CN102898291A - Method for synthesizing pentanedial from cyclopentene in presence of niobium peroxide and formic acid peroxide - Google Patents
Method for synthesizing pentanedial from cyclopentene in presence of niobium peroxide and formic acid peroxide Download PDFInfo
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- CN102898291A CN102898291A CN2012103853384A CN201210385338A CN102898291A CN 102898291 A CN102898291 A CN 102898291A CN 2012103853384 A CN2012103853384 A CN 2012103853384A CN 201210385338 A CN201210385338 A CN 201210385338A CN 102898291 A CN102898291 A CN 102898291A
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Abstract
The invention discloses a method for synthesizing pentanedial from cyclopentene in the presence of niobium peroxide and formic acid peroxide, and belongs to the technical field of pentanedial preparation. The method comprises the following steps of: adding niobic acid with catalyst activity, 95 weight percent of ethanol solvent and 30 weight percent of hydrogen peroxide into a reaction kettle with a constant-pressure dropping funnel; stirring for 20 minutes at normal temperature, and heating to 35 to 38 DEG C; dripping 99 weight percent of cyclopentene and 90 weight percent of formic acid by using the constant-pressure funnel respectively within 20 to 30 minutes; at the temperature, continuing to stir the mixture for 1 to 1.5 hours; and settling the oxidation solution, separating, rectifying and decolorizing to obtain pure pentanedial, wherein the molar ratio of the cyclopentene to the formic acid to the hydrogen peroxide to the niobium peroxide is 1:(1.5-2.0):(2.2-2.5):(0.05-0.08), and the volume ratio of ethanol to cyclopentene is (3.5-5):1. Compared with the prior art, the method has the advantages of higher selectivity and industrialization value, and time required is reduced by about 9/10.
Description
Technical field
The present invention relates to cyclopentenes under formic acid peroxidation condition, take peroxy niobic acid as catalyst oxidation becomes the method for glutaraldehyde, belong to the glutaraldehyde preparing technical field.
Background technology
Glutaraldehyde be only second to oxalic dialdehyde most important representative examples of saturated aliphatic dialdehyde; be good tanning agent, organize solidifying agent, protein cross agent and efficient sterilization disinfectant, be widely used in the fields such as biomedical engineering, cellular immunology, biological chemistry, leather chemistry, histological chemistry and food, microbiological industry, environment protection, oil production, treatment of cooling water.
At present with cyclopentenes-H
2o
2oxidation style, adopt catalyzer mostly to be wolframic acid, niobic acid or to load to MCM-41, MCM-48 molecular sieve and TiO
2microsphere supported upper, carry out homogeneous phase or heterogeneous catalytic oxidation method synthesis of glutaraldehyde, the yield of glutaraldehyde reaches 60～69%.This technique exists speed of response slow, the shortcoming that active ingredient easily runs off, as the ZL03114723.2 of Fudan University patent " a kind of tungstic acid catalyst of the loading type for the synthesis of glutaraldehyde and manufacture method thereof " adopts the synthetic TiO with nanometer central hole structure of homogeneous phase alcohol-hydrothermal method
2microballoon, then flood tungstic acid catalyst, synthetic WO
3/ TiO
2loaded catalyst, under this catalyzer, carry out H
2o
2oxidation 12～60 hours, glutaraldehyde yield 60～69%.The ZL200410015894.8 of Fudan University patent " oxidizing-synthesizing glutaric dialdehyde with cyclopentene is with containing niobium mesopore molecular sieve heterogeneous catalyst and preparation method thereof " is immobilized to mesoporous molecular sieve MCM-41 by niobic acid, obtain the Nb/MCM-41 loaded catalyst containing the catalytic oxidation activity center, under this catalyzer, carry out H
2o
2oxidation 12～24 hours, the glutaraldehyde yield reaches 42～50%.
The people such as the Chen Jie of Fudan University are in Fudan Journal " natural science edition " 03 phase in 2002, " under peroxy niobic acid catalysis, hydrogen peroxide selective oxidation cyclopentenes prepares glutaraldehyde " article of delivering, by niobium oxides, be that raw material prepares peroxy niobic acid, take ethanol in solvent, the system that is oxygenant at hydrogen peroxide, peroxy niobic acid was as catalyst reaction 24 hours, the cyclopentenes of catalysis efficiently is prepared into glutaraldehyde, and the yield of glutaraldehyde is up to 72%.But this process catalyst peroxidation biobic acid a little less than, so that cyclopentenes is produced intermediate product beta-hydroxy cyclopentyl hydrogen peroxide manufacture is slower, easily and water effect generation by-product 1,2-encircles pentanediol, makes rear section from very difficult.
Summary of the invention
The object of the invention is to solve the problem that prior art exists, and the method for a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence is provided, and to shorten generated time, is suitable for suitability for industrialized production.
Technical scheme of the present invention is
:
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, according to following step, carry out: (1) is in being equipped with the reactor of constant pressure funnel, add successively the catalyzer peroxy niobic acid, ethanol and hydrogen peroxide, stir 20min under normal temperature, then be warming up to 35～38 ℃, drip cyclopentenes and formic acid by constant pressure funnel respectively simultaneously, be added dropwise to complete in 20～30min.At this temperature, continue to stir 1～1.5 hour,
?rear oxidation liquid is through precipitate and separate, rectifying, the glutaraldehyde sterling of decolouring to obtain.
The mol ratio of wherein said cyclopentenes, formic acid, hydrogen peroxide and peroxy niobic acid is 1:1.5～2.0:2.2～2.5:0.05～0.08, and ethanol and cyclopentenes volume ratio are 3.5～5:1.
Wherein said cyclopentenes is the 99wt% cyclopentenes, and described formic acid is 90wt% formic acid, the ethanol that wherein said ethanol is 95wt%, and described hydrogen peroxide is the 30wt% hydrogen peroxide.
The method of above-mentioned cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid catalyzer and formic acid peroxidation existence, preferred described cyclopentenes, formic acid, hydrogen peroxide and peroxy niobic acid mol ratio are 1:1.7:2.3:0.06.
The reaction mechanism that is oxidized to glutaraldehyde due to cyclopentenes is that at first cyclopentenes is become initial product-cyclopentene oxide by hydrogen peroxide oxidation under acidic conditions; Cyclopentene oxide changes into intermediate compound beta-hydroxy cyclopentyl hydrogen peroxide more afterwards, and in this process, beta-hydroxy cyclopentyl hydrogen peroxide is subject to the catalysis of WOOH or NbOOH active group, is converted into glutaraldehyde.Document and patent report adopt niobic acid or wolframic acid as catalytic active component before, pay close attention at beta-hydroxy cyclopentyl catalytic oxidation of hydrogen peroxide to become on the reactions steps of glutaraldehyde, it is less that the first step cyclopentenes is become intermediate product to consider by hydrogen peroxide oxidation, because document and patent adopt solvent before, hydrogen peroxide, catalyzer, cyclopentenes is disposable to add, form intermediate compound beta-hydroxy cyclopentyl hydrogen peroxide process very long, cause the whole reaction process time long, the glutaraldehyde product reaction times that obtains 50% above yield generally will be controlled at more than 20 hours.And long intermediate compound of reaction times is easy to the reaction with water and generates by product 1, and 2-encircles pentanediol, brings difficulty to the later separation operation.
The present invention compared with prior art, has following significant effect:
(1) dropping method when the present invention adopts formic acid and cyclopentenes, at first the hydrogen peroxide in formic acid and system forms the formic acid peroxidation, it is a kind of oxygenant stronger than hydrogen peroxide, and formic acid provides again wolframic acid and the stronger acidity of peroxy niobic acid simultaneously, and peroxy niobic acid
againcan well be dissolved in formic acid
.reactant, catalyzer are under etoh solvent and formic acid environment like this
,the homogeneous phase solution that the easier height of formation of reaction system disperses, improve the activity of peroxy niobic acid, the very big like this speed of response that improved, accelerated intermediate compound beta-hydroxy cyclopentyl hydrogen peroxide generating rate, shortened the reaction times, whole reaction completes in 1.5～2.0 hours.
(2) cyclopentenes of the present invention adopts the dropping mode, can be at first and the formic acid peroxidation, to avoid being generated 1,2-ring pentanediol by product by the water nucleophilic attack, and the product glutaraldehyde has higher selectivity.
embodiment:
embodiment 1
Now by embodiment, the present invention is described in detail as follows: the method for a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence is comprised of following process steps;
(1) preparation of peroxy niobic acid catalyzer: in corundum crucible, add 1molNb successively
20
5, 2molK
2c
2o
7, mix, in 600 ℃ of air atmospheres, heating is 3 hours, make to melt fully, after fused solution is cooling, after the 1mol/L oxalic acid dipping 5h that is enough to pickup, suction filtration, washing, filtrate adds enough ammoniacal liquor, and solution produces white precipitate, standing over night, suction filtration obtains white precipitate, dries, and obtains the activated catalyzer peroxy niobic acid of tool standby.
(2) cyclopentenes oxidation: in the reactor of constant pressure funnel is housed, the peroxy niobic acid 0.25mol that adds successively above-mentioned (1) to make, 95wt% ethanol 27.5mol and 30wt% hydrogen peroxide 11mol, stir 20min under normal temperature, then be warming up to 35 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 7.5mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 25min.At this temperature, continue to stir 1 hour, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.33%, selectivity 77.86%.
embodiment 2
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, in the reactor of constant pressure funnel is housed, add successively the peroxy niobic acid 0.26mol that in above-described embodiment 1, (1) makes, 95wt% ethanol 30mol and 30wt% hydrogen peroxide 11.2mol, stir 25min under normal temperature, then be warming up to 38 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 7.9mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 30min.At this temperature, continue to stir 1.5 hours, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.50%, selectivity 78.05%.
embodiment 3
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, in the reactor of constant pressure funnel is housed, add successively the peroxy niobic acid 0.28mol that in above-described embodiment 1, (1) makes, 95wt% ethanol 30.5mol and 30wt% hydrogen peroxide 11.4mol, stir 25min under normal temperature, then be warming up to 38 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 8mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 30min.At this temperature, continue to stir 1.2 hours, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.17%, selectivity 78.23%.
embodiment 4
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, in the reactor of constant pressure funnel is housed, add successively the peroxy niobic acid 0.3mol that in above-described embodiment 1, (1) makes, 95wt% ethanol 33.5mol and 30wt% hydrogen peroxide 11.7mol, stir 20min under normal temperature, then be warming up to 35 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 8.5mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 25min.At this temperature, continue to stir 1 hour, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.59%, selectivity 78.31%.
embodiment 5
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, in the reactor of constant pressure funnel is housed, add successively the peroxy niobic acid 0.35mol that in above-described embodiment 1, (1) makes, 95wt% ethanol 33.8mol and 30wt% hydrogen peroxide 12mol, stir 25min under normal temperature, then be warming up to 35 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 9.5mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 30min.At this temperature, continue to stir 1.2 hours, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.29%, selectivity 78.05%.
embodiment 6
The method of a kind of cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, in the reactor of constant pressure funnel is housed, add successively the peroxy niobic acid 0.4mol that in above-described embodiment 1, (1) makes, 95wt% ethanol 34mol and 30wt% hydrogen peroxide 12.5mol, stir 20min under normal temperature, then be warming up to 38 ℃, drip 99wt% cyclopentenes 5mol and 90wt% formic acid 10mol by constant pressure funnel respectively simultaneously, be added dropwise to complete in 25min.At this temperature, continue to stir 1 hour, reaction finishes.The gas chromatographic analysis glutaraldehyde content, glutaraldehyde yield 64.02%, selectivity 77.98%.
Claims (5)
1. the method for cyclopentenes synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation exist, it is characterized in that carrying out according to following step: (1) is in being equipped with the reactor of constant pressure funnel, add successively the catalyzer peroxy niobic acid, ethanol and hydrogen peroxide, stir 20min under normal temperature, then be warming up to 35～38 ℃, drip cyclopentenes and formic acid by constant pressure funnel respectively simultaneously, be added dropwise to complete in 20～30min.
2. at this temperature, continue to stir 1～1.5 hour, last oxidation solution is through precipitate and separate, rectifying, the glutaraldehyde sterling of decolouring to obtain.
3. the method for a kind of cyclopentenes according to claim 1 synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation exist, the mol ratio that it is characterized in that wherein said cyclopentenes, formic acid, hydrogen peroxide and peroxy niobic acid is 1:1.5～2.0:2.2～2.5:0.05～0.08, and ethanol and cyclopentenes volume ratio are 3.5～5:1.
4. the method for a kind of cyclopentenes according to claim 1 synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation exist, it is characterized in that wherein said cyclopentenes is the 99wt% cyclopentenes, described formic acid is 90wt% formic acid, the ethanol that wherein said ethanol is 95wt%, described hydrogen peroxide is the 30wt% hydrogen peroxide.
5. the method for a kind of cyclopentenes according to claim 1 synthesis of glutaraldehyde under peroxy niobic acid and formic acid peroxidation existence, is characterized in that described cyclopentenes, formic acid, hydrogen peroxide and peroxy niobic acid mol ratio are 1:1.7:2.3:0.06.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192141A (en) * | 2021-11-26 | 2022-03-18 | 广东省科学院化工研究所 | Preparation method of glutaraldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485307A (en) * | 2002-09-27 | 2004-03-31 | 中国科学院大连化学物理研究所 | Cyclopentene oxidizing process for synthesizing glutaraldehyde in formic acid system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485307A (en) * | 2002-09-27 | 2004-03-31 | 中国科学院大连化学物理研究所 | Cyclopentene oxidizing process for synthesizing glutaraldehyde in formic acid system |
Non-Patent Citations (1)
| Title |
|---|
| 徐建华等: "新型MCM-41固载化铌酸催化氧化环戊烯制备戊二醛", 《化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192141A (en) * | 2021-11-26 | 2022-03-18 | 广东省科学院化工研究所 | Preparation method of glutaraldehyde |
| CN114192141B (en) * | 2021-11-26 | 2024-03-19 | 广东省科学院化工研究所 | Preparation method of glutaraldehyde |
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Application publication date: 20130130 |