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In the field of alternative diesel fuels, so-called oxymethylene ethers (OMEs) are currently intensely investigated. Particularly OMEs of the type CH3O(CH2O)nCH3 with n = 3–5 exhibit promising fuel properties and combustion characteristics with strongly reduced particle and NOx emissions. According to their molecular structure, OMEs can be produced from methanol thus enabling sustainable production strategies from CO2 and renewable resources. Compared to the methyl derivatives, analogous compounds with higher alkyl groups (oxymethylene dialkyl ethers, OMDAEs) have been investigated to a much lesser extent. Thus, commercially available OMDAEs, i.e. compounds of the type ROCH2OR bearing ethyl, propyl, butyl and 2-ethylhexyl groups, have been studied. Furthermore, asymmetric compounds of the type R1OCH2OR2 have been synthesized from the symmetric compounds employing transacetalization reactions catalyzed by zeolite BEA-25. The OMDAEs have been characterized by spectroscopic and spectrometric methods and several physico-chemical, thermodynamic and fuel-related data have been determined and compared. Despite their structural peculiarities, such as the oxygen-containing acetal moiety in the molecular backbone, all OMDAEs exhibit properties similar to conventional diesel fuels. Based on experimental and analytical data, the development of tools for the prediction of properties by a simple regression method is described. Furthermore, the suitability of group contribution modelling is investigated for OMDAE compounds.

A three-site mean-field extended microkinetic model was developed based on ab initio DFT calculations from the literature, in order to simulate the conversion of syngas (H2/CO/CO2) to methanol on Cu (211) and Cu/Zn (211). The reaction network consists of 25 reversible reactions, including CO and CO2 hydrogenation to methanol and the water-gas shift reaction. Catalyst structural changes are also considered in the model. Experiments were performed in a plug flow reactor on Cu/ZnO/Al2O3 at various gas hourly space velocities (24–40 L h−1 gcat−1), temperatures (210–260 °C), pressures (40–60 bar), hydrogen feed concentrations (35–60% v/v), CO feed concentrations (3–30% v/v), and CO2 feed concentrations (0–20% v/v). These experiments, together with experimental data from the literature, were used for a broad validation of the model (a total of 690 points), which adequately reproduced the measurements. A degree of rate control analysis showed that the hydrogenation of formic acid is the major rate controlling step, and formate is the most sensitive surface species. The developed model contributes to the understanding of the reaction kinetics, and should be applicable for industrial processes (e.g. scale-up and optimization).

Reaction kinetic modeling, model-based optimization and experimental validation are performed for the direct synthesis of dimethyl ether from CO2 rich synthesis gas. Among these disciplines, experimental methods and models are aligned in a stringent way of action, i.e., the same setup and models are applied throughout the whole contribution. First, a lumped reaction kinetic model from the literature is modified and parametrized to fit a vast array of 240 data points measured in a laboratory fixed bed reactor. The data were acquired using a mechanical mixture of the commercial catalysts CuO/ZnO/Al2O3 and γ-Al2O3. For this setup, a predictive model is derived and applied within dynamic model-based optimization. Here, the single-pass COx conversion serves as objective function while the operating conditions and composition of the mixed catalyst bed are the optimization variables. Finally, the optimization results obtained numerically are validated experimentally verifying the identified performance enhancement qualitatively. The remaining quantitative deviations yield valuable insights into model and methodological weaknesses or inaccuracies, closing the loop between kinetic investigations, model-based optimization and experimental validation.

Oligomeric oxymethylene dimethyl ethers (DMEs; OMDMEn) are acetals of the type CH3O(CH2O)nCH3 with a high oxygen content and without carbon–carbon bonds in the molecular structure. Therefore, formation of soot and NOx emissions is largely suppressed during combustion. Oligomers with n = 3–5 exhibit properties similar to conventional diesel fuel and this stimulated extensive research in this field. Reactions of OMDME1, the corresponding ethyl derivative OMDEE1 and dimethyl ether (DME) with trioxane have been carried out employing zeolite BEA25 as acidic catalyst. Thus, oligomer mixtures with n = 1–5 are obtained and very small amounts of higher oligomers are also formed. OMDMEn- or OMDEEn-forming reactions from the starting materials take place as well as subsequent transacetalization reactions which lead usually to a product distribution according to a Schulz–Flory distribution. Several transacetalization reactions have been studied, e.g. reactions of OMDME1 with OMDME3 and OMDEE1 with OMDEE3, which lead to the typical mixtures with n = 1–5. Reactions of OMDME1 with OMDEE1 yielded ethoxymethoxymethane, i.e. the acetal with mixed end groups. This allows for the tuning of oligomer mixtures and adjustment of properties according to the required demands of the respective application. Regarding DME as starting compound, the transacetalization reaction with OMDME3 yielded only small amounts of OMDME1–5 while the reaction of DME with trioxane yielded considerable amounts of the oligomers. The reaction is comparatively slow enabling a kinetic control of the oligomer distribution which exhibits an elevated selectivity for the desired OMDME3–5 fraction in the beginning of the reaction.

Lignin represents the most significant potential source of sustainable aromatic compounds. Currently, the vast majority of technical lignin could be sourced from industrial paper production and in particular the Kraft process, where it is conventionally combusted for chemicals recovery and heat generation (e.g. for plant operation). While in recent years several efforts have concerned the conversion of native lignin (i.e. as found in nature) during biomass processing, there has also been significant focus on the “Base Catalyzed” conversion of technical lignin. This process is of significant interest, since it could be potentially integrated into existing Kraft mill infrastructure. The following review paper focuses on the development of the hydrothermal base catalyzed depolymerization (HBCD) of lignin, as a basis to produce valuable chemical compounds. Focus will be placed on NaOH catalyzed reactions in the aqueous phase, as this approach is considered the most promising. Focus is placed on reaction conditions and characterization of monomeric aromatic compounds from the HBCD approach. Oligomers, as largest product fraction, is also considered, however, these are seldom analyzed in detail in the literature and ideas on further use are scarce. The review also addresses findings in literature concerning the assessment of the solid, liquid, and gas product streams arising from HBCD. From this paper, process conditions for HBCD reactions can be derived and it is shown that the solid phase has a high potential for further valorization and downstream processing.

Industrial Kraft Lignin (KL) prepared by LignoBoost® technology was treated via hydrothermal base catalysed depolymerisation (HBCD). KL was dried and divided into methanol soluble and insoluble fractions. The insoluble fraction was treated in 1 M NaOH (aq) at 300 °C. After precipitation with HCl (aq), the solids yield was ca. 60 wt%. These solids demonstrated improved thermal stability and carbon content, increased solubility in MeOH and reduction in polydispersity. With a view to the use of the product in the preparation of carbon-based materials (e.g. carbon fibres (CF)), thermal analysis was undertaken, revealing a lack of a glass transition below the decomposition temperature, excluding melt pinning. However, a high solubility in organic solvents renders the product a suitable candidate for solvent spinning and for the production of renewable low-cost CFs. Additionally, the process generated an oily liquid phase with yields of ca. 10 wt% containing valuable catechol and methylated derivatives., RJW acknowledges financial support of the Fraunhofer Society and Fraunhofer Institute for Solar Energy Systems ISE through an “ATTRACT” award. PSS gratefully acknowledges the Spanish Ministry for Economy and Enterprise (MINECO) for a Ramón y Cajal fellowship (RYC-2014-16759) and a proyecto de I+D+I para jóvenes investigadores (MAT2014-59674-JIN). RJW and MO would also like to acknowledge the support of the joint Max Planck Society/Fraunhofer Society project “Dendrorefining”. Dr. H. Scherer (AK Krossing; University of Freiburg, Germany) is especially thanked for his assistance with NMR measurements. The authors would like to thank the ICTP-CSIC characterisation service for their help in measuring the DSCs of the samples. The Fraunhofer IAP (Potsdam, Germany) is thanked for assistance with GPC measurements.

Hierarchical H-ZSM-5 zeolites are a promising class of heterogeneous catalysts that have shown encouraging results in lab-scale studies for the production of gasoline from dimethyl ether (DTG conversion). However, the influences of mesopore formation and shaping on various catalyst properties are still under debate. In this study, a series of H-ZSM-5 zeolites with hierarchical pore structures were prepared by modifying commercially available zeolites via alkaline treatment ("desilication"). The powdered zeolites were shaped into technical catalyst bodies by wet extrusion using either silica or alumina binders. All materials were extensively characterized. The different interactions during alkaline treatment were related to the observed modifications in the zeolite properties of the materials obtained. Although many properties of modified and untreated zeolite powders remained predominantly unchanged in their shaped catalyst equivalents, both binders affected certain material characteristics, particularly those related to their acidity. Finally, preliminary tests showed enhanced catalytic performance of hierarchical ZSM-5 catalysts in DTG conversion.

Well-defined Pd/Ga-nanoparticles were prepared and used as a precursor for the methanol active component in a bifunctional syngas-to-dimethyl ether catalyst. In situ X-ray absorption spectroscopy experiments were employed both to unravel the initial formation of the active catalyst phase in reductive H 2 atmosphere and to further monitor changes of the nanoparticles under conditions of dimethyl ether synthesis at a pressure up to 20 bar (250 °C). The catalytic studies were conducted using simulated biomass-derived, CO-rich syngas in a continuous-flow reactor, with the bifunctional catalyst offering the two types of active sites, i.e. for methanol synthesis (Pd/Ga nanoparticles) and its subsequent dehydration (γ-Al 2 O 3 ), in close proximity. As compared to the conventional Cu/Zn-based reference catalyst prepared via a similar procedure, the Pd/Ga-based catalyst showed a promising activity together with a notable stability with time on stream and a high temperature tolerance (up to 300 °C). A kinetic model which considers the individual reactions involved in direct DME synthesis based on power law equations was used to fit the experimental data, and the apparent activation energies were compared to the Cu/Zn-based catalyst.

Hybrid catalysts were prepared using well-defined, colloidal Cu/Zn-based nanoparticles as building units. The nanoparticles were immobilized on acidic supports (i.e., γ-Al2O3, HZSM-5, and HY) to yield a series of bifunctional catalysts with a close proximity of active sites for both methanol synthesis and its further conversion to dimethyl ether (DME) or hydrocarbons (HCs). By this model kit principle, a high comparability of the bifunctional catalysts was ensured. The catalysts were characterized in depth regarding their structure and catalytic performance in the conversion of CO-rich synthesis gas. In situ XAS studies demonstrated the formation of the active phase under reducing conditions. The present study revealed important material parameters to control activity and selectivity of the bifunctional catalysts either towards DME or liquefied petroleum gas (LPG) products in the direct conversion of simulated biomass-derived synthesis gas. In particular, Cu loading, pore structure and Si:Al ratio were investigated.

Oligomeric oxymethylene ethers (OMEs) are promising fuels for internal combustion engines with self-ignition. A tremendous reduction of soot, nitrogen oxide and hydrocarbon emissions can be realized by employing OMEs. This work describes the synthesis of OMEs from dimethyl ether (DME) and trioxane. Zeolite H-BEA 25 was found to be a suitable catalyst for this reaction and a study on reaction parameters (e.g. temperature, reactant feed ratio and reaction time) has been carried out. A maximum DME conversion of 13.9 wt% could be obtained and the maximum reactant-related product yield for OME3–5 was 8.2 wt%. An OME formation mechanism is proposed which explains the observed product spectrum.

Oligomeric oxymethylene dimethyl ethers (OMEs) of the type CH3O-(CH2O)n-CH3 are promising diesel fuels with an enormous potential for the reduction of soot and NOx emissions. Oligomers with n = 3–5 are particularly advantageous, since their physicochemical and combustion properties are similar to conventional diesel. OMEs can be produced from methanol and formaldehyde but a series of byproducts, especially hemiformals, glycols, water and minor amounts of cyclic ethers, are also formed. These need to be separated from the product mixtures, which affects efficiency of this synthesis pathway. To isolate the desired OMEs, a one-step synthesis/extraction procedure is described. It implies highly selective extraction of OMEs from aqueous reaction solutions employing hydrocarbons as extraction agents. If fuel-type hydrocarbons are used, the resulting OME-hydrocarbon blends can be directly used in fuel applications. The corresponding oxymethylene diethyl ethers (OMDEEs) have also been investigated. Compared to OMEs, OMDEEs exhibit an increased solubility in nonpolar media but, as a result, solubility of educts and byproducts also increases. OME blends with hydrogenated vegetable oil and diesel have been prepared containing 10% of OMEs. It could be shown that such blends meet current diesel standards to a large extent.

Oligomeric oxymethylene dimethyl ethers (OME n , CH 3 O(CH 2 O) n CH 3 ) bearing three to five CH 2 O units are promising diesel fuels for the reduction of soot and NO x emissions. Regarding the production of OMEs, a highly optimized process has not been realized yet. This work describes efficient synthesis of OMEs from dimethoxymethane (DMM) and trioxane in batch experiments at room temperature and atmospheric pressure. To ensure high reactivity and high OME yields, dry educts have been used and the influence of water has been investigated in detail. The ion exchange resin Amberlyst36 and zeolites have been employed as acidic catalysts. Zeolite BEA25 exhibited highest catalytic activity and the reaction could be completed within 12 min at 25 °C. Furthermore, the formation of byproducts could be fully eliminated.

A catalyst screening comprising zeolites and ion exchange resins for the synthesis of oligomeric oxymethylene dimethyl ethers (OME) from methanol (MeOH) and formaldehyde (FA) has been carried out. All catalysts led to the same product spectrum and parameters for chemical equilibrium have been determined. The ion exchange resin Dowex50Wx2 showed highest activity and reaction kinetics has been investigated employing this catalyst. The influence of the FA:MeOH ratio and water as well as refeeding of OMEs with undesired chain lengths have been considered in the kinetic model, which is based on a hyperbolic approach. Experiments have been carried out in the temperature range between 40 and 120 °C and variable FA:MeOH ratios from 0.5 to 1.5 g/g have been employed. Regarding water, up to 23 wt.% have been added to the reaction mixtures to investigate its influence on yield and reaction rate. Low water contents lead to high OME selectivities. By varying the FA:MeOH ratio, chain lengths of the OMEs can be influenced. Regarding the most active catalyst Dowex50Wx2, 90% of equilibrium conversion is reached after 5 min at 60 °C employing a catalyst loading of 1 wt.%. A study on the long term performance of the catalyst has been carried out and after 17 days the decrease of activity was below 10% while selectivity remained the same. For different Dowex catalysts a general kinetic model could be developed, which is not limited to Dowex50Wx2.

Lignocellulosic biomasses are strongly connected composites of cellulose, hemicelluloses, and lignin. A pretreatment is required in order to make these components available for their later conversion into chemicals. At this point, two strategies have to be considered: to either produce chemicals via microorganism or enzymes (1), or by chemical conversion (2). The focus of this article is the second strategy, which is chemical conversion, performed in water to produce the final products furfural and 5-hydroxymethylfurfural (HMF). Reviewed first is the composition of cellulose and hemicelluloses as well as their degradation chemistry in water. Then, fundamental modes of action and process parameters of pretreatment methods in aqueous solution are summarized. The pretreatment methods discussed here are steam explosion, treatment with hot liquid water, diluted and concentrated acids, as well as alkaline solutions. Finally, the advantages and disadvantages of these pretreatments are discussed for lignocellulosic biomass.

Oligomeric oxymethylene dimethyl ethers (OMEn, CH3(OCH2)nOCH3, n = 1 – 5) are promising diesel fuels for the reduction of harmful emissions. If OMEs are produced from dimethoxymethane and trioxane, the resulting OME mixtures usually contain residual trioxane which appears, after rectification, in the OME2 fraction. To circumvent this obstacle, substoichiometric amounts of trioxane have been employed in OME synthesis. Thus, OME2 samples with high purity could be prepared. Physicochemical and fuel data of high purity OME2 and higher OMEs have been determined to supplement previously reported data.

Hydrolysis of lignocellulosic biomass is a crucial step for the production of sugars and biobased platform chemicals. Pretreatment experiments in a semi-continuous plant with diluted sulphuric acid as catalyst were carried out to measure the time-dependent formation of sugars (glucose, xylose, mannose), furfurals, and organic acids (acetic, formic, and levulinic acid) at different hydrolysis temperatures (180, 200, 220 &deg, C) of one representative of each basic type of lignocellulose: hardwood, softwood, and grass. The addition of the acid catalyst is followed by a sharp increase in the sugar concentration. Xylose and mannose were mainly formed in the initial stages of the process, while glucose was released slowly. Increasing the reaction temperature had a positive effect on the formation of furfurals and organic acids, especially on hydroxymehtylfurfural (HMF) and levulinic acid, regardless of biomass type. In addition, large amounts of formic acid were released during the hydrolysis of miscanthus grass. Structural changes in the solid residue show a complete hydrolysis of hemicellulose at 180 &deg, C and of cellulose at 200 &deg, C after around 120 min reaction time. The results obtained in this study can be used for the optimisation of the hydrolysis conditions and reactor design to maximise the yields of desired products, which might be sugars or furfurals.

Within the so-called bioliq® process, renewable carbon resources, especially agricultural residues, are converted to gasoline. The process chain comprises pyrolysis of the feedstocks, gasification to synthesis gas, gas cleaning and conversion of synthesis gas to dimethyl ether (DME) followed by conversion of DME to hydrocarbons. Construction of all process units has been completed now and the entire plant has been successfully operated in several campaigns. Thus, hundreds of liters of a new alternative gasoline are available now, which allow for an extensive testing. The basic characteristics of the resulting bioliq®/100 fuel are described. It is rich in aromatics and a blend consisting of 90 Vol.−% of conventional RON95 E5 fuel and 10 Vol.−% of bioliq®/100, designated as bioliq®/10, has been produced which meets the DIN EN 228 standard. Initial measurements on a single cylinder research engine have been carried out focusing on efficiency and emissions. A comparison of bioliq®/10 with neat RON95 E5 revealed an improved knocking behavior of bioliq®/10 even by a small fraction of regenerative bioliq® fuel. Particle as well as hydrocarbon emissions from bioliq®/10 are significantly higher than in the case of RON95 E5. Increased particle emissions are attributed to the higher content of aromatics. Soot reactivity has been investigated and soot from bioliq®/10 exhibits higher reactivity than soot from RON95 E5.

Gasification in supercritical water can be assisted with heterogeneous catalysts. Effective salt separation upstream of the catalyst is important to avoid poisoning of the catalyst and to recover nutrients. Recovery of phosphorus and nitrogen as well as gasification of a significant portion of the organic carbon were demonstrated on the pilot plant scale. A Ru/C catalyst was applied to catalyze the formation of CH4, which was the desired primary gasification product. On top of the catalyst, a bed of ZnO was used as sulfur adsorbent to protect the catalyst from deactivation. As feedstock for the process, glycerol, ethanol, and digestate sludge were studied. The results confirm the activity of the catalyst under the applied conditions. At a reaction temperature of 420 °C and a pressure of 280 bar, a gas composition close to thermodynamic equilibrium was achieved. Salt separation performed at 470 °C was effective, but the separation efficiency was less for potassium than for phosphorus. Fifty-six percent of the ash contained in digestate sludge was separated and recovered. Sulfur partly escaped the salt separation system and reached the reactor. The ZnO layer trapped most of this remaining sulfur. The remaining sulfur contamination was low enough not to poison the Ru/C catalyst completely. In total, 326 kg of glycerol, 334 kg of digestate sludge, and 167 kg of ethanol were gasified without any operational issues.

A methanol catalyst based on Cu/ZnO/Al 2 O 3 (CZA) was prepared and mixed with four different solid acids, a pure γ-Al 2 O 3 , a SiO 2 -doped γ-Al 2 O 3 , an AlPO 4 -doped γ-Al 2 O 3 and the zeolite H-MFI 400, respectively. These admixed catalyst systems were tested in the direct synthesis of dimethyl ether from CO-rich synthesis gas (CO:H 2 = 1), which is typical for biomass-derived synthesis gas. Reactions were carried out in a laboratory plant at 250 °C and 51 bar for 120 h time-on-stream followed by catalyst passivation with O 2 and regeneration by hydrogenation. After catalyst regeneration, the reaction was run again for another 72 h. The catalyst system containing the zeolite exhibited highest CO-conversion. However, all catalysts showed a drop of activity after the passivation- and regeneration-process and the system with the SiO 2 -doped γ-Al 2 O 3 showed the lowest loss of activity. Investigation of the catalysts after reaction by N 2 O-pulse chemisorption and XRD revealed that agglomeration of catalyst species took place leading to an increased Cu 0 -particle size for all systems. This phenomenon was less pronounced in the case of the system containing the SiO 2 -doped γ-Al 2 O 3 . Thus, the main cause of catalyst deactivation was found to be sintering of the catalytically active components.

Bio-ethanol is a renewable fuel and can be converted to high-values chemicals. This study showed that more aromatics and gas products could be obtained at a low weight hourly space velocity (WHSV) than that at high WHSV using HZSM-5 and Ni/HZSM-5 catalysts. A low WHSV offered an increased tendency to build up aromatics and paraffins. Real bio-ethanol broth was tested and gave the similar result as pure ethanol solution. That catalysts could retain full catalytic activity after 168 h in reaction provides evidence for their long stability. This study advantageously demonstrates a promising approach to generate high-value products from bio-ethanol.

The single‐step syngas‐to‐dimethyl ether (STD) process entails economic and technical advantages over the current industrial two‐step process. Pd/ZnO‐based catalysts have recently emerged as interesting alternatives to currently used Cu/ZnO/Al2O3 catalysts, but the nature of the active site(s), the reaction mechanism, and the role of Pd and ZnO in the solid catalyst are not well established. Now, Zn‐stabilized Pd colloids with a size of 2 nm served as the key building blocks for the methanol active component in bifunctional Pd/ZnO‐γ‐Al2O3 catalysts. The catalysts were characterized by combining high‐pressure operando X‐ray absorption spectroscopy and DFT calculations. The enhanced stability, longevity, and high dimethyl ether selectivity observed makes Pd/ZnO‐γ‐Al2O3 an effective alternative system for the STD process compared to Cu/ZnO/γ‐Al2O3., Zinc‐stabilized palladium colloids with a size of about 2 nm are the key building units for bifunctional syngas‐to‐dimethyl ether catalysts with enhanced stability, longevity, and high dimethyl ether selectivity. The catalysts were characterized by combining high‐pressure operando X‐ray absorption spectroscopy and DFT calculations.

The hydrothermal base-catalysed treatment of industrial Kraft lignin (KL) is investigated as a basis for production of a sustainable carbon fibre precursor, with a focus on the time-dependent evolution and impact on precursor properties. Hydrothermal treatment was performed at T = 300 °C and p = 180 bar, with the retention time (t) varied between 8, 12, 16, 20, and 24 mins. Molecular weight distribution and thermal stability of the processed lignin were close to maximum after 8 min, and 12–16 min respectively. Chemical modification was found to continue (e.g. demethoxylation) over the entire t range (24 min). Analysis of the recovered oily phase indicated catechol derivatives were stable end-products with, e.g., vanillin and guaiacol as intermediates. A techno-economic analysis indicated a price of ca. 1600 €/t at a production capacity of 10 kt/a is achievable, with main cost-drivers being lignin (60%), fixed costs (20%), and energy (10%)., RJW acknowledges financial support of the Fraunhofer Society and Fraunhofer Institute for Solar Energy Systems ISE through an “ATTRACT” award. PSS gratefully acknowledges the Spanish Ministry for Economy and Enterprise (MINECO) for a Ramón y Cajal fellowship (RYC-2014-16759) and a proyecto de I+D+I para jóvenes investigadores (MAT2014-59674-JIN). RJW and MO would also like to acknowledge the support of the joint Max Planck Society/Fraunhofer Society project “Dendrorefining”. Dr. H. Scherer (AK Krossing; University of Freiburg, Germany) is thanked for his assistance with NMR measurements. The authors would like to thank the ICTP-CSIC characterisation service for their help in measuring the DSCs of the samples. The Fraunhofer IAP (Potsdam, Germany) is thanked for assistance with GPC measurement

Well-defined colloidal Cu/Zn-based nanoparticles were synthesized and employed as precursors for the methanol active component in bifunctional syngas-to-dimethyl ether (STD) catalysts. The experiments were conducted using simulated biomass-derived, CO-rich syngas (H2 : CO ratio of 1 : 1) in a single continuous-flow reactor by combining the two catalytically active components (i.e., Cu/ZnO for methanol synthesis and γ-Al2O3 for its subsequent dehydration). Two different synthetic pathways were developed for synthesizing the colloidal Cu/Zn-based nanoparticles, while ensuring close contacts between the Cu nanoparticles and the Zn phase. Pure Cu nanoparticles were used as a reference. A series of bifunctional STD catalysts was prepared, where the nanoparticles were either directly supported on the dehydration catalyst or integrated into the STD catalyst by physical mixing. With this approach, active catalysts for the STD reaction with high DME selectivity were obtained.

Catalysts of the type Cu/Co/ZnO/SiO2 were prepared by impregnation, subsequent calcination and reduction with hydrogen. Characterization of the catalysts was carried out by ICP-AES, BET measurements and powder X-ray diffraction analyses. Furthermore, temperature programmed reduction was employed to investigate their reduction behavior. The catalysts were tested in the conversion of synthesis gas to hydrocarbons and alcohols. High CO conversions could be reached in a single reactor pass. Selectivity was highest for methane, and short-chain hydrocarbons, but alcohols were also formed.

Palladium compounds (Pd(OAc) 2 and Pd(acac) 2 ) were dissolved in commercially available epoxy resins (glycidyl derivatives of bisphenol A and p -aminophenol) and the formulations were polymerized employing the ionic liquid 1-ethyl-2-methylimidazolium acetate (EMIM acetate) as polymerization initiator. Thus, palladium species could be incorporated in the network of the resulting polyether materials. Polymerization reactions were investigated by DSC and the curing behavior of different formulations was compared. High polymerization enthalpies were observed indicating high crosslinking in the materials. Accordingly, the materials exhibited high glass transition temperatures and thermogravimetric data revealed high thermal stability. Due to the good solubility of the palladium compounds in the epoxy resins, a widely homogeneous dispersion of palladium species in the polyether matrix could be realized. This was confirmed by SEM-EDX and TEM measurements. XPS measurements revealed that reduction of Pd(II) to Pd(0) species occurred during catalyst preparation and this was also proven by XRD. The materials were ground and successfully employed as catalysts for the hydrogenation of several alkenes under mild reaction conditions. High conversions and selectivities could be reached within a few hours at room temperature and moderate hydrogen pressure of 2.5 bar. Palladium leaching from the catalysts to reaction solutions was investigated. To determine very low quantities, metal concentrations were enriched by removal of volatile components. Subsequent ICP-AES measurements revealed low palladium contents in the range of a few μg. These amounts correspond to values around 0.007% with respect to palladium originally loaded on the polymer. Catalyst recycling experiments were also carried out and it was shown that the catalysts can be employed in numerous consecutive reactions without any catalyst treatment and without loss of activity. Within a series of reactions, palladium leaching decreased while catalytic activity was not affected.

Bio-fuels of the 2nd generation constitute a key approach to tackle both Greenhouse Gas (GHG) and air quality challenges associated with combustion emissions of the transport sector. Since these fuels are obtained of residual materials of the agricultural industry, well-totank CO2 emissions can be significantly lowered by a closed-cycle of formation and absorption of CO2. Furthermore, studies of bio-fuels have shown reduced formation of particulate matter on account of the fuels’ high oxygen content therefore addressing air quality issues. However, due to the high oxygen content and other physical parameters these fuels are expected to exhibit different ignition behaviour. Moreover, the question is whether there is a positive superimposition of the fuels ignition behaviour with the benefits of an alternative ignition system, such as a corona ignition. To shed light on these questions two oxygenic compounds, oxymethylene ether-1 (OME1) and dimethyl carbonate (DMC) have been studied with respect to OH* emission throughout ignition and onset of flame-front propagation in a combustion chamber with a large optical access via a quartz window. OH* measurements have been recorded via a highspeed optical camera (5 kHz) coupled with 308 nm optical filter and image intensifier. Sealing material swelling tests have yielded a perfluoroelastomer (FFKM 72) as an ideal, cost-efficient material regardless of the applied fuel. Comparative measurements with both ignition systems for combustion of gasoline as well as moderate blend admixtures of OME1 and DMC have demonstrated the superior ignition stability with likewise implications on flame-kernel development for the corona ignition. Furthermore a strong influence of the mode of discharge on OH* formation rates was observed especially for the oxygenic blends. Finally, for admixture variations of both oxygenates, an increased OH* level was shown during discharge thereby proving the hypothesis of a positive superimposition of oxygenic fuel and corona ignition system.

Zeolite-based bifunctional catalysts for the production of dimethyl ether (DME) from CO-rich synthesis gas (H2:CO = 1) were prepared via various preparation methods including co-precipitation–impregnation, impregnation, co-precipitation sedimentation and oxalate co-precipitation. The catalysts comprise a Cu/ZnO/Al2O3 component for methanol formation and zeolite H-MFI 400 as acidic component for methanol dehydration to DME. An admixed catalyst system was used as reference and all catalysts were characterized by SEM-EDX, XRF, N2-physisorption, XRD, H2-TPR, NH3-TPD, N2O-pulse chemisorption and TEM. The catalysts were tested in a continuously operating laboratory plant and the experiments revealed that the synthesis strategy strongly influences catalyst properties and hence catalyst activity. Especially a bifunctional catalyst prepared via oxalate co-precipitation proved to be highly active and could compete with conventional admixed catalyst systems. High CO-conversion and a high DME-selectivity could be reached. Catalyst characterization revealed that high Cu surface areas, small Cu particle sizes and a high number of moderate acidic sites are crucial to achieve maximum catalytic performance.

The majority of platform chemicals are currently provided through crude oil processes. Nevertheless, the substitution of the crude oil with biomass should be the ecological aim. Lignin, an aromatic macromolecule, may play an important role in that exchange, as it is the only bio based source of aromatic compounds. For instance, it could be a source of bifunctional aromatic molecules, like the monocyclic compounds catechol or guaiacol, or bifunctional oligomers. However, no process for the production of aromatics from lignin in technical scale has been established until now. Hence, the focus of this work is to clarify the chemical degradation mechanism under hydrothermal conditions, to liquefy lignin delivering high functional molecules and to increase the yield and selectivity of the cleavage towards bifunctional molecules like catechol. The combination of fast hydrolysis, thermal degradation reactions and hydrogenation drives the hydrothermal liquefaction; this gives the possibility to narrow down the product spectrum in comparison to other “dry” cleavage methods, towards a higher yield of e.g. catechols.

Renewable fuels from biomass have to be produced in large facilities to profit from the economy of scale. Unfortunately, most biomass residues have only a low energy density and are collected in wide areas, which hampers the transport to a large central conversion plant. Therefore, energy densification is a crucial point which can be achieved by thermochemical process like fast pyrolysis, yielding liquid bio-oil and solids consisting of char and ash. High energy densities can be obtained by mixing of the solid and liquid conversion products to produce bio-slurries also referred to as biosyncrude. In the bioliq® process, these liquid-like suspensions are used as feed for high pressure entrained flow gasification and downstream synthesis of fuels and chemicals. The article describes the mixing process of bio-slurries and the most relevant parameters, which have to be taken into consideration. The materials used are mainly derived from the pyrolysis of beech wood, wheat straw, and oil palm residues, but also model mixtures of char with ethylene glycol and water show principal features of the bio-slurries. Small char particles with low porosity promote flowability of the bio-slurry and stability with regard to sedimentation, but also examples are worked out, where liquid–liquid phase separation have negative influence of the handling of bio-slurries. The power consumption of the bio-slurry production and the viscosity of a bio-slurry depend highly on the selected technologies by which deagglomeration and milling is carried out. A successful bio-slurry preparation results in a flowable suspension of at least reasonable stability with an energy content of > 85% of the energy of the biomass feedstock.

In view of a world-wide growing fuel demand coming along with a strong environmental impact, exploration of alternative resources, preferably renewable ones, is vastly stimulated. Regarding carbon-based fuels, biomass is the only renewable feedstock which can be converted efficiently to fuels employing either fermentative or chemical processes. Naturally, the use of residues and wastes is preferred to circumvent competition with customary markets, especially the nutrition sector. Typical fermentative procedures, which are already employed on large scale, are the production of ethanol from sugars, starch or cellulose as well as methane production via anaerobic digestion of biomass.

When deprived of essential nutrients, the non-diazotrophic cyanobacterium Synechococcus sp. strain PCC 7942 undergoes a proteolytic degradation of the phycobiliproteins, its major light-harvesting pigments. This process is known as chlorosis. This paper presents evidence that the degradation of phycobiliproteins is part of an acclimation process in which growing cells differentiate into non-pigmented cells able to endure long periods of starvation. The time course of degradation processes differs for various photosynthetic pigments, for photosystem I and photosystem II activities and is strongly influenced by the illumination and by the experimental conditions of nutrient deprivation. Under standard experimental conditions of combined nitrogen deprivation, three phases of the differentiation process can be defined. The first phase corresponds to the well-known phycobiliprotein degradation, in phase 2 the cells lose chlorophyll a prior to entering phase 3, the fully differentiated state, in which the cells are still able to regenerate pigmentation after the addition of nitrate to the culture. An analysis of the protein synthesis patterns by two-dimensional gel electrophoresis during nitrogen starvation indicates extensive differential gene expression, suggesting the operation of tight regulatory mechanisms.

For the single step synthesis of dimethyl ether (DME) from synthesis gas a Cu/ZnO/Al 2 O 3 -catalyst has been prepared using flame-spray pyrolysis. The resulting powder was co-mixed with γ-alumina to give an admixed system for DME production. The flame-made catalyst was analyzed using the BET method, in situ XRD, N 2 O decomposition, TPR and XPS. These studies unraveled that the catalyst exhibited a high Cu surface area including good contact with zinc oxide and alumina as well as small Cu particles resulting in high catalytic activity and product selectivity, also in comparison to a commercially available catalyst.

This article contains sections titled: 1. General Plug Flow Reactor Characteristics 1.1. Fundamental Types of Chemical Reactors 1.2. Flow Patterns in Tubular Reactors 1.3. PFR Heating and Cooling via Tube Wall 1.4. Mass and Energy Balance 1.5. Adiabatic Temperature Increase 1.6. Pressure Drop 1.7. Residence Time Distribution 1.8. Dimensional Analysis of PFRs for Design and Scale-Up 2. PFR Types and Configurations 2.1. Adiabatic PFRs 2.1.1. Single-Stage Adiabatic PFR 2.1.2. Multistage PFRs with Interstage Heat Exchange 2.1.3. Stepwise Cold Shot Cooling 2.1.4. Feed-Effluent Heat Exchange 2.2. Polytropic PFRs 2.2.1. Jacketed PFRs 2.2.2. Radiation Heating 2.2.3. Tubular Loop Reactor 2.3. Multitubular PFR Configurations 3. Technical Applications 3.1. General Aspects 3.2. Large Scale Commercial Applications 3.2.1. Olefins by Steam Cracking of Naphtha 3.2.2. Gas Oil Cracking in the FCC Riser Reactor 3.2.3. Vinyl Chloride Production by EDC Dehydrochlorination 3.2.4. High Pressure Ethylene Polymerization for Low Density Polyethylene (LDPE) Polyethylene 3.3. Other Commercial Applications 3.3.1. Gas Phase Halogenation of Methane and Light Alkanes 3.3.2. HCN-Production in the Degussa BMA Process 3.3.3. Ketene via Acetic Acid or Acetone Cracking 3.3.4. Ethylene Glycol via Ethylene Oxide Hydrolysis 3.3.5. Various Additional Applications 3.4. Research and Development

An experimental investigation in a tube wall reactor with catalyst-coated inner wall is presented. Yields of formaldehyde of more than 70% can be obtained in the selective methanol dehydrogenation over alkalialuminate. Models for the reactor and the system of most important homogeneous reactions are derived. Different models describing the catalytic action are proposed. The results can only be explained by a new type of catalytic reaction, not described so far in the literature. Reducing gases like hydrogen and methanol lead to a volatilization of material from alkalialuminate which apparently catalyzes the dehydrogenation in the gas phase. Calculations and experimental evidence lead to the conclusion that this material should be sodium atoms. These are engaged in the homogeneous radical chain reaction by regulating the concentration of hydrogen atoms.

The sections in this article are Introduction The Andrussow Process History Fundamentals Production of Liquid Hydrocyanic Acid Pressure Variant Oxygen Variant Ammonia Recycling Reactor and Catalyst The BMA Process Overview Development of the Catalyst Development of the BMA Tubes Reactor Design Mechanism and Kinetics of HCN formation in the BMA and Andrussow Processes Kinetics and Mechanism of the BMA Process Thermodynamic Context HCN and N2 Formation Coke Formation On the Role of Gas-Phase Reactions Catalytically Active Centers Kinetics and Mechanism of the Andrussow Process Thermodynamic Relationships HCN Formation HCN Hydrolysis Catalytically Active Centers Final Remarks Keywords: shawinigan process; Andrussow process; BMA process; reactor design and development; thermodynamics; high temperatures catalysis

Cells of the non-diazotrophic cyanobacteriumSynechococcus sp. strain PCC 7942 acclimate to nitrogen deprivation by differentiating into non-pigmented resting cells, which are able to survive prolonged periods of starvation. In this study, the physiological properties of the long-term nitrogen-starved cells are investigated in an attempt to elucidate the mechanisms of maintenance of viability. Preservation of energetic homeostasis is based on a low level of residual photosynthesis; activities of photosystem II and photosystem I were approximately 0.1% of activities of vegetatively growing cells. The low levels of photosystem I activity were measured by a novel colorimetric assay developed from the activity staining of ferredoxin:NADP+ oxidoreductase. Photosystem II reaction centers, as determined by chlorophyll fluorescence measurements, exhibited normal properties, although the efficiency of light harvesting was significantly reduced compared with that of control cells. Long-term chlorotic cells carried out protein synthesis at a very low, but detectable level, as revealed by in vivo [35S]methionine labeling and two-dimensional gel electrophoresis. In conjunction with the very low levels of total cellular protein contents, this implies a continuous protein turnover during chlorosis. Synthesis of components of the photosynthetic apparatus could be detected, whereas factors of the translational machinery were stringently down-regulated. Beyond the massive loss of protein during acclimation to nitrogen deprivation, two proteins that were identified as SomA and SomB accumulated due to an induced expression following nitrogen reduction.