Simulation of multi-step pressure swing adsorption process

for production of pure hydrogen with high recovery

Faculty of Chemical Engineering, University of Tehran.

Simulation of pressure swing adsorption (PSA) process of has been performed for
production of high purity H2 form steam reforming off-gas. PSA is an efficient process
to produce pure H2 from the steam methane reformer off-gas. In this work, simulation of
a multi-step PSA process was performed for bulk separation of H 2 from
H2/CO/CO2/CH4/N2 (75.7/0.7/18/3.2/2.4 vol %) mixture. A two layered activated
carbon/zeolite bed was used as the adsorbents. The influence of feed flow rate, purge to
feed ratio and lengths and diameter of adsorbent layers on the system performance is
investigated. When the pressure is cycled between 1 and 22.5 bar, 75.7% H 2 in the feed
could be concentrated to more than 99.95% in the product with 82.5% recovery.

1. Introduction
In its natural and elemental form H2 is scarce, making crucial its production. The most
common economical method for production of H2 is steam methane reforming (SMR)
(Collodi and Wheeler, 2010; Vicente et al., 2009). However, the SMR reactor produces
H2 with several impurities such as H2O, CO2, CO, CH4 and, in some cases, N2. Pressure
swing adsorption (PSA) units are commonly used in H2 purification from SMR off-
gases. A PSA process relies on the fact that under pressure, gases tend to be adsorbed.
The adsorber is regenerated by rapidly reducing the partial pressure of the adsorbate,
either by lowering the total pressure or by additionally using a purge gas (Yang et al.,
1995). A number of studies dealing with PSA processes for H2 purification have been
published (Yang and Lee, 1997; Yang et al., 1995). However, only a limited number of
them (Ribeiro et al., 2008) reported the optimization of PSA process for H2 purification
in a single column. Zeolite and activated carbon (AC) have been widely used as
adsorbent in gas separation processes because these adsorbents have high selectivities of
major impurities (Yang and Lee, 1997).
The purpose of this work is to simulate a multi-step cyclic pressure swing adsorption
(PSA) consisting of pressurization, adsorption, two- step equalization and purge with
product in a cycle to improve the process for highly purification of H2 from other
constituents comprising SMR off-gas with high recovery. The physical and equilibrium
parameters of the adsorbents are determined in our other research. The simulation has
been carried out by Adsim Aspen simulator with appropriate assumptions in dynamic
adsorption. Finally, the effect of feed/purge ratio, the amount of activated carbon, feed
flow rate and column diameter were analyzed on the process efficiency to optimize the
operational condition for maximizing the hydrogen purity.
2. Experiment and simulation
A single column, two-bed PSA process cycle (Fig. 1) to produce high purity H2 from a 5
component mixture (H2/CO/CO2/CH4/N2) was experimented and simulated.

Figure 1: Schematic of H2 purification simulator

The PSA cycle consisted of the following steps: (i) adsorption (ii) blow down, (iii)
purge and (iv) pressurizing step. The simulation has been conducted in Adsim Aspen
simulator with the schematic diagram of Figure 1. As shown in Figure 1, three
interaction vessels B, D and E are used to store pure H2 during simulation and prepare
H2 for the other steps such as purge and pressurizing steps.
The following assumptions have been considered in the model development:
The gas phase is ideal, the temperature is constant, lump model is assumed in the
adsorbents' particle, a linear driving force exists between saturated and unsaturated solid
state.
The isotherm parameters (IP) were determined experimentally using extended
Langmuir, the equilibrium parameters were derived from the other research (Ebrahimi
et al.)
𝐼𝑃1𝑖𝑃𝑖
𝑞1 = (1)
1 + 𝑘(𝐼𝑃2𝑘𝑃𝑘 )

Pressure dropping through the column is determined using Ergun equation:

𝜕𝑝 1.5 × 10−3 1 − 𝜀 2
(1 − 𝜀) 2
= −[ 𝜇𝜗𝑔 + 1.75 × 10−5 𝑀𝜌𝑔 𝜗 ] (2)
𝜕𝑧 2
2𝑟𝑝 𝜓 𝜀 3 2𝑟𝑝 𝜓𝜀 3 𝑔

The resulting mass balance equation for component i in each bed is presented as
follow:

𝜕 𝜕𝑐𝑖 𝜕 𝜕𝑐𝑖
𝜖𝐷𝑧 − 𝜖 𝑐𝑖 𝑢𝑔 + 1 − 𝜖 𝑛𝑖 = 𝜖 (3)
𝜕𝑧 𝜕𝑧 𝜕𝑧 𝜕𝑡
 𝜕(𝑢𝑐 𝑇 ) 𝜕𝑐 𝑇
Eq. (3) − + 1−𝜖 . 𝑛𝑖 = 𝜖 (4)
𝜕𝑧 𝜕𝑡

𝜕𝑐𝑝1 𝜕𝑞1
𝑛𝑖 = 𝜖𝑝 + 1 − 𝜖𝑝 𝜌𝑠 (5)
𝜕𝑡 𝜕𝑡
𝜕𝑞𝑖
𝜌𝑠 = 𝑘 𝑐𝑖 − 𝑐𝑖∗ (6)
𝜕𝑡

The boundary and initial conditions needed for solving these equations are as follow:
𝜕𝑐𝑖
𝑧 = 0 − 𝐷𝑧 = 𝑐𝑖0 − 𝑐𝑖 𝑢
𝜕𝑧
𝜕𝑐𝑖
𝑧=1 =0
𝜕𝑧
𝑡 = 0 𝑐𝑖 = 0 , 𝑐𝐻2 = 1.0

Where ci : Bulk gas phase concetration, ci* : Interface gas phase concetration, cpi : Pore
gas phase concetration,ε :Interaparticle voidage, ρ :Bulk density of solid.
The general behavior of the system will be discussed considering the results of one
simulation. Then the effect of several operating conditions such as the column diameter,
length of activated carbon layer, feed flow rate and purge to feed ratio will be evaluated
on the PSA performance.

3. Results and Discussion

Table 1: The bed characteristic and isotherm adsorption parameters (Ebrahimi et al.)
Characterization of bed layer 2 (Zeolite) layer 1 (AC)
Height of adsorbent layer (m) 1.87 5.38
Adsorbent particle radius (m) 1.50×10-3 2.20×10-3
IP1,CO 2.63×10-4 3.40×10-4
IP1,CO2 0.002921 0.001399
IP1,H2 0 0
IP1,CH4 2.46×10-4 7.02×10-4
IP1,N2 1.21×10-4 2.21×10-4
IP2,CO 0.149 0.117
IP2,CO2 1.094 0.246
IP2,H2 0.007 0.0085
IP2,CH4 0.143 0.177
IP2,N2 0.07 0.085
* IP: Isotherm parameter
The isotherm parameters are determined by fitting the Langmuir equation on the
equilibrium data derived in the static experiments. The pressure obtained at the column
outlet is shown in Figure 2. As shown during the pressure equalization steps a
considerable amount of H2 is recycled which improves the recovery of the process.

Figure 2: Pressure profile obtained at the column outlet

Figure 3 presents the mol fraction of H2 and impurities (CO, CO2, CH4 and N2) in the
outlet flow. It can be seen at longer time (cycles 2, 3 and 4) the cyclic steady state was
attained. Excluding the first unsteady cycle, in each cycle the high pressure (21.5 bar)
adsorption step has taken time of 90 s. At blow down step, pressure decreased in 3 steps
from 21.5 to atmosphere. The bed is then purged with pure H 2. Finally, the bed was
pressurized with feed to the same pressure of adsorption step.
For evaluating the effect of different parameters, at a first approach, the effect of the
AC length was studied on the purity and recovery of H2 (Figure 4). The H2 purity
increases when the length of AC layer is increased. In this case, as the purity decreases
the process recovery increases. Figure 4 also illustrates the effect of purge to feed ratio
on the purity of H2. When this parameter is increased from 5 × 10-5 to 4.4 × 10-3 the H2
purity increases from 99.65% to 99.95%.
Increasing column diameter leads decrease of H2 purity. In other words, increasing
diameter of column from 3 m to 5.22 m decreases purity of H2, about 0.05% (Figure 5).
Figure 5 also presents the effect of feed flow rate on the purity of H2. As shown,
increasing the feed flow rate causes H2 purity to decreases. In all cases, as the purity
increases the process recovery decreases.
 Figure 3: Mole fraction of H2 in the outlet stream

Figure 4: Effect of purge to feed ratio and AC layer length on the H2 purity
 Figure 5: Influence of feed flow rate and column diameter on the H2 purity

4. Conclusion
The purification of H2 by a layered AC/zeolite PSA process from a feed stream mixture
containing impurities of CO2, CH4, CO and N2 was studied. The results of PSA process
simulation showed that H2 was concentrated from 75.7 (vol%) in feed to 99.95 (vol%)
in product with recovery of 82.5 (vol%). Yang and Lee (1997) reported concentration of
70% H2 to 99.99% with a recovery of 75.8%. Ribeiro et al. (2008) reported a 99.9994%
purity hydrogen stream with recovery of 51.84%. Although the purity of H2 product in
our study is not as high as other studies, the recovery is significant. Our cyclic process
can be used in industries in which the high quantity of H2 is very important. Increasing
length of activated carbon layer and purge to feed ratio caused increase of H2 purity.
The purity of H2 product is decreased when diameter and feed flow rate are increased.

References
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