Cuprous oxide production

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). 

Less activated substrates such as uorohaloben2enes also undergo nucleophilic displacement and thereby permit entry to other useful compounds. Bromine is preferentially displaced in -bromofluoroben2ene [460-00-4] by hydroxyl ion under the following conditions calcium hydroxide, water, cuprous oxide catalyst, 250°C, 3.46 MPa (500 psi), to give -fluorophenol [371-41-5] in 79% yield (162,163). This product is a key precursor to sorbinil, an en2yme inhibitor (aldose reductase). 

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. 

Ofner Method. This method is for the determination of invert sugar in products with up to 10% invert in the presence of sucrose and is a copper-reduction method that uses Ofner s solution instead of Fehling s. The reduced cuprous oxide is treated with excess standardized iodine, which is black-titrated with thiosulfate using starch indicator. 

Calcium carbonate has normal pH and inverse temperature solubilities. Hence, such deposits readily form as pH and water temperature rise. Copper carbonate can form beneath deposit accumulations, producing a friable bluish-white corrosion product (Fig. 4.17). Beneath the carbonate, sparkling, ruby-red cuprous oxide crystals will often be found on copper alloys (Fig. 4.18). The cuprous oxide is friable, as these crystals are small and do not readily cling to one another or other surfaces (Fig. 4.19). If chloride concentrations are high, a white copper chloride corrosion product may be present beneath the cuprous oxide layer. However, experience shows that copper chloride accumulation is usually slight relative to other corrosion product masses in most natural waters. 

The condenser was plagued by rapid attack on waterside surfaces. The entire internal surface was fouled with silt and other deposits, beneath which a cuprous oxide layer was present (Fig. 4.23). Localized areas of metal loss were present beneath mounds of corrosion product. Some of these localized areas were deep enough to threaten tube integrity. 

Figure 4.25 As in Figs. 4.23 and 4.24. Corrosion product mound broken open to reveal sparkling cuprous oxide crystals.

Internal surfaces of all tubes were severely attacked (Fig. 4.29). A brown deposit layer consisting of magnetite, iron oxide hydroxide, and silica covered all surfaces. Deposition was thicker and more tenacious along the bottom of tubes. These deposits had a distinct greenish-blue cast caused by copper corrosion products beneath the deposit. Underlying corrosion products were ruby-red cuprous oxide crystals (Fig. 4.29). Areas not covered with deposits suffered only superficial attack, but below deposits wastage was severe. 

Internal surfaces were covered by loosely adherent corrosion product and deposit. Much of the corrosion product was cuprous oxide. Substantial amounts of iron, silicon, aluminum, zinc, and nickel were also found. Not unexpectedly, chlorine concentrations up to 2% by weight were present sulfur concentrations of about 1% were also found. 

Photovoltaic cells. The selenium photographic exposure meter has already been mentioned it goes back to Adams and Day s (1877) study of selenium, was further developed by Charles Fritt in 1885 and finally became a commercial product in the 1930s, in competition with a device based on cuprous oxide. This meter was efficient enough for photographic purposes but would not have been acceptable as an electric generator. 

The ammonia production is less than in hydrazine, but there may be a perceived of copper and brass corrosion. In fact, any corrosion risk is small, provided that DEHA-treated boiler plants are subjected to the same requirements as hydrazine-treated units, namely, ensuring that all in-leakage of oxygen in the condensate system is fully eliminated. If this objective is achieved, the oxidation of cuprous oxide to cupric oxide tends not occur to any significant degree, and the susceptibility for copper corrosion in the presence of ammonia is equally low. 

Lewin and Cohen (1967) determined the products of dediazoniation of ben-zophenone-2-diazonium salt (10.42, Scheme 10-77) in five different aqueous systems (Table 10-7). About one-third of the yield is 2-hydroxybenzophenone (10.46) and two-thirds is fluorenone (10.45, run 1) copper has no effect (run 2). On the other hand, addition of cuprous oxide (run 3) has a striking effect on product ratio and rate. The reaction occurs practically instantaneously and yields predominantly fluorenone. As shown in Scheme 10-77, the authors propose that, after primary dediazoniation and electron transfer from Cu1 to 10.43 the sigma-complex radical 10.44 yields fluorenone by retro-electron-transfer to Cu11 and deprotonation. In the presence of the external hydrogen atom source dioxane (run 12) the reaction yields benzophenone cleanly (10.47) after hydrogen atom abstraction from dioxane by the radical 10.43. 

Propene is an intermediate utilized in the chemical and pharmaceutical industries. The partial oxidation of propene on cuprous oxide (CU2O) yields acrolein as a thermodynamically imstable intermediate, and hence has to be performed under kinetically controlled conditions [37]. Thus in principle it is a good test reaction for micro reactors. The aim is to maximize acrolein selectivity while reducing the other by-products CO, CO2 and H2O. Propene may also react directly to give these products. The key to promoting the partial oxidation at the expense of the total oxidation is to use the CU2O phase and avoid having the CuO phase. 

By-products from capture of nucleophilic anions may be observed.53 Phenols can be formed under milder conditions by an alternative redox mechanism.98 The reaction is initiated by cuprous oxide, which effects reduction and decomposition to an aryl radical, and is run in the presence of Cu(II) salts. The radical is captured by Cu(II) and converted to the phenol by reductive elimination. This procedure is very rapid and gives good yields of phenols over a range of structural types. 

In the case of the production of copper wire, additional complications are present because of the chemical reduction of cupric oxide to a cuprous oxide coating, which cannot be removed by sulfuric acid. This coating has normally been treated by a secondary pickle of chromic acid-sulfuric acid, chromic acid-ammonium bifluoride mixtures, or by nitric acid. All of these techniques produce additional pollutants. Each of the three to four drawing steps required to produce fine copper wire from copper rod requires these pickling and rinse steps. 

Technical grade cuprous oxide obtained from Baker and Adamson Products, General Chemical Division, Allied Chemical Corp., was used. 

All of the sulfone diols were able to form oligomers in the second step of the reaction sequence, the Ullmann ether synthesis. As with the synthesis of the mono(bromophenoxy)phenol products, two methods were used to form the dibromo materials. Method A used pyridine, potassium carbonate and cuprous iodide, while Method B employed collidine and cuprous oxide with the dibromobenzene and higher molecular weight diol (IV). The major difference between the syntheses of the mono(bromophenoxy)phenols described earlier and these lies in the stoichiometry of the reactions. In order to... 

Method B A mixture of diol (50 mmol), dibromobenzene (47.Og, 200 mmol), cuprous oxide (1.97g, 15 mmol) and 2,4,6-collidine (100ml) was heated to reflux under nitrogen for 20h. The product was isolated as in Method A. 

Method B After combining 2,4,6-collidine (9mL), IV (10.25 mmol), dibromobenzene (24.2g, 102.5 mmol) and cuprous oxide (2.95g, 20.51 mmol), the reaction mixture was heated at reflux under nitrogen for 24h. When the reaction had cooled to approx. 80°C, the mixture was filtered, then diluted with chloroform. The organic phase was warmed to 60°C with lOOmL cone. HC1, washed with water and then was filtered through a short bed of silica gel. The product, a light amorphous solid, was obtained in 75-90% yield. 

By-products from capture of nucleophilic anions may be observed.79 Phenols can be formed under milder conditions by an alternative redox mechanism.90 91 The reaction is initiated by cuprous oxide, which effects reduction and decomposition to an aryl radical. 

The oxidation of propene is at present the most extensively studied gas phase heterogeneous oxidation process. The selective production of acrolein over cuprous oxide has been known for a very long time. However, the discovery of bismuth molybdates as highly active and selective catalysts for the oxidation to acrolein, and particularly the ammoxidation to acrylonitrile, has opened a new era in oxidation catalysis. 

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