3.1. Characterization of UC
The UC’s specific mass (SM) was equivalent to 2.05 g/cm
3 (
Table 4) in accordance with the literature [
26,
44]. This result confirms the great performance of the fraction separation process, based on the difference in specific mass between the UC and FA, which presents a specific mass in the range of 2.3 to 2.45 g/cm
3 [
11,
31]. The value obtained for UC was expected since the employment of high temperature in the gasification process promotes a decrease in the specific mass, which may be related to an increase in porosity [
8,
45]. The surface area (SA) was 23.984 m
2/g, which is in the range of 16.5 to 58 m
2/g obtained by other authors for UC [
26,
44,
46]. Carbons derived from class F fly ash, which are obtained from the burning of low-calcium bituminous coal, normally have low surface areas when compared to active carbons [
26,
47].
The measurement of pore diameter (APD) was 0.844 nm, which is similar to the range indicated by the literature and, according to IUPAC, is classified as a micropore (<2 nm) [
48]. The low SA can also be explained by the number of pores as well as by the low APD and PV, as these properties are related to each other [
44]. Based on the calorimetric analysis, it was possible to observe an increase in the CV when compared to the coal from the Candiota mine, which presented values in the range of 3847.7 to 4701.8 cal/g.
Table 5 shows the colorimetric analysis.
The colorimetric analysis indicated a tendency of the UC to be black in color as the value obtained for the
L * parameter was lower than 28.44. This result can be related to the success of FA separation since the colorimetric analysis can be used as a technique to identify the presence, or not, of UC [
49]. Based on these authors, a lighter sample indicates higher content of UC. The authors of [
12] presented a colorimetric analysis of FA, obtaining an
L * value of 10.34, which, compared to the value obtained in the present work and according to other literature [
12], indicates an increase in UC content after the decantation process. Analyzing the data obtained, it is possible to observe an increase in
L * value in the order RC > UC > FA, which is in accordance with another study [
49], as this order follows the same tendency of the gasification process, where the raw material (RC) is the lightest, followed by the other products (UC and FA).
Figure 1 shows the FTIR spectra, which present peaks similar to the ones obtained by the literature [
50] when analyzing high-density coal (>1.8 g/cm
3). First, is possible to observe at approximately 3600 cm
−1 (OH stretching region) four bands that are characteristic of the kaolinite compound [
50,
51,
52,
53]. The first one is located at 3620 cm
−1 representing the inner hydroxyl groups; then the peaks at 3653 and 3669 cm
−1 indicate the in-phase symmetric stretching vibration and 3695 cm
−1 the out-of-phase stretching vibration [
52]. The peaks at 2929 and 2853 cm
−1 (
Figure 2) indicate CH
2 asymmetric and symmetric stretching vibration, respectively [
50,
54]. The low intensity of the peak at 2929 cm
−1 may be related to the fact that the proportion of aliphatic -CH
3 hydrogen is substituted by hydroxyl groups [
53]. The 1438 cm
−1 peak represents the CH
3 asymmetric deformation vibration [
50,
53,
54]. The peaks at 934 and 915 cm
−1 may be related to the hydroxyl group in the carboxylic acid structure and phenolic hydroxyl group, respectively [
50,
55]. The peak located at 777 cm
−1 is related to Si-O-Si bending vibration [
56], and the band in the region near 600 cm
−1 denotes the bending of Si-OH groups [
57].
The fluorescence X-ray analysis (
Table 6) indicated that the UC is mainly composed of mineral compounds, such as SiO
2, Al
2O
3, and Fe
2O
3, corroborating the information indicated by the FT-IR spectrum, and the results obtained for high-carbon FA [
28]. When compared to coal from the same mine, it is possible to observe that after the separation there is a decrease in mineral content, which was expected due to the separation process from FA.
The pH
CZ was 5.1, as indicated in
Figure 2, which means that, in solutions with pH lower than this value, the adsorbent surface presents a positive charge, and at a higher pH value it has a negative charge. This value was similar to the results obtained by other authors, with pH
CZ equivalent to values lower than 7 [
24,
58]. The UC presented a wide range of pH values above the pH
CZ, indicating that it has favorable characteristics for interaction with cationic dyes, such as MB, CV, and BF [
11,
24,
58]. The industrial conditions of UC production lead to acid functional group formation, such as carboxylic, lactonic, phenolic, and acyls in acid anhydrides, and neutral groups, such as carbonyl functional groups on the UC surface, as indicated by the FTIR analysis, which confirms its ability to interact with positively charged molecules [
16].
Figure 3 and
Figure 4 present the adsorption capacity and removal of industrial dyes, which show results in the following order: IC (1.66 mg/g) < BG (5.84 mg/g) < BF (13.83 mg/g) < MB (16 mg/g) < CV (16.34 mg/g). It is possible to notice that the UC allowed the more efficient removal of cationic dyes, such as CV, MB, and BF in accordance with the information presented by the pH
CZ analysis. However, there is a difference between the values obtained for these dyes, and this behavior may be associated with molecule dye dimensions, as well as the charge effect indicated previously by the PCZ study [
24]. As reported by the literature, CV adsorption occurs through a bond between dye and oxygen atoms present on SiO
2 and Al
2O
3 [
59], which, as reported by FRX analysis, were the major mineral compounds present in the UC. Reported adsorption capacity values were in the range of 33.46 to 80.36 mg/g for CV when applying an adsorbent material similar to UC. The difference between these values and those observed in the present study may be related to the employment of higher temperatures in the literature [
58]. With regard to the MB adsorption onto UC, the literature has reported values near 79.96 mg/g, and the difference between this value and the one obtained in the present study may be related to the gasification conditions, which play an important role in adsorbent properties, such as surface functional groups, pore volume and size, surface area, and others [
60,
61]. The literature has indicated adsorption capacity values of BF in the range of 7.16 to 34 mg/g by material with similar properties to UC [
51]. The values obtained for BG and IC are in agreement with values reported by other authors and may be related to the anionic nature of these dyes [
62].
Figure 5 presents the kinetic data, which indicates that the first step of the adsorption process is characterized by a fast increase in dye adsorption capacity within the first five minutes. According to the literature, this may be related to the occupation of available adsorption sites at the beginning, which leads to a higher difficulty for other dye molecules to be adsorbed due to repulsion forces between the adsorbent and the dye surface [
63]. Considering the high adsorption rate, it is possible to assume that the process adsorptive was determined mostly by the mass transfer mechanism convective, which was confirmed by the kinetic model fitting (
Table 7). It is possible to observe that the adsorption capacity at equilibrium was equal to almost 50 mg/g, which is lower than the value obtained by Wang et al. [
58] and must be related to the adsorbent dosage since the adsorption capacity may be related to the availability of adsorption sites.
The two kinetic models showed a good fit to the experimental data with high correlation coefficients (
R2 > 0.999); however, the PSO model presented the best fit. This result is consistent with those observed by other authors in their studies on the adsorption kinetics of dyes on UC [
24,
35,
51,
64,
65]. The PSO model describes an adsorption process that occurs on a heterogeneous surface which has a random distribution and, also, indicates that the interaction between dye and adsorbate is chemical, which involves the sharing or exchange of electrons [
59,
66,
67]. The fact that the adsorption process is mainly governed by chemisorption is related to the electrostatic interaction between the dye and the UC, which occurs due to the cationic nature of MB and the UC surface composed of negative charges. Another important aspect is the difference between the UC pore diameter and the MB molecule size. According to the characterization analysis, the UC has smaller pores than the MB molecule, which is unfavorable for diffusion adsorption and suggests surface adsorption related to a convective adsorption mechanism [
68,
69].
The equilibrium value
k2 is related to the adsorption rate, and the low value observed by the fit is in agreement with the fact that the system reaches equilibrium quickly. This result may be related to the high active sites and the O-containing functional groups on the surface of UC, which improve the electrostatic relationship between the UC and MB molecules [
70].
3.2. Adsorption Isotherms
The adsorption studies were conducted at two different temperatures, 303 and 328 K to evaluate the influence of temperature on the adsorption process; the experimental data are shown in
Figure 6.
According to IUPAC classification, the isotherms shown below may be classified as Type I, which is considered reversible and is given to microporous solids with small external surfaces, information that is in accordance with the results obtained through the BET analysis [
48]. It was possible to observe that the Freundlich model presented the best fit for the lowest temperature of 218 K, which was also observed by other authors in a study regarding the adsorption of Naphthol Green B on UC at a temperature of 273 K [
46]. This result (
Table 8) suggests that the surface and pores of the UC are heterogeneous at lower temperatures, have non-uniform heat distribution and adsorption affinities, and have a multilayer adsorption mechanism [
24,
70,
71,
72,
73].
It is possible to observe a decrease in the value of
kF with increasing temperature. The value of
kF obtained at 291 and 328 K were, respectively, s 5.48 and 4.65, which indicates the higher the temperature, the more favorable is the adsorption process [
74]. The value of
n indicates heterogeneity, with
n higher than one (
n > 1) [
75]. For the maximum temperature of 328 K, the
n obtained was 1.91. Thus, the higher the temperature, the less favorable it is to multilayer adsorption, and at a higher temperature, the behavior of the adsorbent will be heterogeneous. For the maximum temperature of 328 K, the best model was the Langmuir model, with a maximum adsorption capacity of 476 mg/g, higher than those reported by other authors in their studies on the adsorption of MB onto FA and UC [
24,
32]. It is possible to observe an increase in maximum adsorption capacity with the temperature, which can be related to an increase in the rate of diffusion of the adsorbate, also observed by Wang and Li [
24]. According to the
RL value, determined through the Langmuir parameters, it is possible to observe that the isothermal form is favorable at both temperatures presented in the present work, given that 0 <
RL < 1 [
71]. The
kL is a constant that may be related to the adsorption energy. In a study conducted by another author on methylene adsorption, it was observed that the
kL values ranged from 0.21 to 0.48 [
60]. In the present study, at the temperature of 328 K, the best fit was the Langmuir model, obtaining a value of 0.26 for
kL. The results obtained indicate that the MB adsorption mechanism onto UC is related to the temperature.