US3918959A - Process for production of magnesium - Google Patents

Process for production of magnesium Download PDF

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US3918959A
US3918959A US536175A US53617574A US3918959A US 3918959 A US3918959 A US 3918959A US 536175 A US536175 A US 536175A US 53617574 A US53617574 A US 53617574A US 3918959 A US3918959 A US 3918959A
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briquets
magnesium
calcium
pressure
reaction
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Tomoo Matsushima
Tsutou Odajima
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Resonac Holdings Corp
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Showa Denko KK
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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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium

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  • PROCESS FOR PRODUCTION OF MAGNESIUM BACKGROUND OF THE INVENTION This invention relates to an improved process for the production of metallic magnesium by the thermic reduction of magnesium oxide at an elevated temperature.
  • the present invention relates to a vacuum reduction method and, more particularly. to the silicothermic reduction method.
  • the reduction reaction gives birth to a reaction residue, which is discharged in the form of a high-temperature solid in the case of the Pidgeon Process and in the form of a high-temperature molten slag in the case of the Magnetherm Process.
  • the capacity for magnesium production per unit reactor namely one retort in the Pidgeon Process or one electric furnace in the Magnetherm Process, is 50 to 90 kg/day or 2.5 to 7.5 tons/day. Thus, the unit capacity is much greater by the Magnetherm Process.
  • the reaction residue is discharged in the form of a high-temperature molten slag and, owing to addition of alumina to the raw materials, the melting point of the reaction residue is lowered so that at the working temperature of the electric furnace, the reaction residue retains a mo]- ten state possessed of suitable electricconductivity.
  • Said reaction residue therefore, constitutes itself an electric resistor and, because of the Joule effect, functions as an internal heat source of the electric furnace. Further, the molten slag can easily be discharged by means of tapping procedure. Because of these advantages, this process permits use of a large capacity electric furnace.
  • An object of this invention is to provide an improved process of notably high yield for the manufacture of 2 magnesium by the dry thermic reduction of magnesium oxide.
  • a process which comprises, as a first stage, blending a substance composed of magnesium oxide and calcium oxide, generally known as dolomite, with silicon or ferrosilicon or a mixture thereof, shaping the blend in the form of briquets, subsequently heating the briquets in an inert atmosphere under temperature and pressure conditions capable of substantially inhibiting formation of magnesium vapor, said temperature being not lower than the melting temperature of calcium-silicon alloy, and thereby forming calcium-silicon alloy within said briquets, and, as a second stage, placing the briquets containing the calcium-silicon alloy in a steel retort or tightly closed electric furnace and heating the briquets therein to produce magnesium vapor.
  • a substance composed of magnesium oxide and calcium oxide generally known as dolomite
  • silicon or ferrosilicon or a mixture thereof shaping the blend in the form of briquets, subsequently heating the briquets in an inert atmosphere under temperature and pressure conditions capable of substantially inhibiting formation of magnesium vapor, said
  • the magnesium vapor is solidified at a cooled section of the steel retort or it is introduced into a separate condenser to be liquefied.
  • the briquets having calcium-silicon alloy formed therein are hard enough to resist disintegration and show high thermal conductivity. Particularly the fact that magnesium oxide and the calcium-silicon alloy are held in a state of intimate contact within the briquets brings about highly advantageous conditions for the reduction reaction.
  • reaction velocity is notably high, the rate of reaction achieved is high and the vapor pressure of magnesium is also high as compared with those obtained by known methods, there is enjoyed an advantage that the operation can be performed not only under a pressure above normal pressure but even under a pressure even below normal pressure, the production rate or yield of magnesium is higher than that of known methods and production can be made more economical.
  • FIG. 1 is a graph showing the results of a test conducted on the rate of reaction in the formation of calcium-silicon alloy by the reaction between calcium oxide from calcined dolomite and silicon.
  • FIG. 2 is a graph showing the relation between the atomic fraction of Ca and Si and the vapor pressure of magnesium observed in the reduction of magnesium oxide with calcium-silicon alloy.
  • FIG. 3 represents X-ray diffraction patterns substantiating presence of reactants and products described in the specification of this invention.
  • FIG. 4 is a reaction apparatus used in Example 1 for calcining crude briquets.
  • FIG. 5 is a reducing apparatus used in Example 1 and Comparative Example 1.
  • FIG. 6 is a graph showing the relation between the reaction time and the rate of reaction determined in Example 1 and Comparative Example '1.
  • FIG. 7 is a reducing apparatus used in Example 2 and Comparative Example 2.
  • This invention relates to improvements pertaining to and in the method for the manufacture of magnesium 3 by the silicothermic reduction of calcined dolomite.
  • This invention originates in the mechanism of reaction newly brought to light by the inventors and is concerned with a process for the production of magnesium by the thermic reduction of calcined magnesium oxide with silicon accomplished at an efficiency higher than is obtained by known methods.
  • calcined dolomite used herein below in the description shall be interpreted as either calcined natural or artificial dolomite containing magnesium oxide and calcium oxide substantially equimolarily and products obtained by calcining mixture of magnesium oxide with calcium oxide and mixtures thereof with carbonates or hydroxides.
  • inert gas shall refer to gases which refrain from reacting with other coexisting substances in the course of a reaction. Specifically for the purpose of the present invention, argon, neon, helium and hydrogen are used either singly or in the form of a mixture as the inert gas.
  • the test results covering the reaction velocity in the formation of the calcium-silicon alloy by the reaction between the calcium oxide from the calcined dolomite and silicon are shown in FIG. 1.
  • Powdered calcium oxide and silicon were intimately blended in amounts to give a ratio of 4 mol of CaO to 5 mol of Si sufficient for producing calcium silicon alloy particularly calcium disilicide (CaSi by reducing calcium oxide from the calcined dolomite without excess or deficiency and the resultant blend was shaped in the form of briquets having an apparent density of about 1.4 to 2.2.
  • the sample briquets were heated in an inert atmosphere of argon at varying temperatures of 850, 950, 1 100 and l200C for a prescribed time.
  • the heating was carried out in a high-frequency furnace for the temperature of briquets to be elevated quickly to the indicated levels, so that the initial conditions of reaction and their possible effects were negligible.
  • Yields of CaSi were determined by X-ray diffraction analysis and differential thermal analysis.
  • the rate of reaction in the formation of CaSi is indicated by the ordinate and the reaction time (in minutes) by the abscissa.
  • the coordinates for the temperatures of 1100 and l200C correspond to the upper abscissa graduation and those for the temperatures of 950 and 850C to the lower abscissa graduation respectively.
  • the present invention resides in applying what the inventors have thus brought to light to the process for magnesium production.
  • the reaction of the calciumsilicon alloy with the calcined dolomite proceeds in the paths expressed by the following elementary reaction formulas (1) through (4).
  • the vapor pressure of magnesium is represented in accordance with reaction (2) through (4).
  • P denotes the vapor pressure of magnesium, a the activity of silicon and a the activity of calcium respectively.
  • n and m are reaction fractions of the formulae (2) and (3) respectively. Accordingly, m/n equals the ratio of the corresponding elementary reactions.
  • FIG. 2 shows the results.
  • Sample briquets having an apparent density of about 1.8 were prepared by mixing magnesium oxide, calcium oxide and calcium-silicon alloy having a different Si/Ca atomic ratio, and shaping the blends.
  • the reaction temperature was fixed at 1200C and the heating was given in a stream of argon to measure the equilibrium pressure of magnesium vapor.
  • the ordinate indicates the vapor pressure of magnesium in mmHg (P and the abscissa indicates the atomic fraction of Ca and Si.
  • A represents thermodynamically calculated values and B experimentally found values.
  • L is liquidus point of the alloy in which the primary precipitation of Ca-Si occurs
  • L is liquidus point of the alloy in which the primary precipitation of Si occurs.
  • the deviation of B from A results from the fact that thermodynamic data under consideration are presumably not settled.
  • the curve of B the observed value of vapor pressure at the atomic fraction of 0.667Si and of 0.333Ca is found to be approximately equal to the condition expressed by the reaction formula of the Pidgeon Process and this vapor pressure is in agreement with the value observed by investigators. Both the experimentally and thermodynamically determined curves show that the vapor pressure versus composition depends upon the content of calcium.
  • .P denotes the vapor pressure of magnesium of standard state thermodynamically, and a a a denote the activities of Si, MgO and SiO respectively.
  • the process can be operated at a notably high vapor pressure of magnesium which is established by the reaction under consideration. This advantage brings about an effect of inhibiting subsidiary reaction products such as CO and SiO which pose a serious problem to the Magnetherm Process.
  • the production of calcium-silicon alloy can be obtained by using ferrosilicon instead of silicon. It has been demonstrated by X-ray diffraction analysis that in the substitute use, silicon corresponding to the amount of silicon resulting from the deduction of the compound equivalent to FeSi in the case of 75% ferrosilicon and that from the deduction of the compound equivalent to FeSi in the case of ferrosilicon respectively take part in the reaction preferentially.
  • FIG. 3 represents X-ray diffraction patterns obtained by reactants and products in the various tests mentioned above.
  • the diagrams No. l A through F are standard diffraction lines used to detect reactants and products.
  • the diagram A represents use of pure silicon and the diagram B use of ferrosilicon; in the range of the used composition, FeSi is also detected.
  • the diagram C represents use of 50% ferrosilicon, although presence of FeSi is detected besides the compound mentioned above.
  • the diagram D represents a calcium-silicon alloy having a composition of 62.9% of Si, 30.1% of Ca and the remainder of Fe.
  • the diagram E represents use of calcium disilicide prepared stoichiometrically.
  • the diagram F represents use of calcined dolomite as the raw material.
  • the diagrams No. 2 through No. 5 relate to briquets which were stoichiometrically prepared, with the aim of producing CaSi to include calcium oxide and pure silicon or 75% or 50% ferrosilicon at a molar ratio of said CaO to free silicon of 4 to 5 and which were thereafter subjected to heat treatment in the first stage to produce CaSi and accompanying Ca- SiO so that unreacted Si is recognizable.
  • the diagrams No. 6 and No. 7 represent the preparations having calcium oxide and silicon blended in amounts to give a molar ratio CaO/Sifl/3 and 4/2 respectively, each having silicon content of less than is stoichiometrically required.
  • the diagrams furnish a clear proof that silicon does not react with magnesium oxide directly but reacts preferentially with calcium oxide to produce CaSi,
  • this invention relates to a process which comprises, as a first stage, adding silicon or ferrosilicon to calcined dolomite or a magnesium-containing raw material having magnesium de mixed with calcium oxide, homogeneously blendand shaping the mixture in the form of briquets, lting the briquets in an inert atmosphere under the iperature and pressure conditions capable of subntially inhibiting the formation of magnesium vapor 1 thereby giving rise to calcium-silicon alloy within briquets and, as a second stage, heating the briquets itaining the calcium-silicon alloy to effect the rered reduction.
  • the briquets are generprepared by pulverizing natural or artificial dolo- 1e and silicon or ferrosilicon to a particle size finer n 80 mesh and blending the resultant powders.
  • ferrosilicon is used as the silicon tree, it is adequate to determine the amount of ferrocon so as to meet the aforementioned molar ratio in ms of free silicon equivalent.
  • the briquets thus preed are then heated.
  • temperature for s heating since the ratio of reaction is extremely low temperatures under 950 C as indicated in FIG. 1, lower limit of reaction temperature is fixed at 50C.
  • the upper limit of temperature for this heating st satisfy the conditions capable of substantially initing the formation of magnesium vapor during the iting. Said conditions are selected from the formula ressing the relation between the temperature and vapor pressure of magnesium touched upon in (3) the results of test described above.
  • T stand for absolute temperature required for heating the brizts under normal pressure, and the pressure (in iHg) is required to exceed the value of P, which is culated from the following equation.
  • the heating is given advantageously at a nperature of about 1500C under normal pressure 1 of about l200C under a reduced pressure of about mmHg. If the briquets are heated at the temperature isfying the conditions just described, then the reacn leading to the formation of calcium-silicon alloy is :elerated, the formed calcium-silicon alloy is obied in a molten state, the briquets consequently ac- .re hardness enough to withstand disintegration. the rmal conductivity is enriched, the magnesium oxide 1 the reducing agent in the briquets are brought into tate of intimate contact and conditions highly advaneous for the reducing reaction in the subsequent p are brought about.
  • the briquets are subsequently vjected to solid-phase reduction in the following p. If, in this case, they are exposed to a temperature :eeding the melting point of the calcium-silicon alloy itained therein, or even after they have thoroughly eased magnesium vapor, the briquets themselves are ained fast by the magnesium oxide or the high meltdicalcium silicate resulting from the reduction and, refore, are kept from being disintegrated. Jow a description will be given of the reduction to ich the briquets containing the calcium-silicon alloy subjected.
  • the reaction conditions (temperature 1 pressure) for this reduction can be selected in acdance with the vapor pressure of magnesium and reaction velocity.
  • the heating is required to be given under a pressure lower than the pressure which is calculated from the formula of the relation between the pressure P (mmHg) and the absolute temperature T touched upon in (3) of the test results described above.
  • T stand for the absolute temperature of heating, and the pressure will have to be lower than the pressure P (in mmHg) to be calculated from the following equation.
  • the equilibrium pressure of magnesium vapor at the operation temperature is of the order of several tens of mmHg at most.
  • the countertype of the present invention plainly exceeds this level.
  • the lower limit of the temperatures at which the present invention can manifest its characteristic features should, therefore, be fixed at l200C (the temperature at which the equilibrated pressure of magnesium vapor exceeds 40 mmHg).
  • the equilibrium pressure of magnesium vapor notably increases as the temperature raises from the limit l200C and the degree to which the operating pressure within the reaction system is decreased can be mitigated in proportion as the temperature increases over this level.
  • the reaction can be carried out under a pressure above 25 mmHg.
  • Conditions desirable for obtaining high productivity are 5 to 10 mmHg at l200C and 50 to 100 mmHg at lSO0C, for example.
  • the upper limit of temperature for the reduction reaction no restrictive factor arises from the reaction itself. It is determined by such factors as the durability of the reaction system to heat and the thermal stability of the molten slag. With a view to permitting the mineral slag to be discharged in a molten stage, therefore, the upper limit of temperature determinable from the data on phase diagram of mineral slag is l700C.
  • the briquets having the calcium-silicon alloy formed therein are placed within the heating furnace kept at l200C to l700C, the reduction of magnesium oxide by the calcium-silicon alloy is carried out very rapidly and a major amount of magnesium vapor is evolved. Then the magnesium vapor is introduced to the condenser and collected in the liquid state. If an internally heated furnace is employed as the heating furnace, the molten slag is retained continuously within the furnace throughout the continuous operation thereof.
  • the briquets having the calcium-silicon alloy formed therein at times float on the surface of the molten slag or may be partially or totally submerged in the molten slag, and complete the magnesium production with notably high vapor pressure of magnesium.
  • the process of this invention when carried out by using such furnace as is employed in practicing the Magnetherm Process, Pidgeon Process or some other similar known process, brings about a notable improvement in the productivity and yield of magnesium permits continuous feeding of raw materials provides effective inhibition of harmful secondary reactions, and so on.
  • the heat treatment in the first stage and all the treatments in the second stage according to the method of the present invention can be carried out in one furnace by using an internally heated furnace containing therein a molten slag and having such a construction that the crude briquet to be cast into the furnace forms therein a calcium-silicon alloy before it reaches the molten slag, and the resultant briquet reaches the molten slag.
  • 1 denotes an upper hopper, 2 a reaction zone, 3 a briquet receptacle, 4 and 5 a gas inlet and outlet, 6 an external auxiliary heater, (with a metal or carbon serving as a heating element; a proper external gas flame heater or electric resistance generator may be used as occasion demands) 7 a high-frequency generator, 8 crude briquets and 9 briquets having calciumsilicon alloy formed therein.
  • an external auxiliary heater with a metal or carbon serving as a heating element; a proper external gas flame heater or electric resistance generator may be used as occasion demands
  • 7 a high-frequency generator
  • the fired briquets 9 stored in the raw material bin ll were conveyed by the screw feeder l2, thrown into the internally heated reaction furnace l3 and retained for a fixed length of time in the furnace interior.
  • the solid siag formed was discharged by the screw 14 through the outlet 15. Inside this furnace, the fired briquets were heated and MgO in the briquets was reduced to give rise to magnesium vapor.
  • the furnace interior was maintained under conditions of l0 to 10 mmHg of pressure and l300C of temperature.
  • Example 2 The procedure of Example 1 was followed by using entirely the same raw materials to produce briquets 1 1 having calcium-silicon alloy formed therein. The fired briquets were then subjected to reduction reaction by using an apparatus like the one shown in FIG. 7 under the various conditions described hereinbelow.
  • 2] denotes a vertically movable electrode, 22 a carbonaceous furnace base, 23 a tap for the molten mineral slag, 24, 25 and 26 each a briquet bin, 27 the molten mineral slag composed preponderantly of Ca SiO Al O system, 28 a magnesium vapor pump, 29 a magnesium vapor condenser, 30 a magnesium receptacle and 31 an air discharge outlet.
  • the apparatus shown in FIG. 7 is an improved vacuum-tight, single-electrode furnace whose electrode is rendered vertically movable under reduced pressure.
  • the reaction ratio was studied under various conditions by changing the feed rate of raw materials, with the fumace interior maintained under 50 mmHg of pressure and l400 or 1500C of temperature.
  • the results of the test are shown in the ac companying table under the columns, B-l through B-S.
  • the actual power load was 48 to 55 KW/kgMg/hr.
  • the reaction ratio was calculated on the basis of the yield of magnesium.
  • COMPARATIVE EXAMPLE 2 An apparatus like the one shown in FIG. 7 and described in Example 2 was used, calcined natural dolomite (containing 37.4% by weight of MgO and 59.7% by weight of CaO coarsely crushed into grains 5 to 14mm in diameter was thrown into the bin 24, 80% ferrosilicon coarsely crushed into grains 5 to l4mm in diameter was fed into the bin 25 and powdered alumina prepared by the Bayer Process for use in electrolysis of aluminum was introduced into the bin 26. They were blended to a regulated composition and treated in accordance with the Magnetherm Process. To be specific, the calcined natural dolomite. ferrosilicon and alumina were blended in amounts to give a weight ratio of 77/14/9 and fed into a molten slag (consisting of 54.8%
  • Example 2 The results of Example 2 and those of Comparative Example 2 are compared in the table.
  • This table furnishes a clear proof that the effects of the present invention are conspicuous.
  • the data of B series are seen to be superior to those of A clearly in terms of consumption of raw materials, feed rate of raw materials, yield of magnesium (kg/hr.) and reaction ratio of magnesium.
  • EXAMPLE 3 Briquets having calcium-silicon alloy formed therein were prepared by faithfully following the procedure of Example 1. These briquets were subjected to operations performed under varying magnitudes of pressure not lower than normal pressure. According to (3) of the results of test described in the detailed description, the temperature at which the equilibrium pressure of magnesium vapor issuing from the briquets of this invention reaches 760 mmHg is calculated to be about 1520C. Actually in the present example, however, the reaction temperature was fixed at I600C. At this reaction temperature, the vapor pressure of magnesium reached 1330 mmHg, a value amply sufficient for smooth progress of the reaction.
  • the vacuum system was so controlled that the inner pressure of the reaction apparatus reached 760 mmHg and 1 I00 mmHg during the operation.
  • the results of the operation were as shown in the table under the column, B-6 and B7.
  • the actual electric power against the re action was invariably about 5.5 KW/kgMg/hr.
  • the operation of the present invention could be carried out when the apparatus interior pressure is higher than normal pressure. In this case, both productivity and reaction ratio were decidedly higher than could be obtained by the conventional process (data under the column A, in the of Cao, 28.5% of SiO 15% of A1 0 and 15-29: of same table).
  • the values for the 8 series are those proportionate to the value (h25 ing/hour) for A.
  • a process for obtaining metallic magnesium from a mixture of magnesium oxide with calcium oxide as the raw material by reducing said mixture at an elevated temperature to give rise to magnesium vapor and cooling said magnesium vapor the improvement which comprises two stages, the first stage of adding at least one member selected from the group consisting of silicon and ferrosilicon to said mixture consisting of magnesium oxide and calcium oxide, blending and shaping the resultant mixture in the form of briquets, and heating said briquets in an inert atmosphere under temperature and pressure conditions capable of substantially inhibiting the formation of magnesium vapor, said temperature being not lower than the melting point of calcium-silicon alloy and thereby giving rise to calciumsilicon alloy within said briquets and the second stage of heating, in a heating furnace, the briquets having calcium-silicon alloy formed therein for thereby reducing the magnesium oxide present in said briquets into metallic magnesium.
  • said heating furnace is an internally heated furnace containing therein a molten slag and having such a construction that the crude briquets to be cast into the furnace are heated to each form therein a calcium-silicon alloy before they reach the molten slag, and the resultant briquets reach the molten slag so as to allow the reduction of magnesium oxide, in which the heat treatment in the first stage and all the treatments in the second stage are carried out.
  • the heating furnace is an internally heated furnace containing a molten slag
  • the pressure of the inert atmosphere is at least 25 mmHg
  • the briquets having calcium-silicon alloy formed therein are heated in a state such that the briquets float on said molten slag.
  • the heating furnace is an internally heated furnace containing a molten slag
  • the pressure of the inert atmosphere is at least 25 mmHg
  • the briquets having calcium-silicon alloy formed therein are heated in a state such that the briquets are wholly or partially submerged in said molten slag.
  • the briquets are generally prepared by pulmarizing natural or artificial dolomite and silicon or ferrosilicon particle size timer than 80 an? blending the resultant powders.
  • the raw materials are desired. to be mixed at a stoichiometric ratio or roughly at a molar: ratio MqO/CaO/Si l/l/C. 5.
  • the equimolar ratio LlgO/CaO 1/1 is practically satisfied in natural dolomite.
  • i'errosilicon is used as the. silicon source, it is adequate to de1;;e.rr:::i2:e the :mount of ferrozailicon so as to meet the aforementioned molar ratio in terms of free silicon equivalent.
  • Patent No. 3 ,918 ,959 Page 4 of 4 the heatin is: given a'tw zmtzxgreously at a temperature of about 150 "C under normal pressure and of about l200"C under .7 "viuce-i! prev-zsn'u a o: arm-1t .J'J m5; the Lriquets are heat-e0.
  • the briquets consequently acquire hardness GIICZgh to withstand disintegration, the th rmal conductivity is enricherl;
  • the meqncsium oxide and the r-e'iucinq agent in the briquets are intimate contact and conditions highly brought into a state 0 advantageous for the reducing reaction in the subsequent step are brought about.
  • the briqzzets are subsequently subjected. to solid phase .roouction in the 013. wing step. If, in this case, they are ed to a temperature exceeding the melting point of the c:1l-t:i1in sj.i. co;1 alloy cow. ins-3 tr; rein, or e en after they have thoroughl released magnesium vapor, the briquets themselves retained! fast by the magnesium oxide or the high melting dicalcium silicate resulting from the reduction and, therefore, are kept from being disintegrated.
  • reaction conditions for this re--- cluction can be selected in accordance with the vapor pressure of Cally, the heating mngnerziuta and the reaotion velocity. Specif is re?

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4015978A (en) * 1975-02-21 1977-04-05 Showa Denko Kabushiki Kaisha Method for production of magnesium-containing briquets and magnesium
GB2532784A (en) * 2014-11-28 2016-06-01 Hugh D'arcy-Evans Donald Reduction furnace method and apparatus
CN107523701A (zh) * 2017-08-22 2017-12-29 西安交通大学 一种常压硅热还原金属镁的方法

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JP2015514875A (ja) * 2012-04-27 2015-05-21 カン ウォンソプＫＡＮＧ， Ｗｏｎ Ｓｕｂ フェロニッケルスラグを利用したフェロシリコンとマグネシウムの製造方法及びそれに用いられる製造装置及び溶融還元炉

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Publication number Priority date Publication date Assignee Title
US2390016A (en) * 1944-03-10 1945-11-27 New Jersey Zinc Co Charge preparation
US3441402A (en) * 1965-12-15 1969-04-29 Exxon Research Engineering Co Continuous process for the production of magnesium
US3837843A (en) * 1972-10-30 1974-09-24 Fr D Electrometallurgie Soc Process for thermal production of magnesium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2390016A (en) * 1944-03-10 1945-11-27 New Jersey Zinc Co Charge preparation
US3441402A (en) * 1965-12-15 1969-04-29 Exxon Research Engineering Co Continuous process for the production of magnesium
US3837843A (en) * 1972-10-30 1974-09-24 Fr D Electrometallurgie Soc Process for thermal production of magnesium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4015978A (en) * 1975-02-21 1977-04-05 Showa Denko Kabushiki Kaisha Method for production of magnesium-containing briquets and magnesium
GB2532784A (en) * 2014-11-28 2016-06-01 Hugh D'arcy-Evans Donald Reduction furnace method and apparatus
CN107523701A (zh) * 2017-08-22 2017-12-29 西安交通大学 一种常压硅热还原金属镁的方法

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BE828971A (fr) 1975-09-01
ZA748168B (en) 1976-01-28
NO744699L (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-07-28
IT1027186B (it) 1978-11-20
FR2256254A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-07-25
JPS538287B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1978-03-27
PH10534A (en) 1977-05-30
DE2460563A1 (de) 1975-07-10
CA1031574A (en) 1978-05-23
JPS5096413A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-07-31
FR2256254B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1978-12-22

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