Optimization of a Pressure Swing Adsorption Process for

Nitrogen Rejection from Natural Gas

Surya Effendy, Chen Xu and Shamsuzzaman Farooq*

Department of Chemical & Biomolecular Engineering, National University of Singapore,

4 Engineering Drive, Singapore, 117585
* Corresponding author. Email: chesf@nus.edu.sg; Tel: (65)-6516 6545; Fax: (65)-6516 1936

Summary

Model equations, boundary conditions and solution methodologies are based on past

works published by this laboratory1, 2. There are, however, some key differences. Sections S1,

S2, S3, S4 and S5 highlight and provide reasoning for those differences. Section S6 gives a

summary of all non-dimensional mass and energy balances, as well as the list of all non-

dimensional groups. Section S7 discusses the performance measures used in this study.

Section S8 describes key solution algorithms used reduce the computational time. Section S9

discusses model validation. In Section S10, the concept of maximum allowable recovery is

discussed in depth. Section S11 lists all the parameter value used to generate the results in

this paper.

S1.1. External Fluid-Phase Balances

For an arbitrary (𝑁𝑁1 ) number of components, there exists 3𝑁𝑁1 mass balances and 1

energy balance in the external fluid-phase. The component and overall mass balances take the

following forms:

𝜕𝜕𝑦𝑦𝑖𝑖 𝑦𝑦𝑖𝑖 𝜕𝜕𝜕𝜕 𝑦𝑦𝑖𝑖 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕 𝑃𝑃 𝜕𝜕𝑦𝑦𝑖𝑖 𝑇𝑇 𝜕𝜕 𝑦𝑦𝑖𝑖 𝑃𝑃𝑃𝑃 1−𝜀𝜀𝑏𝑏 3𝑘𝑘𝑓𝑓,𝑖𝑖
+ − = �𝐷𝐷𝐿𝐿,𝑖𝑖 �− � �− �𝑦𝑦𝑖𝑖 − 𝑦𝑦𝑝𝑝,𝑖𝑖 �𝑅𝑅=𝑅𝑅 � (S1)
𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜀𝜀𝑏𝑏 𝑅𝑅𝑝𝑝 𝑝𝑝

1 𝜕𝜕𝜕𝜕 1 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕 𝑃𝑃𝑃𝑃 1−𝜀𝜀𝑏𝑏 3𝑘𝑘𝑓𝑓,𝑖𝑖

− =− � �− ∑𝑖𝑖 �𝑦𝑦𝑖𝑖 − 𝑦𝑦𝑝𝑝,𝑖𝑖 �𝑅𝑅=𝑅𝑅 � (S2)
𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑇𝑇 𝜀𝜀𝑏𝑏 𝑅𝑅𝑝𝑝 𝑝𝑝

The left-hand sides of these equations represent the external fluid-phase accumulation, while

the three terms on the right-hand side of Eq. (S1) correspond to axial dispersion, convection

S1
and uptake into macropores respectively. The terms 𝐷𝐷𝐿𝐿,𝑖𝑖 and 𝑘𝑘𝑓𝑓,𝑖𝑖 are the axial dispersion- and

film-coefficient respectively, which are dependent on the local temperature, pressure and

interstitial velocity. The fluid velocity is assumed to be related to pressure drop by the

Darcy’s Law:

4 𝜀𝜀𝑏𝑏 2 𝜕𝜕𝜕𝜕
𝑣𝑣 = � � 𝑅𝑅𝑝𝑝2 �− � (S3)
150𝜇𝜇𝐹𝐹 1−𝜀𝜀𝑏𝑏 𝜕𝜕𝜕𝜕

The viscosity (𝜇𝜇𝐹𝐹 ) is assumed to be independent of fluid composition, but is dependent on

temperature, following Sutherland’s correction for gas viscosity3.

The column energy balance is given by:

1−𝜀𝜀𝑏𝑏 𝜕𝜕𝜕𝜕 𝜕𝜕 𝐶𝐶𝑝𝑝,𝑔𝑔 𝜕𝜕𝜕𝜕

�𝜌𝜌𝑠𝑠 𝐶𝐶𝑝𝑝,𝑠𝑠 + 𝐶𝐶𝑝𝑝,𝑎𝑎 ∑𝑖𝑖 �𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 𝑇𝑇�� + = (4)
𝜀𝜀𝑏𝑏 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 𝑅𝑅 𝜕𝜕𝜕𝜕

𝐾𝐾𝑧𝑧 𝜕𝜕2 𝑇𝑇 𝐶𝐶𝑝𝑝,𝑔𝑔 𝜕𝜕 1−𝜀𝜀𝑏𝑏 𝜕𝜕𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 2ℎ𝑖𝑖𝑖𝑖

− (𝑣𝑣𝑣𝑣) + ∑𝑖𝑖�−Δ𝐻𝐻𝑖𝑖 − �𝐶𝐶𝑝𝑝,𝑎𝑎 − 𝐶𝐶𝑝𝑝,𝑔𝑔 �𝑇𝑇� − (𝑇𝑇 − 𝑇𝑇𝑤𝑤 ) (S4)
𝜀𝜀𝑏𝑏 𝜕𝜕𝑧𝑧 2 𝑅𝑅 𝜕𝜕𝜕𝜕 𝜀𝜀𝑏𝑏 𝜕𝜕𝜕𝜕 𝜀𝜀𝑏𝑏 𝑟𝑟𝑖𝑖𝑖𝑖

The two terms on the left-hand side of Eq. (S4) correspond to solid- and gas-phase enthalpy

accumulation respectively, while the four terms on the right-hand side correspond to axial

dispersion, convection, heat of adsorption, and heat transfer to steel wall respectively. The

fluid- and adsorbed-phase heat capacities (𝐶𝐶𝑝𝑝,𝑔𝑔 & 𝐶𝐶𝑝𝑝.𝑎𝑎 ) are calculated via linear mixing rule,

and 𝐾𝐾𝑧𝑧 is calculated from a correlation taken from the literature4. The correlations used to

estimate the temperature/pressure/velocity dependence of various coefficients used in Eqs.

(S1) to (S4) i.e. 𝐷𝐷𝐿𝐿,𝑖𝑖 , 𝑘𝑘𝑓𝑓,𝑖𝑖 , 𝜇𝜇𝐹𝐹 , 𝐶𝐶𝑝𝑝,𝑔𝑔 , 𝐶𝐶𝑝𝑝.𝑎𝑎 & 𝐾𝐾𝑧𝑧 are provided in the Supporting Information. Note

that Eq. (S4) requires evaluation of average solid-phase loading (𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 ). This is done using

the usual Gauss quadrature.

S1.2. Energy Balance for the Column Wall

The energy balance for the column wall is given by

S2
 𝜕𝜕𝑇𝑇𝑤𝑤 𝜕𝜕2 𝑇𝑇𝑤𝑤 2𝑟𝑟𝑖𝑖𝑖𝑖 ℎ𝑖𝑖𝑖𝑖 2𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 ℎ𝑜𝑜𝑜𝑜𝑜𝑜
𝜌𝜌𝑤𝑤 𝐶𝐶𝑝𝑝,𝑤𝑤 = 𝐾𝐾𝑤𝑤 2 + 2 −𝑟𝑟 2 (𝑇𝑇 − 𝑇𝑇𝑤𝑤 ) − 2 −𝑟𝑟 2 (𝑇𝑇𝑤𝑤 − 𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏ℎ ) (S5)
𝜕𝜕𝜕𝜕 𝜕𝜕𝑇𝑇𝑤𝑤 𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 𝑖𝑖𝑖𝑖 𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 𝑖𝑖𝑖𝑖

S2. Model Equations

Key differences in model derivation lie in Eqs. (6) and (10). Bhadra et al. (2011) and

Qinglin et al. (2003) used an implicit imaginary concentration phase formulation in place of

Eq. (6):

𝜕𝜕𝑞𝑞𝑖𝑖 1 𝜕𝜕 𝑞𝑞𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖

= �𝑟𝑟 2 (𝐷𝐷𝑐𝑐𝑐𝑐 )𝑖𝑖 � (S6)
𝜕𝜕𝜕𝜕 𝑟𝑟 2 𝜕𝜕𝜕𝜕 𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝜕𝜕

The imaginary concentration variable ( 𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 ) is defined as the concentration of

component i in fluid phase which would have been at equilibrium with 𝑞𝑞𝑖𝑖 . This fluid phase is

not real, since there is no fluid phase in the micropore. This formulation has the advantage of

generality since it does not require the knowledge of the isotherm. In this study, Eq. (S6) is

found to be numerically disadvantageous since it requires solving the implicit multi-site

isotherm at every iteration of Eq. (S6). Application of chain rule on Eq. (S6) yields:

𝜕𝜕𝑞𝑞𝑖𝑖 1 𝜕𝜕 𝑞𝑞𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗

= �𝑟𝑟 2 (𝐷𝐷𝑐𝑐𝑐𝑐 )𝑖𝑖 ∑𝑗𝑗 � (S7)
𝜕𝜕𝜕𝜕 𝑟𝑟 2 𝜕𝜕𝜕𝜕 𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕

𝑞𝑞𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖
The term may be directly obtained from the isotherm:
𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗

𝑞𝑞
𝑎𝑎𝑖𝑖 𝑖𝑖
⎧𝑖𝑖 = 𝑗𝑗 ⇒ 1 + 𝑞𝑞𝑠𝑠,𝑖𝑖𝑞𝑞 ⎫
⎪ 1−∑𝑖𝑖 𝑖𝑖 ⎪
𝑞𝑞𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝑞𝑞 𝑠𝑠,𝑖𝑖
= 𝑞𝑞 (S8)
𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 ⎨ ⎬ 𝑎𝑎𝑖𝑖 𝑖𝑖
𝑞𝑞𝑠𝑠,𝑖𝑖
⎪ 𝑖𝑖 ≠ 𝑗𝑗 ⇒ 1−∑ 𝑞𝑞𝑖𝑖 ⎪
⎩ 𝑖𝑖𝑞𝑞
𝑠𝑠,𝑖𝑖 ⎭

Substitution of Eq. (S8) into Eq. (S7) yields Eq. (6).

Eq. (10) is obtained by equating flux at the outer and inner surface of the microparticles:

3(𝐷𝐷𝑐𝑐0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖

� = � (S9)
𝑟𝑟𝑐𝑐 𝜕𝜕𝜕𝜕 𝑟𝑟𝑐𝑐 𝜕𝜕𝜕𝜕
𝑟𝑟=𝑟𝑟𝑐𝑐− 𝑟𝑟=𝑟𝑟𝑐𝑐+

S3
Here (𝐷𝐷𝑏𝑏0 )𝑖𝑖 refers to the intrinsic diffusivity of the ith component as it travels across the

barrier. By applying chain rule, Eq. (S9) is transformed to its explicit formulation:

3(𝐷𝐷𝑐𝑐0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗

∑𝑗𝑗 � = ∑𝑗𝑗 � (S10)
𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕 𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕
𝑟𝑟=𝑟𝑟𝑐𝑐− 𝑟𝑟=𝑟𝑟𝑐𝑐+

Eq. (S8) is substituted to the left-hand side of Eq. (S10) to give the left-hand side of Eq. (10).

The right-hand side of Eq. (S10) is simplified by assuming that the mouth of the micropore is

at equilibrium with the micropore. Let the thickness of the barrier according to the ith

component be Δ𝑟𝑟𝑖𝑖 . The right-hand side of Eq. (S10) is simplified to:

3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝑞𝑞𝑝𝑝,𝑗𝑗 −𝑞𝑞𝑗𝑗 �

𝑟𝑟=𝑟𝑟𝑐𝑐
∑𝑗𝑗 � = ∑𝑗𝑗 � (S11)
𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕 𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 Δ𝑟𝑟𝑗𝑗
𝑟𝑟=𝑟𝑟𝑐𝑐+ 𝑟𝑟=𝑟𝑟𝑐𝑐+

𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖
Bhadra et al. and Qinglin et al. assumes that 𝑖𝑖 ≠ 𝑗𝑗 ⟹ � ≈ 0 and thus:
𝜕𝜕𝑞𝑞𝑗𝑗
𝑟𝑟=𝑟𝑟𝑐𝑐+

3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖

∑𝑗𝑗 � = � �𝑞𝑞𝑝𝑝,𝑖𝑖 − 𝑞𝑞𝑖𝑖 |𝑟𝑟=𝑟𝑟𝑐𝑐 � ≡ (S12)
𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕 𝑟𝑟𝑐𝑐 Δ𝑟𝑟𝑖𝑖 𝜕𝜕𝑞𝑞𝑖𝑖
𝑟𝑟=𝑟𝑟𝑐𝑐+ 𝑟𝑟=𝑟𝑟𝑐𝑐+

𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖
(𝑘𝑘𝑏𝑏0 )𝑖𝑖 � �𝑞𝑞𝑝𝑝,𝑖𝑖 − 𝑞𝑞𝑖𝑖 |𝑟𝑟=𝑟𝑟𝑐𝑐 � (S12)
𝜕𝜕𝑞𝑞𝑖𝑖
𝑟𝑟=𝑟𝑟𝑐𝑐+

In general, when barrier resistance is low, or when particle loading is low, this approximation

introduces little error. It is not immediately clear whether this approximation is appropriate in

this paper. Eq. (S11) is therefore preferentially manipulated to:

3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 3(𝐷𝐷𝑏𝑏0 )𝑖𝑖 𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 Δ𝑟𝑟𝑖𝑖

∑𝑗𝑗 � = ∑𝑗𝑗 � �𝑞𝑞𝑝𝑝,𝑗𝑗 − 𝑞𝑞𝑗𝑗 �𝑟𝑟=𝑟𝑟 � (S13)
𝑟𝑟𝑐𝑐 𝜕𝜕𝑞𝑞𝑗𝑗 𝜕𝜕𝜕𝜕 𝑟𝑟𝑐𝑐 Δ𝑟𝑟𝑖𝑖 𝜕𝜕𝑞𝑞𝑗𝑗 𝑐𝑐 Δ𝑟𝑟𝑗𝑗
𝑟𝑟=𝑟𝑟𝑐𝑐+ 𝑟𝑟=𝑟𝑟𝑐𝑐+

𝜕𝜕𝑐𝑐𝑖𝑖𝑖𝑖𝑖𝑖 Δ𝑟𝑟𝑖𝑖
≡ (𝑘𝑘𝑏𝑏0 )𝑖𝑖 ∑𝑗𝑗 � �𝑞𝑞𝑝𝑝,𝑗𝑗 − 𝑞𝑞𝑗𝑗 �𝑟𝑟=𝑟𝑟 � (S13)
𝜕𝜕𝑞𝑞𝑗𝑗 𝑐𝑐 Δ𝑟𝑟𝑗𝑗
𝑟𝑟=𝑟𝑟𝑐𝑐+

Δ𝑟𝑟𝑖𝑖
Finally, it is assumed that ≈ 1. Upon substitution with Eq. (S8), the right-hand side of Eq.
Δ𝑟𝑟𝑗𝑗

(10) is obtained.

S4
 From a more qualitative aspect, the model implemented by Bhadra1 assumes isothermal

and isobaric operation, as opposed to the present work, which does not. These assumptions

deviate from reality for industrial-scale columns, which are known to possess significant

pressure drop, and are almost adiabatic. Here, the average result corresponding to all points

on Figure 14 for a feed containing 15% N2 in feed is shown in Table S1 for the present work,

the model implemented by Bhadra, and a non-isothermal, isobaric model.

Table S1. Effect of assuming isothermal and isobaric operation.

Present Work i.e. Non-Isothermal, Non-Isobaric

Product Purity Recovery Productivity Energy Use
(%) (%) (molCH4/kgads-s) (J/ molCH4)
95.8 91.8 2.20e-3 201
Model Implemented by Bhadra i.e. Isothermal, Isobaric
Product Purity Recovery Productivity Energy Use
(%) (%) (molCH4/kgads-s) (J/ molCH4)
12.1 85.8 3.85e-5 4210
Non-Isothermal, Isobaric
Product Purity Recovery Productivity Energy Use
(%) (%) (molCH4/kgads-s) (J/ molCH4)
95.8% 91.6% 2.70e-3 172

To maintain parity, the duration and velocity of each step is fixed to be the same for all

three cases. It is obvious that the performance of the column drops precipitously when the

column is assumed to be isothermal and isobaric. At a first glance, this may appear to be

counterintuitive due to the accepted heuristic that isothermal operation improves column

performance. For the present setup, it is discovered that the evacuation process results in a

significant decrease in column temperature (circa 50 K). By assuming an isothermal

operation, a significant amount of nitrogen is desorbed during the CnEv step. However, since

the duration and velocity of the CnEv step is fixed to be same as that of the non-isothermal
S5
case, the amount of nitrogen desorbed exceeds the amount which can be removed by the

evacuation pump. During the subsequent HPA step, the desorbed nitrogen is expelled through

the product end. The product purity therefore decreases dramatically from 95.8% to 12.1%.

In other words, if the column had been isothermal, a significantly higher evacuation velocity

would be needed to regenerate the column. Since the amount of methane produced during the

HPA step is reduced, the productivity decreases, and the energy use, defined as electricity

consumed per unit mole of methane produced, increases.

The effect of assuming non-isothermal but isobaric operation is relatively mild. The

increase in productivity arises due to the decrease in the duration of the CnEv step, which

occurs more rapidly for an isobaric column. It should be noted that the present work will

eventually be extended to include longer columns i.e. in excess of 2.4 m. A manuscript is

currently under preparation for comparative study between PVSA and cryogenic distillation

for methane-nitrogen separation. The effect seen in Table S1 is expected to be even more

prominent for such long, large-diameter columns.

S3. Non-Dimensionalization

Eqs. (1) to (7) and Eqs. (S1) to (S5) are non-dimensionalized by dividing time

coordinate (𝑡𝑡), axial coordinate (𝑧𝑧), radial coordinate along the macroparticles (𝑅𝑅), radial

coordinate along the microparticles (𝑟𝑟), column pressure (𝑃𝑃), column temperature (𝑇𝑇), wall

temperature (𝑇𝑇𝑤𝑤 ), adsorbed-phase concentration (𝑞𝑞) and fluid interstitial velocity (𝑣𝑣) against

some reference values:

𝑡𝑡
𝑡𝑡 ≡ (S14a)
𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐

𝑧𝑧
𝑧𝑧 ≡ (S14b)
𝐿𝐿

𝑅𝑅
𝑅𝑅 ≡ (S14c)
𝑅𝑅𝑝𝑝
S6
 𝑟𝑟
𝑟𝑟 ≡ (S14d)
𝑟𝑟𝑐𝑐

𝑃𝑃
𝑃𝑃 ≡ (S14e)
𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎

𝑇𝑇
𝑇𝑇 ≡ (S14f)
𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

𝑇𝑇𝑤𝑤
𝑇𝑇𝑤𝑤 ≡ (S14g)
𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

𝑞𝑞𝑖𝑖
𝑞𝑞𝑖𝑖 ≡ (S14h)
𝑞𝑞𝑠𝑠,𝑖𝑖

𝑣𝑣
𝑣𝑣 ≡ (S14i)
𝑣𝑣𝐹𝐹,𝑙𝑙

Here the overbar notation (¯) implies a non-dimensional form of the variable, 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 is the total

cycle time, 𝐿𝐿 is the length of the column, 𝑅𝑅𝑝𝑝 is the radius of the macroparticle, 𝑟𝑟𝑐𝑐 is the radius

of the microparticle, 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 is the ambient pressure, 𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 is the ambient temperature, 𝑞𝑞𝑠𝑠,𝑖𝑖 is the

saturation loading of component “i”, and 𝑣𝑣𝐹𝐹,𝑙𝑙 is the characteristic velocity for step “l”.

A brief investigation suggests that non-dimensionalization is only essential for the two

radial coordinates ( 𝑅𝑅 and 𝑟𝑟 ), which are subject to severe rounding errors during the

construction of the collocation matrices. All other variables are non-dimensionalized to allow

for rapid pen-and-paper analysis of the system under consideration, but seems to affect neither

the computational speed nor the accuracy of the simulation.

S4. Correlations and Dimensionless Groups

As a general design philosophy, the model has been written in a way such that all

parameters do not vary by more than 5%. To illustrate this point, consider the model

presented in Haghpanah et al. (2013). They have opted to use constant axial thermal

dispersion coefficient. In practice, due to axial and temporal variations in pressure,

S7
temperature, velocity and composition, axial thermal dispersion coefficient varies by an order

of magnitude throughout the simulation. There is an excellent reason for doing so, namely,

that the model becomes much easier to code, while losing very little accuracy, since

dispersion effects are several orders of magnitude smaller than convective and adsorptive

effects.

In this paper, we have opted to model variation in molecular diffusivity, dispersion

effects, film coefficient, viscosity and heat capacities, so as to provide the freedom to

investigate the effects of assuming constant values for these parameters. These are achieved

using correlations and/or linear mixing rules. By necessity, some of the relationships require

approximations. If so, these approximations must introduce no more than 5% error in

parameter values throughout the simulation.

Molecular diffusivity is modelled using a simplified version of the Chapman-Enskog

theory:

1.5
𝐷𝐷𝑚𝑚,𝑖𝑖 𝑇𝑇
∅ = (S15)
𝐷𝐷𝑚𝑚,𝑖𝑖 𝑃𝑃

Dispersion effects are calculated using the usual expression:

𝐷𝐷𝐿𝐿,𝑖𝑖 = 0.7𝐷𝐷𝑚𝑚,𝑖𝑖 + |𝑣𝑣| × 𝑟𝑟𝑝𝑝 (S16)

Note that the absolute value of velocity is taken, since backflow is a possibility in

micropore-controlled separation. Axial thermal dispersion is calculated from the correlation

presented by Yagi et al. (1960):

𝐾𝐾𝑧𝑧 𝐾𝐾𝑧𝑧∅
= + 𝛿𝛿 × 𝑃𝑃𝑃𝑃 × 𝑅𝑅𝑅𝑅 (S17)
𝑘𝑘𝑔𝑔 𝑘𝑘𝑔𝑔

S8
CMS is not one of the listed materials. The closest approximation appears to be glass beads

𝐾𝐾𝑧𝑧∅
with = 3 and 𝛿𝛿 = 0.8. Gas-phase conductivity is correlated to temperature in the domain
𝑘𝑘𝑔𝑔

of interest (approximately 298 ± 20 𝐾𝐾) using published data from the literature5. The effect

of gas composition on conductivity is neglected, since 𝐾𝐾𝑧𝑧 does not change significantly with

composition throughout the simulations. Correlation takes on the form:

𝑘𝑘𝑔𝑔
∅ = 1 + 𝛽𝛽𝑘𝑘 �𝑇𝑇 − 1� (S18)
𝑘𝑘𝑔𝑔

Here 𝑘𝑘𝑔𝑔∅ is the conductivity of a mixture containing 85% CH4 and balance N2. Film

coefficient is calculated using the correlation presented by Wakao and Funazkri (1978):

1
𝑆𝑆ℎ = 2 + 1.1 × 𝑅𝑅𝑒𝑒 0.6 × 𝑆𝑆𝑐𝑐 3 (S19)

Gas viscosity is corrected for changes in temperature following Sutherland’s formula:

𝑇𝑇0 +𝐶𝐶 𝑇𝑇 1.5

𝜇𝜇𝑓𝑓 = 𝜇𝜇𝑓𝑓∅ � � (S20)
𝑇𝑇+𝐶𝐶 𝑇𝑇0

This equation yields a complicated expression upon substitution. Eq. (S20) is refitted in the

domain of interest using least-square criterion to give:

𝜇𝜇𝑓𝑓
= 𝑇𝑇 (S21)
𝜇𝜇𝑓𝑓∅

Here 𝜇𝜇𝑓𝑓∅ is the viscosity at reference temperature, taken to be 1.97 × 10−5 kg/m/s. Heat

capacities are calculated using linear mixing rules:

∑𝑖𝑖 𝐶𝐶𝑝𝑝,𝑖𝑖 𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖

𝐶𝐶𝑝𝑝,𝑎𝑎 = ∑𝑖𝑖 𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖
& 𝐶𝐶𝑝𝑝,𝑔𝑔 = ∑𝑖𝑖 𝐶𝐶𝑝𝑝,𝑖𝑖 𝑦𝑦𝑖𝑖 (S22)

S9
 Very generally speaking, it appears that these variations are not necessary to model.

The impact of neglecting these variations is less than the numerical error introduced due to

discretization and numerical integration. Dispersion terms are several orders of magnitude

lower than convective and adsorptive terms. Likewise, mass transfer resistance due to

molecular diffusion is several orders of magnitude lower than crystal diffusion. The only

effect worth noticing is perhaps variation in viscosity. However, it largely impacts energy use

calculation, and as stated prior, energy use is not a relevant measure in this study.

S5. Boundary Conditions

Boundary conditions used to simulate the 6- and 9-step cycles are shown in Table S2.

These boundary conditions differ from those used in Bhadra et al. (2011) and Qinglin et al.

(2003) in several significant ways. For FP, feed is introduced into the column at constant

velocity, as opposed to using a hypothetical exponential pressure profile. For DPE and PPE,

mass flux is calculated from the pressure difference between the equalizing ends of the

columns, assuming constant line resistance calculated from rough pipe law. This assumption

is found to be reasonable since the pipe Reynolds number is of the order 105 to 106

throughout the simulation. For CnBd, mass flux out of the column is calculated from the

difference between feed and ambient pressure, likewise assuming constant line resistance

calculated from rough pipe law. For CoBd, CoEv and CnEv, fluid is withdrawn from the

appropriate end of the column at constant velocity, again avoiding the use of hypothetical

pressure profiles.

There are several physical and numerical advantages to using constant velocity

boundary conditions, as opposed to hypothetical pressure profiles. In practice, the behavior of

a pressure pump (used for introducing feed in FP) and an evacuation pump (used for

removing mass in CoBd, CoEv and CnEv) is well-described by constant feed or evacuation

velocity. For these systems, the best approximating pressure profile is linear. On the other
S10
hand, for CnBd, DPE and PPE, the best approximating pressure profile is exponential. The

constants of these pressure profiles are difficult to obtain a priori, and is subsequently

assumed to be constant in Bhadra et al. (2011) and Qinglin et al. (2003). This introduces an

error of unknown magnitude. It should also be noted that, since the system under

investigation is kinetically-controlled, the duration of different steps may impact column

performance significantly. Exponential pressure profile during FP also introduces backflow

in subsequent HPA step, which is not observed in practice.

Despite the “blowdown” appellation in “CoBn”, this step assumes fluid removal at

constant velocity at the product end of the column, as opposed to flow driven by difference

between column and ambient pressure. This is necessary because the pressure of the column

undergoing RP is in general higher than the column undergoing CoBn. Evacuation pump is

therefore used to raise the pressure of the CH4-rich stream to the pressure of the feed end of

the RP column. The “blowdown” nomenclature is retained to reflect the fact that, where

appropriate, this step will be followed by CnBn, and consequently the CoBn step cannot be

run below ambient pressure.

In the RP step, mass flux into the product end is fixed by the fluid removal rate in CoBn

and CoEv steps. Pressure and velocity at the feed end of the column are solved

simultaneously using mass flux constraint and Darcy’s law to give the formulation in Table

S2. Duration of RP is equal to sum of the durations of CoBn and CoEv. In most simulations

done in this study, column pressure is always lower than adsorption pressure at the end of RP.

Remaining difference is eliminated via FP.

Bhadra et al. (2011) and Qinglin et al. (2003) uses 3-point forward Weighted

Essentially Non-Oscillating flux limiter. This flux limiter is designed for material flow from

the feed end to the product end. For steps with counter-current flow e.g. CnBn and CnEv, we
S11
have opted to simply perform the mapping 𝑗𝑗 → 𝑁𝑁1 + 1 − 𝑗𝑗, equivalent to flipping the product

and the feed ends of the column.

Table S2. List of boundary conditions

Step Feed End Product End

2𝑁𝑁1 𝑦𝑦𝑖𝑖,1 + 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

RP 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1
2𝑁𝑁1 + 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

𝑇𝑇�0.5
2𝑁𝑁1 𝑇𝑇�1 + 𝜋𝜋30 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1
=
2𝑁𝑁1 + 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖𝑖𝑖,𝑙𝑙 𝜋𝜋𝑖𝑖.29

𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

2
−𝑄𝑄21 + �𝑄𝑄21 + 4𝑄𝑄22 𝑣𝑣̅𝑁𝑁1 +0.5 = 0
𝑣𝑣̅0.5 =
2

𝑇𝑇�0.5 𝑣𝑣̅0.5
𝑃𝑃�0.5 = 𝑃𝑃�1 + 𝑃𝑃�𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1
2𝑁𝑁1 𝜋𝜋25

2𝑁𝑁1 𝜋𝜋25
𝑄𝑄21 = 𝑃𝑃1
𝜋𝜋30

𝑃𝑃𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝑄𝑄22 = 2𝑁𝑁1 𝜋𝜋25
𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

2𝑁𝑁1 𝑦𝑦𝑖𝑖,1 + 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

FP 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1
2𝑁𝑁1 + 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

𝑇𝑇�0.5
2𝑁𝑁1 𝑇𝑇�1 + 𝜋𝜋30 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1
=
2𝑁𝑁1 + 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29

𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑣𝑣̅0.5 = 1 𝑣𝑣̅𝑁𝑁1 +0.5 = 0

𝜋𝜋30 𝑣𝑣̅0.5
𝑃𝑃�0.5 = 𝑃𝑃�1 + 𝑃𝑃�𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1
2𝑁𝑁1 𝜋𝜋25
S12
 2𝑁𝑁1 𝑦𝑦𝑖𝑖,1 + 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28
HPA 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1
2𝑁𝑁1 + 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

𝑇𝑇�0.5
2𝑁𝑁1 𝑇𝑇�1 + 𝜋𝜋30 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1
=
2𝑁𝑁1 + 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29

𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝜋𝜋25
𝑣𝑣̅0.5 = 1 𝑣𝑣̅𝑁𝑁1 +0.5 = 2𝑁𝑁1 �𝑃𝑃� − 𝑃𝑃�𝑁𝑁1 +0.5 �
𝑇𝑇�𝑁𝑁1 𝑁𝑁1

𝜋𝜋30 𝑣𝑣̅0.5
𝑃𝑃�0.5 = 𝑃𝑃�1 + 𝑃𝑃�𝑁𝑁1 +0.5 = 𝑃𝑃𝐹𝐹,𝑙𝑙
2𝑁𝑁1 𝜋𝜋25

DPE 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,1 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1

𝑇𝑇0.5 = 𝑇𝑇1 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1

𝑇𝑇𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑣𝑣𝑁𝑁1 +0.5

𝑣𝑣0.5 = 0 2
−𝑄𝑄13 + �𝑄𝑄13 + 4𝑄𝑄14 max�𝑃𝑃𝑁𝑁1 − 𝑃𝑃1,𝑃𝑃𝑃𝑃𝑃𝑃 , 0�
=
2𝑄𝑄14

𝑣𝑣𝑁𝑁1 +0.5 𝑇𝑇𝑁𝑁1 +0.5

𝑃𝑃0.5 = 𝑃𝑃1 𝑃𝑃𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1 −
2𝑁𝑁1 𝜋𝜋25

𝑇𝑇𝑁𝑁1 +0.5 𝑃𝑃𝑁𝑁1 2

𝜋𝜋30
𝑄𝑄13 = +
2𝑁𝑁1 𝜋𝜋25 𝑃𝑃1,𝑃𝑃𝑃𝑃𝑃𝑃 𝑇𝑇𝑁𝑁1 +0.5 2𝑁𝑁1 𝜋𝜋25

S13
 2𝑃𝑃𝑁𝑁21 1
𝑄𝑄14 = � 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 𝜋𝜋𝑖𝑖,38
𝑃𝑃𝑁𝑁1 + 𝑃𝑃1,𝑃𝑃𝑃𝑃𝑃𝑃 𝑇𝑇𝑁𝑁1 +0.5
𝑖𝑖

CoBd 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,1 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1

CoEv
𝑇𝑇0.5 = 𝑇𝑇1 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1

CnEv
𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑣𝑣0.5 = 0 𝑣𝑣𝑁𝑁1 +0.5 = 1

𝑣𝑣𝑁𝑁1 +0.5 𝑇𝑇𝑁𝑁1 +0.5

𝑃𝑃0.5 = 𝑃𝑃1 𝑃𝑃𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1 −
2𝑁𝑁1 𝜋𝜋25

S14
CnBd 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,1 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1

𝑇𝑇0.5 = 𝑇𝑇1 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1

𝑇𝑇𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑃𝑃0.5 = 𝑃𝑃1 𝑣𝑣𝑁𝑁1 +0.5

2
𝑣𝑣0.5 = 0 −𝑄𝑄13 + �𝑄𝑄13 + 4𝑄𝑄14 max�𝑃𝑃𝑁𝑁1 − 𝑃𝑃𝐹𝐹,𝑙𝑙 , 0�
=
2𝑄𝑄14

𝑣𝑣𝑁𝑁1 +0.5 𝑇𝑇𝑁𝑁1 +0.5

𝑃𝑃𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1 −
2𝑁𝑁1 𝜋𝜋25

𝑇𝑇𝑁𝑁1 +0.5
𝑄𝑄13 =
2𝑁𝑁1 𝜋𝜋25

2
2𝑃𝑃𝑁𝑁1 𝑦𝑦𝑖𝑖,𝑁𝑁+0.5 𝜋𝜋𝑖𝑖,38
𝑄𝑄14 = �
𝑖𝑖
𝑃𝑃𝑁𝑁1 + 𝑃𝑃𝐹𝐹,𝑙𝑙 𝑇𝑇𝑁𝑁1 +0.5

PPE 2𝑁𝑁1 𝑦𝑦𝑖𝑖,1 + 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1
2𝑁𝑁1 + 𝑣𝑣̅0.5 𝜋𝜋𝑖𝑖,28

𝑇𝑇�0.5

2𝑁𝑁1 𝑇𝑇�1 + 𝜋𝜋30 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖,𝐹𝐹,𝑙𝑙 𝜋𝜋𝑖𝑖.29 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1

=
2𝑁𝑁1 + 𝑣𝑣̅0.5 ∑𝑖𝑖 𝑦𝑦𝑖𝑖𝑖𝑖,𝑙𝑙 𝜋𝜋𝑖𝑖.29

S15
 𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑣𝑣0.5

𝑃𝑃𝑁𝑁1 ,𝐷𝐷𝐷𝐷𝐷𝐷 𝜋𝜋30 𝑣𝑣̅𝑁𝑁1 +0.5 = 0

= 𝑣𝑣𝑁𝑁1 +0.5,𝐷𝐷𝐷𝐷𝐷𝐷
𝑃𝑃1 𝑇𝑇𝑁𝑁1 +0.5,𝐷𝐷𝐷𝐷𝐷𝐷

𝜋𝜋30 𝑣𝑣̅0.5
𝑃𝑃0.5 = 𝑃𝑃1 + 𝑃𝑃�𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1
2𝑁𝑁1 𝜋𝜋25

IDL 𝑦𝑦𝑖𝑖,0.5 = 𝑦𝑦𝑖𝑖,1 𝑦𝑦𝑖𝑖,𝑁𝑁1 +0.5 = 𝑦𝑦𝑖𝑖,𝑁𝑁1

𝑇𝑇0.5 = 𝑇𝑇1 𝑇𝑇�𝑁𝑁1+0.5 = 𝑇𝑇�𝑁𝑁1

𝑇𝑇�𝑤𝑤,0.5 = 𝜋𝜋40 𝑇𝑇�𝑤𝑤,𝑁𝑁1 +0.5 = 𝜋𝜋40

𝑣𝑣̅0.5 = 0 𝑣𝑣̅𝑁𝑁1 +0.5 = 0

𝑃𝑃0.5 = 𝑃𝑃1 𝑃𝑃�𝑁𝑁1 +0.5 = 𝑃𝑃𝑁𝑁1

Note that some boundary conditions (RP, DPE and PPE) require information from other

steps. In RP, feed composition (𝑦𝑦𝑖𝑖,𝐹𝐹 ), pressure (𝑃𝑃𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ) and temperature (𝑇𝑇𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 ) are taken from

the evacuation stream of the previous CoBn and CoEv steps. Product- and feed-end boundary

conditions of DPE and PPE respectively are not, strictly speaking, boundary conditions, since

these two steps are simulated together. Rather, they represent the relationship between the

two columns, which is used to complete the ODE function.

S6. Non-Dimensional Equations and Groups

Upon substituting Eqs. (S14) to (S22) into the relevant mass and energy balances, the

following equations are obtained:

S16
Total Mass Balance

3
1 𝜕𝜕𝑃𝑃 1 𝜕𝜕𝑇𝑇 𝑇𝑇 𝜕𝜕 𝑇𝑇2 𝑃𝑃 𝜕𝜕𝑦𝑦𝑖𝑖 𝑇𝑇 𝜕𝜕 𝑃𝑃𝑣𝑣
− = ∑𝑖𝑖 ��𝜋𝜋𝑖𝑖,1 + 𝜋𝜋2 � � − 𝜋𝜋3 𝑃𝑃 𝜕𝜕𝑧𝑧 � 𝑇𝑇 � (S23)
𝑃𝑃 𝜕𝜕𝑡𝑡 𝑇𝑇 𝜕𝜕𝑡𝑡 𝑃𝑃 𝜕𝜕𝑧𝑧 𝑃𝑃 𝑇𝑇 𝜕𝜕𝑧𝑧

3 23
𝑇𝑇 2 𝑇𝑇15 0.6
− ∑𝑖𝑖 �𝜋𝜋𝑖𝑖,4 + 𝜋𝜋𝑖𝑖,5 14 𝑣𝑣 � �𝑦𝑦𝑖𝑖 − 𝑦𝑦𝑝𝑝,𝑖𝑖 �𝑅𝑅=1 � (S23)
𝑃𝑃
𝑃𝑃15

Component Mass Balance

3
𝜕𝜕𝑦𝑦𝑖𝑖 𝑦𝑦𝑖𝑖 𝜕𝜕𝑃𝑃 𝑦𝑦𝑖𝑖 𝜕𝜕𝑇𝑇 𝑇𝑇 𝜕𝜕 𝑇𝑇2 𝑃𝑃 𝜕𝜕𝑦𝑦𝑖𝑖 𝑇𝑇 𝜕𝜕 𝑦𝑦𝑖𝑖 𝑃𝑃𝑣𝑣
+ − = ��𝜋𝜋𝑖𝑖,1 + 𝜋𝜋2 � � − 𝜋𝜋3 𝑃𝑃 𝜕𝜕𝑧𝑧 � � (S24)
𝜕𝜕𝑡𝑡 𝑃𝑃 𝜕𝜕𝑡𝑡 𝑇𝑇 𝜕𝜕𝑡𝑡 𝑃𝑃 𝜕𝜕𝑧𝑧 𝑃𝑃 𝑇𝑇 𝜕𝜕𝑧𝑧 𝑇𝑇

3 23
𝑇𝑇2 𝑇𝑇15 0.6
− �𝜋𝜋𝑖𝑖,4 + 𝜋𝜋𝑖𝑖,5 14 𝑣𝑣 � �𝑦𝑦𝑖𝑖 − 𝑦𝑦𝑝𝑝,𝑖𝑖 �𝑅𝑅=1 � (S24)
𝑃𝑃
𝑃𝑃15

Column Energy Balance

𝜕𝜕𝑇𝑇 𝜕𝜕𝑃𝑃 𝜕𝜕 𝜕𝜕𝑇𝑇 𝜕𝜕

𝜃𝜃1 + = �𝜃𝜃2 � − 𝜋𝜋3 �𝑣𝑣𝑃𝑃� − 𝑄𝑄3 ∑𝑖𝑖 𝜃𝜃𝑖𝑖,3 + (S25a)
𝜕𝜕𝑡𝑡 𝜕𝜕𝑡𝑡 𝜕𝜕𝑧𝑧 𝜕𝜕𝑧𝑧 𝜕𝜕𝑧𝑧

1 𝜃𝜃𝑖𝑖,3 𝑇𝑇−𝑇𝑇𝑤𝑤
∑𝑖𝑖 � + 1 − 𝑄𝑄3 � × −∑ (S25a)
∑𝑗𝑗 𝑦𝑦𝑗𝑗 𝜋𝜋𝑖𝑖,𝑗𝑗,18 𝑇𝑇 𝑖𝑖 𝑦𝑦𝑖𝑖 𝜋𝜋𝑖𝑖,19

1
𝜃𝜃1 = ∑ + 𝑄𝑄3 × ∑𝑖𝑖 𝜋𝜋𝑖𝑖,15 𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 (S25b)
𝑖𝑖 𝑦𝑦𝑖𝑖 𝜋𝜋𝑖𝑖,14

1 𝑃𝑃 𝑃𝑃 𝐾𝐾𝑧𝑧,0 𝐾𝐾𝑧𝑧,0
𝜃𝜃2 = ∑ �2𝛿𝛿�1 + 𝛽𝛽𝑘𝑘,𝑔𝑔 �𝜋𝜋17 𝑣𝑣 − 2𝛿𝛿𝛽𝛽𝑘𝑘,𝑔𝑔 𝜋𝜋17 2 𝑣𝑣 + �1 + 𝛽𝛽𝑘𝑘,𝑔𝑔 �𝑇𝑇 − 𝛽𝛽𝑘𝑘,𝑔𝑔 � (S25c)
𝑖𝑖 𝑦𝑦𝑖𝑖 𝜋𝜋𝑖𝑖,16 𝑇𝑇 𝑇𝑇 𝑘𝑘𝑔𝑔 𝑘𝑘𝑔𝑔
3 23
𝑇𝑇 2 𝑇𝑇15 0.6
𝜃𝜃𝑖𝑖,3 = �𝜋𝜋𝑖𝑖,4 + 𝜋𝜋𝑖𝑖,5 14 𝑣𝑣 � �𝑦𝑦𝑖𝑖 − 𝑦𝑦𝑝𝑝,𝑖𝑖 �𝑅𝑅=1 � (S25d)
𝑃𝑃
𝑃𝑃15

∑𝑖𝑖 𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 𝐶𝐶𝑝𝑝𝑝𝑝,𝑖𝑖

𝑄𝑄3 = ∑ (S25e)
𝑖𝑖 𝑞𝑞𝑎𝑎𝑎𝑎𝑎𝑎,𝑝𝑝,𝑖𝑖 ×∑𝑖𝑖 𝑦𝑦𝑖𝑖 𝐶𝐶𝑝𝑝𝑝𝑝,𝑖𝑖

Wall Energy Balance

𝜕𝜕𝑇𝑇𝑤𝑤 𝜕𝜕2 𝑇𝑇𝑤𝑤

= 𝜋𝜋20 2 + 𝜋𝜋21 �𝑇𝑇 − 𝑇𝑇𝑤𝑤 � + 𝜋𝜋22 �𝑇𝑇𝑤𝑤 − 𝜋𝜋40 � (S26)
𝜕𝜕𝑡𝑡 𝜕𝜕𝑧𝑧

Macropore Mass Balance

𝜕𝜕𝑦𝑦𝑝𝑝,𝑖𝑖 𝑦𝑦𝑝𝑝,𝑖𝑖 𝜕𝜕𝑃𝑃 𝑦𝑦𝑝𝑝,𝑖𝑖 𝜕𝜕𝑇𝑇

+ − (S27)
𝜕𝜕𝑡𝑡 𝑃𝑃 𝜕𝜕𝑡𝑡 𝑇𝑇 𝜕𝜕𝑡𝑡
𝜋𝜋𝑖𝑖,7 𝑇𝑇
= −𝜋𝜋𝑖𝑖,6 exp �− � 𝑄𝑄2𝑏𝑏 |𝑟𝑟=1 ��𝑞𝑞𝑝𝑝,𝑖𝑖 − 𝑞𝑞𝑖𝑖 � � + �𝑄𝑄𝑖𝑖,1 − 1� ∑𝑗𝑗 �𝑞𝑞𝑝𝑝,𝑗𝑗 − 𝑞𝑞𝑗𝑗 � �� (S27)
𝑇𝑇 𝑃𝑃 𝑟𝑟=1 𝑟𝑟=1

S17
 3
𝑇𝑇2 𝜕𝜕2 𝑦𝑦𝑝𝑝,𝑖𝑖 2 𝜕𝜕𝑦𝑦𝑝𝑝,𝑖𝑖
+𝜋𝜋𝑖𝑖,8 � 2 + � (S27)
𝑃𝑃 𝜕𝜕𝑅𝑅 𝑅𝑅 𝜕𝜕𝑅𝑅

Micropore Mass Balance

𝜕𝜕𝑞𝑞𝑖𝑖 𝜋𝜋𝑖𝑖,11 𝜋𝜋𝑖𝑖,12 𝜕𝜕 2 𝜕𝜕𝑞𝑞𝑖𝑖 2 𝜕𝜕𝑞𝑞𝑗𝑗

= 2 exp �− � �𝑟𝑟 𝑄𝑄2𝑝𝑝 + 𝑟𝑟 𝑄𝑄2𝑝𝑝 �𝑄𝑄𝑖𝑖,1 − 1� ∑𝑗𝑗 � (S28)
𝜕𝜕𝑡𝑡 𝑟𝑟 𝑇𝑇 𝜕𝜕𝑟𝑟 𝜕𝜕𝑟𝑟 𝜕𝜕𝜕𝜕

Darcy’s Law

𝜋𝜋25 𝜕𝜕𝑃𝑃
𝑣𝑣 = �− � (S29)
𝑇𝑇 𝜕𝜕𝑧𝑧

Multi-Site Langmuir Isotherm

𝜋𝜋𝑖𝑖,27 𝑃𝑃 𝑞𝑞𝑝𝑝,𝑖𝑖
𝜋𝜋𝑖𝑖,26 exp �− � 𝑦𝑦𝑝𝑝.𝑖𝑖 = 𝑎𝑎𝑖𝑖 (S30)
𝑇𝑇 𝑇𝑇 �1−∑𝑖𝑖 𝑞𝑞𝑝𝑝,𝑖𝑖 �

It remains to define the dimensionless groups used throughout the equations. These are

listed in Table S3. Some dimensionless parameters e.g. 𝜋𝜋31 through 𝜋𝜋37 are missing from

Table S3. Missing parameters are used exclusively for code development and debugging

procedures, and are therefore not relevant to this paper.

Table S3. List of dimensionless parameters

∅
𝐷𝐷𝑚𝑚,𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑣𝑣𝐹𝐹,𝑙𝑙 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑅𝑅𝑝𝑝
𝜋𝜋𝑖𝑖,1 = 0.7 𝜋𝜋2 =
𝐿𝐿2 𝐿𝐿 𝐿𝐿

𝑣𝑣𝐹𝐹,𝑙𝑙 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 ∅
1 − 𝜀𝜀𝑏𝑏 𝐷𝐷𝑚𝑚,𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐
𝜋𝜋3 = 𝜋𝜋𝑖𝑖,4 =3
𝐿𝐿 𝜀𝜀𝑏𝑏 𝑅𝑅𝑝𝑝2

∅
4 1 − 𝜀𝜀𝑝𝑝 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 ′
1 − 𝜀𝜀𝑏𝑏 𝜌𝜌𝑓𝑓 15 ∅ 23 𝑣𝑣𝐹𝐹,𝑙𝑙
0.6
𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝜋𝜋𝑖𝑖,6 = 𝑞𝑞𝑠𝑠,𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑘𝑘𝑏𝑏0,𝑖𝑖
𝜋𝜋𝑖𝑖,5 = 2.5 0.4 � ∅ � �𝐷𝐷𝑚𝑚,𝑖𝑖 � 𝜀𝜀𝑝𝑝 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎
𝜀𝜀𝑏𝑏 𝜇𝜇𝑓𝑓 𝑅𝑅𝑝𝑝1.4

𝐸𝐸𝑏𝑏,𝑖𝑖 ∅
1 𝐷𝐷𝑚𝑚,𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐
𝜋𝜋𝑖𝑖,7 = 𝜋𝜋𝑖𝑖,8 =
𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝜏𝜏 𝑅𝑅𝑝𝑝2

S18
 𝜏𝜏 4
𝜋𝜋9 = 0.6 0.6 𝜌𝜌 ∅ 15
𝜀𝜀𝑏𝑏 𝑅𝑅𝑝𝑝
𝜀𝜀𝑝𝑝 𝑓𝑓 0.6
𝜋𝜋𝑖𝑖,10 = 0.834 1 � ∅ � 𝑣𝑣𝐹𝐹,𝑙𝑙
∅ 3 𝜇𝜇𝑓𝑓
�𝐷𝐷𝑚𝑚,𝑖𝑖 �

′ 𝐸𝐸𝑝𝑝,𝑖𝑖
𝐷𝐷𝑐𝑐0,𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐
𝜋𝜋𝑖𝑖,11 = 𝜋𝜋𝑖𝑖,12 =
2
𝑟𝑟𝑐𝑐 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

′ 𝜀𝜀𝑏𝑏 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝑝𝑝,𝑔𝑔,𝑖𝑖

𝑘𝑘𝑏𝑏0,𝑖𝑖 𝑟𝑟𝑐𝑐2
𝜋𝜋𝑖𝑖,13 = 𝜋𝜋𝑖𝑖,14 =
′
3 𝐷𝐷𝑐𝑐0,𝑖𝑖 1 − 𝜀𝜀𝑏𝑏 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝜌𝜌𝑠𝑠 𝐶𝐶𝑝𝑝,𝑠𝑠

1 − 𝜀𝜀𝑏𝑏 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝑝𝑝,𝑔𝑔,𝑖𝑖 𝐿𝐿2

𝜋𝜋𝑖𝑖,15 = 𝑞𝑞 𝜋𝜋𝑖𝑖,16 = 𝜀𝜀𝑏𝑏
𝜀𝜀𝑏𝑏 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝑠𝑠,𝑖𝑖 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑔𝑔∅ 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐

𝑣𝑣𝐹𝐹,𝑙𝑙 𝜌𝜌𝑓𝑓∅ 𝑅𝑅𝑝𝑝 𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝑝𝑝,𝑔𝑔,𝑗𝑗

𝜋𝜋17 = 𝜀𝜀𝑏𝑏 𝑃𝑃𝑃𝑃𝐹𝐹 𝜋𝜋𝑖𝑖,𝑗𝑗,18 =
𝜇𝜇𝑓𝑓∅ −Δ𝑈𝑈𝑖𝑖 + 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

𝜀𝜀𝑏𝑏 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝑝𝑝,𝑔𝑔,𝑖𝑖 𝑟𝑟𝑖𝑖𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑘𝑘𝑤𝑤

𝜋𝜋𝑖𝑖,19 = 𝜋𝜋20 =
2 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 ℎ𝑖𝑖𝑖𝑖 𝜌𝜌𝑤𝑤 𝐶𝐶𝑝𝑝,𝑤𝑤 𝐿𝐿2

𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑟𝑟𝑖𝑖𝑖𝑖 ℎ𝑖𝑖𝑖𝑖 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐 𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 ℎ𝑜𝑜𝑜𝑜𝑜𝑜

𝜋𝜋21 = 2 2 2 𝜋𝜋22 = 2 2 2
𝜌𝜌𝑤𝑤 𝐶𝐶𝑝𝑝,𝑤𝑤 𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 − 𝑟𝑟𝑖𝑖𝑖𝑖 𝜌𝜌𝑤𝑤 𝐶𝐶𝑝𝑝,𝑤𝑤 𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 − 𝑟𝑟𝑖𝑖𝑖𝑖

3𝜀𝜀𝑝𝑝 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝜋𝜋24 = 9�1 − 𝜀𝜀𝑝𝑝 �

𝜋𝜋𝑖𝑖,23 =
𝑞𝑞𝑠𝑠,𝑖𝑖 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

4 𝜀𝜀𝑏𝑏 2 2 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎

𝜋𝜋25 = � � 𝑅𝑅𝑝𝑝 ∅ 𝜋𝜋𝑖𝑖,26 = 𝑏𝑏0,𝑖𝑖
150 1 − 𝜀𝜀𝑏𝑏 𝜇𝜇𝑓𝑓 𝑣𝑣𝐹𝐹,𝑙𝑙 𝐿𝐿 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

Δ𝑈𝑈𝑖𝑖 𝑣𝑣𝐹𝐹,𝑙𝑙 𝐿𝐿
𝜋𝜋𝑖𝑖,27 = 𝜋𝜋𝑖𝑖,28 = 3
𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎
𝑇𝑇 2 𝑃𝑃
∅
0.7𝐷𝐷𝑚𝑚,𝑖𝑖 �𝑇𝑇 𝐹𝐹,𝑙𝑙 � 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑣𝑣𝐹𝐹,𝑙𝑙 𝑅𝑅𝑝𝑝
𝑎𝑎𝑎𝑎𝑎𝑎 𝐹𝐹,𝑙𝑙

S19
𝜋𝜋𝑖𝑖,29

𝑃𝑃𝐹𝐹,𝑙𝑙
𝜀𝜀𝑏𝑏 𝑣𝑣𝐹𝐹,𝑙𝑙 𝐿𝐿
𝐶𝐶
𝑅𝑅𝑇𝑇𝐹𝐹,𝑙𝑙 𝑝𝑝,𝑔𝑔,𝑖𝑖
= 2
𝑃𝑃 𝑇𝑇 𝑃𝑃 𝑇𝑇 𝐾𝐾 𝑇𝑇 𝐾𝐾
𝑘𝑘𝑔𝑔∅ �2𝛿𝛿�1 + 𝛽𝛽𝑘𝑘,𝑔𝑔 �𝜋𝜋17 𝐹𝐹,𝑙𝑙 𝑎𝑎𝑎𝑎𝑎𝑎 − 2𝛿𝛿𝛽𝛽𝑘𝑘,𝑔𝑔 𝜋𝜋17 𝐹𝐹,𝑙𝑙 � 𝑎𝑎𝑎𝑎𝑎𝑎 � + 𝑧𝑧,0 �1 + 𝛽𝛽𝑘𝑘,𝑔𝑔 � 𝐹𝐹,𝑙𝑙 − 𝑧𝑧,0 𝛽𝛽
𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝑇𝑇𝐹𝐹,𝑙𝑙 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝑇𝑇𝐹𝐹,𝑙𝑙 𝑘𝑘𝑔𝑔 𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑘𝑘𝑔𝑔

𝑇𝑇𝐹𝐹,𝑙𝑙 𝑒𝑒
𝜋𝜋30 = 𝜋𝜋39 =
𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑟𝑟𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

4
𝑀𝑀𝑟𝑟𝑖𝑖 𝑟𝑟𝑖𝑖𝑖𝑖 𝐿𝐿 𝐾𝐾𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝
𝜋𝜋𝑖𝑖,38 = 𝜀𝜀𝑏𝑏2 𝑣𝑣𝐹𝐹,𝑙𝑙
2
� � � (4 log10 {0.135 × 𝜋𝜋39 })−2 + �
𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝑟𝑟𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑟𝑟𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 2

𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏ℎ
𝜋𝜋40 =
𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎

S7. Miscellaneous Notes on Performance Measures

The performance measures used in this paper are largely identical to those used by

Bhadra et al. (2011) and Qinglin et al. (2003). Note that energy use is not strongly affected by

pressure drop in external piping during RP, FP, HPA, CoBn and CoEv steps. This is

primarily due to low column velocities (of order 0.01 m/s), equivalent to pipe flows of order

1 m/s. However, effect of pressure drop becomes significant when column velocity

approaches 1 m/s. Simulations done at higher adsorption / evacuation velocities should

account for pressure drop in external piping and pump performance curves.

In this study, the effect of re-pressurizing CH4 to pipeline pressure has not been

considered, so as to enforce parity with established mobile NRUs. It is worth considering this

issue in greater detail. One of the primary concerns regarding established NRUs (cryogenic

distillation, PSA using activated carbon, membrane processing, and low-temperature oil

production) is that they produce CH4 at low pressure, which requires subsequent
S20
recompression to pipeline pressure6. Our calculation suggests that the cost of recompression

is of the same order as the cost of running the NRU.

One of the clear trends that arise in our study is that, at the Pareto front, recovery

increases with decreasing adsorption pressure. However, with decreasing adsorption pressure,

more energy is needed to recompress the product stream. In view of this, future studies

should consider the following two-pronged, conservative approach. From the simulation side,

energy for recompressing product stream should be added to the energy use of the PSA

column. Costing of the proposed PSA NRU therefore contains consideration of product

recompression to pipeline pressure.

From the design side, a coupled turboexpander-compressor system should be installed

to recover the energy lost when feed is reduced from the source to the adsorption pressure.

This design is appealing because, in general, it does not need additional electricity to run.

Typical coupled turboexpander-compressor system has an efficiency of 80%. However, since

the mass flow rate of the stream passing through the compressor is approximately 70 to 90%

of that passing through the turboexpander (depending on feed composition, product purity

and product recovery), the energy required for recompression is greatly reduced. The energy

required to run the coupled turboexpander-compressor system per mole of CH4 produced is

given by:

𝑃𝑃𝑃𝑃𝑃𝑃 𝛾𝛾−1
1−𝜂𝜂1
𝑅𝑅𝑅𝑅𝑅𝑅×𝑦𝑦𝑖𝑖,𝐹𝐹 𝛾𝛾 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝛾𝛾
𝑖𝑖𝑖𝑖 > 0 → × 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 �� � − 1�
𝜂𝜂×𝑃𝑃𝑃𝑃𝑃𝑃 𝛾𝛾−1 𝑃𝑃𝐻𝐻
𝑃𝑃𝑃𝑃𝑃𝑃 𝛾𝛾−1
(S31)
1−𝜂𝜂1
𝑅𝑅𝑅𝑅𝑅𝑅×𝑦𝑦𝑖𝑖,𝐹𝐹 𝛾𝛾 𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝛾𝛾
𝑖𝑖𝑖𝑖 ≤ 0 → × 𝑅𝑅𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 �� � − 1�
𝑃𝑃𝑃𝑃𝑃𝑃 𝛾𝛾−1 𝑃𝑃𝐻𝐻

S8. Solution Algorithms

S21
 The model proposed in this work is computationally intensive. For this reason, the form

of the solution algorithm is central to the execution of the model. In this section, we describe

two solution algorithms necessary to run the model within a reasonable time-scale.

Solution to Multi-Site Isotherm

Eq. (S30) is nonlinear in 𝑞𝑞𝑝𝑝,𝑖𝑖 and involves simultaneously solving for 𝑁𝑁1 variables

(𝑞𝑞𝑝𝑝,𝑖𝑖 ) given all other variable values (𝑃𝑃, 𝑇𝑇 & 𝑦𝑦𝑝𝑝.𝑖𝑖 ). It also possesses an unacceptably high

failure rate when coupled to the default nonlinear equation solver in MATLAB i.e. fsolve.

This equation may be solved more favorably via the following manipulation:

𝜋𝜋𝑖𝑖,27 𝑃𝑃 𝑎𝑎𝑖𝑖
∑𝑖𝑖 �𝜋𝜋𝑖𝑖,26 exp �− � 𝑦𝑦𝑝𝑝.𝑖𝑖 �1 − ∑𝑖𝑖 𝑞𝑞𝑝𝑝,𝑖𝑖 � � = ∑𝑖𝑖 𝑞𝑞𝑝𝑝,𝑖𝑖 (S32a)
𝑇𝑇 𝑇𝑇

We now substitute 𝑋𝑋 ≡ ∑𝑖𝑖 𝑞𝑞𝑝𝑝,𝑖𝑖

𝜋𝜋𝑖𝑖,27 𝑃𝑃
∑𝑖𝑖 �𝜋𝜋𝑖𝑖,26 exp �− � 𝑦𝑦𝑝𝑝.𝑖𝑖 (1 − 𝑋𝑋)𝑎𝑎𝑖𝑖 � = 𝑋𝑋 (S32b)
𝑇𝑇 𝑇𝑇

Eq. (S32b) is a single-variable nonlinear equation, which is guaranteed to converge for

nonnegative macropore concentrations (𝐶𝐶𝑝𝑝,𝑖𝑖 ). The proof is considered trivial. Very aggressive

algorithms e.g. Newton’s method may now be used to solve Eq. (S32b). Note that the

reduction in the number of variables greatly improves the scaling of the problem with respect

to the number of components. Once 𝑋𝑋 is known, the values of 𝑞𝑞𝑝𝑝,𝑖𝑖 may be obtained from:

𝜋𝜋𝑖𝑖,27 𝑃𝑃
𝑞𝑞𝑝𝑝,𝑖𝑖 = 𝜋𝜋𝑖𝑖,26 exp �− � 𝑦𝑦𝑝𝑝.𝑖𝑖 (1 − 𝑋𝑋)𝑎𝑎𝑖𝑖 (S32c)
𝑇𝑇 𝑇𝑇

Solution to Micropore Boundary Condition

S22
 Eq. (10) faces the same problems as Eq. (S30). In this case, we would like to find

𝑞𝑞𝑖𝑖 � given all other variables (𝑇𝑇 & 𝑞𝑞𝑝𝑝,𝑖𝑖 ). As before, it is desirable to have a stable, rapidly
𝑟𝑟=1

converging algorithm which scales well with the number of components. The following set of

update procedures are used:

𝑓𝑓(𝑋𝑋𝑚𝑚 )
𝑋𝑋𝑚𝑚+1 = 𝑋𝑋𝑚𝑚 − (S33a)
𝑓𝑓′ (𝑋𝑋𝑚𝑚 )

𝜃𝜃𝑖𝑖,𝑚𝑚,7
𝑓𝑓(𝑋𝑋𝑚𝑚 ) = 𝑋𝑋𝑚𝑚 − ∑𝑖𝑖 (S33b)
𝜃𝜃𝑖𝑖,𝑚𝑚,8

−𝜃𝜃𝑖𝑖,3 𝜃𝜃𝑖𝑖,𝑚𝑚,6 +𝜃𝜃𝑖𝑖,2 (𝑎𝑎𝑖𝑖 −1)�𝜃𝜃1 +𝜃𝜃𝑖𝑖,𝑚𝑚,6 �𝜃𝜃𝑖𝑖,𝑚𝑚,7

𝑓𝑓 ′ (𝑋𝑋𝑚𝑚 ) = 1 − ∑𝑖𝑖 � − 2 � (S33c)
𝜃𝜃𝑖𝑖,𝑚𝑚,8 𝜃𝜃𝑖𝑖,𝑚𝑚,8

𝜃𝜃𝑖𝑖,𝑚𝑚,8 = 𝜃𝜃1 (1 − 𝑋𝑋𝑚𝑚 ) + 𝑎𝑎𝑖𝑖 (𝜃𝜃1 𝑋𝑋𝑚𝑚 + 𝜃𝜃4 ) + 𝜃𝜃𝑖𝑖,𝑚𝑚,6 (1 − 𝑋𝑋𝑚𝑚 ) − 𝜃𝜃𝑖𝑖,𝑚𝑚,6 𝑎𝑎𝑖𝑖 (𝜃𝜃5 − 𝑋𝑋𝑚𝑚 ) (S33d)

𝜃𝜃𝑖𝑖,𝑚𝑚,7 = �𝜃𝜃𝑖𝑖,3 𝜃𝜃𝑖𝑖,𝑚𝑚,6 − 𝜃𝜃𝑖𝑖,2 �(1 − 𝑋𝑋𝑚𝑚 ) (S33e)

1+∑𝑖𝑖�𝛽𝛽𝑏𝑏,𝑖𝑖 −1�𝑞𝑞𝑖𝑖,𝑚𝑚−1
𝜃𝜃𝑖𝑖,𝑚𝑚,6 = 𝑄𝑄𝑖𝑖,5 (S33f)
1+∑𝑖𝑖�𝛽𝛽𝑝𝑝,𝑖𝑖 −1�𝑞𝑞𝑖𝑖,𝑚𝑚−1

𝜃𝜃5 = ∑𝑖𝑖 𝜃𝜃𝑖𝑖,3 (S33g)

𝜃𝜃4 = ∑𝑖𝑖 𝜃𝜃𝑖𝑖,2 (S33h)

𝜃𝜃𝑖𝑖,3 = 𝑞𝑞𝑝𝑝,𝑖𝑖 (S33i)

𝑞𝑞𝑖𝑖 �
𝑟𝑟=𝑟𝑟1
𝜃𝜃𝑖𝑖,2 = 𝐴𝐴(𝑁𝑁3 + 1,1: 𝑁𝑁3 ) � … � (S33j)
𝑞𝑞𝑖𝑖 �
𝑟𝑟=𝑟𝑟𝑁𝑁3

𝜃𝜃1 = 𝐴𝐴(𝑁𝑁3 + 1, 𝑁𝑁3 + 1) (S33k)

𝜋𝜋𝑖𝑖,7 −𝜋𝜋𝑖𝑖,12
𝑄𝑄𝑖𝑖,5 = 𝜋𝜋𝑖𝑖,13 exp �− � (S33l)
𝑇𝑇

S23
Here the subscript “m” refers to the iteration number and 𝐴𝐴 is the collocation matrix such that:

𝑞𝑞𝑖𝑖 �
𝜕𝜕𝑞𝑞𝑖𝑖 𝑟𝑟=𝑟𝑟1
= 𝐴𝐴(𝑁𝑁3 + 1,1: 𝑁𝑁3 + 1) � … � (S33m)
𝜕𝜕𝑟𝑟
𝑞𝑞𝑖𝑖 �
𝑟𝑟=1

The notation 𝐴𝐴(𝑁𝑁3 + 1,1: 𝑁𝑁3 + 1) implies the 𝑁𝑁3 + 1-th row of the collocation matrix. At the

end of each iteration i.e. evaluation of Eq. (S33a), a secondary update procedure is run:

𝜃𝜃𝑖𝑖,𝑚𝑚,9
𝑞𝑞𝑖𝑖,𝑚𝑚 = (S33n)
𝜃𝜃𝑖𝑖,𝑚𝑚,10

𝜃𝜃𝑖𝑖,𝑚𝑚,9 = �𝜃𝜃𝑖𝑖,3 𝜃𝜃𝑖𝑖,𝑚𝑚,6 − 𝜃𝜃𝑖𝑖,2 �(1 − 𝑋𝑋𝑚𝑚+1 ) (S33o)

𝜃𝜃𝑖𝑖,𝑚𝑚,10 = 𝜃𝜃1 (1 − 𝑋𝑋𝑚𝑚+1 ) + 𝑎𝑎𝑖𝑖 (𝜃𝜃1 𝑋𝑋𝑚𝑚+1 + 𝜃𝜃4 ) + 𝜃𝜃𝑖𝑖,𝑚𝑚,6 (1 − 𝑋𝑋𝑚𝑚+1 ) − 𝜃𝜃𝑖𝑖,𝑚𝑚,6 𝑎𝑎𝑖𝑖 (𝜃𝜃5 − 𝑋𝑋𝑚𝑚+1 ) (S33p)

Note that Eq. (S33) calculates the values of 𝑞𝑞𝑖𝑖 at the surface of the microparticle. For clarity,

all references to this fact i.e. the single bracket |𝑟𝑟=1 has been removed from Eq. (S33).

Unless otherwise stated, the values of 𝑋𝑋𝑚𝑚 and 𝑞𝑞𝑖𝑖 refers to the surface of the microparticle.

This complex formulation exploits the fact that Eq. (S33f) is relatively insensitive to the

value of 𝑞𝑞𝑖𝑖,𝑚𝑚 � and therefore does not require an aggressive update procedure. Eq. (S33)
𝑟𝑟=1

converges rapidly and scales well with the number of components, but cannot be proven to

converge for all cases. Nevertheless, Eq. (S33) is found to be very stable, with a failure rate

in the order of 10-8.

S9. Model Validation

The proposed model is validated against the experimental data published by Qinglin7.

Validation is done for runs 9 through 20 in Table 6.2 of the aforementioned work. For runs 9

through 12, the column is initially saturated with 48% N2 and 52% O2, and subsequently

purged with either pure oxygen or pure nitrogen. For runs 13 through 16, the column is
S24
initially saturated with 78% N2 and 22% O2, and likewise purged with either pure oxygen or

pure nitrogen. For runs 17 through 20, the column is initially saturated with pure nitrogen,

and subsequently purged with pure oxygen. For each run, the exit composition and velocity is

recorded and compared against the simulation result obtained using the present model. Note

that Figures S1 through S8 are composed of four comparisons (a) exit composition of oxygen,

where the column has been purged with pure oxygen, (b) corresponding exit velocity, (c) exit

composition of nitrogen, where the column has been purged with nitrogen, and (d)

corresponding exit velocity. Figures S9 through S12 are composed of two comparisons (a)

exit composition of oxygen, and (b) corresponding exit velocity.

1.4
1.2 Data Simulation

1
(yO2-0.52)/0.48

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S25
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.48)/0.52

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S26
 1.6
1.4 Data Simulation

Exit Velocity (m/s)

1.2
1
0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S1. Validation result corresponding to run 9.

1.4
1.2 Data Simulation

1
(yO2-0.52)/0.48

0.8
0.6
0.4
0.2
(a)
0
0 400 800 1200
Time (s)

S27
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 400 800 1200
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.48)/0.52

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S28
 1.6
1.4 Data Simulation

Exit Velocity (m/s)

1.2
1
0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S2. Validation result corresponding to run 10.

1.4
1.2 Data Simulation

1
(yO2-0.52)/0.48

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S29
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.48)/0.52

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S30
 1.6
1.4 Data Simulation

Exit Velocity (m/s)

1.2
1
0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S3. Validation result corresponding to run 11.

1.4
1.2 Data Simulation

1
(yO2-0.52)/0.48

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S31
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.48)/0.52

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S32
 1.6
1.4 Data Simulation

Exit Velocity (m/s)

1.2
1
0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S4. Validation result corresponding to run 12.

1.4
1.2 Data Simulation

1
(yO2-0.22)/0.78

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S33
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.78)/0.22

0.8
0.6
0.4
0.2
(c)
0
0 500 1000 1500
Time (s)

S34
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(d)
0
0 500 1000 1500
Time (s)

Figure S5. Validation result corresponding to run 13.

1.4
1.2 Data Simulation

1
(yO2-0.22)/0.78

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S35
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.78)/0.22

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S36
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S6. Validation result corresponding to run 14.

1.4
1.2 Data Simulation

1
(yO2-0.22)/0.78

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S37
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.78)/0.22

0.8
0.6
0.4
0.2
(c)
0
0 400 800 1200
Time (s)

S38
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(d)
0
0 400 800 1200
Time (s)

Figure S7. Validation result corresponding to run 15.

1.4
1.2 Data Simulation

1
(yO2-0.22)/0.78

0.8
0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S39
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

1.4
1.2 Data Simulation

1
(yN2-0.78)/0.22

0.8
0.6
0.4
0.2
(c)
0
0 400 800
Time (s)

S40
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(d)
0
0 400 800
Time (s)

Figure S8. Validation result corresponding to run 16.

1.4
1.2 Data Simulation

1
0.8
yO2

0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S41
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

Figure S9. Validation result corresponding to run 17.

1.4
1.2 Data Simulation

1
0.8
yO2

0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S42
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

Figure S10. Validation result corresponding to run 18.

1.4
1.2 Data Simulation

1
0.8
yO2

0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S43
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

Figure S11. Validation result corresponding to run 19.

1.4
1.2 Data Simulation

1
0.8
yO2

0.6
0.4
0.2
(a)
0
0 500 1000 1500
Time (s)

S44
 1.4
1.2 Data Simulation

Exit Velocity (m/s) 1

0.8
0.6
0.4
0.2
(b)
0
0 500 1000 1500
Time (s)

Figure S12. Validation result corresponding to run 20.

S10. Maximum Allowable Recovery

In general, CH4 is more valuable when recovered than when combusted in an on-site

furnace. Therefore, maximum CH4 recovery is desirable. However, increased recovery

reduces the fraction of CH4 in the blowdown gas, which, upon blending with air, may not

form a combustible mixture. This presents legal concern due to mandated limits on

industrially-emitted CH4. The other option would be to use air enriched in O2, with the

associated cost of purchasing purified O2, or of on-site production of enriched air.

The following analysis assumes that blowdown gas is blended with air. Let

𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 , Π & Ρ be the mole fraction of CH4 in feed, the product purity and the product recovery

respectively. Assuming a basis of 1 mole of feed, composition of feed, product and

blowdown gases are:

Table S4. Composition of feed, product and blowdown gases

Feed Product Blowdown

S45
 CH4 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 Ρ × 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 (1 − Ρ)𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹

N2 1 − 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 1−Π 1−Π

Ρ × 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 1 − 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 − Ρ × 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹
Π Π

Let 𝜇𝜇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 be the blending ratio, defined as the number of moles of air blended with

blowdown gas for each mole of feed gas. It is trivial to show that the resulting blend will

contain CH4 and O2 in the following proportions:

(1−𝑅𝑅𝑅𝑅𝑅𝑅)𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹
𝑦𝑦𝐶𝐶𝐻𝐻4 = 1−𝑃𝑃𝑃𝑃𝑃𝑃 (S34)
1−𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 − 𝑃𝑃𝑃𝑃𝑃𝑃 𝑅𝑅𝑅𝑅𝑅𝑅×𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 −𝜇𝜇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏

0.21𝜇𝜇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝑦𝑦𝑂𝑂2 = 1−𝑃𝑃𝑃𝑃𝑃𝑃 (S35)
1−𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 − 𝑃𝑃𝑃𝑃𝑃𝑃 𝑅𝑅𝑅𝑅𝑅𝑅×𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 −𝜇𝜇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏

Eqs. (S34) and (S35) are parametric in 𝜇𝜇𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 and may be simplified by elimination, yielding:

1−𝑃𝑃𝑃𝑃𝑃𝑃
�𝑦𝑦𝐶𝐶𝐻𝐻4 𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 +𝑦𝑦𝐶𝐶𝐻𝐻4 𝑅𝑅𝑅𝑅𝑅𝑅×𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 −𝑦𝑦𝐶𝐶𝐻𝐻4 +(1−𝑅𝑅𝑅𝑅𝑅𝑅)𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹 �
𝑃𝑃𝑃𝑃𝑃𝑃
𝑦𝑦𝑂𝑂2 = 0.21 (1−𝑅𝑅𝑅𝑅𝑅𝑅)𝑦𝑦𝐶𝐶𝐻𝐻4 ,𝐹𝐹
(S36)

Eq. (S36) describes a “blending line”, corresponding to the set of all possible composition of

blended gas for each feed composition, product purity and product recovery. In order for the

blended gas to be flammable, it must be in between its Lower Flammability Limit (LFL) and

its Upper Flammability Limit (UFL). LFL and UFL data are obtained from Zhao (2011)8.

Moreover, for the combustion to be complete, the ratio of O2 to CH4 in the blended gas must

be greater than 2. These constraints are illustrated in Figure S13:

S46
 0.20

O2 fraction 0.15

0.10

0.05

0.00
0.00 0.02 0.04 0.06 0.08 0.10
CH4 fraction

Figure S13. Derivation of maximum allowable recovery

As recovery increases, the amount of CH4 in blowdown gas decreases, and therefore for

a given blending ratio, the fraction of CH4 in blended gas decreases. Subsequently, the

mixing line moves downward. The black line in Figure S13 denotes the upper limit of O2

fraction at corresponding CH4 fraction, i.e. the blowdown gas is purely methane. The purple

line in Figure S13 denotes the flammability of methane in air. Outside of the triangular region

bounded by the purple line, blended gas contains either too little CH4 or too little O2 to

maintain combustion. Red line in Figure S13 describes the effect of stoichiometry. Below the

red line, there is insufficient O2 to allow for complete combustion of CH4. This does not

necessarily imply that combusted mixture will contain CH4 in excess of legal limit, or that

above the stoichiometry line, CH4 will undergo complete combustion. However, for a first

approximation, the region below the red line may be considered undesirable.

These constraints are brought together in Figure S13. Product recovery is varied until

the blending line is tangent to the feasible region. This corresponds to the case where the

blowdown gas contains sufficient CH4, such that for exactly one blending ratio with air, the

S47
resulting mixture is combustible. Several trivial mathematical manipulations are then

performed to yield the result in Figure 10.

It should be noted that the analysis above may be extended to purified air by modifying

the “0.21” constant. Figure 10 is only applicable to N2 inert, since change in identity of inert

will cause the LFL and UFL to shift in heat capacity and combustion kinetics. However, this

shift is likely to be small, and therefore Figure 10 may be used for other inert gases as a first

approximation.

S11. Parameter Values

Parameters used throughout the simulation is listed in Tables S5 to S9.

Table S5. Fluid properties

Parameter Unit Component

𝐶𝐶𝐻𝐻4 𝑁𝑁2
∅
𝐷𝐷𝑚𝑚,𝑖𝑖 𝑚𝑚2 𝑠𝑠 −1 2.19 × 10−5 2.19 × 10−5

𝜌𝜌𝑓𝑓∅ 𝑘𝑘𝑘𝑘 ∙ 𝑚𝑚−3 1.18

𝜇𝜇𝑓𝑓∅ 𝑘𝑘𝑘𝑘 ∙ 𝑚𝑚−1 𝑠𝑠 −1 1.97 × 10−5

𝐶𝐶𝑝𝑝,𝑔𝑔,𝑖𝑖 𝐽𝐽 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙 −1 𝐾𝐾 −1 35.62 29.12
𝑃𝑃𝑃𝑃𝐹𝐹 0.736
𝛽𝛽𝑘𝑘,𝑔𝑔 0.285
𝑘𝑘𝑔𝑔∅ 𝐽𝐽 ∙ 𝑚𝑚−1 𝐾𝐾 −1 𝑠𝑠 −1 0.0326
𝑀𝑀𝑀𝑀𝑖𝑖 𝑘𝑘𝑘𝑘 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙−1 0.016 0.028
𝛾𝛾𝐹𝐹 1.33

Table S6. Adsorbent properties

Parameter Unit Component

𝐶𝐶𝐻𝐻4 𝑁𝑁2
𝑅𝑅𝑝𝑝 𝑚𝑚 0.0015
𝑞𝑞𝑠𝑠,𝑖𝑖 𝑚𝑚𝑚𝑚𝑚𝑚 ∙ 𝑚𝑚−3 7,320 7,400

S48
 Δ𝑈𝑈𝑖𝑖 𝐽𝐽 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙 −1 -25,020 -19,748
𝑏𝑏0,𝑖𝑖 𝑚𝑚3 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙−1 5.02 × 10−7 7.40 × 10−7
𝑎𝑎𝑖𝑖 3.55 3.51
′
𝑘𝑘𝑏𝑏0,𝑖𝑖 𝑠𝑠 −1 468.7 819.8
𝐸𝐸𝑏𝑏,𝑖𝑖 𝐽𝐽 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙 −1 41,212 28,786
𝜀𝜀𝑝𝑝 0.33
′
𝐷𝐷𝑐𝑐0,𝑖𝑖 /𝑟𝑟𝑐𝑐2 𝑠𝑠 −1 2.77 706.3
𝐸𝐸𝑝𝑝,𝑖𝑖 𝐽𝐽 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙 −1 35,271 35,229
𝛽𝛽𝑏𝑏,𝑖𝑖 6.06 7.93
𝛽𝛽𝑝𝑝,𝑖𝑖 5.52 2.28
𝜏𝜏 3.5

Table S7. Bed properties

Parameter Unit Component

𝐶𝐶𝐻𝐻4 𝑁𝑁2
𝐶𝐶𝑝𝑝,𝑠𝑠 𝐽𝐽 ∙ 𝐾𝐾𝐾𝐾−1 𝐾𝐾 −1 960
𝐶𝐶𝑝𝑝,𝑤𝑤 𝐽𝐽 ∙ 𝐾𝐾𝐾𝐾−1 𝐾𝐾 −1 502
𝑘𝑘𝑤𝑤 𝐽𝐽 ∙ 𝑚𝑚−1 𝐾𝐾 −1 𝑠𝑠 −1 16
𝐾𝐾𝑧𝑧,0 /𝑘𝑘𝑔𝑔∅ 3
𝐿𝐿 𝑚𝑚 1
𝑇𝑇𝑏𝑏𝑏𝑏𝑏𝑏ℎ 𝐾𝐾 303.15
𝛿𝛿 0.8
𝜀𝜀𝑏𝑏 0.35
ℎ𝑖𝑖𝑖𝑖 𝑊𝑊 ∙ 𝑚𝑚−2 𝐾𝐾 −1 8.6
ℎ𝑜𝑜𝑜𝑜𝑜𝑜 𝑊𝑊 ∙ 𝑚𝑚−2 𝐾𝐾 −1 2.5
𝑟𝑟𝑖𝑖𝑖𝑖 𝑚𝑚 0.1
𝑟𝑟𝑜𝑜𝑜𝑜𝑜𝑜 𝑚𝑚 0.12
𝜌𝜌𝑠𝑠 𝑘𝑘𝑘𝑘 ∙ 𝑚𝑚−3 1,020
𝜌𝜌𝑤𝑤 𝑘𝑘𝑘𝑘 ∙ 𝑚𝑚−3 7,800

Table S8. Miscellaneous properties

Parameter Unit Component

S49
 𝐶𝐶𝐻𝐻4 𝑁𝑁2
𝐿𝐿𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚 1.4
𝑟𝑟𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑚𝑚 0.005
𝑒𝑒 𝑚𝑚 8 × 10−7
𝐾𝐾𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 5
𝑃𝑃𝑎𝑎𝑎𝑎𝑎𝑎 𝑃𝑃𝑃𝑃 101,300
𝑅𝑅 𝐽𝐽 ∙ 𝑚𝑚𝑚𝑚𝑙𝑙 −1 𝐾𝐾 −1 8.314
𝑇𝑇𝑎𝑎𝑎𝑎𝑎𝑎 𝐾𝐾 298.15
𝜂𝜂 0.72
𝜂𝜂1 0.8

Table S9. Feed properties

Parameter Unit Component

𝐶𝐶𝐻𝐻4 𝑁𝑁2
𝑇𝑇𝐹𝐹 𝐾𝐾 303.15

References
(1) Bhadra, S. J.; Farooq, S. Separation of Methane-Nitrogen Mixture by Pressure Swing
Adsorption for Natural Gas Upgrading. Ind. Eng. Chem. Res. 2011, 50, 14030.
(2) Qinglin, H.; Farooq, S.; Karimi, I. Binary and Ternary Adsorption Kinetics of Gases in Carbon
Molecular Sieves. Langmuir 2003, 19, 5722.
(3) Smits, A. J.; Dussauge, J.-P. Turbulent Shear Layers in Supersonic Flow. Springer-Verlag New
York: New York, USA, 2006.
(4) Yagi, S.; Kunii, D.; Wakao, N. Studies on Axial Effective Thermal Conductivities in Packed Beds.
AlChE J. 1960, 6, 543.
(5) Welty, J. R.; Wicks, C. E.; Rorrer, G.; Wilson, R. E. Fundamentals of Momentum, Heat, and
Mass Transfer. John Wiley & Sons: 2009.
(6) Mitariten, M. In Nitrogen Removal from Natural Gas with the Molecular Gate Adsorption
Process, 88th Annual Convention Proceedings, Mar 8-11, 2009 - San Antonio, Texas, USA. GPA
Midstream Association: 2009; 544.
(7) Qinglin, H. Multi Component Diffusion of Gases in the Micropores of Carbon Molecular Sieve.
Ph.D. Dissertation, National University of Singapore, Singapore, 2002.
(8) Zhao, F. Inert Gas Dilution Effect on Flamability Limits of Hydrocarbon Mixtures. Texas A&M
University, Texas, USA, 2011.

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