Search Results (17)

The catalytically supported upgrading of green ethanol and green methanol mixtures can produce higher alcohols, such as iso-butanol, in a sustainable manner. Iso-butanol can be used as a feedstock to defossilize the chemical and transportation sectors. MgO-Al₂O₃ hydrotalcite-based catalysts are a promising option for this purpose. In this paper, samples were synthesized using co-precipitation and urea methods with different Mg/Al molar ratios with Ni acting as the active catalytic component. Thereby, the catalysts synthesized using the urea method exhibited the greatest activity, producing iso-butanol concentrations of up to 170 mmol L⁻¹ at 185 °C, with selectivities towards iso-butanol of 85–89% and a maximum space–time yield of 8.2 mmol g⁻¹ h⁻¹. The most active catalyst among all samples from this paper was characterized by 100% proportions of strong basic and medium acidic catalyst sites and the largest specific surface area. XRD analysis revealed the presence of NiO, MgO and the spinels Al₂NiO₄ and Al₂MgO₄ in both synthesis variants as well as elemental Ni in one sample from the urea synthesis. CO₂-TPD and NH₃-TPD experiments showed the dominance of strong basic and medium/strong acidic catalyst sites in both synthesis pathways. Full article

Ethanol upgrading via catalytic C–C coupling, commonly known as the Guerbet reaction, offers a sustainable route to produce 1-butanol, a high-performance biofuel. To address gaps in the mechanistic understanding of the catalytic reaction, we investigated the process involving a fixed-bed reactor, operated at 275–325 °C, 21 bar, and weight hourly space velocities of 0.25–2.5 g_EtOH/(g_cat·h), using helium as a carrier gas, with a 5:1 He/EtOH molar ratio. The catalyst was a MgO–Al₂O₃ mixed oxide (Mg/Al = 2:1), derived from a hydrotalcite precursor. A detailed kinetic model was developed, encompassing 15 species and 27 reversible steps (10 sorption and 17 reaction steps), within a 1+1D sorption–reaction–transport framework. Four C₄-forming pathways were included: aldol condensation to form crotonaldehyde, semi-direct coupling to form butyraldehyde and crotyl alcohol, and direct coupling to form 1-butanol. To avoid overfitting, Arrhenius parameters were grouped by reaction type, resulting in sixty rate parameters and one active site-specific density parameter. The optimized model achieved high accuracy, with an average prediction error of 1.44 times the experimental standard deviation. The mechanistic analysis revealed aldol condensation as the dominant pathway below 335 °C, with semi-direct coupling to crotyl alcohol prevailing above 340 °C. The resulting model provides a robust framework for understanding and predicting complex reaction networks in ethanol upgrading systems. Full article

The advancement in catalytic processes utilizing sustainable raw materials, such as bioethanol, represents a key scientific challenge in this century. One potential approach to producing 1-butanol, a compound primarily obtained from petroleum-derived sources, is through the Guerbet reaction. For this transformation, various multifunctional catalysts have been explored, some of which incorporate Cu and/or Ni nanoparticles that facilitate hydrogenation and dehydrogenation reactions, along with magnesium oxide, which provides the necessary acid/base functionality. To promote nanoparticle formation and maximize the exposed active surface area, high-surface-area graphite (HSAG), a hydrophobic and inert support material, emerges as a promising candidate. In this study, different catalyst formulations containing these components were tested under moderate reaction conditions, at temperatures between 440 and 580 K and a pressure of 50 bar. A strong correlation was observed between butanol selectivity and the presence of medium–high strength basic sites, complemented by moderate acidity. Furthermore, optimizing the copper and nickel loadings to 4 wt.% Cu and 1 wt.% Ni significantly minimized the formation of unwanted byproducts. The highest butanol selectivity (44%) was achieved using a 4Cu1Ni-Mg/HSAG catalyst, which had been pretreated in helium at 723 K before H₂ reduction, yielding approximately 9% 1-butanol. Full article

Hydrotalcite-derived mixed metal oxides (MgAlO)-based catalysts are used for the catalytic upgrade of ethanol to butanol which adjust the catalyst structure and number of relevant active sites through changes in the Mg/Al ratio. By performing a series of reaction activity tests, kinetic experiments, FTIR characterization, CO₂-TGA analysis, and in situ active center titration, qualitative and quantitative relationships between catalyst structure and catalytic performance are obtained. We found the MgAlO mixed metal oxide system can catalyze the ethanol-to-butanol process through a Guerbet reaction pathway, though the process is kinetically limited. The data suggest that strong basic centers hosted in Mg-O sites are the most catalytically relevant function in the MgAlO material, as they control enolate formation, which is likely the rate limiting step of the aldol condensation stage in the Guerbet reaction. Full article

This study investigates the potential of bimetallic alloy catalysts, specifically Ni₉₉Pt₁, Cu₉₉Ni₁, Cu₉₉Fe₁, Fe₉₉Pt₁, and Fe₉₉Pd₁, for the synthesis of isobutanol via the Guerbet route. The catalysts were synthesized with a doping of 1 at% Ni, Fe, Pt, and Pd in the base metals Fe, Cu, and Ni. The catalytic properties of these bimetallic alloy catalysts were explored for their potential for promoting the Guerbet reaction. The study aims to test the usability of the theoretically predicted d-band values in the synthesized bimetallic catalysts, which were prepared by means of incipient wetness impregnation, and shows that doping amounts smaller than 1 at% already significantly improved the catalytic activity of the base metals. In particular, the doping of nickel with platinum yielded an effective catalyst for the synthesis of isobutanol via the Guerbet pathway. The Ni₉₉Pt₁/C catalyst from the presented experiments had the highest Space Time Yield (STY) and is, therefore, also a promising catalyst for the hydrogen-borrowing reactions class. Full article

Mixtures of ethanol and methanol being synthesized from CO₂ and green H₂ can serve as sustainable base chemicals for a number of chemical processes. Amongst these processes, the catalytically supported synthesis of CO₂-neutral C₄ to C₁₀ alcohols is of increasing importance as, e.g., iso-butanol can be used as a drop-in fuel or after dehydration to produce iso-butene as a feedstock for the synthesis of plastics. 2-ethyl-hexanol can be further refined into solvents, tensides, or monomers. In this respect, NiPt alloys on an activated carbon support were found to be active and stable catalysts for the synthesis of iso-butanol following the Guerbet reaction scheme. In this study, two different routes are applied to the synthesis of these NiPt catalysts: a more conventional one based on the impregnation of Ni and Pt salts and an advanced path with a surface redox reaction between elemental Ni on the support and Pt ions in a polar solution. The experimental evaluation shows that the Pt particles from the surface redox reaction being exposed on the Ni particles are more active than those on the impregnated catalysts due to their high surface energy. Their specific space-time yields are 10–20 times higher. Full article

Catalytic conversion of biomass-derived ethanol into n-butanol through Guerbet coupling reaction has become one of the key reactions in biomass valorization, thus attracting significant attention recently. Herein, a series of supported Cu catalysts derived from Ni-based hydrotalcite (HT) were prepared and performed in the continuous catalytic conversion of ethanol into butanol. Among the prepared catalysts, Cu/NiAlO_x shows the best performance in terms of butanol selectivity and catalyst stability, with a sustained ethanol conversion of ~35% and butanol selectivity of 25% in a time-on-stream (TOS) of 110 h at 280 °C. While for the Cu/NiFeO_x and Cu/NiCoO_x, obvious catalyst deactivation and/or low butanol selectivity were obtained. Extensive characterization studies of the fresh and spent catalysts, i.e., X-ray diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Hydrogen temperature-programmed reduction (H₂-TPR), reveal that the catalysts’ deactivation is mainly caused by the support deconstruction during catalysis, which is highly dependent on the reducibility. Additionally, an appropriate acid–base property is pivotal for enhancing the product selectivity, which is beneficial for the key process of aldol-condensation to produce butanol. Full article

The catalytic upgrading of ethanol into butanol through the Guerbet coupling reaction has received increasing attention recently due to the sufficient supply of bioethanol and the versatile applications of butanol. In this work, four different supported Cu catalysts, i.e., Cu/Al₂O₃, Cu/NiO, Cu/Ni₃AlO_x, and Cu/Ni₁AlO_x (Ni²⁺/Al³⁺ molar ratios of 3 and 1), were applied to investigate the catalytic performances for ethanol conversion. From the results, Ni-containing catalysts exhibit better reactivity; Al-containing catalysts exhibit better stability; but in terms of ethanol conversion, butanol selectivity, and catalyst stability, a corporative effect between Ni–Al catalytic systems can be clearly observed. Combined characterizations such as XRD, TEM, XPS, H₂-TPR, and CO₂/NH₃-TPD were applied to analyze the properties of different catalysts. Based on the results, Cu species provide the active sites for ethanol dehydrogenation/hydrogenation, and the support derived from Ni–Al–LDH supplies appropriate acid–base sites for the aldol condensation, contributing to the high butanol selectivity. In addition, catalysts with strong reducibility (i.e., Cu/NiO) may be easily deconstructed during catalysis, leading to fast deactivation of the catalysts in the Guerbet coupling process. Full article

Catalytic conversion of ethanol to 1-butanol was studied over MgO–Al₂O₃ mixed oxide-based catalysts. Relationships between acid-base and catalytic properties and the effect of active metal on the hydrogen transfer reaction steps were investigated. The acid-base properties were studied by temperature-programmed desorption of CO₂ and NH₃ and by the FT-IR spectroscopic examination of adsorbed pyridine. Dispersion of the metal promoter (Pd, Pt, Ru, Ni) was determined by CO pulse chemisorption. The ethanol coupling reaction was studied using a flow-through microreactor system, He or H₂ carrier gas, WHSV = 1 ${\mathrm{g}}_{\mathrm{E}\mathrm{t}\mathrm{O}\mathrm{H}}·{\mathrm{g}}_{\mathrm{c}\mathrm{a}\mathrm{t}.}^{-1}·{\mathrm{h}}^{-1}$, at 21 bar, and 200–350 °C. Formation and transformation of surface species under catalytic conditions were studied by DRIFT spectroscopy. The highest butanol selectivity and yield was observed when the MgO–Al₂O₃ catalyst contained a relatively high amount of strong-base and medium-strong Lewis acid sites. The presence of metal improved the activity both in He and H₂; however, the butanol selectivity significantly decreased at temperatures ≥ 300 °C due to acceleration of undesired side reactions. DRIFT spectroscopic results showed that the active metal promoted H-transfer from H₂ over the narrow temperature range of 200–250 °C, where the equilibrium allowed significant concentrations of both dehydrogenated and hydrogenated products. Full article

The direct conversion of biomass-derived ethanol to high-valued-added chemicals has attracted widespread attention recently due to the great economic and environmental advantages. In the present study, the conversion of bioethanol through the Guerbet coupling process was studied in a fixed-bed reactor for MgAlO_x and ZnAlO_x mixed-oxides supported Cu catalysts. From the results, Cu adding into the system greatly enhance the dehydrogenation of ethanol and increase the H-transfer in the course of Guerbet coupling process. Simultaneously, the porous mixed-oxides provide the acid-base property of the catalysts for intermediate transformation. Notably, for Cu/MgAlO_x, the main product of ethanol conversion is butanol, but for Cu/ZnAlO_x, the primary product is ethyl acetate. Characterizations such as X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and CO₂ temperature programmed desorption (TPD) were carried out to evaluate the structure and property of the catalysts. In combination with the catalytic performances with the characterization results, the synergistic catalytic effect between metal sites and acid-base sites were elaborated. Full article

Being the major renewable source of bio-aromatics, lignin possesses considerable potential for the chemical industry as raw material. Kraft lignin is a couple product of paper industry with an annual production of 55,000,000 ton/y and is considered the largest share of available lignin. Here we report a facile approach of Kraft lignin depolymerization to defined oligomeric units with yields of up to 70 wt.%. The process implies utilization of an aqueous base in combination with a metal containing catalyst and an alcohol under non-oxidative atmosphere at 300 °C. An advantage of the developed approach is the facile separation of the oligomer product that precipitates from the reaction mixture. In addition, the process proceeds without char formation; both factors make it attractive for industrialization. The suppression of the repolymerization processes that lead to char formation is possible when the combination of metal containing catalyst in the presence of an alcohol is used. It was found that the oligomer units have structural features found in phenol-acetaldehyde resins. These features result from the base catalyzed condensation of lignin fragments with in situ formed aldehydes. Catalytic dehydrogenation of the alcohol provides the latter. This reaction pathway is confirmed by the presence condensation products of Guerbet type reactions. Full article

The purpose of the study was the development of water-resistant catalyst and catalytic processes for the conversion of hydrous ethanol to 1-butanol. Water, in hydrous ethanol, strongly inhibits conversion to 1-butanol on solid catalysts. In this study, the nonstoichiometric P-deficient hydroxyapatite containing carbonate anions (C-HAP), Ca_10−x/2(PO₄)_6−x(CO₃)_x(OH)₂, displayed good performance in the Guerbet condensation of hydrated ethanol to 1-butanol, after proper stabilization of reaction conditions. Hydrous ethanol (96 wt%) was converted on C-HAP formed as extrudates with silica binder at 400 °C and weight hour space velocity (WHSV) = 0.5–1.0 h⁻¹ to yield 21–23% 1-butanol and 73–74% selectivity. It displayed stable operation for up to 170 h on streams conducted in bench and mini-pilot rigs with catalyst loadings of 2 and 50 cm³, respectively. The process simulation employed the recycling of ethanol without laboratory verification to reach 68% theoretical yield of 1-butanol. The techno-economic analysis demonstrated the feasibility of this process, showing that it may be profitable depending on the prices of hydrated ethanol and 1-butanol. Full article

To upgrade biomass-derived alcohol mixtures to biofuels under solvent-free conditions, MgO–Al₂O₃ mixed metal oxides (MMO) decorated with Ni nanoparticles (Ni–MgO–Al₂O₃) are synthesized and characterized. Based on the result, Ni nanoparticles are highly dispersed on the surface of MgAl MMO. As the Ni loading content varies from 2 to 10 wt.%, there is a slight increase in the mean Ni particle size from 6.7 to 8.5 nm. The effects of Ni loading amount, reducing temperature, and Mg/Al ratio on the conversion and product distribution are investigated. With the increase in both the Ni loading amount and reducing temperature, dehydrogenation (the first step of the entire reaction network) is accelerated. This results in an increase in the conversion process and a higher selectivity for the dialkylated compounds. Due to the higher strength and density of basic sites under high Mg/Al ratios, double alkylation is preferred and more long-chain hydrocarbons are obtained. A conversion of 89.2% coupled with a total yield of 79.9% for C₅–C₁₅ compounds is acquired by the as-prepared catalyst (prepared with Ni loading of 6 wt.%, reducing temperature of 700 °C, and Mg/Al molar ratio of 3. After four runs, the conversion drops by 17.1%, and this loss in the catalytic activity can be attributed to the decrease in the surface area of the catalyst and the increase in the Ni mean particle size. Full article

As the search for carbon-efficient synthesis pathways for green alternatives to fossil fuels continues, an expanding class of catalysts have been developed for the upgrading of lower alcohols. Understanding of the acid base functionalities has greatly influenced the search for new materials, but the influence of the metal used in catalysts cannot be explained in a broader sense. We address this herein and correlate our findings with the most fundamental understanding of chemistry to date by applying it to d-band theory as part of an experimental investigation. The commercial catalysts of Pt, Rh, Ru, Cu, Pd, and Ir on carbon as a support have been characterized by means of SEM, EDX-mapping, STEM, XRD, N₂-physisorption, and H₂-chemisorption. Their catalytic activity has been established by means of c-methylation of ethanol with methanol. For all catalysts, the TOF with respect to i-butanol was examined. The Pt/C reached the highest TOF with a selectivity towards i-butanol of 89%. The trend for the TOFs could be well correlated with the d-band centers of the metal, which formed a volcano curve. Therefore, this study is another step towards the rationalization of catalyst design for the upgrading of alcohols into carbon-neutral fuels or chemical feedstock. Full article

The self-condensation and cross-condensation reactions of ethanol and isoamyl alcohol are examined to better understand the potential routes to value-added byproducts from fuel ethanol production. Reactions have been carried out in both batch autoclave and continuous condensed-phase reactors using a lanthanum-promoted, alumina-supported nickel catalyst at near-critical condensed phase conditions. Analysis of multiple candidate kinetic models led to a Langmuir–Hinshelwood rate expression that is first-order in alcohol with water as the strongly adsorbed species. This model provides the best fit of data from both batch and continuous reactor experiments. Activation energies for primary condensation reactions increase as carbon chain lengths increase. Selectivities to higher alcohols of 94% and 87% for ethanol and isoamyl alcohol, respectively, were observed at different operating conditions. Full article