Hydrocarbon product selectivity

Fig. 6 Hydrocarbon product selectivity as a function of TiOx coverage on a Rh foil (12). The indicated TiOx coverages should be multiplied by a factor of 3.3 to account for the corrections recently reported by Williams et al. (9).

Agricultural Products. Pesticides are frequendy appHed as emulsiftable concentrates. The active insecticide or herbicide is dissolved in a hydrocarbon solvent which also contains an emulsifier. Hydrocarbon solvent selection is critical for this appHcation. It can seriously impact the efficacy of the formulation. The solvent should have adequate solvency for the pesticide, promote good dispersion when diluted with water, and have a dash point high enough to minimise dammabiUty ha2ards. When used in herbicide formulas, low solvent phytotoxicity is important to avoid crop damage. Hydrocarbon solvents used in post-harvest appHcation require special testing to ensure that polycycHc aromatics are absent. 

It is obvious that one can use the basic ideas concerning the effect of alkali promoters on hydrogen and CO chemisorption (section 2.5.1) to explain their effect on the catalytic activity and selectivity of the CO hydrogenation reaction. For typical methanation catalysts, such as Ni, where the selectivity to CH4 can be as high as 95% or higher (at 500 to 550 K), the modification of the catalyst by alkali metals increases the rate of heavier hydrocarbon production and decreases the rate of methane formation.128 Promotion in this way makes the alkali promoted nickel surface to behave like an unpromoted iron surface for this catalytic action. The same behavior has been observed in model studies of the methanation reaction on Ni single crystals.129... 

Wan et al. [61] also reported the highly effective conversion of methane to aromatic hydrocarbons over Cu, Ni, Fe, and Al catalysts. The effects of the type of catalyst, its configuration, and the microwave irradiation conditions on reaction path and product selectivity were examined under both batch and continuous-flow conditions. 

Along with catalyst activity, product selectivity is a key issue in cobalt-based FTS.1 For GTL processes the preferred product is long-chain waxy hydrocarbons. It is well known that FT reaction conditions have an important effect on product selectivities. High temperatures and H2/CO ratios are associated with higher methane selectivity, lower probability of hydrocarbon chain growth, and lower olefinicity in the products.105... 

Traditionally, iron-based catalysts have been used for FT synthesis when the syngas is coal derived, because of their activity in both FTS and WGS reactions. Complex mixtures of straight-chain paraffins, olefins, and oxygenate (in substantial proportions) compounds are known to be formed during iron-based FTS. Olefin selectivity of iron catalysts is typically greater than 50% of the hydrocarbon products at low carbon numbers, and more than 60% of the produced olefins are a-olefins.13 For iron-based catalysts, the olefin selectivity decreases asymptotically with increasing carbon number. 

Finding ethane to be the major product is a significant result, because for all the other systems described above, and indeed for Fischer-Tropsch catalysts in general, methane is the major hydrocarbon product. Furthermore, as is discussed in Section III, high selectivity to C2 could have important mechanistic as well as commercial implications. 

These adducts are more active than the iron ones in the conversion of syngas. At 250°C, a higher yield of methane is observed (Table U) and carbon dioxide is produced in smaller amounts. Inspection of Table 5 summarizing the influence of the H2/CO ratio on products selectivity also indicates a higher production of saturated hydrocarbons. This behavior is typical for cobalt catalysts in F-T synthesis (j2,25). The chain-length distribution is similar to that observed for catalysts derived... 

After the initial volume estimate has been determined, testing of a pilot recovery system should be initiated to evaluate recovery rates. However, factors that significantly affect recovery rates include the areal distribution and geometry of the free-hydrocarbon product plume, type(s) and design of recovery system selected, and the performance and efficiency of the system with time. 

Numerous chemical intermediates are oxygen rich. Methanol, acetic acid and ethylene glycol show a O/C atomic ratio of 1, as does biomass. Other major chemicals intermediates show a lower O/C ratio, typically between 1/3 and 2/3. This holds for instance for propene and butene glycols, ethanol, (meth)acrylic acids, adipic acid and many others. The presence of some oxygen atoms is required to confer the desired physical and chemicals properties to the product. Selective and partial deoxygenation of biomass may represent an attractive and competitive route compared with the selective and partial oxidation of hydrocarbon feedstock. 

Catalytic dewaxing, in which straight-chain paraffin hydrocarbons are selectively cracked on zeolite-type catalysts, and the lower-boiling reaction products are separated from the dewaxed lubricating oil by fractionation. 

Fig. 2. Relation of the product selectivity between methylene and aryl groups and relative basicity (n complex) of two corresponding hydrocarbons.

Yuen, L-T., Zones, S.I., Harris, T.V., Gallegos, E.J., and Auroux, A. (1994) Product selectivity in methanol to hydrocarbons conversion for isostruc-tural compositions of AEI and CHA molecular sieves. Micropor. Mater., 2, 105. 

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