Supporting Information
Computational Screening of Porous Carbons, Zeolites and Metal Organic Frameworks
for Desulfurization and Decarburization of Biogas, Natural Gas and Flue Gas
Xuan Peng*1, 2 and Dapeng Cao3*
1
College of Information Science and Technology, Beijing University of Chemical Technology, Beijing
100029, 2 State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, 3
Division of Molecular and Materials Simulation, State Key Laboratory of Organic-Inorganic Composites,
Beijing University of Chemical Technology, Beijing 100029, P. R. China
This Supporting Information provides the parameters for EOS calculations (Table S1),
atomic charges in the fragmental clusters of NOTT-103 material from ab initio calculations
(Figure S0), adsorption selectivity and isotherms of each component of eighteen porous
materials (Figure S1-S18).
* Corresponding Authors. Email: pengxuan@mail.buct.edu.cn and caodp@mail.buct.edu.cn
1
Table S1 Critical properties1 and binary interaction parameters2 kij of PR EOS
species
1.
ω
Tc
Pc
(K)
(MPa)
N2
126.2
3.4
0.038
CH4
190.6
4.599
0.012
CO2
304.2
7.383
0.224
H2S
373.5
8.963
0.094
SO2
430.8
7.884
0.245
kij
N2
CH4
CO2
H2S
SO2
0.0311
-0.017
0.1767
0.08
0.0919
0.1356
0.0974
Smith, J. M.; Van Ness, H. C.; Abbott, M. M. Introduction to Chemical Engineering Thermodynamics;
McGraw-Hill Press: New York, 2001.
2.
Reid, R. C.; Prausnitz, J. M.; Poling, B. E. The properties of gases and liquids; McGraw-Hill Press:
New York, 1987.
2
Figure S0 Atomic charges in the fragmental clusters of NOTT-103 from ab initio calculations.
Figure S0 shows the fragmental clusters cleaved from the unit cells of NOTT-103 with dangling bonds
terminated by H atoms. The ChelpG electrostatic charge calculation method and unrestricted B3LYP
density-functional theory (DFT) were adopted in this work. In addition, LANL2DZ basis set was used for
the transitional metal Cu, and 6-31G(d) basis set was used for all other atoms to avoid the derived charges
fluctuation with small basis sets. For Cu atoms, effective core potential (ECP) is chosen to reduce the
necessary computing effort. The computed partial charges were also given in Figure S0, where six types of
C atoms are recognized by different carbon hybridization and bonding modes.
3
10
10
8
Absolute adsorption (mmol/g)
(a)
Selectivity
6
4
2
H2S/CO2
H2S/CH4
(b)
8
6
4
H2 S
CO2
CH4
2
CO2/CH4
0
0
1
2
3
4
0
1
Pressure (MPa)
10
4
3
4
8
Absolute adsorption (mmol/g)
Selectivity
3
Pressure (MPa)
2
(c)
10
2
1
SO2/CO2
SO2/N2
(d)
6
SO2
CO2
4
N2
2
CO2/N2
10
0
0
0
1
2
Pressure (MPa)
3
4
0
1
2
Pressure (MPa)
Figure S1 Adsorption selectivities and isotherms of ternary mixtures in MOF-5 at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
4
10
2
(a)
(b)
H2S/CO2
Absolute adsorption (mmol/g)
10
H2S/CH4
Selectivity
CO2/CH4
10
10
1
0
8
6
4
H2 S
CO2
2
CH4
0
0
1
2
3
0
4
1
10
4
10
3
(c)
(d)
SO2/CO2
SO2/N2
Selectivity
CO2/N2
10
2
10
1
10
0
4
10
Absolute adsorption (mmol/g)
10
3
Pressure (MPa)
Pressure (MPa)
5
2
8
6
SO2
CO2
4
N2
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S2 Adsorption selectivities and isotherms of ternary mixtures in HKUST-1 at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
5
10
3
10
H2S/CO2
(a)
Absolute adsorption (mmol/g)
H2S/CH4
CO2/CH4
Selectivity
10
10
10
H2 S
(b)
2
1
0
CO2
8
CH4
6
4
2
0
0
1
2
3
0
4
1
10
10
5
(d)
SO2/CO2
Absolute adsorption (mmol/g)
SO2/N2
Selectivity
CO2/N2
4
10
3
10
2
10
1
10
0
4
8
(c)
10
3
Pressure (MPa)
Pressure (MPa)
6
2
SO2
CO2
N2
6
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S3 Adsorption selectivities and isotherms of ternary mixtures in MIL-47(V) at 303 K, where panels
a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c
and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
6
10
2
8
(a)
(b)
H2S/CO2
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
10
1
0
6
4
H2 S
CO2
2
CH4
0
0
1
2
3
0
4
1
4
SO2/CO2
(d)
10
2
10
1
10
0
Absolute adsorption (mmol/g)
Selectivity
SO2/N2
3
4
8
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
CO2/N2
6
SO2
4
CO2
N2
2
0
0
1
2
3
4
0
1
Pressure (MPa)
2
3
4
Pressure (MPa)
Figure S4 Adsorption selectivities and isotherms of ternary mixtures in ZIF-3 at 303 K, where panels a and
b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and d are
for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
7
10
2
8
(a)
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
10
H2 S
(b)
H2S/CO2
1
0
CO2
CH4
6
4
2
0
0
1
2
3
0
4
1
10
4
(d)
(c)
SO2/CO2
SO2/N2
Selectivity
CO2/N2
10
3
10
2
10
1
10
0
4
8
Absolute adsorption (mmol/g)
10
3
Pressure (MPa)
Pressure (MPa)
5
2
SO2
CO2
6
N2
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S5 Adsorption selectivities and isotherms of ternary mixtures in ZIF-96 at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
8
10
2
20
(a)
(b)
Absolute adsorption (mmol/g)
H2S/CO2
H2S/CH4
Selectivity
CO2/CH4
10
10
1
0
16
12
8
H2 S
CO2
CH4
4
0
0
1
2
3
0
4
1
SO2
(d)
Absolute adsorption (mmol/g)
Selectivity
10
4
20
3
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
2
1
SO2/CO2
SO2/N2
CO2
16
N2
12
8
4
CO2/N2
10
0
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S6 Adsorption selectivities and isotherms of ternary mixtures in COF-102 at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
9
2
20
(a)
H2S/CH4
Selectivity
CO2/CH4
10
10
H2 S
(b)
H2S/CO2
Absolute adsorption (mmol/g)
10
1
0
CO2
16
CH4
12
8
4
0
0
1
2
3
0
4
1
3
(d)
SO2/CO2
Absolute adsorption (mmol/g)
SO2/N2
CO2/N2
Selectivity
10
10
4
10
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
2
1
0
8
6
4
SO2
CO2
N2
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S7 Adsorption selectivities and isotherms of ternary mixtures in MOF-177 at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
10
10
2
16
H2S/CO2
(a)
Absolute adsorption (mmol/g)
Selectivity
CO2/CH4
10
10
H2 S
(b)
H2S/CH4
1
0
CO2
CH4
12
8
4
0
0
1
2
3
0
4
1
4
10
2
10
1
10
0
SO2
(d)
SO2/N2
Absolute adsorption (mmol/g)
Selectivity
3
4
16
SO2/CO2
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
CO2/N2
CO2
12
N2
8
4
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S8 Adsorption selectivities and isotherms of ternary mixtures in NOTT-103 at 303 K, where panels
a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c
and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
11
10
3
3
H2S/CO2
(a)
(b)
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
2
10
1
10
0
H2 S
CO2
CH4
2
1
0
0
1
2
3
0
4
1
10
10
5
Absolute adsorption (mmol/g)
Selectivity
(d)
4
SO2/CO2
SO2/N2
10
3
10
2
10
1
4
3
(c)
10
3
Pressure (MPa)
Pressure (MPa)
6
2
CO2/N2
SO2
CO2
N2
2
1
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S9 Adsorption selectivities and isotherms of ternary mixtures in SWNT(6,6) bundle at 303 K,
where panels a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002,
and panels c and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
12
10
3
5
(a)
(b)
H2S/CO2
Absolute adsorption (mmol/g)
H2S/CH4
CO2/CH4
Selectivity
10
10
10
2
1
0
4
3
H2 S
CO2
CH4
2
1
0
0
1
2
3
0
4
1
5
10
10
(d)
SO2/CO2
SO2/N2
4
Absolute adsorption (mmol/g)
Selectivity
10
4
5
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
CO2/N2
3
2
1
SO2
4
CO2
N2
3
2
1
0
0
1
2
3
4
0
1
Pressure (MPa)
2
3
4
Pressure (MPa)
Figure S10 Adsorption selectivities and isotherms of ternary mixtures in CIG at 303 K, where panels a and
b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and d are
for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
13
10
6
10
5
8
(a)
(b)
H2S/CO2
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
4
10
3
10
2
10
1
10
0
H2 S
CO2
CH4
6
4
2
0
0
1
2
3
0
4
1
10
10
6
(a)
(b)
SO2/CO2
10
4
10
3
10
2
10
1
10
0
Absolute adsorption (mmol/g)
Selectivity
10
4
8
SO2/N2
5
3
Pressure (MPa)
Pressure (MPa)
7
2
CO2/N2
SO2
CO2
6
N2
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S11 Adsorption selectivities and isotherms of ternary mixtures in Na-13X at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
14
6
10
5
10
4
10
3
8
(a)
(b)
H2S/CO2
H2S/CH4
Absolute adsorption (mmol/g)
10
Selectivity
CO2/CH4
10
2
10
1
10
0
6
H2 S
4
CO2
CH4
2
0
0
1
2
3
0
4
1
10
10
6
10
5
(c)
(d)
SO2/CO2
10
3
10
2
10
1
10
0
Absolute adsorption (mmol/g)
Selectivity
4
4
8
SO2/N2
10
3
Pressure (MPa)
Pressure (MPa)
7
2
CO2/N2
SO2
6
CO2
N2
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S12 Adsorption selectivities and isotherms of ternary mixtures in Na-5A at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
15
10
4
8
H2S/CO2
(a)
(b)
10
3
10
2
10
1
10
0
Absolute adsorption (mmol/g)
Selectivity
H2S/CH4
CO2/CH4
H2 S
CO2
6
CH4
4
2
0
0
1
2
3
0
4
1
10
5
(c)
SO2/CO2
Selectivity
4
10
3
10
2
10
1
10
0
SO2
(d)
SO2/N2
CO2/N2
10
4
5
Absolute adsorption (mmol/g)
10
3
Pressure (MPa)
Pressure (MPa)
6
2
CO2
4
N2
3
2
1
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S13 Adsorption selectivities and isotherms of ternary mixtures in Na-4A at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
16
10
2
10
H2S/CO2
(a)
(b)
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
10
1
0
8
H2 S
6
CO2
CH4
4
2
0
0
1
2
3
0
4
1
5
SO2/CO2
(d)
SO2/N2
4
Absolute adsorption (mmol/g)
Selectivity
10
CO2/N2
3
10
2
10
1
10
0
4
8
(c)
10
3
Pressure (MPa)
Pressure (MPa)
10
2
6
SO2
CO2
4
N2
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S14 Adsorption selectivities and isotherms of ternary mixtures in MOF-74-Zn at 303 K, where
panels a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and
panels c and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
17
2
10
H2S/CO2
(a)
(b)
H2S/CH4
Absolute adsorption (mmol/g)
10
Selectivity
CO2/CH4
10
10
1
0
8
H2 S
6
CO2
CH4
4
2
0
0
1
2
3
4
0
1
Pressure (MPa)
10
10
(d)
1
Absolute adsorption (mmol/g)
Selectivity
10
2
SO2/CO2
SO2/N2
CO2/N2
10
4
10
(c)
3
3
Pressure (MPa)
4
10
2
0
8
6
SO2
CO2
4
N2
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S15 Adsorption selectivities and isotherms of ternary mixtures in MOF-74-Co at 303 K, where
panels a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and
panels c and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
18
10
2
10
H2S/CO2
(a)
(b)
Absolute adsorption (mmol/g)
H2S/CH4
Selectivity
CO2/CH4
10
10
1
0
8
6
H2 S
CO2
4
CH4
2
0
0
1
2
3
0
4
1
4
10
2
10
SO2
(d)
Absolute adsorption (mmol/g)
Selectivity
10
4
10
(c)
3
3
Pressure (MPa)
Pressure (MPa)
10
2
1
SO2/CO2
SO2/N2
CO2
8
N2
6
4
2
CO2/N2
10
0
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S16 Adsorption selectivities and isotherms of ternary mixtures in MOF-74-Ni at 303 K, where
panels a and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and
panels c and d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
19
5
10
4
10
(a)
H2S/CH4
Selectivity
CO2/CH4
10
3
10
2
10
1
10
0
H2 S
(b)
H2S/CO2
Absolute adsorption (mmol/g)
10
CO2
8
CH4
6
4
2
0
0
1
2
3
4
0
1
Pressure (MPa)
10
5
Selectivity
4
10
3
10
2
10
1
10
0
4
8
(c)
(d)
SO2/CO2
SO2/N2
10
3
Pressure (MPa)
Absolute adsorption (mmol/g)
10
6
2
CO2/N2
SO2
CO2
6
N2
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S17 Adsorption selectivities and isotherms of ternary mixtures in socMOF at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
20
5
10
(a)
10
4
H2S/CH4
Selectivity
CO2/CH4
10
3
10
2
10
1
10
0
H2 S
(b)
H2S/CO2
Absolute adsorption (mmol/g)
10
CO2
8
CH4
6
4
2
0
0
1
2
3
4
0
1
10
10
5
10
4
10
3
10
2
10
1
10
0
3
4
Pressure (MPa)
8
(c)
(d)
SO2/CO2
Absolute adsorption (mmol/g)
Selectivity
Pressure (MPa)
6
2
SO2/N2
CO2/N2
SO2
CO2
6
N2
4
2
0
0
1
2
Pressure (MPa)
3
4
0
1
2
3
4
Pressure (MPa)
Figure S18 Adsorption selectivities and isotherms of ternary mixtures in zMOF at 303 K, where panels a
and b denote the CH4-CO2-H2S system with the bulk gas molar ratios of 0.7:0.298:0.002, and panels c and
d are for the N2-CO2-SO2 mixture with the bulk composition of 0.8:0.198:0.002.
21