Oxidation of methanol

Oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was first patented in 1921 (90), followed in 1933 by a patent for an iron oxide—molybdenum oxide catalyst (91), which is stiU the choice in the 1990s. Catalysts are improved by modification with small amounts of other metal oxides (92), support on inert carriers (93), and methods of preparation (94,95) and activation (96). In 1952, the first commercial plant using an iron—molybdenum oxide catalyst was put into operation (97). It is estimated that 70% of the new formaldehyde installed capacity is the metal oxide process (98). 

Several activities, if successful, would strongly boost the prospects for fuel ceU technology. These include the development of (/) an active electrocatalyst for the direct electrochemical oxidation of methanol (2) improved electrocatalysts for oxygen reduction and (2) a more CO-tolerant electrocatalyst for hydrogen. A comprehensive assessment of the research needs for advancing fuel ceU technologies, conducted in the 1980s, is available (22). 

A viable electrocatalyst operating with minimal polarization for the direct electrochemical oxidation of methanol at low temperature would strongly enhance the competitive position of fuel ceU systems for transportation appHcations. Fuel ceUs that directiy oxidize CH OH would eliminate the need for an external reformer in fuel ceU systems resulting in a less complex, more lightweight system occupying less volume and having lower cost. Improvement in the performance of PFFCs for transportation appHcations, which operate close to ambient temperatures and utilize steam-reformed CH OH, would be a more CO-tolerant anode electrocatalyst. Such an electrocatalyst would reduce the need to pretreat the steam-reformed CH OH to lower the CO content in the anode fuel gas. Platinum—mthenium alloys show encouraging performance for the direct oxidation of methanol. 

Methanol is not classified as carcinogenic, but can be acutely toxic if ingested 100—250 mL may be fatal or result in blindness. The principal physiological effect is acidosis resulting from oxidation of methanol to formic acid. Methanol is a general irritant to the skin and mucous membranes. Prolonged skin contact with methanol vapor or Hquid can cause dermatitis. Methanol vapor can cause eye and respiratory tract irritation, nausea, headaches, and dizziness. 

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

However, this advance has an important shortcoming the lack of context. More than one idea is expressed in a document a patent on oxidation catalysts, for example, could include examples of the oxidation of methanol to formaldehyde and of 2-propanol to acetone. A simple coordinate search for conversion of methanol to acetone would retrieve such a document from a file that provides no context. 

Another method, utilized by Ube Industries, Ltd. (Japan), involves the oxidation of methanol and carbon monoxide to form an oxaUc diester. This then reacts with ammonia in a second step to form oxamide. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

Molybdenum compounds Hydrodesulphurization and hydrotreating of petroleum Oxidation of methanol to formaldehdye Epoxidation of olefins Decomposition of alkali metal nitrides Irritation of eyes and respiratory tract Pneumoconiosis... 

Many low-molecular-weight aldehydes and ketones are important industrial chemicals. Formaldehyde, a starting material for a number of plastics, is prepared by oxidation of methanol over a silver or non oxide/rnolybdenurn oxide catalyst at elevated temperature. 

The main industrial route for producing formaldehyde is the catalyzed air oxidation of methanol. 

In the chemical industry, simple aldehydes and ketones are produced in large quantities for use as solvents and as starting materials to prepare a host of other compounds. For example, more than 1.9 million tons per year of formaldehyde, H2C=0, is produced in the United States for use in building insulation materials and in the adhesive resins that bind particle hoard and plywood. Acetone, (CH.3)2C"0, is widely used as an industrial solvent approximately 1.2 million tons per year is produced in the United States. Formaldehyde is synthesized industrial ) by catalytic oxidation of methanol, and one method of acetone preparation involves oxidation of 2-propanol. 

From this completed half-reaction we see that the conversion of methanol to formic acid involves the loss of four electrons. Since the oxidation of methanol to formaldehyde was only a two-electron change, it is clear that formic acid is a more highly oxidized compound of carbon than formaldehyde or methanol. 

J.K. Hong, I.-H. Oh, S.-A. Hong, and W.Y. Lee, Electrochemical Oxidation of Methanol over a Silver Electrode Deposited on Yttria-Stabilized Zirconia Electrolyte, /. Catal. 163, 95-105 (1996). 

Formaldehyde is prepared industrially (for the manufacture of phenol-formaldehyde resins) by the catalytic oxidation of methanol ... 

In this chapter, we focus on the methods to deposit gold NPs on a number of materials and on gas-phase oxidation of methanol, its decomposed derivatives, and pollutants in ambient air at room temperature. 

A packed-bed nonpermselective membrane reactor (PBNMR) is presented by Diakov et al. [31], who increased the operational stability in the partial oxidation of methanol by feeding oxygen directly and methanol through a macroporous stainless steel membrane to the PB. Al-Juaied et al. [32] used an inert membrane to distribute either oxygen or ethylene in the selective ethylene oxidation. By accounting for the proper kinetics of the reaction, the selectivity and yield of ethylene oxide could be enhanced over the fixed-bed reactor operation. 

The present work demonstrates that the mixed oxide catalyst with inhomogeneous nanocrystalline MosOu-type oxide with minor amount of M0O3- and Mo02-type material. Thermal treatment of the catalyst shows a better performance in the formation of the crystals and the catalytic activity. The structural analysis suggests that the catalytic performance of the MoVW- mixed oxide catalyst in the partial oxidation of methanol is related to the formation of the M05O14 t3 e mixed oxide. 

The electrocatalytic oxidation of methanol has been widely investigated for exploitation in the so-called direct methanol fuel cell (DMFC). The most likely type of DMFC to be commercialized in the near future seems to be the polymer electrolyte membrane DMFC using proton exchange membrane, a special form of low-temperature fuel cell based on PEM technology. In this cell, methanol (a liquid fuel available at low cost, easily handled, stored, and transported) is dissolved in an acid electrolyte and burned directly by air to carbon dioxide. The prominence of the DMFCs with respect to safety, simple device fabrication, and low cost has rendered them promising candidates for applications ranging from portable power sources to secondary cells for prospective electric vehicles. Notwithstanding, DMFCs were... 

The analogous quantitative oxidation of methanolic allyl alcohol to 2,3-di-bromopropan-l-ol shows unusual kinetics viz. 

Fig. 3. Induced oxidation of methanol by permanganate in the H202-KMn04 system. According to data of Waters et...

In such a device, the electrons liberated at the anode by the oxidation of methanol circulate in the external electrical circuit, producing electrical energy, and reach the cathode, where they reduce the oxidant, usually oxygen from air. The overall reaction thus corresponds to the catalytic combustion of methanol with oxygen, i.e.,... 

The electrochemical oxidation of methanol occurs on the anode electrocatalyst (e.g., dispersed platinum), which constitutes the negative electrode of the cell ... 

The electrocatalytic oxidation of methanol has been thoroughly investigated during the past three decades (see reviews in Refs. 21-27), particularly in regard to the possible development of DMFCs. The oxidation of methanol, the electrocatalytic reaction, consists of several steps, which also include adsorbed species. The determination of the mechanism of this reaction needs two kinds of information (1) the electrode kinetics of the formation of partially oxidized and completely oxidized products (main and side products) and (2) the nature and the distribution of intermediates adsorbed at the electrode surface. 

Since oxidation of methanol is an electrocatalytic reaction with different adsorption steps, interactions of the adsorbed species with the metallic surface are important. Using platinum single-crystal electrodes, it has been proven that the electrooxidation of methanol is a surface-sensitive reaction. The initial activity of the Pt(llO) plane is much higher than that of the other low-index planes, but the poisoning phenomenon is so rapid that it causes a fast decrease in the current densities. The... 

The effects of dispersion of the electrocatalyst and of particle size on the kinetics of electrooxidation of methanol have been the subject of numerous studies because of the utilization of carbon support in DMFC anodes. The main objective is to determine the optimum size of the platinum anode particles in order to increase the effectiveness factor of platinum. Such a size effect, which is widely recognized in the case of the reduction of oxygen, is still a subject of discussion for the oxidation of methanol. According to some investigators, an optimum of 2 nm for the platinum particle size exists, but studying particle sizes up to 1.4 nm, other authors observed no size effect. According to a recent study, the rate of oxidation of methanol remains constant for particles greater than 4.5 nm, but decreases with size for smaller particles (up to 2.2 nm). 

Another convenient way to disperse platinum-based electrocatalysts is to use electron-conducting polymers, such as polyaniline (PAni) or polypyrrole (PPy), which play the role of a three-dimensional electrode.In such a way very dispersed electrocatalysts are obtained, with particle sizes on the order of a few nanometers, leading to a very high activity for the oxidation of methanol (Fig. 10). 

In addition to these different types of alloys, some studies were also devoted to alternatives to platinum as electrocatalysts. Unfortunately, it is clear that even if some catalytic activities were observed, they are far from those obtained with platinum. Nickel tungsten carbides were investigated, but the electrocatalytic activity recorded for methanol oxidation was very low. Tungsten carbide was also considered as a possible alternative owing to its ability to catalyze the electrooxidation of hydrogen. However, it had no activity for the oxidation of methanol and recently some groups showed that a codeposit of Pt and WO3 led to an enhancement of the activity of platinum. ... 

Another very interesting result obtained from these FURS measurements is the difference between adsorbed CO obtained from dissolved CO and that from the dissociation of adsorbed methanol. The shift in wave number is more important with dissolved CO. These shifts may also be correlated with the superficial composition of the alloys, and it was observed that the optimized composition for the oxidation of CO (about 50 at.% Ru) is different from that for the oxidation of methanol (about 15 at.% Ru). FTIR spectra also revealed that the amount of adsorbed CO formed from methanol dissociation is considerably higher on R than on Pt-Ru. For a Ptog-Ru-o i alloy, the amount of linearly adsorbed CO is very small (Fig. 8), suggesting a low coverage in the poisoning species. Moreover, by observing the potentials at which the COj IR absorption band appears, it is possible to conclude that the oxidation of both (CHO)ads and (CO)acis species occurs at much lower potentials on a R-Ru alloy electrode than on pure Pt. 

These conclusions from the infrared reflectance spectra recorded with Pt and Pt-Ru bulk alloys were confirmed in electrocatalysis studies on small bimetallic particles dispersed on high surface area carbon powders.Concerning the structure of bimetallic Pt-Ru particles, in situ Extended X-Ray Absorption Fine Structure (EXAFS>XANES experiments showed that the particle is a true alloy. For practical application, it is very important to determine the optimum composition of the R-Ru alloys. Even if there are still some discrepancies, several recent studies have concluded that an optimum composition about 15 to 20 at.% in ruthenium gives the best results for the oxidation of methanol. This composition is different from that for the oxidation of dissolved CO (about 50 at.% Ru), confirming a different spatial distribution of the adsorbed species. 

Sinee no oxidation of methanol was observed on pure Ru, it is probable that there is no -( CHO)ads on Ru. However, adsorption of CO was observed on an Ru eleetrode from solution eontaining dissolved CO. The adsorbed CO observed on a R-Ru eleetrode during the adsorption of methanol may arise mainly from the dissoeiation of methanol at Pt sites, followed by the migration of sueh CO speeies toward the neighboring Ru sites. The removal of adsorbed CO by oxidation with adsorbed OH may oeeur by one of two ways (1) at R sites aeeording to reaetions (26) or (27) and (25), and (2) at Ru sites aeeording to reaetion (26 ) ... 

---