PREPARATION PROCESS FOR RARE EARTH METAL FLUORIDES

Abstract

A method of fluorinating a solid compound of a rare earth metal to produce a fluorinated rare earth metal compound in solid form includes reacting, in a reaction zone, a solid compound of the rare earth metal and gaseous hydrofluoric acid, thus producing the fluorinated rare earth metal compound in solid form. The reaction takes place, in the reaction zone, in the presence of exogenous water, which is water that is exogenous to water that is produced in the reaction zone as water of reaction due to the reaction of the solid compound of the rare earth metal and the hydrofluoric acid. Conditions of temperature and pressure in the reaction zone avoid condensation of the exogenous water, the water of reaction when present, and the hydrofluoric acid.

Claims

1-18. (canceled)

19. A method of fluorinating a solid compound of a rare earth metal to produce a fluorinated rare earth metal compound in solid form, the method including reacting, in a reaction zone, a solid compound of the rare earth metal; and gaseous hydrofluoric acid, thus producing the fluorinated rare earth metal compound in solid form, wherein the reaction takes place, in the reaction zone, in the presence of exogenous water, which is water that is exogenous to water that is produced in the reaction zone as water of reaction due to the reaction of the solid compound of the rare earth metal and the hydrofluoric acid; and under conditions of temperature and pressure which avoid condensation of the exogenous water, the water of reaction when present, and the hydrofluoric acid.

20. The method according to claim 19, wherein the fluorinated rare earth metal compound is a rare earth metal fluoride.

21. The method according to claim 19 wherein the fluorinated rare earth metal compound is a fluorine-containing precursor of a rare earth metal fluoride.

22. The method according to claim 19, wherein the solid compound of the rare earth metal, that is subjected to the fluorination, is a hydrated form thereof, and the exogenous water comprises crystalline water of the hydrated form.

23. The method according to claim 19, wherein the exogenous water comprises water vapour that is not formed in the reaction zone.

24. The method according to claim 23, wherein the water vapour comprises water vapour that is formed outside of the reaction zone as water of reaction due to reaction between the compound of the rare earth metal and the hydrofluoric acid outside of the reaction zone, and/or water vapour that is intentionally fed into the reaction zone.

25. The method according to claim 23, wherein the fluorinated rare earth metal compound is a rare earth metal fluoride which is neodymium trifluoride (NdF.sub.3); and the solid compound of the rare earth metal is neodymium carbonate (Nd.sub.2(CO.sub.3).sub.3); and the neodymium trifluoride is produced according to reaction equation 1:
Nd.sub.2(CO.sub.3).sub.3(s)+6HF(g).fwdarw.2NdF.sub.3(s)+3CO.sub.2(g)+3H.sub.2O(g)(Eq. 1).

26. The method according to claim 25, wherein the neodymium carbonate comprises hydrated neodymium carbonate (Nd.sub.2(CO.sub.3).sub.3.xH.sub.2O).

27. The method according to claim 26, wherein the exogenous water comprises crystalline water of the hydrated neodymium carbonate.

28. The method according to claim 27, wherein the conditions of temperature and pressure under which the reaction according to reaction equation 1 takes place in the reaction zone are such that the hydrated neodymium carbonate is not dehydrated, at least not until the reaction has commenced.

29. The method according to claim 19, wherein the reaction takes place in the reaction zone at a temperature of 20 C. or more.

30. The method according to claim 29, wherein the reaction takes place in the reaction zone at atmospheric pressure and at a temperature that is equal to or greater than 80 C. and less than 300 C.

31. The method according to claim 29, wherein the solid compound of the rare earth metal is a hydrated form thereof and the reaction takes place at a temperature of 300 C. or more, at a pressure that is above atmospheric pressure and is selected such that the hydrated form is not dehydrated, at least not until the reaction has commenced.

32. The method according to claim 19, which includes introducing the solid compound of the rare earth metal, in granular form, into the reaction zone under gravity, and introducing the gaseous hydrofluoric acid into the reaction zone in counter-current fashion to the solid compound of the rare earth metal.

33. The method according to claim 32, which includes feeding exogenous water vapour, as exogenous water, into the reaction zone.

34. The method according to claim 19, which includes introducing the gaseous hydrofluoric acid into the reaction zone using a carrier gas, which is carbon dioxide that is recovered from carbon dioxide produced due to prior reaction between the solid compound of the rare earth metal and the gaseous hydrofluoric acid.

35. The method according to claim 19, wherein the hydrofluoric acid is anhydrous hydrofluoric acid.

36. A fluorinated rare earth metal compound produced in accordance with the method of claim 19.

Description

DESCRIPTION OF THE DRAWING

[0047] FIG. 1 is a method for producing neodymium trifluoride in accordance with the present invention.

DETAILED DESCRIPTION OF AN EXEMPLARY EMBODIMENT OF THE INVENTION

[0048] THE INVENTION WILL NOW BE DESCRIBED IN MORE DETAIL, with reference to the accompanying drawing which diagrammatically shows a process for implementing a method of producing neodymium trifluoride in accordance with the invention.

[0049] Referring to the drawing, reference numeral 100 generally indicates a process for implementing a method of producing, as a fluorinated rare earth metal compound in solid form, neodymium trifluoride in accordance with the invention.

[0050] The process 100 includes a reactor vessel 102 in which hydrated neodymium carbonate pellets are reacted with anhydrous hydrofluoric acid (HF) in the presence of a carrier gas, which is carbon dioxide, to form neodymium trifluoride, carbon dioxide and water according to reaction equation 1. The reactor vessel 102 is, in particular, an inclined plate reactor.

[0051] The reactor vessel 102 is a vertical column reactor vessel, including downwardly inclined plates that are configured to achieve a predetermined residence time of the neodymium carbonate pellets in the reactor vessel 102, when the pellets are fed to the top of the reactor vessel 102 as hereinafter described.

[0052] Further features of the process 100 will appear from the description of its typical operation, which follows.

[0053] HF is withdrawn from a storage vessel or other source thereof (see C) along line 1, and is evaporated and heated to 80 C. in an evaporator 104, thereby obtaining evaporated, heated HF.

[0054] The evaporated, heated HF is, at start-up, mixed at mixing point 105 with carbon dioxide gas make-up from B, along line 15, to obtain a gas mixture of HF and carbon dioxide at an HF mass concentration of 10%. After start-up, the heated, evaporated HF is mixed, at mixing point 107, with carbon dioxide gas along line 9, which carbon dioxide gas is recovered from the reactor vessel 102 as hereinafter described, thereby to obtain the gas mixture of HF and carbon dioxide.

[0055] The gas mixture is fed to a heat exchanger 106 along line 2 and is heated with hot off-gas from the reactor vessel 102, along line 7, thereby obtaining a heated gas mixture.

[0056] The heated gas mixture is then fed to an electrical heater 108, which heats the mixture further, to a temperature of from 100 C. to 350 C. in the present embodiment, thereby obtaining a further heated gas mixture. The temperature to which the further heated gas mixture is heated is preferably from 10 C. to 50 C. higher than the operating temperature of the reactor vessel 102. Generally, the temperature and pressure of the further heated gas mixture, particularly at the inlet thereof to the reactor vessel 102, is preferably such that conditions that are conducive to condensation of water and/or HF in the feed line thereof (line 3 in the drawing) and in the reactor vessel 102 are avoided.

[0057] The further heated gas mixture is fed to the bottom of the reactor vessel 102, along line 3, thus rising through the reactor vessel 102. Simultaneously, the hydrated neodymium carbonate pellets are fed, along line 4 at a predetermined rate, to the top of the reactor vessel 102 from a feed hopper 112 by means of a screw conveyor 114, thus descending through the reactor vessel 102 under gravity. The neodymium carbonate pellets are fed to the hopper 112 from a source of neodymium carbonate pellets (see A).

[0058] Thus, the HF and neodymium carbonate pellets are contacted in a counter-current manner in the reactor vessel 102.

[0059] Operating conditions of the reactor vessel 102 include a temperature of between 90 C. and 300 C., preferably <300 C., and a pressure that is such that condensation of water and HF in the reactor vessel 102 is avoided. These conditions of temperature and pressure are selected to avoid condensation of HF and water vapour and to avoid dehydration of the hydrated neodymium carbonate.

[0060] Contact between the HF and the neodymium carbonate in the reactor vessel 102 results in reaction between the HF and the neodymium carbonate in accordance with reaction equation 1. The reaction is exothermic and the heat of reaction is removed by air cooling with air cooler 110. The reaction forms neodymium trifluoride, water vapour (as water of reaction) and carbon dioxide. The neodymium trifluoride collects to the bottom of the reactor vessel 102 while the water vapour and carbon dioxide, along with unreacted HF, rise to the top of the reactor vessel 102 to leave the reactor vessel 102, along line 7, as off-gas.

[0061] It will be appreciated that wherever in the reactor vessel 102 the reaction takes place, a reaction zone exists. A reaction zone may therefore comprise a single neodymium carbonate pellet that is in contact with HF, a plurality of neodymium carbonate pellets that are in contact with HF, or even all of the neodymium carbonate pellets that are in contact with HF inside the reactor vessel 102.

[0062] Exogenous water may be present in each reaction zone, or in at least some of the reaction zones, the exogenous water at least comprising the crystalline water of the hydrated neodymium carbonate. When the reaction zone is not regarded as comprising all of the neodymium carbonate pellets that are in contact with HF inside the reactor vessel 102, the exogenous water present in any particular reaction zone may also comprise water vapour generated as water of reaction in another reaction zone, in accordance with reaction equation 1.

[0063] The neodymium trifluoride is removed from the bottom of the reactor vessel 102 along line 5 and is cooled in a counter-current cooler 116 with carbon dioxide that is fed to the cooler 116 along line 12. Thus, cooled neodymium trifluoride is obtained, which is fed to a product vessel 118.

[0064] The cooled neodymium trifluoride is purged, in the product vessel 118, with nitrogen gas to remove residual traces of HF. The nitrogen gas is fed to the product vessel 118 along line 13, from a nitrogen source (see D).

[0065] After purging, the neodymium trifluoride is withdrawn from the product vessel 118 along line 6 for further handling (see G).

[0066] The off-gas of carbon dioxide, water vapour and un-reacted HF that rises to the top of the reactor vessel 102 is withdrawn, as an off-gas mixture, from the reactor vessel 102 along line 7. The mixture is filtered in filter 120 and is cooled by heat exchange with the hot gas mixture in heat exchanger 106, thereby obtaining a cooled off-gas mixture.

[0067] The cooled off-gas mixture is compressed in a compressor 122, which also sustains the operating pressure of the reactor vessel 102, thereby obtaining a cooled, compressed off-gas mixture. The cooled, compressed off-gas mixture is withdrawn from the compressor 122 along line 8.

[0068] Excess carbon dioxide is bled off from the cooled, compressed off-gas mixture along line 11 (and see F), which also contains some water vapour and unreacted HF. Remaining carbon dioxide is stripped of water vapour by condensation of the water vapour in a condenser 124. The condensed water, leaving the condenser along line 10, contains dissolved HF and carbon dioxide.

[0069] Carbon dioxide, containing uncondensed HF and moisture, is withdrawn from the condenser 124 along line 9 and is mixed with the heated gas mixture, including HF from the HF evaporator, at the mixing point 107. The water content of this stream, which forms part of the stream that is ultimately fed to the reactor vessel 102, is one possible source of exogenous water that is intentionally fed to the reactor vessel 102.

[0070] A small stream of carbon dioxide is bled along line 16 from line 9 and stripped of HF in a HF scrubber 126. The resulting scrubbed carbon dioxide stream is utilized to cool the neodymium product, being fed to the cooler 116 along line 12.

[0071] The Applicant believes that by operating the reactor vessel 102 such that condensation of HF, water of reaction and exogenous water, and dehydration of hydrated neodymium carbonate, are avoided, reaction, and more specifically mass transfer during reaction, between HF and neodymium carbonate is encouraged by the presence of water, specifically adsorbed water. Thus, the Applicant has found that neodymium trifluoride can be produced at more moderate temperatures, while still showing an acceptable rate of reaction. Generally, in the Applicant's experience, conventional wisdom suggests conducting a reaction such as reaction equation 1 at relatively high temperatures (300 C. and higher at atmospheric pressure) to exploit the higher reactivity of HF at such higher temperatures. This requirement is obviated by the present invention.