Industrial Organic Chemicals Through Utilization of Synthesis Gas
01 Nov 1977-Annals of the New York Academy of Sciences (John Wiley & Sons, Ltd)-Vol. 295, Iss: 1, pp 239-248
TL;DR: In this article, the present or potential commercial synthesis of two large volume organic chemicals, aldehydes produced by hydroformylation, or the 0x0 reaction, and ethylene glycol, was discussed.
Abstract: This paper will emphasize two areas of homogeneous transition metal catalysis. These areas concern the present or potential commercial synthesis of two largevolume organic chemicals, aldehydes produced by hydroformylation, or the 0x0 reaction, and ethylene glycol. The aldehydes are used to make monohydric alcohols for plasticizers, esters, or detergents; the principal uses of ethylene glycol are as an antifreeze agent or for polyester fabrics. Both products are produced in billionpound quantities each year. Synthesis gas, that is, a mixture of hydrogen and carbon monoxide, is an important raw material for industrial organic chemicals and is expected to increase in importance during the next decade. It can be produced from a variety of carbonaceous sources, ranging from coal to garbage. In the hydroformylation processes, the part that it contributes to the aldehyde product varies from 51% of propionaldehyde to 14% of a detergent range product and is 42% of butyraldehyde, the major single product. However, the potential ethylene glycol process would utilize 100°, of a 3 : 2 hydrogen/carbon monoxide mixture. Presently, synthesis gas is the sole raw material for the latest technology in methanol and acetic acid manufacture. The hydroformylation of olefins to produce aldehydes, and ultimately alcohols or acids, is conducted in practically every major industrial country. Until the last year, every announced plant has used cobalt as a catalyst. The general reaction is depicted in SCHEME 1. The mechanism for this reaction was proposed by Heck and Breslow in 1960’ and is shown in SCHEME 2. The cobalt-catalyzed hydroformylation depicted in SCHEME 1 is beset with several difficulties. The linear isomer is of higher value than is the branched isomer, and only little control can be exercised over the reaction. Cobalt hydrocarbonyl is a volatile, unstable complex that is difficult to separate from the products and recycle into the system. The high temperatures usually employed promote the
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336 citations
TL;DR: In this paper, the authors describe the beginnings and development of biphasic homogeneous catalysis with water-soluble triphenylphosphine trisulfonate as the ligand.
297 citations
TL;DR: In this article, the significance of typical model reactions, both with regard to some fundamental aspects of synthesis gas chemistry, and in comparison with previous views concerning the mechanism of the Fischer-Tropsch synthesis, is discussed.
Abstract: The Fischer-Tropsch Synthesis counts among the industrial-scale processes having a versatile and broad product range, and has for decades offered the most attractive possibility for the use of coal as a source of heating oil and fuels. This conceivably simple reaction, the catalytic hydrogenation of carbon monoxide, generally leads to simple hydrocarbons as well (i.e. short chain olefins) that have been sought as chemical feedstocks since the oil crisis of the seventies, but fails to provide the large-scale, economic process required, due in large part to the minimal selectivity of traditional Fischer-Tropsch processes. In an effort to solve this problem current research in this sector is concerned not only with the optimization of old and the development of new catalytic systems, but also increasingly with the elucidation of numerous relevant reaction mechanisms. This article will discuss, from the viewpoint of an organometallic chemist, the significance of typical model reactions, both with regard to some fundamental aspects of synthesis gas chemistry, and in comparison with previous views concerning the mechanism of the Fischer-Tropsch Synthesis. The importance of various unique classes of complexes that have been studied in the context of Fischer-Tropsch chemistry is also evaluated with regard to their importance in the synthesis of hydrocarbons from carbon monoxide and hydrogen. It emerges that the primary steps of the reductive oligomerization of carbon monoxide are best described by the carbide/methylene mechanism, as originally proposed by Hans Fischer and Franz Tropsch.
241 citations
TL;DR: In this article, the authors applied the techniques of high resolution electron energy loss spectroscopy (ELS), thermal desorption mass spectrometry (TDS) and low energy electron diffraction (LEED) to a study of CO and CO 2 chemisorption on the Rh(111) single crystal surface.
213 citations
References
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TL;DR: In this paper, the Schulz-Flory equation is used to describe the molecular weight distribution of the primary products in the Fischer-Tropsch procedure for the production of hydrocarbons and alcohols.
Abstract: An evaluation of literature data concerning the production of hydrocarbons and alcohols by the Fischer-Tropsch procedure indicates that the molecular weight distribution of the primary products can be described by the Schulz-Flory equation (“normal” or “most probable” distribution). It follows that the highest attainable selectivity for a given molecular weight range can be calculated. A reaction mechanism is suggested.
338 citations
192 citations
TL;DR: In this paper, the first acyl cluster compounds were synthesized in the presence of tertiary phosphines and catalytic synthesis was performed together with decomposition of the phosphine.
Abstract: Hydroformylation of propene using stoicheiometric amounts of Rh4(CO)12 and hydrogen, and direct synthesis of the first acyl cluster compounds are reported; catalytic synthesis in the presence of tertiary phosphines takes place together with decomposition of the phosphine.
33 citations
TL;DR: In this article, the steric strain energies in various NiL4 complexes and ΔG for their formation from nickel metal are estimated, showing that both the extent of reaction and mean Ni-P bond strength tend to decrease with increasing ligand size.
32 citations