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Patented May 20, 1941 2,242,493 o'rso ‘STATES PATENT OFFICE 2,242,493 PROCESS FOR THE PRODUCTION OF BERYLLIUM COMPOUNDS Helmut von Zeppelin, Bitterfeld, Germany, as-v signor, by mesne assignments, to Walther H. Duisberg, New York, N. Y. No Drawing. Application April 1, 1939, Serial No. 265,510. In Germany April 5, 1938 6 Claims. (0]. 23-24) This invention relates to a process for the obtained a solution of sodium-beryllium double production of beryllium compounds which are ?uoride which contains a quantity of beryllium free from ?uorine. corresponding to 5.25 grams per liter of BeO. To Minerals containing beryllium are usually de 10 liters of this solution, at a temperature of composed by treatment with ?uorine compounds, 50° C., are added 233 grams of calcium oxide, such as hydro?uoric acid or ammonium ?uoride, while stirring. After stirring for 20 minutes, yielding solutions containing the beryllium in the carbon dioxide is passed through the solution, in form of a ?uoride. Since the production of me order to convert any caustic soda formed by reac tallic beryllium from such ?uoride compounds is tion with the calcium hydroxide, into sodium bi attended with di?iculties, it is frequently prefer 10 canbonate, whereupon 2000 grams of ammonium able to produce the metal from an oxide or chlo carbonate are added to the solution. After stir ride of beryllium. ring for 30 minutes the whole is ?ltered and the The present invention accordingly aims at con residue obtained is washed with a solution of am verting the beryllium ?uoride or beryllium double monium carbonate. On boiling the ?ltrate for ?uoride contained in such solutions, into beryl 15 about an hour, the beryllium separates out in the lium oxide or beryllium chloride, while separating form of its basic carbonate. This carbonate con out the ?uoride therefrom in the form of an in tains 45.1 grams of beryllium oxide which corre soluble compound. - sponds to a yield of 85.8%, calculated on the To this end, according to the invention, solu - beryllium oxide content of the initial material. tions containing beryllium in the form of ?uorine 20 compounds are treated with a hydroxide of an al Example II kaline earth metal, preferably calcium hydroxide, 500 grams of a beryllium ore containing 58 so as to convert the beryllium compounds into grams of beryllium oxide are decomposed with beryllium hydroxide and whereupon a beryllium 580 grams of sodium silico ?uoride. The decom compound is separated from the mixture of pre 25 position product is ?nely ground and then leached cipitates obtained by treating said mixture with for twohours at 40° C. with 8 liters of water. a solution of a caustic alkali or with a solution of 300 grams of calcium hydroxide are then added an alkali metal or ammonium carbonate. in the form of an aqueous suspension and the The removal of the beryllium from the mix whole is stirred for a further period of 20 minutes ture of precipitates is preferably effected di at a temperature of 50° C‘. in order to complete rectly after precipitation, since, as is known, the the reaction. Carbon dioxide is then passed freshly precipitated hydroxide soon becomes dim through the suspension in order to convert any cultly soluble by “ageing.” caustic soda formed into sodium bicarbonate, This inconvenience of “ageing” may also be which is particularly suitable for the subsequent avoided by converting the beryllium hydroxide of I‘ Li recovery of the beryllium compound from the the mixture into beryllium chloride, by known mixture. After adding 2000 grams of ammo methods for the preparation of beryllium chloride nium carbonate, stirring is continued for a fur from beryllium compounds, at an elevated tem ther 20 minutes, after which the insoluble matter perature in the presence of carbon, and thus is separated by ?ltration. The insoluble matter causing the beryllium to volatilize, in the form of -‘1 mainly consists of the gangue i. e. silica and its chloride, the precipitated ?uoride remaining aluminium compounds and calcium ?uoride. as residue. In order to avoid the formation of From the ?ltrate, basic beryllium carbonate is hydrochloric acid with its consequent reaction on precipitated by boiling for about one hour. The - the ?uoride to form volatile ?uorine compounds, quantity of beryllium carbonate obtained in this it is, however, necessary to previously calcine the manner corresponds to 48.7 grams of beryllium , mixture to be chlorinated, for a short period, at a oxide and thus represents a yield of 84% of temperature’lbetween 500° and 700° C., so as to beryllium oxide recovered in a commercially pure convert the beryllium hydroxide into the oxide. form. The volatilized beryllium chloride produced in the I claim: manner hereinbefore set forth can be recovered 5‘ 1. A process for the production of beryllium in a practically pure form by condensation. compounds which are free from ?uorine, from Example I an aqueous solution containing beryllium in the - form of ?uorine compounds, which comprises By the decomposition of a beryllium ore by treating such solution with a hydroxide of an means of sodium silico ?uoride (NazsiFe) there is 55 alkaline earth metal so as to precipitate a mix 2 2,242,493 ture of alkaline earth metal ?uoride, beryllium and gangue, introducing carbon dioxide into the hydroxide, and gangue, and thereupon separating reaction mixture so as to neutralize any caustic the beryllium compound from such mixture of soda formed in the reactiomseparating the mixd precipitates obtained by treating said mixture ture of precipitates obtained from the residual with a solution of at least one compound of the solution and removing the beryllium compound group consisting of the alkali metal hydroxides from such mixture by treating such mixture with and the alkali metal and ammonium carbonates, a solution of at least one compound of the group so as to convert the beryllium hydroxide into consisting of the alkali metal hydroxide and the solution, this solution being separated from the alkali metal and ammonium carbonates, so as to residue. > 10 convert the beryllium hydroxide into solution, 2. A process for the production of beryllium this solution being separated from the residue. compounds which are free from ?uorine,from>an 5. -A process for the production of beryllium aqueous solution containing beryllium in the form compounds which are free from ?uorine, from an of ?uorine compounds, which comprises treating aqueous solution containing beryllium in the form such solution with a hydroxide of an alkaline 15 of ?uorine compounds, which comprises treating earth metal so as to precipitate a mixture of such solution with a hydroxide of an alkaline alkaline earth metal ?uoride, beryllium hydroxide, earth metal so as to precipitate a mixture of and gangue, and separating the mixture of pre alkaline earth metal ?uoride, beryllium hydroxide, cipitates obtained from the residual solution and and gangue, and thereupon separating the beryl removing the beryllium compound from such 20 lium compound from such mixture of precipitates mixture by treating such mixture with a solution obtained by treating said mixture with ammonium of at least one compound of the group consisting carbonate so as to re-dissolve beryllium com of the alkali metal hydroxides and the alkali pounds from the mixture of precipitates obtained, metal and ammonium carbonates, so as to con separating the solution from the remaining pre vert the beryllium hydroxide into solution, this cipitate consisting of an alkaline earth metal solution being separated from the residue. ?uoride and gangue, and boiling the ?ltrate so as 3. A process for the production of beryllium to precipitate basic beryllium carbonate there compounds which are free from ?uorine, from from. an aqueous ‘solution containing beryllium in the 6. A process for the production of beryllium form of ?uorine compounds, ‘which comprises 531) compounds which are free from ?uorine, from an treating such solution with calcium hydroxide aqueous solution containing berylliumin the form so as to precipitate a mixture of calcium ?uoride, of ?uorine compounds, which comprises treating beryllium hydroxide, and gangue, and thereupon such solution with a hydroxide of an alkaline separating the beryllium compound from such earth metal so as to precipitate a mixture of al mixture of precipitates obtained by treating said C35 kaline earth metal ?uoride, beryllium hydroxide, mixture with a solution of at least one compound and gangue, separating the mixture of precipi of the group consisting of the alkali metal hy tates obtained from the residual solution and re droxides and the alkali metal and ammonium car moving the beryllium compounds from such mix bonates, so as to convert-the beryllium hydroxide ture by treating such mixture with an ammonium into solution, this solution being separated from 40 carbonate solution so as to re-dissolve beryllium the residue. compounds from the mixture of precipitates ob 4. A process for the production of beryllium tained, separating the solution from the remain compounds which are free from ?uorine, from an ing precipitate consisting of an alkaline earth aqueous solution containing beryllium in the form metal ?uoride and gangue, and boiling the ?l of ‘fluorine compounds, which comprises treating trate so as to precipitate basic beryllium car such solution with a hydroxide of an alkaline bonate therefrom. earth dmetal so as to precipitate a mixture of HELMUT VON ZEPPELIN. alkaline earth metal ?uoride, beryllium hydroxide, .