CN115724439A - Titanium-silicon molecular sieve containing halogen and preparation method thereof - Google Patents

Titanium-silicon molecular sieve containing halogen and preparation method thereof Download PDF

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CN115724439A
CN115724439A CN202111006070.4A CN202111006070A CN115724439A CN 115724439 A CN115724439 A CN 115724439A CN 202111006070 A CN202111006070 A CN 202111006070A CN 115724439 A CN115724439 A CN 115724439A
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molecular sieve
titanium silicalite
halogen
titanium
silicalite molecular
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彭欣欣
梁晓航
夏长久
林民
朱斌
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a titanium-silicon molecular sieve containing halogen, which is characterized by containing halogen and carbon accounting for 0.5-5 percent and 0.5-4 percent of the total weight of the molecular sieve respectively. The molecular sieve has halogen groups and organic groups, and the groups mainly exist in the pore channels of the molecular sieve, so that the compatibility of the titanium-silicon molecular sieve and an organic substrate can be effectively improved, and the catalysis or separation performance is improved.

Description

Titanium-silicon molecular sieve containing halogen and preparation method thereof
Technical Field
The invention relates to a titanium-silicon molecular sieve and a preparation method thereof, in particular to a halogen-containing titanium-silicon molecular sieve and a preparation method thereof.
Background
The titanium silicalite molecular sieve is a heteroatom molecular sieve with a framework containing isolated four-coordinate titanium, has excellent selective oxidation performance for catalyzing hydrocarbons, particularly has the advantages of mild reaction conditions, high atom utilization rate, environment-friendly and pollution-free process and the like in a reaction taking hydrogen peroxide as an oxidant, and has great industrial application value.
The titanium-silicon molecular sieve comprises MFI type, BEA type, MWW type, MEL type and other structures according to the difference of framework structures, wherein the successful development of TS-1 with MFI structure is regarded as the milestone in the field of molecular sieve catalysis. CN1260241A discloses a method for synthesizing a novel titanium silicalite molecular sieve HTS with a unique hollow structure by a rearrangement technology, which increases the size of a molecular sieve pore, greatly improves the mass transfer diffusion rate of reactant molecules in the molecular sieve pore and enhances the catalytic performance. At present, the HTS molecular sieve is applied to the processes of phenol hydroxylation, cyclohexanone ammoximation and the like by catalytic oxidation, has already been industrialized, and has the advantages of mild reaction conditions, high atom utilization rate, simple process, cleanness, high efficiency and the like.
Because the hydrophilicity of the titanium silicalite molecular sieve is stronger than lipophilicity, the titanium silicalite molecular sieve has lower catalytic performance in the reaction of catalyzing organic matters, and the existing conventional method mainly aims at the active center regulation of the titanium silicalite molecular sieve to prepare the titanium silicalite molecular sieve with more skeleton four-coordinate titanium, and lacks sufficient attention on the regulation of the surface properties of the titanium silicalite molecular sieve.
Silicatization provides a new method for regulating and controlling the surface property of the molecular sieve. CN101121524a discloses a method for preparing organosilicon microporous zeolite, which uses halosilane, silazane, and alkoxysilane as silane for synthesizing a silicon-aluminum molecular sieve, and directly introduces organic groups into the molecular sieve. CN101528341A discloses a preparation method of a hydrophobic coating molecular sieve, which is prepared by reacting a zeolite molecular sieve with silane and is used for improving the use effect of the zeolite molecular sieve in an electronic element. CN102992341A discloses a hydrophobic modification method of a zeolite molecular sieve, which comprises reacting a silicon-aluminum molecular sieve with a silylation reagent with substituted benzene ring groups to obtain the silicon-aluminum molecular sieve with a hydrophobic surface. CN104119300A discloses a method for silanization graft modification of mesoporous silica, which is characterized in that mesoporous carbon dioxide silicon is mixed with any one of methyltrimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane and trimethylethoxysilane.
Therefore, the prior art mainly relates to silanization modification treatment of the silicon-aluminum molecular sieve, and less relates to relative preparation of the titanium-silicon molecular sieve, and the prior art mainly carries out modification on the outer surface of the molecular sieve, has less influence on the inner surface, and is difficult to fulfill the aim of surface property regulation and control to the maximum extent.
Disclosure of Invention
One of the objectives of the present invention is to provide a halogen-containing titanium silicalite molecular sieve, which contains halogen groups and organic groups.
The other purpose of the invention is to provide a preparation method of the halogen-containing titanium silicalite molecular sieve.
The invention also provides the application of the titanium silicalite molecular sieve containing halogen.
In order to achieve one of the above objects, a first aspect of the present invention provides a halogen-containing titanium silicalite molecular sieve, characterized by containing 0.5% to 5% and 0.5% to 4% of halogen and carbon, respectively, based on the total weight of the molecular sieve.
In order to achieve the second object, a second aspect of the present invention provides a method for preparing a halogen-containing titanium silicalite molecular sieve, comprising: contacting a titanium silicalite molecular sieve roasted for removing the template agent with an organic amine solution with the carbon number of C1-C3 at 40-100 ℃, and washing and drying a separated solid product; then contacting with solution containing micromolecular silanization reagent at 50-120 ℃, and separating and drying to obtain the titanium-silicon molecular sieve containing halogen.
In order to achieve the third objective, a third aspect of the present invention is to provide a halogen-containing titanium silicalite molecular sieve as an active component of a catalyst for organic matter conversion reaction, or as an adsorbent component.
The halogen-containing titanium silicalite molecular sieve provided by the invention has halogen groups and organic groups, and the halogen groups and the organic groups mainly exist in the pore channels of the molecular sieve, so that the compatibility of the titanium silicalite molecular sieve and an organic substrate can be effectively improved, and the catalysis or separation performance is improved.
Drawings
FIG. 1 is an infrared hydroxyl group spectrum of the TS-1-A molecular sieve of preparation example 1.
FIG. 2 is an XRD spectrum of the halogen-containing titanium silicalite molecular sieve of example 1.
FIG. 3 is an infrared hydroxyl spectrum of the halogen-containing titanium silicalite molecular sieve of example 1.
Detailed Description
The invention provides a titanium silicalite molecular sieve containing halogen, which is characterized by containing halogen and carbon accounting for 0.5-5 percent and 0.5-4 percent of the total weight of the molecular sieve, preferably 1-3 percent and 0.8-2.5 percent of the total weight of the molecular sieve respectively. Wherein, the halogen is one or more of fluorine, chlorine, bromine and iodine, and the preferred halogen is chlorine.
The halogen-containing titanium silicalite molecular sieve is preferably R XRF /R XPS A value of greater than 2, preferably from 2.5 to 4,R XRF Atomic ratio of bulk halogen to silicon for molecular sieves analyzed by XRF (X-ray fluorescence Spectroscopy), R XPS Is the atomic ratio of halogen to silicon on the surface of the molecular sieve analyzed by XPS. The characterization data indicated that the halogen atoms were distributed predominantly on the inner surface, i.e., in the channels, of the molecular sieve.
The halogen-containing titanium silicalite molecular sieve is preferably characterized by infrared spectrum and has characteristic peak intensity ratio I 3740 /I 3530 Is 4 to 10, preferably 5 to 8, wherein I 3740 Is 3740cm in infrared hydroxyl spectrum of molecular sieve -1 The absorption peak intensity represents the content of the hydroxyl at the end of the molecular sieve; i is 3530 Is 3530cm in the infrared hydroxyl spectrum of the molecular sieve -1 The intensity of the absorption peak represents the content of the hydroxyl group of the nest. I.C. A 3740 /I 3530 A higher value of (D) indicates fewer molecular sieve defect sites (Catalysis Today,1997,37 (4): 353-366). The halogen-containing titanium silicon molecular sieve of the invention has higher I because the halogen atoms are mainly distributed in the pore channels of the molecular sieve and are combined with the defect sites of the molecular sieve through the groups, thereby reducing the defect sites 3740 /I 3530 Numerical values.
The invention is not limited to the titanium-silicon molar ratio of the halogen-containing titanium-silicon molecular sieve, preferably, the titanium-silicon molar ratio is (0.001-0.05): 1, further preferably (0.01-0.03): 1. the framework structure of the molecular sieve is not limited in the invention, and can be a topological structure such as MFI, BEA, MEL, MWW, SVR, MOR, EWT and the like, and preferably is an MFI structure. When the molecular sieve is of an MFI structure, the specific surface area and the pore volume of the molecular sieve are measured by a low-temperature nitrogen adsorption and desorption method, and the specific surface area of micropores is 350-420m 2 Per g, preferably from 360 to 400m 2 The volume of the pores is 0.130 to 0.170mL/g, preferably 0.140 to 0.160mL/g. The BET specific surface area and micropore volume data of the titanium-silicon molecular sieve containing the halogen are lower than those of the conventional titanium-silicon molecular sieve, which shows that the data are reduced because the halogen-containing group enters the inside of a molecular sieve pore channel.
The invention also provides a preparation method of the halogen-containing titanium silicalite molecular sieve, which is characterized by comprising the following steps: contacting a titanium-silicon molecular sieve roasted for removing the template agent with an organic amine solution with carbon number of C1-C3 at 40-100 ℃, and washing and drying a separated solid product; then contacting with solution containing micromolecular silanization reagent at 50-120 ℃, and separating and drying to obtain the titanium-silicon molecular sieve containing halogen.
In the preparation method provided by the invention, the titanium silicalite molecular sieve can be synthesized by a traditional hydrothermal method, a dry glue method, a post-insertion method and a rearrangement method. In the titanium-silicon molecular sieve for roasting to remove the template agent, the content of organic matters is less than 0.01 percent of the weight of the molecular sieve. The operation of roasting to remove the template agent can be carried out in an oxygen-rich or oxygen-poor atmosphere at the temperature of more than 300 ℃, and can also be carried out in a water vapor, ammonia atmosphere, alcohol amine atmosphere and alcohol atmosphere, so long as the content of organic matters in the titanium-silicon molecular sieve is reduced to be less than 0.01 percent of the weight of the molecular sieve. The roasting temperature is preferably 350-800 deg.C, more preferably 400-600 deg.C, and the roasting time is 0.5-6h.
In the preparation method provided by the invention, the titanium silicalite molecular sieve subjected to roasting and template removal is contacted with the organic amine solution with the carbon number of C1-C3 at 40-100 ℃ to clean the pore channels of the titanium silicalite molecular sieve, and the operation has a good effect on activating the framework of the titanium silicalite molecular sieve. The organic amine with the carbon number of C1-C3 comprises primary amine, secondary amine, tertiary amine, alcohol amine, diamine and the like; the organic amine having C1 to C3 is not particularly limited to one or more selected from methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethanolamine, propanolamine, ethylenediamine, and propylenediamine.
In the preparation method provided by the invention, in the organic amine solution with the carbon number of C1-C3, the solvent is selected from water, C1-C10 alcohol, C2-C10 ester or C3-C8 ketone. Examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, cyclopentanol, n-hexanol, cyclohexanol, n-octanol, methyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone. The organic amine solution with the carbon number of C1-C3 is preferably an aqueous solution.
In the preparation method provided by the invention, in the organic amine solution with the carbon number of C1-C3, the mass fraction of the organic amine is preferably 0.1-1.5%, and more preferably 0.2-1.0%.
In the preparation method provided by the invention, in the step of contacting the titanium silicalite molecular sieve roasted for removing the template agent with the organic amine solution with the carbon number of C1-C3 at 40-100 ℃, and washing and drying the separated solid product, the contacting is preferably carried out at 60-80 ℃ for 30-120min, and the separation can be in a mode of centrifugation, evaporation, membrane separation, filtration and the like; the washing is preferably carried out by adopting water or an alcohol solution, and after the washing is carried out until the pH value of the liquid is less than 8, the liquid is dried. The drying is preferably carried out at 80-200 deg.C for 0.5-12h.
In the preparation method provided by the invention, the small molecule silanization reagent has the following structure:R 1(m) -Si-OR 2(n) or R is 1(m) -Si-X (n) In the formula, R 1 Is of the general formula C x H y X z ，R 2 Is methyl or ethyl, m and n are positive integers, m + n =4, y + z =2x +1 and X is a positive integer from 1 to 3, and X is at least one of fluorine, chlorine, bromine and iodine. Preferably, m =1,R 2 Is methyl, z =1 or 2, more preferably 1, and halogen is chlorine. More specifically, but not limited thereto, the small molecule silylating agent is selected from the group consisting of chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethyltriethoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, dichloromethyldimethoxysilane, dichloromethyldiethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloroethyltriethoxysilane, 1,2-dichloropropyltrimethoxysilane, 1,2-dichloropropyltriethoxysilane, chloromethyltrichlorosilane, dichloromethyldichlorosilane, chloroethyltrichlorosilane, dichloroethyldichlorosilane, chloropropyltrichlorosilane, dichloropropyldichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, bis (1,2-dichloropropyl) dichlorosilane, bis (1,2-dichloropropyl) dichlorosilane; preferred small molecule silylating agents are chloromethyltrimethoxysilane, chloroethyltrimethoxysilane, chloropropyltrimethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloropropyltrimethoxysilane, chloromethyltrichlorosilane, chloroethyltrichlorosilane, chloropropyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloropropyltrichlorosilane.
In the preparation method provided by the invention, in the solution containing the small molecule silanization reagent, the solvent is selected from C3-C8 ketone, C2-C10 ester or C6-C12 alkane. For example: acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, cumene, xylene, and trimethylbenzene. Preferably, the ketone is a solvent, and more preferably, the solvent is one or more of acetone, butanone, cyclopentanone, and acetylacetone.
In the preparation method provided by the invention, the molar ratio of the small molecule silylation reagent to the titanium silicalite molecular sieve is preferably (0.001-0.05): 1. preferably (0.005-0.03): 1; the molar ratio of the solvent containing the micromolecular silanization reagent to the titanium silicalite molecular sieve is preferably (5-100): 1. more preferably (20-60): 1, the silylation reagent is Si, and the titanium silicalite molecular sieve is SiO 2 And (6) counting.
The invention further provides an application of the halogen-containing titanium silicalite molecular sieve, and the specific application is that the halogen-containing titanium silicalite molecular sieve is used as an active component of a catalyst for organic matter conversion reaction or is used as an adsorbent component. The halogen-containing titanium silicalite molecular sieve can be directly used as a catalyst, can also be mixed with other catalysts, promoters, carriers and the like for use, can be used after being formed, and preferably has the mass content of more than or equal to 5 percent. The organic conversion reaction may be, for example, oxidation of benzene to produce phenol.
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the examples, the X-ray powder diffraction (XRD) pattern of the titanium-silicon molecular sieve was measured on a Siemens D5005 type X-ray diffractometer. XRF was measured by X-ray fluorescence spectrometer type 3013 manufactured by Nippon Denshi electric Co. XPS was measured on an ESCALB model 250X-ray photoelectron spectrometer manufactured by ThermoFisher Scientific. The determination of infrared hydroxyl spectrograms of the titanium-silicon molecular sieve is carried out on a Nicolet 870 type Fourier transform infrared spectrometer, a sample is pressed into a self-supporting sheet and is placed in an infrared cell at the temperature of 1 multiplied by 10 -3 And (3) treating the sample for 3h at 450 ℃ under the Pa condition, and measuring the infrared hydroxyl spectrum of the sample.
In the examples, the carbon content of the titanium silicalite molecular sieve was measured using a CS-844 high frequency infrared carbon sulfur analyzer (LECO analyzer ltd., usa), and the procedure was to place a weighed sample together with a flux in a high frequency induction furnace, and to burn the sample at a high temperature after oxygen introduction. And (3) detecting CO2 gas generated by carbon by an infrared detector, and calculating the carbon content of the titanium-silicon molecular sieve. (refer to Shen Shan. High frequency infrared absorption method for determination of carbon, sulfur, noble metals in noble metal catalysts, 2001).
The raw materials used in the examples and comparative examples were all commercially available and analytically pure.
Preparation examples 1 and 2 illustrate the preparation of titanium silicalite TS-1 as a starting material, both according to the procedures of Zeolite, 1992, vol.12, pages 943 to 950.
Preparation example 1
At room temperature, according to tetraethoxysilane (as SiO) 2 Meter): tetrabutyl titanate (in TiO) 2 Meter): tetrapropylammonium hydroxide (as N): the molar ratio of the deionized water is 1:0.03:0.2:25 mixing the substances evenly under the condition of stirring to obtain a mixture, transferring the mixture into a pressure-resistant stainless steel reaction kettle, crystallizing for 72 hours at 170 ℃ under the autogenous pressure, filtering, washing and recovering a solid product, drying the obtained solid product in a 120 ℃ oven for 12 hours, and roasting for 6 hours at 550 ℃ in the air atmosphere, wherein the content of organic matters is less than 0.01 percent of the weight of the molecular sieve to obtain the titanium silicalite molecular sieve with the number of TS-1-A.
The XRF, XPS and low-temperature nitrogen adsorption and desorption characterization results are shown in Table 1.
FIG. 1 is an infrared hydroxyl group spectrum of the TS-1-A molecular sieve of preparation example 1. As can be seen from FIG. 1, the molecular sieve has a terminal hydroxyl signal peak of 3740cm-1 and a nested hydroxyl signal peak of 3530cm-1, I 3740 /I 3530 The number is 2.4, which indicates that the molecular sieve has more defect sites in the pore channels.
Preparation example 2
At room temperature, according to tetraethoxysilane (as SiO) 2 Meter): tetrabutyl titanate (in TiO) 2 Meter): tetrapropylammonium hydroxide (as N): the molar ratio of the deionized water is 1:0.01:0.2:25 mixing the above materials under stirring to obtain a mixture, transferring to a pressure-resistant stainless steel reaction kettle, crystallizing at 170 deg.C under autogenous pressure for 72 hr, filtering, washing to recover solid product, and collecting the solid productDrying in a 120 ℃ oven for 12 hours, and roasting at 550 ℃ for 6 hours in the air atmosphere until the organic matter content is less than 0.01 percent of the weight of the molecular sieve, thereby obtaining the titanium silicalite molecular sieve with the serial number of TS-1-B.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Comparative example 1
This comparative example illustrates the case of treatment with organic amine only.
Mixing the titanium silicalite TS-1-A with an aqueous solution of methylamine, wherein the mass fraction of organic amine is 0.5%. Then treating at 80 deg.C for 120min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Comparative example 2
This comparative example illustrates the treatment with a conventional silylating agent.
Titanium silicalite TS-1-A was mixed with a toluene solution containing 3- (phenylamino) propyltrimethoxysilane and treated at 80 ℃ for 6h with a silylating agent (calculated as Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.02:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Meter) =60:1 (molar ratio), then separating the molecular sieve, and drying at 120 ℃ for 12 hours to obtain the titanium silicalite molecular sieve with the silanized surface.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Comparative example 3
This comparative example illustrates the case where only the halogen-containing siliconizing agent was treated.
Mixing titanium silicon molecule TS-1-A with butanone solution containing chloromethyl trimethoxy silane, and treating at 80 ℃ for 6h, wherein the silanization reagent (calculated by Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.02:1 (molar ratio), solvent: titanium silicalite molecular sieveSiO 2 Meter) =60:1 (molar ratio), then separating the molecular sieve, and drying at 120 ℃ for 12h to obtain the titanium silicalite molecular sieve with the surface silanized treatment.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 1
(1) Mixing the titanium silicalite TS-1-A with an aqueous solution of methylamine, wherein the mass fraction of organic amine is 0.5%. Then treating at 80 deg.C for 120min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with butanone solution containing chloromethyl trimethoxy silane, and treating for 6h at 80 ℃, wherein the silanization reagent (calculated by Si): titanium silicalite molecular sieve (SiO 2) 2 Meter) =0.02:1 (molar ratio), solvent: titanium silicalite molecular sieve (SiO 2) 2 Meter) =60:1 (molar ratio), then separating out the molecular sieve, and drying at 120 ℃ for 12h to obtain the halogen-containing titanium silicalite molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
FIG. 2 is an XRD spectrum of the halogen-containing titanium silicalite molecular sieve prepared in example 1. As can be seen from FIG. 1, the halogen-containing titanium silicalite molecular sieve prepared by the method of the present invention still has a "five-finger" diffraction spectrum between 22 ℃ and 25 ℃, which indicates that the molecular sieve still has an MFI structure, i.e., the method does not change the crystal structure of the molecular sieve.
FIG. 3 is an infrared hydroxyl spectrum of a halogen-containing titanium silicalite molecular sieve prepared in example 1. I.C. A 3740 /I 3530 And 7.4, which shows that the number of the defect sites in the pore channels of the molecular sieve is obviously reduced compared with TS-1-A after the treatment by the method.
Example 2
(1) Mixing the titanium-silicon molecular sieve TS-1-A with an aqueous solution of ethylamine, wherein the mass fraction of the organic amine is 1.0%. Then processing at 80 deg.C for 90min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with a cyclopentanone solution containing chloropropyltrimethoxysilane, and treating at 70 ℃ for 6h, wherein the silanization reagent (calculated by Si): titanium silicalite molecular sieve (SiO 2) 2 Meter) =0.01:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Meter) =40:1 (molar ratio), then separating out the molecular sieve, and drying at 120 ℃ for 12h to obtain the halogen-containing titanium silicalite molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 3
(1) Mixing the titanium silicalite TS-1-A with an aqueous solution of ethanolamine, wherein the mass fraction of organic amine is 0.5%. Then treating at 80 deg.C for 60min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with acetylacetone solution containing chloroethyl trichlorosilane, and treating at 90 ℃ for 4h, wherein a silanization reagent (calculated by Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.005:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Count) =20:1 (molar ratio), then separating the molecular sieve, and drying at 120 ℃ for 12 hours to obtain the halogen-containing titanium-silicon molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 4
(1) Mixing titanium silicalite TS-1-A with an aqueous solution of ethylenediamine, wherein the mass fraction of organic amine is 0.2%. Then treating at 80 deg.C for 120min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with butanone solution containing chloroethyl trimethoxy silane, and treating for 2h at 70 ℃, wherein a silanization reagent (calculated by Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.03:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Meter) =40:1 (molar ratio), then separating the molecular sieve, and drying at 120 ℃ for 12 hours to obtain the halogen-containing titanium-silicon molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 5
(1) Mixing the titanium silicalite TS-1-A with aqueous solution of dimethylamine, wherein the mass fraction of organic amine is 1.0%. Then treating at 60 deg.C for 120min, separating TS-1-A molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with an acetone solution containing 1,2-dichloropropyltrichlorosilane, and treating at 60 ℃ for 8 hours, wherein a silanization reagent (calculated by Si): titanium silicalite molecular sieve (SiO 2) 2 Meter) =0.025:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Count) =20:1 (molar ratio), then separating out the molecular sieve, and drying at 120 ℃ for 12h to obtain the halogen-containing titanium silicalite molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 6
(1) Mixing the titanium-silicon molecular sieve TS-1-B with an aqueous solution of propylamine, wherein the mass fraction of organic amine is 1.0%. Then treating at 80 deg.C for 90min, separating TS-1-B molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with a cyclopentanone solution containing chloromethyl trichlorosilane, and treating at 80 ℃ for 4h, wherein a silanization reagent (calculated according to Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.02:1 (molar ratio), solvent: titanium silicalite molecular sieve (SiO 2) 2 Meter) =60:1 (molar ratio), then separating out the molecular sieve, and drying at 120 ℃ for 12h to obtain the halogen-containing titanium silicalite molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 7
(1) Mixing the titanium silicalite TS-1-B with a methanol solution of methylamine, wherein the mass fraction of organic amine is 0.1%. Then treating at 50 deg.C for 180min, separating TS-1-B molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with an ethyl acetate solution containing dichloromethyldimethoxysilane, and treating at 50 ℃ for 12h, wherein the silanization reagent (calculated by Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.05:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Meter) =100:1 (molar ratio), then separating the molecular sieve, and drying at 120 ℃ for 12 hours to obtain the halogen-containing titanium-silicon molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
Example 8
(1) Mixing the titanium silicalite TS-1-B with an ethanol solution of trimethylamine, wherein the mass fraction of the organic amine is 1.5%. Then treating at 40 deg.C for 180min, separating TS-1-B molecular sieve, washing with deionized water until pH is less than 8, and drying at 120 deg.C for 12h.
(2) Mixing the titanium silicalite molecular sieve obtained in the step (1) with an isopropyl acetate solution containing dichloromethyl dichlorosilane, and treating at 100 ℃ for 24h, wherein a silanization reagent (calculated by Si): titanium silicon molecular Sieve (SiO) 2 Meter) =0.001:1 (molar ratio), solvent: titanium silicon molecular Sieve (SiO) 2 Count) =10:1 (molar ratio), then separating and removing the molecular sieve, and drying at 120 ℃ for 12h to obtain the halogen-containing titanium silicalite molecular sieve.
XRF, XPS, low-temperature nitrogen adsorption and desorption characterization results and infrared spectrum characterization characteristic peak intensity ratio I 3740 /I 3530 See table 1.
TABLE 1
Figure BDA0003237244370000111
Figure BDA0003237244370000121
As can be seen from Table 1, the titanium silicalite molecular sieve provided by the invention contains halogen atoms and organic groups, R XRF /R XPS Greater than 2, between 2.2 and 3.7, I 3740 /I 3530 Greater than 4, between 4.4 and 7.4; the specific surface area and the pore volume of the micropores are lower than those of the samples of the preparation examples and the comparative examples, and the halogen atoms and the organic groups are mainly present in the pore channels of the molecular sieve.
Evaluation examples 1 to 13
To illustrate the catalytic performance of the halogen-containing titanium silicalite molecular sieves of the present invention, benzene oxidation was used for evaluation.
The benzene oxidation reaction is carried out under the following conditions:
the raw materials are mixed according to the proportion of benzene: hydrogen peroxide: water (molar ratio) 1. After the reaction is finished, filtering to obtain a liquid product, adding a proper amount of acetone to adjust the liquid product to be homogeneous, and analyzing the composition of the product by adopting gas chromatography. Wherein, the benzene conversion rate = (amount of benzene in raw material-amount of benzene in product)/amount of benzene in raw material x 100%
Target product selectivity = (amount of phenol in product + amount of benzenediol)/(amount of benzene in raw material-amount of benzene in product) × 100%
The evaluation results are shown in Table 2.
TABLE 2
Evaluation example number Source of molecular sieves Conversion rate Selectivity is
1 Preparation example 1 18％ 85％
2 Preparation example 2 12％ 85％
3 Comparative example 1 21％ 89％
4 Comparative example 2 20％ 88％
5 Comparative example 3 22％ 90％
6 Example 1 32％ 95％
7 Example 2 30％ 97％
8 Example 3 31％ 95％
9 Example 4 33％ 95％
10 Example 5 35％ 98％
11 Example 6 28％ 96％
12 Example 7 24％ 94％
13 Example 8 25％ 94％
As can be seen from Table 2, the halogen-containing titanium silicalite molecular sieve provided by the invention has higher benzene conversion rate and product selectivity in the reaction of benzene oxidation to prepare phenol.

Claims (21)

1. A halogen-containing titanium silicalite molecular sieve characterized in that it contains halogen and carbon in amounts of 0.5% to 5% and 0.5% to 4%, respectively, preferably 1% to 3% and 0.8% to 2.5%, respectively, by total weight of the molecular sieve.
2. The titanium silicalite molecular sieve of claim 1, wherein the halogen is one or more of fluorine, chlorine, bromine, and iodine.
3. The titanium silicalite molecular sieve of claim 1, wherein R is XRF /R XPS A value greater than 2, preferably in the range of 2.5 to 4,R XRF For atomic ratio of halogen to silicon in the molecular sieve phase analyzed by XRF, R XPS Is the atomic ratio of halogen to silicon on the surface of the molecular sieve analyzed by XPS.
4. The titanium silicalite molecular sieve of claim 1 characterized by an infrared spectrum characterized by a characteristic peak intensity ratio I 3740 /I 3530 Is 4 to 10, wherein, I 3740 Is 3740cm in infrared hydroxyl spectrum of molecular sieve -1 Intensity of absorption peak of (A), I 3530 Is 3530cm in infrared hydroxyl spectrum of a molecular sieve -1 The intensity of the absorption peak at (c).
5. The titanium silicalite molecular sieve of any one of claims 1 to 4, wherein the molecular sieve has a titanium to silica molar ratio of (0.001 to 0.05): 1.
6. the titanium silicalite molecular sieve according to any one of claims 1 to 4, wherein the micropore specific surface area is from 350 to 420m 2 The volume of the micro pores is 0.130-0.170mL/g.
7. A titanium silicalite molecular sieve according to claim 1, characterized in that the framework structure of the molecular sieve is the MFI, BEA, MEL, MWW, SVR, MOR, EWT structure, the preferred framework structure being the MFI structure.
8. A method for preparing a halogen-containing titanium silicalite molecular sieve is characterized by comprising the following steps: contacting a titanium silicalite molecular sieve roasted for removing the template agent with an organic amine solution with the carbon number of C1-C3 at 40-100 ℃, and washing and drying a separated solid product; then contacting with solution containing micromolecular silanization reagent at 50-120 ℃, and separating and drying to obtain the titanium-silicon molecular sieve containing halogen.
9. The method according to claim 8, wherein the organic amine having a carbon number of C1 to C3 is one or more selected from methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethanolamine, propanolamine, ethylenediamine and propylenediamine.
10. The method according to claim 8, wherein the solvent in the solution of C1-C3 organic amine is selected from water, C1-C10 alcohol, C2-C10 ester or C3-C8 ketone.
11. The method according to claim 8, wherein the organic amine having a carbon number of C1 to C3 is an aqueous solution.
12. The method according to claim 8, wherein the organic amine solution having a carbon number of C1 to C3 has a mass fraction of 0.1% to 1.5%, preferably 0.2% to 1.0%.
13. The method of claim 8, wherein the small molecule silylating agent has the following structure: r 1(m) -Si-OR 2(n) Or R is 1(m) -Si-X (n) In the formula, R 1 Is of the general formula C x H y X z ，R 2 Is methyl or ethyl, m and n are positive integers, m + n =4, y + z =2x +1 and X is a positive integer from 1 to 3, and X is at least one of fluorine, chlorine, bromine and iodine.
14. The process of claim 8 wherein the small molecule silylating agent is selected from the group consisting of chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethyltriethoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, dichloromethyldimethoxysilane, dichloromethyldiethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloroethyltriethoxysilane, 1,2-dichloropropyltrimethoxysilane, 1,2-dichloropropyltriethoxysilane, chloromethyltrichlorosilane, dichloromethyldichlorosilane, chloroethyltrichlorosilane, dichloroethyldichlorosilane, chloropropyltrichlorosilane, dichloropropyldichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, bis (1,2-dichloropropyl) dichlorosilane, bis (1,2-dichloropropyl) dichlorosilane; preferably, the small molecule silanization reagent is selected from one or more of chloromethyltrimethoxysilane, chloroethyltrimethoxysilane, chloropropyltrimethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloropropyltrimethoxysilane, chloromethyltrichlorosilane, chloroethyltrichlorosilane, chloropropyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloropropyltrichlorosilane.
15. The method according to claim 8, wherein the solvent in the solution containing the small molecule silylation agent is selected from C3-C8 ketones, C2-C10 esters or C6-C12 alkanes.
16. The method of claim 8, wherein the molar ratio of the small molecule silylating agent to the titanium silicalite is (0.001-0.05): 1. preferably (0.005-0.03): 1; the molar ratio of the solvent containing the micromolecular silanization reagent to the titanium silicalite molecular sieve is (5-100): 1. preferably (20-60): 1, the silylation reagent is Si, and the titanium silicalite molecular sieve is SiO 2 And (6) counting.
17. The preparation process of claim 8, wherein the template removing agent is roasted at 350-800 deg.c for 0.5-6 hr; the drying is carried out at the temperature of 80-200 ℃ for 0.5-12h.
18. Use of the halogen-containing titanium silicalite molecular sieve of claims 1 to 7.
19. The use according to claim 18, wherein the halogen-containing titanium silicalite is used as an active component of a catalyst for organic conversion reactions or as an adsorbent component.
20. The method as claimed in claim 19, wherein the catalyst contains halogen-containing titanium silicalite molecular sieve in an amount of 5% or more by mass.
21. The use according to claim 19, wherein said organic conversion reaction is benzene oxidation.
CN202111006070.4A 2021-08-30 2021-08-30 Titanium-silicon molecular sieve containing halogen and preparation method thereof Pending CN115724439A (en)

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