Journal of Applied Science and Technology (JAST), Vol. 17, Nos. 1 & 2, 2012, pp.

58 - 62

BENEFICIATION OF TRONA (HYDRATED SODIUM CARBONATE) DEPOSITS IN

NIGERIA FOR GLASS MAKING

I.I. Akomolafe, T. Yakubu †, O.O. Ige ‡ and L.E. Umoru ‡

Department of Glass and Ceramic Technology, The Federal Polytechnic, Ado-Ekiti, Nigeria
† Triplex Safety Glass, Ibadan, Nigeria
‡ Department of Materials Science & Engineering, Obafemi Awolowo University, Ile-Ife, Nigeria

ABSTRACT
Production of sodium carbonate from natural trona deposits in Yobe State (Nigeria) for utilization in the glass
industry was investigated. The ore existed in cakes, flakes and ash forms, and nine samples were beneficiated
and test melted. The samples were analyzed and processed using monohydrate and sesquicarbonate methods.
The sesquicarbonate method was more efficient than monohydrate technique. The average yield of sodium car-
bonate was 69.5 %, 40.0 % and 33.0 % for the cake, ash and flakes, respectively; while the mean combined alk-
ali (Na2O + K2O) content was 41.2 %. The beneficiated samples were melted for soda-lime silicate and lead sil-
icate glass batch compositions, which in terms of fluxing efficiency and glass colour, compared favourably with
the glass test melt using industrial soda ash. The trona samples could be utilized in glass making both in benefi-
ciated and natural forms.

1. INTRODUCTION 2. TRONA CHEMISTRY

The glass industry depends on sodium
carbonate or commercial soda ash, as a key in-
gredient in production. Sodium carbonate can
be obtained by refining from natural sources
(lake waters and soda deposits) or manufactur-
ed by chemical process using solvay method
[1]. The trend is towards production from nat-
ural sources because of the comparative produ-
ction cost advantages over artificial soda ash
production, with respect to raw materials, ene-
rgy cost and environmental considerations.
Sodium carbonate minerals used in commerci-
ial production of soda are natrone (Na2CO310
H2O), thermonatrite (Na2CO3H2O) and trona
(Na2CO3NaHCO32H2O(S)) [2]. In the study re-
ported in this paper, natural trona deposits fr-
om Yobe State (Nigeria) were investigated to
determine the suitability for glass making, as
the ores are abundant and underutilized.
Sodium carbonates used in local glass
production are imported, despite the abundant
natural deposits in the North Eastern Nigeria.
The ores are known as “kanwa” or “kaun” and
are mined on small scale for medicinal purpo-
ses and food processing [3]. The deposits exist
close to the ground surface in the form of cak-
es, flakes and ashes, and are usually grey, bla-
ck or light brown in colour. No systematic ev-
aluation has been made to estimate the reserve,
but for commercial utilization, the ores must
be beneficiated and chemically purified to me-
et industrial standards and requirements [4].
Trona occurs as natural ores worldwi-
de, especially, in United States (Wyoming or
Green River), Turkey (Beypazari), Kenya (La-
ke Magadi) and Egpyt (Nile Valley). Natural
trona (sodium sesquicarbonate) is a hydrated
double salt of sodium carbonate and bicarbon-
ate (Na2CO3NaHCO32H2O(S)) The ore is non-
metallic mineral, which if pure contains 70.39
% sodium carbonate (Na2CO3), and the excess
carbon dioxide (CO2) and water (H2O) can be
driven off by calcinations to yield natural Na2
CO3 [5 - 8]. The sodium in Na2CO3 exhibits
fluxing properties essential for the glass and
silicate industries by reducing viscosity of the
melts [9]. The viscosity of glassy material is
directly related to the melting temperature and
the lowering of temperature ultimately leads to
significant energy saving and reduction in cost
of operation.
Natural sodium carbonate can be proc-
essed by sesquicarbonate, monohydrate, alkali
extraction and carbonation methods; but the fi-
rst two are the dominant processes used to co-
nvert mined trona to Na2CO3 and were adopted
for the research.
In the sesquicarbonate process, the tro-
na ore is dissolved in aqueous solution, and af-
ter separating the solution from the insoluble,
sodium sesquicarbonate is crystallized from
the solution by cooling. The sesquicarbonate
crystals are then separated from the mother li-
quor and calcined to recover the anhydrous
Na2CO3 [9].

58
Akomolafe et. al., Journal of Applied Science and Technology, Vol. 17, Nos. 1 & 2, 2012, pp. 58 - 62
In the monohydrate process, natural
sodium sesquicarbonate is crushed, ground
and calcined, and the product is dissolved in
water, treated with activated carbon to remove
soluble organic compounds, filtered and cryst-
allized by evaporation to obtain crystals of Na2
CO3 monohydrate. The monohydrate crystals
are then separated from the mother liquor and
dried to recover the Na2CO3 [10].
The conversion of trona to anhydrous
Na2CO3 follows the steps of breaking up the
crystal lattice and discharge of the crystal wat-
er; conversion of bicarbonate to carbonate and
discharge of carbon-dioxide; and formation of
Na2CO3 crystals by nucleation and growth.
The decomposition occurs as [11],
2(Na2CO3NaHCO32H2O)=3Na2CO3+5H20+CO2 (1)
and commences at temperatures > 70 oC, but
the rate does not become significant until the
temperature exceeds 120 oC. At lower temper-
atures, wegscheiderite (Na2CO33NaHCO3) and
sodium carbohydrate monohydrate (Na2CO3
2H2O) form as intermediates [11-12];
3(Na2CO3.NaHCO3.2H2O) = (Na2CO33NaH CO3)(s)
+ 2Na2CO3 + 6H2O (2)
2(Na2CO33NaHCO3)(s) = 5Na2CO3+3H20+3CO2 (3)
3. EXPERIMENTAL WORK
3.1. Sampling
The trona samples were collected from
Gashua, Nguru and Geidam towns in Yobe St-
ate, where the trona cakes, flakes and ashes
were obtained from each town, making a total
of 9 samples. The ores were ground by mortar
and pestle, and milled to sizes of 25 mm.
3.2. Beneficiation
For monohydrate processing, the grou-
nd samples were calcined in a platinum crucib-
le at 150 oC for 45 mins, for the ores to dissoc-
iate and CO2 and H2O to be driven off by the
reaction eqn. (1) [11]. The calcined products
were combined with water to dissolve the Na2
CO3 and for the insoluble materials to be disc-
arded. The resultant clear liquid was then eva-
porated and the dissolved Na2CO3 precipitat-
ed out as Na2CO32H2O, by the reaction,
Na2CO3 + 2H20 = Na2CO32H2O (4)
The precipitated products were calcined for se-
cond time to remove the water of crystallizati
on by the reaction,
Na2CO32H2O = Na2CO3 + 2H2O (5)
In the sesquicarbonate process, each
59
sample was dissolved in water to form a conc-
entrated solution, and filtered using Whatman
41 filter paper. The filtrate was evaporated, co-
oled to obtain white fine sesquicarbonate crys-
tals, dried and calcined at 150 oC for 45 mins
to form dense soda ash by the reaction eqn.(1).
3.3. Chemical Analysis
The beneficiated trona samples were
analysed to determine Na2O and K2O content
using Corning EEL 450 flame photometer eq-
uipped with Na and K filters. Standard soluti-
ons were prepared by diluting Na2CO3 solutio-
ns into 100 mL volumetric flasks. The instru-
ment was warmed between 5 - 10 mins, the st-
andard solutions were aspirated, and the equip-
ment calibrated (with concentration as abscissa
and instrument readouts as ordinate values).
Concentrations of K+ and Na+ in the test soluti-
on were obtained from the calibration curve.
The Mg2+ and Ca2+ concentrations we-
re determined by Stepwise Complexometric
method [13]. The analytical reagents included
mixed indicator I (0.08 g of Naphthol Green
mixed with 0.05 g of o-cresolphthalein compl-
exone and 20 g of ammonium chloride); Calc-
ein indicator (0.2 g Calcein mixed with 20 g
KCl); thymolphthalein (0.1 % in 30 % TEA
solution) and mixed with indicator II (0.03 g
of Eriochrome Black T mixed with 0.04 g Tit-
an Yellow and 0.01 g Naphthol Green dissolv-
ed in 25 mL of TEA).
Twenty five milliliters (25 mL) of be-
neficiated trona solution were diluted with ~
100 mL of water, and 20 mL of 30 % TEA
was added, and thoroughly mixed. A mixture
of 30 mL of buffer (pH 10) and 30 mL of 19
% of KCN solution was slowly added via swi-
rling. The solution was diluted to 200 mL, air
was bubbled through for 10 mins and titrated
with EDTA using 0.2 g of mixed indicator I
for Ca and Mg. The end-point was indicated
by a sharp change of colour from pink to gre-
en. The Ca2+ was determined by diluting 25
mL of the beneficiated trona with about 150
mL of water, and 2 mL of thymolphthalein
added drop wise until the solution turned blue
or green. Then 5 mL of 10 % KCN solution
and 15 mL of 5M KOH were added, followed
by titration with EDTA in the presence of 0.2
g calcein indicator, and the end point was sho-
wn by a colour change to red with disappeara-
nce of the green fluorescence.
Akomolafe et. al., Journal of Applied Science and Technology, Vol. 17, Nos. 1 & 2, 2012, pp. 58 - 62

3.4. Suitability of Trona as Flux hest value, for all the deposits from Nguru,
The suitability of trona as a flux in gl- Geidam and Gashua. The cakes gave higher
ass and glaze was determined by test melting soda ash yield of between 69 and 70 % in each
soda lime silica and lead silicate compositions. of the three deposits compared to 39 - 41 %
The same compositions were prepared using for ashes and 32 - 34 % for the flakes.
the 3 soda ash sources for both soda lime glass
and lead silicate in crucibles. The soda lime Table 1. Percentage yield of Soda Ash
Sample Monohydrate Sesqui-carbonate
glass in different crucibles was melted in the Process (g) Process (g)
day tank furnace for 16 h, while the lead silica- Nguru
te was subjected to the same treatment for 13 Trona flake 33.01 34.00
Trona cake 69.80 70.21
h. The batch was melted in a gas fired glass Trona ash 40.80 40.18
melting day tank furnace at 1250 oC in an oxi- Geidam
dizing atmosphere to obtain the glass composi- Trona flake 32.84 32.14
Trona cake 69.93 70.00
tions and thereby evaluate the suitability. Trona ash 39.90 40.23
Industrial soda ash was also used to Gashua
Trona flake 33.90 33.98
prepare glass batch of same composition in or- Trona cake 70.12 69.99
der to compare the fluxing ability of the trona Trona ash 41.01 39.67
from Nigeria. Average 47.82 47.82

4. RESULTS The chemical composition of the puri-

4.1. Yield and Composition
Table 1 shows the percentage yield of
trona, and indicates the effect of process meth-
od and the natural form of the ore. The flakes
gave lowest yield, while the cakes yielded hig-
fied trona is presented in Table 2. The amount
of Na2O ranged between 34 and 36 %, K2O
was about 6 %, CO2 was about 38 %, and wat-
er content of about 18 %.

Table 2. Chemical analysis of purified Trona

Sample Na2O K2O MgO CaO H2O CO2 SO3 Others
Nguru
Trona flake 35.01 6.19 0.09 0.02 18.00 38.00 0.06 0.19
Trona cake 36.00 5.19 0.06 0.05 18.21 37.91 0.69 0.17
Trona ash 35.23 5.99 0.08 0.02 19.00 37.77 0.68 0.86
Geidam
Trona flake 34.91 6.30 0.02 0.04 18.70 38.11 0.71 0.32
Trona cake 34.99 6.22 0.06 0.05 20.10 37.22 0.70 0.51
Trona ash 35.00 6.22 0.02 0.01 20.00 36.91 0.69 0.80
Gashua
Trona flake 36.00 5.22 0.05 0.09 19.20 38.00 0.69 0.19
Trona cake 35.11 6.11 0.09 0.06 20.00 37.90 0.69 0.39
Trona ash 35.12 6.10 0.07 0.02 18.02 39.91 0.70 0.18
Average 35.26 5.95 0.06 0.04 19.02 37.66 0.68 0.47

4.2. Batch Constituents within 7 h using the day tank furnace fired to
The batch composition used for the 1250 oC, thereby confirming the fluxing effici-
soda-lime glass and lead glass is presented in ency of the trona compared with industrial so-
Table 3. The efficiency of Na2O and K2O in da ash. The glass melted with the crude ore
the raw trona and beneficiated trona as flux in cakes and flakes gave deep green colour, while
the glass batch was compared to that of ind-
ustrial soda ash. Table 3. Glass Composition
The glass batch prepared with the pro- Oxides Soda Lime Lead Glass
Glass (%) (%)
cessed trona gave a clear bubble free glass wi- Silicon Dioxide (%) 60.00 50.00
th slight green tint similar to the same batch Sodium Oxide (%) 21.50 7.74
melted with industrial soda ash. The green tint Potassium Oxide (%) 3.50 1.26
could be attributed to the ferrous ions (Fe+2) Calcium Oxide (%) 10.00 6.00
content in the glass sand. Both batches melted Magnesium Oxide (%) 5.00 -
Lead Oxide (%) - 35.00

60
Akomolafe et. al., Journal of Applied Science and Technology, Vol. 17, Nos. 1 & 2, 2012, pp. 58 - 62
the batch containing crude ore ashes gave am-
ber brown colour. The non-beneficiated trona
impacted colours ranging from green to amber
on the glass and hence could be used only for
production of coloured glass and fluxing of
ceramic glazes.
5. DISCUSSION
The Na2CO3 yields using sesquicarbo-
nate process were higher than obtained by mo-
nohydrate process, which involved double cal-
cinations. The calcination temperature for raw
trona was 150 oC, and as calcination processes
are highly endothermic, kinetics of the reactio-
ns occur at high temperatures [12]. The sesqu-
icarbonate process involved leaching, and the
calcination was facilitated, unlike the monohy-
drate process where gaseous fumes were evol-
ved requiring additional costs in controlling
the fumes.
The beneficiation processes produced
high quality soda ash as indicated by the white
colour when compared to the grey, black and
light brown colours of the ores. The trona dep-
osits contained 20 - 26 % pure ash [14], and
the high soda ash yield makes commercial ex-
ploitation of the trona deposits viable.
Chemical analysis of industrial trona
from USA and Egypt were obtained from Mc
Leods [14], and the tronas were equally test
melted using the same techniques for tronas
sourced from Yobe (Nigeria).
The beneficiated samples gave combi-
ned alkali (Na2O + K2O) average content of
41.24 % which is of comparable grade to trona
found in the USA (41.00 %) and Egypt (41.22
%) as shown in Table 4. The presence of K2O
in the trona from Nigeria is an advantage over
trona from other sources, because K enhances
the quality and purity of colour in crystal glass
batch.
The test melting showed the trona cou-
ld be used effectively as a fluxing agent in gla-
ss, either in beneficiated or crude form, and the
processed trona gave a fluxing efficiency and
glass quality comparable with that of industrial
soda ash [14].
In glass technology, the time taken for
a batch to be free from defects, such as unmel-
ted raw materials, seed and blisters are used to
assess the materials utilization, or otherwise
[14]. The different batch compositions attain-
ed the goal at the set time, with the exception
61
Table 4. Chemical analyses of tronas from Nigeria, USA
and Egypt [14]
Composition Yobe Trona USA Trona* Egypt Trona*
Na2O 35.26 41.00 41.22
K2O 5.95 - -
CO2 37.66 38.13 37.98
H2O 19.02 20.07 19.13
SO3 0.08 0.70 0.70
CaO, MgO 0.10 0.02 0.08
& NaHCO3
Others 0.47 0.19 0.86
of variation in colour of the batch containing
the raw trona which was brown.
With the soda and potash contents kn-
own, the beneficiated trona could be used to
substitute soda ash in soda lime and lead sili-
cate glass composition without any limitations
in terms of batch free time and optical quality,
while the raw trona might be only suitable for
brown coloured glass. The presence of K2O in
Nigerian trona, but absent in trona from other
sources [14] is a production advantage, while
the 38 % CO2 and 20 % H2O content were ne-
arly the same for trona from the other sources.
6. CONCLUSIONS
The suitability of the local trona as a
source of Na2CO3 for the glass industry, and
the most appropriate method for processing
natural trona were determined. The sesquicar-
bonate method for beneficiation of the trona
should be adopted, instead of monohydrate
method, because of process simplicity and ea-
sy operation. The trona could be used either in
crude state or processed as a fluxing agent in
glass batch or ceramic glaze with varied colour
effects depending on the purity.
7. REFERENCES
1. Thieme C., Sodium Carbonates, Ullmann’s
Encyclopedia of Industrial Chemistry, Vol. A2,
1993, pp. 299 – 316.
2. Dermibas A., Production of Sodium Carbonate
from Soda Ash via Flash Calcination in a drop
tube Furnace, Chemical Engng & Processing,
Vol. 41, 2002, pp. 215 – 221.
3. Multi-Disciplinary Task Force Report, RMR
DC, Non Metallic Minerals for Nigerian Indus-
tries, http:// www.rmrdc.gov.ng/MTF 96/NON-
METALLIC.PDF, 2008.
4. Multi-Disciplinary Committee Report, RMR
DC, A Techno-Economic Survey on Metallic
Minerals Sector, 4th Update, www.rmrdc.
gov.ng/MDC 2003/NON-METALLIC %20
Akomolafe et. al., Journal of Applied Science and Technology, Vol. 17, Nos. 1 & 2, 2012, pp. 58 - 62

MINERALS.PDF,2008).
5. Gartner R.S. and Gert-Jan W., Mixed Solvent
Reactive Recrystallization of Trona (Sodium
Carbonate Anhydrate), Hydrometallurgy, Vol.
88, 2007, pp. 75 – 91.
6. Nasun-Saygili G. and Okutan H., Application of
the Solution Mining Process to the Turkish
Trona Deposit, Hydrometallurgy, Vol. 42,
1996a, pp. 103-113.
7. Nasun-Saygili G. and Okutan H., Mechanism of
the Dissolution of Turkish Trona, Hydrometal-
lurgy, Vol 43, 1996b, pp. 317 – 329.
8. Nasun-Saygili G., Effect of Temperature on
Dissolution of Turkish Trona, Hydrometallurgy
Vol. 68, Nos. 1-3, 2003, pp. 43 – 49.
9. Sibel O., Evaluation of Soda Ash Production
Parameters from Beypazari Trona Ore, PhD
Thesis, 2003, School of Natural and Applied
Sciences, Middle East Technical University,
Ankara, Turkey.
10. Colak S., Ekmekyapar A., Ersahan H., Kunkal
A. and Modoglu O. Flash Calcination of Trona
Ore in a Free-fall Reactor and Production of
Soda from Trona, Energy Educ. Sci. Technol.,
Vol. 4, 2000, pp. 48 – 59.
11. Ball M.C., Strachan A.N. and Strachan R.M.,
Thermal Decomposition of Solid Wegscheider-
ite, Na2CO3.3Na2CO3, J. Chem. Soc. Faraday
Trans., Vol. 87, No 12, 1991, pp. 1911 – 1914.
12. Dogan M., Gulder C., Dogu G. and Dogu T.,
Soda Ash Production from Trona in Spray Dry-
er, J. Chem. Tech. Biotechol., Vol. 68, 1997, pp.
157 – 162.
13. Sinha B.C. and Dasgupta S., Masking of Man-
ganese in Relation to Stepwise Complexometric
Determination of Calcium, Magnesium and
Manganes, Talanta, Vol. 25, 1978, pp. 693-695.
14. Mcleod J.E., Trona Mine - Soda Ash Prod-
uction, in A.G. Pincus and D.H. Davies, Raw
Materials in the Glass Industry, Ashley Publish-
ing Co. Inc., N.Y. 1983.

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