Zirconia-based porous body and method for producing same
This invention provides a zirconia-based porous body having a pore diameter suitable for supporting catalytic active species, such as precious metals, small variability in pore diameter, and a sufficient specific surface area even after 12-hour heating at 1000° C. Specifically, the invention provides a zirconia-based porous body in particle form having (1) a pore diameter peak at 20 to 100 nm in the pore distribution by BJH method, a P/W ratio of 0.05 or more wherein W represents half width of the peak and P represents height of the peak in the measured pore distribution curve, and a total pore volume of 0.5 cm 3 /g or more; and (2) a pore diameter peak at 20 to 100 nm, the P/W ratio of 0.03 or more, a specific surface area of at least 40 m 2 /g, and a total pore volume of 0.3 cm 3 /g or more, after heat treatment at 1000° C. for 12 hours.
1. A zirconia-based porous body in the form of particles,
(1) the zirconia-based porous body having a pore diameter peak at 20 to 100 nm in the pore diameter distribution by BJH method, a P/W ratio of 0.05 or more wherein W represents half width of the peak and P represents height of the peak in the measured pore distribution curve, and a total pore volume of 0.5 cm 3 /g or more; and
(2) the zirconia-based porous body having a pore diameter peak at 20 to 100 nm, the P/W ratio of 0.03 or more, a specific surface area of at least 40 m 2 /g, and a total pore volume of 0.3 cm 3 /g or more, after heat treatment at 1000° C. for 12 hours.
2. The zirconia-based porous body according to claim 1 , wherein the zirconia-based porous body has a specific surface area of at least 20 m 2 /g after heat treatment at 1100° C. for 12 hours.
3. The zirconia-based porous body according to claim 1 , wherein each of the particles is spherical or approximately spherical as identified in an SEM image, and has a circularity coefficient of 0.85 to 1.0.
4. A method for producing a zirconia-based porous body, the method sequentially comprising the following steps:
(1) separately heating a zirconium salt solution and a solution of sulfatizing agent to 95° C. or higher;
(2) contacting and mixing the zirconium salt solution after heating and the solution of sulfatizing agent after heating to obtain a basic zirconium sulfate-containing reaction liquid as a liquid mixture, wherein, from initiation to completion of the mixing, the weight ratio of SO 4 2− /ZrO 2 in the liquid mixture is maintained within a range of 0.3 to 0.8, and the temperature of the liquid mixture is maintained at 95° C. or higher;
(3) aging the basic zirconium sulfate-containing reaction liquid obtained by completing the mixing in step 2, the aging being performed at 95° C. or higher for 3 hours or more;
(4) adding an alkali to the basic zirconium sulfate-containing reaction liquid obtained after aging in step 3 to obtain a zirconium-containing hydroxide; and
(5) subjecting the zirconium-containing hydroxide obtained in step 4 to heat treatment to obtain a zirconia-based porous body,
wherein the zirconia-based porous body in the form of particles,
(i) the zirconia-based porous body having a pore diameter peak at 20 to 100 nm in the pore diameter distribution by BJH method, a P/W ratio of 0.05 or more wherein W represents half width of the peak and P represents height of the peak in the measured pore distribution curve, and a total pore volume of 0.5 cm 3 /g or more; and
(ii) the zirconia-based porous body having a pore diameter peak at 20 to 100 nm, the P/W ratio of 0.03 or more, a specific surface area of at least 40 m 2 /g, and a total pore volume of 0.3 cm 3 /g or more, after heat treatment at 1000° C. for 12 hours.
5. The zirconia-based porous body production method according to claim 4 , the method comprising adding a salt of at least one metal selected from the group consisting of rare earth elements, transition metal elements other than rare earth elements, alkali earth metal elements, Al, In, Si, Sn, and Bi, in any one of steps 1 to 4.
6. The zirconia-based porous body according to claim 2 , wherein each of the particles is spherical or approximately spherical as identified in an SEM image, and has a circularity coefficient of 0.85 to 1.0.
7. The method for producing a zirconia-based porous body according to claim 4 , wherein the zirconia-based porous body has a specific surface area of at least 20 m 2 /g after heat treatment at 1100° C. for 12 hours.
8. The method for producing a zirconia-based porous body according to claim 4 , wherein each of the particles is spherical or approximately spherical as identified in an SEM image, and has a circularity coefficient of 0.85 to 1.0.
9. The method for producing a zirconia-based porous body according to claim 4 , wherein the weight ratio of SO 4 2− /ZrO 2 in the liquid mixture is maintained at a specific value within a range of 0.3 to 0.8 in step (2).
10. The zirconia-based porous body according to claim 1 , further including at least one metal selected from the group consisting of rare earth elements, transition metal elements other than rare earth elements, alkali earth metal elements, Al, In, Si, Sn, and Bi.