CN102093183A - Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst - Google Patents
Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst Download PDFInfo
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- CN102093183A CN102093183A CN2010106004953A CN201010600495A CN102093183A CN 102093183 A CN102093183 A CN 102093183A CN 2010106004953 A CN2010106004953 A CN 2010106004953A CN 201010600495 A CN201010600495 A CN 201010600495A CN 102093183 A CN102093183 A CN 102093183A
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- base catalyst
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- butyraldehyde
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Abstract
The invention relates to the technical field of green chemistry, belongs to a method for preparing 2-ethyl-2-hexenoicaldehyde and in particular relates to a method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of a novel solid base catalyst. The n-butanal is subjected to the condensation reaction under the action of the solid base catalyst to obtain the 2-ethyl-2-hexenoicaldehyde, wherein the mass ratio of a solvent to the n-butanal is between 0:1 and 20:1; the using amount of the solid base catalyst is 1 to 50 percent of the weight of the n-butanal; and the reaction is performed at the temperature of between 20 to 160 DEG C for 0.5 to 48 hours. In the method, the technological process is simple; the catalyst can be reused; the product is not required to be neutralized and washed; and no industrial waste water is generated.
Description
Technical field
The present invention relates to the Green Chemical Technology field, belong to a kind of 2-ethyl-2-hexenoic aldehyde novel preparation method, refer in particular to and adopt novel solid body base catalyst catalysis n butyraldehyde aldolization to prepare the method for 2-ethyl-2-hexenoic aldehyde.
Background technology
2-ethyl-2-hexenoic aldehyde is a kind of important chemical material, at medicine, and spices, makeup and medicinal intermediates all have a wide range of applications, and it still is the important source material of industrial Synthetic 2-ethyl-n-hexyl aldehyde and 2-ethyl-hexane-1-alcohol.And the latter also has very important commercial use, comprises production rubber, the antioxidant of wear-resistant polyvinyladehydes and polymer and lubricating oil.Industrial, 2-ethyl-2-hexenoic aldehyde mainly is that butyraldehyde generation self-condensation reaction generates under the katalysis of liquid bases such as NaOH or KOH, because this process need consumption surpasses stoichiometric ratio KOH/NaOH, so it is a kind of reaction of non-economy.In addition, reaction finishes the back alkalimetal oxide to be needed in a large amount of water and washing, and this has also caused very big pollution to environment.
Summary of the invention
The present invention seeks to overcome the shortcoming that the homogeneous phase legal system is equipped with 2-ethyl-2-hexenoic aldehyde, a kind of method that adopts solid base catalyst to prepare 2-ethyl-2-hexenoic aldehyde is provided, it is simple that solid base catalyst is used for this n butyraldehyde aldolization reaction production technique, it is neutral that product is, do not need the neutralization washing, can not produce trade effluent, convenient post-treatment, catalyzer can repeatedly use.
Concrete technical scheme of the present invention is as follows:
The present invention is a kind of method for preparing 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization, be to be raw material with the butyraldehyde-n, add solvent, add catalyzer, effect obtains 2-ethyl-2-hexenoic aldehyde through n butyraldehyde aldolization, the steps include: in round-bottomed flask, to add solvent, butyraldehyde-n, the mass ratio of solvent and butyraldehyde-n at 0:1 between the 20:1; Add solid base catalyst again,, the solid base catalyst consumption is the 1-50% of butyraldehyde-n weight, magnetic agitation is 20～160
oC reacted 0.5～48 hour down; Suction filtration while hot after the reaction is isolated solid base catalyst; Solvent and butyraldehyde-n are reclaimed in the liquid phase redistillation; Product 2-ethyl-2-hexenoic aldehyde obtains through rectifying.
Solid base catalyst of the present invention is an alkaline earth metal oxide, described alkaline earth metal oxide be in magnesium oxide, calcium oxide, the strontium oxide a kind of or wherein mixing more than two kinds and two kinds (MgO, CaO, SrO); The maturing temperature of solid base catalyst is 300-900
oC, roasting time is 1-24h.
Solid base catalyst of the present invention is for being carrier with the oxide compound, and an alkali metal salt, alkaline earth salt are the load type solid body base catalyst of active ingredient, and oxide carrier is SiO
2, Al
2O
3, ZrO
2In a kind of; An alkali metal salt, alkaline earth salt are LiNO
3, LiF, Li
2CO
3, NaNO
3, NaF, Na
2CO
3, KNO
3, KF, K
2CO
3, CsNO
3, CsF, Mg (NO
3)
2, Ca (NO
3)
2, Sr (NO
3)
2In a kind of; The maturing temperature of load type solid body base catalyst is 300-900
oC, roasting time is 1-24h.
Load type solid body base catalyst of the present invention, it consists of LiNO
3/ SiO
2, LiF/SiO
2, Li
2CO
3/ SiO
2, NaNO
3/ SiO
2, NaF/SiO
2, Na
2CO
3/ SiO
2, KNO
3/ SiO
2, KF/SiO
2, K
2CO
3/ SiO
2, CsNO
3/ SiO
2, CsF/SiO
2, Mg (NO
3)
2/ SiO
2, Ca (NO
3)
2/ SiO
2, Sr (NO
3)
2/ SiO
2, LiNO
3/ Al
2O
3, LiF/Al
2O
3, Li
2CO
3/ Al
2O
3, NaNO
3/ Al
2O
3, NaF/Al
2O
3, Na
2CO
3/ Al
2O
3, KNO
3/ Al
2O
3, KF/Al
2O
3, K
2CO
3/ Al
2O
3, CsNO
3/ Al
2O
3, CsF/Al
2O
3, Mg (NO
3)
2/ Al
2O
3, Ca (NO
3)
2/ Al
2O
3, Sr (NO
3)
2/ Al
2O
3, LiNO
3/ ZrO
2, LiF/ZrO
2, Li
2CO
3/ ZrO
2, NaNO
3/ ZrO
2, NaF/ZrO
2, Na
2CO
3/ ZrO
2, KNO
3/ ZrO
2, KF/ZrO
2, K
2CO
3/ ZrO
2, CsNO
3/ ZrO
2, CsF/ZrO
2, Mg (NO
3)
2/ ZrO
2, Ca (NO
3)
2/ ZrO
2, Sr (NO
3)
2/ ZrO
2In a kind of.
Solvent of the present invention is a kind of in water, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, n-hexyl alcohol, normal hexane, hexanaphthene, toluene, the p-Xylol; Its used quality is 0 ~ 20 times of butyraldehyde-n.
Under this condition, prepare biofuel suddenly as the above-mentioned Walk that states, the reaction times is 0.5～48h, and the butyraldehyde-n transformation efficiency is about 95%, and the yield of 2-ethyl-2-hexenoic aldehyde is about 70%, and the effect of solvent is to improve temperature of reaction.
The invention has the beneficial effects as follows: adopt the catalyzer of solid alkali as n butyraldehyde aldolization prepared in reaction 2-ethyl-2-hexenoic aldehyde, can reduce the usage quantity of catalyzer in 2-ethyl-2-hexenoic aldehyde production process greatly, solvent after the recovery, butyraldehyde-n all can repeatedly reuse, great advantage of the present invention is a convenient post-treatment, do not need the neutralization washing, do not have trade effluent to produce.
Embodiment
Embodiment 1
In the 100ml round-bottomed flask, add the 20g deionized water, the 5g butyraldehyde-n, add weight and be about 10% heavy MgO catalyzer 0.5g of butyraldehyde-n, temperature of reaction is controlled at 100 ℃, and magnetic agitation speed is 600rpm, reaction times 24h, suction filtration while hot after reaction finishes is isolated catalyzer.Reclaim butyraldehyde-n through distillation, further obtain 2-ethyl-2-hexenoic aldehyde after the rectification and purification.Reaction system is neutral, has save the trade effluent that produces because of the neutralization washing, has reduced environmental pollution.Through gas chromatographic detection, the transformation efficiency of butyraldehyde-n is 93.2%, and the yield of 2-ethyl-2-hexenoic aldehyde is 68.7%.
Embodiment 2
In the 100ml autoclave, add 20g toluene, the 1g butyraldehyde-n adds weight and is about 50% heavy KF/Al of butyraldehyde-n
2O
3Catalyzer 0.5g, temperature of reaction is controlled at 160 ℃, and magnetic agitation speed is 600rpm, reaction times 48h.Suction filtration while hot after reaction finishes is isolated catalyzer.Reclaim butyraldehyde-n through distillation, further obtain 2-ethyl-2-hexenoic aldehyde after the rectification and purification.Through gas chromatographic detection, the transformation efficiency of butyraldehyde-n is 96.8%, and the yield of 2-ethyl-2-hexenoic aldehyde is 56.0%.
Embodiment 3
In the 100ml round-bottomed flask, add the 20g propyl carbinol, the 1g butyraldehyde-n adds weight and is about 25% heavy CaO catalyzer 0.25g of butyraldehyde-n, and temperature of reaction is controlled at 90 ℃, and magnetic agitation speed is 600rpm, reaction times 0.5h.Suction filtration while hot after reaction finishes is isolated catalyzer.Reclaim butyraldehyde-n through distillation, further obtain 2-ethyl-2-hexenoic aldehyde after the rectification and purification.Through gas chromatographic detection, the transformation efficiency of butyraldehyde-n is 93.9%, and the yield of 2-ethyl-2-hexenoic aldehyde is 42.6%.
Embodiment 4
In the 100ml round-bottomed flask, add the 20g propyl carbinol, the 2.5g butyraldehyde-n adds weight and is about 10% heavy MgO catalyzer 0.25g of butyraldehyde-n, and temperature of reaction is controlled at 110 ℃, and magnetic agitation speed is 600rpm, reaction times 8h.Suction filtration while hot after reaction finishes is isolated catalyzer.Reclaim butyraldehyde-n through distillation, further obtain 2-ethyl-2-hexenoic aldehyde after the rectification and purification.Through gas chromatographic detection, the transformation efficiency of butyraldehyde-n is 94.7%, and the yield of 2-ethyl-2-hexenoic aldehyde is 71.5%.
Embodiment 5
In the 100ml round-bottomed flask, add the 20g butyraldehyde-n, add weight and be about 1% heavy Mg (NO of butyraldehyde-n
3)
2/ ZrO
2Catalyzer 0.2g, temperature of reaction is controlled at 20 ℃, and magnetic agitation speed is 600rpm, reaction times 12h.Suction filtration while hot after reaction finishes is isolated catalyzer.Reclaim butyraldehyde-n through distillation, further obtain 2-ethyl-2-hexenoic aldehyde after the rectification and purification.Through gas chromatographic detection, the transformation efficiency of butyraldehyde-n is 29.5%, and the yield of 2-ethyl-2-hexenoic aldehyde is 18.4%.
Five embodiment summary sheets are as follows:
Claims (9)
1. method for preparing 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization, it is characterized in that with the butyraldehyde-n being raw material, add solvent, add catalyzer, effect obtains 2-ethyl-2-hexenoic aldehyde through n butyraldehyde aldolization, the steps include: in round-bottomed flask, to add solvent, butyraldehyde-n, the mass ratio of solvent and butyraldehyde-n at 0:1 between the 20:1; Add solid base catalyst again, the solid base catalyst consumption is the 1-50% of butyraldehyde-n weight, and magnetic agitation is 20～160
oC reacted 0.5～48 hour down; Suction filtration while hot after the reaction is isolated solid base catalyst; Solvent and butyraldehyde-n are reclaimed in the liquid phase redistillation; Product 2-ethyl-2-hexenoic aldehyde obtains through rectifying.
2. the method for preparing 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization according to claim 1, it is characterized in that described solid base catalyst is an alkaline earth metal oxide, described alkaline earth metal oxide is a kind of or wherein mixing more than two kinds and two kinds in magnesium oxide, calcium oxide, the strontium oxide.
3. the maturing temperature of solid base catalyst according to claim 2 is 300-900
oC, roasting time is 1-24h.
4. the method for preparing 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization according to claim 1, it is characterized in that described solid base catalyst for being carrier with the oxide compound, an alkali metal salt, alkaline earth salt are the load type solid body base catalyst of active ingredient.
5. according to claim 4ly prepare the method for 2-ethyl-2-hexenoic aldehyde, it is characterized in that described oxide carrier is SiO with solid base catalyst catalysis n butyraldehyde aldolization
2, Al
2O
3, ZrO
2In a kind of.
6. according to claim 4ly prepare the method for 2-ethyl-2-hexenoic aldehyde, it is characterized in that described an alkali metal salt, alkaline earth salt are LiNO with solid base catalyst catalysis n butyraldehyde aldolization
3, LiF, Li
2CO
3, NaNO
3, NaF, Na
2CO
3, KNO
3, KF, K
2CO
3, CsNO
3, CsF, Mg (NO
3)
2, Ca (NO
3)
2, Sr (NO
3)
2In a kind of.
7. describedly prepare the method for 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization according to claim 4 or 5 or 6, it is characterized in that described load type solid body base catalyst, it consists of LiNO
3/ SiO
2, LiF/SiO
2, Li
2CO
3/ SiO
2, NaNO
3/ SiO
2, NaF/SiO
2, Na
2CO
3/ SiO
2, KNO
3/ SiO
2, KF/SiO
2, K
2CO
3/ SiO
2, CsNO
3/ SiO
2, CsF/SiO
2, Mg (NO
3)
2/ SiO
2, Ca (NO
3)
2/ SiO
2, Sr (NO
3)
2/ SiO
2, LiNO
3/ Al
2O
3, LiF/Al
2O
3, Li
2CO
3/ Al
2O
3, NaNO
3/ Al
2O
3, NaF/Al
2O
3, Na
2CO
3/ Al
2O
3, KNO
3/ Al
2O
3, KF/Al
2O
3, K
2CO
3/ Al
2O
3, CsNO
3/ Al
2O
3, CsF/Al
2O
3, Mg (NO
3)
2/ Al
2O
3, Ca (NO
3)
2/ Al
2O
3, Sr (NO
3)
2/ Al
2O
3, LiNO
3/ ZrO
2, LiF/ZrO
2, Li
2CO
3/ ZrO
2, NaNO
3/ ZrO
2, NaF/ZrO
2, Na
2CO
3/ ZrO
2, KNO
3/ ZrO
2, KF/ZrO
2, K
2CO
3/ ZrO
2, CsNO
3/ ZrO
2, CsF/ZrO
2, Mg (NO
3)
2/ ZrO
2, Ca (NO
3)
2/ ZrO
2, Sr (NO
3)
2/ ZrO
2In a kind of.
8. according to claim 7ly prepare the method for 2-ethyl-2-hexenoic aldehyde with solid base catalyst catalysis n butyraldehyde aldolization, the maturing temperature that it is characterized in that described load type solid body base catalyst is 300-900
oC, roasting time is 1-24h.
9. according to claim 1ly prepare the method for 2-ethyl-2-hexenoic aldehyde, it is characterized in that described solvent is a kind of in water, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, n-hexyl alcohol, normal hexane, hexanaphthene, toluene, the p-Xylol with solid base catalyst catalysis n butyraldehyde aldolization.
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|---|---|---|---|
| CN2010106004953A CN102093183A (en) | 2010-12-22 | 2010-12-22 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
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|---|---|---|---|
| CN2010106004953A CN102093183A (en) | 2010-12-22 | 2010-12-22 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086856A (en) * | 2013-02-16 | 2013-05-08 | 河北工业大学 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
| CN103508864A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of 2-isopropyl-5-methyl-2-hexenal |
| CN103864587A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Method for synthesizing 2-ethyl-2-hexenal |
| CN104672073A (en) * | 2014-12-12 | 2015-06-03 | 辽宁石油化工大学 | Method for preparing trans3-heptylene-2-ketone |
| CN106914270A (en) * | 2017-03-21 | 2017-07-04 | 河海大学 | A kind of method of the composite oxide catalysts for preparing 1,2-dimethoxy benzene |
| CN111097523A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method thereof |
-
2010
- 2010-12-22 CN CN2010106004953A patent/CN102093183A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张媛媛: "正丁醛自缩合生成辛烯醛新型催化工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508864A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of 2-isopropyl-5-methyl-2-hexenal |
| CN103508864B (en) * | 2012-06-27 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of preparation method of 2-sec.-propyl-5-methyl-2-hexenoic aldehyde |
| CN103864587A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Method for synthesizing 2-ethyl-2-hexenal |
| CN103864587B (en) * | 2012-12-10 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of method of synthetic 2-ethyl-2-hexenoic aldehyde |
| CN103086856A (en) * | 2013-02-16 | 2013-05-08 | 河北工业大学 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
| CN103086856B (en) * | 2013-02-16 | 2015-07-22 | 河北工业大学 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
| CN104672073A (en) * | 2014-12-12 | 2015-06-03 | 辽宁石油化工大学 | Method for preparing trans3-heptylene-2-ketone |
| CN104672073B (en) * | 2014-12-12 | 2017-01-04 | 辽宁石油化工大学 | A kind of method preparing trans 3-hepten-2-one |
| CN106914270A (en) * | 2017-03-21 | 2017-07-04 | 河海大学 | A kind of method of the composite oxide catalysts for preparing 1,2-dimethoxy benzene |
| CN111097523A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method thereof |
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