CN106984356B - Method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst - Google Patents
Method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst Download PDFInfo
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Abstract
The invention discloses a method for simultaneously preparing methyl allyl alcohol and acetal by utilizing an Sn- β catalyst, which comprises the steps of taking an H- β molecular sieve as a parent body, grinding and roasting the H- β molecular sieve and tin acetate after dealumination to obtain an Sn- β catalyst Sn- β, obtaining Sn- β -Ar and Sn- β -Ar-Na by using an Ar pretreatment and Na exchange post-treatment method to reduce the content of a tin species outside a framework and the content of B acid in the catalyst, further improving the catalytic activity and selectivity, then utilizing the Sn- β catalyst, taking methacrolein as a substrate and ethanol as a solvent and a hydrogen source, and simultaneously preparing two important chemicals of the methyl allyl alcohol and the acetal at a lower temperature.
Description
Technical Field
The invention belongs to the technical field of preparation of methyl allyl alcohol and acetal, and particularly relates to a method for simultaneously preparing methyl allyl alcohol and acetal by using an Sn- β catalyst.
Background
Methallyl alcohol is an important organic intermediate for the synthesis of perfumes, resins, and the like. Methyl allyl alcohol and ethylene oxide are used as raw materials to synthesize methyl allyl alcohol polyoxyethylene ether (HPEG), which is used for a new generation of high-performance concrete water reducing agent. The methallyl alcohol can be used for synthesizing methacrylic acid and esters thereof, can also be used for synthesizing esters containing allyl with other organic acids, and has important application in the aspects of polymerized monomers, surfactants and the like.
The traditional method for preparing methallyl alcohol is to produce methallyl alcohol by using 2-methallyl chloride as a starting material and adopting an alkaline hydrolysis method. US2072015, US2323781, US2313767, etc. are all some improvements over this conventional approach. The alkaline hydrolysis method is one of the most important methods for producing methallyl alcohol, but has certain problems: the hydrolysis process requires the addition of a large amount of alkali reagents and organic solvents, requires high temperature and pressure, causes great environmental pollution, and results in low yield due to the presence of by-product ethers.
The unsaturated alcohol obtained by reduction reaction with unsaturated aldehyde as a substrate is an environment-friendly and economical method, and JP-B56-36176 and US2779801 disclose that the unsaturated alcohol is prepared by reaction with aluminum alkoxide as a catalyst, but the demand of isopropanol is large, and a homogeneous system is difficult to separate. US2767221 uses magnesium oxide as a catalyst to prepare unsaturated alcohols, which can avoid the above problems, but the reaction temperature requirement is high and the energy consumption is large.
US4072727 and CN102167657 reduce unsaturated aldehydes by catalytic hydrogenation to prepare unsaturated alcohols, but since C ═ O needs to be selectively reduced without reducing C ═ C base, noble metals are often needed as catalysts, the preparation process of the catalysts is complicated, the cost of the catalysts is high, and the selectivity is difficult to control. Therefore, the development of a novel method for reducing methacrolein to methallyl alcohol is of great significance.
Acetal is also an important chemical, mainly used as solvent, and in organic synthesis and in the manufacture of cosmetics, perfumes, and also as diesel additive to reduce NOxAnd (4) discharging. The preparation conditions of the acetal are harsh, and the preparation methods of the acetal and the ketal are introduced in CN104478844 and CN103717564, but the temperature conditions and the selection of raw materials are harsh. Therefore, the development of a process for producing acetal is also an important subject. At present, no method for simultaneously preparing methyl allyl alcohol and acetal without high temperature and high pressure and with simple and convenient separation exists.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for simultaneously preparing methyl allyl alcohol and acetal by using an Sn- β catalyst, wherein two important chemicals, namely methyl allyl alcohol and acetal, can be simultaneously prepared at a lower temperature by using the Sn- β catalyst, methylacrolein as a substrate, ethanol as a solvent and a hydrogen source.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a process for the simultaneous preparation of methallyl alcohol and acetal using a Sn- β type catalyst comprising:
1) 65-68% of HNO at 370-375K3Dealuminizing H- β for 18-22H, wherein 65-68% of HNO3The formula ratio of the powder to H- β is 18-22 ml: 1g, the obtained powder is washed and dried, and is physically ground with tin acetate for 15-25 min, the ratio of the powder to the tin acetate is 4-6: 1, and then the powder is roasted for 2.5-3.5H at 820-825K in the flowing atmosphere of air to obtain a Sn- β catalyst, namely Sn- β;
2) and (2) taking methacrolein as a substrate, ethanol as a solvent and a hydrogen source, adding the Sn- β catalyst, and carrying out liquid-phase hydrogen transfer reduction reaction for 1-3 h at 67-87 ℃ under a reflux condition to obtain methallyl alcohol and acetal, wherein the formula ratio of the methacrolein, the ethanol and the Sn- β catalyst is 0.8-3.0 mmol, 78-82 mmol and 0.05-0.5 g.
In one embodiment, in the step 1), after the powder is washed, dried and physically ground with tin acetate for 15-25 min, the powder is roasted for 2.5-3.5 h at 820-825K in an argon gas flowing atmosphere, and then the powder is roasted for 2.5-3.5 h at 820-825K in an air flowing atmosphere, so as to obtain the Sn- β catalyst, namely Sn- β -Ar.
In one embodiment, in the step 1), after the powder is washed, dried and physically ground with tin acetate for 15-25 min, the powder is roasted for 2.5-3.5 h at 820-825K in an argon gas flowing atmosphere, and then the powder is roasted for 2.5-3.5 h at 820-825K in an air flowing atmosphere to obtain an Sn- β catalyst, namely Sn- β -Ar, and the obtained catalyst is roasted under 350-355KSn- β -Ar and 0.8-1.2M NaNO3Ion exchange is carried out for 10-14 h, the Sn- β -Ar and 0.8-1.2M NaNO are added3The formula proportion of the catalyst is 1 g: 45-55 ml, the obtained product is centrifugally washed and then roasted for 4-6 hours at 770-775K, and the Sn- β catalyst is obtained, and is Sn- β -Ar-Na.
In one embodiment: in the step 1), the molar ratio of the methacrolein to the methanol is 0.9: 80.
In one embodiment, in the step 1), the ratio of the methacrolein, the ethanol and the Sn- β catalyst is 0.9-2.8 mmol, 80mmol and 0.5 g.
In one embodiment: in the step 2), the temperature of the liquid-phase hydrogen transfer reduction reaction is 77 ℃.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a Sn- β catalyst comprises the step of adding 65-68% of HNO under 370-375K3Dealuminizing H- β for 18-22H, wherein 65-68% of HNO3The formula ratio of the Sn- β catalyst to H- β is 18-22 ml: 1g, the obtained powder is washed and dried, is physically ground with tin acetate for 15-25 min, the ratio of the powder to the tin acetate is 4-6: 1, and then is roasted for 2.5-3.5H at 820-825K in the flowing atmosphere of air to obtain the Sn- β catalyst, namely Sn- β.
In one embodiment, after the powder is washed, dried and physically ground with tin acetate for 15-25 min, the powder is roasted for 2.5-3.5 h at 820-825K under argon as a flowing atmosphere, and then the powder is roasted for 2.5-3.5 h at 820-825K under air as a flowing atmosphere, so that the Sn- β catalyst, namely Sn- β -Ar, is obtained.
In one embodiment, in the step 1), after the powder is washed, dried and physically ground with tin acetate for 15-25 min, the powder is roasted for 2.5-3.5 h at 820-825K under argon as a flowing atmosphere, and then the powder is roasted for 2.5-3.5 h at 820-825K under air as a flowing atmosphere to obtain a Sn- β catalyst, namely Sn- β -Ar, and the obtained Sn- β -Ar and 0.8-1.2M NaNO are mixed under 350-355K3Ion exchange is carried out for 10-14 h, the Sn- β -Ar and 0.8-1.2M NaNO are added3The formula proportion of (1 g): 45-55 ml, and 7 portions of the obtained product after centrifugal washingRoasting for 4-6 h at 70-775K to obtain the Sn- β catalyst which is Sn- β -Ar-Na.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
a Sn- β based catalyst prepared according to the above preparation method.
The invention reduces methacrolein by MPV reduction mechanism to prepare methallyl alcohol, ethanol transfers hydrogen and then reduces the hydrogen to acetaldehyde, and the generated acetaldehyde undergoes an acetal reaction to obtain the high value-added chemical acetal.
The Sn- β catalyst is prepared by a post-treatment solid ion exchange method, tin acetate and a parent H- β molecular sieve are subjected to solid ion exchange after dealumination treatment, aluminum is substituted, the number of Sn species in a framework is increased by an Ar pretreatment method, the number of Sn species outside the framework is reduced, the selectivity is improved, and the catalyst is further removed by a Na exchange method
Acid sites, increasing selectivity.
Compared with the background technology, the technical scheme has the following advantages:
the method has the advantages that the Sn- β catalyst has high activity, the methyl allyl alcohol and the acetal with the yield of 90 percent and 96 percent can be obtained, the catalyst has high stability and can be circulated for many times without inactivation, the reaction can be carried out at lower temperature without high temperature and high pressure, the reaction is a heterogeneous reaction system, and the separation of the catalyst and the product is simple and convenient.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is an X-ray diffraction chart of Sn- β, Sn- β -Ar and Sn- β -Ar-Na catalysts of Sn- β type.
FIG. 2 shows the ultraviolet-visible diffuse reflection spectrums of Sn- β, Sn- β -Ar and Sn- β -Ar-Na as Sn- β catalysts.
FIG. 3 shows in-situ pyridine absorption infrared spectra of Sn- β, Sn- β -Ar and Sn- β -Ar-Na catalysts of Sn- β.
FIG. 4 shows the results of activity evaluation of various catalyst addition amounts in examples 7 to 11, wherein conversion is the conversion of methacrolein, Mol is methallyl alcohol, and Dal is acetal.
FIG. 5 shows the results of evaluating the recycling activity of the Sn- β -Ar-Na catalyst of Sn- β type in example 15.
Detailed Description
The present invention will be described in detail with reference to the following examples:
example 1
1) The Sn- β preparation method comprises the step of adding 65-68% of HNO under 373K3Dealuminizing H- β for 20H, wherein the content of HNO is 65-68%3The formula ratio of the powder to H- β is 20 ml: 1g, the obtained powder is washed and dried, and is physically ground with tin acetate for 20min, the ratio of the powder to the tin acetate is 5:1, and then the powder is roasted for 3H at 823K in a tubular furnace by taking air as flowing atmosphere, so that the Sn- β catalyst is Sn- β.
2) The Sn- β -Ar preparation method comprises the step of adding 65-68% of HNO under 373K3Dealuminizing H- β for 20H, wherein the content of HNO is 65-68%3The formula ratio of the powder to H- β is 20 ml: 1g, the obtained powder is washed and dried, and is physically ground with tin acetate for 20min, the mass ratio of the powder to the tin acetate is 5:1, the powder is roasted for 3H at 823K in a tubular furnace by taking argon as flowing atmosphere, and then the powder is roasted for 3H at 823K by taking air as flowing atmosphere, and the Sn- β catalyst is Sn- β -Ar.
3) Sn- β -Ar-Na is prepared by preparing Sn- β -Ar according to the method, and then mixing the obtained Sn- β -Ar with 1.0M NaNO at 353K3Ion exchange is carried out for 12h, and the Sn- β -Ar and 1.0M NaNO are mixed3The formula proportion of (1 g) to (50 ml), and the obtained product is centrifugally washed and then roasted for 5 hours in a muffle furnace at 773K to obtain the Sn- β catalyst which is Sn- β -Ar-Na.
And performing X-ray diffraction characterization, ultraviolet-visible diffuse reflection characterization and in-situ adsorption pyridine infrared characterization on the Sn- β, Sn- β -Ar and Sn- β -Ar-Na, wherein the characterization results are respectively shown in the figures 1, 2 and 3.
Example 2
Specifically, 2.8mmol of methacrolein and 80mmol of ethanol are added into the 10ml round bottom flask, 0.2g of Sn- β type catalyst Sn- β is added, the mixture is heated to 77 ℃ by taking the methacrolein as a substrate and the ethanol as a solvent and a hydrogen source, and the mixture is refluxed for 2 hours, so that the methallyl alcohol and the acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector after filtration, the catalyst activity was evaluated as shown in Table 1. the conversion of methacrolein was 69.9%, and the yields of methallyl alcohol and acetal were 35.4% and 41.0%, respectively, based on methacrolein.
Example 3
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.2g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 2h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector after filtration, the catalyst activity was evaluated as shown in Table 1. the conversion of methacrolein was 76.6% and the yields of methallyl alcohol and acetal were 42.8% and 50.6%, respectively, based on methacrolein.
Example 4
0.9mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.2g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 2h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector after filtration, the catalyst activity was evaluated as shown in Table 1. the conversion of methacrolein was 88.8%, and the yields of methallyl alcohol and acetal were 53.6% and 59.4%, respectively, based on methacrolein.
Example 5
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.2g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 67 ℃, and the reflux reaction is carried out for 1h, so as to obtain the methyl allyl alcohol and the acetal.
The reaction product was filtered and then qualitatively analyzed by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively analyzed by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in Table 2. the conversion of methacrolein was 51.2% and the yields of methallyl alcohol and acetal were 18.4% and 26.7%, respectively, based on methacrolein.
Example 6
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.2g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then qualitatively analyzed by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively analyzed by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in Table 2. the conversion of methacrolein was 61.6% and the yields of methallyl alcohol and acetal were 28.4% and 37.7%, respectively, based on methacrolein.
Example 7
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.05g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in FIG. 4. the conversion of methacrolein was 41.5% and the yields of methallyl alcohol and acetal were 0.7% and 10.0%, respectively, based on methacrolein.
Example 8
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.1g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in FIG. 4. the conversion of methacrolein was 49.5% and the yields of methallyl alcohol and acetal were 14.7% and 21%, respectively, based on methacrolein.
Example 9
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.2g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in FIG. 4. the conversion of methacrolein was 61.6% and the yields of methallyl alcohol and acetal were 28.4% and 37.7%, respectively, based on methacrolein.
Example 10
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.3g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in FIG. 4. the conversion of methacrolein was 73.7% and the yields of methallyl alcohol and acetal were 40.9% and 48.8%, respectively, based on methacrolein.
Example 11
1.8mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.5g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 1h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in FIG. 4. the conversion of methacrolein was 80.3% and the yields of methallyl alcohol and acetal were 52.4% and 58.7%, respectively, based on methacrolein.
Example 12
0.9mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.5g of Sn- β catalyst Sn- β is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 2h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then qualitatively analyzed by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively analyzed by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in Table 3. the conversion of methacrolein was 97.2% and the yields of methallyl alcohol and acetal were 71.3% and 94.7%, respectively, based on methacrolein.
Example 13
0.9mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.5g of Sn- β type catalyst Sn- β -Ar is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for 2h, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then qualitatively analyzed by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively analyzed by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, the activity of the catalyst was evaluated as shown in Table 3. the conversion of methacrolein was 99.5% and the yields of methallyl alcohol and acetal were 85.0% and 99.1%, respectively, based on methacrolein.
Example 14
0.9mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.5g of Sn- β type catalyst Sn- β -Ar-Na is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for reaction for 3 hours, and then methyl allyl alcohol and acetal are obtained.
The reaction product was filtered and then analyzed qualitatively by GC-MS (HP-5 capillary 30m × 0.25.25 mm × 0.25.25 μm) and quantitatively by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector after filtration, the catalyst activity was evaluated as shown in Table 3. the conversion of methacrolein was 98.9%, and the yields of methallyl alcohol and acetal were 90.2% and 96.6%, respectively, based on methacrolein.
Example 15
0.9mmol of methacrolein and 80mmol of ethanol are added into a 10ml round bottom flask, 0.5g of Sn- β type catalyst Sn- β -Ar-Na is added, methacrolein is used as a substrate, ethanol is used as a solvent and a hydrogen source, the mixture is heated to 77 ℃ and refluxed for reaction for 3 hours, and then methyl allyl alcohol and acetal are obtained.
The reacted product was filtered and then qualitatively analyzed by GC-MS (HP-5 capillary 30m × 0.25mm × 0.25.25 μm) and quantitatively analyzed by gas chromatography (Thermo Trace 1310, HP-5 capillary 30m × 0.25mm × 0.25.25 μm) hydrogen flame ionization detector, and the activity of the catalyst was measured after 1 use.
Centrifugally recovering the catalyst subjected to activity evaluation, drying in an oven at 110 ℃ overnight, and roasting in a muffle furnace at 550 ℃ for 5 hours; then, the catalyst is repeatedly used according to the steps to synthesize the methallyl alcohol and the acetal, the activity of the catalyst which is recycled for 2 times, 3 times, 4 times and 5 times is detected, and the evaluation result of the activity of the catalyst is shown in figure 5.
TABLE 1 evaluation results of the activity of the molar ratio of substrate to solvent
The reaction conditions are that the temperature is 77 ℃, the reaction time is 2 hours, 80mmol of ethanol and 0.2g of Sn- β
TABLE 2 results of evaluation of Activity at reaction temperature
The reaction conditions were reflux of 1.8mmol of methacrolein, 1h, 80mmol of ethanol, 0.2g of Sn- β
TABLE 3 evaluation of the activity of the catalysts by different aftertreatment methods
The reaction conditions were reflux of 0.9mmol of methacrolein, 77 ℃ C., 80mmol of ethanol, 0.5g of Sn- β
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (4)
1. A method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst is characterized by comprising the following steps:
1) 65-68% of HNO at 370-375K3Dealuminizing H- β for 18-22H, wherein 65-68% of HNO3The proportion of the formula and H- β is18-22 ml: 1g, washing and drying the obtained powder, physically grinding the powder and tin acetate for 15-25 min, wherein the ratio of the powder to the tin acetate is 4-6: 1, roasting the powder for 2.5-3.5 h at 820-825K under argon as a flowing atmosphere, then roasting the powder for 2.5-3.5 h at 820-825K under air as a flowing atmosphere to obtain a Sn- β catalyst, namely Sn- β -Ar, and mixing the obtained Sn- β -Ar and 0.8-1.2M NaNO under 350-355K3Ion exchange is carried out for 10-14 h, the Sn- β -Ar and 0.8-1.2M NaNO are added3The formula proportion of the catalyst is 1 g: 45-55 ml, the obtained product is centrifugally washed and then roasted for 4-6 hours at 770-775K to obtain an Sn- β catalyst which is Sn- β -Ar-Na;
2) and (2) taking methacrolein as a substrate, ethanol as a solvent and a hydrogen source, adding the Sn- β catalyst, and carrying out liquid-phase hydrogen transfer reduction reaction for 1-3 h at 67-87 ℃ under a reflux condition to obtain methallyl alcohol and acetal, wherein the formula ratio of the methacrolein, the ethanol and the Sn- β catalyst is 0.8-3.0 mmol, 78-82 mmol and 0.05-0.5 g.
2. The process for simultaneously preparing methallyl alcohol and acetal using a Sn- β type catalyst according to claim 1, wherein the molar ratio of methacrolein to ethanol in step 2) is 0.9: 80.
3. The method for simultaneously preparing methallyl alcohol and acetal by using Sn- β catalyst according to claim 1, wherein the ratio of the formulation of methacrolein, ethanol and Sn- β catalyst in step 2) is 0.9-2.8 mmol/80 mmol/0.5 g.
4. The process for simultaneously preparing methallyl alcohol and acetal according to claim 1, wherein the temperature of the liquid phase hydrogen transfer reduction reaction in step 2) is 77 ℃.
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| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
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| Ceri Hammond et al..Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis.《ChemCatChem》.2015,第7卷 * |
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