Supported core-shell bimetallic catalyst with high selectivity for propane dehydrogenation
A supported core-shell bimetallic catalyst with high selectivity, and preparation method and an application thereof are provided. SBA-15 is used as support, platinum (Pt) is used as active component, 3d transition metal is used as cocatalysts. In the core-shell bimetallic catalyst formed by the 3d transition metal and Pt, in one aspect, by the addition of the 3d metal in the core, the d-band center of surface Pt atoms is down shifted, and the absorption of propylene is weakened, thereby improving the selectivity for propylene. In another aspect, the use of Pt is reduced by the addition of the 3d transition metal, improving the utilization of Pt. The catalyst is applicable in a hydrogen atmosphere, has a good effect on the preparation of propylene by propane dehydrogenation and causes high dehydrogenation activity under high temperature conditions. The total selectivity for propylene may reach 85%, which achieves high propylene selectivity.
1. A supported core-shell bimetallic catalyst having a high selectivity,
comprising: a metal Pt, a 3d metal, and a support, wherein the metal Pt and the 3d metal are loaded onto the support, wherein for a mass of the support of 100 wt %, a content of the metal Pt ranges from 0.5 wt % to 1 wt %, the mole ratio of the metal Pt to the 3d metal is (3-5):(1-1.5), a shell layer composed of the metal Pt is formed on a surface of the supported core-shell bimetallic catalyst, an inner core composed of the metal Pt and the 3d metal is formed in the supported core-shell bimetallic catalyst, and from the surface to the inner core, the content distribution of the metal Pt gradually decreases, and the content distribution of the 3d metal gradually increases; and the 3d metal is Fe, Co or Ni, wherein the support is commercial Santa Barbara Amorphous-15 (SBA-15).
2. The supported core-shell bimetallic catalyst having the high selectivity of claim 1 , wherein, the content of the metal Pt ranges from 0.75 wt % to 0.8 wt %, and the mole ratio of the metal Pt to the 3d metal is 3:(0.75-0.85).
3. A method for preparing a supported core-shell bimetallic catalyst having a high selectivity, comprising the following steps:
step 1, providing a support and an impregnation system, wherein the impregnation system comprises a solvent and metal precursors, wherein the solvent comprises deionization water and ethanol, and wherein the metal precursors provide a metal Pt and a 3d metal;
step 2, adding the support to the impregnation system and then stirring and impregnating until the solvent in the impregnation system evaporates to load the metal Pt and the 3d metal on the support in the impregnation system; wherein the 3d metal is Fe, Co or Ni; a volume ratio of deionization water to ethanol is (1-2):(1-3); in the aqueous of metal precursors, the mole ratio of the metal Pt to the 3d metal is (3-5):(1-1.5); for a mass of the support of 100 wt %, a content of the metal Pt ranges from 0.5 wt % to 1 wt %;
step 3, drying the support loaded with the metal Pt and the 3d metal, and then calcining in air to form metal oxides at 300-350° C. for 2-4 hours with a ramp rate of 2-5° C./min from the room temperature of 20-25° C.;
step 4: performing a high temperature reduction on the support in the step 2 in an atmosphere of hydrogen and argon at 400-450° C. for 4-6 hours with a ramp rate of 2-5° C./min from the room temperature of 20-25° C. to obtain a high temperature reduced catalyst; wherein in a mixed gas of the atmosphere of hydrogen and argon, the volume percentage of hydrogen is 5-10%; the metal Pt tends to enrich the surface of the support, and the 3d metal tends to enrich in the core of the support; from the surface to the core of the support, the metal Pt exhibits an opposite distribution trend to the 3d metal; wherein, the content distribution of the metal Pt gradually decreases, and the content distribution of the 3d metal gradually increases; and
step 5: performing an acid treatment on the high temperature reduced catalyst in the step 3 to remove the 3d metal at the surface of the support, thereby forming a shell layer composed of the metal Pt and the inner core composed of the metal Pt and the 3d metal,
wherein, in the step 1, the support is commercial Santa Barbara Amorphous-15 (SBA-15), and the stirring and impregnating are performed by a mechanical or ultrasonic agitator for 20-24 hours, with a speed of 200-300 revolutions per minute at 20-25° C.
4. The method for preparing the supported core-shell bimetallic catalyst having the high selectivity of claim 3 , wherein, in the step 1, the volume ratio of deionization water to ethanol is 1:1; in the aqueous of metal precursors, the mole ratio of the metal Pt to the 3d metal is 3:(1-1.5) or (3-5):1; for the mass of the support of 100 wt %, the content of platinum ranges from 0.75 wt % to 0.8 wt %.
5. The method for preparing the supported core-shell bimetallic catalyst having the high selectivity of claim 3 , wherein, in the step 4, an acid used in the acid treatment dissolves the 3d metal but does not react with the metal Pt.
6. The method for preparing the supported core-shell bimetallic catalyst having the high selectivity of claim 5 , wherein, in the step 4, the acid for the acid treatment is a dilute nitric acid solution with a concentration of 5×10 −4 mol/L.
7. The method for preparing the supported core-shell bimetallic catalyst having the high selectivity of claim 3 , wherein, in the step 4, the acid treatment is performed at 20-25° C. and lasts 1-20 minutes.
8. The method for preparing the supported core-shell bimetallic catalyst having the high selectivity of claim 7 , wherein, in the step 4, the acid treatment is performed at 20-25° C. for 10-20 minutes.
9. A method of propane dehydrogenation, comprising: mixing the supported core-shell bimetallic catalyst having the high selectivity of claim 1 with propane in the propane dehydrogenation to produce propylene.
10. The method of propane dehydrogenation of claim 9 , wherein, during use, the supported core-shell bimetallic catalyst is subjected to a pelleting treatment to obtain a granular catalyst having a 20-40 mesh size distribution for subsequent use.
11. The method of propane dehydrogenation of claim 9 , wherein, during use, the supported core-shell bimetallic catalyst is loaded into a reactor, a mixed gas of nitrogen and hydrogen is introduced, a temperature in the reactor is increased from room temperature of 20-25° C. to 600-620° C. with a ramp rate of 3-5° C./min, and a reduction is performed at 600-620° C.; after the reduction, the temperature in the reactor is controlled to be 550-650° C., propane is introduced into the reactor at a weight hourly space velocity of 3-10 h −1 for reaction, wherein the molar ratio of propane to hydrogen is 1:1, nitrogen is used as equilibrium gas, and a volume ratio of propane, hydrogen and nitrogen is 7:7:11.
12. The method of propane dehydrogenation of claim 11 , wherein, during use, the reduction lasts at least for 0.5 hour, and in the mixed gas of nitrogen and hydrogen, the hydrogen is 10-15% by volume.
13. The method of propane dehydrogenation of claim 11 , wherein, during use, the reduction lasts for 1-2 hours.