Supported low temperature

Zhang X, Robertson M, Deces-Petit C, Xie Y, Hui R, Yick S et al. NiO-YSZ cermet-supported low temperature solid oxide fuel cells. J. Power Sources 2006 161 301-307. 

Cryogenic facilities are needed to support low-temperature operations. A major consumer is cold water of 5 °C for acrylonitrile absorption, with a duty of 7.7 MW. The power W needed to extract the heat duty Qj can be roughly estimated by assuming a reversible Carnot cycle and global efficiency of 0.6, by using the relation ... 

The process is based on a novel reaction using the otherwise well-studied metal-organic CVD process under conditions which support low temperature growth, i.e., catalysis of the reaction by protic hydrocarbon solvents and catalysis of whisker growth by metallic indium flux particles (droplets). The flux particles, in turn were produced in-situ during the reaction as a partial decomposition product of t-BusIn (Equation 13). 

Another method, which is especiafly suitable for low melting point solids or solids which decompose at low temperatures, is to place the material on a porous plate or pad of drying paper, and to cover the latter with another sheet of Alter paper perforated with a number of holes or with a large clock glass or sheet of glass supported upon corks. The air drying is continued until the solvent has been completely eliminated. 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Initially, aluminum chloride was the catalyst used to isomerize butane, pentane, and hexane. Siace then, supported metal catalysts have been developed for use ia high temperature processes that operate at 370—480°C and 2070—5170 kPa (300—750 psi), whereas aluminum chloride and hydrogen chloride are universally used for the low temperature processes. 

The low temperature limitation of homogeneous catalysis has been overcome with heterogeneous catalysts such as modified Ziegler-Natta (28) sohd-supported protonic acids (29,30) and metal oxides (31). Temperatures as high as 80°C in toluene can be employed to yield, for example, crystalline... 

The most popular SCR catalyst formulations are those that were developed in Japan in the late 1970s comprised of base metal oxides such as vanadium pentoxide [1314-62-1J, V20, supported on titanium dioxide [13463-67-7] Ti02 (1). As for low temperature catalysts, NO conversion rises with increasing temperatures to a plateau and then falls as ammonia oxidation begins to dominate the SCR reaction. However, peak conversion occurs in the temperature range between 300 and 450°C, and the fah-off in NO conversion is more gradual than for low temperature catalysis (44). 

In the present work low temperature adsoi ption of fluoroform and CO, were used to characterize surface basicity of silica, both pure and exposed to bases. It was found that adsorption of deuterated ammonia results in appearance of a new CH stretching vibration band of adsorbed CHF, with the position typical of strong basic sites, absent on the surface of pure silica. Low-frequency shift of mode of adsorbed CO, supports the conclusion about such basicity induced by the presence of H-bonded bases. 

Hence if a laboratory measurement at 25°C yields a conductivity of 100 pS/m the same liquid at -10°C will have a conductivity of about 30 pS/m. The effects of low temperature combined with the elevated dielectric constants of many nonconductive chemicals support use of the 100 pS/m demarcation for nonconductive liquids (5-2.5) rather than the 50 pS/m demarcation used since the 1950s by the petroleum industry. For most hydrocarbons used as fuels, the dielectric constant is roughly 2 and a demarcation of 50 pS/m is adequate, provided the conductivity is determined at the lowest probable handling temperature. 

The mechanism of this reaction has been studied by several groups [133,174-177]. The consensus is that interaction of ester with the phenolic resole leads to a quinone methide at relatively low temperature. The quinone methide then reacts rapidly leading to cure. Scheme 11 shows the mechanism that we believe is operative. This mechanism is also supported by the work of Lemon, Murray, and Conner. It is challenged by Pizzi et al. Murray has made the most complete study available in the literature [133]. Ester accelerators include cyclic esters (such as y-butyrolactone and propylene carbonate), aliphatic esters (especially methyl formate and triacetin), aromatic esters (phthalates) and phenolic-resin esters [178]. Carbamates give analogous results but may raise toxicity concerns not usually seen with esters. 

The close agreement of the three methods supports the contention that protonation at low temperatures first occurs at nitrogen and is followed by a proton shift to give the iminium salt (M). The rate of this rearrangement is dependent on temperature, the nature of the amine, and the nature of the carbonyl compound from which the enamine was made. Even with this complication the availability of iminium salts is not impaired since the protonation reaction is usually carried out at higher temperatures than —70°. Structurally complicated enamines such as trichlorovinyl amine can be readily protonated (17,18). 

Polyphosphoric acid supported on diatomaceous earth (p. 342) is a petrochemicals catalyst for the polymerization, alkylation, dehydrogenation, and low-temperature isomerization of hydrocarbons. Phosphoric acid is also used in the production of activated carbon (p. 274). In addition to its massive use in the fertilizer industry (p. 524) free phosphoric acid can be used as a stabilizer for clay soils small additions of H3PO4 under moist conditions gradually leach out A1 and Fe from the clay and these form polymeric phosphates which bind the clay particles together. An allied though more refined use is in the setting of dental cements. 

That mechanism is supported by the detection of such cr-complexes at low temperatures. An analogous mechanism can be formulated with a polarized species 4 instead of the free carbenium ion 5. 

The metathetic reaction occurs in the gas phase at relatively high temperatures (150°-350°C) with molybdenum or tungsten supported catalysts or at low temperature (=50°C) with rhenium-based catalyst in either liquid or gas-phase. The liquid-phase process gives a better conversion. Equilibrium conversion in the range of 55-65% could be realized, depending on the reaction temperature. ... 

---