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METHOD FOR PREPARING Y TYPE MOLECULAR SIEVE HAVING HIGH SILICA TO ALUMINA RATIO

20170260059 · 2017-09-14

    Inventors

    Cpc classification

    International classification

    Abstract

    Provided is a method for preparing a Y type molecular sieve having a high silica-to-alumina ratio, comprising: mixing deionized water, a silicon source, an aluminum source, an alkali source, and a tetraalkylammoniumcation source as a template agent to obtain an initial gel mixture; after aging the initial gel mixture at an appropriate temperature, feeding the gel mixture into a high pressure synthesis kettle for crystallization; separating a solid product, and drying to obtain the Y type molecular sieve having a high silica-to-alumina ratio. The method provides a phase-pure Y type molecular sieve having a high crystallinity, the SiO.sub.2/Al.sub.2O.sub.3 thereof being not less than 6.

    Claims

    1. A method for preparing a Y type molecular sieve having a SiO.sub.2/Al.sub.2O.sub.3 ratio of 6 or more, wherein the Y type molecular sieve is prepared by using a compound containing a tetraalkylammonium cation as a template agent, the compound containing a tetraalkylammonium cation has a chemical structural formula as represented by formula (1): ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently selected from an alkyl group having a carbon atom number of 1 to 10; X.sup.−m represents an m-valent negative ion; and m is any one selected from 1, 2, and 3.

    2. The method according to claim 1, wherein, in said formula (1), R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently selected from an alkyl group having a carbon atom number of 1 to 5; and X.sup.−m is at least one selected from the group consisting of OH.sup.−, BF.sub.4.sup.−, F.sup.−, Cl.sup.−, Br.sup.−, I.sup.−, NO.sub.3.sup.−, H.sub.2PO.sub.3.sup.−, HPO.sub.3.sup.2−, PO.sub.3.sup.3−, SO.sub.4.sup.2−, and HSO.sub.4.sup.−.

    3. The method according to claim 1, wherein, the compound containing a tetraalkylammonium cation is at least one selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammoniumtetrafluoroborate, tetrabutyl ammonium hydroxide, tetramethylammonium hydroxide, and tetrapropyl ammonium hydroxide.

    4. The method according to claim 1, comprising at least the following steps: a) mixing deionized water, a silicon source, an aluminum source, an alkali source, and the compound containing a tetraalkylammonium cation to obtain an initial gel mixture having the following molar ratios: SiO.sub.2/Al.sub.2O.sub.3=6-20; alkali source/Al.sub.2O.sub.3=1-8, wherein the mole number of the alkali source is based on the mole number of oxides of metal elements in the alkali source; H.sub.2O/Al.sub.2O.sub.3=100-400; and compound containing a tetraalkylammoniumcation/Al.sub.2O.sub.3=0.1-6, wherein the mole number of the compound containing a tetraalkylammoniumcation is based on the mole number of nitrogen element in the compound; and b) after aging the initial gel mixture obtained in step a), feeding the gel mixture into a high pressure synthesis kettle, closing the kettle, performing crystallization at 70-130° C. for 1-30 days, washing, and drying to obtain the Y type molecular sieve.

    5. The method according to claim 4, wherein, in said step b), the initial gel mixture is aged at a temperature of no more than 50° C. for 1-100 hours and then fed into the high pressure synthesis kettle.

    6. The method according to claim 4, wherein, in said step a), the silicon source is at least one selected from the group consisting of silica sol, activated silica, and orthosilicate; the aluminum source is at least one selected from the group consisting of sodium aluminate, activated alumina, and aluminum alkoxide; and the alkali source is sodium hydroxide and/or potassium hydroxide.

    7. The method according to claim 4, wherein, in said step b), the initial gel mixture is aged at a temperature of 10-50° C. for 8-72 hours and then fed into the high pressure synthesis kettle.

    8. The method according to claim 4, wherein, in said step b), the crystallization temperature is 80-120° C. and the crystallization time is 3-20 days.

    9. The method according to claim 4, wherein, in said step b), the crystallization is performed in a static or dynamic state.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0044] FIG. 1 is X-ray diffraction spectrum of sample 1.

    [0045] FIG. 2 is a scanning electron microscope (SEM) photograph of sample 1.

    [0046] FIG. 3 is a silicon nuclear magnetic resonance spectrum (.sup.29Si-NMR) of sample 1.

    DESCRIPTION OF EMBODIMENTS

    [0047] The present application will be described in detail below by Examples, but the present application is not limited to these Examples.

    [0048] In the present application, 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, and 533. By comparing to the crystallinity of sample 1, which is 100%, the relative crystallinities of other samples are obtained.

    [0049] In the present application, SU8020 scanning electron microscope of Hitachis is used in SEM morphologic analysis of the product.

    [0050] In the present application, the silica-to-alumina ratio of the product is measured by using Magix 2424 X-ray fluorescence analyzer (XRF) of Philips Corporation.

    [0051] In the present invention, 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 9.4T. The silica-to-alumina ratio of the product may also be calculated from the result of .sup.29Si MAS NMR, according to the following equation:


    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)

    [0052] 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.

    Example 1. Preparation of Samples 1-41

    [0053] A compound containing a tetraalkylammonium cation and an alkali source were dissolved in deionized water, an aluminum source was then added and stirred until a clarified liquid was obtained; then a silicon source was further added, and an initial gel mixture was obtained after homogeneously mixing; 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.

    [0054] The high pressure synthesis kettle was closed and placed in an oven, and crystallization was performed under an autogenic pressure for a period of time. 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 sample.

    [0055] Nos. of the obtained samples, types and molar amounts of respective raw materials, crystallization temperature, and crystallization time, were detailed shown in Table 1.

    TABLE-US-00001 TABLE 1 Type and amount Aluminum Silicon Alkali of compound source and source and source and Crystal- Crystal- Relative containing tetra- mole number mole number mole number lization lization Type of crystal- XRF NMR Sample alkylammonium of Al.sub.2O.sub.3 SiO.sub.2 of Na.sub.2O/K.sub.2O temperature time crystal linity (SiO.sub.2/ (SiO.sub.2/ No. cation contained contained contained H.sub.2O (° C.) (day) structure (%) Al.sub.2O.sub.3) Al.sub.2O.sub.3) 1 TEAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 7.2 6.9 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 2 TEAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.5 6.3 0.01 mol aluminate 1.2 mol  0.5 mol molecular 0.10 mol sieve 3 TEAOH Sodium Silica sol NaOH 10 mol 110 7 Y type 100 6.2 6.1 0.18 mol aluminate 0.6 mol  0.1 mol molecular 0.10 mol sieve 4 TEAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.5 6.3 0.18 mol aluminate 1.0 mol  0.1 mol molecular 0.10 mol sieve 5 TEAOH Sodium Silica sol NaOH 30 mol 110 7 Y type 100 6.8 6.6 0.30 mol aluminate 1.5 mol 0.25 mol molecular 0.10 mol sieve 6 TEAOH Sodium Silica sol NaOH 40 mol 110 7 Y type 100 6.8 6.6 0.60 mol aluminate 2.0 mol  0.8 mol molecular 0.10 mol sieve 7 TEAOH Sodium Silica sol NaOH 22 mol 70 30 Y type 85 6.2 6.1 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 8 TEAOH Sodium Silica sol NaOH 22 mol 80 20 Y type 85 6.2 6.1 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 9 TEAOH Sodium Silica sol NaOH 22 mol 90 15 Y type 90 6.4 6.2 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 10 TEAOH Sodium Silica sol NaOH 22 mol 100 10 Y type 100 6.8 6.6 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 11 TEAOH Sodium Silica sol NaOH 22 mol 120 5 Y type 100 7.2 6.9 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 12 TEAOH Sodium Silica sol NaOH 22 mol 130 1 Y type 90 6.5 6.2 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 13 TEAOH Sodium Activated NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate silica 0.25 mol molecular 0.10 mol 1.2 mol sieve 14 TEAOH Sodium Orthosilicate NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.25 mol molecular 0.10 mol sieve 15 TEAOH Activated Silica sol KOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol alumina 1.2 mol 0.25 mol molecular 0.10 mol sieve 16 TEAOH Aluminum Silica sol KOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol alkoxide 1.2 mol 0.25 mol molecular 0.10 mol sieve 17 TEACl Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 18 TEACl Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.2 6.1 0.18 mol aluminate 1.2 mol  0.5 mol molecular 0.10 mol sieve 19 TEACl Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.5 6.2  0.6 mol aluminate 2.0 mol  0.8 mol molecular 0.10 mol sieve 20 TEACl Sodium Silica sol NaOH 22 mol 70 30 Y type 80 6.2 6.1 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 21 TEACl Sodium Silica sol NaOH 22 mol 130 1 Y type 95 6.5 6.2 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 22 TEACl Sodium Activated NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate silica 0.35 mol molecular 0.10 mol 1.2 mol sieve 23 TEACl Activated Silica sol KOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol alumina 1.2 mol   0.1 mol + molecular 0.10 mol NaOH sieve 0.25 mol 24 TEABr Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 25 TEABr Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.2 6.1 0.18 mol aluminate 1.2 mol  0.5 mol molecular 0.10 mol sieve 26 TEABr Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.5 6.2  0.6 mol aluminate 2.0 mol  0.8 mol molecular 0.10 mol sieve 27 TEABr Sodium Silica sol NaOH 22 mol 70 30 Y type 80 6.2 6.1 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 28 TEABr Sodium Silica sol NaOH 22 mol 130 1 Y type 95 6.5 6.2 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 29 TEABr Sodium Activated NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate silica 0.35 mol molecular 0.10 mol 1.2 mol sieve 30 TEABr Activated Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol alumina 1.2 mol 0.35 mol molecular 0.10 mol sieve 31 TEAI Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 32 TEABF.sub.4 Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 33 TEABF.sub.4 Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.2 6.1 0.18 mol aluminate 1.2 mol  0.5 mol molecular 0.10 mol sieve 34 TEABF.sub.4 Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.5 6.2  0.6 mol aluminate 2.0 mol  0.8 mol molecular 0.10 mol sieve 35 TEABF.sub.4 Sodium Silica sol NaOH 22 mol 70 30 Y type 80 6.2 6.1 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 36 TEABF.sub.4 Sodium Silica sol NaOH 22 mol 130 1 Y type 95 6.5 6.2 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 37 TEABF.sub.4 Sodium Activated NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate silica 0.35 mol molecular 0.10 mol 1.2 mol sieve 38 TEABF.sub.4 Activated Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.6 0.18 mol alumina 1.2 mol 0.35 mol molecular 0.10 mol sieve 39 TMAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 40 TPAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.7 6.4 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 41 TBAOH Sodium Silica sol NaOH 22 mol 110 7 Y type 100 6.8 6.5 0.18 mol aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve 42 — Sodium Silica sol NaOH 22 mol 110 7 Y type 70 5.4 5.1 aluminate 1.2 mol 0.35 mol molecular 0.10 mol sieve

    Comparative Example 1. Preparation of Sample 42

    [0056] The synthesis process, raw material formulations, and the analysis process were the same as those of Example 1, except that tetraethylammonium hydroxide was not added in the initial gel, and the obtained sample was denoted by sample 42. As for specific raw material formulations, conditions of crystallization reaction, and analytical results, details can be seen in Table 1.

    Example 2. XRD Structure Characterization of Samples 1-42

    [0057] Samples 1-42 were characterized using X-ray powder diffraction. The results showed that all of samples 1-42 had structural characteristics of a Y type molecular sieve. Taking sample 1 as a typical representative, the XRD diffraction data result thereof was shown in Table 2 and the XRD spectrum was shown in FIG. 1. X-ray powder diffraction data results of samples 2-42 were all 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.

    [0058] The relative crystallinity of the sample was calculated based on the sum of XRD peak intensities of crystal planes 111, 331, 533. By comparing to the crystallinity of the sample 1, which was 100%, the relative crystallinities of other samples were obtained.

    TABLE-US-00002 TABLE 2 XRD result of sample 1 No. 2θ d (Å) 100 × I/I.sup.0 1 6.194 14.26957 100 2 10.1407 8.72308 26.18 3 11.8979 7.43842 6.14 4 12.4092 7.13307 0.63 5 15.6745 5.65369 47.47 6 17.6158 5.0348 0.53 7 18.7174 4.74087 15.69 8 20.3974 4.35403 14.99 9 22.8376 3.89404 3.79 10 23.6939 3.7552 34.54 11 25.0653 3.55277 0.62 12 25.8287 3.44948 2.53 13 27.1013 3.29031 16.62 14 27.8352 3.20522 1.27 15 29.7052 3.00755 4.2 16 30.8127 2.90193 8.1 17 31.4627 2.84346 16.22 18 32.5277 2.75274 4.91 19 33.1534 2.70221 2.08 20 34.1594 2.6249 6.63 21 34.7572 2.58111 3.88 22 35.7072 2.51459 0.77 23 36.3146 2.47391 0.41 24 37.2516 2.41381 0.85 25 37.9873 2.36874 3.56 26 39.5125 2.28075 0.19 27 40.6606 2.21896 1.34 28 41.5084 2.17558 2.35 29 42.0199 2.15027 1.27 30 42.8813 2.10905 0.47 31 43.3394 2.08782 2.31 32 44.1624 2.0508 1.81 33 45.9746 1.97409 0.32

    Example 3

    [0059] Morphological characterization was performed on samples 1-41 using a scanning electron microscope. The results showed that most of them were octahedral crystal grains and had particle sizes in a range of 0.5 μm to 30 μm. Taking sample 1 as a typical representative, it had a scanning electron microscope photograph as shown in FIG. 2 and a particle size in a range of 1 μm to 20 μm.

    Example 4

    [0060] The silica-to-alumina ratios of samples 1-42 were measured using an X-ray fluorescence analyzer (XRF), and details of results were shown in the column “XRF (SiO.sub.2/Al.sub.2O.sub.3)” in Table 1.

    [0061] Samples 1-42 were measured using silicon nuclear magnetic resonance (.sup.29Si MAS NMR) and the silica-to-alumina ratios in backbones were obtained by calculation, the details of results being shown in the column “NMR (SiO.sub.2/Al.sub.2O.sub.3)” in Table 1. The results of silicon nuclear magnetic resonance spectra (.sup.29Si-NMR) of samples 1-41 were similar, and the .sup.29Si-NMR of sample 1 as a typical representative was shown in FIG. 3.

    [0062] As seen from the results of above Table 1, all of the Y type molecular sieve samples 1-41 synthesized according to the method of the present disclosure had silica-to-alumina ratios, either silica-to-alumina ratios of the product determined by XRF method or silica-to-alumina ratios in the backbone of the product determined by silicon nuclear magnetic resonance spectrum data, of no less than 6. For sample 42 synthesized in Comparative Example without use of tetraalkylammonium cation, however, both the crystallinity and the silica-to-alumina ratio were lower than those of samples 1-41. According to the study on catalytic cracking process, the Y type molecular sieve having a high crystallinity and a high silica-to-alumina ratio can significantly improve the catalytic cracking in terms of activity and stability.

    [0063] Although the present application has been disclosed as above by means of preferred examples, these examples are not intended to limit the claims. Several possible variations and modifications may be made by any person skilled in the art without departing from the concept of the present application. Therefore, the protection scope of the present application should be defined by the claims of the present application.