CN110002981B - Method for preparing pseudo ionone - Google Patents
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- CN110002981B CN110002981B CN201910317190.2A CN201910317190A CN110002981B CN 110002981 B CN110002981 B CN 110002981B CN 201910317190 A CN201910317190 A CN 201910317190A CN 110002981 B CN110002981 B CN 110002981B
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention discloses a method for preparing pseudo ionone. According to the method, phosphate is used as a catalyst, the pseudo ionone is prepared by a liquid-liquid two-phase method, the self-polymerization of citral can be inhibited, the catalytic selectivity is improved, the catalyst activity is high, the catalyst can be recycled, and the method is green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to a method for preparing pseudo ionone.
Background
The pseudo ionone can be synthesized by Aldol condensation of citral obtained from the separation of the litsea cubeba oil and acetone under the action of a sodium hydroxide solution as a catalyst. The pseudo ionone is an important intermediate for synthesizing essence and flavor such as ionone, vitamin A, E and beta-carotene. The commonly used condensation catalyst is strong alkaline aqueous solution such as NaOH/KOH, etc., although the catalyst can lead the yield to be about 85 percent, the catalyst has the defects of long reaction time, complex post-treatment process, etc., and is not favorable for reducing the production cost and continuously producing. Moreover, the alkali liquor catalyst is difficult to separate from reactants after the reaction, and the excessive alkalinity makes the raw material citral easy to generate self-polymerization, so that the yield is reduced; the citral self-polymerization generates wastewater and polymers, is not beneficial to the separation of products in the later period, cannot be reused, corrodes equipment, generates alkaline waste water, pollutes the environment, and is not easy to be used for industrial production.
The research on the improvement of the synthesis process of the pseudo ionone by scholars at home and abroad is continuously carried out for a long time. In order to allow the reaction to be carried out under mild conditions, processes have emerged that employ solid base catalysts instead of liquid bases. However, compared with common liquid alkali catalysts such as sodium hydroxide and the like, the solid alkali catalyst has the defects of complex preparation process, high cost, poor selectivity, low catalytic efficiency, poor catalyst application effect and the like in the reaction, and the liquid alkali catalyst has obvious advantages in the process.
PL147748 describes a process for preparing pseudoionones by condensing citral and acetone at 56 ℃ with basic ion exchangers, which has the disadvantage of very low space-time yields.
Soviet union patent SU704938(1978) used a 15-20 fold excess of acetone, acetone and water in a ratio of 1: 0.15 to 1: 0.45, the product yield is better, but the main defects are that the acetone is greatly excessive, the energy consumption is higher, the reaction efficiency is low, and the reaction time is longer.
U.S. Pat. No. 4,487,4900 (1989) describes a process for preparing pseudoionone by lithium hydroxide-catalyzed condensation of citral with acetone by batchwise or continuous condensation at-20 to 240 ℃. This process requires the excess catalyst to be filtered off at the completion of the reaction. The method has the defects of long reaction time, more side reactions, low yield, difficult treatment of solid wastes and the like.
In view of the above-mentioned drawbacks, no alkali solution catalyst with both efficiency and cost effective for solving the problems has been found, and dilute NaOH, KOH, Ba (OH) is still used in industry2Equal strengthThe pseudoionone is prepared by catalyzing citral to condense with acetone under the catalysis of aqueous alkali (PH 10-12). However, although the catalyst is easy to obtain and the production cost is not high, the reaction liquid has high toxic and corrosive properties, and the treatment of the used waste alkali is also concerned; meanwhile, the yield of the method is not high and is generally 60-80%.
Therefore, in view of the above-mentioned disadvantages in the prior art, there is a need to develop a new liquid alkali catalyst for the preparation of pseudo ionone.
Disclosure of Invention
The invention aims to provide a method for preparing pseudo ionone. The method adopts a phosphate catalytic system to catalyze the aldol condensation of acetone and citral to synthesize the pseudo ionone, has high catalytic activity, can inhibit the self-polymerization of the citral, can realize the recovery of the catalyst through liquid separation, and has the advantages of high yield, high efficiency, mild reaction conditions, recoverable catalyst and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing pseudo ionone is to react acetone with citral under the catalysis of a phosphate catalyst to prepare the pseudo ionone.
The phosphate catalyst comprises K2HPO4And KH2PO4(ii) a Consisting of K in the catalyst2HPO4And KH2PO4The total weight is as follows: k2HPO4 80-95wt％，KH2PO45-20 wt%; preferably K2HPO4 90-95wt％，KH2PO4 5-10wt％。
In the present invention, the phosphate catalyst is K2HPO4And KH2PO4The mixed aqueous solution of (1) has a mass concentration range of K2HPO4 0.048-0.057wt％，KH2PO40.003-0.012 wt%; preferably K2HPO4 0.054-0.057wt％，KH2PO40.003-0.006 wt%. In some embodiments of the invention, K is2HPO4And KH2PO4OfAqueous solution, most preferably K2HPO4 0.056wt％，KH2PO4 0.0041wt％，H2O 99.9399wt％。
In the present invention, said K2HPO4And KH2PO4The pH of the mixed aqueous solution of (a) is 7.2 to 8, preferably 7.5 to 8, most preferably 7.8 to 8.
In the invention, the preparation method of the catalyst phosphate aqueous solution is not limited, and any solution preparation method which can be realized in the prior art can be adopted, and specific examples are as follows: mixing the two phosphates according to the proportion, slowly adding water for dilution, and stirring until the mixture is clear, thereby obtaining the phosphate catalyst solution.
In the invention, liquid alkali catalyst and aldol condensation reaction of acetone and citral are adopted to synthesize pseudo ionone. The chemical reaction formula for synthesizing the pseudo ionone by the aldol condensation reaction of the acetone and the citral is as follows:
in the present invention, the amount of the phosphate catalyst (i.e., K) is used2HPO4And KH2PO4The total weight of the mixed aqueous solution) of 5 to 20%, preferably 10 to 15%, of the sum of the masses of acetone and citral.
In the invention, the molar ratio of acetone to citral is 1-10: 1, preferably 5 to 10: 1.
in the invention, the reaction temperature is 40-150 ℃, preferably 60-80 ℃, the reaction time is 2-8h, preferably 3-4h, and the reaction pressure is normal pressure.
According to the preparation method of the pseudo ionone, after the reaction is finished, the conversion rate of the citral can reach 100%, the selectivity of the pseudo ionone product can reach 98%, and the self-polymerization rate of the citral is lower than 4%.
The preparation method of the pseudo ionone takes phosphate as a catalyst, synthesizes the pseudo ionone by a liquid-liquid two-phase method, and recovers the catalyst by liquid separation after the reaction is finished. Because the pH of the reaction system is low, the self-polymerization side reaction of the materials is inhibited, the content of the polymer in the reaction liquid is low, the separation difficulty is reduced, and the direct liquid separation can be realized without acid neutralization treatment. The present invention has no particular requirement on the method of separation, and the following methods can be adopted: and pouring the reaction liquid into a separating funnel, standing for 30min, and separating and recovering the lower-layer aqueous phase catalyst.
Meanwhile, after the actual pH value of the recovered catalyst phosphate solution is tested, solid phosphate is added or water is added according to the pH value to adjust the pH value to 7.2-8, and the catalyst can be directly used for the next catalytic reaction.
The existing method for preparing pseudo ionone by liquid base catalysis of citral and acetone needs to be carried out in a strong alkaline environment (preferably pH 10-12), and the problem of high self-polymerization rate of raw material citral is also brought while high-efficiency catalysis efficiency is ensured under strong alkalinity, so that the yield is reduced. The phosphate catalyst of the present invention enables the reaction of the present invention to be stably carried out in an extremely low alkaline environment. The two phosphates are used in a compounding way, the proportion of the two phosphates and the concentration of the solution are limited within a specific range, the two phosphates are used as a catalyst to be added into a reaction system of the citral and the acetone, the buffer function is realized while the catalytic action is exerted, the reaction stability is obviously enhanced, the alkalinity is not influenced by the change of the system composition in the reaction process, the pH value of the system can be stably controlled to be 7.2-8 in the whole reaction process, the self-polymerization of the citral is effectively inhibited, and the occurrence of side reactions is reduced.
In addition, the alkaline metal salt aqueous solution is usually in an acetone-containing system, and the acetone, the water and the citral are mutually dissolved to form a three-phase mutually soluble system of the acetone, the water and the citral, and salting-out is easy to occur, so that the base number of the system is damaged.
Compared with the prior art, the invention has the beneficial effects that: the alkalescent composite phosphate catalyst has dual functions of catalysis and buffering, can stably control the pH value of a system to be 7.2-8 in the reaction process, still has high catalytic activity and high selectivity in a weak base environment, and simultaneously inhibits self-polymerization of citral, thereby improving the production efficiency and yield; the catalyst can be recovered by liquid separation, the reaction condition is mild, the method is green and environment-friendly, and the catalyst is cheap and easy to obtain, so that the method is suitable for industrial production.
Detailed description of the invention
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Firstly, the main raw material sources are as follows:
the specification of citral is as follows: 96% pure BASF;
acetone specification: chemical industry of 99% of west longas;
specification of potassium dihydrogen phosphate: chemical industry of 99% of west longas;
dipotassium hydrogen phosphate specification: 99% chemical industry of west longas.
Secondly, a reaction product analysis method comprises the following steps:
the reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method.
The analysis method comprises the following steps:
the initial temperature was 60 ℃ and held for 1 minute; raising the temperature to 80 ℃ at the speed of 10 ℃/min, and keeping the temperature for 1 minute; then the temperature was raised to 250 ℃ at a rate of 15 ℃/min and held for 8 minutes. Carrier gas high purity N2The split ratio is 30: 1, the flow rate of the split stream is 39 mL/min. Carrier gas saving: 20mL/min, start wait time 2 min. The sample introduction temperature is 250 ℃, the detector is FID, the detector temperature is 260 ℃, the air flow is 350mL/min, the hydrogen flow is 35mL/min, the tail gas blowing flow is 25.6mL/min, and the sample introduction amount is 0.2 mu L.
EXAMPLE 1 preparation of the catalyst
Will K2HPO4(5.60g) and KH2PO4(0.41g) and then slowly adding 9994.00g of deionized water for dilution, and stirring for 1h until the mixture is uniformly mixed to obtain a phosphate catalyst solution. The composition is as follows: k2HPO4 0.056wt％，KH2PO4 0.0041wt％，H2O 99.94wt％；pH7.8。
Example 2 citral condensation reaction
Citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of the phosphate catalyst solution prepared in example 1 were added to a 250.0mL three-necked flask, the flask was purged with nitrogen through two rows of tubes, stirred with a magneton, condensed water was opened, the flask was refluxed, heated to 60.0 ℃ and refluxed for 3 hours, and the reaction was maintained at normal pressure during the reaction. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 100%, the selectivity of pseudo ionone is 97.8%, and the self-polymerization of citral is about 1.0%.
Examples 3-9 condensation of citrates
The temperature, the aldehyde to ketone ratio (molar ratio of citral to acetone), the catalyst K were varied according to the procedure of example 22HPO4/KH2PO4The mass ratio (preparation method is the same as example 1) and the reaction time is 3h, the experiment is carried out, and the reaction conditions and the results are shown in Table 1.
TABLE 1 reaction conditions and results
EXAMPLE 10 Recycling of catalyst
In example 2, the reaction solution was poured into a separatory funnel and allowed to stand for 30min, the lower-layer aqueous phase catalyst was separated and recovered, the pH of the recovered phosphate catalyst solution was 7.2, and K was added2HPO4The pH was adjusted to 7.8 to obtain a phosphate catalyst solution.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of the phosphate catalyst solution into a 250.0mL three-neck flask, performing nitrogen replacement protection by a double-row pipe, stirring by using a magneton, opening condensed water, refluxing by using a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, performing reflux reaction by using the condensing tube for 3 hours, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 100%, the selectivity of pseudo ionone is 97.2%, and the self-polymerization of citral is about 1.0%.
The recovered phosphate catalyst was used again in the above manner, and the results are shown in Table 2.
TABLE 2 results of catalyst application
| Number of times of application | Self-polymerization rate of citral | Conversion rate | Selectivity is |
| 10 | 1％ | 100％ | 97％ |
| 20 | 1％ | 99％ | 97％ |
| 30 | 2％ | 98％ | 96％ |
| 50 | 2％ | 98％ | 96％ |
Comparative example 1
Catalyst synthesis # 2 (without addition of K)2HPO4)
Mixing KH with water2PO4(0.41g) 9994.00g of deionized water was slowly added for dilution and stirred for 1h until well mixed to give a phosphate catalyst solution, pH 6.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 2 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 1.2%, the selectivity of pseudo ionone is 20.5%, and the self-polymerization rate of citral is about 1.0%.
Comparative example 2
3# catalyst Synthesis (without addition of KH)2PO4)
Will K2HPO4(5.60g) 9994.00g of deionized water was slowly added for dilution and stirred for 1h until well mixed to give a phosphate catalyst solution at pH 8.5.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 3 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 60.2%, the selectivity of pseudo ionone is 52.5%, and the self-polymerization rate of citral is about 5.0%.
Comparative example 3
Catalyst synthesis No. 4 (K)2HPO4Excess)
Will K2HPO4(10.60g) and KH2PO4(0.41g) mixed, slowly added with 9994.00g deionized water for dilution, stirredMixing for 1h to obtain a phosphate catalyst solution with the pH of 8.2.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 4 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 80.2%, the selectivity of pseudo ionone is 42.5%, and the self-polymerization rate of citral is about 10.0%.
Comparative example 4
5# catalyst Synthesis (K)2HPO4Deficiency of the design reside in the fact that
Will K2HPO4(0.60g) and KH2PO4(0.41g) and then 9994.00g of deionized water was slowly added to dilute the solution and stirred for 1 hour until the mixture was well mixed to obtain a phosphate catalyst solution, pH 6.8.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of 5# catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, and refluxing and reacting for 3 hours through the condensing tube, wherein the reaction process is kept at normal pressure. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 70.2%, the selectivity of pseudo ionone is 42.5%, and the self-polymerization rate of citral is about 11.0%.
Comparative example 5
Catalyst synthesis of No. 6 (Na)2HPO4And NaH2PO4)
Mixing Na2HPO4(5.60g) and NaH2PO4(0.41g) and then 9994.00g of deionized water was slowly added to dilute the solution and stirred for 1 hour until uniform mixing was achieved to give a phosphate catalyst solution at pH 7.8.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 6 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 60.2%, the selectivity of pseudo ionone is 53%, and the self-polymerization of citral is about 5.0%. In the comparative example, the sodium phosphate is separated out under the action of acetone, so that the balance of a catalytic system is damaged, and the effect is obviously poorer than that of the potassium phosphate.
Comparative example 6
Catalyst synthesis of No. 6 (K)2HPO3And KH2PO3)
Will K2HPO3(5.60g) and KH2PO3(0.41g), slowly adding 9994.00g of deionized water for dilution, and stirring for 1h until the mixture is uniformly mixed to obtain a phosphite catalyst solution with the pH value of 8.3.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 6 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 90.2%, the selectivity of pseudo ionone is 53%, and the self-polymerization of citral is about 10.0%.
Comparative example 7
Catalyst synthesis of No. 6 (K)3PO4And H3PO3)
Will K3PO4(5.60g) and H3PO3(0.41g) and then 9994.00g of deionized water was slowly added to dilute the solution and stirred for 1 hour until uniform mixing was achieved to obtain a phosphate catalyst solution, pH 5.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 6 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 20.2%, the selectivity of pseudo ionone is 15%, and the self-polymerization rate of citral is about 15.0%.
Comparative example 8
Synthesis of No. 7 catalyst (KOH dilute alkali solution with pH value of 7.8-8)
KOH (0.01g) was slowly diluted to pH 7.8 with deionized water to give a catalyst solution of KOH in dilute aqueous base.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 7 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 20.2%, the selectivity of pseudo ionone is 10%, and the self-polymerization rate of citral is about 10.0%. The raw material citral contains a small amount of oxidizing acid, consumes part of alkali, and causes insufficient alkali value and poor reaction result.
Comparative example 9
Synthesis of catalyst No. 8 (KOH dilute alkali solution with pH value of 7.8-8 and phosphate buffer solution)
Will K2HPO4(5.60g) and KH2PO4(0.41g) and slowly adding 9994.00g of deionized water for dilution, and stirring for 1h until the mixture is uniformly mixed to obtain a phosphate solution, wherein the phosphate solution comprises the following components: k2HPO4 0.056wt％，KH2PO4 0.0041wt％，H2O 99.94wt％；pH7.8。
KOH (0.01g) is slowly added with deionized water to be diluted to pH 7.8 to obtain a KOH diluted alkali aqueous solution, and then 0.01g of phosphate solution is added to prepare the KOH diluted alkali aqueous solution with the pH value of 7.8-8 and phosphate buffer solution.
Adding citral (0.1mol, 15.22g), acetone (0.5mol, 29.04g) and 4.91g of No. 8 catalyst into a 250.0mL three-neck flask, replacing and protecting with nitrogen in a double-row pipe, stirring with a magnet, opening condensed water, refluxing through a condensing tube, heating to raise the temperature of the reaction solution to 60.0 ℃, refluxing and reacting for 3 hours through the condensing tube, and keeping the normal pressure in the reaction process. And after the reaction is finished, cooling and separating liquid to obtain a reaction product. The reaction product is qualitatively analyzed by a chromatograph-mass spectrometer, quantitatively analyzed by a gas chromatograph and quantitatively analyzed by a correction normalization method. The conversion rate of citral is 50.2%, the selectivity of pseudo ionone is 30%, and the self-polymerization of citral is about 5.0%. The raw material citral contains a small amount of oxidizing acid, consumes partial alkali, causes insufficient alkali value, has low buffer solution content, causes poor buffer capacity, cannot balance the alkali value of a reaction system, and causes poor reaction result.
Claims (17)
1. A method for preparing pseudo ionone is characterized in that acetone and citral react under the catalysis of a phosphate catalyst to prepare the pseudo ionone, and the phosphate catalyst comprises K2HPO4And KH2PO4。
2. The method of claim 1, wherein the phosphate catalyst is comprised of K in the catalyst2HPO4And KH2PO4The total weight is as follows: k2HPO4 80-95wt％，KH2PO4 5-20wt％。
3. The process according to claim 2, characterized in that the phosphate catalyst, of which composition K is2HPO490-95wt％，KH2PO4 5-10wt％。
4. The method of claim 1, wherein the phosphate catalyst is K2HPO4And KH2PO4Mixed water solution ofA liquid having a mass concentration in the range of K2HPO4 0.048-0.057wt％，KH2PO40.003-0.012wt％。
5. The method of claim 4, wherein the concentration range is K2HPO40.054-0.057wt％，KH2PO4 0.003-0.006wt％。
6. The method of claim 5, wherein the concentration is K2HPO4 0.056wt％，KH2PO40.0041wt％。
7. The method of claim 4, wherein K is2HPO4And KH2PO4The pH of the mixed aqueous solution of (A) is 7.2 to 8.
8. The method of claim 7, wherein the mixed aqueous solution has a pH of 7.5 to 8.
9. The method of claim 8, wherein the mixed aqueous solution has a pH of 7.8 to 8.
10. The method according to claim 1, wherein the phosphate catalyst is used in an amount of 5 to 20% by mass of the sum of acetone and citral.
11. The method according to claim 10, wherein the amount of the phosphate catalyst is 10-15% of the sum of the mass of acetone and citral.
12. The method according to claim 1, wherein the molar ratio of acetone to citral is from 1 to 10: 1.
13. the method of claim 12, wherein the molar ratio of acetone to citral is from 5 to 10: 1.
14. the method according to claim 1, wherein the reaction temperature is 40-150 ℃ and the reaction time is 2-8 h.
15. The method according to claim 14, wherein the reaction temperature is 60-80 ℃ and the reaction time is 3-4 h.
16. The process according to any one of claims 1 to 15, wherein the catalyst is recovered by separation after completion of the reaction.
17. The method of claim 16, wherein the recovered catalyst is adjusted to pH 7.2-8 by adding phosphate or water for the next reaction.
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