Bimetallic Cu-Ni catalysts supported on MCM-41 and Ti-MCM-41 porous materials for hydrodeoxygenation of lignin model compound into transportation fuels

Significance 

Bio-oils are becoming alternatives to fossil fuels in view of the ever rising global energy demands, greenhouse emissions, and crude oil shortage. Bio-oils extracted from lignocellulosic biomass are composed of multicomponent molecules extracted from lignin, cellulose, and hemicellulose. The lignin component of lignocellulose is a promising renewable feedstock for the production of a number of chemicals and fuels. Lignin has an advantage over its counterparts hemicellulose and cellulose considering that bio-oils extracted from lignin can be upgraded to higher quality transportation fuels. This is in view of the high stability of the lignin aromatic structures with reference to resonance stabilization.

Fast pyrolysis has been an extensively applied method for converting lignin into bio-oil. Unfortunately, the potential of the resulting bio-oil is limited by the presence of a number of oxygenated functional groups, which in consequence lead to undesirable physicochemical attributes including low thermal and chemical stability, low heating values, easy corrosiveness and high density. In addition, lignin-extracted bio-oils are incompatible with either direct use or in combination with a petroleum fraction. This has forced researchers to look for alternative strategies which can enhance the commercial viability of lignin-extracted bio-fuels for use as a transportation fuel.

One method to remove chemically bonded oxygen from lignin-extracted oil and therefore enable the use of lignin-extracted bio-fuels is through catalytic hydrodeoxygenation processes. However, the direct application of catalysts in such processes is associated with numerous challenges owing to the complex nature of its oxygenated aromatic elements such as anisole, furan, benzofuran, and phenols. In order to overcome these issues, heterogeneous catalysts are attracting much attention, containing both a metal centre for the hydrogenation of the acidic support and an aromatic ring for the deoxygenation. While noble metals such as platinum, palladium, and ruthenium have been used in this process, their application is limited by the high cost and scarcity of these noble metals. Therefore, researchers have focused their attention on transition metal based catalysts including cobalt, nickel, iron, and copper-nickel.

Putla Sudarsanam and Suresh Bhargava at the Centre for Advanced Materials and Industrial Chemistry, School of Science, RMIT University in Australia in collaboration with Murtala Ambursa, Lee Hwei Voon, and Sharifah Bee Abd Hamid at the University of Malaya investigated the preparation, characterization and catalytic application of bimetallic Cu-Ni catalysts supported on Ti-MCM-41 for the hydrodeoxygenation of guaiacol. Their research work is published in the journal Fuel Processing Technology.

The authors prepared Cu-Ni catalysts supported on either Ti-MCM-41 or pure MCM-41 and compared their catalytic efficiencies for the hydrodeoxygenation of guaiacol. They performed the catalytic experiments in an autoclave reactor and investigated the effect of hydrogen pressure on guaiacol conversion as well as product selectivity.

Through the catalytic activity investigation, the authors observed that the CuNi/Ti-MCM-41 catalysts had a higher catalytic performance in guaiacol conversion as well as cyclohexane selectivity as opposed to a CuNi/MCM-41 catalyst. The high catalytic activity of the CuNi/Ti-MCM-41 catalyst was as a result of the cooperative function of the larger surface area, hexagonal pore geometry, medium-sized mesopores, adequate acidic sites, and excellent redox attributes. For this reason, Ti-MCM-41 is an efficient catalyst support for the hydrodeoxygenation of oxygenated elements to saturated hydrocarbons.

The research team also found that increased hydrogen pressures improved the guaiacol conversion and selectivity of the oxygenated compounds to hydrocarbons over the Ti-MCM-41 supported CuNi catalyst, increasing the impact of these catalysts within this important field of research.

Bimetallic Cu-Ni catalysts supported on MCM-41 and Ti-MCM-41 porous materials- renewable energy global innovations

About the author

Dr. Putla Sudarsanam obtained his PhD in chemistry at the CSIR-Indian Institute of Chemical Technology (Hyderabad, India) in 2015. He is currently working at the KU Leuven (Leuven, Belgium) as a Marie Curie individual post-doctoral fellow on the topic of designing nanostructured metal oxide based catalysts for the efficient conversion of agricultural bio-waste to produce biodegradable polymer building blocks and fuel grade chemicals.

He has been honoured for his work with many prestigious awards/fellowships including the Marie Skłodowska-Curie individual post-doc fellowship (2017); participation in the 67th Lindau Nobel Laureate meeting (Germany, 2017); Leibniz-DAAD post-doc fellowship (Germany, 2016);  all India level best PhD thesis award (Catalysis Society of India, 2015); EFCATS PhD student award (XIth EuropaCat conference, France, 2013); Australian endeavour research fellowship (Australia, 2013) and many others.

His expertise is mainly designing novel nanostructured metal oxide based catalysts for the 1) selective conversion of alcohols, olefins, and amines to useful fine chemicals; 2) transformation of renewable biomass feedstocks to value-added fine chemicals and bio-fuels and 3) efficient catalytic abatement of auto-exhaust pollutants (e.g., carbon monoxide, particulate matter, and nitrogen oxides). He has contributed over 44 refereed journal articles and 1 book chapter. He has in excess of 1170 citations with an h-index of 23 and an i10-index of 29.

About the author

Professor Bhargava is a world-renowned interdisciplinary scientist and is recognised for delivering research excellence that underpins significant industrial applications. As a passionate advocate in the application of technological science and engineering to innovation, he provides consultancy and advisory services to many government and industrial bodies around the world including BHP Billiton, Alcoa World Alumina, Rio Tinto and Mobil Exxon. He was also a member of the independent board of directors of one of the Aditya Birla group of industries. Out of his 7 patents, 5 have been adopted by the industrial partners and one has been licenced for commercialization.

During his distinguished career, Professor Bhargava has been awarded many prestigious national and international awards including the 2017 Non-Resident Indian of the Year Award by the TIMES Network. This award recognised him as the most outstanding Indian academic in the Asia-Pacific region, with the Bombay ceremony being broadcast to more than 110 countries around the world. Other notable awards he has received include the 2016 Khwarizmi International Award (KIA) by the Government of Iran, the 2015 CHEMECA medal (The most prestigious award in the chemical engineering profession in Australia and New Zealand), the highly esteemed Indian National Science Academy’s P. C. Ray Chair (distinguished lecture series 2014), RMIT University Vice Chancellor’s Research Excellence Award (2006 and 2014), and the Applied Research Award (2013) and the R. K. Murphy Medal (2008) from the Royal Australian Chemical Institute. He is also an elected fellow of six learned academies around the world including the Australian Academy of Technological Sciences and Engineering and the National Academy of Sciences, India.

Professor Bhargava has contributed over 410 refereed journal articles, 1 book and 10 book chapters. He has also co-authored more than 200 refereed full conference papers. He has in excess of 9,700 citations (5/day) with an h-index of 47 and an i10-index of 242.

He has strived over the years to create solid and sustainable global research partnerships to improve and advance Science and Technology. The establishment of the Indian Institute of Chemical Technology (IICT)-RMIT joint research centre, which is jointly funded by the Government of India (CSIR) and RMIT University, is one of the best examples of his international efforts. He has also applied this innovative model to connect RMIT University with the Academy of Scientific and Innovative Research (AcSIR), linking RMIT with a network of CSIR laboratories across India.

Reference

Murtala M. Ambursa, Putla Sudarsanam, Lee Hwei Voon, Sharifah Bee Abd Hamid, Suresh K. Bhargava. Bimetallic Cu-Ni catalysts supported on MCM-41 and Ti-MCM-41 porous materials for hydro-deoxygenation of lignin model compound into transportation fuels. Fuel Processing Technology, volume 162 (2017), pages 87–97.

 

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