Methacrylic acid, from oxidation methacrolein

Important classes of reactions not included in the above list, because they are not yet used on a commercial scale, are (i) the oxidative dehydrogenation of C2-C5 alkanes, (ii) the selective oxidation of alkanes, such as the synthesis of maleic and phthalic anhydride from n-pentane and methacrolein or methacrylic acid from isobutene, and (iii) propane ammoxidation to acrylonitrile [317-319]. 

Unsaturated organic acids(e.g., acrylic acid, CH2=CHC(0)0H and its derivatives) are produced as minor products in the ozonolysis of dienes, and from the OH-initiated oxidation of unsaturated aldehydes. The most important examples in the atmosphere involve the formation of methacrylic and acrylic acids from the ozonolysis of isoprene (Orzechowska and Paulson, 2005a) and the formation of methacrylic acid from the oxidation of methacrolein, itself a by-product of isoprene oxidation ... 

Only with propanal are very high conversions (99%) and selectivity (> 98 0) to MMA and MAA possible at this time. Although nearly 95% selective, the highest reported conversions with propionic acid or methyl propionate are only 30—40%. This results in large recycle streams and added production costs. The propanal route suffers from the added expense of the additional step required to oxidize methacrolein to methacrylic acid. 

The first-stage catalysts for the oxidation to methacrolein are based on complex mixed metal oxides of molybdenum, bismuth, and iron, often with the addition of cobalt, nickel, antimony, tungsten, and an alkaU metal. Process optimization continues to be in the form of incremental improvements in catalyst yield and lifetime. Typically, a dilute stream, 5—10% of isobutylene tert-huty alcohol) in steam (10%) and air, is passed over the catalyst at 300—420°C. Conversion is often nearly quantitative, with selectivities to methacrolein ranging from 85% to better than 95% (114—118). Often there is accompanying selectivity to methacrylic acid of an additional 2—5%. A patent by Mitsui Toatsu Chemicals reports selectivity to methacrolein of better than 97% at conversions of 98.7% for a yield of methacrolein of nearly 96% (119). 

The oxidation of methacrolein to methacrylic acid is most often performed over a phosphomolybdic acid-based catalyst, usually with copper, vanadium, and a heavy alkaU metal added. Arsenic and antimony are other common dopants. Conversions of methacrolein range from 85—95%, with selectivities to methacrylic acid of 85—95%. Although numerous catalyst improvements have been reported since the 1980s (120—123), the highest claimed yield of methacryhc acid (86%) is still that described in a 1981 patent to Air Products (124). 

Several variations of the above process are practiced. In the Sumitomo-Nippon Shokubai process, the effluent from the first-stage reactor containing methacrolein and methacrylic acid is fed directiy to the second-stage oxidation without isolation or purification (125,126). In this process, overall yields are maximized by optimizing selectivity to methacrolein plus methacrylic acid in the first stage. Conversion of isobutjiene or tert-huty alcohol must be high because no recycling of material is possible. In another variation, Asahi Chemical has reported the oxidative esterification of methacrolein directiy to MMA in 80% yield without isolation of the intermediate MAA (127,128). 

The handling of toxic materials and disposal of ammonium bisulfate have led to the development of alternative methods to produce this acid and the methyl ester. There are two technologies for production from isobutylene now available ammoxidation to methyl methacrylate (the Sohio process), which is then solvolyzed, similar to acetone cyanohydrin, to methyl methacrylate and direct oxidation of isobutylene in two stages via methacrolein [78-85-3] to methacryhc acid, which is then esterified (125). Since direct oxidation avoids the need for HCN and NH, and thus toxic wastes, all new plants have elected to use this technology. Two plants, Oxirane and Rohm and Haas (126), came on-stream in the early 1980s. The Oxirane plant uses the coproduct tert-huty alcohol direcdy rather than dehydrating it first to isobutylene (see Methacrylic acid). 

The performance of many metal-ion catalysts can be enhanced by doping with cesium compounds. This is a result both of the low ionization potential of cesium and its abiUty to stabilize high oxidation states of transition-metal oxo anions (50). Catalyst doping is one of the principal commercial uses of cesium. Cesium is a more powerflil oxidant than potassium, which it can replace. The amount of replacement is often a matter of economic benefit. Cesium-doped catalysts are used for the production of styrene monomer from ethyl benzene at metal oxide contacts or from toluene and methanol as Cs-exchanged zeofltes ethylene oxide ammonoxidation, acrolein (methacrolein) acryflc acid (methacrylic acid) methyl methacrylate monomer methanol phthahc anhydride anthraquinone various olefins chlorinations in low pressure ammonia synthesis and in the conversion of SO2 to SO in sulfuric acid production. 

Figure 14.2 shows the simplified flow sheet of the process, as reported in patents issued to Sumitomo. CO2 is maintained in the recycle loop to act as a ballast component the desired concentration of CO2 is obtained by combustion of CO, while excess CO2 is separated. Methacrolein is separated and recycled to the oxidation reactor. An overall recycle yield of 52% to methacrylic acid is reported, with a recycle conversion of 96% and a per-pass isobutane conversion of 10%. The heat of reaction produced, mainly deriving from the combustion reaction, is recovered as steam. 

It was proposed that the increase in activity during the equilibration period was due to the generation of new active sites,consisting of the Mo species located in the cationic position in the secondary framework of the POM. A similar hypothesis was formulated by other authors for the methacrolein oxidation to methacrylic acid." " More generally, it is currently believed that for exothermic reactions, and specifically for oxidations, the true working state of the POM, does not correspond to its crystalline form." The presence of steam and the large amount of heat released provoke an incipient surface decomposition, which leads to the expulsion of the Mo species from the anion as a metastable defective... 

Heteropoly catalysts have significant activities for the oxidation of isobutane into methacrolein and methacrylic acid. The yield increased up to 6% by vanadium substitution or salt formation, as follows. With Cs2.5Ni0.08H0.34+JrPV,Mo12 - O40, the highest conversion and selectivity were observed at x 1 (355). Increases in the reaction temperature to 613 K led to increased yields, up to 9.0%. A similar increase in the yield resulted from the substitution of As for P as a heteroatom or from the addition of various transition metals (106, 356). 

Applications of POMs to catalysis have been periodically reviewed [33 0]. Several industrial processes were developed and commercialized, mainly in Japan. Examples include liquid-phase hydration ofpropene to isopropanol in 1972, vapor-phase oxidation of methacrolein to methacrylic acid in 1982, liquid-phase hydration of isobutene for its separation from butane-butene fractions in 1984, biphasic polymerization of THE to polymeric diol in 1985 and hydration of -butene to 2-butanol in 1989. In 1997 direct oxidation of ethylene to acetic acid was industrialized by Showa Denko and in 2001 production of ethyl acetate by BP Amoco. 

However, with the former catalyst the mechanism is essentially an ionic one, with evolution to a dioxyalkylidene species which can yield either methacrolein, or a carboxylate species, precursor of methacrylic acid. No isobutene is detected among the reaction products since the dioxyalkylidene species is strongly bound to the surface. The overall process involves the transfer of 8 electrons from the organic substrate to the catalyst per molecule of methacrylic acid produced. In the case of W-containing heteropolycompounds the mechanism is essentially a radical one (analogous to that proposed for the radical-like chemistry exhbited by W-containing heteropolycompounds in liquid phase oxidations (46)). In the absence of centres able to insert O species, the radical alkoxy intermediate converts to isobutene. The process only involves 2 electrons. 

Vapor-phase aerobic oxidations of lower olefins, e. g. propylene to acrolein or acrylic acid and isobutene to methacrolein or methacrylic acid, are well-established bulk chemical processes [1,2], They are usually performed over oxidic catalysts, such as bismuth molybdate or heteropoly compounds, although the scope of these allylic oxidations is limited to olefins that cannot form 1,3-dienes via oxidative dehydrogenation. Thus 1- and 2-butene are converted to butadiene, and methylbutenes to isoprene, and with higher olefins complex mixtures result from further oxidation. Hence, such methodologies are not relevant in the context of fine chemicals. 

Methyl Methcrylate from Propionaldehyde. Propionaldehyde is produced by the oxo reaction of syngas with ethylene. Reaction of propionaldehyde with formaldehyde and dimethylamine in acetic acid form a Man-nich base salt that can be thermally cracked to methacrolein. Methacrolein can be oxidized to methacrylic acid which is then converted to methyl methacrylate by esterification with methanol. The chemistry is illustrated in Eqs. (31)-(34) ... 

Most of the selective oxidation chemicals are produced from olefins and to a lesser extent from aromatic hydrocarbons. Thus, ethylene oxide, acrylonitrile, acrylic acid, acrolein, methacrolein, methacrylic acid, and 1,2-dichloroethane can be achieved from the corresponding olefins, while phthalic anhydride, benzoni-trUe, or benzoic acid are produced from aromatic hydrocarbons. The relatively easy production from petroleum, together with their high reactivity (moderate reaction temperatures can be employed, in the range of 300-450 C) have made olefins... 

On the other hand, new processes are being researched, such as i) the named Alpha process via ethylene carbonylation to methyl propionate, very similar to the aforementioned BASF route ii) the one-step method of propyne catal3dic carbonylation and iii) direct oxidation of isobutane to methacrolein or methacrylic acid. The use of isobutyraldehyde and isobutyric acid as feedstocks has also been explored. Among all these methods, the one employing the alkane in a one-step reaction to form methacrylic acid is the most simple and interesting process from both... 

---