Patented Dec. 4, 1934 1,982,873

UNITED STATES PATENT OFFICE

1982,873 TREATMENT OF BERYLLUM-BEARING ORES Charles James, Durham, N. H.; Marion E. James, executrix of said Charles James, deceased, as signor to Skinner & Sherman, Inc., Boston, Mass., a corporation of Massachusetts No Drawing. Application October 27, 1928, Serial No. 315,595 6 Claims. (C. 23-16) This invention relates to the treatment of beryl liun-bearing ores, and more particularly to the (1) Fusion of the ore recovery of beryllium from such ores, especially The beryllium ore is preferably first finely from beryl, and also to the recovery of caesium, 5 ground and mixed with finely ground lime, pref rubidium and lithium from ores bearing them, erably in the form of calcium hydroxide. Usul 60 aid particularly from ores which also bear beryl ally about six parts of quick lime are mixed with liurn. ten parts of beryl. This ratio may, of course, be The beryllium, caesium, rubidium and lithium varied. The proportions of lime and beryl will are recovered as compounds of these metals al govern the fluidity of the slag. though for convenience, such recovery is spoken In order to avoid using a dry dusty mixture in 65 Of as the recovery of beryllium, caesium, rubidium the furnace, the lime is preferably first slaked and lithium. with water and then mixed with the ground beryl The beryllium is preferably obtained as a basic to the consistency of mortar. This mixture is carbonate or as hydroxide, both of which may be Spread out and allowed to dry. The product is Converted into a pure beryllium oxide by heat. is quite firm and can withstand the burden of the 70 The caesium and rubidium are preferably recov blast furnace used for melting it down. ered aS alums, and the lithium as a carbonate. Instead of pulverizing the beryllium ore and The most common ore of beryllium is a beryl the line, as above described, lump calcium oxide Which contains the beryllium, principally as a () or calcium carbonate and lump ore may be used, complex Silicate of beryllium and aluminum along particularly in a larger furnace. 75 With various metallic compounds, such as those of The mixture of beryl and lime is melted down iron, and frequently those of an alkali metal or to a slag in a furnace. The beryl can be decom Inetals, such as caesium, rubidium and lithium, posed by heating the mixture just below fusion. as well as potassium and Sodium. Complete fusion, however, gives a better decon The present invention will therefore be de position and is more easily carried Out commer Scribed with particular reference to its preferred cially. 80 enbodiment in the treatment of beryl, although it The fusion is preferably carried out in a blast may be applied to the treatment of other beryl furnace, although other furnaces, such as an lium-bearing ores, such as chrysoberyl, trimerite, 0 electric furnace, may be employed. An initial phenacite, leucophanite, meliphanite, bertran starter charge of coke or other fuel is first put 85 dite, eudidymite, epididymite, euclase and ham into the blast furnace and ignited and blown bergite, and also may be applied to beryllium until the coke and the lower part of the furnace containing phosphates which may be decomposed have reached a white heat. Then the charge, with hydrochloric acid instead of the Sulphuric consisting of the beryl-lime mixture, together acid which is preferably used in decomposing with one-half to two-thirds of its Volume Of coke, 90 beryl. is added and supplied from time to time to keep The preferred process as applied to beryl may the blast furnace filled. The heat of the coke be briefly outlined as follows: melts the bery-line mixture and the slag may 1. Fusion of the ores with an alkaline material, be tapped off from the bottom of the furnace in referably line, to form a slag. a fluid state. The ratio of coke to the beryl 95 2. Recomposition of the slag with an acid, pref lime mixture is adjusted so as to maintain the erably Sulphuric acid, heating to render the silica necessary high temperature for fusion, but with inSoluble, and Water extraction of the thus de out employing more coke than is necessary for cQaposed slag. this purpose. 3. RecoVey of rubidium and caesium as alums. A Small furnace which has been found to op 100 4. Removal of aluminum as ammonium alum. erate satisfactorily to carry out the fusion step 5. Reno Val of iron and remaining traces of of my process had approximately the following aluminum as hydroxides and remaining iron as dimensions: a Sulphide. O 6. Recovery of beryllium as a basic carbonate. 40 centimeters diameter at the middle; 7. Recovery of ammonium Sulphate by crystal 30 centimeters diameter at the top; 05 lization. 110 centimeters in height. 8. Recovery of lithium as a carbonate. The preferred procedure will now be described This furnace was set upon a base of firebrick. 5 5 in detail. The base was provided with a substantially U shaped passage or inverted siphon-like channel 110 2 1,982,873 about two inches in diameter. This siphon-like ing off fumes of sulphuric acid. The mass is channel allowed the Sag to run freely from the stirred to prevent the formation of hard lumps furnace, but prevented flame energing there aad is 2dded with thorough stirring into a Vat from, thereby tending to prevent the loss of of water which is heated, preferably to the boil volatile caesium, lithium and rubidium present ri ing point by means of steam. The resultant ma 80 the beryl. The blast was furnished with a cen terial, which consists of the undissolved residue trifugal blower and the air was introduced by and Supernatant water solution, may be then fil three tuyeres placed symmetrically around the tered through a filter press, although it is pre furnace about ten centimeters from the botton. ferred to allow the material to stand for about 0. The product of the furnace is entirely the slag twelve hours and then again heat it to the boil formed by the fusion of the beryl-line mixture. ing point with stirring. The material is then No reduction of metal takes place in the blast filtered through a filter press to Separate the So furnace. On a larger scale commercial produc lution from the undissolved residue. The residue tion, the size of the furnace will, of course, be is then washed, the wash water being used in dis increased. solving the next batch of Sulphated slag. 90 In the fusion of the beryl with the lime, no dis The heating of the material renders the silica, tinct chemical reaction appears to take place. insoluble and in condition so that the material The beryl is essentially a silicate of beryllium may be satisfactorily filtered through a filter and aluminum, often carrying Small amounts of preSS. the rare alkali metals, such as caesium, rubidium The Solution consists mainly of the Sulphates 95 and lithium, as well as potassium and Sodium. of beryllium and aluminum, together with Small When this is fused with the lime, it is changed to amounts of iron, compounds of the alkali metals a basic silicate which, of course, contains besides and a little dissolved silica. Sulphuric acid is the elements just enumerated a certain amount the preferred acid used for decomposing the slag of lime. The ratio of lime to beryl which is pref because of its cheapness, because the calcium is 100 erably employed is slightly over one part of the converted into its Sulphate which is insoluble lime to two parts of the beryl, although it is pos and is removed during the filtration operation, sible to use either a greater or a Smaller ratio. and because it converts the metallic constituents The ratio of approximately one-half of line to into Sulphates So that certain of them may be 30 beryl is found to give about the right melting removed as alums in the Subsequent treatment. 105 point to the slag. Moreover, if a greater amount ring the filtration, the calcium which was in of lime is used, more acid has to be used in the troduced by the line and which may have been subsequent step of the process in order to decom present in the ore, is removed along with the pose the fused mass. greater part of the silica. The insoluble calcium 3. 5 I prefer to use line as the basic or alkaline Sulphate assists in the removal of the Silica. 10 material to open up the beryl because of its low While, as above stated, it is preferred to use cost, and also because the calcium Sulphate which the Sulphuric acid, other acid treatment may be is formed in the latter step of treatment with employed. For example, the slag may be decom sulphuric acid is insoluble and may be removed posed with a solution of sodium acid sulphate in 40 along with the silica and aids in the silica filtra the form of nitre cake, although such a procedure 115 tion. However, other alkaline materials may be introduces Sodium which would interfere with the used, such as other alkaline earth metals, hy recovery of rubidium and caesium, in case these droxides or carbonates, as those of magnesium. metals are present in Sufficient amounts to war The carbonates or hydroxides of the alkali metals, rant, recovery. While I prefer to use either the such as potassium or sodium, may be mixed with Sulphuric acid or an acid salt of Sulphuric acid, 120 lime or may be used alone. Also chlorides of it is possible to decompose the slag with other the alkali metals or alkaline earth metals may mineral acids, Such for example, as hydrochloric be mixed with the oxides or carbonates of the acid, particularly where beryllium-containing alkaline earth metals or alkali metals. The blast phosphates are treated. furnace is of considerable advantage in case the The amount of water added after the sulphuric oxides or hydroxides or carbonates of the alkali acid treatment is preferably sufficient to give the metals, such for example, as sodium hydroxide, resultant Solution a specific gravity of about 1.36. are used, since the blast furnace may be made Usually, and for all practical purposes, the of firebrick So that the slag is not contaminated heating of the water solution formed by stirring with metal as it Would be if the beryl were fused the Sulphuric acid-treated mass into a vat of 130 with sodium hydroxide in an iron pot. Water as described above, is sufficient to render If it is desired to Sublimate the compounds of practically all of the silica insoluble. However, the rare alkaline earth metals, Such as caesium, as a variation in the process in case such solution rubidium and lithium, alkali metal chlorides may is not heated to the boiling point or in case it g be introduced with the charge to convert these should be desirable to further remove silica, the metas into their chlorides which are Sublimated Solution may be evaporated to dryness to render in the flames from the furnace and may be col any remaining Silica insoluble and then redis lected. Preferably, however, the operation is car Solved with boiling water and filtered to remove ried on so as to prevent Subination of the caesium, Such Silica. rubidium and lithium compounds so that they (3) Recovery of rubidium and coesium 140 may be recovered as hereinafter described. The solution resulting from the next previous (2) Decomposition of the Slag and 2UGier step in the operation is allowed to cool and to eactraction, Stand until the crystallization of the alums de The ninet from the furnace is allowed to cool rived from the rubidium, caesium and potassium 145 and is crushed and ground to fine powder. It has ceased. These alums are then carefully re is then mixed with approximately an equal vol royed and Saved for the caesium and rubidium. ume of water and treated with slightly more Sul These alums all have the same general formula as phuric acid than theoretically required to decom potash alum. The sodium and lithium sulphates 5 pose it. The acid acts violently, boiling and giv 'errain in solution. i 5O 1,982,878 3 The caesium rubidium and potash alums are tion to remove further amounts of aluminum dissolved and subjected to a fractional recrystal as the ammonium alum, the greater part of the lization during which the caesium alums with a aluminum may be removed by the simple crystal minute amount of rubidium alum rapidly accumu lization without the concentration and the re lates in the least soluble portions. The alums are maining aluminum may be removed along with 80 separated from each other by further fractional the iron in the next step. crystallization, or the separation may be carried While it is preferred to use ammonium sulphate Out by the precipitation of caesium antimony and to Separate the aluminum as ammonium O chloride and the crystallization of rubidium acid alum, it is possible to use other sulphates, such as tartarate. The steps heretofore described may potassium sulphate, in which case the aluminum 85 be applied to ores which contain caesium and is precipitated as a potash alum. If this is done, rubidium, other than beryllium-bearing ores, the ammonium compounds in the subsequent particularly the silicate ores of caesium and steps are replaced with corresponding potassium rubidium, Such as feldspars, lepidolites, etc., in Salts and more dilute Solutions should be em case the process is to be carried out primarily for ployed. Furthermore, if, at the end of the re 90 the recovery of caesium and rubidium. This fea covery of beryllium as beryllium basic carbonate, ture of the invention, therefore, is not limited to aS described later, there is ammonium carbonate the treatment of beryllium-bearing ores, insofar mixed with the beryllium basic carbonate, the am 20 as the recovery of caesium and rubidium is con monium carbonate may be removed by heating, cerned, but may be applied to other caesium and which removal by heating would not apply to the 95 rubidium-bearing ores. potassium salts. Furthermore, if the beryllium is (4) Removal of aluminum. precipitated as a hydroxide as later described, an exceSS of annonium hydroxide does not re 2 5 The aluminum is separated from the beryllium dissolve the precipitate, whereas an excess of po as ammonium aluminum Sulphate (ammonium taSSium hydroxide Would redissolve it. There 100 alum). The mother liquor from which the fore, I prefer to use ammonium Sulphate as the caesium, rubidium and potassium alums were reagent to remove the aluminum as annonium crystallized is treated with an excess of am alum, although it would be possible to use reagents monium Sulphate. A slight excess of ammonium Such as potassium Sulphate, to remove the alu Sulphate, say i0% or over may be used, although minum as another alum. the excess may be more than this, if desired. 105 The ammonium Sulphate converts the aluminum (5) Removal of iron and remaining traces of sulphate into ammonium alum, which may be re aluminum moved by crystallization. 3 5 The filtrate from the ammonium alum crystals The ammonium sulphate is preferably added is next heated, preferably in a stoneware, wood 10 to the boiling mother liquor and then the liquor or lead vessel, by means of a lead steam coil, to Set aside to cool and deposit the alum. The liquor boiling point and thoroughly oxidized. This Ox is cooled, preferably to about 15° C. or even lower, idation may be carried out in any suitable way, Which causes the ammonium alum to crystallize Such as by blowing air through the solution, or out. The Solution is allowed to stand until no it may be accomplished with chlorine, hydrogen 5 further crystallization of the ammonium alum peroxide, Sodium peroxide, Sodium perborate, po takes place. taSSium bromate or any oxidizing agent. The Then, in order to effect further crystallization, liquor is then treated with ammonium hydroxide the mother liquor is evaporated to about one-half or other alkaline hydroxides or salts, such for ex of its original volume and allowed to cool and ample, as calcium or Sodium hydroxide, or calcium 120 stand for several hours, usually from twenty-four Or Sodium carbonate, with very thorough stirring to forty-eight hours. The solution is preferably and boiling. cooled to 15 or even 0°. While it is preferred to The precipitated hydroxides rapidly dissolve at 50 cool the solutions from which the ammonium first. As the addition of ammonium hydroxide is alum is crystallized, crystallization may be ef continued, the liquid turns reddish and then 125 fected at ordinary room temperatures. The re finally ferric hydroxide separates as a very finely maining aluminum is thus precipitated as further divided precipitate. The addition of ammonium amounts of ammonium alum until substantially hydroxide is stopped as Soon as the Supernatant 5 5 all of the aluminum is thus separated. Some liquid gives a white precipitate upon dilution with traces of aluminum, however, remain, which are water, indicating that the liquid is basic. It is 130 later removed along with the iron in the next rather important at this stage of the process to Subsequent step. add the ammonium hydroxide carefully and See In Order that no beryllium be lost, the am that the mass is thoroughly stirred and well boiled. 60 monium alum crystals first obtained are dissolved The precipitated hydroxides should be given time in the wash water obtained from the basic beryl to react with the solution so that beryllium hy 135 lium carbonate from a later stage in the process droxide redissolves. and are re-crystallized from this wash Water. The final precipitate consists mainly of ferric The crystals are removed and the mother liquor hydroxide, together with some aluminum used to dissolve and re-crystallize the second hydroxide and a Small amount of beryllium crop of ammonium crystals obtained after the hydroxide, as well as the hydroxides of scan 140 Solution has been concentrated as above de dium and gallium in case these latter two Scribed. The Crystals thus obtained are then metals are present in the ore. While I prefer treated with the wash water from the beryllium to use ammonium hydroxide to render the Solution basic carbonate step, like the crystals obtained basic, other basic materials may be used, such as in the first ammonium alum crystallization. milk of lime or sodium hydroxide. The milk of 145 The Solution from which the ammonium alum lime may be used with substantially the Same re is re-crystallized and containing some beryllium Sults as the ammonium hydroxide. Sodium hy is retained and added to the solution from which droxide, however, tends to contaminate the ann 5 ammonium alum is to be crystallized. monium sulphate which is recovered at the end While it is preferred to concentrate the solu of the operation, and therefore, the preferred re 50 4 1982,873 agents to render the Solution basic are either cipitated as above described is of a variable com ammonia or milk of lime. position. It may contain, for example, as low Aside from throwing Out Some of the iron and as 20% of beryllium oxide or as high as 40%. Instead of using a mixture of ammonium hy aluminum as the hydroxides, these basic reagents 80 5 reduce the hydrogen-ion concentration Sufi droxide and ammonium carbonate, as indicated, ciently So that the hydrogen sulphide in the next it is possible to use ammonium hydroxide and Step can completely remove the final traces of carbon dioxide gas. iron as iron Sulphide and at the same time re Any excess of ammonium carbonate Which is mixed with the beryllium basic carbonate may be move copper and other heavy metals. 85 20 The hydroxides formed by the treatment of the readily removed by heat. Solution with ammonium hydroxide or lime are The precipitation of the beryllium basic car removed by filtration, preferably through a large bonate may also be accomplished by treating the lead Buchner funnel. Any beryllium accompany Solution. With an alkali carbonate or bicarbonate, ing the ferric hydroxide can be largely saved by Such as Sodium or potassium carbonate or bi stirring the residue with water, boiling and treat carbonate. ing with Sulphuric acid until, after long stirring, Instead of precipitating the beryllium as the the filtered liquid shows the presence of Some iron basic carbonate, which is the preferred proced by its brownish tint. This liquid after filtration ure, the beryllium may be precipitated as a beryl may be returned to the vessel and carefully lium hydroxide by treating the Solution. With a 20 treated with ammonium hydroxide as previously hydroxide alone, Such as ammonium hydroxide, described, to precipitate ferric hydroxide which Sodium hydroxide or potassium hydroxide. In may be filtered out. The filtrate may be added precipitating the beryllium hydroxide With ann to the solution containing the beryllium. In Onium hydroxide, an exceSS of annonium hy The basic acetate method may also be used for droxide does not redissolve the precipitate as 10.) 2 s separating the iron from the Solution. A minute does an excess of potassium or Sodium hydroxide. amount of iron usually remains in Solution. The It is therefore preferred to use ammonium hy introduction of ammonium acetate causes a little droxide. more bother in subsequent operations, Owing to If it is desired to obtain a pure beryllium ox the frothing when the beryllium is thrown out as ide, it is only necessary to heat the beryllium basic carbonate or the beryllium hydroxide to a () 5 3) basic carbonate. It also remains in the amino nium sulphate mother liquors which are used over red heat, thus converting it into the oxide. An again for the separation of aluminum. It is advantage of keeping the beryllium in the form therefore preferred to effect the separation of the Of its basic carbonate is that in this form it is iron as ferric hydroxide. Soluble in acids, whereas the oxide is soluble The filtrate from which the ferric and alumi Only in hot concentrated Sulphuric acid. num hydroxides are removed is then further treated to remove the remaining amountS of iro. (7) Recovery of ammonium Sulphate and any members of the copper group. This is The filtrate obtained after the precipitation preferably done by treating the filtrate with hyr and filtration of the beryllium basic carbonate drogen sulphide under slight pressure. Other is evaporated, allowing the ammonium sulphate 5 Sulphides may be used in place of hydrogen Sul to crystallize out. The crystals of ammonium phide, such for example, as the alkali metal Sul Sulphate are separated from the mother liquor phides, Sodium, potassium or amnonium Sul and are re-used for the removal of aluminum in phides. This precipitates the iron, copper, etc. the treatment of further batches of the beryl as sulphides which may be filtered out. lium ore, as described under the previous step of O I have found that the solution obtained after the renoval of the aluminum. The ammonium such filtration remains clear when treated With Sulphate recovered at this stage of the operation solid ammonium carbonate and warmed. This is sufficient to meet the major requirements if clear solution did not become discolored by treat not all the requirements for the removal of the 25 5) ment with hydrogen sulphide, indicating the ab aluminum. sence of iron. Should there be a darkening of (8) Recovery of lithium the solution, owing to the presence of traces of iron, the solution should again be saturated with The mother liquor from which annonium hydrogen Sulphide. Any difficulty in removing sulphate is separated by crystallization is next 55 iron at this stage indicates that the Solution Was treated with sodium carbonate to precipitate the :30 not made sufficiently basic during the removal lithium as lithium carbonate. The liquor may be of the major part of the ferric hydroxide. treated with other carbonates, such as potas sium or ammonium carbonate, to effect the pre (6) Recovery of beryllium. cipitation of lithium carbonate. The lithium car The beryllium is recovered preferably as a bonate thus formed is separated from the filtrate 60 precipitate of beryllium basic carbonate. The by filtration and the filtrate is discarded. iron and aluminum free filtrate from the next While I have described in detail the preferred previous step is heated to drive off any hydrogen procedure in carrying out my invention and the sulphide. The beryllium is then precipitated by preferred ores and materials employed, it is to be the addition of annonium carbonate and an understood that the invention may be otherwise 40 monium hydroxide in slight excess. Boiling the carried out within the scope of the following solution for a short time causes the precipitate claims. to become granular so that it may be readily I claim: 1. That step in the herein described process of filtered and Washed. The first Wash Water is recovering beryllium, which comprises fusing a 70 added to the main filtrate, While the Wash Waters 45 that are later obtained are used for recrystalliz mixture of a beryllium-bearing Ore and line with ing the crude ammonium alum, as described un a carbonaceous fuel in the blast furnace. der the step of the removal of aluminum. By so 2. That step in the herein described process of using the wash water, the ammonium sulphate extracting beryllium, which comprises fusing a 5. is not lost. The beryllium basic carbonate pre beryllium silicate Ore in a blast furnace together 50 1,982,873 5 with a basic material so as to form a slag con taining a basic beryllium Silicate. form a slag, decomposing the slag with Sulphuric 3. The process of treating beryllium-bearing acid and forming a Water Solution of the acid ores, which comprises fusing the ore with line to Soluble constituents of the slag, evaporating the form a slag, decomposing the slag with acid and Solution to render contained silica insoluble, forming a Water Solution of the acid-Soluble con Crystallizing out the aluminum as ammonium 80 Stituents of the slag, adding ammonium Sulphate alum, redissolving the soluble material, oxidizing to the Solution, removing aluminum from the and rendering the solution basic to precipitate Solution by crystallizing it out as ammonium iron as iron hydroxide and thereafter treating O alum, removing the iron and the remaining traces the basic Solution. With a Sulphide to precipitate of aluminum from the Solution by Oxidizing the the further iron as iron sulphide, and treating Solution and rendering basic and treating it with a the resulting Solution which contains the beryl Sulphide leaving the beryllium in Solution, and lium. With a carbonate so as to precipitate a basic then recovering the beryllium by precipitating it beryllium carbonate. as a basic compound from the solution. 6. The process of treating beryllium-bearing 4. The process of treating beryllium-bearing Ores, which comprises fusing the ore with lime 90 Ores, which comprises fusing the ore with lime to to form a slag, decomposing the slag with sul form a slag, decomposing the slag with Sulphuric phuric acid and forming a water solution of the acid and forming a Water Solution of the acid acid-Soluble constituents of the slag, evaporating 20 Soluble constituents of the Slag, evaporating the the Solution to render contained silica insoluble, solution to render contained silica insoluble, re redissolving the soluble material, adding am 95 dissolving the soluble material, adding ammonium monium Sulphate to the Solution and crystallizing Sulphate to the Solution, crystallizing out the Out the aluminum as ammonium alum, oxidizing aluminum as ammonium alum, Oxidizing and and rendering the solution basic to precipitate 3 rendering the Solution basic to precipitate iron iron as iron hydroxide and treating the solution as iron hydroxide and treating the basic solution With a Sulphide to precipitate further iron as iron 100 with a Sulphide to precipitate the further iron Sulphide, treating the resulting solution which as iron Sulphide, and treating the resulting solu contains the beryllium with a basic material so tion which contains the beryllium with a basic as to precipitate a basic beryllium compound, reagent So as to precipitate a basic beryllium evaporating the filtrate to crystallize out and compound. thereby recover ammonium Sulphate, and treat 5. The process of treating beryllium-bearing ing the mother liquor with a carbonate to recover ores, which comprises fusing the ore with lime to contained lithium as lithium carbonate. CHARLES JAMES.

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