Method for treating or regenerating metal catalyst and application

A regeneration method of metal supported catalyst, the metal supported catalyst is a Ma-Mb-Mc metal supported catalyst, wherein the metal supported catalyst does not contain Mc metal, the method comprising:

• step A, removing substances which cause the metal supported catalyst poisoned or deactivated to regenerate the metal supported catalyst;
• step B, treating the catalyst obtained from step A by ammonia or a nitrogen-containing organic at 10-700° C. to obtain an activated catalyst;
• in the step A, the substances which cause the catalyst deactivated comprise coke and/or sulfur;
• the removing comprises:
• oxidation removing by O2, oxidation removing by air, or reduction removing by H2;
• wherein Ma metal is an active metal which is selected from one or more of noble metal and transition metal, wherein the noble metal is selected from one or more mixtures of Pt, Au, Ru, Rh, Pd, Ir and Ag, the transition metal is selected from La, Fe, Co, Mn, Cr, Ni or Cu;
• alternatively, the active metal is Pt, Ru, Pd, Ir, Cr, Ni, PtPd, IrPt, IrPd, or IrPtPd;
• Mb metal is selected from one or more combinations of Zn, Co and Al, alternatively Mb metal is Zn, Co or Zn—Co mixed metal;
• the support is selected from alumina, silica-alumina, zirconia, cerium oxide, titanium oxide, or molecular sieve or the mixture thereof;
• alternatively the support is γ-alumina, titanium oxide, silica or NaY molecular sieve;
• the Ma metal is loaded on the support in a state of single-atom sites, or in a state of coexistence of single-atom sites with clusters and/or nanoparticles;
• alternatively, the Ma metal is loaded on the support in the state of single-atom sites, or in the state of coexistence of single-atom sites and clusters, or in the state of coexistence of single-atom sites, clusters and nanoparticles;
• the content of Ma is 0.01-5 wt %, or 0.05-2 wt % based on catalyst weight;
• the content of Mb is 0.1-20 wt %, 0.1-10 wt %, or 0.5-4 wt % based on catalyst weight;
• the nitrogen-containing organic is selected from C1-6 alkyl amines, C2-6 alkenyl amine, C6-20 aryl amine, C4-20 cyclic alkyl amine, C4-20 nitrogen-containing heterocyclic ring, C4-20 nitrogen-containing heteroaromatic ring and (RCO)xNR3-x, wherein R is H or C1-6 alkyl, x is 1 or 2;
• the amine is a monamine or polyamine;
• optionally, the alkyl, alkenyl, aryl, nitrogen-containing heterocycle ring, and nitrogen-containing heteroaromatic ring are independently further substituted by oxygen, carbonyl, carboxyl, ester group, or amino group;
• the aryl is monocyclic aryl or fused polycyclic aryl;
• the nitrogen-containing heterocyclic ring is a monocyclic or fused non-aromatic ring containing cyclic nitrogen atom, and a cyclic carbon atom is optionally replaced by oxygen;
• the nitrogen-containing heteroaromatic ring is a monocyclic or fused polycyclic heteroaromatic ring containing cyclic nitrogen atom, and a cyclic carbon is optionally replaced by oxygen;
• alternatively, the nitrogen-containing organic is C1-6 alkyl amine, C1-6 alkyl diamine, C6-20 aryl amine, dimethyl formamide.

A regeneration method of Ma-Mb-Mc metal supported catalyst, comprising:

• step A, removing substances which cause the Ma-Mb-Mc metal supported catalyst to be poisoned or deactivated to regenerate the catalyst;
• step B, treating the catalyst with ammonia or nitrogen-containing organic in the range of room temperature to 700° C. to obtain an activated catalyst;
• wherein Ma is Ir, Mb is selected from Zn, Sn and the mixture of both, Mc is selected from K, Na or the mixture of both, the content of Ma is 0.1-2 wt % based on catalyst weight, the content of the Mb is 0.1-3.0 wt % based on catalyst weight, the content of the Mc is 0.1-2.0 wt % based on catalyst weight, a support of the Ma-Mb-Mc metal supported catalyst is alumina, or shaped alumina support;
• the Ma metal is dispersed and loaded on the support in a state of single-atom sites, clusters or nanoparticles;
• alternatively Ma metal is dispersed and loaded on the support in the state of single-atom sites, or in the state of coexistence of single-atom sites with clusters and/or nanoparticles;
• in the step A, the substances which cause the Ma-Mb-Mc metal supported catalyst poisoned or deactivated comprise coke and/or sulfur;
• the removing comprises:
• oxidation removing by O2, oxidation removing by air, or reduction removing by H2;
• in the step B, treating the catalyst by ammonia or nitrogen-containing organic, wherein the nitrogen-containing organic is optionally selected from ethylenediamine, triethylamine, butylamine, aniline and dimethyl formamide, the treatment temperature is optionally 300-700° C.