Effect of Potassium Doping on the Catalytic Behavior of Mo–V–Sb Mixed Oxide Catalysts in the Oxidation of Propane to Acrylic Acid

Small addition of potassium to a Mo–V–Sb mixed oxide catalyst (previously prepared by hydrothermal synthesis) strongly modifies its catalytic behavior. Thus, while acetic acid is mainly observed in the K-free catalysts, acrylic acid is selectively obtained in K-doped catalysts. In this case, a selectivity to acrylic acid of about 30% is achieved at propane conversions of 30%. This catalytic behavior is apparently not due to modification of the crystalline phases in the K-doped catalysts but to the elimination of the acid sites of the undoped Mo–V–Sb mixed oxide catalyst.     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

Kinetics modelling of Fischer-Tropsch synthesis over an industrial Fe-Cu-K catalyst

The kinetic experiments of Fischer-Tropsch synthesis (FTS) over an industrial Fe-Cu-K catalyst are carried out in a micro-fixed-bed reactor under the conditions as follows: temperature of 493-542 K, pressure of 10.9-30.9 bar, H₂/CO feed ratio of 0.98-2.99, and space velocity of 4000-10?000 h⁻¹. The effects of secondary reactions of olefins are investigated by co-feeding C₂H₄ and C₃H₆. A detailed kinetics model taking into account the increasingly proven evidence of the olefin re-adsorption mechanism is then proposed. In this model, different sites are assumed for FTS reactions and water gas shift (WGS) reaction, respectively. Rate expressions for FTS reactions are based on the carbide polymerisation mechanism, in which olefin re-adsorption is considered to be a reverse step of olefin desorption reaction. Rate expression for WGS reaction is based on the formate mechanism. An integral reactor model considering both FTS and WGS kinetics is used to describe the reaction system, and the simultaneous estimation of kinetic parameters is conducted with non-linear regression procedure. The optimal model shows that the rate determining steps in FTS reactions proceed via the desorption of hydrocarbon products and the adsorption of CO and the slowest step in WGS reaction is the desorption of gaseous carbon dioxide via formate intermediate species. The activation energies of FTS reactions and WGS reaction are in good agreement with literature values.     

Low-temperature methanol synthesis in a circulating slurry bubble reactor

A circulating slurry bubble reactor was developed to synthesise methanol via methyl formate from the gas mixture of carbon monoxide and hydrogen at low temperature. The strategy for designing and scaling up the bubble reactor involved a preliminary understanding of fluid dynamics in a cold model, continuous operations under industrial conditions and a parallel experiment in an autoclave. Per-pass syngas conversion was investigated during 100-h operations. The axial profile of solid catalyst concentration was measured just before the shutdown and the composition of liquid product was analysed after the shutdown. These results show that the circulating slurry bubble column will become a potential reactor for the commercial process of low-temperature methanol synthesis after the catalyst system has been improved.     

Premixed metal fibre burners based on a Pd catalyst

As an alternative to previously developed catalytic FeCrAlloy fibre mat burners based on perovskite catalysts, new catalytic burners have been developed based on Pd catalyst on lantana-stabilised Al₂O₃ and different fibre structures (NIT100A, NIT100S and NIT200S by ACOTECH NV). All development steps are considered, shifting from catalyst preparation (based on combustion synthesis of γ-Al₂O₃) to the optimisation of lantana and Pd loadings, from the definitions of the best catalyst-deposition conditions (washcoating) to the catalytic burners performances, determined in an ad hoc developed combustion chamber. The results show almost half pollutants emissions and better performance compared to various non-catalytic counterparts, especially as far as CO and NO_x emissions are concerned. Some flame instability problems were though registered, especially for one of the catalytic burner mattresses employed, at low specific power inputs and excesses of air (<375 kW/m² and <12%, respectively). Further, PdO/Pd transition is shown to influence the dynamic behaviour of the catalytic burners.     

Methanol Decomposition to Synthesis Gas Over Supported Pd Catalysts Prepared from Hydrotalcite Precursors

Supported Pd catalysts were prepared by solid-phase crystallization (spc) starting from MgAl hydrotalcite anionic clay minerals as the precursors, and were tested for the methanol decomposition to synthesis gas. The precursors based on [Mg₆Al₂(OH)₁₆CO₃ ^2-] · 4H₂O were prepared by coprecipitation from raw materials containing Pd²⁺, Mg²⁺ and Al³⁺ ions as the components of hydrotalcite. The precursors were thermally decomposed and reduced to afford supported Pd catalysts on MgAl mixed oxide. Pd-supported catalysts as a reference were also prepared by the impregnation (imp) method. The spc-Pd catalysts thus prepared afforded highly dispersed Pd metal particles and showed higher activity as well as lower activation energy than the imp-Pd catalysts. When the precursor was prepared under mild conditions, finer particles of Pd metal were formed over the catalyst, resulting in a high activity. In the case of spc-Pd catalysts, carbon monoxide adsorbed on Pd easily desorbed, compared with imp-Pd catalysts. It is likely that the high activity is due to the highly dispersed and stable Pd metal particles and the easy desorption of carbon monoxide.     

质量交换网络集成的状态空间法

State space approach is an effective method to mass-exchange network (MEN) synthesis. By decomposing the network into two interactive parts, a distribution network and a process operator, the synthesis problem can be formulated into a mixed integer nonlinear programming (MINLP) model. In this article, a generalized state space model based on typical MEN is established and verified in two cases. A new asymmetrical operator and cost index are also adopted to speed up the solution process. The results demonstrate the efficiency of the proposed approach.     

Telechelic polydimethylsiloxanes with terminal acetylenic groups prepared by phase-transfer catalysis

Telechelic, hydroxyalkyl terminated polydimethylsiloxanes were obtained under mild conditions via hydrosilylation of allyl alcohol or ethylene glycol monoallyl ether by oligomeric αω-hydride terminated polydimethylsiloxanes, with the use of a platinum catalyst. They were subsequently modified in a phase transfer catalyzed reaction by propargyl bromide, to give telechelic polysiloxanes terminated by acetylenic groups. The synthetic pathway is described and the characterization of the obtained products is presented.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.     

Novel positive‐working aqueous‐base developable photosensitive polyimide precursors based on diazonaphthoquinone‐capped polyamic esters

Novel positive‐working aqueous‐base developable photosensitive polyimide (PSPI) precursors based on partially diazonaphthoquinone (DNQ)‐capped polyamic esters bearing phenolic hydroxyl groups and a DNQ photosensitive compound (PIC‐3) were developed. The partially DNQ capped polyamic esters were prepared from an esterification reaction of 1,2‐naphthoquinone diazide‐5‐sulfonyl chloride with the polyamic esters. The partially DNQ capped polyamic esters decreased the dark film loss effectively in the aqueous‐base developer and were able to make thicker film resists compared to the uncapped polyamic esters. The 25 mol % DNQ‐capped BisAPAF–PMDA polyamic ester and BisAPAF–ODPA polyamic ester containing 25 wt % PIC‐3 photosensitive compound showed a sensitivity of 176 and 185 mJ/cm², and a contrast of 1.68 and 1.02, respectively, in a 3‐μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 5 μm was obtained from both PSPI precursor compositions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2293–2300, 2003