Process and apparatus for vacuum distillation of high-purity magnesium

Abstract

A process for producing high-purity magnesium by means of distillation at reduced pressure, characterized in that, the high-purity magnesium condenses in the liquid state, whereby the starting material in the form of a magnesium-containing melt is present together with the upper region of a condensation vessel in the upper region of a retort, whereby the retort consist of a material that releases no volatile impurities into the magnesium steam, whereby the upper region of the retort is brought to a temperature above the boiling point of magnesium, within the limits of two level lines, and is then held constant, such that steam rises from the boiling magnesium-containing metal melt and fills the interior of the upper region of the retort, whereby the steam infiltrating the upper region of the condensation vessel condenses below the lower level line and collects as high-purity melt in the lower region of the condensation vessel, and whereby in order to prevent contaminated melt that drops from the region above the upper level line from reaching the opening of the condensation vessel, this is protected by a cover, which conveys the impure magnesium back again into the melt.

Claims

1. An apparatus for producing high-purity magnesium by means of distillation at reduced pressure, the apparatus comprising: a retort and a condensation vessel protected by a cover, whereby an upper region of the condensation vessel is in an upper region of the retort, whereby the upper region of the retort is surrounded by a heating element, suitable for heating the upper region of the retort between two different level lines to a temperature above the boiling point of magnesium, and whereby the condensation vessel is arranged in a way, that the lower part of the condensation vessel is located below the level lines and at a temperature below the boiling point of magnesium, further whereby the condensation vessel is integrally constructed with a closed bottom.

2. The apparatus according to claim 1, characterized in that, the retort is made of stainless steel.

3. The apparatus according to claim 1, characterized in that, the cover comprises graphite.

4. The apparatus according to claim 1, characterized in that, a supply chamber is connected to the retort, whereby the supply chamber is connected with means for evacuating the retort.

5. The apparatus according to claim 4, whereby the supply chamber is arranged above the retort.

6. The apparatus according to claim 1, whereby the lower part of the condensation vessel is surrounded by an insulation layer dimensioned to hold the temperature between the melting temperature and the boiling temperature.

7. The apparatus according to claim 1, whereby the bottom of the condensation vessel is not insulated.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The process according to the invention will be explained hereinafter on the basis of three apparatus examples.

(2) FIG. 1 shows a diagram of an apparatus according to the invention having the features essential to the invention in accordance with the teaching of the independent patent claim.

(3) FIG. 2 shows a cross section through an exemplary apparatus for producing high-purity magnesium.

(4) FIG. 3 shows a cross section through a further exemplary apparatus for producing high-purity magnesium.

DETAILED DESCRIPTION

(5) In FIG. 1 the elements of the first apparatus example are illustrated purposefully in geometrically simple form in order to emphasize the fact that the central inventive concept is based less on the specific form of these parts, but more on the functionality of these parts in conjunction with the temperature distribution within the retort. The starting material 2 in the form of a magnesium-containing metal melt is present together with the upper region 32 of a condensation vessel 3, preferably made of a high-purity graphite, in the upper region 11 of a retort 1 produced for example from stainless steel and having an arbitrary cross section, wherein a cylindrical cross section is most favourable in practice. The upper region 11 of the retort is brought by a heating element 5 surrounding it, for example in the form of a resistance furnace, to a temperature above the boiling point of the magnesium, within the limits of the level lines 8 and 81, and is then held constant, such that steam rises from the boiling magnesium-containing metal melt 2 in accordance with the arrows 91 and fills the interior of the upper region 11 of the retort 1, wherein it can also condense into liquid above the level line 81 and then flows back downwards again into the melt 2. Since stainless steel reacts slightly with liquid magnesium, the magnesium melt is contaminated by the alloy elements of the stainless steel upon contact therewith, however, since these elements have an irregularly lower steam pressure compared with magnesium, this contamination is not noticeable in the steam.

(6) In order to prevent contaminated melt that drops from the region above the level line from reaching the opening 31 of the condensation vessel 3, this is protected by a cover 4, selectively also consisting of graphite, which conveys the impure magnesium back again into the melt 2. The cover 4 can be supported here directly on the upper region 32 of the condensation vessel 3 or can also be connected laterally or from above to the inner wall of the retort. In any case however, the fastening has to be formed such that the cover can be removed temporarily without difficulty in order to remove the solidified high-purity magnesium 21 from the condensation vessel 3.

(7) The melt of the magnesium-containing starting material 2 is in direct contact with the outer surface of the condensation vessel 3 in the region 32 during the distillation process in the case of this apparatus example. Since, at the end of the distillation process, practically all starting material is evaporated, the condensation vessel is empty again. Any melt that has infiltrated into the gap between the region 31 of the condensation vessel and the region 12 of the retort is irrelevant here, since the condensation vessel does not necessarily have to be removed from the retort in order to remove the solidified magnesium. The steam infiltrating into the upper region 32 of the graphite crucible in accordance with the arrow 92 condenses below the level line 8 and collects as high-purity melt 21 in the lower region 33 of the graphite crucible. In order to prevent a boiling of this high-purity melt 21, a minimum pressure can be maintained within the retort by means of an inert gas, for example argon, which brings the boiling point of the magnesium above the temperature prevailing in the region 33. Here, the temperature profile in particular of the lower part 33 of the condensation vessel 3 is determined by a separately adjustable heating element 51.

(8) Via a barrier unit 6, for example in the form of a disc valve, which is pressed against a seat 62, for example in the form of a ceramic or graphite felt packing, via an externally actuatable push rod 61 that can be displaced through a vacuum feedthrough, the retort 1 can be connected to the supply chamber 13 upon movement of the push rod 61 in the direction of the arrow 93. Here, the barrier unit 6 with the valve disc and the seat 62 is present in the current example together with the upper region 11 of the retort 1 above the level line 81, that is to say at a temperature above the melting point of magnesium, such that solid magnesium cannot be deposited in the region of the barrier unit, whereby the function thereof is ensured.

(9) The supply chamber 13, in its colder region above the level line 82, which symbolises the isotherm of the melting point, has a cover 14, preferably in the form of a removable vacuum flange, which has a number of connections besides the vacuum feedthrough 63. Here, one connection leads via a line 71 and a valve 72 to a vacuum pump 73, a further connection leads via a line 74 to a vacuum measuring instrument 75, and a third connection leads via a line 76, a valve 77 and a pressure and/or flow regulator 78 to an inert gas source 79, for example in the form of an argon pressure cylinder.

(10) Once the retort 1 has been evacuated via the supply chamber 13 and then brought to the temperatures necessary for the distillation process, the barrier unit 6 is then opened only for a short period for the purpose of pressure adjustment and pressure correction so as to avoid excessive condensation of magnesium steam in the supply chamber 13. The duration of the closed periods is dependent here on the rise of pressure during the closed periods. In the ideal case, with sufficient degassing of highly gas-releasing parts, for example consisting of a graphite of low quality, or with use of parts made of high-purity graphite, the barrier unit 6 can remain closed for a long period of time and is only opened briefly at long intervals for the purpose of pressure monitoring. If the pressure in the meantime rises above an upper setpoint value, whereby the evaporation process of the starting material 2 is hindered, the retort 1 can be connected to the vacuum pump 73, by opening the valve 72, until the pressure has reduced again into the setpoint range. If, however, the pressure has fallen below the setpoint range, whereby there is a risk of evaporation of the high-purity magnesium melt present in the lower region 33 of the condensation vessel 3, the retort 1 is connected to the inert gas source 79 via the flow and/or pressure regulator 78 by opening the valve 77 until the pressure has risen again into the setpoint range. In both cases the barrier unit 6 is closed immediately once the setpoint pressure range has been reached in order to prevent excess infiltration of magnesium steam into the supply chamber 31.

(11) As soon as the distillation process in accordance with the apparatus example of image 1 is finished and the retort 1 is cooled with its contents to room temperature, the retort can be opened, for example by a sawn cut along the dashed level line 83, whereupon the high-purity magnesium 21 present in the lower region 33 of the condensation vessel 3 can be removed from the crucible following removal of the cover 4, for example by turning the entire apparatus on its head. New starting material 2 can be introduced through the opening into the evaporation region 111 of the retort in a similar manner. Then, the retort 1 has to be joined together again to the supply chamber 13 in a vacuum-tight manner, for example by means of a welding or soldering process.

(12) The heating elements 5 and 51 used in this example according to FIG. 1 are resistance heating elements controlled to constant temperatures, which are located at points of the retort relevant for the distillation process, that is to say for example in the region of the upper region of the retort contacted by the melt of the starting material in order to adjust the temperature of the evaporation process, and in the lower region 33 of the condensation vessel 3 and the immediate environment of the barrier unit 6 in order to check whether the temperature in these regions is above the melting point of magnesium. Instead of the resistance heating elements 5 and 51, two induction coils or a single induction coil wound in accordance with the temperature distribution can of course also be provided, which heat the retort and/or the materials present therein.

(13) FIG. 2 shows an example of an apparatus according to the invention that is particularly suitable for rational operation under industrial conditions, wherein like numbers denote parts having the same function as in FIG. 1. Here, the retort 1 is welded together as central symmetrical tubular body to an upper region 11 of larger diameter and to a lower region 33 of smaller diameter consisting of a superalloy, wherein the lower region 12 extends in a tubular extension 15 into the upper region 11 of the retort. The melt of the starting material 2 is thus present in an annular crucible, of which the side walls are formed by the wall region 111 of the upper region 11 of the retort 1 and the tubular extension 15, such that the melt does not come into contact with the outer wall of the condensation vessel.

(14) In this example of the apparatus according to the invention, the tubular extension 15 and the lower region 33 of the retort have, internally, an inner wall with continuous conicity, such that the condensation vessel 3 in the form of a crucible consisting of high-purity graphite, which has a corresponding conicity of the outer lateral surface, does not provide a gap for the infiltration of condensing magnesium melt. In contrast to the apparatus example according to FIG. 1, where the condensation vessel 3 has a cylindrical inner bore, since the solidified pure magnesium block can generally be easily removed as a result of the large shrinkage, the condensation vessel 3 in the present apparatus example also has a conical inner face, such that the high-purity magnesium block 21 can be removed even more easily following solidification.

(15) The opening 31 in the condensation vessel 3 is covered by a roof-shaped graphite cover 41 with radial bores leading upwardly at an incline for the entry of the magnesium steam according to arrow 92. The cover 41 can also be formed in a manner more complex than that in the figure, for example by also placing lateral screens in front of the radial bores, such that no splashes of the fiercely boiling melt of the starting material 2 can be flung directly into the condensation vessel 3.

(16) The barrier unit is configured here in the form of a conical metal stopper 64, which seals with respect to the conical seat 113 of the intermediate wall 112. This sealing process is also assisted by the fact that liquid magnesium condenses in the seal gap between the metal stopper 64 and the seat 113 and prevents the passage of magnesium steam. The push rod 61, by means of which the barrier unit can be closed in the direction of the arrow 92, is actuated externally through a vacuum feedthrough 63 with ring seal 631, wherein this can be performed manually or automatically via a control pulse. Instead of the ring seal 631, the push rod 61 could also be introduced through the flange 14 into the supply chamber 13 in a sealing manner, for example by means of a metal bellow. The flange 14 is sealed in the example by means of a ring seal 141 with respect to the cylindrical supply chamber 13.

(17) The lines 71, 74 and 76 lead, as in the previous example, to a vacuum pump 73, a vacuum measuring instrument 75 and selectively to an inert gas source, however electrically actuatable valves 72 and 77 are used here, and therefore, besides the barrier unit 64 for connecting the retort 1 to the supply chamber 13, the pressure can also be reduced and increased automatically in the direction of a setpoint pressure range in the sense described with the previous example within the scope of a control circuit.

(18) In contrast to the previous example, only the upper region 11 of the retort 1 is heated in this apparatus with a heating element 5, for example in the form of a tubular resistance heating furnace, whereas the lower region 33 is surrounded by an insulation layer 52, which is dimensioned such that the heat passing from the upper region by means of thermal conduction through the retort wall 12 and the wall 32 of the condensation vessel as well as the downwardly travelling heat caused by the condensation of the magnesium steam, in combination with the cooling effect of the region of the retort wall 12 not insulated at the bottom, holds the temperature of the condensed high-purity magnesium melt in the desired range between the melting temperature and the boiling temperature. The temperature profile within the retort 1 can also be changed as desired within a certain range by shifting the retort in the vertical direction with respect to the furnace and insulation.

(19) The temperature of the high-purity magnesium melt 21 can be controlled via a temperature sensor 53, for example a jacket thermocouple of type K or J, which extends via a protuberance of the wall 12 into the foot of the lower region 32 of the condensation vessel 3, and, where applicable, can be controlled such that it does not fall below the melting point of the magnesium. The moment at which the last residue of the starting material is evaporated can be determined by means of a second temperature sensor 54, for example likewise a jacket thermocouple, which measures the temperature within the melt of the starting material 2 via a protuberance of the wall of the region 111 of the retort. At this moment, where the cooling effect of the evaporation process ceases, there is specifically a sudden increase of the temperature of this thermocouple. The third temperature sensor 55 sits tightly above the barrier unit 64 in a protuberance of the lower region of the wall of the supply chamber 13 and makes it possible to check whether this barrier unit is above the temperature of the melting point of magnesium, since only then is the correct function of this barrier unit ensured. At the end of a furnace cycle, that is to say prior to the cooling of the facility, the barrier unit 64 should be lifted from the seat face 113 so that it is not soldered thereto.

(20) In the first example of an apparatus, a variant of the heating system with two independent heating elements is presented, but in the present second example the upper retort region is heated by means of a heating element 5, wherein the lower region 33 surrounded by the thermal insulation is also heated indirectly by the upper region, wherein the heat introduced by the condensation of the magnesium steam also contributes. In the sense of the process according to the invention, apparatuses having a plurality of furnaces arranged in succession in the vertical direction are also possible, such that the upper and the lower part of the retort and additionally also the region of the barrier unit 6 can be controlled separately in each case to their specific temperature by means of a dedicated heating element.

(21) FIG. 3 shows a third example of an apparatus according to the invention, which is largely similar to the apparatus shown in FIG. 2. In contrast to this apparatus shown there, however, the condensation vessel 3 in the present example has a cylindrical outer face, whereby an annular gap is produced between this outer face and the inner lateral surface of the lower region 33 of the retort 1. By removing a selectively water-cooled flange 15, the crucible can be removed downwardly from the retort. In order to prevent magnesium steam from infiltrating into this gap and condensing into liquid in its lower region or into solid below the crucible base 34, this flange 15 has a feed line 761 with a flow regulation element 781, through which gas originating from an inert gas source can be introduced into the space beneath the base 34 of the condensation vessel 3. The quantity of the fed inert gas is such here that its speed in the gap outside the condensation vessel 3 is so high that it exceeds the diffusion rate of the magnesium steam potentially ready for migration in the opposite direction. As a result of this addition of inert gas, the pressure rise within the retort is indeed accelerated, whereby the intervals within which the barrier unit 64 has to be opened for the purpose of pressure control and regulation are somewhat shorter, however this reduction is insignificant, since only small quantities of inert gas are necessary to keep the gap free.

(22) The figures do not show the control circuits and mechanisms that are necessary to keep constant the temperatures and the pressure of the apparatuses, since their functioning, apart from the accuracy necessary for the execution of the process, is insignificant for the execution of the process.

LIST OF REFERENCE SIGNS

(23) 1 retort, generally 11 upper region of retort 111 region of 11 in contact with starting material 112 intermediate wall of 11 and 13 113 conical seat for 64 in 112 114 protuberance of the retort wall as protection for temperature sensor 54 12 lower tapered region of retort 121 protuberance of the supply chamber wall as protection for temperature sensor 53 13 supply chamber 131 protuberance of the retort wall as protection for temperature sensor 55 14 vacuum flange 141 ring seal 15 vacuum flange 151 ring seal 2 magnesium-containing metal starting melt 21 high-purity magnesium melt 3 condensation vessel, generally 31 opening in condensation crucible 32 upper zone of condensation crucible 33 lower zone of condensation crucible 4 cover 41 cover with lateral openings 5 heating system for region 11 51 heating system for region 12 52 insulation for region 12 53 temperature sensor in base zone of condensation vessel 531 protective pipe for temperature sensor 54 temperature sensor for evaporation zone 55 temperature sensor for region of barrier unit 64 6 barrier unit 61 push rod of barrier unit 62 seal seat for barrier unit 63 vacuum feedthrough for push rod 631 ring seal 64 barrier unit with conical seat 71 connection line to vacuum pump 72 barrier unit to vacuum pump 73 vacuum pump 74 connection line to vacuum measuring instrument 75 vacuum measuring instrument 76 connection line to barrier unit 761 connection line to flow regulator for inert gas 77 barrier unit 78 flow regulator for inert gas 781 flow regulator for inert gas 79 inert gas source 8 lower level limit for temperature range above boiling point 81 upper level limit for temperature range above boiling point 82 upper level limit for temperature range above melting point 83 level line of possible sawn cut 91 arrow, steam generation 92 arrow, steam entry into condensation vessel 93 arrow, lifting direction of barrier unit 6