CN114289042A - 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, the catalyst has rich mesoporous pore channels, and acetic acid is added in the active metal Zr loading process to effectively adjust the hydrolysis rate of organic Zr salt, so that the high dispersion of Zr metal on a carrier is realized, the utilization rate of Zr metal and the activity of the catalyst are improved, and the catalyst used for synthesizing menthyl isovalerate has the advantages of low reaction temperature, high yield, good catalyst stability and easy recovery.
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 spice, has the unique cool feeling and flavor of menthol, has higher heat resistance than the menthol, and is mainly applied to the industries of cosmetics, soaps, cigarettes and the like. The structural formula is as follows:
the classical synthesis method of the menthyl isovalerate (3) is to heat isovaleric acid (2) and menthol (1) in the presence of concentrated sulfuric acid or p-toluenesulfonic acid, although the traditional esterification method is mature in process, the strong corrosivity of sulfuric acid or p-toluenesulfonic acid shortens the service life of equipment, acidic waste liquid pollutes the environment, and the post-treatment process is complex. Catalysis synthesis of menthyl isovalerate [ J ] (4+) by Zhao Yan Ru (Zhao Yan Ru, Liuchun Jinghui, macroporous resin supported Ce-]Proceedings of the Schachung, 2009(2):3.) and the like, using macroporous resin to immobilize Ce4+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 recover, but the use temperature is high, and the reaction yield is only 80%.
Therefore, it is necessary to develop an isovaleric acid esterification catalyst with high catalytic activity, which avoids the pollution of waste acid, etc., improves the yield of esterification reaction, reduces the reaction energy consumption, and prolongs the service life of the catalyst.
Disclosure of Invention
The invention aims to provide Zr-P/Meso-La with rich mesoporous pore canals and low-temperature efficient catalytic esterification function2O3-ZnO-SiO2The composite metal supported solid acid catalyst catalyzes the esterification of isovaleric acid and menthol to prepare the isovaleric acid menthyl ester. The method has the advantages of environmental friendliness, mild reaction conditions, high product yield, easy recycling of the catalyst and the like. Under optimum conditions, the method can be used for preparing the isovaleric acid mint from isovaleric acid and mentholThe reaction selectivity of the ester 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 purpose, the technical scheme provided by the invention is as follows:
in one aspect, the invention provides a mesoporous solid acid catalyst, which has the composition of Zr-P/Meso-La2O3-ZnO-SiO2Which is a composite metal oxide Meso-La rich in mesoporous channels2O3-ZnO-SiO2The catalyst is prepared by taking a phenylphosphonate compound as a doped P source and taking an organic zirconium salt as a precursor of active metal as a carrier, impregnating and roasting in a nitrogen atmosphere.
Preferably, the catalyst is Zr-P/Meso-La2O3-ZnO-SiO2The Zr/Si molar ratio is 0.04-0.17:1, preferably 0.06-0.11: 1; the molar ratio of P/Si is 0.17-0.46:1, preferably 0.27-0.38: 1; the molar ratio of La/Si 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.
On the other hand, the invention provides a preparation method of a mesoporous solid acid catalyst, which comprises the following steps:
(1) making mesoporous SiO2Placing in water solution, adding inorganic zinc salt and inorganic lanthanum salt, soaking for a period of time, taking out, filtering, washing, drying, and finally placing in an air roasting furnace for roasting, thereby preparing the composite metal oxide carrier Meso-La2O3-ZnO-SiO2。
(2) Adding the calcined carrier obtained in the step (1) into an organic solvent, then respectively adding a certain amount of phenyl phosphonate compounds and organic zirconium salt, and stirring and loading under the condition of existence of an acetic acid hydrolysis inhibitor.
(3) Filtering and separating solid from the liquid in the step (2), drying the solid, and roasting in a nitrogen atmosphere to prepare Zr-P/Meso-La2O3-ZnO-SiO2。
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), and zinc nitrate is preferred; the inorganic lanthanum salt is one or more of lanthanum nitrate (hexahydrate) and lanthanum sulfate (anhydrous or nonahydrate), and lanthanum nitrate is preferred.
In the present invention, in the step (1), the mesoporous SiO2Selected from one or the combination of MCM-41 and SBA-15, mesoporous SiO2The mass fraction in water is 10-20 wt%, preferably 12-15 wt%; the amount of the inorganic zinc salt (calculated by ZnO) is mesoporous SiO2Amounts of 20 to 40 wt%, preferably 25 to 30 wt%; the amount of inorganic lanthanum salt (La)2O3Calculated) is mesoporous SiO2Amounts of 28 to 64 wt.%, preferably 40 to 45 wt.%.
In the invention, in the step (1), the dipping temperature is 10-40 ℃, preferably 20-30 ℃; the dipping time is 0.5 to 5 hours, preferably 2.5 to 3.5 hours; the drying temperature is 100-150 ℃, preferably 120-130 ℃; the drying time is 1-3h, preferably 1.5-2 h; the roasting temperature is 400-550 ℃, preferably 450-500 ℃; the roasting time is 2-8h, preferably 4-5 h; the roasting pressure is normal pressure.
In the present invention, the organic solvent of step (2) includes but is not limited to one or more of methanol, ethanol, tetrahydrofuran, and benzene; the phenyl phosphonate compounds are dimethyl phenyl phosphonate and diethyl phenyl phosphonate, and preferably ethyl phenyl phosphonate; the organic zirconium salt is zirconium n-propoxide;
in the present invention, in the steps (2) and (3), the vector Meso-La2O3-ZnO-SiO2The amount is 5-10 wt%, preferably 6-8 wt% of the organic solvent; the dosage of the phenylphosphonate compound is Meso-La2O3-ZnO-SiO2The amount is 18 to 36 wt.% (calculated as P), preferably 28 to 30 wt.%; the dosage of the organic zirconium salt is Meso-La2O3-ZnO-SiO215-40 wt% (calculated as Zr), preferably 20-25 wt%; the amount of acetic acid is 10-20 wt%, preferably 12-15 wt% of the organic zirconium salt (calculated as Zr);
in the invention, the stirring temperature of the step (2) is 40-60 ℃, preferably 50-55 ℃; the stirring time is 1-8h, preferably 3-4 h; the drying temperature in the step (3) is 90-150 ℃, preferably 110-120 ℃; the drying time is 5-10h, preferably 6-8 h; the roasting temperature is 450-650 ℃, preferably 550-600 ℃; the roasting time is 5-9h, preferably 7-8 h.
Preferably, in one embodiment, the Zr-P/Meso-La is2O3-ZnO-SiO2The catalyst can be prepared by the following method: making mesoporous SiO2(SBA-15) is placed in an aqueous solution, zinc nitrate and lanthanum nitrate are added, the mixture is soaked for 2.5 to 3.5 hours at the temperature of between 20 and 30 ℃, then taken out, filtered, washed and dried, and finally the mixture is placed in an air roasting furnace and roasted for 4 to 5 hours at the temperature of between 450 and 500 ℃; and (3) placing the cooled roasted product into methanol, adding diethyl phenylphosphonate, then adding zirconium n-propoxide, and stirring for 3-4h at the temperature of 50-55 ℃ to realize Zr loading. Finally, the solid is filtered and dried and then is placed in a nitrogen roasting furnace for roasting, the preferable roasting condition is 550-600 ℃, and 7-8h are carried out, thus obtaining the Zr-P/Meso-La2O3-ZnO-SiO2A catalyst.
In still another aspect, the invention also provides a catalyst prepared from Zr-P/Meso-La2O3-ZnO-SiO2The method for preparing menthyl isovalerate by catalyzing isovaleric acid and menthol to carry out esterification by using the catalyst comprises the following steps:
adding a certain amount of isovaleric acid, menthol and Zr-P/Meso-La into a three-neck flask under the condition of normal pressure2O3-ZnO-SiO2Heating the catalyst to a certain temperature for reaction, adding water-separating agent petroleum ether (30-60 ℃) under a stirring state, carrying out reflux water separation, after the reaction is finished, sequentially adding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-fold 150 ℃/2Kpa fraction which is the menthyl isovalerate.
In the invention, the molar ratio of the isovaleric acid to the menthol is 1.0-4.0:1, preferably 1.5-2.5: 1; the Zr-P/Meso-La2O3-ZnO-SiO2The amount of the catalyst is 0.5-2.0 wt%, preferably 1.0-1.5 wt% of the weight of the menthol; the water-separating agent petroleum ether (30-60 ℃) is used in an amount of 5-20 wt%, preferably 10-15 wt% of the mass of the menthol.
Further, the reaction temperature is 30-60 ℃, preferably 40-50 ℃; the reaction time is 2-10h, preferably 6-8 h; the pressure is normal pressure.
The invention has the positive effects that:
(1) Zr-P/Meso-La prepared by the invention2O3-ZnO-SiO2The catalyst has rich mesoporous channels, and increases the active sites of acid centers. Acetic acid is added in the active metal Zr loading process, and the aim is to effectively adjust the hydrolysis rate of the organic Zr salt, inhibit the uncontrollable hydrolysis of the organic Zr salt, realize the high dispersion of the Zr metal on the carrier and improve the utilization rate of the Zr metal. The coordination of the phenylphosphonate compound provides more active centers through PO3The charge and coordination of the group and metal Zr indirectly realize the high dispersion of Zr on the carrier, and aims to reduce the size of Zr particles and improve the stability of the catalyst. In the process of preparing the carrier, commercial mesoporous SiO is adopted2Loaded with ZnO and La2O3Two metal oxides, wherein the supported ZnO increases the B acid position of the catalyst, and SiO2The two have active sites of B acid and L acid, and the synergistic effect of the two acid centers improves the reaction efficiency; la2O3The load of the catalyst modulates the acidity and alkalinity of the carrier, reduces the occurrence of side reactions and enables the catalyst to show good selectivity.
(2) By using Zr-P/Meso-La2O3-ZnO-SiO2The catalyst, the reaction selectivity of the isovaleric acid and menthol for preparing the isovaleric acid menthyl ester 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, and the catalyst can be recycled, thereby conforming to the concept of environmental protection.
Detailed Description
The following examples are not intended to limit the scope of the present invention, and modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is defined in the appended claims.
In the examples, the raw materials used are conventional in the art, and the purity specification used is analytical or chemical purity;
first, the raw material source information in each of the following examples:
mesoporous silica (MCM-41 and SBA-15), lanthanum nitrate hexahydrate, zinc sulfate hexahydrate, anhydrous lanthanum sulfate, zirconium n-propoxide, acetic acid, methanol, ethanol, tetrahydrofuran, benzene, isovaleric acid, menthol, petroleum ether, and sodium carbonate are all of analytical grade purity and are all purchased from Shanghai Aladdin Biotechnology, Inc. Dimethyl phenylphosphonate and diethyl phenylphosphonate were of analytical grade purity and were purchased from Beijing carbofuran technologies, Inc.
Secondly, the following test method is adopted in each embodiment of the invention:
the menthyl isovalerate is analyzed by a GC-9800 chromatograph under the following chromatographic conditions: the initial temperature is 80 ℃, the temperature is kept for 2min, the temperature is programmed to 280 ℃ at the speed of 10 ℃/min, and the temperature is kept for 5 min; the temperature of the gasification chamber is 300 ℃, and the temperature of the detection chamber is 300 ℃; FID detection; the sample size was 0.2. mu.l.
Example 1
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 60g of mesoporous SiO into 500g of deionized water2(SBA-15,12 wt.%), to water was added 65.8g of zinc nitrate hexahydrate (as mesoporous SiO230 wt% of the mass, calculated as ZnO), and 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) was then added240 wt% of the mass as La2O3Metering), stirring and soaking for 2.5h at the temperature of 20 ℃, filtering and washing the solid, drying for 1.5h at the temperature of 120 ℃, finally placing the dried solid in a muffle furnace at the temperature of 450 ℃, and roasting for 4h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
30g of the support (6% by weight) prepared in the above-described manner were taken and added to 500g of methanol, 57.1g of diethyl phenylphosphonate (28% by weight based on the mass of the support, calculated as P) and then 27.0g of zirconium n-propoxide (25% by weight based on the mass of the support, calculated as Zr) were added to the system, and then 1.1g of acetic acid (15% by weight based on the mass of the organic zirconium salt, calculated as Zr) was added to the solution. The impregnation was carried out at 50 ℃ for 3h with stirring. Then the impregnated solid is filtered and washed,drying at 110 deg.C for 6h, and calcining in nitrogen gas calcining furnace at 550 deg.C for 7h to obtain Zr-P/Meso-La with mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.09:1, P/Si molar ratio of 0.31:1, La/Si molar ratio of 0.14:1 and Zn/Si molar ratio of 0.22:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 674m2Per g, pore volume 0.85cm3The pore size distribution is 3.2-18 nm.
2) Evaluation of catalyst reaction:
a three-neck flask was charged with a quantity of 98g isovaleric acid and 100g menthol (mol/mol ═ 1.5) and 1g mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 50 ℃ for reaction, adding 10g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing and diverting water, after the reaction is finished after 6h, sequentially adding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-DEG C/2 Kpa fraction which is 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:
as can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Example 2
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 50g of mesoporous SiO into 500g of deionized water2(MCM-41,10 wt.%) to water was added 66.2g of zinc sulfate hexahydrate (as mesoporous SiO)240 wt% of the mass, calculated as ZnO), and then 85.1g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) was added264% by weight of La2O3Metering), stirring and soaking for 0.5h at the temperature of 40 ℃, filtering and washing the solid, drying for 1h at the temperature of 150 ℃, finally placing the dried solid in a muffle furnace at the temperature of 550 ℃, and roasting for 8h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
50g of the support (10% by weight) prepared in the above-described manner were added to 500g of ethanol, 53.2g of dimethyl phenylphosphonate (18% by weight based on the mass of the support, calculated as P) and then 27.0g of zirconium n-propoxide (15% by weight based on the mass of the support, calculated as Zr) were added to the system, and subsequently 1.5g of acetic acid (20% by weight based on the mass of the organic zirconium salt, calculated as Zr) were added to the solution. The impregnation was carried out at 40 ℃ for 8h with stirring. Then filtering and washing the impregnated solid, drying the solid for 10 hours at the temperature of 90 ℃, finally roasting the solid in a nitrogen roasting furnace for 9 hours at the roasting condition of 650 ℃, and obtaining the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.04:1, P/Si molar ratio of 0.16:1, La/Si molar ratio of 0.23:1 and Zn/Si molar ratio of 0.29:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 824m2Per g, pore volume 0.79cm3The pore size distribution is 3.4-16 nm.
2) Evaluation of catalyst reaction:
into a three-necked flask were charged 261.3g of isovaleric acid and 100g of menthol (mol/mol. RTM.4) in certain amounts and 0.5g of mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 60 ℃ for reaction, adding 5g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, adding saturated sodium carbonate solution and distilled water for washing after 10h of reaction is finished until the solution becomes neutral, and finally placing the organic phase in a reduced pressure distillation device for reactionVacuum distillation is carried out, and the fraction of 148 ℃ and 150 ℃/2Kpa is collected to be 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 |
As can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Example 3
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 100g of mesoporous SiO into 500g of deionized water2(MCM-41,20 wt.%), 73.1g of zinc nitrate hexahydrate (as mesoporous SiO) was added to the water220% by mass in terms of ZnO), and then 97.3g of lanthanum sulfate hexahydrate (accounting for mesoporous SiO) was added228% by mass as La2O3Metering), stirring and soaking at the temperature of 10 ℃ for 5h, filtering and washing the solid, drying at the temperature of 100 ℃ for 3h, finally placing the dried solid in a muffle furnace at the temperature of 400 ℃, and roasting in the air atmosphere for 2h to obtain the carrier Meso-La2O3-ZnO-SiO2。
25g of the carrier prepared in the above-described manner (5% by weight) were taken and added to 500g of tetrahydrofuran, 61.2g of diethyl phenylphosphonate (36% by weight based on the mass of the carrier, calculated as P) and then 35.9g of zirconium n-propoxide (40% by weight based on the mass of the carrier, calculated as Zr) were added to the system, and then 1.0g of acetic acid (10% by weight based on the mass of the organic zirconium salt, calculated as Zr) was added to the solution. The impregnation was carried out at 60 ℃ for 1h with stirring. Then filtering and washing the impregnated solid, drying for 5h at 150 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 450 ℃ for 5h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.17:1, P/Si molar ratio of 0.46:1, La/Si molar ratio of 0.10:1 and Zn/Si molar ratio of 0.14:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 719m2Per g, pore volume 0.74cm3The pore size distribution is 2.8-19 nm.
2) Evaluation of catalyst reaction:
a three-necked flask was charged with a quantity of 65.3g isovaleric acid and 100g menthol (mol/mol ═ 1) and 2g mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 30 ℃ for reaction, adding 20g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, adding saturated sodium carbonate solution and distilled water for washing after 2 hours of reaction is finished until the solution becomes neutral, and finally, adding the organic solventAnd (3) putting the phases into a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fractions, namely 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 |
As can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Example 4
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 75g of mesoporous SiO into 500g of deionized water2(SBA-15,15 wt.%), 62.1g zinc sulfate hexahydrate (as mesoporous SiO) was added to the water225 wt% of the mass, calculated as ZnO), 117.3g of lanthanum sulphate hexahydrate (constituting the mesoporous SiO) are then added245 wt% of the mass as La2O3Metering), stirring and soaking for 3.5h at the temperature of 30 ℃, filtering and washing the solid, drying for 2h at the temperature of 130 ℃, finally placing the dried solid in a muffle furnace at the temperature of 500 ℃, and roasting for 5h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
40g of the support (8% by weight) prepared as described above were added to 500g of benzene, 70.9g of diethyl phenylphosphonate (30% by weight of the support, calculated as P) and then 28.7g of zirconium n-propoxide (20% by weight of the support, calculated as Zr) were added to the system, followed by 0.96g of acetic acid (12% by weight of the organic zirconium salt, calculated as Zr) being added to the solution. The impregnation was carried out at 55 ℃ for 4h with stirring. Then filtering and washing the impregnated solid, drying for 8h at 120 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 600 ℃ for 8h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.07:1, P/Si molar ratio of 0.33:1, La/Si molar ratio of 0.16:1 and Zn/Si molar ratio of 0.18:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 837m2Per g, pore volume 0.84cm3The pore size distribution is 3.6-17 nm.
2) Evaluation of catalyst reaction:
into a three-necked flask were charged 163.3g of isovaleric acid and 100g of menthol (mol/mol. RTM. 2.5) in certain amounts and 1.5g of mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating catalyst to 40 deg.C for reaction, adding 15g water-separating agent petroleum ether (30-60 deg.C) under stirring, refluxing for water separation, after 8 hr, sequentially adding saturated sodium carbonate solution and distilled water for washing until dissolvedAnd (3) changing the liquid phase into neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fraction which is 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 |
As can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Example 5
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 70g of mesoporous SiO into 500g of deionized water2(SBA-15,14 wt.%), to water was added 71.6g of zinc nitrate hexahydrate (as mesoporous SiO)228 wt% of the mass, calculated as ZnO), and then 78.1g of lanthanum nitrate hexahydrate (as mesoporous SiO) was added242% by mass of La2O3Metering), stirring and soaking for 3h at the temperature of 25 ℃, filtering and washing the solid, drying for 1.8h at the temperature of 125 ℃, finally placing the dried solid in a muffle furnace at the temperature of 480 ℃, and roasting for 4.5h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
35g of the support (7% by weight) prepared in the above-described manner were taken and introduced into 500g of methanol, 69.0g of diethyl phenylphosphonate (29% by weight based on the mass of the support, calculated as P) and then 27.6g of zirconium n-propoxide (22% by weight based on the mass of the support, calculated as Zr) were added to the system, and subsequently 1.1g of acetic acid (14% by weight based on the mass of the organic zirconium salt, calculated as Zr) were added to the solution. The impregnation was carried out at 52 ℃ for 3.5h with stirring. Then filtering and washing the impregnated solid, drying for 7h at 115 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 580 ℃ for 7.5h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.08:1, P/Si molar ratio of 0.32:1, La/Si molar ratio of 0.15:1 and Zn/Si molar ratio of 0.20:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 769m2Per g, pore volume 0.79cm3(ii)/g, the pore size distribution is 3.4-21 nm.
2) Evaluation of catalyst reaction:
a three-necked flask was charged with a quantity of 130.6g isovaleric acid and 100g menthol (mol/mol 2) and 1.2g mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 45 ℃ for reaction, adding 12g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, and adding saturated sodium carbonate solution after 7h of reactionWashing the solution with distilled water until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fraction which is 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 |
As can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Example 6
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 90g of mesoporous SiO into 500g of deionized water2(SBA-15,18 wt.%), 72.4g of zinc nitrate hexahydrate (as mesoporous SiO) was added to the water222 wt% of the mass, calculated as ZnO), and then 76.6g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) was added232% by mass of La2O3Metering), stirring and soaking for 4h at the temperature of 15 ℃, filtering and washing the solid, drying for 2.5h at the temperature of 110 ℃, finally placing the dried solid in a muffle furnace at the temperature of 420 ℃, and roasting for 3h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
30g of the support (6% by weight) prepared in the above-described manner were taken and added to 500g of methanol, 40.8g of diethyl phenylphosphonate (20% by weight based on the mass of the support, calculated as P) and then 19.4g of zirconium n-propoxide (18% by weight based on the mass of the support, calculated as Zr) were added to the system, followed by 0.97g of acetic acid (18% by weight based on the mass of the organic zirconium salt, calculated as Zr) being added to the solution. The impregnation was carried out at 45 ℃ for 7h with stirring. Then filtering and washing the impregnated solid, drying for 9h at 100 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 500 ℃ for 6h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.07:1, P/Si molar ratio of 0.24:1, La/Si molar ratio of 0.11:1 and Zn/Si molar ratio of 0.16:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 769m2Per g, pore volume 0.79cm3(ii)/g, the pore size distribution is 3.4-21 nm.
2) Evaluation of catalyst reaction:
a three-necked flask was charged with a quantity of 196.0g isovaleric acid and 100g menthol (mol/mol. RTM.3) and 0.8g mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 35 ℃ for reaction, adding 8g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, and finishing the reaction after 9 hoursAdding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fraction which is 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 |
As can be seen from the above table, the catalyst still has excellent catalytic performance after being reused for many times.
Comparative example 1
1) Preparation of Zr-P/Meso-La2O3-ZnO-SiO2Catalyst:
adding 60g of mesoporous SiO into 500g of deionized water2(SBA-15,12 wt.%), to water was added 65.8g of zinc nitrate hexahydrate (as mesoporous SiO230 wt% of the mass, calculated as ZnO), and 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) was then added240 wt% of the mass as La2O3Metering), stirring and soaking for 2.5h at the temperature of 20 ℃, filtering and washing the solid, drying for 1.5h at the temperature of 120 ℃, finally placing the dried solid in a muffle furnace at the temperature of 450 ℃, and roasting for 4h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
30g of the carrier (6 wt%) prepared in the above manner was added to 500g of methanol, and 57.1g of diethyl phenylphosphonate (28 wt% of the carrier in terms of P) and 27.0g of zirconium n-propoxide (25 wt% of the carrier in terms of Zr) were added to the system without using a hydrolysis inhibitor such as acetic acid. The impregnation was carried out at 50 ℃ for 3h with stirring. Then filtering and washing the impregnated solid, drying for 6h at 110 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 550 ℃ for 7h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has Zr/Si molar ratio of 0.07:1, P/Si molar ratio of 0.30:1, La/Si molar ratio of 0.13:1 and Zn/Si molar ratio of 0.22:1 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 631m2Per g, pore volume 0.57cm3The pore size distribution is 2.9-19 nm.
2) Evaluation of catalyst reaction:
a three-neck flask was charged with a quantity of 98g isovaleric acid and 100g menthol (mol/mol ═ 1.5) and 1g mesoporous Zr-P/Meso-La2O3-ZnO-SiO2Heating the catalyst to 50 ℃ for reaction, adding 10g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, and adding the water diversion agent petroleum ether successively after 6 hours of reactionAnd (3) adding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fraction which is 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 reused for many times, the reaction selectivity and yield are both significantly reduced, i.e., the performance of the catalyst is reduced.
Comparative example 2
1) Preparation of Zr/Meso-La2O3-ZnO-SiO2Catalyst:
adding 60g of mesoporous SiO into 500g of deionized water2(SBA-15,12 wt.%), to water was added 65.8g of zinc nitrate hexahydrate (as mesoporous SiO230 wt% of the mass, calculated as ZnO), and 63.8g of lanthanum nitrate hexahydrate (accounting for mesoporous SiO) was then added240 wt% of the mass as La2O3Metering), stirring and soaking for 2.5h at the temperature of 20 ℃, filtering and washing the solid, drying for 1.5h at the temperature of 120 ℃, finally placing the dried solid in a muffle furnace at the temperature of 450 ℃, and roasting for 4h in the air atmosphere to obtain the carrier Meso-La2O3-ZnO-SiO2。
30g of the carrier (6 wt%) prepared in the above manner was taken and added to 500g of methanol, 27.0g of zirconium n-propoxide (25 wt% based on the mass of the carrier, calculated as Zr) was added without adding a ligand such as a phenylphosphonate compound, and then 1.1g of acetic acid (15 wt% based on the mass of the organic zirconium salt, calculated as Zr) was added to the solution. The impregnation was carried out at 50 ℃ for 3h with stirring. Then filtering and washing the impregnated solid, drying for 6h at 110 ℃, finally placing the solid in a nitrogen roasting furnace for roasting at 550 ℃ for 7h to obtain the Zr-P/Meso-La with the mesoporous structure2O3-ZnO-SiO2A catalyst. The catalyst prepared above has 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 by element analysis.
The characterization data of the catalyst obtained above are as follows: BET surface area 711m2Per g, pore volume 0.78cm3The pore size distribution is 3.5-17 nm.
2) Evaluation of catalyst reaction:
a three-necked flask was charged with a certain amount of 98g isovaleric acid and 100g menthol (mol/mol ═ 1.5) and 1g mesoporous Zr/Meso-La2O3-ZnO-SiO2Heating the catalyst to 50 ℃ for reaction, adding 10g of water diversion agent petroleum ether (30-60 ℃) under the stirring state, refluxing for water diversion, ending the reaction after 6 hours, and firstlyThen adding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing the organic phase in a reduced pressure distillation device for reduced pressure distillation, and collecting 148-150 ℃/2Kpa fraction which is 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 reused for many times, the reaction selectivity and yield are both significantly reduced, i.e., the performance of the catalyst is reduced.
Zr-P/Meso-La prepared in example 1, as compared with the catalyst prepared in comparative examples 1-22O3-ZnO-SiO2The catalyst has higher catalytic selectivity and reaction yield, and can still maintain excellent catalytic activity after being recycled for multiple times.
Claims (10)
1. The mesoporous solid acid catalyst is characterized by comprising the following components of Zr-P/Meso-La2O3-ZnO-SiO2Which is a composite metal oxide Meso-La containing mesoporous channels2O3-ZnO-SiO2The catalyst is prepared by taking a phenylphosphonate compound as a doped P source and taking an organic zirconium salt as a precursor of active metal as a carrier through impregnation and roasting.
2. The catalyst of claim 1, wherein the catalyst is Zr-P/Meso-La2O3-ZnO-SiO2The Zr/Si molar ratio is 0.04-0.17:1, preferably 0.06-0.11: 1; the molar ratio of P/Si is 0.17-0.46:1, preferably 0.27-0.38: 1; the molar ratio of La/Si 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.
3. The method for preparing the mesoporous solid acid catalyst according to claim 1 or 2, comprising the steps of:
(1) making mesoporous SiO2Placing in water solution, adding inorganic zinc salt and inorganic lanthanum salt, soaking for a period of time, taking out, filtering, washing, drying, and finally placing in an air roasting furnace for roasting, thereby preparing the composite metal oxide carrier Meso-La2O3-ZnO-SiO2。
(2) Adding the calcined carrier obtained in the step (1) into an organic solvent, then respectively adding a certain amount of phenyl phosphonate compounds and organic zirconium salt, and stirring and loading under the condition of existence of an acetic acid hydrolysis inhibitor.
(3) Filtering and separating solid from the liquid in the step (2), drying the solid, and roasting in a nitrogen atmosphere to prepare Zr-P/Meso-La2O3-ZnO-SiO2。
4. The preparation method according to claim 3, wherein in the step (1), the inorganic zinc salt is one or more of zinc nitrate hexahydrate, zinc sulfate hexahydrate and zinc sulfate heptahydrate, preferably zinc nitrate hexahydrate; the inorganic lanthanum salt is one or more of lanthanum nitrate hexahydrate, anhydrous lanthanum sulfate or nonahydrate lanthanum sulfate, and lanthanum nitrate is preferred.
5. The method of claim 3 or 4, wherein in step (1), the mesoporous SiO is2Selected from one or the combination of MCM-41 and SBA-15, mesoporous SiO2The mass fraction in water is 10-20 wt%, preferably 12-15 wt%; calculated by ZnO, the consumption of inorganic zinc salt is mesoporous SiO2Amounts of 20 to 40 wt%, preferably 25 to 30 wt%; with La2O3The dosage of the inorganic lanthanum salt is mesoporous SiO2Amounts of 28 to 64 wt.%, preferably 40 to 45 wt.%.
6. The method according to any one of claims 3 to 5, wherein in step (1), the impregnation temperature is 10 to 40 ℃, preferably 20 to 30 ℃; the dipping time is 0.5 to 5 hours, preferably 2.5 to 3.5 hours; the drying temperature is 100-150 ℃, preferably 120-130 ℃; the drying time is 1-3h, preferably 1.5-2 h; the roasting temperature is 400-550 ℃, preferably 450-500 ℃; the roasting time is 2-8h, preferably 4-5 h; the roasting pressure is normal pressure.
7. The method according to any one of claims 3 to 6, wherein the stirring temperature in step (2) is 40 to 60 ℃, preferably 50 to 55 ℃; the stirring time is 1-8h, preferably 3-4 h; the drying temperature in the step (3) is 90-150 ℃, preferably 110-120 ℃; the drying time is 5-10h, preferably 6-8 h; the roasting temperature is 450-650 ℃, preferably 550-600 ℃; the roasting time is 5-9h, preferably 7-8 h.
8. A preparation method of menthyl isovalerate is characterized by comprising the following steps: adding a certain amount of isovaleric acid, menthol and Zr-P/Meso-La into a three-neck flask under the condition of normal pressure2O3-ZnO-SiO2Heating a catalyst to a certain temperature for reaction, adding water-separating agent petroleum ether (30-60 ℃) under a stirring state, carrying out reflux water separation, after the reaction is finished, sequentially adding saturated sodium carbonate solution and distilled water for washing until the solution becomes neutral, finally placing an organic phase in a reduced pressure distillation device for reduced pressure distillation, collecting 148-value 150 ℃/2Kpa fraction which is menthyl isovalerate, wherein the Zr-P/Meso-La2O3-ZnO-SiO2The catalyst is selected from the group consisting of the catalysts according to claim 1 or 2 or the catalysts obtained by the preparation process according to any one of claims 3 to 7.
9. The method of claim 8, wherein the molar ratio of isovaleric acid to menthol is 1.0 to 4.0:1, preferably 1.5 to 2.5: 1; the Zr-P/Meso-La2O3-ZnO-SiO2The amount of the catalyst is 0.5-2.0 wt%, preferably 1.0-1.5 wt% of the weight of the menthol; the water-separating agent petroleum ether (30-60 ℃) is used in an amount of 5-20 wt%, preferably 10-15 wt% of the mass of the menthol.
10. The process according to claim 8 or 9, wherein the reaction temperature is 30 to 60 ℃, preferably 40 to 50 ℃; the reaction time is 2-10h, preferably 6-8 h; the pressure is normal pressure.
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