CN110407680A - A method of preparing isoamyl olefine aldehydr - Google Patents
A method of preparing isoamyl olefine aldehydr Download PDFInfo
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- olefine aldehydr
- isoamyl olefine
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- 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
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Abstract
The invention discloses a kind of methods for preparing isoamyl olefine aldehydr, include: different prenol through oxidation obtain the organic phase containing different prenol and isoamyl olefine aldehydr after, optionally by the organic phase different prenol and isoamyl olefine aldehydr separate, prenol and/or 2-M3BOL are added in the organic phase of Xiang Hanyi isoamyl olefine aldehydr or the isoamyl olefine aldehydr after separation as rearrangement reaction auxiliary agent, and micro citral can be optionally added into as inhibitor.This method can significantly improve the selectivity of isoamyl olefine aldehydr, and inhibit to generate the generation of tar side reaction.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of method for preparing isoamyl olefine aldehydr by isoamyl olefine aldehydr, more particularly to
A kind of rearranged method for preparing isoamyl olefine aldehydr of isoamyl olefine aldehydr.
Background technique
Isoamyl olefine aldehydr (chemical name: 3- methyl-2-butene -1- aldehyde), is that high atom economy is continuously synthesizing to citral
Intermediate.And citral is other than being used as fragrance, it is main a large amount of as the key intermediates for producing vitamin A.
According to the difference of starting material, the preparation of isoamyl olefine aldehydr mainly has 3 kinds of process routes, respectively with prenol (3-
Methyl-2-butene -1- alcohol), different prenol (3- methyl-3-butene-1-alcohol) and 2- methyl -3- butyne-2-alcohol be raw material,
Purpose product is synthesized by different oxidation rearrangement methods；Other such as isopentyl aldehyde dehydrogenations.The patent DE2041976 of BASF is introduced
A kind of method that catalysis oxidation prenol prepares isoamyl olefine aldehydr, the process route cost of material is high, and conversion ratio is lower, yield
It is low；CN101381292B describes a kind of using 2- methyl -3- butyne-2-alcohol as raw material, the method that rearrangement prepares isoamyl olefine aldehydr, but
It is that this method side reaction is more, yield is low, and catalyst is easy inactivation.
Patent GB1338698, US4192820, US3894916 of BASF describe one kind with different prenol as original
Material, the method that isoamyl olefine aldehydr is prepared by oxidation, rearrangement, separation.The usual preparation method the following steps are included:
A) different prenol be catalyzed by oxygen-containing gas aoxidize to obtain isoamyl olefine aldehydr (3- methyl-3- butene-1-aldehyde) and
Water.
B) mixture of different prenol and isoamyl olefine aldehydr acid or base catalysis carry out reordering operations, obtain different iso-amylene
The mixture of pure and mild isoamyl olefine aldehydr.
C) said mixture is through suitable condition separation.
In above-mentioned steps a), not every different prenol all reacts.The conversion ratio of oxidation reaction is generally controlled
System is 50% or so.When conversion ratio continues to increase, side reaction selectively increases, and causes the inefficiency loss of different prenol.It is described
Unreacted different prenol is recycled into oxidation reactor.
In in the step a) and b), oxidation reaction and rearrangement reaction joint operation.The mixture that oxidation reaction obtains is
The mixture of different prenol and isoamyl olefine aldehydr, is directly entered rearrangement reactor.
In above-mentioned steps b), by-products of tar generation is had, the yield of isoamyl olefine aldehydr is not only reduced, raw material is caused to damage
It loses, and increases the energy consumption of later separation process.Therefore need to improve the conversion ratio and selectivity of step b).
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, Atom economy is improved, the present invention provides a kind of isoamyl olefine aldehydrs
The rearranged method for isoamyl olefine aldehydr.
The inventors discovered that in the rearrangement reaction of isoamyl olefine aldehydr, prenol (3-M2BOL) and
2-M3BOL has important facilitation to the rearrangement reaction, can significantly improve the selectivity of isoamyl olefine aldehydr,
And inhibit to generate the generation of tar side reaction.Speculate that the addition of prenol or 2-M3BOL changes rearrangement instead
The selectivity and conversion ratio of rearrangement reaction greatly improved in the mechanism answered, and obtains higher isoamyl olefine aldehydr yield.Further grind
Study carefully discovery, after the different prenol of oxidation reaction outlet and the separation of isoamyl olefine aldehydr, prenol and/or 2- methyl-is added
3- butene-2 -ol, also can be improved the yield of rearrangement reaction, and rearrangement reaction mixture can be directly as preparing citral
Raw material reduces the separating energy consumption of process.It finds, can also be optionally added into rearrangement reaction system micro- simultaneously in research process
The citral for measuring (0~10ppm) has the effect for inhibiting by-products of tar to generate.
Based on the above discovery, scheme proposed by the present invention is as follows: obtaining through oxidation containing different iso-amylene in different prenol
After the organic phase of pure and mild isoamyl olefine aldehydr, optionally by the organic phase different prenol and isoamyl olefine aldehydr separate, to
Prenol and/or 2-M3BOL are added in isoamyl olefine aldehydr after the organic phase of the olefine aldehydr containing isoamyl or separation
As rearrangement reaction auxiliary agent.
In the method for the present invention, the oxidation can be carried out by any suitable method known in the art, for example, its
The middle different prenol of raw material is gas phase, and oxidant is oxygen-containing gas, catalyst be the silver being carried on alkali metal or copper or other
Suitable catalyst.In general, the reaction controlling that different prenol gaseous oxidation is isoamyl olefine aldehydr is carried out at 300~500 DEG C, it is excellent
Select 350~450 DEG C；In general, pressure at the top of oxidation reactor vessel is from normal pressure to 10 × 105N/m2。
The catalytic oxidation of different prenol carries out in the gas phase, and can carry out in the presence of a diluent.It is described
Diluent is under the cited reaction conditions preferably gas and the compound that does not react with raw material and obtained product, such as water
Steam or nitrogen, the dosage of the diluent can be 0.2~1.5 times of different prenol quality.
After reaction solution is emitted from oxidation reactor, it can be separated by phase separation tank or coalescer and 1. be contained
The organic phase of different prenol and isoamyl olefine aldehydr and 2. aqueous phase stream stock.Organic matter in aqueous phase stream stock can pass through the side of rectifying
Formula recycling.
The organic phase that above-mentioned oxidation reaction obtains can be without subsequent processing, directly progress rearrangement reaction, can also will be different
Rearrangement reaction is carried out again after isoamyl olefine aldehydr and the separation of different prenol, after preferably separating isoamyl olefine aldehydr and different prenol again
Rearrangement reaction is carried out, the inlet amount of rearrangement reactor can be reduced in this way, and then reduce reactor volume.The isolated method
It is carried out for any proper method known in the art, such as rectifying.
In general, isoamyl olefine aldehydr rearrangement catalyst is existing acid or alkali, it is homogeneous or heterogeneous catalysis.Such as ammonium hydroxide
(concentration can be 25~28wt%), sodium acetate aqueous solution (20-25wt%) etc., the dosage of catalyst can be 50~
1000ppm (not including catalyst with the raw material meter of rearrangement reaction).
The adding manner of rearrangement reaction catalyst is not particularly limited, can be by catalyst, rearrangement reaction raw material (containing different
The organic phase of prenol and isoamyl olefine aldehydr, or isoamyl olefine aldehydr after separation) and rearrangement reaction auxiliary agent (prenol
And/or 2-M3BOL, preferred 2-M3BOL) enter rearrangement reactor after mixing, it can also divide
Not Jin Ru rearrangement reactor, can also wherein two strands first mix and enter back into reactor afterwards.
The addition time of rearrangement reaction auxiliary agent (prenol and/or 2-M3BOL) does not limit particularly
System, can be added, and can be added during rearrangement reaction, with catalysis after can also mixing with rearrangement catalyst before rearrangement reaction
Agent is added.
Preferably, the rearrangement reaction auxiliary agent being added in the method makes rearrangement reaction auxiliary agent in itself and rearrangement reaction raw material
(organic phase containing different prenol and isoamyl olefine aldehydr, or isoamyl olefine aldehydr after separation, do not include catalyst) is mixed
Close object in concentration be 0.01-10wt% (such as 0.01%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 3%,
4.5%, 5%, 10% etc.), preferably 1-5wt%, more preferable 3-4.5wt%.
It finds simultaneously, micro citral is added in Xiang Shangshu isomerization (rearrangement) reaction system as inhibitor has inhibition burnt
The effect that oil generates, citral additional amount control effect in 0~10ppm, preferably 5~10ppm are good (with rearrangement reaction combined feed
Meter, including rearrangement reaction raw material, catalyst, rearrangement reaction auxiliary agent and inhibitor).
In general, isoamyl olefine aldehydr rearrangement reactor can be using insulation tubular reactor, isothermal tube reactor, insulation kettle
Formula reactor, outer circulation move the reactor of hot tank reactor or other forms.
The pressure of rearrangement reactor described in this method be it is unessential, select optimal pressure depending on concrete condition.In general,
Pressure at the top of rearrangement reactor can be for from normal pressure to 10 × 105N/m2, preferably 5 × 105~7 × 105N/m2。
This method needs to control the temperature of rearrangement reactor, selects optimal operation temperature depending on concrete condition.In general, resetting
The temperature of reaction is controlled at 80~160 DEG C, and preferably 120~140 DEG C.
This method needs to control the residence time of rearrangement reaction, selects the optimal residence time depending on concrete condition.In general, weight
The residence time of reaction is arranged in 30~100min, preferably 50~80min.
In the method for the invention, the mixture that rearrangement reaction obtains can obtain isoamyl olefine aldehydr by rectifying.Iso-amylene
Aldehyde product can be used for preparing in citral technique or other techniques.
If rearrangement reaction directly does raw material with the organic phase of oxidation reaction, reaction product can be distinguished by rectifying separation
Obtain isoamyl olefine aldehydr, rearrangement reaction auxiliary agent and different prenol etc..Usually during separating isoamyl olefine aldehydr and different prenol,
It needs by way of extracting rectifying.Extractant can be water and glycerol etc., can use the conventional method of this field, this field
Technical staff can optimize as the case may be.
If rearrangement reaction raw material is the isoamyl olefine aldehydr for separating the organic phase of oxidation reaction and obtaining, reaction product passes through
Rectifying separation can respectively obtain isoamyl olefine aldehydr and rearrangement reaction auxiliary agent etc..When the auxiliary agent of addition includes prenol, separate
Impurity obtains the mixture of isoamyl olefine aldehydr and prenol, directly using the mixture as the raw material for preparing citral, this field
Technical staff can optimize as the case may be.
The beneficial effects of the present invention are:
By adding rearrangement reaction auxiliary agent in the reaction that isoamyl olefine aldehydr is rearranged to isoamyl olefine aldehydr, rearrangement reaction can be accelerated
Rate, improve the selectivity of rearrangement reaction, total recovery can be improved 3~9 percentage points.It can inhibit recombination by adding inhibitor
The generation divided improves economy.
Detailed description of the invention:
Fig. 1 and Fig. 2 is that isoamyl olefine aldehydr in comparative example 1 and Examples 1 to 4, by-product concentration change with time figure respectively；
Fig. 3 and Fig. 4 is that isoamyl olefine aldehydr in comparative example 2 and embodiment 5, by-product concentration change with time figure respectively；
Fig. 5 is that by-product concentration changes with time figure in embodiment 1 and embodiment 6.
Specific embodiment
Chromatographiccondition:
Instrument model: SHIMADZU 2010Plus
Chromatographic column: DB-5 (30m × 0.32mm × 0.25um)
Column temperature: temperature programming (40 DEG C of holding 4min, 15 DEG C/min heating rates rise to 250 DEG C, and keep 12min)
Injector temperature: 200 DEG C
FID temperature: 260 DEG C
H2 flow: 40mL/min
Air flow: 350mL/min.
Dottle pin purges (N2) flow velocity: 3mL/min
Carrier gas (N2) flow velocity: 1mL/min
Split sampling, split ratio 45:1
Sample volume: 0.4 μ L
The present invention is further illustrated by following embodiment.
Comparative example 1
It is 1:1,25wt% is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
Ammonium hydroxide 0.4g is placed in 2 liters of rustless steel container reactors equipped with blender.
Reactor is forced into 750kPaG with nitrogen, and temperature of reactor is controlled at 135 DEG C, is subject to play at this temperature
Strong stirring keeps temperature of reactor to stablize at 135 DEG C.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including the quality of ammonia-catalyzed agent in terms of mixture gross mass after reaction) of object each component.It the results are shown in Table 1.
Embodiment 1
It is 1:1,25wt% ammonia is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
1g prenol is added into said mixture by water 0.4g, repeats the experiment of comparative example 1.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst and auxiliary agent in terms of mixture gross mass after reaction) of object each component.It the results are shown in Table 1.
Embodiment 2
It is 1:1,25wt% ammonia is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
10g prenol is added into said mixture by water 0.4g, repeats the experiment of comparative example 1.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst and auxiliary agent in terms of mixture gross mass after reaction) of object each component, the results are shown in Table 1.
Embodiment 3
It is 1:1,25wt% ammonia is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
30g prenol is added into said mixture by water 0.4g, repeats the experiment of comparative example 1.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst and auxiliary agent in terms of mixture gross mass after reaction) of object each component.It the results are shown in Table 1.
Embodiment 4
It is 1:1,25wt% ammonia is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
30g 2-M3BOL is added into said mixture by water 0.4g, repeats the experiment of comparative example 1.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst and auxiliary agent in terms of mixture gross mass after reaction) of object each component, the results are shown in Table 1.
Comparative example 2
The experiment of comparative example 1 is repeated, the raw material only used is isoamyl olefine aldehydr 1kg, 25wt% ammonium hydroxide 0.4g is added, no
Containing different prenol.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst in terms of mixture gross mass after reaction) of object each component, the results are shown in Table 1.
Embodiment 5
25wt% ammonium hydroxide 0.4g is added into 1kg isoamyl olefine aldehydr, the prenol of 5g, weight are added into said mixture
The experiment of multiple comparative example 2.
Different time points during the reaction take out the sample of reaction mixture, are mixed by coefficients data measured by chromatography quantitative response
The concentration (not including catalyst and auxiliary agent in terms of mixture gross mass after reaction) of object each component, the results are shown in Table 1.
Embodiment 6
The experiment of embodiment 1 is repeated, the difference is that the citral of 0.01g is added also into reacting material mixture.
Comparative example 3
It is 1:1,25wt% is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
Ammonium hydroxide 0.4g is placed in 2 liters of rustless steel container reactors equipped with blender.
Reactor vessel is forced into 750kPaG with nitrogen, and temperature of reactor is controlled at 85 DEG C, is subject at this temperature
Violent stirring keeps temperature of reactor to stablize at 85 DEG C.
Pass through the concentration of coefficients data measured by chromatography quantitative response mixture each component, isoamyl olefine aldehydr matter in reaction product after reaction 60min
Measuring score is 38%, and it (does not include ammonia-catalyzed agent in terms of mixture gross mass after reaction that by-product mass fraction, which is 0.5%,
Quality).
Embodiment 7
It is 1:1,25wt% is added in the organic phase that gross mass is 1kg to different prenol and isoamyl olefine aldehydr mass ratio
The prenol of 1g is added into said mixture, is placed in 2 liters of rustless steel container reactors equipped with blender by ammonium hydroxide 0.4g
In.
Reactor is forced into 750kPaG with nitrogen, and temperature of reactor is controlled at 85 DEG C, is subject at this temperature acutely
Stirring, keep temperature of reactor stablize at 85 DEG C.
Pass through the concentration of coefficients data measured by chromatography quantitative response mixture each component, isoamyl olefine aldehydr matter in reaction product after reaction 60min
Measuring score is 42%, and it (does not include ammonium hydroxide and auxiliary agent in terms of mixture gross mass after reaction that by-product mass fraction, which is 0.3%,
Quality).
The results show that being 135 DEG C in reaction temperature, reaction pressure is to add only small amounts of isoamyl in the experiment of 750kPaG
Enol or 2-M3BOL are remarkably improved the yield of isoamyl olefine aldehydr, inhibit the generation of by-product, improve and reset instead
The Atom economy answered.The selectivity of by-product can be further decreased by adding a small amount of citral.
The above experiment shows when conversion ratio is identical, and prenol or 2- methyl -3- butylene-are added into reaction raw materials
2- alcohol can shorten the reaction time as auxiliary agent, improve reaction rate.Shortening (raising of the conversion ratio) right and wrong in this reaction time
It is often advantageous.It is remarkably improved the yield of isoamyl olefine aldehydr.
Meanwhile the experimental result is shown, by adding prenol or 2- methyl -3- fourth in rearrangement reaction is fed
Alkene -2- alcohol can reduce the selectivity of by-product as auxiliary agent, the atom economy for improving the yield of isoamyl olefine aldehydr and entirely reacting
Property.
In addition, the experimental result is shown, it, can be into one as inhibitor by the addition citral in rearrangement reaction is fed
Step reduces the selectivity of by-product, improves the Atom economy entirely reacted.
Table 1
Claims (8)
1. a kind of method for preparing isoamyl olefine aldehydr, which is characterized in that the method includes anti-to the rearrangement comprising isoamyl olefine aldehydr
It answers and catalyst is added in raw material, and prenol and/or 2-M3BOL is added as auxiliary agent, be optionally added into lemon
Lemon aldehyde is as inhibitor, and rearranged reaction obtains isoamyl olefine aldehydr to isoamyl olefine aldehydr under the action of catalyst.
2. the method according to claim 1, wherein the rearrangement reaction raw material comprising isoamyl olefine aldehydr is different
Prenol is aoxidized the obtained organic phase containing different prenol and isoamyl olefine aldehydr or the organic phase after separation
Isoamyl olefine aldehydr.
3. method according to claim 1 or 2, which is characterized in that the additional amount of the auxiliary agent be so that auxiliary agent its with
Concentration in the mixture of rearrangement reaction raw material is 0.01-10wt%, preferably 1-5wt%, more preferable 3-4.5wt%.
4. method according to claim 1-3, which is characterized in that the additional amount of citral is 0~10ppm, excellent
5~10ppm is selected, in terms of rearrangement reaction combined feed.
5. method according to claim 1-4, which is characterized in that the catalyst includes but is not limited to that concentration is
The ammonium hydroxide of 25~28wt%, the sodium acetate aqueous solution that concentration is 20-25wt%.
6. method according to claim 1-5, which is characterized in that the dosage of catalyst is 50~1000ppm, base
In rearrangement reaction raw material meter.
7. method according to claim 1-6, which is characterized in that the temperature of rearrangement reaction is 80~160 DEG C, excellent
Select 120~140 DEG C.
8. method according to claim 1-7, which is characterized in that the time of rearrangement reaction is 30~100min,
It is preferred that 50~80min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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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