High-pressure catalytic technique

In situ studies of catalytic reactions have also been a prime focus of our group. The high-pressure spectroscopic technique used in our research is polarization modulation IR reflection absorption spectroscopy (PM-IRAS). Like SFG, PM-IRAS is a highly surface-sensitive technique that yields vibrational information about adsorbed surface species. Unlike SFG, however, PM-IRAS... 

With the technical development achieved in the last 30 years, pressure has become a common variable in several chemical and biochemical laboratories. In addition to temperature, concentration, pH, solvent, ionic strength, etc., it helps provide a better understanding of structures and reactions in chemical, biochemical, catalytic-mechanistic studies and industrial applications. Two of the first industrial examples of the effect of pressure on reactions are the Haber process for the synthesis of ammonia and the conversion of carbon to diamond. The production of NH3 and synthetic diamonds illustrate completely different fields of use of high pressures the first application concerns reactions involving pressurized gases and the second deals with the effect of very high hydrostatic pressure on chemical reactions. High pressure analytical techniques have been developed for the majority of the physicochemical methods (spectroscopies e. g. NMR, IR, UV-visible and electrochemistry, flow methods, etc.). 

A tremendous amount of work has been done to delineate the detailed reaction mechanisms for many catalytic reactions on well characterized surfaces [1, 45]. Many of tiiese studies involved impinging molecules onto surfaces at relatively low pressures, and then interrogating the surfaces in vacuum with surface science teclmiques. For example, a usefiil technique for catalytic studies is TPD, as the reactants can be adsorbed onto the sample in one step, and the products fonned in a second step when the sample is heated. Note that catalytic surface studies have also been perfonned by reacting samples in a high-pressure cell, and then returning them to vacuum for measurement. 

The implementation of high-pressure reaction cells in conjunction with UFIV surface science techniques allowed the first tme in situ postmortem studies of a heterogeneous catalytic reaction. These cells penult exposure of a sample to ambient pressures without any significant contamination of the UFIV enviromnent. The first such cell was internal to the main vacuum chamber and consisted of a metal bellows attached to a reactor cup [34]- The cup could be translated using a hydraulic piston to envelop the sample, sealing it from... 

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

Flue gas treatment (FGT) is more effective in reducing NO, emissions than are combustion controls, although at higher cost. FGT is also useful where combustion controls are not applicable. Pollution prevention measures, such as using a high-pressure process in nitric acid plants, is more cost-effective in controlling NO, emissions. FGT technologies have been primarily developed and are most widely used in Japan. The techniques can be classified as selective catalytic reduction, selective noncatalytic reduction, and adsorption. 

At UOP, Ipatieff had the opportunity to apply his former research in catalytic promoters and high-pressure technique to develop important catalytic petroleum processing technologies. In contrast to the way he conducted science, Ipatieff s technical efforts were conducted in teams comprised of a wide assortment of specialists. 

Mikroreaktoren sind so klein wie ein Fingerhut, Handdsblatt, May 1998 Steep progress in microelectronics, sensor and analytical techniques in the past transport intensification for catalysis first catalytic micro reactors available partial oxidation to acrolein partial hydrogenation to cyclododecene anodically oxidized catalyst supports as alternatives to non-porous supports study group on micro reactors at Dechema safety, selectivity, high pressure exclusion of using particle solutions limited experience with lifetime of micro reactors [236],... 

The autocatalytic reaction mechanism apparent at low temperatures is expected to apply to catalytic hydrogen oxidation at high pressures. In addition, the above study is the first to use STM to observe the formation of dynamic surface patterns at the mesoscopic level, which had previously been observed by other imaging techniques in surface reactions with nonlinear kinetics [57]. This study illustrates the ability of in situ STM to visualize reaction intermediates and to reveal the reaction pathway with atomic resolution. 

To investigate whether a relationship exists between the solution structures of the hydridorhodium diphosphite species [RhH(CO)2(diphosphite)] [48] and catalytic performance, van Leeuwen and co-workers extensively studied the rhodium-diphosphite complexes formed under hydroformylation conditions by high-pressure NMR (HPNMR) techniques. It is well known that these complexes have a trigonal bipyramidal (TBP) structure. Two isomeric structures of these complexes, one containing the diphosphite coordinated in a bis-equatorial (ee) fashion and one containing the diphosphite in an equatorial-axial (ea) fashion, are possible (Fig. 4). 

IR-cell can be used as an on-line detector connected to a reaction vessel. Both techniques play an important role in the study of the variation of the ligand environment of the catalytic complexes in a controlled manner. Both IR and NMR spectroscopy can be used at high pressure in dedicated tubes or cells. The specific advantages and disadvantages of both techniques are summarised below ... 

A technique that allows rapid evaluation of molecular stability using small (20-30 mg) samples has been demonstrated and applied to three different families of strained molecules. All of the molecules studied are stable at room temperature, though most must be stored in nonmetallic containers to avoid catalytic decomposition. Of the four molecules shown in Fig. 4.1, the least thermally stable was quadricyclane, for which decomposition lifetimes drop below 10 ms at about 500 K. The other three molecules had similar stabilities, with lifetimes dropping below 10 ms above 700 K. For all systems studied, decomposition by loss of small hydrocarbon fragments (acetylene or ethene) was an important decomposition mechanism in the gas phase. For all but AEBCB, isomerization was also a significant decomposition mechanism. At high pressures, one would expect more isomerization because the very rapid collision rate should allow collisional stabilization of the isomerization products. 

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