CN106854196B - A kind of synthesis technology of organic synthesis intermediate cyclohexanone ethylene ketal - Google Patents
A kind of synthesis technology of organic synthesis intermediate cyclohexanone ethylene ketal Download PDFInfo
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- CN106854196B CN106854196B CN201611163333.1A CN201611163333A CN106854196B CN 106854196 B CN106854196 B CN 106854196B CN 201611163333 A CN201611163333 A CN 201611163333A CN 106854196 B CN106854196 B CN 106854196B
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a kind of synthesis technologies of organic synthesis intermediate cyclohexanone ethylene ketal, with cyclohexanone, ethylene glycol, water entrainer hexamethylene, the raw materials such as the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3 solid acid catalyst pass through condensing reflux, vacuum distillation, the operational means such as magnetic agitation prepare cyclohexanone ethylene ketal.
Description
Technical field
The present invention relates to a kind of synthesis technologies of organic synthesis intermediate cyclohexanone ethylene ketal, belong to organic synthesis neck
Domain.
Background technique
Ketal (aldehyde) is a kind of important compound, is widely used in wine essence and daily essence, also can be used as organic
Carbonyl-protection in synthetic intermediate and organic synthesis.Cyclohexanone ethylene ketal is one of such fragrance, it has flower
It is wooden, mint flavored, usually it is condensed under the catalysis of the inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid by cyclohexanone and ethylene glycol.It should
The advantages of method is that catalyst is cheap and easy to get, and product yield is high, but that there is also side reactions is more, product purity is low, equipment for this method
The disadvantages of a large amount of acid contained in seriously corroded, waste water cause environmental pollution.I have invented a kind of homemade cerium modified nanometers
The cyclohexanone ethylene ketal technique of compound Fe2 (SO4) the 3/Al2O3 solid acid catalyst synthesis of grade, the technological operation is simple, urges
Agent is also easily made, product purity, high income.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of contractings of organic synthesis intermediate cyclohexanone ethylene glycol
The synthesis technology of ketone.
To achieve the goals above, the technical solution adopted by the present invention is that: a kind of organic synthesis intermediate cyclohexanone second two
The synthesis technology of alcohol ketal.The following steps are included:
Step 1, first by cyclohexanone, ethylene glycol, water entrainer hexamethylene ultrasonication 3h under nitrogen atmosphere；
Then cyclohexanone, ethylene glycol, water entrainer hexamethylene are transferred in three-necked flask, while being added homemade by step 2
Cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst is then turned on 80 DEG C of oil bath reaction 4h of magnetic agitation,
Condenser pipe is opened simultaneously；
It is solid that step 3, after reaction vacuum filtration recycle the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3
Body acid catalyst filtrate is washed till neutrality with saturated sodium carbonate solution, then dry to clear and transparent, vacuum distillation with anhydrous calcium chloride
Recycle low-boiling water entrainer hexamethylene；
Step 4 is further continued for the fraction that heating collects 176 DEG C~178 DEG C, produces up to the colorless and transparent liquid with fruit flavor
Product cyclohexanone ethylene ketal；
Step 5, then recrystallization is handled in ethanol solution, finally obtains the cyclohexanone ethylene glycol contracting of high-purity
Ketone.
Preparing for cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst is as follows:
Step 1, first by 10gAl2O3 under nitrogen atmosphere, 120 DEG C of ultrasonication 3h；
Step 2, then by the H2SO4 solution of processed Al2O3 and 65% in solid-liquid mass ratio 1:12 ratio mixing,
Return stirring 8h；
After step 3, return stirring, it is then allowed to stand 5h, is centrifugated, is dried at 110 DEG C to constant weight to get work is arrived
For the Al2O3 of catalyst active carrier；
Step 4 mixes active al2o3 with the 3 solution 1:8 in mass ratio of Fe2 (SO4) of 0.5mol/L, return stirring 5h；
Step 5, vacuum filtration separation, by the solid isolated again with 3 solution of the Fe2 of same concentrations same volume (SO4)
Mixing, and return stirring 5h under the same conditions, centrifuge separation are dried at 110 DEG C to constant weight；
Step 6, using infusion process, back catalyst tentatively obtained is immersed in 0.5mol/L cerous sulfate solution,
Magnetic agitation processing 6h is opened simultaneously；
Then product is being washed with deionized in step 7,110 DEG C of drying process 8h in thermostatic drying chamber；
Step 8, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 4:1, temperature
300 DEG C, 0.5kpa calcination processing 5h, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa finally obtains cerium and changes
Nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst of property.
It is urged the utility model has the advantages that the present invention is a kind of with the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3 solid acid
The cyclohexanone ethylene ketal technique of agent synthesis, the technological operation is simple, and catalyst is easy to be made, and raw material relatively easily obtains
It takes, by the way that the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3 solid acid catalyst is added, effectively raises anti-
Rate is answered, the generation of side reaction is reduced, in the synthesis process by the processing such as magnetic agitation, activation can be played to reactant
Effect go on smoothly reaction can more, carries out reaction towards expected direction, is improved the yield of target product.Pass through
It is condensed back, vacuum distillation can obtain purer cyclohexanone ethylene ketal.Cyclohexanone, ethylene glycol are wherein taken, it is cerium modified
The sample of nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio 40:38:0.6.Cyclohexanone 40g, ethylene glycol 38g,
Cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst 0.6g, water entrainer hexamethylene 30ml.And produce ring
Hexanone, ethylene glycol, the sample of cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio 30:32:0.5.
Cyclohexanone 30g, ethylene glycol 32g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst 0.5g, water entrainer
Hexamethylene 25ml.Both operate cyclohexanone ethylene ketal purity obtained, and yield is best.
Specific embodiment
Embodiment 1
Preparing for solid acid catalyst is as follows:
Step 1, first by 10gAl2O3 under nitrogen atmosphere, 120 DEG C of ultrasonication 3h；
Step 2, then by the H2SO4 solution of processed Al2O3 and 65% in solid-liquid mass ratio 1:12 ratio mixing,
Return stirring 8h；
After step 3, return stirring, it is then allowed to stand 5h, is centrifugated, is dried at 110 DEG C to constant weight to get work is arrived
For the Al2O3 of catalyst active carrier；
Step 4 mixes active al2o3 with the 3 solution 1:8 in mass ratio of Fe2 (SO4) of 0.5mol/L, return stirring 5h；
Step 5, vacuum filtration separation, by the solid isolated again with 3 solution of the Fe2 of same concentrations same volume (SO4)
Mixing, and return stirring 5h under the same conditions, centrifuge separation are dried at 110 DEG C to constant weight；
Step 6, using infusion process, back catalyst tentatively obtained is immersed in 0.5mol/L cerous sulfate solution,
Magnetic agitation processing 6h is opened simultaneously；
Then product is being washed with deionized in step 7,110 DEG C of drying process 8h in thermostatic drying chamber；
Step 8, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 4:1, temperature
300 DEG C, 0.5kpa calcination processing 5h, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa finally obtains cerium and changes
Nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst of property.
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.6 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.6g, water entrainer hexamethylene 30ml.Cyclohexanone ethylene ketal synthesis technology:
Step 1, first will be at 40g cyclohexanone, 38g ethylene glycol, 30ml water entrainer hexamethylene under nitrogen atmosphere ultrasonic wave
Manage 3h；
Then cyclohexanone, ethylene glycol, water entrainer hexamethylene are transferred in three-necked flask by step 2, while 0.6g is added certainly
Cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst of system, it is anti-to be then turned on 80 DEG C of oil baths of magnetic agitation
4h is answered, while opening condenser pipe；
It is solid that step 3, after reaction vacuum filtration recycle the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3
Body acid catalyst filtrate is washed till neutrality with saturated sodium carbonate solution, then dry to clear and transparent, vacuum distillation with anhydrous calcium chloride
Recycle low-boiling water entrainer hexamethylene；
Step 4 is further continued for the fraction that heating collects 176 DEG C~178 DEG C, produces up to the colorless and transparent liquid with fruit flavor
Product cyclohexanone ethylene ketal；Step 5, then recrystallization is handled in ethanol solution, finally obtains the hexamethylene of high-purity
Ketone ethylene ketal.
Embodiment 2
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
30:32:0.5 sample.Cyclohexanone 30g, ethylene glycol 32g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.5g, water entrainer hexamethylene 25ml.Operating procedure is as embodiment 1.
Embodiment 3
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.5 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.5g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 4
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.4 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.4g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 5
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.3 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.3g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 6
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.2 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 7
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.1 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 8
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.7 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.7g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 9
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.8 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.8g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 10
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.9 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.9g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 11
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:1.0 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 1.0g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 12
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:1.1 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 1.1g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 13
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:1.2 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 1.2g.Other raw materials, operating procedure is as embodiment 1.
Embodiment 14
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:1.3 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 1.3g.Other raw materials, operating procedure is as embodiment 1.
Reference examples 15
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:1.4 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 1.4g.Other raw materials, operating procedure is as embodiment 1.
Reference examples 1
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.6 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.6g.It wherein in cyclohexanone ethylene ketal technique, is operated without being condensed back, other raw materials, operating procedure is with implementing
As example 1.
Reference examples 2
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.6 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.6g.Wherein in cyclohexanone ethylene ketal technique, without ultrasonication, other raw materials, operating procedure is with embodiment 1
Equally.
Reference examples 3
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.6 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.6g.Wherein in cyclohexanone ethylene ketal technique, without magnetic agitation processing, other raw materials, operating procedure is with implementing
As example 1.
Reference examples 4
Produce cyclohexanone, ethylene glycol, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst mass ratio
40:38:0.6 sample.Cyclohexanone 40g, ethylene glycol 38g, cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalysis
Agent 0.6g.Wherein in cyclohexanone ethylene ketal technique, it is dried without anhydrous calcium chloride, other raw materials, operating procedure
As embodiment 1.
Reference examples 5
It is added without the homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3 solid acid catalyst, other raw materials are used
Amount, operating procedure is as embodiment 1.
Reference examples 6
Inorganic acid phosphoric acid catalyst 0.6g is added, other raw materials, operating procedure is as embodiment 1.
Reference examples 7,
Technique, proportion, raw material and embodiment are just the same, the difference is that, solid acid catalyst preparation method, mainly
Difference is, step 8, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 1:1, and temperature
300 DEG C, 0.5kpa calcination processing 5h, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa finally obtains cerium and changes
Nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst of property.
Reference examples 8,
Technique, proportion, raw material and embodiment 1 are just the same, the difference is that, solid acid catalyst preparation method is main
Otherwise with being, step 8, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 3:1, temperature
300 DEG C, 0.5kpa calcination processing 5h of degree, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa finally obtains cerium
Modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst.
Reference examples 9,
Technique, proportion, raw material and embodiment 1 are just the same, the difference is that, solid acid catalyst preparation method is main
Otherwise with being, step 8, then in Muffle furnace calcination processing: 350 DEG C under nitrogen atmosphere, calcination processing 5h under 0.6kpa, most
Cerium modified nanoscale compound Fe2 (SO4) 3/Al2O3 solid acid catalyst is obtained eventually.
Reference examples 10, technique, proportion, raw material and embodiment 1 are just the same, the difference is that, solid acid catalyst system
Preparation Method is added without Ce elements, and the specific method is as follows:
Step 1, first by 10gAl2O3 under nitrogen atmosphere, 120 DEG C of ultrasonication 3h；
Step 2, then by the H2SO4 solution of processed Al2O3 and 65% in solid-liquid mass ratio 1:12 ratio mixing,
Return stirring 8h；
After step 3, return stirring, it is then allowed to stand 5h, is centrifugated, is dried at 110 DEG C to constant weight to get work is arrived
For the Al2O3 of catalyst active carrier；
Step 4 mixes active al2o3 with the 3 solution 1:8 in mass ratio of Fe2 (SO4) of 0.5mol/L, return stirring 5h；
Step 5, vacuum filtration separation, by the solid isolated again with 3 solution of the Fe2 of same concentrations same volume (SO4)
Mixing, and return stirring 5h under the same conditions, centrifuge separation are dried at 110 DEG C to constant weight；
Step 6, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 4:1, temperature
300 DEG C, 0.5kpa calcination processing 5h, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa finally obtains nanometer
Compound Fe2 (SO4) the 3/Al2O3 solid acid catalyst of grade.
Test the yield purity of test product:
Liquid chromatogram: 1200 high performance liquid chromatograph of Agilent, chromatographic column: PhenomenexPFP (250mm ×
4.6mm, 5 μm)；Column temperature: 25 DEG C；Mobile phase: A phase is aqueous solution (formic acid containing 0.1%), and B phase is the first containing 20% isopropanol
Alcoholic solution, (formic acid containing 0.1%)；Condition of gradient elution: 0-2.0min, 32%B；2-2.1min, 32%B~70%B；2.1-
5.0min, linearly increasing by 70%B is 85%B；5.0-15min, linearly increasing by 85%B is 90%B；15-15.1min,
90%B~100%B；15.1-25min, keeping B Phase Proportion is 100%；25.1-30min is linearly down to 32%B by 100%B.
Flow velocity: 1.2ml/min；Detection wavelength 311nm.Sample volume: 1o μ L.Calculated purity, yield.
The purity of the cyclohexanone ethylene ketal of each product of table one, yield result
The results showed that it can be found that the cyclohexanone ethylene ketal product purity that 1,2 technique of embodiment obtains, yield
Preferably, illustrate both techniques in the proportion of raw material, the production of the operation of technique most beneficial for target product.It is made under other techniques
The product obtained is not especially desirable in purity, yield.Comparative example 1, comparative example 1,2,3,4,5,6 are can be found that.No
It is condensed back, is dried, is added without without Carbon Dioxide calcium without magnetic agitation without ultrasonication
The homemade compound Fe2 of cerium modified nanoscale (SO4) 3/Al2O3 solid acid catalyst is added what inorganic acid phosphoric acid catalyst obtained
The purity of cyclohexanone ethylene ketal, yield be not high.
Control group 7-10 shows that the preparation factor of solid acid catalyst for cyclohexanone ethylene ketal product purity, is received
Rate has a great impact.
Claims (1)
1. a kind of synthesis technology of organic synthesis intermediate cyclohexanone ethylene ketal, which comprises the steps of:
Step 1, first by 40g cyclohexanone, 38g ethylene glycol, 30ml water entrainer hexamethylene ultrasonication 3h under nitrogen atmosphere；
Then cyclohexanone, ethylene glycol, water entrainer hexamethylene are transferred in three-necked flask by step 2, while it is cerium modified that 0.6g is added
The compound Fe of nanoscale2(SO4) 3/Al2O3Solid acid catalyst is then turned on 80 DEG C of oil bath reaction 4h of magnetic agitation, opens simultaneously
Open condenser pipe；
Step 3, after reaction, vacuum filtration recycle the cerium modified compound Fe of nanoscale2(SO4) 3/Al2O3Solid acid catalysis
Agent, filtrate are washed till neutrality with saturated sodium carbonate solution, then dry to clear and transparent, vacuum distillation recycling low boiling with anhydrous calcium chloride
The water entrainer hexamethylene of point；
Step 4 is further continued for the fraction that heating collects 176 DEG C~178 DEG C, up to the colorless and transparent liquid product with fruit flavor
Cyclohexanone ethylene ketal；
Step 5, then recrystallization is handled in ethanol solution, finally obtains cyclohexanone ethylene ketal；
The compound Fe of cerium modified nanoscale2(SO4) 3/Al2O3Solid acid catalyst the preparation method is as follows:
Step 1, first by 10g Al2O3Under nitrogen atmosphere, 120 DEG C of ultrasonication 3h；
Step 2, then by processed Al2O3With 65% H2SO4Solution is mixed in the ratio of solid-liquid mass ratio 1:12, and reflux is stirred
Mix 8h；
After step 3, return stirring, it is then allowed to stand 5h, is centrifugated, drying is urged to constant weight to get to conduct at 110 DEG C
The Al of agent active carrier2O3；
Step 4, by active Al2O3With the Fe of 0.5mol/L2(SO4) 3Solution 1:8 in mass ratio mixing, return stirring 5h；
Step 5, vacuum filtration separation, by the solid the isolated Fe with 4 same concentrations same volume of above-mentioned steps again2(SO4) 3
Solution mixing, and return stirring 5h under the same conditions, centrifuge separation are dried at 110 DEG C to constant weight；
Step 6, using infusion process, back catalyst tentatively obtained is immersed in 0.5mol/L cerous sulfate solution, simultaneously
It opens magnetic agitation and handles 6h；
Then product is washed with deionized in step 7 again, 110 DEG C of drying process 8h in thermostatic drying chamber；
Step 8, then in Muffle furnace calcination processing: first under nitrogen and carbon monoxide atmosphere, volume ratio 4:1, temperature 300
DEG C, 0.5kpa calcination processing 5h, then under nitrogen atmosphere 350 DEG C, calcination processing 5h under 0.6kpa is finally obtained cerium modified
The compound Fe of nanoscale2(SO4) 3/Al2O3Solid acid catalyst.
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