Vanadium oxidation reactions

Patents claiming specific catalysts and processes for thek use in each of the two reactions have been assigned to Japan Catalytic (45,47—49), Sohio (50), Toyo Soda (51), Rohm and Haas (52), Sumitomo (53), BASF (54), Mitsubishi Petrochemical (56,57), Celanese (55), and others. The catalysts used for these reactions remain based on bismuth molybdate for the first stage and molybdenum vanadium oxides for the second stage, but improvements in minor component composition and catalyst preparation have resulted in yields that can reach the 85—90% range and lifetimes of several years under optimum conditions. Since plants operate under more productive conditions than those optimum for yield and life, the economically most attractive yields and productive lifetimes maybe somewhat lower. 

Butane-Based Fixed-Bed Process Technology. Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphoms oxide heterogeneous catalyst discussed earlier. The butane oxidation reaction to produce maleic anhydride is very exothermic. The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows ... 

Minor uses of vanadium chemicals are preparation of vanadium metal from refined pentoxide or vanadium tetrachloride Hquid-phase organic oxidation reactions, eg, production of aniline black dyes for textile use and printing inks color modifiers in mercury-vapor lamps vanadyl fatty acids as driers in paints and varnish and ammonium or sodium vanadates as corrosion inhibitors in flue-gas scmbbers. 

The feasibility of synthesizing oxovanadium phthalocyanine (VOPc) from vanadium oxide, dicyanobenzene, and ethylene ycol using the microwave synthesis was investigated by comparing reaction temperatures under the microwave irradiations with the same factors of conventional synthesis. The efficiency of microwave synthesis over the conventional synthesis was illustrated by the yield of crude VOPc. Polymorph of VOPc was obtained ttough the acid-treatment and recrystallization step. The VOPos synthesized in various conditions were characterized hy the means of an X-ray dif actometry (XRD), a scanning electron microscopy (SEM), and a transmission electron Microscopy (TEM). 

The introduction of microwave pr ents an excellent new option for the synthesis of VOPc from vanadium oxide, dicyanobenzene, and ethylene glycol. In the present study, the effectiveness of synthesizing crude VOPc liom vanadium oxide and dicyanobenzene rmder the two synthetic methods was investigate by comparing reaction temperatures. Also, the preparation of fine crystal VOPc was investigated from the crude VOPc synthesized at... 

By modifying the catalyst with a so-called promoter (in this case vanadium oxide) it is possible to largely eliminate the intermediate. As Fig. 2.6 shows, the rate constant of the reaction from the hydroxylamine to the amine is much larger when the promoted catalyst is used, and thus the intermediate reacts instantaneously, resulting in a safer and environmentally friendlier process. 

This reaction was first demonstrated over V, Mo and W oxides [6]. At 823 K vanadium oxide provided phenol selectivity up to 71%, which was much higher than it had been ever achieved with O2. This result stimulated further efforts in searching for more efficient catalytic systems. As a result, in 1988 three groups of researchers [7-9] have independently discovered ZSM-5 zeolites to be the most efficient catalysts. They allowed the reaction to proceed at much lower temperature (573-623 K) with nearly a 100% selectivity. Later, more complex aromatic compounds were also hydroxylated in this way [2]. 

Catalyst cost constitutes 15-20% of the capital cost of an SCR unit therefore, it is essential to operate at temperatures as high as possible to maximize space velocity and thus minimize catalyst volume. At the same time, it is necessary to minimize the rate of oxidation of S02 to S03, which is more temperature sensitive than the SCR reaction. The optimum operating temperature for the SCR process using titanium and vanadium oxide catalysts is about 38CM180oC. Most installations use an economizer bypass to provide flue gas to the reactors at the desired temperature during periods when flue gas temperatures are low, such as low-load operation. 

The presence of zinc with bidentate nitrogen donor ligands in the formation of novel composite materials by hydrothermal reactions has been studied. A zinc-containing one-dimensional material, [Zn(phenanthroline)Mo04] was isolated from molybdate, and from vanadium oxide in the presence of zinc 2,2 -bipyridine [Zn(2,2,-bipyridine)2V40i2] was obtained.212,213... 

In the bulk form, vanadium oxides display different oxidation states and V—O coordination spheres and exhibit a broad variety of electronic, magnetic, and structural properties [96, 97], which make these materials attractive for many industrial applications. Prominent examples range from the area of catalysis, where V-oxides are used as components of important industrial catalysts for oxidation reactions [98] and environment pollution control [99], to optoelectronics, for the construction of light-induced electrical switching devices [100] and smart thermo-chromic windows. In view of the importance of vanadium oxides in different technological applications, the fabrication of this material in nanostructured form is a particularly attractive goal. 

Figure 2.8 The surface reaction between adsorbed carbon monoxide and hydrogen to methane over rhodium catalysts occurs at lower temperatures in the presence of a vanadium oxide promoter, which is known to enhance the rate of CO dissociation (from Koerts el al. 113]). 

The reactions of the vanadium oxide cluster cations with CCI4 were of three types (248). The small cluster ions reacted by transfer of a chloride ion. The larger clusters starting with the V4OJ+ series reacted by the addition of a chlorine atom to the cluster or the loss of one oxygen atom and the addition of two chlorine atoms. 

Sulphuric acid catalysts are not truly heterogeneous catalysts but so-called supported liquid phase (SLP) catalysts, where the oxidation of S02 takes place as a homogeneous reaction in a liquid film covering the internal surface of the support material [2], This was proposed already in 1940 by Frazer and Kirkpatrick [6], who found that the promoting action of the common alkali metals was due to their ability to form relatively low-melting pyrosulphates, which dissolve vanadium oxides, e.g. for potassium... 

The process. A typical process for phthalic anhydride starts with mixing hor q-xylene vapor with excess preheated air in a ratio of 20 1 air to o-xylene by weight. The gaseous mixture is then fed to a reactor consisting of tubes packed with vanadium pentoxide catalyst on a silica gel. The reaction takes place at 800—1000°F. Like most oxidation reactions, this one is exothermic, and the heat of reaction must be removed from the tubes to maintain the reaction temperature. 

Murphy et al. made an extensive study of a number of vanadium oxides and discovered the excellent electrochemical behavior of the partially reduced vanadium oxide, VeOis, which reacts with up to 1 LiA/. They also recognized that the method of preparation, which determines the V 0 ratio, critically controls the capacity for reaction with lithium. The structure consists of alternating double and single sheets of vanadium oxide sheets made up of distorted VOe octahedra. A variety of sites are available for lithium intercalation, which if filled sequentially would lead to the various steps seen in the discharge curve. The lattice first expands along the c-axis and then along the b-axis. Thomas et ai 87 91 an in-depth study of the complex... 

All oxidation reactions are coupled to reduction reactions. In many cases redox reactions can also involve or be affected by changes in the surrounding environment, such as changes in the pH or temperature (i.e., endothermic or exothermic reactions). Many elements in the subsurface can exist in various oxidation states, some examples include elements like carbon, nitrogen, oxygen, sulfur, iron, cobalt, vanadium, and nickel. 

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