CN111939975A - Bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof - Google Patents

Bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof Download PDF

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CN111939975A
CN111939975A CN202010855082.3A CN202010855082A CN111939975A CN 111939975 A CN111939975 A CN 111939975A CN 202010855082 A CN202010855082 A CN 202010855082A CN 111939975 A CN111939975 A CN 111939975A
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戴卫理
雷琦峰
李兰冬
武光军
关乃佳
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Nankai University
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Abstract

The invention relates to a bifunctional Beta molecular sieve catalyst for catalyzing olefin to be directly converted into 1, 2-diol and application thereof. The TiSn-Beta molecular sieve catalyst containing double Lewis acid sites is prepared by a two-step post-synthesis method, wherein the molar loading amounts of Ti and Sn are both 5%. The catalyst has simple and expandable preparation method, simultaneously contains double sites of titanium and tin, can effectively catalyze olefin epoxidation-hydration tandem reaction, and realizes the one-step conversion of olefin into 1, 2-diol, wherein the selectivity of the 1, 2-diol reaches more than 90 percent. The reaction process flow is simple, the condition is mild, the corrosion to equipment is small, the environment is friendly, the catalyst is easy to recover and can be recycled, and the method has good industrial application prospect.

Description

Bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof
Technical Field
The invention belongs to the technical field of olefin epoxidation, and mainly relates to a heterogeneous catalyst for olefin epoxidation reaction and a method for preparing 1, 2-diol by catalyzing olefin with the catalyst through a one-step method.
Background
1, 2-diols are produced primarily by the hydration of epoxides and are widely used as intermediates in the production of antifreeze, polyester resins, pharmaceuticals, cosmetics, and other chemicals. To date, various acid and base catalysts, such as ion exchange resins (CN201711111494.0), metal oxides (CN201210186971.0), titanium silicalite-based catalysts (CN201680068836.2), and the like, have been applied to the hydration of epoxides. Epoxy compounds are prepared primarily by the oxidation of olefins, and the direct preparation of 1, 2-diols from olefins is a preferred route in order to reduce the cost of epoxide isolation and purification.
The method for preparing 1, 2-cyclohexanediol from cyclohexene is introduced in CN201110386229.X, cyclohexene, hydrogen peroxide and a titanium silicalite molecular sieve are contacted in an organic solvent, the contact is carried out in the presence of acidic substances (sulfuric acid, phosphoric acid, formic acid, salicylic acid and the like), and the conversion rate of the cyclohexene and the selectivity of the 1, 2-cyclohexanediol can reach 91.7% and 96.1%. Although the method has good catalytic effect, liquid acid is introduced in the reaction process, so that the corrosion to equipment is large, waste acid is discharged, and the method does not meet the requirement of environmental protection.
CN201410512813.9 introduces a method for preparing 1, 2-cyclohexanediol from cyclohexene, wherein the method is used for catalyzing cyclohexene to react with hydrogen peroxide through a modified titanium silicalite molecular sieve to obtain the 1, 2-cyclohexanediol. The method has mild operation conditions, little corrosion to equipment and environmental friendliness, but the selectivity of the 1, 2-cyclohexanediol is lower and is only 66 percent.
Cn201410375699.x describes a process for preparing 1, 2-cyclopentanediol from cyclopentene by 1) epoxidation: reacting cyclopentene, a catalyst, a cocatalyst and hydrogen peroxide for 4-6 hours at 35-45 ℃ to generate cyclopentane epoxide; 2) and (3) hydrolysis reaction: adding solid protonic acid into the cyclopentane epoxide as a catalyst, and carrying out hydrolysis reaction at 70-90 ℃ for 80-110 hours to finally generate the cyclopentanediol. In the method, two catalysts are added step by step, and the catalytic system and the process flow are complex.
In CN201711348992.7, the 1, 2-cyclohexanediol is obtained by the mixture of cyclohexene, hydrogen peroxide and acetic acid and acetic anhydride under the catalysis of inorganic acid. Although the acidity in the reaction system is reduced, the method also has the problem of waste acid discharge, and the yield of the 1, 2-cyclohexanediol is only about 60 percent.
CN201410169234.9 discloses a catalyst for preparing 1, 2-diol by epoxy compound hydration, a preparation method and application thereof. In addition, titanium silicalite molecular sieves show excellent catalytic performance in olefin epoxidation with hydrogen peroxide (Green chem.2014,16, 2281-2291). However, the two catalysts only have good catalytic activity in the hydration of epoxy compounds and the stepwise reaction of olefin epoxidation, and the reaction for preparing 1, 2-diol by the olefin one-step method still lacks corresponding research, so that the research can not only reduce the separation cost of products, but also greatly improve the utilization rate of energy, and has good industrial application prospect.
CN110003138A discloses a method for removing aldehyde and ketone in HPPO process by molecular sieve catalytic reaction, wherein mention is made of the preparation of modified molecular sieve: the molecular sieve is one or more of ZSM-5, NaY, A, MCM and Beta molecular sieve, the modification method is an ion exchange method, and the modification reagent is Sn2+、Zn2+、Ca2+、Ni2+、NH4 +、Ti4+、Ag+、Co2+One or more of a hydrochloride or a nitrate. However, the document does not specifically disclose a Beta molecular sieve catalyst modified by introducing two metals simultaneously and the application thereof.
Disclosure of Invention
The invention aims to provide a bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof, which can overcome the defects of low selectivity and conversion rate, complex operation, high energy consumption, environmental pollution and the like in the prior art for preparing 1, 2-diol and provide an olefin epoxidation-hydration series reaction catalyst with simple preparation process and less byproducts. The catalyst has the function of catalyzing olefin epoxidation and hydration reaction simultaneously, and the preparation method is that the catalyst is synthesized by utilizing Beta molecular sieve dealumination and subsequent metal introduction two-step method. Preferably, two metals are introduced simultaneously in the introduction process, so that the metals are ensured to enter a molecular sieve framework, and meanwhile, the multifunctional active sites have good compatibility, so that the metal is prevented from existing in an oxide form to influence the catalytic performance. The catalyst shows excellent activity in the reaction of preparing 1, 2-diol by an olefin one-step method, the selectivity of the 1, 2-diol reaches over 90 percent at lower temperature and short reaction time, and the catalyst has good recycling property.
The bifunctional molecular sieve catalyst for directly preparing the 1, 2-diol by catalyzing the olefin is a bifunctional TiSn-Beta molecular sieve simultaneously containing titanium and tin sites, wherein the loading amounts of Ti and Sn are 0-10% respectively. The preferable load is 2.5-7.5%. Further preferably, the Ti and Sn are supported in amounts of 5%.
The preparation method comprises the following steps: the dealuminization of the H-Beta molecular sieve is used for preparing the all-silicon molecular sieve and the introduction of a metal active center. And (3) dealuminizing the H-Beta molecular sieve raw powder by concentrated nitric acid treatment to obtain the all-silicon molecular sieve Si-Beta. Removing the water physically adsorbed on the surface of the sample in vacuum environment, and adding a certain amount of metal precursor Ti (Cp)2Cl2And/or (CH)3)2SnCl2The mixture is ground and mixed evenly in a glove box, then the mixture is moved to a vacuum tube type furnace, the temperature is raised to 550 ℃, the mixture is roasted for 6 hours, and then the mixture is placed in a muffle furnace to be roasted for 6 hours at 550 ℃, so that molecular sieve catalysts Ti-Beta, Sn-Beta and TiSn-Beta are obtained.
The Ti-Sn-Beta and Sn-Ti-Beta molecular sieves are prepared by the same method as the method, but the introduction sequence of metal Ti and Sn is different, TiSn-Beta is introduced and recorded, Ti is introduced firstly and then Sn is introduced and recorded as Ti-Sn-Beta, and Sn is introduced firstly and then Ti is introduced and recorded as Sn-Ti-Beta.
The second Sn metal active center other than Ti is extended to Zr, Ta and Nb. TiZr-Beta, TiTa-Beta and TiNb-Beta molecular sieves are prepared by the same method.
The preparation method of the bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin comprises the following steps: dealuminizing to obtain the all-silicon molecular sieve, and then introducing metal Ti and Sn, i.e. the all-silicon molecular sieve and an organic metal precursor Cp2TiCl2And (CH)3)2SnCl2And grinding and uniformly mixing the mixture in a glove box, then roasting the mixture in a vacuum tube furnace at 550 ℃ for 6h, and further roasting in a muffle furnace at 550 ℃ for 6h to obtain the TiSn-Beta molecular sieve.
1) Firstly, uniformly mixing raw powder of the H-Beta molecular sieve with concentrated nitric acid, placing the mixture in an oil bath pot, heating the mixture to 100 ℃ and 110 ℃, refluxing and stirring the mixture for 20 to 25 hours, cooling the mixture to room temperature, washing the mixture to be neutral by using deionized water, and drying the mixture at 80 to 100 ℃ to obtain the all-silicon Si-Beta molecular sieve;
2) pretreating the full-silicon Si-Beta molecular sieve in a vacuum tube furnace at 180 ℃ and 200 ℃ for 10-12h to remove water adsorbed on the surface, and cooling the sample to room temperature;
3) then with a metal precursor Ti (Cp)2Cl2And/or (CH)3)2SnCl2Grinding and mixing uniformly in a glove box;
4) and then placing the mixed sample into a vacuum tube furnace, heating to 500-550 ℃ for roasting for 5-6h, and then placing the sample into a muffle furnace for roasting at 500-550 ℃ for 5-6h to obtain the molecular sieve catalyst: TiSn-Beta, Ti-Beta, Sn-Beta.
The silicon/aluminum ratio of the raw powder of the H-Beta molecular sieve in the step 1) is 13.5 (n)Si/nAl＝13.5)。
In the vacuum tube furnace in the step 4), the heating rate is 5 ℃/min.
Optionally, mixing the sample obtained in the step 2) with Ti (Cp)2Cl2Grinding and mixing uniformly in a glove box, transferring to a vacuum tube furnace, heating to 500-550 ℃, roasting for 5-6h, and then placing in a muffle furnace, roasting for 5-6h at 500-550 ℃, so as to obtain the Ti-Beta molecular sieve; mixing the obtained sample with (CH)3)2SnCl2Mixing, grinding in glove box, mixing, and transferring to vacuum tube furnaceHeating to 500-550 ℃ for roasting for 5-6h, and then placing in a muffle furnace for roasting at 500-550 ℃ for 5-6h to obtain a catalyst Ti-Sn-Beta; in the above process, Ti (Cp)2Cl2And (CH)3)2SnCl2The order of addition was reversed.
The invention provides an application of a bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin. The application method comprises the following steps:
putting the bimetallic Beta molecular sieve catalyst into a reaction kettle equipped with a stirring and electric heating device, adding a solution of an olefin substrate, a solvent and hydrogen peroxide, and reacting for 0.2-8 h at 25-100 ℃. After the reaction is finished, cooling to room temperature, centrifugally filtering the catalyst from the reaction solution, and analyzing the filtrate by gas chromatography to calculate the conversion rate and selectivity. Chlorobenzene was used as an internal standard.
The molar ratio of the olefin substrate to the hydrogen peroxide is 1: 1;
the solvent is one of methanol, ethanol, acetone, 1, 4-dioxane, gamma-valerolactone and acetonitrile. Methanol, ethanol, acetone are preferred.
The reaction temperature is 40-80 ℃, and the reaction time is 0.5-6 h. Stirring was carried out at 500 rpm.
The olefin substrate is one of cyclopentene, 2-cyclopentene-1-ketone, cyclohexene, 1-methyl-1-cyclohexene, 2-cyclohexene-1-ketone and 3-methyl-2-cyclohexene-1-ketone.
The concentration of the hydrogen peroxide solution is 31 wt%.
The invention provides application of a bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin, wherein the selectivity of the 1, 2-diol obtained by catalyzing olefin epoxidation hydration reaction for the first time reaches over 90 percent, and the conversion rate of the olefin directly recycled without activation regeneration is reduced to some extent, because macromolecular byproducts formed in the reaction process cover part of the active sites of the molecular sieve. The recovered catalyst is activated and regenerated through roasting treatment, and is recycled for 3 times, the olefin conversion rate and the 1, 2-diol selectivity are basically not obviously changed, and the catalyst activity is completely reproduced.
The invention has the following advantages: the bifunctional molecular sieve catalyst TiSn-Beta is prepared by a two-step post-synthesis method. The catalyst has double Lewis acid sites, and meanwhile, the specific cage structure of the molecular sieve well ensures the efficient series connection of olefin epoxidation and epoxide hydration and high selectivity of expected products. The preparation method of the catalyst is simple, no other solvent is required to be added, the catalytic activity is high, the selectivity of the target product is high, and the catalyst can be recycled. The catalyst prepared by the method is used for directly synthesizing 1, 2-diol from olefin through a series reaction, the selectivity of a target product exceeds 90%, and the yield can reach 70% at most. The method reduces the separation cost of the epoxide, improves the utilization rate of reactant atoms, provides a new research idea for the industrial reaction of directly preparing 1, 2-diol from olefin, and provides reference for other similar reactions.
Drawings
Figure 1 is the XRD pattern of the sample of example 1.
FIG. 2 is a HRTEM image of a sample of example 1.
FIG. 3 is a UV-vis plot of the sample of example 1.
FIG. 4 is a UV-vis plot of the sample of example 4.
FIG. 5 is a graph of UV-vis for the samples of example 5.
Detailed Description
The present invention will be described in more detail and fully hereinafter with reference to specific examples. The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
Example 1
The synthesis process of the titanium and tin-containing molecular sieve comprises two steps: the dealuminization of the H-Beta molecular sieve is used for preparing the all-silicon molecular sieve and the introduction of a metal active center. 10g H-Beta molecular sieve raw powder (n)Si/nAl13.5) and 200mL of concentrated nitric acid (13mol/L) are added into a round bottom three-neck flask, the round bottom three-neck flask is placed into an oil bath pot and heated to 100 ℃, reflux and stirring are carried out for 20h, the round bottom three-neck flask is cooled to room temperature, the round bottom three-neck flask is washed to be neutral by deionized water and dried at 80 ℃, and the all-silicon Si-Beta molecular sieve is obtained. The sample was pretreated in a vacuum tube furnace at 200 ℃ for 12 hours to remove surface adsorbed water, and 1.0g of the treated sample was mixed with 0.26g of Ti (Cp)2Cl2And 0.09g (CH)3)2SnCl2Grinding and mixing the mixture in a glove box uniformly, transferring the mixture into a vacuum tube furnace, heating to 550 ℃ (5 ℃/min), roasting for 6h, and then placing the mixture into a muffle furnace, roasting for 6h at 550 ℃, thus obtaining the catalyst A, namely TiSn-Beta. The loading amounts of Ti and Sn were both 5%.
Example 2
Using the same procedure as in example 1, with only a single metal of Ti, 1.0g of treated Si-Beta and 0.26g of Ti (Cp)2Cl2Grinding and uniformly mixing the mixture in a glove box, transferring the mixture into a vacuum tube furnace, heating to 550 ℃, roasting for 6h, and then placing the mixture into a muffle furnace, roasting for 6h at 550 ℃, thus obtaining the catalyst B, namely Ti-Beta. The amount of Ti supported was 5%.
Example 3
Using the same procedure as in example 1, with the introduction of only Sn as the single metal, 1.0g of treated Si-Beta was combined with 0.09g (CH)3)2SnCl2And grinding and uniformly mixing the mixture in a glove box, transferring the mixture into a vacuum tube furnace, heating to 550 ℃, roasting for 6h, and then placing the mixture in a muffle furnace, roasting for 6h at 550 ℃, thus obtaining the catalyst C, namely Sn-Beta. The supported amount of Sn was 5%.
Example 4
Using the same procedure as in example 1, the order of introduction of Ti, Sn metal, 1.0g of treated Si-Beta and 0.26g of Ti (Cp)2Cl2And grinding and uniformly mixing the mixture in a glove box, transferring the mixture into a vacuum tube furnace, heating to 550 ℃, roasting for 6h, and then placing the mixture in a muffle furnace, roasting for 6h at 550 ℃, so as to obtain the Ti-Beta molecular sieve. The resulting sample was mixed with 0.09g (CH)3)2SnCl2The mixture is ground and mixed evenly in a glove box, then the mixture is moved to a vacuum tube type furnace, the temperature is raised to 550 ℃, the mixture is roasted for 6 hours, and then the mixture is placed in a muffle furnace and roasted for 6 hours at 550 ℃, so that the catalyst D, Ti-Sn-Beta, is obtained. The loading amounts of Ti and Sn were both 5%.
Example 5
Using the same procedure as in example 1, the order of introduction of Ti, Sn metals was changed, 1.0g of treated Si-Beta was compared with 0.09g (CH)3)2SnCl2Grinding the mixture in a glove box, mixing, transferring to a vacuum tube furnace, heating to 550 deg.C, calcining for 6 hr, and roastingThen placing the mixture in a muffle furnace to roast for 6h at 550 ℃ to obtain the Sn-Beta molecular sieve. The obtained sample was mixed with 0.26g of Ti (Cp)2Cl2The mixture is ground and mixed evenly in a glove box, then the mixture is moved to a vacuum tube type furnace, the temperature is raised to 550 ℃, the mixture is roasted for 6 hours, and then the mixture is placed in a muffle furnace and roasted for 6 hours at 550 ℃, so that the catalyst E, Sn-Ti-Beta, is obtained. The loading amounts of Ti and Sn were both 5%.
Example 6
The same procedure as in example 1 was used, with varying amounts of Ti and Sn. 1.0g of treated Si-Beta with 0.13g of Ti (Cp)2Cl2And 0.14g (CH)3)2SnCl2The mixture is ground and mixed evenly in a glove box, transferred to a vacuum tube furnace, heated to 550 ℃ and roasted for 6h, and then placed in a muffle furnace to be roasted for 6h at 550 ℃ to obtain the catalyst F, namely 2.5 Ti7.5Sn-Beta. Wherein the loading amounts of Ti and Sn were 2.5 and 7.5%, respectively.
Example 7
The same procedure as in example 1 was used, with varying amounts of Ti and Sn. 1.0g of treated Si-Beta with 0.39g of Ti (Cp)2Cl2And 0.05g (CH)3)2SnCl2The mixture is ground and mixed evenly in a glove box, transferred to a vacuum tube furnace, heated to 550 ℃ and roasted for 6h, and then placed in a muffle furnace to be roasted for 6h at 550 ℃ to obtain the catalyst G, namely 7.5 Ti2.5Sn-Beta. Wherein the loading amounts of Ti and Sn were 7.5 and 2.5%, respectively.
Example 8
The same procedure as in example 1 was used to replace the metal precursor of Sn with a metal precursor of Zr, Ta or Nb. 1.0g of treated Si-Beta with 0.39g of Ti (Cp)2Cl2And 0.16g Zr (Cp)2Cl2、0.09g TaCl5Or 0.39g Nb (Cp)2Cl2The mixture is ground and mixed evenly in a glove box, transferred to a vacuum tube furnace, heated to 550 ℃ and roasted for 6h, and then placed in a muffle furnace to be roasted for 6h at 550 ℃ to obtain the catalysts TiZr-Beta, TiTa-Beta and TiNb-Beta. Both metals were loaded at 5%.
In order to prove the beneficial effects of the invention, the heterogeneous catalyst prepared in examples 1 to 7 is used for preparing 1, 2-diol by epoxidation hydration with olefin, and the specific test is as follows.
Example 9
Respectively placing 0.1g of catalyst A, B, C, D, E, F, G in a reaction kettle containing polytetrafluoroethylene lining, wherein the reaction kettle is provided with a magnetic stirrer and an electric heating device, and adding 5mmol of cyclohexene and 5mmol of H2O2(31 wt% aqueous solution) and 2.5ml acetonitrile, 60 ℃ reaction for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 1. We found that the order of introduction of the metals Ti and Sn had a large effect on the catalytic activity. The catalyst A (TiSn-Beta) obtained by introducing the Ti and the Sn is the best in catalytic performance, and the catalysts D (Ti-Sn-Beta) and E (Sn-Ti-Beta) obtained by introducing the Ti and the Sn gradually are lower in catalytic activity. This is probably due to the formation of the inert, non-framework metal compound TiO during the stepwise introduction2Or SnO2. As shown in the sample UV-vis diagram, a distinct absorption peak appears at 207nm in fig. 3, the formation of which is caused by the charge transition of the ligand O to the metal, indicating the incorporation of titanium and tin species into the molecular sieve framework. In FIGS. 4 and 5, in addition to the absorption peaks at 218nm and 207nm, which are attributable to framework Ti and framework Sn species, respectively, a shoulder peak is observed at 255nm, which is particularly evident in FIG. 5, indicating that some of the metals in the samples Ti-Sn-Beta and Sn-Ti-Beta are present as oxides. These results demonstrate that the simultaneous introduction of metals ensures the formation of isolated skeletal Ti and Sn species, whereas the stepwise introduction process results in the presence of the post-introduced metal as a non-skeletal oxide, such as TiO2Or SnO2Species, are not conducive to catalyzing cyclohexene conversion.
TABLE 1 hydration results of the catalyst of the invention for olefin epoxidation
Figure BDA0002646144040000061
Figure BDA0002646144040000071
Example 10
Respectively to be provided with0.1g of catalyst TiZr-Beta, TiTa-Beta and TiNb-Beta is placed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution) and 2.5ml acetonitrile, 60 ℃ reaction for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 1.
TABLE 2 hydration results of the catalyst of the invention for olefin epoxidation
Figure BDA0002646144040000072
Example 11
0.1g of catalyst A is weighed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, and 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution), adding 2.5ml solvent methanol, ethanol, acetone, 1, 4-dioxane, gamma-valerolactone and acetonitrile respectively, reacting at 60 deg.C for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 3.
TABLE 3 results of cyclohexene reaction catalyzed by catalyst A in different solvents
Figure BDA0002646144040000073
Figure BDA0002646144040000081
Example 12
0.1g of catalyst A is weighed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, and 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution) and 2.5ml acetone, the reaction temperature was controlled to 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ respectively, and the reaction was carried out for 2 hours (magnetic stirring 500 rpm). Determination of conversion of starting materials and products by gas chromatographyAnd selectivity, results are shown in table 4.
TABLE 4 results of catalyst A catalyzing cyclohexene reaction at different temperatures
Figure BDA0002646144040000082
Example 13
0.1g of catalyst A is weighed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, and 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution) and 2.5ml acetone, and reacting at 60 deg.C for 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 4h and 6h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 5.
TABLE 5 results of catalyst A catalyzing cyclohexene reaction at various times
Figure BDA0002646144040000091
Example 14
0.1g of catalyst A is weighed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, and 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution) and 2.5ml acetone, at 60 ℃ for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 6.
Example 15
The catalyst used once in example 14 was recovered and regenerated without activation, and its catalytic performance was examined under the same catalytic conditions as in example 14, and the results are shown in Table 6.
Example 16
The catalyst used twice in example 15 was recovered and regenerated without activation, and its catalytic performance was examined under the same catalytic conditions as in examples 14 and 15, and the results are shown in Table 6.
Example 17
The catalyst used in example 16 was recovered three times and regenerated without activation, and its catalytic performance was examined under the same catalytic conditions as in examples 14, 15 and 16, and the results are shown in Table 6.
TABLE 6 Cyclic usability of catalyst A
Figure BDA0002646144040000092
Figure BDA0002646144040000101
Example 18
0.1g of catalyst A is weighed in a reaction kettle containing polytetrafluoroethylene lining, the reaction kettle is provided with a magnetic stirrer and an electric heating device, and 5mmol of cyclohexene and 5mmol of H are added2O2(31 wt% aqueous solution) and 2.5ml acetone, at 60 ℃ for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 7.
Example 19
The catalyst used once in example 18 was recovered, calcined at 550 ℃ in a muffle furnace for 4 hours, regenerated by activation, and examined for its catalytic performance under the same catalytic conditions as in example 18, and the results are shown in Table 7.
Example 20
The catalyst used twice in example 19 was recovered, calcined at 550 ℃ in a muffle furnace for 4 hours, regenerated by activation, and examined for its catalytic properties under the same catalytic conditions as in examples 18 and 19, and the results are shown in Table 7.
Example 21
The catalyst used in example 20 was recovered three times, calcined at 550 ℃ in a muffle furnace for 4 hours, regenerated by activation, and examined for its catalytic performance under the same catalytic conditions as in examples 18, 19, and 20, and the results are shown in Table 7.
TABLE 7 Cyclic usability of catalyst A
Circulation of Example 16 Example 17 Example 18 Example 19
Cyclohexene conversion (%) 74.6 73.4 70.4 69.2
1, 2-diol selectivity (%) 91.4 92.3 90.4 90.5
Example 22
0.1g of the catalyst from example 1 was placed in a reaction vessel containing a polytetrafluoroethylene lining, equipped with a magnetic stirrer and an electric heater, and 5mmol of the olefinic substrates cyclohexene, 1-methyl-1-cyclohexene, cyclopentene, 2-cyclopentene-1-one, 2-cyclohexen-1-one, 3-methyl-2-cyclohexen-1-one, respectively, were added, and 5mmol of H were added2O2(31 wt% aqueous solution) and 2.5ml acetone, at 60 ℃ for 2h (magnetic stirring 500 rpm). The conversion and selectivity of the starting material and product were determined by gas chromatography and the results are shown in Table 8.
TABLE 8 results of reaction of catalyst A with catalysis of various olefinic substrates
Figure BDA0002646144040000102
Figure BDA0002646144040000111
The results in tables 1-8 are combined to show that the bifunctional catalyst has good catalytic activity when used for preparing 1, 2-diol by alkene epoxidation hydration. Meanwhile, the molecular sieve confinement effect promotes the efficient series connection of olefin epoxidation and epoxide hydration and high selectivity of target products. Under the same condition, the difunctional TiSn-Beta molecular sieve is used as a catalyst, the highest selectivity of the 1, 2-cyclohexanediol reaches over 90 percent, and the yield is 70 percent.
Comparative example
Placing 0.05g of catalyst A and 0.05g of catalyst B in a reaction kettle with polytetrafluoroethylene lining, wherein the reaction kettle is provided with a magnetic stirrer and an electric heating device, and adding 5mmol of cyclohexene and 5mmol of H2O2(31 wt% aqueous solution) and 2.5ml acetonitrile, 60 ℃ reaction for 2h (magnetic stirring 500 rpm). Conversion and selectivity of the starting material and product were determined by gas chromatography analysis. The cyclohexene conversion was 46.9% and the 1, 2-cyclohexanediol selectivity was 42.3%. The result shows that the single bifunctional catalyst TiSn-Beta has far better catalytic effect than the mixed catalytic system.

Claims (10)

1. A bifunctional molecular sieve catalyst for catalyzing olefin to directly prepare 1, 2-diol is characterized in that: the double-function TiSn-Beta molecular sieve contains titanium and tin sites, wherein the loading amounts of Ti and Sn are 0-10% respectively;
the preparation method comprises the following steps: dealuminizing an H-Beta molecular sieve to prepare an all-silicon molecular sieve and introducing a metal active center, and dealuminizing raw powder of the H-Beta molecular sieve by concentrated nitric acid treatment to obtain an all-silicon molecular sieve Si-Beta; removing the water physically adsorbed on the surface of the sample under vacuum environment, and removing the water and the metal precursor Ti (Cp)2Cl2And/or (CH)3)2SnCl2The mixture is ground and mixed evenly in a glove box and then moved into a vacuum tube furnaceHeating to 550 ℃, roasting for 6h, and then placing in a muffle furnace, roasting for 6h at 550 ℃, so as to obtain molecular sieve catalysts Ti-Beta, Sn-Beta and TiSn-Beta.
2. The catalyst of claim 1, wherein: the load capacity of Ti and Sn in the TiSn-Beta molecular sieve is respectively 2.5-7.5%; preferably, the Ti and Sn loadings are both 5%.
3. The catalyst according to claim 1 or 2, characterized in that: sn is replaced by Zr, Ta or Nb.
4. A method for preparing the catalyst of claim 2, characterized by comprising the steps of:
1) firstly, uniformly mixing raw powder of the H-Beta molecular sieve with concentrated nitric acid, placing the mixture in an oil bath pot, heating the mixture to 100 ℃ and 110 ℃, refluxing and stirring the mixture for 20 to 25 hours, cooling the mixture to room temperature, washing the mixture to be neutral by using deionized water, and drying the mixture at 80 to 100 ℃ to obtain the all-silicon Si-Beta molecular sieve;
2) pretreating the full-silicon Si-Beta molecular sieve in a vacuum tube furnace at 180 ℃ and 200 ℃ for 10-12h, removing water adsorbed on the surface, and cooling the sample to room temperature;
3) then with a metal precursor Ti (Cp)2Cl2And (CH)3)2SnCl2Grinding and mixing uniformly in a glove box;
4) and then placing the mixed sample into a vacuum tube furnace, heating to 500-550 ℃ for roasting for 5-6h, and then placing the sample into a muffle furnace for roasting at 500-550 ℃ for 5-6h to obtain the molecular sieve catalyst: TiSn-Beta; or
The sample obtained in the step 2) is mixed with Ti (Cp)2Cl2Grinding and mixing uniformly in a glove box, transferring to a vacuum tube furnace, heating to 500-550 ℃, roasting for 5-6h, and then placing in a muffle furnace, roasting for 5-6h at 500-550 ℃, so as to obtain the Ti-Beta molecular sieve; mixing the obtained sample with (CH)3)2SnCl2Mixing the mixture in a glove box, grinding and mixing the mixture evenly, moving the mixture to a vacuum tube furnace, heating the mixture to 500-550 ℃, roasting the mixture for 5 to 6 hours, and then placing the mixture in a muffle furnace for roasting the mixture for 5 to 6 hours at 500-550 ℃ to obtain a catalyst Ti-Sn-Beta; or, in the above process, Ti (Cp)2Cl2And (CH)3)2SnCl2The order of addition was reversed.
5. The method according to claim 4, wherein the ratio of Si/Al in the raw powder of H-Beta molecular sieve in step 1) is 13.5 (n)Si/nAl= 13.5）。
6. The method according to claim 4, wherein the temperature of the vacuum tube furnace in step 4) is increased at a rate of 5 ℃/min.
7. The use of the bifunctional molecular sieve catalyst of claim 2 for the direct preparation of 1, 2-diol from olefin, characterized in that the application method comprises the steps of:
putting a bimetallic Beta molecular sieve catalyst into a reaction kettle provided with a stirring and electric heating device, adding a solution of an olefin substrate, a solvent and hydrogen peroxide, reacting at 25-100 ℃ for 0.2-8 h, cooling to room temperature after the reaction is finished, centrifugally filtering the catalyst from the reaction solution, and analyzing the filtrate by gas chromatography to calculate the conversion rate and selectivity, wherein chlorobenzene is used as an internal standard substance.
8. The use of claim 7, wherein the molar ratio of olefin substrate to hydrogen peroxide is 1: 1;
the solvent is one of methanol, ethanol, acetone, 1, 4-dioxane, gamma-valerolactone and acetonitrile; methanol, ethanol, acetone are preferred.
9. The use according to claim 7, wherein the reaction temperature is 40-80 ℃, the reaction time is 0.5-6 h, and the stirring speed is 500 rpm.
10. The use according to claim 7, wherein said olefinic substrate is one of cyclopentene, 2-cyclopenten-1-one, cyclohexene, 1-methyl-1-cyclohexene, 2-cyclohexen-1-one, 3-methyl-2-cyclohexen-1-one; the concentration of the hydrogen peroxide solution is 31 wt%.
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Publication number Priority date Publication date Assignee Title
CN103130614A (en) * 2011-11-29 2013-06-05 岳阳昌德化工实业有限公司 Method for preparing 1,2-cyclohexanediol through oxidation of cyclohexene
CN103920527A (en) * 2014-04-24 2014-07-16 南开大学 Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof
CN107879893A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of method that catalytic oxidation prepares vicinal diamines class compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130614A (en) * 2011-11-29 2013-06-05 岳阳昌德化工实业有限公司 Method for preparing 1,2-cyclohexanediol through oxidation of cyclohexene
CN103920527A (en) * 2014-04-24 2014-07-16 南开大学 Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof
CN107879893A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of method that catalytic oxidation prepares vicinal diamines class compound

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