Methane Pyrolysis for Hydrogen
Production
Copyright (c) 2023 by Aspen Technology, Inc. All rights reserved.
Aspen Plus, Aspen HYSYS, and the aspen leaf logo are trademarks or registered trademarks of Aspen Technology,
Inc., Bedford, MA.
All other brand and product names are trademarks or registered trademarks of their respective companies.
Contents
Abstract..................................................................................................... ii
1 Background .......................................................................................... 1
2 Process description ................................................................................ 1
3 Model Description .................................................................................. 2
4 Simulation Results ................................................................................. 3
5 Conclusion ............................................................................................ 4
Abstract
Methane can be an effective source of hydrogen and a more efficient storage and
transportation option than molecular hydrogen. This example simulates methane
pyrolysis to convert methane into hydrogen and carbon char, where excess feed
methane provides energy for the desired reactions. The major units in this process
are represented by a CSTR reactor, a conversion reactor, compressors, heat
exchangers, and a steam cycle for electricity production via a combined heat/power
cycle. This example can be used as a starting point for further model development.
ii
1 Background
Industrially, hydrogen is mainly generated via steam methane reforming, which has
significant CO2 emissions and contributes to the greenhouse effect. With the global
energy transition initiatives, the Hydrogen Economy is rising as a crucial pathway to
reach net zero targets. To address the increase in hydrogen demand, several
technologies have emerged to replace traditional methods. One alternative method
of hydrogen production is via cracking methane into H2 and char, with theoretical
CO/CO2 emissions close to zero. It is a newly emerging technology under-
development that has received significant attention due to its potential for low cost
H2 production and the abundance of natural gas resources in many locations.
In this example, the objective is to simulate catalytic methane pyrolysis (CMP) to
demonstrate hydrogen production from methane.
2 Process description
Methane pyrolysis has two primary scenario options. Case 1 is a net-zero emission
process and uses a portion of the product H2 stream to provide energy for the desired
reactions. Case 2 uses excess feed methane, not a portion of the product H 2 stream,
in a fired heater to provide the necessary heat load for the desired reactions, thereby
producing a CO2 stream. Figure 1 displays a simplified block flow diagram for both
case studies.
Figure 1. Flow diagram catalytic methane pyrolysis to produce H2 and solid C
For this process simulation, Case 1 is simulated. CH4 enters the reactor at varying
temperature conditions of 1013–1413 K for the CMP unit and undergoes pyrolysis.
The product stream containing the unreacted CH4 and product H2 and solid C pass
through the units of cyclone and pressure swing adsorption (PSA) for separating solid
1
C and H2, respectively. A portion of this purified hydrogen product is used in the
hydrogen combustor, which operates at about 1000°C and 3 bar, to supply the heat
required by the catalytic reactor. For the waste heat recovery system, the steam
cycle is heated to high pressure steam, which is utilized in a turbine to provide
electricity for the pumps and compressors in the process.
The model includes the following key features:
Methane pyrolysis unit
Reaction heat supply system
Waste heat recovery system
The main reaction occurring during the process is:
CH4(g) → C(s) + 2H2(g) ∆H0 25 ◦C = 74.85 kJ/mol of CH4
3 Model Description
The methane pyrolysis unit is modeled using Aspen HYSYS as shown in Figure 2. In
this simulation, Peng-Robinson is selected as the Fluid Package for the simulation.
Figure 2. Simulation of catalytic methane pyrolysis in Aspen HYSYS
Pure methane feed (F-CH4) from the compressor unit (COMP) is mixed with the
recycled gas from the separation unit, which contains methane. This mixture is then
heated to 950°C by heat exchange with the reactor product (HE5) prior to entering
the reactor. The solid product C(S) is cooled by cooler (HE6A). Heat is recovered in
the steam cycle via HE6B and is indicated as Q40 in Figure 2. The product gas is
2
initially cooled to 204.2°C by HE5 and then cooled further to 59.2°C by HE7 and HE8,
where the final purified hydrogen gas exits the SEP unit at 3 bar and 59.4°C.
A portion of this purified hydrogen product is used in the hydrogen combustor (H2-
COMB), which operates at 999.1°C and 3 bar, to supply the heat required by the
catalytic reactor. The air required in this combustor is compressed to 3 bar and
preheated to 900°C by combustor product stream economizers (HE3 and HE4).
Combustion products, which in this case are just water and excess air, are cooled via
these same cooler as well as HE5A. The heat from HE5A is recovered in the steam
cycle via HE5B, as indicated by Q20. The cooled combustion products then drive a
turbine (TURB2) that provides electricity to offset some of the usage of the process.
The steam cycle consists of pumped water (70 bar) that is split into two streams prior
to being fed to heat exchangers HE5B and HE6B, where the water is heated to
become high pressure steam at 499.4°C and 70 bar. The high-pressure steam is
utilized in an expander (TURB1) to provide electricity for the pumps and compressors
in the process.
4 Simulation Results
The key simulation results are listed in Table 1.
Table 1. The key simulation results of the catalytic methane pyrolysis process
mol % CH4 inlet Reactor outlet Product H2 outlet
Stream F-CH4 S7 S-PRODUCT H2
CH4 1 0.1586 0 0
H2 0 0.8414 0 1
H2O 0 0 0 0
CO2 0 0 0 0
N2 0 0 0 0
O2 0 0 0 0
C(S) 0 0 1 0
T, C 25 1060 1060 59.42
Mole flow, kmol/h 2586 6147 2586 3879
P, bar 1 3 3 3
The key simulation results of the heat supply system are listed in Table 2.
Table 2. The key simulation results of the heat supply system
mol % Recycle H2 Air inlet H2-COMB outlet
Stream S27 AIR S18
CH4 0 0 0
H2 1 0 0.009
H2O 0 0 0.3440
CO2 0 0 0
3
mol % Recycle H2 Air inlet H2-COMB outlet
N2 0 0.79 0.6470
O2 0 0.21 0
C(S) 0 0 0
T, C 59.42 25 999.1
Mole flow, kmol/h 1293 3000 3663
P, bar 3 1 3
Figure 3 shows CO2 equivalent and total carbon tax results in simulation dashboard.
You can click the dashboard and view more information for the process CO2 emissions
calculation, see Figure 4.
Figure 3. Greenhouse Gas Emission dashboard in Aspen HYSYS
Figure 4. CO2 equivalent and carbon fee details in Aspen HYSYS
5 Conclusion
This example shows how to model catalytic methane pyrolysis using Aspen HYSYS.
The main reaction is simulated with a CSTR reactor. About 33% of the hydrogen
product is combusted to produce the required heat for the process. A ~92%
conversion of methane can be achieved, where CO2 emissions from the CMP unit are
zero. This example can be used as a starting point for further model development.
4
References
[1] Jarrett Rileya, Chris Atallaha, Ranjani Siriwardanea, et al., “Technoeconomic
analysis for Hydrogen and Carbon Co-Production via catalytic pyrolysis of
methane”: Elsevier; 2021.
[2] Malek Msheik, Sylvain Rodat, Stéphane Abanades,” Methane Cracking for
Hydrogen Production: A Review of Catalytic and Molten Media Pyrolysis”: Energies
2021, 14, 3107.
[3] Seunghyun Cheon, Manhee Byun, et al., “Parametric Study for Thermal and
Catalytic Methane Pyrolysis for Hydrogen Production: Techno-Economic and
Scenario Analysis”: Energies 2021, 14, 6102.
