Publications
105 results found
Kennema M, de Castro IBD, Meemken F, et al., 2017, Liquid-phase H-transfer from 2-propanol to phenol on Raney Ni: surface processes and inhibition, ACS Catalysis, Vol: 7, Pages: 2437-2445, ISSN: 2155-5435
Raney Ni is perhaps the most widely used catalyst for the transformation of biogenic molecules in industrial practice (e.g., as in the production of sugar alcohols and hardening of vegetable oils). Currently, Raney Ni has found another key application; the catalytic upstream biorefining (CUB) of lignocellulose in which the soluble products released from the lignocellulosic matrix undergo reductive processes, rendering depolymerized lignin oils in addition to high-quality holocellulosic pulps. Despite the industrial importance of Raney Ni, its surface chemistry is poorly understood. In this study, using the H-transfer reaction between 2-propanol (2-PrOH) and phenol as a model reaction, we studied the influence of various alcohols on the catalytic performance of Raney Ni. For the H-transfer hydrogenation of phenol to cyclohexanol, the inhibition of the catalyst increases in the order of secondary alcohols < primary alcohols < polyols at 130 °C. To better understand the observed inhibition, we also studied the molecular interactions of the various alcohols at the catalytic solid–liquid interface using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. The in situ spectroscopic data revealed that 2-PrOH adsorbs on at least two chemically different sites on the surface of Raney Ni. One of these two adsorption sites was attributed to the Ni site responsible for the saturation of the phenolic ring. The ATR-IR spectroscopic data also shows that the adsorption of phenol involves its hydroxyl group. Notably, the phenolic ring was found to be tilted with respect to the surface. Competitive adsorption of various other alcohols was also investigated at the catalytic solid–liquid interface. The presence of methanol inhibited the adsorption of 2-PrOH to a significantly greater degree than phenol. Therefore, it is proposed that hydrogen transfer hydrogenation of the phenolic ring is inhibited in the presence of additional alcohols mainly due t
Calvaruso G, Burak JA, Clough MT, et al., 2017, On the Reactivity of Dihydro-p-coumaryl Alcohol towards Reductive Processes Catalyzed by Raney Nickel, CHEMCATCHEM, Vol: 9, Pages: 2627-2632, ISSN: 1867-3880
Cao Z, Engelhardt J, Dierks M, et al., 2017, Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil, Angewandte Chemie, Vol: 129, Pages: 2374-2379, ISSN: 0044-8249
Calvaruso G, Clough MT, Rinaldi R, 2017, Biphasic extraction of mechanocatalytically-depolymerized lignin from water-soluble wood and its catalytic downstream processing, GREEN CHEMISTRY, Vol: 19, Pages: 2803-2811, ISSN: 1463-9262
Cao Z, Engelhardt J, Dierks M, et al., 2017, Catalysis meets nonthermal separation for the production of (alkyl)phenols and hydrocarbons from pyrolysis oil., Angewandte Chemie International Edition, Vol: 56, Pages: 2334-2339, ISSN: 1433-7851
A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoCx /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules.
de Oliveira HFN, Clough MT, Rinaldi R, 2016, Thermally Triggered Phase Separation of Organic Electrolyte-Cellulose Solutions, CHEMSUSCHEM, Vol: 9, Pages: 3324-3329, ISSN: 1864-5631
Ferrini P, Rezende CA, Rinaldi R, 2016, Catalytic Upstream Biorefining through Hydrogen Transfer Reactions: Understanding the Process from the Pulp Perspective, CHEMSUSCHEM, Vol: 9, Pages: 3171-3180, ISSN: 1864-5631
Gallo JMR, Rinaldi R, 2016, Editorial, Journal of Molecular Catalysis A: Chemical, Vol: 422, Pages: 1-2, ISSN: 1381-1169
Wang GH, Cao Z, Gu D, et al., 2016, Nitrogen-doped ordered mesoporous carbon supported bimetallic PtCo nanoparticles for upgrading of biophenolics, Angewandte Chemie International Edition, Vol: 55, Pages: 8850-8855, ISSN: 1433-7851
Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity.
Rinaldi R, Jastrzebski R, Clough MT, et al., 2016, Wege zur Verwertung von Lignin: Fortschritte in der Biotechnik, der Bioraffination und der Katalyse, Angewandte Chemie, Vol: 128, Pages: 8296-8354, ISSN: 0044-8249
Rinaldi R, Jastrzebski R, Clough MT, et al., 2016, Paving the way for lignin valorisation: recent advances in bioengineering, biorefining and catalysis, Angewandte Chemie - International Edition, Vol: 55, Pages: 8164-8215, ISSN: 1433-7851
Lignin is an abundant biopolymer with a high carbon content and high aromaticity. Despite its potential as a raw material for the fuel and chemical industries, lignin remains the most poorly utilised of the lignocellulosic biopolymers. Effective valorisation of lignin requires careful fine-tuning of multiple “upstream” (i.e., lignin bioengineering, lignin isolation and “early-stage catalytic conversion of lignin”) and “downstream” (i.e., lignin depolymerisation and upgrading) process stages, demanding input and understanding from a broad array of scientific disciplines. This review provides a “beginning-to-end” analysis of the recent advances reported in lignin valorisation. Particular emphasis is placed on the improved understanding of lignin's biosynthesis and structure, differences in structure and chemical bonding between native and technical lignins, emerging catalytic valorisation strategies, and the relationships between lignin structure and catalyst performance.
Chesi C, de Castro IBD, Clough MT, et al., 2016, The Influence of Hemicellulose Sugars on Product Distribution of Early-Stage Conversion of Lignin Oligomers Catalysed by Raney Nickel, Chemcatchem, Vol: 8, Pages: 2079-2088, ISSN: 1867-3899
We recently introduced catalytic upstream biorefining, a fractionation process performed on whole lignocellulosic materials, based on the early-stage conversion of lignin by hydrogen-transfer reactions (using Raney Ni as the catalyst and 2-PrOH as a hydrogen-donor). The process fractionates lignocellulose, isolating lignin as an extensively depolymerised oil, opening up new avenues in the catalytic upgrading of bio-derived phenolic streams to chemicals and fuels. In addition, highly delignified holocellulose pulps are obtained, holding potential as a feedstock for the production of paper, chemicals, and biofuels. Herein, we report our first results on the chemistry underlying this process under nearly neutral to slightly alkaline conditions achieved by the addition of inorganic bases. This report sheds light on the influence of hemicellulose sugars on the product distribution obtained from the early-stage catalytic conversion of lignin oligomers released from lignocellulose. The increase in the pH value of the medium suppressed the hydrolysis of xylans. As a result, a dramatic increase in the xylans retention from 10 % (at pH 4.5) up to 60 % (at pH>7.5) was achieved. Interestingly, the pH value of the liquor did not affect the delignification extent of lignocellulose or the absolute content of glucans retained in the holocellulose. By enhancing xylans retention, we provide evidence that hemicellulose sugars decrease the activity of Raney Ni towards full hydrogenation of the aromatic species composing the lignin stream. In fact, the yield of selected cyclohexanols increases from 0.8 % (no added bases) to 4.4 % (added NaOH), whereas the yield of selected phenols decreases from 12.9 % (no added bases) to 7.2 % (added NaOH).
Wang X, Rinaldi R, 2016, Bifunctional Ni catalysts for the one-pot conversion of Organosolv lignin into cycloalkanes, Catalysis Today, Vol: 269, Pages: 48-55, ISSN: 1873-4308
de Oliveira HFN, Farès C, Rinaldi R, 2015, Beyond a solvent: The roles of 1-butyl-3-methylimidazolium chloride in the acid-catalysis for cellulose depolymerisation, Chemical Science, Vol: 6, Pages: 5215-5224, ISSN: 2041-6539
In this report, 1-butyl-3-methylimidazolium chloride ([C4C1im]Cl) is demonstrated to enhance the kinetics of acid-catalysed hydrolysis of 1,4-β-glucans in binary solvent mixtures. [C4C1im]Cl plays other roles in the reaction beyond acting as a solvent for cellulose, as currently accepted. In fact, the presence of the IL increases the Hammett acidity of the catalyst dissolved in the reaction medium. The kinetic data from cellobiose and cellulose hydrolysis directly correlate with the acid strength found for p-toluenesulfonic acid in the different reaction media studied here. The current report identifies neglected, but yet very important phenomena occurring in cellulose depolymerisation.
Ji N, Wang X, Weidenthaler C, et al., 2015, Iron(II) disulfides as precursors of highly selective catalysts for hydrodeoxygenation of dibenzyl ether into toluene, ChemCatChem, Vol: 7, Pages: 960-966, ISSN: 1867-3880
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. In this report, we show that nanocrystalline pyrite and marcasite (FeS 2 ), supported on SBA-15, aerosil SiO 2 , activated carbon or Al 2 O 3 , are precursors of highly active catalysts for the hydrodeoxygenation of dibenzyl ether into toluene. High yields of toluene (up to 100 %) were achieved in experiments performed at 250 C under initial H 2 pressure of 100 bar for 2 h. In the recycling experiments, results from XRD and XPS analyses indicate that a fresh surface, formed upon the chemical transformation of FeS 2 into Fe (1-x) S, is responsible for the high activity and high selectivity achieved in the conversion of dibenzyl ether into toluene.
Ji N, Wang X, Weidenthaler C, et al., 2015, Iron (II) Disulfides as Precursors of Highly Selective Catalysts for Hydrodeoxygenation of Dibenzyl Ether into Toluene, ChemCatChem, Vol: 7, Pages: 960-966, ISSN: 1867-3899
Bruijnincx PCA, Rinaldi R, Weckhuysen BM, 2015, Unlocking the potential of a sleeping giant: lignins as sustainable raw materials for renewable fuels, chemicals and materials, GREEN CHEMISTRY, Vol: 17, Pages: 4860-4861, ISSN: 1463-9262
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Kaufman Rechulski MD, Käldström M, Richter U, et al., 2015, Mechanocatalytic depolymerization of lignocellulose performed on hectogram-and kilogram-scales, Industrial & Engineering Chemistry Research, ISSN: 0888-5885
de Oliveira HFN, Rinaldi R, 2015, Understanding Cellulose Dissolution: Energetics of Interactions of Ionic Liquids and Cellobiose Revealed by Solution Microcalorimetry
Käldström M, Meine N, Farès C, et al., 2014, Erratum: Deciphering 'water-soluble lignocellulose' obtained by mechanocatalysis: New insights into the chemical processes leading to deep depolymerization (Green Chemistry (2014) 16 (3528-3538)), Green Chemistry, Vol: 16, Pages: 4994-4994
Rinaldi R, 2014, Solvents and Solvent Effects in Biomass Conversion, Catalytic Hydrogenation for Biomass Valorization, Editors: Rinaldi, Publisher: Royal Society of Chemistry, ISBN: 9781849738019
Rinaldi R, 2014, Catalytic Hydrogenation for Biomass Valorization, Publisher: Royal Society of Chemistry, ISBN: 9781849738019
The efficient conversion of biomass to value-added products has become a major research area in the pursuit of alternatives to petroleum-based feedstocks; hydrogenation and hydrogenolysis are important tools to achieving this aim. This book presents comprehensive coverage of the different catalysts for these reactions, targeting the efficient conversion of bio-based molecules and biopolymers.The editor, Roberto Rinaldi, is an acknowledged leader in the field of biomass conversion, and has brought together experts from across the globe to examine all aspects of the process, including the solvents, catalysts and feedstocks used in modern biorefineries. Consideration is also given to the fundamentals of running a plant, such as equipment and safety issues.As the biorefinery industry expands to meet the latest discoveries in biomass conversion, this book provides a thorough grounding in the subject and is an essential reference to researchers at the forefront of discovering new products, companies wishing to scale-up biomass conversion, and postgraduate students of sustainable chemistry and chemical engineering.
Ferrini P, Rinaldi R, 2014, Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions, Angewandte Chemie International Edition, Vol: 53, Pages: 8634-8639, ISSN: 1433-7851
Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin—a non‐pyrolytic lignin bio‐oil—in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio‐oil is highly susceptible to further hydrodeoxygenation under low‐severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported.
Rinaldi R, Wang X, 2014, Lignin into arenes: A new platform for the production of liquid fuels by catalytic H-transfer reactions, 248th National Meeting of the American-Chemical-Society (ACS), Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727
de Oliveira HFN, Rinaldi R, 2014, On the promoting effects of salts upon acid-catalyzed hydrolysis of 1,4-β-glucans, 248th National Meeting of the American-Chemical-Society (ACS), Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727
Käldström M, Meine N, Farès C, et al., 2014, Deciphering 'water-soluble lignocellulose' obtained by mechanocatalysis: New insights into the chemical processes leading to deep depolymerization, Green Chemistry, Vol: 16, Pages: 3528-3538
Rinaldi R, 2014, Plant biomass fractionation meets catalysis, Angewandte Chemie - International Edition, Vol: 53, Pages: 8559-8560
Käldström M, Meine N, Farès C, et al., 2014, Fractionation of 'water-soluble lignocellulose' into C5/C 6 sugars and sulfur-free lignins, Green Chemistry, Vol: 16, Pages: 2454-2462
Geboers J, Wang X, De Carvalho AB, et al., 2014, Densification of biorefinery schemes by H-transfer with Raney Ni and 2-propanol: A case study of a potential avenue for valorization of alkyl levulinates to alkyl γ-hydroxypentanoates and γ-valerolactone, Journal of Molecular Catalysis A: Chemical, Vol: 388-389, Pages: 106-115
Schüth F, Rinaldi R, Meine N, et al., 2014, Mechanocatalytic depolymerization of cellulose and raw biomass and downstream processing of the products, Catalysis Today, Vol: 234, Pages: 24-30
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