Abstract
Utilizing the abundant biogas resources in an efficient and sustainable way helps to mitigate the energy and environmental problems. CH4 oxy-CO2 reforming reaction is a promising technic and an efficient catalyst for the reaction is in great demand. In this work, Ru was incorporated into monometallic Co/MgO-Al2O3 aerogel catalyst via supercritical drying process combined with sol–gel method and a series of Co-Ru bimetallic aerogel catalyst with different Ru contents was synthesized. Catalytic performance screening for the catalysts indicated that combination of Ru and Co significantly raised the activity of monometallic catalysts, e.g., the activity of Co15-Ru0.2 (Co content: 15 wt.%, Ru content: 0.2 wt.%) was 64.7% and 63.9% higher than those of the monometallic Co15 and Ru0.5 catalysts, respectively. The results also indicated that Co/Ru ratio had a great influence on the catalytic activity: Co15-Ru0.2 > Co15-Ru0.1 ≈ Co15-Ru0.5 > Co15-Ru0.05 > Ru0.5 > Co15. XRD, BET, H2-TPR, XPS, TEM, TG/DSC, and FESEM analyses were performed, disclosing that the reducibility and active metal particle size of the catalysts can be manipulated by the Co/Ru ratio due to the transportation of bulk Co2+ to the surface. The Co15-Ru0.2 catalyst had a mean active metal particle size below 10 nm and medium reducibility, resulting in a high activity and stable performance.
Highlights
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A Co-Ru/MgO-Al2O3 aerogel was prepared by sol-gel combined with supercritical deposition method.
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The addition of Ru destabilized the Co spinel and promoted the reduction of Co species.
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The synergy between Co-Ru promoted the catalytic performance which were better than the monometallic catalysts.
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Co15-Ru0.2 showed the highest CH4 reforming activity and resistance to inactive carbon.
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References
Jang WJ, Shim JO, Kim HM, Yoo SY, Roh HS (2019) A review on dry reforming of methane in aspect of catalytic properties. Catal Today 324:15–26
Zain MM, Mohamed AR (2018) An overview on conversion technologies to produce value added products from CH4 and CO2 as major biogas constituents. Renew Sustain Energy Rev 98:56–63
Yan X, Hu T, Liu P, Li S, Zhao B, Zhang Q (2019) Highly efficient and stable Ni/CeO2-SiO2 catalyst for dry reforming of methane: effect of interfacial structure of Ni/CeO2 on SiO2. Appl Catal B 246:221–231
Yang T, Chen W, Chen L, Liu W, Zhang D (2016) Promotion effect between Ni and Co aerogel catalysts in CH4 reforming with CO2 and O2. J CO2 Util 16:130–137
Oemar U, Hidajat K, Kawi S (2015) Pd-Ni catalyst over spherical nanostructured Y2O3 support for oxy-CO2 reforming of methane: role of surface oxygen mobility. Int J Hydrog Energy 40:12227–12238
Choudhary TV, Choudhary VR (2008) Energy-efficient syngas production through catalytic oxy-methane reforming reactions. Angew Chem Int Ed 47:1828–1847
Chen L, Huang Q, Zhang D, Liu W, Yang T (2019) Temperature programmed surface reaction test of Co–Ni bimetallic aerogel catalysts for methane reforming. React Kinet Mech Cat 126:951–962
Jabbour K, Hassan NE, Casale S, Estephane J,HE (2014) Promotional effect of Ru on the activity and stability of Co/SBA-15 catalysts in dry reforming of methane. Int J Hydrog Energy 39:7780–7787
Nagaoka K, Takanabe K, Aika K (2004) Modification of Co/TiO2 for dry reforming of methane at 2MPa by Pt, Ru or Ni. Appl Catal A 268:151–158
Itkulova SS, Zhunusova KZ, Zakumbaeva GD (2005) CO2 reforming of methane over Co-Pd/Al2O3 catalysts. B Korean Chem Soc 26:2017–2020
Chen L, Huang Q, Wang Y, Xiao H, Liu W, Zhang D, Yang T (2019) Tailoring performance of Co–Pt/MgO–Al2O3 bimetallic aerogel catalyst for methane oxidative carbon dioxide reforming: effect of Pt/Co ratio. Int J Hydrog Energy 44:1988–19889
Rui Z, Feng D, Chen H, Ji H (2014) Anodic TiO2 nanotube array supported nickel – noble metal bimetallic catalysts for activation of CH4 and CO2 to syngas. Int J Hydrog Energy 39:16252–16261
Alvarez-Galvan C, Melian M, Ruiz-Matas L, Eslava JL, Navarro RM, Ahmadi M, Cuenya BR, Fierro JLG (2019) Partial oxidation of methane to syngas over nickel-based catalysts: influence of support type, addition of rhodium, and preparation method Front Chem 7:104
Rad SJH, Haghighi M, Eslami AA, Rahmani F, Rahemi N (2016) Sol–gel vs. impregnation preparation of MgO and CeO2 doped Ni/Al2O3 nanocatalysts used in dry reforming of methane: effect of process conditions, synthesis method and support composition. Int J Hydrog Energy 41:5335–5350
Gunes H, Ozbakir Y, Barim SB, Yousefzadeh H, Bozbag SE, Erkey C (2020) A remarkable class of nanocomposites: aerogel supported bimetallic nanoparticles. Front Mater 7:18–38
Kim J, Suh DJ, Park T, Kim K (2000) Effect of metal particle size on coking during CO2 reforming of CH4 over Ni–alumina aerogel catalysts. Appl Catal A 197:191–200
Xu Z, Li Y, Zhang J, Chang L, Zhou R, Duan Z (2001) Ultrafine NiO–La2O3–Al2O3 aerogel: a promising catalyst for CH4/CO2 reforming. Appl Catal A 213:65–71
Chen M, Hallstedt B, Gauckler LJ (2003) Thermodynamic assessment of the Co-O system. J Phase Equilibria 24:212–227
Jose-Alonso DS, Uldn-Gdmez MJ, Roman-Martinez MC (2013) Low metal content Co and Ni alumina supported catalysts for the CO2 reforming of methane. Int J Hydrog Energy 38:2230–2239
Jafarbegloo M, Tarlani A, Mesbah W, Muzart J, Sahebdelfar S (2016) NiO–MgO solid solution prepared by sol–gel method as precursor for Ni/MgO methane dry reforming catalyst: effect of calcination temperature on catalytic performance. Catal Lett 146:238–248
Zhang X, Peng L, Fang X, Cheng Q, Liu W, Peng H, Gao Z, Zhou W, Wang X (2018) Ni/Y2B2O7 (BTi, Sn, Zr and Ce) catalysts for methane steam reforming: on the effects of B site replacement. Int J Hydrog Energy 43:8298–8312
Chen L, Zhu Q, Wu R (2011) Effect of Co-Ni ratio on the activity and stability of Co-Ni bimetallic aerogel catalyst for methane Oxy-CO2 reforming. Int J Hydrog Energy 36:2128–2136
Sidik SM, Triwahyono S, Jalil AA, Majid ZA, Salamun N, Talib NB (2016) CO2 reforming of CH4 over Ni–Co/MSN for syngas production: role of Co as a binder and optimization using RSM. Chem Eng J 295:1–10
Pang Y, Dou Y, Zhong A (2018) Nanostructured Ru-Co@SiO2: highly efficient yet durable for CO2 reforming of methane with a desirable H2/CO ratio. Appl Catal A 555:27–35
Takanabe K, Nagaoka K, Nariai K, Aika KI (2005) Titania-supported cobalt and nickel bimetallic catalysts for carbon dioxide reforming of methane. J Catal 232:268–275
Natile MM, Glisenti A (2002) Study of surface reactivity of cobalt oxides: interaction with methanol. Chem Mater 14:3090–3099
Wang H, Miller JT, Shakouri M, Xi C, Wu T, Zhao H (2013) XANES and EXAFS studies on metal nanoparticle growth and bimetallic interaction of Ni-based catalysts for CO2 reforming of CH4. Catal Today 207:3–12
Tang S, Ji L, Lin J, Zeng HC, Tan KL, Li K (2000) CO2 reforming of methane to synthesis gas over sol-gel-made Ni/[gamma]-Al2O3 catalysts from organometallic precursors. J Catal 194:424–430
Carvalho DC, Filho JM, Oliveira AC, Campos A, Milet ERC, Sousa FF, Padron-Hernandez E,AC (2014) A study on the modification of mesoporous mixed oxides supports for dry reforming of methane by Pt or Ru. Appl Catal A 473:132–145
Hou Z, Gao J, Guo J, Liang D, Lou H, Zheng X (2007) Deactivation of Ni catalysts during methane autothermal reforming with CO2 and O2 in a fluidized-bed reactor. J Catal 250:331–341
Zhang ZL, Verykios XE (1994) Carbon dioxide reforming of methane to synthesis gas over supported Ni catalysts. Catal Today 21:257–263
Zhang L, Wang F, Zhu J, Han B, Fan W, Zhao L (2019) CO2 reforming with methane reaction over Ni@SiO2 catalysts coupled by size effect and metal-support interaction. Fuel 256:1–10
Acknowledgements
The financial supports from the National Science foundation of China (No. 21306231), China Postdoctoral Science Foundation (No. 2018M632988), and Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds and Applications (No. 2021XGJSKFJJ01) are gratefully acknowledged.
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Chen, L., Wu, H., Chen, P. et al. Influence of Ru incorporation on the catalytic performance of Co/MgO-Al2O3 aerogel catalysts for biogas reforming. J Sol-Gel Sci Technol 99, 589–599 (2021). https://doi.org/10.1007/s10971-021-05610-1
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DOI: https://doi.org/10.1007/s10971-021-05610-1