Iron catalyst ethane

The first reported work on the kinetics of hydrogenolysis reactions of simple hydrocarbons appears to be that of Taylor and associates at Princeton (2-4, 14, 15), primarily on the hydrogenolysis of ethane to methane. The studies were conducted on nickel, cobalt, and iron catalysts. More recently, extensive studies on ethane hydrogenolysis kinetics have been conducted on all the group VIII metals and on certain other metals as well (16,28-83). 

A good way to prepare p-diketones consists of heating a,p-epoxy ketones at 80-140°C in toluene with small amounts of (Ph3P)4Pd and l,2-bis(diphenyl-phosphino)ethane. ° Epoxides are converted to 1,2-diketones with Bi, DMSO, O2, and a catalytic amounts of Cu(OTf)2 at 100°C. a,p-Epoxy ketones are also converted to 1,2-diketones with a ruthenium catalyst or an iron catalyst. Epoxides with an a-hydroxyalkyl substituent give a pinacol rearrangement product in the presence of a ZnBr2 " or Tb(OTf)3 catalyst to give a y-hydroxy ketone. 

The reaction of norbornadiene with dimethylallene and buta-1,3-diene to give 1 and 3 has been tested in the presence of several iron catalysts. The three component system tris(acetylacetonato) iron/diethylaluminum chloride/bis( 1,2-diphenylphosphino)ethane was the most effective, yet lacks chemioselectivity." ... 

Cimino, A. Boudart, M. and Taylor, H.S. "Ethane hydrogenation-cracking on iron catalysts with and without alkali." /. Phys. Chem. 58 796-800 1954. 

In 1930, Smith, Hawk, and Golden (16) discovered that ethylene, when added to the synthesis gas, enters into the oil-producing reaction on a Co-Cu-MnO catalyst but not on an Fe-Cu catalyst. In the latter case, most of the ethylene appears as ethane in the products. It was pointed out also that water was the main oxygenated product from the cobalt catalyst, whereas carbon dioxide was the chief corresponding product on the iron catalyst. The behavior of ethylene when added to 83mthesi8 gas and passed over a cobalt catalyst was verified by Craxford (17) in 1939. 

This report is remarkable in that only 17% methane plus ethane is specified. Others who have experimented with iron catalysts at 300-320°C., with little or no recycle of end gases, have reported much higher yields of methane ai d ethane. The cost of operation of this process is markedly dependent upon the pressure drop across the catalyst bed. This was reported to be 1 meter water/meter of catalyst depth. Increased gradients would result with increasing carbon deposition, and the operating temperature is dangerously close to that at which a rapid rate of carbon formation occurs. 

The compositional modulation technique has been applied to the Fischer-Tropsch synthesis (FTS) reaction [2-5], It was found that the cyclic feeding of CO/H2 had an influence on the selectivity of the FTS products. Among the conclusions was that for an iron catalyst the selectivity for methane increased under periodic operation compared to the steady state operation [5], In the study [5] it was found that the propane/propene ratio increased under periodic operation and the largest changes were with periods between one and ten minutes. Due to the limitations of the anal5dical technique utilized, they could not separate ethane and ethene so that the selectivity basis was for the C3 hydrocarbons. In this study the analytical procedure permitted analysis of products only to the Cg-compoimds. 

In the direct ammoxidation of propane over Fe-zeolite catalysts the product mixture consisted of propene, acrylonitrile (AN), acetonitrile (AcN), and carbon oxides. Traces of methane, ethane, ethene and HCN were also detected with selectivity not exceeding 3%. The catalytic performances of the investigated catalysts are summarized in the Table 1. It must be noted that catalytic activity of MTW and silicalite matrix without iron (Fe concentration is lower than 50 ppm) was negligible. The propane conversion was below 1.5 % and no nitriles were detected. It is clearly seen from the Table 1 that the activity and selectivity of catalysts are influenced not only by the content of iron, but also by the zeolite framework structure. Typically, the Fe-MTW zeolites exhibit higher selectivity to propene (even at higher propane conversion than in the case of Fe-silicalite) and substantially lower selectivity to nitriles (both acrylonitrile and acetonitrile). The Fe-silicalite catalyst exhibits acrylonitrile selectivity 31.5 %, whereas the Fe-MTW catalysts with Fe concentration 1400 and 18900 ppm exhibit, at similar propane conversion, the AN selectivity 19.2 and 15.2 %, respectively. On the other hand, Fe-MTW zeolites exhibit higher AN/AcN ratio in comparison with Fe-silicalite catalyst (see Table 1). Fe-MTW-11500 catalyst reveals rather rare behavior. The concentration of Fe ions in the sample is comparable to Fe-sil-12900 catalyst, as well as... 

Iron tetrafo-nitrophenyI (porphyrin is such a powerful catalyst that the simplest alkanes, even methane and ethane, are converted to the corresponding alcohols.145... 

One of the characteristic features of the metal-catalysed reaction of acetylene with hydrogen is that, in addition to ethylene and ethane, hydrocarbons containing more than two carbon atoms are frequently observed in appreciable yields. The hydropolymerisation of acetylene over nickel—pumice catalysts was investigated in some detail by Sheridan [169] who found that, between 200 and 250°C, extensive polymerisation to yield predominantly C4 - and C6 -polymers occurred, although small amounts of all polymers up to Cn, where n > 31, were also observed. It was also shown that the polymeric products were aliphatic hydrocarbons, although subsequent studies with nickel—alumina [176] revealed that, whilst the main products were aliphatic hydrocarbons, small amounts of cyclohexene, cyclohexane and aromatic hydrocarbons were also formed. The extent of polymerisation appears to be greater with the first row metals, iron, cobalt, nickel and copper, where up to 60% of the acetylene may polymerise, than with the second and third row noble Group VIII metals. With alumina-supported noble metals, the polymerisation prod-... 

The other example to be discussed in this context comes from Pettit s group. Simultaneous treatment of the iron complex (/u.-CH2)[Fe(CO)4]2 (35) with hydrogen and ethylene gives both methane (66%) and propylene (6%), the expected products from the two separate reactions. In addition, ethane (—600%) is formed, with the actual hydrogenation catalyst still to be determined (72). Because simple diazoalkanes provide the cleanest method to metal-attached alkylidenes, and with the expectation that dissociative chemisorption of diazomethane to absorbed CH2 and free N2 would occur, the reactions of CH2N2 with and without H2 over various transition metals were examined in a careful study with regard to the product ratio (73). It was found, that gas-phase decomposition of the parent diazoalkane upon passage over active Ni, Pd, Fe, Co, Ru, or Cu-... 

Aldol reactions of aldehydes with cycloakanones were performed in ionic liquids and catalyzed by FeCl3-6H20 [32]. Mukaiyama aldol reactions of silylenol ethers with aldehydes can be carried out in aqueous media however, among several Lewis acidic catalysts investigated, iron compounds were not the optimal ones [33], If silyl ketene acetals are applied as carbon nucleophiles in Mukaiyama aldol reactions, cationic Fe(II) complexes give good results. As catalysts, CpFe(CO)2Cl [34] and [CpFe(dppe) (acetone)] BF4 [35] [dppe = l,2-bis(diphenylphosphano)ethane] were applied (Scheme 8.8). No diastereomeric ratio was reported for product 26a. 

The first investigations on iron-catalyzed Michael reactions utilized Fe(acac)3 as catalyst. However, this metal complex is itself catalytically almost inactive. Yields of only up to 63% could be achieved, if BF3OEt2 is used as a co-catalyst [55], Polystyrene-bound Fe(acac)3 catalysts were also reported to give yields up to 63% [56], FeCl3 was used as a co-catalyst for clay-supported Ni(II). Yields achieved with this heterogeneous system ranged from 40 to 98% [57]. The double Michael addition of acrylonitrile to ethyl cyanoacetate is smoothly catalyzed by a complex generated from [Fe(N2) (depe)2] [depe = l,2-bis(diethylphosphano)ethane]. At 23 °C and after 36h, an 88% yield is obtained with 1 mol% of this Fe(0) catalyst [58]. 

Ruthenium supported on oxides is a catalyst of various reactions. It is active in methanation reactions [e.g. 1, 2, 3], in Fischer-Tropsch synthesis [e.g. 4, 5, 6], in CO oxidation [7, 8], in the synthesis of methyl alcohol [9], 1" the redu ction of NO to nitrogen CIO] and in hydrogenolysis of ethane [11] and of butane [12]. Ru supported on carbon is supposed to replace the iron in ammonia synthesis [13]. Lately ruthenium supported on oxides is intensively investigated as a potential... 

Fe20(0Ac)2Cl2(bipy)2 successfully hydroxylates C6, C3, and C2 alkanes when tert-butyl hydrogen peroxide (TBHP) is used as the oxygen donor ([5] [TBHP]-.[substrate] = 1 150 1100) the observed reactivity is C6 > C3 > C2 (Table IV). This work represents the first report of the oxidation of a small molecular weight alkane (ethane) by a characterized iron model compound. Reactions of this complex with Zn dust and acetic acid under 1 atm of dioxygen with cyclohexane gave rise to only cyclohexanone (turnover number 2.5). The parent tetrameric compound, 6, was reported to be a more efficient catalyst. 

Rare earth oxides are useful for partial oxidation of natural gas to ethane and ethylene. Samarium oxide doped with alkali metal halides is the most effective catalyst for producing predominantly ethylene. In syngas chemistry, addition of rare earths has proven to be useful to catalyst activity and selectivity. Formerly thorium oxide was used in the Fisher-Tropsch process. Recently ruthenium supported on rare earth oxides was found selective for lower olefin production. Also praseodymium-iron/alumina catalysts produce hydrocarbons in the middle distillate range. Further unusual catalytic properties have been found for lanthanide intermetallics like CeCo2, CeNi2, ThNis- Rare earth compounds (Ce, La) are effective promoters in alcohol synthesis, steam reforming of hydrocarbons, alcohol carbonylation and selective oxidation of olefins. 

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