Vanadium catalysts oxidation

Benzoquinone ( quinone ) is obtained as the end product of the oxidation of aniline by acid dichromate solution. Industrially, the crude product is reduced with sulphur dioxide to hydroquinone, and the latter is oxidised either with dichromate mixture or in very dilute sulphuric acid solution with sodium chlorate in the presence of a little vanadium pentoxide as catalyst. For the preparation in the laboratory, it is best to oxidise the inexpensive hydroquinone with chromic acid or with sodium chlorate in the presence of vanadium pent-oxide. Naphthalene may be converted into 1 4-naphthoquinone by oxidation with chromic acid. 

Although many variations of the cyclohexane oxidation step have been developed or evaluated, technology for conversion of the intermediate ketone—alcohol mixture to adipic acid is fundamentally the same as originally developed by Du Pont in the early 1940s (98,99). This step is accomplished by oxidation with 40—60% nitric acid in the presence of copper and vanadium catalysts. The reaction proceeds at high rate, and is quite exothermic. Yield of adipic acid is 92—96%, the major by-products being the shorter chain dicarboxytic acids, glutaric and succinic acids,and CO2. Nitric acid is reduced to a combination of NO2, NO, N2O, and N2. Since essentially all commercial adipic acid production arises from nitric acid oxidation, the trace impurities patterns ate similar in the products of most manufacturers. 

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

Promoters are sometimes added to the vanadium phosphoms oxide (VPO) catalyst during synthesis (129,130) to increase its overall activity and/or selectivity. Promoters may be added during formation of the catalyst precursor (VOHPO O.5H2O), or impregnated onto the surface of the precursor before transformation into its activated phase. They ate thought to play a twofold stmctural role in the catalyst (130). First, promoters facilitate transformation of the catalyst precursor into the desired vanadium phosphoms oxide active phase, while decreasing the amount of nonselective VPO phases in the catalyst. The second role of promoters is to participate in formation of a soHd solution which controls the activity of the catalyst. 

Vanadium phosphoms oxide-based catalysts ate unstable in that they tend to lose phosphoms over time at reaction temperatures. Hot spots in fixed-bed reactors tend to accelerate this loss of phosphoms. This loss of phosphoms also produces a decrease in selectivity (70,136). Many steps have been taken, however, to aHeviate these problems and create an environment where the catalyst can operate at lower temperatures. For example, volatile organophosphoms compounds are fed to the reactor to mitigate the problem of phosphoms loss by the catalyst (137). The phosphoms feed also has the effect of controlling catalyst activity and thus improving catalyst selectivity in the reactor. The catalyst pack in the reactor may be stratified with an inert material (138,139). Stratification has the effect of reducing the extent of reaction pet unit volume and thus reducing the observed catalyst temperature (hot... 

Fluidized-bed reactor systems put other unique stresses on the VPO catalyst system. The mixing action inside the reactor creates an environment that is too harsh for the mechanical strength of a vanadium phosphoms oxide catalyst, and thus requires that the catalyst be attrition resistant (121,140,141). To achieve this goal, vanadium phosphoms oxide is usually spray dried with coUoidal siUca [7631-86-9] or polysiUcic acid [1343-98-2]. Vanadium phosphoms oxide catalysts made with coUoidal sUica are reported to have a loss of selectivity, while no loss in selectivity is reported for catalysts spray dried with polysUicic acid (140). 

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 ... 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

Cyclohexenone has been prepared by dehydrohalogenation of 2-bromocyclohexanone, by the hydrolysis and oxidation of 3-chlorocyclohexene, by the dehydration of a-hydroxycyclohexa- ione, by the oxidation of cyclohexene with chromic acid or hydrogen peroxide in the presence of a vanadium catalyst, by I lie addition of acroleiti to ethyl acetoacctate followed by cycliza-lion, hydroly.sis, and decar])oxylation, by the reduction of N,N-dimelliyliiniline with sodium and ethanol itt liquid ammonia... 

The modem process uses a potassium-sulfate-promoted vanadium(V) oxide catalyst on a silica or kie,selguhr support. The SO2 is obtained either by burning pure sulfur or by roasting sulfide minerals (p. 651) notably iron pyrite, or ores of Cu, Ni and Zn during the production of these metals. On a worldwide basis about 65% of the SO2 comes from the burning of sulfur and some 35% by the roasting of sulfide ores but in some countries (e.g, the UK) over 95% conies from the former. 

A new process for the partial oxidation of n-butane to maleic anhydride was developed by DuPont. The important feature of this process is the use of a circulating fluidized bed-reactor. Solids flux in the rizer-reactor is high and the superficial gas velocities are also high, which encounters short residence times usually in seconds. The developed catalyst for this process is based on vanadium phosphorous oxides... 

Vanadium in the feed poisons the FCC catalyst when it is deposited on the catalyst as coke by vanadyl porphydrine in the feed. During regeneration, this coke is burned off and vanadium is oxidized to a oxidation state. The vanadium oxide (V O ) reacts with water vapor in the regenerator to vanadic acid, HjVO. Vanadic acid is mobile and it destroys zeolite crystal through acid-catalyzed hydrolysis. Vanadic acid formation is related to the steam and oxygen concentration in the regenerator. 

One stage in the manufacture of sulfuric acid is the formation of sulfur trioxide by the reaction of S02 with 02 in the presence of a vanadium(V) oxide catalyst. Predict how the equilibrium composition for the sulfur trioxide synthesis will tend to change when the temperature is raised. 

It has been reported that titanium supported vanadium catalyst is active for ammonia oxidation at temperatures above 523 K [2,3]. Also, supported vanadium oxides are known to be efficient catalyst for the catalytic reduction of nitrogen oxides (NO ) in the presence of ammonia [4]. This work investigates the nanostructured vanadia/Ti02 for low temperature catalytic remediation of ammonia in air. 

Acrolein, in turn, can be oxidized further to acrylic acid. The catalyst for this step is a mixed vanadium-molybdenum oxide. 

The mechanism by which the enantioselective oxidation occurs is generally similar to that for the vanadium-catalyzed oxidations. The allylic alcohol serves to coordinate the substrate to titanium. The tartrate esters are also coordinated at titanium, creating a chiral environment. The active catalyst is believed to be a dimeric species, and the mechanism involves rapid exchange of the allylic alcohol and /-butylhydroperoxide at the titanium ion. 

Balzhinimaev, B. S., Belyeava. N. P., and Ivanov, A. A., Kinetics of dissolution of inactive crystalline phase in vanadium catalysts for S02 oxidation. React. Kinet. Catal. Letters 29, 465-472 (1985). 

The effects of various metal oxides and salts which promote ignition of amine-red fuming nitric acid systems were examined. Among soluble catalysts, copperQ oxide, ammonium metavanadate, sodium metavanadate, iron(III) chloride (and potassium hexacyanoferrate(II) with o-toluidine) are most effective. Of the insoluble materials, copper(II) oxide, iron(III) oxide, vanadium(V) oxide, potassium chromate, potassium dichromate, potassium hexacyanoferrate(III) and sodium pentacyanonitrosylferrate(II) were effective. 

Oxidation of Aldonic Acids. Preferential oxidation of the secondary alcoholic group adjacent to the carboxyl group in sugar acids or aldonic acids such as L-gulonic acid (XXV) can be carried out with chromic acid12 or with chlorates in the presence of a vanadium catalyst.13... 

In the second stage, a mixture of sulphur dioxide and air is passed over a catalyst of vanadium (V) oxide, V205, at a temperature of about 430°C. This is called the Contact process. 

Stretford A process for removing hydrogen sulfide and organic sulfur compounds from coal gas and general refinery streams by air oxidation to elementary sulfur, using a cyclic process involving an aqueous solution of a vanadium catalyst and anthraquinone disulfonic acid. Developed in the late 1950s by the North West Gas Board (later British Gas) and the Clayton Aniline Company, in Stretford, near Manchester. It is the principle process used today, with over 150 plants licensed in Western countries and at least 100 in China. 

Eklund, R.B. (1956), The Rate of Oxidation of Sulfur Dioxide with a Commercial Vanadium Catalyst, Almgvist and Wik-sell, Stockholm. 

The selective oxidation of ra-butane to give maleic anhydride (MA) catalyzed by vanadium phosphorus oxides is an important commercial process (99). MA is subsequently used in catalytic processes to make tetrahydrofurans and agricultural chemicals. The active phase in the selective butane oxidation catalyst is identified as vanadyl pyrophosphate, (V0)2P207, referred to as VPO. The three-dimensional structure of orthorhombic VPO, consisting of vanadyl octahedra and phosphate tetrahedra, is shown in Fig. 17, with a= 1.6594 nm, b = 0.776 nm, and c = 0.958 nm (100), with (010) as the active plane (99). Conventional crystallographic notations of round brackets (), and triangular point brackets (), are used to denote a crystal plane and crystallographic directions in the VPO structure, respectively. The latter refers to symmetrically equivalent directions present in a crystal. 

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