3.1. Synthesis of LiTiO2 and LiBO2 Powders
Figure 1 depicts TG-DTA trends for the chemically synthesized products heated to 623 K in a CO
2 environment as the second heat treatment. The samples were prepared by heating the gel at 773 K (marked as LiTiO
2-A) and 973 K (marked as LiTiO
2-B), respectively. LiTiO
2-A and LiTiO
2-B showed similar TG behavior as the temperature increased. TG of LiTiO
2-A increased gradually with a temperature up to approximately 360 K and subsequently decreased immediately at 360–573 K. The remarkable rise and decline of mass of LiTiO
2-A corresponded to CO
2 absorption and desorption. Above 573 K, the value of mass loss transfer changed from positive to negative. The difference in the amount of CO
2 before absorption and after desorption can be attributed to the characteristics of the sol–gel synthesized powders. A carbonated phase is said to have formed when heat treatment breaks down any remaining organic materials in wet gels.
DTA curve of LiTiO2-A showed a strong endothermic peak at the beginning of the reaction, indicating CO2 absorption, while LiTiO2-B exhibited a relatively low endothermic DTA peak. At approximately 360 K, the mass loss of LiTiO2-A reached its maximum of 0.9 mg, which is 4.5 times higher than that of LiTiO2-B (0.2 mg at 330 K), revealing that LiTiO2-A has better CO2 capture property than that of LiTiO2-B. For this reason, the gel was heated at 773 K in the subsequent experiment.
Figure 2 displays the TG-DTA profiles for the synthetic products heated to 650 K in an environment of Ar. The mass of LiTiO
2-A decreased at above 320 K, which was lower than that treated under CO
2 atmosphere (360 K), as shown in
Figure 1a.
Table 2 lists the weight losses of sample prepared by heating the gel at 773–973 K. This mass loss may potentially be related to CO
2 desorption, which results from the initial remaining organic component’s dissociation. The decomposition temperature of carbonates decreases with the fall of CO
2 partial pressure under the Ar atmosphere. Both the TG and DTA curve also saturate to a constant at 630 K, and there is no further drop in mass beyond 623 K under the Ar atmosphere. Therefore, all the adsorbent CO
2 can be assumed to be released at 623 K. Hence, CO
2 capture properties were studied after heating the samples to 623 K under an Ar atmosphere.
XRD patterns of synthetic LiTiO
2 before and after CO
2 absorption are shown in
Figure 3. This sample reacted with CO
2 at 373 K for 11.75 h for the absorption degree of 43%, which will be discussed later in detail. Before CO
2 absorption, diffraction peaks corresponding to single LiTiO
2 have been confirmed in
Figure 3a. During CO
2 adsorption, the intermediate product Li
xTi
zO
2 is generated (
Figure 3b) and after five cycles of adsorption LiTiO
2 is re-formed (
Figure 3c).
The SSA of LiTiO2 before and after CO2 absorption was found to be 55.63 and 61.56 m2∙g−1, respectively. If we assume that the mass of LiTiO2 is 188 g, the system theory volume can be calculated according to the density of LiTiO2 (3.15 g∙cm−3). Similarly, the system volume after CO2 absorption is calculated with the densities of LiCO3 and Ti2O3 (2.11 and 4.49 g∙cm−3, respectively). The system theory volume increased by 11% following with CO2 absorption progress, indicating that SSA of LiTiO2 should be enlarged during the CO2 absorption process.
3.2. CO2 Absorption Properties of LiTiO2 and LiBO2
Figure 4 shows the absorption curves of LiTiO
2 for an absorption time of 11.75 h obtained from TG. The temperature increased with a rate of 5 °C·min
−1 and then maintained at 293 K, 333 K, 373 K, and 393 K, respectively. As shown in
Table 3, the absorption degree attained 37%, 40.8%, 45.5%, and 50.1% at the maintained temperature of 293 K, 333 K, 373 K, and 393 K, respectively. CO
2 absorption degrees of sol–gel synthesized Li
2ZrO
3 were also considered for comparison [
29]. The CO
2 absorption degree of Li
2ZrO
3 only attained 17%, 20%, and 22% at the same conditions [
29].
Repetitive CO
2 absorption degree of LiTiO
2 was obtained from TG analysis as shown in
Figure 5. The repetitive CO
2 absorption degree decreased slightly every time with a mean drop of 0.5%. As shown in
Table 4, the absorption degree of LiTiO
2 decreases with the increasing number of cycles. This result is similar with that of sol–gel synthesized Li
2ZrO
3 [
29].
Figure 6 shows the influence of variation of CO
2 concentration on the absorption degree of LiTiO
2 at different temperatures. As shown in
Table 5, the absorption degree enlarges with the augmentation of CO
2 concentration. The absorption degree of LiTiO
2 is approximately 30% under pure CO
2 atmosphere. Moreover, the absorption degree of LiTiO
2 decreases from 25% to 23% as CO
2 concentration reduces from 40% to 10%. Finally, the absorption degree is a minuscule 1% even after an absorption time of 1.4 h at a CO
2 concentration of 0.05%.
The mass percentage of synthetic LiBO
2 at 333–423 K is shown in
Figure 7. As shown in
Table 6, the mass percentage of synthetic LiBO
2 enlarged with the augment of CO
2 absorption temperature. LiBO
2 reacted with CO
2 with the extension of the absorption time. Higher explored temperatures improved the reaction activation energy and then increased the mass percentage of LiBO
2. The mass percentage of synthetic LiBO
2 at 393 and 423 K presents a second mass increment in the last part of these curves. Usually, similar behaviors have been associated with physical adsorption. Therefore, absorption of LiBO
2 is the mixture of both the physical adsorption and chemical absorption of CO
2.
Table 7 lists the specific surface area and mass percentage of synthetic LiBO
2. Following the increasing absorption temperature, SSA of synthetic LiBO
2 obviously increased. SSA of synthetic LiBO
2 is larger than that of Li
2ZrO
3 (SSA value of 6.9 m
2/g). Similar to LiBO
2, Li
3BO
3 exhibits exceptionally quick kinetics and a high ability to collect CO
2 [
32].
Figure 8 shows the evaluation of CO
2 absorption properties of LiBO
2 with the gas chromatography method. As the absorption time extended, CO
2 concentrations lessened firstly and then reached a saturation value at 363 K and 393 K. As shown in
Table 8, higher absorption temperatures can shorten the absorption time for saturation, which is the same as the result of mass percentage (
Figure 7). However, the variation of CO
2 concentration for the absorption at 363 K is larger than that for the absorption at 393 K because the equilibrium temperature of LiBO
2 is 333 K.
3.3. Kinetic Calculation Analysis
The kinetic consecutive reaction model for CO
2 capture on lithium ceramic absorbents was connected with the CO
2 flow rate [
33]. The conversion kinetics for the interaction combining LiTiO
2 and CO
2 are shown in
Figure 9. This reaction mechanism for LiTiO
2 was similar to the reported model of high-temperature CO
2 capture on Li
2ZrO
3 [
34,
35]
. The following rate equations were employed for analyzing the experimental data, as shown in
Figure 4:
- (1)
equations generated from mobility modeling procedures where gas diffusion through the Li
2CO
3 and Ti
2O
3 layer is the rate-limiting phase, especially, the Yander formula [
36], Y
1 = (1 − (1 − R)
1/3)
2 =
kt; and Gistling model [
37], Y
2 = 1 − 2α/3 − (1 − α)
2/3 =
kt;
- (2)
equation for reactions in cylinder-shaped particles that are constrained by interfacial processes, Y1 = 1 − (1 − α)1/2 = kt; and Y2 =1 − (1 − α)1/3.
In
Figure 9, data analysis shows that the highest correlation coefficient is achieved between 293 K and 393 K when the Yander equation [
38] and Gistling equation [
39] are fit. The formula of interactions restricted by contact processes just fits for the absorption at low temperature (293 K) and fails at high temperature due to the change of shape of the LiTiO
2 particle and the thickness of the product layer. These equations apply only for a sphere when the radius is very large as compared with the thickness of the product layer. An approximately linear dependence is found to a relatively high absorption degree. Therefore, the rate-determining step might be the gas diffusion in the Li
2CO
3 and Ti
2O
3 layer.
The Gistling equation is provided below [
39]:
where
R denotes the percentage of absorption, (%);
M is the reactant’s molecular mass, (g∙mol
−1);
D is the intra-particle efficient diffusivity, (cm
2∙s
−1);
C stands for the reagent concentration;
α means the stoichiometric ratio;
ρ indicates the reactant density;
r0 is the reactant’s initial particle diameter, (cm);
t is the reaction time, (s); and
k’ is the rate parameter.
Accorded to Equation (4), the values of rate constant
k’ are calculated. Rate constant
k’ showed linear temperature dependence. The effective kinetic energy (ΔE) is determined from the values of the slope and is calculated as 15 kJ∙mol
−1. This value is slightly smaller than that of sol–gel synthesized Li
2ZrO
3 (24 kJ∙mol
−1 [
40]). As a further comparison, the apparent activation energy of zeolite pores with the approximate diameter of 0.4 nm is approximately 20 kJ∙mol
−1 during CO
2 diffusion through [
41]. The rate-determining step of CO
2 capture in the instance of LiTiO
2 is likewise assumed to be its dispersion in the chemical process of diffusion.
3.4. Evaluation of CO2 Capture Properties of Sol–Gel Prepared Lithium Ceramic Absorbents
Figure 10 shows a comparison of mass percentage of sol–gel synthesized lithium ceramic absorbents at 333K. Compared with other lithium ceramic absorbents, LiTiO
2 has the maximal mass percentage as shown in
Table 9. It might be attributed to the larger specific surface area SSA (
Table 3) and lower activation energy of sol–gel synthesized LiTiO
2. On comparison of the ambient temperature CO
2 absorption properties of LiTiO
2 and Li
2ZrO
3 powders [
29] synthesized by the same sol–gel process, the absorption degree of LiTiO
2 was two times higher than that of Li
2ZrO
3. This difference should be attributed to the major difference in specific surface areas of 55.63 m
2∙g
−1 of LiTiO
2 as compared with 12.25 m
2∙g
−1 of Li
2ZrO
3, determined before CO
2 absorption.
Table 10 summarizes the CO
2 capture properties of lithium ceramic absorbents synthesized by the sol–gel method. These lithium ceramic absorbents, which have different CO
2 emission temperatures, can be employed at an altered temperature range. LiTiO
2 has the highest CO
2 absorptivity and largest mass percentage among these lithium ceramic absorbents due to its smallest activation energy. The equilibrium temperature of LiTiO
2 (393 K) is considerably lower than that of Li
2ZrO
3 (992 K), indicating that LiTiO
2 is easier to renew compared with Li
2ZrO
3; that is, LiTiO
2 is a more efficient CO
2 absorption material than Li
2ZrO
3. The sol–gel synthesized LiTiO
2 powders can be employed as a solid CO
2 sorbent at near-ambient temperatures.