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3.2 Baamples of Indusval Pocsses [67 Ir catalysts are considerably more stable than Rh under the preferred ,Jow water ‘operation conditions (0.5%) and are also more active. The technology has been in corporated worldwide in high capacity plants up to $00,000 va 323 Selective Ethylene Oxidation by the Wacker Process ‘The Wacker process was the first organometallic catalytic xidation (15, 16]. It was developed 1959 by Smidt and co-workers at the Wacker Consortium for Industrial Electrochemistry in Munich and is mainly used for the production of acetaldehyde from ethylene and oxygen (Eq. 3-5) cih=ci; + 120, > cHycHo 65) ‘The process proceeds by homogencous catalysis on PdCly. It had been known rch ealir that solutions of Pal! complexes stoichiometrcally oxidize ethylene to acetalehyil, but the erucil discovery was the exploitation of this reaction in a cat alytic eyele. A elosed-eycle process was developed in which an excess ofthe oxiiz~ ing agent Cu re-oxidizes the palladium formed in the process without its depo ing on the reactor walls. The Cu" formed inthe redox process is re-oxidized to Cu" by oxygen, The reaction steps are described by Equations 3-6 to 3-8 CH=CH, + H,0 + PaCl; —> CH,CHO+Pd+2 HCI 6-6) Pd +2CuCl, —> PdCls +2 CuCl co 2CuCI+ +0, +2HCL —» 2CuCl: +H,0 G8) ‘The complete catalytic process is depicted in Scheme 3-4 & Lb oa eo) CH,CHO +H 40 fa Pd H woh on Titouon | > 8 BN pe oH.-LoHoH © Scheme 3-4 Mechaniem for the oxidation of ethylene to acetaldehyde inthe Wacker process (chionide ligands omitted) 68 3 Homogeneous Carahzed Industrial Processes [A mechanistic study of the Wacker process involving detailed stereochemical in- vestigations showed that CO bond formation occurs with trans stereochemistry; that is, the ethylene molecule is not attacked intramolecularly by a coordinated water rolecule. Instead, an additional, uncomplexed water molecule attacks the double bona. ‘The formation of B by addition of water is followed by two further steps in which the coordinated alcohol is isomerized. First, a jehyride elimination gives C, and then an insertion reaction forms D. The elimination of the product acetaldehyde and HF gives Pa, whichis oxidized back to Pd by Cu""/O>. With the exception of this last step, the oxidation state of palladium in all steps ofthe eyele is +2 [7]. In industry, bubble column reactors are use to react the gaseous stating materi als ethylene and air (or oxygen) with the aqueous hydrochloric acid solution of the catalyst. Two process variants compete with one another Inthe one-step process, reaction and regeneration with oxygen are carried out sic smultancously, while inthe two-step process they are carried out separately. In the latter ease, ar can be used for regeneration, and complete ethylene conversion is achieved. A disadvantage isthe higher eneray requirement for eatayst circulation compared to the gas circulation used in the one-stage process. In addition, the dou ble reactor design for higher pressures and the use of corrosion-resistant materials lead to higher investment costs, “The two-step process operates at 100-110°C and 10 bar; catalyst regeneration is carried out at 100° C/10 bar. Selectivites of 94% are attained. Side products, such as acetic acid and erotonaldehyde, and chlorinated compounds are removed by {woe stage distillation, and the erude aldehyde is concentrated (Fig. 3-2). Ths process ac- counts for about 85 % of total acetaldehyde production. ude coal Presse Sw senate rat ofgas AL Etene s © ae Ho Text, eaten Fig. 32 Accaldehyde production inthe twostage Wacker-Hoechst process