CO2 Methanation Research Articles

Design and Development of Integrated Direct Air Capture and Methanation Processes

AbstractThe synergies from integrating direct air capture and CO2 methanation are assessed and quantified. Three direct air capture and methanation processes with different integration strategies are proposed: only heat integration, direct air capture sorbent regeneration with high‐pressure H2, and complete integration in a single unit. The heat integration study via pinch analysis evaluated the potential energy demand reduction. Overall autothermal operation is achievable, as the heat generated in methanation often exceeds that required for direct air capture sorbent regeneration. A novel process combining CO2 adsorption and methanation in one reactor provided the best productivity and energy demand results. However, this design requires complex cycles and strict demands on the sorbent and catalyst, requiring further development and experimental demonstration.

Environmental tradeoff on integrated carbon capture and in-situ methanation technology

Compared to conventional CO2 removal methods, carbon capture and in-situ conversion using dual function materials avoid compression and transportation of CO2, which is regarded as a promising technology. Although it brings additional economic benefits, the environmental impacts of CO2 capture and conversion remain unclear. A life cycle assessment of an integrated CO2 capture and methanation system using dual function materials is conducted to investigate its feasibility to reduce global warming. Life cycle inventory is obtained through construction, operation, and disposal process of the integrated system. A dynamic model of CO2 capture and methanation is developed to obtain the operating parameters. Results show that the optimal global warming potential is 0.706 kg CO2,eq per kilogram captured CO2, which indicates the advantages of using dual function materials for carbon mitigation. Global warming potential is a minor factor among the overall normalized environmental impacts, only accounting for 0.5 % of the total normalized impact, while the main factor marine aquatic ecotoxicity accounts for around 73 %, and fresh water aquatic ecotoxicity accounts for around 23 %. Global warming potential is the most affected by green hydrogen input, followed by dual function material input. Results reveal that the integrated CO2 capture and conversion using dual function materials is conducive to carbon mitigation but has significant other environmental impacts, such as marine aquatic ecotoxicity, and the main contributors to the environmental impacts are wind electricity, green hydrogen, refrigerator, and dual function material.

Identification of Deactivation Mechanisms by the Periodic Transient Kinetic Method

AbstractThe understanding of deactivation processes in heterogeneous catalysis is key for the development of new materials and exploration of new operation windows. In this contribution, the periodic transient kinetic method (PTK) is used to identify and separate catalyst deactivation processes for the first time. The PTK method is applied for a standard Ni/Al2O3 catalyst in CO and CO2 methanation for 24 h and compared to steady‐state experiments. For the example reactions, the study exhibits different deactivation behavior for CO and CO2 methanation. The results demonstrate that the PTK method delivers an insight into the deactivation process and furthermore gives evidence for the underlying mechanism.

Continuous Biological Ex Situ Methanation of CO2 and H2 in a Novel Inverse Membrane Reactor (IMR)

A promising approach for carbon dioxide (CO2) valorization and storing excess electricity is the biological methanation of hydrogen and carbon dioxide to methane. The primary challenge here is to supply sufficient quantities of dissolved hydrogen. The newly developed Inverse Membrane Reactor (IMR) allows for the spatial separation of the required reactant gases, hydrogen (H2) and carbon dioxide (CO2), and the degassing area for methane (CH4) output through commercially available ultrafiltration membranes, enabling a reactor design as a closed circuit for continuous methane production. In addition, the Inverse Membrane Reactor (IMR) facilitates the utilization of hydraulic pressure to enhance hydrogen (H2) input. One of the process’s advantages is the potential to utilize both carbon dioxide (CO2) from conventional biogas and CO2-rich industrial waste gas streams. An outstanding result from investigating the IMR revealed that, employing the membrane gassing concept, methane concentrations of over 90 vol.% could be consistently achieved through flexible gas input over a one-year test series. Following startup, only three supplemental nutrient additions were required in addition to hydrogen (H2) and carbon dioxide (CO2), which served as energy and carbon sources, respectively. The maximum achieved methane formation rate specific to membrane area was 87.7 LN of methane per m2 of membrane area per day at a product gas composition of 94 vol.% methane, 2 vol.% H2, and 4 vol.% CO2.

Abundant interfacial and intrinsic oxygen vacancies enabling small nickel/ceria nanocrystal efficient CO2 methanation

Smaller nano-sizes typically result in supported catalysts with abundant interfacial and intrinsic oxygen vacancies for better adsorption and activation of small molecules, including CO2, leading to improved efficiency of CO2 methanation. Here, Ni/CeO2-S with the smaller nano-size of around 4.2 nm is used to catalyze CO2 methanation, which exhibits significantly enhanced activity compared to larger nano-sized Ni/CeO2-L catalyst, even surpassing the most majority of previously reported catalysts using CeO2 as the support or Ni as the active metal. The coexistence of interfacial defects and intrinsic oxygen vacancies allows for enhanced adsorption and activation of CO2 molecules as well as H spillover, resulting in such improved CO2 methanation. In-situ DRIFTS demonstrate a nearly sole Formate pathway on Ni/CeO2-S for efficient CO2 hydrogenation. This research provides valuable insights into the reaction mechanism over a small nanosize supported catalyst.

Numerical simulation for subsidence control in CO2 storage and methane hydrate extraction

Gas hydrates are increasingly viewed as a promising alternative to traditional fossil fuels. However, their extraction process poses risks to structural integrity, potentially causing significant subsidence. In this study, we developed a Thermo-Hydro-Mechanical-Chemical (THMC) model to analyze the impact of gas hydrate extraction on seabed subsidence. Our investigation focused on the influence of bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity on subsidence during gas hydrate extraction via depressurization.The results show that seabed subsidence is affected by various factors such as bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity. It was noted that significant subsidence is associated with low initial hydrate concentration, high permeability, porosity, low gas saturation, low rock thermal conductivity, and a notable pressure drop of 79.31%.To address this issue, we propose a seabed subsidence mitigation strategy involving CO2 injection. This approach not only safeguards offshore infrastructure and coastal communities but also helps reduce CO2 emissions, aligning with global climate change mitigation efforts. In our model, CO2 injection occurs in the subsurface reservoir at the interface between the free water zone and hydrate-bearing formations. The CO2 hydrates formation process releases heat, which dissociates methane hydrates, allowing the methane to be replaced by CO2 molecules and move towards the production well.Our analysis reveals that increasing injection temperature and rate significantly reduces subsidence. Additionally, the range of investigated injection pressures, which included pressures equal to and more than double the initial reservoir pressure, showed inconsequential impacts on seabed subsidence.The effectiveness of subsidence reduction is significantly enhanced by injecting a CO2/N2 mixture compared to pure CO2 injection. The most substantial reduction in subsidence occurred when a mixture of CO2 and N2 in a 50/50 vol/vol ratio was injected at a high rate.These findings offer crucial insights for optimizing the efficiency and control of gas hydrate extraction methods. They emphasize the importance of employing balanced injection strategies to minimize environmental risks and ensure sustainable energy extraction.

Comparative Study of Porous High‐Entropy Oxides as Low‐Temperature Catalysts for CO2 Methanation

AbstractHigh‐entropy oxides (HEOs) are an emerging class of materials whose compositional complexity has garnered attention because of their tailorable chemistries and unique properties arising from extreme configurational entropy. Solid‐state methods are often employed to synthesize HEOs, but such methods result in poor material properties for catalytic processes, leaving HEOs less studied for catalysis. Here we utilize different wet‐synthesis strategies to produce porous HEOs and investigate their performance in heterogeneous CO2 hydrogenation to methane. Specifically, HEOs were synthesized using hydrothermal, co‐precipitation, and solvothermal methods, resulting in different morphologies like platelets or spheres. Of the tested materials, HEOs with 2‐D platelets derived from hydrothermally‐synthesized high‐entropy layered double hydroxides had superior catalytic performance, especially in low‐temperature regimes (<300 °C). K‐edge XANES indicated that metallic sites (Ni0‐Co0) were formed during the reaction, and these metallic sites are dispersed into the HEO matrix which is confirmed by STEM/elemental mapping. This facile synthesis approach allows for realized synergy between the metallic sites and the HEO support, leading to superior performance for CO2 methanation compared to low‐entropy counterparts. Finally, this study illustrates how HEOs offer new avenues of tailorability in terms of the interplay between support, active site and reaction temperatures for heterogeneous catalysis.

Highly dispersed Ni-Ce catalyst over clay montmorillonite K10 in low-temperature CO2 methanation

The Carbon Capture and Utilization (CCU) option can be an efficient solution for CO2 emission mitigation. To this end, we have investigated the carbon dioxide methanation at low temperatures. Highly active, selective, stable, low-cost catalysts are required for energy and carbon balance benefits. Supported nickel-based catalysts result as the most studied and promising candidates showing a good compromise between performance and low preparation costs. The catalyst design role is key to obtaining the best performance, requiring many experiments and optimisation procedures. Herein, the enhanced Montmorillonite MK10-supported Ni(0)Ce(III) catalyst, prepared by consecutive hydrothermal and electrostatic adsorption methods followed by reduction under hydrogen flow, was used in batch CO2 methanation, exhibiting 76 % of CO2 conversion with 100 % CH4 selectivity after 3 h. The catalytic system reveals very high robustness preserving the same activity and selectivity for at least 5 reaction cycles if compared with γ-Al2O3-supported Ni(0)Ce(III) catalyst, the latter showing the same activity but only in the first cycle. EDX, XPS, SEM, TPD, TPR, and BET characterisation techniques were used to elucidate and evaluate the potential synergistic effect of the active metal centre-promoter-support interfaces, highlighting their role in the activity and robustness of the catalyst, comparing the same effect using different alumina and silicate solid supports. The effects of the reaction conditions on the methane yield and selectivity were also evaluated.

Ni Catalysts for Thermochemical CO2 Methanation: A Review

Ni Catalysts for Thermochemical CO2 Methanation: A Review

Seasonal dynamics and regional distribution patterns of CO2 and CH4 in the north-eastern Baltic Sea

Abstract. Significant research has been carried out in the last decade to describe the CO2 system dynamics in the Baltic Sea. However, there is a lack of knowledge in this field in the NE Baltic Sea, which is the main focus of the present study. We analysed the physical forcing and hydrographic background in the study year (2018) and tried to elucidate the observed patterns of surface water CO2 partial pressure (pCO2) and methane concentrations (cCH4). Surface water pCO2 and cCH4 were continuously measured during six monitoring cruises onboard R/V Salme, covering the Northern Baltic Proper (NBP), the Gulf of Finland (GoF), and the Gulf of Riga (GoR) and all seasons in 2018. The general seasonal pCO2 pattern showed oversaturation in autumn–winter (average relative CO2 saturation 1.2) and undersaturation in spring–summer (average relative CO2 saturation 0.5), but it locally reached the saturation level during the cruises in April, May, and August in the GoR and in August in the GoF. The cCH4 was oversaturated during the entire study period, and the seasonal course was not well exposed on the background of high variability. Surface water pCO2 and cCH4 distributions showed larger spatial variability in the GoR and GoF than in the NBP for all six cruises. We linked the observed local maxima to river bulges, coastal upwelling events, fronts, and occasions when vertical mixing reached the seabed in shallow areas. Seasonal averaging over the CO2 flux suggests a weak sink for atmospheric CO2 for all basins, but high variability and the long periods between cruises (temporal gaps in observation) preclude a clear statement.

High-Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates-Stabilized *CO Intermediate.

Stabilizing specific intermediates to produce CH4 remains a main challenge in solar-driven CO2 reduction. Herein, g-C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x = 12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80% and 40.8 μmol·g-1·h-1 evolution rate for PW9/g-C3N4. Conversely, g-C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g-C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g-C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g-C3N4 (x = 12, 11) compared with that of PW9/g-C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate

Stabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x = 12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80% and 40.8 μmol·g‐1·h‐1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x = 12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

NiO Nano- and Microparticles Prepared by Solvothermal Method—Amazing Catalysts for CO2 Methanation

Nickel oxide (NiO) is one of the most popular hydrogenation catalysts. In heterogeneous catalysis, nickel oxide is used, for example, as a suitable methanation catalyst in the Fischer–Tropsch reaction not only for CO hydrogenation but also in the modified Fischer–Tropsch reaction with CO2. However, CH4 selectivity and CO2 conversion strongly depend on NiO micro- (MPs) and nanoparticles’ (NPs) shape, size, and surface area. In this study, the synthesis of NiO micro- and nanoparticles was conducted using the simple solvothermal method. Different morphologies (microspheres, sheet clusters, hexagonal microparticles, and nanodiscs) were prepared using this method with different solvents and stabilizers. The prepared catalysts were tested in the hydrogenation of CO2 in a gas phase with excellent conversion values and high selectivity to produce CH4. The best results were obtained with the NiO with disc or sphere morphology, which produced methane with selectivity at a level near 100% and conversion close to 90%.

Catalytic Impedance Spectroscopy: Concept and Application on CO2 Methanation.

Complex modeling of periodic excitation combined with time-resolved product detection is used to describe the complex response function of a catalytic system. We describe this concept of catalytic impedance spectroscopy (CIS) and the underlying general experimental approach and a concrete setup. The feasibility of CIS is experimentally demonstrated along the catalytic CO2 methanation reaction. The measurements confirm the theoretically anticipated rate-determining step of HCO* → CH* on Ni catalysts. Limitations and prospects of CIS to unravel reaction mechanisms are discussed.

Solar‐Assisted CO2 Methanation via Photocatalytic Sabatier Reaction by Calcined Titanium‐based Organic Framework Supported RuOx Nanoparticles

AbstractCO2 reduction by sunlight under mild reaction conditions is a research area of increasing interest expected to favor decarbonization and produce fuels and chemicals in the circular economy. We hereby report on the development of a series of titanium oxide‐based solids produced by calcination of MIL‐125(Ti)‐NH2 decorated with RuOx nanoparticles (1 wt %) material at temperatures from 350 to 650 °C and used as photocatalysts for CO2 methanation under simulated sunlight irradiation (45 mW/cm2) at <200 °C and 1.5 atm total pressure. The material synthesized at 350 °C produced the highest photoactivity of the series (4.73 mmol g−1 CH4 at 22 h and an apparent quantum yield at 400, 500 and 750 nm of 0.76, 0.65 and 0.54 %, respectively), comparing favorably with the activities of other MOF‐based materials reported so far. Insights into the material's photocatalytic performance and a study of the possible reaction pathways during CO2 methanation were obtained by electrochemical impedance, electron spin resonance, photoluminescence and in situ FT‐IR spectroscopies together with transient photocurrent and hydrogen temperature programed desorption measurements. The study showed the possibility of using MOF‐based materials as precursors to develop metal oxide photocatalysts with enhanced activities for solar‐driven gaseous CO2 photomethanation.

Facilitating CO2 methanation over oxygen vacancy-rich Ni/CeO2: Insights into the synergistic effect between oxygen vacancy and metal-support interaction

The catalytic hydrogenation of CO2 into CH4 is a versatile strategy to realize green development goals, whereas developing low-cost and high-performance catalysts remains a significant challenge. Herein, highly active Ni0/NiO supported on oxygen vacancy-rich CeO2 (Ni/CeO2-Ov-R) was designed, which exhibited ∼76 % CO2 conversion coupled with 100 % CH4 selectivity at a low temperature of 250 °C. In addition, such satisfactory reaction performance could be maintained over 80 h at 300 °C. The density functional theory (DFT) calculations elaborated that oxygen vacancies were more easily formed on the CeO2 (1 1 0) plane of Ni/CeO2-Ov-R. Compared with Ni/CeO2-Ov-medium (Ni/CeO2-Ov-M) and Ni/CeO2-Ov-poor (Ni/CeO2-Ov-P) with relatively insufficient oxygen vacancy, the copious oxygen vacancies of Ni/CeO2-Ov-rich was apt to enhance the interaction between the CeO2 support and Ni species as confirmed through H2-TPR and XPS. Noteworthily, the abundant medium-strength basic sites and surface oxygen vacancy of Ni/CeO2-Ov-rich were more conducive to upshifting the activation adsorption of CO2 and accelerate the conversion of intermediates. Besides, the oxygen vacancies also make a great contribution to the enhancement of the potential for hydrogen dissociation because of the enhanced number of exposed Ni0. In situ DRIFTS displayed that the CO and formate (HCOO–) routes co-existed on Ni/CeO2 catalysts, revealing that oxygen vacancy and exposed Ni0 boosted the CO2 and H2 activation. This work proposes a deeper insight into the precise regulation of the oxygen vacancy of Ni/CeO2 catalyst and opens a path for exploiting CO2 methanation catalysts with a potential application.

Insight and comprehensive study of Ni-based catalysts supported on various metal oxides for CO2 methanation

In this study, nickel supported on various metal oxides were prepared by simple impregnation and the performance for CO2 methanation was tested. The oxide supports were all prepared by thermal decomposition of metal salts to provide comparable oxide properties such as surface area. Among the investigated oxides, nickel supported on CeO2 and Y2O3 showed the highest CO2 conversion of 90% at 320 °C with highest CH4 selectivity of 99%. The order of catalyst activity (XCO2@320°C) was reported: Ni/CeO2 ~ Ni/Y2O3 > > Ni/La2O3 > Ni/ZrO2 > Ni/Al2O3 > Ni/MgO > Ni/CaO > > Ni/MnO. The physicochemical properties of the catalysts were analyzed by TEM, BET, XRD, ICP, H2-TPR, CO2-TPD, H2 chemisorption, TGA, Raman, and XPS. From the characterization results, the catalyst activity was independent to specific surface area of catalyst and crystallite size of Ni. The amount of oxygen vacancies and weak-to-medium basic sites exhibited major roles for enhancing catalyst activity. The CeO2 and Y2O3 as reducible oxide supports not only provided abundant oxygen vacancies / basic sites, but also promoted Ni dispersion with appropriate interaction between metal and support, resulting in higher reducibility at low temperature. The reduction of catalyst at high temperature can significantly improve the performance of Ni supported on non-reducible MgO. However, the Ni/CeO2 and Ni/Y2O3 reduced at high temperature suffered from coalescence of CeO2 and Y2O3, though Ni crystallite sizes are well preserved from sintering.

Low Temperature Sabatier CO2 Methanation

AbstractThe CO2 methanation reaction, or Sabatier reaction, is experiencing renewed interest in the context of large‐scale recycling of point CO2 emissions, leading to the power‐to‐gas technology. The reaction represents a flexible route to transform CO2 into methane by hydrogenation with (green) dihydrogen. This exothermic transformation takes place at a reasonable rate at temperatures above 200 °C and is directed to the targeted product at low temperatures. The CO2 methanation nevertheless remains kinetically limited due to the chemical stability of CO2 and the high bond dissociation energy for C═O in CO2. Therefore, the current urgent demand is for the development of catalysts and associated processes with superior activity for CO2 activation at low temperatures. This critical review aims to overview the state of the art of this low‐temperature technology using thermal, plasma and photo‐assisted catalysis. We summarize research advances around low‐temperature CO2 methanation, focusing on catalyst formulations (metal, supports and promoters), reaction mechanisms and suitable activation processes. We discuss each of these critical aspects of the technology and identify the main challenges and opportunities for low temperature (≤200 °C) CO2 methanation.

Cobalt-doped Ni-based catalysts for low-temperature CO2 methanation

The study of the process and mechanism of CO2 activation and the development of low-temperature, high-activity and selective catalysts for CO2 methanation are current research hotspots. In this paper, a series of Ni/Al2O3 catalysts with different Co contents were prepared by using layered double hydroxides (LDHs) as precursors for low-temperature CO2 methanation, and the incorporation of Co promoted the electron transfer from Ni to Co, which facilitated the adsorption and activation of CO2 and H2. The spent catalyst still maintained the layered structure with no significant change in the metal particle size, indicating that the addition of Co significantly improved the long-term stability of the catalysts. The CO2 conversion was 55.5 % and STYCH4 was 148.0 mmol·gcat−1 h−1 at 200 °C, 2.0 MPa and 1000 h−1. The in situ DRIFTS experiments showed that the addition of Co accelerated the conversion of the reaction intermediates and promoted the generation of methane.

CO2 valorisation from lime production via Columbus process to produce E-methane for transport sector – A comprehensive life cycle assessment

In the next decades, CO2 capture and utilisation (CCU) technologies can contribute to climate change mitigation. The Columbus project is an example of a CCU initiative in which CO2 is captured from lime production and converted into E-methane via CO2 methanation. E-methane can serve as fuel for ships and lorries to replace heavy fuel oil and diesel, respectively. This paper aims to assess the environmental impacts of E-methane production via the Columbus process, powered by renewable electricity, and its utilisation in the transport sector benchmarked to conventional fuel production (references) through life cycle assessment (LCA). A basket of products approach was used to also consider the co-products obtained from the Columbus process in the assessment. Both emission and resource based indicators were selected for the LCA. The results show that E-methane production and its utilisation in ships and lorries result in a decrease of the impact on climate change (35 %), particulate matter formation (94 %) and fossil resource use (85 %) compared to the references. For this comparison, the conventional production of the co-products was also taken into account. However, the production and utilisation of this fuel consumes more minerals and metals than the references. The higher mineral and metal extraction from the environment can be explained by the construction of the solar panels required to provide electricity for electrolysis. Future research should focus on the social acceptance and techno-economic assessment of the Columbus process.