Rhone water

Super-Phenix 1 operation after fuel storage drum shutdown period (July-August 1989 limited power due to Rhone water temperature and flow and A turbine unavailable). 

Although rhodium recovery is efficient it is difficult to separate it from heavies that are formed in small amounts. Over time these heavies tend to result in some catalyst deactivation. One solution to this problem has been developed by Ruhrchemie/Rhone-Poulenc. In this process sulfonated triphenyl phosphine is used as the ligand, which imparts water solubility to the catalyst. The reaction is two-phase, a lower aqueous phase containing the catalyst and an upper organic phase. Fortunately the catalyst appears to sit at the interface enabling reaction to proceed efficiently. At the end of... 

An example of a large scale application of the aqueous biphasic concept is the Ruhrchemie/Rhone-Poulenc process for the hydroformylation of propylene to n-butanal (Eqn. (15)), which employs a water-soluble rhodium(I) complex of trisulphonated triphenylphosphine (tppts) as the catalyst (Cornils and Wiebus, 1996). 

The adoption of a second liquid phase has also proved useful in the hydroformylation reaction of propylene for which Ruhrchemie and Rhone-Poulenc have used Rh based water... 

Immobilization of catalysts is an important process design feature (see Chapter 9.9). A recent example of catalyst immobilization is the biphasic approach which seems superior to immobilization on solids, as successfully proven in the Ruhrchemie/Rhone Poulenc process for the hydro-formylation of olefins.286 Supported liquid phase catalysis was devised as a method for the immobilization of homogeneous catalysts on solids. When the liquid phase is water, a water-soluble catalyst may be physically bound to the solid. 

Figure 5.13. Large-scale oxo plant using the water-soluble Ruhrchemie/Rhone-Poulenc catalyst [HRh(COXTPPTS)3]. Note the horizontal decanter in front of the reactor...

Zhang H, Wollast R (1990) Distributions of dissolved cobalt and nickel in the Rhone and the Gulf of Lyons. In Martin JM, Barth H (eds) Water pollution research report 20, ERO 2000, 2nd Workshop on the northwest mediterranean sea. Blanes, Spain pp 397-414... 

RCH/RP [Ruhrchemie/Rhone Poulenc] A variation of the 0X0 process in which the triphenyl phosphine (part of the Wilkinson catalyst) is sulfonated, in order to render the catalyst soluble in water for easier recovery. First commercialized in 1984 for the manufacture of butyraldehyde. 

Aqueous two-phase hydrogenation may be a method of choice for synthetic purposes when no incompatibility problems between water and the substrates, products, or catalyst arise. It has already been proven by the success of the Ruhrchemie-Rhone-Poulenc hydroformylation process, that the catalyst can be retained in the aqueous phase with very high efficiency, and that aqueous-organic biphasic processes using organometallic catalysts are suitable for indus-... 

The synthesis of aldehydes via hydroformylation of alkenes is an important industrial process used to produce in the region of 6 million tonnes a year of aldehydes. These compounds are used as intermediates in the manufacture of plasticizers, soaps, detergents and pharmaceutical products [7], While the majority of aldehydes prepared from alkene hydroformylation are done so in organic solvents, some research in 1975 showed that rhodium complexes with sulfonated phosphine ligands immobilized in water were able to hydroformylate propene with virtually complete retention of rhodium in the aqueous phase [8], Since catalyst loss is a major problem in the production of bulk chemicals of this nature, the process was scaled up, culminating in the Ruhrchemie-Rhone-Poulenc process for hydroformylation of propene, initially on a 120000 tonne per year scale [9], The development of this biphasic process represents one of the major transitions since the discovery of the hydroformylation reaction. The key transitions in this field include [10] ... 

The third generation process concerns the Ruhrchemie/Rhone-Poulenc process utilizing a two-phase system containing water-soluble rhodium-tppts in one phase and the product butanal in the organic phase. The process has been in operation since 1984 by Ruhrchemie (or Celanese, nowadays). The system will be discussed in section 8.2.5. Since 1995 this process is also used for the hydroformylation of 1-butene. 

As mentioned earlier, in the Ruhrchemie-Rhone Poulenc process for propene hydroformylation the pH of the aqueous phase is kept between 5 and 6. This seems to be an optimum in order to avoid acid- and base-catalyzed side reactions of aldehydes and degradation of TPPTS. Nevertheless, it has been observed in this [93] and in many other cases [38,94-96,104,128,131] that the [RhH(CO)(P)3] (P = water-soluble phosphine) catalysts work more actively at higher pH. This is unusual for a reaction in which (seemingly) no charged species are involved. For example, in 1-octene hydroformylation with [ RhCl(COD) 2] + TPPTS catalyst in a biphasic medium the rates increased by two- to five-fold when the pH was changed from 7 to 10 [93,96]. In the same detailed kinetic studies [93,96] it was also established that the rate of 1-octene hydroformylation was a significantly different function of reaction parameters such as catalyst concentration, CO and hydrogen pressure at pH 7 than at pH 10. 

Hydrocyanation of olefins and dienes is an extremely important reaction [32] (about 75 % of the world s adiponitrile production is based on the hydrocyanation of 1,3-butediene). Not surprisingly, already one of the first Rhone Poluenc patents on the use of water soluble complexes of TPPTS described the Ni-catalyzed hydration of butadiene and 3-pentenenitrile (Scheme 9.10). The aqueous phase with the catalyst could be recycled, however the reaction was found not sufficiently selective. 

Peter A (2010) A plea for the restoration of Alpine rivers basic principles derived from the Rhone-Thur case study. In Bundi U (ed.) Alpine Waters. Handbook of Environmental Chemistry, Vol. 6. Springer, Heidelberg... 

For Switzerland the water balance has been established for the four most important river basins (Table 2) Rhine (27,970 km northern part), Rhone (5,220 km western inner Alpine part), Ticino (1,515 km southern part), and Inn (1,944 km eastern inner alpine region of Switzerland) and also for the entire territory of Switzerland (41,287 km ). 

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