CN111905798B - Preparation method and application of titanium-containing mesoporous material MCM-41 - Google Patents

Preparation method and application of titanium-containing mesoporous material MCM-41 Download PDF

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CN111905798B
CN111905798B CN201910382356.9A CN201910382356A CN111905798B CN 111905798 B CN111905798 B CN 111905798B CN 201910382356 A CN201910382356 A CN 201910382356A CN 111905798 B CN111905798 B CN 111905798B
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titanium
silicon
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CN111905798A (en
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邢嘉成
袁丹华
徐云鹏
刘中民
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • 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
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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    • 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
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract

The application discloses a preparation method and application of a titanium-containing mesoporous material MCM-41. The method can obtain the titanium mesoporous MCM-41 material, the silicon and the titanium in the silicon-titanium ester polymer are uniformly connected on the same polymer, the hydrolysis rate is equivalent during hydrolysis, and TiO can be prevented 2 The deposition reduces the generation of non-framework titanium, and has important promotion effect on expanding the application of the mesoporous material MCM-41 in the field of catalysis.

Description

Preparation method and application of titanium-containing mesoporous material MCM-41
Technical Field
The application relates to a preparation method and application of a titanium-containing mesoporous material MCM-41, belonging to the field of mesoporous materials.
Background
The MCM-41 molecular sieve has the characteristics of narrow pore size distribution, large specific surface area, large adsorption capacity and the like, and is widely applied to the fields of heterogeneous catalysis, adsorption, separation and the like. After metals such as titanium, iron, zirconium and the like are introduced into the MCM-41 molecular sieve, the catalytic activity of the molecular sieve can be effectively improved.
Ti-MCM-41 molecular sieves were prepared by introducing titanium metal ions into MCM-41 molecular sieves by Corma A et al (J Chem Soc 368 (1994) 147). Because the titanium metal ions have the characteristics of exchangeability, valence variability and the like, after the titanium metal ions are introduced into the molecular sieve framework, the redox capability of the molecular sieve can be improved, so that the catalytic performance of the molecular sieve is obviously improved.
Meanwhile, the Ti-MCM-41 molecular sieve has larger aperture and specific surface area than the microporous molecular sieves such as TS-1, and particularly shows excellent catalytic performance for chemical reactions involving macromolecular organic compounds.
The main factors influencing the activity and stability of Ti-MCM-41 are the contents of framework titanium and non-framework titanium in the molecular sieve, and the titanium source is easy to hydrolyze and polymerize into titanium dioxide precipitate, so that the generation of non-framework titanium such as titanium dioxide is difficult to avoid in the synthesis of the Ti-MCM-41 molecular sieve, and the existence of non-framework titanium species can promote H 2 O 2 The ineffective decomposition of (A) is not beneficial to the oxidation reaction catalyzed by Ti-MCM-41.
The Ti-MCM-41 molecular sieve adopts tetraethyl titanate as a titanium source at the earliest, the tetraethyl titanate is very easy to hydrolyze, the hydrolysis rate is difficult to control in the synthesis, and a titanium dioxide phase is generated in the synthesized Ti-MCM-41, so that the oxidation reaction is not facilitated.
Disclosure of Invention
According to one aspect of the application, a method for preparing a titanium-containing mesoporous material MCM-41 is provided, in the method, a silicon-titanium ester polymer is used as a titanium silicon source, the silicon source and the titanium source required by the reaction are connected to the same polymer, and the polymer can enable the hydrolysis rates of the silicon source and the titanium source to be more matched, so that TiO is prevented 2 The obtained titanium-containing mesoporous material MCM-41 has higher catalytic activity, regular pore channels and less non-framework titanium.
The preparation method of the titanium-containing mesoporous material MCM-41 is characterized in that a silicon-titanium ester polymer is used as a titanium-silicon source.
As an embodiment, the method for preparing the titanium-containing mesoporous material MCM-41 is characterized by comprising: crystallizing a mixture containing a silicon-titanium ester polymer, a surfactant, water and an alkali source to obtain the titanium-containing mesoporous material MCM-41; the crystallization is hydrothermal crystallization.
Preferably, the alkali source contains at least one of organic bases.
Further preferably, the organic base is selected from at least one compound having a formula shown in formula I:
Figure BDA0002053748660000021
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in the formula I, R 1 、R 2 、R 3 、R 4 Independently C 1 ～C 5 Alkyl group of (1).
Still more preferably, the organic base is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide or triethylpropylammonium halide.
Preferably, the surfactant comprises at least one of quaternary ammonium cationic surfactants.
Further preferably, the quaternary ammonium salt cationic surfactant is at least one selected from compounds having a structural formula shown in formula II:
Figure BDA0002053748660000031
in the formula I, R 5 、R 6 、R 7 、R 8 Independently C 1 ～C 18 Alkyl groups of (a); and is
R 5 、R 6 、R 7 、R 8 Is independently selected from C 1 ～C 5 And the remaining one is selected from C 12 ～C 18 Alkyl groups of (a);
x is at least one selected from halogens.
Even more preferably, X is Cl and/or Br.
Still more preferably, the quaternary ammonium salt cationic surfactant is selected from at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride.
Optionally, the molar ratio of the silicon-titanium ester polymer, the surfactant, the water and the alkali source in the mixture satisfies:
surfactant (b): the silicon-titanium ester polymer = 0.05-10;
water: the silicon-titanium ester polymer = 5-500;
alkali source: silicon-titanium ester polymer = 0.05-5
Wherein the mole number of the surfactant is calculated by the mole number of N element in the quaternary ammonium salt cationic surfactant;
the number of moles of the alkali source is calculated by the number of moles of the N element in the organic alkali;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer;
the mole number of the water is H 2 Moles of O itself.
Alternatively, the upper limit of the molar ratio of the surfactant to the titanium silicate-based polymer is selected from 0.08, 0.10, 0.15, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or 10.0; the lower limit is selected from 0.05, 0.08, 0.10, 0.15, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0. Wherein the mole number of the surfactant is calculated by the mole number of N atoms in the template; the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer.
Alternatively, the upper limit of the molar ratio of the alkali source to the titanium silicate-based polymer is selected from 0.08, 0.10, 0.15, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, or 10.0; the lower limit is selected from 0.05, 0.08, 0.10, 0.15, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, or 9.0. Wherein the number of moles of the alkali source is based on the number of moles of N atoms in the organic base; the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer.
Optionally, the upper limit of the molar ratio of water to the titanium silicon ester polymer is selected from 8, 10, 30, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 480 or 500; the lower limit is selected from 5, 8, 10, 30, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, or 480. Wherein the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer; the mole number of the water is H 2 The moles of O itself.
Optionally, the molar ratio of the silicon-titanium ester polymer, the surfactant, the alkali source and the water satisfies:
surfactant (b): the silicon-titanium ester polymer = 0.1-5;
water: the silicon-titanium ester polymer = 30-300;
alkali source: silicon-titanium ester polymer = 0.1-5
Wherein the mole number of the surfactant is calculated by the mole number of N element in the quaternary ammonium salt cationic surfactant;
the number of moles of the alkali source is calculated by the number of moles of the N element in the organic alkali;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer;
the mole number of the water is H 2 The moles of O itself.
Optionally, the hydrothermal crystallization conditions are as follows: heating to 100-200 deg.c in sealed condition, and crystallizing under autogenous pressure for no more than 30 days.
Optionally, the hydrothermal crystallization conditions are as follows: heating to 120-180 ℃ under a closed condition, and crystallizing for 1-15 days under autogenous pressure.
Optionally, the upper limit of the temperature of the hydrothermal 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 limit of time for the hydrothermal 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 hydrothermal crystallization is performed under dynamic or static conditions.
Alternatively, the mixture may be directly subjected to hydrothermal crystallization or the mixture may be aged and then subjected to hydrothermal crystallization.
Preferably, the mixture is aged and then subjected to hydrothermal crystallization; the aging conditions are as follows: and aging the mixture at an aging temperature of not higher than 120 ℃ for 0 to 100 hours.
Optionally, the aging temperature is 0 to 120 ℃, and the aging time is 0 to 100 hours.
Optionally, the aging temperature is 20 to 100 ℃, and the aging time is 1 to 50 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 titanium mesoporous material MCM-41.
The method for preparing the titanium-containing mesoporous material MCM-41 comprises the following steps:
a) Aging a mixture containing a silicon-titanium ester polymer, a surfactant, an alkali source and water at the temperature of 0-120 ℃ for 0-100 hours to obtain a gel mixture;
b) Heating the gel mixture obtained in the step a) to 120-180 ℃ under a closed condition, and crystallizing for 1-15 days under autogenous pressure to obtain the titanium-containing mesoporous material MCM-41.
Optionally, the silicon-titanium ester polymer is selected from at least one of compounds having a chemical formula shown in formula III:
[Ti a (R 9 O x ) 4/x Si (1-a) ] n formula III
Wherein a is more than 0 and less than or equal to 0.5 x Is an organic polyol R 9 (OH) x Radicals formed by H on OH, R 9 One selected from the group consisting of hydrocarbon compounds which are deprived of x hydrogen atoms, wherein x is a positive integer of 2 or more;
n＝2～30；
preferably, said x in formula I is 2, 3 or 4.
Optionally, the silicon-titanium ester polymer has the following formula: [ Ti ] a (R 9 O x ) 4/x Si (1-a) ] n (ii) a Wherein a is more than 0 and less than or equal to 0.5; r 9 O x Is an organic polyol, x is greater than or equal to 2, preferably 2, 3 and 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.
Alternatively, R in formula I 9 One selected from the group consisting of hydrocarbons which have lost x hydrogen atoms.
Alternatively, R in formula I 9 Is selected from C 1 ～C 8 The hydrocarbon compound of (a) loses one of the groups formed by the x hydrogen atoms.
Specifically, optionally, the silicon-titanium ester polymer includes at least one of a silicon-titanium polyethylene glycol ester polymer, a silicon-titanium ethylene glycol ester polymer, and a silicon-titanium terephthalate polymer.
In one embodiment, the silicon-titanium ester polymer is obtained by performing ester exchange reaction on raw materials containing silicate, titanate and polyhydric alcohol.
Optionally, the transesterification is carried out under stirring conditions.
Optionally, the reaction conditions of the transesterification are: reacting for 2-10 hours at 80-180 ℃ in an inert atmosphere. Optionally, the reaction conditions of the transesterification are: introducing nitrogen for protection, wherein the reaction temperature is between 80 and 180 ℃, and the reaction time is between 2 and 10 hours.
Optionally, the reaction conditions of the transesterification are: reacting for 2-10 hours at 100-160 ℃ in an inert atmosphere.
Optionally, the reaction conditions of the transesterification are: reacting for 4-8 hours at 100-160 ℃ in an inert atmosphere.
Optionally, the reaction conditions of the transesterification are: under the protection of nitrogen, the reaction temperature is between 100 and 160 ℃, and the reaction time is between 4 and 8 hours.
Optionally, the transesterification reaction temperature is at an upper limit selected from 85 ℃, 90 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃,170 ℃, 175 ℃ or 180 ℃; the lower limit is selected from 80 deg.C, 85 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, 170 deg.C, and 175 deg.C.
Alternatively, the upper reaction time limit for the transesterification is selected from 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 9.5 hours, or 10 hours; the lower limit is selected from 2 hours, 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 9.5 hours.
Optionally, the inert atmosphere comprises at least one of nitrogen and an inert gas.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium, neon, argon, xenon.
Optionally, the transesterification further comprises distillation under reduced pressure.
Preferably, the reduced pressure distillation operation is performed when the transesterification conversion rate reaches between 60% and 80%.
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 vacuum degree is 0.05 to 3Kpa.
Optionally, the upper temperature limit of the reduced pressure distillation is selected from 175 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃, or 230 ℃; the lower limit is selected from 170 deg.C, 175 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C or 225 deg.C.
Optionally, the upper limit of time for the reduced pressure distillation is selected from 0.8 hour, 1 hour, 2 hours, 3 hours, 4 hours, 4.5 hours, or 5 hours; the lower limit is selected from 0.5 hour, 0.8 hour, 1 hour, 2 hours, 3 hours, 4 hours, or 4.5 hours.
Optionally, the upper vacuum limit of the reduced pressure distillation is selected from 0.02Kpa, 0.03Kpa, 0.05Kpa, 0.08Kpa, 0.1Kpa, 0.5Kpa, 1Kpa, 1.5Kpa, 2Kpa, 2.5Kpa, 3Kpa, 3.5Kpa, 4Kpa, 4.5Kpa, or 5Kpa; the lower limit is selected from 0.01KPa, 0.02KPa, 0.03KPa, 0.05KPa, 0.08KPa, 0.1KPa, 0.5KPa, 1KPa, 1.5KPa, 2KPa, 2.5KPa, 3KPa, 3.5KPa, 4KPa or 4.5KPa.
Optionally, the silicate, titanate and polyol are in a molar ratio such that:
titanate ester: silicate = 0.001-0.2;
(titanate + silicate): polyol = (0.5 to 5) x:4
Wherein x is the number of moles of hydroxyl groups contained in each mole of the polyol;
the number of moles of each of the above substances is calculated as the number of moles of the substance itself.
Optionally, the silicate, titanate and polyol are in a molar ratio such that:
titanate ester: silicate = 0.005-0.1;
(titanate + silicate): polyol = (0.8 to 1.2) x:4
Wherein x is the number of moles of hydroxyl groups contained per mole of the polyol;
the number of moles of each of the above substances is calculated from the number of moles of the substance itself.
Alternatively, the upper limit of the molar ratio of titanate to silicate is selected from 0.002, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.18 or 0.2; the lower limit is selected from 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15 or 0.18.
Alternatively, the upper limit of the molar ratio of the (titanate + silicate) to polyol is selected from 0.85x; the lower limit is selected from 0.8x; wherein x is the number of moles of hydroxyl groups contained per mole of the polyol.
Optionally, at least one of the silicates selected from compounds having the formula shown in formula IV:
Figure BDA0002053748660000081
wherein R is 10 ，R 11 ，R 12 ，R 13 Is independently selected from C 1 ～C 10 One of the alkyl groups of (1).
Alternatively, R in formula IV 10 ，R 11 ，R 12 ，R 13 Independently selected from C 1 ～C 4 One of the alkyl groups of (1).
Optionally, the silicate comprises at least one of methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate.
Optionally, the silicate is one or more of methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate and the like.
Optionally, the titanate is selected from at least one of the compounds having the formula shown in formula V:
Figure BDA0002053748660000082
wherein R is 14 ，R 15 ，R 16 ，R 17 Is independently selected from C 1 ～C 10 One of the alkyl groups of (1).
Alternatively, R in formula V 14 ，R 15 ，R 16 ，R 17 Independently selected from C 1 ～C 4 One of the alkyl groups of (1).
Optionally, the titanate is selected from at least one of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, and tetraisooctyl titanate.
Optionally, the titanate is selected from at least one of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, and tetraisooctyl titanate.
The polyol is selected from at least one organic compound containing-OH number more than or equal to 2.
Optionally, the polyol is selected from at least one of compounds having a formula as shown below: r 9 (OH) x Wherein R is 9 Is one selected from the group consisting of hydrocarbons which have x hydrogen atoms missing, wherein x is a positive integer of 2 or more.
Optionally, the polyhydric alcohol is selected from at least one of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 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, and sorbitol.
As an embodiment, the preparation method of the silicon titanium ester polymer comprises the following steps:
1) Putting raw materials containing silicate ester, titanate and polyalcohol at a reaction temperature of between 80 and 180 ℃ and carrying out ester exchange reaction under the protection of inactive atmosphere;
2) And c) carrying out reduced pressure distillation on the product obtained after the reaction in the step a), controlling the vacuum degree of the system to be 0.01-5 KPa, the reaction temperature to be 170-230 ℃, and the reaction time to be 0.5-5 hours, thus obtaining the silicon-titanium ester polymer.
Optionally, the titanium-containing mesoporous material MCM-41 contains mesopores, and the pore diameter of the mesopores is 2-10 nm.
Optionally, the titanium-containing mesoporous material MCM-41 contains mesopores, and the pore diameter of the mesopores is 2-3 nm.
Alternatively, the titanium-containing mesoporous material MCM-41 has a mesoporous structure with a narrow pore size distribution and less non-framework titanium.
As an implementation mode, the synthesis process of the titanium-containing mesoporous material MCM-41 disclosed by the invention comprises two steps of: mixing silicon ester, titanium ester and polyhydric alcohol for ester exchange reaction, and evaporating generated alcohol to obtain a silicon-titanium ester polymer; and secondly, carrying out hydrothermal crystallization on the silicon-titanium ester polymer, the surfactant, the alkali source, the water and the like in a reaction kettle to obtain the titanium-containing mesoporous material MCM-41. 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 prevented 2 The precipitation of (2) reduces the formation of non-framework titanium.
Specifically, the preparation method of the titanium mesoporous material MCM-41 comprises the following steps:
i) Uniformly mixing silicate ester, titanate and polyalcohol, carrying out ester exchange reaction under the stirring state, introducing nitrogen for protection, and reacting at the temperature of 80-180 ℃ for 2-10 hours, wherein the reaction time can be up to 60-80% of the conversion rate of the ester exchange reaction;
ii) carrying out reduced pressure distillation after the reaction in the step i), controlling the vacuum degree of the system to be 0.01-5 KPa, the reaction temperature to be 170-230 ℃, and the reaction time to be 0.5-5 hours, thus obtaining the silicon-titanium ester polymer;
iii) Mixing the silicon-titanium ester polymer obtained in the step ii) with a surfactant, water and water, and aging for 0-100 hours at a temperature not higher than 120 ℃ to obtain a gel mixture;
iv) heating the gel mixture obtained in the step iii) to 100-200 ℃ under a closed condition, and crystallizing for 0-30 days under autogenous pressure to obtain the titanium mesoporous material MCM-41.
According to still another aspect of the present application, there is provided a titanium-containing mesoporous material MCM-41 prepared by the method according to any one of the above methods, and the titanium-containing mesoporous material MCM-41 contains H 2 O 2 And/or tert-butyl hydroperoxide in organic selective oxidation reactions.
In the present application, "C 1 ～C 10 、C 1 ～C 4 "and the like" each refer to the number of carbon atoms contained in a group.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound.
In the present application, the "hydrocarbon compound" includes an alkane compound (straight-chain alkane, branched-chain alkane, and cyclic alkane), an alkene compound, an alkyne compound, and an aromatic hydrocarbon compound. Such as p-tolyl group in which toluene loses the hydrogen atom para to the methyl group on the phenyl ring, or benzyl group in which toluene loses any of the hydrogen atoms on the methyl group, and the like.
The beneficial effects that this application can produce include:
1) According to the preparation method of the titanium-containing mesoporous material MCM-41, silicon and titanium are uniformly connected to the same polymer, the hydrolysis rate is equivalent during hydrolysis, and TiO can be prevented 2 Inhibiting the formation of non-framework titanium. Reduction of H 2 O 2 The ineffective decomposition of the catalyst is beneficial to the oxidation reaction catalyzed by Ti-MCM-41.
2) According to the preparation method of the titanium-containing mesoporous material MCM-41, the use of tetraethyl titanate as a titanium source is avoided, and the hydrolysis rate of the titanium source and the silicon source in synthesis is favorably controlled.
3) The preparation method of the titanium-containing mesoporous material MCM-41 improves the catalytic activity of the obtained material by reducing the formation of non-framework titanium, especially in the presence of H 2 O 2 And/or the catalytic effect in the selective oxidation reaction of organic compounds of t-butyl hydroperoxide.
Drawings
FIG. 1 is an XRD pattern of sample A1 according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of sample A1 according to example 1 of the present invention;
FIG. 3 is an ultraviolet-visible (UV-VIS) spectrum of sample A1 according to example 1 of the present invention;
FIG. 4 is a plot of the pore size distribution of sample A1 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.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
in the present application, X' Pert PRO X-ray diffractometer from pananace (PANalytical) of the netherlands, cu target, ka radiation source (λ =0.15418 nm), voltage 40KV, current 40mA, X-ray powder diffraction phase analysis (XRD) was performed on the product.
In this application, the SEM morphology of the product was analyzed using Hitachi's SU8020 scanning electron microscope.
In this application, the UV-visible diffuse reflectance spectrum of the product was measured using a Varian Cary500Scan model UV-Vis spectrophotometer equipped with an integrating sphere.
In this application, the product was analyzed for physical adsorption and pore distribution using a fully automated physical analyzer, ASAP2020, mike corporation.
In the present application, the conversion of the transesterification reaction is calculated on a carbon mole basis by the following method:
determining the number n of groups participating in the transesterification reaction according to the mole number n of the alcohol serving as a by-product distilled in the reaction process, wherein the sum of the mole numbers of titanate and silicate in the reaction raw materials is m, and then the conversion rate of the transesterification reaction is as follows: n/4m.
The titanium-containing mesoporous material MCM-41 is prepared by taking a silicon-titanium ester polymer as a silicon source and a titanium source at the same time, adding an alkali source, a surfactant and deionized water and under a hydrothermal condition.
According to one embodiment of the present application, the method for preparing the titanium-containing mesoporous material MCM-41 is as follows:
a1 Silicate ester, titanate and polyalcohol are added into a three-neck flask to be uniformly mixed, ester exchange reaction is carried out under the stirring state, a distillation device is connected, nitrogen is introduced for protection, the reaction temperature is between 80 and 180 ℃, the reaction time is between 2 and 10 hours, and the conversion rate of the ester exchange reaction is between 60 and 80 percent.
Preferably, the silicate, titanate and polyol in the step a 1) have the following molar ratio:
titanate/silicate = 0.005-0.1
[ titanate + silicate ]/polyol = (0.8-1.2) x/4.
Wherein x is the number of moles of hydroxyl groups contained in each mole of polyol;
b1 Connecting the device after the reaction in the step a 1) with a water pump or an oil pump to perform reduced pressure distillation so as to ensure that the ester exchange reaction is more completely performed, 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 ester exchange reaction to be more than 90 percent to obtain the silicon-titanium ester polymer.
c1 Mixing the silicon-titanium ester polymer obtained in the step b 1) with an organic base template agent and water, and keeping the mixture at a temperature of not higher than 120 ℃ to stir or stand and age for 0 to 100 hours to obtain a gel mixture:
preferably, the silicon-titanium ester polymer, the surfactant, the alkali source and the water in the step c 1) have the following molar ratio:
surfactant/(SiO) 2 +TiO 2 )＝0.1～5；
H 2 O/(SiO 2 +TiO 2 )＝30～300
Alkali source/(SiO) 2 +TiO 2 )＝0.1～5；
Wherein the silicon content in the silicon-titanium ester polymer is SiO 2 In terms of mole number, the titanium content in the silicon-titanium ester polymer is calculated according to TiO 2 Counting the number of moles; the content of the surfactant is calculated by the mole number of N atoms; the content of the alkali source is in terms of moles of N atoms.
d1 Loading the gel mixture obtained in the step c 1) into a high-pressure synthesis kettle, sealing, heating to 100-200 ℃, and crystallizing for 0-30 days under autogenous pressure;
e1 After crystallization is completed, separating a solid product, washing the solid product to be neutral by using deionized water, and drying to obtain the titanium-containing mesoporous material MCM-41;
the silicate in the step a 1) is at least one of methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate;
the titanate in the step a 1) is at least one of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate and tetraisooctyl titanate;
the polyol in the step a 1) has a general formula of R- (OH) x Wherein x is more than or equal to 2;
preferably, the polyol is: at least one of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 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 and sorbitol.
Preferably, the reaction in the step a 1) is carried out under the protection of nitrogen, the reaction temperature is between 80 and 180 ℃, and the reaction time is between 2 and 10 hours.
Preferably, the conversion rate of the transesterification reaction in step a) is between 65% and 80%.
Preferably, the step b 1) is carried out under reduced pressure distillation conditions, and the vacuum degree of the reaction system is in the range of 0.05-3 Kpa.
Preferably, the reaction temperature in the step b 1) is 170-230 ℃, and the reaction time is 0.5-5 hours.
Preferably, the conversion of the transesterification reaction in said step b 1) is greater than 90%.
The surfactant used in the step c 1) is dodecyl trimethyl ammonium bromide; cetyl trimethylammonium bromide; at least one of octadecyl trimethyl ammonium chloride.
The alkali source used in step c 1) is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide and triethylpropylammonium halide
Preferably, the aging process in step c 1) can be omitted or performed, and the aging temperature is 20-100 ℃ and the aging time is 1-50 hours.
Preferably, the aging process in step c 1) is performed in a static or dynamic state.
Preferably, the temperature of the crystallization step in the step d 1) is 120-180 ℃, and the crystallization time is 1-15 days.
Preferably, the crystallization process in step d 1) is performed in a static or dynamic state.
Preferably, the titanium-containing mesoporous material MCM-41 obtained in the step e 1) has a mesoporous structure with narrow pore size distribution and less non-framework titanium.
Example 1
The specific batching process is as follows: adding 5g of tetraethoxysilane, 0.29g of tetraethyl titanate and 10g of polyethylene glycol 200 into a three-neck flask, uniformly mixing, carrying out transesterification reaction under a stirring state, connecting a distillation device, introducing nitrogen for protection, heating to 175 ℃, reacting for 5 hours, wherein the conversion rate of the transesterification reaction is 75 percent, connecting a water pump for reduced pressure distillation to ensure that the transesterification reaction is more complete, controlling the vacuum degree of a system to be 3KPa, the reaction temperature to be 200 ℃, the reaction time to be 1 hour, and carrying out transesterification reactionThe conversion rate of the reaction is 92%, and a silicon-titanium polyethylene glycol ester polymer is obtained and is marked as a silicon-titanium polymer sample 1 # 。
The resulting silicon titanium polyethylene glycol ester polymer was mixed with 8g tetrapropylammonium hydroxide (25 wt.% aqueous solution), 10g cetyltrimethylammonium bromide, and 12g water, stirred at room temperature for aging for 2 hours, and then transferred to a stainless steel high-pressure synthesis kettle. At this time, the molar ratio of each component of the synthesis system is
Ti 0.05 (PEG-200) 2 Si 0.95 :0.4TPAOH:1.125CTAB 40H 2 O。
The high-pressure synthesis kettle is sealed and put into an oven which is heated to the constant temperature of 120 ℃, and the crystallization is carried out for 2 days under the autogenous pressure. And after the 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 the air at 110 ℃ to obtain the titanium-containing mesoporous material MCM-41 which is marked as a sample A1.
Taking a sample A1 of the raw powder to perform XRD analysis, wherein the result is shown in figure 1, and as can be seen from figure 1, the sample A1 is a titanium-containing mesoporous material MCM-41; a Scanning Electron Microscope (SEM) image of sample A1 is shown in FIG. 2; the UV-VIS diffuse reflection spectrum of sample A1 is shown in fig. 3, and as can be seen from fig. 3, there is almost no titanium dioxide in sample A1; the physical adsorption and pore distribution curves of sample A1 are shown in table 1, and it can be seen from the figure that the sample has mesopores of about 2 nm.
TABLE 1 specific surface area and pore distribution of the sample of example 1
Figure BDA0002053748660000151
Example 2
The specific batching process is as follows: adding 5g of tetraethoxysilane, 0.05g of tetraethyl titanate and 3.13g of ethylene glycol into a three-neck flask, uniformly mixing, carrying out transesterification reaction under a stirring state, connecting a distillation device, introducing nitrogen for protection, heating to 100 ℃, reacting for 5 hours, wherein the conversion rate of the transesterification reaction is 70%, connecting a water pump for reduced pressure distillation to ensure that the transesterification reaction is more complete, controlling the vacuum degree of a system to be 3KPa, the reaction temperature to be 170 ℃, the reaction time to be 1 hour, and converting the transesterification reactionThe percent conversion is 90 percent, and the silicon titanium glycol ester polymer is obtained and is marked as a silicon titanium polymer sample 2 # 。
The resulting silicon titanium glycol ester polymer was mixed with 2g tetrapropylammonium hydroxide (25% by weight aqueous solution), 8.9g cetyltrimethylammonium bromide, and 3g water, aged for 2 hours with stirring at room temperature, and transferred to a stainless steel autoclave synthesis reactor. At the moment, the molar ratio of each component of the synthesis system is Ti 0.01 (OCH 2 CH 2 O) 2 Si 0.99 :0.1TPAOH:1CTAB：10H 2 O。
The high-pressure synthesis kettle is sealed and put into an oven which is heated to the constant temperature of 150 ℃, and crystallized for 15 days under the autogenous pressure. And after the 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 the air at the temperature of 110 ℃ to obtain the titanium-containing mesoporous material MCM-41 marked as A2.
Example 3
The specific batching process is as follows: adding 5g of methyl orthosilicate, 2.8g of tetrabutyl titanate and 11.35g of terephthalyl alcohol into a three-neck flask, uniformly mixing, carrying out transesterification reaction under a stirring state, connecting a distillation device, introducing nitrogen for protection, heating to 160 ℃, reacting for 5 hours, wherein the conversion rate of the transesterification reaction is 80%, connecting a water pump for reduced pressure distillation to ensure that the transesterification reaction is more complete, controlling the vacuum degree of a system to be 3KPa, the reaction temperature to be 230 ℃, the reaction time to be 1 hour and the conversion rate of the transesterification reaction to be 95%, thus obtaining the silicon-titanium-p-xylylene glycol ester polymer, which is marked as a silicon-titanium polymer sample 3 # 。
The resulting silicon titanium terephthalate polymer was mixed with 330g tetrapropylammonium hydroxide (25 wt.% aqueous solution), 88.7g cetyltrimethylammonium bromide and 120g water, aged for 2 hours with stirring at room temperature, and then transferred to a stainless steel high pressure synthesis kettle. At this time, the molar ratio of each component of the synthesis system is Ti 0.2 (OC 6 H 4 O) 2 Si 0.8 :10TPAOH:6CTAB：500H 2 O。
The autoclave was closed and placed in an oven heated to a constant temperature of 170 ℃ and crystallized under autogenous pressure for 1 day. And after the 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 the air at the temperature of 110 ℃ to obtain the titanium-containing mesoporous material MCM-41 marked as A3.
The crystallization described in examples 1 to 3 is static crystallization.
Example 4
Titanium-containing mesoporous material MCM-41 was prepared by the same method as in example 1, and the specific preparation conditions were different from those in example 1, as shown in tables 2 and 3.
Table 2 results of physical adsorption and pore distribution of the synthesized products
Figure BDA0002053748660000161
TABLE 3 Synthesis of mesoporous Material MCM-41 containing titanium
Figure BDA0002053748660000162
Figure BDA0002053748660000171
The crystallization referred to in example 4 was dynamic crystallization, and the crystallization conditions were: a rotary oven was used, the crystallization temperature and crystallization time were as shown in Table 2, and the rotation speed of the rotary oven was 35rpm.
Example 5 phase Structure analysis
XRD phase structure analysis was performed on the samples A1 to A7 of examples 1 to 4, and it was found that all of the samples A1 to A7 were MCM-41, a titanium-containing mesoporous material.
Typically represented as sample A1, with the XRD spectrum shown in figure 1. As can be seen from FIG. 1, the sample A1 is a titanium-containing mesoporous material MCM-41.
The XRD patterns of samples A2 to A7 are similar to those of fig. 1, i.e., the peak positions and peak shapes of the diffraction peaks are substantially the same, and the peak intensities are slightly different.
Example 6 topography testing
SEM topography analysis was performed on the samples A1 to A7 of examples 1 to 4, and the results showed that the samples A1 to A7 all had similar morphologies.
Representative is sample A1, whose SEM is shown in FIG. 2.
Example 7 spectral analysis
The samples A1 to A7 of examples 1 to 4 were subjected to UV-VIS diffuse reflection spectroscopy, and the results showed that none of the samples A1 to A7 had almost no non-skeleton titanium of the titanium dioxide phase.
Typical representative is sample A1, whose UV-VIS diffuse reflectance spectrum is shown in FIG. 3. As can be seen from FIG. 3, the samples had almost no non-skeleton titanium of the titanium dioxide phase.
Example 8 pore distribution analysis
Physical adsorption and pore distribution analysis of the samples A1 to A7 of examples 1 to 4 revealed that the samples A1 to A7 each had mesopores of 2 to 10nm, and the mesopore size distribution of the individual samples was concentrated within a range of ± 1nm in the peak pore size.
Typical example is sample A1, the result of physical adsorption and pore distribution is shown in FIG. 4, from which it can be seen that sample A1 has mesopores of about 4.7nm, and the pore size of the mesopores is concentrated between 4 nm and 5 nm.
Example 9 measurement of Oxidation reaction Performance
And hydrogen peroxide is used as an oxidant to measure the reaction performance of cyclohexene oxide.
Typically represented as sample A1, comprising the steps of:
taking 0.1g of sample A1 (serving as a catalyst), adding 10ml of acetonitrile, 0.36g of cyclohexene and 0.5g of hydrogen peroxide (30 mass percent) into a round-bottom flask, condensing and refluxing under the condition of heating in a water bath at the temperature of 60 ℃, and reacting for 4 hours.
The reaction results for sample A1 are: the conversion rate of cyclohexene is 40%, the selectivity of epoxidation products is 74.5%, the conversion rate of hydrogen peroxide is 71.2%, and the selectivity is 68.2%.
The samples A2 to A7 were subjected to the performance measurement according to the above procedure, and the reaction results were similar to those of the sample A1.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (18)

1. A method for preparing titanium-containing mesoporous material MCM-41 is characterized in that a silicon-titanium ester polymer is used as a titanium-silicon source;
the silicon-titanium ester polymer is selected from at least one of compounds with a chemical formula shown in a formula III:
[Ti a (R 9 O x ) 4/x Si (1-a) ] n formula III
Wherein a is more than 0 and less than or equal to 0.5 9 O x Is an organic polyol R 9 (OH) x Radicals formed by H on OH, R 9 One of the groups formed by losing x hydrogen atoms from hydrocarbon compounds, wherein x is more than or equal to 2, n = 2-30;
the silicon-titanium ester polymer is obtained by carrying out ester exchange reaction on raw materials containing silicate ester, titanate and polyhydric alcohol.
2. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, comprising: crystallizing a mixture containing a silicon-titanium ester polymer, a surfactant, water and an alkali source to obtain the titanium-containing mesoporous material MCM-41;
the crystallization is hydrothermal crystallization.
3. The method for preparing titanium-containing mesoporous material MCM-41 of claim 2, wherein the alkali source comprises at least one of organic alkali;
the surfactant contains at least one of quaternary ammonium salt cationic surfactants.
4. The method for preparing titanium-containing mesoporous material MCM-41 of claim 3, wherein the organic base is at least one selected from compounds having a structural formula shown in formula I:
Figure QLYQS_1
in the formula I, R 1 、R 2 、R 3 、R 4 Independently C 1 ～C 5 Alkyl group of (1).
5. The method for preparing titanium-containing mesoporous material MCM-41 of claim 3, wherein the organic base is at least one selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide or triethylpropylammonium halide.
6. The method for preparing titanium-containing mesoporous material MCM-41 of claim 3, wherein the quaternary ammonium salt cationic surfactant is selected from at least one of compounds having a structural formula shown in formula II:
Figure QLYQS_2
in the formula I, R 5 、R 6 、R 7 、R 8 Independently C 1 ～C 18 Alkyl groups of (a); and is
R 5 、R 6 、R 7 、R 8 Is independently selected from C 1 ～C 5 And the remaining one is selected from C 12 ～C 18 Alkyl groups of (a);
x is at least one selected from halogens.
7. The method for preparing titanium-containing mesoporous material MCM-41 of claim 3, wherein the quaternary ammonium salt cationic surfactant is selected from at least one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride.
8. The method for preparing titanium-containing mesoporous material MCM-41 of claim 2, wherein the molar ratio of the silicon-titanium ester polymer, the surfactant, the water and the alkali source in the mixture satisfies:
surfactant (b): the silicon-titanium ester polymer = 0.05-10;
water: the silicon-titanium ester polymer = 5-500;
alkali source: silicon-titanium ester polymer = 0.05-5
Wherein the mole number of the surfactant is calculated by the mole number of N element in the quaternary ammonium salt cationic surfactant;
the number of moles of the alkali source is calculated by the number of moles of the N element in the organic alkali;
the mole number of the silicon-titanium ester polymer is calculated by the sum of the mole number of silicon element and the mole number of titanium element in the silicon-titanium ester polymer;
the mole number of the water is H 2 The moles of O itself.
9. The method for preparing titanium-containing mesoporous material MCM-41 of claim 2, wherein the hydrothermal crystallization conditions are as follows: heating to 100-200 ℃ under a closed condition, and crystallizing for no more than 30 days under autogenous pressure.
10. The method for preparing titanium-containing mesoporous material MCM-41 of claim 2, wherein the hydrothermal crystallization conditions are as follows: heating to 120-180 ℃ under a closed condition, and crystallizing for 1-15 days under autogenous pressure.
11. The method for preparing the titanium-containing mesoporous material MCM-41 of claim 2, wherein the mixture is aged and then hydrothermal crystallized;
the aging conditions are as follows: aging the mixture at a temperature of not higher than 120 ℃ for 0 to 100 hours.
12. The method for preparing titanium-containing mesoporous material MCM-41 of claim 2, wherein the method for preparing titanium-containing mesoporous material MCM-41 comprises:
a) Aging a mixture containing a silicon-titanium ester polymer, a surfactant, an alkali source and water at the temperature of 0-120 ℃ for 0-100 hours to obtain a gel mixture;
b) Heating the gel mixture obtained in the step a) to 120-180 ℃ under a closed condition, and crystallizing for 1-15 days under autogenous pressure to obtain the titanium-containing mesoporous material MCM-41.
13. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, wherein the transesterification reaction further comprises vacuum distillation;
the reduced pressure distillation conditions are as follows: reacting for 0.5-5 hours at 170-230 ℃ under the condition that the vacuum degree is 0.01-5 KPa.
14. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, wherein at least one of the silicates selected from the compounds having the formula shown in formula IV:
Figure QLYQS_3
wherein R is 10 ，R 11 ，R 12 ，R 13 Independently selected from C 1 ～C 10 One of the alkyl groups of (a);
the titanate is at least one selected from compounds having the chemical formula shown in formula V:
Figure QLYQS_4
wherein R is 14 ，R 15 ，R 16 ，R 17 Is independently selected from C 1 ～C 10 One of the alkyl groups of (a);
the polyhydric alcohol is at least one selected from compounds having a structural formula shown as the following formula: r 9 (OH) x Wherein R is 9 And x is a positive integer of 2 or more, and is one selected from the group consisting of hydrocarbons which have lost x hydrogen atoms.
15. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, wherein the molar ratio of silicate, titanate and polyol is as follows:
titanate ester: silicate = 0.001-0.2;
(titanate + silicate): polyol = (0.5 to 5) x:4;
wherein x is the number of moles of hydroxyl groups contained in each mole of the polyol;
the moles of silicate, titanate and polyol are all based on the moles of the substance itself.
16. The method for preparing mesoporous material MCM-41 containing titanium of claim 1, wherein the molar ratio of silicate, titanate and polyol is as follows:
titanate ester: silicate = 0.005-0.1;
(titanate + silicate): polyol = (0.8 to 1.2) x:4;
wherein x is the number of moles of hydroxyl groups contained in each mole of the polyol;
the moles of silicate, titanate and polyol are all based on the moles of the substance itself.
17. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, wherein the method for preparing the silicon-titanium ester polymer comprises the following steps:
1) Putting raw materials containing silicate ester, titanate and polyalcohol at a reaction temperature of 80-180 ℃ for ester exchange reaction under the protection of inactive atmosphere;
2) And (2) carrying out reduced pressure distillation on the product obtained after the reaction in the step 1), controlling the vacuum degree of a system to be 0.01-5 KPa, the reaction temperature to be 170-230 ℃, and the reaction time to be 0.5-5 hours, thus obtaining the silicon-titanium ester polymer.
18. The method for preparing titanium-containing mesoporous material MCM-41 of claim 1, wherein the titanium-containing mesoporous MCM-41 material contains regular mesopores, and the pore diameter of the mesopores is 2-10 nm.
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