Selective surface impregnation method for catalytically active materials on particulate catalyst support using mutual repulsive force and soblubility difference between hydrophilic solvent and hydrophobic solvent
A method for preparing a catalyst having catalytically active materials selectively impregnated or supported only in the surface region of the catalyst particle using the mutual repulsive force of a hydrophobic solution and a hydrophilic solution and the solubility difference to a metal salt precursor between the hydrophobic and hydrophilic solutions. The hydrophobic solvent is a C2-C6 alcohol. The hydrophobic solvent is introduced into the catalyst support and then removed of a part of the pores connected to the outer part of the catalyst particle by drying under appropriate conditions. Then, a hydrophilic solution containing a metal salt is introduced to occupy the void spaces removed of the hydrophobic solvent, and the catalyst particle is dried at a low rate to selectively support or impregnate the catalytically active material or the precursor of the catalytically active material only in the outer part of the catalyst particle.
1. An impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and a solubility difference between a hydrophilic solvent and a hydrophobic solvent, the method consisting of:
a catalyst support preparation step T 100 of preparing a spherical or cylindrical porous inorganic oxide as a catalyst support;
a first immersion step T 200 of filling inner pores and surface pores of the catalyst support with a hydrophobic solvent;
a second immersion step T 300 of dissolving catalytically active material or a precursor of the catalytically active material in a hydrophilic solvent to prepare a hydrophilic solution and then immersing the catalyst support obtained from the first immersion step in the hydrophilic solution to diffuse the hydrophilic solution from an outer surface of the catalyst support to an inner part of the catalyst support;
a drying step T 400 of drying the catalyst support obtained from the second immersion step to position the catalytically active material or the precursor of the catalytically active material only in a surface region of the catalyst support or in an outer region of the inner pores; and
a supporting or impregnation step T 500 of performing a calcination or reduction process to form the catalytically active material or the precursor of the catalytically active material selectively only in the surface region of the catalyst support and an outer region of the catalyst support, wherein the outer region of the catalyst support is an inner pore region under the surface region of the catalyst support,
wherein the first immersion step includes immersing the catalyst support in the hydrophobic solvent to fill the surface pores and the inner pores of the catalyst support with the hydrophobic solvent,
wherein the drying step includes eliminating both the hydrophobic solvent and the hydrophilic solution filled in the surface pores and the inner pores of the catalyst support to position the catalytically active material or the precursor of the catalytically active material in the inner pores placed at an outer part of the catalyst support which is in a range of one fifth to one half of a distance from a surface of the catalyst support to a center of the catalyst support, and
wherein the hydrophobic solvent is at least one selected from the group consisting of ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, diethylene glycol, and glycerol.
2. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the porous inorganic oxide is at least one selected from the group consisting of silica, alumina, titania, zirconia, and cerin.
3. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the second immersion step includes filling the hydrophilic solution containing the catalytically active material or the precursor of the catalytically active material in the surface region of the catalyst support and the inner pore region placed at the outer part of the catalyst support which is in the range of one fifth to one half of the distance from the surface of the catalyst support to the center of the catalyst support.
4. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the catalytically active material or the precursor of the catalytically active material is a metal salt of any one metal selected from platinum, ruthenium, rhodium, cobalt, nickel, or palladium, or a precursor of the metal salt.
5. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the first immersion, step includes performing sonication to easily fill the inner pores of the catalyst support particle with the hydrophobic solvent.
6. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the immersion time of the second immersion step is in the range of 1 to 60 minutes.
7. The impregnation method for catalytically active materials on a particulate catalyst support using a mutual repulsive force and the solubility difference between a hydrophilic solvent and a hydrophobic solvent as claimed in claim 1 , wherein the concentration of the aqueous solution containing the catalytically active material or the precursor of the catalytically active material in the second immersion step is 0.5 to 5 M.