Efficient C3H6/C3H8 separation within a bifunctional ultramicroporous metal-organic framework with high purity and record packing density
Shan-Qing Yang , Lu-Lu Wang , Rajamani Krishna , Bo Xing , Lei Zhou , Fei-Yang Zhang , Qiang Zhang , Yi-Long Li , Chao-Sheng Bao , Tong-Liang Hu
Propylene (C3H6) is an important chemical feedstock for producing high value-added fine chemicals and polymers including but not limited to polypropylene, acrylonitrile, and isopropanol [1–3], second in significance to ethylene, which the global production is expected to reach 160 million tons by 2030 [4]. At the current stage, propylene is primarily manufactured by the thermal or catalytic cracking of hydrocarbons, where normally yields propane (C3H8) as the main byproduct [5]. The highly similar physiochemical properties such as boiling point (225.4 K for C3H6 and 231.1 K for C3H8, respectively) and polarizability (62.6 × 10−25 cm3 for C3H6 and 62.9 × 10−25 cm3 for C3H8, respectively) for propylene and propane pose an enormous challenge to obtain high purity propylene [6–8]. The traditional established technology for C3H6/C3H8 separation involves repeated distillation at low temperatures and high pressures, which is identified as an energy-intensive process [9]. For instance, it is estimated that such energy-intensive process consumes approximately 7.0–13.5 GJ to manufacture per ton of C3H6 [10,11], and the energy consumed by the separation process is about 3% along with an analogous intensity of carbon emission [2]. From the perspective of energy conservation and environmental protection, it is imperative to explore alternative separation technology with suppressed carbon emission and a lower energy input. In this context, adsorptive separation based on porous solid materials featuring high-efficiency and low-cost represents an advance approach for isolating C3H6/C3H8 mixture [12–14], which could decrease the energy intensity by the factor of 10 [15].
Developing porous solid adsorbents is the key to the successful implementation of highly efficient separation of C3H6/C3H8 mixture based on adsorptive separation technology. In recent years, various porous solid materials, ranging from porous carbons, zeolites, metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), to hydrogen-bonded organic frameworks (HOFs) have been spaciously explored as a C3H6/C3H8 splitter [9,16–19]. In particular, the high tunability and versatile functionality of MOF materials make them become promising adsorbents for gas adsorption and separation field [20–25], besides MOFs exhibit the momentum of rapid development currently [26–32]. With respect to the propylene/propane separation using MOF materials, selective recognition of propylene over propane could be achieved by exploiting the pore engineering, or the dynamic nature of flexible structures through kinetic, equilibrium or combined mechanism [1,33–38]. Furthermore, fine-tuning of pore environment of MOF materials including pore size/shape/functionality to match propylene molecule and enable size-exclusion of slightly larger propane is the most powerful strategy to realize highly efficient separation of the C3H6/C3H8 mixture. However, there is a greatly challenge studies on good sieving separation performance owing to their subtle molecular structure difference of C3H6 and C3H8. Meanwhile, the ultramicroporous MOFs generally are short of high-density selective binding sites, resulting in the insufficient utilization of pore space and low packing density. To target this matter, the well-designed pore environment within ultramicroporous MOFs, i.e., embedding adsorption binding sites into MOFs with suitable pore size, could make full use of pore space to achieve highly efficient C3H6/C3H8 separation and excellent C3H6 packing density. Moreover, from the perspective of the ultimate goal of the development of materials in industrial utility, some key factors including but not limited to cost, stability, scale-up along with the separation performance should also be considered. On the one hand, a small amount of acidic gases or water possibly existed in the raw streams, which compels that the MOF materials should possess high chemical tolerance. On the other hand, economic feasibility is a crucial factor in determining the industrial practical implementation, which is highly related to the cost and scalability of the materials. Most of the top-performing MOF materials reported for C3H6/C3H8 separation are faced with high cost, poor stability, or deficient adsorption and separation performance, severely restricting their industrial practical implementation. For instance, although some benchmark MOF materials such as HIAM-301 and Y-dbai [4,39], exhibit optimal C3H6/C3H8 separation performance, they are synthesized by expensive organic linkers that are obtained via the intricate synthesis rendering them unfavorable for practical industrial application. A target MOF adsorbent material for highly efficient purification of C3H6 should have an excellent balance between economy feasibility, stability, and separation performance. Thus, developing such ideal MOF adsorbents is important yet daunting for the challenging C3H6/C3H8 separation.
Taken the above into consideration, we herein reported the efficient separation of propylene/propane mixture using a bifunctional ultramicroporous metal-organic framework (Co-aip-pyz) with customized pore environment and selective binding sites. Consequently, Co-aip-pyz exhibits good C3H6 uptake, particularly at 298 K and 0.05 bar (37.28 cm3/cm3), producing a record high C3H6 packing density with 931 g/L at 298 K and 859 g/L at 313 K and 1.0 bar. In addition, Co-aip-pyz displays a good C3H6/C3H8 uptake ratio (991%) and excellent C3H6/C3H8 adsorption selectivity (>104) at 298 K and 1.0 bar. Computational study proves that C3H6 molecule indeed preferentially adsorbed through electrostatic and hydrogen-bonding interactions. Dynamic breakthrough experiments including simulated and experimental demonstrate that Co-aip-pyz is capable of effectively separating C3H6 from C3H6/C3H8 mixture with an excellent performance. By virtue of the robust framework, highly great stability, low-cost precursors, along with good adsorption and separation performance, Co-aip-pyz would be a benchmark adsorbent for industrial C3H6/C3H8 separation.
Co-aip-pyz microcrystalline powder was prepared by the low-cost precursors including Co(CH3COO)2·4H2O, 5-aminoisophthalic acid (AIP), pyrazine (pyz), methanol, and water via the solvothermal method based on the previously reported procedure with some modification [40]. In the structure of activated Co-aip-pyz, it crystallizes in the monoclinic space group of C2/c, in which each Co2+ ion with a distorted square pyramidal configuration is coordinated by three oxygen atoms from two different AIP linkers, one nitrogen atom from pyz unit and one nitrogen atom from AIP linker, leaving one open metal site for each metal node. The CoO3N2 square pyramidal is connected by the linkers to further form a pillar-layer framework, which exists one-dimensional channels with a size of 4.41 × 5.67 Å2 along the b axis (Figs. 1a and b). The characteristics of ultramicroporous pore channel and customized binding sites for Co-aip-pyz showcase its potential separation of C3H6/C3H8 mixture (Fig. 1c). The powder X-ray diffraction (PXRD) pattern of the synthesized Co-aip-pyz sample was identical to the simulated one deported from the single crystal structure, suggesting the bulk phase with high purity (Fig. S1 in Supporting information). The stability of product Co-aip-pyz was further established by PXRD and thermogravimetry analysis (TGA). It could maintain the framework in water aqueous over the pH range of 3–11 and different organic solvents, as unveiled by the retained peaks in their corresponding PXRD patterns (Figs. S2 and S3 in Supporting information). The thermogravimetry curve suggested that Co-aip-pyz exhibits a food thermal stability up to 620 K (Fig. S4 in Supporting information). The in-situ variable temperature PXRD was carried out to further confirm its thermal stability (Fig. S5 in Supporting information), which matched well with the thermogravimetry curve. After removing the guest molecules under 393 K and high vacuum, the framework of Co-aip-pyz is conserved, as proved by in powder X-ray diffraction (Fig. S6 in Supporting information), which further confirmed the thermal stability of Co-aip-pyz. Combined with the good thermal and chemical stability, and the low-cost precursors suggest that Co-aip-pyz could be a promising candidate for industrial implementation. Thus, such characteristic allowed to test its gas sorption properties.
The Brunauer-Emmett-Teller surface area and pore volume of activated Co-aip-pyz were estimated to be 164 m2/g and 0.08 cm3/g, respectively, by CO2 adsorption experiment at 273 K (Figs. S7 and S8 in Supporting information), which is consistent well with the previously reported work [41]. The pore size distribution (PSD), determined by Horvath-Kawazoe model, exhibits a pore size of 4.3 Å (Fig. S9 in Supporting information), which is agreed with the result displayed from crystal structure. Then, single component gas sorption isotherms for C3H6 and C3H8 were collected at different temperatures (273, 298, 303 and 313 K, respectively) up to 1.0 bar. As shown in Figs. 2a and b, detailed analysis unveils that Co-aip-pyz manifests the steep adsorption curve with the C3H6 uptake of 63.62 cm3/cm3 at 298 K and 1.0 bar, which is comparable to that of Co-gallate (66.6 cm3/cm3) [42] and superior to those of numerous best-performing MOF adsorbents such as NTU-85-WNT (20.9 cm3/cm3) [17], and KAUST-7 (54.3 cm3/cm3) [3]. In contrast, a lower C3H8 sorption was 6.98 cm3/cm3 at 298 K and 1.0 bar, resulting in an obvious adsorption difference with a high uptake ratio (911%), which is rare among MOF materials for C3H6/C3H8 separation. This uptake ratio value is superior to many MOF materials, such as ZJU-75a (142%) [10], CoNi-piz (188%) [43], ZJUT-2a (<150%) [44], JNU-3a (<150%) [1], ELM-12 (108%) [45], NKU-FlexMOF-1 (~120%) [46], ZnAtzPO4 (179%) [35], Ni-NP (168%) [47], and ATC-Cu (115%) [16], and lower than that a small amount of best-performing MOFs such as HIAM-301 (~1100%) [4] and Co-gallate (1280%) [42]. The Co-aip-pyz with sieving effect is promising for highly efficient separation C3H6/C3H8 mixture through the pressure swing adsorption. In particular, Co-aip-pyz exhibits a significant C3H6 uptake with 37.28 cm3/cm3 at 298 K and 0.05 bar (Fig. 2c), higher than other MOFs with sieving-type such as NTU-85-WNT (<15 cm3/cm3) [17], Co-gallate (~10 cm3/cm3) [42], KAUST-7 (<5 cm3/cm3) [3], and UTSA-400 (~20 cm3/cm3) (Fig. 2d) [48]. Remarkably, based on the determined pore volume and C3H6 uptake, the density of adsorbed C3H6 in Co-aip-pyz was estimated to be ultrahigh of 931 g/L at 298 K and 1.0 bar, which is 545 times higher than that of the gaseous C3H6 density (1.707 g/L). Furthermore, when the temperature increases to 313 K, the C3H6 packing density in Co-aip-pyz could also be up to record-high 859 g/L, which is unprecedented in MOFs for C3H6/C3H8 separation. Notably, this C3H6 packing density is the highest among the reported adsorbents, along with far exceeding other top-performing materials including but not limited to ZJU-75a (818 g/L, 296 K and 1.0 bar, 666 g/L, 318 K and 1.0 bar, respectively) [10], HIAM-301 (530 g/L, 298 K and 1.0 bar, 433 g/L, 318 K and 1.0 bar, respectively) [4], JNU-3a (404 g/L, 303 K and 1.0 bar, 350 g/L, 313 K and 1.0 bar, respectively) [1], Co-gallate (360 g/L, 298 K and 1.0 bar, 161 g/L, 313 K and 1.0 bar, respectively) [42], UTSA-400 (930 g/L, 298 K and 1.0 bar, ~780 g/L, 313 K and 1.0 bar, respectively) [48], Y-abtc (467 g/L, 296 K and 1.0 bar, 433 g/L, 313 K and 1.0 bar, respectively) (Fig. 2e and Fig. S10 in Supporting information) [49]. Such record high C3H6 packing density of Co-aip-pyz suggests the most effective occupancy of approachable pore volumes for adsorption, resulting in a maximum C3H6 adsorption within the limited pore volume. Moreover, cycling C3H6 adsorption measurements on Co-aip-pyz demonstrated that the adsorption capacity was maintained in 5 cycles (Fig. 2f), indicating its facile reactivation and good cycling stability.
Such ultrahigh packing density and uptake at low-pressure area discloses the strong binding nature with C3H6 in Co-aip-pyz. Thus, to quantitatively assess the binding strength between Co-aip-pyz and guest molecules, the coverage-dependent adsorption enthalpy (Qst) for C3H6 was evaluated experimentally from single component gas adsorption isotherms by fitting a classic Virial equation. In addition, from the practical application of MOF materials point of view, the Qst parameter could also be an important evaluation index as MOFs with low Qst reduce the energy consumption of adsorbate recycling and adsorbent regeneration. As shown in Fig. 3a, the Qst value for C3H6 is estimated to be 29.14 kJ/mol at near zero-coverage loading on Co-aip-pyz. Notably, this Qst value is markedly lower than those of MOF materials with benchmark C3H6/C3H8 separation performance, such as ZJU-75a (65.9 kJ/mol) [10], ATC-Cu (65.4 kJ/mol) [16], UTSA-400 (60.5 kJ/mol) [48], NbOFFIVE-1-Ni (57.4 kJ/mol) [3], NTU-85-WNT (49.9 kJ/mol) [17], ZJUT-2a (45 kJ/mol) [44], Y-dbai (55 kJ/mol) [39], Co-gallate (41 kJ/mol) [42], CoNi-piz (38 kJ/mol) [43], ZU-36-Co (42 kJ/mol) [50], and comparable to ZnAtzPO4 (27.5 kJ/mol) [35], HIAM-301(27 kJ/mol) [4], JNU-3a (29.3 kJ/mol) (Fig. 3b) [1]. Such a relatively low Qst value for C3H6 implies that Co-aip-pyz could be regenerated with mild conditions, which may be greatly beneficial for energy-efficient C3H6/C3H8 separation.
To depict the potential of Co-aip-pyz in separation of the challenging C3H6/C3H8 mixture, the calculation was conducted with the commonly used method in light of the ideal adsorbed solution theory (IAST). As shown in Fig. 3c, the calculated adsorption selectivity of Co-aip-pyz for the equimolar C3H6/C3H8 binary mixture is estimated to be >104 at 1.0 bar and 298 K. Notably, this high selectivity of Co-aip-pyz is superior to those of a number of top-performing MOF materials, such as Co-gallate (330) [42], HIAM-301 (150) [4], ZJU-75a (54.2) [10], Co-MOF-74 (46) [51], MFM-520 (17) [52], ZU-36-Ni (15) [50], and NiNi-Pyz (7.5) [53]. However, what needs illustration is that the IAST selectivity is only used to be qualitatively compared, as possible error may be produced from the lower C3H8 uptake. Nonetheless, such result could demonstrate that Co-aip-pyz possesses the potential for the C3H6/C3H8 separation. The conspicuous uptake difference, record C3H6 packing density, low Qst value, as well as excellent IAST selectivity established the promising potential of Co-aip-pyz for highly efficient separation of C3H6/C3H8 mixture in the industrial implementation (Fig. 3d).
To comprehensive understand the ultrahigh C3H6 packing density and separation performance of Co-aip-pyz, modeling study using grand canonical Monte Carlo (GCMC) simulations was conducted to provide insight about the host-guest interactions between Co-aip-pyz framework and C3H6 molecule. The lowest-energy binding configuration for C3H6 molecule in Co-aip-pyz as shown in Fig. 4a, the primary adsorption site for C3H6 molecule is located at the middle of the pore channels. The C3H6 molecule interacts with three oxygens from three AIP ligands through C-H···O hydrogen-bonded interactions with distances of 2.481–3.710 Å. Further, the C3H6 molecule also interacts with aromatic rings through weak C-H···π interactions (4.033–4.109 Å). Other powerful binding interactions also exist, such as C-Co Coulombic interactions with longer distances of 3.991–4.147 Å. The C-Co bonds distances are longer, suggesting its small contribution on host-guest interactions, in addition, this result is agreed well with the low heat of adsorption. Moreover, the electrostatic potentials of C3H6 molecule and Co-aip-pyz framework were performed to further prove the GCMC result. As shown in Fig. 4b, the C3H6 molecule exhibits the positively-charged hydrogen atom and the oxygen atom surroundings of Co-aip-pyz framework exhibit the electronegative environment. Besides the electronegative oxygen atoms could lead to a negative pore environment and form hydrogen bonding or electrostatic interactions to the positively-charged hydrogen atoms on C3H6 molecule. In short, the abundant binding interactions and customized pore environment endowed Co-aip-pyz strong affinity to C3H6 molecule.
To intuitively evaluate the C3H6/C3H8 separation performance, transient breakthrough simulations were carried out in fixed-bed adsorption processes. The results display that highly effective separations could be accomplished by Co-aip-pyz with different flow rates (Fig. 5a). Then we further performed the experimental dynamic column breakthrough studies on Co-aip-pyz for equimolar C3H6/C3H8 mixture with a flow rate of 1.5/2.0/3.0 mL/min at ambient conditions. As shown in Fig. 5b, a clear isolation of C3H6/C3H8 was observed with obvious separation window for tested flow rates. Notably, the separation of C3H6/C3H8 mixture could be achieved under different flow rates. Based on the dynamic breakthrough curves under the flow rate of 1.5 mL/min, C3H8 quickly broke breakthrough the fixed-bed after 6 min/g, whereas the retention time of C3H6 on the fixed-bed was 26 min/g, leading to a long breakthrough time with 20 min/g. The dynamic adsorption capacity of C3H6 was estimated to be 43.13 cm3/cm3. Subsequently, the regeneration experiment was conducted to access the purity of the collected C3H6. As shown in Fig. S11 (Supporting information), the yields of C3H6 with 97% and 98.5% purity are 18.11 L/kg and 12.25 L/kg, respectively, which is superior to that of DL-mal-MOF (2.1 L/kg with 95%) [54], Y-abtc (1.3 L/kg with 90%) [49], and NTU-85-WNT (0.78 L/kg with 98.8%) [17], yet inferior to that of JNU-3a (34.2 L/kg with 99.5%) [1]. Multiple dynamic breakthrough experiments indicated that the separation performance of Co-aip-pyz could be remained over three continuous cycles (Fig. 5c), demonstrating its good recyclability and recoverability. In addition, to examine the effect of moisture, the dynamic breakthrough tests for a wet C3H6/C3H8 mixture under different humidity conditions were performed. As shown in Fig. S12 (Supporting information), the C3H6/C3H8 mixture could be separated under 70% humid, suggesting the good moisture tolerance of Co-aip-pyz. Benefiting from the meritorious C3H6/C3H8 separation performance, Co-aip-pyz is a promising candidate to efficiently trap C3H6 from C3H6/C3H8 mixture. In particular, Co-aip-pyz, with stable framework, easy synthesis procedure and low-cost precursors (Fig. S15 in Supporting information), low heat of adsorption, high C3H6 packing density is promising used to be implemented in the petrochemical industry (Fig. 5d, Tables S2 and S3 in Supporting information).
In conclusion, inaugurating a new generation of MOF materials into practical gas separation implementation should not only pursue adsorption and separation performance but also consider of stability and costs for the MOFs. The ultramicroporous Co-aip-pyz constructed by low-cost precursors with customized pore environment and selective binding sites exhibits excellent C3H6 adsorption performance, particularly at 298 K and 0.05 bar (37.28 cm3/cm3), and the record-high C3H6 packing density (931 g/L at 298 K and 859 g/L at 313 K and 1.0 bar, respectively). In addition, the high stability, the good C3H6/C3H8 uptake ratio (911%) and adsorption selectivity (>104) were achieved in the robust Co-aip-pyz, demonstrating the greatly practical promising in the industrial. The fundamental C3H6 packing mechanisms and binding site of Co-aip-pyz have been visually unveiled by computational modeling study. Experimental and simulated breakthrough experiments demonstrate an outstanding C3H6/C3H8 separation performance, which could be a promising splitter for such challenging separation. In a short, Co-aip-pyz is proved to be a desired realistic MOF adsorbent for industrial C3H6/C3H8 separation, and its development provides valuable comprehensive insights into the integration of multi-characteristics to enhance the industrial implementations of MOF materials. This study will facilitate future exploration and implementation of effective porous MOF materials for isolating important chemicals.
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Shan-Qing Yang: Writing – original draft, Methodology, Investigation. Lu-Lu Wang: Investigation. Rajamani Krishna: Software, Investigation. Bo Xing: Investigation. Lei Zhou: Investigation. Fei-Yang Zhang: Investigation. Qiang Zhang: Investigation. Yi-Long Li: Investigation. Chao-Sheng Bao: Investigation. Tong-Liang Hu: Writing – review & editing, Supervision, Project administration, Methodology.
This work was financially supported by the National Natural Science Foundation of China (No. 22275102), and NCC Fund (No. NCC2022FH01).
Supplementary material associated with this article can be found, in the online version, at doi:
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Figure 1 (a) The crystal structure of Co-aip-pyz viewed along the b axis. Co, C, N, O, H in Co-aip-pyz are presented by purple, gray, blue, red, and white, respectively. (b) Connolly surface void spaces of Co-aip-pyz view along b axis with aperture size of 4.41 × 5.67 Å2. (c) The minimum cross-sectional dimensions of propylene (4.1 × 5.1 Å2) and propane (5.3 × 5.1 Å2), respectively.
Figure 2 (a) The sorption isotherms of Co-aip-pyz at 273, 298, 303, and 313 K, respectively. (b) The C3H6 and C3H8 sorption isotherms of Co-aip-pyz at 298 K. (c) C3H6 uptake of Co-aip-pyz at 0.05 bar. (d) Comparison of C3H6 uptake at 0.05 bar and 1.0 bar for Co-aip-pyz and other top-performing MOFs. (e) Comparison of C3H6 packing density for Co-aip-pyz and other best-performing MOF materials at 313 K and 1.0 bar. (f) Cycling test of C3H6 sorption measurements on Co-aip-pyz at 298 K from 0 to 1.0 bar.
Figure 3 (a) Isosteric heat of adsorption of C3H6 for Co-aip-pyz. (b) Comparison of the zero-coverage heat of adsorption with those of other MOF materials for C3H6/C3H8 separation. (c) IAST selectivity of Co-aip-pyz for equimolar C3H6/C3H8 mixture at different temperatures. (d) Comparison of C3H6 packing density and isosteric heat of adsorption under ambient conditions for Co-aip-pyz and other best-performing MOF materials.
Figure 4 (a) Illustration of C3H6 preferential adsorption sites in Co-aip-pyz by theoretical calculation. (b) The electrostatic potential of C3H6 molecule (top), and Co-aip-pyz pore surfaces (bottom).
Figure 5 (a) Simulated breakthrough curves for an equimolar C3H6/C3H8 mixture with different flow rates in the fixed bed packed with Co-aip-pyz at ambient conditions. (b) Dynamic breakthrough experiments carried out with different flow rates on Co-aip-pyz at ambient conditions. (c) Cycling tests of the equimolar C3H6/C3H8 mixture on Co-aip-pyz with a total flow of 2 mL/min at ambient conditions. (d) Comparison of the comprehensive performance with other reported excellent MOFs for C3H6/C3H8 separation.
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