Sustainable Materials and Technologies

Volume 23, April 2020, e00129

A sustainable process for recovery of potash fertilizer

from glauconite through simultaneous production of
pigment grade red oxide
Saurabh Shekhar a b, S. Sinha b, D. Mishra b, A. Agrawal b, K.K. Sahu b

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Abstract

A sustainable process is proposed and developed for the recovery of potash fertilizer from glauconitic clay
with simultaneous production of pigment grade iron oxide. Potassium is a part of stable structure
(dioctahedral T-O-T) in glauconite and locked in alumino-silicate matrix. In order to break this matrix and
maximize potassium dissolution, the glauconite sample containing 5.6% K2O and 31.9% Fe2O3 was subjected
to reduction with coke followed by oxidation cooling (redox roasting). The process simultaneously releases
potash and convert iron in the matrix to ferric state. The redox roasted sample was leached in hydrochloric
acid and the leach liquor containing 6.1 g/L of potassium and 30.2 g/L of iron was subjected to solvent
extraction using mixed solvent system (20% Aliquat 336 and 15% TBP) to separate iron prior to recovery of
potash. Based on McCabe–Thiele plot, two stage counter current extraction at O:A ratio of 1:0.75 and three
stage stripping at O:A ratio of 0.4:1 are sufficient to remove >99% of iron from the leach solution. The strip
solution was hydrothermally treated to produce red iron oxide suitable for pigment application and iron
free raffinate was treated to produce fertilizer grade potassium chloride.

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Introduction

Potassium (K) is the seventh most abundant element on the earth crust and one of the most essential
macronutrients for crops, human and animal with no known substitute. Specifically, >95% of potassium
produced today is used for the production of potash (K2O equivalent for different type of K-salts) fertilizers,
which is directly applied to the farms in the form of K- salt or with combination of nitrogen and phosphorus
(NPK) [[1], [2], [3]]. Global potash fertilizer capacity has been raise to ~59 million tons in 2017 from 1
million tons in 1921 due to the rapid growth of world population, which is expected to be 9.8 billion in 2050
from 7.6 billion in 2017 [4] and greater purchasing power of peoples in developing countries leads to
anticipated growth for crop production. This increase in demand has to come from limited amount of arable
land present due to rapid urbanization. Therefore, potash is required in huge quantity to increase both the
quality and quantity of crops. It allows more crops to be produced per hectare from the agricultural field
which guarantee present as well as future food security [5,6]. Currently the major resource of potash
production is marine evaporative deposits and potash rich brine. These deposits are mainly located in
Canada, Russia, Belarus, Chile, USA and Germany [7,8] on which other countries have to rely for the import
of potash fertilizer. Continents like Asia (China and India) and Africa are currently facing K deficits in their
soils, as the difference between demand and supply is negative [9,10]. To meet the required demand,
governments are paying huge amount of money for the import of potash along with the subsidy paid to the
farmers. India and many other countries are currently importing total requirement of their potash demand
by spending huge foreign currencies per annum which will be much more in near future if no indigenous
production comes up. Therefore, to reduce the import of potash and to ensure self-sufficiency, there is an
urgent need for exploitation of alternative resources of potassium (mainly potassium rich silicate minerals).
This will not only help to allow stronger negotiation with the potash exporting countries but also will lead
to utilization of several complex natural resources available globally. Glauconitic clay is considered as one of
the alternative resource for the production of potassium and its occurrences throughout the world make it
potential future resource [[11], [12], [13], [14]].

Glauconite is a naturally occurring group of dioctahedral, potassium, iron-rich micaceous clay mineral of
marine origin with very low weathering resistant and friability. The structure of glauconite consists of
dioctahedral T-O-T (Tetrahedral-Octahedral-Tetrahedral) sheets. The octahedral sites were usually
containing more Fe3+ than Al3+ and significant amounts of Mg2+ and Fe2+. Iron is mainly present in Fe3+ form
in glauconite structure [15,16]. Extensive work has been carried out towards occurrence, formation, physico-
chemical characterization of glauconite. However very scanty literature is available on its processing for the
recovery of potash and other valuables products [[17], [18], [19], [20], [21], [22], [23], [24], [25], [26]]. The
reported processes mainly include thermal treatment, microwave roasting, alkali fusion and acid leaching
[[27], [28], [29], [30], [31], [32], [33], [34]]. Almost all the processes developed earlier, targeted recovery of
low value potash and did not focus on simultaneous recovery of high value by-products.

Therefore, the major focus in our recent work is the simultaneous recovery of valuable by-products along
with recovery of potash fertilizer from glauconite [35,36]. The present authors have studied and reported a
process of reduction roasting followed by hydrochloric acid leaching for the recovery of potash and
magnetite from a low iron containing glauconite [36]. This process may not be suitable for high iron
containing glauconite due to high alkali consumption and formation of very thick iron hydroxide slurry
during precipitation of iron. In order to avoid these complications, the authors have proposed a clean and
sustainable method to take care of concentrated iron in leach solution containing potash. Iron rich
glauconite was first subjected to a novel redox treatment process followed by mild hydrochloric acid
leaching in order to maximize potassium dissolution as well as to obtain iron directly in ferric state, which
can easily be separated quantitatively by solvent extraction [37,38] and subsequently converted to high
grade red oxide after hydrothermal treatment. A mixed solvent system containing Aliquat 336 (aquaternary
ammonium salt) and TBP (Tri-n-butyl phosphate) was used for selective extraction of iron from acidic iron
rich potash solution. The raffinate solution and the strip solution were further treated to produce potash
fertilizer and pigment grade red iron oxide. Various process parameters for pretreatment, acid dissolution
and separation of dissolved iron by SX were optimized and discussed.

Section snippets

Materials

High iron containing glauconitic clay sample used in this study was collected from Umarsar area of Gujarat,
India. Chemical compositions of the sample analyzed by both wet chemical as well as instrumental methods
are listed in Table 1.

The glauconitic clay contains 5.6% K2O, 31.8% Fe2O3 and 44.7% SiO2 as its major constituents. The coke
containing 77% of fixed carbon was used as reductant for reduction roasting of glauconitic clay. The
hydrochloric acid used for leaching was obtained from Merck, …

Chemical and physical characterization

The run-of-mine (ROM) glauconite sample was crushed and screened to below 210 μm size for experimental
study. The size wise distribution of potassium and total iron (TFe) values is given in the Table 2. More than
75% particles lie between −210 + 105 μm sizes. The amount of glauconite phase present in studied sample in
this size fraction is 50.82 mass %.

The percentage of iron and potassium both increases with reduction in particle size due to better liberation
in finer size fraction. The…

Product recovery

Final products such as potassium chloride and red oxide pigment were produced subsequent to
optimization study of various unit operations. Under optimized conditions, 500 g of glauconite was
pretreated and leached in 3 M hydrochloric acid. The leach solution was subjected to two stage extraction
(O/A - 1:0.75) and three stage stripping (O/A - 0.4:1) of iron to generate sufficient raffinate and strip
solution for recovery of both the products. Potassium chloride was recovered from the raffinate…
Conclusion

The present work was performed to study and explore a novel idea for the development of sustainable
process to recovery potassium and pigment grade red oxide as value added products from high iron
containing glauconitic clay of composition 5.6% K2O and 31.9% Fe2O3. Direct acid leaching of raw sample
with 4 M HCl at 80 °C for 3 h of leaching shows only 24.5% of potassium dissolution. This is mainly due to
stable alumino-silicate dioctahedral T-O-T matrix of glauconite in which potassium is…

Acknowledgements
The authors are thankful to the Director, CSIR-National Metallurgical Laboratory for his permission to
publish this paper. Thanks to Mr. Hajaj Basheer, Geologist (Sr.) for helping us in collecting the samples.…

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