CN115124411B - Method for preparing 3-methyl-3-pentene-2-one - Google Patents
Method for preparing 3-methyl-3-pentene-2-one Download PDFInfo
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- CN115124411B CN115124411B CN202210911757.0A CN202210911757A CN115124411B CN 115124411 B CN115124411 B CN 115124411B CN 202210911757 A CN202210911757 A CN 202210911757A CN 115124411 B CN115124411 B CN 115124411B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- 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
- C07C45/67—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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application relates to the technical field of organic synthesis, and particularly discloses a method for preparing 3-methyl-3-pentene-2-ketone, which is characterized by comprising the following steps: s1, butanone and acetaldehyde are subjected to aldol condensation reaction under the action of a solid acid catalyst to obtain a crude product; the solid acid catalyst is obtained by using Zn < 2+ > to modify NKC-9 strongly acidic cation exchange resin; s2, separating and purifying the crude product to obtain the 3-methyl-3-pentene-2-one. The application prevents acetaldehyde from self polymerization in the production process of 3-methyl-3-penten-2-one and improves the yield of 3-methyl-3-penten-2-one.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a method for preparing 3-methyl-3-pentene-2-ketone.
Background
The synthesis of 3-methyl-3-pentene-2-ketone is that butanone and acetaldehyde undergo aldol condensation reaction under the action of a catalyst, and the reaction formula is as follows:
wherein, the catalyst can be an alkali catalyst or an acid catalyst. For example: sodium hydroxide, sulfuric acid. However, sodium hydroxide and sulfuric acid, which are used as conditions for the aldol condensation reaction between butanone and acetaldehyde, not only have high production costs, but also have serious environmental pollution.
In order to simplify the production process, reduce the production cost and be environment-friendly. Patent ZL201410038017.6 discloses a preparation method of 3-methyl-3-penten-2-one, wherein butanone and a solid acid catalyst are mixed at the temperature of 0-80 ℃, then acetaldehyde is added, the mixture is fully mixed and then continuously reacted, and after the reaction is finished, the obtained product is separated and purified to obtain 3-methyl-3-penten-2-one; wherein the solid acid catalyst is selected from Amberlyst 35 of Rohm and Haas, lewatit K2620 of Langshan, purolite SGC650 (H) of the company Mirabilite, NKC-9 of the university of southern Kao, or a mixture of two or more thereof in any proportion. Patent ZL201410336419.4 discloses a green process for the preparation of 3-methyl-3-penten-2-one comprising reacting acetaldehyde with methyl ethyl ketone in a fixed bed reactor in the presence of a solid acid catalyst which is a polymeric resin supported solid acid catalyst.
However, acetaldehyde is easily self-polymerized in the production process of 3-methyl-3-penten-2-one, and the polymerization mechanism of acetaldehyde under the action of acid is a cationic mechanism, which is shown as follows:
and (3) initiation:
increase in length：
When the molecular chain of the reaction product reaches or exceeds three oxygen atom chains, the molecules can generate intramolecular linkage to form paraldehyde, metaldehyde, pentaacetadehyde, hexaacetadehyde and the like, and as for the reaction, a plurality of polymers are generated and are subjected to the reasons of various factors such as reaction temperature, reaction time, catalyst types and the like. At temperatures above 0 c, the reaction produces almost all paraldehyde with selectivity approaching 100%.
Therefore, it is desirable to prevent acetaldehyde from self-polymerizing during the production of 3-methyl-3-penten-2-one.
Disclosure of Invention
In order to prevent acetaldehyde self polymerization in the production process of 3-methyl-3-pentene-2-ketone and improve the yield of 3-methyl-3-pentene-2-ketone, the application provides a method for preparing 3-methyl-3-pentene-2-ketone, which adopts the following technical scheme:
a process for preparing 3-methyl-3-penten-2-one, comprising the steps of:
s1, butanone and acetaldehyde are subjected to aldol condensation reaction under the action of a solid acid catalyst to obtain a crude product; the solid acid catalyst utilizes Zn 2+ Modified NKC-9 strong acid cation exchange resin;
s2, separating and purifying the crude product to obtain the 3-methyl-3-pentene-2-one.
In some embodiments, in step S1, the method of modifying comprises the steps of:
p1, washing NKC-9 strong-acid cation exchange resin by using deionized water until clear water flows out;
p2, soaking the NKC-9 strong-acid cation exchange resin obtained in the step P1 in a sodium hydroxide aqueous solution, and then washing the obtained product with water until the pH is =7;
p3, soaking the NKC-9 strong-acid cation exchange resin obtained in the step P2 in a hydrochloric acid aqueous solution, then washing with water until the pH is =6, and drying;
p4, performing strong acid cation exchange on the NKC-9 obtained in the step P3Soaking the resin in zinc chloride water solution, and washing with water until no Cl is formed - And (4) existence and drying are carried out to obtain the solid acid catalyst.
In some embodiments, in step P2, the concentration of the aqueous sodium hydroxide solution is 3 to 10wt%, for example: 4wt%. In the step P2, the soaking time is 4-8 h.
In some embodiments, in step P3, the concentration of the aqueous hydrochloric acid solution is 3 to 10wt%, for example: 4wt%. In the step P3, the soaking time is 4-8 h.
In some embodiments, in step P3, the temperature of the drying is between 35 and 45 ℃, for example: at 40 deg.c.
In some embodiments, in step P4, the concentration of the aqueous zinc chloride solution is 1 to 5wt%, for example: 2wt%. In the step P4, the soaking time is 2-4 h.
In some embodiments, in step P4, the temperature of the drying is 35 to 45 ℃, for example: at 40 deg.c.
In some embodiments, in step S1, the aldol condensation reaction is carried out in a fixed bed reactor.
In some embodiments, the fixed bed reactor is a tubular fixed bed reactor, for example: a tubular fixed bed reactor having an internal diameter of 0.25 m and a length of 2.5 m.
In some embodiments, in step S1, the molar ratio of butanone and acetaldehyde to acetaldehyde is (2-5): 1, for example: 3:1.
In some embodiments, in step S1, the reaction temperature of the aldol condensation reaction is 50 to 70 ℃, for example: at 60 deg.C.
In some embodiments, in step S1, the reaction pressure of the aldol condensation reaction is 150 to 200mmHg.
In some embodiments, in step S2, the separation and purification method is rectification.
In some embodiments, the rectifying process is: firstly, rectifying and recovering the butanone under the conditions of vacuum degree of 150mmHg and temperature of 60 ℃; then rectifying under the conditions that the vacuum degree is 15mmHg and the temperature is 70-90 ℃ to obtain the 3-methyl-3-penten-2-one.
In summary, the present application has the following beneficial effects:
the application needs to prevent acetaldehyde self-polymerization in the production process of 3-methyl-3-penten-2-one and improve the yield of 3-methyl-3-penten-2-one. By means of Zn 2+ The solid acid catalyst obtained by modifying the NKC-9 strongly acidic cation exchange resin can prevent acetaldehyde from self-polymerization when butanone and acetaldehyde are subjected to aldol condensation reaction, so that the yield of 3-methyl-3-pentene-2-ketone is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example of solid acid catalyst
Preparation example 1
Preparation example 1 solid acid catalyst Using Zn 2+ Modified NKC-9 strong acid cation exchange resin. Wherein, the modification method comprises the following steps:
p1, washing NKC-9 strong-acid cation exchange resin by using deionized water until clear water flows out;
p2, putting the NKC-9 strong-acid cation exchange resin obtained in the step P1 into a sodium hydroxide deionized water solution with the concentration of 4wt% for soaking for 4-8 h, and then washing with deionized water until the pH is =7;
p3, putting the NKC-9 strong-acid cation exchange resin obtained in the step P2 into a hydrochloric acid deionized water solution with the concentration of 4wt% to soak for 4-8 h, then washing with deionized water until the pH is =6, and drying in a vacuum oven at 40 ℃;
and P4, putting the NKC-9 strong-acid cation exchange resin obtained in the step P3 into a zinc chloride deionized water solution with the concentration of 2wt% to soak for 2-4 h, washing with deionized water until no Cl-exists, and drying in a vacuum oven at 40 ℃ to constant weight to obtain the solid acid catalyst.
Preparation of comparative example 1
Comparative example 1 preparation of solid acid catalyst by using Al 3+ Modified NKC-9 strongly acidic cation exchangeObtaining the resin. Wherein the modification method comprises the step of adding 2wt% of zinc chloride deionized water solution (with the molecular formula of ZnCl) in preparation example 1 2 Molecular weight 136.315 with aluminum chloride deionized water solution (1.96 wt%, molecular formula is AlCl) 3 Molecular weight 133.340).
Preparation of comparative example 2
Comparative example 2 preparation of solid acid catalyst using Fe 3+ Modified NKC-9 strong acid cation exchange resin. Wherein the modification method comprises the step of adding 2wt% of zinc chloride deionized water solution (with the molecular formula of ZnCl) in preparation example 1 2 Molecular weight 136.315) was replaced with ferric chloride deionized water solution (2.380 wt%, molecular formula FeCl) 3 Molecular weight 162.204).
Preparation of comparative example 3
Comparative example 3 preparation of solid acid catalyst by using Sn 2+ Modified NKC-9 strong acid cation exchange resin. Wherein the modification method comprises the step of adding 2wt% of zinc chloride deionized water solution (with the molecular formula of ZnCl) in preparation example 1 2 Molecular weight of 136.315 is replaced by stannous chloride deionized water solution (2.782 wt%, molecular formula of SnCl) 2 Molecular weight 189.616).
Preparation of comparative example 4
Comparative example 4 preparation of solid acid catalyst by using Zn 2+ Modified Amberlyst-15 strong acid cation exchange resin. Wherein, the NKC-9 strong acid cation exchange resin in preparation example 1 is replaced by Amberlyst-15 strong acid cation exchange resin.
Example for the preparation of 3-methyl-3-penten-2-one
A process for preparing 3-methyl-3-penten-2-one comprising the steps of:
s1, filling 80Kg of solid acid catalyst into a tubular fixed bed reactor with the inner diameter of 0.25 meter and the length of 2.5 meters, wherein glass fibers are respectively filled in the upper end and the lower end of the tubular fixed bed reactor on the solid acid catalyst;
under nitrogen purging, heating a tubular fixed bed reactor to 60 ℃, and pressurizing to 150-200 mmHg; butanone and acetaldehyde in a molar ratio of 3:1 were pumped into a tubular fixed bed reactor at a rate of 70Kg/h using a quantitative pump, and a crude product was collected (the solid acid catalyst was continuously used under the reaction conditions for 10 days);
s2, conveying the crude product into a rectifying still through a pipeline, and rectifying and recovering butanone under the conditions that the vacuum degree is 150mmHg and the temperature is 60 ℃; then rectifying under the conditions of vacuum degree of 15mmHg and temperature of 70-90 ℃ to obtain the 3-methyl-3-penten-2-one.
Example 1 and comparative examples 1 to 5
Example 1 differs from comparative examples 1 to 5 in that different solid acid catalysts were used. The sources of the solid acid catalysts in example 1 and comparative examples 1 to 5 are shown in table 1.
Table 1 source of solid acid catalyst in example 1 and comparative examples 1 to 5
| Sources of solid acid catalysts | |
| Example 1 | Preparation example 1 |
| Comparative example 1 | Preparation of comparative example 1 |
| Comparative example 2 | Preparation of comparative example 2 |
| Comparative example 3 | Preparation of comparative example 3 |
| Comparative example 4 | Preparation of comparative example 4 |
| Comparative example 5 | NKC-9 strong acid cation exchange resin |
In example 1 and comparative examples 1 to 4, the conversion of butanone and the self-polymerization of acetaldehyde were measured by gas chromatography on the n-th day during the continuous use of the solid acid catalyst under the reaction conditions for 10 days, and the results are shown in tables 2 and 3.
The conversion rate of butanone is calculated by the following formula:
the calculation formula of the self-polymerization rate of acetaldehyde is as follows:
TABLE 2 conversion of butanone on day n in example 1 and comparative examples 1 to 5
TABLE 3 self-polymerization rate of acetaldehyde at the n-th day of use in example 1 and comparative examples 1 to 5
After n days of production, the yield of 3-methyl-3-penten-2-one (in terms of acetaldehyde) was calculated from the total amount of acetaldehyde and the total amount of 3-methyl-3-penten-2-one, and the calculation results are shown in table 4.
TABLE 4 yield of 3-methyl-3-penten-2-one in example 1 and comparative examples 1 to 5
As can be seen from the combination of tables 2 to 4, zn is used 2+ When the solid acid catalyst obtained by modifying the NKC-9 strongly acidic cation exchange resin is used for catalyzing the aldol condensation reaction of butanone and acetaldehyde, the conversion rate of butanone is high, the self-polymerization rate of acetaldehyde is low, and the yield of 3-methyl-3-pentene-2-ketone is high.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A process for preparing 3-methyl-3-penten-2-one, comprising the steps of:
s1, butanone and acetaldehyde are subjected to aldol condensation reaction under the action of a solid acid catalyst to obtain a crude product; the solid acid catalyst is Zn 2+ Modified NKC-9 strong acid cation exchange resin;
s2, separating and purifying the crude product to obtain the 3-methyl-3-pentene-2-one.
2. The method according to claim 1, wherein in step S1, the method of modifying comprises the steps of:
p1, washing NKC-9 strong-acid cation exchange resin by using deionized water until clear water flows out;
p2, putting the NKC-9 strong-acid cation exchange resin obtained in the step P1 into a sodium hydroxide aqueous solution, soaking for 4-8 h, and then washing with water until the pH is =7;
p3, putting the NKC-9 strong-acid cation exchange resin obtained in the step P2 into a hydrochloric acid aqueous solution, soaking for 4-8 h, then washing with water until the pH is =6, and drying;
p4, soaking the NKC-9 strong-acid cation exchange resin obtained in the step P3 in a zinc chloride aqueous solution, and then washing the solution until no Cl exists - And (4) existence and drying are carried out to obtain the solid acid catalyst.
3. The method according to claim 2, wherein in step P2, the concentration of the aqueous sodium hydroxide solution is 3 to 10wt%;
in the step P3, the concentration of the hydrochloric acid aqueous solution is 3-10 wt%;
in the step P4, the concentration of the zinc chloride aqueous solution is 1-5 wt%.
4. The process according to claim 1, characterized in that in step S1, the aldol condensation reaction is carried out in a fixed bed reactor.
5. The method of claim 4, wherein the fixed bed reactor is a tubular fixed bed reactor.
6. The method according to claim 1, wherein in step S1, the molar ratio of the butanone to the acetaldehyde is (2-5): 1.
7. The method according to claim 1, wherein the reaction temperature of the aldol condensation reaction in step S1 is 50 to 70 ℃.
8. The method according to claim 1, wherein the reaction pressure in the aldol condensation reaction in step S1 is 150 to 200mmHg.
9. The method according to claim 1, wherein in step S2, the separation and purification method is rectification.
10. The method according to claim 9, characterized in that the rectification process is: firstly, rectifying and recovering the butanone under the conditions of vacuum degree of 150mmHg and temperature of 60 ℃; then rectifying under the conditions that the vacuum degree is 15mmHg and the temperature is 70-90 ℃ to obtain the 3-methyl-3-penten-2-one.
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| US6977314B2 (en) * | 2001-12-19 | 2005-12-20 | Rohm And Haas Company | Metal-doped sulfonated ion exchange resin catalysts |
| CN103804160B (en) * | 2014-01-27 | 2016-03-02 | 南京运华立太能源科技有限公司 | The preparation method of 3-methyl-3-amylene-2-ketone |
| CN104355975B (en) * | 2014-11-07 | 2016-01-20 | 中国海洋石油总公司 | A kind of method of acetone two step synthesis methyl iso-butyl ketone (MIBK) |
| US11661391B2 (en) * | 2020-09-22 | 2023-05-30 | Indian Institute Of Technology Bombay | Continuous production of methyl pentenone using cation exchange resin in a fixed bed reactor |
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