mama 14, 1944 ' 2,344,480 UNITED STATES PATENT-err 2,344,480 ice PROCESS FOR OBTAINING SOLUBLE BERYL LIUM COMPOUNDS STARTING FROM ORES CONTAINING BER Carlo Adamoli, Milan Italy, assignpr to Pero'sa Corporation, Wilmington, DeL, a corporation of Delaware Application February 10, 1941, Serial No. 378,218 ' a In Italy July 20, 1936 5 Claims. (01. 23-19) ‘ This invention relates to a, process for the ex one alkalineearth metal compound capable of traction of beryllium from beryllium ores, and binding the silica in form of an insoluble silicate, more speci?cally to an .embodiment of the proc by roasting the ore with the attacking agent at a ' ess disclosed in my prior application .Serial No. temperature highenough to sinter but low enough 154,236 ?led on July 17, 1937 v(Patent 2,238,206 5 to avoid fusion of the mass (for instance between granted April l5, 1941), of which the present ' 1000 and 1200° C.) , and then in treating the reac application is a‘ continuation-in-part. tion products in the presence of an aqueous phase The processes utilized for the extractionéof and at elevated temperature with an alkali-metal beryllium contained in ores containing beryl compound capable of reacting with the silica to lii?n which are met with in general in nature in 10 form a soluble silica compound, causing to act the form of ores with a basis of silicates, may be on the solution a carbonating agent which ?rst connected for the greater part with the ordi converts the beryllium hydroxide into insoluble nary processes of analytical disintegration of sili beryllium carbonate and - then causes insoluble cates. . - beryllium» carbonate to pass into the-state of a Thus there have already been proposed var is compound in solution, separating the said com ious processes of extraction comprising in their pounds from the other compound formed and cal most general aspect in the ?rst place the fusion dining it to obtain beryllium oxide. The complete of the ore with an excess of carbonate such as operation takes place under these conditions with , calcium or sodium carbonate or other carbon ' , out requiring employment of acid agents. ates, or of anhydrous oxide or hydrate of any 20 "As alkaline earth metal compoundcapable of alkaline‘ earth or alkali metal (for example _ binding the silica‘in form of an insoluble silicate, caustic soda or potash) in an anhydrous oxide or onemay use. an anhydrous oxide or hydrate or a hydrate or an alkaline earth or alkali metal (for carbonate of an alkaline earth metal‘ or mixtures example caustic soda or potash in an anhydrous thereof. - state) as well. as in a second phase the decom 25 As alkali metal compound capable of reacting position qf the ‘reaction product containing with the insoluble silicate to form ‘a soluble silica beryllium by means of a strong acid, for example compound, one may use more particularly sodium hydrochloric acid or sulphuric acid. . _ hydroxide NaOH. "This compound is used prefer» The principal-known processes of this kind in ably in a boiling solution, 'the treatment being fact-employ, after'disintegration of the ore by 30 performed either at the atmospheric pressure or fusion with alkalies, the decomposition ,of the under pressure. ' ' ‘ fused mass‘ by means of strong acids. From‘ As carbonating agents, one may use carbon di this result dimculties of the well known'teéh ' oxide and the'carbonates and bicarbonates of the nical kind, for example dimculties arising from > alkali metals. the necessity of rendering insoluble large masses 35 n, for instance, the treatment according to the of gelatinous silica and 'dimculties in separating I invention is applied to beryl, thelatter 'being sub beryllium from impurities such as iron and mitted to a-roasting operation with carbonate of alumina. . calcium COaCa, then by causing soda to act upon .Moreover the processes in question have never the product of the roasting operation and by car allowed working to be carried out under eco 40 bonating ?nally with ‘CO2, the complete operation ,nomical and industrial conditions by reason in . of disintegration of the ore and of solubilization particular of the considerable consumption of ’ of the beryllium takes place according to vthe fol alkaline reagents required during the ?rst phase > lowing reactions: ' 7 v ‘ of the operation (disintegration of the ore); these reagents are during the second phase neu tralised by acids both being thus lost in the form > (I) of salts having no industrial value, for example, in the form of NaCl, CaCl-z, Na?soi', 'CaSOl or , other salts of this kind. (II) The present invention has for its object a proc- __ 50 ess"of treatment which permits the beryllium to be extracted starting from its silicate ores such as beryl for example, in the form of beryllium oxide, and which allows at the same timethe disadvan . tages mentioned above to be avoided and in par 55 The process which forms the subject of the _~ ticular the utilisation oi’ acid, agents to be avoided ' present invention is advantageously carried out and all the di?iculties which: arise therefrom. commercially according to a cycle of. operations This process consists-essentially in the ?rst ' which can be illustrated by a diagram such as ‘the place in causing to act .upon beryllium sili- ‘ diagram which is‘ shown'o'n the appended draw- - cate ore an attacking reagent comprising, at least‘ 60 ins. This diagram relates'to an example which is v 2 2,344,480 given by way of simple illustration which is in perature. Under these conditions about half of no way limitative and in which beryl is attacked the COsNa: precipitate; ‘at this moment, the CO2 by means of calcium carbonate COaCa according of the gasometer is introduced into ‘the vat, this to the Reaction ‘(1), the product of the roasting gas causing the conversion of a remaining portion operation being then lixiviated and alkalized by of the COzNa: to COaNaH. The liquid is de means of'sodium hydroxide NaOH according to canted, in‘order to separate it from the salt de the reaction (II) and ?nally carbonated by means posit and introduced into the boiler f where the of CO: according to the Reaction (III). carbonate of beryllium BeCO: is precipitated In the example of the appended drawing, a through a boiling operation and separated by de represents a rotary furnace in which the mass is 10 cantation from the alkali liquid formed by the roasted, b a crusher, c a boiling apparatus and d ‘carbonate CO3Na-z and then washed and dried a series of ?lters from whence the alkaline solu in a hydro-extractor. From the said carbonate tion containing the beryllium ?ows out through of beryllium, one directly arrives at the beryllium ?ltration. This alkaline solution containing the oxide BeO through calcination in the furnace g. beryllium passes through a cooling vat of wood e The alkali liquid in which BeCOs has been pre-_ in order to precipitate the sodium carbonate cipitatedin the boiler f and which contains which has been formed and arrives at a boiler f - COaNaz returns into the cycle after conversion from which the soluble compound (salt) of beryl ' into sodium hydroxide by means of quick lime lium which is to be obtained is then collected; g arising from a lime furnace (not, shown). is a furnace for the calcination of this compound 20 The yields obtained by the cycle of operations and for the obtention of the beryllium oxide. which the process comprises with respect to the The device which is so-formed works as follows beryllium present in the starting ore attain 95%. for carrying out the cycle of operations to be The development of the cycle described above effected from the attack of the beryl by means well shows the great simplicity of the process; the industrial apparatus is not costly for there is of calcium carbonate COsCa. . . 25 In the rotary furnace a the roasting of the no need of special materials for the formation of beryl is e?ected with this COaCa through burning the necessary apparatus and none of theliquids at a temperature of about 1100 to 1200° 0., in which take part in the phases of the process is order to cause the disintegration of the ore in a corrosive.‘ The sole- effective expense is that of the CaCOa and of the lime, which are produced ‘ state of frit but without arriving, however,‘ at 30 the melting of the mass. Thus, silica SiOz is con at little cost. The ?ltration of the mass after verted into SiOaCa according to the Reaction (I) I - boiling in the boiling apparatus 0 is very simple. The furnace a is connected, at the outlet of the Due to the fact that the utilisation of acid agents gases, to the water separator k which works as a is avoided, the gelatinisation of the silica and the necessity of thenrending it‘ insoluble is avoided. - device adapted for washing and regenerating C02. 35 On leaving the furnace a the roasted mass is Moreover, the residue obtained after ?ltration crushed in the crusher b and vintroduced into ' has a composition which allows it to be used, for the boiling apparatus 0 which serves also as de example, in the mnaufactureof cement. composition apparatus, this apparatus being made The decomposition of the product arising from of iron and provided with a stirring device as '40 the disintegration of the ore may also-be re?ected ' well as with a heating device for heating with in an autoclave under pressure. In this case, direct'steam. _A solution of NaOH is brought to according to a modi?ed operation of the process this boiling device. This ‘solution of NaOH re described above, the product of roasting disin acts on the disintegrated ore according to the tegrated material by the reaction corresponding to Reaction (II); the SlOaCa is decomposed and 45 Reaction (1) is taken and the silicate formed is gives SiOaNa: which is soluble, the reaction liber . extracted with the alumina by treating the said ating the basic oxides of the beryl: BeO and product in an autoclave under pressure by means A1203, while the alkaline-earths are regenerated ‘ - of a dilute caustic soda solution, for example, as well as superheated steam under a‘pressure of as Ca(OH) 2. _ When the reactionis achieved, the CO2 coming 60 5-6 atmospheres, the sodium silicate NazSiO: from the gas holder 1 is introduced at the boil formed and the greater part of the alumina then ing point so as to‘ precipitate the Ca(OH)2 as enter into solution. The treatment is then car 0030a and ‘to e?'ect the carbonation according ried out as above described. to the Reaction (III) in order to convert BeO The invention is illustrated in the following into BeCOa, A1203, into .A12(CO3)3 and SiOaNaz 55 non-limitating numerical example. into sodium carbonate COsNaa and SiO: which is 100 kg. of beryl containing 12.5% of BeO, ~ freed as crystalline powder. Then the tempera ?nely crushed, are mixed with 150 kg. of lime ture is lowered to 40-45° C. and a predetermined stone ?nely crushed and the mixture is bricketted quantity of CO: coming from the gas holder is and submitted to heating to a temperature of introduced in order to convert only a portion of 60 1000-1200° C. in a continuous furnace for .4 to 6 the NazCOa to NaI-ICO: until a conantration of hours. The heated product does not melt at the 8-9% of this salt is obtained, which dissolves temperature of, the reaction but forms into a the BeCOs. Care must be taken that the quantity . frlt. of CO2 which is introduced during this (stepyis The frit is removed from the furnace and is not in excess over the quantity which is neces 65 ?nely crushed in presence of water. It is then sary, in order to avoid any separation of CO3NaH introducedwith the water into the boiling ap paratus and submitted to boiling with 1200;litres which is little soluble. , - . After dissolution of the beryllium salt, the liquid of a solution of caustic soda at 36° Bé. resulting which comprises the ‘alkaline solution containing from the dissociation by means of quicklime of the beryllium is ?ltered and after‘having sepa 70 the NaaCO: recovered in a preceding operation. rated the residue therefrom as a mixture of The boiling temperature is maintained until the CaCOa, SiOa, 1120.1, the ?ltered solution is intro reaction according to the Equation II is achieved. duced into the cooling vat e‘ which is provided When this reaction is achieved, carbon dioxide on the bottom with a‘ draining opening and it isv arising from the fritting furnace and from'the allowed to cool down to the ‘surrounding tem lime furnace and collected in the gas container is 2,844,480 introduced into the boiling apparatus-and is ab ,3. A process for obtaining soluble compounds sorbed by the solution. The calcium carbonate, . starting from beryllium silicate ores, comprising the basic aluminium carbonate and the silica, the steps of roasting the ore withcalcium car which are formed according to the Reaction‘III, bonate in amount suilicient to convert the silica of precipitate. - the ore into calcium silicate, at a temperature The remaining solution which contains beryl high enough to sinter but low enough to avoid lium carbonate, sodium carbonate and sodium bi fusion of the mass,. treating the reaction product carbonate is then ?ltered and submitted to boil containing beryllium oxide and calcium silicate at ing until the precipitation takesplace of 30' kg. » boiling temperature with a solution of sodium. of BeCOz which by calcination provides 11.5 kg. 10 hydroxide, thereby converting the beryllium oxide of BeO. to beryllium hydroxide and converting the calcium What I claim is: . I ' sllicateto a soluble silicate, treating the product 1. A process for obtaining beryllium oxide start with CO: at elevated temperature to convert the ing from beryllium silicate ores, comprising the beryllium hydroxide into- insoluble beryllium car steps of roasting the ore with an attacking agent, 15 bonate and form sodium carbonate, lowering the comprising at least one alkaline-earth compound temperature and treating the product with 00: of the class consisting of the anhydrous oxides, whereby a'portion oi.’ the sodium carbonate is hydrates and carbonates iniamount su?icient to converted into sodium bicarbonate and the in convert the silica of the ore into alkaline-earth soluble beryllium carbonate is solubilized, separat silicate, at a temperature high enough to sinter 20 ing the solution containingsolubilized beryllium ' but low enough to avoid fusion of the mass, treat carbonate and sodium carbonate and sodium bi ing the reaction product containing beryllium carbonate trom the insoluble compounds, pre oxide and alkaline-earthsilicate in the presence cipitating beryllium carbonate from the solution of an aqueous phase and at elevated temperature and calcining it to obtain beryllium oxide. _ I with an alkali-metal comp'oimd capable of re 4. A process for obtaining beryllium oxide from acting with the beryllium oxide to convert it to beryllium silicate ores, comprising the steps of beryllium hydroxide, and of reacting with the al roasting the ore with calcium carbonate in amount kaline-earth silicate to form a soluble silica com su?icient to convert the silica of the ore into . pound, treating the product with CO: at elevated calcium silicate, at a temperature between 1900° temperature to ‘convert the beryllium hydroxide and 1200’ C., treating the reaction product con into insoluble beryllium carbonate and form al taining beryllium oxide and calcium silicate at ' kali metal carbonate, lowering the temperature boiling temperature with a solution of sodium - and treating the product with CO: whereby a por hydroxide, thereby converting the beryllium oxide tion of the alkali metal carbonate is converted to to beryllium hydroxide and converting the cal alkali metal bicarbonate and the insoluble beryl 35 cium silicate to a soluble silicate, treating the lium carbonate is solubilized, separating the solu product with CO: at elevated temperature to con tion containing solubilized beryllium carbonate vert the. beryllium hydroxide into insoluble beryl and alkali metal carbonate and alkali metal bi lluim carbonate and form sodium carbonate, carbonate from the insoluble - compounds, pre lowering the temperature and treating the prod cipitating- beryllium carbonate from the solution 40 uct with 00: whereby a portion of the sodium car and calcining it to obtain beryllium oxide. ‘ bonate is converted into sodium bicarbonate and 2. A process for obtaining beryllium oxide the insoluble beryllium carbonate is solubilized. starting from beryllium silicate ores, comprising separating the‘ solution containing solubllized the steps or roasting‘the ore with an attacking beryllium carbonate and sodium carbonate and agent comprising at least one alkaline-earth com sodium bicarbonate ‘from the insoluble com pound of the class consisting of the anhydrous _ pounds, precipitating beryllium carbonate from oxides, hydrates and carbonates in amount sum the solution and calcining it to obtain beryllium cient to convert the silica of the ore into alkaline! oxide earth silicate, at a temperature between MW and 5. A'process for obtaining beryllium oxide from 1200’ 0., treating the reaction product contain beryllium silicate ores with cyclic recovery or the ing beryllium oxide and alkaline-earth silicate in reacting agent employed, which consists in roast the presence of an aqueous phase and at elevated ' inc tbdi ore with calcium carbonate in amount temperature witlr an alkali-metal compoimd sumcient to convert the silica o! the ore into capable of reacting with the berylliumoxidc to calcium silicate, at a temperature between 1000 convert it to beryllium hydroxide, and 01' react and W 0., treating the reaction product at .' ing with'thealkaline-earth silicate to form a boiling temperature with a solution ‘of-sodium hy soluble silicacompound, treating the product with ' droxide. then carbonating the resulting solution 00: at elevated temperature to convert the beryl- - with carbon dioxide in amount sumcient to cause lium- hydroxide into insoluble beryllium carbonate; the iormation of soluble beryllium carbonate and , and form alkali metal carbonate. lowering the ‘of-sodium carbonate and sodium bicarbonate; ~' temperature and treatina ‘the product with CO: while cooling the solution, separating in solution ., ' wherebya portion of the alkalimetal carbonate - the beryllium carbonate, sodium bicarbonate and is converted to alkali metal bicarbonate and the sodium carbonate from the insoluble compounds, insoluble beryllium carbonate is ‘solubilised, sep - precipitating beryllium carbonate from the solu arating thesolution contalningsolubillxed beryl tion and calciniihit toiorm beryllium oxide, re lium carbonate and alkali metal carbonate coverlngthssodiumcarbonatatreatingitwlth alkali metal bicarbonate from the insoluble com calcium hydroxide to reform sodium hydroxide pounds, precipitating beryllium :carbonstc'trom ' solution and calclnlngit to obtain beryllium andzign?zthecarbogtdioxideevolvedintherosst to