Boro-silicate molecular sieve and its rapid preparation method
By using [B]-MFI borosilicate molecular sieves as silicon and boron sources, borosilicate molecular sieves with various topologies can be rapidly synthesized, solving the problems of long synthesis time and high equipment requirements in traditional methods, and realizing efficient synthesis of borosilicate molecular sieves and excellent catalytic performance.
Patent Information
- Application Number
- CN202211367271.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-11-02
- Publication Date
- 2025-12-23
- Estimated Expiration
- 2042-11-02
AI Technical Summary
Existing methods for synthesizing borosilicate molecular sieves are lengthy and require sophisticated equipment, lacking versatility and making it difficult to achieve rapid synthesis and a wide variety of silicon and boron sources.
Using [B]-MFI borosilicate molecular sieves as silicon and boron sources, borosilicate molecular sieves with different topologies were rapidly synthesized through a simple mixing, heating and crystallization process, shortening the crystallization time to 1-4 days.
Rapid synthesis of borosilicate molecular sieves was achieved, simplifying the synthesis steps. Furthermore, borosilicate molecular sieves with various topologies were provided, which exhibited high conversion rates and olefin selectivity when used as catalysts for acid-catalyzed reactions.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a boron-silicon molecular sieve and a rapid preparation method thereof, and belongs to the field of molecular sieve synthesis. BACKGROUND
[0002] Molecular sieves are a class of inorganic porous crystalline materials with different size channels or cage structures composed of TO4 tetrahedrons. Due to its unique channel structure, good hydrothermal stability and suitable acidity, it is widely used in adsorption separation, ion exchange, catalysis and other petroleum and chemical industries. Among them, boron-silicon molecular sieves have unique weak acidity and excellent catalytic performance in Beckmann rearrangement, propane dehydrogenation and other reactions. At the same time, B atoms are relatively easy to remove, and after removing boron from silicon-boron molecular sieves, aluminum can be inserted into the site after boron removal to realize accurate regulation of strong B acid sites (Si-OH-Al).
[0003] At present, among the 255 molecular sieve framework structures certified by the International Molecular Sieve Association, only 28 framework structures have been reported to be able to synthesize boron-silicon molecular sieves. And the synthesis methods of these boron-silicon molecular sieves are mainly concentrated in traditional hydrothermal synthesis, and the crystallization time is also relatively long. Saleh Elomari et al. prepared B-SSZ-56 by crystal transformation method, and Stacey I. Zones et al. also prepared B-SSZ-24 and B-SSZ-33 by crystal transformation method (Microporous and Mesoporous Materials 2009, 118, 325-333; Microporous Materials 1994, 2, 543-555), but the crystallization time is still relatively long, such as [B]-beta crystal transformation to generate SSZ-56 needs 12-18 days. And the mother material used in the preparation of B-SSZ-56, B-SSZ-24 and SSZ-33 by crystal transformation method is [B]-beta. In addition, Rajib Bandyopadhyay et al. realized the synthesis of [B]-BEA, [B]-MFI and [B]-MTW by dry gel conversion method, but the dry gel conversion method has high requirements for production equipment in practical application, and the application of dry gel conversion method is less at present, which is not universal (Sugi, Microporous and Mesoporous Materials 1999, 32, 81-91). Therefore, it is an urgent technical problem to synthesize boron-silicon molecular sieves with shorter crystallization time and rich types of silicon source and boron source. SUMMARY
[0004] According to a first aspect of the present application, there is provided a borosilicate molecular sieve, the borosilicate molecular sieve having different topologies, including but not limited to borosilicate molecular sieves having ERI, TUN, MSE, CON, *BEA, MTW, IWV, SSZ-43 and ITQ-58 framework structures.
[0005] A borosilicate molecular sieve, the borosilicate molecular sieve having an anhydrous chemical composition as shown in Formula I:
[0006] kM·mR·(Si x B y )O2 Formula I wherein M represents an inorganic cation, and R represents a template;
[0007] k represents the number of moles of inorganic cation M corresponding to each mole of (Si x B y )O2, k = 0.01-0.06;
[0008] m represents the number of moles of template R corresponding to each mole of (Si x B y )O2, m = 0.01-0.10;
[0009] x, y respectively represent the mole fraction of Si, B corresponding to (Si x B y )O2, and range respectively x = 0.75-0.95, y = 0.05-0.25, and x + y = 1.
[0010] Optionally, the template R in Formula I is selected from at least one of 1,4-bis(N- trimethyl)butanediyl dimmonium hydroxide, 1,4-bis(N-methylpyrrolidine)butanediyl dimmonium hydroxide, 1,4-bis(N-methylpiperidine)butanediyl dimmonium hydroxide, 1,4-bis(N- cyclohexylpyrrolidine)butanediyl dimmonium hydroxide, 1,4-bis(1,2,4,5 tetramethylimidazole)butanediyl dimmonium hydroxide, 1,4-bis(1,2 dimethylimidazole)butanediyl dimmonium hydroxide, 1,4-(1,4-diazabicyclo[2.2.2]octane)butanediyl dimmonium hydroxide, 1,4-bis(P-trimethylammonio)butanediyl diphosphonium hydroxide, 1,5-bis(N-methylpyrrolidine)pentanediyl dimmonium hydroxide, and 1,5-bis(N-methylpiperidine)pentanediyl dimmonium hydroxide.
[0011] Optionally, the inorganic cation M in Formula I is an alkali metal ion.
[0012] Optionally, the alkali metal ion is selected from Li + , Na + , K + , Rb + , Cs+ at least one of the group consisting of ERI, TUN, MSE, CON, *BEA, MTW, IWV, SSZ-43, ITQ-58.
[0013] Optionally, the framework structure of the borosilicate molecular sieve is selected from one of the group consisting of ERI, TUN, MSE, CON, *BEA, MTW, IWV, SSZ-43, ITQ-58.
[0014] The borosilicate molecular sieve with ERI framework structure ([B]-ERI) is of formula I, wherein the template R is preferably 1,4-bis(N-trimethyl)butane diammonium hydroxide, and M is preferably K + .
[0015] The particles of [B]-ERI are shuttle-like rods of about 5 μm in length.
[0016] The borosilicate molecular sieve with TUN framework structure ([B]-TUN) is of formula I, wherein the template R is preferably 1,4-bis(N-methylpyrrolidine)butane diammonium hydroxide, and M is preferably Na + .
[0017] The primary particles of [B]-TUN are rod-like particles of 1 x 0.5 x 0.2 μm in size.
[0018] The borosilicate molecular sieve with MSE framework structure ([B]-MSE) is of formula I, wherein the template R is preferably 1,4-bis(N-methylpiperidine)butane diammonium hydroxide, and M is preferably Na + and K + .
[0019] The particles of [B]-MSE are round discs of 100 nm in diameter and 20 nm to 50 nm in thickness.
[0020] The borosilicate molecular sieve with CON framework structure ([B]-CON) is of formula I, wherein the template R is preferably 1,4-bis(N-cyclohexylpyrrolidine)butane diammonium hydroxide, and M is preferably Na + .
[0021] The particles of [B]-CON are shuttle-like rods of 2 x 0.5 x 0.2 μm in size.
[0022] The borosilicate molecular sieve with IWV framework structure ([B]-IWV) is of formula I, wherein the template R is preferably 1,4-bis(1,2,4,5 tetramethylimidazole)butane diammonium hydroxide, and M is preferably Na + .
[0023] The particles of [B]-IWV are stacked discs.
[0024] The borosilicate molecular sieve with the SSZ-43 framework structure ([B]-SSZ-43), wherein the template R in the formula I is preferably 1,4-bis(1,2,4,5 tetramethylimidazole)butane diammonium hydroxide, and M is preferably Na + .
[0025] The particles of the [B]-SSZ-43 are rod-shaped and stacked in a size of about 1.5 x 0.2 x 0.2 μm.
[0026] The borosilicate molecular sieve with the ITQ-58 framework structure ([B]-ITQ-58), wherein the template R in the formula I is preferably 1,4-bis(P-tridimethylamino)butane diphosphonium hydroxide, and M is preferably Na + .
[0027] The particles of the [B]-ITQ-58 are irregularly shaped and stacked in a size of about 2 μm.
[0028] Optionally, the number of moles k of inorganic cations corresponding to each mole of (Si x B y )O2 is independently selected from any value or a range value between any two values of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06.
[0029] Optionally, the number of moles m of template R corresponding to each mole of (Si x B y )O2 is independently selected from any value or a range value between any two values of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10.
[0030] According to a second aspect of the present application, a method for preparing a borosilicate molecular sieve is provided, which utilizes [B]-MFI borosilicate molecular sieve as a silicon source and a boron source for the first time to rapidly synthesize a series of borosilicate molecular sieves with different topological structures. The method can simply and efficiently shorten the crystallization time of the borosilicate molecular sieve to 1-4 days.
[0031] The method for preparing the borosilicate molecular sieve described above comprises the following steps:
[0032] S1, stirring a mixture containing a silicon source, a boron source, a template R, an inorganic base and water to obtain an initial gel mixture;
[0033] S2, placing the initial gel mixture in a sealed container to react to obtain a borosilicate molecular sieve.
[0034] Optionally, heating is performed after step S1.
[0035] Optionally, after heating, the gel mixture has the following gel ratio:
[0036] 1SiO2:aB2O3:bR:cMOH:dH2O;
[0037] a, b, c, d represent the molar ratio of B2O3 / SiO2, R / SiO2, MOH / SiO2, H2O / SiO2, respectively, and the range of a = 0.10-0.50, b = 0.10-0.50, c = 0.10-1.0, d = 5-50;
[0038] wherein the water is in terms of its own moles, the silicon source is in terms of moles of SiO2, the boron source is in terms of moles of B2O3, the inorganic base is in terms of its own moles of MOH, and the template R is in terms of its own moles of R.
[0039] Optionally, the molar ratio of B2O3 / SiO2, a, is independently selected from any value or a range between any two values of 0.10, 0.12, 0.16, 0.18, 0.20, 0.22, 0.25, 0.28, 0.30, 0.33, 0.36, 0.40, 0.45, 0.50.
[0040] Optionally, the molar ratio of R / SiO2, b, is independently selected from any value or a range between any two values of 0.10, 0.12, 0.15, 0.16, 0.18, 0.20, 0.22, 0.25, 0.28, 0.30, 0.33, 0.35, 0.37, 0.40, 0.42, 0.45, 0.50.
[0041] Optionally, the molar ratio of MOH / SiO2, c, is independently selected from any value or a range between any two values of 0.10, 0.12, 0.15, 0.18, 0.20, 0.25, 0.30, 0.33, 0.35, 0.40, 0.45, 0.50, 0.55, 0.62, 0.75, 0.83, 0.90, 1.0.
[0042] Optionally, the molar ratio of H2O / SiO2, d, is independently selected from any value or a range between any two values of 5, 6.5, 10, 13, 15, 18, 20, 25, 28, 33, 35, 38, 42, 45, 50.
[0043] Optionally, the silicon source is selected from at least one of silica sol, white carbon black, silica gel, water glass, orthosilicate, [B]-MFI borosilicate molecular sieve.
[0044] Optionally, the boron source is selected from at least one of boric acid, sodium borate decahydrate, boron oxide, [B]-MFI borosilicate molecular sieve.
[0045] Optionally, the inorganic base is selected from at least one of LiOH, NaOH, KOH, RbOH, CsOH.
[0046] Optionally, in step S2, the reaction is carried out under the following conditions:
[0047] The temperature is 130-200°C.
[0048] The time is 6-96h.
[0049] Optionally, the time is 24-96h.
[0050] Optionally, the temperature is independently selected from any value or a range between any two values selected from 130°C, 140°C, 150°C, 160°C, 170°C, 175°C, 180°C, 185°C, 190°C, 200°C.
[0051] Optionally, the time is independently selected from any value or a range between any two values selected from 6h, 12h, 18h, 24h, 36h, 48h, 72h, 96h.
[0052] Optionally, the method comprises the following steps:
[0053] A1. stirring a mixture containing a silicon source, a boron source, a template agent R, an inorganic base, and water to obtain an initial gel mixture;
[0054] A2. heating the initial gel mixture obtained in step A1 to remove excess water to obtain a final gel mixture;
[0055] A3. placing the final gel mixture in a sealed container and crystallizing under rotating or static conditions, the crystallization temperature being 130-200°C and the crystallization time being 6-96h;
[0056] A4. after the crystallization is completed, separating and washing the solid product to obtain a boron-silicon molecular sieve.
[0057] Optionally, the sealed container is a high-pressure synthesis kettle.
[0058] According to a third aspect of the present application, a kind of acid catalytic reaction catalyst is provided.
[0059] A kind of acid catalytic reaction catalyst, the mixture containing boron-silicon molecular sieve is calcined under 500-700°C air atmosphere to obtain;
[0060] The boron-silicon molecular sieve is selected from the above-mentioned boron-silicon molecular sieve and / or the boron-silicon molecular sieve obtained by the above-mentioned preparation method.
[0061] Optionally, the calcination time is 3-5 hours.
[0062] Optionally, the acid catalytic reaction catalyst is the borosilicate molecular sieve with TUN, MSE framework structure or the borosilicate molecular sieve with TUN, MSE framework structure prepared by the method described above, which is obtained by calcining at 500-700 DEG C in air.
[0063] Optionally, the acid catalytic reaction is propane oxidative dehydrogenation reaction (ODPH).
[0064] Optionally, the acid catalyst is used in ODPH reaction, the propane conversion rate is above 30%, and the olefin (propylene and ethylene) selectivity is above 80%.
[0065] The beneficial effects that can be produced by the present application include:
[0066] 1) The borosilicate molecular sieve provided by the present application has ERI, TUN, MSE, CON, *BEA, MTW, IWV, SSZ-43 and ITQ-58 framework structures.
[0067] 2) The preparation method of the borosilicate molecular sieve provided by the present application has a simple synthesis process, effectively simplifies the steps of synthesizing the borosilicate molecular sieve, and shortens the crystallization time to 1-4 days.
[0068] 3) The acid catalytic reaction catalyst provided by the present application has high conversion rate and olefin selectivity; and is used in ODPH reaction, the propane conversion rate is above 30%, and the olefin (propylene and ethylene) selectivity is above 80%. BRIEF DESCRIPTION OF DRAWINGS
[0069] Figure 1 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 1 of the present application.
[0070] Figure 2 is the scanning electron microscope graph (SEM) of the product obtained in Example 1 of the present application.
[0071] Figure 3 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 2 of the present application.
[0072] Figure 4 is the scanning electron microscope graph (SEM) of the product obtained in Example 2 of the present application.
[0073] Figure 5 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 3 of the present application.
[0074] Figure 6 is the scanning electron microscope graph (SEM) of the product obtained in Example 3 of the present application.
[0075] Figure 7is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 4 of the present application.
[0076] Figure 8 is the scanning electron microscope graph (SEM) of the product obtained in Example 4 of the present application.
[0077] Figure 9 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 5 of the present application.
[0078] Figure 10 is the scanning electron microscope graph (SEM) of the product obtained in Example 5 of the present application.
[0079] Figure 11 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 6 of the present application.
[0080] Figure 12 is the scanning electron microscope graph (SEM) of the product obtained in Example 6 of the present application.
[0081] Figure 13 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 7 of the present application.
[0082] Figure 14 is the scanning electron microscope graph (SEM) of the product obtained in Example 7 of the present application.
[0083] Figure 15 is the X-ray powder diffraction spectrum (XRD) of the product obtained in Example 8 of the present application.
[0084] Figure 16 is the scanning electron microscope graph (SEM) of the product obtained in Example 8 of the present application. DETAILED DESCRIPTION
[0085] The present application will be described in detail below with reference to Examples, but the present application is not limited to these Examples.
[0086] The raw materials in the Examples of the present application are all purchased through commercial channels unless otherwise specified.
[0087] The analysis method in the Examples of the present application is as follows:
[0088] The sample phase analysis adopts X-ray powder diffraction (XRD) analysis, and the instrument used is X’Pert PRO X-ray diffractometer of PANalytical Company in the Netherlands, using Cu target, Kα light source 40KV voltage, 40mA current.
[0089] The sample morphology was analyzed by scanning electron microscopy (SEM), and the instrument used was a Hitachi SU8020 field emission scanning electron microscope.
[0090] The sample composition was analyzed by TAQ-600 thermal analyzer and PerkinElmer ICP-OES 7300DV inductively coupled plasma optical emission spectrometer (ICP-OES).
[0091] In the embodiments of the present application, the conversion rate and selectivity were calculated as follows:
[0092] In the embodiments of the present application, the propane conversion rate (%) = the number of moles of products / the total number of moles of propane;
[0093] The total selectivity of olefins (propylene + ethylene) (%) = (the number of moles of propylene + the number of moles of ethylene) / the number of moles of propane conversion.
[0094] Preparation of sample 1 of example 1
[0095] After 3.14 g of white carbon black, 1.294 g of H3BO3 (99.5%), 10.168 g of tetrapropylammonium hydroxide (25%) and 28.414 g of H2O were mixed and stirred uniformly, 0.06 g of pure silicon MFI molecular sieve was added as seed crystal, and the mixture was continuously stirred for 30 minutes, then the mixture was moved to a stainless steel high-pressure reaction kettle, and static crystallization was carried out at 175°C for 72 hours under autogenous pressure. After the crystallization was completed, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 1. The X-ray powder diffraction pattern (XRD) of sample 1 is shown in Figure 1 , which shows that sample 1 is a borosilicate molecular sieve with MFI framework structure ([B]-MFI). The scanning electron microscope photograph (SEM) is shown in Figure 2 , which shows that the [B]-MFI particles are spherical with a diameter of about 2 μm.
[0096] Preparation of sample 2 of example 2
[0097] After 0.516 g of [B]-MFI borosilicate molecular sieve, 0.184 g of H3BO3 (99.5%), 2.168 g of 1,4-bis(N-trimethyl)butane diammonium hydroxide (12% aqueous solution) and 0.165 g of KOH (85%) were mixed and stirred uniformly, the mixture was heated in a water bath at 80°C to remove 0.931 g of water, then the mixture was moved to a stainless steel high-pressure reaction kettle, and dynamic crystallization was carried out at 140°C (rotation speed 30 rpm / min) for 24 hours under autogenous pressure. After the crystallization was completed, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 2. The X-ray powder diffraction pattern (XRD) of sample 2 is shown in Figure 3As shown, sample 2 is a borosilicate molecular sieve with ERI framework structure ([B]-ERI). Scanning electron micrograph (SEM) is shown in Figure 2. Figure 4 As shown, the particles of [B]-ERI are shuttle-like rods with a length of about 5 μm.
[0098] Preparation of sample 3 in Example 3
[0099] A mixture of 0.516 g of [B]-MFI borosilicate molecular sieve, 2.442 g of 1,4-bis(N- methylpyrrolidinium) butane dihydroxide (13.3% aqueous solution), and 0.119 g of NaOH (98%) was stirred until homogeneous and heated in a 80 °C water bath to remove 0.615 g of water. The mixture was then transferred to a stainless steel autoclave and crystallized at 175 °C for 2 days under autogenous pressure. After the crystallization was complete, the solid product was centrifuged, washed, and dried in air at 120 °C to give sample 3. The X-ray powder diffraction pattern (XRD) of sample 3 is shown in Figure 3. Figure 5 As shown, sample 3 is a borosilicate molecular sieve with TUN framework structure ([B]-TUN). Scanning electron micrograph (SEM) is shown in Figure 4. Figure 6 As shown, [B]-TUN is rod-like particles with a size of about 1 x 0.5 x 0.2 μm.
[0100] Preparation of sample 4 in Example 4
[0101] A mixture of 0.516 g of [B]-MFI borosilicate molecular sieve, 0.081 g of H3BO3 (99.5%), 3.038 g of 1,4-bis(N-methylpiperidinium) butane dihydroxide (11.87% aqueous solution), 0.051 g of NaOH (98%), and 0.082 g of KOH (85%) was stirred until homogeneous and heated in a 80 °C water bath to remove 1.176 g of water. The mixture was then transferred to a stainless steel autoclave and crystallized at 175 °C for 2 days under autogenous pressure. After the crystallization was complete, the solid product was centrifuged, washed, and dried in air at 120 °C to give sample 4. The X-ray powder diffraction pattern (XRD) of sample 4 is shown in Figure 5. Figure 7 As shown, sample 4 is a borosilicate molecular sieve with MSE framework structure ([B]-MSE). Scanning electron micrograph (SEM) is shown in Figure 6. Figure 8 As shown, the particles of [B]-MSE are short cylindrical rods with a diameter of about 100 nm and a thickness of about 20-50 nm.
[0102] Preparation of sample 5 in Example 5
[0103] 0.516 g of [B]-MFI borosilicate molecular sieve, 0.012 g of H3BO3 (99.5%), 6.162 g of 1,4-bis(N-cyclohexylpyrrolidine)butane diammonium hydroxide (13.41% aqueous solution), and 0.085 g of NaOH (98%) were mixed and stirred until homogeneous. The mixture was then heated in an 80°C water bath to remove 4.360 g of water. The mixture was then transferred to a stainless steel high-pressure reactor and dynamically crystallized at 160°C (40 rpm / min) under autogenous pressure for 4 days. After crystallization, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 5. The X-ray powder diffraction (XRD) pattern of sample 5 is shown below. Figure 9 As shown, sample 5 is a borosilicate molecular sieve ([B]-CON) with a CON framework structure. Scanning electron microscopy (SEM) images are shown below. Figure 10 As shown, the [B]-CON particles are spindle-shaped rods, with a size of approximately 2 × 0.5 × 0.2 μm.
[0104] Preparation of Sample 6 in Example 6
[0105] 0.516 g of [B]-MFI borosilicate molecular sieve, 0.029 g of H3BO3 (99.5%), 5.4245 g of 1,4-bis(1,2,4,5-tetramethylimidazolium)butane diammonium hydroxide (7.8% aqueous solution), and 0.085 g of NaOH (98%) were mixed and stirred until homogeneous. The mixture was then heated in an 80°C water bath to remove 2.748 g of water. The mixture was then transferred to a stainless steel high-pressure reactor and dynamically crystallized at 160°C (40 rpm / min) under autogenous pressure for 4 days. After crystallization, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 6. The X-ray powder diffraction (XRD) pattern of sample 6 is shown below. Figure 11 As shown, sample 6 is a borosilicate molecular sieve ([B]-IWV) with an IWV framework structure. Scanning electron microscopy (SEM) images are shown below. Figure 12 As shown, the [B]-IWV particles are stacked in a plate-like manner.
[0106] Example 7 Preparation of Sample 7
[0107] 0.516 g of [B]-MFI borosilicate molecular sieve, 4.051 g of 1,4-bis(1,2,4,5-tetramethylimidazolium)butane diammonium hydroxide (10.44% aqueous solution), and 0.085 g of NaOH (98%) were mixed and stirred until homogeneous. The mixture was then heated in an 80°C water bath to remove 1.375 g of water. The mixture was then transferred to a stainless steel high-pressure reactor and dynamically crystallized at 160°C (40 rpm / min) under autogenous pressure for 4 days. After crystallization, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 7. The X-ray powder diffraction (XRD) pattern of sample 7 is shown below. Figure 13As shown, it indicates that sample 7 is a borosilicate molecular sieve with SSZ-43 framework structure ([B]-SSZ-43). The scanning electron micrograph (SEM) is as shown in Figure 14 As shown, the particles of [B]-SSZ-43 are rod-like accumulation with a size of about 1.5 x 0.2 x 0.2 μm.
[0108] Preparation of sample 8 of Example 8
[0109] 0.516 g of [B]-MFI borosilicate molecular sieve, 0.081 g of H3BO3 (99.5%), 5.213 g of 1,4-bis(P-trimethylammonio)butane bisphosphonium hydroxide (9.99% aqueous solution) and 0.119 g of NaOH (98%) were mixed and stirred uniformly, and then placed in a 80°C water bath to remove 3.191 g of water. After that, the mixture was moved to a stainless steel high-pressure reactor, and crystallized under dynamic conditions at 150°C (rotation speed 40 rpm / min) for 2 days under autogenous pressure. After the crystallization was completed, the solid product was centrifuged, washed, and dried in air at 120°C to obtain sample 8. The X-ray powder diffraction pattern (XRD) of sample 8 is as shown in Figure 15 As shown, it indicates that sample 8 is a borosilicate molecular sieve with ITQ-58 framework structure ([B]-ITQ-58). The scanning electron micrograph (SEM) is as shown in Figure 16 As shown, the particles of [B]-ITQ-58 are block-like accumulation with a size of about 2 μm.
[0110] Preparation of samples 9-11 of Examples 9-11
[0111] The gel preparation process of Examples 9-11 is the same as that of Example 2, and the specific proportions of the ingredients and the crystallization conditions are shown in Table 1. The XRD pattern and SEM image of the obtained sample are similar to those of sample 2 prepared in Example 2. The phase identification results of the obtained sample are shown in Table 1.
[0112] Table 1: Proportions of ingredients and crystallization conditions of Examples 9-11
[0113] (The proportions of ingredients are as follows: 1 SiO2:aB2O3:bR:cMOH:dH2O, wherein a, b, c and d represent the molar ratios of B2O3 / SiO2, R / SiO2, MOH / SiO2 and H2O / SiO2, respectively)
[0114]
[0115] Preparation of samples 12-14 of Examples 12-14
[0116] The gel preparation process of Examples 12-14 is the same as that of Example 3, and the specific proportions of the ingredients and the crystallization conditions are shown in Table 2. The XRD pattern and SEM image of the obtained sample are similar to those of sample 3 prepared in Example 3. The phase identification results of the obtained sample are shown in Table 2.
[0117] Table 2: Table of ingredient ratio, crystallization condition of Examples 12-14
[0118] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, d represent molar ratio of B2O3 / SiO2, R / SiO2, MOH / SiO2, H2O / SiO2, respectively)
[0119]
[0120] Preparation of samples 15-18 of Examples 15-18
[0121] The gel preparation process of Examples 15-18 is the same as that of Example 4, and the specific ingredient ratio and crystallization condition are shown in Table 3. The XRD spectrum and SEM image of the obtained sample are similar to those of sample 4 prepared in Example 4. The phase identification results of the obtained sample are shown in Table 3.
[0122] Table 3: Table of ingredient ratio, crystallization condition of Examples 15-18
[0123] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, d represent molar ratio of B2O3 / SiO2, R / SiO2, MOH / SiO2, H2O / SiO2, respectively)
[0124]
[0125] Preparation of samples 19-21 of Examples 19-21
[0126] The gel preparation process of Examples 19-21 is the same as that of Example 5, and the specific ingredient ratio and crystallization condition are shown in Table 4. The XRD spectrum and SEM image of the obtained sample are similar to those of sample 5 prepared in Example 5. The phase identification results of the obtained sample are shown in Table 4.
[0127] Table 4: Table of ingredient ratio, crystallization condition of Examples 19-21
[0128] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, d represent molar ratio of B2O3 / SiO2, R / SiO2, MOH / SiO2, H2O / SiO2, respectively)
[0129]
[0130]
[0131] Preparation of samples 22-24 of Examples 22-24
[0132] The gel preparation process of Examples 22-24 was the same as that of Example 6, and the specific ingredient proportions and crystallization conditions are shown in Table 5. The XRD patterns and SEM images of the obtained samples were similar to those of sample 6 prepared in Example 6. The phase identification results of the obtained samples are shown in Table 5.
[0133] Table 5 Ingredient proportions and crystallization conditions of Examples 22-24
[0134] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, and d represent the molar ratios of B2O3 / SiO2, R / SiO2, MOH / SiO2, and H2O / SiO2, respectively)
[0135]
[0136] Preparation of samples 25-27 of Examples 25-27
[0137] The gel preparation process of Examples 25-27 was the same as that of Example 7, and the specific ingredient proportions and crystallization conditions are shown in Table 6. The XRD patterns and SEM images of the obtained samples were similar to those of sample 7 prepared in Example 7. The phase identification results of the obtained samples are shown in Table 6.
[0138] Table 6 Ingredient proportions and crystallization conditions of Examples 25-27
[0139] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, and d represent the molar ratios of B2O3 / SiO2, R / SiO2, MOH / SiO2, and H2O / SiO2, respectively)
[0140]
[0141]
[0142] Preparation of samples 28-30 of Examples 28-30
[0143] The gel preparation process of Examples 28-30 was the same as that of Example 8, and the specific ingredient proportions and crystallization conditions are shown in Table 7. The XRD patterns and SEM images of the obtained samples were similar to those of sample 8 prepared in Example 8. The phase identification results of the obtained samples are shown in Table 7.
[0144] Table 7 Ingredient proportions and crystallization conditions of Examples 28-30
[0145] (Ingredient gel ratio: 1 SiO2: a B2O3: b R: c MOH: d H2O, wherein a, b, c, and d represent the molar ratios of B2O3 / SiO2, R / SiO2, MOH / SiO2, and H2O / SiO2, respectively)
[0146]
[0147] Example 31 Catalytic ODPH reaction over calcined borosilicate molecular sieve
[0148] This example is used to illustrate the use of calcined borosilicate molecular sieve as a catalyst for ODPH reaction. However, the borosilicate molecular sieve of the present application is not limited to use as a catalyst for ODPH reaction.
[0149] The samples obtained in Examples 2 and 3 were calcined in air at 550°C for 4 hours, then tabletted and granulated to 40-60 mesh. 0.3 g of the sample was charged into a fixed bed reactor and evaluated for ODPH reaction. The reaction was started at 530°C with a feed gas composition of propane:air = 1:5, a propane flow rate of 5 ml / min and an air flow rate of 25 ml / min. The reaction products were analyzed by on-line gas chromatography. The typical experimental results are shown in Table 8. The results in Table 8 show that the conversion of propane in the catalytic ODPH reaction can reach 69.14% and the total selectivity to olefins (propylene + ethylene) can reach more than 80%. Similar catalytic results were obtained for other samples.
[0150] Table 8 ODPH evaluation results
[0151]
[0152] a Selectivity at 600 minutes of reaction time;
[0153] b Selectivity at 600 minutes of reaction time;
[0154] C1-C2° is alkane with carbon number from 1 to 2;
[0155] C2-C3 ＝ ethylene and propylene;
[0156] C 4+ N non-aromatic product with carbon number greater than 3.
[0157] The above description is only several embodiments of the present application and does not limit the present application in any form. Although the present application is disclosed with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed technical contents without departing from the scope of the present application, which are equivalent to the equivalent embodiments and belong to the scope of the technical solution.
Claims
1. A borosilicate molecular sieve characterized by, The anhydrous chemical composition of the boron-silicon molecular sieve is shown in formula I: kM.mR.(Si x B y )O2Formula I In formula I, M represents an inorganic cation, and R represents a template agent. k represents the number of moles of (Si x B y )O2 corresponds to the number of moles of inorganic cation M, k = 0.01 ~ 0.06; m represents the number of moles of (Si x B y )O2 corresponds to the number of moles of template R, m = 0.01 ~ 0.10; x, y respectively represent the molar fraction of Si, B corresponding to (Si x B y x, y respectively represent the molar fraction of Si, B corresponding to (Si 0.75 ~ 0.95, y = 0.05 ~ 0.25, and x + y = 1. In the boron-silicon molecular sieve, the silicon source and the boron source are [B]-MFI boron-silicon molecular sieves. In formula I, the template agent R is at least one of 1,4-bis(N-trimethyl)butane diammonium hydroxide, 1,4-bis(N-methylpyrrolidine)butane diammonium hydroxide, 1,4-bis(N-methylpiperidine)butane diammonium hydroxide, 1,4-bis(N-cyclohexylpyrrolidine)butane diammonium hydroxide, 1,4-bis(1,2,4,5 tetramethyl imidazole)butane diammonium hydroxide, 1,4-bis(1,2 dimethyl imidazole)butane diammonium hydroxide, 1,4-(1,4-diazabicyclo[2.2.2]octane)butane diammonium hydroxide, 1,4-bis(P-tridimethylamine)butane bisphosphonium hydroxide, 1,5-bis(N-methylpyrrolidine)pentane diammonium hydroxide, and 1,5-bis(N-methylpiperidine)pentane diammonium hydroxide.
2. The borosilicate molecular sieve of claim 1, wherein, In formula I, the inorganic cation M is an alkali metal ion.
3. The borosilicate molecular sieve of claim 2, wherein, The alkali metal ion is selected from at least one of Li + , Na + , K + , Rb + , Cs + .
4. The borosilicate molecular sieve of claim 1, wherein, The framework structure of the boron-silicon molecular sieve is selected from one of ERI, TUN, MSE, CON, *BEA, MTW, IWV, SSZ-43, and ITQ-58.
5. A process for the preparation of the borosilicate molecular sieve of any one of claims 1 to 4, characterized in that, The method comprises the following steps: S1, stirring a mixture containing a silicon source, a boron source, a template agent R, an inorganic base, and water to obtain an initial gel mixture; S2, reacting the initial gel mixture in a sealed container to obtain a boron-silicon molecular sieve.
6. The production method according to claim 5, wherein After step S1, heating is performed.
7. The production method according to claim 6, characterized by, After heating, the gel mixture has the following gel ratio: 1SiO2:aB2O3:bR:cMOH:dH2O; a, b, c, and d represent the molar ratios of B2O3 / SiO2, R / SiO2, MOH / SiO2, and H2O / SiO2, respectively, and range from a=0.10 to 0.50, b=0.10 to 0.50, c=0.10 to 1.0, and d=5 to 50; wherein the water is counted in terms of its own moles, the silicon source is counted in terms of moles of SiO2, the boron source is counted in terms of moles of B2O3, the inorganic base is counted in terms of its own moles of MOH, and the template agent R is counted in terms of its own moles of R.
8. The preparation method according to claim 5, characterized in that, The inorganic base is at least one of LiOH, NaOH, KOH, RbOH, and CsOH.
9. The preparation method according to claim 5, characterized in that, In step S2, the reaction conditions are as follows: The temperature is 130 ℃ to 200 ℃. The time is 6 h to 96 h.
10. The method of claim 5, wherein, In step S2, the reaction time is 24 h to 96 h.
11. The method of claim 5, wherein, The method comprises the following steps: A1, stirring a mixture containing a silicon source, a boron source, a template agent R, an inorganic base, and water to obtain an initial gel mixture; A2, heating the initial gel mixture obtained in step A1 to remove excess water to obtain a final gel mixture; A3, crystallizing the final gel mixture in a sealed container under rotating or static conditions, with a crystallization temperature of 130 ℃ to 200 ℃ and a crystallization time of 6 h to 96 h; A4, after the crystallization is completed, separating and washing the solid product to obtain a boron-silicon molecular sieve.
12. A catalyst for acid catalysed reactions characterised in that, The mixture containing the boron-silicon molecular sieve is calcined at 500-700 ℃ in an air atmosphere to obtain; The boron-silicon molecular sieve is selected from the boron-silicon molecular sieve according to any one of claims 1-4 and / or the boron-silicon molecular sieve obtained by the preparation method according to any one of claims 5-11.