Patent GB-1037818-A (GB)
Title: Improvements in the preparation of unsaturated aldehydes
IPC: C07C45/34
Filed: 1963-10-31
Abstract: Catalysts for oxidizing olefins to aldehydes comprise a heteropoly compound obtained by reacting a heteropolyacid having as a coordinating element a rare earth of the actinide or lanthanide series, e.g. Ce or Th, and as coordinated element W, Mo or V, or an ammonium salt of such an acid, with a salifying compound containing Bi or Te.  Preferred heteropolyacids are H8 AD12O42, where A is Ce or Th and D is W or Mo, and H8Ce(or Th)Mo10V2O41. Preferred salifying compounds are Bi or Te salts of organic or inorganic acids soluble in water, alcohols, ethers or esters.  Preferred catalysts have the formulae MexAD12Oy, where Me is Bi or Te, x is 0.2-18, A is Ce or Th, D is W or Mo, and y is 38-74, and MexAMo10V2Oy, where Me, x and A are the same, and y is 37-73.  They are prepared by reacting the heteropolyacid or its ammonium salt and the salifying compound in a solvent in the presence of a strong mineral acid, e.g. nitric.  After evaporation to dryness, the product may be activated at 400-600 DEG C.  It may be deposited on supports, e.g. silica, alumina, and particularly silica aerogel.  Bismuth and tellurium ceric - molybdates, bismuth ceric - tungstate, and bismuth and tellurium ceric-molybdovanadates are prepared in examples.ALSO:Unsaturated aliphatic aldehydes are prepared by heating an olefin in the gaseous phase with oxygen in the presence of a catalyst comprising a heteropoly compound obtained by reacting a heteropolyacid having as a coordinating element a rare earth of the actinide or lanthanide series, e.g. Ce or Th, and as coordinated element W, Mo or V, or an ammonium salt of such an acid, with a salifying compound containing Bi or Te.  Preferred heteropolyacids are H8AD12O42, where A is Ce or Th and D is W or Mo, and H8Ce (or Th) Mo10V2O41. Preferred salifying compounds are Bi or Te salts of organic or inorganic acids soluble in water, alcohols, ethers or esters.  Preferred catalysts have the formulae MexAD12Oy, where Me is Bi or Te, x is 0.2-18, A is Ce or Th, D is W or Mo, and y is 38-74, and MexAMo10 V2Oy, where Me, x, and A are the same, and y is 37-73.  The olefin, with or without diluents, and oxygen are preferably reacted at 300-600 DEG  C. Conversion of propylene to acrolein and isobutene to methacrolein are exemplified.ALSO:Catalysts for oxidizing olefins to aldehydes comprise a heteropoly compound obtained by reacting a heteropolyacid having as a co-ordinating element a rare earth of the actinide or lanthanide series, e.g. Ce or Th, and as co-ordinated element, W, Mo or V, or an ammonium salt of such an acid, with a salifying compound containing Bi or Te.  Preferred heteropolyacids are H8 AD12 O42, where A is Ce or Th and D is W or Mo, and H8 Ce (or Th) Mo10 V2 O41. Preferred salifying compounds are Bi or Te salts of organic or inorganic acids soluble in water, alcohols, ethers or esters. Preferred catalysts have the formulae MexAD12 Oy, where Me is Bi or Te, x is 0.2-18, A is Ce or Th, D is W or Mo, and y is 38-74, and Mex AMo10 V2 Oy, where Me, x, and A are the same, and y is 37-73.  They are prepared by reacting the heteropolyacid or its ammonium salt and the salifying compound in a solvent in the presence of a strong mineral acid, e.g. nitric.  After evaporation to dryness, the product may be activated at 400-600 DEG C.  It may be deposited on supports, e.g. silica alumina, and particularly silica aerogel. Bismuth and tellurium cericmolybdates, bismuth cerictungstate, and bismuth and tellurium ceric-molybdovanadates are prepared in examples.