3.1. The Elemental Composition of Phosphate Rocks
The elemental analysis results of PRs showed that they were mainly composed of CaO, P2O5, SiO2, F, SO3, and Na2O, as well as MgO, Al2O3, Fe2O3, SrO, and K2O. The CaO content accounted for 48.4–57.1%. The content of P2O5 in PR1, PR2, PR3, PR4, and PR5 was 29.0, 28.7, 30.4, 29.4, and 31.3%, respectively. The smallest concentration of P2O5 was found in PR2, and the largest was in PR5.
The concentration of P
2O
5 in the ore determines the possibility of its processing; therefore, the deposits can be described as rich or poor in phosphorus. Based on the P
2O
5 content, three phosphate grades can be distinguished: low-grade ores (12–16% P
2O
5), medium-grade ores (17–25% P
2O
5), and high-grade ores (26–35% P
2O
5). The phosphate ore enrichment processes allow the gangue minerals to be separated from the economical phosphate value [
18]. Several methods are used to upgrade the low-grade phosphate ore to a marketable-grade product, such as crushing, grinding, screening, scrubbing, heavy media separation, washing, roasting, calcination, and flotation. Phosphate deposits, which after mining and processing, yield a raw material containing 28–38% P
2O
5, are considered economically viable [
19].
There are many considerations when selecting a PR supply for the production of wet-process acid. One of the factors taken into account in assessing the quality of deposits is the CaO/P
2O
5 weight ratio, as this governs the amount of sulfuric acid that is required to acidulate the PR in WPA manufacture. The CaO/P
2O
5 weight ratio is a common measure of phosphate rock quality. For pure apatite, the ratio is 1.32, and the commercially available rock may have a CaO/P
2O
5 ratio of up to 1.6 [
6]. In the analyzed PRs samples, the CaO/P
2O
5 ratio accounted for 1.6–1.9.
The content of major constituents of PRs, such as Al2O3, K2O, MgO, Na2O, SO3, and SrO, varied depending on their origin and accounted for 0.13–0.51% Al2O3, 0.10–0.22% K2O, 0.34–1.31% MgO, 0.52–1.54% Na2O, 1.46–3.36% SO3, and 0.12–0.27% SrO. Those results show no significant differences in the PRs composition, contrary to the content of SiO2 and Fe2O3. A relatively high concentration of SiO2 was found in the PR2 (8.67%) and PR5 (5.77%) samples compared to PR1 (2.93%), PR3 (1.67%), and PR4 (2.66%). The content of Fe2O3 in PRs varied from 0.205 to 0.64%, except for the PR5 deposit, in which the concentration of Fe2O3 was found to be higher (2.31%).
The Al, Fe, and Mg compounds are the main impurities that move from PRs to phosphoric acid in the wet process [
19]. The impurities impart undesired color, turbidity, and viscosity and can increase the corrosiveness of WPA [
20]. An increase in the Al content causes an increase in the density and viscosity of WPA, making it difficult to process it. In the concentrated WPA, it can precipitate in the form of orthophosphates(V). Nevertheless, the presence of Al has a positive effect on acid filtration. The Fe, and likewise the Al, in the concentrated acids can precipitate in the form of orthophosphates(V), causing P
2O
5 losses. The large Fe content affects the viscosity of the WPA negatively. The presence of Mg in WPA is undesirable due to its effect on the increase in viscosity and the formation of insoluble precipitates [
6,
21,
22].
In industrial practice, to determine the degree of purity of the raw material, the MER index (
minor elements ratio) is typically used, which is the sum of the oxides of the major impurities relative to the P
2O
5 content:
where Al
2O
3, Fe
2O
3, MgO and P
2O
5 are expressed in wt.%.
The value of the MER index in PR1, PR2, PR3, PR4, and PR5 was 8.46%, 3.04%, 2.46%, 6.82%, and 10.4%, respectively. Low MER is important for the rock to be processed to WPA and P-fertilizers.
Among the main impurities that move from the phosphate raw material to the WPA, Cl and F ions should also be mentioned. The content of Cl in the analyzed PRs was at the level of 100 mg∙kg
−1, except for PR2 (635 mg∙kg
−1) and PR3 (1278 mg∙kg
−1). Even though the process of obtaining WPA is corrosive and requires the use of acid-resistant steel, too high a concentration of Cl ions (above 0.1% by mass) can cause corrosion of this steel [
6]. The content of F in the phosphate raw material can be as high as 3–4% by mass [
23] which is confirmed in this study. The F content varied from 3.12 to 4.07%. During the extraction process, HF and SiF
4 pass into the flue gases, from which H
2SiF
6 is formed in the absorption process. The silica hexafluoride ion reacts with the Na and K ions precipitate and may hinder the process of exhaust gas purification and filtration [
6]. PRs are generally pretreated by calcination and digestion beneficiation. During the calcination and digestion, F and Cl in PRs can be released by volatilization and dissolution [
24].
Due to the fact that PRs will be used to produce WPA and P-fertilizers, the composition of PRs was compared with the regulatory parameters set up by EU Regulation 2019/1009 relating to the macronutrient inorganic fertilizers. The regulation sets permissible values for the heavy metal (As, Pb, Cd, Ni, Hg) and Cr(VI) contents depending on the type of fertilizer product. The content of As in PRs varied from 5.24 to 23.8 mg∙kg
−1, and all PRs samples had As concentrations below the maximum value (40 mg∙kg
−1). In the case of Pb, all samples also fulfilled the requirement (120 mg∙kg
−1), and the Pb concentration was below the LOQ value (<8 mg∙kg
−1) of the ICP-OES method. The content of Hg was much lower than the maximum concentration (1 mg∙kg
−1) as well as the Cr(VI) content (2 mg∙kg
−1) at the µg∙kg
−1 level. The permissible value for the Cd depends on the P content in macronutrient inorganic fertilizer. Where fertilizer has a total P content of less than 5% P
2O
5 equivalent by mass, the Cd content must not exceed 3 mg∙kg
−1, or if it has a P content equivalent or more by mass of 5% P
2O
5 (P-fertilizers), the Cd content must not exceed 60 mg∙kg
−1 P
2O
5 [
15]. The Cd concentration in PR1, PR2, PR3, PR4, and PR5 was 14.3, 7.52, 24.8, 14.5, and 16.0 mg∙kg
−1, respectively. The results from this study show a good agreement with the literature reports [
2,
25].
The EU Regulation 2019/1009 also determines the permissible levels of Cu (600 mg∙kg−1) and Zn (1500 mg∙kg−1); however, these limit values will not apply where Cu or Zn has been intentionally added to an inorganic fertilizer to correct a soil micronutrient deficiency. Moreover, the Cu and Zn contents in PRs were relatively small, 94–98% and 68–90%, respectively, smaller than the maximum permitted values.
Identification and quantification of key sources of heavy metals and Cr(VI) in the phosphate raw materials and their control are crucial for reducing heavy metal content in the P-fertilizers and reducing contamination releases to the environment through agricultural applications. The results of this study presented in
Table 5 show that the As, Cd, Pb, Ni, Hg, Cu, Zn, and Cr(VI) contents in all analyzed PRs did not exceed the limit values.
PRs contain naturally occurring uranium (U), and the radioactive components of the U decay series are associated with the phosphate material [
26]. During the digestion of PR by the dihydrate process, most of the U is presented in the phosphoric acid solution. It is estimated that 85–95% of the U in the PR feed goes into the solution [
21]. The amount of U varied from 34.7 to 110 mg∙kg
−1 in analyzed samples. In addition, in the composition of the analyzed PRs, the occurrence of trace elements such as Cr, Mn, Ti, and V at the level of mg∙kg
−1 was found.
The analysis of the composition of PRs may not be sufficient to assess whether a given material will be suitable for use in a given plant for WPA and P-fertilizer production. For this reason, before selecting a particular raw material or its mixture, it is necessary to carry out laboratory tests with it as well as pilot production tests (extraction, filtration, concentration), which will allow the selection of appropriate conditions for the technological process.
The precision of the method was evaluated via repeatability and can be expressed as the relative standard deviation (RSD) of a series of measurements. The accuracy expresses the difference between the value found experimentally and the reference value. In this study, Western Phosphate Rock (NIST 694) was used to establish the accuracy through the values calculated using Equation (2).
where the
found value is the analyte concentration determined by the proposed method, and the
certified value is the concentration value of the analyte reported in the SRM certificate of analysis.
The precision and accuracy expressed as RSD (%) and recovery (%), respectively, obtained for the optimized analytical methods, as well as the certified values and the found values for SRM, can be found in
Table 6. The recovery was between 85.3% for U and 109% for K
2O, and the RSD values ranged from 0.67% to 12.8%.
3.2. The Mineralogical Composition of Phosphate Rocks
The content of individual crystalline phases was determined by the semi-quantitative Rietveld method with the crystal structure refinement with the help of the below-mentioned cards from the PDF-4 + database. The total content of apatites was shown compared to the other phases in the samples. The size of the apatite crystallites was not estimated due to the overlapping of many reflections. The width of the reflections in the case of apatites is comparable, so the average size of the crystallites should be similar (
Table 7).
In the sample PR1, there are reflections characteristic of the angle 2θ: 32.0°, 32.3°, 33.3°, and 34.2° of the fluorapatite carbonate phase. The fluorapatite carbonate reflections are widened, in particular, their base on their left side, which is easy to observe at the angles 2θ: 25.5°, 28.9°, and 31.8°. This suggests the presence of hydroxyapatite carbonate with the reflections characteristic of the angle 2θ: 31.9°, 32.2°, 33.1°, and 34.1°, as well as hydroxyapatite with the reflexes characteristic of the 2θ angle: 61.3°, 31.8°, 32.2°, and 32.9°. The hydroxyapatite carbonate and hydroxyapatite phases complement the reflections from fluorapatite carbonate, which is the major part of the overlapping reflections. Due to the similar angular reflexes of these phases, they are denoted in the graphic as Ca
5(PO
4)
3[F,OH,CO
3] as a group of phases with similar characteristic reflections without distinguishing between individual phases of apatite. In addition to the recognized phases of apatite, the sample probably includes the ankerite and dolomite phases, the main reflections of which are visible at the angles of 2θ: 30.8° and 30.9°, respectively. It is possible that the sample also contains calcite, whose reflexes coincide partially with those of apatite and widen them on their right at the angle of 2θ of 29.4°. Another phase that can be attributed to the reflections at the angles of 2θ: 20.8° and 26.5° is quartz. The X-ray powder diffractogram of PR1 is shown in
Figure 4a.
Figure 4b shows the diffractogram of PR4, which in terms of diffraction lines, their width, intensity, and thus the content and occurrence of phases is similar to PR1. The main difference can be observed at the angle of 2θ of 30.8°, based on the presence of ankerite and dolomite phases. In the case of PR4, the reflex is lower, and no “double peak” is visible in it, as was the case with PR1, meaning that the dolomite content must be smaller.
Figure 5a shows the XRD pattern of PR2. Compared to the diffraction patterns described previously, the differences are significant, both in terms of the presence of phases and their content. The reflections characteristic of the apatite phase are shifted towards the smaller 2θ angles, which can be the result of a greater proportion of other apatite phases than the fluorapatite carbonate phase. The dominant phase in this sample is probably hydroxyapatite with the reflections characteristic of 2θ angles: 25.8°, 31.9°, 33.2°, and 46.9°, and presumably the complementary phase, increasing the width of hydroxyapatite reflections at the base is probably hydroxyapatite carbonate with the reflections characteristic of the 2θ angles: 31.9°, 32.2°, 33.1°, and 34.1°. Based on the diffractograms, it is not possible to indicate whether it is fluoroapatite in the PR2 sample. This sample has a much larger quartz content with visible reflections at the angles of 2θ: 20.8°, 26.6°, and 50.0°. It is also possible to indicate clearly the presence of calcite, the reflexes of which are located at the angles 2θ: 29.4°, 35.9°, 43.2°, and 48.5°. Probably it occurs here, as before ankerite.
The XRD pattern of PR3 is presented in
Figure 5b. Similar to the sample PR2, the main phase is probably hydroxyapatite with the reflections characteristic of the 2θ angles: 25.8°, 31.9°, 33.2°, and 46.9°. As for PR2, it is difficult to indicate other phases, such as hydroxyapatite carbonate, the reflections of which can be mostly “covered” by hydroxyapatite. The phase that can be clearly defined based on the visible and high reflections is calcite. The remaining phases with small contents are probably quartz for the angles 2θ of 20.8° and 26.6°; ankerite for the angle 2θ of 30.8°; dolomite for the angle 2θ of 30.9°; and gypsum for 2θ angles of 11.6°, 20.7°, 23.4°, and 29.1°.
In the sample PR5, the dominant phase is that of fluorapatite or hydroxyapatite. The reflections from these phases have similar intensities and locations, hence the difficulty in the qualitative and quantitative determination. In addition, the sample contains calcite with the characteristic reflections at 29.4°, 35.9°, and 43.1°; and quartz with the principal reflections at 26.6° and 28.8°. Dolomite with the prominent feature reflection at the 2θ of 30.9° is likely to be found. The diffractogram of PR5, depending on the intensity of the signal from the angle 2θ, is shown in
Figure 5c.