CN101816950A - Hydrotalcite-like structuring catalyst and method for catalytic synthesis of pseudo-ionone - Google Patents
Hydrotalcite-like structuring catalyst and method for catalytic synthesis of pseudo-ionone Download PDFInfo
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Abstract
The invention discloses a hydrotalcite-like thin membrane which is grown on an aluminum substrate with surface anode oxidation and used as a structuring catalyst in the field of membrane catalysis, so as to catalyze the optimal feed ratio of citral to acetone during the aldol condensation reaction of the citral and the acetone. The in-situ synthesis technology is adopted for preparing the hydrotalcite-like thin membrane on an aluminum sheet after the surface anode oxidation, the high-temperature calcination and the re-hydration are further carried out, and the hydrotalcite-like structuring catalyst which takes aluminum as the substrate is finally obtained. The prepared structuring catalyst can be effectively used for the aldol condensation reaction of the citral and the acetone, solve a series of problems caused by a liquid base catalyst and a solid base catalyst and lead the process to meet the requirements on environmental protection and sustainable development; more importantly, the use of the structuring catalyst can effectively reduce the molar ratio of acetone/citral to 1, thereby obtaining great catalytic effect.
Description
Technical field
The invention belongs to the film catalytic field, be specifically related to be grown in hydrotalcite film on the surperficial anodised aluminum substrate as structural catalyst, the citral the during aldol reaction of catalyzing citral and acetone and the optimum charging ratio of acetone.
Background technology
Pseudoionone is a kind of widely intermediate of purposes ten minutes in the spices compound probability, is again the intermediate that is used for synthetic vitamin A and beta carotene in medical industry simultaneously, therefore further improves necessary to its synthesis technique.At present industrial all is that employing citral and acetone are raw material, carries out aldol reaction and generate pseudoionone under the base catalyst effect.
Two very important factors are arranged in this technology, and one is selection of catalysts: catalyst commonly used in the traditional handicraft is the liquid caustic soda catalyst, as Ba (OH)
2The saturated aqueous solution and the NaOH aqueous solution also have alcoholic solution system such as EtONa/EtOH, NaOH/EtOH and KOH/MeOH etc., at present industrial commonly used be the NaOH aqueous solution.Use these liquid caustic soda inevitably to bring a series of problems such as catalyst to be difficult for reclaiming as catalyst, severe corrosion equipment brings very big pollution to environment, and for the aqueous alkali catalyst, if alkali concn is too high, easily cause polymer build-up, productive rate reduces; If alkali solubility is low excessively, though polymer reduces, the system water content increases, and dissolves a large amount of products, reclaims difficulty.Therefore at present general thinking is to replace the liquid caustic soda catalyst with solid base catalyst, as solid NaOH and KOH, CaO, hydrotalcite and, KF/Al
2O
3And NaOH/Al
2O
3Even load type base catalyst.Though use these solid base catalysts can solve a series of problems that those liquid caustic soda catalyst bring, but because employing is solid base catalyst, causing reaction system like this is a heterogeneous system, has just increased resistance to mass tranfer so undoubtedly, is unfavorable for the diffusion of heterogeneous contact and material.
In recent years, the direction that chemical industry just towards safety, cleaning, efficiently, is finally being realized the production process zero-emission develops, to satisfy the requirement of environmental protection and sustainable development.This just requires aspect catalyst research, not only will consider the active sites of molecule aspect and such as the problem of catalyst engineering aspects such as porosity, catalyst pattern and composition, also will consider the diffusion of effective heterogeneous contact and reaction mass.Structural catalyst arises at the historic moment under this background, and structural catalyst combines Catalyst Design and reactor design, and a catalyst granules is exactly a reactor, does not have boundary between them, thereby has better promoted catalytic action.
Citral and acetone reaction generate the rate of charge that another very important factor is reactant citral and acetone in the pseudoionone technology.It has been generally acknowledged that the rate of charge of suitable raising acetone and citral, can effectively improve the productive rate of reaction, this is because owing to aldehyde is compared with ketone, aldehyde is more active under alkali condition, the condensation reaction of easier generation self, and the condensation rates of ketone self is just slowly, so the content of the acetone that improves, can effectively disperse citral, avoid self condensation of citral.At document CatalysisToday, 60 (2000): among the 297-303, people such as J.C.A.A.Roelofs are under the condition of the catalyst (magnalium hydrotalcite after the process high-temperature roasting is rehydrated) of 273K, reaction 24 hours, adding 1wt.%, the mol ratio that adopts acetone/citral is 250 to react, the conversion ratio that has obtained citral is 65%, and the mol ratio of reduction acetone/citral was by 20 o'clock, this does not take place has reacted, even this does not take place yet and has reacted to 10wt.% in the amount that strengthens catalyst; At document Catalysis Letter, 79 (2002): among the 157-163, people such as Climent are by improving reaction temperature from 273K to 333K, 1 hour reaction time, under the condition of the catalyst of adding 40wt.% (with respect to the amount of citral) (magnalium hydrotalcite after the process high-temperature roasting is rehydrated), investigate the mol ratio from 2.7 to 15 of acetone/citral, obtained the conversion ratio from 99% to 83% of citral.The catalyst of mentioning in the above document all is the magnalium hydrotalcite powder after rehydrated through high-temperature roasting that adopts, magnalium hydrotalcite film after using high-temperature roasting rehydrated yet there are no report as the aldol reaction that structural catalyst is used for citral and acetone, and adopt this structural catalyst to find effectively to reduce the mol ratio to 1 of acetone/citral, and obtain good catalytic effect.
Summary of the invention
The method that the purpose of this invention is to provide a kind of hydrotalcite-like structuring catalyst and catalytic synthesis of pseudo-ionone thereof.The present invention uses with aluminium to the hydrotalcite film of matrix as structural catalyst, the aldol reaction of catalyzing citral and acetone, and optimum feed stock rate of charge under this structural catalyst reaction condition is disclosed.
Hydrotalcite-like structuring catalyst provided by the invention is to be grown in the hydrotalcite film of surface on the aluminium substrate after the anodic oxidation, and the chemical general formula of rete houghite is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 2-)
X/2YH
2O, wherein 0.2≤x≤0.4,0≤y≤2.
The present invention adopts the original position synthetic technology, makes hydrotalcite film on the surface on the aluminium flake after the anodic oxidation, and it is rehydrated to pass through high-temperature roasting again, and obtaining at last with aluminium is the hydrotalcite-like structuring catalyst of substrate, and concrete preparation method is as follows:
A. with purity greater than 80%, thickness is first with ethanol or acetone ultrasonic cleaning 5-10min at the aluminium flake of 0.01-1mm, use the sodium hydroxide solution ultrasonic cleaning 5-10min of 2-15% again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, stereotype or corrosion resistant plate are made negative electrode, electrolyte is the sulfuric acid solution of 0.5-3.0mol/L, oxidation voltage is the 1-5V/cm2 aluminium flake, with taking out behind the aluminium flake anodic oxidation 30-100min, rinse out electrolyte with deionized water, it is standby to obtain anodic alumina film;
B. the solubility magnesium salts is mixed with the solution of 0.001-1.0mol/L in reaction vessel, urea is by [urea]/[Mg
2+The ratio of]=4-12 adds reactor, and makes it to be dissolved in the magnesium salt solution;
C. the anodised aluminium substrate in surface is suspended in the solution of step B preparation, reacted 1-10 days down, take out aluminium substrate at 25-180 ℃, at room temperature dry after the ethanolic solution rinsing, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1-20 ℃/min, rises to 100-1000 ℃ by room temperature, roasting time is 1-50 hour, after roasting is finished, be cooled to room temperature naturally, product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 1-10 hour; reaction finishes; product was placed the 10-60 ℃ of dry 5-48 of following vacuum drying chamber hour; the material that obtains is the hydrotalcite-like structuring catalyst of substrate with aluminium promptly, and the structural catalyst that makes is cut into 0.001-0.01m
2Small pieces standby.
The hydrotalcite-like structuring catalyst that makes is used for the aldol reaction of citral and acetone, and its chemical equation is: C
10H
16O+C
3H
6O → C
13H
20O+H
2O, reaction condition are under the 313-423K, react 3-8 hour, and the mol ratio of acetone/citral is 1-3, and every milliliter of citral adds the catalyst small pieces of 50-100 sheet step e preparation.Preferred reaction conditions is: under the 333K, reacted 5 hours, the mol ratio of acetone/citral is 1, and every milliliter of citral adds the catalyst small pieces of 50-100 sheet step e preparation, the conversion ratio of citral is 80.24% under this condition, and the selectivity of pseudoionone is 84.78%.
The invention has the beneficial effects as follows: prepared is the aldol reaction that the hydrotalcite-like structuring catalyst of substrate can effectively be used for citral and acetone with aluminium, can solve a series of problems of bringing by liquid caustic soda catalyst and solid base catalyst, make this technology satisfy the requirement of environmental protection and sustainable development, priorly can effectively reduce the mol ratio to 1 of acetone/citral after being to use this structural catalyst, and obtain good catalytic effect.
Description of drawings
Fig. 1 is the SEM photograph on the aluminium flake surface after the surperficial anodic oxidation of embodiment 1 steps A gained;
Fig. 2 is the surperficial SEM photograph of the hydrotalcite film sample that obtains of embodiment 1 step C;
Fig. 3 is the XRD figure on the aluminium flake surface after the surperficial anodic oxidation of embodiment 1 steps A gained;
Fig. 4 is the XRD figure of the hydrotalcite film sample that obtains of embodiment 1 step C.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
A. will shear the aluminium flake ultrasonic 5min of acetone of good purity 99.999%, after removing surface oxide layer with the ultrasonic 10min of 8% sodium hydroxide solution again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, stereotype is as negative electrode, and electrolyte is the sulfuric acid solution of 1mol/L, and oxidation voltage is 2V/cm
2Aluminium flake, behind the anodic oxidation 75min, taking-up is also rinsed well standby with deionized water;
B. take by weighing 4.1024g Mg (NO
3)
26H
2O and 7.6877g urea are dissolved in the 800ml deionized water together, after stirring with glass bar, in the polytetrafluoroethylcontainer container of packing into;
C. with the ready aluminium flake in front, getting area is 0.4m
2Small pieces place the mixed solution of step B reaction vessel, behind the good seal, after 3 days, at room temperature dry after the ethanolic solution rinsing again 90 ° of following isothermal reactions, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1 ℃/min, rises to 450 ℃ by room temperature, and roasting time is 8 hours, after roasting is finished, is cooled to room temperature naturally, and product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 4 hours; reaction finishes; product was placed 40 ℃ of vacuum drying chambers dry 8 hours; what obtain promptly is to be the hydrotalcite-like structuring catalyst of substrate with aluminium, and the structural catalyst that makes is cut into 0.0036m
2Small pieces standby.
After getting 5ml citral and 2.2ml acetone at last and mixing, add 75 small pieces said structure catalyst, transfer to together in the there-necked flask of 25ml, reaction is after 5 hours in the 333K water-bath, gas chromatography analysis for sampling, the conversion ratio of citral is 80.24%, and the selectivity of pseudoionone is 84.78%.
Embodiment 2:
A. will shear the aluminium flake ultrasonic 8min of acetone of good purity 99.999%, after removing surface oxide layer with the ultrasonic 8min of 5% sodium hydroxide solution again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, stereotype is as negative electrode, and electrolyte is the sulfuric acid solution of 1mol/L, and oxidation voltage is 2V/cm
2Aluminium flake, behind the anodic oxidation 75min, taking-up is also rinsed well standby with deionized water;
B. take by weighing 2.0512g Mg (NO
3)
26H
2O and 3.8439g urea are dissolved in the 400ml deionized water together, after stirring with glass bar, in the polytetrafluoroethylcontainer container of packing into;
C. with the ready aluminium flake in front, getting area is 0.4m
2Small pieces place the mixed solution of step B reaction vessel, behind the good seal, after 3 days, at room temperature dry after the ethanolic solution rinsing again 90 ° of following isothermal reactions, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1 ℃/min, rises to 450 ℃ by room temperature, and roasting time is 8 hours, after roasting is finished, is cooled to room temperature naturally, and product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 4 hours; reaction finishes; product was placed 40 ℃ of vacuum drying chambers dry 8 hours; what obtain promptly is to be the hydrotalcite-like structuring catalyst of substrate with aluminium, and the structural catalyst that makes is cut into 0.0036m
2Small pieces standby.
After getting 5ml citral and 5.96ml acetone at last and mixing, add 125 small pieces said structure catalyst, transfer to together in the there-necked flask of 25ml, reaction is after 5 hours in the 333K water-bath, gas chromatography analysis for sampling, the conversion ratio of citral is 79.5%, and the selectivity of pseudoionone is 74.88%.
Embodiment 3:
A. will shear the aluminium flake ultrasonic 9min of acetone of good purity 99.999%, after removing surface oxide layer with the ultrasonic 6min of 10% sodium hydroxide solution again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, stereotype is as negative electrode, and electrolyte is the sulfuric acid solution of 1mol/L, and oxidation voltage is 2V/cm
2Aluminium flake, behind the anodic oxidation 75min, taking-up is also rinsed well standby with deionized water;
B. take by weighing 1.282g Mg (NO
3)
26H
2O and 2.4025g urea are dissolved in the 500ml deionized water together, after stirring with glass bar, in the polytetrafluoroethylcontainer container of packing into;
C. with the ready aluminium flake in front, getting area is 0.4m
2Small pieces place the mixed solution of step B reaction vessel, behind the good seal, after 3 days, at room temperature dry after the ethanolic solution rinsing again 90 ° of following isothermal reactions, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1 ℃/min, rises to 450 ℃ by room temperature, and roasting time is 8 hours, after roasting is finished, is cooled to room temperature naturally, and product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 4 hours; reaction finishes; product was placed 40 ℃ of vacuum drying chambers dry 8 hours; what obtain promptly is to be the hydrotalcite-like structuring catalyst of substrate with aluminium, and the structural catalyst that makes is cut into 0.0036m
2Small pieces standby.
After getting 5ml citral and 2.2ml acetone at last and mixing, add 75 small pieces said structure catalyst, transfer to together in the there-necked flask of 25ml, reaction is after 5 hours in the 353K water-bath, gas chromatography analysis for sampling, the conversion ratio of citral is 82.71%, and the selectivity of pseudoionone is 68.16%.
Embodiment 4:
A. will shear the aluminium flake ultrasonic 10min of acetone of good purity 99.999%, after removing surface oxide layer with the ultrasonic 5min of 12% sodium hydroxide solution again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, stereotype is as negative electrode, and electrolyte is the sulfuric acid solution of 1mol/L, and oxidation voltage is 1.5V/cm
2Aluminium flake, behind the anodic oxidation 90min, taking-up is also rinsed well standby with deionized water;
B. take by weighing 1.0256g Mg (NO
3)
26H
2O and 1.9219g urea are dissolved in the 200ml deionized water together, after stirring with glass bar, in the polytetrafluoroethylcontainer container of packing into;
C. with the ready aluminium flake in front, getting area is 0.4m
2Small pieces place the mixed solution of step B reaction vessel, behind the good seal, after 3 days, at room temperature dry after the ethanolic solution rinsing again 90 ° of following isothermal reactions, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1 ℃/min, rises to 450 ℃ by room temperature, and roasting time is 8 hours, after roasting is finished, is cooled to room temperature naturally, and product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 4 hours; reaction finishes; product was placed 40 ℃ of vacuum drying chambers dry 8 hours; what obtain promptly is to be the hydrotalcite-like structuring catalyst of substrate with aluminium, and the structural catalyst that makes is cut into 0.0036m
2Small pieces standby.
After getting 5ml citral and 2.2ml acetone at last and mixing, add 75 small pieces said structure catalyst, transfer to together in the there-necked flask of 25ml, reaction is after 5 hours in the 373K water-bath, gas chromatography analysis for sampling, the conversion ratio of citral is 84.01%, and the selectivity of pseudoionone is 60.24%.
Claims (5)
1. a hydrotalcite-like structuring catalyst is characterized in that, this catalyst is to be grown in the hydrotalcite film of surface on the aluminium substrate after the anodic oxidation, and the chemical general formula of rete houghite is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 2-)
X/2YH
2O, wherein 0.2≤x≤0.4,0≤y≤2.
2. the preparation method of a hydrotalcite-like structuring catalyst is characterized in that, concrete preparation method is as follows:
A. with purity greater than 80%, thickness is first with ethanol or acetone ultrasonic cleaning 5-10min at the aluminium flake of 0.01-1mm, use the sodium hydroxide solution ultrasonic cleaning 5-10min of 2-15% again, clean up with deionized water, put into the anodic oxidation device oxidation, wherein aluminium flake is as anode, and stereotype or corrosion resistant plate are made negative electrode, electrolyte is the sulfuric acid solution of 0.5-3.0mol/L, and oxidation voltage is 1-5V/cm
2Aluminium flake with taking out behind the aluminium flake anodic oxidation 30-100min, rinses out electrolyte with deionized water, and it is standby to obtain anodic alumina film;
B. the solubility magnesium salts is mixed with the solution of 0.001-1.0mol/L in reaction vessel, urea is by [urea]/[Mg
2+The ratio of]=4-12 adds reactor, and makes it to be dissolved in the magnesium salt solution;
C. the anodised aluminium substrate in surface is suspended in the solution of step B preparation, reacted 1-10 days down, take out aluminium substrate at 25-180 ℃, at room temperature dry after the ethanolic solution rinsing, promptly obtain hydrotalcite film;
D. the hydrotalcite film that makes is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1-20 ℃/min, rises to 100-1000 ℃ by room temperature, roasting time is 1-50 hour, after roasting is finished, be cooled to room temperature naturally, product of roasting is the magnesia-alumina hydrotalcite film;
E. the magnesia-alumina hydrotalcite film that obtains is put into CO
2Carry out rehydratedly in the water, remove CO
2The amount of water did not just have all Al-Mg composite metal oxide films to get final product; adopt nitrogen protection; the rehydrated time is 1-10 hour; reaction finishes; product was placed the 10-60 ℃ of dry 5-48 of following vacuum drying chamber hour; the material that obtains is the hydrotalcite-like structuring catalyst of substrate with aluminium promptly, and the small pieces that the structural catalyst that makes are cut into 0.001-0.01m2 are standby.
3. a kind of hydrotalcite-like structuring catalyst according to claim 1 is characterized in that, it is applied to the aldol reaction synthesis of pseudo-ionone of catalyzing citral and acetone, and chemical equation is: C
10H
16O+C
3H
6O → C
13H
20O+H
2O.
4. a kind of hydrotalcite-like structuring catalyst according to claim 3, it is characterized in that, the reaction condition of the aldol reaction synthesis of pseudo-ionone of hydrotalcite-like structuring catalyst catalyzing citral and acetone is under the 313-423K, reacted 3-8 hour, the mol ratio of acetone/citral is 1-3, and every milliliter of citral adds the catalyst small pieces of step e preparation in the 50-100 sheet claim 2.
5. a kind of hydrotalcite-like structuring catalyst according to claim 3, it is characterized in that, the reaction condition of the aldol reaction synthesis of pseudo-ionone of hydrotalcite-like structuring catalyst catalyzing citral and acetone is: under the 333K, reacted 5 hours, the mol ratio of acetone/citral is 1, and every milliliter of citral adds the catalyst small pieces of 50-100 sheet step e preparation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179250A (en) * | 2011-03-18 | 2011-09-14 | 北京化工大学 | Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst |
| CN102344349A (en) * | 2011-08-22 | 2012-02-08 | 无锡百川化工股份有限公司 | Method for preparing 2-methyl-2-pentena |
| CN102634835A (en) * | 2012-04-28 | 2012-08-15 | 北京化工大学 | Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof |
| CN108786867A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of preparation method and purposes of the hydrotalcite-like compound catalyst that fluorine anion is modified |
| CN113117753A (en) * | 2021-04-01 | 2021-07-16 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179250A (en) * | 2011-03-18 | 2011-09-14 | 北京化工大学 | Magnetic nano solid alkaline catalyst and method for synthesizing pseudoionone in presence of magnetic nano solid alkaline catalyst |
| CN102344349A (en) * | 2011-08-22 | 2012-02-08 | 无锡百川化工股份有限公司 | Method for preparing 2-methyl-2-pentena |
| CN102344349B (en) * | 2011-08-22 | 2013-09-18 | 无锡百川化工股份有限公司 | Method for preparing 2-methyl-2-pentena |
| CN102634835A (en) * | 2012-04-28 | 2012-08-15 | 北京化工大学 | Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof |
| CN102634835B (en) * | 2012-04-28 | 2015-01-14 | 北京化工大学 | Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof |
| CN108786867A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of preparation method and purposes of the hydrotalcite-like compound catalyst that fluorine anion is modified |
| CN108786867B (en) * | 2017-04-28 | 2021-06-15 | 山东新和成药业有限公司 | Preparation method and application of fluorine anion modified hydrotalcite-like catalyst |
| CN113117753A (en) * | 2021-04-01 | 2021-07-16 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
| CN113117753B (en) * | 2021-04-01 | 2022-04-19 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
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