Design of Fixed Bed Reactor

`ASSIGNMENT REPORT ON

Design of Fixed Bed Reactor

Submitted to the University of Pune, Pune

in Partial Fulfillment of the Requirements
for the Award of the Degree of

BACHELOR OF ENGINEERING (CHEMICAL)

BY

Janhvi Vijaysinha Tambolkar

(Gr. No.12220112)

Mayank Themaskar
(Gr. No. 12110410)

Mohit Vivek Thengre

(Gr. No. 12110948)

Vaishnavi Shivakumar
(Gr. No. 12110091)

Vicky Jadhav
(Gr. No. 12220066)

Department of Chemical Engineering

BRACT’S Vishwakarma Institute of Technology,
666, Upper Indiranagar, Bibwewadi, Pune – 411 037
March 2024
Design of Fixed Bed Reactor

A cornerstone of chemical processing, the fixed bed reactor is a cylindrical vessel packed with
catalyst particles. Reactant fluids, typically gasses, flow through the catalyst bed where they
undergo a chemical reaction on the catalyst's surface. These reactors offer a simple design,
efficient conversion, and precise temperature control, making them widely used in everything
from large-scale chemical production to pollution control.

Fig 1: Illustration of Fixed Bed Reactor

Fixed bed and fluidized bed reactors are both workhorses in chemical processing, but they differ
in how the catalyst and reactants interact. In a fixed bed, the catalyst particles are stationary,
packed tightly like sand in a filter. Reactant fluids have to weave through the gaps between the
particles to reach the catalyst surface. This can limit how fast reactions occur.

On the other hand, a fluidized bed reactor keeps things moving. The catalyst particles (or
sometimes the reactants themselves) are suspended in a flowing gas or liquid, making them
behave like a fluid. This constant movement ensures excellent mixing and contact between the
reactants and the catalyst, leading to faster reaction rates and more efficient heat transfer.

Fixed bed reactors excel in heterogeneous reactions due to their design and operational
characteristics. The packed catalyst bed offers high catalyst utilization per unit volume,
maximizing product yield. Their simple design with minimal moving parts translates to
cost-effective operation and easy maintenance. Additionally, fixed beds enable precise
temperature control through external heat transfer, crucial for optimizing reaction rates in
heterogeneous processes. Finally, the catalyst bed's accessibility simplifies replacement,
minimizing downtime when dealing with catalysts prone to deactivation. These advantages make
fixed bed reactors a mainstay for various heterogeneous reactions in chemical processing.
Design of Fixed Bed Reactor

Hydrogen (H₂) is a clean-burning fuel with immense potential as we strive for a sustainable
future. Due to its ability to combine with oxygen to produce only water vapor, H₂ offers a
promising alternative to fossil fuels that contribute to greenhouse gas emissions. Production
methods include methane steam reforming, where methane reacts with steam to yield H₂, but
improvements are ongoing to make production cleaner and more efficient.

Methane steam reforming, the kingpin of hydrogen production, utilizes high-temperature steam
(500-1000°C) to convert methane (the main component of natural gas) into hydrogen. The
process isn't magic though; it relies on a catalyst to break methane apart in the presence of steam,
yielding a mixture of hydrogen, carbon monoxide, and a small amount of carbon dioxide. This
hydrogen can then be further purified for use in fuel cells or various industrial processes.
However, this method isn't perfect. It requires significant energy input and generates greenhouse
gasses during the steam creation process.

Methane steam reforming involves two main reactions:

1. Main Reaction: CH₄ (methane) + H₂O (steam) → CO (carbon monoxide) + 3H₂

(hydrogen)

This endothermic (heat-absorbing) reaction is the heart of the process, breaking down
methane and steam into the desired hydrogen product along with carbon monoxide.

2. Water-Gas Shift Reaction (Optional): CO (carbon monoxide) + H₂O (steam) → CO₂

(carbon dioxide) + H₂ (hydrogen)

This exothermic (heat-releasing) reaction is often used in conjunction with the main
reaction to further increase hydrogen yield. It converts leftover carbon monoxide from
the first reaction with steam into additional hydrogen and carbon dioxide.

Methane steam reforming relies on catalysts to efficiently convert methane into hydrogen.

Nickel-Based Catalysts: These are the workhorses of the industry, offering a good balance of
activity, cost, and stability. However, they are susceptible to deactivation from carbon deposition,
especially at lower steam-to-methane ratios.

Noble Metal Promoted Catalysts: Small amounts of precious metals like platinum, rhodium, or
ruthenium can be added to nickel catalysts. These improve coke resistance (reducing carbon
deposition) and enhance reforming activity, but come at a higher cost.
Design of Fixed Bed Reactor

The methane steam reforming (MSR) reaction is endothermic, meaning it absorbs heat from the
surroundings to proceed. Here's a breakdown of the heat effects:

Reaction and Heat:

The main reaction in MSR is:

CH₄ (g) + H₂O (g) → CO (g) + 3H₂ (g) ΔH > 0 (g denotes the gas phase)

ΔH represents the enthalpy change of the reaction.

A positive ΔH signifies an endothermic reaction.

Heat Transfer Considerations:

Heat Input: To maintain the desired reaction temperature and conversion rate, heat needs to be
continuously supplied to the reactor. This heat is absorbed by the reactants, breaking the bonds in
methane and water molecules.
Heat Sources: Common heat sources for MSR reactors include:
Combustion of natural gas or other fuels
Electrical heating elements
Process heat integration with other industrial processes that generate waste heat

Impact of Heat Effects:

Temperature Control: Maintaining a consistent reaction temperature is crucial for optimal

conversion and product yield. Endothermic behavior necessitates careful control of the heat input
to balance the heat required for the reaction with heat losses from the reactor.
Reactor Design: The reactor design needs to consider the efficient transfer of heat from the heat
source to the reaction zone to ensure uniform temperature distribution and prevent overheating.

Consequences of Insufficient Heat Input:

Lower Conversion: If insufficient heat is supplied, the reaction won't proceed at the desired rate,
leading to lower conversion of methane to hydrogen.
Catalyst Deactivation: Extremely low temperatures can promote coking (carbon deposition) on
the catalyst, deactivating it and further reducing reaction efficiency.

The endothermic nature of the MSR reaction necessitates continuous heat input to maintain the
reaction temperature and achieve optimal performance. Understanding the heat effects allows
Design of Fixed Bed Reactor

engineers to design reactors with efficient heat transfer and control systems, ensuring a
successful and sustainable hydrogen production process.

While designing a complete fixed-bed reactor for methane steam reforming is a complex process
requiring detailed calculations and software simulations, breakdown of the key considerations for
a reactor operating at 500°C is given below:

Process Definition:

● Desired Hydrogen Production Rate: Assume your feed according to the amount of
hydrogen produced.
● Product Purity: Define the required hydrogen purity for your application (e.g., 99.5%).
● Feed Composition: Determine the ratio of methane to steam in the feed stream. A higher
steam-to-methane ratio favors hydrogen production but increases operating costs.
● Operating Pressure: Specify the pressure range for the reactor operation. Higher
pressure can improve conversion but also requires a more robust reactor design.

Challenges at 500°C:

● Nickel-based catalyst activity: At this relatively low temperature, nickel-based catalysts,

the workhorses of methane reforming, might exhibit lower activity compared to higher
temperature operation (500-1000°C). This could necessitate a larger reactor volume to
achieve the desired conversion.
● Heat Management: Methane steam reforming is endothermic (absorbs heat).
Maintaining 500°C might require a more robust heat transfer system compared to higher
temperature designs.

Design Considerations:

● Reactor Sizing: Utilize reactor modeling software with kinetic data for methane steam
reforming at 500°C. This will help determine the required reactor volume to achieve your
target conversion considering the chosen catalyst and operating conditions.
● Catalyst Selection: Explore options beyond traditional nickel catalysts. You might
consider:
● Promoted Nickel Catalysts: Adding small amounts of platinum or rhodium can improve
activity at lower temperatures.
● Emerging Technologies: Research alternative catalysts like metal alloys or rare earth
oxide-supported catalysts that might offer better performance at 500°C.
● Reactor Configuration: A single-tube reactor with an external jacket circulating a heat
transfer fluid (e.g., hot oil) might be suitable for efficient heat transfer at this temperature.
Design of Fixed Bed Reactor

● Pressure Drop: Balance minimizing pressure drop with ensuring good contact between
reactants and the catalyst. Packed bed design and particle size play a role here.

Additional Considerations:

● Safety: Methane and hydrogen are flammable. Design for proper venting, pressure relief
systems, and leak detection.
● Material Selection: Reactor materials need to withstand high temperatures (500°C) and
potential for catalyst poisoning (e.g., sulfur poisoning).
● Control System: Implement temperature control using sensors and actuators for the heat
transfer system. Flow rate and pressure monitoring are crucial.

Kinetic models are the secret for understanding reaction rates and designing optimal reactors. By
considering the reaction mechanism, how fast each step occurs, and the influence of temperature
and reactant concentrations, these models predict reaction speed, conversion efficiency, and
product yields. Armed with these predictions, engineers can design reactors that maximize
product output. Simple models provide a quick initial assessment, while detailed models
incorporating complexities like catalyst deactivation offer the most accurate picture but require
more data and computational power. The choice of model depends on the level of accuracy
needed, available resources, and the desired level of process understanding. Ultimately, kinetic
models act as a guide, helping us design efficient reaction processes.

The Langmuir-Hinshelwood-Hougen-Watson (LHHW) Model for Heterogeneous Catalysis

The Langmuir-Hinshelwood-Hougen-Watson (LHHW) model is a widely used approach for

describing heterogeneous catalytic reactions. It provides a framework for understanding how
reactants interact with a catalyst surface and how this interaction influences the reaction rate.
Here's a detailed breakdown of the LHHW model and how it considers reactant-catalyst
interactions:

Basic Assumptions:

1. Adsorption: Reactant molecules from the bulk fluid phase can adsorb onto the active sites
available on the catalyst surface. This adsorption is assumed to be a reversible process.
2. Surface Reaction: The adsorbed reactant molecules react with each other on the catalyst
surface to form products. The LHHW model assumes that the rate-determining step
(slowest step) occurs on the catalyst surface between the adsorbed species.
3. Desorption: The product molecules formed on the surface desorb back into the gas phase,
freeing up active sites for new reactant molecules.
Design of Fixed Bed Reactor

Reactant-Catalyst Interaction:

The LHHW model captures the interaction between reactants and the catalyst surface through the
concept of surface coverage (θ). This represents the fraction of active sites on the catalyst surface
occupied by a specific reactant molecule.

Adsorption Equilibrium: The model assumes an equilibrium exists between adsorbed and
gas-phase reactants. The surface coverage depends on the concentration of the reactant in the
bulk phase, the adsorption constant (K_ads), and the temperature. The Langmuir adsorption
isotherm is typically used to describe this relationship.

Competition for Sites: Different reactant molecules can compete for the same active sites on the
catalyst surface. The surface coverage of each reactant influences the availability of sites for
other reactants, affecting the overall reaction rate.

Rate Equation Development:

Based on the above assumptions, the LHHW model expresses the reaction rate in terms of the
surface coverages of the reactants and the rate constant for the surface reaction (k_r). The rate
equation typically follows a power-law form with exponents related to the surface coverages of
the involved species.

Applying the LHHW Model to Methane Steam Reforming (MSR)

The Langmuir-Hinshelwood-Hougen-Watson (LHHW) model can be a helpful tool for

understanding and modeling the kinetics of methane steam reforming (MSR) in a fixed-bed
reactor. Here's how it's used:

Reaction and Reactants:

The main reaction in MSR is:

CH₄ (g) + H₂O (g) → CO (g) + 3H₂ (g)

Here, (g) denotes the gas phase. The LHHW model considers the adsorption of methane (CH₄)
and steam (H₂O) molecules onto the catalyst surface, followed by their reaction to form carbon
monoxide (CO) and hydrogen (H₂) which desorb back into the gas phase.

Surface Coverage and Competition:

Design of Fixed Bed Reactor

The LHHW model focuses on the competition between CH₄ and H₂O for active sites on the
catalyst surface. Each molecule has its own surface coverage (θ), which depends on the
gas-phase concentration, adsorption constant, and temperature. The Langmuir isotherm is
typically used to relate these factors.

Rate Equation Development:

Based on the assumed reaction mechanism and surface coverages, the LHHW model allows for
the development of a rate equation for MSR. This equation expresses the reaction rate (r) in
terms of:

Rate constant (k_r) for the surface reaction between adsorbed CH₄ and H₂O.
Surface coverages (θ_CH₄ and θ_H₂O) of methane and steam on the catalyst.

The specific form of the rate equation depends on the details of the reaction mechanism assumed.
For simpler models, a power-law expression with exponents related to the surface coverages
might be sufficient.

Extracting Kinetic Parameters:

Kinetic parameters like the rate constant (k_r) and adsorption constants for CH₄ and H₂O
(K_ads,CH₄ and K_ads,H₂O) cannot be directly measured. They are typically obtained by fitting
the model predictions to experimental data from MSR experiments conducted in a controlled
environment.

Here's the process:

1. MSR Experiments: Conduct experiments varying reaction conditions like temperature,

pressure, and feed composition (CH₄/H₂O ratio). Measure the conversion of methane
(fraction of methane reacted) at different reaction times.
2. Model Implementation: Develop a mathematical model for the fixed-bed reactor
incorporating the LHHW model for MSR kinetics. This model will involve equations for
mass and heat transfer, along with the derived rate equation.
3. Parameter Estimation: Use software tools for parameter estimation. These tools adjust the
kinetic parameters (k_r, K_ads,CH₄, K_ads,H₂O) within the model until the model
predictions for conversion closely match the experimental data across different operating
conditions.
Design of Fixed Bed Reactor

Model Validation:

Once the kinetic parameters are estimated, it's crucial to validate the model. This involves
comparing the model predictions with experimental data from conditions not used for parameter
estimation. A good match between predictions and new data indicates the model's validity for
those operating conditions.

The Langmuir-Hinshelwood-Hougen-Watson (LHHW) model, despite its usefulness, has

shortcomings:

Simplified Reaction Mechanism: It assumes a single key step, while real reactions might have
multiple steps, leading to potential inaccuracies.
Ignores Diffusion Limitations: It neglects limitations caused by reactant movement within
catalyst pores, underestimating the impact of factors like particle size.
Excludes Catalyst Deactivation: It doesn't account for catalyst deactivation over time due to
choking or poisoning, missing a crucial real-world aspect.
Limited Applicability at Extremes: The model's validity is limited to specific operating
conditions, and predictions might be inaccurate outside those ranges.
Computational Challenges: While simple for basic mechanisms, incorporating complex
reactions can become computationally expensive.

Freundlich adsorption isotherm

Freundlich adsorption isotherm, developed by Herbert Freundlich in 1906, is an empirical model

that describes the relationship between the amount of gas adsorbed by a solid (adsorbent) and the
pressure of the gas (adsorbate) at a constant temperature. Unlike the Langmuir isotherm, which
assumes monolayer coverage, the Freundlich isotherm applies to situations where multiple layers
of gas molecules can form on the adsorbent surface.

The Freundlich isotherm relates the amount of gas adsorbed per unit mass of adsorbent (x/m) to
the pressure of the gas (P) at a constant temperature.

Mathematical representation:

The Freundlich isotherm is expressed by the equation: x/m = k * P^(1/n)

x: mass of gas adsorbed
m: mass of adsorbent
P: pressure of the gas
k and n: constants that depend on the specific gas-adsorbent system and temperature.
Design of Fixed Bed Reactor

Interpretation of constants:

k: This constant reflects the adsorption capacity of the adsorbent for a specific gas. A higher k
value indicates a higher capacity to adsorb the gas.
n: This dimensionless constant characterizes the favorability of adsorption. Values of:
n > 1: Favorable adsorption, with the amount adsorbed increasing more than proportionally with
pressure.
n = 1: Linear relationship between adsorption and pressure.
0 < n < 1: Less favorable adsorption, with the amount adsorbed increasing less than
proportionally with pressure.

Using Langmuir–Hinshelwood–Hougen–Watson (LH–HW) approach and Freundlich’s

adsorption concept for kinetic model:

Freundlich Isotherm: Freundlich's equation can be used to estimate the surface coverage of
methane and steam on the catalyst based on the gas-phase pressures. This provides an initial
estimate of how much reactant is available for the surface reaction.

LHHW Kinetics: The LHHW model then utilizes these estimated surface coverages along with
reaction rate constants to calculate the reaction rate for methane steam reforming.

Benefits of the model:

Improved Accuracy: Freundlich can account for multilayer adsorption, which might be more
realistic than the Langmuir isotherm's assumption of monolayer coverage in LHHW.
Simpler Implementation: Freundlich is often easier to implement compared to more complex
adsorption models.

Limitations of the model:

Freundlich's Limitations: It's an empirical model, not reflecting the true mechanism of
adsorption. The constants lack a deep physical meaning.
Computational Cost: While simpler than some models, incorporating Freundlich adds
complexity compared to using a Langmuir isotherm within the LHHW framework.

Strategies to increase hydrogen production (H₂) in methane steam reforming (MSR):

Optimizing Operating Conditions:

Design of Fixed Bed Reactor

Temperature: While higher temperatures favor product formation due to increased collision
frequency, excessively high temperatures can lead to undesired side reactions like methane
decomposition, reducing H₂ yield. Finding the optimal temperature balance is crucial.
Pressure: Increasing pressure generally improves H₂ yield by pushing the reaction towards
products according to Le Chatelier's principle. However, high pressures also require more robust
reactor designs and can increase operating costs.
Steam-to-Methane Ratio (S/C Ratio): A higher S/C ratio (more steam) promotes the complete
conversion of methane and reduces CO formation, maximizing H₂ production. However, excess
steam can also lead to energy waste in heating the unreacted steam. Finding the optimal S/C ratio
is important.

Catalyst Considerations:

Catalyst Selection: Choosing a catalyst with high activity and selectivity for H₂ production is
essential. Factors like metal type, support material, and promoter elements can influence the
catalyst's performance.
Catalyst Maintenance: Catalyst deactivation due to coking (carbon deposition) or poisoning can
significantly reduce H₂ yield. Regular regeneration or replacement of the catalyst might be
necessary.

Process Modifications:

Membrane Reactors: Utilizing membranes that selectively allow H₂ to permeate through can
continuously remove H₂ from the product stream, driving the reaction towards further H₂
production.
Pressure Swing Adsorption (PSA): Separating H₂ from the product stream using PSA technology
can improve overall H₂ recovery and potentially increase effective H₂ production.

Alternative Reforming Techniques:

Dry Reforming: This process uses carbon dioxide (CO₂) instead of steam as a reactant,
potentially offering higher H₂ yields but requiring additional CO₂ separation steps.
Partial Oxidation: Partially oxidizing methane with oxygen or air can produce a hydrogen-rich
syngas (mixture of H₂ and CO). Further processing steps might be needed to separate pure H₂.

Choosing the right approach depends on factors like:

● Desired H₂ purity
● Feedstock availability (cost of methane and steam)
● Capital and operating costs
Design of Fixed Bed Reactor

● Integration with existing infrastructure

By carefully considering these strategies and tailoring them to specific process requirements,
engineers can optimize methane steam reforming for efficient hydrogen production.

Catalyst Deactivation in Methane Steam Reforming (MSR)

Catalysts are essential for MSR, but they can deactivate over time, reducing their effectiveness in
promoting the reaction. Here's a breakdown of the main deactivation mechanisms and why it's
not necessarily a reason to avoid catalysts entirely:

Catalyst Deactivation Mechanisms:

Sintering: This involves the migration and agglomeration of metal particles on the catalyst
surface, reducing the active surface area available for reaction.
Coking: Methane decomposition during MSR can lead to carbon deposition (coke) on the
catalyst surface, blocking active sites and hindering reactant access.
Poisoning: Certain impurities in the feed stream like sulfur compounds can irreversibly bind to
the catalyst surface, reducing its activity.

Catalyst Replacement:

Regeneration: In some cases, deactivation can be reversed. For example, coking can sometimes
be mitigated by burning off the deposited carbon at high temperatures in an oxygen-containing
environment.
Replacement: When regeneration is not feasible, the spent catalyst needs to be replaced with a
fresh one. This involves shutting down the reactor, removing the old catalyst, and loading a new
one. This process can be time-consuming and costly, highlighting the importance of strategies to
extend catalyst life.

Strategies to Mitigate Deactivation:

Catalyst Design: Developing catalysts that are resistant to sintering, coking, and poisoning can
significantly improve their lifespan.
Feedstock Purification: Removing impurities like sulfur compounds from the feed stream can
minimize catalyst poisoning.
Operating Condition Optimization: Optimizing reaction temperature, pressure, and
steam-to-methane ratio can help reduce coking and improve catalyst stability.
Design of Fixed Bed Reactor

Conclusion:

Designing a fixed-bed reactor for methane steam reforming (MSR) can benefit from combining
the Langmuir-Hinshelwood-Hougen-Watson (LHHW) approach with Freundlich's adsorption
concept. The LHHW model provides a framework for understanding the reaction kinetics on the
catalyst surface, considering the adsorption of methane and steam, their surface reaction, and
product desorption. However, it typically assumes monolayer coverage. Freundlich's concept,
although an empirical model, can account for multilayer adsorption, which might be more
realistic in some cases.

By incorporating Freundlich's isotherm into the LHHW framework, we can estimate the surface
coverages of methane and steam based on the gas-phase pressures. This provides a more accurate
picture of the reactants available for the surface reaction within the LHHW model. This
combined approach can potentially improve the accuracy of the kinetic model for predicting
MSR behavior.

However, it's important to remember the limitations. Freundlich's model is empirical and doesn't
reflect the true mechanism of adsorption. The constants obtained lack a deep physical meaning.
Additionally, using both models adds complexity compared to a simpler Langmuir isotherm
within the LHHW framework.

Therefore, the choice of this combined approach depends on the desired level of accuracy and
the suspected prevalence of multilayer adsorption. For a more fundamental understanding or
when limitations of Freundlich are critical, detailed kinetic models considering specific reaction
mechanisms might be necessary. Ultimately, this design approach offers a valuable tool for
modeling MSR in fixed-bed reactors, potentially leading to optimized reactor design for efficient
hydrogen production.

The following sheet consist of Material Balance of Steam Reforming of Methane: