Tri-reforming Of Methane Research Articles

Life Cycle Assessment of CO2-Based and Conventional Methanol Production Pathways in Thailand

Methanol production through carbon capture and utilization technologies offers promising alternatives to traditional natural-gas-based methods, potentially mitigating climate change impacts and improving resource efficiency. This study evaluates four methanol production pathways: CO2 hydrogenation, tri-reforming of methane, electrochemical CO2 reduction, and co-electrolysis of CO2 and water. The analysis covers 19 scenarios, combining three electricity mixes (100% Thai grid mix, 50% Thai grid mix and 50% renewable energy, and 100% renewable energy) with two hydrogen production technologies (alkaline water electrolysis and grey hydrogen). Environmental life cycle assessment results showed that most pathways perform well when using the 100% renewable energy with co-electrolysis (CE-100%) showing the most substantial reductions across all impact categories as compared conventional methanol production. Electrochemical reduction demonstrated the poorest environmental performance for all scenarios. In Thailand, implementing the CE-100% pathway could potentially yield 12.4 million tonnes of methanol annually from the cement industry’s CO2 emissions, with an estimated value of approximately USD 5.4 billion, while reducing emissions from the industrial processes and product use (IPPU) sector by 75%. The findings provide valuable insights for policymakers, industry stakeholders, and researchers, supporting Thailand’s transition towards sustainable methanol production and broader climate goals.

Tri-reforming of methane over Ni/ZrO2 catalyst derived from Zr-MOF for the production of synthesis gas.

The increasing concentration of CO2 and CH4 in the environment is a global concern. Tri-reforming of methane (TRM) is a promising route for the conversion of these two greenhouse gases to more valuable synthesis gas with an H2/CO ratio of 1.5-2. In this study, a series of Zr-MOF synthesized via the solvothermal method and impregnation technique was used to synthesize the nickel impregnated on MOF-derived ZrO2 catalyst. The catalyst was characterized by various methods, including N2-porosimetry, X-ray diffraction (XRD), temperature programmed reduction (TPR), CO2-temperature programmed desorption (CO2-TPD), thermo-gravimetric analysis (TGA), chemisorption, field-emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM). Characterization results confirmed the formation of the Zr-MOF and nickel metal dispersed on MOF-derived ZrO2. Further, the tri-reforming activity of the catalyst developed was evaluated in a downflow-packed bed reactor. The various catalysts were screened for TRM activity at different temperatures (600-850°C). Results demonstrated that TRM was highly favorable over the NZ-1000 catalyst due to its desirable physicochemical properties, including nickel metal surface area (2.3 m2/gcat-1), metal dispersion (7.1%), and nickel metal reducibility (45%), respectively. Over the NZ-1000 catalyst, an optimum H2/CO ratio of ~ 1.6-2 was achieved at 750°C, and it was stable for a longer period of time.

Tri‐reforming of Methane over a Hydroxyapatite Supported Nickel Catalyst

AbstractFor the first time, a catalyst containing 5 wt. % Ni supported on a hydroxyapatite support (HAP) has been synthesized and evaluated in tri‐reforming of methane (TRM) for synthetic gas (syngas) production. Nickel nanoparticles could be easily formed on HAP surface by using the conventional incipient wetness impregnation technique. In TRM, under unfavorable reaction conditions from the thermodynamic point of view (e. g. medium reforming temperature of 700–800 °C, low steam‐to‐carbon ratio, etc.), this catalyst showed high methane conversion (up to 90 %), however, some deactivations took place. The latter could be explained by both the thermal sintering of nickel nanoparticles and the solid carbon formation. The impact of the main operational parameters has been studied. Increasing the reaction temperature, the molar ratios of oxygen‐to‐carbon and steam‐to‐carbon are favorable for the methane conversion and mostly for the stability of the catalyst. High methane conversion of ca. 90 % with a perfect catalytic stability during 300 hours‐on‐stream could be achieved at 800 °C and 1.4 bar, using a mixture containing low ratio of oxidant‐to‐carbon (molar ratio of CH4/CO2/H2O/O2/N2=1.0/0.67/0.9/0.1/0). These results offer the opportunity to further design an optimal Ni/HAP catalyst by improving metal‐support interaction and downsizing nickel nanoparticles.

Development and lifecycle assessment of various low- and high-density polyethylene production processes based on CO2 capture and utilization

This work focuses on the design and analysis of innovative environmentally friendly pathways to produce low-density polyethylene and high-density polyethylene, as the main feedstock of petrochemical industries, based on CO2 capture and utilization. For each polymer, the process development and simulation of the proposed pathways are performed using Aspen Plus. Each pathway includes the following units: CO2 capture from flue gas, hydrogen production via electrolysis of water, methanol production, olefin production, and polymerization of ethylene. Moreover, the greenhouse gas emissions of the proposed pathways are compared to those of the conventional method i.e., steam cracking. The midpoint and endpoint lifecycle assessment of each pathway are conducted using TRACI 2.1 and ReCiPe Endpoint (H, A) lifecycle impact assessment methods in the OpenLCA software, respectively, for various geographical locations, electricity sources and assessment scenarios for the incorporation of the by-products. The lifecycle assessment results show that the new pathway is an environmentally attractive option, particularly in regions where renewable (low-carbon) electricity is more prominent, such as Quebec and Ontario provinces in Canada. In such regions, negative CO2 emissions, as low as −6.1 kg CO2eq/kg polymer, can be achieved. However, in locations where coal or natural gas are the main sources of electricity generation, such as Alberta, lifecycle emissions increase to 20 times the emissions of the conventional method. Furthermore, the impact of incorporating alternative methanol production processes is evaluated. Results show that using the tri-reforming of methane as an effective syngas production technology from CO2 and natural gas can reduce the lifecycle greenhouse gas emissions by up to 94% and 62%, compared to the conventional high- and low-density polyethylene production pathways.

Influence of the material as support for nickel on the product selectivity of the tri-reforming of methane

In this work we presented the synthesis and performance of two different materials supports, silica and carbon, impregnated with 5% Nickel and the effect of reaction condition and feed compositions on the tri-reforming for the synthesis gas production. The highest conversions of CH4 and CO2 were obtained at 750 °C and weight hourly space velocity (WHSV) 1250 mL/g.min. The 5%Ni/MWCNT catalysts reached 90.2% and 76.5% conversions of CH4 and CO2, while the catalyst 5%Ni/SBA-15%, 87.4% and 64.7%, respectively. The conversions for the MWCNT are significantly higher than for the SBA-15 at 750 °C, but the yields of H2 and selectivity of CO decreased on the SBA support. The influence of the feed conditions on the activity was tested. Both catalysts demonstrated high activity and good stability. TGA results after reaction showed that the carbon nanotubes were preserved, and SBA-15 is more resistant to carbon formation under such reaction conditions.

Effect of metal amount on the catalytic performance of Ni–Al2O3 catalyst for the Tri-reforming of methane

Mesoporous Ni–Al2O3 catalysts with Ni weight (%) 5 to 15 were synthesized, characterized, and tested for tri-reforming of methane (TRM). The characterization results reveal that the metal loading influences the metal-support interaction of the catalysts. Furthermore, the choice of reduction temperature affected the dispersion of metallic-Ni. It is advantageous to reduce these catalysts at their respective Tmax temperatures, which are obtained from H2-TPR studies. At these conditions, the dispersion was maximum. For TRM at 600 °C, the conversions and yields increased with an increase in Ni loading, and carbon was not detected. Increasing the metal loading from 5 wt% to 15 wt% increased the CH4 conversion from 70.5 to 82.4% and CO2 conversion from 10.2 to 19.7%. In contrast, the H2/CO ratio decreased from 3.8 to 3.2. The conversions and yields during TRM were relatively constant with time-on-stream and were highest for 15Ni–Al. Furthermore, H2/CO ratio was >3, and minimal change in dispersion was observed post-reaction for this catalyst. Thus, the active metal loading and the reduction temperature required are important parameters that need to be considered while designing a suitable catalyst for TRM.

Using greenhouse gases in the synthesis gas production processes: Thermodynamic conditions

The work concerns the thermodynamic analysis of CH4 reforming with various oxidants (CO2, H2O, O2) in the technological variants DRM (Dry Reforming of Methane) and TRM (Tri-reforming of Methane) technological variants. Both processes of synthesis gas production (raw material for the production of value-added products) are problematic in terms of environmental protection. In the process, two components of greenhouse gases are used as a substrate: CO2 and CH4. The influence of temperature, pressure, and the molar ratio of oxidants to methane on the efficiency of both processes was analyzed using the deterministic method: raw material conversion, product efficiency and selectivity - H2 and CO, and the value of the H2/CO ratio characterizing the suitability of the synthesis gas for various syntheses. The problem of carbon deposition tendency in DRM was minimized through the selection of operational process conditions, and in the case of TRM, it was fully reduced. The deterministic method of non-linear programming by defining the objective function with constraints helped formulate allowed one the values of TRM parameters: complete reduction of the coking problem, maintaining the H2/CO ratio at the desired level - 2 and CO2 conversion equal to 90%, led to a hydrogen efficiency of over 90%. This efficiency can be obtained at the process temperature T = 273 K, with a pressure of 1 atm, and the molar ratios of oxidants to methane: CH4/CO2/H2O/O2 = 1/0.36/0.77/0.01.

Tri-Reforming of Methane: Thermodynamics, Operating Conditions, Reactor Technology and Efficiency Evaluation—A Review

The production of syngas with optimal energy usage, a minimal environmental impact, and an adjustable H2/CO molar ratio is possible using tri-reforming of methane (TRM). Despite the number of studies dedicated to the TRM process, this process is still in its infancy, with many technical obstacles to overcome. Except for its kinetics and catalysts, which have been reviewed elsewhere, the TRM process is evaluated thoroughly in this work. First, feasibility studies of TRM and the TRM process are presented. Second, the impacts of various operating conditions on the rate of gas conversions, syngas production, and coke formation are discussed. Third, different reactor configurations are compared. This review then goes through the energy and energetic efficiency, economic, environmental, and safety aspects of the TRM process. Finally, a research path for the future is suggested.

A multi-objective optimization of three conflicting criteria in a methane tri-reforming reactor

For the first time, a multi-objective optimization approach is used to optimize energy efficiency with other conflicting objectives for tri-reforming of methane. A 2-D axisymmetric model over nickel based catalysts is established to maximize the energy efficiency, syngas production and CO2 conversion. The inlet temperature, oxygen/methane and carbon dioxide/methane are considered as the decision variables. The attained results revealed that at the utopia point for maximization of H2/CO ratio and energy efficiency, not only H2/CO ratio and energy efficiency reach 2.76 and 42.21, but also CH4 consumption overtakes 60%. Besides, when we consider maximization of CO2 conversion and energy efficiency as the objectives, 1% compromise in the best value of energy efficiency results in an increment of 40% in the value of CO2 conversion. Finally, the third optimization reveals that the CH4 conversion is above 80% and the final mole fraction of H2 is approximately 0.15.

La1−x(Ce, Sr)xNiO3 perovskite-type oxides as catalyst precursors to syngas production through tri-reforming of methane

LaNiO3 (LN), La0.95Ce0.05NiO3 (LCN) and La0.95Sr0.05NiO3 (LSN) perovskites were synthesized by the polymeric precursor method to act as catalyst precursors for the Tri-reforming of methane (TRM). The majority phase determined for the LCN perovskite was LaNiO3, whereas, for LN and LSN, it was La2NiO4. It was not possible to determine segregated strontium phases for LSN, but LCN presented a small amount of CeO2. All the catalysts presented similar methane conversions (around 75%), however differed in CO2 conversion. LCN was the sample with the highest CO2 conversion (32%), while the values recorded for the LN and LSN samples were 21.9 and 17.1%, respectively. The partial substitution of La3+ by Ce4+ leads to a higher CO2 conversion due to the redox properties of cerium, which promotes CO2 disproportion at the oxygen vacancies generated by cerium, providing more oxygen species that oxidize the coke at the surface. The most active sample for CO2 conversion (LCN) was also the least selective for hydrogen, generating a synthesis gas with an H2/CO ratio of 1.2, while the less active LN and LSN samples were more selective for hydrogen (H2/CO = 1.5–1.6). Thus, it is possible to generate synthesis gas suitable for different applications depending on the metal incorporated into the LaNiO3 perovskite.

Syngas production via chemical looping reforming using methane-based feed and NiO/Al2O3 oxygen carrier

Syngas production based on chemical looping reforming was experimentally studied using a fixed-bead reactor. The 15 wt% NiO/Al2O3 was used as the oxygen carrier. The reaction temperature was fixed as 800 °C. For reactant containing CH4 only, it was termed as chemical looping partial oxidation of methane (CL-POM). With five CL-POM cycles, no decay in oxygen carrier activity was found. A high H2/CO ratio resulted due to dominant H2 production reactions in the reduction stage. Carbon deposition on the oxygen carrier surface can be identified from the CO and CO2 formations in the oxidation stage. With CO2 added in the reactant in addition to CH4, this was referred to as the chemical looping dry reforming of methane (CL-DRM). Near theoretical amounts of H2 and CO yields were obtained. With both H2O and CO2 added in the reactant in addition to CH4, this was referred to as the chemical looping tri-reforming of methane (CL-TRM). Due to coupled steam reforming of methane (SRM), POM, and DRM, higher CH4 conversion, H2 and CO yields resulted compared with the CL-POM and CL-DRM cases. The average H2/CO ratio of 1.2 was obtained with reactant with molar ratio of CH4/CO2/H2O = 1/1/1.

Tri-reforming of methane for syngas production using Ni catalysts: Current status and future outlook

Tri-reforming of methane (TRM) emerged as an attractive approach for syngas production that combines the methane steam reforming (SMR), dry reforming (DRM) and partial oxidation (POX) reactions in a single process. The key merits of the TRM process are the ability to use flue gas directly in the process feedstock, the great flexibility to control the H2/CO ratio for downstream processes, and the relatively lower energy demand and carbon footprint. Considerable progress was achieved over the past decade in catalyst development, process modeling and optimization for syngas production using the TRM process. In this work a critical review of the literature pertaining to Ni-based catalyst development, TRM reaction kinetics, process development, and economics is presented. The use of Ni-based catalysts has received significant attention in recent years; hence this work aims to provide a summary and a critical analysis of the advancement achieved in the design of Ni-based catalysts. Developing active Ni-based catalysts with enhanced resistance to coke formation for the TRM process is anticipated to pave the way for further commercialization ventures. Ni catalysts supported on a wide range of support materials such as Al2O3, CeO2, ZrO2, TiO2, MgO and their mixed oxides are the most widely used catalysts for TRM processes. This review provides a critical analysis of the different attempts made to tune the catalyst properties such as the use of different supports, promotors, and synthesis protocols. Catalyst properties such as Ni dispersion, basicity, Ni particle size, thermal stability is evaluated for various catalytic systems to develop structure-property relationship in TRM processes. Moreover, studies on TRM reaction kinetics, process modeling, and economics are also reviewed. Future outlook in catalysts and process development is also presented in this review to shed lights on the potential pathways to develop TRM processes in an environmentally friendly, and cost-effective manner.

Hydrogen production from biogas: Process optimization using ASPEN Plus®

This work is part of the VABHYOGAZ (valorization of biogas into hydrogen) program, which targeted the industrial deployment of hydrogen production from biogas in France. To-date, different processes of methane reforming, such as steam reforming of methane (SRM), dry reforming of methane (DRM) and tri-reforming of methane (TRM), have been studied in the literature, but only SRM is applied at industrial scale. Since SRM is an energy-intensive process, a critical analysis of these routes for hydrogen production from biogas is indispensable for process optimization. This has been addressed in this work, by using ASPEN Plus® simulation. Different global processes of hydrogen production from biogas, via DRM, SRM, or TRM, with or without tail gas recycling, have been studied. Among them, hydrogen production using TRM technique (H2-TRM0.3C process) with a partial recycling of tail gas (30%) was found to be the best option, leading to the highest hydrogen production rate and the best energy yield. H2-TRM0.3C process was also found to be more efficient than the actual industrial process (H2-REF), which is based on SRM technique. Under the same conditions, H2-TRM0.3C process led to a higher H2 production (8.7% more), a lower total energy consumption (18.6% less), and a lower waste heat generation (15.4% less), in comparison with the actual industrial process (H2-REF).

Projected cost analysis of hybrid methanol production from tri-reforming of methane integrated with various water electrolysis systems: Technical and economic assessment

In this study, a techno-economic analysis for the bridging technology of hybrid methanol production based on tri-reforming of methane integrated with water electrolysis is performed. Focusing on the technical and economic parameters of three representative types of water electrolyzer (alkaline, proton exchange membrane, and solid oxide electrolysis), the process flow diagram for the targeted process is built and key economic parameters are confirmed. Based on the results of the simulation model and values of economic entries, itemized cost estimation reflecting the current status of water electrolyzers is conducted to evaluate the methanol production costs. Furthermore, the future production costs of methanol are estimated according to the projected values of system efficiencies, the lifetimes, and the future investment costs of three different water electrolyzer types. The results of methanol production costs in the present and the future are compared with the market prices of methanol in three different regions (U.S., Europe, and China) to verify the economic viability of the process. Considering the reported annual working hours of electrolyzers and the predicted decline of electricity prices generated from renewable energy sources such as photovoltaics and on-shore wind energy, operating hours of the plant and electricity prices for water electrolysis to be economically competitive are varied for more practical prediction for methanol production costs. In conclusion, the profitable operating conditions of the process to achieve a 20% margin in the regions in the present and the future are suggested concerning plant working hours and the levelized cost of electricity for each water electrolysis system.

Review on the catalytic tri-reforming of methane - Part II: Catalyst development

Methane reforming allows the production of synthesis gas (syngas) which is an important gas mixture feedstock for the production of chemicals and energy carriers. Steam reforming of methane (SRM) and partial oxidation of methane (POM) have been deployed at large industrial scale, while dry reforming of methane (DRM) and more recently tri-reforming of methane (TRM) are intensively studied. TRM simultaneously combines SRM, POM and DRM in a unique process and allows overcoming several weaknesses of each individual methane reforming process: e.g. regulation of the molar ratio of H2/CO by controlling feed composition or adaptation to the variation in biogas composition as renewable resource. TRM process strongly requires a solid catalyst. To date, the design of efficient TRM catalysts remains a challenge. This work reviews recent achievements on the development of catalysts for TRM, and provides a guideline for future work related to TRM catalysts.

CO2 utilization for methanol production; Part I: Process design and life cycle GHG assessment of different pathways

The process design and life cycle assessment (LCA) of various methanol production processes, including the conventional natural gas reforming process and alternative CO2 utilization-based pathways, are performed in this work. Three main technologies are considered for the CO2 conversion to methanol: direct CO2 hydrogenation, dry reforming and tri-reforming of methane. For each pathway, a process simulation that includes the CO2 capture from typical flue gas of a cement kiln, the methanol synthesis and purification steps, is performed using the Aspen engineering suite. In addition, for each process, several heat integration measures are considered to maximize thermal efficiency. According to the simulation results, the thermal efficiency of the direct CO2 hydrogenation process (47.8 % LHV) is higher than the dry reforming (40.6 % LHV) while it is lower than the conventional (68.4 % LHV) and tri-reforming (57.9 % LHV) processes. The LCA results showed that the direct CO2 hydrogenation pathway is an environmentally friendly option, only when the electricity GHG intensity is lower than 0.17 kg CO2 equivalent per kWh of electricity. As a result, in the context of Canada, the CO2 hydrogenation options can be recommended only for the provinces where low-carbon electricity is available, such as Quebec, British Columbia, Manitoba and Ontario.

Review on the catalytic tri-reforming of methane - Part I: Impact of operating conditions, catalyst deactivation and regeneration

Tri-reforming of methane (TRM) allows the production of syngas with a low environmental impact, an optimal energetic consumption, and a modular H2/CO molar ratio. However, despite a large number of publications devoted to TRM reaction, this process is still in its infancy and faces technical issues due to the catalyst deactivation by the formation of solid carbon, thermal sintering, vapor-solid reactions, and poisoning. Moreover, TRM reaction is also highly dependent on the operational conditions. This article provides a critical analysis of the last achievements on the TRM reaction. First, the thermodynamic, kinetic and mechanism aspects are presented and commented. Then, the impact of the operational conditions is analyzed. Finally, the main reasons of catalyst deactivation and the associated methods for catalyst regeneration are discussed. In parallel, catalytic efficiency is tentatively linked to physico-chemical properties of the catalyst, and recommendations are proposed for the future work on TRM process.

Tri-Reforming of Methane over NdM0.25Ni0.75O3 (M = Cr, Fe) Catalysts and the Effect of CO2 Composition

The NdM0.25Ni0.75O3 (M = Cr, Fe) named NCN and NFN catalysts precursors were synthesized and characterized. The CO2 utilization in the feed was studied in the methane tri-reforming to produce syngas at 850 °C. The catalysts presented orthorhombic structure and the elements (Nd, Cr or Fe, Ni and O) on the surface showed homogeneous dispersion. XPS indicates different states of nickel, iron and chromium, respectively, Ni2+, Fe3+ and Fe2+ and Cr3+ (or Cr4+) and Cr6+ species. The Tri-Reforming of Methane (TRM) was performed for conditions 1CH4:0.5CO2:0.5O2 (A) and 1CH4:1CO2:0.25O2 (B), both with 0.25 H2O diluted in He. The conversions of methane were 74% for the NCN and 65% for the NFN catalysts. Both catalysts showed ratios (H2/CO) of 1.5 and 2 for conditions A and B, respectively, at 850 °C.

Adjusting Process Variables in Methane Tri-reforming to Achieve Suitable Syngas Quality and Low Coke Deposition

Tri-reforming of methane (TRM) combines steam reforming, dry reforming, and partial oxidation of CH4 in a single reactor. The H2/CO product ratio usually ranges from 1.5 to 2.5, which makes the TRM...

Towards a recuperative, stationary operated thermochemical reformer: Experimental investigations on the methane conversion and waste heat recovery

In this article, stationary operated, thermochemical recuperation (TCR) based on internal reforming of methane, using oxy-fuel exhaust gases as both heat source and as reactants, is considered. TCR is a promising technology for effective heat recovery from exhaust gases of oxy-fuel furnaces, which could deliver significant increases in combustion efficiency. In order to quantify and validate the potential of TCR, the influence of the main operational parameters on methane conversion and waste heat recovery was experimentally investigated. The experimental investigations presented here differ from previously published work in the following aspects: (I) A stationary, recuperative lab-scale reformer unit filled with industrial nickel catalyst was used to investigate the influence of the oxy-fuel exhaust gas temperature, the exhaust gas recirculation rate and the addition of oxygen to the reactants on the methane conversion and waste heat recovery. (II) The required energy input for the endothermic reforming reaction is provided solely by the thermal energy of the oxy-fuel exhaust gases. (III) The reactants for fuel reforming were exclusively taken from oxy-fuel exhaust gases, resulting in so-called bi- and tri-reforming of methane, depending on the addition of oxygen. The results showed that a maximum CH4 conversion rate of 65.6% was achieved, with a substantial increase in the combustion efficiency of 17.9%, confirming the ability of TCR to improve the combustion efficiency of oxy-fuel furnaces. In addition, the effects of different reactor configurations on the methane conversion were investigated.