High-throughput Screening of Real Metal-organic Frameworks for Adsorption Separation of C4 Olefins

doi:10.6023/A20110526

Abstract

The conventional separation process of olefin/paraffin with cryogenic and high-pressure distillation usually exhibits high energy consumption and low efficiency. The adsorption separation technology is widely promising in the field of olefin/paraffin separation because of its mild operation conditions and high energy efficiency. In this work, high-throughput screening was adopted to find the optimal adsorbents from 12723 real metal-organic framework (MOF) materials, which is available for adsorption separation of 1,3-butadiene from C4 olefin/paraffin mixture. Firstly, 7681 adsorbents with suitable pore size and specific surface area were selected from the total database according to their structural parameters. Then their mechanical properties were computed by molecular mechanics. The mechanical properties of UIO-66 were used as the threshold to obtain 959 candidate MOFs with stable structure. Secondly, the grand canonical Monte Carlo (GCMC) simulation was performed to calculate the selective adsorption behavior of a quinary equimolar C4 olefin mixture in different candidate MOFs at 298 K and 0.1 MPa. According to their adsorption performance scores (APS) of 1,3-butadiene, the candidate MOFs are ranked to obtain 8 MOFs with the optimal adsorption and separation performance. The structural characteristics of MOFs with high adsorption and separation performance are revealed through quantitative structure-activity relationship, adsorption isotherm and ideal adsorption solution theory. The breakthrough curve simulation further verified that 2-cis-butene could effectively separate from 1,3-butadiene in the fixed bed filled with the optimal adsorbent RIGPEE01. Finally, it is determined that the preferential adsorption mechanism of 1,3-butadiene in RIGPEE01 is mainly due to the strong adsorption sites of Cu(I), π bond coupling effect and the size sieving effect based on the radial distribution function and binding energy analysis. The high-throughput screening method and the molecule-level insights on the olefin separation mechanism of MOFs proposed in this work have laid a theoretical foundation for the further development of new adsorbents for the separation of olefin/paraffin mixtures.

Key words: real metal-organic framework, molecular simulation, high-throughput screening, adsorption separation, 1,3-butadiene

Cite this article

Lei Yang, Yujing Wu, Xuanjun Wu, Weiquan Cai. High-throughput Screening of Real Metal-organic Frameworks for Adsorption Separation of C4 Olefins[J]. Acta Chimica Sinica, 2021, 79(4): 520-529.

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Fig. & Tab. 11

Atom type	(ε/k_B)/K	σ/nm	Atom type	(ε/k_B)/K	σ/nm	Atom type	(ε/k_B)/K	σ/nm
C	52.84	0.343	Cu	2.516	0.311	Cd	114.73	0.254
H	22.14	0.257	Zn	62.40	0.246	Ag	18.12	0.280
O	30.19	0.312	Co	7.05	0.256	Ni	7.55	0.252
N	34.72	0.326	Mn	6.54	0.264	Fe	6.54	0.259

Table 1. Lennard-Jones parameters of partial MOFs

Figure 1. PCA on various structural descriptors of 12723 CoRE-MOFs

Figure 2. Flowsheet diagram for computational screening of CoRE-MOFs

Figure 3. Relationship plots of (a), (b) NBD and (c), (d) SBD versus LCD and VSA, respectively, for adsorption of 1,3-butadiene in 400 random MOFs at 298 K and 100 kPa.

MOFs	N_BD/ (mol•kg^–1)	S_BD	APS	LCD/nm	PLD/nm	VSA/ (m²•cm^–3)	Φ	OMS	Linker^a	Q⁰_st,BD/ (kJ•mol^–1)
RIGPEE01	1.90	13.9	26.4	0.433	0.345	566	0.462	Cu	L6	45.26
RIGPEE	1.86	11.5	20.9	0.437	0.350	598	0.468	Cu	L6	50.84
ETIPII	2.28	6.57	15.0	0.441	0.363	795	0.523	Zn	L1, L2	71.60
MORFEG	1.53	8.06	12.3	0.480	0.349	714	0.471	Cu	L5	43.19
IWELIG01	1.35	7.80	10.6	0.469	0.450	512	0.399	none	L4	46.75
YUSGID	1.04	9.96	10.3	0.450	0.372	753	0.425	none	L8, L9	55.54
CUVTIX	1.78	5.77	10.3	0.671	0.342	1159	0.506	none	L7	37.40
FITHIA	1.29	7.76	10.0	0.436	0.385	941	0.431	Sc	L3	55.70

Table 2. Top 8 MOFs with high APS and their physical properties

Figure 4. Relationship plots of (a), (b) bulk modulus; (c), (d) shear modulus versus LCD and VSA, respectively, for 1140 MOFs.

Figure 5. Scatter plots and box plots of NBD versus (a), (c) LCD; (b), (d) VSA. NBD refers to adsorption capacity of 1,3-butadiene in 959 candidate MOFs at 298 K and 100 kPa.

Figure 6. Relationship plots of SBD versus NBD for 1,3-butadiene adsorption in 959 candidate MOFs at 298 K and 100 kPa. All points are colored by adsorption performance score (APS) of 1,3-butadiene.

Figure 7. At 298 K and in RIGPEE01, (a) adsorption isotherms of various pure C4 olefins; (b) adsorption isotherms of quinary equimolar mixture; 1,3-butadiene/2-cis-butene binary equimolar mixture (c) adsorption isotherms; (d) breakthrough curves in fixed column at 0.1 MPa.

Figure 8. Radial distribution functions of interaction atom pairs between various framework atoms of RIGPEE01 and 1,3-butadiene at 298 K and 0.1 MPa.

Figure 9. (a) Equilibrium configuration of 1,3-butadiene adsorbed in RIGPEE01 under molecular simulation, ice blue spheres refer to united carbon atoms of 1,3-butadiene; pink, grey and blue lines refer to Cu, C and N atoms, respectively; equilibrium configuration and binding energy of (b) 1,3-butadiene; (c) 1-butene; (d) 2-cis-butene; (e) 2-trans-butene; (f) isobutene adsorbed in RIGPEE01, calculating by density functional theory for geometrical optimization. Green sphere refers to carbon in guest molecule. Grey, blue and pink spheres refer to C, N and Cu atoms, respectively, in RIGPEE01. H atoms in guest molecule are omitted for clarity. The unit of binding energy E and distance of atom pairs are kJ•mol–1 and nm, respectively.

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