By : Aprilliany Fajrina - 1706986536

Fluoride Extraction Process of

Beryllium
Introduction
Beryllium is the first element in the second main group of the periodic table. It is a
light metal with hexagonal-closest-packed (hcp) structure. Both finely divided
metal and the compounds have serious toxic effects on the lungs. In addition to the
name beryllium, derived from the mineral beryl, this element with atomic number
4 was formerly called glucinium, chiefly in France, because of the pronounced
sweetish taste of its salts. Beryllium has of late come into prominence because of
its immense value as an alloying element in some binary and ternary non-ferrous
alloys. The most important use of this metal is in atomic reactors where it acts as a
moderator for slowing down fast neutrons. It is obtained from the mineral beryl of
which India is one of the principal producers. An electrolytic method for the
extraction of beryllium-oxide from beryl has been developed at the National
Metallurgical Laboratory, which consists in first obtaining the beryllium in solution
as a soluble beryllium salt and then electrolyzing this solution between two graphite
electrodes in a diaphragm cell. A slurry containing the hydroxide of beryllium is
obtained from the cathode cotnpartment, which on washing, drying and ignition,
gives the oxide.

Resources, Raw Material

Beryllium, till recently regarded as a 'raree metal' and of little practical use, has of
late come into prominence in the industrial field. Binary and ternary alloys of
beryllium with some non-ferrous metals like magnesium, aluminium, nickel, cobalt
and particularly those with copper are unique in some of their properties and hence
industrially very useful. Beryllium oxide is an important raw material for
manufacture of special types of refractory wares. Because of its extra-ordinary
resistance to thermal shocks and high electrical resistance even at high
temperatures, it may be rightly called a 'super refractory' which can be used with
great advantage for making crucibles, muffles, laboratory boats, electrical furnace
linings, and vacuum tubes. It is also an important ingredient in 'phosphors' for
fluorescent lamps. By far the most important is its use in the atomic reactor as a
moderator along with pure graphite and heavy water. But because of the extreme
difficulties encountered and hence high cost involved in the manufacture of the high
purity metal, its use there is being gradually supplanted by the other two materials,
graphite and heavy water. Though there are several minerals in nature containing
beryllium. Beryl contains about 11% beryllium oxide (4% Be) and is often obtained
as a by-product of feldspar quarrying. India is one of the principal beryl producing
countries, others being Russia, Argentine and Brazil. Rich deposits ofberyl occur
throughout India, the most productive.
By : Aprilliany Fajrina - 1706986536

Production
Since the density of beryl is close to that of quartz, concentration by density is not
possible. Hand sorting has been the chief means of separation. Flotation is
successful only for a few ores. An automatic machine, the Beryl Picker, has been
used recently the ore is first y-irradiated to render the beryllium atoms radioactive,
The beryl crystals are then selected out by a sorter guided by a neutron counter. The
recovery of beryllium from both beryl and bertrandite includes several stages. The
ores are first converted to an acid-soluble form by fusion. Complex chemical
processes are then used to obtain comparatively pure beryllium hydroxide or oxide
and then beryllium cWoride or fluoride. These halogenides are reduced to metallic
beryllium with other metals or by melt electrolysis. The beryllium metal obtained
is subjected to one or more refining processes and then to further treatment by
powder metallurgy or in some cases fusion metallurgy.

Fluoride Process.
In the fluoride process beryl is melted or sintered at 700°C with sodium
hexafluorosilicate, pressed into briquette form and sintered by heating at 1400°F
for 2 hr in a muffie kiln with a moving hearth. This converts the beryllium oxide
present in the ore to a water-soluble form of beryllium, known as sodium
fluoberyllate, Na2BeF •. It can be considered that silicon tetrafluoride is the active
material which attacks the beryllium oxide (BeO) to form soluble beryllium fluoride
(BeF2 ); however, if sodium fluoride is not present, the BeF2 further reacts with the
silica and insoluble beryllium silicate is the product of re action as follows:

2 BeO + SiF SiO + BeF. [1]

2 BeF + 2 SiO2 SiF + Be.8iO. [2]

By having a form of sodium fluoride present, sodium fluoberyllate is produced from

the BeF2 formed in equation [1]:

2 BeF2 + 4 NaF 2 Na2BeF • [3]

Silicon tetrafluoride and the necessary sodium fluoride are formed from the
decomposition of the sodium fluosilicate at the sintering temperature and by the
reaction of soda ash with part of the sodium fluosilicate as follows:

Na,SiF 2NaF + SiF [4]

Na2SiF + 2 Na2CO 6NaF + CO + SiO2 • [5]

These equations are a guide to the reactions involved. In practice, the amounts of
chemicals required for the BeO content in the ore are based on this combined
reaction:

3BeO· AI2O • 6SiO2 + Na2SiF + Na CO3 Na2BeF + AI2O + 8SiO + CO2 [6]

Actually, an excess of 7 pct F is used to allow for some silicon tetrafluoride losses
in the furnace and for possible variations in the beryl ore mix. This shows that the
BeO is selectively attacked by the fluorides, and the aluminum and silicon oxide
By : Aprilliany Fajrina - 1706986536

remain unreacted and insoluble in water. If any alumina does react, an insoluble
aluminum fluoride is formed, wh ich remains with the gangue mud in the leaching
step. With the proper type of muffie furnace having controlled ventilation to
minimize the loss of silicon tetrafluoride, as sinter breakdown yield of 95 to 96 pct
is obtained from the BeO in the ore to the soluble sodium fluoberyllate. If the
furnace is partially open so that silicon tetrafluoride rapidly escapes from the
briquettes, then the yield is considerably lower. The sintered briquettes are jaw
crushed or hammer milled and then wet pebble-milled. This pebble milling is not
critical. Leaching is done in stages by adding controlled amounts of water to the
ground sinter in agitated tanks, then fiItering or decanting the solution and adding
fresh water to the mud slurry. A three-stage leach with hot water gives a Partial
view of sinter furnace in foreground, and sinter wet milling equipment in
background. combined BeO concentration of 5 to 6 gpl. If room temperature water
is used, a five-sta,ge leach is required, and the leach concentration is about 3.5 g
BeO per liter. The concentration of beryllium extracted is higher in the first leach
liquors and decreases with subsequent leaching. It is found that the beryllium
content in the first leach is above the measured solubility of sodium fluoberyllate
(Na2BeF,) and the ratio of fluorine to beryllium approximates that of NaBeFa,
implying the presence of the more soluble BeF2 in solution wh ich is formed in the
sinter re action as shown by equation [1] above. In subsequent leaching steps, the
ratio of fluorine to beryllium approaches the normal order of 4 to 1. With hot-water
leaching, each leach cycle is limited to a total period of 2 hr in order to minimize
silica pick-up in solution and in the plantgrade BeO product. Some 90 to 95 pet of
the beryllium is extracted from the ore to the fluoride leach solution and is
precipitated from this solution as beryllium hydroxide by the use of caustic soda.
The nature of the precipitated hydroxide can vary greatly from a slimy gelatinous
precipitate to a dense crystalline one, depending upon the temperature of
precipitation, the amount of sodium hydroxide used, and the method of
precipitation. To obtain a dense granular hydroxide which is preferred because it
occ1udes fewer impurities than the gelatinous material a batch aging method of
precipitation is used. The total requisite amount of caustic.

Conclusion
Beryl is treated mainly by the sulfate and fluoride processes. The cWoride process
is a direct, inexpensive process for recovering beryllium chloride for electrolysis.
The steps used in producing high-purity BeO and beryllium metal, including recent
modifications to production processes, are described. Particular emphasis is placed
on the fluoride extraction process in which beryllium is attacked preferentially, and
beryllium oxide is converted into a water-soluble form of beryllium fluoride so that
no additional chemicals are required to react with other materials present in beryl
ores. Beryllium is processed from the ore in four major steps: (1) the beryl ore is
converted into a standard grade of beryllium hydroxide, (2) the hydroxide is
purified, (3) purified beryllium hydroxide is reacted with ammonium bifluoride for
conversion into ammonium beryllium fluoride, and (4) then reduced to beryllium
metal. The fluoride process is attractive economically and offers an additional
advantage of versatility.
By : Aprilliany Fajrina - 1706986536

References

Walsh, Kenneth A. (2009). Beryllium Chemistry and Processing. ASM

International. MLA.

Fathi Habashi. (1997). Handbook of Extractive Metallurgy I ed. by Fathi

Habashi. Weinheirn; New York; Chichester; Brisbane; Singapore; Toronto.

Morana, S.J. & Simons, G.F. JOM (1962).

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