CN111186845B - Method for preparing hierarchical pore TS-1 molecular sieve - Google Patents
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Abstract
The application discloses a method for preparing a hierarchical pore TS-1 molecular sieve, which takes a silicon-titanium ester polymer as a titanium-silicon source. In the method, silicon and titanium are uniformly connected on the same polymer, the hydrolysis rate is equivalent during hydrolysis, and TiO can be prevented2The generation of non-skeleton titanium is reduced; and the silicon-titanium ester polymer can be used as a silicon source and a titanium source and can also be used as a mesoporous template agent in the synthesis process, and the obtained TS-1 molecular sieve has a mesoporous structure and narrow pore size distribution, and has an important promotion effect on expanding the application of the TS-1 molecular sieve in the field of catalysis.
Description
Technical Field
The application relates to a method for preparing a hierarchical pore TS-1 molecular sieve, belonging to the field of molecular sieve preparation.
Background
The TS-1 molecular sieve is a microporous molecular sieve with MFI topological structure, and has tetrahedral Ti in its skeleton structure4+Center, thus pair has H2O2The selective oxidation reaction of the organic matters has good catalysis, such as the epoxidation of olefin, the hydroxylation of phenol, the ammoximation of ketone, the oxidation of alkane and other selective oxidation reactions. The TS-1 molecular sieve catalytic oxidation process has no pollution and mild reaction conditions, and overcomes the defects of serious pollution and long reaction process in the traditional process.
There are two major factors affecting TS-1 activity and stability: the contents of framework titanium and non-framework titanium of the molecular sieve, and the diffusion performance of the molecular sieve. For the former, because the titanium atom has larger radius and is difficult to enter an MFI framework, and a titanium source is easy to hydrolyze and polymerize into titanium dioxide precipitate, the generation of hexa-coordinated non-framework titanium is difficult to avoid in the synthesis of the TS-1 molecular sieve, and the existence of non-framework titanium species can promote H2O2Does not favor the oxidation reaction catalyzed by TS-1; in the latter case, the pore size of the TS-1 molecular sieve is too small, only 0.55nm, which greatly limits the transmission and diffusion of organic macromolecules in the catalyst, thereby inhibiting the reactivity and service life of the catalyst.
The synthesis of TS-1 is initially reported by Taramasso et al (US4410501), and is obtained by hydrothermal crystallization in an autoclave at 130-200 ℃ for 6-30 days, using tetraethyl silicate (TEOS) as a silicon source, tetraethyl titanate (TEOT) as a titanium source, and tetrapropylammonium hydroxide (TPAOH) as a template. However, the method is complicated to operate, the conditions are not easy to control, the experimental repeatability is poor, and due to the difference of the hydrolysis rates of the silicon source and the titanium source, a large amount of non-framework titanium is formed, so that the catalytic performance of the TS-1 molecular sieve is influenced. Subsequently, Thangaraj et al (zeolite,12(1992),943) obtained a TS-1 molecular sieve with reduced non-framework titanium by prehydrolyzing ethyl orthosilicate in aqueous TPAOH solution, and then slowly adding a solution of tetrabutyl titanate in isopropanol, which hydrolyzes more slowly, with vigorous stirring. The improvement mainly comprises the steps of controlling the hydrolysis process of the silicon source and the titanium source, enabling the hydrolysis rates of the silicon source and the titanium source to be more matched, inhibiting the formation of non-framework titanium and improving the framework titanium content in the TS-1 molecular sieve.
For the diffusion problem of the TS-1 molecular sieve, a common solution is to prepare a hierarchical pore molecular sieve by introducing mesopores into a zeolite molecular sieve system. Due to the existence of the multilevel pore channels, the flow diffusion performance of the catalyst material is greatly improved, so that the interaction between the guest molecules and the active sites is effectively enhanced. The construction of mesoporous or macroporous structures in molecular sieve materials by using a template agent is the most effective way for preparing the hierarchical pore molecular sieve at present, and comprises a soft template method and a hard template method. Wherein the soft template method such as Zhongxing et al (CN103357432A) utilizes polyether Pluronic F127 as mesoporous template agent, and the xerogel method synthesizes mesoporous nanometer TS-1 molecular sieve; zhang Shufen (CN102910643A) uses cetyl trimethyl ammonium bromide as a mesoporous template agent to introduce a mesoporous channel into the titanium-silicon molecular sieve; wherein the hard template method such as Chenlihua (CN104058423A) takes a three-dimensional ordered macroporous-mesoporous hierarchical porous carbon material as a hard template, TS-1 nanocrystals are grown in a three-dimensional ordered pore passage of the hard template in a limited domain manner, and the hierarchical porous TS-1 molecular sieve is prepared after the hard template is removed; plum steel and the like (CN101962195A) use cheap sugar to replace a porous carbon material as a macroporous-mesoporous template agent, and in the process of thermally treating sugar-containing TS-1 molecular sieve synthetic sol and drying the sol, sugar is heated, carbonized and dehydrated to directly form a hard template so as to obtain the multi-level pore TS-1 molecular sieve, but the activity and the stability of the TS-1 molecular sieve are required to be improved.
Disclosure of Invention
According to one aspect of the application, a method for preparing the hierarchical pore TS-1 molecular sieve is provided, wherein the silicon-titanium ester polymer in the method is formed by connecting a silicon source and a titanium source on the same polymer, so that the hydrolysis rates of the silicon source and the titanium source can be matched better, and TiO is prevented2The precipitation is more beneficial to the titanium entering the molecular sieve framework; in addition, the silicon-titanium ester polymer can be used as a silicon source and a titanium source and also can be used as a mesoporous template agent in the synthesis process, so that the TS-1 molecular sieve obtained by the method has a mesoporous structure, is narrow in pore size distribution and contains less non-framework titanium.
The method for preparing the hierarchical pore TS-1 molecular sieve is characterized in that a silicon-titanium ester polymer is used as a titanium source.
Optionally, the silicon-titanium ester polymer is used as a titanium source and a silicon source.
Optionally, the method comprises: and crystallizing a mixture containing a silicon-titanium ester polymer, a template agent and water to obtain the hierarchical porous TS-1 molecular sieve.
Optionally, the crystallization is hydrothermal crystallization.
Optionally, the silicon-titanium ester polymer is represented by formula I:
[Tia(ROx)4/x Si(1-a)]nformula I
Wherein a is more than 0 and less than or equal to 0.5, ROxIs an organic polyol R (OH)xThe group formed by H on OH is lost, R is selected from one of the groups formed by losing x hydrogen atoms of the hydrocarbon compound, and x is more than or equal to 2;
n＝2～30。
alternatively, said x in formula I is 2, 3 or 4.
Optionally, the silicon-titanium ester polymer has the following formula: [ Ti ]a(ROx)4/x Si(1-a)]n(ii) a Wherein a is more than 0 and less than or equal to 0.5; ROxIs an organic polyol, x is greater than or equal to 2, preferably 2, 3, 4.
Alternatively, the upper limit of said a in formula I is selected from 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5; the lower limit is selected from 0.001, 0.005, 0.01, 0.02, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4 or 0.45.
Optionally, the R in the formula I is selected from one of groups formed by losing x hydrogen atoms of the hydrocarbon compound.
Alternatively, in formula I, R is selected from C1～C8The hydrocarbon compound of (a) loses one of the groups formed by the x hydrogen atoms.
Optionally, the silicon titanate-based polymer is selected from at least one of silicon titanate ethylene glycol polyester, silicon titanate butanediol polyester, silicon titanate polyethylene glycol polyester, silicon titanate glycerol polyester and silicon titanate terephthalyl alcohol polyester.
Optionally, the silicon-titanium acid polyethylene glycol polyester is at least one selected from silicon-titanium acid polyethylene glycol 200 polyester, silicon-titanium acid polyethylene glycol 400 polyester, silicon-titanium acid polyethylene glycol 600 polyester and silicon-titanium acid polyethylene glycol 800 polyester.
Optionally, the preparation method of the silicon-titanium ester polymer comprises the following steps: carrying out ester exchange reaction on raw materials containing titanate, silicate and polyhydric alcohol to obtain the silicon-titanium ester polymer.
Optionally, the titanate is selected from at least one of the compounds having the formula shown in formula II:
wherein R is1，R2，R3，R4Independently selected from C1～C8Alkyl group of (1).
Optionally, the titanate comprises at least one of tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, tetrahexyl titanate, and tetraisooctyl titanate.
Optionally, the silicate is at least one selected from compounds having the formula shown in formula III:
wherein R is5，R6，R7，R8Independently selected from C1～C4Alkyl group of (1).
Optionally, the silicate comprises at least one of methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate.
Optionally, the number of hydroxyl groups in the polyol is not less than two.
Optionally, the polyhydric alcohol comprises at least one of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, terephthalyl alcohol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol.
Optionally, the polyethylene glycol may be one or a mixture of any several of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, and polyethylene glycol 800.
Optionally, the polyethylene glycol comprises at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, and polyethylene glycol 800.
Optionally, the molar ratio of the polyol, titanate and silicate is such that:
(titanate + silicate): (ii) polyol ═ (0.8 to 1.2) x/4;
titanate ester: 0.01 to 1% of silicate ester;
wherein x is the number of moles of hydroxyl groups contained in each mole of polyol;
the moles of the titanate, the silicate and the polyol are calculated by the moles of the substance.
Alternatively, the upper limit of the molar ratio of the (titanate + silicate) to polyol is selected from 0.85x/4, 0.9x/4, 0.95x/4, 1.0x/4, 1.1x/4, 1.15x/4, or 1.2 x/4; the lower limit is selected from 0.8x/4, 0.85x/4, 0.9x/4, 0.95x/4, 1.0x/4, 1.1x/4 or 1.15x/4
Alternatively, the upper limit of the molar ratio of titanate to silicate is selected from 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 0.8 or 1; the lower limit is selected from 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5 or 0.8. Optionally, the transesterification reaction conditions are: reacting for 2-10 hours at 80-180 ℃ in an inert atmosphere.
Optionally, the inert atmosphere comprises at least one of nitrogen and an inert gas.
Alternatively, the transesterification reaction is carried out under stirring.
Optionally, the upper temperature limit of the reaction is selected from 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃; the lower limit is selected from 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C or 170 deg.C.
Alternatively, the upper limit of time for the reaction is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours.
Optionally, the reaction time is 2-6 hours.
Optionally, the conversion rate of the transesterification reaction is 60% to 80%.
Optionally, the conditions of the transesterification reaction further comprise: after the reaction, distillation under reduced pressure was carried out.
Optionally, the reduced pressure distillation conditions are: reacting for 0.5-5 hours at 170-230 ℃ under the condition that the vacuum degree is 0.01-5 KPa.
Optionally, the upper limit of the vacuum degree in the vacuum distillation process is selected from 0.02Kpa, 0.05Kpa, 0.1Kpa, 0.5Kpa, 1Kpa, 2Kpa, 3Kpa, 4Kpa, or 5 Kpa; the lower limit is selected from 0.01Kpa, 0.02Kpa, 0.05Kpa, 0.1Kpa, 0.5Kpa, 1Kpa, 2Kpa, 3Kpa or 4 Kpa.
Optionally, in the reduced pressure distillation process, the upper limit of the reaction temperature is selected from 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 230 ℃; the lower limit is selected from 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C or 220 deg.C.
Alternatively, in the vacuum distillation process, the upper limit of the reaction time is selected from 1 hour, 2 hours, 3 hours, 4 hours or 5 hours; the lower limit is selected from 0.5 hour, 1 hour, 2 hours, 3 hours, or 4 hours.
Optionally, the vacuum degree is 1-5 KPa.
Alternatively, the conversion of the transesterification reaction is greater than 90%.
Optionally, the method comprises:
a) mixing polyol, titanate and silicate ester, carrying out ester exchange reaction under the stirring state, introducing inactive atmosphere for protection, wherein the reaction temperature is 80-180 ℃, and the reaction time is 2-10 hours;
b) and c), carrying out reduced pressure distillation after the reaction in the step a), controlling the vacuum degree of a system to be 0.01-5 KPa, controlling the reaction temperature to be 170-230 ℃ and the reaction time to be 0.5-5 hours, and preparing the high molecular ultraviolet absorbent.
As a specific embodiment, the method comprises:
1) uniformly mixing polyol, titanate and silicate in a three-neck flask, carrying out ester exchange reaction under the stirring state, connecting with a distillation device, introducing nitrogen for protection, wherein the reaction temperature is 80-180 ℃, the reaction time is 2-10 hours, and the conversion rate of the ester exchange reaction is 60-80%;
2) connecting the device after the reaction in the step 1) with a water pump or an oil pump for reduced pressure distillation to ensure that the transesterification reaction is carried out more completely, controlling the vacuum degree of the system to be 0.01-5 KPa, the reaction temperature to be 170-230 ℃, the reaction time to be 0.5-5 hours, and the conversion rate of the transesterification reaction to be more than 90%.
Optionally, the molar ratio of the silicon-titanium ester polymer to the template to the water satisfies:
template agent: 0.01-10% of silicon-titanium ester polymer;
water: 5-500 parts of a silicon-titanium ester polymer;
wherein the number of moles of the template is calculated by the number of moles of N atoms in the template;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer;
the silicon titanium esterThe silicon content in the polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles;
the mole number of the water is H2Moles of O itself.
Optionally, the upper limit of the molar ratio of the template agent to the silicon-titanium ester polymer is selected from 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 0.8, 1,2, 5, 8 or 10; the lower limit is selected from 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 0.8, 1,2, 5 or 8. Wherein the number of moles of the template is calculated by the number of moles of N atoms in the template; the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer; the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In moles of (a).
Optionally, the upper limit of the molar ratio of water to the titanium silicon ester polymer is selected from 8, 10, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450 or 500; the lower limit is selected from 5, 8, 10, 50, 80, 100, 150, 200, 250, 300, 350, 400, or 450. Wherein the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer; the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles; the mole number of the water is H2Moles of O itself.
Optionally, the molar ratio of the silicon-titanium ester polymer to the template to the water satisfies:
template agent: 0.05-8% of silicon-titanium ester polymer;
water: 10-300 parts of silicon-titanium ester polymer;
wherein the number of moles of the template is calculated by the number of moles of N atoms in the template;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer;
the silicon content in the silicon-titanium ester polymer is SiO2In terms of the number of moles of (a),the titanium content in the silicon-titanium ester polymer is TiO2In terms of moles;
the mole number of the water is H2Moles of O itself.
Optionally, the templating agent is selected from at least one of organic base templating agents.
Optionally, the silicon-titanium ester polymer, the organic base template and the water have the following molar ratio:
organic base template agent/(SiO)2+TiO2)＝0.01～10；
H2O/(SiO2+TiO2)＝5～500；
Wherein the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles; the organic base template is calculated by the mole number of N atoms.
Optionally, the organic base templating agent comprises a; the A is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide and triethylpropylammonium halide.
Optionally, the organic base templating agent further comprises B; and B is at least one of fatty amine and alcohol amine compounds.
Optionally, the B includes at least one of ethylamine, diethylamine, triethylamine, n-butylamine, butanediamine, hexanediamine, octanediamine, monoethanolamine, diethanolamine, triethanolamine.
Optionally, the organic base template agent is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide, triethylpropylammonium halide, and the like, or a mixture of these quaternary ammonium salts or quaternary ammonium bases and aliphatic amines or alcohol amine compounds such as ethylamine, diethylamine, triethylamine, n-butylamine, butanediamine, hexanediamine, octanediamine, monoethanolamine, diethanolamine, triethanolamine, and the like.
Optionally, the crystallization conditions are: heating to 100-200 ℃ under a closed condition, and crystallizing for no more than 30 days under the autogenous pressure.
Optionally, the crystallization conditions are: and (3) heating to 110-180 ℃ under a closed condition, and crystallizing for 1-28 days under the autogenous pressure.
Optionally, the crystallization conditions are: and (3) heating to 120-190 ℃ under a closed condition, and crystallizing for 1-15 days under the autogenous pressure.
Optionally, the upper temperature limit for crystallization is selected from 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃; the lower limit is selected from 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C or 190 deg.C.
Optionally, the upper time limit for crystallization is selected from 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 1 day, 2 days, 5 days, 10 days, 12 days, 15 days, 20 days, 25 days, 28 days, or 30 days; the lower limit is selected from 0.5 hour, 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, 1 day, 2 days, 5 days, 10 days, 12 days, 15 days, 20 days, 25 days, or 28 days.
Optionally, the crystallization is performed in a dynamic or static state.
Optionally, the mixture is aged or not aged to obtain a gel mixture.
Optionally, the mixture is aged and then crystallized;
the aging conditions are as follows: aging at 120 ℃ or below for 0-100 hours.
Optionally, the aging condition is: aging at 0-120 ℃ for 0-100 hours.
Optionally, the aging condition is: the temperature is 20-80 ℃ and the time is 0-80 hours.
Optionally, the aging is performed statically or dynamically.
Optionally, after crystallization is completed, separating the solid product, washing to be neutral, and drying to obtain the hierarchical pore TS-1 molecular sieve.
Optionally, the preparation method of the TS-1 molecular sieve comprises the following steps:
a) mixing a silicon-titanium ester polymer with an organic base template agent and water, and aging for 0-100 hours at a temperature not higher than 120 ℃ to obtain a gel mixture;
b) heating the gel mixture obtained in the step a) to 100-200 ℃ under a closed condition, and crystallizing for 0-30 days under autogenous pressure to obtain the hierarchical porous TS-1 molecular sieve.
As a specific embodiment, the preparation method of the hierarchical pore TS-1 molecular sieve comprises the following steps:
a') mixing a silicon-titanium ester polymer with an organic base template agent, water and the like, and stirring or statically aging for 0-100 hours at a temperature of not higher than 120 ℃ to obtain a gel mixture;
b ') putting the gel mixture obtained in the step a') into a high-pressure synthesis kettle, sealing, heating to 100-200 ℃, and crystallizing for 0-30 days under autogenous pressure;
e') after crystallization is completed, separating the solid product, washing the solid product to be neutral by using deionized water, and drying the product to obtain the TS-1 molecular sieve with the hierarchical pores.
Optionally, the TS-1 molecular sieve contains mesopores, and the pore diameter of the mesopores is 2-50 nm.
Optionally, the TS-1 molecular sieve contains mesopores, and the pore diameter of the mesopores is 2-5 nm.
Optionally, the TS-1 molecular sieve contains mesopores, and the pore diameter of the mesopores is 2-3 nm.
Optionally, the particle size of the hierarchical pore TS-1 molecular sieve is 100-500 nm.
Optionally, the particle size of the hierarchical pore TS-1 molecular sieve is 100-300 nm.
Optionally, the hierarchical pore TS-1 molecular sieve has a mesoporous structure with a narrow pore size distribution and less non-framework titanium.
Alternatively, the TS-1 molecular sieve is used for containing H2O2Selective oxidation reaction of the organic matter.
The synthesis process of the hierarchical pore TS-1 molecular sieve comprises two steps: mixing silicon ester, titanium ester and polyhydric alcohol for ester exchange reaction, and evaporating generated alcohol to obtain a silicon-titanium ester polymer; second oneCarrying out hydrothermal crystallization on a silicon-titanium ester polymer, an organic base template agent, water and the like in a reaction kettle to obtain the hierarchical pore TS-1 molecular sieve. Compared with the existing synthesis method, the synthesis method has the advantages that silicon and titanium are uniformly connected on the same polymer, the hydrolysis rate is equivalent during hydrolysis, and TiO can be prevented2The generation of non-skeleton titanium is reduced; and the novel silicon-titanium ester polymer can be used as a silicon source and a titanium source and also can be used as a mesoporous template agent in the synthesis process, and the obtained TS-1 molecular sieve has a mesoporous structure and narrow pore size distribution.
In the present application, "C1～C8"and the like" each refer to the number of carbon atoms contained in a group.
The beneficial effects that this application can produce include:
1) the silicon-titanium ester polymer provided by the application is used as a silicon source and a titanium source at the same time, and the proportion of silicon and titanium in the polymer is adjustable and is uniformly distributed;
2) in the method, silicon and titanium are uniformly connected on the same polymer, and the hydrolysis rate is equivalent during hydrolysis, so that TiO can be prevented2Precipitation of (4);
3) according to the method, the silicon-titanium ester polymer is used as a silicon source and a titanium source, and can also be used as a mesoporous template agent in a synthesis process, and the obtained TS-1 molecular sieve has a mesoporous structure and narrow pore size distribution, and has an important promotion effect on expanding the application of the TS-1 molecular sieve in the catalysis field.
Drawings
Figure 1 is an XRD pattern of the product synthesized according to example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a product synthesized according to example 1 of the present invention.
FIG. 3 is an ultraviolet-visible (UV-VIS) spectrum of a product synthesized according to example 1 of the present invention.
FIG. 4 shows the results of physical adsorption and pore distribution of the product synthesized according to example 1 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the present application, the product was subjected to X-ray powder diffraction phase analysis (XRD) using an X' Pert PRO X-ray diffractometer from pananace (PANalytical), netherlands, a Cu target, a K α radiation source (λ ═ 0.15418nm), a voltage of 40KV and a current of 40 mA.
In this application, SEM morphology analysis of the product was performed using Hitachi's TM3000 scanning electron microscope.
In the present application, the UV-visible diffuse reflectance spectrum of the product is determined using a Varian Cary500 Scan model UV-Vis spectrophotometer equipped with an integrating sphere.
In this application, the physical adsorption, external specific surface area and pore distribution analysis of the product were performed by using a fully automated physical analyzer, ASAP2020 available from Mike corporation.
The invention takes silicon-titanium ester polymer as silicon source and titanium source at the same time, adds organic alkali template agent and deionized water, and synthesizes the hierarchical pore TS-1 molecular sieve under hydrothermal condition.
According to one embodiment of the present application, a process for preparing a hierarchical pore TS-1 molecular sieve is as follows:
a) mixing a silicon-titanium ester polymer, an organic base template agent, water and the like according to a certain proportion to obtain a gel mixture, wherein the gel mixture preferably has the following molar ratio:
organic base template agent/(SiO)2+TiO2)＝0.01～10；
H2O/(SiO2+TiO2)＝5～500
Wherein the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles; the content of the organic base template agent is calculated by the mole number of N atoms.
b) Aging the gel mixture obtained in the step a) at 0-120 ℃ for 0-100 hours under stirring or standing conditions, wherein the aging process can be omitted or carried out;
c) putting the gel mixture obtained in the step b) into a high-pressure synthesis kettle, sealing, heating to 100-200 ℃, and crystallizing for 1-30 days;
d) after crystallization is completed, separating a solid product, washing the solid product to be neutral by using deionized water, and drying to obtain the hierarchical pore TS-1 molecular sieve;
the organic base template agent used in the step a) is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide, triethylpropylammonium halide and the like, or a mixture of the quaternary ammonium salt or the quaternary ammonium base and aliphatic amine or alcohol amine compounds such as ethylamine, n-butylamine, butanediamine, hexamethylenediamine, octanediamine, monoethanolamine, diethanolamine, triethanolamine and the like.
Preferably, the organic base template/(SiO) is present in the gel mixture of step a)2+TiO2)＝0.05～8。
Preferably, H is present in the gel mixture of step a)2O/(SiO2+TiO2)＝10～300。
Preferably, the aging process in the step a) can be omitted or carried out, wherein the aging temperature is 20-80 ℃ and the aging time is 0-80 hours.
Preferably, the crystallization temperature in the step b) is 120-190 ℃, and the crystallization time is 1-15 days.
Preferably, the crystallization in step b) is performed in a static or dynamic state.
Preferably, the hierarchical pore TS-1 molecular sieve is obtained in the step c).
Example 1
8g of silicon-titanium polyethylene glycol-200 ester polymer is added with 4.88g of tetrapropylammonium hydroxide (25 wt.%) aqueous solution and 5g of water, mixed evenly, stirred for 2 hours at room temperature and then transferred into a stainless steel high-pressure synthesis kettle. At this time, the molar ratio of each component of the synthesis system is [ Ti0.05(ROx)4/xSi0.95]n:0.5TPAOH:50H2O and R are hexyl, x is 2 and n is 20. Sealing the autoclave and placing the autoclave at a constant temperature of 170 DEG CIn an oven, the crystals were crystallized under autogenous pressure for 2 days. And after crystallization is finished, centrifugally separating the solid product, washing the solid product to be neutral by using deionized water, and drying the solid product in air at 110 ℃ to obtain the TS-1 molecular sieve with the hierarchical pores. Taking a sample of the raw powder to perform XRD analysis, wherein the result is shown in figure 1, and the sample is a TS-1 molecular sieve; the Scanning Electron Microscope (SEM) image of the sample is shown in FIG. 2, and as can be seen, the particle size of the sample is about 100 nm; the UV-VIS diffuse reflectance spectrum of this sample is shown in FIG. 3, from which it can be seen that there is almost no non-framework titanium in the sample; the physical adsorption and pore distribution curves of the sample are shown in fig. 4, and it can be seen that the sample has mesopores of about 2 nm.
(ROxRadical formed by loss of x hydrogen atoms from the hydroxyl group on polyethylene glycol-200)
The preparation method of the silicon-titanium polyethylene glycol-200 ester polymer comprises the following steps:
16.8g of PEG-200, 8.3g of tetraethoxysilane and 0.5g of tetraethyl titanate are added into a three-neck flask, a distillation device is connected, the temperature is raised to 175 ℃ under the conditions of stirring and nitrogen protection, and the reaction is carried out for 4 hours. In the process, a large amount of ethanol is distilled out, and the conversion rate of the ester exchange reaction is 90 percent; then connecting to a vacuum extractor, reacting under the condition of reduced pressure distillation, controlling the vacuum degree of the system at 1KPa, heating to 200 ℃, stopping the reaction after reacting for one hour, naturally cooling to room temperature, taking out a sample, and ensuring that the conversion rate of the ester exchange reaction is 95%.
In the examples of the present application, the conversion of the transesterification reaction was calculated in the following manner
According to the mol number n of the distilled by-product alcohol in the reaction process, determining the number of groups participating in the ester exchange reaction as n, and the sum of the mol numbers of esters in the reaction raw materials as m, wherein the conversion rate of the ester exchange reaction is as follows: n/xm. x depends on the number of alkoxy groups attached to the central atom in the ester.
The prepared sample was subjected to thermogravimetric testing and thermogravimetric analysis using a thermogravimetric analyzer, model TA Q-600, manufactured by TA Instruments. The nitrogen flow rate was 100ml/min and the temperature was raised to 700 ℃ at a rate of 10 ℃/min. According to the reaction conversion xThe degree of polymerization n of the product can be determined: n is 1/(1-x). The chemical formula of the obtained sample is [ Ti ]0.05(ROx)4/xSi0.95]nR is a radical formed by polyethylene glycol 200 losing two hydrogen atoms on the hydroxyl group, x is 2, and n is 20.
Examples 2 to 13
The specific ingredients, materials, reaction conditions and analysis results are shown in table 1 below, the synthesis process is similar to example 1, and other analysis results of the product are shown in table 1 below.
Table 1 raw material composition, compounding ratio and crystallization conditions of examples 2 to 13
In Table 1, R is selected from the group consisting of hydrocarbon compounds in which x hydrogen atoms are lost, ethyl, propyl, butyl, polyethylene glycol, p-xylylene, etc., and x is 2 to 6.
The crystallization in examples 1 to 13 was static crystallization.
Among them, the preparation methods of the silicon titanium ester polymers in examples 2 to 13 are the same as the preparation method of the silicon titanium polyethylene glycol-200 ester polymer in example 1 except that 16.8g of polyethylene glycol 200 is replaced with 5g of ethylene glycol, 6.1g of 1, 3-propanediol, 5g of glycerol, 7.2g of 1, 4-butanediol, 9.5g of 1, 6-hexanediol, 11.1g of p-xylylene glycol, 9.3g of 1, 4-cyclohexanediol, 11.5g of 1, 4-cyclohexanedimethanol, 33.8g of polyethylene glycol 400, 65.6g of polyethylene glycol 800, and 5.5g of pentaerythritol, respectively, to obtain the silicon titanium ester polymers corresponding to examples 2 to 13.
Example 14
The temperature of crystallization was 100 ℃ and the time of crystallization was 30 days, and the other conditions were the same as in example 1.
The crystallization is dynamic crystallization, and the crystallization conditions are as follows: the crystallization temperature and crystallization time were the same as in example 1, using a rotary oven with a rotation speed of 35 rpm.
Example 15
Aging is carried out before crystallization, and the aging conditions are as follows: static ageing was carried out at 120 ℃ for 2 hours, the other conditions being the same as in example 1.
Example 16
Aging is carried out before crystallization, and the aging conditions are as follows: the aging was carried out at 20 ℃ for 80 hours with stirring, and the other conditions were the same as in example 1.
Example 17 phase Structure analysis
XRD phase structure analysis was performed on the samples of examples 1 to 16, as shown typically in fig. 1. FIG. 1 is an XRD pattern of the sample prepared in example 1, from which it can be seen that the sample in example 1 is a TS-1 molecular sieve;
the test results of other samples are only slightly different from the spectrum of the sample in the example 1 in the intensity of diffraction peaks, and are TS-1 molecular sieves.
Example 18 topography testing
SEM morphology analysis was performed on the samples from example 1 to example 16, as shown typically in figure 2. FIG. 2 is an SEM image of the sample prepared in example 1, and it can be seen that the particle size of the sample in example 1 is about 200 nm.
The test results of other samples are similar to the test results of the sample in the embodiment 1, and the particle size of the sample is 100-300 nm.
Example 19 spectral analysis
The samples from example 1 to example 16 were subjected to UV-VIS diffuse reflectance spectroscopy analysis, as shown typically in figure 3. FIG. 3 is a UV-VIS diffuse reflectance spectrum of the sample prepared in example 1, from which it can be seen that there is almost no non-framework titanium in the sample in example 1.
The test results for the other samples were similar to the test results for the sample in example 1, with little non-framework titanium in the sample.
Example 20 pore distribution analysis
The samples from examples 1 to 16 were subjected to physical adsorption and pore distribution analysis, as shown typically in fig. 4. Fig. 4 shows the results of physical adsorption and pore distribution of the sample prepared in example 1, and it can be seen that the sample has mesopores of about 2nm and has a narrow pore size distribution.
The test results of other samples are similar to the test results of sample 1 in example 1, and the samples all have 2-50 nm mesopores.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (17)
1. A method for preparing hierarchical pore TS-1 molecular sieve is characterized in that a silicon-titanium ester polymer is used as a titanium-silicon source;
the silicon-titanium ester polymer is shown as a formula I:
[Tia(ROx)4/xSi(1-a)]nformula I
Wherein a is more than 0 and less than or equal to 0.5, ROxIs an organic polyol R (OH)xThe group formed by H on OH is lost, R is selected from one of the groups formed by losing x hydrogen atoms of the hydrocarbon compound, and x is more than or equal to 2;
n=2~30。
2. the method according to claim 1, characterized in that it comprises: crystallizing a mixture containing a silicon-titanium ester polymer, a template agent and water to obtain the hierarchical pore TS-1 molecular sieve;
the crystallization is hydrothermal crystallization.
3. The method of claim 1, wherein x in formula I is 2, 3, or 4.
4. The method according to claim 1, wherein the silicon-titanium ester polymer is at least one selected from the group consisting of silicon-titanium glycol polyester, silicon-titanium butanediol polyester, silicon-titanium polyethylene glycol polyester, silicon-titanium glycerol polyester, and silicon-titanium terephthalyl glycol polyester.
5. The method according to claim 1, wherein the molar ratio of the silicon-titanium ester polymer to the template to the water satisfies the following condition:
template agent: the silicon-titanium ester polymer = 0.01-10;
water: the silicon-titanium ester polymer = 5-500;
wherein the number of moles of the template is calculated by the number of moles of N atoms in the template;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer;
the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles;
the mole number of the water is H2Moles of O itself.
6. The method according to claim 5, wherein the molar ratio of the silicon-titanium ester polymer to the template to the water satisfies the following condition:
template agent: the silicon-titanium ester polymer = 0.05-8;
water: the silicon-titanium ester polymer = 10-300;
wherein the number of moles of the template is calculated by the number of moles of N atoms in the template;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the silicon content and the titanium content in the silicon-titanium ester polymer;
the silicon content in the silicon-titanium ester polymer is SiO2The titanium content in the silicon-titanium ester polymer is calculated according to the mole number of TiO2In terms of moles;
the mole number of the water is H2Moles of O itself.
7. The method of claim 2, wherein the templating agent is selected from at least one of organic base templating agents.
8. The method of claim 7, wherein the organic base templating agent comprises A; the A is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide and triethylpropylammonium halide.
9. The method of claim 8, wherein the organic base templating agent further comprises B; and B is at least one of fatty amine and alcohol amine compounds.
10. The method of claim 9, wherein B comprises at least one of ethylamine, diethylamine, triethylamine, n-butylamine, butanediamine, hexanediamine, octanediamine, monoethanolamine, diethanolamine, triethanolamine.
11. The method according to claim 2, wherein the crystallization conditions are: heating to 100-200 deg.C under sealed conditionoAnd C, crystallizing under autogenous pressure for no more than 30 days.
12. The method according to claim 11, wherein the crystallization conditions are: heating to 110-180 ℃ under a closed conditionoAnd C, crystallizing for 1-28 days under the autogenous pressure.
13. The method according to claim 11, wherein the crystallization conditions are: heating to 120-190 ℃ under a closed conditionoAnd C, crystallizing for 1-15 days under the autogenous pressure.
14. The method according to claim 2, characterized in that the mixture is aged and then crystallized;
the aging conditions are as follows: aging at 120 ℃ or below for 0-100 hours.
15. The method of claim 1, wherein the method of preparing the TS-1 molecular sieve comprises:
a) mixing the silicon-titanium ester polymer with an organic base template agent and water, and keeping the mixture at not higher than 120 DEGoAging for 0-100 hours at the temperature of C to obtain a gel mixture;
b) heating the gel mixture obtained in the step a) to 100-200 ℃ under a closed conditionoAnd C, crystallizing for no more than 30 days under the autogenous pressure to obtain the hierarchical porous TS-1 molecular sieve.
16. The method of claim 1, wherein the hierarchical pore TS-1 molecular sieve contains mesopores, and the pore diameter of the mesopores is 2-50 nm.
17. The method of claim 1, wherein the hierarchical pore TS-1 molecular sieve has a particle size of 100 to 500 nm.
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