CN110127714B - Open hierarchical pore titanium silicalite molecular sieve with high framework titanium content and preparation method and application thereof - Google Patents
Open hierarchical pore titanium silicalite molecular sieve with high framework titanium content and preparation method and application thereof Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 162
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 161
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 104
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 108
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 46
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 230000009286 beneficial effect Effects 0.000 claims abstract description 5
- 238000012546 transfer Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 7
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- 239000010457 zeolite Substances 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
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- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000007262 aromatic hydroxylation reaction Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
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- 230000007935 neutral effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 150000002118 epoxides Chemical class 0.000 description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention belongs to the field of catalytic materials, and particularly relates to an open hierarchical pore titanium silicalite molecular sieve with high framework titanium content, and a preparation method and application thereof. The titanium-silicon molecular sieve has a hierarchical distribution multi-level pore channel structure with high framework titanium content and open pore channels, wherein: the content of framework titanium is more than 80at percent, and titanium species are uniformly distributed in the whole titanium silicalite molecular sieve crystal and are not limited on the surface of the titanium silicalite molecular sieve crystal; the hierarchical distribution multistage pore canal is composed of: the titanium-silicon molecular sieve consists of a submicron/nanometer main pore canal which is radially distributed from the center of a titanium-silicon molecular sieve crystal and is communicated with the outer surface of the titanium-silicon molecular sieve, a nanometer secondary mesoporous pore canal which is communicated with the main pore canal and angstrom-level micropores of the titanium-silicon molecular sieve. The titanium silicalite molecular sieve raw material is subjected to high-temperature water heat treatment in tetrapropylammonium hydroxide aqueous solution, and then is cleaned, dried and roasted to obtain the titanium silicalite molecular sieve. The titanium-silicon molecular sieve has small crystal grain size, contains open multilevel pore channels, has high framework titanium content, and is beneficial to mass transfer and improvement of catalytic efficiency.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to an open hierarchical pore titanium silicalite molecular sieve with high framework titanium content, and a preparation method and application thereof.
Background
The TS-1 type titanium silicalite molecular sieve attracts much attention due to its excellent catalytic oxidation performance. In many oxidation processes, TS-1 is an effective catalyst under mild reaction conditions with hydrogen peroxide as an oxidant, and has found widespread use in the ammoximation of cyclohexanone, the hydroxylation of phenol, and the epoxidation of olefins.
In TS-1 crystals, there are two types of titanium species, namely, framework titanium and non-framework titanium. Generally, framework titanium is the active site for epoxide formation during epoxidation, while non-framework titanium promotes side reactions. Non-framework titanium species include anatase and rutile titanium dioxide and amorphous titanium species, which decompose H 2 O 2 And cause side reactions such as: hydrolysis and ring opening of the epoxide.
The traditional synthesis method of TS-1 inevitably produces non-framework titanium, especially when synthesizing TS-1 with low silicon-titanium ratio. Furthermore, due to the microporous structure of the MFI zeolite, which has a large diffusion resistance in the crystals, only active sites at the crystal surface and pore sites may participate in many reactions, which results in a lower utilization of the active sites of the catalyst. Therefore, in order to improve the catalytic performance of the TS-1 catalyst, two key technical problems should be solved. Firstly, TS-1 with more active sites and higher framework titanium should be prepared, and secondly diffusion and steric hindrance in the crystal should be minimized.
Currently, the common method for TS-1 modification is to use sodium hydroxide for post-treatment to create secondary channels that serve to improve diffusion and reduce steric hindrance. Although sodium hydroxide can create secondary channels in the MFI zeolite, it also reduces the relative crystallinity of the zeolite crystals and increases the amount of non-framework titanium in TS-1.
Disclosure of Invention
The invention aims to provide an open hierarchical pore titanium silicalite molecular sieve with high framework titanium content, a preparation method and application thereof, and solves the problems of low activity of the existing TS-1 type titanium silicalite molecular sieve on macromolecules, poor selectivity of target products and low utilization rate of hydrogen peroxide.
The technical scheme of the invention is as follows:
a high-framework titanium content open hierarchical pore titanium silicalite molecular sieve is provided, which has a hierarchical distribution hierarchical pore channel structure with high-framework titanium content and open pore channels, wherein: the content of framework titanium is more than 80at percent, and titanium species are uniformly distributed in the whole titanium silicalite molecular sieve crystal and are not limited on the surface of the titanium silicalite molecular sieve crystal; the hierarchical distribution multistage pore canal is composed of: the titanium-silicon molecular sieve consists of a submicron/nanometer main pore canal which is radially distributed from the center of a titanium-silicon molecular sieve crystal and is communicated with the outer surface of the titanium-silicon molecular sieve, a nanometer secondary mesoporous pore canal which is communicated with the main pore canal and angstrom-level micropores of the titanium-silicon molecular sieve.
The open hierarchical pore titanium silicalite molecular sieve with high framework titanium content has the crystal size of below 800 nanometers and the silicon-titanium atomic ratio of 11-100.
Preferably, the titanium silicalite molecular sieve is of an MFI type ten-ring pore channel structure, the silicon-titanium atomic ratio is 15-80, the crystal size of the titanium silicalite molecular sieve is 50-550 nanometers, and the MFI type ten-ring pore channel structure titanium silicalite molecular sieve has 0.51-0.56 nanometer angstrom micropores.
The open hierarchical pore titanium silicalite molecular sieve with high framework titanium content is preferably more than 90at percent of framework titanium content.
The preparation method of the open hierarchical pore titanium silicalite molecular sieve with high framework titanium content comprises the steps of adding a titanium silicalite raw material into 0.05-1.5 mol/L tetrapropylammonium hydroxide aqueous solution, and carrying out hydrothermal treatment in a closed container at 50-200 ℃ for 1-200 hours; and after treatment, separating, cleaning, drying at 90-120 ℃ for 5-20 hours, and roasting at 400-650 ℃ for 2-50 hours to obtain the open hierarchical pore titanium-silicon molecular sieve with high framework titanium content.
The preparation method of the open hierarchical pore titanium silicalite molecular sieve with high framework titanium content comprises the following steps of mixing a titanium silicalite molecular sieve raw material and a tetrapropylammonium hydroxide aqueous solution in a mass ratio of 1: (5-50).
The application of the open hierarchical pore titanium silicalite molecular sieve with high framework titanium content comprises the following reactions: olefin epoxidation, phenol oxidation, aromatic hydroxylation, ketone ammoxidation, alkane partial oxidation or alcohol partial oxidation.
The titanium silicalite molecular sieve has small crystal size, contains open hierarchical pore canals, has high framework titanium content, is favorable for mass transfer and improvement of catalytic efficiency, and particularly shows higher activity, target product selectivity and oxidant utilization rate in liquid-phase reaction with participation of macromolecules.
The design idea of the invention is as follows:
the invention provides a TS-1 zeolite material with open macropore, mesopore, micropore multilevel pore channel structure, high skeleton titanium content and small crystal grain for macromolecule participating reaction and a preparation method thereof, wherein the method comprises the steps of carrying out hydrothermal post-treatment on an original TS-1 titanium silicalite molecular sieve crystal form by using a high-concentration tetrapropylammonium hydroxide solution at a higher temperature, dissolving non-skeleton titanium in an original sample, recrystallizing and reinserting the non-skeleton titanium into a skeleton position. In order to prepare open secondary pore channels in the TS-1 titanium silicalite molecular sieve crystal and control the insertion of non-framework titanium into the framework, the silicon-titanium ratio, the grain size, the crystallinity of the original TS-1 titanium silicalite molecular sieve, the concentration of tetrapropylammonium hydroxide, the hydrothermal synthesis time and the hydrothermal synthesis temperature must be controlled, so that the steps of dissolution and recrystallization can be accurately controlled. The titanium-silicon molecular sieve has small grain size, contains open multilevel pore canals, has high framework titanium content, is beneficial to mass transfer and improvement of catalytic efficiency, and particularly shows higher activity, target product selectivity and oxidant utilization rate in liquid-phase reaction with participation of macromolecules.
The invention has the following advantages and beneficial effects:
1. the ultrafine crystal grain TS-1 type titanium silicalite molecular sieve obtained by the invention has a hierarchical distribution open pore structure, is beneficial to reaction mass transfer, particularly in the reaction with participation of macromolecules, greatly improves the conversion rate of reactants, and obtains higher selectivity of target products.
2. The ultrafine crystal grain TS-1 type titanium silicalite molecular sieve obtained by the invention has lower silicon-titanium ratio, higher framework titanium content and higher activity, reduces the occurrence of side reaction and improves the utilization rate of hydrogen peroxide.
3. The framework titanium is uniformly distributed in the whole molecular sieve crystal and is not limited on the outer surface of the crystal.
4. The fine-grain TS-1 type titanium silicalite molecular sieve can be separated by a conventional filtering method, so that the problem of filtering separation in the reaction process of the nano molecular sieve is solved.
Drawings
Fig. 1 is a schematic diagram of a titanium silicon molecular sieve pore structure. In the figure, 1 main hole; 2 secondary mesoporous pore canal; 3 angstrom scale micropores.
FIGS. 2 a-2 b show the high resolution transmission electron microscope morphology of the ultrafine titanium silicalite molecular sieve. Wherein, fig. 2a is a macro topography, and fig. 2b is a partially enlarged view.
FIG. 3 shows the high resolution scanning transmission electron microscope morphology of the ultrafine titanium silicalite molecular sieve.
Fig. 4 a-4 b are nitrogen adsorption/desorption curves and pore size distribution diagrams of the ultrafine titanium silicalite molecular sieve. Wherein FIG. 4a is a nitrogen adsorption/desorption curve, the abscissa Ralative Pressure represents the relative Pressure (P/P0), and the ordinate represents the relative PressureVolume adsorbed represents the Volume adsorption amount (cm) 3 STP,/g); FIG. 4b is a graph of Pore size distribution, with the abscissa Pore Width representing the Pore Width: (
Angstrom), the ordinate (left) cumulant Pore Volume represents the Cumulative Pore Volume (cm) of the catalyst 3 In/g), the ordinate (right) dV/dlogd Pore Volume represents the differential Pore size distribution (cm) of the catalyst 3 /g nm)。
FIG. 5 shows ultraviolet spectra before and after hydrothermal treatment of the ultrafine titanium silicalite molecular sieve tetrapropylammonium hydroxide. Wherein, the abscissa Wave number is the wavelength (cm), and the ordinate Normalized F is the Normalized spectral intensity (R).
Detailed Description
In the specific implementation process, the TS-1 type titanium silicalite molecular sieve is used as a raw material, and the titanium silicalite molecular sieve is obtained by cleaning, drying and roasting the raw material after high-temperature water heat treatment in tetrapropylammonium hydroxide aqueous solution. A typical preparation procedure is as follows:
1) solution preparation
Mixing tetrapropylammonium hydroxide and deionized water in proportion to form 0.05-1.5 mol/L (preferably 0.2-1.0 mol/L) tetrapropylammonium hydroxide aqueous solution;
2) hydrothermal synthesis
The physicochemical property parameter ranges of the TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is less than 800 nanometers, the silicon-titanium atomic ratio is 11-200, and the specific surface area is 300-500 cm 2 A micro-pore area of 200-450 cm 2 The volume of the micro pores is 0.08-0.18 cm 3 (ii) a total pore volume of 0.15 to 0.25cm 3 And/g, secondary pore channels are stacking pores among crystals, the proportion of framework titanium accounts for 65-85 at% of all titanium species, and the rest species are silicon and oxygen.
Introducing a TS-1 type titanium silicalite molecular sieve raw material into a tetrapropyl ammonium hydroxide aqueous solution; the weight ratio of the titanium silicalite molecular sieve raw material to the tetrapropylammonium hydroxide aqueous solution is 1:5 to 50 (preferably 1:5 to 20); the temperature of the hydrothermal synthesis is 50-200 ℃ (preferably 100-200 ℃), the reaction time is 1-200 hours, the stirring speed is 200-600 r/min, and the pressure is the autogenous pressure of the solution;
3) roasting
And drying the cleaned sample, roasting for 2-50 hours at 400-650 ℃ in an air atmosphere, and removing the template agent to obtain a final product.
The titanium-silicon molecular sieve has a hierarchical distribution multistage pore channel structure with high framework titanium content and open pore channels, wherein the hierarchical distribution multistage pore channel consists of a submicron or nanometer main pore channel communicated with the outer surface of the molecular sieve, a nanometer secondary mesoporous pore channel communicated with the main pore channel and angstrom-level micropores of the titanium-silicon molecular sieve. The ranges of physicochemical property parameters of the final product are as follows: the particle diameter is less than 800 nm (preferably 50-550 nm), the silicon-titanium atomic ratio is 11-100 (preferably 15-80), and the specific surface area is 350-750 cm 2 G, the micropore area is 300-600 cm 2 Per g, micropore volume of 0.15-0.18 cm 3 Per gram, total pore volume of 0.25-0.85 cm 3 Per gram, the pore volume of the secondary pore channel is 0.15-0.70 cm 3 (iv) per gram, wherein the open secondary pore volume is 50 to 85%. The titanium-silicon molecular sieve contains high framework titanium content, the framework titanium content can reach more than 90at percent, and titanium species are uniformly distributed in the whole titanium-silicon molecular sieve crystal and are not limited on the surface of the titanium-silicon molecular sieve crystal.
The present invention will be explained in further detail below by way of examples and figures.
Example 1
In this example, the parameters of the physicochemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 550 nanometers, the silicon-titanium atomic ratio is 40, and the specific surface area is 410cm 2 G, micropore area 380cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.22cm 3 And/g, secondary pore channels are stacking pores among crystals, and the proportion of framework titanium accounts for 76 at% of all titanium species.
2kg of the superfine TS-1 type titanium silicalite molecular sieve raw material is put into a reaction kettle filled with 40kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.6 mol/L, and is hydrothermally treated for 24 hours at 160 ℃, and the stirring speed is 200 r/min. Filtering and separating the sample after hydrothermal treatment, washing the sample to be neutral by using deionized water, drying the sample for 12 hours at 120 ℃ at 500 DEG CRoasting for 10 hours in air atmosphere to obtain the final product with the following specific physicochemical property parameters: particle size of 530 nm, Si/Ti atomic ratio of 36, and specific surface area of 750cm 2 G, micropore area 450cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.8cm 3 G, secondary pore volume 0.63cm 3 In which the open secondary pore volume represents 75% and the proportion of framework titanium represents 96 at% of all titanium species.
Example 2
In this example, the parameters of the physicochemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 750 nanometers, the silicon-titanium atomic ratio is 15, and the specific surface area is 350cm 2 G, micropore area 330cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.21cm 3 And/g, secondary pore channels are stacking pores among crystals, and the proportion of framework titanium accounts for 83 at% of all titanium species.
2kg of the superfine TS-1 type titanium silicalite molecular sieve raw material is put into a reaction kettle filled with 20kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.8 mol/L, and is hydrothermally treated at the temperature of 170 ℃ for 12 hours, and the stirring speed is 300 r/min. After hydrothermal treatment, filtering and separating a sample, washing the sample to be neutral by using deionized water, drying the sample for 12 hours at 120 ℃, and roasting the sample for 10 hours at 500 ℃ in an air atmosphere to obtain a final product with the following specific physicochemical property parameters: the grain diameter is 730 nanometers, the silicon-titanium atomic ratio is 13, and the specific surface area is 650cm 2 G, micropore area 350cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.6cm 3 Per g, secondary pore volume 0.43cm 3 In which the open secondary pore volume represents 80% and the proportion of framework titanium represents 99 at% of all titanium species.
Example 3
In this example, the specific physical and chemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 450 nanometers, the silicon-titanium atomic ratio is 65, and the specific surface area is 450cm 2 G, micropore area 430cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.23cm 3 And/g, secondary pore channels are stacking pores among crystals, and the proportion of framework titanium accounts for 78 at% of all titanium species.
Boiling 2kg of the superfine TS-1 type titanium silicaliteThe stone molecular sieve raw material is put into a reaction kettle filled with 30kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.9 mol/L, and is hydrothermally treated for 36 hours at the temperature of 170 ℃, and the stirring speed is 300 r/min. After hydrothermal treatment, a sample is filtered and separated, washed to be neutral by deionized water, dried at 120 ℃ for 12 hours, and roasted at 560 ℃ for 8 hours in air atmosphere to obtain a final product with the following specific physical and chemical property parameters: particle size of 430 nm, silicon-titanium atom ratio of 60, and specific surface area of 680cm 2 G, micropore area 330cm 2 G, micropore volume 0.16cm 3 G, total pore volume 0.75cm 3 Per g, secondary pore volume 0.59cm 3 In which the open secondary pore volume is 85% and the proportion of framework titanium is 98 at% of all titanium species.
Example 4
In this example, the parameters of the physicochemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 350 nanometers, the silicon-titanium atomic ratio is 25, and the specific surface area is 480cm 2 G, micropore area 430cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.25cm 3 And/g, secondary pore channels are stacked pores among crystals, and the proportion of framework titanium accounts for 68 at% of all titanium species.
2kg of the superfine TS-1 type titanium silicalite molecular sieve raw material is put into a reaction kettle filled with 40kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.4 mol/L, and is hydrothermally treated at 170 ℃ for 12 hours, and the stirring speed is 500 r/min. After hydrothermal treatment, filtering and separating a sample, washing the sample to be neutral by using deionized water, drying the sample at 120 ℃ for 12 hours, and roasting the sample at 550 ℃ for 8 hours in an air atmosphere to obtain a final product with the following specific physicochemical property parameters: the grain diameter is 350 nanometers, the silicon-titanium atomic ratio is 23, and the specific surface area is 780cm 2 G, micropore area 430cm 2 G, micropore volume 0.16cm 3 In terms of/g, total pore volume 0.76cm 3 G, secondary pore volume 0.6cm 3 In which the open secondary pore volume is 78% and the proportion of framework titanium is 93 at% of all titanium species.
Example 5
In this example, the specific physical and chemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 650 nanometers, the silicon-titanium atomic ratio is 25, and the specific surface area is 380cm 2 G, micropore area 340cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.2cm 3 And/g, secondary pore channels are stacked pores among crystals, and the proportion of framework titanium accounts for 79 at% of all titanium species.
2kg of the superfine TS-1 type titanium silicalite molecular sieve raw material is put into a reaction kettle filled with 40kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.4 mol/L, and is hydrothermally treated at 170 ℃ for 12 hours, and the stirring speed is 500 r/min. After hydrothermal treatment, a sample is filtered and separated, washed to be neutral by deionized water, dried at 120 ℃ for 12 hours, and roasted at 550 ℃ for 8 hours in air atmosphere, and the specific physical and chemical property parameters of the final product are as follows: the grain diameter is 660 nanometers, the silicon-titanium atomic ratio is 24, and the specific surface area is 580cm 2 G, micropore area 330cm 2 G, micropore volume 0.17cm 3 G, total pore volume 0.66cm 3 G, secondary pore volume 0.50cm 3 In which the open secondary pore volume is 83% and the proportion of framework titanium is 91 at% of all titanium species.
Example 6
In this example, the specific physical and chemical properties of the ultra-fine TS-1 type titanium silicalite molecular sieve raw material are as follows: the grain diameter is 150 nanometers, the silicon-titanium atomic ratio is 50, and the specific surface area is 450cm 2 G, micropore area 310cm 2 G, micropore volume 0.15cm 3 G, total pore volume 0.25cm 3 And/g, secondary pore channels are stacked pores among crystals, and the proportion of framework titanium accounts for 65 at% of all titanium species.
2kg of the superfine TS-1 type titanium silicalite molecular sieve raw material is put into a reaction kettle containing 60kg of tetrapropylammonium hydroxide aqueous solution with the concentration of 0.6 mol/L, and is hydrothermally treated for 18 hours at the temperature of 170 ℃, and the stirring speed is 200 r/min. After hydrothermal treatment, a sample is filtered and separated, washed to be neutral by deionized water, dried at 120 ℃ for 12 hours, and roasted at 530 ℃ for 10 hours in air atmosphere, and the specific physical and chemical property parameters of the final product are as follows: particle diameter of 130 nm, silicon-titanium atom ratio of 43 and specific surface area of 650cm 2 G, micropore area 330cm 2 G, micropore volume 0.17cm 3 In terms of/g, total pore volume 0.43cm 3 G, secondary pore volume 0.26cm 3 Per g, wherein the open secondary pore volume is 56%,the framework titanium proportion accounts for 90at% of all titanium species.
Application example
The application example adopts the open hierarchical pore titanium silicalite molecular sieve with high framework titanium content obtained in the examples 1-6 as a catalyst, and cyclohexene epoxidation reaction as a probe for reaction, and the reaction conditions are as follows: the pressure was 3bar, the temperature was 65 ℃, the reaction time was 6 hours, the stirring speed was 500 rpm, and the results are shown in Table 1.
TABLE 1 catalyst Performance Table
As can be seen from table 1, the titanium silicalite molecular sieve subjected to the hydrothermal post-treatment with tetrapropylammonium hydroxide solution has higher cyclohexene conversion rate and selectivity, which are attributed to the open secondary pore structure and higher framework titanium content of the modified titanium silicalite molecular sieve.
As shown in figure 1, the pore canal of the TS-1 titanium silicalite molecular sieve with the hierarchical pore structure consists of a main pore canal 4 radially distributed from the center of a crystal to the outer surface of the crystal, a secondary mesoporous pore canal 2 connected with the main pore canal, and angstrom-scale micropores 3 of zeolite.
As shown in fig. 2 a-2 b, the titanium silicalite molecular sieve after the hydrothermal post-treatment with tetrapropylammonium hydroxide solution has secondary pores radially penetrating from the center of the crystal to the surface of the crystal, and the secondary pores are connected with mesopores of several nanometers to several tens of nanometers.
As shown in fig. 3, the secondary pore channels in the titanium silicalite molecular sieve crystal after the hydrothermal post-treatment with tetrapropylammonium hydroxide solution are communicated with the crystal surface and are open secondary pore channels.
As shown in fig. 4 a-4 b, secondary channels are generated inside the titanium silicalite molecular sieve crystal after the hydrothermal post-treatment of the tetrapropylammonium hydroxide solution, and the size of the secondary channels is from several nanometers to several hundred nanometers as can be seen from the pore size distribution curve.
As shown in fig. 5, in the titanium silicalite molecular sieve after the hydrothermal post-treatment with tetrapropylammonium hydroxide solution, the content of framework titanium is greatly increased.
The embodiment result shows that the high-concentration tetrapropylammonium hydroxide hydrothermal post-treatment can generate a multi-stage pore canal consisting of open mesopores and macropores in the small-grain titanium silicalite molecular sieve; the intra-crystal open multilevel pore channel structure not only accelerates the diffusion of reaction molecules, obviously improves the accessibility of an active center, but also greatly enhances the coke capacity and obviously prolongs the service life of the catalyst. The content of the modified framework titanium can reach more than 90at percent, so that the side reaction is obviously inhibited, and the utilization rate of hydrogen peroxide is improved.
Claims (6)
1. A high-framework titanium content open hierarchical pore titanium silicalite molecular sieve is characterized in that the titanium silicalite molecular sieve has a hierarchical distribution hierarchical pore channel structure with high-framework titanium content and open pore channels, wherein: the content of framework titanium is more than 80at percent, and titanium species are uniformly distributed in the whole titanium silicalite molecular sieve crystal instead of being limited on the surface of the titanium silicalite molecular sieve crystal; the hierarchical distribution multistage pore canal is composed of: the titanium-silicon molecular sieve consists of a submicron/nanometer main pore canal, a nanometer secondary mesoporous pore canal and angstrom-scale micropores, wherein the submicron/nanometer main pore canal is radially distributed from the center of a titanium-silicon molecular sieve crystal and is communicated with the outer surface of the titanium-silicon molecular sieve;
the crystal size of the titanium-silicon molecular sieve is below 800 nanometers, and the silicon-titanium atomic ratio is 11-100.
2. The open multi-stage pore titanium silicalite molecular sieve with high framework titanium content according to claim 1, wherein the titanium silicalite molecular sieve is of an MFI type ten-ring pore channel structure, the silicon-titanium atomic ratio is 15-80, the crystal size of the titanium silicalite molecular sieve is 50-550 nm, and the titanium silicalite molecular sieve with the MFI type ten-ring pore channel structure has 0.51-0.56 nm angstrom micropores.
3. The high framework titanium content open multigraded pore titanium silicalite molecular sieve of claim 1, wherein the framework titanium content is greater than 90 at%.
4. A process for the preparation of the high framework titanium content open multigrade pore titanium silicalite molecular sieves of any one of claims 1 to 3 wherein titanium silicalite is reactedAdding a molecular sieve raw material into 0.05-1.5 mol/L tetrapropylammonium hydroxide aqueous solution, and carrying out hydrothermal treatment in a closed container at 50-200 ℃ for 1-200 hours; after treatment, separating, cleaning, drying at 90-120 ℃ for 5-20 hours, and roasting at 400-650 ℃ for 2-50 hours to obtain the open hierarchical pore titanium-silicon molecular sieve with high framework titanium content; wherein the mass ratio of the titanium-silicon molecular sieve raw material to the tetrapropylammonium hydroxide aqueous solution is 1: (5-50); the titanium-silicon molecular sieve is a TS-1 type titanium-silicon zeolite molecular sieve raw material, and the physicochemical property parameter ranges are as follows: the particle diameter is less than 800 nanometers, the silicon-titanium atomic ratio is 11-200, and the specific surface area is 300-500 cm 2 G, the area of the micropores is 200-450 cm 2 The volume of the micro pores is 0.08-0.18 cm 3 Per gram, total pore volume of 0.15-0.25 cm 3 And/g, secondary pore channels are stacking pores among the crystals, the proportion of framework titanium accounts for 65-85 at% of all titanium species, and the rest species are silicon and oxygen.
5. Use of the high framework titanium content open multiwell titanium silicalite molecular sieve of any one of claims 1 to 3 in a reaction involving the use of the titanium silicalite molecular sieve comprising: olefin epoxidation, phenol oxidation, aromatic hydroxylation, ketone ammoxidation, alkane partial oxidation or alcohol partial oxidation.
6. The use of the open multinary pore titanium silicalite molecular sieve with high framework titanium content according to claim 5, wherein the titanium silicalite molecular sieve has a small crystal size, contains open multinary pore channels, has a high framework titanium content, is beneficial to mass transfer and improvement of catalytic efficiency, and particularly shows high activity, target product selectivity and oxidant utilization rate in a liquid phase reaction in which macromolecules participate.
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