Accepted Manuscript

Recovery of rare earth metals as critical raw materials from

phosphorus slag of long-term storage

Zinesh Sadyrovna Abisheva, Zaure Baytasovna Karshigina,

Yelena Gennadyevna Bochevskaya, Ata Akcil, Elmira
Abdikhalikovna Sargelova, Kvyatkovskaya Marina Nikolayevna,
Igor Yurievich Silachyov

PII: S0304-386X(17)30362-6
DOI: doi: 10.1016/j.hydromet.2017.08.022
Reference: HYDROM 4644
To appear in: Hydrometallurgy
Received date: 29 April 2017
Revised date: 27 July 2017
Accepted date: 25 August 2017

Please cite this article as: Zinesh Sadyrovna Abisheva, Zaure Baytasovna Karshigina,
Yelena Gennadyevna Bochevskaya, Ata Akcil, Elmira Abdikhalikovna Sargelova,
Kvyatkovskaya Marina Nikolayevna, Igor Yurievich Silachyov , Recovery of rare earth
metals as critical raw materials from phosphorus slag of long-term storage. The address
for the corresponding author was captured as affiliation for all authors. Please check if
appropriate. Hydrom(2017), doi: 10.1016/j.hydromet.2017.08.022

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 ACCEPTED MANUSCRIPT
Recovery of Rare Earth Metals as Critical Raw Materials from Phosphorus
Slag of Long-term Storage

Zinesh Sadyrovna Abishevaa, Zaure Baytasovna Karshiginaa, Yelena Gennadyevna

Bochevskayaa, Ata Akcilb,* , Elmira Abdikhalikovna Sargelovaa, Kvyatkovskaya Marina
Nikolayevnaa, Igor Yurievich Silachyovc
a
The Institute of Metallurgy and Ore Benefication, Shevchenko st., 29/133, 050010, Almaty, Kazakhstan
b
Mineral-Metal Recovery and Recycling (MMR&R) Research Group, Mineral Processing Division,

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Department of Mining Engineering, Suleyman Demirel University, TR32260, Isparta, Turkey
c
The Institute of Nuclear Physics, Ibragimova st., 1, 050032, Almaty, Kazakhstan

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* Corresponding author: Tel: +90-246-211-1321. E-mail: ataakcil@sdu.edu.tr (A. Akcil).

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Abstract

The present research is directed to processing of slag originating during the yellow phosphorus
production. Slag was investigated using a complex of physical and chemical treatment methods.
The presence of the following elements of rare earth group in phosphorus slag was identified as:
Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Tm, Yb, Lu. Thermodynamic calculation of reactions
probability of phosphorous slag components interaction with nitric acid was made. Nitric-acid
leaching of phosphorus production slag for extraction of rare earth metals (REMs) was

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investigated. Silicon containing cake obtained after leaching was fond to be suitable for
precipitated silicon dioxide production. Behaviour during the leaching of associated components

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such as calcium, aluminum, and iron were studied. The following optimum parameters were
selected for leaching studies: nitric acid concentration is 7.5 mol/dm3 ; solid-to-liquid ratio is

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1:2.6-3; temperature is 50-80 ºС; process duration is 1 hour; pulp stirring rate is 500 rpm and the
recovery of rare-earth metals, calcium, aluminum and iron into the solution were seen to be 85
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%, 98 %, 80.7 %, and 11.8 %, respectively. Cake produced as a result of leaching contained ~80-
85 % of amorphous SiO 2 . A solution after phosphorus slag leaching was processed with the
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solvent extraction methods to concentrate and separate it from basic macroimpurities. After
precipitating of REMs oxalates from strip liquor and calcination of the precipitate a concentrate
had been obtained, which contained ~17% of ∑REMs oxides.
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Key words: rare-earth metals; phosphorus slag; leaching; nitric acid; lanthanides
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1. Introduction and background

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At present, the processing of phosphorite ores is carried out using a high-temperature method
and liquid processing technologies. Natural phosphoric ores are divided into two main types -
apatite and phosphorite, in which phosphorus is found in the minerals of the apatite group. The
main quantity of processed phosphorus-containing raw materials is used to produce phosphoric
acid, which, depending on the method of production, is called thermic or extraction. The most
widely used method is the acid decomposition of phosphates. As acid for decomposition, sulfur
or nitric acid is more often used. The sulfuric acid scheme for the processing of apatite
concentrate is based on the following decomposition reaction of the mineral:
Ca5 (PO 4 )3 F + 5H2 SO4 + 5nH2 O → 2CaSO 4 ∙nH2 O↓ + 3H3 PO 4 + HF (1)
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The nitric acid decomposition of the apatite proceeds according to the reaction:

Ca5 (PO 4 )3 F + 10HNO 3 → 5Ca(NO 3 )2 + 3H3 PO4 + HF (2)

When choosing the method of processing, the quality of the phosphorite raw material is of great
importance. Natural phosphates, not containing significant impurities of calcium and magnesium
carbonates, magnesium silicates, iron and aluminum compounds are suitable for acidic

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decomposition. These impurities make it difficult to process phosphates and deteriorate the
quality of the obtained products. The thermic method of processing allows to process less quality

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raw materials and receive fertilizers of better quality. Initially, elemental phosphorus is obtained,
for the production of which phosphorite, coke and quartzite are used. The method consists in the

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reduction of phosphates by carbon in the presence of silica according to the reaction:
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Ca3 (PO 4 )2 + 5С + 3SiO 2 → 2P↑ + 5CO↑+ 3CaSiO 3 (3)

The P2 O5 pentoxide, obtained after the combustion of phosphorus, forms phosphoric acid, when
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reacted with water. The advantage of the thermic method for obtaining phosphoric acid consists
in the possibility of producing acid of any concentration (up to 100 % P 2 O5 ) and high purity
when using any phosphates, including low-quality ones without their preliminary enrichment.
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The leading countries of yellow phosphorus producers are the USA, the Netherlands, China and
Kazakhstan. According to (Infomine Research Group, 2016), at present the world production of
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phosphorus is ~20 million tons per year. During processing of Karatau phosphate rocks
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(Kazakhstan) at Kazphosphate LLP (New Dzhambul Phosphorus Plant NDPhP), Zhambyl

Branch, electro-thermic distillation of phosphorus results in formation of the large quantity of
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fiery-liquid melted slags (Fig. 1a). For decades, the phosphorous slag is stored in the slag
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disposal areas thereby polluting the environment and creating ecological problems in the regions.
Dump fields of Kazakhstan contain over 25 million tons of phosphorous slag (Fig. 1b,c,d). Many
studies have been conducted to find the way of phosphorus slag recycling. Research on this issue
mainly focuses on recycling of phosphorus slag for the production of building materials and their
items (Kennedy, 1987; Shi and Qian, 2000; Jiang et al., 2011; Qi and Peng, 2011; Qian et al.,
2013; Sun et al., 2013, Falaleeva et al., 2014). In spite of all the measures designed to
recycle phosphorus slag (Akhmetov et al., 1981), the major part of it remains at the slag disposal
areas thereby deteriorating environment in Southern regions of Kazakhstan. Phosphorus slag
utilization is limited for certain reasons such as the presence of harmful impurities and low cost
of slag products.
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To ensure the most comprehensive recycling of phosphorus slags, it is necessary to seek out
methods for removal of the contaminating impurities and for production of high value added
marketable products. Precipitated silicon dioxide is among such value added products (In the
international market the value of precipitated silicon dioxide varies from USD 650 to 2000 per
ton depending on the grade).

Su et al. (2010) obtained precipitated silicon dioxide from slag of the yellow phosphorus
production by leaching with phosphoric acid where calcium was separated in form of calcium

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phosphate monobasic. The content of iron in the precipitated silicon dioxide is seen to be higher
than the established standards. Therefore nitric acid solution is used for its purification allowing

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up to ~ 0.02% decrease in iron concentration (Li et al., 2012).

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In our previous works (Abisheva et al., 2005, 2006, 2008, 2013) on phosphorus slag processing
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for the production of precipitated silicon dioxide, slag was leached with sodium carbonate
solution for silicate solution production. The solution was subjected to purification from
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aluminum and the silicon dioxide having high specific surface area was then precipitated from
the solution by carbonization.
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Phosphorus slags which are mainly composed of calcium and silicon compounds also contain
rare-earth metals (REMs), the production of which is currently one of the top-priority goals.
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Phosphorous production slags contain REMs being among the most demanded ones in the modern
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high-technology industries: yttrium, neodymium, europium, and lutetium. A strong demand

nowadays for rare-earth metals is related to the development of such knowledge-intensive
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industries as radio electronics, information technology, nuclear power, aviation, rocket

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technologies, biomedicine, etc. Rare-earth metals are crucial for “green technologies”. They are
used for the production of wind turbines, energy-saving bulbs and for the increasing production
of electric and hybrid vehicles.

Lately China being the absolute world leader producing rare earth metals announced reduction of
the export quotas for these metals by 72% in connection with the intention to stop depletion of its
deposits (Smirnov, 2011). Severe reduction by China of rare-earth metal supplies to the external
market stimulated the importing countries to generate their own resource base. A definite problem
is that the percentage of rare-earth metals, which are in great demand, is not very high in natural
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raw materials. “BRK – Leasing” Co. Ltd. Subsidiary of Joint Stock Company “Development
Bank of Kazakhstan” (2007) noted that total production of REMs increased from 33 thousand
tons to 75 thousand tons or 2.3 times from 1990 to 1999 while the demand for neodymium and
dysprosium oxides increased 9-10 times during the same period. Alonso et al. (2012) аssumed
that in the next 25 years demand for neodymium and dysprosium will rise by 700 % and 2600 %
respectively. According to HEFA Rare Earth (Goncharov, 2015) in May 2015, the exchange prices
of rare earth metals for neodymium, dysprosium and europium oxide were USD 87, 470 and 680
per kilo, respectively.

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In connection with the steady tendency to growth of the world demand for rare earth metals there

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is a need to search new raw material sources for their production. F.Yang et al. (2013),

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Binnemans et al. (2013), Innocenzi et al. (2014), Tunsu et al. (2014) and X.Yang et al. (2014)
studied REMs recovery from waste of permanent magnets, wastes of nickel hybrid batteries and
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fluorescent lamps. Technogenic wastes of chemical and metallurgical industries along with the
wastes of products of end-of-life are promising.
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Interest has recently increased to products of processing of phosphate raw materials as a source
of rare-earth raw materials. As noted by authors Wang et al., 2010, the total reserves of
phosphorite ores in the world are about 100 billion tons, which on average contain 0.5 % REMs.
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Many studies (Lokshin et al., (2010; 2012); Goldinov et al., 1982; Lebedev, 2010; Bandara
and Senanayake, 2015; Jorjani et al., 2011; Kosynkin et al., 2012) available on the ore and
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technogenic phosphorus-containing raw materials generally refer to apatite ores and concentrates
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or intermediate products and wastes from their acid processing, which significantly differ by
their phase and chemical compositions from phosphorous production slags obtained after
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electrothermic smelting of Karatau phosphate rocks. Sulphuric or nitric acids were used as a
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decomposition agent in these studies. A recent paper (Mugdha Walawalkar et al., 2016) presents
the research on the leaching of REMs from phosphogypsum with using sulfuric, nitric and
hydrochloric acids. Thus, the efficiency of the REMs leaching was increased by using nitric and
hydrochloric acids.

Despite the world's tendency to reduce production volumes, the processing of phosphate
raw materials by thermic method in Kazakhstan has great prospects. The Zhambyl branch of
Kazphosphate LLP (NDPhP) is increasing its capacity (120 thousand tons per year of yellow
phosphorus). In the production of one ton of phosphorus, 10-12 tons of slag is formed, which
contains precious metals such as rare earths. Until now, no studies have been performed on the
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processing of phosphorus slag with the extraction of REMs in the literature. Therefore, it is
important to study the extraction of the REMs from phosphorus slag.
While selecting the phosphorous slag breaker it is necessary to keep in mind the possibility
for complex processing of phosphorous slag with recovery of rare earth metals and production of
precipitated silicon dioxide. Meanwhile the perspective of further processing of REMs-containing
solutions is of considerable interest. During the processing of raw with law content of valuable
components for concentration and separation them from accompanying impurities solvent
extraction methods are being more perspective. One of the most widespread and effective

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extractants in the processing of REMs-containing solutions is tributyl phosphate (C 4 H9 O)3 PO
(TBP). TBP belongs to the class of neutral extractants. This group of extractants is characterized

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by solvate, hydrated-solvate and onium types of extraction. REMs extraction with tributyl
phosphate proceeds via a solvate mechanism that consists in attaching the extractant molecules

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to the cation of the neutral undissociated salt molecule (Voldman and Zelikman, 2003) and is
described by the equation:
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- ̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
La3+ + 3NO3 + 3TBP = La (NO3 )3 ∙ 3TBP (4)
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Starting from equation (4),

[La( NO3 )3 ∙3TBP]

𝐷= [ La3+ ]
(5)
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where D is the equilibrium distribution coefficient, which is the ratio of the equilibrium
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concentrations of the extracted element in the organic and aqueous phases.

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REMs is extracted from nitrate media with tributyl phosphate from neutral and acidic solutions.
The energy costs for the transition of molecules from the aqueous phase to the organic phase are
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compensated by the energy of solvation of these molecules by the extractant. The best conditions
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for extraction are created if neutral molecules are present in the solution, which promote a high
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concentration of the ion of the same name in solution, i.e. in the case of nitrates – the NO3 ion.
This is achieved by introduction of excess nitric acid or its salts, which are salting-out agents.
Salting out agent is an inorganic substance that improves extraction performance. Addition to the
aqueous solution of the salting out agent promotes the formation of lighter extractable
undissociated molecules or leads to the formation of extractable complexes.

The use of TBP is most suitable for extracting REMs from nitric acid solutions. Taking into
account in preliminary studies (Karshigina et al., 2015) nitric acid was selected for the primary
processing of phosphorous slag (Table 1). Slag decomposition by nitric acid results in prevention
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of gypsum formation in the solid residue and possibility to obtain easy-processing cake with
higher silicon concentration. During the complex processing of slag it is preferable to take into
consideration behaviour of associate components, such as calcium, aluminum and iron, in
addition to REMs, already in the early stage. During the nitric-acid leaching rare earth metals,
calcium, aluminum and iron sufficiently pass into solution (Table 1).

Presence of calcium and aluminum nitrates can have a salting-out effect in case of further REMs
recovery from the solutions by the method of solvent extraction. The action of the salting out

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agent is experienced due to an increase in D due to an increase in the concentration of the anion
involved in the formation of the extractable compound and the hydration of ion of the salting out

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agent that reduces the concentration of unbound water, which in turn promotes the dehydration

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of the ions of the recovered metals in the solution and the increase in their activity. Iron can
affect further processing of REM-containin NU g solutions. Therefore, it is desirable to minimize
iron dissolution. To make processing of the obtained solutions more effective, the increase of
REMs concentration in them is important.
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Improvement of nitric-acid leaching (decrease in nitric acid consumption, increase of REMs

concentration in the solution, and others) requires studies on the influence of different process
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parameters on dissolution of REMs and associated components of aluminium, iron, and calcium.
In addition, the possibility of obtaining REMs concentrate from solution after the leaching
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containing macroimpurities of calcium, aluminum and iron is of interest.

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2. Experimental
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2.1 Materials

The raw material used for experimental purposes is long-storage phosphorous production slag
from slag disposal areas of KazPhosphate LLP, Zhambyl Branch, (NDPhP), collected since 1990
till 1995 (Fig. 1b,c,d). The slag composition is shown in Tables 2 and 3. The following elements
of rare-earth metals group have been identified in phosphorus slag: Sc, Y, La, Ce, Pr, Nd, Sm,
Eu, Gd, Tb, Ho, Tm, Yb, Lu (Table 3).
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The leaching reagent solution was prepared with the use 12.2 mol/dm3 nitric acid (57 % of
HNO 3 ). Rare-earth metals were extracted with the use of TBP. Kerosene was used as a diluent.
99.5% of Н2 С2 О 4 was used for preparation of oxalic acid solution. Distilled water was used for
slag pulping.

2.2 Methods

Slag was pre-ground in a centrifugal mill and was sieved to obtain a powder of 0.05 mm size.

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XRD analysis of phosphorus slag was made using D8 ADVANCE (Bruker AXS GmbH)
instrument with cobalt anode, а-Cu emission. Infrared analysis of phosphorous production slag

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was made using infrared Fourier-transform spectrometer Avatar CsJ 370 with attachment
Transmission E.S.P. Thermal analysis of slag was conducted using the apparatus of synchronous

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thermal analysis STA 449 F3 Jupiter. Before heating the furnace space was pumped out (the
level of reached vacuum was 92 %) and then blown off with inert gas for 5 min. Heating of
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samples was carried out at the rate of 10 °С/min., in the atmosphere of highly purified argon.
The total volume of in-going gas was kept within 80 cm3 /min. Processing of results was carried
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out using NETZSCH Proteus. The experiments were run in a constant temperature air-tight cell
according to a standard procedure. Pulp was stirred by an “OST basic” brand agitator having
variable rotary speed. The constant temperature was stabilized using a ТL-ТС-01 thermostat.
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During the contact of the whole amount of concentrated nitric acid solution with phosphorus
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slag, very badly filtered silicon-containing cake with high degree of dispersion is formed. The
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fine-dispersed cake formed consists for the most part of silica sols, which are likely changed
during the adherence into gel structure (Iler, 1979; Shabanova and Sarkisov, 2004).
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Sinegribov and Yudina (2005) in their patent suggested conditions for decreasing the
decomposition rate of calcium silicates compounds to prevent an active transfer of silica into
gelled substance during phosphorus slag leaching with nitric acid. In accordance with these
conditions, an advance preparation – phosphorus slag pulp dilution is carried out prior to
leaching. In other words, slag is mixed with water at S: L ratio of 1: 1 and at the same time pulp
is heated up to preset temperature. The temperature of phosphorus slag advance dilution with
water was maintained at 10ºС lower than leaching temperature. After that concentrated nitric
acid was slowly was added to the pulp during 1 hour and the pulp was intensively stirred at the
same time. Then the pulp heating temperature was increased by 10 ºС and leaching performed.
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The experiments on leaching were run in compliance to the following constant conditions: HNO 3
concentration was 7.5 mol/dm3 ; temperature was 90 ºС; S: L: ratio was 1: 2.6; experiment time
was 1 hour; speed of stirrer rotation was 500 rpm. Solvent extraction and stripping experiments
were carried out in separating funnel 20  50 С and in predetermined proportions of the organic
and aqueous phases. The phases were mixed mechanically. The contact time of the phases was
being 5 minutes. Experiments in calcination of a precipitate was carried out in «SNOL 7.2/1300»
muffle furnace at a given temperature and a holding period.

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The resultant solutions and cakes were analyzed to determine the content of calcium, aluminum,
iron, and ∑REMs. The quantitative content of major elements and compounds was determined

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by chemical methods of analysis. An Optima 8300DV ICP atomic emission spectrometer was
used to determine the quantitative content of rare-earth metals. Samples of the phosphorus slag
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and REMs concentrate also were analyzed with using of neutron activation analysis (NAA) on
the content of rare earth metals at the Institute of Nuclear Physics (INP). XRF analysis was
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carried out on the RLI-21T laboratory energy dispersive spectrometer in the INP.

3. Results and Discussion

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3.1 Physico-chemical study of phosphorus slag

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Rare earth elements are highly chemical active and interact with almost all elements. To obtain
rare earth metals, electrolysis from molten salts is usually used, as well as methods for metal-
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thermal reduction of their galloid salts (fluorides, chlorides) or oxides. The reducing agents are
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calcium, sodium, aluminum and magnesium. Therefore, under conditions of electrothermal

melting of phosphorites at temperatures of 1400-1600 ° C in the presence of carbon as a reducing
agent, the rare earth elements are not reduced to the metallic phase. REM oxides melt at
temperatures above 2000 ° C and do not decompose to melting point. On this basis, REM
compounds or their oxides, which can be formed in the case of dissociation of REM compounds,
remain largely in the slag.

XRD analysis of phosphorus slag established that the matter of the sample was in the amorphous
condition and contained insignificant quantity of СаСО 3 (Fig. 2). Infrared analysis of
phosphorous production slag was made (Fig. 3). The IR spectrum of phosphorus slag is
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characterized by three absorption bands in the regions ~1100-800, ~713-650 and ~600-400 cm-1
(Fig. 3). In the infrared spectrum of the slag sample there is a “diffuse” absorption line with
maxima characterizing fluctuations νas SiOSi – 1083, 1004 cm-1 , ν SiO ¯ - 951 cm-1 (Lazarev,
1968). Displacement of the fluctuation maximum νas SiOSi into a long-wave region up to 1004
cm-1 speaks for entering the anionic component of the glass structure of tetrahedrons like MgO 4
and AlO 4 (Kolessova, 1960; 1966). In the low-frequency region, the absorption bands of 511-
472 cm-1 result from the deformation vibration (δs, δas) of bridge (Si-O-Si) and terminal O-– Si –
O - -groups, and also metal-oxygen polyhedra (CaO n ). The absorption region at ~ 713-650 cm-1

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corresponds to the Al-O and Si-O bonds and shows the presence of pseudowollastonite α-CaSiO 3
in the slag. The band with the wave number 951 cm‾1 shows presence of the glass-like earth

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silicon with significant number of unbridged connections of Si – O emerging in the result of
breach of the polymer network Si – O – Si of frame at introduction of Са atoms to the network

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with replacement of Si atoms in it. It was established that in the sample composition there is
quartz SiO 2 – 1083, 799, 779, 695, 511, 398 and 372 cm-1 (Moenke, 1962; Vlassov et al., 1972)
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and calcite CaCO 3 - 1419, 876 and 713 cm-1 .

Analyzing the data of the IR spectrum, the chemical composition of phosphorus slag and
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publications (Dyakova et al.,1981; Yestemesov et al., 1987), it can be said that the phosphorus
slag consists mainly of pseudowollastonite glass (90-92%).

To study the phase composition of the sample of phosphorous slag by the thermal analysis
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method, it was heated to 1000 °С. The results are presented in Figures 4 and 5. Figure 4 shows a
thermogram of the phosphorous slag sample under investigation. The DTA curve reflects
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recorded endothermic effects with maximum development at 729 and 810 °С and intensive
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exothermic effect with the peak at 909 °С.

Within the temperature range of development of the first endothermic effect on the DTA curve
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the TG curve demonstrates decrease of the sample weight. The DTG curve shows the effect with
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the minimum at 717.6 °С. Another minimum with the extremum at 742 °С was recorded on the
ascending branch of the said effect.

Using NETZSCH Proteus software the first derivative of the DTA curve – dDTA curve was
obtained. Analysis of that curve showed that endothermic effect with the extremum at 746 °С
corresponds to the minimum at 742 °С. Also, exothermic effect with the peak at 817 °С can be
noted on this curve.
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It can be supposed that combination of endothermic effect with the maximum development at
729 °С and exothermic effect with the peak at 909 °С was manifestation of gyrolite – calcium
silicate hydrate Ca4 (H2 O)4 [Si6 O 15 ](OH)2. The first effect reflects the process of dehydration and
amorphous product formation, and the second effect reflected the process of amorphous phase
crystallization. Combination of endothermic effect with the extremum at 754 °С and exothermic
effect with the peak at 817 °С can be interpreted as manifestation of a small amount of
serpentine – Mg6 [Si4 O10 ](OH)8 .

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In the overlapping, endothermic effect with the maximum development at 729 °С reflected
presence of carbonate apatite Ca10 [PO 4 ]6 CO 3 or rare-earth apatite impurities in the sample. Also,

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in the overlapping, combination of endothermic effects with the extremums at 702 and 784.5 °С

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and exothermic effect with the peak at 900 °С on the dDTA curve reflected manifestation of
hydrated calcium aluminosilicate impurities CaO∙2Al2 O3 ∙2SiO 2 ∙H2 O. Here, the first effect
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reflected dehydration, the second one reflected destruction of the lattice, the third (exothermic)
reflected crystallization of the decomposition products.
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To identify possible phases of rare-earth metals the candle-end of the phosphorous slag sample
was heated to 1000 °С at the rate of 10 °С /min. The thermal curves obtained are shown in
Figure 5. The dDTA curve has two endothermic effects with the extremums at 730 and 910 °С.
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No REMs phase manifestation was found for the first temperature. The second endothermic
effect presumably can reflect the phase changes of the compound La 2 S3 . Taking into account
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results of the physical and chemical analyses of phosphorous production slag performed, it is
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determined that the slag consists mainly of pseudowollastonite glass (90-92%) , it was assumed
that phosphorous slag contains the following compounds: gyrolite Ca 4 (H2 O)4 [Si6 O15 ](OH)2 ,
small amount of serpentine Mg6 [Si4 O10 ](OH)8 , hydrated calcium aluminosilicate impurities
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CaO∙2Al2 O3 ∙2SiO 2 ∙H2 O, quartz SiO 2, and calcite CaCO 3 . Rare earths are present in the slag in
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the form of carbonate apatite Ca10 [PO 4 ]6 CO 3 or rare-earth apatite impurities, in the crystal lattice
of which REMs ions can isomorphically replace calcium ions close in radius. REMs are also
present in the form of the compound La2 S3 .

3.2 Thermodynamics of interaction reactions of phosphorous slag components with nitric acid

Thermodynamic calculation of probability of interaction processes of phosphorous slag

components with nitric acid was made taking into account phase and chemical compositions of
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the primary product. Calculations were made using НSC 5 Chemistry by Outokumpu Oy
(Finland).

From the point of view of REMs extraction, calcium compounds, which can penetrate in the
form of impurities of rare earth compounds, were of interest. Calcium compounds are
represented mainly by pseudowollastonite α-CaSiO 3 , and also by gyrolite phase
Ca4 (H2 O)4 [Si6 O15 ](OH)2 , and hydrated calcium aluminosilicate impurities
CaO∙2Al2 O3 ∙2SiO 2 ∙H2 O, and calcite CaCO 3 . Gyrolite Ca4 (H2 O)4 [Si6 O15 ](OH)2 can be presented

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as 2(2CaO·3SiO 2 ·2.5H2 O), therefore the compound 2CaO·3SiO 2 ·2.5H2 O available in the
database of НSC 5 Chemistry was used for calculations. Due to the absence in the database of

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the compound CaO∙2Al2 O3 ∙2SiO 2 ∙H2 О, the compound CaO∙Al2 O3 ∙2SiO 2 ∙2H2 О close in its

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composition was used for thermodynamic calculations.
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Rare earth compounds represented in phosphorous slag in the form of carbonate apatite
Ca10 [PO 4 ]6 CO3 or rare-earth apatite are not available in the database of НSC 5 Chemistry. One
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of apatite types is hydroxyapatites, in which form rare-earth apatite can be present in

phosphorous slag. As it is known hydroxyapatite has an ionic crystal lattice where Ca2+ ions can
be replaced to the REMs ions and OH- and 𝑃𝑂43− ions – to the 𝐶𝑂32− ions and to others.
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Therefore, for the thermodynamic calculations assumptions were made, and REMs carbonate-
and dihydrogen phosphate ions, for which data is available in the computer program, were also
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used as primary REMs-containing components of phosphorous slag in addition to phosphates.

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Phosphorous slag contains in small amounts aluminum and iron compounds, which can pass into
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solution during interaction with nitric acid and affect further processing of REMs-containing
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solutions. It is commonly known that slag mostly consists of oxides, which can form complex
compounds while interacting with each other. Aluminum in phosphorous slag is represented by
the phase of hydrated calcium aluminosilicate CaO∙2Al2 O3 ∙2SiO 2 ∙H2 О. Therefore, for
thermodynamic calculations aluminum oxide Al2 O3 was also used in addition to hydrated
calcium aluminosilicate compound.

For thermodynamic calculations of interaction of iron compounds with nitric acid its oxide Fe2 O3
was used. Thermodynamic calculations on The Gibbs energy determination for the interaction
reactions of phosphorous slag components with nitric acid were made for the temperature range
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from 50 to 100 0 С. Negative value of the Gibbs energy shows the possibility of the reaction
under investigation. Assumed reactions and calculation results of the Gibbs energy are shown in
Table 4. As Table 4 shows, almost in all cases calculated values of the Gibbs energy of
represented reactions have a negative value. This is indicative of thermodynamic probability of
reactions. The process temperature increase over 80 о С is unfavourable for scandium extraction
into solution. For all the other rare-earth elements use of nitric acid as an opening agent in the
whole temperature range from 50 to 100 о С under review is acceptable.

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It should be noted that, except for calcite, carbonate and dihydrogen phosphate ions of rare-earth
elements, with increase of the process temperature the Gibbs energy of interaction reactions of

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phosphorous slag components with nitric acid is slightly growing. This is indicative of the fact

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that increase of the process temperature can slightly reduce the rate of some reactions.
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Associated components of phosphorous slag, such as calcium, aluminum and iron, can pass into
solution well when being leached with nitric acid. In case of effective REMs extraction presence
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of calcium, aluminum and iron in the solution can affect selection of the method of processing of
REMs-containing solutions in the future. Thus, preliminary thermodynamic calculations showed
that use of nitric acid as an opening agent for phosphorous slag is favourable for both
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decomposition of the main components of phosphorous slag with production of siliceous cake
and formation of soluble nitrates of rare-earth elements. Therefore, taking into account results of
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thermodynamic calculations, it was necessary to optimize the conditions of leaching of

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phosphorous slag with nitric acid and improve the process performance.
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3.3 Determination of optimum conditions for phosphorus slag nitric acid leaching
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3.3.1 Effect of pulp stirring intensity

The following values of rotation rates were maintained during studies: 100, 200, 300, 400, 500,
600, 700, and 800 rpm. The results of the experiments are shown in Fig. 6. As Figure 6 shows,
recovery of ∑REMs, calcium, aluminum, and iron almost reached the maximum values already
at the stirring rates of 100-200 rpm and at the further increase of rotations of the stirrer, while
growing a bit more, it made up ~80 %, ~96 %, ~75 %, and ~14 %, accordingly. That is, the
interaction of the constituents of phosphorus slag with nitric acid is high enough and the supply
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of the reagent to the surface of the reaction does not have significant limitations even at low
agitator speeds.

Iron recovery tends to increase, however at the very beginning a sharp rise up to ~21 % is
observed when rotation speed of the agitator is 100 rpm. Possibly, it was associated with
recovery’s reduction into solutions of calcium and aluminum and, therefore by presence of not
reacted nitric acid which is needed for dissolution. Or, due to insufficiently good mixing of pulp
during the addition of nitric acid, local acid peroxides occur, which contributes to a more

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intensive dissolution of iron. It’s worth noting that when the rates of agitator rotation were 100
to 400 rpm, a pulp break was observed indicating a poor stirring quality. So the most optimum

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pulp stirring speed of 500 rpm was selected.

3.3.2 Effect of reagent concentration

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The experiments were run at the following values of nitric acid concentrations – 5.5; 6;
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6.5; 7; 7.5; 8; 8.5; 9 mol/dm3 . Fig. 7 shows the results of the experiments. Figure 7 shows that
increase of HNO 3 concentration results in increase of recovery of the components under
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investigation, at that they passed to the solution to the maximum extent at the concentrations of
HNO 3 7.5 mol/dm3 and above. Maintaining the required concentration of nitric acid it is possible
to extract better ∑REMs, calcium, aluminum and iron to the solution, which was confirmed by
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the preliminary thermodynamic calculations. With the increase of HNO 3 concentration to 7.5
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mol/dm3 iron recovery increased to 14 %, and at HNO 3 concentrations over 8 mol/dm3 it reached
~ 74-80 %. According to the literature data (Liner, 1982), in the initial period (10-20 min) the
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kinetic curves of dissolution of iron hydroxide have a pronounced maximum, i.e. the soluble iron
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nitrate is intensively formed, in the next period (30 min) the kinetic curves reach a minimum
level accompanied by precipitation of iron hydroxide precipitate as a result of hydrolysis of iron
nitrate by the reaction 6:

nFe(NO 3 )3 + nH2 O → nFe(OH)(NO 3 )2 → nFe(OH)2 (NO 3 ) → nFe(OH)3 + nHNO 3 (6)

The duration of the leaching process in this series of experiments is 1 hour, i.e. the
composition of the resulting solutions taking into account the hydrolysis process. The increase in
the concentration of hydroxyl ions due to dissociation of water contributes to the flow of reaction
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(6). With an increase in the concentration of nitric acid, i.e. with increasing acidity of the
solution, hydrolysis of iron is suppressed. Therefore, at acid concentrations above 8 mol/dm3 , the
recovery of iron into the solution increases. With a lack of acid and an elevated temperature,
hydrolysis of aluminum nitrate (reaction 7) proceeds analogously:

nAl(NO 3 )3 + nH2 O → nAl(OH)(NO 3 )2 → nAl(OH)2 (NO 3 ) → nAl(OH)3 + nHNO 3 (7)

The dashed line drawn in Fig. 7 shows the percentage of HNO 3 from stoichiometry for

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reaction of nitric acid interaction with all major components of phosphorus slag. As can be seen
from Fig. 7, the aluminum extraction in a solution of ~73% occurred at a nitric acid

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concentration of 7.5 mol/dm3 , corresponding to ~ 104 % of the stoichiometric amount. For
sufficiently complete recovery of the REMs (~82-88%), a nitric acid concentration of at least 7.5

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mol/dm3 is also required. Calcium had high recovery to the solution from ~71 to ~97 % almost in
the whole range of HNO 3 concentrations under investigation, which was indicative of good
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decomposition of main silicate components of phosphorous slag.
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It should be taken into account that with further processing of solutions by the method of solvent
extraction, the use of concentrated nitric acid is needed to assure a high concentration of nitrate
ions in the leachate, needed for the extraction of REMs with TBP. Therefore, the most optimal
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HNO 3 concentration was selected 7.5 mol/dm3 , where the extraction of ΣREMs into the solution
was ~ 82%.
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3.3.3 Effect of solid-to-liquid ratio

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In the investigations for determination of dependence of the leaching process on S: L ratio the
volume of nitric acid solution per unit of phosphorous slag amount was changed. The
experiments were run at the following S: L ratios: 1:2; 1:2.6; 1:3; 1:3.5 and 1:4 and the results
have been shown in Fig. 8. Figure 8 shows that recovery of all components under investigation
increased with increase of S: L ratio. At S: L ratios of 1:2.6 and 1:3, corresponding to ~104 and
120 % HNO 3 of stoichiometry, accordingly, recovery of calcium, ∑REMs and aluminum made
up 73-95 %. Iron recovery at S: L ratio under 1:3 did not exceed 20 % and only at a ratio of S: L =
1: 3.5, corresponding to ~139 % HNO 3 from stoichiometry, reached 87 %. Perhaps an excess
amount of nitric acid ~39 % was necessary to suppress the hydrolysis of iron nitrate in solution.
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The most optimal S: L ratios were selected 1:2.6 and 1:3, where the recovery of ΣREMs into the
solution reached 82 and ~88 %, respectively.

3.3.4 Effect of process temperature

The studies have been pursued at the following temperatures of leaching: 50, 60, 70, 80, 90
and 98 ºС and the results have been showed in Fig. 9. Recovery of calcium, aluminum and
∑REMs to the solution (Figure 9) reached ~99, ~78 and ~86 %, accordingly, at 50 ºС, with

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insignificant decrease in recovery of aluminum and ∑REMs at the temperature over 70-80ºС.
This can be explained by the evaporation of part of nitric acid at elevated temperatures. The

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possibility of lowering the degree of recovery of studied components into solution with
increasing of temperature was also indicated by an increase in Gibbs energy for the expected

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reactions of the process. The recovery of iron with increase of the temperature reduced
significantly from ~ 42 to ~6 %, as noted above, this is the result of the hydrolysis of iron nitrate.
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As the temperature increases, the degree of dissociation of water increases, which intensifies the
course of reactions (6) and (7). The optimal temperature range of phosphorous slag leaching 50–
80 ºС was selected, within which the selection was determined by the rate of iron extraction to
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the solution.
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3.3.5 Effect of time

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Leaching experiments were run having kept up the following values of the duration of the
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process – 0.5; 1; 1.5; 2 and 2.5 hours and the results are shown in Fig. 10. Recovery of ∑REMs,
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aluminum and calcium, having reached 80, 73 and ~93 %, accordingly, at the leaching time 0.5
hours, remained unchanged growing a little with further increase of time. The recovery of iron
changed insignificantly and amounted to ~ 12-15%. The results of the experiments suggest that
phosphorus slag leaching with nitric acid only slightly depends on the duration of the process.
This can be explained by the effect of advance slag dilution and gradual acid injection into the
pulp during 1 hour when phosphorus slag components have started interacting with HNO 3 . The
most optimum 1 hour duration of the process has been chosen. During this time ∑REMs
recovery into solution was 82 %.
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Taking into consideration the results of the experiments, leaching of phosphorus slag with
nitric acid proceeded with adherence to the following conditions: nitric acid concentration – 7.5
mol/dm3 ; S: L ratio – 1:2.6; temperature – 60 0 С; process time – 1 hour; pulp stirring rate – 500
rpm. Concentration in the solution under this conditions made up, g/dm3 : 0.203 ∑REMs; 229.7
CaO; 18.6 Al2 O3 ; 0.1 Fe2 O3 . Recovery of ∑REMs, calcium and aluminum reached 85 %, 98 %
and 80.7 %, respectively. Iron recovery was 11.8 %. REMs containing solutions are expected to
be sent for the solvent extraction to recovery and concentrate REMs. Silicon containing cake

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produced has the following composition, % (mas.): 80-85 SiO2 ; 0.11 CaO; 0.11 Al2 O3 ; 2.7
Fe2 O3 ; 0,0027 ∑ REMs oxides. The cake was studied by the XRD analysis, according to which it

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was established that the matter of the sample analyzed is in the amorphous condition.
Amorphous silicon dioxide passes to the filtrate easily at its leaching with sodium hydroxide

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solution. In the future it is supposed to be used to produce precipitated silicon dioxide – “white
soot”.
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4.1 The processing of solutions after nitric acid leaching of the phosphorus slag by solvent
extraction method.
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The high efficacy of a tributyl phosphate can permit to recovery REMs to the organic phase on
high grade and to separate them from macro impurities, which are being in the solution. In the
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investigations for solvent extraction method were used nitrate solutions of a such content
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(g/dm3 ): 0,198 of ∑REMs; 177 of СаО; 17,3 of Al2 O3 ; 1,7 of Fe2 O3 . Apparently, compounds of
the metals are being in the solution as the soluble nitrates. The solution contains calcium nitrate in
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a large amount, aluminum and iron in a smaller amount.

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It is known that calcium, as well as aluminum and iron, is able to have salting out effect during
solvent extraction. In some cases, even the addition of calcium nitrate to the nitrate solution is
recommended before the solvent extraction of REM with tributyl phosphate. In the patent (Valkov,
1984), after dissolving apatite in nitric acid, further freezing out of the calcium nitrate solution,
precipitation of the hydrate-phosphate precipitate of the REMs, the latter is dissolved in nitric acid,
while calcium nitrate melt is added to the solution to obtain a concentration of 800-100 g/dm3 , then
the solution is sent for solvent extraction by TBP. However, the solutions directed to solvent
extraction contain 40-60 g/dm3 of REMs oxides. The solutions obtained after the nitric acid
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leaching of phosphorus slag, the REMs content is significantly lower. Therefore, it was studied the
possibility of carrying out the solvent extraction process by tributyl phosphate from nitrate solutions
with a low REMs content in the presence of macro quantities of calcium, aluminum, and iron
impurity.

Investigation of the REMs solvent extraction from nitrate solutions with tributyl phosphate
was carried out with the study of the influence of the extractant concentration from 0.73 to 3.66
mol/dm3 in the range of O: A ratios from 1: 1 to 1:20 and the contact time of the phases was being

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5 minutes. Multistage counter-current solvent extraction process is the most effective method for
recovery of value metals from solutions with high results and separation of components. The

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indicative number of counter-current solvent extraction steps was graphically determined on the

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solvent extraction isotherm equal to 3. To confirm the correctness of the determined number of
solvent extraction steps, a three-step counter-current process of REMs solvent extraction was
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modelled. The work (Karshigina et al., 2016) presents study results and shows that rare-earth
metals may be separated from the related impurities of calcium, aluminium, and, partially, iron
and concentrated by TBP solvent extraction. As the experiments showed, aluminium has not
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extracted into the organic phase, calcium was not extracted, too, except for O:A ratio =1:1, at 60 %
TBP concentration the recovery was 0.6 % (DCa = 0.006) and O:A ratio =1:1 and 1:2 at 100 %
TBP concentration, the recovery was from ~4 (DCa = 0.04) to~16 % (DCa = 0.38), respectively. It is
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more efficient to perform solvent extraction at 50 % TBP counter-current in three steps at O:A =
1:6 or at 100 % TBP in one step at O:A = 1:20. The degree of extraction of REMs into the
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loaded organic phase under these conditions was ~ 87-97% and ~ 95%, respectively. The
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distribution coefficients for REMs and iron at the selected optimal conditions are presented in
Table 5. Calcium and aluminum under these conditions of extraction into the organic phase were
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not shown. As can be seen from Table 5, in order to concentrate and separate the REMs from the
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iron impurity, it is more efficient to extract 100% of TBP at 0: B = 1: 20. The distribution
coefficient D for iron under both conditions is kept at the same level, and for REMs, with the
process of 100% TBP and O: B = 1: 20, it increases by 10.7 times.

REMs stripping can be carried out with water (Kuzmin et al., 2007). Stripping was carried out
with water when the ratio of O: A was varied from 2: 1 to 10: 1 (Table 6).
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With the increasing in parts of the organic phase volumes from 2 to 10, the recovery of
ΣREMs into the strip liquor decreases from 99.98 to 52.43 %, where at the ratio O:A of 6: 1, the
recovery is 94.81 % and the process is characterized by the maximum concentration Σ REMs in
the aqueous phase is 5.85 g/dm3 . The aqueous solution obtained after stripping of ΣREMs at the
ratio О: A = 6: 1 has the following composition, g/dm3 : ΣREMs - 5.85; calcium - 22.88;
aluminum - 0,05; iron - 0.05. In view of the fact that the stripping of the REMs was carried out
with water, washing of the rich organic phase after extraction was not possible. In this regard, the
presence of calcium and aluminum impurities in the strip liquor can be explained by the capture

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by the organic phase of a part of the raffinate during extraction.

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4.2 Preparation of rare earth metals concentrate.
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The principal possibility of obtaining from REMs concentrate from aqueous solutions obtained
after stripping is shown. A precipitate was precipitated from the REMs-containing strip liquor
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using a solution of oxalic acid at a concentration of 2 mol/dm3 . The amount of precipitant was
calculated on 100% of the stoichiometry of the reactions of formation of oxalates of REMs,
calcium, aluminum and iron. The data on the metal precipitation test are presented in Table 7.
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The resulting oxalate precipitate, after washing and drying at 105 °C, was calcined in a muffle
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furnace at 900 °C for 2 hours. The composition of the calcined sediment (REMs concentrate)
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which containing 17.3 % of the REMs oxides is shown in Table 8. The REMs containing mother
solution can be returned to precipitation of oxalates in order to recovery valuable components.
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The X-ray fluorescence spectrum of the obtained REMs concentrate is shown in Fig. 11. The
presence in the spectrum of characteristic peaks corresponding to the REMs indicates their
presence in the sample. The intensity of the spectral lines indicates a significant content of
yttrium in the sample. The greatest concentration, ~830 times, in the resulting concentrate occurs
according to praseodymium (Figure 12), the remaining REMs (excluding scandium) are
concentrated in 120-250 times. It should be noted that in the final product from lanthanum to
lutetium and yttrium, i.e. from light REMs to heavy, the concentration increases, increasing by ~
2 times. This circumstance is important if one considers that the metals of the heavy REMs
group are presented in the raw material in a much smaller quantity and are of great value. Thus,
the conducted studies show that when processing of phosphorus slag that containing about ~0.06
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% ΣREMs, with the processes of nitric acid leaching, solvent extraction of TBP, stripping with
water, precipitation of oxalate precipitate and its calcination, it is possible to obtain a concentrate
with a content of 17.3 % of the ΣREMs oxides (Fig. 13).

4. Conclusions

1. Using XRD, IR and thermal analyses it was established that the main components of

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phosphorous slag are in amorphous condition and are present in the form of
pseudowollastonite α-CaSiO 3 . In the slag there are also the following compounds: gyrolite

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Ca4 (H2 O)4 [Si6 O 15 ](OH)2 , small amount of serpentine Mg6 [Si4 O10 ](OH)8 , hydrated calcium
aluminosilicate impurities CaO∙2Al2 O3 ∙2SiO 2 ∙H2 O, small quantity of quartz and calcite. Rare

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earths in slag are present in the form of carbonate apatite Ca 10 [PO 4 ]6 CO3 or rare-earth apatite
impurities, and in the form of the compound La2 S3 .
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2. The composition of phosphorus slag by rare-earth metal contents was determined and the
presence of the following rare-earth group elements was identified: Sc, Y, La, Ce, Pr, Nd, Sm,
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Eu, Gd, Tb, Ho, Tm, Yb, Lu.

3. Thermodynamic calculations confirmed the possibility to use nitric acid for phosphorous slag
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decomposition with production of the siliceous cake and for REMs leaching.

4. The following optimum parameters of phosphorus slag leaching with nitric acid were
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obtained: nitric acid concentration is 7.5 mol/dm3 ; S: L ratio = 1:2.6 and 1:3; temperature –
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50-80 ºС; process time – 1 hour; pulp stirring rate – 500 rpm. At that, ∑REMs concentration
in the solution reached 0.19 g/dm3 . Recovery of rare-earth metals, calcium, aluminum and
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iron reached 85 %, 98 %, 80.7 % and 11.8%, respectively.

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5. Solvent extraction processing of the nitrate solution after leaching of phosphorus slag with
further precipitation of the REMs concentrate produced a concentrate, where yttrium and
heavy REMs are concentrated in ~2 times more than light and medium.

Acknowledgments

The study has been completed by means of the grant №1220 GF/4 received from the Ministry of
Education and Science of the Republic of Kazakhstan. This collaborative research was based on
the results of bilateral contacts of the Centre of Earth Sciences, Metallurgy and Ore
Beneficiation, Almaty, Kazakhstan and the Mineral-Metal Recovery and Recycling Research
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Group, Mineral Processing Division, Department of Mining Engineering, Suleyman Demirel
University, Isparta, Turkey.

List of symbols

∑REMs – total rare-earth metals

∑REMs oxides - the sum of rare earth metal oxides

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S: L –solid-to-liquid ratio

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rpm – revolutions per minute

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concrete. Key Engineering Materials, 477, 112-117.
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Qian, G., Bai, S., Ju, S., Huang, T., 2013. Laboratory evaluation on recycling waste phosphorus
slag as the mineral filler in hot-mix asphalt. Journal of Materials in Civil Engineering,
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25 (7), 846-850.
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Ralph, K. Iler., 1979. The chemistry of silica. John Wiley and Sons, New York, xxiv + 866 pp.
Figs. and tables.
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Rare-Earth Metals Market Review “BRK – Leasing” Co. Ltd. Subsidiary of Joint Stock
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Company “Development Bank of Kazakhstan”, 2007. Astana, p.42. (in Russian).

Shabanova, N.A., Sarkisov, P.D., 2004. Fundamentals of Sol-Gel Technology of Nanodispersed

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Shi, C., Qian, J., 2000. High performance cementing materials from industrial slags - A review //
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Sinegribov,V.A., Yudina, T.B., 2005. Method for Acid Decomposition of Calcium Silicate and
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Smirnov, S., 2011. Rare Metals and Earth Give a Rare Change to MMIW. International Business
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Tunsu, C., Ekberg, C., Retegan, T., 2014. Characterization and leaching of real fluorescent lamp
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Valkov, A.V.E., 1984. A method for extracting rare-earth elements from hydrate-phosphate
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higher education institutions. Intermet Engineering, Мoscow, p. 464. (in Russian).

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Yang, F., Kubota, F., Baba, Y., Kamiya, N., Goto, M., 2013. Selective extraction and recovery of
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Figure Captions:

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c) d)
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Fig. 1. Pictures of production of phosphorous slag (а) and slag disposal areas (b,c,d) of
Kazphosphate LLP (NDPhP), Zhambyl Branch.
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- СаСО 3

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Intensity

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10 20 30 40 50 60 70 80 90
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2-Theta-scale

Fig. 2. XRD analysis of the phosphorus slag.

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80

70 NU
60
1419

50
/%
Пропускание

695
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713
Transmission

40

372
779
799

30

398
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472
511

311
20
876
1083

951
1004

10
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0
1600 1400 1200 1000 800 600 400
(см-1)-1
Волновое число /cm
Wavelength
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Fig. 3. IR spectrum of the Phosphorous Slag.

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Fig. 4. Thermogram of the sample of long storage phosphorous production slag.
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Fig. 5. Thermogram of candle-end obtained from the sample of phosphorous production slag
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100

80

Recovery / %
60 Са

Al
40
Fe

REMs
20

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0
0 100 200 300 400 500 600 700 800 900

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Stirring speed / rpm

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Fig. 6. The effect of stirring intensity on recovering Ca, Al, Fe and ∑REMs 90 ºС, 7.5 mol/dm3
of HNO 3 , 1: 2.6 ratio of solid to liquid, 1 hour of experiment time.
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100 140

% HNO3 from the stoichiometric

120
80
Recovery /% 100
Са
60 80
Al

40 Fe 60

REMs 40
20
% from the 20

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stoichiometric
0 0
5 6 7 8 9 10

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HNO3 concentration / mol/dm3

Fig. 7. The effect of HNO 3 concentration on Ca, Al, Fe and ∑REMs recovery 90 ºС, 1: 2.6 ratio

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of solid to liquid, 1 hour of experiment time, 500 rpm of stirrer rotation speed.
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160
100
140

% HNO3 from the stoichiometric

80 120

Recovery /% Са 100
60
Al 80
Fe 60
40
REMs 40
20

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% from the 20
stoichiometric
0 0
1:1,5 1:3

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1:2 1:2,5 1:3,5 1:4
Solid - liquid ratio

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Fig. 8. The effect of S: L ratio in the pulp on Ca, Al, Fe and ∑REMs recovery 90 ºС, 7.5
mol/dm3 of HNO 3 , 1 hour of experiment time, 500 rpm of stirrer rotation speed.
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100

80

Recovery / % 60

40
Са

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Al
20
Fe

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REMs
0

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40 60 80 100
0
Temperature / C

Fig. 9. The effect of leaching temperature on Ca, Al, Fe and ∑REMs recovery 7.5 mol/dm3 of
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HNO 3 , 1: 2.6 ratio of solid to liquid, 1 hour of experiment time, 500 rpm of stirrer rotation speed.
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80

Recovery / %
Са
60
Fe

40 REMs

Al
20

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0 0.5 1 1.5 2 2.5

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Duration / hours

Fig. 10. The effect of the duration of leaching process on Ca, Al, Fe and ∑REMs recovery 90 ºС,
7.5 mol/dm3 of HNO 3 , 1: 2.6 ratio of solid to liquid, 500 rpm of stirrer rotation speed.
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Counts

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Energy / keV

Fig. 11. XRF spectrum of the sample of REMs concentrate.

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Degree of the element concentration

800
700
600
500
400
300
200

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Y Sc La Ce Pr Nd Sm Eu Gd Tb Ho Tm Yb Lu

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Fig. 12. The degree of concentration of rare earth metals in the concentrate.

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Phosphorus slag

GRINDING
HNO3 solution

LEACHING

FILTRATION

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REMs-containing
TBP solution Si-containing
cake
For the production

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SOLVENT EXTRACTION precipitated silicon
dioxide

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For the Raffinate Loaded organic phase
production H2 O
construction
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materials and
STRIPPING
fertilizers

Used extractant Strip liquor

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Н2 С2 О4 solution
ТBP REGENERATION
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REMs
OXALATES
PRECIPITATION
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FILTRATION

Precipitate H2 O Solution
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FLUSHING
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Precipitate
After flushing
water
CALCINATION

REMs concentrate

Fig. 13. The flowsheet on the processing of phosphorus production slag.

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Graphical abstract
The degree of concentration of rare earth metals in the concentrate
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Degree of the element concentration

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600

500

400

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200

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Y Sc La Ce Pr Nd Sm Eu Gd Tb Ho Tm Yb Lu
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Table 1 Leaching phosphorus slag by nitric acid (Karshigina et al., 2015).

Concentration in the solution
HNO 3 Recovery into solution (%)
(g/dm3 )
concentration
(%) CaO Al2 O3 Fe2 O3 ∑ REMs CaO Al2 O 3 Fe2 O 3 ∑ REMs
46.5 120.3 1.1 4.5 0.1089 99.1 96.5 96.5 98.3
58.8 101.2 0.9 3.5 0.0972 99.5 98.6 94.9 98.6
0
Note: Leaching conditions: S:L ratio =1:5, temperature = 90 С, duration = 1 hour

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Table 2 Chemical composition of phosphorus slag
Content of the phosphorus slag (wt %)
SiO 2 CaO Al2 O 3 P2 O 5 Fe2 O3 Na2 O MgO TiO2 Cl- F-
36.9 43.2 5.2 2.0 1.63 0.58 2.4 0.14 0.15 0.15

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Table 3 Phosphorus slag content of rare-earth elements

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Rare- Sc Y La Ce Pr Nd Sm Eu Gd Tb Ho Tm Yb Lu
earth

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element
ppm 4.7 213 114 105 11.6 90.9 18.8 3.8 NU 19.2 2.9 2.9 1.1 6.1 0.7

Table 4 The Gibbs energy values for the interaction reactions of phosphorous slag
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components with nitric acid.

Gibbs energy Δ GT0 (kJ/mol)

Reactions Temperature (0 С)
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50 60 70 80 90 100
α-CaSiO 3 +2HNO 3 =Ca(NO 3 )2 +SiO 2 +H2 O - - - - - -
162.2 161.5 160.8 160.0 159.2 158.3
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2CaO·3SiO 2 ·2.5H2 O + 4HNO 3 = 2Ca(NO 3 )2 + - - - - - -

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3SiO2 + 4.5H2 O 324.9 324.9 324.8 324.6 324.4 324.1

CaCO 3 + 2HNO 3 = Ca(NO 3 )2 + CO 2 + H2 O - - - - - -
120.9 121.9 122.9 123.8 124.6 125.4
CaO·Al2 O 3 ·2SiO 2 ·2H2 O + 8HNO 3 = Ca(NO 3 )2 + - - - - - -
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2Al(NO 3 )3 + 2SiO 2 +6 H2 O 388.7 382.6 376.3 369.6 362.6 355.3

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Al2 O3 + 6HNO 3 = 2Al(NO 3 )3 + 3H2 O - - - - - -

271.8 265.5 258.9 251.9 244.7 237.2
Fe2 O3 + 6HNO 3 = 2Fe(NO 3 )3 + 3H2 O - - - - - -
148.2 142.1 135.7 129.3 122.6 115.9
ScPO 4 + 3 HNO 3 = Sc3+ + 3NO 3 - + H3 PO4 - 9.2 - 6.6 - 3.9 - 1.0 2.0 5.2
YPO 4 + 3HNO 3 = Y3+ + 3NO 3 - + H3 PO4 - - - - - -
46.1 43.3 40.4 37.3 34.1 30.8
LaPO 4 + 3HNO 3 = LaNO 3 2+ + 2NO 3 - + H3 PO4 - - - - - -
108.9 105.8 102.7 99.4 96.0 92.6
LaCO 3 + + 2HNO 3 = LaNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 220.8 222.4 224.1 225.7 227.4 229.2
La2 S3 + 6HNO 3 = 2 LaNO 3 2+ +4NO 3 - + 3H2 S - - - - - -
424.9 420.1 415.1 410.1 404.9 399.6
CeH2 PO4 2+ + 2OH- + 3HNO 3 = CeNO 3 2+ + - - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 230.7 231.8 233.0 234.2 235.4 236.6
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CeCO 3 + + 2HNO 3 = CeNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 224.8 226.5 228.2 229.9 231.7 233.5
PrH2 PO 4 2+ + 2OH- + 3HNO 3 = PrNO 3 2+ + 2NO 3 - - - - - - -
+ H3 PO 4 + 2H2 O 231.4 232.5 233.7 234.8 236.0 237.2
PrCO 3 + + 2HNO 3 = PrNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 224.4 226.0 227.7 229.4 231.1 232.9
NdPO 4 +3HNO 3 = NdNO 3 2++2NO 3- + H3 PO 4 - - - - - -
106.3 103.2 100.1 96.8 93.5 90.0
NdH2 PO4 2+ + 2OH- + 3HNO 3 = NdNO 3 2+ + - - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 232.1 233.2 234.4 235.6 236.7 238.0
NdCO 3 + + 2HNO 3 = NdNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 223.9 225.6 227.3 229.0 230.7 232.4

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SmH2 PO4 2+ + 2OH- + 3HNO 3 = SmNO 3 2+ + - - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 232.5 233.6 234.8 235.9 237.1 238.3
SmCO 3 + + 2HNO 3 = SmNO 3 2+ + NO 3 - + H2 O + - - - - - -

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CO2 221.5 223.1 224.7 226.4 228.1 229.8
EuH2 PO 4 2+ + 2OH- + 3HNO 3 = EuNO 3 2+ + - - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 233.0 234.1 235.2 236.3 237.4 238.5

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EuCO 3 + + 2HNO 3 = EuNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 224.1 225.6 227.3 228.9 230.6 232.3
GdH2 PO4 2+ + 2OH- + 3HNO 3 = GdNO 3 2+ + - - - - - -
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2NO 3 + H3 PO4 + 2H2 O 231.0 232.1 233.3 234.5 235.6 236.9
GdCO 3 + + 2HNO 3 = GdNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 220.5 222.2 223.9 225.6 227.4 229.3
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TbH2 PO 4 2+ + 2OH- + 3HNO 3 = TbNO 3 2+ + - - - - - -

-
2NO 3 + H3 PO4 + 2H2 O 230.9 231.9 232.8 233.7 234.6 235.4
TbCO 3 + + 2HNO 3 = TbNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 221.2 222.7 224.2 225.8 227.5 229.1
HoH2 PO4 2+ + 2OH- + 3HNO 3 = HoNO 3 2+ +
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- - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 229.2 230.3 231.4 232.5 233.6 234.7
HoCO 3 + + 2HNO 3 = HoNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 219.2 220.8 222.4 224.0 225.7 227.4
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TmH2 PO4 2+ + 2OH- + 3HNO 3 = TmNO 3 2+ + - - - - - -

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2NO 3 -+ H3 PO4 + 2H2 O 228.3 229.3 230.3 231.3 232.4 233.4

TmCO 3 + + 2HNO 3 = TmNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 217.0 218.4 219.9 221.4 223.0 224.5
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YbH2 PO4 2+ + 2OH- + 3HNO 3 = YbNO 3 2+ + - - - - - -

2NO 3 -+ H3 PO4 + 2H2 O 228.6 229.6 230.6 231.7 232.7 233.8
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YbCO 3 + + 2HNO 3 = YbNO 3 2+ + NO 3 - + H2 O + - - - - - -

CO2 213.6 215.0 216.5 218.1 219.6 221.2
LuH2 PO 4 2+ + 2OH- + 3HNO 3 = LuNO 3 2+ + - - - - - -
2NO 3 -+ H3 PO4 + 2H2 O 230.0 230.9 231.8 232.7 233.6 234.6
LuCO 3 + + 2HNO 3 = LuNO 3 2+ + NO 3 - + H2 O + - - - - - -
CO2 212.1 213.4 214.8 216.2 217.6 219.0

Table 5. Distribution coefficients for REMs and iron in solvent extraction with tributyl
phosphate from nitrate solutions .

50 % TBP, О:A = 1: 6 100 % TBP, О:A = 1: 20

D∑REMs DFe D∑REMs DFe
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38,7 8,6 415,2 8,3

Table 6.
Effect of the O: A ratio on the REMs stripping. The concentration of ΣREMs in the loaded
organic phase is 1.028 g/dm3 .

The equilibrium concentration of ΣREMs (g/dm3 ) Recovery of

O:A ΣREMs into strip

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ratio aqueous phase organic phase liquor
(%)
2:1 2.06 2.06∙10-4 99.98

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4:1 3.83 7.02∙10-2 93.17
6:1 5.85 5.34∙10-2 94.81

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8:1 5.68 0.32 69.09
10:1 5.39 NU 0.49 52.43
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Table 7. Recovery of metals into the oxalate precipitate from the strip liquor.

Composition of the initial solution for

Recovery into the oxalate precipitate (%)
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precipitation (g/dm3 )
∑REMs Са Al Fe ∑REMs Са Al Fe
2.97 16.51 0.28 0.09 76.17 33.54 59.17 54.63
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Table 8. Composition of the obtained concentrate of ΣREMs oxides.

Concentrate content (%)

∑REMs oxides СаО Аl2 O3 Fe2 O3
17.30 59.28 2.39 0.54

Research Highlights:
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 Rare earths in phosphorus slag are present in the form of carbonate apatite

Ca10[PO4]6CO3 or rare-earth apatite impurities, and in the form of the compound

La2S3

 Under optimum conditions 85 % REMs pass effectively enough into the solution

 Small amounts rare-earth metals can be separated from the related

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macroimpurities of calcium, aluminium, and, partially, iron and concentrated by

tributyl phosphate solvent extraction.

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 Yttrium and heavy REMs are concentrated in ~2 times more than light and

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medium.


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The cake containing ~80-85% of silicon based on dioxide has been produced
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