Understanding the Upgrading of Sewage Sludge-Derived Hydrothermal Liquefaction Biocrude via Advanced Characterization.

Hydrothermal liquefaction (HTL) can thermochemically transform sewage sludge into a biocrude with high energy content, high chemical complexity, and high O and N content. The development of an efficient upgrading process for such complex feedstocks necessitates detailed knowledge of the molecular composition and the specific heteroatom-containing compounds to understand and optimize the hydrotreating reactions. In this study, we present the upgrading of sewage sludge-derived HTL biocrude via a two-stage hydrotreatment process and perform advanced chemical characterization of the feedstock, intermediate, and final upgraded products with gas chromatography-mass spectrometry (GC-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). We show that hydrotreatment significantly improves the quality of the oil, primarily succeeding in cracking the heavy molecules and removing the sulfur- and oxygen-containing components. FTICR-MS analysis shows that the HTL biocrude has a high concentration of fatty acid amides that readily lose their oxygen and nitrogen during hydrotreating and are converted into saturated hydrocarbons, whereas the aromatic OxNy compounds are converted into N1 and N2 classes, which are more resistant to hydrotreating. We also demonstrate that the upgraded HTL oil can be successfully blended with intermediate refinery streams, such as vacuum gas oil (VGO), for further co-processing to in-spec fuels in conventional processes. This provides an alternative route to introduce renewable carbon in existing fossil-based refineries.

Scaling-Up of Bio-Oil Upgrading during Biomass Pyrolysis over ZrO2 /ZSM-5-Attapulgite.

Ex situ catalytic biomass pyrolysis was investigated at both laboratory and bench scale by using a zeolite ZSM-5-based catalyst for selectively upgrading the bio-oil vapors. The catalyst consisted of nanocrystalline ZSM-5, modified by incorporation of ZrO2 and agglomerated with attapulgite (ZrO2 /n-ZSM-5-ATP). Characterization of this material by means of different techniques, including CO2 and NH3 temperature-programmed desorption (TPD), NMR spectroscopy, UV/Vis microspectroscopy, and fluorescence microscopy, showed that it possessed the right combination of accessibility and acid-base properties for promoting the conversion of the bulky molecules formed by lignocellulose pyrolysis and their subsequent deoxygenation to upgraded liquid organic fractions (bio-oil). The results obtained at the laboratory scale by varying the catalyst-to-biomass ratio (C/B) indicated that the ZrO2 /n-ZSM-5-ATP catalyst was more efficient for bio-oil deoxygenation than the parent zeolite n-ZSM-5, producing upgraded bio-oils with better combinations of mass and energy yields with respect to the oxygen content. The excellent performance of the ZrO2 /n-ZSM-5-ATP system was confirmed by working with a continuous bench-scale plant. The scale-up of the process, even with different raw biomasses as the feedstock, reaction conditions, and operation modes, was in line with the laboratory-scale results, leading to deoxygenation degrees of approximately 60 % with energy yields of approximately 70 % with respect to those of the thermal bio-oil.

Impact of Macroporosity on Catalytic Upgrading of Fast Pyrolysis Bio-Oil by Esterification over Silica Sulfonic Acids.

Fast pyrolysis bio-oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom- and energy-efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid (PrSO3 H) silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA-15 architectures (post-functionalized by hydrothermal saline-promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C3 ) to 110 % (C12 ). Macroporous-mesoporous PrSO3 H/SBA-15 also provides a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast-pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, as determined by GC×GC-time-of-flight mass spectrometry (GC×GC-ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.

Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil.

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.

A study by electrical conductivity measurements of the semiconductive and redox properties of Nb-doped NiO catalysts in correlation with the oxidative dehydrogenation of ethane.

Nb-doped nickel oxides with Nb contents in the range from 1 to 20% and, for comparison, pure NiO, were characterized using in situ electrical conductivity measurements in correlation with their catalytic performances for the oxidative dehydrogenation (ODH) of ethane into ethylene. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure and was followed with time during sequential exposures to air, ethane-air mixture (reaction mixture) and pure ethane in conditions similar to those of catalysis. All the oxides were p-type semiconductors under air. Their electrical conductivity in the reaction temperature range decreased in the following order: NiO > Nb(1)NiO > Nb(5)NiO > Nb(10)NiO > Nb(15)NiO > Nb(20)NiO. This correlates well with the catalytic activity expressed as the intrinsic rate of ethane consumption. All the catalysts were partially reduced under the reaction mixture in the reaction temperature range, an inverse correlation between their conductivity in these conditions and the ODH selectivity being observed. The ODH reaction of ethane takes place via a heterogeneous redox mechanism involving the surface lattice O(-) species.

Study by electrical conductivity measurements of semiconductive and redox properties of M-doped NiO (M = Li, Mg, Al, Ga, Ti, Nb) catalysts for the oxidative dehydrogenation of ethane.

Pure and M-doped nickel oxides with M = Li, Mg, Al, Ga, Ti, Nb, catalysts for the oxidative dehydrogenation of ethane into ethylene, were characterized by in situ electrical conductivity measurements. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure and was followed with time during sequential exposures to air, an ethane-air mixture (reaction mixture) and pure ethane under conditions similar to those of catalysis. All the materials appeared to be p-type semiconductors under air with positive holes as the main charge carriers and their electrical conductivity decreased in the following order: Li-NiO > NiO > Mg-NiO > Nb-NiO > Ga-NiO > Al-NiO > Ti-NiO. All the catalysts remained p-type semiconductors in the reaction mixture at 400 °C. Correlations between the p-type semiconductivity and the catalytic properties have been evidenced. The reaction mechanism involves surface lattice O(-) species and can be assimilated to a Mars and van Krevelen mechanism.