International Journal of Innovative Technology and Exploring Engineering (IJITEE)

ISSN: 2278-3075, Volume-8, Issue- 9S2, July 2019

Research on the Carbonization Process of

Potassium Chloride Solutions in the Presence of
Diethylamine
Bobokulov Akbar Nosirovich, Erkaev Aktam Ulashevich, Kucharov Bakhrom Khayrievich,
Toirov Zakir Kalandarovich

Abstract-: BACKGROUND: Currently in the country there is the preparation of liquid and solid carbon dioxide, in
no production of potassium carbonates, which, as a rule, they are construction and agriculture. Despite the presence of
purchased in the CIS countries. At the same time, there has potassium chloride deposits, potash production is absent.
explored sufficient reserves of potassium-containing raw
In this work, we studied the possibility of an amine
materials, which, according to technological, economic and, most
importantly, rational utilization levels, will provide an method for obtaining potash from local raw materials —
opportunity to get their own potassium carbonate to ensure potassium chloride, produced at the UE “Dekhkanabad
internal and external consumption markets. Potash Fertilizer Plant” (UE “DPFP”), and carbon dioxide,
In this regard, the development of a method of producing which is waste of nitrogenous production.
potash based on local raw materials is currently actual. This method of obtaining potash is based on the
RESULTS: The process of obtaining potassium bicarbonate by carbonization under pressure of a solution of potassium
the amine method has been studied for the first time. The optimal chloride in the presence of diethylamine NH (R)2.
process parameters were established: ΔP = 2 atm, duration - 45
min. KCl+ NH(R)2+CO2+H2O=KHCO3+ NH(R)2*HCl
CONCLUSION: The study found that the resulting potassium When it is cooled, crystalline KHCO3 precipitates and it
bicarbonate precipitates quickly from the suspension and is easily is easily separated from diethylamine hydrochloride
filtered, which allows us to recommend the use of existing solution. The latter is again converted to free diethylamine
standard thickeners and filtering plants with a minimum working by the reaction.
surface. NH(R)2*HCl+Са(ОН)2= NH(R)2+СаСl2+2H2O
Keywords: potassium bicarbonate, potassium chloride, amine,
carbonization, method..
II. CARBONIZATION PROCESS OF POTASSIUM
I. INTRODUCTION CHLORIDE SOLUTIONS IN THE PRESENCE OF
DIETHYLAMINE
Prospects for the use of potassium carbonates, in
particular, as chlorine-free potassium mineral fertilizers, The experiments were carried out in a laboratory setting
consisting of a cylindrical metal reactor with a heat-
create certain conditions for the organization of their
exchange jacket, equipped with a barbater and temperature
production in the country. There is currently no production
of potassium carbonates, which, as a rule, they are and pressure sensors in the reaction zone. The starting
purchased in the CIS countries. At the same time, there has material used was potassium chloride UE DPFP, reactive
proven reserves of potassium-containing raw materials, DEA, carbon dioxide and water. In the experiments, the
which, according to technological, economic and, most calculated amount of potassium chloride, diethylamine
(DEA) and water was fed into the carbonization reactor and
importantly, rational utilization levels, will provide an
carbon dioxide was passed in for 5-40 minutes at a given
opportunity to get their own potassium carbonate to provide
domestic and foreign consumption markets 1-2. pressure. The kinetics of temperature change in the reaction
All existing industrial methods for the production of mass was fixed by thermometer.
potassium carbonate can be divided into two groups. The
first group of schemes is based on the production of III. METHODOLOGY
potassium bicarbonate (KHCO3), similar to the ammonia The experiments were carried out in a laboratory setting
method of producing soda by carbonization of potassium consisting of a cylindrical metal reactor with a heat-
chloride (KC1) in the presence of various aliphatic amines exchange jacket, equipped with a barbater and temperature
and their salts 4-5. and pressure sensors in the reaction zone. The starting
Potash is used in the manufacture of glass, from high- material used was potassium chloride Ltd. DPP, reactive
grade grades of which medical, optical, electro vacuum, art DEA, carbon dioxide and water. In the experiments, the
glass, and also crystal. Potash is employed for the synthesis calculated amount of potassium chloride, diethylamine
of certain salts, liquid potassium salt, synthetic detergents, in (DEA) and water was fed into the carbonization reactor and
carbon dioxide was passed in for 5-40 minutes at a given
pressure. The kinetics of temperature change in the reaction
Revised Manuscript Received on July 18, 2019. mass was fixed by thermometer.
Bobokulov Akbar Nosirovich, Tashkent chemical-technological
institute, 32, Navoi Str., Tashkent, Uzbekistan
Erkaev Aktam Ulashevich, Tashkent chemical-technological institute,
32, Navoi Str., Tashkent, Uzbekistan
Kucharov Bakhrom Khayrievich, Tashkent chemical-technological
institute, 32, Navoi Str., Tashkent, Uzbekistan
Toirov Zakir Kalandarovich, Tashkent chemical-technological
institute, 32, Navoi Str., Tashkent, Uzbekistan

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DOI : 10.35940/ijitee.I1048.0789S219 237 & Sciences Publication
 RESEARCH ON THE CARBONIZATION PROCESS OF POTASSIUM CHLORIDE SOLUTIONS IN THE
PRESENCE OF DIETHYLAMINE
The samples visualization was conducted on a A further increase in the rate of DEA to 147% slightly
microscope (Leica, Germany) controlling with computer. increases the yield of bicarbonate. For example, at a
The optical system of the Leica DM500 microscope pressure of CO2 of 2 kgf / cm2, the rate of DEA from 100 to
includes a lens, an eyepiece and a lighting device - a 133%, the yield of KHCO3 increases by 14.4%. A further
condenser with a diaphragm with a light filter and an increase in the norm to 147% increases the product yield by
electric illuminator. A Leica DM500 optical binocular only 2.64%. In the figure, the AB line shows the optimal
microscope gives an increase in the range of 4 to 100 times. CO2 pressure, which ensures the maximum yield of
The magnifications of the lens are indicated by numbers on potassium bicarbonate at the given DEA norms.
the handle - x4, x10, x40, x100. From Fig. 2 (a) it is seen that with an increase in the DEA
The thermal stability of the studied crystal samples was rate, the yield of potassium bicarbonate passes through a
determined on a Netzsch Simultaneous Analyzer STA 409 maximum at a rate of 148%, and its further increase leads to
PG instrument, with a K-type thermocouple (Low RG a decrease in product yield.
Silver) and aluminum crucibles. All measurements were < Figure 2 (a) near here >
carried out in an inert nitrogen atmosphere with a nitrogen From Fig. 2 (b) it can be seen that at ΔP-2 atm and a rate
flow rate of 50 ml / min. The temperature range of of 147% within 8-9 minutes, the yield reaches more than
measurements was 25-400 ° C, the heating rate was 5K / 63% and a further increase in the duration to 24 and 40
min. The amount of sample per measurement is 5-6 mg. The minutes increases the degree of yield by 15 and 8%,
measuring system was calibrated with a standard set of respectively. It is necessary to take into account that with an
substances KNO3, In, Bi, Sn, Zn, CsCl. increase in the duration of the process losses CO2 increase
Samples were identified on the basis of diffraction proportionally.
pattern, which were recorded on a XRD-6100 apparatus < Figure 2 (b) near here >
(Shimadzu, Japan), controlling with computer. CuKα- At the optimizing of the parameters of the technology for
radiation (β-filter, Ni, 1.54178 mode of the tube current and producing potassium bicarbonate, the process of separating
voltage 30 mA, 30 kV) and a constant rotational speed of is of no small importance in the resulting product from the
the detector of 4 deg / min with a step of 0.02 deg were carbonized suspension, which was studied by decanting and
used. (ω / 2θ-clutch), and the scanning angle was changed filtering (Figure 3.4 and Table 2).
from 4 to 80o. < Figures 3,4 near here >
< Table 2 near here >
IV. RESULTS AND DISCUSSION Decantation was carried out in a 500 ml measuring
The separation of potassium bicarbonate crystals was cylinder with visual observation of the kinetics of changes in
carried out by decantation with further filtration of the the transparent part.
thickened part and the initial suspension. The chemical At a DEA rate of 57% for 60 seconds, the degree of
composition of potassium bicarbonate and the filtrate was clarification of the suspension reaches to 51%, the
determined by chemical analysis methods. The yield of maximum of which 65% is reached after 120 minutes and
potassium bicarbonate was calculated and the changes in pH then the precipitation process ends in practice (Figure. 3).
and density of the liquid phase were determined depending < Figure 3 near here >
on the value of the technological parameters. With an increase in the DEA rate to 100% or more
From the data in the Table 1 it is seen that with an compared to the 57% rate, the degree of precipitation
increase in the DEA rate from 53 to 147%, the pH of the sharply decreases from 65 to 20-22% with the same duration
reaction mass increases from 8.35 to 9.31. Increasing the of settling. The maximum degree of deposition reaches
pressure at the same rates of DEA also leads to an increase 43.45, 37.3 and 41.17%, respectively, with the norms of
in pH, for example, with an increase in pressure from 0.5 to 100, 133 and 147% DEA for 300 seconds.
2 kgf / cm2, the pH of the reaction mass increases from In Figure 3, the kinetic curve of the dependence of the
9.04; 9.14; 9.21 to 9.14; 9.25; 9.31, respectively, at the rate degree of deposition consists of a straight and curvilinear
of DEA 100, 133, 147%. The density of the liquid phase has segment, which is explained by the course of the process in
the same dependence on technological parameters and varies two stages. In the first stage, free crystallization occurs with
in the intervals of 1.044-1.085 g / cm3. overcoming the resistance of only the liquid phase, which
It can be seen in the table and figure. 1 that the yield of explains the constant deposition rate. The second stage is
potassium bicarbonate is clearly influenced by the rate of characterized by overcoming the additional resistance of the
DEA and the carbon dioxide supply pressure. At 100% DEA layer, which increases over time, which causes a decrease in
rate, an increase in CO2 pressure up to 3 kgf / cm2 the deposition rate until the advancement of the upper layer
practically does not affect the yield of KHCO3, and its of sediment stops.
further increase to 4 kgf / cm2 reduces the output of The duration of the transition of the first stage to the
potassium bicarbonate from 69.0% (at 2 kgf / cm2) to 64, second is limited by the line AB, which shows that with an
46%. This is due to the increase in the degree and blowing increase in the DEA rate, the duration of the first stage
of the DEA from the gas phase. Increasing the DEA rate to increases from 60 to 300 seconds simultaneously with a
133% provides an increase in the yield of KHCO3 as decrease in the deposition rate from 51 to 37.3% (Figure 3).
compared with the 100% DEA rate, especially at pressures
above 2 kgf / cm2 (Figure. 1, curve 2).
< Figure 1 near here >
< Table 1 near here >

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DOI : 10.35940/ijitee.I1048.0789S219 238 & Sciences Publication
 International Journal of Innovative Technology and Exploring Engineering (IJITEE)
ISSN: 2278-3075, Volume-8, Issue- 9S2, July 2019

< Figure 3 near here > VI. LIST OF CAPTIONS

Isochrones were conducted at 30; 60; 120 and 240 sec for Figure 1. The change in the degree of yield of potassium
a more accurate elucidation of the influence of the DEA bicarbonate depending on the pressure of carbon dioxide
rates on the settling stage (Fig.4), which showed that the and the norm of DEA. Norm DEA, %: 1-100, 2-133, 3-147.
dependence on the norms for the degree of deposition has a Figure 2 (a, b). Change in the degree of potassium
complex wave-like dependence. bicarbonate yield depending on the carbon dioxide pressure
< Figure 4 near here > (a) and the process duration (b).
A wide practically stable zone of minimum isochrone is Figure 3. Kinetics of precipitation of potassium
observed in the intervals of the DEA rate of 100-150%. bicarbonate suspension. Norma DEA,%:1-57, 2-100, 3-
With an increase in the duration of settling, the wave-like 133, 4-147.
change in the isochrone gradually levels off and after 300 Figure 4 Change the degree of deposition depending on
seconds, curve 5 passes into a smooth curve in practice with the rate of DEA. Isochranes, sec: 1-30, 2-60, 3-120, 4-240,
shallow minima of the corresponding DEA-100-150% rates. 5-300.
The table shows that with an increase in the rate of DEA Figure 5. Thermogram of potassium bicarbonate sample
from 100 to 147%, the filtration rate of the suspension by No. 8 tab.2
the solid and by the liquid phase increases from 417.3; Figure 6 Radiograph of the product of potassium
921.97 and 1290.04; 2789.4 to 8950.8; 2867.17 and bicarbonate obtained under the conditions of the experience
3098.92; 7462.34 kg / m2 * h, respectively, at a carbon 8 tab.2.
dioxide pressure of 0.5 and 2.0 kgf / sm2.
The resulting graph based on thermal analysis will show
that on the curve of digestion of the obtained sample of Fig.
5, two endothermic peaks are observed. The first Tmax =
125.8oC corresponds to the melting of the sample, the
second Tmax = 181.6oC – to the decomposition of the
sample with a maximum rate of 5% / min. The total mass
loss during decomposition is 29%. The total activation
energy is ∆Q = - 703.4 J / g.
The resulting potassium bicarbonate is identified by X-
ray and microscopic methods. According to the X-ray
analysis of Fig. 6, that the obtained sample (Table 2,
experiment 8, Figures 5,6) contain potassium bicarbonate
and potassium chloride; which correspond to characteristic Figure 1. The change in the degree of yield of
peaks; KHСO3 - 2.953, 2.846, 2.614 and KCl - 3.125, potassium bicarbonate depending on the pressure of
2.214. carbon dioxide and the norm of DEA. Norm DEA, %: 1-
< Figures 5,6 near here > 100, 2-133, 3-147.
< Table 2 near here >
As shown by X-ray analysis of the samples with a single
sprinkling with growth of potassium bicarbonate with a ratio
of L:S 1÷1, the residual potassium chloride is 5.05. It is
recommended to increase L:S more than 1.5.

V. CONCLUSION
Thus, on the basis of the foregoing, the optimal
conditions for obtaining potassium bicarbonate are the rate
of DEA –140%, the pressure in the reaction zone is 2.3–3.1
kgf / cm2, the process takes 25 minutes with a product yield
of more than 86%.
It was also found that the resulting potassium bicarbonate Figure 2 (a, b). Change in the degree of potassium
precipitates quickly from the suspension and is easily bicarbonate yield depending on the carbon dioxide
filtered, which allows us to recommend the use of existing pressure (a) and the process duration (b).
standard thickeners and filtering plants with a minimum
working surface. The influence of the DEA rates, the
pressure of carbon dioxide and the duration of the
carbonization process of a mixture of solutions of potassium
chloride and DEA was studied. The optimal technological
parameters were established: ΔP-2 atm, the norm - 140%,
the process duration - 25 minutes. The degree of output of
potassium bicarbonate reaches to more than 86%.

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DOI : 10.35940/ijitee.I1048.0789S219 239 & Sciences Publication
 RESEARCH ON THE CARBONIZATION PROCESS OF POTASSIUM CHLORIDE SOLUTIONS IN THE
PRESENCE OF DIETHYLAMINE

Figure 6. Radiograph of the product of potassium

bicarbonate obtained under the conditions of the
Figure 3. Kinetics of precipitation of potassium
experience 8 tab.2.
bicarbonate suspension. Norma DEA,%:1-57, 2-100, 3-
Table 1
133, 4-147.
The influence of technological parameters on the
process of carbonization of a solution of potassium
chloride in the presence of DEA

Figure 4. Change the degree of deposition depending

on the rate of DEA. Isochranes, sec: 1-30, 2-60, 3-120, 4-
240, 5-300.
Table 2
The influence of technological parameters on the
filtration rate of the suspension

Figure 5. Thermogram of potassium bicarbonate

sample No. 8 tab.2

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 International Journal of Innovative Technology and Exploring Engineering (IJITEE)
ISSN: 2278-3075, Volume-8, Issue- 9S2, July 2019

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DOI : 10.35940/ijitee.I1048.0789S219 241 & Sciences Publication