Ethanol Coupling Reactions over MgO-Al2O3 Mixed Oxide-Based Catalysts for Producing Biofuel Additives.

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 gEtOH·gcat.-1·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.

Catalytic Decomposition of Long-Chain Olefins to Propylene via Isomerization-Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene-Ruthenium Olefin Metathesis Catalysts.

One of the most exciting scientific challenges today is the catalytic degradation of non-biodegradable polymers into value-added chemical feedstocks. The mild pyrolysis of polyolefins, including high-density polyethylene (HDPE), results in pyrolysis oils containing long-chain olefins as major products. In this paper, novel bicyclic (alkyl)(amino)carbene ruthenium (BICAAC-Ru) temperature-activated latent olefin metathesis catalysts, which can be used for catalytic decomposition of long-chain olefins to propylene are reported. These thermally stable catalysts show significantly higher selectivity to propylene at a reaction temperature of 75 °C compared to second generation Hoveyda-Grubbs or CAAC-Ru catalysts under ethenolysis conditions. The conversion of long-chain olefins (e.g., 1-octadecene or methyl oleate) to propylene via isomerization-metathesis is performed by using a (RuHCl)(CO)(PPh3 )3 isomerization co-catalyst. The reactions can be carried out at a BICAAC-Ru catalyst loading as low as 1 ppm at elevated reaction temperature (75 °C). The observed turnover number and turnover frequency are as high as 55 000 and 10 000 molpropylene molcatalyst -1 h-1 , respectively.

Evaluation of Co/SSZ-13 Zeolite Catalysts Prepared by Solid-Phase Reaction for NO-SCR by Methane.

Co/SSZ-13 zeolites were prepared by heating the finely dispersed mixture of NH4-SSZ-13 and different cobalt salts up to 550 °C. Investigations by thermogravimetry - differential scanning calorimetry - mass spectrometry provided new insight into details of the solid-state reaction. Formation of Co carrying hydrate melt or volatile species was shown to proceed from chloride, nitrate, or acetylacetonate Co precursor salts upon thermal treatment. This phase change allows the transport of the Co species into the zeolite pores. The reaction of the NH4+ or H+ zeolite cations and the mobile Co precursors generates vapor or gas products, readily leaving the zeolite pores, and cobalt ions in lattice positions suggesting that solid-state ion-exchange is the prevailing process. The obtained catalysts are of good activity and N2 selectivity in the CH4/NO-SCR reaction. The thermal treatment of acetate or formate salts give solid intermediates that are unable to get in contact and react with the cations in the zeolite micropores. These catalysts contain mainly Co-oxide clusters located on the outer surface of the zeolite crystallites and have poor catalytic performance.

Hydrocracking of Fischer-Tropsch Paraffin Mixtures over Strong Acid Bifunctional Catalysts to Engine Fuels.

Biomass-based Fischer-Tropsch paraffin mixtures, having C16-C46 and C11-C45 carbon number range, were hydrocracked over platinum-supported beta, ZSM-5, and mordenite catalysts. The aim of the study was to investigate the effects of the feedstock composition, the process parameters, and the catalyst properties (acidity and zeolite structure) on the C21+ conversions, the product yields, and the isoparaffin contents. It was stated that lower C21+ conversions and higher JET and diesel fuel yields can be obtained for feedstock comprising C11-C45 hydrocarbons. Under identical reaction conditions, the activity order of the catalysts was Pt/H-beta > Pt/H-ZSM-5 > Pt/H-mordenite. This order corresponds to the relative number of accessible acid sites. Among the tested catalysts, platinum-supported beta zeolite showed the highest hydroisomerization activity; meanwhile, in the pores of Pt/ZSM-5 and Pt/H-mordenite, diffusion constraints were observed. As the product of hydrocracking valuable gasoline, JET and diesel fuels having high hydrogen content and excellent burning properties were produced.

Diesel fuel blending components from mixture of waste animal fat and light cycle oil from fluid catalytic cracking.

Sustainable production of renewable fuels has become an imperative goal but also remains a huge challenge faced by the chemical industry. A variety of low-value, renewable sources of carbon such as wastes and by-products must be evaluated for their potential as feedstock to achieve this goal. Hydrogenation of blends comprising waste animal fat (≤70 wt%) and low-value fluid catalytic cracking light cycle oil (≥30 wt%), with a total aromatic content of 87.2 wt%, was studied on a commercial sulfided NiMo/Al2O3 catalyst. The fuel fraction in the diesel boiling range was separated by fractional distillation from the organic liquid product obtained from the catalytic conversion of the blend of 70 wt% waste animal fat and 30 wt% light cycle oil. Diesel fuel of the best quality was obtained under the following reaction conditions: T = 615-635 K, P = 6 MPa, LHSV = 1.0 h-1, H2/feedstock ratio = 600 Nm3/m3. The presence of fat in the feedstock was found to promote the conversion of light cycle oil to a paraffinic blending component for diesel fuel. Thus, a value-added alternative fuel with high biocontent can be obtained from low-value refinery stream and waste animal fat. The resultant disposal of waste animal fat, and the use of fuel containing less fossil carbon for combustion helps reduce the emission of pollutants.

Hexane isomerization and cracking activity and intrinsic acidity of H-zeolites and sulfated zirconia-titania.

Adsorption of N2 was studied on zeolite H-Y, ultrastabilized H-Y (H-USY), H-mordenite, H-ZSM-5, H-beta, and on sulfated zirconia-titania (SZT) mixed oxide by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) at 298 K and at N2 pressures up to 9 bar. The adsorption-induced DeltanuOH red-shift of the nuOH bands was used as a measure of the intrinsic acid strength of the Brnønsted acid sites. The intrinsic acid strength of the solids follows the order of H-ZSM-5 approximately H-mordenite approximately H-beta > H-USY > SZT approximately H-Y. The solids were characterized by their hexane conversion activities at 553 K and 6.1 kPa hexane partial pressure. The reaction was shown to proceed predominantly by a bimolecular mechanism, while the reaction was first order in hexane and zero order in alkenes. The site-specific apparent rate constant of the bimolecular hexane conversion was shown to parallel the intrinsic acid strength of the samples, suggesting that the ratio of the apparent and the intrinsic activity, that is, the KA' equilibrium constant of alkane adsorption on the hydrocarbon-covered sorption sites, is hardly dependent on the catalyst structure.