Metal oxides, catalysts oxidation

Dehydrogenation of ethylbenzene to styrene occurs over a wide variety of metal oxide catalysts. Oxides of Ee, Cr, Si, Co, Zn, or their mixtures can be used for the dehydrogenation reaction. Typical reaction... 

Wachs, I.E. Molecular engineering of supported metal oxide catalysts Oxidation reactions over supported vanadia catalysts. Catalysis 1997,13, 37-54. 

Molecular Engineering of Supported Metal Oxide Catalysts Oxidation Reactions over Supported Vanadia Catalysts ... 

Most oxidation reactions over oxide catalysts are well nnderstood in terms of the redox mechanism, for example, repeated rednction and oxidation of the surface layer or bulk of the oxide catalyst. In the first step, a metal oxide catalyst oxidizes reactant molecules, such as carbon monoxide to carbon dioxide (equation 1 reduction of catalyst). In the second step, the reduced catalyst is oxidized back to its initial state by oxygen molecules supplied by the gas phase (equation 2 reoxidation of catalyst). The catalytic oxidation (equation 3) proceeds by repetition of this redox cycle. 

Metal Oxide Catalysts. Oxides of transition metals have been used for catalytic oxidation. These catalysts may be either non-selective, as in the oxidation of hydrocarbons, or selective, as in the oxidation of olefins using molybdates. Examples of oxidants added in the process are molecular oxygen, hydrogen peroxide, ozone, and other inorganic oxygen donors, such as NaClO, NaBrO, HNO3, and KHSO3 (7). 

Of little use commercially except as a route to anthraquinone. For this purpose it is oxidized with acid potassium dichromate solution, or better, by a catalytic air oxidation at 180-280 C, using vanadates or other metal oxide catalysts. 

Vibrational Spectroscopy. Infrared absorption spectra may be obtained using convention IR or FTIR instrumentation the catalyst may be present as a compressed disk, allowing transmission spectroscopy. If the surface area is high, there can be enough chemisorbed species for their spectra to be recorded. This approach is widely used to follow actual catalyzed reactions see, for example. Refs. 26 (metal oxide catalysts) and 27 (zeolitic catalysts). Diffuse reflectance infrared reflection spectroscopy (DRIFT S) may be used on films [e.g.. Ref. 28—Si02 films on Mo(llO)]. Laser Raman spectroscopy (e.g.. Refs. 29, 30) and infrared emission spectroscopy may give greater detail [31]. 

The second reaction is favoured by sunlight and by catalysts such as platinum black or metallic oxides (cf. the decomposition of... 

Processes have been developed whereby the oxygen is suppHed from the crystal lattice of a metal-oxide catalyst (5) (see Acrylonitrile Methacrylic acid AND derivatives). 

Today the most efficient catalysts are complex mixed metal oxides that consist of Bi, Mo, Fe, Ni, and/or Co, K, and either P, B, W, or Sb. Many additional combinations of metals have been patented, along with specific catalyst preparation methods. Most catalysts used commercially today are extmded neat metal oxides as opposed to supported impregnated metal oxides. Propylene conversions are generally better than 93%. Acrolein selectivities of 80 to 90% are typical. 

The vapor-phase reduction of acrolein with isopropyl alcohol in the presence of a mixed metal oxide catalyst yields aHyl alcohol in a one-pass yield of 90.4%, with a selectivity (60) to the alcohol of 96.4%. Acrolein may also be selectively reduced to yield propionaldehyde by treatment with a variety of reducing reagents. 

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). 

The elimination of alcohol from P-alkoxypropionates can also be carried out by passing the alkyl P-alkoxypropionate at 200—400°C over metal phosphates, sihcates, metal oxide catalysts (99), or base-treated zeoHtes (98). In addition to the route via oxidative carbonylation of ethylene, alkyl P-alkoxypropionates can be prepared by reaction of dialkoxy methane and ketene (100). 

Although acrylonitrile manufacture from propylene and ammonia was first patented in 1949 (30), it was not until 1959, when Sohio developed a catalyst capable of producing acrylonitrile with high selectivity, that commercial manufacture from propylene became economically viable (1). Production improvements over the past 30 years have stemmed largely from development of several generations of increasingly more efficient catalysts. These catalysts are multicomponent mixed metal oxides mostly based on bismuth—molybdenum oxide. Other types of catalysts that have been used commercially are based on iron—antimony oxide, uranium—antimony oxide, and tellurium-molybdenum oxide. 

Numerous patents have been issued disclosing catalysts and process schemes for manufacture of acrylonitrile from propane. These include the direct heterogeneously cataly2ed ammoxidation of propane to acrylonitrile using mixed metal oxide catalysts (61—64). 

The molten salts quickly dissolve the metal oxides at high temperatures to form a clean metal surface. Other uses are as catalysts and in fire-retardant formulations (see Flame retardants). 

Formaldehyde is readily reduced to methanol by hydrogen over many metal and metal oxide catalysts. It is oxidized to formic acid or carbon dioxide and water. The Cannizzaro reaction gives formic acid and methanol. Similarly, a vapor-phase Tischenko reaction is catalyzed by copper (34) and boric acid (38) to produce methyl formate ... 

Most of the world s commercial formaldehyde is manufactured from methanol and air either by a process using a silver catalyst or one using a metal oxide catalyst. Reactor feed to the former is on the methanol-rich side of a flammable mixture and virtually complete reaction of oxygen is obtained conversely, feed to the metal oxide catalyst is lean in methanol and almost complete conversion of methanol is achieved. 

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). 

Fig. 2. Flow scheme of a typical metal oxide catalyst process. S = steam CW = cooling water.

Oxidative processes can also be used to prepare DMF. For example, it can be produced from tetraoxane (a source of formaldehyde (qv)), oxygen, and dimethylamine over Pd—AI2O2 (24) or from trimethylamine and oxygen ia the presence of a metal haUde catalyst (25). 

The process can be operated in two modes co-fed and redox. The co-fed mode employs addition of O2 to the methane/natural gas feed and subsequent conversion over a metal oxide catalyst. The redox mode requires the oxidant to be from the lattice oxygen of a reducible metal oxide in the reactor bed. After methane oxidation has consumed nearly all the lattice oxygen, the reduced metal oxide is reoxidized using an air stream. Both methods have processing advantages and disadvantages. In all cases, however, the process is mn to maximize production of the more desired ethylene product. 

Although catalytic hydration of ethylene oxide to maximize ethylene glycol production has been studied by a number of companies with numerous materials patented as catalysts, there has been no reported industrial manufacture of ethylene glycol via catalytic ethylene oxide hydrolysis. Studied catalysts include sulfonic acids, carboxyUc acids and salts, cation-exchange resins, acidic zeoHtes, haUdes, anion-exchange resins, metals, metal oxides, and metal salts (21—26). Carbon dioxide as a cocatalyst with many of the same materials has also received extensive study. 

In the three-step process acetone first undergoes a Uquid-phase alkah-cataly2ed condensation to form diacetone alcohol. Many alkaU metal oxides, metal hydroxides (eg, sodium, barium, potassium, magnesium, and lanthanium), and anion-exchange resins are described in the Uterature as suitable catalysts. The selectivity to diacetone alcohol is typicaUy 90—95 wt % (64). In the second step diacetone alcohol is dehydrated to mesityl oxide over an acid catalyst such as phosphoric or sulfuric acid. The reaction takes place at 95—130°C and selectivity to mesityl oxide is 80—85 wt % (64). A one-step conversion of acetone to mesityl oxide is also possible. 

In the vapor phase, acetone vapor is passed over a catalyst bed of magnesium aluminate (206), 2iac oxide—bismuth oxide (207), calcium oxide (208), lithium or 2iac-doped mixed magnesia—alumina (209), calcium on alumina (210), or basic mixed-metal oxide catalysts (211—214). Temperatures ranging... 

N. Singh, "VOC Destmetion at Low Temperatures Using a Novel Thermally Stable Transition-Metal Oxide-Based Catalyst," presented at the First North American Conference on Emerging Clean Air Technologies and Business Opportunities, Toronto, Canada, Sept. 1994. 

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). 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

Technical-Grade Terephthalic Acid. All technical-grade terephthahc acid is produced by catalytic, hquid-phase air oxidation of xylene. Several processes have been developed, but they all use acetic acid as a solvent and a multivalent heavy metal or metals as catalysts. Cobalt is always used. In the most popular process, cobalt and manganese are the multivalent heavy-metal catalysts and bromine is the renewable source for free radicals (51,52). 

About 100,000 t of titanium dioxide aimuaHy are used as formulation components in the production of glass (qv), ceramics, electroceramics, catalysts, and in the production of mixed-metal oxide pigments. 

---