Hydrometallurgy 109 (2011) 18–22

Contents lists available at ScienceDirect

Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Extraction of beryllium from Indian beryl by ammonium hydrofluoride

D.D. Thorat ⁎, B.M. Tripathi, D. Sathiyamoorthy
Powder Metallurgy Division, Bhabha Atomic Research Centre, Vashi Complex, Turbhe, Navi Mumbai 400705, India

a r t i c l e i n f o a b s t r a c t

Article history: A new technique of decomposing beryl ore at low temperature with ammonium hydrofluoride (NH4HF2) is
Received 22 November 2010 proposed. Removing the fluorides of silicon and aluminium from the reaction product as volatile and insoluble
Received in revised form 2 May 2011 compounds, respectively, have been investigated experimentally and the feasibility of the process has been
Accepted 3 May 2011
established to extract beryllium fluoride (BeF2) as a soluble compound. The sequence of reaction of beryl ore
Available online 10 May 2011
with the strong fluorinating agent NH4HF2 has been studied by TG/DSC, intermediates and final products were
Keywords:
identified by XRD. The product yield was found to be up to 93%. A process flow sheet to produce beryllia (BeO)
Beryl ore and BeF2 for subsequent magnesiothermic reduction to produce beryllium metal is proposed based on the
Fluorinating agents experiments conducted at bench scale. Methods of recycling NH4HF2 have been suggested, thereby making
Ammonium hydrofluoride the proposed route superior to the conventional methods in terms of recovery, low temperature of operation,
Beryllium oxide fluoride recycling, and significant reduction in effluent as well as improved safety in handling of beryllium.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction One of the priority applications of beryllium in fusion reactors is in

Beryllium is rare in the earth's crust (6 × 10 − 4% per weight) and its
presence is rather limited (Zaki et al., 2005). It does not occur as free
metal in nature. There are about 30 minerals containing beryllium,
the most significant of them being beryl (3BeO·Al2O3·6SiO2),
phenacite (2BeO·SiO2), chrysoberyl (BeO·Al2O3) and bertrandite
(4BeO·2SiO2·H2O) (Zaki et al., 2005).
The main interest in beryllium is its unique combination of
mechanical, thermal and nuclear properties. Properties of such as high
melting point (1285 ± 5 °C) (Zaki et al., 2005), low neutron absorption
and high scattering cross sections make beryllium attractive for use in
nuclear reactors as neutron reflector and moderator. Beryllium, because
of its neutron multiplication properties by (n, 2n) reaction for high
energy neutrons, coupled with low neutron damage in displacements
per atom (dpa) (Argentina et al., 2000), is considered as neutron
multiplier material in the solid breeder blanket of the International
Thermonuclear Experimental Reactor (ITER). Beryllium is also consid-
ered as plasma facing material (PFM) (Argentina et al., 2000) in ITER.
Because of its high thermal conductivity combined with electrical
resistivity, BeO is an ideal material for heat sinks in electronic circuits
and packages. The high melting point (2570 °C), coupled with
negligible vapour pressure right up to the temperature of melting,
make BeO a suitable crucible material for many melting and sintering
operations (SAHA, 1994a).
⁎ Corresponding author. Tel.: + 91 22 2788 7178; fax: + 91 22 27840032.
E-mail addresses: thoratdd@yahoo.com (D.D. Thorat), biranchi.barc@gmail.com
(B.M. Tripathi), dsathiyamoorthy@gmail.com (D. Sathiyamoorthy).
the form of molten salt mixture of LiF and BeF2 commonly referred to
as Flibe. This salt system has been considered for application as a
renewable plasma-facing surface in advanced concepts of fusion
reactors and also as a coolant (Argentina et al., 2000).
Beryllium intermetallics, particularly Be12Ti are an advanced
material under consideration as neutron multiplier for fusion demon-
stration blanket (Kawamura et al., 2002). Aluminium matrix-beryllium
composites can find special applications in avionics, space related
optical systems, structural components for satellites, propellants etc.
These composites combine the high modulus and low density of
beryllium with the favourable fracture toughness, ductility and
fabrication characteristics of aluminium.
Because of an ever increasing number of applications for beryllium
and its compounds in various domains of science and technology, it is
important to develop an efficient method for extracting beryllium
from its ore and it has been a thrust area of research and development
in beryllium technology till date.
In the present study, an attempt has been made to develop an
economically viable, efficient, and waste free process for extracting
beryllium from Indian beryl using ammonium hydrofluoride.
2. Background
In India, beryllium is extracted from beryl ore. There are fairly large
deposits of this ore available in India at locations in Andhra Pradesh,
Rajasthan and Bihar.
In its pure form, beryl ore is a beryllium-aluminium silicate
(3BeO·Al2O3·6SiO2). A typical composition of Indian Beryl is about
11–12% BeO, 19% Al2O3, 64% SiO2, 1–2% alkali metal oxides, and minor
amounts of other oxides (SAHA, 1994b).

0304-386X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.05.003
 D.D. Thorat et al. / Hydrometallurgy 109 (2011) 18–22 19

The extraction of beryllium from beryl ore is a cumbersome

process because beryl ore is very inert in the sense that no mineral
acids under the normal conditions of temperature and pressure attack
it (except HF). The extraction process is further complicated due to
the requirement of eliminating silica from the reaction products.
Although a large number of methods have been proposed, only two
are currently used commercially for extracting beryllium from the ore.
These are the sulphate and the fluoride process (SAHA, 1994b). In the
sulphate process, either molten beryl is water quenched or beryl is fused
with alkali in the presence of sodium or potassium carbonate and then
digested in sulphuric acid, followed by leaching with water. The aqueous
leach liquor contains sulphates of aluminium and beryllium with other
impurities. Silica remains as insoluble residue. After aluminium is
removed by precipitating as alum, this purified leach liquor is generally
subjected to solvent extraction to obtain a high purity beryllium bearing
solution.
The fluoride route, on the other hand, involves sintering of the beryl
ore with sodium silicofluoride or sodium ferric fluoride. The reagent Fig. 1. TG/DSC curves of the reaction between beryl and NH4HF2.
selectively converts the beryllium value of the ore into water soluble
sodium beryllium fluoride. This method has been adapted for beryllium pure nitrogen atmosphere in alumina crucible. Quantification of
extraction in the beryllium pilot plant of Bhabha Atomic Research aluminium, beryllium and silicon in reaction products was accom-
Centre. This process, however, involves a number of intermediate plished through JY-Horiba, France, ULTIMA 2C Inductively Coupled
hydrometallurgical operations and it is highly energy intensive. Plasma Atomic Emission Spectrometer (ICP-AES).
Furthermore it generates a large quantity of toxic solid waste.
Recently, it was found that ammonium fluoride (NH4F) and
hydrofluoride (NH4HF2) as alternate fluorinating agents can be used 4. Results and discussion
for extracting beryllium from the ore. At room temperature, ammonium
fluoride (NH4F) and hydrofluoride (NH4HF2) are safe, non-volatile and 4.1. TG/DSC and XRD analysis
environmentally benign crystalline substances. The melting point of
NH4HF2 is 126.8 °C (Rimkevich et al., 2009). Andreev et al., 2008 have Ammonium hydrofluoride attacks beryl ore and transforms it into
claimed a promising method of extracting beryllium from bertrandite a mixture of fluoride salts of Be Al, and Si which on further heating
and phenacite ores using NH4F and NH4HF2 as fluorinating agents. convert into BeF2 and AlF3 with removal of ammonia and water
Molten NH4F and NH4HF2 act as strong fluorinating agents with according to the reaction (1).
reactivity exceeding that of fluorine and HF. The fluorinating capacity
is exhibited in the temperature range 126–240 °C (Andreev et al., 2008). 3BeOAl2 O3 6SiO2 þ 30NH4 HF2 →3ðNH4 Þ2 BeF4 þ 2ðNH4 Þ3 AlF6 ð1Þ
Removal of silica is an important step in extraction of beryllium from þ6ðNH4 Þ2 SiF6 þ 6NH3 þ 18H2 O
beryl ore. The reagent NH4HF2 reacts with silica forming a complex
(NH4)2SiF6. At temperatures above 320 °C, this compound sublimes The differential scanning calorimetric (DSC) pattern of the reaction
(Andreev et al., 2008) and leaves behind solid residue. Reaction of
between beryl and NH4HF2 (Fig. 1) shows three endothermic peaks at
NH4HF2 with BeO and Al2O3 at elevated temperatures is found to yield 126 °C, 227 °C and 286 °C. The peak at 126 °C is due to melting of
double fluorides (NH4)2BeF4 and (NH4)3AlF6, respectively, as reported NH4HF2. In the molten state, NH4HF2 acts as a very strong fluorinating
in the literature (White and Burke, 1955). On further heating, agent and therefore fluorination of beryl ore takes place at high rate.
(NH4)2BeF4 and (NH4)3AlF6 decompose into BeF2 and AlF3, respectively, This is confirmed by the TG curve (Fig. 1), where it can be seen that
liberating ammonia and HF (White and Burke, 1955). These reactions weight loss commences after melting of NH4HF2. The fluorination of
are employed commercially for obtaining metal fluorides in high purity. beryl ore gives a mixture of (NH4)2BeF4, (NH4)3AlF6, and (NH4)2SiF6.
These promising physicochemical properties of NH4HF2 motivated us to These intermediates are formed at different temperatures and were
examine its potential for extracting beryllium directly from beryl ore. identified by XRD. The samples from reaction mixture of beryl and
NH4HF2 were treated at 200 °C, 300 °C, and 400 °C and named as S20,
3. Experimental S30 and S40 respectively. From the XRD pattern of these samples,
lattice parameters were determined and are summarised in Table 1.
Ground beryl ore (−200 mesh) size with the chemical composition, The measured lattice parameters clearly show the presence of
11–12% BeO, 19% Al2O3, 64% SiO2 and 1–2% alkali metal oxides was (NH4)3AlF6, NH4AlF4 and (NH4)2SiF6 in S20. It reveals that NH4HF2
thoroughly mixed with analytical grade NH4HF2 (SD fine-chem Ltd.,
India) in an alumina crucible. The quantity of NH4HF2 in the mixer was
kept slightly above the stoichiometric value. Sample weight was varied Table 1
Lattice parameters from XRD analysis of the samples S20, S30 and S40.
from 4 to 1000 g. All samples were heated in an induction furnace at
temperatures ranging from 150 to 400 °C. Heating was performed in Sample Compounds Lattice parameters Reference
three steps. During the first step, the samples were heated and kept at identified (JCPDS
Our study Calculated
file no.)
150 °C for an hour, followed by further heating to 200 °C and retaining
them at this temperature for another hour. After completion of this S20 (NH4)2SiF6 a = 8.37 ± 0.01 a = 8.382 72-1759
(NH4)3AlF6 a = 8.39 ± 0.01 a = 8.4 73-1510
heating sequence, the product was slowly heated and kept at 400 °C for
NH4AlF4 a = 5.079 ± 0.040 a = 5.078 c = 12.715 83-2416
an hour in order to liberate it from silica which volatalised as SiF4. c = 12.699 ± 0.040
The intermediate and final phases of the products were identified S30 NH4AlF4 a = 5.070 ± 0.027 a = 5.078 c = 12.715 83-2416
using a Philips PW-1830 X-ray diffraction spectrometer. Thermogravi- c = 12.705 ± 0.027
metric analysis of the sample (~18 mg) was performed using Setaram S40 AlF3 a = 6.92 ± 0.05 a = 6.93 c = 7.125 43-0435
c = 7.122 ± 0.055
Setsys, France, TG/DSC instrument at a heating rate of 10 °C/min in a
20 D.D. Thorat et al. / Hydrometallurgy 109 (2011) 18–22
Fig. 2. Water soluble beryllium recovered in the course of reaction of beryl ore with
NH4HF2 as a function of time.
has greater affinity towards Al2O3 and SiO2 components of beryl under
the present experimental conditions. Therefore, molten NH4HF2
initially attacks Al2O3 and SiO2 giving a mixture of (NH4)3AlF6,
(NH4)2SiF6 and finally reacts with BeO to give (NH4)2BeF4. On further
heating, (NH4)3AlF6, (NH4)2SiF6 and (NH4)2BeF4 start decomposing
into their respective fluorides releasing gaseous ammonia, and this
can be confirmed from the DSC peak at 227 °C, which is the deepest
(Fig. 1). This is probably due to simultaneous decomposition of
(NH4)2SiF6 along with (NH4)3AlF6. TG curve (Fig. 1) shows a total
weight loss of 81%, which is in agreement with proposed reaction (1).
The weight loss takes place in three steps. The first step shows 48% of
weight loss in the temperature range 100 °C–230 °C, second 7% in
230 °C–250 °C and third 26% in 250 °C–400 °C as shown in Fig. 1. Since
SiO2 content of beryl ore is the highest, major weight loss is due to the
removal of (NH4)2SiF6. A fraction of (NH4)2SiF6 decomposes into
ammonia and gaseous SiF4 in the temperature range 100 °C–230 °C
(48% wt loss region) and the remaining fraction is probably removed in
the 26% weight loss region (250 °C–400 °C). The DSC peak at 286 °C
corresponds to the final conversion of (NH4)3AlF6 into AlF3. XRD analysis
of S30 and S40 (Table 1) confirms the presence of NH4AlF4 and AlF3 in
the reaction mixture. This shows that (NH4)3AlF6 decomposes into AlF3
through the formation of NH4AlF4 as an intermediate. Similarly,
Fig. 3. Effect of temperature on concentration of silica in the product.
Fig. 4. Effect of pH on recovery of beryllium from Indian beryl.
(NH4)2BeF4 transforms into BeF2. These sequences of transformations
are in close agreement with the results obtained by Andreev et al.
(2008). Neither weight loss nor DSC peaks were observed between
350 °C and 1000 °C. The final reaction product was identified as a
mixture of BeF2 and AlF3.
4.2. ICP-AES analysis
4.2.1. Kinetic study of the process
Samples were prepared by mixing beryl ore and NH4HF2 in
appropriate ratio and variously heated at 190 °C from 10 min to
120 min, at intervals of 10 min. The reaction temperature (190 °C) was
fixed on the basis of TG/DSC studies (Fig. 1) showing maximum rate of
reaction at temperature around 200 °C. Molten NH4HF2 (m.p.126 °C)
reacts vigorously with the ore and the entire reaction mixture starts
boiling at this temperature (190 °C). The temperature remains constant
until the reaction has completed. After heat treatment samples were
quenched in cold water and concentration of beryllium in each sample
was determined by ICP-AES. The recovery (%) of water soluble beryllium
was plotted with respect to time and is shown in Fig. 2. It can be seen that
more than 90% of beryllium value of the ore is recovered as water soluble
beryllium within 1 hour. Andreev et al. (2008) also found similar results
in his study on phenacite ore.
4.2.2. Temperature optimization for complete removal of silica from the ore
The samples were collected from the reaction mixture of beryl and
NH4HF2 at 100 °C, 200 °C, 300 °C, 400 °C and 800 °C. Concentrations of
Be, Al and Si were determined by the ICP-AES technique, and the data
obtained were plotted as a function of temperature (Fig. 3). It can be
seen that concentration of silica decreases significantly with increase
in temperature. This is due to thermal decomposition of (NH4)2SiF6
giving off gaseous SiF4, which is confirmed by TG/DSC (Fig. 1) and XRD
analysis (Table 1). Fig. 3 shows that product becomes completely free
from silica at temperature around 400 °C while the concentrations of
Be and Al are almost unaffected up to this temperature.
Table 2
Recovery of beryllium for various batch sizes from beryl ore processed by NH4HF2.
Quantity of beryl (g) Quantity of NH4HF2(g) Be recovery (%)
4.0 20.0 91.0
5.0 25.0 86.0
50.0 250.0 92.8
100.0 500.0 90.7
1000 5000 80
 D.D. Thorat et al. / Hydrometallurgy 109 (2011) 18–22
Fig. 5. XRD of high purity beryllium oxide.
4.2.3. Separation of BeF2 and AlF3 from the mixture
Based on significant difference in solubility of BeF2 and AlF3 in
water at room temperature (25 °C), the product mixture was
subjected to water leaching. Beryllium fluoride is highly soluble in
water while aluminium fluoride the least, therefore BeF2 dissolves in
aqueous solution, leaving AlF3 as residue. After filtration, the
beryllium content was precipitated as Be(OH)2 with 25% NaOH
solution. Effect of pH on recovery of beryllium from the solution was
studied by ICP-AES, and the results are shown in Fig. 4. At pH around 6
iron and aluminium impurities precipitate as hydroxides, while most
of the beryllium remains in the solution (Fig. 4). Beryllium pre-
cipitates as hydroxide at pH N 11 (Fig. 4). Therefore, the BeF2 solution
was initially adjusted to pH 5.3 using 25% NaOH solution. At this pH
Fig. 6. Novel route for extracting beryllium from Indian beryl using ammonium hydrofluoride.
21
most of Fe and Al impurities precipitate as hydroxides. These
impurities were filtered off and pH of the solution was increased to
11.5 in order to precipitate Be(OH)2. Crude beryllium hydroxide was
further purified by dissolving it in excess of NaOH solution, forming
sodium beryllate and leaving the impurities. Sodium beryllate, upon
hydrolysis under boiling condition, produces pure beryllium hydrox-
ide. Different batches of beryl ore, ranging from 4 g to 1000 g, were
processed and the recovery of beryllium for different batch sizes was
measured using ICP-AES. The results obtained are given in Table 2. The
average recovery of beryllium value was found to be more than 90%.
The lower recovery with larger batch size is due to lack of provision
for proper mixing of beryl ore and NH4HF2, and precise temperature
control in our existing experimental set-up.
4.2.4. Preparation and characterisation of BeO
BeO was prepared by calcining pure Be(OH)2 at 850 °C for 2 hours
in a resistance-heated furnace. The product was characterised by XRD
(Fig. 5). All the peaks of BeO are seen and matching with standard. The
product BeO was analysed by ICP-AES and found to have following
impurities (%): total Be assay (99.34); Li (0.01); Na (0.3); K (0.01); Al
(0.03); Ca (0.05); Fe (0.01); Zn (0.01); B, Cd, Cr, Cu, Mn and Ni
(b0.01).
5. Recycling options for ammonium hydrofluoride
It is possible to regenerate ammonium fluoride from the
volatilized SiF4 as well as AlF3 residue. Ammonia hydrolysis of
volatilized SiF4 gives ammonium fluoride and SiO2 as a commercial
by-product (reaction 2). AlF3 mixed with SiO2 when treated with
H2SO4 gives SiF4 that in turn can be used to regenerate ammonium
fluoride (reaction 3).
SiF4 þ 4NH3 þ 2H2 O→SiO2 þ 4NH4 F ð2Þ
4AlF3 þ 3SiO2 þ 6H2 SO4 →2Al2 ðSO4 Þ3 þ 3SiF4 þ 6H2 O ð3Þ
22 D.D. Thorat et al. / Hydrometallurgy 109 (2011) 18–22

Table 3
Comparison between existing fluoride process and the proposed process for extraction of beryllium.

Figures of merit Fluoride process Proposed process

Process steps involved Involves 6-steps: mixing, briquetting, sintering, crushing, ball milling Only 3-steps: mixing, heating and water leaching are involved.
and three-stage leaching.
Process 750 °C (sintering) 200–400 °C
temperature
Process time All steps are time consuming: mixing (6 hours), briquetting (5 hours), Overall process time is significantly reduced due to the
sintering (8 hours), crushing (5 hours), ball milling (2 hours) and complete elimination of briquetting, crushing and ball
leaching (6 hours) for 60 kg batch size milling operations.
Total process time is 7 hours.
Energy All steps are energy intensive. Elimination of three energy intensive steps viz. briquetting,
consumption crushing and ball milling makes the process economical.
Fluoride Fluoride is only partially recovered in the form of iron cryolite (Na3FeF6) by NH4HF2 can be fully recovered and recycled. SiO2 is produced as
recovery treating NaF (liquid effluent) with ferric chloride. commercial by-product.
Waste generation Generates 1.5 kg of solid waste for processing of 1 kg of beryl ore Generates only 0.37 kg of solid waste for processing of 1 kg
beryl ore
Beryllium Generates airborne beryllium contamination which is a potential hazard of Beryllium airborne contamination and personnel exposure can be
toxicity inhalation by personnel during exposure during mixing and crushing operations. effectively controlled due to close and wet operations.
Plant features Process requires large floor space, big size process equipments which are Feasible to instal a compact, integrated and fully automated plant.
unsuitable for scaling up and automation.
Yield 70% up to beryllium hydroxide 88% up to beryllium hydroxide

6. Novel extraction technique for beryllium from Indian beryl using
ammonium hydrofluoride
After the feasibility of decomposition of beryl ore by reaction with
NH4HF2 was established, a flow sheet of the process for producing water
soluble beryllium fluoride from Indian beryl is presented (Fig. 6).This
process involves only three stages of operations: mixing, heat treatment
(150 °C–400 °C) and room temperature (RT) water leaching for
converting beryllium value of the beryl ore into water soluble beryllium
fluoride with recovery of more than 90%. By contrast, conventional
beryllium extraction processes involve cumbersome multiple opera-
tions with relatively lower recovery. After producing beryllium fluoride
as a water soluble compound, the subsequent methods of preparation of
either BeO by calcination of Be(OH)2 or Be metal by magnesiothermic
reduction of beryllium fluoride are well established. A technical
comparison between the Fluoride Process (existing process) and the
proposed process is also presented (Table 3). This comparison with
respect to energy, recovery, and safety aspects clearly indicates that the
proposed process is relatively more advantageous than the conventional
process.
7. Conclusions
Ammonium hydrofluoride is found to be a potential fluorinating
agent for the processing of beryl ore. A complete technological scheme
for preparing high purity beryllium oxide from beryl ore using
ammonium hydrofluoride has been proposed. The major advantages
of this process over the conventional fluoride process of beryllium
extraction are the following: (i) elimination of most of the tedious
hydrometallurgical operations, (ii) virtually waste free mode, and
(iii) safe and relatively less energy intensive. It is possible to use
standard chemical equipments for setting up a commercial plant.
Additionally, another important economical advantage is the possi-
bility of regenerating major part of hydrofluoride from SiF4. Based on
the aforementioned distinctive features, this new route appears to be
promising for extraction of beryllium with minimal toxicity, solid and
liquid waste generation.
Acknowledgements
The authors are grateful to Dr. A. K. Suri , Director, Materials Group,
Bhabha Atomic Research Centre for giving motivation and encour-
agement during the work. The authors are also thankful to S.
Narsimhan and S. J. Ghanwat, Powder Metallurgy Division, Bhabha
Atomic Research Centre for providing technical support.
References
Andreev, A., D'yachenko, A.N., Kraidenko, R.I., 2008. Fluorination of beryllium
concentrates with ammonium fluorides. Russian Journal of Applied Chemistry 81 (2),
178–182.
Argentina, F.S., Longhurst, G.R., Shestakov, V., Kawamura, H., 2000. Beryllium R&D for
fusion applications. Fusion Engineering and Design 51–52, 23–41.
Kawamura, H., Takahashi, H., Yoshida, N., Shestakov, V., Ito, Y., Uchida, M., Yamada, H.,
Nakamichi, M., Ishitsuka, E., 2002. Application of beryllium intermetallic com-
pounds to neutron multiplier of fusion blanket. Fusion Engineering and Design 61–62,
391–397.
Rimkevich, V.S., Pushkin, A.A., Malovitskii, Yu.N., Dem'yanova, L.P., Girenko, I.V., 2009.
Fluoride processing of non-bauxite ores. Russian Journal of Applied Chemistry 82 (1),
6–11.
Saha, S., 1994a. Preparation of high purity beryllia and synthesis of alexandrite. Mineral
Processing and Extractive Metallurgy Review 13, 69–75.
Saha, S., 1994b. Hydrometallurgy of beryllium in the Indian perspective. Mineral
Processing and Extractive Metallurgy Review 13, 43–52.
White, D.W., Burke, J.E. (Eds.), 1955. The Metal Beryllium. American Chemical Society
for Metals Cleveland, Ohio.
Zaki, E.E., Ismail, Z.H., Daoud, J.A., Aly, H.F., 2005. Extraction equilibrium of beryllium
and aluminium and recovery of beryllium from Egyptian beryl solution using
CYANEX 921. Hydrometallurgy 80, 221–231.