Pyrolysis Reaction Research Articles

Numerical simulation of a reactor for heterogeneous pyrolysis of hydrocarbon gases over biochar granules

Numerical simulation of a reactor for heterogeneous pyrolysis of hydrocarbon gases over biochar granules

Exergy Analysis of Hydrogen-Rich Syngas Production System Utilizing Palm Oil Empty Fruit Bunch using Pyrolysis Connected with Steam Methane Reformer

Fossil fuel consumption on a large scale continues to increase yearly, causing a shortage of energy sources. Hydrogen can help to overcome the shortage of energy sources. It can be produced from renewable energy sources, such as oil palm Empty Fruit Bunch (EFB) as biomass using pyrolysis processes equipped with steam methane reformer and water gas shift reactions. This research was conducted to determine the amount of hydrogen that can be produced and to analyze the exergy of the existing systems in the hydrogen production process. Aspen Plus has been used to design and analyze pyrolysis processes, steam methane reform, and water gas shift reactions. The results showed that when 6.54 kg Empty Fruit Bunch was used as raw material in a pyrolysis reactor, hydrogen could be produced in the amounts of 0.435 kg. The exergy values of raw materials and fuels are relatively high because the chemical exergy values of the compounds contained therein are also high. Based on the calculations, it is found that the combustion process is the process that experiences the most significant exergy destruction. The exergy efficiency of this hydrogen production process system is 22.77%.

Co‐Pyrolytic Recycling of Bakelite and Polymethyl Methacrylate: Kinetic, Synergistic, and Thermodynamic Analysis

AbstractBakelite, a thermosetting plastic, has limited feasibility for thermal recycling processes such as pyrolysis, unlike thermoplastics, due to its inherent tendency to get charred upon heating and difficulty in being converted into valuable fuel and chemical compounds. In this study, the co‐pyrolysis of bakelite and poly methyl methacrylate is explored to improve the thermal degradation and thus recycling feasibility of bakelite by pyrolysis. The kinetics and thermodynamics of the co‐pyrolysis of blended samples are analyzed using different kinetics models. The thermal degradation experiments of the sample are conducted from ambient to 1000 °C at five various heating rates of 5, 10, 20, 30, and 50 °C/min in an inert N2 gas environment. The results showed that adding poly methyl methacrylate to bakelite changes the pyrolytic degradation temperature and weight loss trend. The kinetic analysis reveals that the thermal degradation at 220–345 °C follows an F2.5 order‐based model with an average activation energy of 181 kJ/mol, while the degradation at 345–475 °C follows an F2 order‐based model with an average activation energy of 318 kJ/mol. The enthalpy changes and free energy change associated with thermal degradation exhibit a positive trend while that of entropy change shows a negative trend. With blending the free energy change and entropy change decreased while enthalpy change increased. During batch pyrolysis at 450 °C, the PMMA‐Bakelite blend generates oil (49.17 %), wax (12.36 %), residue (15.36 %), and gas (23.11 %). According to FTIR and GC‐MS analyses, the pyrolytic oil produced by the co‐pyrolysis of the blended sample at 450 °C comprises 32.23 % saturated hydrocarbons (C9–40), 20.97 % unsaturated hydrocarbons (C6–24), and 46.80 % oxygenated material (C5–19). These findings can assist in the optimization of pyrolysis reactor design for the recycling of thermosetting plastics.

Applications of H2-Enriched syngas and slag products from plastic wastes via novel plasma dual-stage-arc pyrolysis

Sustainable plastic waste management in the prevailing ‘new-normal’ post-pandemic scenario calls for calorific waste plastic up-cycling into high-end product recovery pathways. The present work employed a novel dual-stage arc plasma pyrolysis reactor to recover syngas and slag products from mixed plastics and Low-Density Polyethylene and Polyethylene Terephthalate (LDPE-PET) plastic waste feeds. Syngas product yield decreased while the solid slag yield increased with rising arc current, attaining 75% and 25% for mixed plastic waste feed and 59% and 41% for LDPE-PET wastes, respectively, at 200A arc current. The resultant syngas composition showed 83% and 77% H2 while 1.7% and 2.7% CO for mixed plastic waste-feed and LDPE-PET wastes, respectively, with no significant presence of CO2. Slag characterization studies revealed the presence of scattered pores on the slag surface, graphitic nanostructures due to scraped carbon depositions from electrode tips and the absence of aromatic groups due to complete conversion. High carbon content was observed in the slag due to the dissociation of lighter hydrocarbon and carbon dioxide on dual-arc exposure in two stages, underscoring the higher efficiency. For holistic integrated circular onsite ‘plastic waste-to-resource’ recovery-cum-application, electricity was generated from the resultant syngas and the slag was used for the manufacture of tiles in the community platform. Techno-economic evaluation of an up-scaled plasma pyrolysis facility shows the power recovery of 3.5 kWh/kg of waste plastic, with a net annual profit of $2800 and a payback period of 1.7 years. The findings of the present work suggest that the proposed integrated dual-arc plasma pyrolysis based plastic waste-to-resource recovery in circular-economy model has a viable outcome.

Creating pyrolysis reactor for disposal of municipal solid waste

In order to utilize municipal solid waste (MSW), a prototype reactor for thermal processing was created using materials developed at the National Research Center “Kurchatov Institute” – Central Research Institute of Structural materials “Prometey”, the technology for decomposing MSW in the reactor was developed, and its tests were carried out. The test results allowed us to conclude that the use of pyrolysis reactors for recycling ensures the environmental safety of the process and produces high-temperature gas (1000–1200°C) suitable for further use in power plants. Technical requirements were determined for the development of an industrial reactor for the disposal of solid waste with a productivity of up to 10 t/h, taking into account the shortcomings identified during testing of the prototype.

Comprehensive experimental assessment of biomass steam gasification with different types: correlation and multiple linear regression analysis with feedstock characteristics

In order to reveal the correlation between gasification behavior and products with feedstock characteristics, the steam gasification of 13 biomasses was investigated using a thermogravimetric analyzer and a fixed-bed reactor. Meanwhile, a multiple linear regression was used to construct correlation models. The results showed that cellulose content and crystallinity had the greatest influence on pyrolysis reactivity, which was reflected that the cellulose content was strongly positively correlated with the pyrolysis reactivity (Pmax = 0.77), while the lignin content and cellulose crystallinity were opposite. H/C, O/C ratios and SiO2 content had the greatest influence on gasification stage. O/C were strongly negatively correlated with gasification reactivity (Pmax = −0.81). But correlations of K and Ca contents were much less than that of Si. Husk has the best gasification performance than straw and woody with highest H2 and total gas yield of 28.26 and 68.93 mmol·g−1. H2 concentration and yield were significantly affected by the cellulose crystallinity and the fixed carbon content with positively correlation (P = 0.69–0.85). CH4 and CnHm were also influenced by them, but the trend was opposite to that of H2. Cellulose content, followed by SiO2 content mainly affected CO and CO2 and negatively correlated with CO while positively with CO2.

A Carbon Capture and Utilization Process for the Production of Solid Carbon Materials from Atmospheric CO2 - Part 2: Carbon Characterization.

This article is the second part of a study reporting the results of a novel carbon capture and utilization (CCU) process, which converts atmospheric CO2 into solid carbon materials. The CCU process combines direct air capture (DAC) with catalytic methanation, which is then followed by methane pyrolysis in a reactor filled with liquid tin. While Part 1 discussed the performance of the overall process and individual process steps regarding conversions and yields, Part 2 characterizes the solid carbon products obtained under various synthesis conditions. The effects of the pyrolysis temperature and the composition of the gas mixture from the methanation step on the solid carbon product are analyzed. Carbon powder is synthesized from methane with either H2 or CO2 as most important impurity. Carbon samples are characterized using SEM, TEM, Raman spectroscopy, XPS and XRD analysis. Very thin, disordered carbon flakes, soot aggregates and large carbon onions are identified as the main solid products of the process. Their formation mechanisms in the liquid metal-filled pyrolysis reactor are discussed.

Post-Extractivism and Bioeconomy: An Experimental Analysis of Combustion and Pyrolysis Processes as Alternatives to Add Value to Agro-Residues (Coffee Husks) Generated in Farmer Cooperatives of the Ecuadorian Amazon

A post-extractivist development model for communities in the Amazon that is not based on non-renewable resource extraction demands the study and demonstration, in the field, of alternative economic activities that add value to currently generated residual biomass. Following the principles of bioeconomy, this study presents an experimental analysis of a retort burner and a pilot-scale auger-type pyrolysis reactor used to convert coffee husks generated in a collection and post-harvesting center of a farmer’s cooperative into thermal energy and biochar, respectively. This study shows that coffee husks, whether used as feedstock for combustion or pyrolysis processes, can supply the thermal energy required by the post-harvesting processes. The combustion or pyrolysis of coffee husks avoids its accumulation and decomposition while replacing fossil fuels used in post-harvesting operations, reducing costs and making farmers independent of fossil fuel subsidies. Unlike combustion (11,029.4 mg/Nm3), the CO concentration in the flue gas during the pyrolysis process was 458.3 mg/Nm3, which is below the eco-design standard of 500 mg/Nm3. According to the European Biochar Certificate, carbon content (67.4 wt%) and H/Corg, O/Corg (0.6 and 0.1, respectively) are within the typical values of biochars used for soil amendment and carbon sequestration. Nonetheless, the concentration of polycyclic aromatic hydrocarbons must be assessed to fully regard this material as biochar. Finally, further studies are required to assess the ability of cooperatives to generate and trade carbon credits linked with the application of biochar in their cropping systems.

Investigation of Cephalexin Removal Using Biochar Derived from Nephelium lappaceum Seeds

<p class="MsoNormal" style="line-height:200%;margin-bottom:0cm;mso-layout-grid-align:none;text-align:justify;text-autospace:none;"><span style="font-family:"Times New Roman",serif;font-size:12.0pt;line-height:200%;" lang="EN-US">The improper disposal of drugs into bodies of water has become a severe environmental and health issue. Biochar synthesized from different agro residues could be a potential material for the adsorption of pollutants in aqueous environments. </span><em><i style="mso-bidi-font-style:normal;"><span style="font-family:"Times New Roman",serif;font-size:12.0pt;line-height:200%;" lang="EN-US">Nephelium lappaceum</span></i></em><span style="font-family:"Times New Roman",serif;font-size:12.0pt;line-height:200%;" lang="EN-US"> seeds were pyrolyzed at 600 °C in a pyrolysis reactor incorporating a slow pyrolysis process for carbonization. Fourier-Transform Infrared (FTIR), Scanning Electron Microscope (SEM), and X-ray diffraction (XRD) were used to characterize the biochar before and after adsorption of the pharmaceutical pollutant cephalexin. The effects of several factors, including initial cephalexin concentration, time of contact, dosage of adsorbent, and pH, were considered for the sorption. The findings showed that the Freundlich model offered the greatest fit for adsorption. The better-fitted kinetic model was the pseudo-second-order kinetic. Based on Langmuir isotherm model, the maximum adsorption capacity of cephalexin was obtained as 63.69 mg/g. The adsorption process involves hydrogen bonding, surface complexation, electrostatic and π−π EDA interactions. The current study offers a feasible and optimistic method for using agricultural waste and an alternative adsorbent substance for recovering highly concentrated cephalexin from water-based solutions.<o:p></o:p></span></p>

Comprehensive Review of Biomass Pyrolysis: Conventional and Advanced Technologies, Reactor Designs, Product Compositions and Yields, and Techno-Economic Analysis

Pyrolysis is an environmentally friendly and efficient method for converting biomass into a wide range of products, including fuels, chemicals, fertilizers, catalysts, and sorption materials. This review confirms that scientific research on biomass pyrolysis has remained strong over the past 10 years. The authors examine the operating conditions of different types of pyrolysis, including slow, intermediate, fast, and flash, highlighting the distinct heating rates for each. Furthermore, biomass pyrolysis reactors are categorized into four groups, pneumatic bed reactors, gravity reactors, stationary bed reactors, and mechanical reactors, with a discussion on each type. The review then focuses on recent advancements in pyrolysis technologies that have improved efficiency, yield, and product quality, which, in turn, support sustainable energy production and effective waste management. The composition and yields of products from the different types of pyrolysis have been also reviewed. Finally, a techno-economic analysis has been conducted for both the pyrolysis of biomass alone and the co-pyrolysis of biomass with other raw materials.

Environmentally Benign and Expeditious Access to 4‐Aryl Methylene‐isoxazole‐5(4H)‐Ones Using Magnetically Separable Nanoparticles

AbstractAn environmentally benign and expeditious protocol was developed for the one‐pot multicomponent synthesis of 4‐aryl‐3‐methylisoxazol‐5(4H)‐ones by the condensation of aldehyde, hydroxyl amine hydrochloride, and ethyl acetoacetate in 50% aq. ethanol at 50 °C. The reaction was catalyzed by magnetically separable carbon microspheres co‐decorated with nanosized iron sulfide and magnetite nanoparticles in 10 wt% amount. The FeS1‐x‐Fe3O4/C nanocatalyst was prepared from iron(III) sulfate loaded iminodiacetate group functionalized styrene‐divinylbenzene based ion exchanger by pyrolysis reaction performed at 600 °C for 4 h. The use of magnetically separable heterogeneous catalyst, aqueous ethanol, short reaction time (30 min), and nonchromatographic purification methods are the striking features of the developed protocol. The isolated yield of the condensation products varied between 81% and 96%. Furthermore, the protocol exhibits high functional group tolerance and includes the use of noncorrosive, nonhazardous reaction conditions affording the product in excellent yields and short reaction time.

Intrinsic Metal Component-Assisted Microwave Pyrolysis and Kinetic Study of Waste Printed Circuit Boards

Waste printed circuit boards (WPCBs) hold great recycling value, but improper recycling can lead to environmental issues. This study combines pyrolysis and microwave technologies, leveraging the unique phenomenon where metal materials tend to “spark” in a microwave field, to develop a microwave pyrolysis process for WPCBs that incorporates metal fillers. The research analyzes the effects of microwave power, metal filler addition, and pyrolysis time on the efficiency of microwave pyrolysis. It explores the mechanisms of microwave pyrolysis and the pathways of pyrolysis product formation, and the kinetics of the pyrolysis reaction of WPCBs. The results indicate that microwave-assisted pyrolysis greatly improves efficiency. Within the experimental range, the optimal conditions are found to be a microwave power of 1600–1800 W, a metal filler addition of 10%, and a pyrolysis time of 10 min. Under these conditions, the yield of pyrolysis liquid was 12.8%, with approximately 5–12 different components, while the yield of pyrolysis gas was 12.7–13.4%, with about 9–11 different components. Compared to conventional pyrolysis products, the liquid products from microwave pyrolysis are simpler and more advantageous for resource utilization. Theoretical calculations show that the average activation energy for the microwave pyrolysis process is 81.05 kJ/mol, with an average reaction order of 0.93, which is greatly better than the 147.75 kJ/mol of the conventional pyrolysis process.

Investigating the formation of soot in CH4 pyrolysis reactor: A numerical, experimental, and characterization study

Methane pyrolysis is a promising method for eco-friendly hydrogen production, but soot formation and carbon interaction pose challenges for scaling up. Therefore, understanding the dynamics of soot formation and carbon deposition is crucial. This study delves into the intricacies of soot formation in methane pyrolysis under industrially relevant conditions, namely operations at atmospheric pressure, employing a H2:CH4 ratio of 2 and exploring a range of hot zone temperatures (1473 K, 1573 K, 1673 K, and 1773 K) with a 5 s residence time. Utilizing a detailed gas-phase kinetic model with direct carbon deposition reactions, the research adopts the method of moments coupled with a one-dimensional plug flow reactor model to simulate soot formation. The model is validated by characterizing soot particles that were produced in a pyrolysis reactor by means of transmission electron microscopy, Dynamic light scattering (DLS), and Raman spectroscopy. Results show that lower temperatures lead to nucleation-dominated growth, whereas higher temperatures significantly restrain particle growth due to carbon deposition. DLS data indicate a complex balance between particle growth and deposition processes. These findings provide insights into operational parameters that can enhance reactor performance and sustainability in hydrogen production processes by mitigating soot and carbon deposition.

The effect of temperature on the Emission Factor of air emissions from pyrolysis of used tyres

Used tyres pyrolysis is an efficient solid waste management strategy for used tyres and a growing method of fuel oil production. However, the impact of air emissions associated at different temperature on ambient air quality has not been determined. To solve this problem, a pyrolysis fixed bed reactor and a condensing unit for separating liquid from produced gas were designed and constructed. 0.20 kg of used tyres were pyrolysed in the reactor and air emissions from the reactor chamber was characterized for air pollutants using the E-instrument E8500. Using a combination of measured mass of pollutants, mass of tyre pyrolzed and time taken during pyrolysis, Emission Factors of the air pollutants were established from the study at 200 °C, 300 °C and 400 °C. The concentration measured between 200 °C - 400 °C were in the range of 15 -7497 mg/m3, 0 – 4680 mg/m3, 38.25 – 103, 277.76 mg/m3 and 2 – 293 mg/m3 for CO, NOx, HC and H2S respectively. The developed emission factors were in the range of 16.52 – 8370.04 g kg-1, 0 – 4470.26 g kg-1, 42.126 – 104,055.9 g kg-1 and 2.20 – 322.69 g kg-1. The designed and constructed pyrolysis reactor and condenser unit were effective for used tyre pyrolysis while the measured air pollutants concentration were higher for all pollutants except H2S using the Federal Ministry of Environment (FEPA, 1991) standard. Hence, it is necessary to carry out further studies on air pollution control from waste tyre pyrolysis at lower temperature.

Hydrodynamics of molten media bubble columns for hydrogen production through methane pyrolysis

Methane pyrolysis using a molten media bubble column reactor is a promising technique for hydrogen production with low carbon dioxide emissions at a feasible price. Understanding the bubble dynamics in molten media is essential to elucidate the reaction mechanisms and establish design requirements for efficient reactors. Computational fluid dynamics provides an effective means to understand the hydrodynamics in opaque molten media. This research used the volume of fluid method to study the effects of gas injection rate as well as variations in gas and molten media (iron, aluminum, and a salt mixture of sodium bromide and potassium bromide in a 48.7:51.3 molar ratio) properties on bubble dynamics. The computational model was first validated using existing experimental and empirical observations. This study makes fundamental contributions to the understanding of bubble dynamics in molten media. First, it was confirmed that gas properties had a small effect on bubble dynamics. The difference in bubble diameters between argon at ambient temperature and 1600 °C was less than 10%. Second, it was found that the volumetric gas injection rate and molten media properties significantly impacted the bubble dynamics, including the bubble diameter and flow regime. Future work will build on these findings to recommend appropriate operating conditions and molten media for specific pyrolysis reactor designs.

Comprehensive evaluation of the physicochemical properties and pyrolysis mechanism of products from the slow pyrolysis of waste coffee shells

Slow pyrolysis is an efficient method for converting agricultural and forestry wastes into valuable resources, thereby addressing energy shortage and environmental pollution. In this study, a slow-pyrolysis experiment of coffee shells (CS) at 450–850 °C was conducted in a tube furnace. The resulting pyrolysis products were comprehensively characterized via FTIR, Raman spectroscopy, nitrogen adsorption analysis via BET theory, SEM, XPS, and PY-GC-MS. Moreover, the pyrolysis reaction mechanism and N transformation pathway of CS were proposed. The results showed that with the increase in pyrolysis temperature, the yield of biochar gradually decreased, and the yield of biogas gradually increased. At 850°C, the yields of biochar, bio-oil and biogas of CS were 27.13, 35.16 and 37.71 %, respectively (on a dry, ash-free basis). The bio-oil yield was highest at 550 °C, reaching 35.7 %. Notably, biochar exhibited favorable characteristics such as high specific surface area and porosity, demonstrating its potential as both a biomass fuel and an adsorption material. Acetone (78.30 %) and caffeine (8.29 %) was the predominant substance in bio-oil. Biogas was predominantly composed of CO2, CO, CH4 and H2. The pyrolysis process of CS mainly involved the degradation of macromolecules into small molecules, the repyrolysis of small molecules, dehydrogenation, deoxygenation, alkylation, isomerization, and self-condensation. These results provide a theoretical basis for the recycling of waste biomass CS, which has environmental protection significance and economic value.

Insight into evolution characteristics of pyrolysis products of HLH and HL coal with Py-VUVPI-MS and DFT

To achieve a comprehensive understanding of the influence of chemical structure on the evolution characteristics of coal pyrolysis products, pyrolysis reaction of two kinds of low rank coal (Huolinhe and Huangling coal) were investigated with pyrolysis-vacuum ultraviolet photoionization mass spectrometry (Py-VUVPI-MS). The soft ionized mass spectral detection can provide evolved information of original pyrolysis product. The chemical structure of coal samples was characterized by solid-state 13C-NMR, indicating HLH coal with more branched chain and longer aliphatic chain structure. The bond dissociation enthalpies (BDE) of β-Cal-Cal and β-Cal-O within model compounds were obtained with density functional theory. The difference of peak temperature with maximum evolution was collected to investigate the effect of the chemical environment on evolution behavior of pyrolysis products. The results reveal that branched and long aliphatic side-chains can reduces BDE of β-Cal-Cal and β-Cal-O, resulting in the lower peak temperature of pyrolysis products derived from HLH coal. Substituent groups (such as alkyl and hydroxyl groups) attached on the aromatic rings can reduce peak temperatures. Moreover, the effects of the different substituted position on the aromatic ring of the methyl group presented on differences of the BDE. An increase in aromatic ring size correlates with a certain degree of reduction in BDE for β-Cal-Cal; consequently, peak temperature of pyrolysis products with larger aromatic rings is lower. The pyrolysis behavior of coal were discussed based on the experimental observations and theoretical calculation, which are beneficial to understand the reaction route and mechanism of coal pyrolysis.

Research on modeling the lignin waste molecular structure and pyrolytic reactions using ReaxFF MD method

The lack of clarity in characterizing the chemical structure model of lignin waste hinders the comprehensive understanding of its pyrolysis reaction mechanism. The characterization results revealed that the de–alkalized lignin sample contained larger amounts of aliphatic and aromatic carbons compared to carbonyl carbons. Additionally, the aliphatic carbon molecules exhibited a higher presence of oxygenated carbons. The degree of aromaticity (fa) was determined to be 63.93 %. The resulting single–molecule structural model exhibited a molecular formula of C33H26O11 and a molecular weight of 598.56. Furthermore, the evolutions patterns and formation pathways of primary volatile components (H2, CH4, CO, and CO2) in pyrolysis reactions were revealed. The number of H2 molecules exhibited a positive correlation with the rise in pyrolysis reaction temperature. CH4 molecules exhibited a pattern of initially increasing and subsequently decreasing. The number of CO molecules exhibited a positive correlation with the rise in pyrolysis temperature. Conversely, the number of CO2 molecules demonstrated an initial increase followed by a decrease as the pyrolysis temperature increased. Finally, the generation pathway analysis of pyrolysis products shows that the H2 molecule is composed of two hydrogen atoms bonded together that have been dissociated from the carboxyl group. Alternatively, it can be produced through hydrogenation reactions involving hydrogen atoms detached from the carboxyl group and methyl groups. CH4 is primarily generated through the reaction between –CH3 and free hydrogen ions. CO is primarily produced through the cleavage of the carbonyl group. CO2 is primarily produced through the cleavage of carboxyl and ester groups.

Numerical simulation of an externally heated fixed bed reactor for coal pyrolysis based on porous media

A cutting-edge three-dimensional transient model utilizing porous media has been developed to accurately simulate the pyrolysis process of externally heated coal. This innovative model comprehensively considers the evaporation and condensation of water, as well as the release of volatiles. In addition, it meticulously examines the change in coal seam porosity and the interphase heat transfer between pyrolysis gas and solid coal seam. The model's precision has been appropriately confirmed through validation against the central temperature evolution inside the experimental reactor. Notably, this model systematically illustrates various aspects, including the evolution of coal layer temperature, evaporation and moisture density, changes in coal layer density, porosity distribution, volatile release, and interphase heat transfer. The obtained results reveal that the heat absorption by moisture phase change causes the coal seam temperature to relatively stabilize at around the water boiling point for a period, thus delaying the initiation of the coal pyrolysis reaction. The pyrolysis gas released by center coal seam pyrolysis tends to flow radially toward the heating wall before flowing out of the reactor. Additionally, the change in coal seam porosity increases the heat transfer rate by an average of 1.5 °C/min during the rapid heating stage. The analysis also highlights the significant occurrence of interphase heat transfer throughout the pyrolysis process and elucidates its mechanism in various stages. Ultimately, this work offers essential theoretical guidance for the design, optimization, and scaling of subsequent externally heated fixed-bed coal pyrolysis reactors.

Nonprecious Single Atom Catalyst for Methane Pyrolysis.

The development of a suitable catalytic system for methane pyrolysis reactions requires a detailed investigation of the activation energy of C-H bonds on catalysts, as well as their stability against sintering and coke formation. In this work, both single-metal Ni atoms and small clusters of Ni atoms deposited on titanium nitride (TiN) plasmonic nanoparticles were characterized for the C-H bond activation of a methane pyrolysis reaction using ab initio spin-polarized density functional theory (DFT) calculations. The present work shows the complete reaction pathway, including energy barriers for C-H bond activation and dehydrogenated fragments, during the methane pyrolysis reaction on catalytic systems. Interestingly, the C-H bond activation barriers were low for both Ni single-atom and Ni-clusters, showing the energy barriers of ~1.10 eV and ~0.88 eV, respectively. Additionally, single-atom Ni-TiN showed weaker binding to adsorbates, and a net endothermic reaction pathway indicated that the single-atom Ni-TiN was expected to resist coke formation on its surface. However, these Ni single-atom catalysts can sinter, aggregate into a small cluster, and form a coke layer from the highly exothermic reaction pathway that the cluster takes despite the facile reaction pathway.