Method for preparing NaY molecular sieve of high silica-alumina ratio and product thereof

Abstract

A method for preparing a NaY molecular sieve having a high silica-to-alumina ratio, wherein deionized water, a silicon source, an aluminum source, an alkali source, and ILs as a template agent are mixed to obtain an initial gel mixture; the initial gel mixture is maintained at a proper temperature and aged, then fed into a high pressure synthesis kettle for crystallization; the solid product is separated and dried, to obtain the NaY molecular sieve having a high silica-to-alumina ratio, wherein the ILs is a short-chain alkylimidazolium ionic liquid, the template agent is less volatile, and the resultant high-silicon Y molecular sieve has a high crystallinity and a silica-to-alumina ratio of 6 or more.

Claims

1. A method for preparing a NaY molecular sieve having a high silica-to-alumina ratio, wherein the method comprises the steps of: a) mixing deionized water, a silicon source, an aluminum source, an alkali source, and ILs as a template agent to obtain an initial gel mixture; b) maintaining the initial gel mixture obtained in step a) at a temperature of no more than 50° C., and stirring and aging for 1-100 hours to obtain a homogeneous gel mixture; c) feeding the homogeneous gel mixture obtained in step b) into a high pressure synthesis kettle, closing the kettle, increasing the temperature to 70-130° C., and allowing crystallization to be conducted under an autogenic pressure for 3-30 days; and d) after the crystallization is complete, separating the solid product, washing with deionized water to neutral and drying, to obtain the NaY molecular sieve having a high silica-to-alumina ratio, wherein the obtained NaY molecular sieve has a silica-to-alumina ratio of 6 or more, and the ILs is a short-chain alkylimidazolium ionic liquid, wherein the short-chain alkylimidazolium ionic liquid is any one of or a mixture of two or more of 1-ethyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, and 1-butyl-3-methylimidazolium chloride.

2. The method according to claim 1, wherein the initial gel mixture obtained in the step a) has the following molar ratios: SiO.sub.2/Al.sub.2O.sub.3=6-20; Na.sub.2O/Al.sub.2O.sub.3=1-8; H.sub.2O/Al.sub.2O.sub.3=100-400; and ILs/Al.sub.2O.sub.3=0.1-6, wherein the silicon source is based on SiO.sub.2, the aluminum source is based on Al.sub.2O.sub.3, and the alkali source is based on Na.sub.2O.

3. The method according to claim 1, wherein the silicon source used in the step a) is any one of or a mixture of two or more of a silica sol, an activated silica, and an orthosilicate; the aluminum source is any one or a mixture of two or more of sodium aluminate, an activated alumina, and an aluminum alkoxide; and the alkali source is sodium hydroxide.

4. The method according to claim 1, wherein the aging temperature is 10-50° C. and the aging time is 8-72 hours in the step b).

5. The method according to claim 1, wherein the temperature for crystallization is 80-110° C. and the crystallization time is 8-24 days in the step c).

6. The method according to claim 1, wherein the crystallization process in the step c) is performed in a static or dynamic state.

7. A molecular sieve having a high silica-to-alumina ratio comprising an ILs which is a short-chain alkylimidazolium ionic liquid, wherein the short-chain alkylimidazolium ionic liquid is any one of or a mixture of two or more of 1-ethyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, and 1-butyl-3-methylimidazolium chloride and; prepared by the method according to claim 1, wherein the NaY molecular sieve has a silica-to-alumina ratio of 6 or more.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an XRD pattern of the product synthesized according to Example 1 of the present disclosure.

(2) FIG. 2 is a scanning electron microscope (SEM) image of the product synthesized according to Example 1 of the present disclosure.

(3) FIG. 3 is a silicon nuclear magnetic resonance (.sup.29Si-NMR) spectrum of the product synthesized according to Example 1 of the present disclosure.

DESCRIPTION OF EMBODIMENTS

(4) In the present invention, a phase-pure NaY molecular sieve having a high silica-to-alumina ratio is synthesized under a hydrothermal condition by using a short-chain alkylimidazolium ionic liquid as a template agent or a structure directing agent and mixing an appropriate silicon source, an appropriate aluminum source, and an appropriate alkali source in deionized water.

(5) In one preferred embodiment, the method for preparing a NaY molecular sieve having a high silica-to-alumina ratio (the silica-to-alumina ratio is 6 or more) of the present disclosure comprises the following steps:

(6) a) mixing deionized water, a silicon source, an aluminum source, an alkali source, and a template agent at a certain ratio to obtain an initial gel mixture. Preferably, the initial gel mixture has the following molar ratios:

(7) SiO.sub.2/Al.sub.2O.sub.3=6-20;

(8) Na.sub.2O/Al.sub.2O.sub.3=1-8;

(9) H.sub.2O/Al.sub.2O.sub.3=100-400; and

(10) ILs/Al.sub.2O.sub.3=0.1-6, wherein ILs is a short-chain alkylimidazolium ionic liquid, the silicon source is based on SiO.sub.2, the aluminum source is based on Al.sub.2O.sub.3, and the alkali source is based on Na.sub.2O;

(11) b) maintaining the initial gel mixture obtained in step a) under a condition of no more than 50° C., and stirring and aging for 1-100 hours to obtain a homogeneous gel mixture;

(12) c) feeding the homogeneous gel mixture obtained in step b) into a high pressure synthesis kettle, closing the kettle, increasing the temperature to 70-130° C., and allowing crystallization to be conducted under an autogenic pressure for 3-30 days; and

(13) d) after the crystallization is complete, separating the solid product, washing with deionized water to neutral and drying, to obtain the high-silicon NaY molecular sieve.

(14) The short-chain alkylimidazolium ionic liquid used in the step a) is any one of or a mixture of two or more of 1-ethyl-3-methylimidazolium bromide ([Emim]Br), 1-allyl-3-methylimidazolium bromide ([Amim]Br), 1-butyl-3-methylimidazolium bromide ([Bmim]Br), 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), 1-allyl-3-methylimidazolium chloride ([Amim]Cl), and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl).

(15) Preferably, the silicon source used in the step a) is any one of or a mixture of two or more of a silica sol, an activated silica, and an orthosilicate; the aluminum source is any one of or a mixture of two or more of sodium aluminate, an activated alumina, or an aluminum alkoxide; and the alkali source is sodium hydroxide.

(16) Preferably, in the initial gel mixture of the step a), SiO.sub.2/Al.sub.2O.sub.3=10-18.

(17) Preferably, in the initial gel mixture of the step a), Na.sub.2O/Al.sub.2O.sub.3=2-6.

(18) Preferably, in the initial gel mixture of the step a), H.sub.2O/Al.sub.2O.sub.3=180-300.

(19) Preferably, in the initial gel mixture of the step a), ILs/Al.sub.2O.sub.3=0.5-5.

(20) Preferably, the aging temperature is 10-50° C. and the aging time is 8-72 hours in the step b).

(21) Preferably, the crystallization temperature is 80-110° C. and the crystallization time is 8-24 days in the step c).

(22) Preferably, the crystallization process in the step c) is performed in a static or dynamic state.

(23) In the present disclosure, the X-ray powder diffraction phase analysis (XRD) of the product is carried out on X'Pert PRO X-ray diffractometer of PANalytical Corporation, Netherlands, using a Cu target, Kα radiation source (λ=0.15418 nm), a voltage of 40 KV, and a current of 40 mA. The relative crystallinity of the product is calculated based on the sum of XRD peak intensities of crystal planes 111, 331, 533. By comparing to the crystallinity of the sample in Example 1, which is 100%, the relative crystallinities of other samples are obtained.

(24) In the present disclosure, SU8020 scanning electron microscope of Hitach is used in SEM morphologic analysis of the product.

(25) In the present disclosure, the silica-to-alumina ratio of the product is measured by using Magix 2424 X-ray fluorescence analyzer (XRF) of Philips Corporation.

(26) In the present disclosure, Infinity plus 400WB solid nuclear magnetic resonance spectrum analyzer of Varian Corporation, U.S., is used in silicon nuclear magnetic resonance (.sup.29Si MAS NMR) analysis of the product, with a BBO MAS probe and an operational magnetic field strength of 9.4 T. The silica-to-alumina ratio of the product may also be calculated from the result of .sup.29Si MAS NMR, and the equation is as follows:
NMR SiO.sub.2/Al.sub.2O.sub.3=8*(S.sub.Q0+S.sub.Q1+S.sub.Q2+S.sub.Q3+S.sub.Q4)/(S.sub.Q1+2S.sub.Q2+3S.sub.Q3+4S.sub.Q4)

(27) wherein Qi represents the difference in the number of aluminum atoms surrounding a silicon-oxygen tetrahedron (SiO.sub.4) (i=0, 1, 2, 3, 4), and S.sub.Qi represents a corresponding peak area of Qi on the silicon nuclear magnetic resonance spectrum.

(28) The present disclosure will be described in detail below by Examples, but the present disclosure is not limited to these Examples.

Example 1

(29) Types and molar amounts for respective raw materials, crystallization temperatures and crystallization times, crystal forms, relative crystallinities, and silica-to-alumina ratios (SiO.sub.2/Al.sub.2O.sub.3) determined by XRF and NMR were shown in the following Table 1.

(30) In Example 1, the formulating process was as follows: 1.94 g of 1-ethyl-3-methylimidazolium bromide ([Emim]Br) and 1.19 g of sodium hydroxide were dissolved in 23 g of deionized water, to which 2 g of sodium aluminate (the content percentage by mass of Al.sub.2O.sub.3 was 52%) was then added, and they were stirred until a clarified liquid is obtained; then 24.48 g of silica sol (the content percentage by mass of SiO.sub.2 was 30.45%) was further added to obtain an initial gel mixture. This initial gel mixture was stirred at room temperature for 24 hours to produce a homogeneous gel mixture; and this homogeneous gel mixture was transferred to a stainless high pressure synthesis kettle. At this time, molar ratio of respective components in the synthesis system is 1.0[Emim]Br:12SiO.sub.2:1Al.sub.2O.sub.3:3.2Na.sub.2O:220H.sub.2O.

(31) The high pressure synthesis kettle was closed and placed in an oven of which the temperature had been increased to a constant temperature of 110° C., and static crystallization was performed at an autogenic pressure for 14 days. After the crystallization was complete, the solid product was separated by centrifugation, washed with deionized water to neutral, and then dried in air at 100° C. to obtain a raw powder. The sample of this raw powder was taken for XRD analysis, and the result thereof was shown in FIG. 1 and Table 2; the scanning electron microscope (SEM) image of this sample was shown in FIG. 2; and the silicon nuclear magnetic resonance (.sup.29Si MAS NMR) spectrum of this sample was shown in FIG. 3. At the meanwhile, the silica-to-alumina ratio of the product was calculated by XRF and silicon nuclear magnetic resonance spectrum, respectively. By summarizing the results of the analyses described above, it was indicated and determined that the synthesized product was a NaY molecular sieve having a silica-to-alumina ratio of greater than 6.

Examples 2-24

(32) Types and amounts of the materials used, and reaction conditions as well as analytical results were shown in the following Table 1, and the processes for synthesis and analysis were the same as those of Example 1.

(33) The synthesized samples were subjected to XRD analysis, and data results thereof were similar to those in Table 2. That is, the positions and shapes of peaks were the same, and relative peak intensities fluctuated in a range of ±20% according to the change of the synthesis conditions. It was demonstrated that the synthetic product had the characteristics of a NaY molecular sieve structure. Other analytical results of these samples were shown in the following Table 1.

Comparative Example

(34) Types and amounts of the materials used, and reaction conditions as well as analytical results were shown in the following Table 1, and the processes for synthesis and analysis were the same as those of Example 1, except for using 0.1 mol of triethylamine as a template agent. The obtained sample was subjected to XRD analysis, and the data thereof demonstrated that the synthesized product had the structural characteristics of a NaY molecular sieve. Other analytical results of this sample were shown in the following Table 1.

(35) TABLE-US-00001 TABLE 1 Type and Aluminum source Silicon source Alkali source Crystal- Crystal- Relative amount of and moles and moles and moles lization lization crystal- XRF NMR template of Al.sub.2O.sub.3 of SiO.sub.2 of Na.sub.2O temper- time Crystal linity (SiO.sub.2/ (SiO.sub.2/ Example agent contained contained contained H.sub.2O ature(° C.) (day) form (%) Al.sub.2O.sub.3) Al.sub.2O.sub.3) 1 [Emim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 7.2 6.8 0.1 mol 0.10 mol 1.2 mol 2 [Bmim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 7.1 6.8 0.1 mol 0.10 mol 1.2 mol 3 [Amim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.9 6.7 0.1 mol 0.10 mol 1.2 mol 4 [Emim]Cl Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 7.2 6.8 0.1 mol 0.10 mol 1.2 mol 5 [Bmim]Cl Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 7.1 6.8 0.1 mol 0.10 mol 1.2 mol 6 [Amim]Cl Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.9 6.7 0.1 mol 0.10 mol 1.2 mol 7 [Emim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.2 6.1 0.1 mol 0.10 mol 0.6 mol 8 [Bmim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.1 6.0 0.1 mol 0.10 mol 0.6 mol 9 [Amim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.3 6.2 0.1 mol 0.10 mol 0.6 mol 10 [Emim]Br Sodium aluminate Silica sol 0.50 mol 22 mol 110 14 NaY 100 7.2 6.8 0.1 mol 0.10 mol 2.0 mol 11 [Bmim]Br Sodium aluminate Silica sol 0.50 mol 22 mol 110 14 NaY 100 7.3 6.9 0.1 mol 0.10 mol 2.0 mol 12 [Amim]Br Sodium aluminate Silica sol 0.50 mol 22 mol 110 14 NaY 100 7.1 6.7 0.1 mol 0.10 mol 2.0 mol 13 [Emim]Br Sodium aluminate Activated silica 0.32 mol 22 mol 110 14 NaY 95 7.1 6.7 0.1 mol 0.10 mol 1.2 mol 14 [Bmim]Br Sodium aluminate Activated silica 0.32 mol 22 mol 110 14 NaY 95 7.0 6.6 0.1 mol 0.10 mol 1.2 mol 15 [Amim]Br Sodium aluminate Activated silica 0.32 mol 22 mol 110 14 NaY 90 6.9 6.7 0.1 mol 0.10 mol 1.2 mol 16 [Emim]Br Activated alumina Silica sol 0.32 mol 22 mol 110 14 NaY 100 6.4 6.2 0.1 mol 0.10 mol 1.2 mol 17 [Bmim]Br Activated alumina Silica sol 0.32 mol 22 mol 110 14 NaY 95 6.6 6.4 0.1 mol 0.10 mol 1.2 mol 18 [Amim]Br Activated alumina Silica sol 0.32 mol 22 mol 110 14 NaY 90 6.5 6.2 0.1 mol 0.10 mol 1.2 mol 19 [Emim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 70 30 NaY 80 6.2 6.0 0.1 mol 0.10 mol 1.2 mol 20 [Bmim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 70 30 NaY 85 6.1 6.0 0.1 mol 0.10 mol 1.2 mol 21 [Amim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 70 30 NaY 80 6.2 6.1 0.1 mol 0.10 mol 1.2 mol 22 [Emim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 130 3 NaY 95 7.5 7.2 0.1 mol 0.10 mol 1.2 mol 23 [Bmim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 130 3 NaY 95 7.4 7.1 0.1 mol 0.10 mol 1.2 mol 24 [Amim]Br Sodium aluminate Silica sol 0.32 mol 22 mol 130 3 NaY 95 7.6 7.3 0.1 mol 0.10 mol 1.2 mol Comparative Triethylamine Sodium aluminate Silica sol 0.32 mol 22 mol 100 7 NaY 70 5.4 5.1 Example 0.1 mol 0.10 mol 1.2 mol

(36) TABLE-US-00002 TABLE 2 XRD result of the sample of Example 1 No. 2θ d(Å) 100 × I/I.sup.0 1 6.2041 14.24645 100 2 10.1409 8.72289 20.15 3 11.8975 7.4387 8.47 4 15.6692 5.6556 40.16 5 18.7069 4.74353 15.78 6 20.3883 4.35596 14.41 7 22.8253 3.8961 3.26 8 23.6769 3.75787 36.24 9 25.0092 3.56062 0.44 10 25.8118 3.4517 2.89 11 27.0779 3.29311 17.44 12 27.7943 3.20983 1.11 13 29.6723 3.01082 3.78 14 30.7843 2.90455 8.7 15 31.4336 2.84602 17.04 16 32.4937 2.75555 5.67 17 33.1205 2.70482 1.83 18 34.1286 2.6272 6.5 19 34.7195 2.58383 3.64 20 35.7076 2.51456 0.89 21 37.2197 2.4158 0.79 22 37.9445 2.37131 3.64 23 39.3958 2.28723 0.34 24 40.6107 2.22157 1.61 25 41.4555 2.17823 2.56 26 41.9693 2.15275 1.41 27 42.8121 2.1123 0.67 28 43.2876 2.0902 2.43 29 44.1074 2.05323 1.93 30 45.8438 1.97942 0.44 31 47.2353 1.92431 1.46 32 47.8334 1.90163 1.63 33 49.4874 1.84188 1

(37) It can be seen from the results of above Table 1 and Table 2 that with respect to the NaY molecular sieve synthesized by the method of the present disclosure, the silica-to-alumina ratio of each of molecular sieve samples in Examples 1-24, either a silica-to-alumina ratio of the product determined by XRF method or a silica-to-alumina ratio of the backbone of the product determined by silicon nuclear magnetic resonance spectrum data, is remarkably higher than the silica-to-alumina ratio of the molecular sieve sample obtained in Comparative Example. On the one hand, it is indicated that in the case of using a conventional amine as a template agent, the silica-to-alumina ratio of the resultant sample is relatively low and is difficult to reach 6, and the crystallinity is relatively low; and on the other hand, it is indicated that in the case of using a short-chain alkylimidazolium ionic liquid as a template agent, the silica-to-alumina ratio of the resultant product is 6 or more, or even higher, and the crystallinity is high. The use of this NaY molecular sieve having a high crystallinity and a high silica-to-alumina ratio can significantly improve the catalytic cracking in terms of activity, stability, and the like.

(38) The present invention has been described in detail above, but the present invention is not limited to specific embodiments described herein. It is to be understood by the person skilled in the art that other modifications and variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.