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Phosphoric rock (PR) is the basic building block to produce animal feed, fertilizers, and industrial phosphates. Global demand for PR is estimated to grow from 207 Mtons in 2018 to 263 Mtons in 2035, of which Colombia contributes approximately 0.06 Mtons per year. A novel technology to carry out calcination is the plasma torch, where the electrical resistivity of the system is increased and ionized gas is produced that can reach temperatures above 10,000°C, which facilitates the transformation of PR into thermophosphates. Two samples of PR from the region central of the Boyacá department, Colombia, were subjected to calcination through a plasma torch and as a result, showed a maximum concentration of total phosphorus between 27 and 33% of P2O5 and assimilable phosphorus corresponding to the range between 3.0 and 4.8% of P2O5 respectively. Finally, the energy consumption for calcination is ≤1.14 kW-h/Kg, respectively.
National Learning Service Sena, Mining Center, Sogamoso, Colombia
Faculty of Science, Student of Doctorate in Chemical Science, Pedagogical and Technological University of Colombia, Tunja, Colombia
*Address all correspondence to: nelespinel@gmail.com
1. Introduction
Phosphoric rock is one commodity type and is considered a strategic mineral of Colombia with 20 million hectares of reserves. Global demand for phosphoric rock is estimated to grow from 207 Mton in 2018 to 263 Mton in 2035, of which Colombia contributes approximately 0.06 Mtons/year [1]. The crucial phosphoric rock deposits in Colombia are in the departments of Boyacá (Sogamoso, Pesca, Iza, Cuitiva, Tota, Monguí, Úmbita, and Turmequé), North Santander (Sardinata, Lourdes, Cúcuta, Bochalema, Durania, Santiago and Zulio), Huila (Tesalia and Aipe), Cundinamarca (Zipaquirá and Pacho) and Tolima (Natagaima). According to previous reports [2], the production was 2016 of 66,324 tons/year, being the department of Boyacá the most prominent producer with 34,501 tons/year, Huila with 20,615 tons/, and North Santander with 11,208 tons/year, respectively [3]. Figure 1 shows the primary phosphoric rock deposits in Colombia.
Figure 1.
Main phosphoric rock deposits in Colombia [4].
On the other hand, 75% of the phosphoric rock does using for the wet production of phosphoric acid as an intermediate product, required to obtain fertilizers and other products such as diammonium phosphate (DAP), monoammonium phosphate (MAP), triple superphosphate (TSP), dicalcium phosphate (DCP), sodium tripolyphosphate (STPP), thermal phosphoric acid (TPA), simple superphosphate, (SSP) and direct application phosphoric rock (DAPR) [1]. According to previous reports, more than 10% of the world fertilizer market produces by calcination [5], and a novel technology to carry out this operation is through the plasma torch [6]. It creates an electric arc through which gas passes, producing a stream of ionized gas or plasma. The system’s electrical resistivity increases and ionized gas is created that can reach temperatures above 10,000°C, which facilitates the transformation of phosphoric rock into thermophosphates. The samples of phosphoric rock (PR) were taken from the localities of Iza and Sogamoso Boyacá – Colombia. Then the phosphoric rock beneficiation was carried out by drying, crushing, grinding, and sieving operations by obtaining particle sizes of 0.075 mm, because of a granulometric analysis that passed 200 meshes. To facilitate the agglomeration of the sieved mineral, a mixture of phosphoric rock, wheat flour, and water was prepared, forming a homogenized paste and pressed through a hydraulic system to obtain briquettes 2.5 cm in diameter and 1.2 cm thick. They were then calcined in a plasma reactor and the thermophosphates were obtained.
Sustainable development goals (SDGs) seek to end poverty, defend the planet, and ensure prosperity for all people in 2030. Some goals like 1, 2, and 10, no poverty, zero hunger, and reduced inequalities [7], respectively, aim at improving living conditions worldwide. However, goal 2 is critical due to population growth, where every day needs to meet the demand for food. For food production, phosphoric rock is the primary source of phosphorus in fertilizers and can be obtained by a thermal or wet process; furthermore, your application, like soluble phosphorus, can increase the yield of crops and is a critical factor for the agriculture due to do not have a substitute for the growth of plants. Likewise, phosphorus in the shape of phosphate or its esters is involved in many biological processes, including relevant structural, metabolic, and transport functions, and it’s a structural element in nucleic acids or phospholipids in biomembranes [8, 9]. In addition, nutrients like nitrogen are used less efficiently when soils contain less phosphate and potash [10]. Even if all other conditions and nutrients are plentiful, only phosphorus can make crops thrive [11]. On the other hand, the disponible of this raw material, nonrenewable in nature, depends on the extraction speed, and consumption determines the depletion rate [12]. Finally, the farmers must be conscientious about the efficient use of phosphorus fertilizers, and fertilizer producers should consider about developing materials that gradually release phosphorus and avoid dilution losses due to rainfall or other factors. Likewise, it must be carried on an equitable distribution of fertilizers that avoid social issues, favor economic growth, improve agricultural productivity, and improve food security worldwide.
In nature, phosphates are present in igneous, sedimentary, and metamorphic rocks, as well as marine and biogenic deposits. The most important group is the apatites, whose generic formula is M10(XO4)6Y2. Likewise, the most common natural deposits are fluorapatite (Ca10(PO4)6F2), hydroxyapatite (Ca10(PO4)6(OH)2), carbonate of hydroxyapatite (Ca10(PO4,CO3)6(OH)2), francolite (Ca10-x-yNaxMgy(PO4)6-z(CO3)zF0.4zF2), dahllite (3Ca3(PO4)2·CaCO3) and collophane 3Ca3(PO4)2·nCa(CO3,F2, O)·xH2O [5]. Table 1 summary of the chemical composition of apatites.
The thermal treatment of phosphate rock allows the production of thermophosphate fertilizers, sometimes with additives. At high temperatures, changes in the crystal structure of apatite occur, facilitating the availability of phosphorus to plants [16]. Three types of conventional thermal processes are applied to phosphoric rock [17]: calcination, sintering, and melting. Thermal plasma is a novel method, and its description is carried out later.
4.1 Calcination
It is a process that decomposes existing carbonates and eliminates CO2.
4.2 Sintering
It is the process of agglomerating of small particles to form larger ones without reaching the melting point.
4.3 Melting
The raw ore is heated to above the melting point.
On the other hand, electric furnaces are widely used for calcinating phosphoric rock, and the thermal treatment carries on to specific temperatures, as described in Table 2.
Plasma is considered the fourth state of matter and consists of a mixture of electrons, ions, and neutral particles, which are generally electrically neutral. Figure 2 shows the characteristics of process ionized plasma.
Figure 2.
Characteristic of process ionized plasma.
The creation of an electric arc sustained by the passage of electric current through a gas produces an increase in electrical resistivity throughout the system, generating heat, stripping electrons from the gas molecules, and resulting in a stream of ionized gas or plasma [18]. Plasmas are classified into thermal and cold plasmas: the former are known as hot, high-pressure, or equilibrium plasmas and are characterized by the fact that the temperature of the ions is very similar to that of the electrons. The second is low-pressure and non-equilibrium plasmas and is characterized by less frequent collisions between ions and electrons, generating a higher electron energy level (temperature) [19]. On the other hand, plasma torches can be classified into transferred, and non-transferred arcs. The difference is that the former has a wider physical separation between the cathode and the anode, which can vary between 1 cm and almost 1 m [18].
The phosphoric rock (PR) samples were taken in the central-eastern region of the Boyacá Department, Colombia, specifically in the municipalities of Iza (San Miguel) and Sogamoso (Pilar and Ceibita).
5.1 Benefit of minerals
Table 3 describes the benefits of minerals of raw phosphoric rock (PR).
Unitary operation
Conditions
Equipment
Drying PR
50°C/8 h
Electric oven
Grinding
250 rpm/5 min.
Retsch planetary ball mill pm 400
Sieving
particle size ≤0.075 mm, passes 200 mesh/5 min.
Fritsch Analysette 3 Pro vibratory sieve and a sieve Tyler normalized series numbers 8, 16, 30, 50, 100, 200 and −200
Agglomeration
Proportions of 65 wt.% - 70 wt.% PR and 35 wt.% - 30 wt.% wheat flour in water paste
Laboratory material
Pressed
Pressure 119.84 Mpa, circular briquettes of 2.5 cm in diameter and 1.2 cm in height
Hydraulic press
Drying briquettes
105°C/2 days
Electric oven
Table 3.
Benefits of minerals and operation condition.
5.2 Calcination process in plasma torch reactor
A plasma torch reactor was used to obtain thermophosphates by calcinating the phosphoric rock (RP) under the conditions described in Table 4 and using the equipment Victor Cut Master A60™.
Feature
Description
Type of plasma
Thermal
Type of plasma torch
Transferred arc
Current output
20–80 A
Plasma gas
Air
Working pressure
4.1–6.5 Bar
Gas flow
142–235 L/min
Time calcination
30–40 s
Number of briquettes
4 briquettes/stainless-steel crucible
Table 4.
Conditions of calcination of phosphoric rock (PR) in plasma torch reactor.
The thermophosphates obtained were then cooled and ground in the Retsch planetary ball mill pm 400 for 5 min and sieved to get a particle size ≤0.075 mm. Figure 3 is shown the process required to obtain thermophosphates fertilizers.
Figure 3.
Process for obtaining thermophosphates by a plasma torch.
5.3 Design experiments
In a 24 – factorial design of experiments, two levels (high and low) and four factors were established: (a): current intensity (30–45 A); (b): mineral source, A: phosphoric rock Iza (PRIZA) and B: phosphoric rock Pilar and Ceibita (PRPC); (c): time (30–40 s) and (d): mineral mixture for briquette preparation (65–70 wt. % PR and 35–30 wt. % wheat flour in water paste). Table 5 shows the design of experiments to obtain thermophosphates in a plasma reactor, likewise, through Minitab 17 software.
Levels
Factors
x1a
x2b
x3c
x4d
−1
30
A
30
65
+1
45
B
40
70
Table 5.
Design of experiments to obtain thermophosphates in a plasma reactor.
5.4 Analytic methods
Different analytical techniques were used to characterize the thermophosphates obtained by plasma torch, among which we find: X-ray diffraction (XRD) through equipment GNR XRD 600 of Cu Kα radiation (λ = 1.5418 Å), the diffraction angle range (2Ɵ) varying from 20° to 70°, with a step of 0.02 and integration time 35 min. This technique facilitates the identification and quantification of the crystalline phases of samples (Rietveld refinement method). The X-Ray Fluorescence (XRF) carries out through the Epsilon 4™ equipment of Malvern PANalytical and the Omnian software. This equipment allows the quantification of the elemental chemical composition. The Shimadzu spectrophotometer UV-VIS 1601™ was used to quantify assimilable phosphorus, taking into account, as a reference, the AOAC standards: 963.03, 960.02960.03, and 993.31 [20].
The elemental analysis was performed by XRF on the Iza phosphoric rock feedstock (PRIZA), as well as its thermophosphates (TPPT-IZA), and the results are shown in Table 6. The concentration of the original raw material of Iza (PRIZA) is 27.05 wt. % P2O5, while the thermophosphates M1 to M8 report lower concentration (≤27.00 wt. % P2O5) due to loss on ignition caused by thermal treatment. On the other hand, some samples of thermophosphates increase the concentration of CaO > 37.05 wt. % concerning PRIZA due to the thermal dissociation of carbonates, which is carried out at temperatures between 850 and 1000°C [5]. Likewise, this dissociation of carbonates required greater amounts of energy due to endothermic reaction, and as a result of calcination, there is low reactivity and lower relation between CaO/P2O5 [21]. According to previous reports, the original raw material of Iza (PRIZA) is composed of quartz-sandstone, and the highest concentration of SiO2 was reported as 45.5 wt. % [22], respectively. This is the reason for the high SiO2 concentration of M1 to M8 thermophosphate samples (>29 wt. %), exceeding the optimal concentration required for industrial use (5–15 wt. %) [23]. As a result, it could affect the solubility of the fertilizers. Table 6 summarizes the composition of PRIZA oxides and their thermophosphates.
Chemical composition of thermophosphates samples (wt.%)
PRIZA
M1
M2
M3
M4
M5
M6
M7
M8
Na2O
0.32
0.00
0.00
0.00
0.24
0.35
0.00
0.00
0.19
MgO
0.14
0.19
0.18
0.19
0.17
0.18
0.19
0.19
0.21
Al2O3
3.29
3.25
3.27
3.19
3.36
3.33
3.22
3.31
3.14
SiO2
29.93
30.26
30.42
31.06
31.21
30.62
29.67
29.87
29.46
P205
27.05
27.00
26.62
26.44
26.67
26.59
26.31
26.46
26.24
SO3
0.16
0.24
0.20
0.19
0.18
0.21
0.25
0.21
0.20
K2O
0.30
0.45
0.45
0.42
0.41
0.43
0.47
0.45
0.48
CaO
37.05
36.80
37.08
36.65
35.96
36.48
37.97
37.51
38.03
TiO2
0.14
0.14
0.14
0.14
0.14
0.14
0.16
0.15
0.14
Fe2O3
1.28
1.41
1.40
1.46
1.39
1.41
1.50
1.42
1.49
Others
0.34
0.26
0.26
0.26
0.26
0.27
0.27
0.43
0.43
Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
Table 6.
Chemical composition of thermophosphates obtained by a plasma torch TPPT–IZA (30 A–45 A), copied from [6].
Table 7 shows the method for determining quality indexes of thermophosphates (TPPT-IZA), which include optimal values as CaO/P2O5 ≤ 1.6; MgO/P2O5 ≤ 0.022; R2O3 (Al2O3 + Fe2O3)/P2O5 ≤ 0.1 [23, 24]. Concerning relations CaO/P2O5 and MgO/P2O5, all samples of thermophosphates (TPPT-IZA) comply with quality indexes, facilitating the production of phosphoric acid. However, the ratio of R2O3/P2O5 exceeds these parameters due to high concentrations of Al2O3 and Fe2O3, affecting the solubility.
Table 8 shows the results of elemental analysis by XRF of the Pilar and Ceibita phosphoric rock feedstock (PRPC), and their thermophosphates (TPPT-PC). As a result, PRPC raw material reported a concentration of 32.07 wt. % P2O5, while their thermophosphates (M9, M10, M11, M13, M14, M15, and M16) showed concentration less than this due to loss on ignition, high temperatures of plasma torch reactor, an increase of speed of heat transfer and chemical reactions [25]. However, the sample of thermophosphates M12 showed a higher concentration of 33.12 wt. % P2O5, due to the decomposition of absorbed and combined water, burns organic matter and combination with carbon dioxide, increasing the concentration of calcined phosphate [26]. Regarding the concentration of CaO 54.43 wt. % of PRPC, there were fluctuations in their thermophosphates due to the dissociation of carbonates and the variation of the experimental conditions. On the other hand, SiO2 concentration of M9 to M16 are within previously reported parameters (5–15 wt. %) and is the optimal concentration required for industrial use [23].
Chemical composition of thermophosphates samples (wt.%)
PRPC
M9
M10
M11
M12
M13
M14
M15
M16
Na2O
0.52
0.74
0.00
0.39
0.91
0.53
0.70
0.45
0.50
MgO
0.10
0.16
0.15
0.15
0.16
0.17
0.18
0.14
0.15
Al2O3
1.22
1.10
1.23
1.32
1.18
1.29
1.37
1.18
1.18
SiO2
9.76
9.57
9.91
10.51
10.27
10.18
10.19
9.74
9.50
P205
32.07
31.78
30.96
31.86
33.12
31.29
31.84
30.90
31.65
SO3
0.38
0.49
0.44
0.42
0.41
0.43
0.42
0.43
0.45
K2O
0.13
0.27
0.29
0.25
0.23
0.27
0.27
0.29
0.29
CaO
54.43
54.48
55.66
53.86
52.49
54.30
53.30
55.27
54.64
Fe2O3
0.85
1.04
0.98
0.91
0.89
0.91
0.87
0.97
1.02
Others
0.54
0.39
0.38
0.34
0.34
0.63
0.85
1.81
0.63
Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
Table 8.
Chemical composition of thermophosphates obtained by plasma torch TPPT–PC (30 A–45 A), copied from [6].
According to the optimal values (CaO/P2O5 ≤ 1.6; MgO/P2O5 ≤ 0.022; R2O3 (Al2O3 + Fe2O3)/P2O5 ≤ 0.1) [23, 24], Table 9 summary the quality indexes of thermophosphates (TPPT-PC) from M9 to M16. The relation CaO/P2O5 only met in sample M12, and the others samples are above the expected results due to higher concentrations of CaO coming from the original raw material. Therefore, more elevated amounts of acid could be required to produce fertilizers [24]. Nevertheless, all samples of thermophosphates (TPPT-PC) comply with quality indexes according to the relations MgO/P2O5 and R2O3/P2O5, facilitating the solubility of fertilizers as the final product.
According to a previous study, the Rietveld refinement of the thermophosphate samples of Iza (TPPT-IZA) and Pilar y Ceibita (TPPT-PC) is carried out to identify and quantify the phases with their respective adjustment criteria, such as Rexp, Rwp and x2or GOF (goodness of fit) [6]. As a consequence of the analysis XRD of thermophosphates, the best results of assimilable phosphorus and solubility were taken as a reference to show results. Regarding database standards, the following samples and their phases are referenced, M3 (TPPT-IZA) quartz low ICSD (No 08–3849) and apatite–(CaOH) ICSD (No 08–1442); M9 (TPPT-PC) quartz low ICSD (No 08–3849), calcite ICSD (No 01–8166) and fluorapatite carbonate ICSD (No 07–1855); M10 (TPPT-PC) quartz low ICSD (No 06–2406), calcite ICSD (No 01–8165), hatrurite ICSD (No 08–1100), and fluorapatite carbonate ICSD(No 07–1854), and M12 (TPPT-PC) quartz low ICSD (No 20–0726), calcite ICSD (No 18–0349), and apatite–CaF ICSD(No 09–4082).
On the other hand, Figures 4–7 show crosses representing the experimental data, and lines correspond to simulated XRD patterns. Likewise, Rietveld refinement permitted to establish that the samples of thermophosphates M3, M9, M10, and M12 presented a hexagonal crystalline system with space group P63/m (#176), and the lattice parameters are shown in Table 10.
Figure 4.
XRD pattern of sample M3 TPPT-IZA (30 A, 70 wt. % PR, 30 s). Phases A: Quartz low; B: Apatite–(CaOH).
Crystallographic parameters of thermophosphate, obtained from Rietveld analyses.
According to a previous study, overgrowth of substructures of the material could generate a variation of lattice parameters a and c [27] during plasma torch calcination. In addition, different experimental conditions of thermophosphates could affect the increase of lattice parameters and particle size.
Consequently, the Rietveld analyses allowed for establishing the strongest signals for angles 2θ, and their corresponding crystal lattice planes (hkl) or Miller indices, shown in Table 11.
Sample
TPPT-IZA-M3
TPPT-PC-M9
TPPT-PC-M10
TPPT-PC-M12
Phase
apatite–(CaOH)
fluorapatite carbonate
fluorapatite carbonate
apatite–CaF
hkl
2θ
2θ
2θ
2θ
200
21.93
22.05
22.15
22.33
111
22.96
23.02
23.23
23.36
201
25.49
25.55
25.77
25.94
102
28.12
28.15
28.38
28.57
120
29.15
29.21
29.36
29.54
121
31.97
32.02
32.17
32.35
002
25.89
25.93
26.09
26.21
112
32.24
32.36
32.44
32.62
300
33.24
33.22
32.37
33.54
202
34.22
34.18
34.33
34.51
130
40.11
40.17
40.42
40.48
222
46.93
46.97
47.24
47.28
213
49.57
49.60
49.74
50.04
004
53.25
53.11
53.26
53.43
052
63.41
63.45
63.76
63.73
150
64.14
64.01
64.15
64.46
151
65.54
65.78
65.72
65.86
Table 11.
Crystal structure, lattice parameters, and miller indices of thermophosphates.
6.3 Analysis of assimilable phosphorus and solubility index by UV visible spectrophotometry
Table 12 summarizes the indexes of assimilable phosphorus and solubility obtained by the extraction method with neutral ammonium citrate solution (NAC) and visible UV spectrophotometry [6]. Regarding TPPT-IZA, we can observe that sample M3 subjected to thermal treatment of plasma torch 30 A, showed values of assimilable phosphorus and a solubility index of 3.07 wt. % P2O5 and 11.60 wt. % P2O5, respectively, overcoming the samples M5 to M8, subjected to 45 A current intensities. Likewise, the sample M10 (TPPT-PC), also subjected to thermal treatment of plasma torch 30 A, obtained the highest concentrations: assimilable phosphorus of 4.83% and solubility index of 15.59%, respectively. According to previous reports that used the method NAC, the solubility takes the following values: high >5.4 wt. % P2O5, medium 3.2–4.5 > wt. % P2O5 and lower <2.7 wt. % P2O5 [28]. Therefore, when comparing the solubility of samples M1 to M16, we found that all samples meet high solubility, while the assimilable phosphorus (an extractable fraction with weak acids) shown in Table 12, is low compared to sample superphosphate from the Cuban phosphoric rock (12.28 wt. % P2O5) [29]. However, the Colombian Agricultural Institute (ICA in Spanish) indicates that the minimum acceptable contents for solid fertilizers (NPK) for soil application must be at least 3.0 wt. % P2O5 as assimilable phosphorus [30]. In conclusion, the samples that comply with the parameters of assimilable phosphorus and solubility are M3 (TPPT-IZA) and M9, M10, M12, M13, M14, M15, and M16 (TPPT-PC), despite the non-use of additives to improve the quality indexes and the influence of novel plasma torch method in the results.
TPPT
Sample
P2O5 Total [wt.%]
P2O5 Assimilable [wt.%]
Solubility Index [wt.%]
IZA
M1
27.00
2.45
9.09
M2
26.62
2.70
10.14
M3
26.44
3.07
11.60
M4
26.67
2.98
11.17
M5
26.59
2.96
11.12
M6
26.31
2.89
10.99
M7
26.46
2.66
10.05
M8
26.24
2.48
9.46
PC
M9
31.78
4.03
12.69
M10
30.96
4.83
15.59
M11
31.86
2.64
8.28
M12
33.12
3.47
10.49
M13
31.29
3.14
10.04
M14
31.84
3.09
9.72
M15
30.9
3.03
9.80
M16
31.65
3.41
10.78
PRIZA
27.05
3.62
13.38
PRPC
32.07
4.02
12.54
Table 12.
Analysis of assimilable phosphorus and solubility index, copied from [6].
As a consequence of the above, it is shown that the use of the plasma torch reactor technology under conditions 30 A, 70% PRPC, and 40 s (TPPT-PC-M12) favors the calcination and conversion of phosphoric rock and increases the concentrations of assimilable phosphorus, solubility index, and total phosphorus, as reported in the previous studies [25, 31].
6.4 Comparison of the composition of organic fertilizers with thermophosphates
Natural materials such as organic fertilizers from different animal or plant sources, including livestock manure, green manures, crop residues, household waste, and compost, improve soil fertility and increase water retention and NPK content [32]. According to certificate requirements of organic fertilizers, values of N-P-K must be 4%, respectively [33]. Table 13 shows different sources of organic fertilizers, and all comply with this standard. However, total phosphorus (% P2O5 Total) in organic fertilizers is low (less than 10%) compared with thermophosphates (≥26%) in Table 12 due to their origin from natural sources. At the same time, the thermophosphates were obtained from mineral deposits with high concentrations of phosphate and calcination process.
Chemical characterization for different sources of organic fertilizers.
On the other hand, many factors affect the P dynamic in soils, such as pH, salinity, interaction with micronutrients, redox potential, soil structure and texture, and enzymatic activity [38]. However, the advantage of organic fertilizers is directly lead nutrients to plants, slow-release, increase organic matter and improve soil biological activity [32]. Finally, due to the growth of the world population and the need to obtain different sources of nutrients to produce food, organic fertilizers are a cheap, globally available, and environmentally friendly resource. However, inorganic fertilizers such as thermophosphates generated fast solutions for crops due to high concentration and production in scale.
6.5 Analysis of energy consumption
According to a study on energy consumption in an electric oven, the rank of the value is 12.0 kW-h/Kg-14.0 kW-h/Kg [39]. At the same time, thermophosphates shown in Table 14 TPPT-IZA and TPPT-PC, submitted low energy consumption between 0.64 kW-h/Kg and 1.28 kW-h/Kg, respectively, for treating samples with a plasma torch to 30 A–45 A. Likewise, a previous study indicated that plasma energy consumption is 1.1 kW-h/Kg and 0.8–1 kW-h/Kg, values very close for this study [40, 41]. Plasma reactor technology also is used for tread waste of printed circuit board (PCB) and recovery metals, precious elements, and hazardous elements, with 2.0 kW-h/Kg electricity consumption [42]. Moreover, plasma technology has been used to simulate the production of biofuels starting from syngas with an electrical consumption of 0.48–2.2 kW-h/Kg for organic waste and 2.23 kW-h/Kg for wood sawdust [43, 44].
TPPT
Current intensity (A)
Plasma torch (KW)
Calcination time (h)
(KW-h)
(KW-h/Kg)
IZA
30
3.24
0.0083
0.027
0.64
45
4.86
0.0111
0.054
1.28
PC
30
3.24
0.0083
0.027
0.64
45
4.86
0.0111
0.054
1.28
Table 14.
Energetic consumption for thermophosphates produced by a plasma torch, copied from [6].
As a result of the thermal treatment of plasma torch for samples PRIZA and PRPC subjected to current intensities 30 A–45 A, thermophosphates fertilizers were obtained, likewise, shown the Rietveld analysis of experimental diffraction patterns.
The thermophosphates have a hexagonal crystalline system with space group P63/m (#176). Likewise, the Rietveld analysis shows that the most representative crystalline phases of thermophosphates are fluorapatite carbonate, apatite-(CaF), and apatite-(CaOH), respectively. Quality indices were determined as follows, total phosphorus, assimilable phosphorus, and solubility. The most representative results of TPPT-IZA sample M3 correspond to 26.44 wt. % P2O5, 3.07 wt.% P2O5, and 11.60 wt.% P2O5, respectively. On the other hand, the same analysis was carried out for TPPT–PC samples M9, M10, and M12, and the result was: 31,78 wt.% P2O5, 4.03 wt.% P2O5, and 12.69 wt.% P2O5; 30.96 wt.% P2O5, 4.83 wt.% P2O5, and 15.59 wt.% P2O5; 33.12 wt.% P2O5, 3.47 wt.% P2O5, and 10.49 wt.% P2O5, respectively. The best results shown above were obtained under current intensities of 30 A, while the percentage by weight and calcination times of PR can vary depending on the mineral source. TPPT-IZA and TPPT-PC thermophosphates showed low energy consumption between 0.64 kWh/Kg and 1.28 kWh/Kg, respectively. For samples treated with a plasma torch of 30 A–45 A, it was shown that a plasma torch technology is a viable alternative for obtaining thermophosphates at a low cost and using less calcination time for each sample. In addition, it makes the process more efficient and sustainable.
National Learning Service Sena, Mining Center and Sennova, Sogamoso, Colombia; Enterprise Phosphate Boyacá, Pesca, Colombia; Pedagogical and Technological University of Colombia IRME, Sogamoso, Colombia.
1.CRU Consulting. Roca Fósfórica Caracterización y análisis de mercado internacional de minerales en el corto, mediano, y largo plazo con vigencia al año 2035. Santiago de Chile: CRU; 2018. pp. 1-51
2.CRU Strategies. Estudio para caracterizar el mercado nacional e internacional de los minerales estratégicos Reporte final preparado para UPME. Santiago de Chile: Upme; 2013. p. 957
3.Ministerio de Minas y Energía República de Colombia. Plan Nacional de Desarrollo Minero con Horizonte a 2025. Bogotá D.C.: Minería responsable con el territorio; 2017. p. 174. Available from: www.upme.gov.co
4.National Mining Agency. Roca Fosfórica. Bogotá D.C.: National Mining Agency; 2016. Available from: https://www.anm.gov.co/sites/default/files/ficha_roca_fosforica_es.pdf
5.Abouzeid AZM. Physical and thermal treatment of phosphate ores - An overview. International Journal of Mineral Processing. 2008;85(4):59-84
6.Espinel Pérez NM, Pazos MC, Parra E, Martínez D. Calcination of phosphoric rock by plasma torch, to obtain thermophosphates fertilizers. Revista Colombiana de Materiales. 2021;18:54-68. Available from: https://revistas.udea.edu.co/index.php/materiales/article/view/345653
7.Departamento Nacional de Planeación R de C. Objetivos de Desarrollo Sostenible (ODS) Colombia 2030. Comisión ODS; 2015. Available from: https://www.ods.gov.co/es [Accessed: April 8, 2022]
8.Richardson AE. Regulating the phosphorus nutrition of plants: Molecular biology meeting agronomic needs. Plant and Soil. 2009;322(1):17-24
9.Yang XJ, Finnegan PM. Regulation of phosphate starvation responses in higher plants. Annals of Botany. 2010;105(4):513-526
10.Johnston AE. Potassium and Nitrogen Interactions in Crops. Harpenden: Potash Development Association; 2012. pp. 1-16. Available from: http://www.pda.org.uk
11.Ridder M De, Jong S De, Polchar J, Lingemann S. Risks and opportunities in the global phosphate rock market: Robust strategies in times of uncertainty. 2012. 96. Available from: https://www.econbiz.de/Record/risks-and-opportunities-in-the-global-phosphate-rock-market-robust-strategies-in-times-of-uncertainty-ridder-marjolein/10009713558. [Accessed: October 18, 2013]
12.Kooroshy J, Meindersma C, Podkolinski R, Rademaker M, Sweijs T, Diederen AM, et al. Scarcity of minerals. A strategic security issue. The Hague: The Hague Centre for Strategies Studies; 2009. pp. 23-28. Available from: https://hcss.nl/wp-content/uploads/2010/01/HCSS_Scarcity_of_Minerals.pdf
13.Fahami A, Nasiri-Tabrizi B, Ebrahimi-Kahrizsangi R. Mechanosynthesis and characterization of chlorapatite nanopowders. Materials Letters. 2013;110:117-121
14.Legeros RZ, Ito A, Ishikawa K, Sakae T, Legeros JP. Fundamentals of hydroxyapatite and related calcium phosphates. Advanced Biomaterials: Fundamentals, Processing, and Applications. 2010:19-52
15.Kijkowska R, Lin S, LeGeros RZ. Physico-chemical and thermal properties of chlor-, fluor- and hydroxyapatites. Key Engineering Materials. 2002;218–220:31-34
16.Pereira SCC, Cekinski E, Valarelli JV. Process for production of calcined phosphate in a grate furnace. Fertility Research. 1988;16(2):169-177
17.Watti A, Alnjjar M, Hammal A. Improving the specifications of Syrian raw phosphate by thermal treatment. Arabian Journal of Chemistry. 2016;9:S637-S642. DOI: 10.1016/j.arabjc.2011.07.009
18.Gomez E, Rani DA, Cheeseman CR, Deegan D, Wise M, Boccaccini AR. Thermal plasma technology for the treatment of wastes: A critical review. Journal of Hazardous Materials. 2009;161(2–3):614-626
19.Bustinza NK. Aplicaciones Medioambientales del Plasma. DYNA. 1994;6:45-47
20.AOAC. Official Methods of Analysis. 15th ed. Vol. 1. Arlington Virginia USA: Association Official of Analitycal Chemists; 1990. pp. 12-16
21.Shariati S, Ramadi A, Salsani A. Beneficiation of low-grade phosphate deposits by a combination of calcination and shaking tables: Southwest Iran. Minerals. 2015;5(3):367-379. Available from: https://www.mdpi.com/2075-163X/5/3/367
22.Cuy Buitrago HL, Martín G. Correlación estratigráfica y caracterización petrográfica de algunos niveles fosfáticos de la formación hermitaño (Kse) aflorantes en los municipios de Iza (vereda centro) y Sogamoso (vereda Pilar y Ceibita). Sogamoso, Boyacá-Colombia: Universidad Pedagógica y Tecnológica de Colombia; 2016
23.Unión Temporal GI. Georecursos. Análisis de la Estructura Productiva y Mercados de la Roca Fosfórica. Bogotá D.C.: Unión Temporal G.I. Georecursos; 2005
24.FAO. Utilización de las rocas fosfóricas para una agricultura sostenible. In: Boletín FAO Fertilizantes y Nutrición Vegetal. 13th ed. Vol. 13. Roma Italia: FAO; 2007. p. 177. Available from: http://www.fao.org/3/a-y5053s.pdf
25.Venkatramani N. Industrial plasma torches and applications. Current Science. 2002;83(3):254-262
26.Elgharbi S, Horchani-Naifer K, Férid M. Investigation of the structural and mineralogical changes of Tunisian phosphorite during calcinations. Journal of Thermal Analysis and Calorimetry. 2015;119(1):265-271
27.Chaabouni A, Chtara C, Nzihou A, El FH. Textural And Mineralogical Studies Of Two Tunisian Sedimentary Phosphates Or Carbonated Fluorapatite Used In The Process Of Production Of Phosphoric Acid. 2016;5:05
28.Ardalan M, Gholizadeh A, Tehrani MM, Hosseini HM, Karimian N. Solubility test in some phosphate rocks and their potential for direct application in soil. World Applied Sciences Journal. 2009;6(2):182-190
29.Ordoñez Sánchez YC, Rodríguez Acosta C, Rodríguez SL. Determinación de las condiciones óptimas para la obtención de un fertilizante fosfatado a partir de la roca fosfórica cubana. Ingenieria y Competitividad. 1969;19(2):137-148
30.Colombian Agricultural Institute. Reglamento Técnico de Fertilizantes y Acondicionadores de Suelos para Colombia [Internet]. Bogotá D.C.: “ICA”, Colombian Agricultural Institute; 2003. p. 71. Available from: https://www.ica.gov.co/areas/agricola/servicios/fertilizantes-y-bio-insumos-agricolas/resolucion-150-de-2003-1-1.aspx
31.Mosse AL, Pechkovsky VV, Dzyuba ED, Krasovskaya LI. Production of condensed phosphate by plasma chemical treatment of phosphate raw material. Plasma Chemistry and Plasma Processing. 1985;5(3):275-282
32.Roba TB. Review on: The effect of mixing organic and inorganic fertilizer on productivity and soil fertility. OALib. 2018;05(06):1-11
33.Widyastuti S, Jupri A, Nikmatullah A, Kurniawan NSH, Kirana IAP, Abidin AS, et al. Analyses of organic matter and heavy metal composition in formulated macroalgae-based organic fertilizer. IOP Conference Series: Earth and Environmental Science. 2021;913(1):1-8. Article ID: 012024
34.Bergstrand KJ. Organic fertilizers in greenhouse production systems – A review. Scientia Horticulturae. 2022;295(2021):1-8. Article ID: 110855
35.De Morais RK, Zacharias MB, Della J, Forti VA. The potential of organic fertilizer application on the production and bromatological composition of millet (Cenchrus americanu). The Interne. 2022:1-13. Available from: https://www.researchsquare.com/article/rs-1486898/v1
36.Cabilovski R, Manojlovic M, Bogdanovic D, Magazin N, Keserovic Z, Sitaula BK. Mulch type and application of manure and composts in strawberry (Fragaria × ananassa Duch.) production: Impact on soil fertility and yield. Zemdirbyste. 2014;101(1):67-74
37.Eckhardt DP, Redin M, Santana NA, De CL, Dominguez J, Jacques RJS, et al. Cattle manure bioconversion effect on the availability of nitrogen, phosphorus, and potassium in soil. Revista Brasileira de Ciência do Solo. 2018;42(0):1-10
38.Lizcano-Toledo R, Reyes-Martín MP, Celi L, Fernández-Ondoño E. Phosphorus dynamics in the soil–plant–environment relationship in cropping systems: A review. Applied Sciences. 2021;11(23)
39.El Ouardi EM. Effect of temperature and residence time of calcination phosphate on the chemical reactivity: Application to the case of Bouchane phosphate (Morocco). International Journal of Innovation and Applied Studies. 2013;4(2):387-407
40.Riegel ER, Kent JA. In: Kent PD JA, editor. Riegel’s Handbook of Industrial Chemistry. Boston, MA: Springer Science & Business Media; 1991. pp. 1-871
41.La T-g P. tecnología de plasma y residuos sólidos. La Tecnol Plasma y Residuos Sólidos. 2009;13(2):51-56
42.Sanito RC, You SJ, Wang YF. Application of plasma technology for treating e-waste: A review. Journal of Environmental Management. 2021;288(200):112380. DOI: 10.1016/j.jenvman.2021.112380
43.Tamayo-Pacheco JJ, Peña-Pupo L, Vázquez-Peña A, Brito-Sauvanell ÁL. Hydrogen-rich syngas production by plasma gasification of existing biomasses in Cuba. Rev Ciencias Técnicas Agropecu. 2020;29(4):53-63. Available from: http://scielo.sld.cu/scielo.php?script=sci_arttext&pid=S2071-00542020000400006&lang=pt
44.Aliferov AI, Anshakov AS, Domarov PV. Plasma gasification of organic waste for production of motor fuel. Journal of Engineering Thermophysics. 2022;31(2):238-247
Written By
Nelson Mauricio Espinel Pérez
Submitted: 29 January 2023Reviewed: 27 February 2023Published: 28 March 2023
Open access peer-reviewed chapter
