CN101928209A - Method for preparing glutaraldehyde - Google Patents
Method for preparing glutaraldehyde Download PDFInfo
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- CN101928209A CN101928209A CN2010102757709A CN201010275770A CN101928209A CN 101928209 A CN101928209 A CN 101928209A CN 2010102757709 A CN2010102757709 A CN 2010102757709A CN 201010275770 A CN201010275770 A CN 201010275770A CN 101928209 A CN101928209 A CN 101928209A
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- glutaraldehyde
- dihydropyrane
- reaction
- alkoxyl group
- water
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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 invention provides a method for preparing glutaraldehyde with high conversion rate, high product purity, simple operation, environmental protection and suitability for small-scale intermittent production and large-scale continuous operation. The method for preparing the glutaraldehyde comprises the following steps of: adding an ion acid catalyst into 2-alkoxy-3,4-dihydropyrane and water, wherein the molar ratio of the 2-alkoxy-3,4-dihydropyrane, the water and the ion acid catalyst is (1-100): (2-300):1; performing hydrolysis reaction under the conditions that the reaction temperature is 20 to 150 DEG C, the reaction time is 1 to 20 hours and the reaction pressure is 0.01MPa to 0.1MPa; and obtaining the glutaraldehyde by negative pressure distillation, wherein the ion acid catalyst can be recycled.
Description
Technical field
The present invention relates to a kind of preparation method of glutaraldehyde.
Background technology
Glutaraldehyde is a kind of extremely important industrial chemicals, is widely used in fields such as biomedical engineering, cellular immunology, biological chemistry, leather chemistry, histological chemistry and food, microbiological industry, health care, environment protection.Present topmost synthetic method is that vinyl ether and propenal are carried out Diels-Alder addition reaction generation 2-alkoxyl group-3, the 4-dihydropyrane, and hydrolysis obtains glutaraldehyde and corresponding alcohol under an acidic catalyst then.
For a long time, 2-alkoxyl group-3, the hydrolysis of 4-dihydropyrane becomes glutaraldehyde many known methods.Prepare glutaraldehyde as described use tart diatomite, storng-acid cation exchange resin etc. in U.S. Pat 4489205 as the solid-carried catalyst continuous hydrolysis.Wherein process is comparatively complicated, and total recovery is lower, the less stable of catalyzer particularly, and cost is higher.
US5600018 has described the method that alkoxyl group dihydropyrans direct hydrolysis under High Temperature High Pressure prepares glutaraldehyde, this method long reaction time, and transformation efficiency is low, and is higher to equipment requirements simultaneously.
JP7226488 has reported and has used mineral acid to be catalyzer that hydrolysis prepares the method for glutaraldehyde.This method is very high to the requirement for anticorrosion of equipment, and more side reaction is arranged simultaneously, poor selectivity, and yield is low, and the feature of environmental protection is poor.
CN1137034, CN200410017890 reported and used microporous crystalline silico aluminate and the heteropolyacid method as the Preparation of Catalyst glutaraldehyde, and its selectivity is better, and is environmentally friendly, low but catalyzer is applied mechanically number of times, and corresponding cost is higher.
Other have many patents again, as CN00812098, US6559346, CN1371348 etc., have introduced the method that the continuous hydrolysis distillation prepares glutaraldehyde, wherein mainly are that the serialization scheme of process has been done many designs, do not relate to but catalysts all had.
Summary of the invention
The invention provides the preparation method of a kind of glutaraldehyde of a kind of transformation efficiency height, product purity height, simple to operate, environmental protection, both being suitable on a small scale, batch production also is applicable to large-scale continuous operation.
A kind of preparation method of glutaraldehyde, comprise the steps: at 2-alkoxyl group-3, add ion acid type catalyzer in 4-dihydropyrane and the water, 2-alkoxyl group-3, the mol ratio of 4-dihydropyrane, water and ion acid type catalyzer is (1-100): (2-300): 1, temperature of reaction is 20 ℃-150 ℃, reaction times is 1 hour-20 hours, and reaction pressure is under the 0.01MPa-0.1MPa condition, and hydrolysis reaction takes place, obtain glutaraldehyde by vacuum distillation then, ion acid type catalyzer can recycle.
Preferably, described 2-alkoxyl group-3, the alkoxyl group in the 4-dihydropyrane are methoxy or ethoxy.
Preferably, described ion acid type catalyzer is the acidic ion liquid with [Rmim] [X], [RPy] [X] and [RR ' R " N] [X] general formula, and wherein [Rmim], [RPy] and [RR ' R " N] are respectively:
R, R ' and R " be H or C
1～C
8Straight-chain paraffin, [X] is HSO
4 -, HSO
3 -, H
2PO
4 -Or CF
3SO
3 -As: when R is respectively H, C
1And C
2The time, [Rmim] is expressed as [Hmim], [C respectively
1Mim] and [C
2Mim].
The maximum characteristics of above ion acid type catalyzer are its good stabilities, are difficult for decomposing, and can apply mechanically continuously more than 20 times yield is not had obvious influence.Simultaneously above ion acid type Catalyst Steam presses more conventional preparation method little, thereby these ion acid type catalyzer will can not lose when the aqueous solution of distillage.Above ion acid type catalyzer can be bought on market, perhaps can be synthetic by known method.
Described 2-alkoxyl group-3,4-dihydropyrane: water: ion liquid mol ratio is (1-100): (2-300): 1 is preferably (40-60): (120-180): 1.
Described temperature of reaction is 20 ℃-150 ℃, is preferably 80 ℃-120 ℃, and the reaction times is 1 hour-20 hours, is preferably 2 hours-6 hours.
Preferably,, add ion acid type catalyzer in 4-dihydropyrane and the water, add Resorcinol again at 2-alkoxyl group-3,2-alkoxyl group-3, the amount of substance of 4-dihydropyrane is 1 with the ratio of the quality of Resorcinol: (0.01-5).
Reaction solution behind the hydrolysis reaction obtains glutaraldehyde by the method separation of vacuum distillation, rough vacuum (reclaims corresponding alcohol 0.07MPa-0.08MPa) and under low temperature (50-60 ℃) condition, (0.099MPa) He under 80 ℃ of conditions take off front-end volatiles, distillation obtains product to high vacuum under high vacuum-0.099MPa and the 100 ℃ of conditions.
Mainly contain low amounts of product in the vinasse, and water and catalyzer, by applying mechanically reaction after the mensuration catalyst concentration to next batch.
It is as follows to adopt the inventive method to prepare the chemical equation of glutaraldehyde:
Compare with general method, technology of the present invention has following characteristic:
1) adopt acidic ion liquid as catalysts, the selectivity of target product has reached more than 96%.
2) catalyzer can recycle the discharging that greatly reduces pollutent, and reduces production costs.
3) the inventive method transformation efficiency height, product purity height, good selectivity of target products both be suitable for large-scale continuous production and also be applicable to batch production on a small scale.
Embodiment
Below by embodiment the present invention is specifically described.It is important to point out that present embodiment only is used for invention is further specified, but can not be interpreted as restriction the invention protection domain.The person skilled in art can make some nonessential improvement and adjustment to the present invention according to the above-mentioned technology contents that provides.
Unless stated otherwise, each raw material and equipment all can obtain by commercial sources in the embodiment.
Embodiment 1
With the 2-oxyethyl group-3 of 128.0g (1.0mol), 4-dihydropyrane, 180.0g (10.0mol) water, 3.5g (0.02mol) [Hmin] [HSO
4] and the 0.01g Resorcinol join in the autoclave of 500ml, be heated to 80 ℃ under stirring fast.Temperature maintenance 80 ℃ the reaction 4 hours after stopped reaction.Reaction solution is taken out in cooling, pack in the there-necked flask, load onto rectifying column, the following 50 ℃ of distillations of-0.08MPa are brought up to vacuum-0.099MPa after collecting ethanolic soln (66.5 gram), and are warmed up to 100 ℃ gradually, and a small amount of (15 gram) interim fraction in the temperature-rise period is applied mechanically to the next batch hydrolysis, collect 100-105 ℃ cut 271.7g, concentration 33.7%, yield 91.6%, organic content (purity) 99.5%.2-oxyethyl group-3, the transformation efficiency of 4-dihydropyrane are 98.7%, and the selectivity of glutaraldehyde is 97.2%.
Embodiment 2
With the 2-methoxyl group-3 of 114.0g (1.0mol), 4-dihydropyrane, 180.0g (10.0mol) water, 7.1g (0.04mol) [C
2Mim] [HSO
3] and the 0.01g Resorcinol join in the autoclave of 500ml, be heated to 100 ℃ under stirring fast.Temperature maintenance 100 ℃ the reaction 2 hours after stopped reaction.Reaction solution is taken out in cooling, pack in the there-necked flask, load onto rectifying column, the following 50 ℃ of distillations of-0.08MPa are brought up to vacuum-0.099MPa after collecting methanol solution (71.7 gram), and are warmed up to 100 ℃ gradually, and a small amount of (13.3 gram) interim fraction in the temperature-rise period is applied mechanically to the next batch hydrolysis, collect 100-105 ℃ cut 268.1g, concentration 31.5%, yield 85.5%, organic content (purity) 99.5%.2-oxyethyl group-3, the transformation efficiency of 4-dihydropyrane are 95.5%, and the selectivity of glutaraldehyde is 98.1%.
Embodiment 3
With the 2-methoxyl group-3 of 114.0g (1.0mol), 4-dihydropyrane, 270.0g (15.0mol) water, 5.0g (0.02mol) [(C
2H5N)
3] [CF
3O
3S] and the 0.01g Resorcinol join in the autoclave of 500ml, be heated to 80 ℃ under stirring fast.Temperature maintenance 80 ℃ the reaction 2 hours after stopped reaction.Reaction solution is taken out in cooling, pack in the there-necked flask, load onto rectifying column, the following 50 ℃ of distillations of-0.08MPa are brought up to vacuum-0.099MPa after collecting methanol solution (58.8 gram), and are warmed up to 100 ℃ gradually, and a small amount of (17.7 gram) interim fraction in the temperature-rise period is applied mechanically to the next batch hydrolysis, collect 100-105 ℃ cut 298.9g, concentration 30.1%, yield 89.97%, organic content (purity) 99.3%.2-oxyethyl group-3, the transformation efficiency of 4-dihydropyrane are 94.6%, and the selectivity of glutaraldehyde is 98.6%.
Embodiment 4
With the 2-methoxyl group-3 of 114.0g (1.0mol), 4-dihydropyrane, 270.0g (15.0mol) water, 3.52g (0.2mol) [Py] [H
2PO
4] and the 0.5g Resorcinol join in the autoclave of 500ml, be heated to 80 ℃ under stirring fast.Temperature maintenance 80 ℃ the reaction 2 hours after stopped reaction.Reaction solution is taken out in cooling, pack in the there-necked flask, load onto rectifying column, the following 50 ℃ of distillations of-0.08MPa are brought up to vacuum-0.099MPa after collecting methanol solution (62.8 gram), and are warmed up to 100 ℃ gradually, and a small amount of (14.7 gram) interim fraction in the temperature-rise period is applied mechanically to the next batch hydrolysis, collect 100-105 ℃ cut 301.1g, concentration 30.3%, yield 91.2%, organic content (purity) 98.5%.2-oxyethyl group-3, the transformation efficiency of 4-dihydropyrane are 98.4%, and the selectivity of glutaraldehyde is 96.1%.
Embodiment 5
With the 2-methoxyl group-3 of 114.0g (1.0mol), 4-dihydropyrane, 270.0g (10.0mol) water, 3.64g (0.2mol) [(C
2H
5N)
3] [HSO
3] and the 5g Resorcinol join in the autoclave of 500ml, be heated to 80 ℃ under stirring fast.Temperature maintenance 80 ℃ the reaction 3 hours after stopped reaction.Reaction solution is taken out in cooling, pack in the there-necked flask, load onto rectifying column, the following 50 ℃ of distillations of-0.08MPa are brought up to vacuum-0.099MPa after collecting methanol solution (70.8 gram), and are warmed up to 100 ℃ gradually, and a small amount of (11.4 gram) interim fraction in the temperature-rise period is applied mechanically to the next batch hydrolysis, collect 100-105 ℃ cut 276.1g, concentration 33.3%, yield 91.9%, organic content (purity) 99.6%.2-oxyethyl group-3, the transformation efficiency of 4-dihydropyrane are 98.6%, and the selectivity of glutaraldehyde is 97.7%.
Embodiment 6
With about 25 grams of the distillation residual liquid among the embodiment 5 by titrimetry and calculate [(C
2H
5N)
3] [HSO
3] residual 3.45 grams, add 0.19g[(C
2H
5N)
3] [HSO
3] and 252 gram water after other operation ratios and process with embodiment 5, test, apply mechanically repeatedly 10 times, experimental data is as follows:
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention, obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (6)
1. the preparation method of a glutaraldehyde, it is characterized in that: comprise the steps: at 2-alkoxyl group-3, add ion acid type catalyzer in 4-dihydropyrane and the water, 2-alkoxyl group-3, the mol ratio of 4-dihydropyrane, water and ion acid type catalyzer is (1-100): (2-300): 1, temperature of reaction is 20 ℃-150 ℃, reaction times is 1 hour-20 hours, reaction pressure is under the 0.01MPa-0.1MPa condition, hydrolysis reaction takes place, obtain glutaraldehyde by vacuum distillation then, ion acid type catalyzer can recycle; Reaction formula is as follows:
2. the preparation method of a kind of glutaraldehyde according to claim 1 is characterized in that, described 2-alkoxyl group-3, the alkoxyl group in the 4-dihydropyrane are methoxy or ethoxy.
3. the preparation method of a kind of glutaraldehyde according to claim 1, it is characterized in that, described ion acid type catalyzer is the acidic ion liquid with [Rmim] [X], [RPy] [X] and [RR ' R " N] [X] general formula, and wherein [Rmim], [RPy] and [RR ' R " N] are respectively:
R, R ' and R " be H or C
1～C
8Straight-chain paraffin, [X] is HSO
4 -, HSO
3 -, H
2PO
4 -Or CF
3SO
3 -
4. the preparation method of a kind of glutaraldehyde according to claim 1 is characterized in that, described 2-alkoxyl group-3, and 4-dihydropyrane: water: ion liquid mol ratio is (40-60): (120-180): 1.
5. the preparation method of a kind of glutaraldehyde according to claim 1 is characterized in that, described reaction temperature is preferably 80 ℃-120 ℃, and the reaction times is 2 hours-6 hours.
6. the preparation method of a kind of glutaraldehyde according to claim 1, it is characterized in that, at 2-alkoxyl group-3, add ion acid type catalyzer in 4-dihydropyrane and the water, add Resorcinol again, 2-alkoxyl group-3, the amount of substance of 4-dihydropyrane is 1 with the ratio of the quality of Resorcinol: (0.01-5).
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| CN2010102757709A CN101928209A (en) | 2010-09-08 | 2010-09-08 | Method for preparing glutaraldehyde |
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|---|---|---|---|
| CN2010102757709A CN101928209A (en) | 2010-09-08 | 2010-09-08 | Method for preparing glutaraldehyde |
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|---|---|
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ID=43367696
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU878760A1 (en) * | 1979-08-13 | 1981-11-07 | Армянский Филиал Ордена Трудового Красного Знамени Всесоюзного Научно-Исследовательского Института Химических Реактивов И Особо Чистых Веществ | Method of producing glutaric aldehyde |
| US5600018A (en) * | 1994-08-18 | 1997-02-04 | Basf Aktiengesellschaft | Preparation of glutaraldehyde |
| WO2001016237A2 (en) * | 1999-08-30 | 2001-03-08 | Basf Aktiengesellschaft | Method for the continuous production of glutaraldehyde |
| CN1569791A (en) * | 2004-04-23 | 2005-01-26 | 上海华谊丙烯酸有限公司 | Method for hydrolyzing pyran to prepare glutaraldehyde using heteropolyacid as catalyst |
-
2010
- 2010-09-08 CN CN2010102757709A patent/CN101928209A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU878760A1 (en) * | 1979-08-13 | 1981-11-07 | Армянский Филиал Ордена Трудового Красного Знамени Всесоюзного Научно-Исследовательского Института Химических Реактивов И Особо Чистых Веществ | Method of producing glutaric aldehyde |
| US5600018A (en) * | 1994-08-18 | 1997-02-04 | Basf Aktiengesellschaft | Preparation of glutaraldehyde |
| WO2001016237A2 (en) * | 1999-08-30 | 2001-03-08 | Basf Aktiengesellschaft | Method for the continuous production of glutaraldehyde |
| CN1569791A (en) * | 2004-04-23 | 2005-01-26 | 上海华谊丙烯酸有限公司 | Method for hydrolyzing pyran to prepare glutaraldehyde using heteropolyacid as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 蔡磊等: "戊二醛的合成方法研究", 《宁夏工程技术》, vol. 3, no. 1, 31 March 2004 (2004-03-31), pages 51 - 54 * |
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Application publication date: 20101229 |