Chromium as catalyst

Conjugated dienes can add hydrogen by 1,2 or 1,4 addition. Selective 1,4 addition can be achieved by hydrogenation in the presence of carbon monoxide, with bis(cyclopentadienyl)chromium as catalyst. With allenes catalytic hydrogenation usually reduces both double bonds. 

Hydrogenations with coppcr-chromium oxide catalyst are usually carried out in the liquid phase in stainless steel autoclaves at pressures up to 5000-6000 lb. per square inch. A solvent is not usually necessary for hydrogenation of an ester at 250° since the original ester and the alcohol or glycol produced serve as the reaction medium. However, when dealing with small quantities and also at temperatures below 200° a solvent is desirable this may be methyl alcohol, ethyi alcohol, dioxan or methylcyc/ohexane. 

Most catalysts for solution processes are either completely soluble or pseudo-homogeneous all their catalyst components are introduced into the reactor as Hquids but produce soHd catalysts when combined. The early Du Pont process employed a three-component catalyst consisting of titanium tetrachloride, vanadium oxytrichloride, and triisobutjlalurninum (80,81), whereas Dow used a mixture of titanium tetrachloride and triisobutylalurninum modified with ammonia (86,87). Because processes are intrinsically suitable for the use of soluble catalysts, they were the first to accommodate highly active metallocene catalysts. Other suitable catalyst systems include heterogeneous catalysts (such as chromium-based catalysts) as well as supported and unsupported Ziegler catalysts (88—90). 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

Ozonation can be enhanced by the addition of ultraviolet (uv) radiation. This combination can be effective in degrading chlorinated organic compounds and pesticides. In addition, metal ions such as iron, nickel, chromium, and titanium [7440-32-6] can act as catalysts, as can ultrasonic mixing. 

These siUca-supported catalysts demonstrate the close connections between catalysis in solutions and catalysis on surfaces, but they are not industrial catalysts. However, siUca is used as a support for chromium complexes, formed either from chromocene or chromium salts, that are industrial catalysts for polymerization of a-olefins (64,65). Supported chromium complex catalysts are used on an enormous scale in the manufacture of linear polyethylene in the Unipol and Phillips processes (see Olefin polymers). The exact stmctures of the surface species are still not known, but it is evident that there is a close analogy linking soluble and supported metal complex catalysts for olefin polymerization. 

Cocatalysts, such as diethylzinc and triethylboron, can be used to alter the molecular-weight distribution of the polymer (89). The same effect can also be had by varying the transition metal in the catalyst chromium-based catalyst systems produce polyethylenes with intermediate or broad molecular-weight distributions, but titanium catalysts tend to give rather narrow molecular-weight distributions. 

The heavy metals, copper, chromium, mercury, nickel, and 2inc, which are used as catalysts and complexing agents for the synthesis of dyes and dye intermediates, are considered priority poUutants (313). 

The non-ferrous alloys include the misleadingly named nickel silver (or German silver) which contains 10-30% Ni, 55-65% Cu and the rest Zn when electroplated with silver (electroplated nickel silver) it is familiar as EPNS tableware. Monel (68% Ni, 32% Cu, traces of Mn and Fe) is used in apparatus for handling corrosive materials such as F2 cupro-nickels (up to 80% Cu) are used for silver coinage Nichrome (60% Ni, 40% Cr), which has a very small temperature coefficient of electrical resistance, and Invar, which has a very small coefficient of expansion are other well-known Ni alloys. Electroplated nickel is an ideal undercoat for electroplated chromium, and smaller amounts of nickel are used as catalysts in the hydrogenation of unsaturated vegetable oils and in storage batteries such as the Ni/Fe batteries. 

Titanium, vanadium or chromium oxides activated with chlorine-free organo-aluminum compounds, triethyl- or triisobutyl aluminum, have also been used as catalysts [285],... 

So far the problem of active center formation in chromium oxide catalysts amounted mainly to a discussion of the oxidation number of chromium that is necessary for catalytic activity. As an active species chromium ions having practically every possible oxidation number—... 

The active component of the chromium oxide catalyst is a surface compound of Cr(VI). In the case of silica as a support this stage may be presented by the schemes ... 

Baker and Carrick (108) have found that in the reduction of the chromium oxide catalyst by ethylene under mild conditions (125°C) formaldehyde was formed as an oxidation product. 

In the propagation centers of chromium oxide catalysts as well as in other catalysts of olefin polymerization the growth of a polymer chain proceeds as olefin insertion into the transition metal-carbon tr-bond. Krauss (70) stated that he succeeded in isolating, in methanol solution from the... 

It is evident [see Eq. (5), Section II[] that for catalysts of the same or similar composition the number of active centers determined must be consistent with the catalytic activity it can be expected that only in the case of highly active supported catalysts a considerable part of the surface transition metal ions will act as propagation centers. However, the results published by different authors for chromium oxide catalysts are hardly comparable, as the polymerization parameters as a rule were very different, and the absolute polymerization rate was not reported. 

The data on the determination of the number of the propagation centers on chromium oxide catalysts by the inhibition method were given in several papers water (61), carbon tetrachloride (167), and diethylamine (69) were used as inhibitors. It was found that the number of propagation centers is about 10% (61), 1% (167), and 20% (69) of the total content of chromium in the catalyst. 

The interpretation of data on the change of Kp as a result of the reduction treatment of the chromium oxide catalyst (97) is hindered by the absence of precise data on the composition of the surface complexes being formed. 

Chromium compounds as catalysts, 188 Chromium oxide in catalytic converter, 62 Chromium oxide catalysts, 175-184 formation of active component, 176,177 of Cr-C bonds, 177, 178 propagation centers formation of, 175-178 number of, 197, 198 change in, 183, 184 reduction of active component, 177 Clear Air Act of 1970, 59, 62 Cobalt oxide in catalytic converter, 62 Cocatalysts, 138-141, 152-154 Competitive reactions, 37-43 Copper chromite, oxidation of CO over, 86-88... 

Figure 9.20. XPS spectra of a chromium polymerization catalyst along with chromium(vi) reference compounds for comparison of the state of chromium in the catalyst. Impregnated chromate in the freshly prepared catalyst shows the same binding energy as alkali chromates/dichromates or bulk Cr03. Upon calcination the binding energy...

With this in view, we studied the development of the dehydrofluorination reaction of CF3CH2CI as function of the degree of fluorination of chromium oxide. Moreover, nickel and chromium oxide catalysts were prepared and tested for the dehydrofluorination reaction. Nickel oxide, a basic compound [S], could poison selectively the tes involved during the dehydrofluorination reaction. 

An intere.sting example in the context of waste minimization is the manufacture of the vitamin K intermediate, menadione. Traditionally it was produced by stoichiometric oxidation of 2-methylnaphthalene with chromium trioxide (Eqn. (8)), which generates 18 kg of solid, chromium containing waste per kg of menadione. Catalytic alternatives have been reported, but selectivities tend to be rather low owing to competing oxidation of the second aromatic ring (the. selectivity in the classical process is only 50-60%). The best results were obtained with a heteropolyanion as catalyst and O2 as the oxidant (Kozhevnikov, 1993). 

More than three decades ago, skeletal rearrangement processes using alkane or cycloalkane reactants were observed on platinum/charcoal catalysts (105) inasmuch as the charcoal support is inert, this can be taken as probably the first demonstration of the activity of metallic platinum as a catalyst for this type of reaction. At about the same time, similar types of catalytic conversions over chromium oxide catalysts were discovered (106, 107). Distinct from these reactions was the use of various types of acidic catalysts (including the well-known silica-alumina) for effecting skeletal reactions via carbonium ion mechanisms, and these led... 

A wide range of nonacidic metal oxides have been examined as catalysts for aromatization and skeletal isomerization. From a mechanistic point of view, chromium oxide catalysts have been, by far, the most thoroughly studied. Reactions over chromium oxide have been carried out either over the pure oxide, or over a catalyst consisting of chromium oxide supported on a carrier, usually alumina. Depending on its history, the alumina can have an acidic function, so that the catalyst as a whole then has a duel function character. However, in this section, we propose only briefly to outline, for comparison with the metal catalyzed reactions described in previous sections, those reactions where the acidic catalyst function is negligible. 

Reactions over chromium oxide catalysts are often carried out without the addition of hydrogen to the reaction mixture, since this addition tends to reduce the catalytic activity. Thus, since chromium oxide is highly active for dehydrogenation, under the usual reaction conditions (temperature >500°C) extensive olefin formation occurs. In the following discussion we shall, in the main, be concerned only with skeletally distinguished products. Information about reaction pathways has been obtained by a study of the reaction product distribution from unlabeled (e.g. 89, 3, 118, 184-186, 38, 187) as well as from 14C-labeled reactants (89, 87, 88, 91-95, 98, 188, 189). The main mechanistic conclusions may be summarized. Although some skeletal isomerization occurs, chromium oxide catalysts are, on the whole, less efficient for skeletal isomerization than are platinum catalysts. Cyclic C5 products are of never more than very minor impor-... 

Another highly active chromium-based catalyst family is the triazacyclohexane series (103).269 Activities are dependent upon the length of the alkyl substituents attached to the nitrogen donors, reaching 717 g mmol- 1h 1 bar-1 for R = n-dodecyl. With higher a-olefins, or when branched R substituents such as 3-propyl-heptyl are employed, these compounds behave as trimerization catalysts 270,271... 

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