Sie sind auf Seite 1von 8

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 9, pp. 1464−1471. © Pleiades Publishing, Ltd.

, 2015.
Original Russian Text © A.Sh. Bikmurzin, A.A. Lamberov, R.G. Romanova, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 9, pp. 1320−1328.

CATALYSIS

Preparation of Cerium Oxalate from Spent Iron–Potassium


Catalyst for Dehydrogenation of Isoamylenes into Isoprene
A. Sh. Bikmurzina, A. A. Lamberovb, and R. G. Romanovac

a Nizhnekamskneftekhim
PAO, Nizhnekamsk, Tatarstan, 423574 Russia
b Kazan
(Volga Region) Federal University, ul. Kremlevskaya 18, Kazan, Tatarstan, 420008 Russia
c Kazan National Research Technological University, ul. Karla Marksa 72, Kazan, Tatarstan, 420015 Russia

e-mail: romanova_rg@mail.ru

Received October 5, 2015

Abstract—The cerium recovery in the oxalate form from spent iron–potassium catalyst for dehydrogenation of
isoamylenes into isoprene was studied. The optimum conditions allowing preparation of the pure product with
high degree of recovery were found. It was proved by X-ray diffraction, thermal gravimetric analysis, differential
scanning calorimetry, and X-ray fluorescence analysis that the product obtained by the precipitation was cerium
oxalate decahydrate containing no less than 98 wt % main substance.
DOI: 10.1134/S107042721509013X

The reprocessing and recycling of components of to study the catalyst dissolution process, to choose the
spent catalysts is an urgent problem for both resource solvent and optimum conditions for transferring the
saving and preservation of natural ecosystems. spent catalyst into the solution, to examine the influence
One of the problems of the modern petrochemical of various chemical and process parameters on the
industry is associated with spent iron–potassium recovery selectivity and on the yield of cerium in the
catalysts used for dehydrogenation of isoamylenes and form of oxalate from the solution of the spent catalyst,
ethylbenzene in production of isoprene and styrene, and to determine the composition and purity of the
respectively. From 300 to 360 t of such spent catalysts cerium oxalate prepared by the developed procedure.
is annually formed only at PAO Nizhnekamskneftekhim
EXPERIMENTAL
[1–4]. These catalysts are systems based on iron
oxides, containing cerium and molybdenum oxides as
The investigation objects were spent iron–potassium
promoters; the cerium content is from 8 to 15 wt %.
catalysts for dehydrogenation of isoamylenes into
Disposal of the spent catalysts requires considerable isoprene. Prior to trials, the catalysts were finely
expenditures because of the need for ensuring special crushed, and the fraction with the particle size no larger
conditions for the utilization of wastes containing toxic than 0.2 mm was taken. Experiments were performed
elements: molybdenum and cerium. Because of high with the spent catalyst containing (wt %) 9.36 K2О,
cost of cerium compounds, it seems appropriate to 9.16 СеО2, 1.96 СаО, 2.01 MgO, 1.83 МоО3, and Fe3O4
recover them from the spent catalysts and return into the the remainder [5].
production process. The starting cerium compound for The solubility of the samples was studied using the
producing iron–potassium catalysts is cerium oxalate procedure described below. A flat-bottomed conical
decahydrate. flask equipped with a reflux condenser was charged
This study was aimed at developing a procedure for with the preset volume of the solvent (25–500 mL),
cerium recovery in the form of oxalate from spent iron– and the contents were heated with stirring to 85–90°С.
potassium catalyst for dehydrogenation of isoamylenes. After this temperature was reached, a ~5-g sample of
The following tasks were set to accomplish this goal: the spent catalyst, weighed on an analytical balance

1464
PREPARATION OF CERIUM OXALATE 1465

with an accuracy of 0.002 g, was added to the solvent. The phase analysis was performed with an XRD
To intensify the dissolution, the mixture in all the 7000S automatic X-ray diffractometer with independent
experiments was stirred at 300 rpm with a magnetic rotation of the sample and counter using long-wave CuKα
stirrer. The dissolution time was counted from the radiation. A graphite monochromator was placed on the
moment of adding the sample into the flask with the diffracting beam. The interval of recording 2θ angles
solvent. The experiment time and catalyst : solvent ratio was 5°–95° with a step of 0.5°. The X-ray diffraction
were different in different experiments, depending on the patterns were recorded under the following conditions:
degree of dissolution. After the experiment completion, 30 kV, 15 mA, exposure time 3 s. The phases were
the solution was filtered off, and the filter was washed identified from the interplanar spacings by comparison
with 100 mL of distilled water. The filter with the with data from the ASTM file and databases [6].
residual amount of the catalyst was dried in an oven at The thermal behavior under dynamic conditions
105°С to constant weight. The degree of dissolution was and the kinetics of thermal decomposition under
determined as the percent ratio of the difference between nonisothermal conditions were studied with an SТА-
the initial catalyst weight and weight of the catalyst 449C Jupiter synchronous thermal analyzer (Netzsch,
remaining on the filter to the initial catalyst weight. Germany) with a coupled QMS 403 Aeolos quadrupole
Cerium oxalates were prepared from solutions of the mass spectrometer. The samples were heated from
spent catalysts in hydrochloric acid as follows. A heat- room temperature to 1000°С at a rate of 10 deg min–1
resistant beaker was charged with 50 mL of concentrated in platinum crucibles with punched lids. The analysis
hydrochloric acid, and a portion of catalyst, finely was performed in an argon atmosphere. The temperature
divided, dried to constant weight, and weighed on an was measured with a platinum/platinum–rhodium
analytical balance, was added. The weighed portion of thermocouple. The resolution of the analytical balance
the catalyst was dissolved at Т = 65°С with stirring within was 0.1 μg, and the accuracy of determining the weight
5 min. Then, distilled water was added to the resulting loss was ±0.5%. The thermostat of the gravimetric unit
solution in a volume equal to the volume of hydrochloric ensured the temperature stability on the level of ±0.03°C.
acid taken for the dissolution, and the solution was The bulk density was determined in accordance
evaporated to the initial volume. After cooling to room with GOST 16190–70. The mean result of two replicate
temperature, the required pH was adjusted by adding measurements whose results differed by no more than
the required volume of the neutralizing agent, and the 0.1 g cm–3 was taken as the test result. The overall
product was precipitated at 95°С by successive addition uncertainty of the measurement result was 0.06 g cm–3
of СаСl2 and oxalic acid solutions. After stirring for 3 h, at the confidence level of 0.95.
the solution with the precipitate was left to crystallize The weight loss on ignition (LOI, wt %) was
for 8–12 h at room temperature. After crystallization, determined in accordance with GOST 26318.14–84.
the precipitate was filtered off on a vacuum filter and The degree of cerium recovery was determined as
washed in succession with a 1% oxalic acid solution and the percent ratio of the cerium dioxide weight in the
with distilled water. The resulting cerium-containing calcined product to the cerium dioxide weight in the
product was dried in an oven at 90°С to constant weight. catalyst taken for the recovery.
After cooling to room temperature, the loss on ignition
at 850°С was determined, and the product was analyzed RESULTS AND DISCUSSION
by X-ray fluorescence analysis. The composition of
cerium oxalate was determined after calcination of the Taking into account the composition and relevant
sample at 850°С to constant weight. chemical properties of the spent catalyst samples, we
The sample compositions were determined by X- chose solvents for transferring the catalysts into the
ray fluorescence analysis. The measurements were per- solution for the subsequent precipitation of cerium
formed with a СleverС-31 spectrometer in accordance salts. We examined the capability of the catalysts
with GOST (State Standard) 28033–89. An X-ray tube to dissolve in concentrated and diluted solutions of
with a rhodium anode served as X-ray radiation sources. mineral acids (nitric, hydrochloric), in solutions of
The maximal voltage was 50 kV, and the current was organic acids (oxalic, citric), and in solutions of sodium
1000 μA. ethylenediaminetetraacetate (EDTA), which acts as

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


1466 BIKMURZIN et al.

Table 1. Conditions and results of dissolution of the spent catalyst, ω(СеО2) = 9.16 wt %
Weight of residue Degree of
Solvent S/L ratio, g mL–1 Process time, min after dissolution, g dissolution, %

Nitric acid:
concentrated 1/16 300 0.251 95
diluted (1 : 1) 1/16 300 3.502 30
Hydrochloric acid:
concentrated 1/5 2 0 100
1/4 3.5 0 100
diluted (1 : 1) 1/5 30 3.008 40
Oxalic acid (20% solution) 1/15 120 2.497 50

Citric acid (20% solution) 1/100 120 4.550 9


EDTA (12% solution) 1/100 120 1.511 70

complexing agent for the sample components. The Therefore, we chose the 1 : 5 ratio as optimum and used
solution concentrations were chosen on the basis of the it in the further experiments.
maximum solubility of the substances at 50°С. To optimize the dissolution of the spent catalyst in
The results of the experiments on studying the hydrochloric acid, we performed a series of experiments
solubility of the spent catalyst samples are given in for choosing the dissolution temperature. The dissolution
Table 1. time was counted from the moment of introducing the
As seen from Table 1, the best solvent is concentrated catalyst weighed portion into the heated solution with
hydrochloric acid, in which the spent catalyst dissolved the fixed temperature. The results of experiments are
completely. The advantages of this acid as solvent are shown in Fig. 1a, from which it is seen that the rate of
high dissolution rate and relatively low acid consumption the catalyst dissolution in concentrated hydrochloric
for complete dissolution of the sample. It should be noted acid increases with temperature.
that, in the experiment with 1 : 4 ratio of the catalyst Analysis of the differential dependence of the
weight to the hydrochloric acid volume, a precipitate dissolution rate on the dissolution temperature,
formed on cooling the solution to room temperature. ∆V/∆T–T (Fig. 1b), shows that the dependence has a

V, g min–1 (a)
(b)

T, °C T, °C

Fig. 1. (a) Dissolution rate V as a function of sample dissolution temperature T and (b) differential form of this dependence.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


PREPARATION OF CERIUM OXALATE 1467

Table 2. Effect of neutralizing agent on the yield and selectivity of precipitation of cerium oxalate
Neutralizing agent and its Precipitate characteristics
characteristics Degree of
Sample СеО2
no. composition, wt % recovery,
volume, weight,
agent ω, wt % LOI, wt % %
mL g
Fe2О3 CeО2 K2О

1 KОН 0.5 200 0.51 47.59 79.0 6.30 11.3 13.7

2 KОН 3.0 140 10.78 68.16 87.5 0.50 12.0 1.1

3 NH4OH 25 40 3.50 70.33 7.20 92.7 – 62.5

4 NH4OH 12.5 58 3.50 70.55 10.0 90.0 – 60.3

maximum at 65°С; this temperature was chosen as pH of the solution, precipitation temperature, and other
optimum for performing the dissolution. An increase process parameters influence the selectivity and degree
in the temperature over 65°С leads to fast evaporation of cerium recovery from the spent iron–potassium
of hydrochloric acid and to subsequent formation of catalysts.
the solid phase as a result of a decrease in the solvent Solutions of alkalis, weak bases, and alkali metal
volume. carbonates are suitable as neutralizing agents for pH
The next step of the studies was the choice of adjustment and subsequent precipitation of the oxalates.
a procedure and conditions for recovery of cerium Because it was planned to return the precipitated cerium
compounds from solutions formed upon dissolution of oxalate into the catalyst production cycle, the choice
the spent catalyst samples in hydrochloric acid. was limited to KОН and NH4OH solutions, as sodium
Taking into account complex composition of the compounds are catalytic poisons for the dehydrogenation
solution containing mainly iron(III) compounds, we of isoamylenes into isoprene [1–4] and, therefore, the
chose the cerium precipitation in the form of poorly use of sodium-containing solutions is inadmissible.
soluble oxalate as the best method for cerium recovery. To determine how neutralizing agents influence the
Another significant factor governing this choice is the fact precipitation of cerium oxalate, we performed a series of
that specifically cerium oxalate is used as raw material experiments using the above compounds and taking them
in production of iron–potassium dehydrogenation in different concentrations. The weight of the samples
catalysts, which can allow the cerium recycling in the for dissolution in hydrochloric acid was 10–11 g, the
production process. precipitation was performed at pH 4.0, and excess acid
Precipitation of poorly soluble cerium oxalates was not removed from the solution. The results of the
was used in [7–9] for the purification and isolation of experiments are given in Table 2, which shows that the
cerium from a mixture of rare earth elements. However, most suitable neutralizing agent is an NH4OH solution,
studies on cerium recovery from the catalysts under because in this case the yield and purity of the cerium-
consideration were not performed previously, probably containing product are the highest.
because of complex and multistep character of the For further studies, we chose a 12.5% NH4OH
process. solution, because with more concentrated solutions it is
The choice of the conditions for the precipitation difficult to adjust the required pH value.
and subsequent crystallization of cerium oxalates from Dissolution of the spent catalyst in concentrated
solution obtained by dissolving the spent catalyst in hydrochloric acid requires excess acid; it, however, makes
hydrochloric acid determines the yield and purity of the conditions for cerium precipitation unfavorable. In
the product. Therefore, we studied how the kind and addition, large amounts of chemicals are required for the
concentration of the neutralizing agent and precipitants, solution neutralization. Therefore, it appears necessary

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


1468 BIKMURZIN et al.

Table 3. Precipitation conditions and characteristics of cerium-containing products


Characteristics of cerium-containing product Degree
Sample Dilution of cerium
no. factor composition, wt % recovery,
color bulk density, g cm–3 LOI, %
Fe2О3 CeО2 CaО %

5 0.0 Grey 0.81 55.19 24.40 72.09 3.51 69.9


6 0.5 '' 0.80 53.50 15.67 82.22 2.11 72.0
7 1.0 White 0.75 54.15 6.81 92.11 1.08 88.9
8 1.5 '' 0.75 54.00 3.00 96.25 0.75 90.1
9 2.0 '' 0.74 53.07 0.46 99.00 0.54 92.1
10 2.5 '' 0.75 53.05 0.73 98.65 0.62 91.9
11 3.0 '' 0.74 53.15 0.87 98.51 0.62 91.6

to remove excess acid from the solution. As noted be seen, the highest degree of cerium oxalate recovery
previously, simple evaporation of excess acid leads to is reached at pH in the interval 4.0–4.5. Under these
the formation of salts owing to a decrease in the solution conditions, the solubility of cerium oxalate reaches a
volume. Therefore, we suggested addition of a certain minimum; therefore, the product precipitation is the
amount of desalinated water to the solution, followed by most complete, and the product contains the smallest
evaporation to the initial volume. amount of impurities. A more detailed study of this pH
To determine the optimum conditions for the removal interval showed that the highest yield and highest purity
of excess hydrochloric acid from the solution, we studied of the product were reached at pH 4.4. This pH value
how the volume of water added to the hydrochloric was taken as optimum for the precipitation.
acid solution influences the degree of cerium recovery To determine the optimum time for the deposition of
in the form of oxalate. After the sample dissolution, cerium oxalate, we performed a series of experiments by
distilled water was added to the solution in different the above-described procedure. The precipitation was
ratios to hydrochloric acid taken for the dissolution. The performed at рН 4.4. The precipitation time was varied
resulting solution was evaporated to the initial volume from 2 to 24 h. The dependence of the cerium oxalate
and, after cooling to room temperature, neutralized weight on the precipitation time is shown in Fig. 2.
with an aqueous ammonia solution (weight fraction of
ammonia 12.5%) to pH 4. The precipitation conditions As seen from Fig. 2, an increase in the precipitation
and characteristics of cerium oxalates obtained under time favors an increase in the precipitate weight up
these conditions are given in Table 3. to a certain moment (8 h), after which no changes
are observed, as the cerium oxalate recovery reaches
As seen from Table 3, the highest degree and
a maximum. Thus, 8 h is sufficient for the maximal
selectivity of the cerium recovery were reached with
precipitation.
sample nos. 9–11, i.e., starting from twofold and higher
dilution. Because an increase in the degree of dilution To evaluate the validity of the developed procedure
leads to an increase in the process time and in the power under the chosen optimum conditions, we prepared
consumption, we chose as optimum the twofold dilution cerium oxalate samples from spent iron–potassium
of the hydrochloric acid solution prior to neutralization. catalysts taken in increased amount (100 g).
To examine the influence of the solution acidity on The results of the experiments (Table 5) demonstrate
the selectivity and degree of precipitation, we performed high degree of the cerium recovery, which is in the
a series of experiments in which the cerium oxalate interval 93.5–95.3%. The oxalates obtained from
precipitation was performed at different pH values. the spent catalyst are finely dispersed white powders
The results obtained are presented in Table 4. As can containing more than 98.50% cerium dioxide in the

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


PREPARATION OF CERIUM OXALATE 1469

calcined sample (Table 5), which suggests their high m, g


purity.
The diffraction patterns of all the samples are
virtually identical. A typical diffraction pattern is shown
in Fig. 3. The presence of reflections corresponding to
the interplanar spacings of 10.31, 7.05, 6.77, 6.63, 5.21,
and 5.01 Å [6] allows unambiguous identification of
the precipitation product as cerium oxalate decahydrate
Се2(С2О4)3·10Н2О. The diffraction patterns contain
no unidentified peaks, which indicates that the sample τ, h
contains no crystalline compounds of other compositions.
Fig. 2. Influence of the precipitation time τ on the weight of
The temperature-programmed heating of the sample the precipitated cerium oxalate.
dried at 90°С is accompanied by the appearance of
four endothermic effects in the DTA curve, caused by
thermal desorption of physically and chemically bound from the data of thermal analysis. As determined from
water, by the evolution of carbon dioxide, and by data of X-ray fluorescence analysis of the calcined
complete decomposition of the product to the oxide in oxide precipitate, the content of cerium dioxide in it
the temperature intervals 117–200, 370–394.3, 394.3– is 98.6 wt %; hence, 100 mg of the precipitate should
531.5, and 531.5–639.2°С and total weight loss of contain 98.6 mg of the cerium salt, or 0.136 mmol of
53.86 wt % (Table 6). Ce2(C2O4)3·10H2O. Hence, the molar ratio of the cerium
The first endothermic effect at 161°С corresponds salt and removed water is 0.136 : 1.35 ≈ 1 : 10. This
to the removal of physically adsorbed (up to 100°С) result proves that the salt is cerium oxalate decahydrate.
and chemically bound (117–200°С) water. Because the The subsequent endothermic effects with the minima at
sample was dried to constant weight, physically adsorbed 410, 503, and 584°С correspond to the decomposition
water was removed virtually completely. Therefore, the of cerium oxalate with the evolution of carbon dioxide.
weight loss in this temperature interval can be attributed In this step, the sample loses 29.52 wt %, or 0.67 mmol
to the removal of water of hydration. In this step, the of СО2. The residue after the decomposition is cerium
sample weight loss is 24.34 wt %, which corresponds dioxide. Its amount corresponds to 47.48 wt %, or
to 1.35 mmol of Н2О per 100 mg of the precipitate. 0.26 mmol of CeO2 per 100 mg of the precipitate.
Proceeding from the assumption that the cerium- Thus, 1.9 (or approximately 2) mol of cerium dioxide is
containing product is cerium oxalate decahydrate, we formed from 1 mol of Ce2(C2O4)3·10H2O upon thermal
can calculate the actual composition of the product decomposition.

I, arb. units Ce(CO)


Ce2(C2O4)·10H2O

2θ, deg
Fig. 3. Diffraction pattern of the cerium-containing products, with the interplanar spacings (Å) indicated (sample no. 20). (I) Intensity
and (2θ) Bragg angle.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


1470 BIKMURZIN et al.

Table 4. Influence of pH of solution before precipitation on the yield and purity of cerium oxalate
Precipitate characteristics
Degree
Sample рН composition, wt % of CeO2
no. weight, g LOI, % recovery, %
CeО2 Fe2О3 СаО

12 2.50 2.00 69.17 26.0 70.6 3.4 10.4


13 3.00 3.60 73.58 71.0 27.2 1.8 43. 9
14 3.50 3.10 66.21 91.4 6.3 2.3 62.2
15 4.00 3.44 58.39 98.0 – 2.0 90.2
16 4.40 3.10 53.07 98.7 0.9 0.4 93.3
17 4.50 3.15 54.00 97.0 1.4 0.6 91.3
18 5.00 3.30 60.52 31.5 67.0 1.5 26.7
19 6.00 3.50 70.33 92.7 6.4 0.8 62.6

Table 5. Degree of cerium recovery and characteristics of cerium-containing precipitation products


Calcined sample composition, wt % CeO2
Sample Degree of CeO2 Bulk density, LOI, wt % content,
no. recovery, % g cm–3 Fe2О3 CeО2 CaО wt %

20 94.4 0.745 53.00 0.65 98.83 0.52 14.32


21 95.3 0.748 53.12 0.97 98.52 0.51 14.37
22 93.5 0.749 53.05 0.99 98.53 0.48 14.44
23 93.8 0.747 53.09 0.90 98.60 0.50 14.37
24 93.9 0.760 53.55 0.86 98.50 0.64 14.50

The decomposition of cerium oxalate is described by CONCLUSIONS


the equation [7]:
(1) The effect of various factors on the selectivity and
Се2(С2О4)3·10Н2О +2О2 → 2CeO2 + 6СО2↑+ 10Н2О. yield of cerium recovery was studied, and the process
for preparing cerium oxalate from spent iron–potassium
The calculated amounts of products formed by dehydrogenation catalysts was simplified. The degree
thermal decomposition of 1 mol of cerium oxalate of cerium recovery from spent iron–potassium catalysts
and the composition and physicochemical characteristics
decahydrate are 10 mol of Н2О, 6 mol of CO2, and
of the precipitation products are well reproducible,
2 mol of СeO2.
confirming the validity of the developed technology.
Comparison of the calculation results with the (2) Examination of the precipitated product by
actual data (Table 6) shows that the thermal behavior X-ray diffraction analysis, thermal gravimetric
of the product obtained from the spent iron–potassium analysis, differential scanning calorimetry, and X-ray
dehydrogenation catalyst is consistent with the published fluorescence analysis shows that the product is cerium
data, and the composition corresponds to cerium(III) oxalate decahydrate containing no less than 98 wt %
oxalate decahydrate. main substance. The impurities are iron and calcium

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015


PREPARATION OF CERIUM OXALATE 1471

Table 6. Calculated and experimental values of weight loss in the course of thermal decomposition (DTA/TGA data) of cerium
oxalate

Weight loss in the temperature interval Δm, wt %


Temperature interval of
actual calculated Peak assignment
endothermic effects, °C
% mmol % mmol

117–200 24.34 1.35 24.84 1.36 H2O removal


370–394.3
Decomposition with CO2
394.3–531.5 29.52 0.64 28.15 0.67
evolution
531.5–639.2

oxides. These compounds are not catalytic poisons in 5. RF Patent 2504594, Publ. 2014.
dehydrogenation of isoamylenes into isoprene. Hence, 6. Crystallography Open Database, http://database.iem.ac.ru/
this product can be used as starting component in mincryst/rus/http://sdpd.univ-lemans.fr/cod (free access).
production of iron–potassium catalysts, which opens 7. Komissarova, L.N., Shatskii, V.M., Pushkina, G.Ya., et al.,
prospects for cerium recycling in the production process. Soedineniya redkozemel’nykh elementov. Karbonaty,
oksalaty, nitraty, titanaty (Compounds of Rare Earth
REFERENCES Elements. Carbonates, Oxalates, Nitrates, Titanates),
Moscow: Nauka, 1984.
1. Lamberov, A.A., Gil’manov, Kh.Kh., Dement’eva, E.V.,
et al., Katal. Prom–sti., 2007, no. 6, pp. 18–25. 8. Khimiya i tekhnologiya redkikh i rasseyannykh elementov
2. Gil’manov, Kh.Kh., Lamberov, A.A., Dement’eva, E.V., (Chemistry and Technology of Rare and Trace Elements),
et al., Inorg. Mater., 2008, vol. 44, no. 1, pp. 89–94. Moscow: Vysshaya Shkola, 1976, vol. 2.
3. Lamberov, A.A., Gil’manov, Kh.Kh., Shatokhina, E.V., 9. Ryabchikov, D.I. and Ryabukhin, V.A., Analiticheskaya
et al., Katal. Prom–sti., 2008, no. 1, pp. 20–26. khimiya redkozemel’nykh elementov i ittriya (Analytical
4. Gil’manov, Kh.Kh., Lamberov, A.A., Shatokhina, E.V., Chemistry of Rare Earth Elements and Yttrium), Moscow:
et al., Russ. J. Appl. Chem., 2008, vol. 81, no. 2, pp. 212–217. Nauka, 1966.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 9 2015