Honghao Li and
Tuerxun Nasiman*
College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi, 830054, China. E-mail: 384546761@qq.com
First published on 4th July 2023
In this study, Li2CO3- and (Li–K)2CO3-based porous carbon composites were synthesized from terephthalic acid, lithium hydroxide and sodium hydroxide through calcination at different temperatures. These materials were fully characterized through X-ray diffraction, Raman spectroscopy, and nitrogen adsorption and desorption. Results showed that the excellent CO2 capture capacities of LiC-700 °C and LiKC-600 °C were 140 and 82 mg CO2 g−1 at 0 °C and 25 °C, respectively. Additionally, it is calculated that the selectivity of LiC-600 °C and LiKC-700 °C with a CO2/N2 (15:85) mixture was about 27.41 and 15.04, respectively. Therefore, Li2CO3- and (Li–K)2CO3-based porous carbon materials could be used to effectively capture CO2 with high capacity and high selectivity.
Recently, solid alkali metal carbonate adsorbents have attracted more and more attention in the CO2 capture due to their higher capture capacity and low cost than those of others. For example, Na2CO3 was reported as a good CO2 adsorbent under (0.1 MPa at >313 K).7,8 Results showed that humidity played a critical role in CO2 capture capacity and the overall reaction rate. With the increase of H2O concentration, both the rate and amount of captured CO2 were increased significantly, because carbonate could capture CO2 under humid conditions to generate bicarbonate (eqn (1)). After the CO2 capture, the adsorbent could be regenerated and recycled after the decomposition of bicarbonate at 100–200 °C (reverse reaction of eqn (1)).9
CO32− + H2O + CO2 ⇌ 2HCO3− | (1) |
Theoretically, the CO2 adsorption capacities of commercial Na2CO3 and K2CO3 were 41.5 wt% and 31.8 wt%, respectively.10 According to the thermogravimetric analysis from Luo et al.,11 with high CO2 and H2O concentrations, pure Na2CO3 reacted with CO2 and H2O to form NaHCO3 directly. However, with low CO2 and H2O concentrations, Na2CO3 preferentially reacted with H2O to generate Na2CO3·H2O, and this hydrate slowly reacted with CO2 to produce Na5H3(CO3)4, which finally slowly reacted with CO2 and H2O to form NaHCO3. Additionally, Cai et al.,12 basing on density functional theory and molecular dynamics simulation, studied the adsorption process and adsorption types of CO2 and H2O on Na2CO3 crystal surfaces from the atomic scale. Their results showed that the carbonation reaction rate of Na2CO3 was not controlled by the kinetics of the surface reaction, was controlled by the phase diffusion of the adsorbent.
Typically, pure carbonate adsorbents have low cost, low energy consumption, high stability, etc., and are widely used in the petrochemical industry. However, the reaction between carbonate and CO2 is slow, and special operation equipment is required, which increase the cost significantly. In practical applications, other materials (such as activated carbon, MgO, zeolite molecular sieve, etc.) have been added to combine with of the adsorbent,11 which can not only increase the adsorption rate and reduce the regeneration temperature, but also increase the CO2 adsorption capacity. For example, the regeneration temperature of Na2CO3–carbon nanocomposite (NaC-NC) was lower than that of Na2CO3, the CO2 capture capability of NaC-NC was also higher with a higher reaction rate that was 1.5 to 2 times that of untreated Na2CO3. When K2CO3–carbon composite (KC–CC) was used instead of NaC-NC, a slightly smaller CO2 amount was captured with a lower regeneration temperature13.
In this study, in order to have high adsorption capacity and adsorption rate, Li2CO3-based porous carbon materials were prepared from terephthalic acid and lithium hydroxide. With the added KOH to these same raw materials, (Li–K)2CO3-based porous carbon materials were further synthesized. With Li2CO3- and (Li–K)2CO3-based porous carbon materials, the CO2 capture performance and cycle stability of these materials were significantly improved, and their regeneration temperature was also reduced.
(2) |
Qst = −RT2 (∂lnP/∂T)q | (3) |
Fig. 3 shows the thermogravimetric curve of LiC-700 °C under a nitrogen atmosphere. This Li2CO3-based porous carbon material had a small weight loss between room temperature and 624.31 °C, mainly due to the adsorbed water vapor and CO2 from the air. There was a significant weight loss of about 45% from 624.31 °C to 820.55 °C because of the loss of the volatile substances through oxidization. As shown in Fig. 3b, the LiKCO3-based porous carbon material only had a small amount of weight loss from 108.33 °C to 184.62 °C, mainly due to the adsorbed impurities such as water vapor and CO2 from the air. The significant weight loss of about 60% from 596.37 °C to 973.13 °C came from the carbonization of material. Fig. 3(c) and (d) showed the weight loss processes of LiC and LiKC material at three calcination temperatures. It was found that the material synthesized at 800 °C was the fastest to lose the weight at the beginning. When the temperature was increased to 900 °C, LiC-600 °C and LiKC-800 °C materials had the lowest ash content.
Fig. 3 Thermogravimetric curves of LiC-700 °C (a) and LiKC-600 °C (b), and thermogravimetric curves of materials with calcination temperatures (c and d). |
Fig. 4 shows SEM images of materials LiC-700 °C and LiKC-600 °C. The irregular porous particle structure on their surface could be clearly observed, which might increase their specific surface area.
As shown in Fig. 5, the two Raman characteristic peaks at 1350 and 1590 cm−1 corresponded to the G band and D band, respectively. The D band indicated the degree of disorder of the amorphous carbon and the defects of the graphite phase, and the G band was due to the bending vibration of sp2 hybridized graphite phase carbon atoms. Relative intensity (ID/IG) of the two peaks indicates the density of defects or the degree of graphitization and a high ratio means high defectivity. With the addition of KOH, the value of ID/IG was increased from 0.92 to 0.99, indicating that the addition of KOH increased the number of defects in the carbon skeleton of LiKC-600 °C.
Fig. 6 shows the N2 adsorption–desorption isotherms and pore size distribution diagrams of these materials, and Table 1 lists their structural properties. They were all type IV isotherms, indicating they were all mesoporous. Typically, the adsorption properties of mesoporous materials are determined by the adsorbent-adsorbed species interactions, as well as the interactions between molecules in the condensed state. In these mesopores, the initial monolayer–multilayer adsorption on the mesoporous walls follows the corresponding partial path of the type II isotherm. However, subsequent condensation can occur within the pore. During the desorption process, a hysteresis loop can be formed due to capillary condensation. Based on the pore size distribution diagrams these two materials (LiC-700 °C and LiKC-600 °C) were dominated by mesopores, and their pore structure data could be calculated according to the adsorption isotherm as listed in Table 1. The specific surface area of LiKC-600 °C was 320.0 m2 g−1, and that of LiKC-600 °C was 126.8 m2 g−1. Their pore volumes were 0.27 cm3 g−1 and 0.145 cm3 g−1 with the average pore diameters of 20.6 nm and 15.4 nm, respectively. Fig. S1(a)–(d) and S2(a), (b)† show the N2 adsorption and desorption isotherm data and pore size distribution of other materials. Data showed that the pore volume and specific surface area of other materials were lower.
Fig. 6 N2 adsorption–desorption isotherms of LiC-700 °C (a) and LiKC-600 °C (b), and pore size distributions of LiC-700 °C (c) and LiKC-600 °C (d). |
Adsorbent | SBET (m2 g−1) | Vtotal (cm3 g−1) | Pore size (nm) |
---|---|---|---|
LiC-600 °C | 136.1 | 0.18 | 14.1 |
LiC-700 °C | 320.0 | 0.27 | 20.6 |
LiC-800 °C | 124.4 | 0.28 | 17.4 |
LiKC-600 °C | 126.8 | 0.15 | 15.4 |
LiKC-700 °C | 23.1 | 0.06 | 15.8 |
LiKC-800 °C | 7.5 | 0.05 | 15.4 |
The CO2-TPD experiment was done to study the effect of adsorbent surface alkalinity on its CO2 adsorption performance. As shown in Fig. 7, both of these two samples had two CO2 desorption peaks in the temperature range of 50–500 °C. The α peak at 100–250 °C was a strong desorption peak, and these strong basic sites could improve their CO2 adsorption performance. The β peak at 300–450 °C was a weak desorption peak due to the adsorption of CO2 by weak alkaline sites on the surface of the adsorbent. Both the strength and number of basic sites of LiC-700 °C were larger than those of LiKC-600 °C, and the significant α peak indicated that the increase in the number and strength of basic sites was beneficial to the adsorption of acid gas CO2. Based on the specific surface area and XRD characterization results of these materials, they should be excellent candidates as adsorbents in the CO2 adsorption process.
Fig. 8 CO2 adsorption isotherms at 0 °C (a) and 25 °C (b) of LiC-700 °C and LiKC-600 °C under a pressure from 0.01 to 1 bar. |
According to adsorption isotherms of these two materials at different temperatures in Fig. 8(a) and (b), the addition of potassium hydroxide in the preparation process decreased their CO2 adsorption capability, while more suitable calcination temperature led to better CO2 adsorption performance. These results indicated that treatment at 700 °C led to both larger pore size and larger specific surface area (as evident from Table 1), which further resulted in greater CO2 adsorption. In order to investigate the CO2 adsorption selectivity, the CO2 and N2 adsorption isotherms were measured (under the 1 bar at 25 °C) for LiC-600 °C and LiKC-700 °C samples as shown in Fig. 9(a) and (b), respectively. It was found that the CO2 adsorption capacity of LiC-600 °C and LiKC-700 °C was significantly higher than that of N2, indicating that these materials could carry out significant selective adsorption in the binary gas mixture of CO2 and N2. Based on these two adsorption isotherms, the ideal adsorption solution theory (IAST) was used to explore the selectivity of CO2/N2. According to formula (3), it is calculated that the selectivity of LiC-600 °C and LiKC-700 °C with a CO2/N2 (15:85) mixture was about 27.41 and 15.04, respectively. These results showed that LiC-600 °C and LiKC-700 °C had excellent selective adsorption of CO2 in gas mixtures with a great potential in gas separation.
Generally, the equivalent adsorption heat (Qst), which can be calculated according to the Clausius–Clapeyron equation, reflects the ability of CO2 molecules to bind to the adsorbent, and a higher value indicates a stronger interaction and a more stable adsorption. As shown in Fig. 10, the initial Qst values of LiC-700 °C and LiKC-600 °C were 40.5 and 34.8 kJ mol−1, respectively, and the Qst values were decreased significantly with the increase of CO2 adsorption, probably due to the gradual decrease of the interaction between the reaction site and CO2. In addition, the Qst value of LiKC-600 °C was 34.8 kJ mol−1, which was lower than the binding energy of a typical covalent bond, indicating that the CO2 adsorption might be a typical physical adsorption, which made the adsorbent regeneration process simple and energy efficient. All results showed that these materials were great candidates to capture CO2 with a low regeneration energy consumption and low regeneration cost.
Table 2 shows the CO2 adsorption capacity and CO2/N2 adsorption selectivity of the LiC-600 °C, LiKC-700 °C, and some other reported adsorbents. These results showed that the MOF material had a higher CO2 adsorption capacity and selectivity than other adsorbents, and Cu-BTC had a significantly higher adsorption capacity. However, due to the high cost and poor durability and mechanical strength of MOF materials, their application in industry was still very rare up to present. Compared with the other molecular sieve and AC adsorbents in Table 2, the LiC-700 °C adsorbents in this study showed both a higher CO2 adsorption capacity and a higher CO2/N2 adsorption selectivity, except of the 13× molecular sieve and modified activated carbon AC2TMAOH. However, carbon material adsorbents had important advantages over zeolite 13× such as hydrophobicity, which could significantly reduce the cost with a lower energy required for regeneration.23 This work mainly focuses on providing a simple method for the preparation of LiC adsorbents and to evaluate the effect of introducing alkali metal ions into LiC support on CO2 adsorption performance. In our future work, in order to improve the CO2 adsorption capacity of LiC adsorbent, further exploration will be done to optimize the matrix and pore structure of the adsorbent.
Adsorbents | Adsorption capacity (mmol g−1) 100 kPa | CO2/N2 selectivity | Ref. |
---|---|---|---|
Cu-BTC | 4.79 (298 K) | ∼50 | 14 |
MIL-101 (Cr) | 2.33 (298 K) | ∼20 | 15 |
MIL-100 (Fe) | 2.25 (298 K) | 6 | 16 |
Zeolite Y | 0.73 (303 K) | 11 | 17 |
20MgO/MCN | 1.15 (298 K) | — | 18 |
ZSM-5 | 1.33 (298 K) | ∼8 | 19 |
AC2TMAOH | 2.49 (303 K) | 31.53 | 20 |
Commercial AC | 1.5 (298 K) | — | 21 |
Zeolite 13× | 4.20 (298 K) | 130 | 22 |
LiC-700 | 3.18 (273 K) | — | This study |
1.86 (298 K) | ∼27.45 | ||
LiKC-600 | 1.36 (273 K) | — | This study |
0.70 (298 K) | ∼15.04 |
In addition to high CO2 adsorption capacity and selectivity, regeneration is also a key factor for the practical application of CO2 adsorbent materials. The adsorbent was degassing for 6 hours at under the ambient pressure at 200 °C, the CO2 adsorption and desorption cyclic experiment was carried out several times to examine the recycling ability of the material. The LiC-700 °C cyclically tested five times at 25 °C. As shown in Fig. 11, after five times regeneration tests, the capacity of the adsorbent did not change substantially. Therefore, it can be speculated that the porous material has a great application prospect in the field of CO2 adsorption.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ra02607h |
This journal is © The Royal Society of Chemistry 2023 |