Preparation method of catalyst with white carbon black modified by Zr—Nd—O

Abstract

The present invention discloses a preparation method of a catalyst with white carbon black modified by Zr—Nd—O and use thereof, and belongs to the field of catalyst technologies. In the present invention, an organic solvent evaporation induced self-assembly method is used to load Zr—Nd—O onto white carbon black to obtain a mesoporous Zr—Nd—O/white carbon black catalyst. The mesoporous Zr—Nd—O/white carbon black catalyst in the present invention has high catalytic activity, contains uniformly distributed mesopores with a relatively large average aperture, and has a simple preparation process, etc.

Claims

1. A preparation method of a catalyst with white carbon black modified by Zr—Nd—O, comprising the following specific steps: (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture; (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 25-45° C. under stirring to adjust a pH value of the system to 7.5-9.5; and conducting aging at 70-110° C. for 10-20 h to obtain white carbon black; (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant, and conducting reaction for 5-10 h to obtain a mixed white carbon black solution; (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 50-70° C. to obtain a precursor; and (5) calcining the precursor in step (4) at 300-500° C. for 2-4 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

2. The preparation method according to claim 1, wherein a ratio of the sodium chloride to the sodium silicate in step (1), i.e., a solid-to-liquid ratio, is 1 g:(10-15) mL, and a volume ratio of the ethanol to the sodium silicate is 1:(0.8-1.2).

3. The preparation method according to claim 1, wherein the surfactant in step (3) is a triblock copolymer P123, F127, or F108.

4. The preparation method according to claim 1, wherein in step (3), a mass ratio of the zirconium nitrate to the white carbon black is 1:(1-2); a mass ratio of the neodymium nitrate to the white carbon black is 1:(3.3-6.7); and a mass ratio of the surfactant to the white carbon black is 1:(1-2).

5. Use of a mesoporous Zr—Nd—O/white carbon black catalyst prepared by using the preparation method of a catalyst with white carbon black modified by Zr—Nd—O according to claim 1 in simultaneously removing PH.sub.3 and AsH.sub.3 through catalysis.

6. Use of a mesoporous Zr—Nd—O/white carbon black catalyst prepared by using the preparation method of a catalyst with white carbon black modified by Zr—Nd—O according to claim 2 in simultaneously removing PH.sub.3 and AsH.sub.3 through catalysis.

7. Use of a mesoporous Zr—Nd—O/white carbon black catalyst prepared by using the preparation method of a catalyst with white carbon black modified by Zr—Nd—O according to claim 3 in simultaneously removing PH.sub.3 and AsH.sub.3 through catalysis.

8. Use of a mesoporous Zr—Nd—O/white carbon black catalyst prepared by using the preparation method of a catalyst with white carbon black modified by Zr—Nd—O according to claim 4 in simultaneously removing PH.sub.3 and AsH.sub.3 through catalysis.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 1;

(2) FIG. 2 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 2;

(3) FIG. 3 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 3;

(4) FIG. 4 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 4;

(5) FIG. 5 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 5;

(6) FIG. 6 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 6;

(7) FIG. 7 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 7;

(8) FIG. 8 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 8; and

(9) FIG. 9 is an effect diagram of simultaneously removing PH.sub.3 and AsH.sub.3 by using a mesoporous Zr—Nd—O/white carbon black catalyst according to Embodiment 9.

DETAILED DESCRIPTION

(10) The present invention will be further described in details below with reference to specific implementations, but the protection scope of the present invention is not limited thereto.

(11) Embodiment 1: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(12) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:10, and a volume ratio of the ethanol to the sodium silicate is 1:0.8;

(13) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(14) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (P123), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1; a mass ratio of the neodymium nitrate to the white carbon black is 1:3.3; and a mass ratio of the surfactant (P123) to the white carbon black is 1:1;

(15) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(16) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(17) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 1. It can be seen from FIG. 1 that the catalyst has a better removal effect on AsH.sub.3 than PH.sub.3 in a removal stage corresponding to the removal efficiency 100%. However, as removal time increases, the catalyst has a better removal effect on PH.sub.3 than AsH.sub.3.

(18) Embodiment 2: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(19) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:12.5, and a volume ratio of the ethanol to the sodium silicate is 1:1;

(20) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(21) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (P123), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1.5; a mass ratio of the neodymium nitrate to the white carbon black is 1:5; and a mass ratio of the surfactant (P123) to the white carbon black is 1:1.5;

(22) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(23) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(24) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 2. It can be seen from FIG. 2 that the AsH.sub.3 removal efficiency 100% of the catalyst can be maintained for 420 min, and the catalyst has a better removal effect on AsH.sub.3 than PH.sub.3 in the whole removal process.

(25) Embodiment 3: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(26) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:15, and a volume ratio of the ethanol to the sodium silicate is 1:1.2;

(27) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(28) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (P123), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:2; a mass ratio of the neodymium nitrate to the white carbon black is 1:6.7; and a mass ratio of the surfactant (P123) to the white carbon black is 1:2;

(29) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(30) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(31) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 3. It can be seen from FIG. 3 that the catalyst has a relatively good removal effect on both AsH.sub.3 and PH.sub.3.

(32) Embodiment 4: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(33) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:10, and a volume ratio of the ethanol to the sodium silicate is 1:0.8;

(34) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(35) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F127), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1; a mass ratio of the neodymium nitrate to the white carbon black is 1:3.3; and a mass ratio of the surfactant (F127) to the white carbon black is 1:1;

(36) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(37) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(38) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a Φ6 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 4. It can be seen from FIG. 4 that a PH.sub.3 removal effect and an AsH.sub.3 removal effect of the catalyst are basically consistent during a removal time of 360 min; and the catalyst has higher PH.sub.3 removal efficiency than the AsH.sub.3 removal efficiency after the removal time of 360 min.

(39) Embodiment 5: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(40) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:12.5, and a volume ratio of the ethanol to the sodium silicate is 1:1;

(41) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(42) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F127), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1.5; a mass ratio of the neodymium nitrate to the white carbon black is 1:5; and a mass ratio of the surfactant (F127) to the white carbon black is 1:1.5;

(43) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(44) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(45) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a Φ6 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 5. It can be seen from FIG. 5 that the catalyst has a better removal effect on PH.sub.3 than AsH.sub.3 during a removal time of 300 min; and the PH.sub.3 removal efficiency and the AsH.sub.3 removal efficiency of the catalyst are basically consistent after 300 min.

(46) Embodiment 6: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(47) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:15, and a volume ratio of the ethanol to the sodium silicate is 1:1.2;

(48) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(49) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F127), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:2; a mass ratio of the neodymium nitrate to the white carbon black is 1:6.7; and a mass ratio of the surfactant (F127) to the white carbon black is 1:2;

(50) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(51) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(52) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mmx 10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 h.sup.−1, and the reaction temperature is 70° C. A test result is shown in FIG. 7. It can be seen from FIG. 7 that, the PH.sub.3 removal efficiency of the catalyst is 100% before 250 min, and the whole AsH.sub.3 removal efficiency of the catalyst is obviously higher than its PH.sub.3 removal efficiency.

(53) Embodiment 7: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(54) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:10, and a volume ratio of the ethanol to the sodium silicate is 1:0.8;

(55) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(56) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F108), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1; a mass ratio of the neodymium nitrate to the white carbon black is 1:3.3; and a mass ratio of the surfactant (F108) to the white carbon black is 1:1;

(57) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(58) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(59) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 7. It can be seen from FIG. 7 that, the PH.sub.3 removal efficiency of the catalyst is 100% before 250 min, and the whole PH.sub.3 removal efficiency of the catalyst is obviously higher than its PH.sub.3 removal efficiency.

(60) Embodiment 8: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(61) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:12.5, and a volume ratio of the ethanol to the sodium silicate is 1:1;

(62) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(63) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F108), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:1.5; a mass ratio of the neodymium nitrate to the white carbon black is 1:5; and a mass ratio of the surfactant (F108) to the white carbon black is 1:1.5;

(64) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(65) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(66) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 and the reaction temperature is 70° C. A test result is shown in FIG. 8. It can be seen from FIG. 8 that, the AsH.sub.3 removal efficiency of the catalyst is 100% before 150 min, and the whole AsH.sub.3 removal efficiency of the catalyst is obviously lower than its PH.sub.3 removal efficiency.

(67) Embodiment 9: a preparation method of a catalyst with white carbon black modified by Zr—Nd—O is provided, including the following specific steps:

(68) (1) adding sodium chloride and ethanol to sodium silicate, uniformly mixing, and slowly adding water under stirring until sodium silicate colloidal particles are dissolved, to obtain an ethanol-sodium silicate solution mixture, where a solid-to-liquid ratio g:mL of the sodium chloride to the sodium silicate is 1:15, and a volume ratio of the ethanol to the sodium silicate is 1:1.2;

(69) (2) adding sulfuric acid to the ethanol-sodium silicate solution mixture in step (1) at 40° C. under stirring to adjust a pH value of the system to 8.0; and conducting aging at 90° C. for 15 h to obtain white carbon black;

(70) (3) adding the white carbon black in step (2) to ethanol under stirring, adding zirconium nitrate, neodymium nitrate, and a surfactant (F108), and conducting reaction for 8 h to obtain a mixed white carbon black solution, where a mass ratio of the zirconium nitrate to the white carbon black is 1:2; a mass ratio of the neodymium nitrate to the white carbon black is 1:6.7; and a mass ratio of the surfactant (F108) to the white carbon black is 1:2;

(71) (4) evaporating ethanol from the mixed white carbon black solution in step (3) at 65° C. to obtain a precursor; and

(72) (5) calcining the precursor in step (4) at 450° for 2.5 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.

(73) The catalytic performance test of the mesoporous Zr—Nd—O/white carbon black catalyst in this embodiment is conducted in a 16 mm×10 cm quartz fixed bed reactor. Reaction conditions are as follows: An initial concentration of PH.sub.3 is 200 ppm, an initial concentration of AsH.sub.3 is 100 ppm, equilibrium gas is C.sub.2H.sub.2, a space velocity is 15000 h.sup.−1, and the reaction temperature is 70° C. A test result is shown in FIG. 9. It can be seen from FIG. 3 that, after 200 min, the AsH.sub.3 removal efficiency of the catalyst is still lower than its PH.sub.3 removal efficiency, but the whole AsH.sub.3 removal efficiency is obviously improved compared with that in Embodiment 8.