CN103044223B - Method for continuously preparing pseudo ionone of vitamin A intermediate - Google Patents
Method for continuously preparing pseudo ionone of vitamin A intermediate Download PDFInfo
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Abstract
The invention discloses a method for continuously preparing pseudo ionone of a vitamin A intermediate. The method evenly mixes acetone, citral and catalyst under the continuous operation condition and introduces in a tubular reactor. The reaction mixture is continuously reacted for 1-120 minutes at the reaction temperature of 20-150 DEG C under the pressure of 0-10 MPa; reaction liquid is relieved pressure to enter a flash column; recovered acetone is obtained from the top of the column; tower bottoms are introduced in a layering machine for layering; after being neutralized, oil layers are relieved pressure and recovered to obtain pseudo ionone crude products, and are further distilled in high vacuum and separated out unreacted citral and pseudo ionone competitive products; and the recovered light-component by-products and the unreacted citral are mixed with the recovered acetone to enter the reactor again. The method has the advantages of low catalyst concentration, low corrosion to equipment, short reaction time and fewer side effects; and part by-products can be recycled.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of method that continuity prepares vitamin A intermediate pseudo ionone.
Background technology
Pseudo ionone, chemical name 6,10-dimethyl-3,5,9-undecane triolefin-2-ketone, weak yellow liquid.Pseudo ionone is the important intermediate of synthesis jononeionone, is widely used in spices, medicine, foodstuff additive industry.A kind of rare spice with banksia rose type fragrance of jononeionone is one of maximum and of paramount importance spices of output in perfume industry; The alpha, beta-lonone simultaneously synthesized is the important intermediate of synthesise vitamins A and β-carotene.
During Chinese scholars is continuing to carry out to the linguistic term of the synthesis technique of pseudo ionone always for a long time.Its main synthetic method be the citral that is separated by litsea cubeba oil in the basic conditions with acetone through Aldol condensation system to.
PL147748 describes and a kind ofly prepares the method for pseudo ionone with alkaline ion exchanger condensation citral and acetone at 56 DEG C, and the method exists the shortcoming of low-down space-time yield.
US Patent No. 4874900(1989) describe the method preparing pseudo ionone with hydrogen-oxygen lithium catalyzing and condensing citral and acetone, the method at-20 ~ 240 DEG C of temperature interval or carry out condensation reaction continuously.The method needs to be leached by excessive catalyzer when having reacted.There is long reaction time in the method, side reaction is many, the low and shortcoming of the difficult grade of solid waste of yield.
The aforementioned patent describes the method for a kind of serialization synthesis pseudo ionone.The method uses excessive high density alkali metal hydroxide aqueous solution, requires very high, and cause a large amount of noxious waste pollution to equipment corrosion.
Summary of the invention
The object of this invention is to provide a kind of method catalyzing and synthesizing the pure pseudo ionone of fragrance under lower concentration catalysts conditions.
For achieving the above object, the present invention adopts following technical scheme:
Continuity prepares a method for vitamin A intermediate pseudo ionone, comprises the steps:
A) by aqueous acetone and citral mixing, mix in static mixer with lower concentration alkali metal hydroxide aqueous solution after preheater heating, enter tubular reactor and carry out condensation reaction;
B) after having reacted, reaction solution enters flashing tower through decompression, is recycled acetone from tower top, and tower bottoms enters quantizer layering after neutralization;
C) oil reservoir obtains pseudo ionone crude product through reclaim under reduced pressure, then rectifying separation goes out unreacted citral and pseudo ionone fine work further, and the light constituent by product of recovery and unreacted citral mix with recovery acetone, again enter reactor.
Wherein, in described step a, aqueous acetone and citral mix continuously with the mol ratio of 2:1 ~ 40:1; In preferred steps a, aqueous acetone and citral mix continuously with the mol ratio of 15:1 ~ 30:1, and wherein, the discharge rate of citral and aqueous acetone is respectively 120-150g/h and 1000-1500g/h; More preferably the mol ratio of acetone and citral is 20:1.Unreacted recover acetone is applied mechanically.
Wherein, the water content of acetone described in step a is 2 ~ 20%, preferably 5 ~ 15%.Acetone moisture content regulates according to the new acetone of recovery acetone mixture moisture applicable part.
Continuity of the present invention prepares the method for vitamin A intermediate pseudo ionone, and the alkali metal hydroxide aqueous solution described in step a is the aqueous solution of one or more mixtures in lithium hydroxide, sodium hydroxide or potassium hydroxide.The mass concentration of described alkali metal hydroxide is 0.005 ~ 5%, preferably 0.01 ~ 2%.The special feature of catalyzer of the present invention does not need filtering catalyst after reaction terminates, and do not produce solid waste.
Continuity of the present invention prepares the method for vitamin A intermediate pseudo ionone, and the temperature of reaction of condensation reaction in described step a is 20 ~ 150 DEG C; Reaction times is 1 ~ 120 minute, and reaction pressure is the pressure 0 ~ 10Mpa higher than saturated vapor pressure at respective reaction temperature, and preferable reaction temperature is 80 ~ 120 DEG C; Reaction times is 5 ~ 60 minutes, and reaction pressure is the pressure 6 ~ 10MPa higher than saturated vapor pressure at respective reaction temperature.
Continuity of the present invention prepares the method for vitamin A intermediate pseudo ionone, in described step b and use neutralizing agent be organic acid, preferred acetic acid or citric acid.
Continuity of the present invention prepares the method for vitamin A intermediate pseudo ionone, and in described step c, rectifying adopts rectification under vacuum, and working pressure is lower than 200Pa.
More specifically, the method that continuity of the present invention prepares vitamin A intermediate pseudo ionone comprises the steps:
A) by water-content be 5 ~ 15% aqueous acetone and citral mix continuously with the mol ratio of 15:1 ~ 30:1, wherein, the discharge rate of citral and aqueous acetone is respectively 120-150g/h and 1000-1500g/h; Mixed solution is forced into 6-10MPa through pump, 80-120 DEG C is heated to through preheater, the alkali metal hydroxide aqueous solution being 0.005 ~ 5% with the mass concentration being forced into uniform pressure mixes through static mixer with the discharge rate of 80-120g/h, enter tubular reactor and carry out condensation reaction, the reaction times is 5-60 minute;
B) after having reacted, reaction solution through decompression enter flashing tower, be recycled acetone from tower top, in tower bottoms and after enter quantizer layering;
C) oil reservoir obtains pseudo ionone crude product through reclaim under reduced pressure, then rectifying separation goes out unreacted citral and pseudo ionone fine work further, and the light constituent by product of recovery and unreacted citral mix with recovery acetone, again enter reactor.
After step b terminates, tower bottoms enters quantizer layering after neutralizing treatment, obtains oil reservoir and neutralized wastewater layer, and namely described oil reservoir comprises target product, light constituent by product and unreacted citral, and neutralized wastewater layer comprises part acetone and Pyranton.Mixture after layering carries out being separated or post-processing operation respectively.Concrete separation and aftertreatment are those skilled in the art and grasp, and the present invention is not particularly limited this.
As preferred forms of the present invention, the method that preferred described continuity prepares vitamin A intermediate pseudo ionone comprises the steps:
A) by water-content be 10% aqueous acetone and citral mix continuously with the mol ratio of 20:1, wherein, the discharge rate of citral and aqueous acetone is respectively 145g/h and 1200g/h; 8MPa is forced into through pump, 100 DEG C are heated to through preheater, the alkali metal hydroxide aqueous solution being 0.4% with the mass concentration being forced into uniform pressure mixes through static mixer with the discharge rate of 100g/h, enters tubular reactor and carries out condensation reaction, and the reaction times is 10 minutes;
B) after having reacted, reaction solution through decompression enter flashing tower, be recycled acetone from tower top, in tower bottoms citric acid and after enter quantizer layering;
C) oil reservoir obtains pseudo ionone crude product through reclaim under reduced pressure, then rectifying separation goes out unreacted citral and pseudo ionone fine work further, and the light constituent by product of recovery and unreacted citral mix with recovery acetone, again enter reactor.
The citral that the present invention purifies through high-vacuum fractionation with litsea cubeba oil is for raw material, the method of continuous production pseudo ionone is studied, it is characterized in that using lower concentration alkali metal hydroxide aqueous solution to catalyze and synthesize the pure pseudo ionone of fragrance, and unreacted citral and part by product are turned back in reaction, make side reaction maintain a low level.In addition, the light constituent by product that in the present invention, vacuum reclaims and unreacted citral with reclaim acetone and mix and turn back in condensation reaction, to reduce the generation of by product.
Adopt technique scheme, the present invention, with citral continuity synthesis pseudo ionone, overcomes space-time yield low, there is the shortcoming of noxious waste pollution, meet the idea of development of green chemical industry.In addition, the present invention synthesizes pseudo ionone yield can reach more than 91%, high purity more than 94.0%, is a kind of desirable synthetic method promoted.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition or replacement, all belong to scope of the present invention.
If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
Embodiment 1
Citral 145g/h(content 97.3%, purify obtained with litsea cubeba oil through high-vacuum fractionation) and the acetone 1200g/h of water content 10% mix, 8MPa is forced into through pump, enter preheater and be heated to 100 DEG C, then mix through static mixer with the NaOH aqueous solution 100g/h of be pressurized to uniform pressure 0.4%, enter tubular reactor and carry out condensation reaction.Reaction time 10 minutes, reaction solution gas chromatographic analysis, reaction solution enters flashing tower after being decompressed to normal pressure, the recovery acetone of moisture 8% is obtained from tower top, tower bottoms with in appropriate citric acid and after enter quantizer layering, oil reservoir obtains pseudo ionone crude product 202.6g/h through reclaim under reduced pressure, gas-chromatography test analysis, crude product more further high vacuum rectification isolate unreacted light constituent and citral and pseudo ionone fine work 171.2g/h, content is 95.2%(two kinds of content of isomer sums), citral transformation efficiency is 97.8%, selectivity is 98.68%, relatively and citral, pseudo ionone yield is 93.3%.In the present embodiment, fed with acetone is that fresh acetone adds water mixing, and water content is about 10%.Table 1 is gas chromatographic analysis result:
Table 1
Embodiment 2
According to the method for embodiment 1, unlike citral with 150g/h(content 97.3%) and the acetone 1000g/h of water content 15% mix (mol ratio of acetone and citral is 15:1), other conditions are constant.Obtain pseudo ionone fine work 177.3g/h, content is 94.9%(two kinds of content of isomer sums), citral transformation efficiency is 96.41%, and selectivity is 98.9%, and relative and citral pseudo ionone yield is 91.23%.
Embodiment 3
According to the method for embodiment 1, unlike citral with 120g/h(content 97.3%) and the acetone 1500g/h of water content 10% mix (mol ratio of acetone and citral is 30:1), other conditions are constant.Obtain pseudo ionone fine work 142.2g/h, content is 95.5%(two kinds of content of isomer sums), relative and citral pseudo ionone yield is 91.44%.
Embodiment 4 ~ 5
According to the method for embodiment 1, unlike carrying out citral condensation reaction (mol ratio of acetone and citral is 20:1) respectively under 6MPa and 10MPa, other conditions are constant.Test-results is as shown in table 2:
Table 2
| Sequence number | Reaction pressure | Transformation efficiency/% | Selectivity/% | Yield/% |
| Embodiment 4 | 6MPa | 97.43 | 98.55 | 92.36 |
| Embodiment 5 | 10MPa | 98.97 | 97.28 | 91.88 |
Embodiment 6 ~ 8
According to the method for embodiment 1, unlike carrying out citral condensation reaction (mol ratio of acetone and citral is 20:1) respectively at different temperatures, with the foundation that citral transformation efficiency in vapor-phase chromatography monitoring reaction mixture is reaction end, other conditions are constant.Test-results is as shown in table 3:
Table 3
| Sequence number | Temperature of reaction | Reaction times | Transformation efficiency/% | Selectivity/% | Yield/% |
| Embodiment 6 | 20℃ | 108min | 98.16 | 98.27 | 92.14 |
| Embodiment 7 | 80℃ | 43min | 98.45 | 98.19 | 92.59 |
| Embodiment 8 | 150℃ | 2min | 98.08 | 97.17 | 91.11 |
Embodiment 9 ~ 11
According to the method for embodiment 1, carry out condensation reaction unlike the acetone different with water content, other conditions are constant.Test-results is as shown in table 4:
Table 4
| Sequence number | Acetone water content | Transformation efficiency/% | Selectivity/% | Yield/% |
| Embodiment 9 | 2% | 97.34 | 98.05 | 91.22 |
| Embodiment 10 | 5% | 98.12 | 98.61 | 92.45 |
| Embodiment 11 | 20% | 97.98 | 98.37 | 91.59 |
Embodiment 12
According to the method for embodiment 1, unlike citral with 142g/h(content 97.3%) and the acetone 1200g/h of water content 10% mix, here acetone is the mixture reclaiming acetone, rectifying light constituent and unreacted citral 2.4g fresh acetone, and other conditions are constant.Obtain pseudo ionone fine work 168.1g/h, content is 94.7%(two kinds of content of isomer sums), citral transformation efficiency is 96.95%, and selectivity is 99.1%, and relative and citral pseudo ionone yield is 93.0%.In the present embodiment, fed with acetone is reclaim the mixture of acetone, rectifying light constituent and unreacted citral fresh acetone, and water content is about 10%.
Table 5 is gas chromatographic analysis result:
Table 5
Embodiment 13 ~ 16
According to the method for embodiment 1,12, unlike being that the LiOH aqueous solution of 0.3% and the KOH aqueous solution of 0.5% carry out catalyzed reaction with the throwing amount speed of 100g/h with mass concentration, other conditions are constant.Test-results is as shown in table 6:
Table 6
Above-mentioned test-results display, the present invention carries out condensation reaction at the alkali metal hydroxide aqueous solution that working concentration is lower as catalyzer and prepares pseudo ionone, side reaction is few, yield is high, there is not unnecessary solid waste, and continuous reaction conditional stability, the pseudo ionone fragrance of output is pure, is easy to realize suitability for industrialized production.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (1)
1. continuity prepares a method for vitamin A intermediate pseudo ionone, it is characterized in that: comprise the steps:
The acetone 1200g/h of citral 145g/h and water content 10% mixes, 8MPa is forced into through pump, enter preheater and be heated to 100 DEG C, then mix through static mixer with the NaOH aqueous solution 100g/h of be pressurized to uniform pressure 0.4%, enter tubular reactor and carry out condensation reaction, described citral content 97.3%, purifies obtained with litsea cubeba oil through high-vacuum fractionation, described acetone is that fresh acetone adds water mixing, reaction time 10 minutes, reaction solution gas chromatographic analysis, reaction solution enters flashing tower after being decompressed to normal pressure, the recovery acetone of moisture 8% is obtained from tower top, tower bottoms with in appropriate citric acid and after enter quantizer layering, oil reservoir obtains pseudo ionone crude product 202.6g/h through reclaim under reduced pressure, gas-chromatography test analysis, crude product more further high vacuum rectification isolate unreacted light constituent and citral and pseudo ionone fine work 171.2g/h, content is 95.2%, citral transformation efficiency is 97.8%, selectivity is 98.68%, relative to citral, pseudo ionone yield is 93.3%.
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| CN103524317B (en) * | 2013-09-22 | 2015-08-12 | 上虞新和成生物化工有限公司 | The synthetic method of pseudo ionone |
| CN103694215B (en) * | 2013-12-10 | 2016-05-11 | 安徽丰原发酵技术工程研究有限公司 | A kind of continuity is prepared method and the device of DXPE |
| CN110002981B (en) * | 2019-04-19 | 2022-01-07 | 万华化学集团股份有限公司 | Method for preparing pseudo ionone |
| CN111825538B (en) * | 2020-07-13 | 2022-08-05 | 万华化学集团股份有限公司 | Method for continuously producing pseudo ionone |
| CN111978165B (en) * | 2020-08-06 | 2023-02-07 | 上海应用技术大学 | Method for improving acetone recovery rate in condensation process of producing pseudo ionone |
| WO2022104581A1 (en) * | 2020-11-18 | 2022-05-27 | 厦门金达威维生素有限公司 | Method for continuously synthesizing pseudoionone |
| CN113563168B (en) * | 2021-07-06 | 2023-03-24 | 万华化学集团股份有限公司 | Method for reducing waste water in production of pseudo ionone |
| CN113548952B (en) * | 2021-07-28 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method of high-quality pseudo ionone |
| CN116496149A (en) * | 2022-01-18 | 2023-07-28 | 浙江医药股份有限公司新昌制药厂 | Method for preparing pseudo ionone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4431844A (en) * | 1981-04-08 | 1984-02-14 | Basf Aktiengesellschaft | Preparation of polyunsaturated ketones |
| CN1711232A (en) * | 2002-11-07 | 2005-12-21 | 巴斯福股份公司 | Continuous process for producing pseudoionones and ionones |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4431844A (en) * | 1981-04-08 | 1984-02-14 | Basf Aktiengesellschaft | Preparation of polyunsaturated ketones |
| CN1711232A (en) * | 2002-11-07 | 2005-12-21 | 巴斯福股份公司 | Continuous process for producing pseudoionones and ionones |
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