Novel Staged Free-Fall Reactor for the (Catalytic) Pyrolysis of Lignocellulosic Biomass and Waste Plastics.

Pyrolysis of lignocellulosic biomass and waste plastics has been intensely studied in the last few decades to obtain renewable fuels and chemicals. Various pyrolysis devices have been developed for use in a laboratory setting, operated either in batch or continuously at scales ranging from milligrams per hour to tenths of g per hour. We report here the design and operation of a novel staged free-fall (catalytic) pyrolysis unit and demonstrate that the concept works very well for the (catalytic) pyrolysis of pinewood sawdust, paper sludge, and polypropylene as representative feeds. The unit consists of a vertical tube with a pretreatment section, a pyrolysis section, a solid residue collection section, a gas-liquid separation/collection section, and a catalytic reaction section to optionally perform ex situ catalytic upgrading of the pyrolysis vapor. The sample is placed in a tube, which is transported by gravity through various sections of the unit. It allows for rapid testing with semicontinuous feeding (e.g., 50 g h-1) and the opportunity to perform reactions under an (inert) gas (e.g., N2) at atmospheric as well as elevated pressure (e.g., 50 bar). Liquid yields for noncatalytic sawdust pyrolysis at optimized conditions (475 °C and atmospheric pressure) were 63 wt % on biomass intake. A lower yield of 51 wt % (on a biomass basis) was obtained for the noncatalytic pyrolysis of paper sludge, likely due to the presence of minerals (e.g., CaCO3) in the feed. The possibility of using the unit for ex situ catalytic pyrolysis (pyrolysis at 475 °C and catalytic upgrading at 550 °C) was also successfully demonstrated using paper sludge as the feed and H-ZSM-5 as the catalyst (21 wt % catalyst on biomass). This resulted in a biphasic liquid product with 25.6 wt % of an aqueous phase and 11 wt % of an oil phase. The yield of benzene, toluene, and xylenes was 1.9 wt % (on a biomass basis). Finally, the concept was also proven for a representative polyolefin (polypropylene), both noncatalytic as well as in situ catalytic pyrolysis using H-ZSM-5 as the catalyst at 500 °C. The liquid yield of thermal, noncatalytic plastic pyrolysis was as high as 77 wt % on plastic intake, while in situ catalytic pyrolysis gave a combined 7.8 wt % yield of benzene, toluene, and xylenes on plastic intake.

Enhanced Bio-BTX Formation by Catalytic Pyrolysis of Glycerol with In Situ Produced Toluene as the Cofeed.

The catalytic coconversion of glycerol and toluene (93/7 wt %) over a technical H-ZSM-5/Al2O3 (60-40 wt %) catalyst was studied, aiming for enhanced production of biobased benzene, toluene, and xylenes (bio-BTX). When using glycerol/toluene cofeed with a mass ratio of 93/7 wt %, a peak BTX carbon yield of 29.7 ± 1.1 C.% (at time on stream (TOS) of 1.5-2.5 h), and an overall BTX carbon yield of 28.7 C.% (during TOS of 8.5 h) were obtained, which are considerably higher than those (19.1 ± 0.4 C.% and 11.0 C.%) for glycerol alone. Synergetic effects when cofeeding toluene on the peak and overall BTX carbon yields were observed and quantified, showing a relative increase of 3.1% and 30.0% for the peak and overall BTX carbon yield (based on the feedstock). These findings indicate that the strategy of cofeeding in situ produced toluene for the conversion of glycerol to aromatics has potential to increase BTX yields. In addition, BTX production on the catalyst (based on the fresh catalyst during the first run for TOS of 8.5 h and without regeneration) is significantly improved to 0.547 ton ton-1catalyst (excluding the 76% of toluene product that is 0.595 ton ton-1catalyst for the recycle in the cofeed) for glycerol/toluene cofeed, which was 0.426 ton ton-1catalyst for glycerol alone. In particular, this self-sufficient toluene product recycling strategy is advantageous for the production and selectivity (relative increase of 84.4% and 43.5% during TOS of 8.5 h) of biobased xylenes.

Bio-adsorption of heavy metals from aqueous solution using the ZnO-modified date pits.

The bio-adsorption of heavy metals (including Cu2+, Ni2+, and Zn2+) in aqueous solution and also in an industry wastewater using the ZnO-modified date pits (MDP) as the bio-adsorbent are investigated. The fresh and used bio-adsorbents were characterized by FT-IR, SEM, BET, and XRD. The bio-adsorption parameters (including the pH of solution, the particle size of MDP, the shaking speed, the initial concentration of heavy metals, the dosing of MDP, the adsorption time, and the adsorption temperature) were screened and the data were used to optimize the bio-adsorption process and to study the bio-adsorption isotherms, kinetics, and thermodynamics. Two adsorption models (Langmuir isotherm model and Freundlich isotherm model) and three kinetic models (pseudo-first-order model, pseudo-second-order model, and intra-particle diffusion model) were applied to model the experimental data. Results show that the maximum adsorption amount of Cu2+, Ni2+, and Zn2+ on a complete monolayer of MDP are 82.4, 71.9, and 66.3 mg g-1, which are over 4 times of those of date pits-based bio-adsorbents reported in literature. The bio-adsorption of heavy metals on MDP is spontaneous and exothermic, and is regulated by chemical adsorption on the homogeneous and heterogeneous adsorption sites of MDP surface. This work demonstrates an effective modification protocol for improved bio-adsorption performance of the date pits-based bio-adsorbent, which is cheap and originally from a waste.

Catalytic conversion of glycerol and co-feeds (fatty acids, alcohols, and alkanes) to bio-based aromatics: remarkable and unprecedented synergetic effects on catalyst performance.

Glycerol is an attractive bio-based platform chemical that can be converted to a variety of bio-based chemicals. We here report a catalytic co-conversion strategy where glycerol in combination with a second (bio-)feed (fatty acids, alcohols, alkanes) is used for the production of bio-based aromatics (BTX). Experiments were performed in a fixed bed reactor (10 g catalyst loading and WHSV of (co-)feed of 1 h-1) at 550 °C using a technical H-ZSM-5/Al2O3 catalyst. Synergistic effects of the co-feeding on the peak BTX carbon yield, product selectivity, total BTX productivity, catalyst life-time, and catalyst regenerability were observed and quantified. Best results were obtained for the co-conversion of glycerol and oleic acid (45/55 wt%), showing a peak BTX carbon yield of 26.7 C%. The distribution of C and H of the individual co-feeds in the BTX product was investigated using an integrated fast pyrolysis-GC-Orbitrap MS unit, showing that the aromatics are formed from both glycerol and the co-feed. The results of this study may be used to develop optimized co-feeding strategies for BTX formation.

Adsorption of methylene blue dye from the aqueous solution via bio-adsorption in the inverse fluidized-bed adsorption column using the torrefied rice husk.

In this work, the inverse fluidized-bed bio-adsorption column is applied for the first time and is demonstrated using the torrefied rice husk (TRH) for the removal of methylene blue from the solution. The bio-adsorbents were characterized by BET, FI-IR, and SEM. The inverse fluidized-bed adsorption column using TRH becomes saturated in the 95-min continuous adsorption, during which the breakthrough time is 22 min, the overall MB removal (R) is 84%, and the adsorption capacity (Qexp) on the TRH is 6.82 mg g-1. These adsorption characteristics are superior to those in the fixed-bed adsorption column (R of 52% and Qexp of 2.76 mg g-1) at a lower flow rate (100 vs. 283 cm3 min-1). Torrefaction of RH significantly increases the surface area (28 vs. 9 m2 g-1) and enhances the surface functional groups, leading to an improved maximum equilibrium adsorption amount from 21.5 to 38.0 mg g-1 according to Langmuir model in the batch adsorption system. Besides, the increased Qexp on the TRH is also obtained in the inverse fluidized-bed (5.25 vs. 2.77 mg g-1, 89% higher) and the fixed-bed (2.76 vs. 1.53 mg g-1, 80% higher) adsorption columns compared to that on the RH.

Catalytic Conversion of Free Fatty Acids to Bio-Based Aromatics: A Model Investigation Using Oleic Acid and an H-ZSM-5/Al2O3 Catalyst.

The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al2O3 catalyst (ϕ 1.2-1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h-1). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g-1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition (ca. 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles (e.g., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged (e.g., >24 h), leading to a significantly enhanced total BTX production (e.g., 3000 mg g-1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N2 and Ar physisorption, XRD, HR-TEM-EDX, 27Al, and 29Si MAS ssNMR, NH3-TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced.

ZnO nanorod arrays assembled on activated carbon fibers for photocatalytic degradation: Characteristics and synergistic effects.

Well-aligned ZnO nanorod arrays were assembled on activated carbon fibers by a stepwise sequence of sol-gel and hydrothermal synthesis methods. These ZnO nanorod arrays on activated carbon fibers having different characteristics such as surface area, rod concentration, aspect ratio and defect level, were applied as catalysts for the photodegradation of an aqueous methylene blue solution. They showed very promising methylene blue adsorbility in the dark (ca. 0.025-0.031 mg methylene blue m-2 catalyst, vs. 0.072 mg methylene blue m-2 activated carbon fibers). Significantly, the defect level of ZnO nanorod arrays has a major effect on the turnover frequency compared to other characteristics. A synergistic effect between activated carbon fibers and ZnO nanocrystals on enhancing turnover frequency was more significant for the well-assembled ZnO nanorod arrays on activated carbon fibers catalysts compared to the mechanically mixed ZnO powder with activated carbon fibers catalyst. Further, turnover frequency for the ZnO nanorod arrays on activated carbon fibers (0.00312 molmethylene blue molZnO-1 h-1) was twice higher than that for the corresponding bare ZnO nanorod arrays, and 3 times higher than that for a commercial ZnO powder. In addition, ZnO nanorod arrays on activated carbon fibers show high degradation (77.5%) and mineralization (55.0%) levels for methylene blue, and also good reusability (or stability) as demonstrated by a sequential 5-time recycle routine. These outstanding features indicate that activated carbon fibers supported ZnO nanorod arrays have significant potential to be used as catalysts for photodegradation.

Triphenylphosphine-Based Covalent Organic Frameworks and Heterogeneous Rh-P-COFs Catalysts.

The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine-based COF family, but also demonstrates their application in immobilizing homogeneous metal-based (e.g., Rh-phosphine) catalysts for application in heterogeneous catalysis.

Synthesis, characterization and properties of a glycol-coordinated ε-Keggin-type Al13 chloride.

Herein we present the first example of a glycol-coordinated ε-Keggin Al13 chloride (gl-ε-Al13), which is the first chelated version since discovery of Al13 in 1960. The molecular structure consists of [AlO4Al12(OH)12(OC2H4OH)12]Cl7·H2O units with chelating mono-anionic ethylene glycol units replacing one bridging and one terminal oxygen site.

The degradation of Isophorone by catalytic wet air oxidation on Ru/TiZrO4.

The catalyst Ru/TiZrO(4) was applied in the degradation of Isophorone by catalytic wet air oxidation. Mathematical models for the effects of reaction conditions on the Isophorone degradation by catalytic wet air oxidation were developed using a response surface methodology. A model was obtained for each response with multiple regression analysis and then was refined. Analysis of variance revealed that the models developed were adequate. The validity of the models was also verified by experimental data. Analysis of response surface showed that total organic carbon removal and Isophorone conversion were significantly affected (P≤0.01) by reaction time, temperature and their interactions, and affected (P≤0.05) by the square of reaction time. The point of zero charge of Ru/TiZrO(4) catalyst was about 1.72. The total organic carbon removal and Isophorone conversion had a great association with the zeta potential of Ru/TiZrO(4) catalyst. Finally, the degradation pathway of Isophorone in catalytic wet air oxidation was proposed. Within 410 h, the total organic carbon removal remained above 95%, indicating that the Ru/TiZrO(4) catalyst had a good stability.

Pt-Sn/γ-Al2O3-catalyzed highly efficient direct synthesis of secondary and tertiary amines and imines.

Versatile syntheses of secondary and tertiary amines by highly efficient direct N-alkylation of primary and secondary amines with alcohols or by deaminative self-coupling of primary amines have been successfully realized by means of a heterogeneous bimetallic Pt-Sn/γ-Al(2)O(3) catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through a borrowing-hydrogen strategy. In the presence of oxygen, imines were also efficiently prepared from the tandem reactions of amines with alcohols or between two primary amines. The proposed mechanism reveals that an alcohol or amine substrate is initially dehydrogenated to an aldehyde/ketone or NH-imine with concomitant formation of a [PtSn] hydride. Condensation of the aldehyde/ketone species or deamination of the NH-imine intermediate with another molecule of amine forms an N-substituted imine which is then reduced to a new amine product by the in-situ generated [PtSn] hydride under a nitrogen atmosphere or remains unchanged as the final product under an oxygen atmosphere. The Pt-Sn/γ-Al(2)O(3) catalyst can be easily recycled without Pt metal leaching and has exhibited very high catalytic activity toward a wide range of amine and alcohol substrates, which suggests potential for application in the direct production of secondary and tertiary amines and N-substituted imines.

[Copper leaching in catalytic wet oxidation of phenol with Cu-containing spinel].

The Cu0.10, Zn0.90 Al1.90 Fe0.10 O4 spinel type catalyst prepared by sol-gel method was tested for catalytic wet air oxidation of phenol. The performances of Cu0.10 Zn0.90 Al1.90 Fe0.10 O4 catalyst in TPR experiment, the influence of phenol as reducer, reaction temperature and phenol-to-catalyst mass ratio on copper leaching were checked respectively. According to the experimental results, it is suggested that the reduced active species can not be easily re-oxidized under low reaction temperature and high phenol-to-catalyst mass ratio are the main reasons for copper leaching. Under high enough reaction temperature and low phenol-to-catalyst mass ratio, the copper leaching reduces remarkably. At 190 degrees C in the presence of 100 mL aqueous solution of 4.29 g x L(-1) of phenol and 2.5 g catalyst, the copper leaching was only 0.96 mg x L(-1) after 2 h of reaction.