PREFACE

The quest for sustainable energy solutions emphasizes the necessity of methane breakdown or catalytic
reforming as an essential area of study. In comparison with conventional methods, this technique offers a
viable path for producing hydrogen with minimal environmental effect. This study explores a wide range
of research centered on this process. This research attempts to offer a thorough overview of methane
reforming technology by examining techniques, important papers, and new developments in catalyst
design. By doing this investigation, we want to find current problems, prospective solutions, and future
lines of inquiry that can further sustainable energy activities.

We would like to thank our primary supervisor, Prof. Rohit Kumar, for his guidance, support, and
encouragement throughout the entire process. His mentorship and expertise were invaluable in helping us
shape the direction of our research and bring our ideas to fruition.

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 INTRODUCTION

Nearly half of the hydrogen produced globally is produced by processes like steam methane reforming (SMR)
and water-gas shift (WGS) reactions, which are made possible by natural gas's availability and high
hydrogen-to-carbon ratio.

Catalytic decomposition of methane (CDM) has gained popularity as a greener option because of its low carbon
dioxide emissions and energy efficiency. Transition metals, like nickel, are essential CDM catalysts, but at high
temperatures, carbon accumulation deactivates them.

This Process is crucial because :

Syngas Production: Syngas, the product of steam reforming, is a versatile intermediate used in various
industrial processes, including chemical synthesis, fuel production, and power generation.

Catalyst deactivation refers to the gradual loss of activity and effectiveness of a catalyst over time
during a chemical reaction. It is a significant problem in industrial processes and can arise due to:

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​ Coking: Coking occurs when carbonaceous particles(coke) form on the catalyst surface by
decomposition of hydrocarbons. These coke deposits block active sites, reduce surface area, and
decrease catalyst effectiveness.

Sintering: Sintering is the agglomeration of catalyst particles at high temperatures, leading to

decrease in surface area and catalytic activity.
​
​ Oxidation:Catalysts undergo oxidative degradation when exposed to oxygen and high temperature.
This process leads to the formation of metal oxides, which reduces the activity of the catalyst.
​

Various other factors influence catalyst performance and longevity in the presence of compounds. Moreover,
economic considerations play an important role in evaluating the feasibility and scalability of catalytic
reforming processes.

● One approach to enhance performance is explored in the first study, focusing on controlled
preparation of Ni–Cu alloy catalysts.
● Another challenge is effectively managing carbon deposits, addressed in the second study concerning
the role of potassium in catalysts synthesized via solution combustion.
● Additionally, thermocatalytic decomposition (TCD) offers a CO2-free hydrogen production method
with valuable solid carbon byproducts. The third study investigates NiCu/CNT catalysts' performance
in TCD, emphasizing variations in Ni/Cu ratios. These studies collectively advance our understanding
of sustainable hydrogen production methods, aiming for efficient, low-emission processes.

This review aims to offer a foundation for future research in the field of catalytic reforming of methane by
consolidating current knowledge through a thorough analysis of these and other works. The knowledge
gathered from this examination of the literature could be extremely helpful in building machine learning
models that anticipate catalyst behavior and optimize process parameters in real time.

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 LITERATURE SURVEY

Controlled preparation of Ni–Cu alloy catalyst via hydrotalcite-like precursor and its
enhanced catalytic performance for methane decomposition

This research examines developing and characterizing uniform, composition-tunable Ni–Cu alloy
catalysts for methane degradation at high temperatures. Hydrotalcite-like compounds (HTlcs) of
Ni–Cu–Al are used to make these catalysts. Among the methods we employ in our thorough analysis are
X-ray diffraction (XRD analysis), X-ray photoelectron spectroscopy (XPS), temperature-programmed
reduction (H2-TPR), hydrogen chemisorption (H2 chemisorption), inspecting transmission electron
microscopy with energy-dispersive X-ray spectroscopy (STEM-EDX), scanning electron microscopy
(SEM), transmission electron microscopy (TEM), and Raman spectroscopy.

The Ni–Cu–Al HTlcs undergo calcination, becoming a rock-salt Ni(Cu, Al)O oxide solid solution with
uniformly distributed nickel and copper ions. Following reduction, well-dispersed Ni–Cu alloy particles
with a homogeneous and adjustable composition are formed, measuring an average of 9.5–10.4 nm in
size.

Catalytic activity and production of carbon increase significantly when nickel is alloyed with the right
proportion of copper. The best carbon yield of 132.9 g-C/g-cat is obtained with an ideal Ni: Cu atomic
ratio of 7:3, which outperforms Ni/Al2O3 catalysts by 78; furthermore, depending on the copper
concentration, the form of the carbon product changes from thin carbon nanotubes (CNTs) to thicker
carbon nanofibers (CNFs) that resemble fishbones and platelets.

When exposed to the reaction environment during methane breakdown, the Ni–Cu alloy particles sinter
into larger aggregates. This sintering process is due to improved carbon bulk diffusion promoted by
Ni–Cu alloying, which limits methane dissociation and promotes CNF development, resulting in a
considerable increase in carbon yield.

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 LITERATURE SURVEY

Effect of potassium in catalysts obtained by the solution combustion synthesis for

co-production of hydrogen and carbon nanofibers by catalytic decomposition of methane

The catalysts used in this investigation were created using solution combustion synthesis and contained
potassium oxide (K2O) in different concentrations (0.25–10 wt%). These catalysts received rigorous
characterization utilizing a range of techniques including X-ray diffraction, transmission electron
microscopy, scanning electron microscopy, and low-temperature nitrogen adsorption. The goal was to find
out how the phase composition and texture of the resulting catalysts were impacted by varying potassium
concentrations.

The inclusion of potassium, even in tiny levels as 0.25 wt% K2O, induced noteworthy alterations in the
particle size distribution of nickel catalysts. In particular, it caused the particle size to decrease from 5 to 30
nm to 5 to 10 nm. This modification made it easier to produce more hydrogen with a higher yield. Peak
performance was seen at 675°C and 750°C. The catalysts Ni-0.25 %K2O/Al2O3 and Ni-1 %K2O/Al2O3
showed the highest hydrogen yields, reaching 11.6 g/gcat and 17.0 g/gcat, respectively.

Furthermore, the investigation explored the time-dependent and temperature-dependent kinetic behavior of
methane decomposition catalysis. It was noted that the addition of 5–10 wt% potassium resulted to a
decrease in hydrogen output, probably due to particle agglomeration, resulting in higher average particle
sizes compared to other samples. However, the Ni-0.25 %K2O/Al2O3 and Ni-1 %K2O/Al2O3 catalysts
maintained high hydrogen yields, indicating the stabilizing effect of potassium on nickel particles, preventing
excessive growth and ensuring sustained catalytic activity.

Furthermore, the presence and concentration of potassium doping additives influenced the quality of carbon
nanofibers formed during methane decomposition. It's interesting to note that higher potassium content
produced nanofibers with significantly smaller diameters (41–44 nm), indicating a non-linear relationship
between potassium concentration and nanofiber diameter. Conversely, lower potassium content (0.25–1 wt%)
led to the formation of larger nanofibers (90–258 nm).

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 LITERATURE SURVEY

Promotional role of NiCu alloy in catalytic performance and carbon properties for CO2-free
H2 production from thermocatalytic decomposition of methane

This study examined different NiCu/CNT catalysts to see how they perform in converting methane to
carbon and hydrogen at different temperatures. The catalysts had varying amounts of nickel and
copper, and they were made using different methods.

The study found that the ratio of nickel to copper, the size of the metal particles, and the temperature at
which the reaction occurs are important for how well the catalyst works and how stable it is.

When the reaction took place at 550°C, adding copper had a negative effect on the catalyst's
performance, but it changed the properties of the carbon produced. However, at 600°C, adding copper
improved the catalyst's performance and stability, and it also changed the properties of the carbon
produced. Above 650°C, only catalysts with more than 10% copper remained effective and stable.

Catalysts with more nickel compared to copper produced larger metal particles and had higher
performance. On the other hand, catalysts with more copper produced smaller metal particles and had
lower performance.

Increasing the amount of copper in the catalyst reduced how quickly it stopped working after the
reaction, while also changing the type of carbon produced. However, adding more copper had less of
an effect on how quickly the catalyst stopped working compared to changing the type of carbon
produced.

Copper plays two roles in the reaction: it changes the shape of the carbon produced to multi-wall
carbon nanotubes and causes the metal particles to become larger, which makes them more stable at
higher temperatures and more selective in producing multi-wall carbon nanotubes.

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