CN114289042B - Mesoporous solid acid catalyst, preparation method and application thereof - Google Patents
Mesoporous solid acid catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a mesoporous solid acid catalyst, a preparation method and application thereof, wherein the catalyst has rich mesoporous pore channels, acetic acid is added in the active metal Zr loading process to effectively adjust the hydrolysis rate of organic Zr salt, the Zr metal is highly dispersed on a carrier, the utilization rate of the Zr metal and the activity of the catalyst are improved, and the catalyst has the advantages of low reaction temperature, high yield, good catalyst stability and easy recovery when being used for synthesizing the isovalerate menthyl ester.
Description
Technical Field
The invention belongs to the field of preparation of menthyl isovalerate, and particularly relates to a catalyst for preparing menthyl isovalerate and a preparation method of menthyl isovalerate.
Background
The menthyl isovalerate is an important mint flavor, has unique cool feel and flavor of menthol, has higher heat resistance than the menthol, and is mainly applied to industries such as cosmetics, soaps, cigarettes and the like. The structural formula is as follows:
the classical synthesis method of the isovalerate menthyl ester (3) is that isovalerate (2) and menthol (1) are heated in the presence of concentrated sulfuric acid or p-toluenesulfonic acid, and the traditional esterification method has mature technology, but the strong corrosiveness of sulfuric acid or p-toluenesulfonic acid shortens the service life of equipment, and the acidic waste liquid can pollute the ringMoreover, the post-processing flow is complex. Zhao Yanru (Zhao Yanru, liu Chunhui. Macroporous resin immobilized Ce-4+) catalytic synthesis of menthyl isovalerate [ J ]]The university of Huchang university newspaper, 2009 (2): 3.) adopts macroporous resin to fix and support Ce 4+ The catalyst is used for catalyzing the esterification reaction of isovaleric acid and menthol, the preparation method of the catalyst is simple and easy to recycle, but the use temperature is higher, and the reaction yield is only 80%.
Therefore, we need to develop an isovalerate esterification catalyst with high catalytic activity, avoid pollution of waste acid and the like, improve the esterification reaction yield, reduce the reaction energy consumption and prolong the service life of the catalyst.
Disclosure of Invention
The invention aims to provide Zr-P/Meso-La with rich mesoporous pore canal and low-temperature efficient catalytic esterification function 2 O 3 -ZnO-SiO 2 And (3) catalyzing the esterification of the isovaleric acid and the menthol to prepare the isovalerate menthyl ester by using a composite metal-supported solid acid catalyst. The method has the advantages of environment friendliness, mild reaction condition, high product yield, easy recycling of the catalyst and the like. Under the optimal condition, the selectivity of the reaction for preparing the isovalerate menthyl ester from the isovaleric acid and the menthol can reach 99.5 percent, the reaction temperature is reduced to 50 ℃, and the yield of the final product reaches more than 92 percent.
In order to achieve the above object, the present invention provides the following technical solutions:
on the one hand, the invention provides a mesoporous solid acid catalyst, which comprises the components of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Which is a composite metal oxide Meso-La rich in mesoporous pore canal 2 O 3 -ZnO-SiO 2 The catalyst is prepared by taking a phenylphosphonate compound as a doped P source, taking organic zirconium salt as a precursor of active metal, dipping and roasting in a nitrogen atmosphere.
Preferably, the catalyst Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The molar ratio of Zr/Si is 0.04-0.17:1, preferably 0.06-0.11:1; the molar ratio P/Si is 0.17-0.46:1, preferably 0.27-0.38:1; the La/Si molar ratio is 0.10-0.23:1, preferably 0.14-0.16:1; the Zn/Si molar ratio is 0.14-0.29:1, preferably 0.18-0.22:1.
In another aspect, the invention provides a method for preparing a mesoporous solid acid catalyst, comprising the steps of:
(1) Mesoporous SiO 2 Placing into water solution, adding inorganic zinc salt and inorganic lanthanum salt, soaking for a period of time, taking out, filtering, washing, drying, and roasting in air roasting furnace to obtain the composite metal oxide carrier Meso-La 2 O 3 -ZnO-SiO 2 。
(2) Adding the calcined carrier in the step (1) into an organic solvent, then adding a certain amount of phenylphosphonate compounds and organic zirconium salts respectively, and carrying out stirring and loading in the presence of an acetic acid hydrolysis inhibitor.
(3) Filtering and separating solid from the liquid in the step (2), drying the solid, and roasting in nitrogen atmosphere to obtain Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 。
In the invention, in the step (1), the inorganic zinc salt is one or more of zinc nitrate (hexahydrate) and zinc sulfate (hexahydrate or heptahydrate), preferably zinc nitrate; the inorganic lanthanum salt is one or more of lanthanum nitrate (hexahydrate) and lanthanum sulfate (anhydrous or nonahydrate), preferably lanthanum nitrate.
In the invention, in the step (1), mesoporous SiO 2 Mesoporous SiO selected from one or combination of MCM-41 and SBA-15 2 The mass fraction in water is 10-20wt%, preferably 12-15wt%; the dosage of inorganic zinc salt (calculated by ZnO) is mesoporous SiO 2 An amount of 20 to 40wt%, preferably 25 to 30wt%; inorganic lanthanum salt dosage (in La 2 O 3 Meter) is mesoporous SiO 2 The amount is 28-64wt%, preferably 40-45wt%.
In the invention, in the step (1), the impregnation temperature is 10-40 ℃, preferably 20-30 ℃; the soaking time is 0.5-5h, preferably 2.5-3.5h; the drying temperature is 100-150deg.C, preferably 120-130deg.C; the drying time is 1-3h, preferably 1.5-2h; the roasting temperature is 400-550 ℃, preferably 450-500 ℃; the roasting time is 2-8h, preferably 4-5h; the roasting pressure is normal pressure.
In the present invention, the organic solvent in the step (2) includes, but is not limited to, one or more of methanol, ethanol, tetrahydrofuran, and benzene; the phenylphosphonate compounds are dimethyl phenylphosphonate and diethyl phenylphosphonate, and are preferably ethyl phenylphosphonate; the organic zirconium salt is zirconium n-propoxide;
in the present invention, in the steps (2) (3), the vector Meso-La 2 O 3 -ZnO-SiO 2 The amount is 5-10wt%, preferably 6-8wt% of the amount of the organic solvent; the dosage of the phenylphosphonate compound is Meso-La 2 O 3 -ZnO-SiO 2 The amount is 18 to 36wt% (calculated as P), preferably 28 to 30wt%; the dosage of the organic zirconium salt is Meso-La 2 O 3 -ZnO-SiO 2 15-40wt% (calculated as Zr), preferably 20-25wt%; the acetic acid is used in an amount of 10 to 20wt% of the organozirconium salt (calculated as Zr), preferably 12 to 15wt%;
in the invention, the stirring temperature in the step (2) is 40-60 ℃, preferably 50-55 ℃; stirring time is 1-8h, preferably 3-4h; the drying temperature of the step (3) is 90-150 ℃, preferably 110-120 ℃; the drying time is 5-10h, preferably 6-8h; the roasting temperature is 450-650 ℃, preferably 550-600 ℃; the calcination time is 5 to 9 hours, preferably 7 to 8 hours.
Preferably, in a specific embodiment, the Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The catalyst can be prepared by the following method: mesoporous SiO 2 (SBA-15) is placed in an aqueous solution, zinc nitrate and lanthanum nitrate are added, the mixture is immersed for 2.5 to 3.5 hours at the temperature of 20 to 30 ℃ and then taken out, and then filtered, washed and dried, and finally placed in an air roasting furnace for roasting for 4 to 5 hours at the temperature of 450 to 500 ℃; placing the cooled roasting material into methanol, adding diethyl phenylphosphonate, then adding zirconium n-propoxide, and stirring for 3-4h at 50-55 ℃ to realize Zr loading. Finally, the solid is filtered and dried and then is put into a nitrogen roasting furnace for roasting, the preferable roasting condition is 550-600 ℃ for 7-8 hours,thus obtaining Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 A catalyst.
In yet another aspect, the present invention also provides a method comprising the steps of 2 O 3 -ZnO-SiO 2 A method for preparing menthyl isovalerate by catalyzing esterification of isovaleric acid and menthol by a catalyst, which comprises the following steps:
under normal pressure, adding isovaleric acid, menthol and Zr-P/Meso-La into a three-neck flask 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to a certain temperature for reaction, adding water-splitting agent petroleum ether (30-60 ℃) under stirring, carrying out reflux water splitting, adding saturated sodium carbonate solution and distilled water successively after the reaction is finished for washing until the solution becomes neutral, finally placing the organic phase into a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
In the invention, the mol ratio of the isovaleric acid to the menthol is 1.0-4.0:1, preferably 1.5-2.5:1; the Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The catalyst is used in an amount of 0.5-2.0wt% based on menthol mass, preferably 1.0-1.5wt%; the petroleum ether (30-60 ℃) of the water diversion agent is 5-20wt%, preferably 10-15wt% of menthol.
Further, the reaction temperature is 30-60 ℃, preferably 40-50 ℃; the reaction time is 2-10h, preferably 6-8h; the pressure is normal pressure.
The invention has the positive effects that:
(1) Zr-P/Meso-La prepared by the invention 2 O 3 -ZnO-SiO 2 The catalyst has rich mesoporous channels, and the active site of an acid center is increased. Acetic acid is added in the active metal Zr loading process, so that the purpose of the acetic acid is to effectively regulate the hydrolysis rate of organic Zr salt, inhibit uncontrollable hydrolysis of the organic Zr salt, realize high dispersion of Zr metal on a carrier and improve the utilization rate of Zr metal. Coordination of phenylphosphonates provides more active sites through PO 3 The charge and coordination of the group and the metal Zr indirectly realize the high dispersion of Zr on the carrier, and the aim is to reduce Zr particlesThe catalyst stability is improved. In the process of preparing the carrier, the invention adopts commercial mesoporous SiO 2 Loaded with ZnO and La 2 O 3 Two metal oxides, wherein the supported ZnO increases the B acid site of the catalyst, and SiO 2 The two have active sites of B acid and L acid, and the synergistic effect of the two acid centers improves the reaction efficiency; la (La) 2 O 3 The acid-base property of the carrier is modulated by the load of the catalyst, the occurrence of side reaction is reduced, and the catalyst shows good selectivity.
(2) By using Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The selectivity of the reaction of the catalyst for preparing the menthyl isovalerate from the isovalerate and the menthol can reach 99.5 percent, the reaction temperature is reduced to 50 ℃, and the final product yield reaches more than 92 percent. The reaction condition is mild, the reaction yield is high, the catalyst can be recycled, and the environment-friendly concept is met.
Detailed Description
The following examples are not intended to limit the scope of the invention, and modifications and equivalent substitutions are intended to be included within the scope of the claims without departing from the spirit and scope of the invention.
The raw materials used in the examples are all conventional in the art, and the purity specifications used are analytically pure or chemically pure;
1. raw material source information in the following examples:
mesoporous silica (MCM-41 and SBA-15), lanthanum nitrate hexahydrate, zinc sulfate hexahydrate, lanthanum sulfate anhydrous, zirconium n-propoxide, acetic acid, methanol, ethanol, tetrahydrofuran, benzene, isovaleric acid, menthol, petroleum ether, sodium carbonate were all analytical grade purities and were all purchased from Shanghai aladine biochemical technologies, inc. Dimethyl phenylphosphonate and diethyl phenylphosphonate were all of analytical grade purity and were purchased from the scientific company, belvedere.
2. The following test methods are used in the various embodiments of the present invention:
menthyl isovalerate was analyzed by GC-9800 chromatograph under the following chromatographic conditions: the initial temperature is 80 ℃, kept for 2min, and the temperature is programmed to be 280 ℃ at the speed of 10 ℃/min, and kept for 5min; the temperature of the gasification chamber is 300 ℃, and the temperature of the detection chamber is 300 ℃; FID detection; the sample loading was 0.2. Mu.l.
Example 1
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
60g of mesoporous SiO was added to 500g of deionized water 2 (SBA-15, 12 wt%) 65.8g of zinc nitrate hexahydrate (mesoporous SiO) 2 30wt% of the mass, calculated as ZnO) followed by 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) 2 40wt% of the mass, la 2 O 3 Meter), stirring and impregnating for 2.5h at 20 ℃, filtering and washing the solid, drying for 1.5h at 120 ℃, finally placing the dried solid in a muffle furnace at 450 ℃, and roasting for 4h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
30g of the carrier (6 wt%) prepared as described above was added to 500g of methanol, 57.1g of diethyl phenylphosphonate (28 wt% based on the mass of the carrier, calculated as P) was added to the system, followed by 27.0g of zirconium n-propoxide (25 wt% based on the mass of the carrier, calculated as Zr) and then 1.1g of acetic acid (15 wt% based on the mass of the organozirconium salt, calculated as Zr) was added to the solution. The impregnation was stirred at 50℃for 3h. Filtering and washing the immersed solid, drying for 6 hours at 110 ℃, and finally roasting in a nitrogen roasting furnace at 550 ℃ for 7 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.09:1, the P/Si molar ratio is 0.31:1, the La/Si molar ratio is 0.14:1, and the Zn/Si molar ratio is 0.22:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 674m 2 Per gram, pore volume of 0.85cm 3 And/g, the pore size distribution is 3.2-18nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 98g of isovaleric acid and 100g of menthol (mol/mol=1.5) and 1g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 50 ℃ for reaction, adding 10g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 6 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 99.6% and the yield was 92.5%.
The selectivity and yield data for multiple catalyst applications are as follows:
from the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Example 2
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
50g of mesoporous SiO was added to 500g of deionized water 2 (MCM-41, 10 wt%) 66.2g of zinc sulphate hexahydrate (mesoporous SiO) 2 40wt% of the mass, calculated as ZnO) followed by 85.1g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) 2 64wt% by mass of La 2 O 3 Counting), stirring and impregnating for 0.5h at 40 ℃, filtering and washing the solid, drying for 1h at 150 ℃, finally placing the dried solid in a muffle furnace at 550 ℃, and roasting for 8h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
50g of the carrier (10 wt%) prepared by the above method was added to 500g of ethanol, 53.2g of dimethyl phenylphosphonate (18 wt% based on the mass of the carrier, calculated as P) was added to the system, and then27.0g of zirconium n-propoxide (15% by weight based on the mass of the support, calculated as Zr) were added, followed by 1.5g of acetic acid (20% by weight based on the mass of the organozirconium salt, calculated as Zr) being added to the solution. The impregnation was stirred at 40℃for 8h. Filtering and washing the immersed solid, drying for 10 hours at 90 ℃, and finally roasting in a nitrogen roasting furnace at 650 ℃ for 9 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.04:1, the P/Si molar ratio is 0.16:1, the La/Si molar ratio is 0.23:1, and the Zn/Si molar ratio is 0.29:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 824m 2 Per gram, pore volume of 0.79cm 3 And/g, the pore size distribution is 3.4-16nm.
2) Catalyst reaction evaluation:
into a three-necked flask, 261.3g of isovaleric acid and 100g of menthol (mol/mol=4) and 0.5g of mesoporous Zr-P/Meso-La were charged in an amount 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 60 ℃ for reaction, adding 5g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 10 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 99.1% and the yield was 90.2%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 99.1 | 90.2 |
| 10 | 98.8 | 89.7 |
| 30 | 98.6 | 89.1 |
| 50 | 98.3 | 88.8 |
From the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Example 3
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
100g of mesoporous SiO was added to 500g of deionized water 2 (MCM-41, 20 wt%) to water was added 73.1g of zinc nitrate hexahydrate (mesoporous SiO) 2 20wt% of the mass, calculated as ZnO) followed by the addition of 97.3g of lanthanum sulphate hexahydrate (occupying mesoporous SiO) 2 28wt% of the mass, as La 2 O 3 Counting), stirring and soaking for 5h at 10 ℃, filtering and washing the solid, drying for 3h at 100 ℃, finally placing the dried solid in a muffle furnace at 400 ℃, and roasting for 2h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
25g of the carrier (5 wt%) prepared by the above method was added to 500g of tetrahydrofuran, and 61.2g of diethyl phenylphosphonate (carrier was added to the system36wt% of the bulk mass, calculated as P), then 35.9g of zirconium n-propoxide (40 wt% of the support mass, calculated as Zr) were added, followed by 1.0g of acetic acid (10 wt% of the organic zirconium salt mass, calculated as Zr) to the solution. The impregnation was stirred at 60℃for 1h. Filtering and washing the immersed solid, drying for 5 hours at 150 ℃, and finally roasting in a nitrogen roasting furnace at 450 ℃ for 5 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.17:1, the P/Si molar ratio is 0.46:1, the La/Si molar ratio is 0.10:1, and the Zn/Si molar ratio is 0.14:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 719m 2 Per gram, pore volume of 0.74cm 3 And/g, the pore size distribution is 2.8-19nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 65.3g of isovaleric acid and 100g of menthol (mol/mol=1) and 2g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 30 ℃ for reaction, adding 20g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 2 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 98.4% and the yield was 90.8%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 98.4 | 90.8 |
| 10 | 98.2 | 90.1 |
| 30 | 98.0 | 89.6 |
| 50 | 97.7 | 89.4 |
From the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Example 4
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
adding 75g of mesoporous SiO into 500g of deionized water 2 (SBA-15, 15 wt%) 62.1g of zinc sulphate hexahydrate (mesoporous SiO) was added to water 2 25wt% of the mass, calculated as ZnO) followed by the addition of 117.3g of lanthanum sulphate hexahydrate (occupying mesoporous SiO) 2 45wt% of the mass, la 2 O 3 Counting), stirring and impregnating for 3.5h at 30 ℃, filtering and washing the solid, drying for 2h at 130 ℃, finally placing the dried solid in a muffle furnace at 500 ℃, and roasting for 5h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
40g of the carrier (8 wt%) prepared by the above method was added to 500g of benzene, and the mixture was added to the system70.9g of diethyl phenylphosphonate (30% by weight of the support mass, calculated as P) followed by 28.7g of zirconium n-propoxide (20% by weight of the support mass, calculated as Zr) followed by 0.96g of acetic acid (12% by weight of the organozirconium salt mass, calculated as Zr) were added to the solution. The impregnation was stirred at 55℃for 4h. Filtering and washing the immersed solid, drying for 8 hours at 120 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 600 ℃ for 8 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.07:1, the P/Si molar ratio is 0.33:1, the La/Si molar ratio is 0.16:1, and the Zn/Si molar ratio is 0.18:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 837m 2 Per gram, pore volume of 0.84cm 3 And/g, pore size distribution is 3.6-17nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 163.3g of isovaleric acid and 100g of menthol (mol/mol=2.5) and 1.5g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 40 ℃ for reaction, adding 15g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and water diversion, after 8 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 98.8% and the yield was 90.2%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 98.8 | 90.2 |
| 10 | 98.7 | 89.9 |
| 30 | 98.5 | 89.6 |
| 50 | 98.2 | 89.3 |
From the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Example 5
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
70g of mesoporous SiO was added to 500g of deionized water 2 (SBA-15, 14 wt%) to water was added 71.6g of zinc nitrate hexahydrate (mesoporous SiO) 2 28wt% of the mass, calculated as ZnO) followed by the addition of 78.1g of lanthanum nitrate hexahydrate (occupying mesoporous SiO) 2 42wt% of the mass, as La 2 O 3 Counting), stirring and soaking for 3 hours at 25 ℃, filtering and washing the solid, drying for 1.8 hours at 125 ℃, finally placing the dried solid in a muffle furnace at 480 ℃, and roasting for 4.5 hours in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
35g of the carrier (7 wt%) prepared by the above method was added toTo 500g of methanol, 69.0g of diethyl phenylphosphonate (29 wt% based on the mass of the support, calculated as P) was added, followed by 27.6g of zirconium n-propoxide (22 wt% based on the mass of the support, calculated as Zr) and then 1.1g of acetic acid (14 wt% based on the mass of the organozirconium salt, calculated as Zr) was added to the solution. The impregnation was stirred at 52℃for 3.5h. Filtering and washing the immersed solid, drying for 7 hours at 115 ℃, and finally roasting in a nitrogen roasting furnace at 580 ℃ for 7.5 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.08:1, the P/Si molar ratio is 0.32:1, the La/Si molar ratio is 0.15:1, and the Zn/Si molar ratio is 0.20:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 769m 2 Per gram, pore volume of 0.79cm 3 And/g, pore size distribution is 3.4-21nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 130.6g of isovaleric acid and 100g of menthol (mol/mol=2) and 1.2g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 45 ℃ for reaction, adding 12g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 7 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 99.0% and the yield was 91.4%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 99.0 | 91.4 |
| 10 | 98.8 | 91.0 |
| 30 | 98.6 | 90.8 |
| 50 | 98.3 | 90.6 |
From the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Example 6
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
90g of mesoporous SiO was added to 500g of deionized water 2 (SBA-15, 18 wt%) to water was added 72.4g of zinc nitrate hexahydrate (mesoporous SiO) 2 22wt% of the mass, calculated as ZnO) and then 76.6g of lanthanum nitrate hexahydrate (occupying mesoporous SiO) are added 2 32wt% of the mass, as La 2 O 3 Counting), stirring and soaking for 4 hours at 15 ℃, filtering and washing the solid, drying for 2.5 hours at 110 ℃, finally placing the dried solid in a muffle furnace at 420 ℃, and roasting for 3 hours in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
Taking the above formula30g of the carrier (6 wt%) prepared by the method was added to 500g of methanol, 40.8g of diethyl phenylphosphonate (20 wt% based on the mass of the carrier, calculated as P) was added to the system, followed by 19.4g of zirconium n-propoxide (18 wt% based on the mass of the carrier, calculated as Zr) and then 0.97g of acetic acid (18 wt% based on the mass of the organozirconium salt, calculated as Zr) was added to the solution. The impregnation was stirred at 45℃for 7h. Filtering and washing the immersed solid, drying for 9 hours at 100 ℃, and finally roasting in a nitrogen roasting furnace at 500 ℃ for 6 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.07:1, the P/Si molar ratio is 0.24:1, the La/Si molar ratio is 0.11:1, and the Zn/Si molar ratio is 0.16:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 769m 2 Per gram, pore volume of 0.79cm 3 And/g, pore size distribution is 3.4-21nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 196.0g of isovaleric acid and 100g of menthol (mol/mol=3) and 0.8g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 35 ℃ for reaction, adding 8g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 9 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 98.7% and the yield was 89.1%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 98.7 | 89.1 |
| 10 | 98.5 | 88.6 |
| 30 | 98.2 | 88.2 |
| 50 | 98.0 | 88.1 |
From the above table, it can be seen that the catalyst still has better catalytic performance after multiple applications.
Comparative example 1
1) Preparation of Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
60g of mesoporous SiO was added to 500g of deionized water 2 (SBA-15, 12 wt%) 65.8g of zinc nitrate hexahydrate (mesoporous SiO) 2 30wt% of the mass, calculated as ZnO) followed by 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) 2 40wt% of the mass, la 2 O 3 Meter), stirring and impregnating for 2.5h at 20 ℃, filtering and washing the solid, drying for 1.5h at 120 ℃, finally placing the dried solid in a muffle furnace at 450 ℃, and roasting for 4h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
30g of the carrier (6 wt%) prepared in the above manner was taken and added to 500g of methanol, followed by adding 57.1g of diethyl phenylphosphonate (28 wt% based on the mass of the carrier, calculated as P) and then adding 27.0g of zirconium n-propoxide (25 wt% based on the mass of the carrier, calculated as Zr) to the system, without using a hydrolysis inhibitor such as acetic acid. The impregnation was stirred at 50℃for 3h. Filtering and washing the immersed solid, drying for 6 hours at 110 ℃, and finally roasting in a nitrogen roasting furnace at 550 ℃ for 7 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared by the method is characterized by element analysis, wherein the Zr/Si molar ratio is 0.07:1, the P/Si molar ratio is 0.30:1, the La/Si molar ratio is 0.13:1, and the Zn/Si molar ratio is 0.22:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 631m 2 Per gram, pore volume of 0.57cm 3 And/g, the pore size distribution is 2.9-19nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 98g of isovaleric acid and 100g of menthol (mol/mol=1.5) and 1g of mesoporous Zr-P/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 50 ℃ for reaction, adding 10g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 6 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 89.1% and the yield was 80.2%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 89.1 | 80.2 |
| 10 | 88.6 | 79.8 |
| 30 | 87.1 | 78.2 |
| 50 | 85.4 | 76.1 |
As can be seen from the above table, after the catalyst is applied for a plurality of times, the reaction selectivity and the yield are obviously reduced, namely the performance of the catalyst is reduced.
Comparative example 2
1) Preparation of Zr/Meso-La 2 O 3 -ZnO-SiO 2 Catalyst:
60g of mesoporous SiO was added to 500g of deionized water 2 (SBA-15, 12 wt%) 65.8g of zinc nitrate hexahydrate (mesoporous SiO) 2 30wt% of the mass, calculated as ZnO) followed by 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) 2 40wt% of the mass, la 2 O 3 Meter), stirring and impregnating for 2.5h at 20 ℃, filtering and washing the solid, drying for 1.5h at 120 ℃, finally placing the dried solid in a muffle furnace at 450 ℃, and roasting for 4h in an air atmosphere to obtain the carrier Meso-La 2 O 3 -ZnO-SiO 2 。
30g of the carrier (6 wt%) prepared in the above-mentioned manner was taken and added to 500g of methanol, and no ligand such as phenylphosphonate compound was added thereto, and 27.0g of zirconium n-propoxide (25 wt% based on the mass of the carrier, calculated as Zr) was added thereto, followed by adding 1.1g of acetic acid (15 wt% based on the mass of the organozirconium salt, calculated as Zr) thereto. The impregnation was stirred at 50℃for 3h. Filtering and washing the immersed solid, drying for 6 hours at 110 ℃, and finally roasting in a nitrogen roasting furnace at 550 ℃ for 7 hours to obtain Zr-P/Meso-La with mesoporous structure 2 O 3 -ZnO-SiO 2 A catalyst. The catalyst prepared above was characterized by elemental analysis in terms of Zr/Si molar ratio of 0.08:1, la/Si molar ratio of 0.14:1, and Zn/Si molar ratio of 0.20:1.
Characterization data of the catalyst obtained above are as follows: BET surface area of 711m 2 Per gram, pore volume of 0.78cm 3 And/g, pore size distribution is 3.5-17nm.
2) Catalyst reaction evaluation:
into a three-necked flask, a certain amount of 98g of isovaleric acid and 100g of menthol (mol/mol=1.5) and 1g of mesoporous Zr/Meso-La were charged 2 O 3 -ZnO-SiO 2 And (3) heating the catalyst to 50 ℃ for reaction, adding 10g of water knockout agent petroleum ether (30-60 ℃) under stirring, refluxing and separating water, after 6 hours, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting the fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate.
The selectivity calculated after analysis of the reaction product and the product obtained by rectification was 87.5% and the yield was 81.9%.
The selectivity and yield data for multiple catalyst applications are as follows:
| number of times of catalyst application | Reaction Selectivity/% | Product yield/% |
| 0 | 87.5 | 81.9 |
| 10 | 86.4 | 80.2 |
| 30 | 85.2 | 78.6 |
| 50 | 82.9 | 76.8 |
As can be seen from the above table, after the catalyst is applied for a plurality of times, the reaction selectivity and the yield are obviously reduced, namely the performance of the catalyst is reduced.
Zr-P/Meso-La prepared in example 1, compared with the catalyst prepared in comparative example 1-2 2 O 3 -ZnO-SiO 2 The catalyst has higher catalytic selectivity and reaction yield, and can still maintain excellent catalytic activity after being used for a plurality of times.
Claims (16)
1. A mesoporous solid acid catalyst is characterized in that the composition of the mesoporous solid acid catalyst is Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 Which is prepared from a composite metal oxide Meso-La containing mesoporous channels 2 O 3 -ZnO-SiO 2 As a carrier, the phenylphosphonate compound is used as a doped P source, and the organicZirconium salt is a precursor of active metal, and is prepared by dipping and roasting.
2. The catalyst of claim 1, wherein the catalyst is Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The molar ratio of Zr/Si is 0.04-0.17:1; the molar ratio of P/Si is 0.17-0.46:1; the La/Si molar ratio is 0.10-0.23:1; the Zn/Si molar ratio is 0.14-0.29:1.
3. The catalyst of claim 2, wherein the catalyst is Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The molar ratio of Zr/Si is 0.06-0.11:1; the molar ratio of P/Si is 0.27-0.38:1; the La/Si molar ratio is 0.14-0.16:1; the Zn/Si molar ratio is 0.18-0.22:1.
4. A method for preparing the mesoporous solid acid catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Mesoporous SiO 2 Placing into water solution, adding inorganic zinc salt and inorganic lanthanum salt, soaking for a period of time, taking out, filtering, washing, drying, and roasting in air roasting furnace to obtain the composite metal oxide carrier Meso-La 2 O 3 -ZnO-SiO 2 ；
(2) Adding the calcined carrier in the step (1) into an organic solvent, then adding a certain amount of phenylphosphonate compounds and organic zirconium salts respectively, and carrying out stirring and loading in the presence of an acetic acid hydrolysis inhibitor;
(3) Filtering and separating solid from the liquid in the step (2), drying the solid, and roasting in nitrogen atmosphere to obtain Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 。
5. The process according to claim 4, wherein in step (1), the inorganic zinc salt is one or more of zinc nitrate hexahydrate, zinc sulfate hexahydrate, and zinc sulfate heptahydrate; the inorganic lanthanum salt is one or more of lanthanum nitrate hexahydrate, anhydrous lanthanum sulfate or lanthanum sulfate nonahydrate.
6. The method of claim 4, wherein in step (1), mesoporous SiO 2 Mesoporous SiO selected from one or combination of MCM-41 and SBA-15 2 The mass fraction in water is 10-20wt%; the inorganic zinc salt is used as mesoporous SiO based on ZnO 2 20-40wt% of the total amount; by La of 2 O 3 The inorganic lanthanum salt is used as mesoporous SiO 2 28-64wt% of the total amount.
7. The method of claim 6, wherein mesoporous SiO 2 The mass fraction in water is 12-15wt%; the inorganic zinc salt is used as mesoporous SiO based on ZnO 2 25-30wt% of the amount; by La of 2 O 3 The inorganic lanthanum salt is used as mesoporous SiO 2 40-45wt% of the total amount.
8. The method according to any one of claims 4 to 7, wherein in step (1), the impregnation temperature is 10 to 40 ℃; the dipping time is 0.5-5 h; the drying temperature is 100-150 ℃; the drying time is 1-3 h; the roasting temperature is 400-550 ℃; roasting time is 2-8 h; the roasting pressure is normal pressure.
9. The method of claim 8, wherein in step (1), the impregnation temperature is 20 to 30 ℃; the dipping time is 2.5-3.5h; the drying temperature is 120-130 ℃; the drying time is 1.5-2h; the roasting temperature is 450-500 ℃; roasting time is 4-5h; the roasting pressure is normal pressure.
10. The method of any one of claims 4-7, wherein the stirring temperature of step (2) is 40-60 ℃; stirring time is 1-8 h; the drying temperature of the step (3) is 90-150 ℃; the drying time is 5-10 h; the roasting temperature is 450-650 ℃; the roasting time is 5-9 h.
11. The method of claim 10, wherein the stirring temperature of step (2) is 50-55 ℃; stirring time is 3-4h; the drying temperature of the step (3) is 110-120 ℃; the drying time is 6-8h; the roasting temperature is 550-600 ℃; the roasting time is 7-8h.
12. The preparation method of the menthyl isovalerate is characterized by comprising the following steps of: under normal pressure, adding isovaleric acid, menthol and Zr-P/Meso-La into a three-neck flask 2 O 3 -ZnO-SiO 2 Heating the catalyst to a certain temperature for reaction, adding petroleum ether serving as a water splitting agent at 30-60 ℃ under stirring, carrying out reflux water splitting, after the reaction is finished, adding saturated sodium carbonate solution and distilled water successively for washing until the solution becomes neutral, finally placing an organic phase into a reduced pressure distillation device for reduced pressure distillation, collecting a fraction of 148-150 ℃/2Kpa to obtain the menthyl isovalerate, wherein Zr-P/Meso-La is prepared by 2 O 3 -ZnO-SiO 2 The catalyst is selected from the group consisting of the catalysts according to any one of claims 1 to 3 or the catalysts obtainable by the preparation process according to any one of claims 4 to 11.
13. The process according to claim 12, wherein the molar ratio of isovaleric acid to menthol is 1.0-4.0:1, and wherein the Zr-P/Meso-La is 2 O 3 -ZnO-SiO 2 The dosage of the catalyst is 0.5-2.0wt% of menthol; the petroleum ether of the water diversion agent at the temperature of 30-60 ℃ accounts for 5-20wt% of the mass of menthol.
14. The process according to claim 13, wherein the molar ratio of isovaleric acid to menthol is 1.5-2.5:1, and the Zr-P/Meso-La 2 O 3 -ZnO-SiO 2 The dosage of the catalyst is 1.0-1.5. 1.5wt percent of the mass of menthol; the petroleum ether content of the water diversion agent at 30-60 ℃ is 10-15wt% of the mass of menthol.
15. The method of any one of claims 12-14, wherein the reaction temperature is 30-60 ℃; the reaction time is 2-10h; the pressure is normal pressure.
16. The method of claim 15, wherein the reaction temperature is 40-50 ℃; the reaction time was 6-8 h.
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