CN106146287A - A kind of air oxidation low-purity valeraldehyde prepares the friendly process of positive valeric acid - Google Patents
A kind of air oxidation low-purity valeraldehyde prepares the friendly process of positive valeric acid Download PDFInfo
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- CN106146287A CN106146287A CN201610396503.4A CN201610396503A CN106146287A CN 106146287 A CN106146287 A CN 106146287A CN 201610396503 A CN201610396503 A CN 201610396503A CN 106146287 A CN106146287 A CN 106146287A
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- air
- purity
- valeraldehyde
- oxygen
- valeric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Abstract
The invention discloses a kind of air oxidation low-purity valeraldehyde and prepare the friendly process of positive valeric acid, its technique is: in the stirring bubbling tank reactor of a band outer circulation, add low-purity valeraldehyde (valeraldehyde content as little as 80%), blast air or oxygen or oxygen-enriched air or oxygen denuded air, air speed is 100～2000 L/min, reaction temperature is 25～100 DEG C, the response time 1～30h.Product after oxidation reaction purifies through rectification under vacuum, obtains the positive valeric acid that purity is more than 98%；Valeraldehyde conversion ratio reaches more than 97%, and selectivity more than 98%, single decompression distillation yield is more than 86%.The present invention uses air as oxidant, it is not necessary to any catalyst, have reaction gentle, efficiently, low cost, the feature such as environmental protection, there is wide application and market prospect.
Description
Technical field
The present invention relates to a kind of air oxidation low-purity valeraldehyde and prepare the friendly process of positive valeric acid.
Background technology
Positive valeric acid is widely used in the odor types such as spice, modulated butter, cheese, Fructus Fragariae Ananssae, it is possible to as organic metal soap
Raw material, perfume base, pesticide and medical material, belong to important industrial chemicals.Positive valeric acid is mainly used in synthesizing valerate, volatilization
The valerate of property, with pleasant abnormal smells from the patient, can be used in perfume and cosmetics.Ethyl valerate and amyl valerate have fruit aroma, use
Make food additive.Positive valeric acid can be obtained through electrolytic oxidation by n-amyl alcohol；Or from the distillation of radix valerianae with other isomery
Body obtains together；Or reacted by butyl bromide and Cyanogran., then the valeronitrile of generation being carried out saponification and prepare, yield is
70～75%；Can also be by valeraldehyde oxidation preparation.The method of positive valeric acid made above all exists that yield is low, environmental pollution big,
The outstanding problem such as relatively costly, it is difficult to realize its industrialization.
In recent years, using air or oxygen as cleaning oxidizer, by the liquid phase green catalysis oxidation technology of formoxy-chemical conversion acid
It is increasingly subject to the attention of people.United States Patent (USP) 4487720, Japan Patent 53-105413 and patent WO 99/054274 describe
Under catalyst presence or absence, prepare routine techniques and the method for organic acid with oxygen or air oxidation aldehyde compound.
According to report, the salt of use transition metal, alkali metal or alkaline-earth metal is as catalyst, for the Oxygen in Liquid of aldehyde compound
Change, corresponding organic acid can be prepared.But, when not using catalyst to react, in order to ensure aldehyde compound and oxygen
Between fully react, need particular design reactor (such as United States Patent (USP) 4350829, Japan Patent 55-17131).United States Patent (USP)
4487720 describe employing copper and manganese compound make catalyst, prepare positive valeric acid with pure oxygen or air oxidation valeraldehyde.Although institute
Need metal concentration low (10-200ppm), but during distilation acid, generate copper film, cause the machinery damage in distillation equipment
Bad.Chinese patent 101018757 B describes by using ionic liquid as reaction dissolvent or catalysts, uses liquid phase
Oxidation, the method that valeraldehyde is changed into positive valeric acid, its preferred oxygen of oxidant used or at least contain the oxygen-enriched of 50% oxygen
Air.Owing to this technique uses ionic liquid as reaction dissolvent or catalysts, commercial production is relatively costly.Chinese patent
It is oxidation that 100567245C describes employing alkali metal carboxylate or alkaline earth metal carboxylation for catalyst, oxygen or oxygen-containing gas
Agent catalysis oxidation valeraldehyde prepares positive valeric acid, and the raw material of employing is the high-purity valeraldehyde of more than 99.6%.The oxidation reaction mistake of aldehyde
Cheng Zhong, in addition to generating target organic acid, it also occur that side reaction, produces multiple by-product, thus causes relatively low productivity.For
Acquisition high-purity organic acid, it is necessary to isolate these by-products from product.And these by-products are most of by conduct
Refuse is abandoned, thus causes the yield of whole reaction to reduce.Therefore, reduce by-product, and improve the conversion ratio of reaction, selectivity
Most important with yield.At present, valeraldehyde prepare the technique of positive valeric acid and mostly relate to the catalysis oxidation of various catalyst, examine
Considering to reaction the most preferably oxygen or oxygen-enriched air is oxidant, and the raw material related to just is being content high-purity more than 99%
Valeral, therefore above each technique production cost is the most of a relatively high.
Mainly there are Dow Chemical, Yuan Lian C.-Chem AG and moral BASF AG in the manufacturing enterprise of raw material valeraldehyde,
Valeraldehyde major part dependence on import needed for China, cost of material is higher.At present, domestic many chemical enterprises are with 1-butylene and synthesis
Gas is raw material, produces valeraldehyde through carbongl group synthesis reaction.The thick product price of valeraldehyde that this technique produces is the lowest, in thick product
Valeraldehyde containing about 94% and the isovaleral of about 3%.If thick for the valeraldehyde of low price product is used suitable technique
Prepare highly purified positive valeric acid, the production cost of positive valeric acid will be substantially reduced, and its application can be expanded.The present invention uses air oxygen
Change low-purity valeraldehyde and prepare the friendly process of the positive valeric acid of high-purity, use air as oxidant, it is not necessary to any catalyst, high
Conversion ratio, is transformed into the positive valeric acid of high-purity with high yield by low-purity valeraldehyde.Present invention process process is simple, equipment investment
Few, oxidant uses air, and reaction condition is gentle, and side reaction is few, and process costs is low, and environmental pollution is little, is suitable for large-scale production.
Summary of the invention
It is an object of the invention to provide a kind of air oxidation low-purity valeraldehyde and prepare the green work of the positive valeric acid of high-purity
Skill.The present invention is without any catalyst, and reaction condition is gentle, has efficiently, low cost, the feature such as environmental protection, has wide
Application and market prospect.
The technical scheme of the technique of the present invention is as follows:
Using reactor is the stirring bubbling tank reactor of band outer circulation, by air compressor blast air or oxygen or
Oxygen-enriched air or oxygen denuded air.Raw material low-purity valeraldehyde (valeraldehyde content as little as 80%) is joined in reactor, blasts
Air or oxygen or oxygen-enriched air or oxygen denuded air, air-blowing speed is 100～2000 L/min, and reaction temperature is 25
～100 DEG C, response time 1～30 h.Product after oxidation reaction purifies through rectification under vacuum, obtains the positive valeric acid of high-purity and produces
Product.
Above-mentioned air oxidation low-purity valeraldehyde is prepared in the friendly process of the positive valeric acid of high-purity, and described aldehyde is low pure
The valeraldehyde of degree (80% ~ 95%).
Above-mentioned air oxidation low-purity valeraldehyde is prepared in the friendly process of the positive valeric acid of high-purity, is passed through air speed excellent
Elect 1000～1500 mL/min as.
Above-mentioned air oxidation low-purity valeraldehyde is prepared in the friendly process of the positive valeric acid of high-purity, and described reaction temperature is excellent
Elect 70～80 DEG C as.
Above-mentioned air oxidation low-purity valeraldehyde is prepared in the friendly process of the positive valeric acid of high-purity, and the described response time is excellent
Elect 10～24 h as.
Above-mentioned air oxidation low-purity valeraldehyde is prepared in the friendly process of the positive valeric acid of high-purity, and described reactor is band
The stirring bubbling tank reactor of outer circulation.
Distinguishing feature: the present invention uses air oxidation low-purity valeraldehyde to prepare the friendly process of the positive valeric acid of high-purity, profit
With cheap air as oxidant, it is not necessary to any catalyst, high conversion, high selectivity, with high yield by low-purity valeraldehyde
It is transformed into the positive valeric acid of high-purity.Present invention process process is simple, and equipment investment is few, and oxidant uses air, and reaction condition is gentle,
Side reaction is few, and conversion ratio is high, and selectivity is high, and process costs is low, and environmental pollution is little, is suitable for large-scale production.
Accompanying drawing illustrates:
Fig. 1 is the stirring bubbling tank reactor device schematic diagram (sky preparing positive valeric acid according to an embodiment of the invention
Gas oxidation valeraldehyde prepares the reactor assembly schematic diagram of positive valeric acid), the most each sequence number represents respectively: (1) motor, and (2) subtract
Speed machine, (3) frame, (4) manhole, (5) valeraldehyde charging hole, (6) cylinder, (7) axially flow agitator, and (8) radial flow stirs
Device, (9) coil pipe, (10) discharging opening, (11) air intlet, (12) chuck, (13) tank body, (14) shaft, (15) gas outlet.
Detailed description of the invention:
In conjunction with embodiment, describe embodiments of the present invention in detail, but the technical scope of the present invention is not only restricted to following enforcement
Mode, on the premise of not changing its main points, can make various change and implement.
Embodiment 1
The preparation of the positive valeric acid of laboratory: in the long 150 centimetres of self-control bubbling reactors with chuck of internal diameter 46 millimeters, uses sky
Gas direct oxidation valeraldehyde prepares positive valeric acid.By using the internal temperature of the water circulating pump regulation bubbling reactor of controllable temperature,
Inside reactor temperature is made to keep constant.Air is blasted below bubble tower.Weigh valeraldehyde 100 g of 93.8%, join tool
Have in the bubbling reactor of glass spring filler, use air compressor to blast air with the speed of 700 mL/min, control anti-
Answering temperature is 80 DEG C, uses gas chromatogram to follow the tracks of reaction.Reacting 8 h, sampling carries out gas chromatogram test, obtains positive valeric acid content
94.5%, valeraldehyde conversion ratio is 99.3%, selectivity 98.5%.
Embodiment 2
Difference with embodiment 1 is: use hydrogen peroxide as oxidant instead.Weigh valeraldehyde 100 g of 93.8%, join 500
In the reaction bulb of mL, by valeraldehyde and mol ratio 1:2 of hydrogen peroxide, the hydrogen peroxide of dropping 30%, anti-temperature controls at 80 DEG C, instead
Control at 8 h between Ying Shi, use gas chromatogram to follow the tracks of reaction.The result obtained by the reaction of embodiment 2: valeraldehyde conversion ratio is
30%, positive valeric acid content is 23%, and impurity content is high.
Embodiment 3
Difference with embodiment 1 is: workshop enlarged experiment.Weigh valeraldehyde 600 kg of 93.8%, join stirring bubbling still
In formula reactor, using air compressor to blast air with the speed of 1500 L/min, controlling reaction temperature is 80 DEG C, uses gas
Phase chromatogram tracking reacts.Reacting 20 h, sampling carries out gas chromatogram test, obtains positive valeric acid content 94.3%, and valeraldehyde conversion ratio is
97.5%, selectivity 99.0%.Take this reactant liquor 500 kg to carry out rectification under vacuum and purify positive valeric acid, collect 118～120 DEG C evaporate
Point.Obtaining fraction 22 kg, fraction 434 kg of positive valeric acid content more than 98% of positive valeric acid content 75.1%, bottom is that positive valeric acid contains
Residual still liquid 35 kg of amount 80.2%, the yield of the positive valeric acid of single rectification purity more than 98% is 86.8%.Component by less than 98% closes
Secondary rectification and purification can be carried out after and.
Claims (4)
1. utilizing the method that air oxidation low-purity valeraldehyde prepares the positive valeric acid of high-purity, the method is by the dress shown in Fig. 1
Put realization, it is characterized in that have employed following operating procedure:
Using reactor is the stirring bubbling tank reactor of band outer circulation, by air compressor blast air or oxygen or
Oxygen-enriched air or oxygen denuded air.Raw material low-purity valeraldehyde (valeraldehyde content as little as 80%) is joined in reactor, blasts
Air or oxygen or oxygen-enriched air or oxygen denuded air, air-blowing speed is 100 2000 L/min, and reaction temperature is 25
100 DEG C, response time 1 30 h.Product after oxidation reaction purifies through rectification under vacuum, obtains high-purity positive valeric acid product.
Method the most according to claim 1, is characterized in that: utilize air oxidation low-purity valeraldehyde to prepare high-purity positive penta
Acid.
Method the most according to claim 1, it is characterised in that: the method uses the stirring bubbling still reaction of band outer circulation
Device, with air or oxygen or oxygen-enriched air or oxygen denuded air as oxidant, direct oxidation low-purity valeraldehyde is prepared high-purity
Spending positive valeric acid, it is not necessary to any catalyst, reaction condition is gentle, has efficiently, low cost, the feature such as environmental protection.
Method the most according to claim 1, it is characterised in that: air-blowing speed: 100-2000 L/min, reaction temperature: 25-
100 DEG C, response time: 1-30h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776412A (en) * | 2019-11-12 | 2020-02-11 | 万华化学集团股份有限公司 | Method for preparing isovaleric acid, ligand, complex and application thereof in catalytic system |
Citations (4)
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| CN1305451A (en) * | 1998-04-21 | 2001-07-25 | 联合碳化化学品及塑料技术公司 | Preparation of organic acids |
| CN101177393A (en) * | 2006-11-08 | 2008-05-14 | 扬州市刘氏化工有限公司 | Process for producing methyl benzoic acid by paraxylene |
| CN101792378A (en) * | 2009-12-29 | 2010-08-04 | 中国科学院广州化学研究所 | Method for preparing anisaldehyde |
| WO2012121145A1 (en) * | 2011-03-10 | 2012-09-13 | 株式会社 村田製作所 | Electrode active material, electrode, and secondary battery |
-
2016
- 2016-06-07 CN CN201610396503.4A patent/CN106146287A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305451A (en) * | 1998-04-21 | 2001-07-25 | 联合碳化化学品及塑料技术公司 | Preparation of organic acids |
| CN101177393A (en) * | 2006-11-08 | 2008-05-14 | 扬州市刘氏化工有限公司 | Process for producing methyl benzoic acid by paraxylene |
| CN101792378A (en) * | 2009-12-29 | 2010-08-04 | 中国科学院广州化学研究所 | Method for preparing anisaldehyde |
| WO2012121145A1 (en) * | 2011-03-10 | 2012-09-13 | 株式会社 村田製作所 | Electrode active material, electrode, and secondary battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776412A (en) * | 2019-11-12 | 2020-02-11 | 万华化学集团股份有限公司 | Method for preparing isovaleric acid, ligand, complex and application thereof in catalytic system |
| CN110776412B (en) * | 2019-11-12 | 2022-04-22 | 万华化学集团股份有限公司 | Method for preparing isovaleric acid, ligand, complex and application thereof in catalytic system |
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Effective date of registration: 20190410 Address after: 414006 439 Qijialing Street College Road, Yueyang Building District, Yueyang City, Hunan Province Applicant after: Hunan Technology College Applicant after: Yueyang Changde Environmental Technology Co., Ltd. Address before: 414006 439 Qijialing Street College Road, Yueyang Building District, Yueyang City, Hunan Province Applicant before: Hunan Technology College Applicant before: Changde Chemical Industry Co., Ltd., Yueyang |
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Application publication date: 20161123 |
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