Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 5/8 ( 113 ) 2021

UDC 662.767.2:636.5/.6
Ammonia has great prospects in the context of the
transition to carbon-free energy. It can be used as fuel DOI: 10.15587/1729-4061.2021.243068
in gas turbines, fuel cells, internal combustion engines,
and burned together with coal. However, industrial pro-
duction of ammonia is based on the Haber-Bosh process,
which involves the use of natural gas and coal, which, in DEVELOPMENT
this case, does not make it really carbon-free. This study
proposes a method to produce ammonia, which is envi- OF AN AMMONIA
ronmentally friendly and does not require the use of fos-
sil fuels. It is based on the approach to adjusting the con-
centration of ammonium nitrogen in a biogas reactor and
PRODUCTION METHOD
implies the sorption of ammonia from the gas phase with
a solution of monoammonium phosphate, obtaining diam-
FOR CARBON-FREE
monium phosphate, and subsequently heating it with the
release of ammonia. The factors influencing the extraction ENERGY GENERATION
of ammonia from waste have been considered, as well as
the influence of temperature on the release of ammonia
from the solution of diammonium phosphate; the energy Sergey Zhadan
efficiency of the method has been assessed. With increas- PhD, Engineer Researcher
ing temperature, the degree of ammonia and the degree of Individual Entrepreneur «A.O. Dyba»
sorbent regeneration increased. Under laboratory condi-
Kudryashova str., 7-B, Kyiv, Ukraine, 03035
tions, 111 J/g of ammonia energy was spent. The higher
the concentration of (NH4)2HPO4 in the solution, the less Yevhenii Shapovalov
energy is required to obtain a unit of ammonia mass. The Corresponding author
total amount of ammonia released varies depending on PhD, Senior Researcher
the temperature. Sorbent regeneration can be carried out Department of Knowledge Systems Creation
using thermal energy obtained at a cogeneration plant. Junior Academy of Sciences of Ukraine
The possibility of using this method to produce ammonia Degtyarivska str., 38/44, Kyiv, Ukraine, 04119
at an industrial scale has been estimated by analyzing the E-mail: [email protected]
ways of ammonia utilization as a fuel. The potential for
ammonia production in the main livestock industries in
Roman Tarasenko
Europe and the United States is up to 11,482,651.15 and Postgraduate Student
11,582,169.5 tons per year, respectively. Applying this Institute of Telecommunications
solution also makes it possible to improve the efficiency of and Global Information Space
biogas production from waste with high nitrogen content. Chokolivskyi blvd., 13, Kyiv, Ukraine, 03186
The proposed method of ammonia production could poten- Anatoliy Salyuk
tially contribute to the development of carbon-free energy PhD, Professor
Keywords: ammonia production, carbon-free ener-
Department of Food Chemistry
gy, anaerobic digestion, ammonium nitrogen, ammonium
phosphates
National University of Food Technologies
Volodymyrska str., 68, Kyiv, Ukraine, 01601

Received date 11.08.2021 How to Cite: Zhadan, S., Shapovalov, Y., Tarasenko, R., Salyuk, A. (2021). Development of an ammonia production method for
Accepted date 17.10.2021 carbon-free energy generation. Eastern-European Journal of Enterprise Technologies, 5 (8 (113)), 66–75. doi: https://doi.org/
Published date 29.10.2021 10.15587/1729-4061.2021.243068

1. Introduction by 2050 [7]; the United Kingdom – by 80 % [8]; Japan,

France, and Canada – by 73–78 %; and Russia – by 48 % [9].
Much attention around the world is directed at reduc- The UN estimates that cities account for up to 70 % of
ing CO2 emissions to prevent the negative effects of global global anthropogenic greenhouse gas emissions [10]. In this
warming. The European Union has decided to reduce green- regard, more than 100 cities announced their intention to be-
house gas emissions by at least 55 % by 2030 compared to come carbon neutral by 2050. Some of them want to achieve
1990 levels [1, 2]. In 2019, the European Commission an- the goal earlier: Stockholm by 2040, Copenhagen by 2025,
nounced plans to adjust the EU economic course to create and Liverpool by 2020 [8].
a climate and carbon-neutral space in Europe by 2050 [3, 4]. American Apple Inc. has announced a goal to reduce total
Most countries have set targets for future reductions carbon dioxide emissions to zero across the entire supply and
in greenhouse gas emissions. For example, the Japanese go- production chain by 2030. Microsoft Corp. has announced
vernment has identified national (INDC) contributions at that it intends to achieve negative emissions by 2030, and,
a 26.0 % reduction in greenhouse gas emissions by the fiscal by 2050, to completely eliminate the effects of carbon di-
year 2030 compared to the fiscal year 2013 [5]. The Japanese oxide emissions over the entire time since the company was
government has also set a long-term goal of reducing green- founded in 1975 [11].
house gas emissions by 80 % by the fiscal year of 2050 [6]. Ger- The reduction of CO2 emissions into the atmosphere is
many plans to reduce greenhouse gas emissions by 80–95 % associated with the transition to carbon-free energy. This

66

Copyright © 2021, Authors. This is an open access article under the Creative Commons CC BY license
Energy-saving technologies and equipment

includes the use of fuels such as hydrogen and ammonia [12]. ammonia during anaerobic fermentation did not provide for
Using the latter has a series of critical advantages. However, the production of ammonia in forms suitable for use as car-
the disadvantage of ammonia is greenhouse gas emissions in bon-free fuels. All these methods are effective in controlling
its production. In order for the use of ammonia to become the nitrogen content in the bioreactor when decomposing
a truly carbon-free solution, it is necessary to develop a method livestock waste; however, they did not make it possible to
of its production that does not involve the use of fossil fuels. ensure the production of ammonia in the form suitable for
its use as fuel.
All this suggests that it is advisable to conduct a study on
2. Literature review and problem statement the extraction of ammonia from livestock waste for carbon-
free energy generation.
The production of ammonia is carried out through the
so-called Haber-Bosh process [12], which was invented by
German chemist and Nobel Prize winner Fritz Haber in 3. The aim and objectives of the study
the early 20th century [13]. The process is based on the syn-
thesis of ammonia from nitrogen and hydrogen at tempera- The purpose of this study was to propose a method
tures of 380–450 °C and a pressure of 250 atm using an iron of ammonia production, which is environmentally friendly,
catalyst [14]. energy-efficient, and does not involve the use of fossil fuels,
The use of the Haber-Bosh process has a negative impact which could potentially contribute to the development of
on the environment. For its implementation, hydrogen is carbon-free energy generation. This would make it possible to
required, which is removed from natural gas or coal as a re- obtain ammonia in a cheap and carbon-free way, which could
sult of a reaction using compressed overheated steam. At the ensure the development of ammonia-based energy generation.
same time, carbon dioxide is formed, which is about half the To accomplish the aim, the following tasks have been set:
emissions of the general process. The second raw material, – to consider a method for controlling the concentration
nitrogen, is easily separated from the air, which is 78 % of it. of ammonium nitrogen (AN) in the biogas reactor, which is
However, creating the pressure required to merge hydrogen planned to be taken as a basis;
and nitrogen into reactors consumes more fossil fuels, which – to adapt the method of controlling the concentration of
means more carbon dioxide is generated [15]. A large amount ammonium nitrogen to produce ammonia;
of ammonia produced in this way worldwide (more than – to evaluate the energy efficiency of the proposed me-
235 million tons) causes 1–2 % of world energy consumption thod of ammonia production;
and causes about 450 million tons of CO2 emissions per year. – to evaluate the potential of ammonia production by the
This is approximately 1 % of all anthropogenic emissions and new method;
more than any other industrial chemical reaction [13]. The – to analyze the techniques of using ammonia produced.
reason for this may be objective difficulties associated with
the lack of alternatives to production, and optimizing the
Haber-Bosh process will not solve the problem fundamental- 4. The study materials and methods
ly, which makes conducting such research impractical.
An option to overcome the corresponding difficulties The kinetics of the release of ammonia from the solution
may be to obtain ammonia from waste during their decom- of diammonium phosphate (DAP), when heated to diffe-
position. Studies on the anaerobic digestion (AD) of poultry rent temperatures, were investigated using the installation
waste [16] report that a high nitrogen content often causes shown in Fig. 1.
problems associated with its toxicity to anaerobic micro-
organisms. Nitrogen extraction and conversion into a form
of ammonia could ensure both the production of a useful
product and ensure intensification of the process of anaero-
bic processing of livestock products. Previously, no such
approach was proposed. For example, work [17] used sulfate
acid, sorption of which led to the formation of ammonium
sulfates and, in [18], iron-containing clay. Other methods
included removal with air [19], nitrogen [20], vacuum [21],
biogas recirculation, and nitrogen extraction by acid sorp-
tion [21], or adding minerals [22]. The use of sulfate acid
and the proposed technology for obtaining a decrease in
ammonia content did not provide for the further production
of ammonia from ammonium sulfates. Nitrogen blowing
and vacuuming are rather energy-consuming methods of
ammonia extraction, which requires additional research on Fig. 1. Installation to study the ammonia release kinetics
economic attractiveness. In addition, they did not provide when heating a solution of diammonium phosphate:
for the receipt of ammonia in the form of usable energy. Gas 1 – laboratory tripod; 2 – test tube with a solution
recirculation is also energy-consuming, and ammonia sorp- of diammonium phosphate; 3 – crystallizer with water;
tion with sulfate acid also did not provide for the production 4 – magnetic heated stirrer; 5 – bottle with a saturated
of ammonia in a form suitable for use as an energy carrier. solution of sodium chloride; 6 – measuring cylinder
The addition of minerals led to the sorption of ammonia
with these minerals, the extraction of ammonia from which Test tube 2 with a DAP solution was immersed in a crys-
was not supposed. Thus, other approaches to obtaining tallizer with heated water 3 and fixed in a laboratory tripod 1.

67
Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 5/8 ( 113 ) 2021

Crystallizer 3 was placed on magnetic stirrer 4. It provided current, and heating time, the amount of energy spent on
water heating and the same temperature value throughout ammonia production was determined.
its layer. The temperature of the water in the crystallizer
was controlled with a digital thermometer. The ammonia, re-
leased during heating, entered bottle 5 filled with a saturated 5. Results of devising an ammonia production method
solution of sodium chloride. In this case, the liquid under
pressure created by the gas entered measuring cylinder 6. 5. 1. Method to control ammonium nitrogen concentra-
The salt solution was used to prevent the dissolution of tion in a biogas reactor
ammonia in water. The amount of sodium chloride solution The proposed ammonia production technology is based
in measuring cylinder 6 was used to estimate the volume on the previously developed method for controlling the con-
of ammonia released as a result of heating. The amount of centration of ammonium nitrogen (AN) directly in the biogas
energy required to obtain ammonia by heating DAP was reactor (BR) [23].
determined at the installation shown in Fig. 2. The essence of the developed method is to remove AN
from the liquid phase by sorption of ammonia from the gas
phase by non-volatile sorbent, which is directly in the appa-
ratus but does not come into contact with the substrate [23].
It was proposed to use as sorbent a solution of phosphoric
acid (PA) since it can react with ammonia, is non-volatile,
and, as a result of the reaction, a product is formed useful for
agriculture (ammonium phosphates) [24].
Depending on the amount of ammonia interacting with
PA, different reaction products are formed: NH4H2PO4,
(NH4)2HPO4 , and (NH4)3PO4. Monoammonium phos-
phate (MAP) and DAP have practical significance [25].
Ammonium orthophosphate (NH4)3PO4 has no practical
application. Given this, the replacement of the sorbent is car-
ried out with the formation of MAP (Fig. 3) or DAP (Fig. 4).
When neutralizing PA to MAP, the depth of removal of
AN from the liquid phase of BR is higher than when neu-
tralizing to diammonium phosphate since the reaction rate is
higher. When neutralizing PA to NH4H2PO4, the solution is
drained at pH 4.5; and to (NH4)2HPO4 – at pH 8.0.
Fig. 2. Installation to estimate the amount of energy Ammonium phosphates can be obtained in solid form. Af-
needed to produce ammonia: 1 – laboratory tripod; ter extraction from the reactor, the resulting solution is cooled
2 – heating wire; 3 – thermal insulation; 4 – glass tube to ambient temperature and becomes oversaturated. Due to
with diammonium phosphate solution; 5 – laboratory the introduction of primer, crystallization centers are formed,
power supply and part of ammonium phosphates are released, which cannot
be dissolved at this temperature (Table 1) [26, 29].
The glass tube, in the middle of which there was ano- The effectiveness of isolating MAP from the solution when
ther glass tube 4 with DAP solution, was fixed in laboratory cooled in the form of crystals is much higher than DAP (Fig. 5).
tripod 1. Heating wire 2 was wound around inner tube 4. NH4H2PO4 is dried at a temperature from 100 °C to
The outer tube was coated with thermal insulation 3. The 110 °C; (NH4)2H2PO4 – at a temperature from 60 °C
solution was heated with heating wire 2, the voltage of to 70 °C. The isolated liquid can be returned to the reactor
which was supplied from laboratory power supply unit 5. The after adding acid solution (Fig. 3, 4) [26].
voltage and current were measured using a voltmeter and The effectiveness of the proposed AN concentration
an ammeter built into power supply unit 5. We controlled control method was shown in ammonium salt solutions that
the temperature of the solution in glass tube 4 with a digital simulate a substrate with a high concentration of the inhi-
thermometer. Taking into consideration the voltage, electric bitor (Fig. 6) [26].

Biogas

Solution Solution
H3PO4+NH4H2PO4
Sorbent H3PO4+NH3→NH4H2PO4
NH4H2PO4
Gas phase NH3

Substrate with high NH3+H2O

nitrogen content
Liquid phase NH4++OH- →NH4OH Digestate

Fig. 3. Adjustment of ammonium nitrogen concentration in a biogas reactor by sorption of ammonia

from the gas phase and obtaining a solution of monoammonium phosphate

68
Energy-saving technologies and equipment

Biogas

Solution Solution
Sorbent H3PO4+NH3→(NH4)2H2PO4
H3PO4+(NH4)2H2PO4 (NH4)2H2PO4
Gas phase NH3
Substrate with high
nitrogen content NH3+H2O

Liquid phase NH4++OH- →NH4OH Digestate

Fig. 4. Adjustment of ammonium nitrogen concentration in a biogas reactor by sorption of ammonia

from the gas phase and production of diammonium phosphate solution

Table 1 by sodium hydroxide to the required pH value, was placed in

Ammonium phosphates solubility at different a dry-air thermostat. The measuring cup containing 0.05 dm3
temperatures, g/100 g H2O of PA solution was placed on the bottom of the bottle. The
contact area of the ammonium chloride solution and gas
Sub- Temperature, °C phase was 71.0 cm2. The contact area of the PA solution
stance 0 10 20 30 40 50
surface and the gas phase was 15.3 cm2. Taking into conside-
ration the data in Fig. 6, sorption proceeds well across the
MAP 22.7 29.5 37.4 46.4 56.7 69.0 entire range of pH values and was most intense at pH = 8.5.
DAP 42.9 62. 9 68.9 75.1 81.8 89.2
In addition, the effectiveness of the proposed method to con-
trol the concentration of AN was shown directly at the AD of
chicken manure under a semi-continuous mode (Fig. 7) [26].
70
60 3,500
Ammonium nitrogen, mg/dm3

50 3,000
Efficiency, %

40 MAP 2,500
30
2,000
20 Experiment
1,500
10 DAP Control
1,000
0 5 10 15 20 25 30 35 40 45 50 500
Temperature, ℃
0
Fig. 5. Theoretical effectiveness of ammonium phosphates 10 20 30 40 50 60 70 80 90
removal from solution when cooled to a certain temperature Process duration, day

Fig. 7. Concentration of ammonium nitrogen in the

8,000
experimental and control reactors during the experiment
AN concentration, mg/dm3

7,000
6,000 pH=7.5 The AD of chicken manure was carried out under ther-
5,000 mophilic conditions at a temperature of 50 °C. The HRT
4,000 in BR was 10 days; the moisture content of the substrate
pH=8.0 was 90 %. The useful volume of the biogas reactors was
3,000
2 dm3. The content of the device was stirred with a mechan-
2,000 ical stirrer at a rotation speed of 38.4 rpm for 15 minutes
pH=8.5 each hour. PA concentration was 4 mol/ dm3. The contact
1,000
area of the sorbent surface with the gas phase was 0.025 m2;
0 20 40 60 80 100 120 140 160 180 200
that of the surface of the substrate with the gas phase was
Process duration, h 0.035 m2 [26].
The application of this method ensured a decrease in the
Fig. 6. Decrease in the concentration of ammonium nitrogen concentration of AN by 33.7 %, and free ammonia by 41.0 %.
in a solution of 0.25 dm3 as a result of ammonia sorption At the same time, the concentration of methane in the biogas
from the gas phase with phosphoric acid with produced in the prototype was 5 % higher than that in the
a concentration of 4 mol/dm3 at different pH values of control in absolute terms, and by 8.3 % in relative terms [26].
the medium and a temperature of 50 °C In addition, the results of mathematical modeling showed
that the proposed method is effective enough to regulate the
The experiment was conducted as follows. A bottle con- concentration of AN under the conditions of liquid phase
taining 0.25 dm3 of ammonium chloride solution, alkalized recirculation (Fig. 8) [27].

69
Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 5/8 ( 113 ) 2021

5,000 60% 4,000

AN concentration, mg/dm3

AN concentration, mg/dm3
50% 60%
3,500
4,000
40% 50%
3,000 40%
30%
3,000 20% 30%
2,500 20%
10%
10%
0% 0%
2,000 2,000
0 20 40 60 80 100 0 20 40 60 80 100
Process duration, day Process duration, day
a b
Fig. 8. Concentration of ammonium nitrogen in the biogas reactor in which ammonia sorption occurs from the gas phase
at the pH of the liquid phase 8.0, after the start of recirculation at its various degrees: a – at the hydraulic retention
time of 5 days; b – at the hydraulic retention time of 10 days

It was accepted that the process is carried out under An experiment was conducted on the effect of tempera-
a thermophilic mode at a temperature of 50 °C, the moisture ture on the process of regeneration of sorbent solution. The
content of the substrate – 90 %, and HRT – 5 and 10 days. decomposition of (NH4)2HPO4 with removal was carried out
The concentration of PA is 4 mol/dm3. The ratio of sorbent at temperatures of 70, 80, 85, 90, 95, and 100 °C. The regener-
area and the substrate is 1:4.6; the diameter of the apparatus ation rate was maximum at the beginning of the process and
to the depth of the substrate is 1:1.5. The concentration of AN decreased over time. Higher temperatures caused a higher
in BR without removal is taken equal to 3,000 mg/dm3. The rate of ammonia release (Fig. 10).
maximum degree of recirculation of the effluent is 60 %, shown
on the plots, corresponds to the complete replacement of water 20
used for breeding chicken manure from the native moisture
Ammonia production, cm3/cm3

content of 75 % to 90 % [27]. The degree of removal can be

significantly increased by changing the geometric dimensions 15
of BR, increasing the area of contact of sorbent with the gas
phase, and the hydraulic retention time (HRT) [27].
10 80 С
5. 2. Adapting the method of controlling the concen- 90 С
tration of ammonium nitrogen to produce ammonia
100 С
The method of controlling the concentration of AN in BR 5
in the case of sorbent regeneration can be considered as an
ammonia production technology.
Regeneration is possible when the resulting sorption
0
product is (NH4)2HPO4. When heating the latter to a tem-
0 2 4 6 8 10
perature above 70 °C, ammonia is released:
Temperature, С
(NH4)2HPO4→NH4H2PO4+NH3↑. Fig. 10. Kinetics of ammonia release from diammonium
phosphate solution at different temperatures
In this case, the sorbent in BR is NH4H2PO4 (Fig. 9).
Our experiment considered the possibility of obtaining That means that the higher the (NH4)2HPO4 concen-
ammonia by heating the solution and (NH4)2HPO4 crystals. tration in solution, the less energy is required to produce
It was found that a DAP solution should be heated since a unit mass of ammonia. The total amount of ammonia isola-
during the heating of DAP crystals there was no significant ted during 10 minutes of sorbent regeneration varies depend-
release of ammonia. ing on the temperature (Fig. 11).

Biogas

Solution Solution
Sorbent H3PO4+NH3→(NH4)2H2PO4 (NH4)2H2PO4
NH4H2PO4
Gas phase NH3

Substrate with high NH3+H2O

nitrogen content
Liquid phase NH4++OH- →NH4OH Digestate

Fig. 9. Adjustment of ammonium nitrogen concentration in a biogas reactor by sorption of ammonia

from the gas phase with a monoammonium phosphate solution

70
Energy-saving technologies and equipment

25
Ammonia production, cm3 /cm3

20

15

10

5
a
0
60 65 70 75 80 85 90 95 100
Temperature, С
Fig. 11. Total ammonia removal from diammonium phosphate
solution at different temperatures

Rising temperatures caused a greater ammonia yield.

Thus, with increasing temperature, it is possible to increase
the yield of ammonia as a product, which, with the use of
energy-saving technologies, can be an important factor in b
justifying technologies.
Fig. 12. Quantity of livestock in the sectors of animal
husbandry: a – in the USA; b – in Europe
5. 3. The energy efficiency of the proposed ammonia
production method
The amount of energy needed to obtain a ton of ammonia Below we consider the potential to produce ammonia
by the Haber-Bosh method is 38 GJ. At the same time, 22.5 GJ from livestock waste in the EU and the USA. To this end,
energy can be obtained from one ton of ammonia. Thus, the using the data given in Table 2, the maximum amount of
amount of energy obtained from one ton of ammonia is much ammonia that can be obtained from one animal per day was
lower than the one that was spent for its production. calculated (Fig. 13).
During the regeneration of sorbent solution in the labo- Table 2
ratory, before gas production stopped, energy consumption
Livestock waste parameters needed to assess the potential
was 111 GJ/t.
of ammonia production
It is important to note that thermal energy produced by
the cogeneration plant can be used to regenerate sorbent. Total nitro- Moisture Waste mass from
For example, at a biogas plant that processes manure from Waste gen, % dry con- one animal,
750 thousand chickens and with the values of the technolo- matter [28] tent, % [29] kg/day [29]
gical regime parameters used in the experiment, this is quite Chicken manure 4.6 75 0.16
feasible even with the consumption of energy of 111 GJ per Pig manure 3.9 86 5.1
ton of ammonia. Under such conditions, one can get 364.2 kg Cattle manure 2.6 86 55
of ammonia per day, which requires 40.4 GJ of energy. At the Cow manure 2.9 86 55
0.3
same time, the amount of heat generated with the help of
a cogeneration unit is 64.1 GJ. One can also use the heat of the
Ammonia production, kg/animal

fermented substrate, which is released from the biogas plant. 0.25

5. 4. The potential of ammonia production by the 0.2

new method
The proposed method of ammonia production can be 0.15
used in the processing of many types of waste with high
nitrogen content. These wastes include chicken manure, pig 0.1
manure, cattle manure, sheep manure, horse manure, slaugh-
ter waste, excess aerobic active silt, etc. 0.05
For example, at a poultry farm with a population of
750 thousand laying hens under the conditions created in the
0
experiment [26], one can get 132 tons of ammonia per year. Cows Cattle Pigs Poultry
The assessment of the potential of ammonia production at Livestock farms
the scale of the EU and the USA was carried out; a detailed
Fig. 13. The potential for the production of ammonia
analysis was performed using an example of a country with from the waste of one animal per day
a developed agricultural sector. The total number of livestock
of animals is higher in the EU than in the USA. However, the
structure of animal husbandry is slightly different. Thus, the EU The largest amount of ammonia can be obtained from poul-
has a much larger number of chicken heads, and in the USA – try waste both in the EU and in the USA. In the EU countries,
much more heads of pigs. Fig. 12 shows the number of live- in comparison with the United States, pig waste has a greater
stock in the U.S. (a) and EU (b) in the main livestock sectors. potential for ammonia production, and cattle waste in the Unit-

71
Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 5/8 ( 113 ) 2021

ed States compared to EU countries. The potential of ammonia capacity of 41.8 kW per mixture of methane and ammonia.
production in the United States and European countries in the Subsequently, they managed to achieve the same output
sectors of animal husbandry is shown in Fig. 14. power with 100 % ammonia [33]. At the same time, given the
constant optimization processes, it is possible to achieve more
power. Given this, it is possible to assert that ammonia, both
in the mixture and in its pure form, can be used for the oper-
ation of turbines. In 2018, industrial tests were carried out on
a two-fuel turbine with a capacity of 2 MW produced by IHI
Corporation, which worked on ammonia and natural gas.
It was found that the operation of the gas turbine engine is
stable in the entire range of ammonia mixing ratios from zero
to 20 %. The combustion efficiency exceeds 99.8 % for all test
conditions [34]. Thus, one of the potential methods of applying
ammonia as a green fuel is to use it to operate turbines.
In 2017, The Japanese Chugoku Electric Power Corpora-
a
tion successfully demonstrated the joint combustion of coal
with 1 % ammonia (in terms of total energy content) at one
of the commercial coal-fired power plants (120 MW). The use
of ammonia as fuel raises concerns about an increase in NOx
emissions but, during the demonstration, it was possible to
keep them within the normal range and avoid ammonia from
entering the exhaust gases [35]. Thus, the use of ammonia in
combination with coal at power plants is possible, and emissions
resulting from the operation of such power plants do not exceed
the standards for the content of nitrogen oxides. The Japanese
manufacturer IHI Corporation announced on March 28, 2018,
that it had successfully demonstrated the joint combustion of
b
ammonia and coal in a 20 % ammonia fuel mixture. It is noted
Fig. 14. The potential of ammonia production in countries that the company’s technology could be adapted to existing coal
by livestock sector: a – in the USA; b – in Europe boilers [25]. Consequently, the joint combustion of ammonia
and coal also has the potential to be applied. In addition, given
When assessing the potential of ammonia production, that it is possible to use existing coal-based boilers, that can
industrial livestock was taken into consideration; animals ensure a significant propagation of such technology.
that are in households of the population were not taken into Ammonia can be used in internal combustion engines.
consideration. This is due to the need to be able to centrally Based on previous studies, in order for ammonia to become
collect livestock waste in large quantities using the means of a viable fuel for internal combustion engines, it must be
mechanization and automation of the process. Poultry and mixed with other fuels as combustion accelerators. To this
cattle have the greatest potential for ammonia production – end, they usually chose a two-fuel approach [36]. It has
88,844 and 88,468 tons, respectively. been demonstrated that internal combustion engines can
In terms of energy content, liquid ammonia contains work successfully on ammonia/gasoline mixture [37–39]
15.6 MJ/dm3. This is 70 % more than liquid hydrogen and ammonia/diesel fuel [40]. Thus, as a rule, for the opera-
(9.1 MJ/dm3 at cryogenic temperatures) or almost three times tion of internal combustion engines running on ammonia, a
more than compressed hydrogen (5.6 MJ/dm3 at 70 MPa) [30]. two-fuel approach is used. Engines powered by ammonia are
This may indicate that ammonia is promising in terms of its characterized by lack of corrosion, low power losses, and low
energy use as a fuel compared to hydrogen. Ammonia is much lubricant consumption [41–43]. Given that road transport
cheaper to store for a long time compared to hydrogen, as creates a significant environmental burden, the use of am-
well as to transport [31]. The infrastructure for the process- monia could reduce this load and change the environmental
ing and transportation of ammonia already exists [15, 31], footprint of road transport.
the supply chain and the rules for handling are already in In July 2015, the Kyoto University research team suc-
place [32]. Given this, it is possible to argue that if there is cessfully demonstrated its solid oxide fuel cell, which ope-
a cheap method of ammonia production, it will be possible rated directly on ammonia, with a capacity of 200 W, which,
to use the existing infrastructure for the implementation of at the time, was “the largest in the world” [44]. The Japanese
ammonia-powered energy technologies. production concern IHI announced on May 16, 2018, that it
Ammonia has many applications in carbon-free energy. “successfully generated a class capacity of 1 kW” using a solid
In August 2014, a team led by Kobayashi and Iki was the oxide fuel cell that worked directly on ammonia [45].
first in the world to use an ammonia turbine to drive the The U.S. Department of Energy’s Advanced Research
generator. Their turbine was optimized for the use of ammo- Projects Agency has demonstrated that ammonia is already
nia with the help of additional turbine blades, which create the cheapest and most proven technology for long-term
a high-temperature mixture of fuel under high pressure. The large-scale energy storage for more than one day [46]. Am-
team uses the system with a maximum output power of 50 monia can be used in heavily decarbonized industries such as
kW. Initially, they managed to achieve a stable output pow- metallurgy and marine transport [47–49]. Given the above,
er of 21 kW using a mixture that contained 30 % ammonia ammonia has a high potential for use while exploiting exist-
and 70 % kerosene. By September 2015, they had reached a ing infrastructure.

72
Energy-saving technologies and equipment

6. Discussion of results of devising the ammonia since the amount of energy spent on obtaining a unit of am-
production method for carbon-free energy generation monia mass depends on those parameters.
It is necessary to consider heating the sorbent solution
The application of the proposed method has a double inside the BR above the AD temperature. Thus, it is theo-
effect – a decrease in AN in bioreactors, which leads to a de- retically possible to increase the concentration of sorbent
crease in their inhibition, and the production of ammonia it- without moisture entering it. That can lead not only to an
self. The need to regulate the concentration of AN during AD increase in the sorption rate of ammonia from the gas phase
is based on its ability to inhibit the process [17, 18, 50, 51]. and, accordingly, to an increase in the depth of removal from
Both AN and sulfides [52] can inhibit the process but, for the the liquid phase but also to an increase in the concentration
processing of manure, AN is more harmful. The toxic effect of the resulting DAP, which could reduce energy consump-
of AN is associated with undissociated ammonia. It has been tion for ammonia production.
shown that it diffuses through cell membranes and is ionized When assessing the potential of ammonia production, it
with the formation of ammonium ions NH4+ , which leads to was assumed to use all the nitrogen contained in the litter of
a pH imbalance in the middle and outside of the bacterial animals, which is impossible. Thus, the obtained values cha-
cell. That negatively affects both the transport of substances racterize the possible limits of ammonia production.
and the activity of enzymes [53]. The factors controlling pro- At the same time, it is important to note that the proposed
cess inhibition are the solids content in the substrate, HRT, method of ammonia production can only be used for organic,
pH, temperature, and the presence of ions that are inhibitor not mineral waste. In addition, such wastes should be suitable
antagonists [54]. Inhibition of the AD process by a high for AD and have a high nitrogen content. As a result of re-
concentration of AN can lead to significant economic losses search, it was found that without optimization in laboratory
during BR operation. As indicated above, it is proposed to conditions, 111 GJ/t of ammonia is required, which requires
use PA as a sorbent. Under a thermophilic mode, it is advis- additional further research in order to reduce this indicator.
able to use PA with a concentration of 4 mol/dm3 since, at Determining the potential of ammonia production allows
this concentration, there is neither a significant decrease in us to draw conclusions about the prospects of using this meth-
volume due to moisture evaporation nor its increase due to od under industrial conditions. Thus, the annual potential of
the hygroscopicity of acid [24]. Fig. 8 demonstrates that the ammonia production in the main livestock sectors in Ukraine is
method is effective at reducing the content of AN in the AD 263,610 tons. This is comparable to the traditional production
process. of ammonia in the country in 2019 (183,000 tons). A similar
The industry produces extraction PA and thermal PA. situation applies to European countries and the United States.
Extraction PA is obtained by decomposition of natural phos- Our analysis of Fig. 14, 15 reveals that the largest amount
phates with sulfuric acid and separation of the formed solid of ammonia in the analyzed countries can be obtained from
phase (calcium sulfate) from the PA solution [55]. Thermal poultry farming. Probably, such a trend is relevant for
PA is produced by electrical distillation of phosphorus and its the world. Thus, the results from the anaerobic fermenta-
oxidizing followed by hydration of the resulting phosphorus tion of chicken manure using the ammonia extraction me-
anhydride to PA [55]. As a sorbent in the BR, one can use thod [26, 27], which were carried out earlier, can be directly
thermal PA or purified extraction PA. used to implement such technology.
In the case of untreated extraction PA, impurities react A separate important issue is the use of ammonia since it is
with ammonia, as a result of which iron, aluminum, gypsum, a new and quite promising type of fuel, provided it is produced
etc. enter the sediment [56]. In order to avoid the accumula- carbon-free. However, its use requires additional research,
tion of salts at the bottom of the tank with acid located inside and its industrial use is only beginning to gain relevance. As
the BR, it is not recommended to use untreated PA. noted above, ammonia has a series of practical applications and
During the regeneration of sorbent solution in the labora- developed infrastructure. In addition, in the context of recent
tory, before the cessation of gas production, energy consump- events, in particular regarding the gas supply infrastructure,
tion was 111 GJ/t. This value is rather given not to compare part of such infrastructure will be left without use or used to
the proposed method with the Gaber-Bosch process but to a lesser extent. Such infrastructure could also be adapted for
show that this amount of energy is already sufficient for the transporting ammonia obtained carbon-free biologically.
production of ammonia. Further work will tackle the optimizing of technological
Of course, it is possible to reduce the energy costs of the parameters to increase the economic efficiency of the pro-
method, since, during the regeneration of sorbent, the task posed carbon-free method of ammonia production.
was not to reduce them due to any special design solutions
or the selection of technological parameters but to determine
its possibility. 7. Conclusions
Based on the peculiarities of measuring the volume of
ammonia generated by DAP heating, the amount of gas ge- 1. When devising a method to produce ammonia, the
nerated is somewhat underestimated. In particular, the den- method of control of AN concentration in BR was taken
sity of the salt solution moved from one container to another, as a basis. It involves removal from the liquid phase by
the levels of liquid in the container into which ammonia sorption of ammonia from the gas phase. The sorbent is
fell, and the height of the salt solution transfusion into the a non-volatile substance that is directly in the apparatus but
measuring cylinder were not taken into consideration. Con- does not come into contact with the substrate.
sequently, the amount of energy needed to obtain a unit mass 2. The proposed method of ammonia production is based
of ammonia observed during the study is overstated. on ammonia sorption from the gas phase of the reactor with
The process of sorbent regeneration with the formation MAP solution. The resulting DAP solution is drained from
of ammonia should be optimized. To this end, it is necessary the BR upon reaching a pH of 8.0 and heated above 70 °C,
to take into consideration the temperature and heating time accompanied by the removal of ammonia.

73
Eastern-European Journal of Enterprise Technologies ISSN 1729-3774 5/8 ( 113 ) 2021

3. During the regeneration of sorbent solution until is up to 263,610 tons per year, which is comparable to the
the cessation of gas production, energy consumption was production of ammonia in the country in the traditional way.
111 GJ/t of ammonia. For the purpose of regeneration, the Ammonia as a fuel can be used as a single component of fuel,
thermal energy of the cogeneration unit can be used. as well as in two-fuel systems. Ammonia can be used in tur-
4. The use of this method to produce ammonia on an bines, for direct combustion, in particular in boilers, for the
industrial scale is feasible. In Europe and the USA, the operation of internal combustion engines, in solid oxide fuel
production potential of ammonia is up to 11,482,651.15 and cells, and in other devices and technologies. Engines running
11,582,169.5 tons per year, respectively. The potential of am- on ammonia are characterized by lack of corrosion, low power
monia production in the main livestock sectors in Ukraine losses, and low lubricant consumption.

References
1. 2030 climate & energy framework. European Commission. Available at: https://ec.europa.eu/clima/policies/strategies/2030_en
2. Reflection Paper - Towards a Sustainable Europe By 2030 (2019). European Commission. Available at: https://ec.europa.eu/info/
sites/default/files/rp_sustainable_europe_30-01_en_web.pdf
3. Going Climate-Neutral by 2050. European Commission. Available at: https://op.europa.eu/en/publication-detail/-/publica-
tion/92f6d5bc-76bc-11e9-9f05-01aa75ed71a1
4. Brouwer, K. M. (2021). Road to EU Climate Neutrality by 2050. Brussels. Available at: https://roadtoclimateneutrality.eu/
Energy_Study_Full.pdf
5. Submission of Japan’s Intended Nationally Determined Contribution (2015). Ministry of Economy, Trade and Industry. Available
at: https://www4.unfccc.int/sites/ndcstaging/PublishedDocuments/Japan%20First/20150717_Japan%27s%20INDC.pdf
6. Kobayashi, H., Hayakawa, A., Somarathne, K. D. K. A., Okafor, E. C. (2019). Science and technology of ammonia combustion.
Proceedings of the Combustion Institute, 37 (1), 109–133. doi: https://doi.org/10.1016/j.proci.2018.09.029
7. Energiekonzept f r eine umweltschonende, zuverl ssige und bezahlbare Energieversorgung (2010). M nchen. Available at:
https://www.bmwi.de/Redaktion/DE/Downloads/E/energiekonzept-2010.pdf?__blob=publicationFile&v=5
8. Climate Change Act 2008. Available at: https://www.legislation.gov.uk/ukpga/2008/27/contents
9. Strategiya. Dolgosrochnogo razvitiya rossiyskoy federacii s nizkim urovnem vybrosov parnikovyh gazov do 2050 goda. Available at:
https://economy.gov.ru/material/file/babacbb75d32d90e28d3298582d13a75/proekt_strategii.pdf
10. Hot Cities: battle-ground for Climate change. Available at: https://mirror.unhabitat.org/downloads/docs/E_Hot_Cities.pdf
11. Apple commits to be 100 percent carbon neutral for its supply chain and products by 2030 (2020). Apple. Available at: https://www.
apple.com/newsroom/2020/07/apple-commits-to-be-100-percent-carbon-neutral-for-its-supply-chain-and-products-by-2030/
12. Salmon, N., Ba ares-Alc ntara, R. (2021). Green ammonia as a spatial energy vector: a review. Sustainable Energy & Fuels, 5 (11),
2814–2839. doi: https://doi.org/10.1039/d1se00345c
13. Researchers aim to make ammonia production 100% green. Available at: https://www.eurekalert.org/news-releases/538445
14. Sosna, M. Kh., Kasym, O. N. (2017). The main trends in the technology development of ammonia production. Oil & Gas Chemistry,
4, 17–21. doi: https://doi.org/10.24411/2310-8266-2017-00036
15. Service, R. F. (2018). Ammonia – a renewable fuel made from sun, air, and water – could power the globe without carbon. Science. Avail-
able at: https://www.science.org/content/article/ammonia-renewable-fuel-made-sun-air-and-water-could-power-globe-without-carbon
16. Abouelenien, F., Elsaidy, N., Nakashimada, Y. (2013). Simultaneous Ammonia removal and Methane Production from Chicken Ma-
nure under Dry Thermophilic Condition. Journal of American Science, 9 (10), 90–94. Available at: http://www.jofamericanscience.
org/journals/am-sci/am0910/011_20294am0910_90_94.pdf
17. Wang, X., Gabauer, W., Li, Z., Ortner, M., Fuchs, W. (2018). Improving exploitation of chicken manure via two-stage anaerobic di-
gestion with an intermediate membrane contactor to extract ammonia. Bioresource Technology, 268, 811–814. doi: https://doi.org/
10.1016/j.biortech.2018.08.027
18. Ivanov, V., Stabnikov, V., Stabnikova, O., Salyuk, A., Shapovalov, E., Ahmed, Z., Tay, J. H. (2019). Iron-containing clay and hema-
tite iron ore in slurry-phase anaerobic digestion of chicken manure. AIMS Materials Science, 6 (5), 821–832. doi: https://doi.org/
10.3934/matersci.2019.5.821
19. Markou, G. (2015). Improved anaerobic digestion performance and biogas production from poultry litter after lowering its nitrogen
content. Bioresource Technology, 196, 726–730. doi: https://doi.org/10.1016/j.biortech.2015.07.067
20. Abouelenien, F., Kitamura, Y., Nishio, N., Nakashimada, Y. (2009). Dry anaerobic ammonia–methane production from chicken ma-
nure. Applied Microbiology and Biotechnology, 82 (4), 757–764. doi: https://doi.org/10.1007/s00253-009-1881-3
21. Abouelenien, F., Fujiwara, W., Namba, Y., Kosseva, M., Nishio, N., Nakashimada, Y. (2010). Improved methane fermentation of chicken
manure via ammonia removal by biogas recycle. Bioresource Technology, 101 (16), 6368–6373. doi: https://doi.org/10.1016/
j.biortech.2010.03.071
22. Habibullin, R. E. (1995). Issledovanie i razrabotka intensivnoy biotehnologii anaerobnoy pererabotki kurinogo pometa. Kazan’, 18.
23. Shapovalov, V. B., Shapovalov, E. B., Zhadan, S. O., Saliuk, A. I. (2015). Pat. No. 105080. Sposib otrymannia biohazu ta dobryva
z vidkhodiv z vysokym vmistom azotu. No. u201505811; declareted: 12.06.2015; published: 10.03.2016, Bul. No. 5. Available at:
https://uapatents.com/3-105080-sposib-otrimannya-biogazu-ta-dobriva-z-vidkhodiv-z-visokim-vmistom-azotu.html
24. Saliuk, A. I., Shapovalov, E. B., Shapovalov, V. B., Zhadan, S. O. (2016). Pat. No. 114655. Sposib oderzhannia tverdoho mineralnoho
dobryva pry metanoviy fermentatsiyi. No. u 201610452; declareted: 17.10.2016; published: 10.03.2017, Bul. No. 5. Available at:
https://uapatents.com/5-114655-sposib-oderzhannya-tverdogo-mineralnogo-dobriva-pri-metanovijj-fermentaci.html

74
Energy-saving technologies and equipment

25. Crolius, S. H. (2018). IHI First to Reach 20% Ammonia-Coal Co-Firing Milestone. Ammonia Energy Association. Available at:
https://www.ammoniaenergy.org/articles/ihi-first-to-reach-20-ammonia-coal-co-firing-milestone/
26. Salyuk, A., Zhadan, S., Shapovalov, E., Tarasenko, R. (2017). Methane fermentation of chicken manure under conditions of reduced
concentration of inhibitors. Alternative Energy and Ecology, 4-6, 89–98. doi: https://doi.org/10.15518/isjaee.2017.04-06.089-098
27. Shapovalov, Ye., Zhadan, S., Salyuk, A., Kotinskiy, A. (2018). Regulation of the ammonia nitrogen concentration at the methane
fermentation of chicken manure under conditions of the liquid phase recirculation. Scientific Works of NUFT, 24 (6), 65–72.
doi: https://doi.org/10.24263/2225-2924-2018-24-6-10
28. Pratt, P. F., Castellanos, J. Z. (1981). Available nitrogen from animal manures. California Agriculture.
29. Vedeneev, A. G., Vedeneeva, T. A. (2006). Biogazovye tehnologii v Kyrgyzskoy respublike. Bishkek: Tipografiya «Evro», 90.
30. Brown, T. (2017). The new generation of fuel cells: fast, furious, and flexible. Ammonia Energy Association. Available at: https://
www.ammoniaenergy.org/articles/the-new-generation-of-fuel-cells-fast-furious-and-flexible/
31. Bartels, J. R. (2008). A feasibility study of implementing an ammonia economy. Iowa State University. doi: https://doi.org/
10.31274/etd-180810-1374
32. Ammonia fuel. Gencell. Available at: https://www.gencellenergy.com/gencell-technology/ammonia-fuel/
33. Ammonia-Fueled Gas Turbine Power Generation (2017). Ammonia Energy Association. Available at: https://www.ammoniaenergy.
org/articles/ammonia-fueled-gas-turbine-power-generation/
34. Ito, S., Uchida, M., Onishi, S., Kato, S., Fujimori, T., Kobayashi, H. (2018). Performance of Ammonia – Natural Gas Co-Fired Gas
Turbine for Power Generation. 2018 AIChE Annual Meeting. Available at: https://www.aiche.org/conferences/aiche-annual-
meeting/2018/proceeding/paper/549b-performance-ammonia-natural-gas-co-fired-gas-turbine-power-generation
35. Crolius, S. H. (2019). The Evolving Context of Ammonia-Coal Co-Firing. Ammonia Energy Association. Available at: https://www.
ammoniaenergy.org/articles/the-evolving-context-of-ammonia-coal-co-firing/
36. Brown, T. (2018). Ammonia for Power: a literature review. Ammonia Energy Association. Available at: https://www.ammoniaenergy.
org/articles/ammonia-for-power-a-literature-review/
37. Grannell, S. M., Assanis, D. N., Bohac, S. V., Gillespie, D. E. (2006). The Operating Features of a Stoichiometric, Ammonia and
Gasoline Dual Fueled Spark Ignition Engine. Energy Conversion and Resources. doi: https://doi.org/10.1115/imece2006-13048
38. Grannell, S. M., Assanis, D. N., Bohac, S. V., Gillespie, D. E. (2008). The Fuel Mix Limits and Efficiency of a Stoichiometric, Am-
monia, and Gasoline Dual Fueled Spark Ignition Engine. Journal of Engineering for Gas Turbines and Power, 130 (4). doi: https://
doi.org/10.1115/1.2898837
39. NH3 Car. NH3CAR. Available at: http://nh3car.com/
40. Reiter, A. J., Kong, S.-C. (2011). Combustion and emissions characteristics of compression-ignition engine using dual ammonia-
diesel fuel. Fuel, 90 (1), 87–97. doi: https://doi.org/10.1016/j.fuel.2010.07.055
41. Reiter, A. J., Kong, S.-C. (2008). Demonstration of Compression-Ignition Engine Combustion Using Ammonia in Reducing Green-
house Gas Emissions. Energy & Fuels, 22 (5), 2963–2971. doi: https://doi.org/10.1021/ef800140f
42. Frigo, S., Gentili, R. (2013). Analysis of the behaviour of a 4-stroke Si engine fuelled with ammonia and hydrogen. International
Journal of Hydrogen Energy, 38 (3), 1607–1615. doi: https://doi.org/10.1016/j.ijhydene.2012.10.114
43. Liu, R., Ting, D. S.-K., Checkel, M. D. (2003). Ammonia as a fuel for SI engine. SAE Technical Papers. doi: https://doi.org/
10.4271/2003-01-3095
44. SIP Energy Carriers -The Innovation for Ammonia Fuel in Japan. Available at: https://www.youtube.com/watch?v=5ejL65tKsGM
45. Crolius, S. H. (2018). Direct Ammonia Fuel Cells Take Another Step Forward in Japan. Ammonia Energy Association. Available at:
https://www.ammoniaenergy.org/articles/direct-ammonia-fuel-cells-take-another-step-forward-in-japan/
46. Technology. Hydrofuel. Available at: https://www.nh3fuel.com/index.php/technology/18-engine-conversions
47. Kelly-Detwiler, P. (2020). A Key To The ‘Hydrogen Economy’ Is Carbon-Free Ammonia. Forbes. Available at: https://www.forbes.
com/sites/peterdetwiler/2020/12/16/maybe-the-hydrogen-economy-will-become-the-ammonia-economy/?sh=4453f9e64936
48. Dolan, R. H., Anderson, J. E., Wallington, T. J. (2021). Outlook for ammonia as a sustainable transportation fuel. Sustainable Energy
& Fuels, 5 (19), 4830–4841. doi: https://doi.org/10.1039/d1se00979f
49. Hansson, J., Brynolf, S., Fridell, E., Lehtveer, M. (2020). The Potential Role of Ammonia as Marine Fuel – Based on Energy Systems
Modeling and Multi-Criteria Decision Analysis. Sustainability, 12 (8), 3265. doi: https://doi.org/10.3390/su12083265
50. Fuchs, W., Wang, X., Gabauer, W., Ortner, M., Li, Z. (2018). Tackling ammonia inhibition for efficient biogas production from
chicken manure: Status and technical trends in Europe and China. Renewable and Sustainable Energy Reviews, 97, 186–199.
doi: https://doi.org/10.1016/j.rser.2018.08.038
51. Shapovalov, Y., Zhadan, S., Bochmann, G., Salyuk, A., Nykyforov, V. (2020). Dry Anaerobic Digestion of Chicken Manure: A Review.
Applied Sciences, 10 (21), 7825. doi: https://doi.org/10.3390/app10217825
52. Plyatsuk, L., Chernish, E. (2014). Intensification of Anaerobic Microbiological Degradation of Sewage Sludge and Gypsum Waste
Under Bio-Sulfidogenic Conditions. The Journal of Solid Waste Technology and Management, 40 (1), 10–23. doi: https://doi.org/
10.5276/jswtm.2014.10
53. Niu, Q., Qiao, W., Qiang, H., Hojo, T., Li, Y.-Y. (2013). Mesophilic methane fermentation of chicken manure at a wide range of ammonia con-
centration: Stability, inhibition and recovery. Bioresource Technology, 137, 358–367. doi: https://doi.org/10.1016/j.biortech.2013.03.080
54. Saliuk, A. I., Zhadan, S. O., Shapovalov, Ye. B., Tarasenko, R. A. (2016). Inhibuvannia vyrobnytstva metanu z kuriachoho poslidu
amoniynym azotom. Vidnovliuvana Enerhetyka, 1, 79–83.
55. Pozin, M. E. (1974). Tehnologiya mineral’nyh soley: Udobreniy, pesticidov, promyshlennyh soley, okislov i kislot. Leningrad: Himiya, 792.
56. Klevke, V. L., Polyakov, N. N., Arsen’eva, L. Z. (1956). Tehnologiya azotnyh udobreniy. Moscow, 290.

75