NOVELTY - A catalytic system comprises iron-based active component and alumina-based microspheroidal carrier.    USE - The catalytic system is useful for producing hydrogen from natural gas. Hydrogen is used both in the oil refining industry (hydrocracking or hydrotreatment) and in petroleum chemistry (synthesis of methyl hydroxide, dimethyl ethanol, ammonia, or hydrocarbon via Fischer-Tropsch reaction).    ADVANTAGE - The inventive catalytic system enables production of hydrogen with high efficiency and high selectivity.    DETAILED DESCRIPTION - A catalytic system comprises iron-based active component and alumina-based microspheroidal carrier. The catalytic system is of formula (I).    (Fex1Mx2Qx2Dx4Alx5)Oy (I)    y = the value required by the oxidation number with which the components are present in the formulation;    x1 = the atomic percentage with which Fe is present in the formulation (i.e. 5-80);    x2, x3 = 0-30;    x4 = 0-35;    x5 = the atomic percentage with which Al is present in the formulation (i.e. 20-95);    M = Cr and/or Mn;    Q = La, lanthanide (e.g. Ce), and/or Zr;    D = Mg, Ca, Ba, Co, Ni, Cu, and/or Zn    xi (with i = 1.5) represents the atomic percentages assuming values which satisfy the equation approximatelySxi = 100.    INDEPENDENT CLAIMS are also included for:    (a) preparation of catalytic system by modifying a microspheroidal alumina by atomizing impregnating solution containing element D on the microspheroidal alumina, maintaining the microspheroidal alumina at predetermined temperature to allow contemporaneous evaporation of the excess solvent, and subsequently thermally treating at 500-900degreesC (preferably 700-800degreesC) to obtain modified alumina structurally comprising a compound with spinel structure and an oxide of element D; and modifying the modified alumina by atomizing impregnating solution containing iron and optionally element M and/or element Q on the modified alumina, maintaining the modified alumina at predetermined temperature to allow the contemporaneous evaporation of the excess solvent, and subsequently thermal treating at 500-900degreesC (preferably 700-800degreesC) to obtain the desired catalytic system; and    (b) production of hydrogen by oxidizing solid (i.e. the above catalytic system) in a first reaction zone in which water enters and hydrogen is produced; supplying heat by exploiting the heat developed by further oxidation of the solid with air in a supplementary thermal support unit; passing the oxidized form of solid to a second reaction zone into which a hydrocarbon is fed and reacts with the oxidized form of solid to form combustion products containing carbon dioxide and water; and recovering and feeding the reduced form of the solid to the first reaction zone.