Activity and deactivation studies for direct dimethyl ether synthesis using CuO-ZnO-Al2O3 with NH(4)ZSM-5, HZSM-5 or gamma-Al2O3

Herein we investigate the use of CuO-ZnO-Al2O3 (CZA) with different solid acid catalysts (NH(4)ZSM-5. HZSM-5 or gamma-Al2O3) for the production of dimethyl ether from syngas. It was found that of the solid acids, which are necessary for the dehydration function of the admixed system, the CZA/HZSM-5 bifunctional catalyst with a 0.25 acid fraction showed high stability over a continuous period of 212 h.

As this particular system was observed to loose around 16.2% of its initial activity over this operating period this study further investigates the CZA/HZSM-5 bifunctional catalyst in terms of its deactivation mechanisms. TPO investigations showed that the catalyst deactivation was related to coke deposited on the metallic sites: interface between the metallic sites and the support near the metal-support: and on the support itself. 

Microwave-assisted Cu-catalyzed Ullmann ether synthesis in a continuous-flow milli-plant

The combination of milli-scale processing and microwave heating has been investigated for the Cu-catalyzed Ullmann etherification in fine-chemical synthesis, providing improved catalytic activity and selective catalyst heating. Wall-coated and fixed-bed milli-reactors were designed and applied in the Cu-catalyzed Ullmann-type CO coupling of phenol and 4-chloropyridine. In a batch reactor the results show clearly increased yields for the microwave heated process at low microwave powers, whereas high powers and catalyst loadings reduced the benefits of microwave heating. Slightly higher yields were found in the Cu/ZnO wall-coated as compared to the Cu/TiO fixed-bed flow-reactor. The benefit here is that the reaction occurs at the surface of the metal nanoparticles confined within a support film making the nano-copper equally accessible. Catalyst deactivation was mainly caused by Cu oxidation and coke formation; however, at longer process times leaching played a significant role. Catalyst activity could partially be recovered by removal of deposited by-product by means of calcination. After 6h on-stream the reactor productivities were 28.3 and 55.1kgprod/(mR3h) for the fresh Cu/ZnO wall-coated and Cu/TiO fixed-bed reactor, respectively. Comparison of single- and multimode microwaves showed a threefold yield increase for single-mode microwaves. Control of nanoparticles size and loading allows to avoid high temperatures in a single-mode microwave field and provides a novel solution to a major problem for combining metal catalysis and microwave heating. Catalyst stability appeared to be more important and provided twofold yield increase for the CuZn/TiO catalyst as compared to the Cu/TiO catalyst due to stabilized copper by preferential oxidation of the zinc. For this catalyst a threefold yield increase was observed in single-mode microwaves which, to the best of our knowledge, led to a not yet reported productivity of 172kgprod/(mR3h) for the microwave and flow Ullmann CO coupling. © 2012 Elsevier B.V.

Influence of a pore-forming agent on swelling, network parameters, and permeability of poly(ethylene glycol)-crosslinked poly(methyl vinyl ether-co-maleic acid) hydrogels:Application in transdermal delivery systems

We characterized hydrogels, prepared from aqueous blends of poly(methyl vinyl ether-co-maleic acid) (PMVE/MA) and poly(ethylene glycol) (PEG 10,000 Daltons) containing a pore-forming agent (sodium bicarbonate, NaHCO ). Increase in NaHCO content increased the equilibrium water content (EWC) and average molecular weight between crosslinks (M ) of hydrogels. For example, the %EWC was 731, 860, 1109, and 7536% and the M was 8.26, 31.64, 30.04, and 3010.00 × 10 g/mol for hydrogels prepared from aqueous blends containing 0, 1, 2, and 5% w/w of NaHCO , respectively. Increase in NaHCO content also resulted in increased permeation of insulin. After 24 h, percentage permeation was 0.94, 3.68, and 25.71% across hydrogel membranes prepared from aqueous blends containing 0, 2, and 5% w/w of NaHCO , respectively. Hydrogels containing the pore-forming agent were fabricated into microneedles (MNs) for transdermal drug delivery applications by integrating the MNs with insulin-loaded patches. It was observed that the mean amount of insulin permeating across neonatal porcine skin in vitro was 20.62% and 52.48% from hydrogel MNs prepared from aqueous blends containing 0 and 5% w/w of NaHCO . We believe that these pore-forming hydrogels are likely to prove extremely useful for applications in transdermal drug delivery of biomolecules. © 2012 Wiley Periodicals, Inc.

Thermosensitive hydrogels of poly(methyl vinyl ether-co-maleic anhydride) - Pluronic (R) F127 copolymers for controlled protein release

Thermosensitive hydrogels are of a great interest due to their many biomedical and pharmaceutical applications. In this study, we synthesized a new series of random poly (methyl vinyl ether-co-maleic anhydride) (Gantrez (R) AN, GZ) and Pluronic (R) F127 (PF127) copolymers (GZ-PF127), that formed thermosensitive hydrogels whose gelation temperature and mechanical properties could be controlled by the molar ratio of GZ and PF127 polymers and the copolymer concentration in water. Gelation temperatures tended to decrease when the GZm/PF127 ratio increased. Thus, at a fixed GZm/PF127 value, sol-gel temperatures decreased at higher copolymer concentrations. Moreover, these hydrogels controlled the release of proteins such as bovine serum albumin (BSA) and recombinant recombinant kinetoplastid membrane protein of Leishmania (rKMP-11) more than the PF127 system. Toxicity studies carried out in J774.2 macrophages showed that cell viability was higher than 80%. Finally, histopathological analysis revealed that subcutaneous administration of low volumes of these hydrogels elicited a tolerable inflammatory response that could be useful to induce immune responses against the protein cargo in the development of vaccine adjuvants.

An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasifi- cation, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day1 of OME3, OME4, and OME5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno- economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Synthesis and Thermophysical Properties of Ether Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis(trifluoromethyl)sulfonylimide, [NTf2]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.