Cobalt salts catalysts

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

The three chemical reactions in the toluene—benzoic acid process are oxidation of toluene to form benzoic acid, oxidation of benzoic acid to form phenyl benzoate, and hydrolysis of phenyl benzoate to form phenol. A typical process consists of two continuous steps (13,14). In the first step, the oxidation of toluene to benzoic acid is achieved with air and cobalt salt catalyst at a temperature between 121 and 177°C. The reactor is operated at 206 kPa gauge (2.1 kg/cm g uge) and the catalyst concentration is between 0.1 and 0.3%. The reactor effluent is distilled and the purified benzoic acid is collected. The overall yield of this process is beheved to be about 68 mol % of toluene. 

Keep injection points for catalyzed sulfite and chelant-containing programs as far apart from each other as possible to avoid inactivation of the cobalt salt catalyst through chelation. 

The injection location also is important, especially where catalyzed sodium sulfite is employed, because of the potential for chelation of the usual cobalt salt catalyst to occur. 

Peracetic acid can also be formed directly by liquid-phase oxidation at 5 to 50°C with a cobalt salt catalyst. Nitric acid oxidation of acetaldehyde yields glyoxal and the oxidation of p-xylene to terephthalic acid and of ethanol to acetic acid is activated by acetaldehyde. 

A novel method was reported for the carbonylation of aryl halides by cobalt salt catalysts, such as Co(OAc)2, CoCl2, C0SO4, Co(OH)2, Co(OH)3, CoO and Co203 in an aqueous alkaline solution and under irradiation214. 

Use Pigment in paints and ceramics, preparation of cobalt salts, catalyst, porcelain enamels, coloring glass, feed additive, cobalt metal powder. 

One of the most unusual features of the dialkylaluminum chloride and cobalt salt catalyst is the extremely high effectiveness of the cobalt compound. Although equimolar amounts of the aluminum and cobalt compounds are an effective catalyst, polymer is still formed at ratios as high as Al/Co = 500, using the normal amount of aluminum compound but only traces of the cobalt salt (Gippin, 1962 Longiave et al., 1961). For example, with as little as 0.002 mmole of cobalt salt 43 gm of cis-l,4-polybutadiene were obtained from 45 gm of monomer (Longiave et al., 1961). 

A cobalt salt catalyst, Amosorb oxygen scavenger (BP Chemicals). 

Because the chemiluminescence intensity can be used to monitor the concentration of peroxyl radicals, factors that influence the rate of autooxidation can easily be measured. Included are the rate and activation energy of initiation, rates of chain transfer in cooxidations, the activities of catalysts such as cobalt salts, and the activities of inhibitors (128). 

Eigure 3 is a flow diagram which gives an example of the commercial practice of the Dynamit Nobel process (73). -Xylene, air, and catalyst are fed continuously to the oxidation reactor where they are joined with recycle methyl -toluate. Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used in combination. Titanium or other expensive metallurgy is not required because bromine and acetic acid are not used. The oxidation reactor is maintained at 140—180°C and 500—800 kPa (5—8 atm). The heat of reaction is removed by vaporization of water and excess -xylene these are condensed, water is separated, and -xylene is returned continuously (72,74). Cooling coils can also be used (70). 

The action of redox metal promoters with MEKP appears to be highly specific. Cobalt salts appear to be a unique component of commercial redox systems, although vanadium appears to provide similar activity with MEKP. Cobalt activity can be supplemented by potassium and 2inc naphthenates in systems requiring low cured resin color lithium and lead naphthenates also act in a similar role. Quaternary ammonium salts (14) and tertiary amines accelerate the reaction rate of redox catalyst systems. The tertiary amines form beneficial complexes with the cobalt promoters, faciUtating the transition to the lower oxidation state. Copper naphthenate exerts a unique influence over cure rate in redox systems and is used widely to delay cure and reduce exotherm development during the cross-linking reaction. 

Catalysts other than the above cobalt salts have been considered. Several patents suggest that cobalt bromide gives improved yields and faster reaction rates (12—16). The bromide salts are, however, very corrosive and require that expensive materials of constmction, such as HastaHoy C or titanium, be used in the reaction system. Only one faciHty, located in the UK, is beHeved to uti1i2e cobalt bromide catalyst in the production of ben2oic acid. 

Cobalt(II) hydroxide [1307-86-4], Co(OH)2, is a pink, rhombic crystalline material containing about 61% cobalt. It is insoluble in water, but dissolves in acids and ammonium salt solutions. The material is prepared by mixing a cobalt salt solution and a sodium hydroxide solution. Because of the tendency of the cobalt(II) to oxidize, antioxidants (qv) are generally added. Dehydration occurs above 150°C. The hydroxide is a common starting material for the preparation of cobalt compounds. It is also used in paints and Hthographic printing inks and as a catalyst (see Paint). 

Cobalt salts are used as activators for catalysts, fuel cells (qv), and batteries. Thermal decomposition of cobalt oxalate is used in the production of cobalt powder. Cobalt compounds have been used as selective absorbers for oxygen, in electrostatographic toners, as fluoridating agents, and in molecular sieves. Cobalt ethyUiexanoate and cobalt naphthenate are used as accelerators with methyl ethyl ketone peroxide for the room temperature cure of polyester resins. 

Where sulfite or bisulfite oxygen scavengers are employed, a catalyst (such as a cobalt salt or an ethorbate) is vital to speed up the rate of deaeration. 

Co balticyanide discovery, 1,3 Cobaltitungstates, 3,1042 Cobalt(II) salts catalysts... 

The liquid-phase autoxidation of cyclohexane is carried out in the presence of dissolved cobalt salts. A lot of heterogeneous catalysts were developed for this process but most catalysts lacked stability. The incorporation of cobalt ions in the framework of aluminophosphate and aluminosilicate structures opens perspectives for heterogenization of this process. CoAPO (cobalt aluminophosphate) molecular sieves were found to be active heterogeneous catalysts of this oxidation.133 Site isolation was critical to get active catalysts.134... 

Cobalt bromide is used as a catalyst in the technology of production of arylcarboxylic acids by the oxidation of methylaromatic hydrocarbons (toluene, p-xylene, o-xylene, polymethyl-benzenes). A cobalt bromide catalyst is a mixture of cobaltous and bromide salts in the presence of which hydrocarbons are oxidized with dioxygen. Acetic acid or a mixture of carboxylic acids serves as the solvent. The catalyst was discovered as early as in the 1950s, and the mechanism of catalysis was studied by many researchers [195-214],... 

It was shown in the previous section that hydrocarbon oxidation catalyzed by cobalt salts occurs under the quasistationary conditions with the rate proportional to the square of the hydrocarbon concentration and independent of the catalyst (Equation [10.9]). This limit with respect to the rate is caused by the fact that at the fast catalytic decomposition of the formed hydroperoxide, the process is limited by the reaction of R02 with RH. The introduction of the bromide ions into the system makes it possible to surmount this limit because these ions create a new additional route of hydrocarbon oxidation. In the reactions with ROOH and R02 the Co2+ ions are oxidized into Co3+, which in the reaction with ROOH are reduced to Co2+ and do not participate in initiation. 

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