US1861656A - Process for producing beryllium metal - Google Patents

Description

Patented June 7, 1932 UNITED STATES PATENT OFFICE HAIR-BY O.OLAI'LIN, OF CLEVELAND, OHIO, ASSIGNOB TO CORPORATION, OF NEW YORK, N. Y A CORPORATION OF BEBYLLIUM DEVELOPMENT DELAWARE PROCESS FOR PRODUCING BEBYLLIUM METAL ll'o Drawing.

This invention relates to the manufacture of be llium metal and its primary object is to ma e such manufacture both slmple and economical.

The nature, objects and advantages of the invention will be best understood from the following brief description of earlier methods.

The methods heretofore employed in the isolation of elementary beryllium have involved the electrol sis of a beryllium halide in the presence of one or more halides of metals more electropositive than beryllium, notably sodium or barium. Of the methods already known, the electrolysis of beryllium chloride in the presence of another chloride is probably the most economical. Such a procedure requires, for the electrolysis itself, no apparatus uncommon to general pyroelectrometallurgy, and its electrolysis chemical and energy costs are also low enough to be commercial.

One of the primary objections to this general method ofmanufacturing beryllium, however, is the difliculty of preparing the anh drous beryllium chloride necessary for the e ectrolysis. Dehydration of the hydrated chloride in the presence of ammonium chloride and sodium chloride, as first suggested by Borchers, yields onl a semi-fusible mass almost entirely hydro yzed to beryllium oxide, the chlorine being lost by hydrolysis in the form of HCl as. Such a mass cannot yield pure metal, i it can give any metal at all, which is highly questionable. It is, therefore, necessary to prepare beryllium chloride by strictly anhydrous processes. From beryllium oxide or carbonate, the compounds of beryllium most common the convenient, the chloride may be made by high temperature treatment with carbon and chloride, sulfur chloride, phosgene, carbon tetrachloride, etc. The beryllium chloride, after formation, is condensed in the cooler ortions of the chlorination apparatus. A ter rakin out from the furnaces, it is stored and hel ready for the electrolysis.

However, the manufacture of berivllium chloride in this manner has proven a andicap to the beryllium industry, and has re- Application filed January 3, 1931. Serial No. 506,498.

tarded commercialization considerably. The exceedingly great tendency of beryllium chloride to hydrolyze (it is like aluminum chloride in this respect) has made impossible the conve ing of the chloride from the synthesizing urnaces to storage receptacles and then to the electrolysis furnaces without significant hydrol sis and therefore partial conversion of the chloride to oxide. Since much of this oxide is carried through to the metal flake produced by the electrolysis, it is obvious that any procedure which could eliminate the constant danger of hydrolysis would greatly improve beryllium manufacturin conditions.

A further difliculty of current beryllium manufacturing procedure is the necessity for adjusting current densities in the electrolysis cells to the beryllium chloride content. The quality of flake (size of flake is an important commercial quality factor) is large- 1 determined by regulation of the concentratlon of beryllium chloride in the bath and regulation of the current densities used.

Periodic addition of beryllium chloride,

while somewhat helpful, is an inadequate method of holding conditions constant, since the interval between each addition will of itself show significant fluctuations.

I have found it possible to solve these problems and make the manufacture of beryllium a continuous process under constant, unchanging conditions, including constant beryl ium chloride concentration, and with a minimum of personal attention. By completely eleminating the condensation of beryllium chloride and uniting the two steps of chloride preparation and electrolysis into one operating unit, passing the vapors resulting from the chlorination of beryllium oxide directly into the bath of sodium or similar chloride (preferably with some beryllium chloride already present to lower the operating temperature), it has proven possible to operate continuously without hydrolysis. The beryllium oxide or carbonate, mixed with carbon, is fed into a chlorinating furnace-I prefer a vertical silica tube externally heated, but this arrangement is by no means essential to the process-and the chlorine resulting from the electrolysis is passed through the heated mixture. This results in gaseous carbon monoxide and vaporized beryllium chloride. Passage of the mixture directly into the halide bath results in the removal of the her llium chloride by solution in the bath, itself unchanged and in no way affecting the bath, andthence to the outside atmosphere. A further advantage of the carbon monoxide passing into and over the bath is its stirring action and its acting as an inert atmosphere for the cell. Since the cell is best 0 erated with an inert atmosphere (such as ydro en heretofore) the use of carbon monoxide or this purpose represents a definite saving.

The electrolysis pro or is conducted in the standard manner, the eryllium flake, which adheres loosely to the sides of the electrolyzing pot, being periodically scraped out, freed from adherin salts as far as ossible, and the remainder o the salt leac ed away with water. Here, however, instead of the chlorine being vented to the atmosphere, or recompressed for later use, as is current practice, it is trapped and passed back to the chlorination chamber, to act on fresh beryllium oxide.

It is obvious that the action of the unit is almost automatic. If, for any reason, it becomes desirable to stop the electrolysis for a while, the chlorine flow will also stop and ber lliumchloride manufacture will similar y automatically stop, keeping the concentration of the electrolyzing salts constant. Of course, a. certain amount of loss of chlorine is inevitable in practice, because of leaks, etc., but ex erience soon shows in the case of each unit how rapid an outside flow of make-up gas is needed'to keep conditions constant.

By the direct passage of the beryllium chloride in the vapor phase into the bath, all danger of h drolysis and oxide contamination is ma e impossible. The invention, therefore, removes this obstacle, too, from commercial beryllium manufacture.

I claim:

1. The process of pre arin a bath for the electrolytic isolation of bery lium comprising condensing ber llium chloride vapor by passin it into a mo ten bath.

2. T e process of preparing a bath for the electrolytic isolation of beryllium comprising condensing beryllium chloride vapor by passing it into a molten halide bath.

3. The process of pre aring a bath for the electrolytic isolation o beryllium comprising condensing beryllium vapor by passing it into a molten chloride bath. 1

4. The process of preparing a bath for the electrolytic isolation of beryllium comprising condensing beryllium chloride vapor by passing it into a molten bath of sodium chloride.

5. The process of preparing a bath for the electrolytic isolation of beryllium comprising condensing beryllium chloride vapor b passing it into a molten bath "of sodium an beryllium chlorides.

6. The process of manufacturing beryllium comprising forming beryllium chloride, condensing the beryllium chloride va or by passing it into a molten bath and subjecting said bath to electrolysis.

7. The process of manufacturing beryllium comprising forming beryllium chloride under essentially anhydrous conditions, condensing the beryllium chloride vapor by passing it into a molten halide bath and subjecting said bath to electrolysis.

8. The process of manufacturing beryllium comprising forming beryllium chloride under essentially anhydrous conditions, condensing the beryllium' chloride vapor by passing it into a molten halide bath and subjecting said gatlli to electrolysis, said bath being a chloride 9. The process of manufacturing beryllium comprising forming beryllium chloride under essentially anhydrous conditions, condensing the beryllium chloride vapor by passing it into a molten halide bath and subjecting said bath to electrolysis, the bath being one of sodium chloride.

10. The process of manufacturing beryllium comprisin forming beryllium chloride under essential y anhydrous conditions, condensing the beryllium chloride vapor by passing it into a molten halide bath and subjecting said bath to electrolysis, the bath being a mixture of sodium and beryllium chlorides.

11. The rocess of manufacturing beryllium whic comprises passing beryllium chloride vapor into a halide bath and subjectin said bath to electrolysis.

12. he process of manufacturing beryllium which comprises passin ber llium chloride vapor into a halide bat% an subjecting said bath to electrolysis, the bath being a chloride bath.

13. The process of manufacturing be 1- lium which comprises passin be llium ch 0- ride vapor into a halide bat an subjecting said bath to electrolysis, the bath being one of sodium chloride.

14. The process of manufacturing beryllium which comprises passin ber llium chloride vapor into a halide bat an subjecting said bath to electrolysis, the bath being a mixture of sodium and beryllium chlorides.

15. The process of manufacturing beryllium comprisin the passing of chlorine resultin from the electrolysis of a bath of beryllium chloride dissolved in a halide or mixture of halides of metals more electropositive, overheated beryllium compounds, in the presence of a reducing agent, and passing the resulting vaporized beryllium chloride into the electrolyzing bath.

16. The process of producing beryllium which comprises chlorln'oting bath.

In testimony whereof I have hereunto signed my name.

HARRY C. CLAFLIR.

CERTIFICATE OF CORRECTION.

Patent No. 1 861, 65ft June 1, 1932.

HARRY c. cmmn It is hereby certified that error appears in the printed specification of the above Mered patent requiring correction as follows:

for "chloride" read chlorine; and

"the" tint occurrence read and, and line 41.

Page 1, line 39, for

that the said Letters Patent ehoold he read with these correction therein that the came may conform to the record of the caae in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1932.

hi. 1. lloore. 'Actim Comiaaioaer of Patents.

which comprises chlorln'oting bath.

In testimony whereof I have hereunto signed my name.

HARRY C. CLAFLIR.

CERTIFICATE OF CORRECTION.

Patent No. 1 861, 65ft June 1, 1932.

HARRY c. cmmn It is hereby certified that error appears in the printed specification of the above Mered patent requiring correction as follows:

for "chloride" read chlorine; and

"the" tint occurrence read and, and line 41.

Page 1, line 39, for

that the said Letters Patent ehoold he read with these correction therein that the came may conform to the record of the caae in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1932.

hi. 1. lloore. 'Actim Comiaaioaer of Patents.