Conversion processes, reactivity

There are many different routes to organic chemicals from biomass because of its high polysaccharide content and reactivity. The practical value of the conversion processes selected for commercial use with biomass will depend strongly on the availabiUty and price of the same chemicals produced from petroleum and natural gas. 

The red tetrathiomolybdate ion appears to be a principal participant in the biological Cu—Mo antagonism and is reactive toward other transition-metal ions to produce a wide variety of heteronuclear transition-metal sulfide complexes and clusters (13,14). For example, tetrathiomolybdate serves as a bidentate ligand for Co, forming Co(MoSTetrathiomolybdates and their mixed metal complexes are of interest as catalyst precursors for the hydrotreating of petroleum (qv) (15) and the hydroHquefaction of coal (see Coal conversion processes) (16). The intermediate forms MoOS Mo02S 2> MoO S have also been prepared (17). 

The availability of large and fast computers, in combination with numerical techniques to compute transient, turbulent flow, has made it possible to simulate the process of turbulent, premixed combustion in a gas explosion in more detail. Hjertager (1982) was the first to develop a code for the computation of transient, compressible, turbulent, reactive flow. Its basic concept can be described as follows A gas explosion is a reactive fluid which expands under the influence of energy addition. Energy is supplied by combustion, which is modeled as a one-step conversion process of reactants into combustion products. The conversion (combustion)... 

Innumerable reactions occur in acid catalyzed hydrocarbon conversion processes. These reactions can be classified into a limited number of reaction families such as (de)-protonation, alkyl shift, P-scission,... Within such a reaction family, the rate coefficient is assumed to depend on the type, n or m cfr. Eq. (1), of the carbenium ions involved as reactant and/or product, secondary or tertiary. The only other structural feature of the reactive moiety which needs to be accounted for is the symmetry number. The ratio of the symmetry number of the... 

Direct Photolysis. Direct photochemical reactions are due to absorption of electromagnetic energy by a pollutant. In this "primary" photochemical process, absorption of a photon promotes a molecule from its ground state to an electronically excited state. The excited molecule then either reacts to yield a photoproduct or decays (via fluorescence, phosphorescence, etc.) to its ground state. The efficiency of each of these energy conversion processes is called its "quantum yield" the law of conservation of energy requires that the primary quantum efficiencies sum to 1.0. Photochemical reactivity is thus composed of two factors the absorption spectrum, and the quantum efficiency for photochemical transformations. 

The contribution of the various classes of hydrocarbons to the formation of particulate organic compounds is a complex function of their relative ambient concentrations, gas-phase reactivity, and ability to form products whose physical properties, especially vapor pressures, are of prime importance in the physical mechanisms controlling the gas-to-aerosol conversion process. In view of the results discussed previously, cyclic olefins appear to be the most important class of organic aerosol precursors. This is due to their high gas-phase reactivity and their ability... 

Eastern coal conversion development may come to be favored because of market proximity, water availability, and coal sources which, because of their high sulfur content, are currently unuse-able and, hence, largely decoupled from other energy prices. Proximity reduces transport costs and allows an increased use of low and medium Btu syngas processes. Reactivity and swelling problems may be overcome by technology. 

The fundamental step in acid-catalyzed hydrocarbon conversion processes is the formation of the intermediate carbocations. Whereas all studies involving isomerization, cracking, and alkylation reactions under acidic conditions (Scheme 5.1) agree that a trivalent carbocation (carbenium ion) is the key intermediate, the mode of their formation of this reactive species from the neutral hydrocarbon remained controversial for many years. 

Nevertheless, with the development of new sensors, microdielectrometry constitutes a nondestructive and convenient method for monitoring in situ and in real time the cure of thermosets (Senturia et al., 1982 Kranbuehl et al., 1986). Great efforts have been made and research is still going on to establish relationships between (i) cure index and actual conversion of reactive groups, (ii) conductivity and viscosity, and iii) conductivity and glass transition temperature, in order to obtain models for smart processing. 

In the field of integrated processes, reactive separations are prominently present due to the high degree of synergy to be achieved in many processes [1, 2]. Reactive separations can have positive effects on the conversion, as well as on the selectivity in a process. 

Selective sensitization gave ODPM rearrangement products, whereas direct photolysis resulted in efficient E Z isomerization and inefficient 1,3-acyl shift processes. The results indicated that y,5-double bonds or benzoyl groups present in these systems did not act as intramolecular triplet quencher. The new argument placed by the authors was the charge transfer interaction within the molecule enhances the internal conversion process there by a reduction in the ODPM rearrangement reactivity. 

A number of techniques have been developed to convert corrosion-prone, clean surfaces to less reactive ones. Three common conversion processes are phosphating, anodizing, and chromating. These processes remove the inconsistent, weak surface on metal substrates and replace it with one that is strong, permanent, and reproducible.58 Figure 15.18 shows the effect of various pretreatments on the durability of aluminum alloy-epoxy joints subjected to aging in water at 50°C. 

Reaction injection molding (RIM) is a fast, low-pressure, low-temperature, low-cost process for one-step conversion of reactive liquids into large finished solid plastic products. Liquid polyol and liquid diisocyanate are mixed by impingement, pumped instantly to fill a large mold cavity, and polymerize/ cure rapidly to form a thermoset polyurethane product. The cured polymer may be a stiffly flexible product such as automotive bumper covers, front ends, and trim or a rigid foamed product such as furniture and housings (cabinets) for computers, business machines, TY and radio. 

Important biomass fuel properties for thermochemical conversion processes are reported as proximate and ultimate analyses. The proximate and ultimate analyses for selected biomass feedstocks are presented in Table 33.5. For comparison, the analyses from two selected coal samples are also presented. Biomass generally has a lower energy density than coal, oils, and natural gas it also has higher oxygen content. The higher volatiles and oxygen content of biomass translate into a higher reactivity compared to traditional fossil fuels. In terms of thermochemical conversions, this means that less severe process conditions (lower temperature and shorter residence time) are required for bio-... 

At present, this conceptual coal conversion process is limited in its application to western coals because of their noncaking character and lower sulfur content compared with eastern bituminous coals. It is of interest to note, however, that certain chemical pretreatment processes (10,11) have been shown to eliminate the caking tendency of the coal and reduce its sulfur content. Recent experiments at ORNL (12) have confirmed the suitability of several chemically treated coals to mild hydrocarbonization. In fact, there is evidence to suggest that some of these pretreated coals are actually more reactive under hydrocarbonization conditions than untreated coal, thereby enhancing the yield of oil or gas. 

Such ammonium-salt-catalyzed processes very likely proceed via reactive silylammonium intermediates that may be useful in other silazane conversion processes. To obtain less highly functionalized polysilazanes suitable for melt spinning, such ammonium-salt-catalyzed processes were examined. 

Figure 6. Highly schematized depiction of the orthogonal influences of coal rank and coal type on coal grade (economic value) as reflected simply by the yield of liquids in a coal conversion (liquefaction) process (( ) reactive ingredients are vitrinite and exinite in higher rank coals, vitrinite and exinite give low yields)...

Pyrolysis results are very important for coal characterization, as all conversion processes of coal such as combustion, liquefaction, and gasification start with a pyrolytic step. For this reason, pyrolysis was frequently used for the analysis of coals [17,18). Pyrolysis data were correlated with coal composition, coal characterization and ranking [18a], prediction of coal reactivity as well as of other properties related to coal utilization. Techniques such as Py-MS, Py-GC/MS with different ionization modes, Py-FTIR, or evolved gas analysis (EGA) [19] were described for coal analysis. Programmed temperature pyrolysis is another technique that has been proposed [17] for a complete evaluation of the two types of molecules present in coal. 

Many factors influence the reactivity and digestibility of the cellulose fractions of lignocellulose materials. These factors include Hgnin and hemicellulose content, crystalhnity of cellulose, and the porosity of the biomass materials. Pretreatment of Hgnocellulosic materials prior to utiHzation is a necessary element in biomass-to-ethanol conversion processes. The objective of the pretreatment is to render biomass materials more accessible to either chemical or enzymatic hydrolysis for efficient product generation. The goals of the pretreatment are ... 

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