CN110407680B - Method for preparing isopentenal - Google Patents
Method for preparing isopentenal Download PDFInfo
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- CN110407680B CN110407680B CN201910771094.5A CN201910771094A CN110407680B CN 110407680 B CN110407680 B CN 110407680B CN 201910771094 A CN201910771094 A CN 201910771094A CN 110407680 B CN110407680 B CN 110407680B
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- 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
Abstract
The invention discloses a method for preparing isopentenal, which comprises the following steps: after isovalerenol is oxidized to obtain an organic phase containing isovalerenol and isovaleraldehyde, optionally separating the isovalerenol and the isovaleraldehyde in the organic phase, adding the isovalerenol and/or 2-methyl-3-butene-2-ol as a rearrangement reaction auxiliary agent into the organic phase containing the isovaleraldehyde or the separated isovaleraldehyde, and optionally adding trace citral as an inhibitor. The method can obviously improve the selectivity of the isopropenylaldehyde and inhibit the side reaction of generating the tar.
Description
Technical Field
The invention belongs to the field of chemical industry, relates to a method for preparing isopentene aldehyde from isoisopentene aldehyde, and particularly relates to a method for preparing the isopentene aldehyde from the isoisopentene aldehyde through rearrangement.
Background
Isopentenal (chemical name: 3-methyl-2-butene-1-aldehyde) is an intermediate for continuously synthesizing citral with high atom economy. Besides being used as a spice, citral is mainly used as a key intermediate for producing vitamin A in a large amount.
According to the difference of starting materials, the preparation of the prenylaldehyde mainly comprises 3 process routes, namely, prenol (3-methyl-2-butene-1-ol), isoprenol (3-methyl-3-butene-1-ol) and 2-methyl-3-butyn-2-ol are respectively used as raw materials, and target products are synthesized by different oxidation rearrangement methods; others such as isovaleraldehyde dehydrogenation, and the like. The patent DE2041976 of Basff introduces a method for preparing the isopentenol by catalytic oxidation, and the process route has high raw material cost, lower conversion rate and low yield; CN101381292B describes a method for preparing the isopentenal by rearrangement by using 2-methyl-3-butyne-2-ol as a raw material, but the method has the advantages of more side reactions, low yield and easy inactivation of the catalyst.
Patents GB1338698, US4192820 and US3894916 of basf describe a process for preparing isopentenal by oxidation, rearrangement and separation of isopentenol as a raw material. Generally, the preparation method comprises the following steps:
a) the isovalerenol is catalyzed and oxidized by oxygen-containing gas to obtain isopentenal (3-methyl-3-butene-1-aldehyde) and water.
b) The mixture of isoprenol and isopentenal is rearranged by acid or base catalysis to obtain the mixture of isoprenol and isopentenal.
c) The mixture is separated under suitable conditions.
In step a) above, not all isoprenols are reacted. The conversion rate of the oxidation reaction is generally controlled to be about 50%. As conversion continues to increase, side reaction selectivity increases, causing inefficient loss of isoprenol. The unreacted isoprenol can be recycled to the oxidation reactor.
In said steps a) and b), the oxidation reaction and the rearrangement reaction are operated in combination. The mixture obtained from the oxidation reaction is a mixture of isoisoamylene alcohol and isopentenal, which directly enters the rearrangement reactor.
In the step b), tar byproducts are generated, so that the yield of the isopropenal is reduced, the raw material loss is caused, and the energy consumption of the subsequent separation process is increased. It is therefore desirable to increase the conversion and selectivity of step b).
Disclosure of Invention
In order to overcome the defects of the prior art and improve the atom economy, the invention provides a method for rearranging iso-pentenal into isopentenal.
The inventor finds that in the rearrangement reaction of the iso-pentenal, the isopentenol (3-methyl-2-butene-1-ol) and the 2-methyl-3-butene-2-ol have important promotion effects on the rearrangement reaction, can obviously improve the selectivity of the iso-pentenal, and can inhibit the side reaction of generating tar. The addition of the prenol or the 2-methyl-3-butene-2-ol is presumed to change the mechanism of the rearrangement reaction, greatly improve the selectivity and the conversion rate of the rearrangement reaction and obtain higher yield of the isopropenylaldehyde. Further research shows that the yield of the rearrangement reaction can be improved by adding isoamylene alcohol and/or 2-methyl-3-butene-2-ol after the isoisoamylene alcohol and the isoisoamylene aldehyde at the outlet of the oxidation reaction are separated, and a rearrangement reaction mixture can be directly used as a raw material for preparing citral, so that the separation energy consumption of the process is reduced. In the research process, the effect of inhibiting the generation of tar byproducts can be achieved by optionally adding a trace amount (0-10 ppm) of citral into a rearrangement reaction system.
Based on the above findings, the proposed solution of the present invention is as follows: after isovalerenol is oxidized to obtain an organic phase containing isovalerenol and isovaleraldehyde, optionally separating the isovalerenol and the isovaleraldehyde in the organic phase, and adding the isovalerenol and/or 2-methyl-3-butene-2-alcohol into the organic phase containing the isovaleraldehyde or the separated isovaleraldehyde to serve as a rearrangement reaction auxiliary agent.
In the process of the present invention, the oxidation may be carried out by any suitable method known in the art, for example, wherein the starting isoprenol is in the gas phase, the oxidizing agent is an oxygen-containing gas, and the catalyst is silver or copper or other suitable catalyst supported on an alkali metal. Generally, the reaction for oxidizing the isovalerenol into the isopentenal in a gas phase is controlled to be carried out at 300-500 ℃, and preferably 350-450 ℃; typically, the pressure at the top of the oxidation reactor vessel is from atmospheric to 10X 10 5 N/m 2 。
The catalytic oxidation reaction of isoprenol is carried out in the gas phase and may be carried out in the presence of a diluent. The diluent is preferably a compound which is gaseous under the reaction conditions and does not react with the raw materials and the obtained product, such as water vapor or nitrogen, and the amount of the diluent may be 0.2 to 1.5 times the mass of isoprenol.
After the reaction liquid is discharged from the oxidation reactor, it may be separated into (i) an organic phase containing isopentenol and isopentenal and (ii) an aqueous phase stream by a phase separation tank or a coalescer. The organics in the aqueous stream can be recovered by means of rectification.
The organic phase obtained by the oxidation reaction can be directly subjected to rearrangement reaction without subsequent treatment, or the organic phase obtained by the oxidation reaction can be subjected to rearrangement reaction after the isopentenal and the isoprenol are separated, preferably the organic phase obtained by the oxidation reaction is subjected to rearrangement reaction after the isopentenal and the isoprenol are separated, so that the feeding amount of a rearrangement reactor can be reduced, and the volume of the reactor is further reduced. The separation is carried out by any suitable method known in the art, such as rectification.
Typically, isovalerenal rearrangement catalysts are either conventional acids or bases, homogeneous or heterogeneous catalysts. For example, ammonia (the concentration may be 25 to 28 wt%), sodium acetate aqueous solution (20 to 25 wt%), etc., and the amount of the catalyst used may be 50 to 1000ppm (based on the amount of the raw material for the rearrangement reaction, excluding the catalyst).
The addition mode of the rearrangement catalyst is not particularly limited, and the catalyst, the rearrangement raw material (an organic phase containing isopentenol and isopentenal, or separated isopentenal) and the rearrangement auxiliary agent (isoamylene alcohol and/or 2-methyl-3-butene-2-ol, preferably 2-methyl-3-butene-2-ol) can be mixed and then enter the rearrangement reactor, or can enter the rearrangement reactor separately, or two of them can be mixed first and then enter the reactor.
The addition time of the rearrangement reaction auxiliary (isoamylene alcohol and/or 2-methyl-3-buten-2-ol) is not particularly limited, and it may be added before the rearrangement reaction, during the rearrangement reaction, or after being mixed with the rearrangement catalyst and then added with the catalyst.
Preferably, the rearrangement reaction auxiliary is added in the present process such that the concentration of the rearrangement reaction auxiliary in its mixture with the rearrangement reaction starting material (organic phase containing isopentenol and isopentenal, or separated isopentenal, excluding catalyst) is 0.01 to 10wt% (e.g. 0.01%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 3%, 4.5%, 5%, 10%, etc.), preferably 1 to 5wt%, more preferably 3 to 4.5 wt%.
Meanwhile, the addition of a trace amount of citral as an inhibitor into the isomerization (rearrangement) reaction system has the effect of inhibiting the generation of tar, and the effect is good when the addition amount of citral is controlled to be 0-10 ppm, preferably 5-10 ppm (based on the total feeding of the rearrangement reaction, including the raw materials of the rearrangement reaction, the catalyst, the auxiliary agent of the rearrangement reaction and the inhibitor).
In general, the isovalerenal rearrangement reactor can adopt an adiabatic tube type reactor, an isothermal tube type reactor, an adiabatic kettle type reactor, an external circulation heat removal kettle type reactor or other types of reactors.
The pressure in the rearrangement reactor used in the process is not critical and the optimum pressure is chosen as the case may be. Generally, the pressure at the top of the rearrangement reactor may be from atmospheric to 10X 10 5 N/m 2 Preferably 5X 10 5 ～7×10 5 N/m 2 。
The process requires controlling the temperature of the rearrangement reactor and selecting the optimum operating temperature as the case may be. The temperature of the rearrangement reaction is usually controlled to be 80 to 160 ℃, preferably 120 to 140 ℃.
The process requires control of the residence time of the rearrangement reaction, the optimum residence time being selected as the case may be. The residence time of the rearrangement reaction is generally 30 to 100min, preferably 50 to 80 min.
In the process of the present invention, the mixture obtained by the rearrangement reaction may be subjected to rectification to obtain the isopentenal. The isopentenal product can be used in a process for preparing citral or other processes.
If the organic phase of the oxidation reaction is directly used as the raw material in the rearrangement reaction, the reaction product can be separated by rectification to obtain the isopropenal, the rearrangement reaction auxiliary agent, the isoprenol and the like. Usually, in the separation of the isopentenol from the isopentenal, extractive rectification is required. The extractant may be water, glycerol, etc., and may be prepared by methods conventional in the art, and may be optimized by those skilled in the art as the case may be.
If the raw material of the rearrangement reaction is isopentenal obtained by separating the organic phase of the oxidation reaction, the reaction product can respectively obtain the isopentenal, the rearrangement reaction auxiliary agent and the like through rectification separation. When the added auxiliary agent comprises the isopentenol, the impurities can be separated to obtain a mixture of the isopentenyl aldehyde and the isopentenyl alcohol, and the mixture can be directly used as a raw material for preparing the citral, and the method can be optimized by a person skilled in the art according to specific situations.
The invention has the beneficial effects that:
by adding the rearrangement reaction auxiliary agent in the reaction of rearranging the isovalerenal into the isopentenal, the rate of the rearrangement reaction can be accelerated, the selectivity of the rearrangement reaction is improved, and the total yield can be improved by 3-9 percent. The generation of heavy components can be inhibited by adding an inhibitor, and the economy is improved.
Description of the drawings:
FIGS. 1 and 2 are graphs showing the change of the concentration of the by-product with time in the case of the isopropenal in comparative example 1 and examples 1 to 4, respectively;
FIGS. 3 and 4 are graphs showing the change of the concentration of the by-products with time in the case of comparative example 2 and example 5, respectively;
FIG. 5 is a graph showing the change in the by-product concentration with time in example 1 and example 6.
Detailed Description
Chromatographic analysis conditions:
the instrument model is as follows: SHIMADZU 2010Plus
A chromatographic column: DB-5(30m 0.32mm 0.25um)
Column temperature: temperature programming (40 ℃ for 4min, 15 ℃/min heating rate to 250 ℃ and 12min).
Sample inlet temperature: 200 deg.C
FID temperature: 260 deg.C
H2 flow rate: 40mL/min
Air flow rate: 350 mL/min.
Septum purge (N2) flow rate: 3mL/min
Carrier gas (N2) flow rate: 1mL/min
Split-flow sample injection, split ratio 45: 1
Sample introduction amount: 0.4. mu.L
The invention is further illustrated by the following examples.
Comparative example 1
0.4g of 25 wt% aqueous ammonia was added to an organic phase having a mass ratio of isovalerenol to isovalerenal of 1:1 and a total mass of 1kg, and the mixture was placed in a 2-liter stainless steel vessel reactor equipped with a stirrer.
The reactor was pressurized to 750kPaG with nitrogen and the reactor temperature was controlled at 135 ℃ with vigorous stirring, keeping the reactor temperature stable at 135 ℃.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentration of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding the mass of the aqueous ammonia catalyst) was measured chromatographically. The results are shown in Table 1.
Example 1
The mass ratio of iso-isoamylene alcohol to iso-isoamylene aldehyde is 1: 1. the experiment of comparative example 1 was repeated by adding 0.4g of 25 wt% aqueous ammonia to 1kg of the organic phase and adding 1g of prenol to the above mixture.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding catalyst and auxiliaries) were determined chromatographically. The results are shown in Table 1.
Example 2
The mass ratio of iso-isoamylene alcohol to iso-isoamylene aldehyde is 1: 1. the experiment of comparative example 1 was repeated by adding 0.4g of 25 wt% aqueous ammonia to 1kg of the organic phase and 10g of prenol to the mixture.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding catalyst and auxiliaries) were determined chromatographically and the results are given in Table 1.
Example 3
The mass ratio of iso-isoamylene alcohol to iso-isoamylene aldehyde is 1: 1. the experiment of comparative example 1 was repeated by adding 0.4g of 25 wt% aqueous ammonia to 1kg of the organic phase and 30g of prenol to the mixture.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding catalyst and auxiliaries) were determined chromatographically. The results are shown in Table 1.
Example 4
The mass ratio of iso-isoamylene alcohol to iso-isoamylene aldehyde is 1: 1. the experiment of comparative example 1 was repeated by adding 0.4g of 25 wt% aqueous ammonia to the organic phase having a total mass of 1kg and adding 30g of 2-methyl-3-buten-2-ol to the above mixture.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding catalyst and auxiliaries) were determined chromatographically and the results are given in Table 1.
Comparative example 2
The experiment of comparative example 1 was repeated except that 1kg of isopentenal was used as the starting material, 0.4g of 25 wt% aqueous ammonia was added, and isoprenol was not contained.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding the catalyst) were determined chromatographically and the results are given in Table 1.
Example 5
To 1kg of isovalerenal was added 0.4g of 25 wt% aqueous ammonia, and to the mixture was added 5g of prenol, and the experiment of comparative example 2 was repeated.
Samples of the reaction mixture were taken at various points in time during the reaction and the concentrations of the individual components of the reaction mixture (based on the total mass of the mixture after the reaction, excluding catalyst and auxiliaries) were determined chromatographically and the results are given in Table 1.
Example 6
The experiment of example 1 was repeated except that 0.01g of citral was also added to the reaction starting mixture.
Comparative example 3
0.4g of 25 wt% aqueous ammonia was added to an organic phase having a mass ratio of isovalerenol to isovalerenal of 1:1 and a total mass of 1kg, and the mixture was placed in a 2-liter stainless steel vessel reactor equipped with a stirrer.
The reactor vessel was pressurized to 750kPaG with nitrogen and the reactor temperature was controlled at 85 deg.C, with vigorous stirring, to maintain the reactor temperature steady at 85 deg.C.
After the reaction for 60min, the concentration of each component of the reaction mixture is measured by chromatography, the mass fraction of the isopentenal in the reaction product is 38%, and the mass fraction of the byproduct is 0.5% (based on the total mass of the mixture after the reaction, excluding the mass of the ammonia catalyst).
Example 7
To an organic phase having a mass ratio of isoprenyl alcohol to isoprenylaldehyde of 1:1 and a total mass of 1kg, 0.4g of 25 wt% aqueous ammonia was added, and to the above mixture was added 1g of isoprenol, and the mixture was placed in a 2 liter stainless steel container reactor equipped with a stirrer.
The reactor was pressurized to 750kPaG with nitrogen and the reactor temperature was controlled at 85 ℃ with vigorous stirring, keeping the reactor temperature stable at 85 ℃.
After the reaction is carried out for 60min, the concentration of each component of the reaction mixture is measured by chromatography, the mass fraction of the isopentenal in the reaction product is 42%, and the mass fraction of the byproduct is 0.3% (based on the total mass of the mixture after the reaction, excluding the mass of ammonia water and auxiliaries).
The results show that in the experiment that the reaction temperature is 135 ℃ and the reaction pressure is 750kPaG, the addition of only a small amount of isopentenol or 2-methyl-3-buten-2-ol can obviously improve the yield of the isopentenal, inhibit the generation of byproducts and improve the atom economy of the rearrangement reaction. The addition of small amounts of citral can further reduce the selectivity of the by-products.
The experiments show that when the conversion rate is the same, the addition of the prenol or 2-methyl-3-buten-2-ol as the auxiliary agent to the reaction raw materials can shorten the reaction time and improve the reaction rate. This reduction in reaction time (improvement in conversion) is highly advantageous. Can obviously improve the yield of the isopropenyl aldehyde.
Meanwhile, the experimental result shows that by adding the isopentenol or the 2-methyl-3-butene-2-ol as an auxiliary agent in the rearrangement reaction feed, the selectivity of the by-product can be reduced, and the yield of the isopropenylaldehyde and the atom economy of the whole reaction are improved.
In addition, the experimental results show that by adding citral as an inhibitor to the rearrangement reaction feed, the selectivity of the by-products can be further reduced, improving the atom economy of the overall reaction.
TABLE 1
Claims (10)
1. A method for preparing the iso-pentenal is characterized by comprising the steps of adding a catalyst into a rearrangement reaction raw material containing the iso-pentenal, adding isoamylene alcohol and/or 2-methyl-3-butene-2-ol as an auxiliary agent, adding citral as an inhibitor, and carrying out rearrangement reaction on the iso-pentenal under the action of the catalyst to obtain the iso-pentenal; the temperature of the rearrangement reaction is 80-160 ℃, and the time of the rearrangement reaction is 30-100 min;
the rearrangement reaction raw material containing the isopentenal is an organic phase containing isopentenol and isopentenal obtained by oxidizing isopentenol, or the isopentenal obtained by separating the organic phase.
2. The process according to claim 1, wherein the auxiliary is added in an amount such that the concentration of the auxiliary in the mixture thereof with the raw material for the rearrangement reaction is from 0.01 to 10% by weight.
3. The process according to claim 2, wherein the auxiliary is added in an amount such that the concentration of the auxiliary in the mixture thereof with the raw material for the rearrangement reaction is 1 to 5% by weight.
4. The process according to claim 1, wherein the auxiliary is added in an amount such that the concentration of the auxiliary in the mixture thereof with the raw material for the rearrangement reaction is 3 to 4.5% by weight.
5. The method according to claim 1, wherein the citral is added in an amount of 0 to 10ppm based on the total feed to the rearrangement reaction.
6. The method according to claim 5, wherein the citral is added in an amount of 5 to 10 ppm.
7. The method of claim 1, wherein the catalyst comprises but is not limited to ammonia water with a concentration of 25-28 wt%, and sodium acetate water with a concentration of 20-25 wt%.
8. The process according to any one of claims 1 to 7, wherein the catalyst is used in an amount of 50 to 1000ppm based on the raw material for the rearrangement reaction.
9. The method according to claim 1, wherein the temperature of the rearrangement reaction is 120 to 140 ℃.
10. The method according to claim 1, wherein the time for the rearrangement reaction is 50 to 80 min.
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| CN111018682A (en) * | 2019-12-17 | 2020-04-17 | 南通天泽化工有限公司 | Preparation method of citral |
| CN113861005A (en) * | 2021-11-15 | 2021-12-31 | 江苏宏邦化工科技有限公司 | Method for continuously synthesizing citral through tubular reactor |
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