Aqueous-phase Processing Research Articles

Improved performance of magnetically recoverable Ce-promoted Ni/Al2O3 catalysts for aqueous-phase hydrogenolysis of sorbitol to glycols

The addition of cerium into Ni/Al2O3 catalysts afforded a remarkable promoting effect on catalytic performance of aqueous-phase hydrogenolysis of sorbitol to produce glycols (e.g., 1,2-propylene glycol and ethylene glycol). This effect was observed whether the catalysts were prepared through deposition–precipitation (DP) or co-precipitation (CP) methods. However, the Ce–Ni/Al2O3-DP catalyst went through rapid deactivation during the consecutive recycles. The Ce–Ni/Al2O3-CP catalyst was recovered easily by magnetic separation and reused over ten times. At a temperature of 513K and pressure of 7.0MPa, the Ce–Ni/Al2O3-CP catalyst maintained sorbitol conversion at above 90% and selectivity to glycols at 55–60% for 12h. Characteristic studies indicate that the addition of cerium to the Ni/Al2O3 catalysts slightly lowered the reduction temperature of nickel oxide but considerably enhanced the H2-chemisorption amount. Furthermore, the co-precipitation method was conducive for preparing the catalyst with high thermal stability, which was shown by 20% Ni/Al2O3-CP being more stable in structure than 20% Ni/Al2O3-DP under higher temperatures. The catalyst deactivation was due to the agglomeration of Ni nanoparticles during hydrogenolysis process in aqueous-phase.

The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol

Abstract. The Pasadena Aerosol Characterization Observatory (PACO) represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1–2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Regardless of regime, organic aerosol (OA) is the most significant constituent of nonrefractory submicron Los Angeles aerosol (42, 43, and 55 % of total submicron mass in regimes I, II, and III, respectively). The overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively), with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA) in Los Angeles. Online analysis of water soluble organic carbon (WSOC) indicates that water soluble organic mass (WSOM) reaches maxima near 14:00–15:00 local time (LT), but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode dominated by organics. Particulate NH4NO3 and (NH4)2SO4 appear to be NH3-limited in regimes I and II, but a significant excess of particulate NH4+ in the hot, dry regime III suggests less SO42− and the presence of either organic amines or NH4+-associated organic acids. C-ToF-AMS data were analyzed by Positive Matrix Factorization (PMF), which resolved three factors, corresponding to a hydrocarbon-like OA (HOA), semivolatile OOA (SV-OOA), and low-volatility OOA (LV-OOA). HOA appears to be a periodic plume source, while SV-OOA exhibits a strong diurnal pattern correlating with ozone. Peaks in SV-OOA concentration correspond to peaks in DMA number concentration and the appearance of a fine organic mode. LV-OOA appears to be an aged accumulation mode constituent that may be associated with aqueous-phase processing, correlating strongly with sulfate and representing the dominant background organic component. Periods characterized by high SV-OOA and LV-OOA were analyzed by filter analysis, revealing a complex mixture of species during periods dominated by SV-OOA and LV-OOA, with LV-OOA periods characterized by shorter-chain dicarboxylic acids (higher O:C ratio), as well as appreciable amounts of nitrate- and sulfate-substituted organics. Phthalic acid was ubiquitous in filter samples, suggesting that PAH photochemistry may be an important SOA pathway in Los Angeles. Aerosol composition was related to water uptake characteristics, and it is concluded that hygroscopicity is largely controlled by organic mass fraction (OMF). The hygroscopicity parameter κ averaged 0.31 ± 0.08, approaching 0.5 at low OMF and 0.1 at high OMF, with increasing OMF suppressing hygroscopic growth and increasing critical dry diameter for CCN activation (Dd). An experiment-averaged κorg of 0.14 was calculated, indicating that the highly-oxidized organic fraction of aerosol in Los Angeles is appreciably more hygroscopic than previously reported in urban areas. Finally, PACO will provide context for results forthcoming from the CalNex field campaign, which involved ground sampling in Pasadena during the spring and summer of 2010.

Isoparaffin production by aqueous phase processing of sorbitol over the Ni/HZSM-5 catalysts: Effect of the calcination temperature of the catalyst

Ni/HZSM-5 catalysts calcined at different temperatures were used in the isoparaffin production by aqueous phase processing of sorbitol and characterized by N2 physical adsorption, temperature-programmed reduction (H2-TPR), temperature-programmed desorption of ammonia (NH3-TPD) and Raman techniques. The effect of calcination temperature of the catalysts on the catalytic performance for the reaction was investigated. The activity test results indicated that the maximal i-C6H14 selectivity of 45.4% and the total i-C6H14 and i-C5H12 yield of 32.3% were obtained over the catalyst calcined at 500°C, which exhibited the optimum surface area and pore structure with 100% of the reducibility of Ni species on the surface of HZSM-5. In addition, the amount and the strength distribution of acidic surface sites of the catalyst decreased with the increase of calcination temperature at 500°C above. All these factors result in an increase in the formation of isoparaffin.

An Enhanced Luminescent CdTe/ZnS Core-Shell Quantum Dot: Synthesis, Characterization, and its Optical Properties

The core-shell CdTe/ZnS quantum dots were prepared with an improved process in aqueous phase. CdTe QDs were synthesized under conditions of pH 9.1, 96 °C, refluxing for 5h, and which was used as core material; ZnS was formed as shell material to enhance the optical properties. Optical properties were characterized with fluorescence spectrum (FS), and morphology of QDs was investigated via transmission electron microscopy (TEM) method. Moreover, composition and formation of CdTe/ZnS core-shell QDs was characterized via x-ray diffraction (XRD) method. Optimum conditions were investigated to obtain the qualified CdTe/ZnS core-shell QDs, the results indicated QDs with high quantum yields and fluorescence intensity were achieved under conditions of pH 9.0, 45 °C, refluxing for 1h, and v/v/v ratio of CdTe/Na2S/ZnSO4 is 4/1/1. The TEM data indicated that average size of 5 nm CdTe core was prepared, and CdTe/ZnS core-shell QDs with average size of 11 nm were achieved under the optimum conditions. ca 30nm of red shift of a maximum emission wavelength from ca 530 nm (CdTe) to 560 nm (CdTe/ZnS) was observed via FS under the optimum conditions, which inferred the growth of QDs and formation of ZnS shells. Furthermore, the enhanced fluorescence intensity of CdTe/ZnS core-shell QDs was detected and over two times of fluorescence intensity was increased after formation of ZnS shell. The obtained QDs will have great potential application in biological researches and biosensing system based on fluorescence resonance energy transition (FRET).

Transformations of biomass-derived platform molecules: from high added-value chemicals to fuels via aqueous-phase processing

Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals.

Renewable gasoline from aqueous phase hydrodeoxygenation of aqueous sugar solutions prepared by hydrolysis of maple wood

In this paper we demonstrate an integrated process for the production of high octane gasoline from maple wood by hydrolysis of maple wood into aqueous carbohydrate solutions followed by aqueous phase hydrodeoxygenation of the sugar solutions. The aqueous carbohydrate solutions were prepared by both hydrolysis in hot water and hydrolysis with dilute acids (H2SO4, oxalic acid). The aqueous carbohydrate solutions were a mixture of xylose, water soluble hemicellulose oligomers, acetic acid, glucose, glucose oligomers, and probably some lignin polymers. Hydrolysis with hot water produced primarily hemicellulose oligomers whereas hydrolysis with acids produced mainly xylose and acetic acid. The hydrolysis co-product was a solid enriched in cellulose and lignin. The aqueous streams were hydrodeoxygenated by a two step catalytic process in which the first catalyst bed contained a Ru/C catalyst at 393 K and the second catalyst bed contained a Pt/zirconium phosphate (Pt/ZrP) catalyst at 518 K. The Ru/C catalyst was able to selectively hydrogenate xylose into xylitol but could not selectively hydrogenate the xylose oligomers. The two stage process was able to convert the aqueous carbohydrate streams derived from maple wood into gasoline range products with carbon yields of up to 57% and an estimated octane number of 96.5. No significant catalyst deactivation was observed indicating that the catalysts are very stable. The highest gasoline yield from this two stage process was obtained from the stream produced by acid hydrolysis of maple wood with 0.5 wt% oxalic acid at 433 K for 0.5 h. These results suggest that aqueous phase processing of sugars obtained by hydrolysis is a promising option for the production of fuels and chemicals from lignocellulosic biomass.

Catalytic production of levulinic acid from cellulose and other biomass-derived carbohydrates with sulfonated hyperbranched poly(arylene oxindole)s

Innovative catalyst design holds the key to fundamental advances in the transformation of cellulose to chemicals and transportation fuels, both of which are vital to meet the challenge of increasing energy costs and the finite nature of fossil fuel reserves. Here we report on the functionalization, characterization and successful application of sulfonated hyperbranched poly(arylene oxindole)s for the direct catalytic conversion of cellulose to levulinic acid. The use of water-soluble hyperbranched polymers in combination with ultrafiltration is conceptually novel and opens new horizons in the aqueous-phase processing of cellulose substrates with various degrees of crystallinity. Compared to most conventional types of acid catalysts, these highly acidic polymers demonstrate superior catalytic performance in terms of both activity and selectivity. Additionally, this molecular approach can be successfully transferred to the acid-catalyzed degradation of other abundant biomass resources, including starch, inulin and xylan.

Hydrogen production by aqueous-phase biomass reforming over carbon textile supported Pt–Ru bimetallic catalysts

The objective of this study is to develop highly efficient and low cost Pt–Ru bimetallic catalyst to convert biomass to bio-hydrogen fuel and chemicals by utilizing an aqueous-phase reforming (APR) reactor. The Pt–Ru bimetallic nanocatalysts on activated carbon supports were uniformly coated on the carbon textile as functionalized mesoporous media by electrophoretic deposition (EPD) method or dip-coating process. The carbon textile containing Pt–Ru nanoparticles was then rolled up and fastened to form pillar-like catalysts, which were placed in the reactor for the APR process. New catalytic processing techniques, which allow the design of catalyst at the atomistic level with controlled adsorption properties, are used to develop highly active catalysts for aqueous-phase process. The microstructure of the catalysts and activity/selectivity were optimized. This study provided a viable option for bio-hydrogen generation and reduced sugar production at the same time via a one-pot process to deal with low-cost energy crops or agriculture wastes as the substrate.

Different photolysis kinetics at the surface of frozen freshwater vs. frozen salt solutions

Abstract. Reactions at air-ice interfaces can proceed at very different rates than those in aqueous solution, due to the unique disordered region at the ice surface known as the quasi-liquid layer (QLL) . The physical and chemical nature of the surfacial region of ice is greatly affected by solutes such as sodium halide salts. In this work, we studied the effects of sodium chloride and sodium bromide on the photolysis kinetics of harmine, an aromatic organic compound, in aqueous solution and at the surface of frozen salt solutions above the eutectic temperature. In common with other aromatic organic compounds we have studied, harmine photolysis is much faster on ice surfaces than in aqueous solution, but the presence of NaCl or NaBr – which does not affect photolysis kinetics in solution – reduces the photolysis rate on ice. The rate decreases monotonically with increasing salt concentration; at the concentrations found in seawater, harmine photolysis at the surface of frozen salt solutions proceeds at the same rate as in aqueous solution. These results suggest that the brine excluded to the surfaces of frozen salt solutions is a true aqueous solution, and so it may be possible to use aqueous-phase kinetics to predict photolysis rates at sea ice surfaces. This is in marked contrast to the result at the surface of frozen freshwater samples, where reaction kinetics are often not well-described by aqueous-phase processes.

Fluorescence Enhanced Quantum Dots: Its Synthesis, Optical Properties, and Ecotoxicity Research

Quantum dots (QDs) are normally based on the semiconductor materials and widely used in biosensing, bioimaging, biolabeling, and biotreatment for their excellent properties. The ecotoxicity research of QDs correspondingly kept in rising in recent years. CdTe and CdTe/ZnS QDs were prepared via an improved process in aqueous phase, morphology of QDs was characterized with transmission electron microscopy, and optical properties were investigated via fluorescence spectrum. Ecotoxicity of CdTe and CdTe/ZnS were assayed by measuring the inhibitory growth of Rhodococcus sp. strain C1 when QDs existed in broth culture, which was screened from sewage, and its morphology was characterized with optical microscope and scanning electron microscope. CdTe QDs showed strong inhibitory effect against growth of Rhodococcus sp. strain C1, and little growth was observed after 72h cultivation. CdTe/ZnS QDs showed prophasic inhibition before 36h, and growth recovery was observed after 48h of cultivation. Enhanced optical properties and decreasing ecotoxicity were validated after ZnS shell formation, these results indicated that CdTe/ZnS QDs with core-shell structure has great potential in bio-applications.

Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

Abstract. This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7). Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes <1% to total predicted SOA masses at any time. Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

Production of furans from rice straw by single-phase and biphasic systems

5-Hydroxymethylfurfural (HMF) and furfural, both of which can be derived from renewable sources, are key components for the production of different chemicals and fuels. In this study, rice straw, a cheap, abundant, and mainly unused agricultural waste, is converted to furans by a dilute acid hydrolysis process. The highest yield of HMF in a single-phase hydrolysis was 15.3 g/kg straw, attained at 180 °C during 3 h with 0.5% sulfuric acid, while the maximum yield of furfural, 59 g/kg straw, was obtained at 150 °C during 5 h. Different extracting solvents, including 2-PrOH, 1-BuOH, methyl isobutyl ketone (MIBK), and acetone at 180 °C for 3 h as well as tetrahydrofuran (THF) at 150 °C for 5 h were examined in biphasic systems. Use of the solvents generally improved the production of HMF compared to the single aqueous phase process. The best results of HMF production, more than 59 g/kg straw, were obtained in the systems containing either 2-PrOH or 1-BuOH. Using THF as an extracting solvent, a relatively high furfural yield, 118.2 g/kg straw, was obtained, and 96% of furfural produced in this system was extracted into THF during the process.

Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization I: high-yield production of synthetic lignins (DHPs) in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol in the presence of nucleophilic reagents

It is known that the conventional dehydrogenative polymerization of sinapyl alcohol (S-alc) gave syringyl synthetic lignins (S-DHPs), but in extremely low yields. In this article, to examine the contribution of syringyl quinone methide intermediates (S-QM) on S-DHP production, horseradish peroxidase (HRP)-catalyzed dehydrogenative polymerization of S-alc was carried out in the presence of nucleophilic reagents that promote the rearomatization of S-QM. First, the HRP-catalyzed polymerization of sinapyl alcohol γ-O-β-D-glucopyranoside (isosyringin, iso-S), which allows us to monitor the polymerization process in a homogeneous aqueous phase, was utilized for screening of a nucleophile used as an S-QM scavenger. Monitoring of iso-S polymerization in the presence of various nucleophilic reagents by UV spectroscopy and gel permeation chromatography with photodiode array detection (GPC-PDA) revealed a high ability of azide ion to convert oligomeric S-QM efficiently to S-DHP. Accordingly, azide ion was utilized as an S-QM scavenger in HRP-catalyzed polymerization of S-alc, which resulted in high-yield production of S-DHPs (∼83%), as expected. The 1H-, 13C-, and 2D-HSQC NMR investigations on the resulting S-DHPs clearly demonstrated that azide ion efficiently performed nucleophilic additions to the C-α of S-QM during the polymerization. These results provide experimental proof that the low reactivity of S-QM with nucleophiles (such as water, phenolic, and aliphatic hydroxyl groups) in the conventional polymerization system critically impedes the production of S-DHPs from S-alc.

Controlling the Locus of Bubble Nucleation by Dissolved Gases in Heterogeneous Liquid−Liquid Systems

We have examined the nucleation of chemically generated nitrogen gas bubbles in microheterogeneous systems, using optical microscopy on a model system consisting of a single liquid-liquid interface. Results clearly show that bubble nucleation occurs in both the aqueous and oil phases, despite the nitrogen production reaction being a purely aqueous phase process. A theoretical model is developed which describes the time evolution of the nitrogen concentration profile, and this reveals that bubbles in the oil are a result of homogeneous nucleation of dissolved N(2) transported across the interface into a (supersaturated) diffusion layer. We further show that bubble nucleation in the oil can be inhibited or eliminated by adding water-soluble surfactants, which facilitates aqueous phase bubble nucleation and then acts as highly effective nitrogen sinks, severely reducing the flux of dissolved gas across the water-oil interface.

Towards an operational aqueous phase chemistry mechanism for regional chemistry-transport models: CAPRAM-RED and its application to the COSMO-MUSCAT model

Mechanism reductions of the detailed aqueous phase chemistry mechanism CAPRAM 3.0i are performed. Manual methods and automatic techniques are both applied in order to provide a less computationally intensive mechanism which is operational in regional chemistry transport models (CTMs). The finally reduced mechanism contains less than 200 reactions (4 times smaller than the detailed CAPRAM 3.0i) and describes the main characteristics of inorganic and organic aqueous phase processes occurring in tropospheric warm clouds. Most of the chemical reduction potential is realized in the CAPRAM 3.0i organic chemistry. The number of aqueous phase species decreases from 380 in the full mechanism to 130 in the final reduced version. The calculated percentage deviations between the full and reduced mechanism are on average below 5% for the most important organic and inorganic target compounds such as oxidants, inorganic and organic acids, carbonyls and alcohols. Comparisons of the required CPU times between the full and reduced mechanisms show reductions of approximately 40%. 2-D test simulations with the CTM MUSCAT were performed using prescribed meteorological conditions in order to examine the applicability of the reduced mechanism at regional scale. Simulations with the reduced CAPRAM 3.0i mechanism and a much less complex mechanism with only limited inorganic chemistry (INORG) were compared to evaluate the effects of more detailed chemistry. The model results show large differences in the level of oxidants and the inorganic and organic mass processing. Prospectively, the reduced mechanism represents the basis for studying aerosol cloud processing effects at regional scale with future CTMs and will allow more adequate interpretation of field data.

Electron transport behavior of individual zinc oxide coated single-walled carbonnanotubes

Uniform zinc oxide coated single-walled nanotubes (SWNTs) were fabricated byultrasonic irradiation with acid-treated SWNTs, zinc acetate, and triethanolamineat low temperature in aqueous phase processing. The ZnO coating process didnot decrease the dark current of the SWNTs, but a real decrease in the steadystate negative photocurrent was observed after ZnO coating, suggesting a clearphotosensitization effect. Transport measurements reveal that the negative photocurrent ins (semiconducting)-SWNTs@ZnO could be described by electron–hole compensationbehavior attributed to the ZnO layer under ultraviolet excitation. This simple coatingmethod for one-dimensional material can open up new possibilities for multifunctionalnanodevices.

Dehydration of butanol to butene over solid acid catalysts in high water environments

The effects were studied of high water concentrations on the kinetics of alcohol dehydration, as encountered in aqueous-phase processing of biomass-derived oxygenated hydrocarbons. These studies were carried out for dehydration of an aqueous solution of 10 wt% 2-butanol at 513 K, and at a total pressure of 52 bar to maintain the water in the liquid state. Under these high pressures of water, silica-alumina, niobium phosphate and niobic acid are found to be stable and active for the dehydration of butanol. These three catalysts showed an increase in rate after contact with liquid water, caused by an increase in the concentration of Brønsted acid sites. Zeolite catalysts (Beta, USY, H-ZSM-5) and zirconia based catalysts (WO x /ZrO 2, MoO x /ZrO 2, and MgO/ZrO 2) were ineffective due to deactivation or low catalytic activity. The flow rate of inert gas at constant aqueous flow rate had a significant effect on the rate of butene production, due to vaporization of butanol and water. At low flow rates of gas, increasing the gas flow rate causes the preferential vaporization of butanol, leading to a decrease in the butanol pressure in the reactor and a corresponding decrease in the rate of dehydration. Above a critical gas flow rate, the liquid feed becomes completely vaporized in the reactor, and increasing the gas flow rate further leads to a decrease in the pressure of water and a corresponding increase in the rate of dehydration. In the vapor–liquid equilibrium regime, kinetic models predict that most of the catalyst is covered with multiple layers of water, and dehydration takes place by reaction of hydrated–adsorbed butanol with a hydrated surface site. In the vapor-only regime, kinetic models suggest that the fraction of vacant active sites increases with increasing gas flow rate, and dehydration takes place by reaction of adsorbed butanol with a vacant surface site.

Production of hydrogen, alkanes and polyols by aqueous phase processing of wood-derived pyrolysis oils

Pyrolysis oils are the cheapest liquid fuel derived from lignocellulosic biomass. However, pyrolysis oils are a very poor quality liquid fuel that cannot be used in conventional diesel and internal combustion engines. In this paper we show that hydrogen, alkanes (ranging from C1 to C6) and polyols (ethylene glycol, 1,2-propanediol, 1,4-butanediol) can be produced from the aqueous fraction of wood-derived pyrolysis oils (bio-oils). The pyrolysis oil was first phase separated into aqueous and non-aqueous fraction by addition of water. The aqueous phase of bio-oil contained sugars; anhydrosugars; acetic acid; hydroxyacetone; furfural and small amounts of guaiacols. The aqueous fraction was subjected to a low temperature hydrogenation with Ru/C catalyst at 125–175 °C and 68.9 bar. The hydrogenation step converts the various functionalities in the bio-oil (including aldehydes; acids; sugars) to corresponding alcohols. Undesired methane and light gases are also produced in this low-temperature hydrogenation step. Diols (ranging from C2 to C4) and sorbitol are obtained as major products in this step. After the low temperature hydrogenation step either hydrogen or alkanes can be produced by aqueous-phase reforming (APR) or aqueous-phase dehydration/hydrogenation (APD/H) respectively. APR was done with a 1 wt% Pt/Al2O3 catalyst at 265 °C and 55.1 bar. Hydrogen selectivities of up to 60% were observed. The hydrogen selectivity was a function of space velocity. A 4 wt% Pt/SiO2-Al2O3 catalyst at 260 °C and 51.7 bar was used for alkane production by APD/H. The carbon conversion to gas phase products of 35% with alkane selectivity of 45% was obtained for a WHSV of 0.96 h−1 when hydrogen is produced in situ from bio-oil. Alkane selectivity can be improved by supplying hydrogen externally. Alkane selectivities as high as 97% can be obtained when HCl is added to the aqueous-phase of the bio-oil and hydrogen is supplied externally. Model compounds for further bio-oil conversion studies are suggested.

The synthesis of propylene glycol and ethylene glycol from glycerol using Raney Ni as a versatile catalyst

A new energy-efficient and atom-economical catalytic route for the direct catalytic synthesis of propylene glycol and ethylene glycol from glycerol under milder reaction conditions is presented. The one-pot aqueous-phase process is based on Raney Ni as a versatile catalyst.

Development of DNPH/HPLC method for the measurement of carbonyl compounds in the aqueous phase: applications to laboratory simulation and field measurement

Environmental context. Carbonyl compounds, a class of oxygenated organic matter, are crucial participants in atmospheric processes. Recently, studies have shown that the aqueous-phase processes of carbonyls have an important contribution to the formation of secondary organic aerosol (SOA), which is considered to have a significant impact on global climate change and human health. We developed the classical DNPH/HPLC method to characterise the aqueous-phase carbonyls, especially methacrolein, methyl vinyl ketone, glyoxal, and methylglyoxal, which are important precursors of SOA, in order to better understand the pathways of SOA formation in the atmosphere. Abstract. The DNPH/HPLC method for characterising monocarbonyls and dicarbonyls in the aqueous phase has been developed. A series of experiments have been carried out using eight atmospheric ubiquitous carbonyl compounds as model dissolved compounds in both acetonitrile and water solution to obtain the optimal derivatisation and analysis qualifications. Compared with the analysis of carbonyls dissolved in acetonitrile, the influence of acidity on the derivatisation efficiency should be carefully considered in determining carbonyls in water and the optimal acidity is pH 2.0. We find that methyl vinyl ketone (MVK) transforms to crotonaldehyde during the derivatisation reaction. This transformation can be controlled to a minor degree by increasing the mixing ratio of DNPH to MVK up to 100 : 1. This improved method has been satisfactorily applied to laboratory simulations and field measurements for better understanding the carbonyl chemistry in the atmosphere.