Methods for synthesizing mesoporous zeolite ETS-10 containing metal without a templating agent

Abstract

The invention provides a method for synthesizing a mesoporous zeolite ETS-10 containing a metal without a templating agent. The method according to the invention comprises the steps of: mixing a silicon source with a NaOH solution to obtain a mixed solution so that the content of Na.sub.2O in the mixed solution is 10.0% to 20.0% by weight; adding a KOH or KF solution so that the content of K.sub.2O is 10.0% to 25.0% by weight and stirring it well; adding a titanium source solution and stirring it well; adding a precursor compound containing metal Ni and/or Co and stirring it well; and subjecting it to a crystallization reaction to obtain the mesoporous zeolite ETS-10. The mesoporous zeolite ETS-10 obtained by the invention has a specific surface area of 320 to 420 m.sup.2/g, a mesoporous volume of 0.11 to 0.21 cm.sup.3/g, and thus can be used as a catalyst and a support thereof in synthesis industry for macromolecular fine chemicals.

Claims

1. A method for synthesizing a mesoporous zeolite ETS-10 containing a metal without a templating agent, comprising the steps of: (1) mixing a silicon source with a NaOH solution to obtain a mixed solution so that the content of Na.sub.2O in the mixed solution is 10.0% to 20.0% by weight; (2) adding a KOH or KF solution into the mixed solution of step (1) so that the content of K.sub.2O is 10.0% to 25.0% by weight and stirring it well; (3) adding a titanium source solution into the mixed solution of step (2) and stirring it well; (4) adding into the mixed solution of step (3) a precursor compound containing metal Ni and/or Co and stirring it well; and (5) subjecting the mixed solution of step (4) to a crystallization reaction to obtain the mesoporous zeolite ETS-10.

2. The method according to claim 1, wherein, the titanium source is titanium trichloride.

3. The method according to claim 1, wherein the precursor compound containing metal Ni is nickel nitrate hexahydrate, and the precursor compound containing metal Co is cobalt nitrate hexahydrate.

4. The method according to claim 1, wherein the total amount of metal Ni and Co comprises 1.5% to 3.0% by weight of the mass of zeolite, and the ratio of the atomic amount of metal Ni to Co is 0-1:1 or 1:1-0.

5. The method according to claim 1, wherein the crystallization reaction is carried out under a condition in which the reaction temperature is 200 C. to 250 C. and the reaction time is 20 to 110 hours.

6. The method according to claim 1, wherein each raw material in the system for synthesis is fed in a molar ratio, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, of (58): 1:(37):(0.52):(100220):(0.020.05), wherein the molar number of sodium oxide is the sum total of sodium elements contained in the water glass as a silicon source and sodium hydroxide.

7. The method according to claim 1, wherein the mesoporous zeolite ETS-10 has a specific surface area of 320 to 420 m.sup.2/g, and a mesopore volume of 0.11 to 0.21 cm.sup.3/g.

8. The method according to claim 1, wherein the crystallization reaction is carried out under a condition in which the reaction temperature is 200 C. to 230 C. and the reaction time is 72 to 110 hours.

9. The method according to claim 1, wherein each raw material in the system for synthesis is fed in a molar ratio, in terms of SiO2:TiO2:Na2O:K2O:H2O:NiO, of (67):1: (35):(11.7):(150200):(0.030.04), wherein the molar number of sodium oxide is the sum total of sodium elements contained in the water glass as a silicon source and sodium hydroxide.

10. The method according to claim 1, wherein the said silicon source is a water glass with a composition of SiO.sub.2 included in an amount of 5.2 to 6.0 mol/L, Na.sub.2O included in an amount of 1.3 to 2.0 mol/L, and H.sub.2O included in an amount of 45.0 to 50.0 mol/L.

11. The method according to claim 10, wherein, the titanium source is titanium trichloride.

12. The method according to claim 11, wherein the precursor compound containing metal Ni is nickel nitrate hexahydrate, and the precursor compound containing metal Co is cobalt nitrate hexahydrate.

13. The method according to claim 11, wherein the crystallization reaction is carried out under a condition in which the reaction temperature is 200 C. to 250 C. and the reaction time is 20 to 110 hours.

14. The method according to claim 11, wherein the total amount of metal Ni and Co comprises 1.5% to 3.0% by weight of the mass of zeolite, and the ratio of the atomic amount of metal Ni to Co is 0-1:1 or 1:1-0.

15. The method according to claim 14, wherein the crystallization reaction is carried out under a condition in which the reaction temperature is 200 C. to 250 C. and the reaction time is 20 to 110 hours.

16. The method according to claim 15, wherein each raw material in the system for synthesis is fed in a molar ratio, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.20:H.sub.2O:NiO, of (58): 1:(37):(0.52):(100220):(0.020.05), wherein the molar number of sodium oxide is the sum total of sodium elements contained in the water glass as a silicon source and sodium hydroxide.

17. The method according to claim 16, wherein the mesoporous zeolite ETS-10 a specific surface area of 320 to 420 m.sup.2/g, and a mesopore volume of 0.11 to 0.21 cm.sup.3/g.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing the adsorption isotherm line and pore size distribution of the zeolite METS-10.

(2) FIG. 2 is SEM micrograph of the zeolite METS-10.

DETAILED DESCRIPTION

(3) The technical solutions of the present invention is now described in detail as follows in order to have a better comprehension of the technical features, purposes and beneficial effects of the present invention, which, however, should not be understood as limiting the implementable range of the present invention.

(4) The raw materials and solutions used in the examples are as follows (various heteroatoms exemplified as Ni, Co):

(5) the components of water glass: SiO.sub.2: 5.472 mol/L, Na.sub.2O: 1.1706 mol/L, H.sub.2O: 49.7493 mol/L;

(6) solution (i): prepared by dissolving an amount of NaOH in 10 g H.sub.2O, adding an amount of water glass and mixing it well;

(7) solution (ii): prepared by dissolving an amount of KOH in 9.4 g H.sub.2O and mixing it well;

(8) solution (iii): prepared by dissolving an amount of KF in 9.4 g H.sub.2O and mixing it well;

(9) solution (iv): prepared by dissolving an amount of Ni(NO.sub.3).sub.2.6H.sub.2O in 3 g H.sub.2O and mixing it well;

(10) solution (v): prepared by dissolving an amount of Co(NO.sub.3).sub.2.9H.sub.2O in 3 g H.sub.2O and mixing it well.

Example 1

(11) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 220 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 7:1:5:1:200:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 2

(12) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 220 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 6.8:1:4.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 3

(13) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 6.8:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 4

(14) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 6:1:3:1.7:150:0.03. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 5

(15) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 90 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 6:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 6

(16) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 90 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 6:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 7

(17) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 110 hours at 200 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 5:1:3:2:100:0.02. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 8

(18) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (iv) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 20 hours at 250 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:NiO, is 8:1:7:0.5:220:0.05. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 9

(19) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 220 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 6.8:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 10

(20) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 220 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 5:1:3:2:100:0.02. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 11

(21) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 6:1:3:1.7:150:0.03. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 12

(22) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 72 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 8:1:7:0.5:220:0.05. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 13

(23) The solution (i) was stirred for 30 minutes and added with solution (ii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 90 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 6.8:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 14

(24) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 90 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 7:1:5:1:200:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 15

(25) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 110 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 6.8:1:4.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

Example 16

(26) The solution (i) was stirred for 30 minutes and added with solution (iii) and stirred for 1 hour, thereafter 13.1 g TiCl.sub.3 solution was added thereto and stirred for 4 hours. The solution (v) was added thereto and stirred for another 20 minutes, then the resulting mixture was transferred into a reactor and sealed, crystallized for 110 hours at 230 C. The molar ratio of each raw material in the system, in terms of SiO.sub.2:TiO.sub.2:Na.sub.2O:K.sub.2O:H.sub.2O:CoO, is 6.8:1:3.7:1.3:163:0.04. The crystallized product was filtered, washed and dried to obtain the mesoporous zeolite ETS-10 containing a metal of this Example.

(27) Table 1 records the mesoporous zeolite ETS-10 and the traditional zeolite ETS-10 with respect to a specific surface area, a mesopore volume, and a micropore volume. It can be seen that the mesoporous zeolite ETS-10 synthesized according to the method of the present invention has a mesopore volume of up to 0.21 cm.sup.3/g, while the traditional zeolite ETS-10 only has a mesopore volume of 0.02 cm.sup.3/g.

(28) TABLE-US-00001 TABLE 1 Texture properties of the mesoporous zeolite ETS-10 and traditional zeolite ETS-10 synthesized under the same conditions BET specific surface mesopore micropore area volume volume Sample (m.sup.2/g) (cm.sup.3/g) (cm.sup.3/g) mesoporous zeolite ETS- 378 0.21 0.11 10 microporous zeolite ETS- 386 0.02 0.13 10

(29) Table 2 records the texture properties of the mesoporous zeolite ETS-10 obtained in Examples 1 to 16.

(30) TABLE-US-00002 TABLE 2 Texture properties of samples obtained in different Examples BET specific surface area mesopore volume micropore volume Example (m.sup.2/g) (cm.sup.3/g) (cm.sup.3/g) Example 1 355 0.14 0.12 Example 2 378 0.21 0.11 Example 3 374 0.15 0.13 Example 4 352 0.12 0.11 Example 5 383 0.17 0.12 Example 6 370 0.18 0.12 Example 7 325 0.11 0.12 Example 8 329 0.12 0.12 Example 9 343 0.16 0.12 Example 10 407 0.12 0.13 Example 11 359 0.14 0.13 Example 12 343 0.13 0.13 Example 13 351 0.15 0.13 Example 14 353 0.14 0.13 Example 15 370 0.17 0.11 Example 16 368 0.16 0.12

(31) FIG. 1 is a graph showing the adsorption isotherm line and pore size distribution of the zeolite METS-10 obtained in Example 2, which molecular seize has a significant mesoporous structure with a pore size centralized in 2 nm, 4.5 nm and 10.5 nm, which is beneficial to increase the reaction rate of a macromolecular sulfur-nitrogen heterocyclic compound. FIG. 2 is a SEM micrograph of the zeolite ETMS-10 obtained in Example 2, which shows that the molecular seize has a grain surface having many fractures, which forms natural side-corner sites possessing high hydrogenation activity.