Catalyst system and process for the preparation of alpha olefins and alpha olefin-containing products from long-chain paraffins

A process for preparing linear alpha-olefins, having a carbon number of 3-42, or products containing linear alpha-olefins, having a carbon number of 3-42,

• which process comprises the following steps a) and b):
• a) paraffin having a carbon number of 11-45, or a paraffin mixture containing paraffins having a carbon number of 11-45 is dehydrogenated using a zeolite-supported heterogeneous Pt, Pd or Ni catalyst, which catalyst is
• characterized by that
• it contains a medium pore-sized zeolite as a support, in which the zeolite Si/Al ratio is 2-250, and which has Pt, Pd or Ni metal introduced into the zeolite support with a molar amount not exceeding the framework aluminum content of the zeolite support, at a dispersity higher than 10% and in the form of neutral metal atoms or neutral metal nanoparticles;
• and/or
• it is produced by the following process steps:
• (i) a Pt, Pd or Ni salt, preferably Pt, Pd or Ni nitrate, acetate, hydroxide, or a Pt, Pd or Ni amine complex, of a molar amount not exceeding the framework aluminum content of the zeolite, is introduced by ion exchange or impregnation into the Na, K, or ammonium ion form of a medium pore-sized zeolite with a Si/Al ratio of 2-250,
• (ii) the material obtained in step (i) is calcined at 300-500° C.
• (iii) the material calcined in step (ii) is reduced with hydrogen at 300-500° C.,
• (iv) the material reduced in step (iii) is ion-exchanged with a Na or K salt solution, or
• it is reacted in solid phase with Na or K salt in an amount equivalent to the lattice aluminum content of the zeolite, and the salt is then decomposed by heat treatment;
• and
• b) the internal monoolefin content of the mixture obtained in step a) is converted to alpha-olefins,
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in ethylene metathesis (ethenolysis) reaction, and/or
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in combination with a homogeneous or heterogeneous olefin isomerization catalyst in an isomerization metathesis (ISOMET) reaction, and/or
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in combination with a homogeneous or heterogeneous olefin isomerization catalyst in an ethylene isomerization metathesis (ethylene ISOMET) reaction;
• or a process comprising the following step b):
• b) an internal monoolefin having a carbon number of 11-45, or the internal monoolefin content of a mixture containing an internal monoolefin having a carbon number of 11-45 is converted to alpha-olefins,
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in ethylene metathesis (ethenolysis) reaction, and/or
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in combination with a homogeneous or heterogeneous olefin isomerization catalyst in an isomerization metathesis (ISOMET) reaction, and/or
• using a homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst in combination with a homogeneous or heterogeneous olefin isomerization catalyst in an ethylene isomerization metathesis (ethylene ISOMET) reaction;
• where the ruthenium complex in the homogeneous or heterogenized homogeneous ruthenium complex metathesis catalyst used in step b) is of formula I, II, III or IV,
• wherein
• X1 and X2 are independently halogen, nitrite, nitrate, sulfate, carboxylate, sulfonate, alkoxy, alkylthio, or
• X1 and X2 represent a heteroatom linked together via a part of an organic molecule, for example, X1 and X2 represent O and form together through a benzene ring a catecholate group, or X1 and X2 are S and form together through a benzene ring a catecho-ditiolate group;
• R1 represents aryl, heteroaryl or alkyl optionally substituted by one or more substituents, where the substituents are independently selected from alkyl, aryl, heteroaryl, amino, alkylamino, dialkylamino, quaternary ammonium ion, nitro, sulfone, sulfonic acid, sulfonic acid derivative, ketone, carboxylic acid, carboxylic acid derivative, alkoxy, preferably an electron donating group such as dimethylamino or trimethylammonium ion,
• with the proviso, that when R1 is aryl or heteroaryl, in the case of a complex containing a BICAAC ligand of formula (III) or (IV) the substituent in the ortho position relative to the nitrogen atom is an alkyl containing at most 1-2 carbon atom(s);
• R2 and R3 are independently alkyl, aryl or heteroaryl, which may be optionally substituted by one or more substituents selected from alkyl, aryl, heteroaryl, amino, alkylamino, dialkylamino, quaternary ammonium ion, nitro, sulfone, sulfonic acid, sulfonic acid derivative, ketone, carboxylic acid, carboxylic acid derivative, alkoxy,
• preferably an electron-donating group,
• or R2 and R3 form together with the carbon atom to which they are linked a cycloalkane ring having 3-12 carbon atoms;
• R4 represents hydrogen, alkyl, nitro, carboxylic acid, carboxylic acid derivative, sulfonic acid, sulfonic acid derivative, aryl, heteroaryl, perfluoroalkyl, perfluoroaryl, sulfone, ketone, preferably an electron-withdrawing group such as perfluoroalkyl or nitro;
• R5 represents alkyl;
• R6 represents hydrogen or alkyl, or a group linked via a linker of 1-24 carbon atoms, wherein the group is selected from aryl, heteroaryl, amino, alkylamino, dialkylamino, ketone, ether, hydroxy, thioether, thiol, carboxylic acid derivative, sulfonic acid derivative, silicon-containing group, or a ligand selected from amine, imine, thioether, sulfoxide, phosphine, ether, nitrile and isonitrile, optionally linked to other variable groups of the molecule, for example, in the case of a bis-BICAAC complex of formula IV, to the R6 group of the other BICAAC ligand;
• with the proviso that at least one of the groups R1, R2, R3 or R6 contains an ionic or an ion-forming group selected from a quaternary ammonium ion, amine, alkylamino having 1-6 carbon atoms, dialkylamino having 1-6 carbon atoms, carboxylic acid, carboxylate, sulfonic acid or a sulfonic acid salt group.