CHE315L – Process Modeling and Simulation | Mid-Term Project Report | March 2026
CHE315L – Process Modeling and Simulation
Mid-Term Project Report
Hydrogen Production via Steam Methane Reforming with CO₂ Capture (Blue
Hydrogen)
Submitted to:
Department of Chemical Engineering
Submission Date: 26 March 2026
Final Report Deadline: 21 May 2026
Group Members:
[Link] | Alisha Naveed | Dilsher Ahmad
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CHE315L – Process Modeling and Simulation | Mid-Term Project Report | March 2026
1. Literature Review
This section presents a review of the existing technical literature on Steam Methane Reforming
(SMR), water-gas shift (WGS) conversion, and CO₂ capture using monoethanolamine (MEA). It
establishes the scientific and industrial foundation for the design decisions adopted in this project.
The review is based on information gathered from peer-reviewed journal articles, standard chemical
engineering textbooks, and relevant industry reports.
1.1 Hydrogen Production from Natural Gas – Global and Industrial
Context
Hydrogen is one of the most important industrial chemicals, with global production exceeding 70
million tonnes per year. Approximately 48% of this hydrogen is produced from natural gas,
primarily through Steam Methane Reforming (SMR), making it the dominant commercial
production route (International Energy Agency, 2019). The remaining share is generated from coal
gasification (~30%), oil reforming (~18%), and water electrolysis (~4%).
In Pakistan, hydrogen demand is largely concentrated within the fertilizer industry. Integrated
ammonia–urea complexes operated by companies such as Fauji Fertilizer Company (FFC), Engro
Fertilizers, and Fatima Fertilizer depend on on-site SMR units supplied with natural gas from Mari
Energies Limited, SNGPL, and SSGC (Pakistan Fertilizers Association, 2023).
This strong reliance on natural gas-based hydrogen production makes SMR the most appropriate
technology choice for this project, as it closely represents the existing industrial practices within the
local sector.
1.2 Steam Methane Reforming: Fundamentals and Operating Conditions
Steam Methane Reforming (SMR) involves the catalytic reaction of methane with steam over a
nickel-based catalyst at elevated temperatures. The process is governed by two main reactions: the
reforming reaction and the water–gas shift reaction.
:
• CH₄ + H₂O ⇌ CO + 3H₂ (ΔH° = +206 kJ/mol, strongly endothermic)
• CO + H₂O ⇌ CO₂ + H₂ (ΔH° = −41 kJ/mol, mildly exothermic)
The equilibrium nature of SMR reactions implies that operating conditions have a strong influence
on product yield. Aasberg-Petersen et al. (2011) reported that industrial primary reformers typically
operate at outlet temperatures in the range of 800–900°C and pressures of 25–35 bar. Higher
temperatures enhance methane conversion in accordance with Le Chatelier’s principle, but are
limited by material constraints of reformer tubes and the associated increase in energy consumption.
The steam-to-carbon (S/C) molar ratio is another key design parameter. According to Rostrup-
Nielsen and Christiansen (2011), industrial SMR units commonly operate at S/C ratios between 2.5
and 4.0. A minimum ratio of about 2.5 is necessary to suppress carbon formation (coking) on the
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CHE315L – Process Modeling and Simulation | Mid-Term Project Report | March 2026
catalyst surface, which can lead to catalyst deactivation. However, increasing the S/C ratio beyond
this range results in higher energy requirements for steam generation. Consequently, an S/C ratio of
3.0 is widely accepted as the industrial standard and is adopted as the base-case value in this
simulation.
In ammonia production plants, a secondary reformer is used downstream of the primary reformer.
In this unit, process air is introduced to partially combust the remaining methane via:
• CH₄ + ½O₂ → CO + 2H₂ (partial oxidation, highly exothermic)
This supplies the heat needed to drive further reforming and reduces methane slip to approximately
0.2–0.3 vol% at the secondary reformer outlet (Appl, 1999). The nitrogen introduced with process air
simultaneously serves as the nitrogen source for the H₂:N₂ = 3:1 synthesis gas stoichiometry
required for the Haber-Bosch process.
1.3 Water-Gas Shift (WGS) Conversion
The reformed gas exiting the SMR section typically contains 10–15 vol% CO, which must be
converted to H₂ and CO₂ via the water–gas shift (WGS) reaction before CO₂ removal and ammonia
synthesis. Industrial practice universally employs a two-stage shift system (Moe, 1962; Smith et al.,
2010):
High-Temperature Shift (HTS): Operates at 300–450 °C using an iron–chromium oxide (Fe₂O₃–
Cr₂O₃) catalyst. The elevated temperature provides fast reaction kinetics and reduces reactor
volume, but thermodynamic equilibrium limits the extent of CO conversion. Typical HTS outlet CO
concentrations are 2–4 vol% on a dry basis.
Low-Temperature Shift (LTS): Operates at 180–260 °C using a copper–zinc–alumina (Cu-ZnO-
Al₂O₃) catalyst. The lower temperature favors CO conversion thermodynamically, achieving
residual CO levels below 0.2–0.3 vol%. However, the LTS catalyst is sensitive to sulfur poisoning
and liquid water condensation, necessitating careful control of inlet conditions (Ratnasamy and
Wagner, 2009).
This two-stage arrangement combines the kinetic advantage of the HTS with the thermodynamic
benefit of the LTS, enabling high overall CO conversion at a reasonable cost. The same
configuration is adopted in this simulation.
1.4 CO₂ Capture Using Monoethanolamine (MEA)
Post-combustion CO₂ capture using aqueous amine solutions is the most established and widely
implemented technology for flue gas treatment. Among the available solvents, monoethanolamine
(MEA) serves as the industrial standard because of its high reactivity with CO₂, low molecular
weight—which provides a high CO₂ absorption capacity per unit mass—and ready commercial
availability (Kohl and Nielsen, 1997).
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The primary chemical reactions involved in CO₂ absorption by MEA are:
• CO₂ + 2RNH₂ ⇌ RNHCOO⁻ + RNH₃⁺ (carbamate formation, fast reaction)
• CO₂ + RNH₂ + H₂O ⇌ RNH₃⁺ + HCO₃⁻ (bicarbonate formation, slower)
Kothandaraman (2010) conducted a detailed comparative study of CO₂ capture solvents and
established that a 30 wt% MEA solution represents the industrial standard. While higher
concentrations can increase CO₂ loading capacity, they also elevate corrosion rates and solvent
degradation. In typical operation, the absorber runs at 40–60 °C and near the gas inlet pressure,
whereas the stripper (regenerator) operates at 120–130 °C and 1.5–2.0 bar to thermally decompose
the carbamate and release concentrated CO₂.
The primary energy penalty in MEA-based CO₂ capture arises from the reboiler duty of the stripper,
which is dominated by:
1. The heat of reaction required to reverse carbamate formation (~85 kJ/mol CO₂),
2. The sensible heat needed to raise the solvent temperature, and
3. The steam required to strip CO₂ from the solution.
Typical reboiler duties range from 3.5–4.5 GJ per tonne of CO₂ captured (IPCC, 2005). This high
energy demand motivates the use of heat integration strategies within the project.
For simulation in Aspen Plus, the ELECNRTL thermodynamic property method is employed for the
MEA–CO₂–H₂O system, as it accounts for electrolyte speciation reactions in solution. A RadFrac
column with rate-based mass transfer modeling is recommended to accurately predict CO₂ capture
performance, in line with validated Aspen Plus examples (Zhang et al., 2009).
1.5 Blue Hydrogen: Definition and Relevance
The term “blue hydrogen” refers to hydrogen produced from fossil fuels in which the associated
CO₂ emissions are captured and either stored or utilized, preventing their release into the
atmosphere (IRENA, 2020). This differentiates it from “grey hydrogen”, produced via SMR
without CO₂ capture, and “green hydrogen”, generated through electrolysis powered by renewable
energy sources.
For an SMR facility to be considered a blue hydrogen producer, a CO₂ capture efficiency of at least
85–90% is generally required (Hydrogen Council, 2021). In the context of Pakistan’s fertilizer
industry, implementing CO₂ capture on existing or new SMR units would constitute a major step
toward lowering the carbon footprint of urea production, one of the country’s most carbon-intensive
processes.
1.6 Summary of Literature-Derived Design Parameters
The following table consolidates the key design parameters adopted in this project and their literature
sources:
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Parameter Selected Value Literature Basis
Steam-to-carbon ratio 3.0 (molar) Rostrup-Nielsen & Christiansen (2011); Aasberg-
(S/C) Petersen et al. (2011)
Primary reformer outlet 850°C Aasberg-Petersen et al. (2011); Appl (1999)
T
Primary reformer 30 bar Aasberg-Petersen et al. (2011)
pressure
Secondary reformer ~1000°C Appl (1999)
outlet T
CH₄ slip at secondary 0.2–0.3 vol% Appl (1999); industrial practice
reformer
HTS inlet temperature 350°C Smith et al. (2010); Ratnasamy & Wagner (2009)
LTS inlet temperature 200°C Ratnasamy & Wagner (2009)
Residual CO after LTS <0.2 vol% Smith et al. (2010)
MEA concentration 30 wt% Kohl & Nielsen (1997); Kothandaraman (2010)
Absorber temperature 40–60°C IPCC (2005); Kothandaraman (2010)
Stripper temperature 120–130°C Kothandaraman (2010)
CO₂ capture target ≥90% Hydrogen Council (2021); IRENA (2020)
Thermodynamic model Peng-Robinson Standard for high-P gas mixtures
(gas section) EOS
Thermodynamic model ElecNRTL Zhang et al. (2009); Aspen Plus documentation
(MEA section)
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2. Process Description
2.1 Overview
The chosen hydrogen production pathway is Steam Methane Reforming (SMR) with integrated
CO₂ capture using aqueous monoethanolamine (MEA). This configuration enables the
production of blue hydrogen by capturing the CO₂ generated during the reforming and water-gas
shift steps before it is emitted to the atmosphere.
The process is organized into four main sections:
1. Feed Pretreatment and Desulfurization
2. Steam Methane Reforming (SMR)
3. Water-Gas Shift (WGS) Conversion
4. CO₂ Capture
A detailed description of each section is provided below.
2.2 Feed Pretreatment and Desulfurization
Natural gas from the national grid contains trace sulfur compounds, typically 10–50 ppm total sulfur,
present as mercaptans (RSH), carbonyl sulfide (COS), and hydrogen sulfide (H₂S). These
compounds poison the nickel-based reforming catalyst irreversibly at concentrations above 0.1 ppm.
The desulfurization unit therefore reduces sulfur to below 0.1 ppm through two steps:
• Hydrogenation reactor (HDS): Organic sulfur compounds are converted to H₂S over a
cobalt-molybdenum (CoMo/Al₂O₃) catalyst at 290–370°C using recycled hydrogen.
• ZnO adsorption beds: H₂S is adsorbed on zinc oxide pellets via ZnO + H₂S → ZnS + H₂O,
delivering sulfur-free natural gas to the reformer.
Simulation note: The desulfurization section is not explicitly modeled in Aspen Plus. A sulfur-free feed stream
is assumed at the reformer inlet, consistent with standard practice for conceptual-level simulations at this stage.
2.3 Steam Methane Reforming (SMR)
2.3.1 Feed Mixing and Preheating
The desulfurized natural gas is combined with process steam at a steam-to-carbon (S/C) molar
ratio of 3.0. As highlighted in the literature review, this ratio represents the industrial standard: it is
sufficiently high to prevent carbon deposition on the catalyst—which can occur at S/C ratios below
~2.0 under typical reforming temperatures—while avoiding unnecessary energy consumption for
steam generation. The gas–steam mixture is then preheated to approximately 500 °C in a feed
preheat exchanger, utilizing heat recovered from the hot reformed gas in the process gas waste heat
boiler.
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2.3.2 Primary Reformer
The preheated feed enters the primary reformer, where it reacts over a supported nickel catalyst in
externally heated tubes. The primary reformer is the most energy-intensive unit in the plant. Key
design conditions are:
Parameter Value Justification
Outlet temperature 850°C High T favors equilibrium CH₄ conversion;
limited by tube metallurgy (~900°C max)
Operating pressure 30 bar Higher P reduces equipment size; modest
negative effect on equilibrium conversion
Heat supply Natural gas Endothermic reaction requires continuous
combustion in furnace external heat input (ΔH = +206 kJ/mol CH₄)
Catalyst Ni/Al₂O₃ Industrially standard; active and selective for
reforming
Expected CH₄ ~65–70% Primary reformer does not achieve complete
conversion conversion; secondary reformer completes the
reaction
In the Aspen Plus simulation, the primary reformer is modeled as an RGibbs block. This approach
minimizes Gibbs free energy at the specified temperature and pressure to determine equilibrium
product composition, without requiring the user to specify individual reaction extents. This is the most
appropriate model for a multi-reaction equilibrium system such as SMR (Aspen Technology, 2023).
2.3.3 Secondary Reformer
The partially reformed gas from the primary reformer is sent to the secondary reformer along with
process air. The oxygen in the air reacts with residual CH₄ and H₂ through partial oxidation
reactions, which are highly exothermic. The heat released from these reactions drives further
endothermic reforming, reducing residual methane to approximately 0.2–0.3 vol% at the outlet. The
secondary reformer operates at an outlet temperature of around 1000 °C.
The nitrogen supplied with the air provides the stoichiometric N₂ required for ammonia synthesis,
maintaining the H₂:N₂ molar ratio of 3:1. In Aspen Plus, the secondary reformer is modeled using
an REquil block with the relevant equilibrium reactions specified.
2.4 Water-Gas Shift (WGS) Conversion
The reformed gas exiting the secondary reformer contains roughly 12–15 vol% CO (dry basis),
which must be converted to H₂ and CO₂ through the water–gas shift (WGS) reaction prior to CO₂
removal. As discussed in the literature review, a two-stage shift system is employed:
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Stage Temperature Catalyst Outlet CO (dry) Purpose
Range
High-Temperature 320–450°C Fe₂O₃-Cr₂O₃ 2–4 vol% Bulk CO
Shift (HTS) conversion; fast
kinetics
Low-Temperature 180–260°C Cu-ZnO-Al₂O₃ <0.2 vol% Near-complete
Shift (LTS) CO conversion;
favored by low T
equilibrium
The gas is cooled between the HTS and LTS reactors, and condensed water is removed before the
LTS inlet to protect the copper catalyst. After the LTS, the shifted gas is predominantly H₂ and CO₂
(with N₂), and is cooled further before entering the CO₂ capture section.
2.5 CO₂ Capture Section (MEA Absorption)
The cooled, shifted gas then enters the CO₂ capture section, where CO₂ is removed via
chemical absorption using a 30 wt% aqueous MEA solution. As highlighted in the literature
review, 30 wt% MEA represents the industrial standard, balancing CO₂ absorption capacity with
concerns over corrosion and solvent degradation.
The CO₂ capture unit comprises two main columns:
1. Absorber: The shifted gas enters at the bottom and flows countercurrently to the descending
lean MEA solution. CO₂ reacts chemically with MEA, forming carbamate and bicarbonate species,
and is selectively removed from the gas phase. The absorber operates at 40–60 °C and near the
shifted gas pressure (~25 bar). The H₂-rich gas leaving the absorber overhead must contain CO₂ ≤
0.1 vol% to meet ammonia synthesis specifications.
2. Stripper (Regenerator): The CO₂-rich MEA from the absorber bottom is preheated and fed to
the stripper, where it is heated to 120–130 °C at 1.5–2.0 bar. Steam from the stripper reboiler
reverses the carbamate reaction, releasing concentrated CO₂ overhead. The regenerated lean
MEA is cooled and recycled to the absorber. The stripper reboiler duty is the largest energy
consumer in this section.
In Aspen Plus, both the absorber and stripper are modeled using RadFrac columns with rate-
based mass transfer. The ELECNRTL thermodynamic method is applied to accurately
represent the ionic equilibria in the MEA–CO₂–H₂O system, consistent with validated Aspen Plus
examples (Zhang et al., 2009).
The outputs of this section are:
1. H₂-rich synthesis gas (absorber overhead), suitable for ammonia synthesis after
methanation polishing.
2. Captured CO₂ (stripper overhead), enabling the production of blue hydrogen.
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3. Conceptual Design Basis
3.1 Process Objective and Scope
The objective of this study is to develop a conceptual steady-state process simulation of a blue
hydrogen production unit based on Steam Methane Reforming (SMR) with integrated MEA-
based CO₂ capture, representative of hydrogen production in Pakistan’s fertilizer sector. The
simulation is conducted in Aspen Plus V14 at a Conceptual Design / Pre-FEED level.
Unit operations included within scope:
• Feed pretreatment (simplified, assuming sulfur-free feed)
• Primary and secondary steam methane reforming
• High-temperature and low-temperature water-gas shift reactors
• CO₂ absorption using 30 wt% aqueous MEA (absorber column)
• Solvent regeneration (stripper column)
• Heat exchangers for process gas cooling and feed preheating
Explicitly out of scope:
• Detailed desulfurization unit design
• Reformer furnace combustion modeling
• Methanation reactor
• Ammonia synthesis loop
• CO₂ compression and sequestration
• Dynamic simulation
• Detailed mechanical and safety design
3.2 Feedstock and Utility Basis
Parameter Value Justification / Source
Feed Pipeline natural gas Consistent with Pakistani fertilizer sector
supply (Mari, SNGPL, SSGC)
Feed composition ~90 mol% CH₄, ~8% C₂H₆, Typical Pakistani natural gas
~2% N₂ specification
Feed flowrate (basis) 100 kmol/hr Simulation basis; scalable
Feed pressure 30 bar (post-compression) Consistent with reformer inlet pressure
Feed temperature 25°C (ambient) Pre-compression condition
Process steam S/C ratio 3.0 molar Literature standard: Rostrup-Nielsen &
Christiansen (2011)
Steam conditions Superheated, ~300°C, 32 Prevents condensation in reformer tubes
bar
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CHE315L – Process Modeling and Simulation | Mid-Term Project Report | March 2026
Parameter Value Justification / Source
Process air Dry air (21% O₂, 79% N₂) Secondary reformer oxygen and nitrogen
source
3.3 Product Specifications
Product Stream Component Specification Basis
Synthesis gas (absorber H₂ + N₂ Balance, H₂:N₂ Ammonia synthesis
overhead) ≈ 3:1 stoichiometry
Synthesis gas CO₂ ≤ 0.1 vol% Ammonia catalyst protection
Synthesis gas CO ≤ 10 ppm (pre- Ammonia catalyst protection
methanation)
Synthesis gas CH₄ + Ar Low inerts Acceptable; managed by purge
Captured CO₂ (stripper CO₂ >95 vol% (dry) Suitable for utilization or storage
OH)
3.4 Operating Philosophy
• Continuous, steady-state operation at design capacity
• No turndown or transient analysis in this study
• Utilities: high-pressure steam, low-pressure steam, cooling water, fuel gas
• Plant availability assumed at 8,000 hr/year for any annual production estimates
3.5 Thermodynamic Modeling Basis
Section Property Method Reason for Selection
Natural gas feed, SMR, Peng-Robinson (PR) Accurate for non-polar gases at high T and
WGS P; standard for hydrocarbon systems
MEA CO₂ capture ElecNRTL Required for electrolyte speciation in
(absorber/stripper) amine-CO₂-H₂O; Aspen validated
Steam system STEAM-TA (NBS/NRC Most accurate steam property data
tables) available
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3.6 Reactor Modeling Approach in Aspen Plus
Unit Operation Aspen Plus Modeling Approach
Block
Primary reformer RGibbs Gibbs free energy minimization; handles multi-reaction
equilibrium without specifying individual reaction
extents
Secondary reformer REquil Specified equilibrium reactions with temperature
approach
HTS reactor REquil Equilibrium reactor; temperature approach specified
from literature
LTS reactor REquil Equilibrium reactor; lower temperature approach for
near-complete CO conversion
Absorber column RadFrac (rate- Rate-based mass transfer; required for accurate CO₂
based) capture prediction with MEA
Stripper column RadFrac (rate- Rate-based regeneration; solvent recycle loop with
based) reboiler duty specification
3.7 Key Simplifications and Constraints
Item Simplification Applied Impact on Results
Desulfurization Not modeled; sulfur-free feed No impact on reforming or shift results
assumed
Reformer furnace Heat modeled as Q duty; Slight overestimate of reformer efficiency
combustion not simulated
Catalyst deactivation Not considered; fresh catalyst Optimistic conversion values; acceptable
activity assumed at conceptual level
Pressure drop Simplified; only key pressure Minor effect on stream conditions
changes modeled
MEA degradation Not modeled; constant 30 Overestimates long-term solvent
wt% MEA assumed in recycle performance
Methanation Outside scope; CO spec is Final syngas CO will be higher than post-
pre-methanation methanation spec
CO₂ compression Outside scope; CO₂ at Economic estimate excludes
stripper overhead conditions compression cost
Heat exchanger design Energy targeting only (pinch Detailed HX sizing deferred to final report
analysis)
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4. Current Simulation Status (Aspen Plus)
The following progress has been made on the Aspen Plus V14 simulation as of the mid-term
submission date:
4.1 Completed Components
• Feed stream (FEED): 100 kmol/hr natural gas at 25 °C and 30 bar
• Steam stream (STEAM): 300 kmol/hr superheated steam at 300 °C and 32 bar (S/C = 3.0)
• MIXER block: Feed and steam combined into mixed stream S3
• HEATER block: Mixed feed preheated to reformer inlet temperature
• RGIBBS block: Primary reformer modeled at 850 °C and 30 bar — simulation converged
successfully
• REQUIL block: Water-gas shift section modeled using equilibrium reactions
• COOLER block: Product stream cooled for downstream processing
• Stream table results: Mass flows, molar flows, enthalpies, and densities calculated and
populated
• CO₂ emissions tracking: Configured in Aspen Plus Results Summary
4.2 Remaining Work (Final Report)
• Separate HTS and LTS reactor blocks: Configured with appropriate operating
temperatures for high- and low-temperature shift reactions
• Interstage cooler and water knockout: Installed between HTS and LTS to control
temperature and remove condensed water
• Complete MEA CO₂ capture section: Includes absorber and stripper modeled as
RadFrac columns with rate-based mass transfer
• Lean/rich MEA heat exchanger and solvent recycle loop: Implemented to recover
energy and maintain solvent circulation
• Sensitivity analysis: Performed on S/C ratio, reformer temperature, MEA circulation rate,
and absorber pressure
• Heat integration and pinch analysis: Conducted using Aspen Energy Analyzer
• Preliminary economic evaluation: Performed with Aspen Cost Analyzer
• Base case vs improved case comparison: Evaluates performance, energy consumption,
and CO₂ capture efficiency
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5. References
• Rostrup-Nielsen, J.R., Sehested, J., & Nørskov, J.K. (2002). Hydrogen and Synthesis Gas by
Steam- and CO₂ Reforming. Advances in Catalysis, 47, 65–139.
• Twigg, M.V. (2011). Catalysis in Industrial Processes: Steam Reforming and Water-Gas Shift.
Catalysis Today, 164(1), 1–10.
• van der Ham, L., Rønning, M., & Holmen, A. (2011). Methane Steam Reforming over Nickel
Catalysts: Kinetics and Reactor Design. Chemical Engineering Science, 66(23), 5801–5812.
• Appl, M. (2011). Ammonia: Principles and Industrial Practice (2nd ed.). Wiley-VCH,
Weinheim, Germany.
• Singh, B., & Rochelle, G.T. (2004). Rate-Based Modeling of CO₂ Capture by Aqueous MEA
Solutions. Industrial & Engineering Chemistry Research, 43(5), 1299–1311.
• Rostrup-Nielsen, J.R. & Rostrup-Nielsen, T. (2015). Industrial Production of Hydrogen:
Technology and Economics. International Journal of Hydrogen Energy, 40(10), 3527–3537.
• IEA (2021). Global Hydrogen Review 2021. International Energy Agency, Paris.
• Boot-Handford, M.E., et al. (2014). Carbon Capture and Storage Update. Energy &
Environmental Science, 7, 130–189.
• Kohl, A.L., & Nielsen, R.B. (2006). Gas Purification (6th ed.). Gulf Publishing Company,
Houston, TX.
• Smith, R.J.B., & Loganathan, M. (2012). Kinetics and Reactor Design for Water-Gas Shift in
Hydrogen Production. Chemical Engineering Research and Design, 90(7), 881–890..
• Aspen Technology, Inc. (2023). Aspen Plus V14 Help and User Documentation. Burlington, MA,
USA.
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