WO1999002287A1 - Method of fluxless melting of magnesium - Google Patents

Method of fluxless melting of magnesium Download PDF

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Publication number
WO1999002287A1
WO1999002287A1 PCT/NO1998/000200 NO9800200W WO9902287A1 WO 1999002287 A1 WO1999002287 A1 WO 1999002287A1 NO 9800200 W NO9800200 W NO 9800200W WO 9902287 A1 WO9902287 A1 WO 9902287A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
mixture
flowmeter
dry air
magnesium
Prior art date
Application number
PCT/NO1998/000200
Other languages
French (fr)
Other versions
WO1999002287A8 (en
Inventor
Jan B. RØNHAUG
Stein Erik Berg
Haavard T. Gjestland
Thomas Bergem Reistad
Øystein SOLLI
Original Assignee
Norsk Hydro Asa
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
Application filed by Norsk Hydro Asa filed Critical Norsk Hydro Asa
Priority to AU87534/98A priority Critical patent/AU8753498A/en
Priority to DE69805195T priority patent/DE69805195D1/en
Priority to AT98939025T priority patent/ATE216932T1/en
Priority to JP2000501854A priority patent/JP2001509543A/en
Priority to EP98939025A priority patent/EP1019211B1/en
Publication of WO1999002287A1 publication Critical patent/WO1999002287A1/en
Publication of WO1999002287A8 publication Critical patent/WO1999002287A8/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/14—Charging or discharging liquid or molten material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
    • F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
    • F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
    • F27D2007/063—Special atmospheres, e.g. high pressure atmospheres

Definitions

  • the present invention concerns a method of fluxless melting of magnesium, and more particularly a method of mixing and controlled feeding of protection gas to melting/holding furnaces and apparatus applied by such method.
  • Magnesium (metal) is known for its high affinity to oxygen and high vapour pressure of molten Mg (alloys) causing operational problems.
  • SO 2 atmosphere strongly reduces the oxidation of molten magnesium by modifying the surface film and that producers of primary metal, sand and die casters have been using SO 2 in gas form or generated (in situ) by adding sulphur powder to furnaces.
  • SO 2 is, however, toxic. In high concentrations and in contact with humidity it results in enhanced corrosion of steel equipment.
  • the present occupational exposure limit in Norway is 2 ppm over an 8 hours period of time corresponding to a concentration of 5 mg/m 3 , and corresponding limits in Germany and North America are similar.
  • Another object of the present invention is to provide an apparatus ensuring environmentally safe mixing and feeding of the SO 2 air mix into the Mg-furnaces/vessels.
  • Still another object of the present invention is to provide an improved method of fluxless melting of magnesium substantially reducing problems connected to formation of scaling on the crucible walls.
  • Fig. 1 shows schematically a flow chart of the mixing/feeding process
  • Fig. 2 illustrates schematically in a vertical, partial cross-section a feeding arrangement (apparatus) usable in the process of fluxless melting of magnesium
  • Fig. 3 shows schematically the applied furnace/vessel in a horizontal cross- section along line I-I
  • a melting furnace 1 is equipped with charging device 2 to feed solid magnesium into the furnace, transferring device, e.g. transfer tube 3 to move subsequently the Mg-melt into and adjacent casting unit (furnace) here depicted as 4.
  • transferring device e.g. transfer tube 3 to move subsequently the Mg-melt into and adjacent casting unit (furnace) here depicted as 4.
  • gas displacement (metering) pump 5 the melt is fed in a controlled manner (doses) into any suitable casting equipment, e.g. the shown high pressure die casting machine 6.
  • an apparatus arrangement for controlled mixing/feeding of the mixture SO 2 /dry air comprises a compressor 13 and a pressure bottle 14 providing (dry) air and SO 2 gas, respectively, into the mixing device 9 comprising a mass flowmeters 10 and 12 for the air and SO 2 , respectively, and a control steering unit 11 to ensure an adequate pre-set concentration of SO 2 in the gas mixture.
  • the resulting gas mixture is then conducted through a feeding line 8 and distributed by means of manifolds (flowmeters) 7 and customary valves into the actual (part of) furnaces 1 and 4.
  • FIG. 2 shows schematically in a partial, vertical cross-section the furnace 1 as a steel vessel accommodated in a thermally insulated furnace shell 20.
  • the melting furnace is provided with a charging device 2 to introduce solid Mg into the furnace, a baffle plate 15 dividing the furnace into a charging sector and a main body of the melting furnace where the furnace design/configuration should assure a high ratio volume/surface area in order to minimise reaction(s) occurring between molten Mg and the atmosphere. Consequently, all lids and hatches must also be well tightened as illustrated in an exploded view showing details of lid seals 16.
  • the gas mixture is provided to the furnace(s) through a sophisticated distribution system allowing the gas mixture to be evenly distributed close to the melt surface, e.g. by means of a ring tube 17 positioned along the furnace periphery in the vicinity of the melt surface as shown in Fig. 3.
  • Fig. 3 illustrating schematically the applied melting furnace 1 in a horizontal cross-section taken along line I-I in Fig. 2, further depicts the charging zone (device) 2, dividing baffle plate 15 and a lid 19 for eventual removal of dross/sludge from the furnace.
  • the ring tube 17 is provided with a plurality of apertures ensuring an even distribution of the protective gas mixture by controlled directional impingement of the melt surface.
  • Tests have been carried out on an industrial scale in a hot-chamber casting machine.
  • a mixing unit built according to the present invention provided SO 2 /dry air mixture for the furnace. Gas samples were frequently monitored (every four hours) both from the mixing unit, the furnace atmosphere and the working atmosphere as well.
  • Gas samples of the atmosphere were collected at three differenct locations in the foundry - at operator level, in the vicinity of the charging lid and approximately 3 m above the floor. No significant differences were measured in the gas concentrations between the locations indicating a safe, controlled operation and an adequate ventilation of the foundry hall.
  • a controlled diluted SO 2 /air mixture was provided and maintained during the test periods, something being of crucial importance also for the life time of the applied steel equipment.

Abstract

Fluxless melting of magnesium (alloy) metal applying a gas mixture of dry air and SO2 as protection atmosphere is provided where a constant pre-set level of SO2 is maintained by means of two mass flowmeters where one of them is in control of the other.

Description

Method of fluxless melting of magnesium
The present invention concerns a method of fluxless melting of magnesium, and more particularly a method of mixing and controlled feeding of protection gas to melting/holding furnaces and apparatus applied by such method.
Magnesium (metal) is known for its high affinity to oxygen and high vapour pressure of molten Mg (alloys) causing operational problems.
Currently SF6 based gas is used by most magnesium die casters for protection against oxidation of molten magnesium metal. Until recently the use of SF6 was not considered to represent any environmental hazard being non-toxic and without negative impact on the working atmosphere in the foundries. However, due to its very high calculated greenhouse warming potential strict restrictions on the use of the gas in applications causing emission to the atmosphere are expected in the near future.
Consequently, a search for an alternative protection medium has focused on switch back to SO2 originally applied by the industry prior to the introduction of SF6 gas.
It is well known that SO2 atmosphere strongly reduces the oxidation of molten magnesium by modifying the surface film and that producers of primary metal, sand and die casters have been using SO2 in gas form or generated (in situ) by adding sulphur powder to furnaces. SO2 is, however, toxic. In high concentrations and in contact with humidity it results in enhanced corrosion of steel equipment. The present occupational exposure limit in Norway is 2 ppm over an 8 hours period of time corresponding to a concentration of 5 mg/m3, and corresponding limits in Germany and North America are similar.
Consequently, it is an object of the present invention to provide a new and improved method of mixing and maintaining a pre-set level of SO2 in an air mix within narrow tolerances.
Another object of the present invention is to provide an apparatus ensuring environmentally safe mixing and feeding of the SO2 air mix into the Mg-furnaces/vessels.
Still another object of the present invention is to provide an improved method of fluxless melting of magnesium substantially reducing problems connected to formation of scaling on the crucible walls.
These and other objects and features are met by provision of the new method and apparatus according to the present invention as it appears from the attached patent claims 1-5.
The new method of mixing and maintaining of the pre-set level of SO2 in the air mix will now be described and readily understood from the following description under reference to the accompanying drawings, Figs. 1-3, and preferred embodiments/modes of operation, where
Fig. 1 shows schematically a flow chart of the mixing/feeding process,
Fig. 2 illustrates schematically in a vertical, partial cross-section a feeding arrangement (apparatus) usable in the process of fluxless melting of magnesium, and Fig. 3 shows schematically the applied furnace/vessel in a horizontal cross- section along line I-I
Referring to Fig. 1 illustrating schematically a flow chart of the mixing/feeding process applicable according to the present invention, a melting furnace 1 is equipped with charging device 2 to feed solid magnesium into the furnace, transferring device, e.g. transfer tube 3 to move subsequently the Mg-melt into and adjacent casting unit (furnace) here depicted as 4. By means of e.g. so-called gas displacement (metering) pump 5 the melt is fed in a controlled manner (doses) into any suitable casting equipment, e.g. the shown high pressure die casting machine 6.
According to the present invention and as an example of a preferred embodiment an apparatus arrangement for controlled mixing/feeding of the mixture SO2/dry air comprises a compressor 13 and a pressure bottle 14 providing (dry) air and SO2 gas, respectively, into the mixing device 9 comprising a mass flowmeters 10 and 12 for the air and SO2, respectively, and a control steering unit 11 to ensure an adequate pre-set concentration of SO2 in the gas mixture. The resulting gas mixture is then conducted through a feeding line 8 and distributed by means of manifolds (flowmeters) 7 and customary valves into the actual (part of) furnaces 1 and 4.
This is achieved by applying a double set of mass flowmeters 10,12 where the mass flowmeter 10 controlling the air flow is also in control of the mass flowmeter 12 so that the concentration of SO2 in the gas mixture will never exceed the pre-set level. In the case of an emergency situation, e.g. break down on the feeding line/equipment providing dry air, this "master" flowmeter 10 will automatically switch off also feeding of SO2. s "dry air" referred to in the description air having a dew point - 30°C is applied.
Using this sophisticated mixing unit ensures that the SO2 concentration may be kept very low and the distribution of the protection gas to the liquid. Mg surface is so uniform that emissions from furnace atmospheres to surroundings will be negligible and represents no hazard for foundry personnel.
With references to Figs. 2 and 3 illustrating schematically an arrangement of feeding means usable in the process of feeding/distribution of SO2/air mixture according to the present invention, Fig. 2 shows schematically in a partial, vertical cross-section the furnace 1 as a steel vessel accommodated in a thermally insulated furnace shell 20. The melting furnace is provided with a charging device 2 to introduce solid Mg into the furnace, a baffle plate 15 dividing the furnace into a charging sector and a main body of the melting furnace where the furnace design/configuration should assure a high ratio volume/surface area in order to minimise reaction(s) occurring between molten Mg and the atmosphere. Consequently, all lids and hatches must also be well tightened as illustrated in an exploded view showing details of lid seals 16. The gas mixture is provided to the furnace(s) through a sophisticated distribution system allowing the gas mixture to be evenly distributed close to the melt surface, e.g. by means of a ring tube 17 positioned along the furnace periphery in the vicinity of the melt surface as shown in Fig. 3. Fig. 3 illustrating schematically the applied melting furnace 1 in a horizontal cross-section taken along line I-I in Fig. 2, further depicts the charging zone (device) 2, dividing baffle plate 15 and a lid 19 for eventual removal of dross/sludge from the furnace.
The ring tube 17 is provided with a plurality of apertures ensuring an even distribution of the protective gas mixture by controlled directional impingement of the melt surface. Experiments conducted in industrial size furnaces with SO2 air mixtures applying the above method confirm that the SO2/air protection atmosphere protects effectively molten magnesium surfaces against oxidation.
The following reactions between the metal and the gas mixture may occur:
Mg(l) + O2 + SO2 → MgSO4(s)
MgSO4(s) + Mg(l) → MgO(s) + Mg(s)
MgS(s) + O2 + SO2 → MgSO4(s)
MgO(s) + SO2 + O2 → MgSO4(s)
It is believed that a sort of "self-reparation" of possibly disrupted/cracked layers of MgO(s) + MgS(s) occurs due to a further reaction between magnesium evaporated through such cracked opening and the cover gas.
Example 1
Summary of pilot trials conducted in full scale furnaces in laboratory:
Temperature of the melt 655-690°C Gas mixture flow rate /m2 melt surface 101/min SO2 concentration in the gas mixture 0.5-1.7% Duration of trials 47 hours Example 2
Tests have been carried out on an industrial scale in a hot-chamber casting machine. A mixing unit built according to the present invention provided SO2/dry air mixture for the furnace. Gas samples were frequently monitored (every four hours) both from the mixing unit, the furnace atmosphere and the working atmosphere as well.
Melt surface area 0.3 m2
Melt temperature 660°C
Flow rate of the gas mixture 7.3 l/min
Duration of trials 3 days
SO2 concentration in the (dry) air mixture 0.8%
SO2 concentration in the atmosphere 0.2 ppm
Gas samples of the atmosphere were collected at three differenct locations in the foundry - at operator level, in the vicinity of the charging lid and approximately 3 m above the floor. No significant differences were measured in the gas concentrations between the locations indicating a safe, controlled operation and an adequate ventilation of the foundry hall.
A controlled diluted SO2/air mixture was provided and maintained during the test periods, something being of crucial importance also for the life time of the applied steel equipment.
It is well known that both SO2 and SF6 in contact with humidity will accelerate steel corrosion. Deposits and reaction products may be formed on e.g. crucible/furnace walls, something which under unfavourable conditions can lead to metal eruptions from the furnace. Consequently, high concentration of SO2 combined with high humidity should be avoided.

Claims

Claims
1. Method of fluxless melting of magnesium and magnesium alloy metal comprising mixing of sulphur dioxide (SO2) and dry air and maintaining a protection gas-mixture atmosphere above molten metal, characterised in that a constant pre-set level of SO2 is maintained in the gas-mixture regardless of variations in actual gas-mixture consumption by means of at least two mass flowmeters (10,12) controlling the flow of dry air and SO2, respectively, where the dry air flowmeter (10) controls the SO2 flowmeter (12).
2. Method according to claim 1 , characterised in that the concentration of SO2 in the gas-mixture is in the range from 0.1 to 5 weight%.
3. Method according to claim 2, characterised in that the SO2 concentration is from 0.2 to 1.5 weight%.
4. Apparatus .for mixing/feeding of a protection gas-mixture comprising sources of dry air (13) and SO2 gas (14) and mixing device (9) comprising a mass flowmeter (10) for dry air and a mass flowmeter (12) for SO2 gas and steering unit (11) for monitoring and maintaining the composition and flow of the gas-mixture characterised in that the air mass flowmeter (10) is also in control of/steering the SO2 gas flowmeter (12). Apparatus according to claim 4, characterised in that the mass flowmeters (10,12) are digital mass flowmeters.
PCT/NO1998/000200 1997-07-07 1998-07-03 Method of fluxless melting of magnesium WO1999002287A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU87534/98A AU8753498A (en) 1997-07-07 1998-07-03 Method of fluxless melting of magnesium
DE69805195T DE69805195D1 (en) 1997-07-07 1998-07-03 METHOD FOR MELAGON-FREE MELTING
AT98939025T ATE216932T1 (en) 1997-07-07 1998-07-03 METHOD FOR THE SLACK-FREE MELTING OF MAGNESIUM
JP2000501854A JP2001509543A (en) 1997-07-07 1998-07-03 Solvent-free melting of magnesium
EP98939025A EP1019211B1 (en) 1997-07-07 1998-07-03 Method of fluxless melting of magnesium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO973149A NO304893B1 (en) 1997-07-07 1997-07-07 Process for melting magnesium without flux and equipment for this
NO973149 1997-07-07

Publications (2)

Publication Number Publication Date
WO1999002287A1 true WO1999002287A1 (en) 1999-01-21
WO1999002287A8 WO1999002287A8 (en) 1999-04-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO1998/000200 WO1999002287A1 (en) 1997-07-07 1998-07-03 Method of fluxless melting of magnesium

Country Status (7)

Country Link
EP (1) EP1019211B1 (en)
JP (1) JP2001509543A (en)
AT (1) ATE216932T1 (en)
AU (1) AU8753498A (en)
DE (1) DE69805195D1 (en)
NO (1) NO304893B1 (en)
WO (1) WO1999002287A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122322A1 (en) * 2000-02-07 2001-08-08 Air Products And Chemicals, Inc. Blanketing molten non-ferrous metals and alloys with fluoride gases having reduced global warming potential
US6521018B2 (en) 2000-02-07 2003-02-18 Air Products And Chemicals, Inc. Blanketing metals and alloys at elevated temperatures with gases having reduced global warming potential
EP1402977A1 (en) * 2002-09-25 2004-03-31 Oskar Frech Gmbh & Co. Shielding gas device for pressure die casting machines
CN107289782A (en) * 2016-03-31 2017-10-24 中国科学院金属研究所 A kind of many stove association type smelting-casting equipments and technique for producing high-cleanness, high magnesium or magnesium alloy

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2018407A1 (en) * 1969-05-05 1971-02-25 Fruehling J Protective atmosphere for magnesium and magnesium alloys
US4478270A (en) * 1981-04-01 1984-10-23 Interlake, Inc. Apparatus for casting low-density alloys
US4550763A (en) * 1980-12-11 1985-11-05 Institute Po Metaloznanie I Technologia Na Metalite Method and machine for pressure diecasting
EP0531810A2 (en) * 1991-09-09 1993-03-17 LOI Thermprocess GmbH Process to change an industrial furnace athmosphere
WO1997021510A1 (en) * 1995-12-14 1997-06-19 Commonwealth Scientific And Industrial Research Organisation Ingot mould system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2018407A1 (en) * 1969-05-05 1971-02-25 Fruehling J Protective atmosphere for magnesium and magnesium alloys
US4550763A (en) * 1980-12-11 1985-11-05 Institute Po Metaloznanie I Technologia Na Metalite Method and machine for pressure diecasting
US4478270A (en) * 1981-04-01 1984-10-23 Interlake, Inc. Apparatus for casting low-density alloys
EP0531810A2 (en) * 1991-09-09 1993-03-17 LOI Thermprocess GmbH Process to change an industrial furnace athmosphere
WO1997021510A1 (en) * 1995-12-14 1997-06-19 Commonwealth Scientific And Industrial Research Organisation Ingot mould system

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122322A1 (en) * 2000-02-07 2001-08-08 Air Products And Chemicals, Inc. Blanketing molten non-ferrous metals and alloys with fluoride gases having reduced global warming potential
US6521018B2 (en) 2000-02-07 2003-02-18 Air Products And Chemicals, Inc. Blanketing metals and alloys at elevated temperatures with gases having reduced global warming potential
EP1402977A1 (en) * 2002-09-25 2004-03-31 Oskar Frech Gmbh & Co. Shielding gas device for pressure die casting machines
WO2004030849A1 (en) * 2002-09-25 2004-04-15 Oskar Frech Gmbh + Co. Kg Protective gas device for pressure die-casting machines
US7290588B2 (en) 2002-09-25 2007-11-06 Oskar Frech Gmbh & Co. Kg Protective gas device for pressure die-casting machines
CN107289782A (en) * 2016-03-31 2017-10-24 中国科学院金属研究所 A kind of many stove association type smelting-casting equipments and technique for producing high-cleanness, high magnesium or magnesium alloy
CN107289782B (en) * 2016-03-31 2019-05-07 中国科学院金属研究所 A kind of more furnace association type smelting-casting equipments and technique producing high-cleanness, high magnesium or magnesium alloy

Also Published As

Publication number Publication date
EP1019211A1 (en) 2000-07-19
JP2001509543A (en) 2001-07-24
EP1019211B1 (en) 2002-05-02
DE69805195D1 (en) 2002-06-06
NO973149D0 (en) 1997-07-07
ATE216932T1 (en) 2002-05-15
WO1999002287A8 (en) 1999-04-15
NO973149L (en) 1999-01-08
NO304893B1 (en) 1999-03-01
AU8753498A (en) 1999-02-08

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