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. 2024 Aug 27;2(1):35–40. doi: 10.1021/cbe.4c00113

A Pillared-Layer Coordination Network for One-Step Ethylene Production from Ternary CO2/C2H2/C2H4 Gas Mixture

Rong Yang 1, Tao Zhang 1, Jinbo Wang 1, Xue Zhang 1, Jian-Wei Cao 1, Yu Wang 1, Kai-Jie Chen 1,*
PMCID: PMC11835269  PMID: 39975808

Abstract

graphic file with name be4c00113_0005.jpg

One-step separation of ethylene (C2H4) from multicomponent mixtures poses significant challenges in the petrochemical industry due to the high similarity of involved gas molecules. Herein, we report a pillared-layer coordination network named Zn-fa-mtrz (H2fa = fumaric acid; Hmtrz = 3-methyl-1,2,4-triazole) possessing pore surfaces decorated with methyl groups and electronegative N/O atoms. Molecular modeling reveals that the pore surface of Zn-fa-mtrz provides more and stronger multiple interaction sites to simultaneously enhance the adsorption affinity for CO2 and C2H2 other than C2H4. The experimental and simulated breakthrough experiments demonstrate the ability to produce high-purity C2H4 (>99.97%) in one-step from ternary CO2/C2H2/C2H4 gas mixtures.

Keywords: adsorption separation, ethylene production, pore engineering, metal−organic frameworks, coordination network

1. Introduction

Ethylene (C2H4) is one of the most important basic chemicals in the petrochemical industry, with an annual output of 214 million tons in 2021.1,2 In the petrochemical process (i.e., steam cracking of naphtha) of C2H4 production, carbon dioxide(CO2) and acetylene (C2H2) are the main impurities in the downstream gas mixture.3,4 Thus, efficient removal of these impurities from related gas mixtures is very important in the chemical industry. The conventional technology used to remove C2H2 and CO2 for C2H4 purification relies on catalytic hydrogenation for C2H2 removal and caustic soda absorption for CO2 removal, which are sophisticated and highly energy-intensive.5 Hence, it is urgent to develop a simple, effective, and energy-efficient C2H4 purification technology for such a requirement.

Physisorbent-based separation technology is a promising alternative to effectively separate and purify hydrocarbon mixtures, thanks to the fast kinetics and low regeneration cost.6−11 Removing C2H4 from complex systems in one step will simplify the separation process and further reduce the total energy. In this context, metal–organic framework (MOF),12,13 also known as porous coordination polymer (PCP)14,15/metal–organic materials (MOMs)16 have made considerable achievements on efficient separation of C2H4 from binary C2 hydrocarbons, such as C2H4/C2H6,17−23 C2H2/C2H4.24−33 However, the one-step separation of C2H4 from ternary CO2/C2H2/C2H4 mixtures is still in its infancy stage. The main obstacle here is the highly similar molecular sizes (kinetic diameter: C2H2, 3.3 Å; CO2, 3.3 Å; C2H4, 4.16 Å) and physicochemical properties (boiling point: C2H2, 188.4 K; CO2, 194.7 K; C2H4, 169.4 K; quadruple moment: C2H2, 33.3 × 10–25 e.s.u. cm2; CO2, 29.1 × 10–25 e.s.u. cm2; C2H4, 42.5 × 10–25 e.s.u. cm2)34−36 in this separation system, which will require the specific recognition sites to simutaneously capture CO2 and C2H2. To date, very limited materials have been reported for the effecient separation of C2H4 from ternary CO2/C2H2/C2H4 mixtures in one single step.28,37−42 Furthermore, the deep understanding of multigas interaction mechanism and discovering the advanced porous materials with better performance is still highly desired.

Herein, a pillared-layer coordination network, [Zn2(fa)(mtrz)2] (named as Zn-fa-mtrz), featuring accessible O/N adsorption sites and methyl groups, was constructed for this purpose. The specific pore structure affords the selective adsorption of CO2 and C2H2 over C2H4. The favorable binding interaction sites in Zn-fa-mtrz for simultaneously strong adsorption of CO2 and C2H2 over C2H4 is the key factor, based on the molecular simulation results. Also, the ability of such a material to produce ethylene from equimolar binary CO2/C2H4 and C2H2/C2H4 mixtures, ternary CO2/C2H2/C2H4 mixtures (1/1/1 and 9/1/90, v/v/v) in one step at room temperature is validated by experimental and simulated breakthrough techniques.

2. Results and Discussion

Square-shaped crystals of Zn-fa-mtrz can be harvested through solvothermal reactions (Figure 1a) (see Supporting Information for detailed synthesis procedures). Single crystal X-ray diffraction data reveals that Zn-fa-mtrz crystallizes in the monoclinic P21/c space group (Table S1), which is isostructural to the networks reported by our research group.43,44 The asymmetric unit of Zn-fa-mtrz includes one four-coordinated Zn2+ ion, one-half fa2– ligand, and one mtrz– ligand. The fa2– and mtrz– ligands contain two uncoordinated carboxyl O atoms and one methyl group on the triazole ring. In Zn-fa-mtrz, triazole rings connects the dinuclear zinc units to form a wavy two-dimensional (2D) layer (Figure 1b). Such layers are bridged by fa2– pillar ligands to afford a 3D pcu network. The porosity of Zn-fa-mtrz was calculated to be 38.1% (by PLATON45). The network contains a one-dimensional pore channel with a maximum pore window size of 5.3 Å × 5.1 Å (excluding the van der Waals radii) (Figure 1c), slightly larger than the kinetic dimensions of these target gas impurities, which is suitable for C2H4 purification. The network displays the specific cavity built by the presence of methyl groups and abundant uncoordinated negatively charged O/N atoms from layer and pillar ligands, which are all suitable potential hydrogen bond acceptors. These features are promising for the selective recognition of C2H2 and CO2.

Figure 1.

Figure 1

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(a) Perspective view of the structure along the 1D channels of Zn-fa-mtrz. (b) The structure of the zinc-triazolate layer. (c) The maximum pore window of Zn-fa-mtrz. Color code: Zn, purple; C, gray; O, red; N, blue; H, white.

Powder X-ray diffraction (PXRD) patterns of the as-synthesized sample matched well with simulated patterns from the crystal structure, indicating the phase purity of the Zn-fa-mtrz sample (Figure S1). Thermogravimetric analysis (TGA) of Zn-fa-mtrz verified its thermal stability up to ca. 350 °C. The obvious weight loss in the TGA curve of as-synthesized sample before 210 °C is due to the release of solvent molecules (Figure S2). Zn-fa-mtrz can be fully exchanged with MeOH, as demonstrated by the PXRD patterns and TGA curves (Figures S1 and S2).

The permanent porosity of Zn-fa-mtrz was established by a reversible type-I N2 sorption experiment at 77 K (Figure S3). The Brunauer–Emmett–Teller (BET) surface area for Zn-fa-mtrz is 633.3 m2 g–1 (Figure S4). The saturated adsorption amount of the 77 K N2 adsorption isotherm is 7.1 mmol g–1 at P/P0 = 0.95. The experimental pore volume was estimated to be 0.245 cm3 g–1, which is comparable with the theoretical value of 0.287 cm3 g–1 obtained from the crystal structure (Table S2). In addition, it is worth mentioning that Zn-fa-mtrz retains its crystalline and porosity after water treatment or exposure to humidity (ca. 53% RH) (Figure S5). The corresponding average pore size distribution based on the Horvath–Kawazoe model is approximately 5.7 Å, which is consistent with the pore size measured from the single-crystal structure.

The adsorption isotherms of CO2, C2H2, and C2H4 for Zn-fa-mtrz were collected at 298 and 273 K (Figures 2a and 2b). At the low-pressure region, Zn-fa-mtrz demonstrates higher adsorption capacities for CO2 and C2H2 than C2H4 (Figure 2a). Furthermore, the slopes of adsorption curves for CO2 and C2H2 are greater than that of C2H4, indicating the stronger binding between CO2 and C2H2 and the network. These results suggested selective adsorption of Zn-fa-mtrz toward CO2 and C2H2 over C2H4. Notably, the uptake values of C2H2 (3.27 mmol g–1) and CO2 (2.74 mmol g–1) at 298 K and 100 kPa significantly surpass that of C2H4 (1.97 mmol g–1). To intuitively assess the interactions between the framework and gas molecules, the adsorption enthalpy (Qst) for CO2, C2H2, and C2H4 in Zn-fa-mtrz were calculated based on single-component adsorption data collected under 273, 298, and 313 K by utilizing the virial eq (Figures S6 and S7). The sequence of the adsorption affinity values follows the trend of C2H2 (−34.1 kJ mol–1) > CO2 (−31.8 kJ mol–1) > C2H4 (−27.2 kJ mol–1) at low loading (Figure 2c and Table S3), which is consistent with the adsorption uptake sequence and the slope of the isotherms. This phenomenon has also appeared in previous literature.46,47 This demonstrates the apparently stronger binding affinity of Zn-fa-mtrz toward CO2, and C2H2 as compared to C2H4.

Figure 2.

Figure 2

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CO2, C2H2, and C2H4 adsorption isotherms at 298 K (a) and 273 K (b); (c) the isosteric enthalpies of CO2, C2H2, and C2H4 based on adsorption isotherms at three different temperature (273, 298, and 313 K), respectively; (d) IAST selectivity for equimolar binary gas mixture of CO2/C2H4 and C2H2/C2H4 in Zn-fa-mtrz.

To assess the separation ability, the selectivity of Zn-fa-mtrz for binary CO2/C2H4, and C2H2/C2H4 mixtures were then calculated using ideal adsorption solution theory (IAST) based on the single-component adsorption isotherms at 298 K fitted by the dual-site Langmuir–Freundlich (DSLF) model (Figure S8 and Table S4). Under 100 kPa, the IAST values for equimolar CO2/C2H4 and C2H2/C2H4 mixtures are 2.5 and 4.7, respectively (Figure 2d and (Table S5), which are comparable to the benchmark porous materials with C2H4 separation ability from three-component gas mixtures, such as Zn-atz-oba (CO2/C2H4, 1.33, C2H2/C2H4, 1.43)43 and Zn-fa-atz (2) (CO2/C2H4, 1.4, C2H2/C2H4, 1.6).44 The high selectivity displayed indicates the great potential of Zn-fa-mtrz for one-step C2H4 purification from ternary CO2/C2H2/C2H4 mixtures under ambient conditions.

To fully understand the adsorption mechanism of these three gas molecules, Grand Canonical Monte Carlo (GCMC) simulations were performed to reveal the first favorable binding sites between Zn-fa-mtrz and gas molecules (see SI for simulation detail, Figure S9). As shown in Figure 3, all of these gas molecules are likely interacting with the framework at the corner formed by the fa2– linkers and mtrz– ligands. C2H2 interacts with fa2– linkers and mtrz– ligands via four C–H···O interactions (2.95–3.91 Å), three C–H···N interactions (3.55–3.98 Å), the multiple binding effect affords the adsorption energy of −42.07 kJ mol–1. For CO2, the terminal O atoms bind with the framework via three C = O···H (2.92–3.37 Å) and two C = O···C (3.43–3.61 Å) electrostatic interactions, while the central C atom interact with neighboring O and N atoms with distance from 3.49 to 3.89 Å, which give a sum of binding energy of −29.19 kJ mol–1. Owing to the shape mismatch, C2H4 insert in the corner with an uncomfortable manner, and only C–H···O/N (2.93–3.54 Å) interactions can be observed, and thus gives binding energy of −24.46 kJ mol–1. Taken together, the binding energy sequence of C2H2 > CO2 > C2H4 is in good agreement with experimental findings and in situ IR testing (Figure S10).

Figure 3.

Figure 3

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Preferential binding sites of CO2, C2H2 and C2H4 in Zn-fa-mtrz. The guest-network interactions are highlighted in orange dashed bonds. Color code: Zn, purple; C, gray; O, red; N, blue; H, white.

The actual separation ability of Zn-fa-mtrz toward CO2 and C2 mixtures was investigated by dynamic breakthrough experiments at 298 K. First, the binary CO2/C2H4 (1/1, v/v) and C2H2/C2H4 (1/1, v/v) mixtures with a flow rate of 1.4 mL/min were passed through a packed column containing Zn-fa-mtrz (Figure 4a and 4b). C2H4 first elutes through the column to directly produce an outflow of pure C2H4 (>99.95% pure) at 59 and 61 min, respectively, while CO2 and C2H2 retained in the column and detected at the outlet at 73 and 113 min, respectively. This also demonstrates the stronger affinity toward CO2 and C2H2 over C2H4 for Zn-fa-mtrz, resulting in long breakthrough time intervals of 14 and 52 min, respectively. Given the excellent separation performance for binary CO2/C2H4 with C2H2/C2H4 mixtures, we further test Zn-fa-mtrz to purify C2H4 from ternary CO2/C2H2/C2H4 mixtures with different ratios (Figure 4c and Figure S11). As demonstrated in Figure 4c, Zn-fa-mtrz can effectively separate these ternary mixtures for CO2/C2H2/C2H4 (1/1/1, v/v/v), in which C2H4 (99.97% pure) first elutes at 43 min, while CO2 and C2H2 do not breakthrough until 53 and 71 min, respectively. When the concentration ratio of CO2/C2H2/C2H4 mixtures was increased to 9:1:90 (Figure S11), Zn-fa-mtrz still exhibited good separation behavior, C2H4 (99.98% pure) flowed out at 11 min, followed by CO2 at 21 min, and finally C2H2 broke through at 42 min. This result is attributed to the highly selective adsorption behavior of CO2 and C2H2 over C2H4 in Zn-fa-mtrz. Moreover, the kinetic data of Zn-fa-mtrz for C2H2 and CO2 were recorded at 298 K (Figure S12). The results showed that the diffusional rate constant of C2H2 (4.0698) is higher than that of CO2 (3.5040), indicating that C2H2 diffused slightly faster than CO2, indicating that in the breakthrough experiment, thermodynamic factors dominate the separation. The C2H4 productivity of Zn-fa-mtrz is calculated to be 0.484 and 1.572 mol kg–1 for CO2/C2H2/C2H4 (1/1/1 and 9/1/90, v/v/v).

Figure 4.

Figure 4

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Experimental breakthrough curves of Zn-fa-mtrz at 298 K for (a) CO2/C2H4 (1/1, v/v) (flow rate: 1.4 mL/min), (b) C2H2/C2H4 (1/1, v/v) (flow rate: 1.4 mL/min; total pressure: 1 bar), and (c) CO2/C2H2/C2H4 (1/1/1, v/v/v) (flow rate: 2.1 mL/min). The simulated breakthrough curves at 298 K for (d) CO2/C2H4 (1/1, v/v), (e) C2H2/C2H4 (1/1, v/v), and (f) CO2/C2H2/C2H4 (1/1/1, v/v/v).

To further confirm the realistic separation property, a single adsorption bed model was built to simulate the breakthrough experiments (Figure 4). All the isotherm parameters were extracted using dual-site Langmuir–Freundlich (DSLF) model as described above and the methodology was set according to the previously established methods (see SI for detail).48−50 The mole fraction in outlet gas was plotted in Figure 4d and 4e, for the CO2/C2H4 (1/1, v/v) and C2H2/C2H4 (1/1, v/v) binary mixtures, the retention times of pure C2H4 were 18.8 and 42.7 min, respectively, kept in reasonable agreement with the experimental findings. For the CO2/C2H2/C2H4 (1/1/1, v/v/v) ternary mixture, C2H4, CO2, C2H2 were first detected at 47, 62, and 73 min (Figure 4f), the outflow order is the same with experimental breakthrough curves.

Combined with high CO2 and C2H2 adsorption capacity and excellent separation performance for binary (CO2/C2H4 and C2H2/C2H4) mixtures, ternary (CO2/C2H2/C2H4) mixtures, Zn-fa-mtrz would be an exceptional material for one-step C2H4 purification. Subsequently, we conducted three cycles of ternary CO2/C2H2/C2H4 (1/1/1) mixtures breakthrough and ten cycles of single-gas C2H4 adsorption experiments to assess the recyclability of Zn-fa-mtrz (Figure S13), with no notable performance loss after cycling.

3. Conclusion

In summary, we reported a pillared-layer coordination network of Zn-fa-mtrz with specific selective binding sites for CO2 and C2H2, other than C2H4. The designed pore structure of Zn-fa-mtrz demonstrates excellent separation performance for C2H4, revealed by thermodynamic single-component gas adsorption and dynamic gas mixture breakthrough experiments. We believe this work will provide the useful insights to design the next-generation porous materials for complex gas mixture separation.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 22071195, K.-J.C., 22101231, Y.W.), the Youth Innovation Team of Shaanxi Universities, China Postdoctoral Science Foundation (No. 2022M712585, T.Z.), and Open Project Program of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry (No. 2024-28, T.Z.). We are also thankful for the help from Mr. Yuan. He, Prof. Dr. Hepeng Zhang.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/cbe.4c00113.

  • Additional experimental details; PXRD patterns; Single crystal X-ray diffraction data, TGA curve; GCMC calculations; IAST selectivity calculations; Qst calculations; gas sorption measurements; and breakthrough experiments (PDF)

  • X-ray data for Zn-fa-mtrz (CIF)

Author Contributions

+ R.Y. and T.Z. contributed equally to this work.

The authors declare no competing financial interest.

Special Issue

Published as part of Chem & Bio Engineeringspecial issue “Advanced Separation Materials and Processes”.

Supplementary Material

be4c00113_si_001.pdf (935.4KB, pdf)
be4c00113_si_002.cif (348.8KB, cif)

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be4c00113_si_002.cif (348.8KB, cif)

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