Title of Invention	A PROCESS FOR PRODUCING A SOLUBLE FLUORO ZIRCONIC ACID COMPOUND
Abstract	Abstract: The present invention relates to a process for producing a soluble fluoro zirconic acid compound comprises reacting a zirconia based material with aqueous hydrogen fluoride, The zirconia based material is plasma dissociated zircon.

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THIS INVENTION relates to a process for producing a soluble flouro zirconic acid compound. According to the invention, there is provided a process for treating a zirconia-based material which comprises, broadly, reacting, in a reaction step, a zirconia-based material with aqueous hydrogen fluoride (HF), to produce a soluble fluorozirconic acid compound. In one embodiment of the invention, the zirconia-based material may be zirconia. In another embodiment of the invention, it may be dissociated zircon ('DZ' or Zr02-Si02) . In yet another embodiment of the invention, it may be a zirconia-containing component of dissociated zircon. When zirconia is used, it may be a naturally occurring zirconium material such as baddeleyite. The reaction then proceeds in accordance with reaction (1): Zr02 + 6HF -* H2ZrF6 + 2H20 (1) Instead, when zirconia is used, it may be that obtained by any suitable thermal process. The dissociated zircon, when used, can be that obtained by any suitable process, particularly a thermal process. Thus, for example, it can be that obtained by destroying the crystal matrix of zircon (ZrSi04) by heating it to a high temperature in a plasma furnace or a plasma generator, under oxidizing, inert or reducing conditions. Zircon is a .mineral which is abundantly available at relatively low cost, but is chemically inert. Thus, inert zircon mineral is rendered amenable to chemical processing in accordance with the invention, by means of said plasma dissociation. During plasma dissociation, zircon is dissociated into separate zirconia (Zr02) and silica (Si02) mineral phases, with the product commonly designated as dissociated zircon (DZ'), plasma dissociated zircon ('PDZ'), or Zr02-Si02. Alternatively, the zircon can be processed in a transfer arc plasma furnace under reducing conditions effecting-essentially the removal of the silica phase with essentially Zr02, popularly designated fused zirconia, remaining behind. Zircon normally contains radioactive elements such as uranium (U) and thorium (Th) and their decay product elements, as well as other common impurities such as Fe, Ca, P, Al, Mg and Ti. These elements are released in the process of the invention, but the process provides an effective manner of dealing with these elements. In particular, the process results in the generation of only relatively small quantities of radioactive element containing wastes. Wherever reference is made in this specification to U and Th as radioactive elements, t?his is to be interpreted as referring instead or additionally also to their decay products. In one embodiment of the invention, the PDZ may be nori-desilicated, in which case the reaction proceeds in accordance with reaction (2) : Zr02-Si02 + 12HF -» H2ZrF6 + H2SiF6 + 4H20 .... (2) In another embodiment of the invention, the PDZ may be partially desilicated,. in which case the reaction 'to produce the fluorozirconic acid is also in accordance with reaction (2). In yet a further embodiment of the invention, the PDZ may be wholly desilicated, in which case the reaction to produce the fluorozirconic acid is in accordance with reaction (1), as given hereinbefore. The desilication of the PDZ can be effected by known means, such as caustic soda leaching. Wholly or partially desilicated PDZ is also known as 'DPDZ'. It is to be appreciated that whenever, in the reactions of the process of the invention, reference is made to hexafluorozirconic acid (H2ZrF6) , this includes the compound ZrF4-2HF-xH20 where x can range from 0 to 5. The concentration of the HF in the aqueous HF or HF solution may be in the range of 5-70% HF by mass. The reaction may be effected at a moderately elevated temperature, which may be between 20°C and 120°C. Reactions (1) and (2) are exothermic. Thus, with a 40% HF solution and using PDZ as feed material, the reaction nixture reaches a temperature of ±90°C within a few ninutes, depending on the rate of feeding the PDZ into the IF solution. At lower HF concentrations, for example 3 0%, Lower final temperatures are reached and in such cases it Ls preferable to heat the reaction mixture from an external source, for example to >80°C for complete reaction to take slace. The reaction period may be between 10 minutes and 4 hours, lepending on the HF concentration, the degree of lissociation of the PDZ and the temperature of the reaction nixture. [nstead of, or in addition to hexafluorozirconic acid, ie I2ZrF6, tetrafluorozirconic acid, ie H2ZrOF4, and/or hydrates :hereof, can be formed. It will be appreciated that, in the reaction step, the zirconia and, when present, silica are dissolved in the HF solution, with the reaction products such as H2ZrF6 and H2SiF6 also being soluble in the aqueous hydrogen fluoride, so that only zircon that was not dissociated in the plasma, as well as poorly soluble or insoluble impurities or trace element such as U, Th, iron (Fe), titanium (Ti), aluminium (Al) and calcium (Ca) remain as more or less undissolved solids. The undissolved solids ('white fraction') can thus be removed as a solids fraction by suitable means, such as' filtration, decantation or settling, optionally preceded, if necessary, by precipitation of the trace element(s) in question. The process accordingly provides an effective means of purifying PDZ or DPDZ to produce a relatively small quantity of residue containing undesirable contaminants such as U and Th, and their decay products. Any .residual zircon which was not dissociated in the plasma can thus be separated out, so that the process is not dependent on the availability of PDZ with 100% degree of dissociation. The zircon which is removed during this step can naturally be recycled back to the plasma stage, after separation of non-zircon materials. To enhance or optimize efficiency of reaction (2) and to reduce or minimize losses of Zr and F to the white fraction, the molar ratio of HF to zirconia plus silica, when present, is important, and will be controlled to obtain desired dissolution levels. Thus, the molar ratio of HF to zirconiaplus silica, when present, may be in the range 1,1:0,9 to 0,9:1,1, more preferably in the range 1,05:0,95 to 0,95:1,05, and most preferably about 1:1. If desired, the solids fraction can be subjected to further treatment to recover elements such as U and Th. For example, it can be subjected to dissolution, eg utilizing suitable acids, eg nitric acid, or bases, followed by filtration and ion exchange, with, as stated hereinbefore, only small quantities of waste products being produced. Instead, any undissociated zircon can be separated from other insoluble compounds by means of physical separation, such as flotation, again resulting in substantially insignificant volumes of waste products. The process may include heating the residual solution containing the H2ZrF6, H2SiF6, H20 and excess HF to recover H2ZrF6. Thus, the solution may, in an evaporation step, be heated to a temperature between 20°C and 120°C at substantially atmospheric pressure, with all H2SiF6, H20 and excess HF being evaporated. These volatiles can then be condensed in a suitable condenser for subsequent recovery of HF and Si species, such as Si02, in known fashion. The 3F thus recovered can be recycled to the reaction step. Thus, in the evaporation step, reaction (3) takes place: H2ZrF6(aq) + H2SiF6(aq) -»H2ZrF6(s) + H2SiF6(g) .. (3) H2ZrF6 (or H2ZrOF4) crystals are obtained from this evaporation step, and the process thus enables substantially complete separation of all Zr and Si species. The H2ZrF6 crystals can then be further purified, in a purification step, in accordance with reaction (4): H2ZrF6(impure) -> H2ZrF6(pure) (4) The purification step may comprise recrystallization or ion exchange. Instead, the H2ZrF6 solution can be only partially evaporated to produce a saturated solution from which H2ZrF6 crystals can be crystallized with or without cooling of the solution. These crystals can be separated from the mother liquid by any suitable means, for example filtration. These crystals can be of high purity due to the fact that most of the impurities remain in solution and are not crystallized with the Zr species. After filtration of the H2ZrF6 crystals, the remaining solution can be completely evaporated to recover all the remaining Zr as H2ZrF6 (or H2ZrOF4) . These crystals will of course contain any accumulated impurities of the mother liquid. As a further alternative, the H2ZrF6/H2SiF6 solution can be fed directly to an ion exchange column to produce a much purer H2ZrF6/H2SiF6 solution, from which pure H2ZrF6 crystals can be crystallized. In one embodiment of the invention, the resultant pure H2ZrF6 can then be converted to zirconia, for example by means of steams pyrolysis, in accordance with reaction (5): The HF produced in reaction (5) can be recovered and reused in the reaction step. In other embodiments of the invention, other zirconium chemicals can instead be produced from the pure H2ZrF6, such as, for example, ZrF4, ZrOF2, fluorozirconates such as K2ZrF6, zirconium sulphate, or zirconium carbonate. Accordingly, the present invention provides a process for producing a soluble fluoro zirconic acid compound, which process comprises reacting, at a temperature between 20°C and 120°C and for between 10 minutes and 4 hours, plasma dissociated zircon with aqueous hydrogen fluoride, with the quantity of hydrogen fluoride, as aqueous hydrogen fluoride, used being such that the molar ratio of hydrogen fluoride to zirconia present in the plasma dissociated zircon is between 1.1:0.9 to 0.9:1.1, and with the concentration of the hydrogen fluoride in the aqueous hydrogen fluoride, before reaction therewith with the plasma dissociated zircon, being in the range of 5-70% hydrogen fluoride by mass, to produce a soluble fluoro zirconic acid compound; and recovering the soluble fluoro zirconic acid compound in a known manner. The invention will, now be described by way of non-limitinc example with reference to the accompanying drawings. In the drawings, FIGURE 1 is a simplified flow diagram of a process according to the invention for treating dissociated zircon; FIGURE 2 is an X-ray diffraction pattern of ZrC-produced in Example 1; FIGURE 3 shows, in simplified flow diagram form, .a small scale production set-up as used in Examples 5 to 7; FIGURE 4 is an X-ray diffraction pattern of undissociated zircon that did not dissolve in HF, as described in Example 2; and .FIGURE 5 is an X-ray diffraction pattern of ZrC; produced in .Example 11. In Figure 1, reference numeral 10 generally indicates a process for treating dissociated zircon. The process 10 includes a plasma dissociation stage 12, with a zircon feed line 14 leading into the stage 12. A PDZ flow line 16 leads from the stage 12 to a reaction step or stage 18, with a HF solution make-up line 20 leading into the stage 18. A transfer line 22 leads from the stage 18 to a liquid/solid separation step or stage 24. A zircon and white fraction withdrawal line 26 leads from the stage 24 to a zircon/white fraction separation stage 25, with a zircon return line 27 leading from the stage 25 back to the stage 12. A transfer line 28 leads from the stage 24 to an svaporation step or stage 30, with a volatile product withdrawal line 32 leading from the stage 30 to a treatment stage 34. A transfer line 36 leads from the stage 30 to a purification step or stage 38. A transfer line 40 leads from the stage 38 to a zirconia production step or stage 12, with a HF withdrawal line 44 as well as a Zr02 withdrawal line 46 leading from the stage 42. Instead, or additionally, a zirconium sulphate production step or stage 18 can be provided, with a flow line 50 then leading from :he stage 3 8 to the stage 48. A H2S04 feed line 52 will :hen also lead into the stage 48 with a HF withdrawal line 54 as well as a zirconium sulphate withdrawal line 56 Leading from the stage 48. Instead, or additionally, a Eluorozirconate production step or stage 58 can be orovided, with a flow line 60 then leading from the stage 38 to the stage 58. A KOH feed line 62 then leads into the stage 58, with a fluorozirconate withdrawal line 64 leading from the stage 58. In use, ZrSi04 is fed, by means of the flow line 14, into the plasma dissociation stage 12, together with recycled zircon entering the stage 12 along the flow line 21. In the stage 12, the zircon is dissociated, by means of plasma dissociation, into PDZ. The PDZ passes along the flow line 16 to the stage 18. In the stage 18, the PDZ is dissolved in a HF solution having a concentration of between 5% and 70% HF, and a temperature of between 20°C and 120°C, and reacts to form H2ZrF6 and H2SiF6 in accordance with reaction (2) : Zr02-Si02 + 12HF -» H2ZrF6 + H2SiF6 + 4H20 .... (2) The preferred HF concentration is 40% and the preferred temperature is 80°C, although the dissolution can also be effected at concentrations up to 100% HF. The solution formed in the stage 18 and containing dissolved H2ZrF6, H2SiF6, H20 and excess HF, as well as any undissolved solids, passes to the liquid/solid separation stage 24 where a solids fraction comprising undissociated zircon as well as any undissolved or precipitated impurities such as U and Th is separated from a liquid fraction comprising excess HF solution, H20, dissolved H2ZrF6 and dissolved H2SiF6. The solids fraction is removed along the line 26, subjected to further treatment in the stage 25 to separate the white fraction from undissociated zircon,_, eg by means of dissolution in H2S04, followed by filtration and ion exchange to remove therefrom the U and Th, before recycling the zircon to the stage 12 along the line 27. Thus, only relatively small volumes of U and Th containing waste are obtained from the process 10. The liquid fraction passes along the line 28 to the' stage 3 0 where a volatile fraction comprising H2SiF6, HF and H20 is withdrawn along the flow line 32, by distilling the solution at a temperature between 40°C and 120°C and at atmospheric pressure. The volatiles enter the stage 34 where they are condensed for recovery of HF and high grade Si species, with the HF being recycled (not shown) to the stage 18. Separation of the HF from the Si species can be effected by means of flame hydrolysis, steam plasma or the like.. Optionally, instead of the liquid fraction passing directly to the stage 30, it can first be fed into an ion exchange stage (not shown) for initial purification thereof, with the liquid fraction thereafter passing to the stage 30. In the stage 30, substantially complete separation of Zr species from Si species is obtained. Thus, in a laboratory scale simulation of the process 10, it was found that the H.ZrF. fraction from the staae 30 contained 46.1% bv mass Zr and less than 0,5% by mass Si, while the volatile fraction from the stage 30, after condensation, contained 55,7g/i'. H2SiF6, and less than 1 ppm Zr. In the stage 30, when more than 20% of the liquid has evaporated, a highly saturated solution of H2ZrF6 is obtained. Depending on the amount of liquid that has evaporated, crystallization of the H2ZrF6 (or H2ZrOF4) takes ' place without cooling or upon cooling thereof to room temperature. This crystallization is in itself a further purification step with regard to impurities such as U, Th, . Fe, Ti and Ca. The crystals can be removed from the residual solution by filtration, while the impurities remain largely in solution and can be removed subsequently by ion exchange (not shown). Instead, in the stage 30, complete evaporation of the H2ZrF6 and H2SiF6 solution can be effected, with H2ZrF6 (or H2ZrOF4) crystals then being obtained. These crystals can be dried in an oven (not shown) . If it is desired to minimize fluorine (F) losses during this drying step, the temperature should not exceed the decomposition temperature of H2ZrF6. Thus, the drying can be effected between 40°C and 90°C, preferably at The relatively impure H2ZrF6 from the stage 3 0 passes to the purification stage 38. The impure H2ZrF6 crystals which pass from the stage 3 0 are highly soluble in water, and solubilities of up to lg/mf of water- are obtainable. Further purification of these crystals can thus easily be effected by dissolution and subsequent recrystallization, or ion exchange, in the stage 38, to produce H2ZrF6 having substantially reduced radioactivity. For recrystallization, the H2ZrF6 crystals are dissolved in the minimum volume of warm watex-, to produce T a highly saturated solution. On cooling to room temperature, recrystallization takes place. The resultant crystals can be recovered by means of filtration, and dried. Instead, for ion exchange, the H2ZrF6 crystals can be dissolved in water in a concentration range of 0,1M to 2,0M. This solution can then be passed through a column containing a suitable ion exchange resin for removing impurities such as U and Th. The solution is again evaporated to produce H2ZrF6 crystals in which the concentration of impurities, especially U and Th, is significantly reduced. The U and Th contaminants can subsequently be eluted from, the ion exchange resin in easily manageable confined volumes. In a laboratory scale simulation of the various steps of the process 10, the following results were obtained: The purified H2ZrF6 crystals from the stage 38 can be converted, in the stage 42, to zirconia (Zr02) by means of steam pyrolysis, at temperatures between 450°C and 850°C, for reaction periods ranging from 30 minutes to 3 holirs in a suitable oven, such as a rotary kiln, in accordance with reactions (6) and (7): H2ZrF6 + 2H20 (steam) -* Zr02 + 6HF (6) H2ZrOF4 + H20 (steam) -* Zr02 + 4HF (7) Further desilication is effected during the steam pyrolysis. An X-ray diffraction pattern of zirconia produced in this manner in the laboratory scale simulation of the process 10 is given in Figure 2. Efficient conversion of H2ZrF6 to Zr02 in the stage 42 is not primarily dependent on feeding the H2ZrF6 as dry crystals. Apart from steam pyrolysis conversion, final evaporation can also be effected in the rotary kiln. Thus, the crystallization effected in the stages 30, 38 can be avoided so that the H2ZrF6/H2SiF6 solution from the stage 24 can • be fed directly into the stage 42, or after partial concentration thereof by evaporation. The HF that is liberated in the stage 42 can be trapped in a suitable condenser or scrubber (not shown) and the thus recovered HF can be recycled to the stage 18. [nstead, or additionally, zirconium sulphate can be sroduced in the stage 48 by reacting the H2ZrF6 with H2S04, with HF also being liberated for recycling. fet further, K2ZrF6 can be produced in the stage 5 8 by reaction of H2ZrF6 with any suitable potassium salt, for example KOH. Still further, the H2ZrF6 can be converted thermally to ZrF4 in a HF atmosphere (not shown) and the resultant ZrF4 purified by means of sublimation/desublimation. further tests to simulate and test the process 10 were also :onducted, on a larger scale than Example 1. Jxamples 2 to 4 and 8 to 10 were done on laboratory ipparatus, while Examples 5 to 7 were carried out on a small scale production setup, in accordance with Figure 3. in Figure 3, reference numeral 100 generally indicates the small scale production setup. The setup 100 comprises a liquid storage tank 102, with a flow line 104 leading from the tank 102 to a stirred reactor 106. An HF solution flow line 110, fitted with a pump 112, leads into the reactor 06, while a solids withdrawal line 114 leads from the bottom of the reactor to a solids storage tank 116. The eactor 106 is fitted with heating and cooling loops (not. shown) and a volatiles withdrawal line 118, fitted with a recycle line 122 leads from the reactor 106 back to the tank 102, and is fitted with a pump 124. In each of Examples 5 to 7, the first step in the production of H2ZrF6 was to pump the required amount of 40% HF into the reactor along the flow line 110. PDZ was then fed into the reactor, under agitation, using a solids feed hopper (not shown) situated on the reactor lid. The solids in the reaction mixture were separated from the liquid product phase using known settling techniques, after which the product (liquid) phase was pumped, along line 122, to the liquid storage tank 102. The solids were flushed, along line 114, to the solids storage tank 116 and ■ the reactor washed. The product phase was then fed back into the reactor along line 104, where separation between H2ZrF6 and H2SiF6 was done by evaporation of the volatile H2SiF6, H20 and HF. The vapours were condensed and analysed. The residue aft'er evaporation was a slurry of H2ZrF6/H2ZrOF4 crystals. ■EXAMPLE 2 500g of plasma dissociated zircon ('PDZ') (with a total dissociation of 90%) was added to l,4f of a 40% aqueous HF continuously stirred throughout the reaction period. The temperature of the reaction mixture rose from 24°C to 86°C within 2 minutes. After 4 hours, the reaction mixture was allowed to cool, and the undissolved solids were separated from the mother liquid by means of filtration and/or decantation/sedimentation. The solids consisted of a fine white fraction and undissociated zircon. The mass of the zircon portion was 45, Og (9% of the original starting material). This corresponds well with the 90% dissociation of the starting material. X-ray diffraction (XRD) analysis confirmed that this portion of the solids was mainly zircon - see Figure 4. The mass of the white fraction was 31,8g (6,4% of the original starting material). XRD analysis of the white fraction showed that it consisted of a mixture of Zr02, ZrOF2, ZrF4 and intermediate oxyf luorides . The mother liquid was evaporated at a temperature >80°C. After all the liquid had evaporated, 348,5g of H2ZrF6 (or H2ZrOF4) crystals remained in the beaker. The chemical analysis of the unreacted zircon, the white fraction and the final product are given in Table 2. EXAMPLE 3 100m£ of the mother liquid (obtained from a typical run as described in Example 2) was evaporated to 50m£, and the solution allowed to cool. The crystals which formed were filtered off and dried. The filtrate was further evaporated until only dried crystals remained. Chemical analyses, summarized in Table 3 below, showed the crystals that formed after the evaporation of the first 50m£ of the mother liquid (sample A) were much purer than the crystals which formed with complete evaporation of the rest of the liquid (sample B). It was also established that 24,77g (82%) crystals formed after evaporation of 50% of the mother liquid (sample A) and a further 5,37g (18%) crystals formed after complete evaporation of the filtrate (sample B). EXAMPLE 4 Using the procedures and parameters of Example 2, it was demonstrated that the amount and the chemical composition of the white fraction can be manipulated by the amount of HF available for reaction. For example, 0,43kg of plasma dissociated zircon, (with a total dissociation of 71%) was added to 910m£ of 4 0% aqueous HF solution. The reaction mixture was stirred throughout the reaction period. After cooling, all the solids were separated from the mother liquid by means of filtration and/or decantation/ sedimentation. The dissociated zircon and the white fraction were further separated. The mass of the undissociated zircon was 121,4g, which is 28,2% of the original starting material. This corresponds well with the starting material which was 71% dissociated. The mass of the white fraction was 154,8g, which is 36% of the starting material. The reaction Zr02-Si02 + xHF -* H2ZrF6 + H2SiF6 + 4H20 (8) was studied further by varying the molar ratio of HF to (Zr02+Si02) in the PDZ. It was found that the molar ratio of HF to zirconia and silica determined the composition and amount of the white fraction, as can be seen from Table 4 . EXAMPLE 5 40^ of a 40% HF mixture were pumped into the reactor 106. This gave a total of 18,56kg pure HF. 17kg of 79% PDZ having a mass of 13,43kg PDZ, was gradually ' fed to the reactor. A temperature of 88°C was reached due to the exothermic nature of the reaction. The mother liquor was analysed as follows: H2ZrF6 = 27,39% (mass base) H2SiF6 = 18,37% HF = 0,46% H20 = 53,78% The white fraction produced in the reaction amounted to 322g, which represented 2,4% of the actual mass of PDZ fed 13,96kg (actual) together with a mass of 9,71kg H2SiF6(n (calculated). » EXAMPLE 6 Again 40l of 40% HF were pumped into the reactor 106, giving a total HF content of 18,56kg HF. 18,4kg of 73% PDZ, giving a mass of 13,43kg PDZ, was fed to the reactor within 30 minutes. The temperature increased to >90°C within 5 minutes, and cooling water was used to stabilize the temperature at between 80°C and 90°C. The mother liquor was analyzed as follows: H2ZrF6 = 26,98% (mass base) H2SiF6 = 18,07% HF = 1,03% H20 - 53,92% The white fraction produced in the reaction amounted to 353g, representing a fraction of 2,63% of the pure PDZ fed to the reactor. 13,75kg H2ZrF6(s) (actual) was produced in the run together with a mass of 9,56kg H2SiF6 (calculated) . EXAMPLE 7 In this example the setup or system 100 was run at full; capacity. ' 45f of 40% HF were pumped into the reactor 106, giving a hett mass of 20,34kg HF. 17,85kg 87% PDZ was fed to the reactor within 30 minutes, 'giving a nett mass of 15,53kg PDZ. Cooling water was used to stabilize the temperature of the reacting mixture at 85°C. • The mother liquor was analysed as follows: H2ZrF6 = 2 6,74% (mass basis) H2SiF6 = 17,03% ' HF = 2,57% H20 = 53,66% A total mass of 407g white fraction was collected which represented 2,62% of the PDZ fed to the reactor. A total mass' of 16,85kg H2ZrF6(s) (actual) was produced in the run together with a mass of 11,72kg H2SiF6 (calculated). In all the abovementioned examples, the crystals were, formed by evaporating between 20% and 40% of the mother liquor. The crystals were extracted and the remaining liquor heated in containers to produce the rest of the H2ZrF6 crystals. During the evaporation of the volatiles, samples were taken ' for analyses, as set out in Table 5. Table 5 shows the compositions of the different samples taken as mass percentages. The total amount of condensate collected was 37% of the liquor (volume) used in the run. As a result of the ever-present HF in the system, no blockages due to Si02(s) precipitation were found in the condenser. No Zr specie could be found in the condensate. Typical analytical results of the materials used and •produced in the reaction, in relation to radioactive components, are summarized in Table 6. EXAMPLE 8 Zl of, a solution containing H2ZrF6 and H2SiF6, with a uranium •concentration of 89,5 μg/mf and 4,5% free hydrofluoric acid, was run through a 50, Og Purolite S940 column at a flow rate of l,32cm/min. The column had an inner diameter of 38mm. Twenty fractions of 100m£ were collected and malysed for uranium by neutron activation analyses. The analysis results showed that the resin was able to remove il% uranium at 200ml solution with a resulting resin tapacity of 0,32mg U/g resin. 90% breakthrough was reached it 2000m£ solution with a resulting capacity of l,llmg U/g ■esin. XAMPLE 9 f of a solution containing H2ZrF6 and H2SiF6, with a uranium oncentration of 45,5μg/m£ and 7,7% free hydrofluoric acid, as run through a 50,Og Purolite S940 column at a flow rate f l,3 2cm/min. The column had an inner diameter of 3 8mm. wenty fractions of 100ml1 were collected and anal/sed for ranium, by neutron activation analysis. The analysis esults showed that the resin was able to remove 71% ranium at 200m£ solution with a resulting resin capacity f 0,15mg U/g resin. Total breakthrough was reached at 900mf solution and the total capacity was 0,:-9mg U/g ssin. 8,75g H2ZrF6 crystals were reacted with 402g of superheated steam over a period of 2 hours in a static oven, at a temperature of 650°C. The evolved HF was condensed in a suitable condenser. 5,25g of Zr02 was formed. XRD-analysis confirmed that the product was Zr02. The HF that was condensed, had a concentration of more than 40%. The> purity of the Zr02 is summarized in Table 6. EXAMPLE 11 1,5kg H2ZrF6 crystals were reacted with 1kg of superheated steam in a dynamic "paddle oven" at a temperature of 730°C. The feed rate of the solids to the oven was 50g/min. The feed rate of the steam was 500g/h. The average residence time of the solids in the oven was 3^ hours. XRD analysis confirmed that the product was Zr02 - see Figure 5. About . 600g of Zr02 was withdrawn from the product outlet, with the rest of the Zr02 still contained in the dead volumes in the inside of the oven. The purity of the final product is - summarized in Table 7. The high Fe content is due to corrosion contamination from a stainless steel oven component. Thus, the process 10 is environmentally friendly in the sense that no unmanageable waste products are produced, and essentially all the HF is recovered for reuse, which enhances cost-effectiveness. further advantages of the process 10 include the following: zirconium products with low U and Th content can be obtained in cost-effective manner from baddeleyite and zircon; primary dissolution of the zirconia or DZ in the reaction stage 18 and secondary purification in the evaporation stage 30 is effected in the same medium, ie HF solution, leading to good efficacy and cost-effective processing; feed contaminants such as Si, Fe, Ti, Al, U andtTh are removed substantially entirely in a cost-effective manner by selective dissolution, selective precipitation, recrystallization, ion exchange and combinations hereof, as described hereinbefore any residual HF in any process or product stream can easily be rendered harmless by means of lime precipitation. WE CLAIM: A process for producing a soluble fluoro zirconic acid compound, which process comprises reacting, at a temperature between 20°C and 120°C and for between 10 minutes and 4 hours, plasma dissociated zircon with aqueous hydrogen fluoride, with the quantity of hydrogen fluoride, as aqueous hydrogen fluoride, used being such that the molar ratio of hydrogen fluoride to zirconia present in the plasma dissociated zircon is between 1.1:0.9 to 0.9:1.1, and with the concentration of the hydrogen fluoride in the aqueous hydrogen fluoride, before reaction therewith with the plasma dissociated zircon, being in the range of 5-70% hydrogen fluoride by mass, to produce a soluble fluoro zirconic acid compound; and recovering the soluble fluoro zirconic acid compound in a known manner. The process according to claim 1, wherein the plasma dissociated zircon is non-desilicated or partially desilicated so that, in addition to the soluble fluoro zirconic acid compound, a soluble fluoro silicic acid compound is produced. The process according to claim 2, wherein the quantity of hydrogen fluoride, as aqueous hydrogen fluoride, used is approximately stoichiometric, on a molar basis, with respect to the zirconia component plus the silica component of the plasma dissociated zircon. The process according to claim 2, wherein the liquid fraction comprising residual aqueous hydrogen fluoride, the soluble fluoro zirconic acid compound, and the soluble fluoro silicic acid compound, are separated from a residual solids fraction. The process according to claim 4, wherein the liquid fraction is heated to a temperature between 20°C and 120°C at substantially atmospheric pressure, to evaporate all the residual aqueous hydrogen fluoride and the fluoro silicic acid compound, with fluoro zirconic acid compound remaining as a purified solids fraction, and condensing the volatiles for subsequent recovery of hydrogen fluoride and silicon species. The process according to claim 4, wherein the fluoro zirconic acid compound which remains as the solids fraction is purified by means of redissolving, recrystallization or ion exchange, and converting the purified fluoro zirconic acid compound to zirconia by means of steam pyrolysis. A process for producing a soluble fluoro zirconic acid compound substantially as described and illustrated herein.

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