and apparatus for adding aluminum and calcium to molten lead

Publications (2)

Publication Number Publication Date
EP0788558A1 EP0788558A1 (en) 1997-08-13
EP0788558B1 true EP0788558B1 (en) 1999-02-10

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ID=4154364

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Application Number Title Priority Date Filing Date
EP95931106A Expired - Lifetime EP0788558B1 (en) 1994-09-20 1995-09-19 Method and apparatus for adding aluminum and calcium to molten lead

Country Status (13)

Country Link
EP (1) EP0788558B1 (cs)
JP (1) JPH10505880A (cs)
AT (1) ATE176688T1 (cs)
AU (1) AU687636B2 (cs)
BR (1) BR9508848A (cs)
CZ (1) CZ82697A3 (cs)
DE (1) DE69507831T2 (cs)
DK (1) DK0788558T3 (cs)
ES (1) ES2128759T3 (cs)
GR (1) GR3029968T3 (cs)
NO (1) NO971138D0 (cs)
NZ (1) NZ292491A (cs)
WO (1) WO1996009418A1 (cs)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1386503A (en) * 1921-08-02 And milo w
US3741754A (en) * 1971-04-29 1973-06-26 States Smelting Refining & Min Method for making metal alloys
US4439398A (en) * 1981-11-13 1984-03-27 Rsr Corporation Method of alloying calcium and aluminum into lead

Also Published As

Publication number Publication date
DE69507831D1 (de) 1999-03-25
DK0788558T3 (da) 1999-09-20
ATE176688T1 (de) 1999-02-15
DE69507831T2 (de) 1999-08-19
JPH10505880A (ja) 1998-06-09
BR9508848A (pt) 2002-04-16
WO1996009418A1 (en) 1996-03-28
EP0788558A1 (en) 1997-08-13
AU3467895A (en) 1996-04-09
AU687636B2 (en) 1998-02-26
ES2128759T3 (es) 1999-05-16
NZ292491A (en) 1997-06-24
CZ82697A3 (en) 1997-12-17
GR3029968T3 (en) 1999-07-30
NO971138L (no) 1997-03-12
NO971138D0 (no) 1997-03-12

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