Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Rhodium carbon catalysts

The ester is prepared by catalytic hydrogenation of 4-tert-butylphenol followed by acetylation of the resulting 4-tert-butylcyclohexanol [132]. If Raney nickel is used as the catalyst, a high percentage of the trans isomer is obtained. A rhodium-carbon catalyst yields a high percentage of the cis isomer. The trans alcohol can be isomerized by alkaline catalysts the lower-boiling cis alcohol is then removed continuously from the mixture by distillation [133]. [Pg.92]

The acetic anhydride process employs a homogeneous rhodium catalyst system for reaction of carbon monoxide with methyl acetate (36). The plant has capacity to coproduce approximately 545,000 t/yr of acetic anhydride, and 150,000 t/yr of acetic acid. One of the many challenges faced in operation of this plant is recovery of the expensive rhodium metal catalyst. Without a high recovery of the catalyst metal, the process would be uneconomical to operate. [Pg.167]

Alkali moderation of supported precious metal catalysts reduces secondary amine formation and generation of ammonia (18). Ammonia in the reaction medium inhibits Rh, but not Ru precious metal catalyst. More secondary amine results from use of more polar protic solvents, CH OH > C2H5OH > Lithium hydroxide is the most effective alkah promoter (19), reducing secondary amine formation and hydrogenolysis. The general order of catalyst procUvity toward secondary amine formation is Pt > Pd Ru > Rh (20). Rhodium s catalyst support contribution to secondary amine formation decreases ia the order carbon > alumina > barium carbonate > barium sulfate > calcium carbonate. [Pg.209]

In one patent (31), a filtered, heated mixture of air, methane, and ammonia ia a volume ratio of 5 1 1 was passed over a 90% platinum—10% rhodium gauze catalyst at 200 kPa (2 atm). The unreacted ammonia was absorbed from the off-gas ia a phosphate solution that was subsequently stripped and refined to 90% ammonia—10% water and recycled to the converter. The yield of hydrogen cyanide from ammonia was about 80%. On the basis of these data, the converter off-gas mol % composition can be estimated nitrogen, 49.9% water, 21.7% hydrogen, 13.5% hydrogen cyanide, 8.1% carbon monoxide, 3.7% carbon dioxide, 0.2% methane, 0.6% and ammonia, 2.3%. [Pg.377]

Olefins can be aminomethylated with carbon monoxide [630-08-0] (CO) and amines in the presence of rhodium-based catalysts. Eor example, pipera2ine reacts with cyclohexene [110-83-8] to form W,Af-di-(l-cyclohexylmethyl)-pipera2ine [79952-94-6] (55). [Pg.43]

G-19 Dicarboxylic Acids. The C-19 dicarboxyhc acids are generally mixtures of isomers formed by the reaction of carbon monoxide on oleic acid. Since the reaction produces a mixture of isomers, no single chemical name can be used to describe them. Names that have been used include 2-nonyldecanedioic acid, 2-octylundecanedioic acid, l,8-(9)-heptadecanedicarboxyhc acid, and 9-(10)-carboxystearic acid. The name 9-(10)-carboxystearic acid can be used correctiy if the product is made with no double bond isomerization (rhodium triphenylphosphine catalyst system). [Pg.63]

The carbonylation of methanol was developed by Monsanto in the late 1960s. It is a large-scale operation employing a rhodium/iodide catalyst converting methanol and carbon monoxide into acetic acid. An older method involves the same carbonylation reaction carried out with a cobalt catalyst (see Section 9.3.2.4). For many years the Monsanto process has been the most attractive route for the preparation of acetic acid, but in recent years the iridium-based CATIVA process, developed by BP, has come on stream (see Section 9.3.2) ... [Pg.142]

The [5 + 2]-cycloadditions of tethered alkyne-VCPs that are 1,2-disubstituted on the cyclopropane ring 5j—1 have been studied and a mechanism has been advanced to explain the regio- and stereoselectivities of the reactions.37 In most cases, the product resulting from cleavage of the less-substituted (sterically less encumbered) carbon-carbon bond is obtained. The [5 + 2]-reaction is stereospecific in that a /ram-rclationship of the substituents on the cyclopropane leads to a m-relationship of the substituents in the product and vice versa (Equations (4) and (5)). For some tethered alkyne-VCPs which contain a functional group that weakens the carbon-carbon bond of the cyclopropane system, the more substituted (weaker) carbon-carbon bond can be cleaved selectively depending on the choice of catalyst. Thus far, the rhodium(l)-catalysts are more selective catalysts than the mthenium(0)-catalysts in the [5 + 2]-reaction of these substituted alkyne-VCPs (Scheme 7).38... [Pg.608]

Under a pressure (20 bar) of carbon monoxide, carbonylative silylcarbocyclization of enyne 92 was examined in the presence of a cationic rhodium-BINAP catalyst (Scheme 31).86 Although the enantioselectivity is low, the five-membered carbocycle functionalized with an alkenylsilane moiety and a formyl group was obtained with high selectivity. [Pg.835]

The use of the diphosphine PHANEPHOS (see Scheme 1.24) permitted Bar-gon, Brown and colleagues to detect and characterize a dihydrido intermediate in the hydrogenation of the enamide MAC by a rhodium-based catalyst The PH IP NMR technique was employed, and showed one of the hydrogen atoms to be agostic between the rhodium center and the /1-carbon of the substrate [85]. By using the same diphosphine and technique it was also possible to detect two diastereomers of the dihydride depicted in Scheme 1.25, which may also be detected using conventional NMR measurements [86]. [Pg.28]

As a case study an acetic acid process has been given. Acetic acid is produced by a liquid-phase methanol carbonylation. Acetic acid is formed by the reaction between methanol and carbon monoxide which is catalysed by rhodium iodocarbonyl catalyst. The process diagram is shown in Figure 7. [Pg.93]

Monsanto developed the rhodium-catalysed process for the carbonylation of methanol to produce acetic acid in the late sixties. It is a large-scale operation employing a rhodium/iodide catalyst converting methanol and carbon monoxide into acetic acid. At standard conditions the reaction is thermodynamically allowed,... [Pg.109]

In a detailed study of the reduction of the xylenes in the liquid phase on a 5% rhodium on carbon catalyst, Siegel and Ku (105) showed that both 1,2- and 2,3-dimethylcyclohexenes are formed from orlAo-xylene (Fig. 19). The initial (extrapolated) ratio, l,2-/2,3-, lies between 0.5 and 1 but rises as the reaction proceeds. If the initial distribution of cyclo-alkenes was random as previously postulated (97) the ratio should be 0.5. [Pg.158]

To make butyraldehyde, the precursor for NBA, the so-called Oxo process is used, reacting chemical grade propylene with hydrogen and. carbon monoxide at 250-300°F and 3500-4000 psi. See Figure 14-4.) Under those conditions, both feeds are liquids. The catalyst is an oil-soluble cobalt carbonyl complex dissolved in the propylene. If rhodium-based catalysts or complexes based on rhodium carbonyls and triphenyl phosphine... [Pg.205]

The regio- and diastereoselective rhodium-catalyzed sequential process, involving allylic alkylation of a stabilized carbon or heteroatom nucleophile 51, followed by a PK reaction, utilizing a single catalyst was also described (Scheme 11.14). Alkylation of an allylic carbonate 53 was accomplished in a regioselective manner at 30 °C using a j-acidic rhodium(I) catalyst under 1 atm CO. The resulting product 54 was then subjected in situ to an elevated reaction temperature to facilitate the PK transformation. [Pg.231]

The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter ( 4). The selectivity to acetic acid is more than 99% under mild conditions (175 C, 28 atm). The homogeneous rhodium catalyst is also effective for the synthesis of acetic anhydride (Ac O) by the carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe) (5-13). However, rhodium is one of the most expensive metals, and its proved reserves are quite limited. It is highly desirable, therefore, to develop a new catalyst as a substitute for rhodium. [Pg.176]

The last explanation for methanol formation, which was proposed by Ponec et al., 26), seems to be well supported by experimental and theoretical results. They established a correlation between the gfiethanol activity and the concentration of Pd , most probably Pd. Furthermore, Anikin et al. (27) performed ab initio calculations and found that a positive charge on the palladium effectively stabilizes formyl species. Metals in a non-zero valent state were also proposed by Klier et al. (28) on Cu/ZnO/Al O, by Apai (29) on Cu/Cr O and by Somorjai for rhodium catalyts (30). Recently results were obtained with different rhodium based catalysts which showed the metal was oxidized by an interaction with the support (Rh-0) (on Rh/Al 0 ) by EXAFS ( -32) and by FT-IR ( ) and on Rh/MgO by EXAFS ( ). The oxidation of the rhodium was promoted by the chemisorption of carbon monoxide (, ). ... [Pg.238]

To a 0.02 M soln of 2-alkyl-2,5-dihydro-l //-pyrrole (85-90% pure) in methanol is added with stirring 5% rhodium on carbon (catalyst/substrate 1 20). The mixture is pressurized (4.6 x 107 Torr) with hydrogen and is stirred at 25 °C for a minimum of 5 h. The catalyst is removed by vacuum filtration, the solution is concentrated under reduced pressure and the residue is purified by bulb-to-bulb distillation to give the product in 95% purity. [Pg.690]

An indirect method for the hydroformylation of olefins involves formation of the tri-alkylborane (5-12) and treatment of this with carbon monoxide and a reducing agent (see 8-26). Hydroacylation of alkenes has been accomplished, in variable yields, by treatment with an acyl halide and a rhodium complex catalyst, e.g.,587... [Pg.811]

Dibutylamine, piperidine, N-ethylcyclohexylamine, N-ethyldicyclohexylamine, and the ketones were reagent grade chemicals. The 5% palladium on carbon, 5% platinum on carbon, sulfided 5% platinum on carbon and sulfided 5% rhodium on carbon catalysts were obtained from Engelhard Industries. The 20% molybdenum sulfide on alumina (Girdler T-318) was obtained from the Chemetron Corp. Palladium chloride was obtained from Matheson, Coleman and Bell. Ruthenium trichloride was obtained from Ventron. [Pg.353]

Finally, it should be mentioned that there is one important commercial application of the organic halide carbonylation. This is in the rhodium and methyl iodide-catalyzed conversion of methanol and carbon monoxide into acetic acid (25). The mechanism of the reaction appears to involve the oxidative addition of methyl iodide to the rhodium(I) catalyst followed by CO insertion and hydrolysis ... [Pg.335]

Acetic acid (CH3COOH) is a bulk commodity chemical with a world production of about 3.1 x 106 Mg/year, a demand increasing at a rate of +2.6% per year and a market price of US 0.44-0.47 per kg (Anon., 2001a). It is obtained primarily by the Monsanto or methanol carbonylation process, in which carbon monoxide reacts with methanol under the influence of a rhodium complex catalyst at 180°C and pressures of 30-40 bar, and secondarily by the oxidation of ethanol (Backus et al., 2003). The acetic fermentation route is limited to the food market and leads to vinegar production from several raw materials (e.g., apples, malt, grapes, grain, wines, and so on). [Pg.326]

Reactions that combine C-H activation with a C-C bond-forming event are invaluable synthetic tools, allowing concise construction of carbon frameworks. Rhodium(i) catalysts have been shown to catalyze alkane carbonylation [21]. Recently, Sakakura and co-workers succeeded in subjecting methane to a catalytic acetaldehyde synthesis [22], They found that, in dense carbon dioxide, the complex [RhCl(PMe3)3] catalyzed the carbonylation of methane with 77 turnovers. [Pg.42]

In the case of rhodium as a catalyst metal for the hydroformylation of methyl oleate, lower pressure and lower temperature have to be compared to cobalt catalysis [20, 21], The use of rhodium is also advantageous because of the lower isomerization. Frankel showed that with a rhodium triphenylphosphine catalyst, hydroformylation occurs only on the ninth and tenth carbon atoms of the methyl oleate [22]. [Pg.109]

Catalyst Description. The LPO catalyst is a triphenylphosphine modified carbonyl complex of rhodium. Triphenylphosphine, carbon monoxide, and hydrogen form labile bonds with rhodium. Exotic catalyst synthesis and complicated catalyst handling steps are avoided since the desired rhodium complex forms under reaction conditions. Early work showed that a variety of rhodium compounds might be charged initially to produce the catalyst. Final selection was made on the basis of high yield of the catalyst precursor from a commodity rhodium salt, low toxicity, and good stability to air, heat, light, and shock. [Pg.80]


See other pages where Rhodium carbon catalysts is mentioned: [Pg.162]    [Pg.162]    [Pg.52]    [Pg.820]    [Pg.109]    [Pg.253]    [Pg.347]    [Pg.340]    [Pg.186]    [Pg.131]    [Pg.145]    [Pg.163]    [Pg.230]    [Pg.123]    [Pg.182]    [Pg.308]    [Pg.218]    [Pg.640]    [Pg.633]    [Pg.614]    [Pg.119]    [Pg.50]    [Pg.155]   
See also in sourсe #XX -- [ Pg.204 ]




SEARCH



Catalysts carbon

Metal catalysts rhodium-on-carbon

Rhodium carbon

Rhodium catalysts carbon monoxide conversion

Rhodium catalysts catalyst

Rhodium catalysts transition metal carbon-hydrogen

Rhodium/alumina catalysts, carbon

© 2024 chempedia.info