Kuhlmann process

FIG. 4 Hydroformylation of higher molecular weight olefins with a cobalt carbonyl catalyst (Kuhlmann process). 

Figure 5.1. The generations of oxo processes [3] (symbolized by full points).A, First generation Ruhrchemie process 1943 (diaden process [4]) B, second generation Ruhrchemie process C, second generation BASF process D, second generation Kuhlmann process E, third generation Shell process F, third generation LPO (UCC) process G, third generation BASF process H, third generation Exxon (Kuhlmann) process I, fourth generation Ruhrchemie/Rhone-Poulenc process...

In the following sections a few typical processes will be described. An example of a cobalt catalysed hydroformylation reaction for higher alkenes is the Kuhlmann process (now Exxon process), for which the flow-scheme -a liquid/liquid separation- is shown in Figure 7.4. In this process the hydroformylation is done in one, organic phase consisting of alkene and aldehyde. The reactor is often a loop reactor or a reactor with an external loop to facilitate heat transfer. 

The basic solution in water containing NaCo(CO)4 is treated with sulphuric acid in the presence of syn-gas and HCo(CO)4 is regenerated. This can be extracted as is shown in the drawing from water into the substrate, alkene. The catalyst is returned to the reactor dissolved in the alkene. Compared to other schemes (BASF, Ruhrchemie) the elegant detail of the Kuhlmann process is... 

The ATOCHEM process utilizes the reaction among ketone, ammonia, and hydrogen peroxide. The process is also called the Ugine Kuhlmann process. The process obtains azine in high yields via the hydrogen peroxide oxidation of ketone-ammonia system in the presence of nitrile (RCN). This synthesis route bypasses chlorination. 

This is all the more surprising as the history of the oxo process actually prescribed the use of aqueous catalysts and catalyst precursors (aqueous cobalt salts as precursors of the earlier Diaden process [21], the at least partially aqueous cycle of the BASF and Kuhlmann process [22b], or the cleavage of solvent-soluble by-products and heavy ends of the oxo process with the aid of water-dissolved metal salts [22c, 23]). 

The Ugine Kuhlmann process uses hydrogen peroxide instead of sodium hypochlorite as a raw material and eliminates the capital and energy costs for crystallizing the by-product NaCl produced in the conventional processes. The capital and the manufacturing costs are estimated to be reduced by 10 percent with the Ugine Kuhlmann process. 

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

In 1838, Frederic Kuhlmann discovered die formation of nitrogen oxide (NO) during die catalytic oxidation of ammonia. Wilhelm Ostwald developed die production mediods in 1902 and established die base for today s major commercial processes. However, industrial production began only after Haber and Bosch developed the synthesis of ammonia around 1916. 

Hentze H-P, Co CC, McKelvey CA, Kaler EW (2003) Templating Vesicles, Microemulsions and Lyotropic Mesophases by Organic Polymerization Processes. 226 197-223 Hergenrother PJ, Martin SE (2000) Phosphatidylcholine-Preferring Phospholipase C from B. cereus. Eunction, Structure, and Mechanism. 2ii 131 -167 Hermann C, see Kuhlmann J (2000) 211 61-116... 

Jarosch, K., Tonkovich, A., Perry, S., Kuhlmann, D., and Wang, Y. (2005) Microreactor Technology and Process Intensification, in ACS Symposium Series, vol. 914, American Chemical Society, New York, pp. 258-273. 

Now chemists at the Central Research Laboratories of Produits Chimiques Ugine Kuhlmann (PCUK) at Lyons, France, developed beginning in 1970, under the direction of Dr F. Weiss, a novel continuous process for manufg hydrazine. The process is based on the discovery that ammonia, hydrogen peroxide, and a carbonyl compd, such as methyl ethyl ketone, react in presence of an amide and catalytic quantities of a phosphate to form an azine intermediate. This intermediate hydrolyzes quantitatively to hydrazine and to carbonyl compd which is recycled. The yield is claimed to be better than 75%... 

F. Kuhlmann obtained better results by increasing the press. The cost of the process renders the process unable to compete with the ammonia process. Patents have been obtained by G. Lunge (1866), W. Bramley (1886), and W. von Baranofi (1895) for modifications of this process. J. L. Smith prepared potassium carbonate by shaking for an hour a mixture of calcium carbonate with a soln. of potassium sulphate sat. with carbon dioxide. H. Jannasch also patented the preparation of potassium carbonate from kainite by treating potassium sulphate with witherite. 

Commercial production of hydrazine from its elements has not been successful. However three processes are available for the commercial production of hydrazine 1) The Raschig Process, 2) The Raschig/Olin Process, 3) The Hoffmann (urea) Process, 4) Bayer Ketazine Process, and 5) the Peroxide process from Produits Chimiques Ugine Kuhlmann (of France). 

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