This review will explore the influences of the active metal, support, promoter, preparation methods, calcination temperature, reducing environment, particle size and reactor choice on catalytic activity and carbon deposition for the dry reforming of methane Bimetallic (Ni−Pt, Ni−Rh, Ni−Ce, Ni−Mo, Ni−Co) and monometallic (Ni) catalysts are preferred for dry reforming compared to noble metals (Rh, Ru and Pt) due to their low-cost Investigation of support materials indicated that ceria−zirconia mixtures, ZrO2 with alkali metals (Mg2+, Ca2+, Y2+) addition, MgO, SBA-15, ZSM-5, CeO2, BaTiO3 and Ca08Sr02TiO3 showed improved catalytic activities and decreased carbon deposition The modifying effects of cerium (Ce), magnesium (Mg) and yttrium (Y) were significant for dry reforming of methane MgO, CeO2 and La2O3 promoters for metal catalysts supported on mesoporous materials had the highest catalyst stability among all the other promoters Preparation methods played an important role in the synthesis of smaller particle size and higher dispersion of active metals Calcination temperature and treatment duration imparted significant changes to the morphology of catalysts as evident by XRD, TPR and XPS Catalyst reduction in different environments (H2, He, H2/He, O2/He, H2−N2 and CH4/O2) indicated that probably the mixture of reducing agents will lead to enhanced catalytic activities Smaller particle size (

Dry reforming of methane: Influence of process parameters—A review

The performance of catalysts used for the dry reforming of methane can strongly depend on the selection of active metals, supports and promoters. This work studies their effects on the activity and stability of selected catalysts. Designing an economically viable catalyst that maintains high catalytic activity and stability can be achieved by exploiting the synergic effects of combining noble and/or non-noble metals to form highly active and stable bi- and tri-metallic catalysts. Perovskite type catalysts can also constitute a potent and cost effective substituent. Metal oxide supports with surface Lewis base sites are able to reduce carbon formation and yield a greater stability to the catalyst, while noble metal promoters have proven to increase both catalyst activity and stability. Moreover, a successful metal-support-promoter combination should lead to higher metal-support interacrtion, lower reduction temperature and enhancement of the anti-coking and anti-amalgamation properties of the catalyst. However, the effect of each parameter on the overall performance of the catalyst is usually complex, and the catalyst designer is often faced with a tradeoff between activity, stability and ease of activation. Based on the review carried out on various studies, it is concluded that a catalyst design must take into consideration not only the separate effects of the active metal, support and promoter, but should also include the combined and mutual interactions of these components.

Catalyst design for dry reforming of methane: Analysis review

The mitigation and utilization of greenhouse gases, such as carbon dioxide and methane, are among the most important challenges in the area of energy research. Dry reforming of CH4 (DRM), which uses both CO2 and CH4 as reactants, is a potential method to utilize the greenhouse gases in the atmosphere. Natural gas containing high concentrations of CO2 and CH4 could therefore be utilized for hydrogen and synthesis gas (syngas) production in the near future, without need for the removal of CO2 from the source gas. Thus, the DRM reaction is a suitable process to convert CH4 and CO2 to syngas, which is a raw material for liquid fuel production, through the Fischer–Tropsch process. Herein, the development of CO2 reforming for syngas production is reviewed, covering process chemistry, catalyst development, and process technologies as well as the potential future direction for this process.

Catalytic Technology for Carbon Dioxide Reforming of Methane to Synthesis Gas

Catalytic reforming of methane (CH4) with carbon dioxide (CO2), known as dry reforming of methane (DRM), produces synthesis gas, which is a mixture of hydrogen (H2) and carbon monoxide (CO). CH4 + CO2 → 2CO + 2H2, ΔH° = 247.3 kJ mol−1, ΔG = 61 770–67.32T. The DRM process has gained much attention recently as it reduces greenhouse gases (GHG), CO2 and CH4, in the atmosphere. In addition to reducing GHG, the DRM process produces valuable chemicals (CO + H2), provides a good approach to utilizing biogas and natural gas with a significant amount of CO2, has good capability as a chemical energy transmission system as compared to steam reforming, and finally yields the desired unity H2/CO ratio for Fischer–Tropsch synthesis. The bimetallic Ni-based catalysts supported on Al2O3/TiO2 and promoted with Ce/ZrO2 show remarkable performances in the DRM process. But, carbonaceous deactivation of the catalysts is the major problem faced during this process. Numerous studies have been cited on various aspects of DRM, and some papers are also devoted to reviewing carbonaceous deposition problems and their remedies. However, some lacunae exist, which are highlighted in the present review paper on strategies to reduce the carbonaceous deactivation of catalysts for improved DRM efficiency by appropriate catalyst development, operating conditions, and flow reactor designs. The disposal of spent catalysts falls under the category of hazardous industrial materials and is also required to comply with stringent environmental regulations. Therefore, regeneration and reclamation techniques for spent catalysts have also been discussed.

An overview on dry reforming of methane: strategies to reduce carbonaceous deactivation of catalysts

A series of ordered mesoporous Ni–Ce–Al composite oxides with various cerium contents were synthesized via a one-pot route: evaporation-induced self-assembly (EISA) strategy and tested in methane dry reforming for hydrogen and synthesis gas production. Using this method, the hydrophobic nickel precursor was directly incorporated into the hydrophobic cores of surfactant micelles, and thus, the highly dispersed Ni nanoparticles were stabilized inside the mesopore channels of an alumina matrix. For comparison, Ni-based catalysts were also prepared by a traditional impregnation method. The characterization results confirmed that the ordered mesostructures were well maintained in all of the cerium-incorporated Ni–Al materials (Ce/(Ce + Al) molar ratio ≤ 3%). The catalyst with a Ce/(Ce + Al) ratio of 1% exhibited the highest catalytic activity (with CO2 and CH4 initial conversions being 70% and 68% at 700 °C, respectively) and remained stable in a methane dry reforming reaction. This improved activity can be at...

Facile Route for Synthesizing Ordered Mesoporous Ni–Ce–Al Oxide Materials and Their Catalytic Performance for Methane Dry Reforming to Hydrogen and Syngas

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

Synthesis gas production from dry reforming of methane over Ni/Al2O3 stabilized by ZrO2

In this work the improvement of stability of Ni/Al 2 O 3 catalyst by ZrO 2 addition for synthesis gas production from CH 4 /CO 2 reforming reaction was investigated. Effect of Ni content was firstly conducted followed by effect of operating temperature in the range of 500-700 o C, and effect of ZrO 2 loading at CH 4 :CO 2 of 1:1 in feed. The experimental results showed that 15%Ni was the minimum nickel loading on alumina giving high feed conversion of 67.26% for CH4 and 61.38% for CO2 and high H 2 , yield of 59.46% and CO yield of 62.23% while maintaining the ratio of H 2 :CO close to 1. The suitable reaction temperature of 700 o C provided the highest CH 4 and CO 2 conversion and H 2 yield. The containing ZrO 2 catalysts (15%Ni-x%ZrO 2 /Al 2 O 3 ; x=5, 10 and 15%ZrO 2 ) showed much higher stability than the ZrO 2 -free/Ni/Al 2 O 3 catalyst due to reduction of coke formation by ZrO 2 probably by suppressing methane dissociation step and facilitating CO 2 dissociation on the Ni active sites indicated by the decrease of CH 4 conversion and H 2 yield.

Chairut Siangchin

Papers

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

Synthesis gas production from dry reforming of methane over Ni/Al2O3 stabilized by ZrO2

CH 4 /CO 2 Reforming over Ni-ZrO 2 /Al 2 O 3 Catalyst for Synthesis Gas Production