Catalyst for producing light aromatics with heavy aromatics, method for preparing the catalyst, and use thereof

Abstract

A catalyst for producing light aromatics with heavy aromatics, a method for preparing the catalyst, and a use thereof are disclosed. The catalyst comprises a carrier, component (1), and component (2), wherein component (1) comprises one metal element or more metal elements selected from a group consisting of Pt, Pd, Ir, and Rh, and component (2) comprises one metal element or more metal elements selected from a group consisting of IA group, IIA group, IIIA group, IVA group, IB group, IIB group, IIIB group, IVB group, VB group, VIB group, VIIB group, La group, and VIII group other than Pt, Pd, Ir, and Rh. The catalyst can be used for producing light aromatics with heavy aromatics, whereby heavy aromatics hydrogenation selectivity and light aromatics yield can be improved.

Claims

1. A catalyst, comprising a carrier, component I, and component II, wherein component I comprises Pt and Pd, Pt and Ir, Pd and Ir, or a combination of Pt, Pd, and Ir, and component II comprises a combination of W and Mo, a combination of Cu and Zn, a combination of Ag and Zn, a combination of Fe and Ni, a combination of Mg and Sr, a combination of La and Ce, a combination of Ga and Sn, a combination of Zr and Nb, or a combination of Y and Sc, and wherein the catalyst has a hydrogen desorption temperature higher than 350° C.

2. The catalyst according to claim 1, wherein component I comprises Pt and Pd.

3. The catalyst according to claim 2, wherein a weight ratio of Pt to Pd is in the range of 0.1:1 to 5:1.

4. The catalyst according to claim 1, wherein: in the combination of W and Mo, a weight ratio of W to Mo is in a range of 0.1:1 to 10:1, in the combination of Cu and Zn, a weight ratio of Cu to Zn is in a range of 0.1:1 to 10:1, in the combination of Ag and Zn, a weight ratio of Ag to Zn is in a range of 0.1:1 to 10:1, in the combination of Fe and Ni, a weight ratio of Fe to Ni is in a range of 0.1:1 to 10:1, in the combination of Mg and Sr, a weight ratio of Mg to Sr is in a range of 0.1:1 to 10:1, in the combination of La and Ce, a weight ratio of La to Ce is in a range of 0.1:1 to 10:1, in the combination of Ga and Sn, a weight ratio of Ga to Sn is in a range of 0.1:1 to 10:1, in the combination of Zr and Nb, a weight ratio of Zr to Nb is in a range of 0.1:1 to 10:1, and in the combination of Y and Sc, a weight ratio of Y to Sc is in a range of 0.1:1 to 10:1.

5. The catalyst according to claim 1, wherein component I accounts for 0.02-3.0 wt % of the catalyst, and component II accounts for 0.01-15 wt % of the catalyst.

6. The catalyst according to claim 1, wherein a weight ratio of component I to component II is in the range of 0.1:1 to 10:1.

7. The catalyst according to claim 1, wherein the carrier is a non-acidic or weakly acidic porous carrier.

8. The catalyst according to claim 7, wherein the carrier is an L acid additive modified carrier.

9. The catalyst according to claim 8, wherein the L acid additive comprises a chloride-containing compound and a fluorine-containing compound.

10. The catalyst according to claim 9, wherein the chloride-containing compound comprises at least one selected from a group consisting of AlCl.sub.3, CuCl.sub.2, FeCl.sub.3, SnCl.sub.4, TiCl.sub.4, and SbCl.sub.5, and the fluorine-containing compound comprises at least one selected from a group consisting of BF.sub.3, NbF.sub.5, SbF.sub.5, TaF.sub.5, and AsF.sub.5.

11. The catalyst according to claim 10, wherein the L acid additive comprises AlCl.sub.3 and NbF.sub.5.

12. The catalyst according to claim 9, wherein a weight ratio of the chloride-containing compound to the fluorine-containing compound is in the range of 0.1:1 to 10:1.

13. The catalyst according to claim 8, wherein the L acid additive accounts for 0.01-20 wt % of the catalyst.

14. The catalyst according to claim 8, wherein the L acid additive comprises at a chloride-containing compound, a fluorine-containing compound, or both.

15. The catalyst according to claim 7, wherein the carrier comprises at least one member selected from a group consisting of alumina, amorphous silica-alumina, kaolin, and aluminosilicate.

16. The catalyst according to claim 1, wherein the catalyst has a hydrogen desorption temperature higher than 380° C.

17. A method for preparing the catalyst according to claim 1, comprising: step A), loading a salt containing component II into a carrier, and performing drying and calcination to obtain a catalyst precursor; and step B), loading a salt containing component I into the catalyst precursor prepared in step A), and performing drying and calcination of the catalyst precursor loaded with the salt containing component I.

18. The method according to claim 17, wherein in step A) and step B), the calcination is performed at a temperature ranging from 400° C. to 600° C.

19. The method according to claim 17, wherein in step A), the salt containing component II is dissolved in water or an organic solvent, and is loaded into the carrier by precipitation, physical bonding, or dipping; and in step B), the salt containing component I is dissolved in water or an organic solvent, and is loaded into the catalyst precursor by precipitation, physical bonding, or dipping.

20. The catalyst according to claim 19, wherein the organic solvent used in step A) or step B) is independently selected from the group consisting of alcohols, ketones and hydrocarbons.

21. The catalyst according to claim 19, wherein the organic solvent used in step A) or step B) is independently selected from the group consisting of ethanol, acetone, cyclohexane, n-heptane, and toluene.

22. A method for producing light aromatics with heavy aromatics, comprising subjecting a raw material containing heavy aromatics to hydrogenation reaction in the presence of the catalyst according to claim 1.

23. The method according to claim 22, wherein a reaction temperature is in the range of 100° C. to 500° C., a reaction pressure is in the range of 0.5 MPa to 8.0 MPa, a molar ratio of hydrogen to heavy aromatics is in the range of 1 to 10; and a feed weight airspeed is in the range of 0.5.sup.−1 to 20.sup.−1.

24. The method according to claim 22, wherein the heavy aromatics are polycyclic aromatics comprising at least one compound selected from a group consisting of naphthalene, anthracene, phenanthrene, and homologues thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows H.sub.2-TPD diagram of the catalyst Pt/Al.sub.2O.sub.3 prepared in Comparative Example 1A, the catalyst Pt@2Mo/Al.sub.2O.sub.3 prepared in Example 1A, and the catalyst Pt@5Mo/Al2O3 prepared in Example 2A. As shown in FIG. 1, with the introduction of Mo, a hydrogen desorption temperature increases, and a hydrogen desorption peak area decreases, which shows that Mo can improve hydrogen adsorption strength of Pt and reduce hydrogen adsorption amount. In this manner, monocyclic aromatics hydrogenation activity can be reduced, and polycyclic aromatics hydrogenation selectivity can be improved.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The present disclosure will be illustrated in detail hereinafter with reference to specific examples, but the present disclosure is not limited to the following examples.

(3) A hydrogen desorption temperature was measured under the following condition. A catalyst was pre-reduced at 450° C. and under normal pressure hydrogen, and then cooled to 50° C. Next, the pre-reduced catalyst was performed hydrogen absorbing under normal pressure to equilibrium. Helium (He) was fed thereinto as purge gas under normal pressure, and a temperature thereof was raised to 600° C. (with a temperature rising rate of 8° C./min). The purge gas was detected by a thermal conductivity detector, and a temperature corresponding to a highest value of a thermal conductivity signal was the hydrogen desorption temperature.

Example 1A

(4) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution of a volume equal to the pore volume of the carrier (i.e. equivalent-volume impregnation), then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Mo content of 2% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.2% (wt).

Example 2A

(5) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Mo content of 5% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.2% (wt).

Example 3A

(6) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Mo content of 2% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.5% (wt).

Example 4A

(7) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Mo content of 2% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.2% (wt).

Example 5A

(8) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Mo content of 2% (wt). The catalyst A5 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.2% (wt).

Example 6A

(9) Alumina ball carrier (20 g) was impregnated with ammonium tungstate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with W content of 2% (wt). The catalyst A6 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.2% (wt).

Example 7A

(10) Alumina ball carrier (20 g) was impregnated with manganese dichloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Mn content of 2% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.2% (wt).

Example 8A

(11) Alumina ball carrier (20 g) was impregnated with perrhenic acid solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Re content of 2% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.2% (wt).

Example 9A

(12) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 10A

(13) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution and manganese chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Mo content of 1% (wt) and Mn content of 1% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 11A

(14) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution and perrhenic acid solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with Mo content of 1% (wt) and Re content of 1% (wt). The catalyst A11 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 12A

(15) Alumina ball carrier (20 g) was impregnated with ammonium tungstate solution and perrhenic acid solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with W content of 1% (wt) and Re content of 1% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 13A

(16) Alumina ball carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with W content of 1% (wt) and Mo content of 1% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.1% (wt) and Ir content of 0.1% (wt).

Example 14A

(17) Amorphous silica-alumina ball carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with W content of 1% (wt) and Mo content of 1% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 15A

(18) Shaped carrier of high silicon Y molecular sieve and alumina (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with W content of 1% (wt) and Mo content of 1% (wt). The catalyst A15 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 16A

(19) Alumina shaped carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Mo content of 0.5% (wt) and W content of 1.5% (wt). The catalyst A16 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 17A

(20) Alumina shaped carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A17 with Mo content of 1.5% (wt) and W content of 0.5% (wt). The catalyst A17 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 18A

(21) Alumina shaped carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A18 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pt content of 0.03% (wt) and Pd content of 0.17% (wt).

Example 19A

(22) Alumina shaped carrier (20 g) was impregnated with ammonium tungstate solution and ammonium molybdate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A19 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A19 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pt content of 0.17% (wt) and Pd content of 0.03% (wt).

Example 20A

(23) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution, palladium chloride solution, ammonium molybdate solution, and ammonium tungstate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B20 with Pt content of 0.1% (wt), Pd content of 0.1% (wt), Mo content of 1% (wt), and W content of 1% (wt).

Example 21A

(24) Alumina ball carrier (20 g) was impregnated with a certain amount of AlCl.sub.3 solution and was calcinated for 3 hours at 500° C. to obtain modified alumina I with AlCl.sub.3 content of 5% (wt). The modified alumina I was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the modified alumina I, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A21 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A21 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B21 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 22A

(25) Alumina ball carrier (20 g) was loaded with a certain amount of NbF.sub.5 solution and was calcinated for 3 hours at 500° C. to obtain modified alumina II with NbF.sub.5 content of 5% (wt). The modified alumina II was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the modified alumina II, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A22 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A22 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B22 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 23A

(26) Alumina ball carrier (20 g) was impregnated with a certain amount of AlCl.sub.3 solution and NbF.sub.5 solution and was calcinated for 3 hours at 500° C. to obtain modified alumina III with AlCl.sub.3 content of 2% (wt) and NbF.sub.5 content of 3% (wt). The modified alumina III was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the modified alumina III, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A23 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A23 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B23 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 24A

(27) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A24 with Mo content of 1% (wt) and W content of 1% (wt). The catalyst A24 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B24 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt). The catalyst B24 was impregnated with a certain amount of AlCl.sub.3 solution and NbF.sub.5 solution and was calcinated for 3 hours at 500° C. to obtain catalyst B24a with AlCl.sub.3 content of 2% (wt) and NbF.sub.5 content of 3% (wt).

Example 25A

(28) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 500° C. to obtain catalyst A25 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt). The catalyst A25 was impregnated with ammonium molybdate solution and ammonium tungstate solution to obtain catalyst B25 with Mo content of 1% (wt) and W content of 1% (wt).

Comparative Example 1A

(29) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B26 with Pt content of 0.2% (wt).

Comparative Example 2A

(30) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B27 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Comparative Example 3A

(31) Alumina ball carrier (20 g) was impregnated with ammonium molybdate solution and ammonium tungstate solution of a volume equal to the pore volume of the carrier to obtain catalyst B28 with Mo content of 1% (wt) and W content of 1% (wt).

(32) The catalysts prepared in Examples 1A to 25A and Comparative Examples 1A to 3A are evaluated by the following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=95:5 (wt). The reaction performances are shown in Table 1, wherein R2/R1 represents a ratio of naphthalene hydrogenation ratio to toluene hydrogenation ratio, and reflects hydrogenation selectivity of each catalyst for polycyclic aromatics.

(33) TABLE-US-00001 TABLE 1 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1A Mo/2.0 Pt/0.2 375 1.9 53.7 28.3  2A Mo/5.0 Pt/0.2 390 1.2 49.9 41.6  3A Mo/2.0 Pt/0.5 361 3.9 59.9 15.4  4A Mo/2.0 Pd/0.2 382 1.1 51.8 47.1  5A Mo/2.0 Ir/0.2 380 1.1 48.5 44.1  6A W/2.0 Pt/0.2 371 2.5 55.7 22.3  7A Mn/2.0 Pt/0.2 373 2.0 53.9 27.0  8A Re/2.0 Pt/0.2 361 2.9 54.1 18.7  9A Mo/1.0- Pt/0.1- 405 1.1 62.1 56.5 W/1.0 Pd/0.1 10A Mo/1.0- Pt/0.1- 377 1.5 57.8 38.5 Mn/1.0 Pd/0.1 11A Mo/1.0- Pt/0.1- 375 1.9 59.2 31.2 Re/1.0 Pd/0.1 12A W/1-Re/1.0 Pt/0.1- 369 2.1 61.8 29.4 Pd/0.1 13A Mo/1.0- Pt/0.1-Ir/0.1 383 1.2 55.9 46.6 W/1.0 14A Mo/1.0- Pt/0.1- 381 1.5 61.8 41.2 W/1.0 Pd/0.1 15A Mo/1.0- Pt/0.1- 378 2.8 63.1 22.5 W/1.0 Pd/0.1 16A Mo/0.5- Pt/0.1- 395 1.2 62.9 52.4 W/1.5 Pd/0.1 17A Mo/1.5- Pt/0.1- 403 1.0 58.3 58.3 W/0.5 Pd/0.1 18A Mo/1.0- Pt/0.03- 401 0.9 52.2 58.0 W/1.0 Pd/0.17 19A Mo/1.0- Pt/0.17- 377 2.1 63.2 30.1 W/1.0 Pd/0.03 20A Mo/1.0- Pt/0.1- 385 1.5 60.9 40.6 W/1.0 Pd/0.1 21A Mo/1.0- Pt/0.1- 391 1.2 66.3 55.3 W/1.0 Pd/0.1 22A Mo/1.0- Pt/0.1- 389 1.2 65.7 54.8 W/1.0 Pd/0.1 23A Mo/1.0- Pt/0.1- 398 1.1 68.9 62.6 W/1.0 Pd/0.1 24A Mo/1.0- Pt/0.1- 401 1.1 64.0 58.2 W/1.0 Pd/0.1 25A Mo/1.0- Pt/0.1- 365 3.5 55.0 15.7 W/1.0 Pd/0.1 Comparative / Pt/0.2 350 33.6 59.3 1.8 Example 1A Comparative Pt/0.1- 360 7.3 58.9 8.1 Example 2A Pd/0.1 Comparative Mo/1.0- 330 0.8 8.9 11.1 Example 3A W/1.0

Example 1B

(34) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Zn content of 5% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.3% (wt).

Example 2B

(35) Alumina ball carrier (20 g) was impregnated with copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Cu content of 5% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.3% (wt).

Example 3B

(36) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Zn content of 2% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.3% (wt).

Example 4B

(37) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Zn content of 5% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.3% (wt).

Example 5B

(38) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Zn content of 5% (wt). The catalyst A5 was impregnated with chloroiridic acid aqueous solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.3% (wt).

Example 6B

(39) Alumina ball carrier (20 g) was impregnated with silver nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with Ag content of 5% (wt). The catalyst A6 was impregnated with chloroplatinic acid ethanol solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.3% (wt).

Example 7B

(40) Alumina ball carrier (20 g) was impregnated with cadmium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Cd content of 5% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.3% (wt).

Example 8B

(41) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.3% (wt).

Example 9B

(42) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 10B

(43) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.1% (wt) and Ir content of 0.2% (wt).

Example 11B

(44) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A11 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 12B

(45) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.2% (wt) and Pd content of 0.1% (wt).

Example 13B

(46) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and silver nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with Zn content of 2% (wt) and Ag content of 3% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 14B

(47) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and cadmium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Zn content of 2% (wt) and Cd content of 3% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 15B

(48) Alumina ball carrier (20 g) was impregnated with copper nitrate solution and cadmium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Cu content of 2% (wt) and Cd content of 3% (wt). The catalyst A15 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 16B

(49) Alumina ball carrier (20 g) was impregnated with copper nitrate solution and silver nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Cu content of 2% (wt) and Ag content of 3% (wt). The catalyst A16 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 17B

(50) Amorphous silica-alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A17 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A17 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 18B

(51) Carrier made of dealuminized mordenite (Si/A1=100) and alumina (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Zn content of 2% (wt) and Cu content of 3% (wt). The catalyst A18 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Comparative Example 1B

(52) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pt content of 0.3% (wt).

Comparative Example 2B

(53) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B20 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Comparative Example 3B

(54) Alumina ball carrier (20 g) was impregnated with zinc nitrate solution and copper nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B21 with Zn content of 2% (wt) and Cu content of 3% (wt).

(55) The catalysts prepared in Examples 1B to 18B and Comparative Examples 1B to 3B are evaluated by the following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt). The reaction performances are shown in Table 2.

(56) TABLE-US-00002 TABLE 2 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1B Zn/5.0 Pt/0.3 370 2.5 55.7 22.3  2B Cu/5.0 Pt/0.3 375 1.8 53.6 29.8  3B Zn/2.0 Pt/0.3 366 3.9 58.9 15.1  4B Zn/5.0 Pd/0.3 376 1.7 51.7 30.4  5B Zn/5.0 Ir/0.3 375 1.6 50.4 31.5  6B Ag/5.0 Pt/0.3 368 2.1 53.9 25.7  7B Cd/5.0 Pt/0.3 374 1.5 46.1 30.7  8B Zn/2.0- Pt/0.3 376 1.6 57.5 35.9 Cu/3.0  9B Zn/2.0- Pt/0.1-Pd/0.2 375 1.6 66.3 41.4 Cu/3.0 10B Zn/2.0- Pt/0.1-Ir/0.2 373 1.5 59.3 39.5 Cu/3.0 11B Zn/2.0- Pt/0.05- 381 1.2 65.7 54.8 Cu/3.0 Pd/0.25 12B Zn/2.0- Pt/0.2-Pd/0.1 377 1.6 63.3 39.6 Cu/3.0 13B Zn/2.0- Pt/0.05- 388 1.2 62.5 52.1 Ag/3.0 Pd/0.25 14B Zn/2.0- Pt/0.05- 381 1.3 61.9 47.6 Cd/3.0 Pd/0.25 15B Cu/2.0- Pt/0.05- 376 1.5 64.8 43.2 Cd/3.0 Pd/0.25 16B Cu/2.0- Pt/0.05- 376 1.4 60.6 43.3 Ag/3.0 Pd/0.25 17B Zn/2.0- Pt/0.05- 379 1.3 66.1 50.8 Cu/3.0 Pd/0.25 18B Zn/2.0- Pt/0.05- 371 1.9 66.8 35.2 Cu/3.0 Pd/0.25 Comparative / Pt/0.3 350 38.6 53.3 1.4 Example 1B Comparative / Pt/0.05- 358 10.3 56.8 5.5 Example 2B Pd/0.25 Comparative Zn/2.0- / 316 0.7 5.2 7.4 Example 3B Cu/3.0

Example 1C

(57) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Ni content of 2% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.2% (wt).

Example 2C

(58) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Ni content of 5% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.2% (wt).

Example 3C

(59) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Ni content of 2% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.5% (wt).

Example 4C

(60) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Ni content of 2% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.2% (wt).

Example 5C

(61) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Ni content of 2% (wt). The catalyst A5 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.2% (wt).

Example 6C

(62) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with Ni content of 2% (wt). The catalyst A6 was impregnated with rhodium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Rh content of 0.2% (wt).

Example 7C

(63) Alumina ball carrier (20 g) was impregnated with ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Fe content of 2% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.2% (wt).

Example 8C

(64) Alumina ball carrier (20 g) was impregnated with cobalt nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Co content of 2% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.2% (wt).

Example 9C

(65) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Example 10C

(66) Beta molecular sieve (20 g) was impregnated with ferric nitrate solution and cobalt nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Fe content of 1% (wt) and Co content of 1% (wt). The catalyst A1.0 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Example 11C

(67) Beta molecular sieve (20 g) was impregnated with nickel nitrate solution and cobalt nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with Ni content of 1% (wt) and Co content of 1% (wt). The catalyst A11 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Example 12C

(68) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.05% (wt) and Ir content of 0.15% (wt).

Example 13C

(69) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.05% (wt) and Rh content of 0.15% (wt).

Example 14C

(70) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A14 was impregnated with palladium chloride solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pd content of 0.05% (wt) and Ir content of 0.15% (wt).

Example 15C

(71) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A1.5 was impregnated with rhodium chloride solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Rh content of 0.05% (wt) and Ir content of 0.15% (wt).

Example 16C

(72) Amorphous silica-alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A16 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Example 17C

(73) Shaped carrier of Beta molecular sieve and alumina (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A17 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A1.7 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Example 18C

(74) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Ni content of 1% (wt) and Fe content of 1% (wt). The catalyst A1.8 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pt content of 0.03% (wt) and Pd content of 0.17% (wt).

Comparative Example 1C

(75) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pt content of 0.2% (wt).

Comparative Example 2C

(76) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B20 with Pt content of 0.05% (wt) and Pd content of 0.15% (wt).

Comparative Example 3C

(77) Alumina ball carrier (20 g) was impregnated with nickel nitrate solution and ferric nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B21 with Ni content of 1% (wt) and Fe content of 1% (wt).

(78) The catalysts prepared in Examples 1C to 18C and Comparative Examples 1C to 3C are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt). The reaction performances are shown in Table 3, wherein R2/R1 represents a ratio of naphthalene hydrogenation ratio to toluene hydrogenation ratio, and reflects hydrogenation selectivity of each catalyst for polycyclic aromatics.

(79) TABLE-US-00003 TABLE 3 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1C Ni/2.0 Pt/0.2 369 2.6 52.7 20.3  2C Ni/5.0 Pt/0.2 387 1.1 49.9 45.4  3C Ni/2.0 Pt/0.5 361 3.8 60.9 16.0  4C Ni/2.0 Pd/0.2 382 1.2 50.8 42.3  5C Ni/2.0 Ir/0.2 385 1.1 50.5 45.9  6C Ni/2.0 Rh/0.2 378 1.4 53.5 38.2  7C Fe/2.0 Pt/0.2 375 1.5 53.9 35.9  8C Co/2.0 Pt/0.2 373 1.4 54.1 38.6  9C Fe/1.0-Ni/1.0 Pt/0.05- 386 1.2 65.1 54.2 Pd/0.15 10C Fe/1.0-Co/1.0 Pt/0.05- 382 1.3 56.9 43.8 Pd/0.15 11C Ni/1.0-Co/1.0 Pt/0.05- 381 1.3 55.8 42.9 Pd/0.15 12C Fe/1.0-Ni/1.0 Pt/0.05- 385 1.1 55.2 50.2 Ir/0.15 13C Fe/1.0-Ni/1.0 Pt/0.05- 382 1.2 56.1 46.8 Rh/0.15 14C Fe/1-Ni/1.0 Pd/0.05- 380 1.3 54.9 42.2 Ir/0.15 15C Fe/1-Ni/1.0 Rh/0.05- 383 1.2 56.8 47.3 Ir/0.15 16C Fe/1.0-Ni/1.0 Pt/0.05- 381 1.3 63.9 49.1 Pd/0.15 17C Fe/1.0-Ni/1.0 Pt/0.05- 376 1.6 64.5 40.3 Pd/0.15 18C Fe/1.0-Ni/1.0 Pt/0.03- 382 1.1 58.6 53.2 Pd/0.17 Comparative / Pt/0.2 350 30.6 57.3 1.9 Example 1C Comparative Pt/0.05- 362 9.1 51.8 5.7 Example 2C Pd/0.15 Comparative Fe/1.0-Ni/1.0 293 0.8 4.7 5.9 Example 3C

Example 1D

(80) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Mg content of 3% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.15% (wt).

Example 2D

(81) Alumina ball carrier (20 g) was impregnated with magnesium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Mg content of 5% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.15% (wt).

Example 3D

(82) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Mg content of 3% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.3% (wt).

Example 4D

(83) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Mg content of 3% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.15% (wt).

Example 5D

(84) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Mg content of 3% (wt). The catalyst A5 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.15% (wt).

Example 6D

(85) Alumina ball carrier (20 g) was impregnated with strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with Sr content of 3% (wt). The catalyst A6 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.15% (wt).

Example 7D

(86) Alumina ball carrier (20 g) was impregnated with calcium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Ca content of 3% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.15% (wt).

Example 8D

(87) Alumina ball carrier (20 g) was impregnated with potassium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with K content of 3% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.15% (wt).

Example 9D

(88) Alumina ball carrier (20 g) was impregnated with lithium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Li content of 3% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.15% (wt).

Example 10D

(89) Alumina ball carrier (20 g) was impregnated with potassium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with K content of 1% (wt) and Sr content of 2% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Example 11D

(90) Alumina ball carrier (20 g) was impregnated with potassium chloride solution and lithium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with K content of 1% (wt) and Li content of 2% (wt). The catalyst A11 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Example 12D

(91) Alumina ball carrier (20 g) was impregnated with potassium chloride solution and magnesium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with K content of 1% (wt) and Mg content of 2% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Example 13D

(92) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.05% (wt) and Pd content of 0.1% (wt).

Example 14D

(93) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Example 15D

(94) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A15 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.03% (wt) and Ir content of 0.12% (wt).

Example 16D

(95) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A16 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.1% (wt) and Ir content of 0.05% (wt).

Example 17D

(96) Amorphous silica-alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A17 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Example 18D

(97) Shaped carrier of dealuminized mordenite and alumina (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Mg content of 1% (wt) and Sr content of 2% (wt). The catalyst A18 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pt content of 0.05% (wt) and Ir content of 0.1% (wt).

Comparative Example 1D

(98) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pt content of 0.15% (wt).

Comparative Example 2D

(99) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B20 with Pt content of 0.03% (wt) and Ir content of 0.12% (wt).

Comparative Example 3D

(100) Alumina ball carrier (20 g) was impregnated with magnesium chloride solution and strontium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B21 with Mg content of 1% (wt) and Sr content of 2% (wt).

(101) The catalysts prepared in Examples 1D to 18D and Comparative Examples 1D to 3D are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt).

(102) The reaction performances are shown in Table 4.

(103) TABLE-US-00004 TABLE 4 Hydrogen Toluene Component Component desorption hydrogenation Naphthalene (2)/content (1)/content temperature ratio (R1) hydrogenation Examples (wt %) (wt %) (° C.) wt % ratio (R2) wt % R2/R1  1D Mg/3.0 Pt/0.15 369 2.1 56.7 27.0  2D Mg/5.0 Pt/0.15 370 1.6 53.3 33.3  3D Mg/3.0 Pt/0.3 362 2.5 61.8 24.7  4D Mg/3.0 Pd/0.15 371 1.5 52.4 34.9  5D Mg/3.0 Ir/0.15 372 1.3 54.7 42.1  6D Sr/3.0 Pt/0.15 374 1.4 62.9 44.9  7D Ca/3.0 Pt/0.15 368 2.1 57.9 27.6  8D K/3.0 Pt/0.15 364 2.3 60.8 26.4  9D Li/3.0 Pt/0.15 365 2.2 61.6 28.0 10D K/1.0-Sr/2.0 Pt/0.05-Ir/0.1 372 1.7 61.8 36.4 11D K/1.0-Li/2.0 Pt/0.05-Ir/0.1 364 2.1 62.7 29.9 12D K/1.0-Mg/2.0 Pt/0.05-Ir/0.1 361 2.4 62.2 25.9 13D Mg/1.0-Sr/2.0 Pt/0.05-Pd/0.1 375 1.4 64.5 46.1 14D Mg/1.0-Sr/2.0 Pt/0.05-Ir/0.1 379 1.2 64.7 53.9 15D Mg/1.0-Sr/2.0 Pt/0.03-Ir/0.12 381 1.1 60.3 54.8 16D Mg/1.0-Sr/2.0 Pt/0.1-Ir/0.05 376 1.5 65.1 43.4 17D Mg/1.0-Sr/2.0 Pt/0.05-Ir/0.1 378 1.3 64.3 49.5 18D Mg/1.0-Sr/2.0 Pt/0.05-Ir/0.1 377 1.5 65.3 43.5 Comparative / Pt/0.15 351 21.1 54.3 2.6 Example 1D Comparative / Pt/0.03-Ir/0.12 366 2.9 54.8 18.9 Example 2D Comparative Mg/1.0-Sr/2.0 325 0.5 3.8 7.6 Example 3D

Example 1E

(104) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with La content of 2% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.2% (wt).

Example 2E

(105) Alumina ball carrier (20 g) was impregnated with cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Ce content of 2% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.2% (wt).

Example 3E

(106) Alumina ball carrier (20 g) was impregnated with praseodymium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Pr content of 2% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.2% (wt).

Example 4E

(107) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with La content of 2% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.2% (wt).

Example 5E

(108) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with La content of 2% (wt). The catalyst A5 was impregnated with chloroiridic acid aqueous solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.2% (wt).

Example 6E

(109) Pseudo Boehmite (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution, filtered, washed, and dried for 4 hours at 120° C. to obtain modified Pseudo Boehmite with La content of 1% (wt) and Ce content of 1% (wt). The modified Pseudo Boehmite was shaped and calcinated for 4 hours at 550° C. to obtain catalyst A6. The catalyst A6 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.2% (wt).

Example 7E

(110) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and praseodymium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with La content of 1% (wt) and Pr content of 1% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.2% (wt).

Example 8E

(111) Alumina ball carrier (20 g) was impregnated with cerium nitrate solution and praseodymium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Ce content of 1% (wt) and Pr content of 1% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.2% (wt).

Example 9E

(112) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 10E

(113) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.1% (wt) and Ir content of 0.1% (wt).

Example 11E

(114) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A11 was impregnated with iridium trichloride solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Ir content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 12E

(115) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.05% (wt) and Ir content of 0.15% (wt).

Example 13E

(116) Amorphous silica-alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.05% (wt) and Ir content of 0.15% (wt).

Example 14E

(117) Shaped carrier of dealuminized Beta zeolite (Si/A1=80) and alumina (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with La content of 1% (wt) and Ce content of 1% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.05% (wt) and Ir content of 0.15% (wt).

Comparative Example 1E

(118) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.2% (wt).

Comparative Example 2E

(119) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.05% (wt) and Ir content of 0.15% (wt).

Comparative Example 3E

(120) Alumina ball carrier (20 g) was impregnated with lanthanum nitrate solution and cerium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B17 with La content of 1% (wt) and Ce content of 1% (wt).

(121) The catalysts prepared in Examples 1E to 14E and Comparative Examples 1E to 3E are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt). The reaction performances are shown in Table 5.

(122) TABLE-US-00005 TABLE 5 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1E La/2.0 Pt/0.2 361 2.4 55.2 23.0  2E Ce/2.0 Pt/0.2 363 2.0 55.1 27.6  3E Pr/2.0 Pt/0.2 365 2.1 54.9 26.1  4E La/2.0 Pd/0.2 373 1.3 50.2 38.6  5E La/2.0 Ir/0.2 374 1.2 52.6 43.8  6E La/1.0- Pt/0.2 375 1.7 57.9 34.1 Ce/1.0  7E La/1.0- Pt/0.2 373 1.9 56.1 29.5 Pr/1.0  8E Ce/1.0- Pt/0.2 376 1.7 60.3 35.5 Pr/1.0  9E La/1.0- Pt/0.1-Pd/0.1 378 1.5 61.7 41.1 Ce/1.0 10E La/1.0- Pt/0.1-Ir/0.1 380 1.4 62.8 44.9 Ce/1.0 11E La/1.0- Pd/0.1-Ir/0.1 379 1.4 61.9 44.2 Ce/1.0 12E La/1.0- Pt/0.05- 383 1.2 62.6 52.2 Ce/1.0 Ir/0.15 13E La/1.0- Pt/0.05- 380 1.4 61.3 43.8 Ce/1.0 Ir/0.15 14E La/1.0- Pt/0.05- 377 1.7 62.3 36.6 Ce/1.0 Ir/0.15 Comparative / Pt/0.2 350 30.6 57.3 1.9 Example 1E Comparative / Pt/0.05- 359 10.4 56.9 5.5 Example 2E Ir/0.15 Comparative La/1.0- 318 0.4 2.5 6.3 Example 3E Ce/1.0

Example 1F

(123) Alumina ball carrier (20 g) was impregnated with gallium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Ga content of 2% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.2% (wt).

Example 2F

(124) Alumina ball carrier (20 g) was impregnated with germanium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Ge content of 2% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain core-shell metal layer catalyst B2 with Pt content of 0.2% (wt).

Example 3F

(125) Alumina ball carrier (20 g) was impregnated with stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Sn content of 2% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.5% (wt).

Example 4F

(126) Alumina ball carrier (20 g) was impregnated with lead nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Pb content of 2% (wt). The catalyst A4 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pt content of 0.2% (wt).

Example 5F

(127) Alumina ball carrier (20 g) was impregnated with gallium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Ga content of 2% (wt). The catalyst A5 was impregnated with palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Pd content of 0.2% (wt).

Example 6F

(128) Alumina ball carrier (20 g) was impregnated with gallium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with Ga content of 2% (wt). The catalyst A6 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Ir content of 0.2% (wt).

Example 7F

(129) Alumina ball carrier (20 g) was impregnated with gallium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Ga content of 2% (wt). The catalyst A7 was impregnated with rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Rh content of 0.2% (wt).

Example 8F

(130) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.2% (wt).

Example 9F

(131) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A9 was impregnated with rhodium chloride solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Rh content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 10F

(132) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 11F

(133) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A11 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A11 was impregnated with chloroiridic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Ir content of 0.1% (wt) and Pd content of 0.1% (wt).

Example 12F

(134) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.1% (wt) and Ir content of 0.1% (wt).

Example 13F

(135) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.1% (wt) and Rh content of 0.1% (wt).

Example 14F

(136) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A14 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pd content of 0.05% (wt) and Rh content of 0.15% (wt).

Example 15F

(137) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A15 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pd content of 0.15% (wt) and Rh content of 0.05% (wt).

Example 16F

(138) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and germanium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Ga content of 1% (wt) and Ge content of 1% (wt). The catalyst A16 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pd content of 0.15% (wt) and Rh content of 0.05% (wt).

Example 17F

(139) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and lead nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A17 with Ga content of 1% (wt) and Pb content of 1% (wt). The catalyst A11 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pd content of 0.15% (wt) and Rh content of 0.05% (wt).

Example 18F

(140) Amorphous silica-alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A18 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pd content of 0.15% (wt) and Rh content of 0.05% (wt).

Example 19F

(141) Shaped carrier of high silicon Y molecular sieve and alumina (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A19 with Ga content of 1% (wt) and Sn content of 1% (wt). The catalyst A19 was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pd content of 0.15% (wt) and Rh content of 0.05% (wt).

Comparative Example 1F

(142) Alumina ball carrier (20 g) was impregnated with palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B20 with Pd content of 0.2% (wt).

Comparative Example 2F

(143) Alumina ball carrier (20 g) was impregnated with palladium chloride solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B21 with Pd content of 0.05% (wt) and Rh content of 0.15% (wt).

Comparative Example 3F

(144) Alumina ball carrier (20 g) was impregnated with gallium chloride solution and stannous chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B22 with Ga content of 1% (wt) and Sn content of 1% (wt).

(145) The catalysts prepared in Examples 1F to 19F and Comparative Examples 1F to 3F are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt). The reaction performances are shown in Table 6.

(146) TABLE-US-00006 TABLE 6 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1F Ga/2.0 Pt/0.2 374 1.6 56.2 35.1  2F Ge/5.0 Pt/0.2 371 1.8 57.9 32.2  3F Sn/2.0 Pt/0.2 376 1.7 59.9 35.2  4F Pb/2.0 Pt/0.2 375 1.7 58.8 34.6  5F Ga/2.0 Pd/0.2 381 1.3 56.5 43.5  6F Ga/2.0 Ir/0.2 382 1.3 55.7 42.8  7F Ga/2.0 Rh/0.2 380 1.4 58.9 42.1  8F Ga/1.0- Pt/0.2 376 1.6 59.1 36.9 Sn/1.0  9F Ga/1.0- Pd/0.1-Rh/0.1 383 1.3 59.1 45.5 Sn/1.0 10F Ga/1.0- Pt/0.1-Pd/0.1 381 1.5 61.8 41.2 Sn/1.0 11F Ga/1.0- Pd/0.1-Ir/0.1 385 1.3 58.2 44.8 Sn/1.0 12F Ga/1.0- Pt/0.1-Ir/0.1 379 1.5 60.7 40.5 Sn/1.0 13F Ga/1.0- Pt/0.1-Rh/0.1 374 1.7 64.9 38.2 Sn/1.0 14F Ga/1.0- Pd/0.05- 386 1.2 58.9 49.1 Sn/1.0 Rh/0.15 15F Ga/1.0- Pd/0.15- 385 1.3 63.6 48.9 Sn/1.0 Rh/0.05 16F Ga/1.0- Pd/0.15- 380 1.4 60.5 43.2 Ge/1.0 Rh/0.05 17F Ga/1.0- Pd/0.15- 382 1.3 57.9 44.5 Pb/1.0 Rh/0.05 18F Ga/1.0- Pd/0.15- 381 1.4 62.8 44.9 Sn/1.0 Rh/0.05 19F Ga/1.0- Pd/0.15- 374 1.8 63.1 35.1 Sn/1.0 Rh/0.05 Comparative / Pd/0.2 363 21.6 54.1 2.5 Example 1F Comparative / Pd/0.05- 367 8.2 57.7 7.0 Example 2F Rh/0.15 Comparative Ga/1.0- 307 0.4 3.1 7.8 Example 3F Sn/11.0

Example 1G

(147) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Zr content of 3% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.3% (wt).

Example 2G

(148) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Zr content of 6% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.3% (wt).

Example 3G

(149) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Zr content of 3% (wt). The catalyst A3 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pt content of 0.5% (wt).

Example 4G

(150) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Zr content of 3% (wt). The catalyst A4 was impregnated with chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Pd content of 0.3% (wt).

Example 5G

(151) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Zr content of 3% (wt). The catalyst A5 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Ir content of 0.3% (wt).

Example 6G

(152) Alumina ball carrier (20 g) was impregnated with vanadium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with V content of 3% (wt). The catalyst A6 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.3% (wt).

Example 7G

(153) Alumina ball carrier (20 g) was impregnated with titanium trichloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Ti content of 3% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.3% (wt).

Example 8G

(154) Alumina ball carrier (20 g) was impregnated with niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Nb content of 3% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.3% (wt).

Example 9G

(155) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and sodium vanadate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Zr content of 1% (wt) and V content of 2% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 10G

(156) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and titanium chloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Zr content of 1% (wt) and Ti content of 2% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 11G

(157) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1l with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A1l was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 12G

(158) Alumina ball carrier (20 g) was impregnated with sodium vanadate solution and titanium trichloride solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with V content of 1% (wt) and Ti content of 2% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 13G

(159) Alumina ball carrier (20 g) was impregnated with sodium vanadate solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with V content of 1% (wt) and Nb content of 2% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 14G

(160) Alumina ball carrier (20 g) was impregnated with titanium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Ti content of 1% (wt) and Nb content of 2% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 15G

(161) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A15 was impregnated with chloroplatinic acid solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.1% (wt) and Rh content of 0.2% (wt).

Example 16G

(162) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A16 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A16 was impregnated with rhodium chloride solution and chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Rh content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 17G

(163) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A17 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A17 was impregnated with rhodium chloride solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Rh content of 0.1% (wt) and Ir content of 0.2% (wt).

Example 18G

(164) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A18 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A18 was impregnated with chloroplatinic acid solution and iridium trichloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B18 with Pt content of 0.1% (wt) and Ir content of 0.2% (wt).

Example 19G

(165) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A19 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A19 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B19 with Pt content of 0.03% (wt) and Pd content of 0.27% (wt).

Example 20G

(166) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A20 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A20 was impregnated with chloroplatinic acid solution and rhodium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B20 with Pt content of 0.1% (wt) and Rh content of 0.2% (wt).

Example 21G

(167) Amorphous silica-alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A21 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A21 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B21 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 22G

(168) Shaped carrier of Y molecular sieve (Si/A1=30) and alumina (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A22 with Zr content of 1% (wt) and Nb content of 2% (wt). The catalyst A22 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B22 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Comparative Example 1G

(169) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B23 with Pt content of 0.3% (wt).

Comparative Example 2G

(170) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and chloropalladium acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B24 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Comparative Example 3G

(171) Alumina ball carrier (20 g) was impregnated with zirconium chloride solution and niobium oxalate solution of a volume equal to the pore volume of the carrier to obtain catalyst B25 with Zr content of 1% (wt) and Nb content of 2% (wt).

(172) The catalysts prepared in Examples 1G to 22G and Comparative Examples 1G to 3G are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 370° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 4.0. In raw materials, toluene:naphthalene=40:60 (wt). The reaction performances are shown in Table 7.

(173) TABLE-US-00007 TABLE 7 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1G Zr/3.0 Pt/0.3 378 1.4 50.7 36.2  2G Zr/6.0 Pt/0.3 385 1.2 47.9 39.9  3G Zr/3.0 Pt/0.5 373 2.1 55.1 26.2  4G Zr/3.0 Pd/0.3 386 1.1 43.8 39.8  5G Zr/3.0 Ir/0.3 387 1.1 44.5 40.5  6G V/3.0 Pt/0.3 382 1.3 51.7 39.8  7G Ti/3.0 Pt/0.3 390 1.1 49.3 44.8  8G Nb/3.0 Pt/0.3 389 1.2 54.2 45.2  9G Zr/1.0-V/2.0 Pt/0.1- 388 1.2 51.8 43.2 Pd/0.2 10G Zr/1.0- Pt/0.1- 385 1.3 50.8 39.1 Ti/2.0 Pd/0.2 11G Zr/1.0- Pt/0.1- 386 1.2 55.2 46.0 Nb/2.0 Pd/0.2 12G V/1.0-Ti/2.0 Pt/0.1- 388 1.1 47.8 43.5 Pd/0.2 13G V/1.0- Pt/0.1- 384 1.3 51.9 39.9 Nb/2.0 Pd/0.2 14G Ti/1.0- Pt/0.1- 385 1.2 52.9 44.1 Nb/2.0 Pd/0.2 15G Zr/1.0- Pt/0.1- 380 1.4 56.9 40.6 Nb/2.0 Rh/0.2 16G Zr/1.0- Rh/0.1- 383 1.3 54.8 42.2 Nb/2.0 Pd/0.2 17G Zr/1.0- Rh/0.1- 382 1.3 53.9 41.5 Nb/2% Ir/0.2 18G Zr/1.0- Pt/0.1- 381 1.2 54.4 45.3 Nb/2.0 Ir/0.2 19G Zr/1.0- Pt/0.03- 396 1.0 44.6 44.6 Nb/2.0 Pd/0.27 20G Zr/1.0- Pt/0.2- 377 1.5 59.8 39.9 Nb/2.0 Pd/0.1 21G Zr/1.0- Pt/0.1- 378 1.4 55.8 39.9 Nb/2.0 Pd/0.2 22G Zr/1.0- Pt/0.1- 375 1.7 56.9 33.5 Nb/2.0 Pd/0.2 Comparative / Pt/0.3 350 11.8 36.9 3.1 Example 1G Comparative / Pt/0.1- 358 9.8 41.9 4.3 Example 2G Pd/0.2 Comparative Zr/1.0- / 309 0.9 7.9 8.8 Example 3G Nb/2.0

Example 1I

(174) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1 with Y content of 5% (wt). The catalyst A1 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B1 with Pt content of 0.3% (wt).

Example 2I

(175) Alumina ball carrier (20 g) was impregnated with scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A2 with Sc content of 5% (wt). The catalyst A2 was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B2 with Pt content of 0.3% (wt).

Example 3I

(176) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A3 with Y content of 5% (wt). The catalyst A3 was impregnated with palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B3 with Pd content of 0.3% (wt).

Example 4I

(177) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A4 with Y content of 5% (wt). The catalyst A4 was impregnated with chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B4 with Ir content of 0.3% (wt).

Example 5I

(178) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A5 with Y content of 5% (wt). The catalyst A5 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B5 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 6I

(179) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A6 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A6 was impregnated with chloroplatinic acid ethanol solution of a volume equal to the pore volume of the carrier to obtain catalyst B6 with Pt content of 0.3% (wt).

Example 7I

(180) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A7 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A7 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B7 with Pt content of 0.1% (wt) and Pd content of 0.2% (wt).

Example 8I

(181) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A8 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A8 was impregnated with chloroplatinic acid solution and chloroiridic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B8 with Pt content of 0.1% (wt) and Ir content of 0.2% (wt).

Example 9I

(182) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A9 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A9 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B9 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 10I

(183) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A10 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A10 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B10 with Pt content of 0.2% (wt) and Pd content of 0.1% (wt).

Example 11I

(184) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A1l with Y content of 1% (wt) and Sc content of 4% (wt). The catalyst A1l was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B11 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 12I

(185) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A12 with Y content of 4% (wt) and Sc content of 1% (wt). The catalyst A12 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B12 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 13I

(186) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A13 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A13 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B13 with Pt content of 0.03% (wt) and Pd content of 0.27% (wt).

Example 14I

(187) Amorphous silica-alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A14 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A14 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B14 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Example 15I

(188) Shaped carrier of high silicon mordenite (Si/A1=50) and alumina (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst A15 with Y content of 2% (wt) and Sc content of 3% (wt). The catalyst A15 was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B15 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Comparative Example 1I

(189) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution of a volume equal to the pore volume of the carrier to obtain catalyst B16 with Pt content of 0.03%.

Comparative Example 2I

(190) Alumina ball carrier (20 g) was impregnated with chloroplatinic acid solution and palladium chloride solution of a volume equal to the pore volume of the carrier to obtain catalyst B17 with Pt content of 0.05% (wt) and Pd content of 0.25% (wt).

Comparative Example 3I

(191) Alumina ball carrier (20 g) was impregnated with yttrium nitrate solution and scandium nitrate solution of a volume equal to the pore volume of the carrier, then dried for 4 hours at 120° C. and calcinated for 4 hours at 550° C. to obtain catalyst B18 with Y content of 2% (wt) and Sc content of 3% (wt).

(192) The catalysts prepared in Examples 1I to 15I and Comparative Examples 1I to 3I are evaluated by a following method. Catalyst (5 g) was placed in a reactor, and hydrogen was fed therein. Reduction reaction was performed for 3 hours at 450° C., and then a temperature thereof was reduced to 350° C. Hydrogen and materials containing toluene and naphthalene are fed therein and contact with the catalyst, and reaction activity was measured. Reaction conditions: a total weight airspeed was 10 h.sup.−1; a reaction temperature was 350° C.; a reaction pressure was 3.0 MPa; and a molecular ratio of hydrogen to hydrocarbon was 3.0. In raw materials, toluene:naphthalene=90:10 (wt). The reaction performances are shown in Table 8.

(193) TABLE-US-00008 TABLE 8 Hydrogen Component Component desorption Toluene Naphthalene (2)/content (1)/content temperature hydrogenation hydrogenation Examples (wt %) (wt %) (° C.) ratio (R1) wt % ratio (R2) wt % R2/R1  1I Y/5.0 Pt/0.3 361 2.4 56.3 23.5  2I Sc/5.0 Pt/0.3 359 2.5 55.9 22.4  3I Y/5.0 Pd/0.3 372 1.9 51.4 27.1  4I Y/5.0 Ir/0.3 374 1.6 50.9 31.8  5I Y/5.0 Pt/0.1-Pd/0.2 365 2.0 58.6 29.3  6I Y/2.0-Sc/3.0 Pt/0.3 370 1.7 58.1 34.2  7I Y/2.0-Sc/3.0 Pt/0.1-Pd/0.2 379 1.3 64.3 49.5  8I Y/2.0-Sc/3.0 Pt/0.1-Ir/0.2 380 1.2 56.3 46.9  9I Y/2.0-Sc/3.0 Pt/0.05- 382 1.2 63.8 53.2 Pd/0.25 10I Y/2.0-Sc/3.0 Pt/0.2-Pd/0.1 368 1.8 63.9 35.5 11I Y/2.0-Sc/3.0 Pd/0.1-Ir/0.2 387 1.1 60.5 55.0 12I Y/1.0-Sc/4.0 Pt/0.05- 381 1.3 61.8 47.5 Pd/0.25 13I Y/4.0-Sc/1.0 Pt/0.05- 385 1.2 62.5 52.1 Pd/0.25 14I Y/2.0-Sc/3.0 Pt/0.05- 383 1.3 64.1 49.3 Pd/0.25 15I Y/2.0-Sc/3.0 Pt/0.05- 378 1.7 65.8 38.7 Pd/0.25 Comparative / Pt/0.3 350 38.6 53.3 1.4 Example 1I Comparative / Pt/0.05- 361 10.3 56.8 5.5 Example 2I Pd/0.25 Comparative Y/2.0-Sc/3.0 / 298 0.6 4.8 8.0 Example 3I

(194) The present disclosure is illustrated in detail in combination with preferred embodiments hereinabove, but it can be understood that the embodiments disclosed herein can be improved or substituted without departing from the protection scope of the present disclosure. In particular, as long as there are no structural conflicts, the technical features disclosed in each and every embodiment of the present disclosure can be combined with one another in any way, and the combined features formed thereby are within the protection scope of the present disclosure. The present disclosure does not describe the combinations of these features in an exhaustive manner for conciseness. The present disclosure is not limited by the specific embodiments disclosed herein, but includes all technical solutions falling into the protection scope of the claims.