CN109912409A - A kind of production method of isoamyl salicylate - Google Patents
A kind of production method of isoamyl salicylate Download PDFInfo
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Abstract
The present invention relates to a kind of production methods of isoamyl salicylate, belong to isoamyl salicylate technical field, including isoamyl salicylate preparation, thick ester separation washing, the vacuum distillation of thick ester, using under conditions of solid super acid catalyst, microwave radiation, gaultherolin, isoamyl alcohol, which react, generates isoamyl salicylate, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, cesium sulfate, and carrier is titanium dioxide.The production method of the isoamyl salicylate reduces the corrosion in production process to equipment, improves the service life of equipment, but also has the advantages that simple process, selectivity are higher, while the easily separated recycling of solid super acid catalyst.
Description
Technical field
The present invention relates to isoamyl salicylate technical fields, more specifically, it is related to a kind of life of isoamyl salicylate
Production method.
Background technique
Isoamyl salicylate is colourless or yellowish liquid, has strong floral odor, and lasting is lasting.Salicylic acid isoamyl
Ester can be added in cymbidium type essence, fragrant common vetch, chypre, can be used for playing the role of fixation in medicine and food.
Currently, the Patent Application Publication that application publication number is CN102249926A discloses a kind of system of isoamyl salicylate
Preparation Method, raw material include salicylic acid 65-75g, isoamyl alcohol 440-460g, concentrated sulfuric acid 18-25g, using esterification, neutralize washing, steaming
The method evaporated prepares isoamyl salicylate.The preparation method of the isoamyl salicylate makees catalyst using the concentrated sulfuric acid, makes salicylic acid
Isoamyl salicylate is obtained with isoamyl alcohol esterification, but the concentrated sulfuric acid is used as catalyst, not only easily corrodes equipment, and
And side reaction is more, to reduce the selectivity of reaction, reduces the yield of isoamyl salicylate.
Summary of the invention
The purpose of the present invention is to provide a kind of production method of isoamyl salicylate, using solid super acid catalyst,
Make gaultherolin and isoamyl alcohol that ester exchange reaction occur, reduces the corrosion in production process to equipment, improve equipment
Service life, but also have the advantages that simple process, selectivity are higher, while the easily separated recycling benefit of solid super acid catalyst
With.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: gaultherolin, isoamyl alcohol, solid super acid catalyst being uniformly mixed, in microwave spoke
Power is penetrated for 200-235W and in the case where being stirred continuously, 30-80min is radiated, obtains thick ester-catalyst mixture and methanol gas
Body；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, component is distillated and condenses to obtain bigcatkin willow
Isoamyl valerate；
Under the conditions of existing for the solid super acid catalyst, the reaction equation of gaultherolin and isoamyl alcohol is as follows:
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, cesium sulfate,
And the weight of lanthanum sulfate accounts for the 1-2wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid superacid as catalyst
The 0.5-1wt% of agent total weight, the weight of cesium sulfate account for the 0.1-0.5wt% of solid super acid catalyst total weight, and carrier is
Titanium dioxide, the acid strength of solid super acid catalyst are -16.1 to -14.5.
By using above-mentioned technical proposal, under the conditions of existing for the solid super acid catalyst, gaultherolin and isoamyl
Alcohol occurs ester exchange reaction and generates isoamyl salicylate, and is made by the collaboration between lanthanum sulfate, molybdenum trisulfate, cesium sulfate three
With, increase lanthanum sulfate, molybdenum trisulfate, cesium sulfate surface active site, improve the selectivity of reaction, reduce by-product,
And the load of lanthanum sulfate, molybdenum trisulfate, cesium sulfate is on the titanium dioxide, recycles the separation and recovery of solid super acid catalyst
It is more convenient, while the synergistic effect between solid super acid catalyst and microwave radiation, it further reduced the reaction of transesterification
Time improves the selectivity and yield of product.
Preferably, the weight of the lanthanum sulfate accounts for the 1.4wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate
Amount accounts for the 0.7wt% of solid super acid catalyst total weight, and the weight of cesium sulfate accounts for solid super acid catalyst total weight
0.3wt%, the acid strength of solid super acid catalyst are -15.2.
By using above-mentioned technical proposal, the active component in solid super acid catalyst is optimized, is further mentioned
The high catalytic performance of solid super acid catalyst.
Preferably, the solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, three oxygen
In change molybdenum, cesium oxide vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 10-20h, filter,
Drying, obtains intermediate；Later, under conditions of temperature is 450-600 DEG C, intermediate is roasted into 3-6h, it is cooling, obtain solid
Super acidic catalyst.
By using above-mentioned technical proposal, on the titanium dioxide by lanthanum sulfate, molybdenum trisulfate, cesium sulfate load, titanium dioxide
Play the role of fixed to lanthanum sulfate, molybdenum trisulfate, cesium sulfate and disperse, not only realizes lanthanum sulfate, molybdenum trisulfate, cesium sulfate and water
Coming into full contact between poplar acid methyl esters, isoamyl alcohol improves the selectivity of reaction, and is convenient for lanthanum sulfate, molybdenum trisulfate, cesium sulfate
Recycling, improve the catalytic performance of solid super acid catalyst.
Preferably, maturing temperature is 510 DEG C, calcining time 4.5h.
By using above-mentioned technical proposal, the preparation condition of solid super acid catalyst is advanced optimized, is improved solid
The catalytic performance of body super acidic catalyst.
Preferably, the gaultherolin, isoamyl alcohol weight proportion be (0.5-2): 1, solid super acid catalyst
Weight account for the 0.3-1.5wt% of gaultherolin and isoamyl alcohol total weight.
By using above-mentioned technical proposal, the proportion of gaultherolin and isoamyl alcohol is optimized, isoamyl alcohol is improved
Conversion ratio, while the dosage of solid super acid catalyst is optimized, meets the dosage of solid super acid catalyst i.e.
The demand of ester exchange reaction, due to and will not excessively increase the production cost of isoamyl salicylate because of its dosage, while reducing solid
Body super acidic catalyst is because of the loss mutually collided.
Preferably, the gaultherolin, isoamyl alcohol weight proportion be 1.2:1, the weight of solid super acid catalyst
Amount accounts for the 0.9wt% of gaultherolin and isoamyl alcohol total weight.
Proportion, the use of solid super acid catalyst by using above-mentioned technical proposal, to gaultherolin and isoamyl alcohol
Amount advanced optimizes, and further improves the conversion ratio of isoamyl alcohol, the selectivity of reaction.
Preferably, the microwave irradiation power in step (1) is 220W, radiated time 55min.
By using above-mentioned technical proposal, the reaction condition of gaultherolin and isoamyl alcohol is optimized, is further mentioned
The high selectivity and yield of reaction.
Preferably, the recovered (distilled) temperature in step (3) is 150-153 DEG C, pressure 2kPa.
By using above-mentioned technical proposal, isoamyl salicylate forms fraction, thus realize the purification of isoamyl salicylate,
Improve the purity of isoamyl salicylate.
Preferably, the methanol gas condensing recovery in step (1) utilizes.
By using above-mentioned technical proposal, the methanol of condensation can be sold or for producing other chemical products, not only drop
Low pollution of the methanol gas to environment, and the secondary value of isoamyl salicylate is increased, meet production requirement.
Preferably, the washing water recycling in step (2).
By using above-mentioned technical proposal, washing water recycling not only reduces pollution of the washing water to environment,
And reduce the production cost of isoamyl salicylate.
In conclusion the invention has the following advantages:
The first, the production method of isoamyl salicylate of the invention makes gaultherolin and different using solid super acid catalyst
Ester exchange reaction occurs for amylalcohol, reduces the corrosion in production process to equipment, improves the service life of equipment, but also has
There are simple process, the higher advantage of selectivity, while the easily separated recycling of solid super acid catalyst.
The second, by the synergistic effect of lanthanum sulfate, molybdenum trisulfate, cesium sulfate, lanthanum sulfate, molybdenum trisulfate, sulfuric acid are not only increased
The active site on caesium surface improves the selectivity of reaction, reduces by-product, and lanthanum sulfate, molybdenum trisulfate, cesium sulfate load
On the titanium dioxide, recycle the separation and recovery of solid super acid catalyst more convenient.
Third, by the synergistic effect of solid super acid catalyst and microwave radiation, accelerate reaction rate, and improve
The selectivity of reaction, and in the case where microwave irradiation power is 200-235W, further improve isoamyl salicylate
Yield.
4th, methanol gas condensing recovery is utilized, washing water is recycled, not only reduce the dirt to environment
Dye, reduces the production cost of benzyl salicylate, and improve the by-product value of benzyl salicylate.
Specific embodiment
Invention is further described in detail with reference to embodiments.It should be understood that described in the embodiment of the present invention
Preparation method is only used for illustrating the present invention, rather than limiting the invention, to this hair under concept thereof of the invention
The simple modifications of bright preparation method belong to the scope of protection of present invention.
Under the conditions of existing for the solid super acid catalyst, the reaction equation of gaultherolin and isoamyl alcohol is as follows:
Embodiment 1
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: 0.5Kg gaultherolin, 1Kg isoamyl alcohol, 4.5g solid super acid catalyst are mixed
Uniformly, at this point, the weight of solid super acid catalyst accounts for the 0.3wt% of gaultherolin and isoamyl alcohol total weight, in microwave spoke
Power is penetrated for 200W and in the case where being stirred continuously, 80min is radiated, obtains thick ester-catalyst mixture and methanol gas, methanol
Gas condensing recovery utilizes；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water, washing water recycling；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, 150 DEG C of temperature, pressure are collected
Component is distillated under the conditions of 2KPa, condensation obtains isoamyl salicylate, isoamyl salicylate sealing packing, storage.
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, sulphur
Sour caesium, and the weight of lanthanum sulfate accounts for the 2wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid super-strong acid and urges
The 0.5wt% of agent total weight, the weight of cesium sulfate account for the 0.1wt% of solid super acid catalyst total weight, and carrier is dioxy
Change titanium, the acid strength of solid super acid catalyst is -16.1.
Wherein solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, oxidation
In caesium vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 20h, filtered, drying, obtain centre
Body；Later, under conditions of temperature is 600 DEG C, intermediate is roasted into 3h, it is cooling, obtain solid super acid catalyst.
Embodiment 2
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: 0.8Kg gaultherolin, 1Kg isoamyl alcohol, 10.8g solid super acid catalyst are mixed
Uniformly, at this point, the weight of solid super acid catalyst accounts for the 0.6wt% of gaultherolin and isoamyl alcohol total weight, in microwave spoke
Power is penetrated for 225W and in the case where being stirred continuously, 60min is radiated, obtains thick ester-catalyst mixture and methanol gas, methanol
Gas condensing recovery utilizes；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water, washing water recycling；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, 151 DEG C of temperature, pressure are collected
Component is distillated under the conditions of 2KPa, condensation obtains isoamyl salicylate, isoamyl salicylate sealing packing, storage.
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, sulphur
Sour caesium, and the weight of lanthanum sulfate accounts for the 1.2wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid super-strong acid
The 0.8wt% of total catalyst weight, the weight of cesium sulfate account for the 0.2wt% of solid super acid catalyst total weight, carrier two
Titanium oxide, the acid strength of solid super acid catalyst are -14.8.
Wherein solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, oxidation
In caesium vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 13h, filtered, drying, obtain centre
Body；Later, under conditions of temperature is 480 DEG C, intermediate is roasted into 5h, it is cooling, obtain solid super acid catalyst.
Embodiment 3
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: 1.2Kg gaultherolin, 1Kg isoamyl alcohol, 19.8g solid super acid catalyst are mixed
Uniformly, at this point, the weight of solid super acid catalyst accounts for the 0.9wt% of gaultherolin and isoamyl alcohol total weight, in microwave spoke
Power is penetrated for 220W and in the case where being stirred continuously, 55min is radiated, obtains thick ester-catalyst mixture and methanol gas, methanol
Gas condensing recovery utilizes；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water, washing water recycling；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, 152 DEG C of temperature, pressure are collected
Component is distillated under the conditions of 2KPa, condensation obtains isoamyl salicylate, isoamyl salicylate sealing packing, storage.
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, sulphur
Sour caesium, and the weight of lanthanum sulfate accounts for the 1.4wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid super-strong acid
The 0.7wt% of total catalyst weight, the weight of cesium sulfate account for the 0.3wt% of solid super acid catalyst total weight, carrier two
Titanium oxide, the acid strength of solid super acid catalyst are -15.2.
Wherein solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, oxidation
In caesium vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 15h, filtered, drying, obtain centre
Body；Later, under conditions of temperature is 510 DEG C, intermediate is roasted into 4.5h, it is cooling, obtain solid super acid catalyst.
Embodiment 4
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: 1.6Kg gaultherolin, 1Kg isoamyl alcohol, 31.2g solid super acid catalyst are mixed
Uniformly, at this point, the weight of solid super acid catalyst accounts for the 1.2wt% of gaultherolin and isoamyl alcohol total weight, in microwave spoke
Power is penetrated for 215W and in the case where being stirred continuously, 50min is radiated, obtains thick ester-catalyst mixture and methanol gas, methanol
Gas condensing recovery utilizes；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water, washing water recycling；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, 153 DEG C of temperature, pressure are collected
Component is distillated under the conditions of 2KPa, condensation obtains isoamyl salicylate, isoamyl salicylate sealing packing, storage.
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, sulphur
Sour caesium, and the weight of lanthanum sulfate accounts for the 1.7wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid super-strong acid
The 0.6wt% of total catalyst weight, the weight of cesium sulfate account for the 0.4wt% of solid super acid catalyst total weight, carrier two
Titanium oxide, the acid strength of solid super acid catalyst are -15.6.
Wherein solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, oxidation
In caesium vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 17h, filtered, drying, obtain centre
Body；Later, under conditions of temperature is 560 DEG C, intermediate is roasted into 4h, it is cooling, obtain solid super acid catalyst.
Embodiment 5
A kind of production method of isoamyl salicylate, includes the following steps:
(1) prepared by isoamyl salicylate: 2Kg gaultherolin, 1Kg isoamyl alcohol, 45g solid super acid catalyst being mixed equal
It is even, at this point, the weight of solid super acid catalyst accounts for the 1.5wt% of gaultherolin and isoamyl alcohol total weight, in microwave radiation
In the case that power is 235W and is stirred continuously, 30min is radiated, thick ester-catalyst mixture and methanol gas, methanol gas are obtained
Body condensing recovery utilizes；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water, washing water recycling；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, 150 DEG C of temperature, pressure are collected
Component is distillated under the conditions of 2KPa, condensation obtains isoamyl salicylate, isoamyl salicylate sealing packing, storage.
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, sulphur
Sour caesium, and the weight of lanthanum sulfate accounts for the 1wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid super-strong acid and urges
The 1wt% of agent total weight, the weight of cesium sulfate account for the 0.5wt% of solid super acid catalyst total weight, and carrier is titanium dioxide
Titanium, the acid strength of solid super acid catalyst are -14.5.
Wherein solid super acid catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, oxidation
In caesium vitriolization, maceration extract is obtained；Then, titanium dioxide is put into maceration extract and impregnates 10h, filtered, drying, obtain centre
Body；Later, under conditions of temperature is 450 DEG C, intermediate is roasted into 6h, it is cooling, obtain solid super acid catalyst.
Comparative example 1
Use application publication number for a kind of preparation of isoamyl salicylate disclosed in the Patent Application Publication of CN102249926A
Method, preparation generate isoamyl salicylate.
Comparative example 2
The difference of comparative example 2 and embodiment 3 is that microwave irradiation power is 0W in step (1).
Comparative example 3
The difference of comparative example 3 and embodiment 3 is that microwave irradiation power is 190W in step (1).
Comparative example 4
The difference of comparative example 4 and embodiment 3 is that microwave irradiation power is 245W in step (1).
Comparative example 5
The difference of comparative example 5 and embodiment 3 is that solid super acid catalyst is not added in (1) for step.
Comparative example 6
The difference of comparative example 6 and embodiment 3 is, is not added with lanthanum sulfate in the active component of solid super acid catalyst.
Comparative example 7
The difference of comparative example 7 and embodiment 3 is, is not added with molybdenum trisulfate in the active component of solid super acid catalyst.
Comparative example 8
The difference of comparative example 8 and embodiment 3 is, is not added with cesium sulfate in the active component of solid super acid catalyst.
To the isoamyl salicylate that embodiment 1-5 and comparative example 1-8 are obtained, following performance detections are carried out, testing result is such as
Shown in table 1.
1 testing result of table
| Detection project | Isoamyl alcohol conversion/% | Reaction selectivity/% | Yield/% | Product purity/% |
| Embodiment 1 | 98.4 | 94.2 | 84.6 | 96.7 |
| Embodiment 2 | 97.6 | 93.4 | 82.1 | 98.2 |
| Embodiment 3 | 98.5 | 95.1 | 84.6 | 97.4 |
| Embodiment 4 | 96.4 | 94.8 | 85.3 | 97.3 |
| Embodiment 5 | 97.3 | 93.4 | 83.7 | 96.6 |
| Comparative example 1 | 85.4 | 78.5 | 62.7 | 90.7 |
| Comparative example 2 | 0 | 0 | 0 | 0 |
| Comparative example 3 | 86.9 | 91.4 | 81.1 | 91.5 |
| Comparative example 4 | 97.5 | 95.3 | 75.4 | 96.5 |
| Comparative example 5 | 46.5 | 52.6 | 40.5 | 84.5 |
| Comparative example 6 | 74.8 | 71.9 | 66.5 | 89.3 |
| Comparative example 7 | 75.6 | 73.5 | 68.4 | 88.4 |
| Comparative example 8 | 78.8 | 76.4 | 70.3 | 90.2 |
From table 1 it follows that a kind of production method of isoamyl salicylate of the invention, prepared by isoamyl salicylate,
It is to realize the production of isoamyl salicylate that thick ester separation washing, thick ester, which are evaporated under reduced pressure three steps, reduces equipment in production process
Corrosion, improves the service life of equipment, also has the advantages that simple process, using solid super acid catalyst and microwave radiation
Synergistic effect, be not only convenient for the recycling of solid super acid catalyst, and improve the selectivity of reaction, isoamyl
Conversion ratio, the yield of alcohol.
By comparative example 3 and comparative example 1, it is comparative example 1 using Shen in place of the difference of comparative example 1 and embodiment 3
Please publication No. be that the preparation method of isoamyl salicylate disclosed in the patent document of CN102249926A a kind of generates salicylic acid
Isopentyl ester, it can thus be seen that making gaultherolin and isoamyl alcohol that ester occur under the conditions of existing for the solid super acid catalyst
Exchange reaction generates isoamyl salicylate, improves the purity of the selectivity of reaction, the conversion ratio of isoamyl alcohol, product, Er Qiegu
Body super acidic catalyst can recycle, and reduce the pollution to environment.
By comparative example 3 and comparative example 2, it is microwave in step (1) in place of the difference of comparative example 2 and embodiment 3
Radiant power is 0W, it can thus be seen that significantly improving selectivity, the yield of reaction using microwave radiation, then passes through comparison
Embodiment 3 and comparative example 3, comparative example 4 are microwave irradiation power in step (1) in place of the difference of comparative example 3 and embodiment 3
For 190W；It is in step (1) that microwave irradiation power is 245W in place of the difference of comparative example 4 and embodiment 3, it is possible thereby to see
Out, under conditions of microwave irradiation power is 200-235W, the yield of product is improved, this is mainly due to microwave irradiation powers
When lower, the reaction of gaultherolin and isopropanol is not complete, and when microwave irradiation power is higher, the isoamyl salicylate of generation
It volatilizees and reduces its yield, therefore, in the case where microwave irradiation power is 200-235W, improve isoamyl salicylate
Yield.
By comparative example 3 and comparative example 5, it is in step (1) not add in place of the difference of comparative example 5 and embodiment 3
Enter solid super acid catalyst, it can thus be seen that solid super acid catalyst, which is added, significantly improves reaction rate, Er Qieming
The aobvious conversion ratio and yield for improving reaction, then pass through comparative example 3 and comparative example 6-8, the area of comparative example 6 and embodiment 3
Place is not to be not added with lanthanum sulfate in the active component of solid super acid catalyst；In place of the difference of comparative example 7 and embodiment 3
It is to be not added with molybdenum trisulfate in the active component of solid super acid catalyst；It is in place of the difference of comparative example 7 and embodiment 3 solid
It is not added with cesium sulfate in the active component of body super acidic catalyst, it can thus be seen that passing through lanthanum sulfate, molybdenum trisulfate, cesium sulfate
The synergistic effect of three realizes the complementation of three, increase lanthanum sulfate, molybdenum trisulfate, cesium sulfate surface active site, and
Contact area between lanthanum sulfate, molybdenum trisulfate, cesium sulfate and gaultherolin, isoamyl alcohol, improves solid super acid catalyst
Catalytic performance, reduce by-product, to improve the selectivity of reaction, improve the yield of product, while lanthanum sulfate, sulphur
Sour molybdenum, cesium sulfate load on the titanium dioxide, not only make the recycling of solid super acid catalyst more convenient, but also two
Titanium oxide further increases the active site of solid super acid catalyst, increases the selectivity of reaction.
Claims (10)
1. a kind of production method of isoamyl salicylate, characterized by the following steps:
(1) prepared by isoamyl salicylate: gaultherolin, isoamyl alcohol, solid super acid catalyst being uniformly mixed, in microwave spoke
Power is penetrated for 200-235W and in the case where being stirred continuously, 30-80min is radiated, obtains thick ester-catalyst mixture and methanol gas
Body；
(2) thick ester separation washing: thick ester-catalyst mixture is filtered, thick ester and solid super acid catalyst, solid are isolated
Super acidic catalyst recycling, is added clear water in thick ester later, washes to thick ester, and it is organic to isolate thick ester
Layer and washing water；
(3) thick ester vacuum distillation: the thick ester organic layer after separation washing is evaporated under reduced pressure, component is distillated and condenses to obtain bigcatkin willow
Isoamyl valerate；
Under the conditions of existing for the solid super acid catalyst, the reaction equation of gaultherolin and isoamyl alcohol is as follows:
Wherein, solid super acid catalyst includes active component and carrier, and active component includes lanthanum sulfate, molybdenum trisulfate, cesium sulfate,
And the weight of lanthanum sulfate accounts for the 1-2wt% of solid super acid catalyst total weight, the weight of molybdenum trisulfate accounts for solid superacid as catalyst
The 0.5-1wt% of agent total weight, the weight of cesium sulfate account for the 0.1-0.5wt% of solid super acid catalyst total weight, and carrier is
Titanium dioxide, the acid strength of solid super acid catalyst are -16.1 to -14.5.
2. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: the weight of the lanthanum sulfate
Amount accounts for the 1.4wt% of solid super acid catalyst total weight, and the weight of molybdenum trisulfate accounts for solid super acid catalyst total weight
0.7wt%, the weight of cesium sulfate account for the 0.3wt% of solid super acid catalyst total weight, and the acid of solid super acid catalyst is strong
Degree is -15.2.
3. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: the solid super-strong acid
Catalyst is prepared using following methods: firstly, by lanthanum sesquioxide, molybdenum trioxide, cesium oxide vitriolization, being impregnated
Liquid；Then, titanium dioxide is put into maceration extract and impregnates 10-20h, filtered, drying, obtain intermediate；Later, it is in temperature
Under conditions of 450-600 DEG C, intermediate is roasted into 3-6h, it is cooling, obtain solid super acid catalyst.
4. a kind of production method of isoamyl salicylate according to claim 3, it is characterised in that: maturing temperature 510
DEG C, calcining time 4.5h.
5. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: the salicylic acid first
Ester, isoamyl alcohol weight proportion be (0.5-2): 1, the weight of solid super acid catalyst accounts for gaultherolin and isoamyl alcohol gross weight
The 0.3-1.5wt% of amount.
6. a kind of production method of isoamyl salicylate according to claim 5, it is characterised in that: the salicylic acid first
Ester, isoamyl alcohol weight proportion be 1.2:1, the weight of solid super acid catalyst accounts for gaultherolin and isoamyl alcohol total weight
0.9wt%.
7. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: micro- in step (1)
Wave radiation power is 220W, radiated time 55min.
8. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: evaporating in step (3)
Temperature is 150-153 DEG C out, pressure 2kPa.
9. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: the first in step (1)
Alcohol gas condensing recovery utilizes.
10. a kind of production method of isoamyl salicylate according to claim 1, it is characterised in that: washing in step (2)
Wash water recycling.
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