CN1277801C - Method for preparation of propionic acid - Google Patents
Method for preparation of propionic acid Download PDFInfo
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- CN1277801C CN1277801C CN 03138831 CN03138831A CN1277801C CN 1277801 C CN1277801 C CN 1277801C CN 03138831 CN03138831 CN 03138831 CN 03138831 A CN03138831 A CN 03138831A CN 1277801 C CN1277801 C CN 1277801C
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Abstract
The present invention relates to a technique for propionic acid, and has simple technical process and easy industrialization. The present invention has the technique that propionaldehyde is used as raw material, oxygen, air or oxygen and gas mixture which is inert in reaction are used as oxidants, the raw material and the oxidizing agents carry out oxidation reaction under the condition without catalysts, and thus, a propionic acid product with high selectivity is prepared. The present invention carries out reaction in a bubbling tower or a tank reactor, the reaction temperature ranges from 10 DEG C to 90 DEG C, the reaction pressure ranges from 0.1 to 1.0MPa, the conversion rate of propionaldehyde is greater than 99%, and the selectivity of propionic acid is greater than 97 %. As the reaction technique can achieve high reaction yield without adopting catalyst, the present invention saves the procedures of catalyst separation, recovery, etc., has low production cost, and high product selectivity, and directly simplifies the separation procedure. The entire technical process is simple, the product yield is high, and the present invention is easily popularized in industry.
Description
1. technical field
The invention relates to a kind of preparation method of propionic acid, particularly a kind of is the propionic acid synthesized processing method of raw material with the propionic aldehyde.
2. background technology
Propionic acid is a kind of important chemical material, and purposes is very extensive.Propionic acid and its esters are used to prevent that effects such as cereal caking, grain fresh keeping, feed anticorrosion are remarkable; In present employed sanitas kind, propionic acid is the most economical material benefit of generally acknowledging in the world, consumption sanitas safely and effectively.In addition, propionic acid can be used as electroplating additives, emulsifying agent, nitrocellulose solvent and softening agent etc., and the derivative of propionic acid can be used for food and perfume industry, medicine industry and low-toxin farm chemicals industry.
Propionic acid is made by sugar or amylofermentation at first, develops the acetic acid synthesized by-product method of light hydrocarbon oxidation, ethene oxo synthesis (Reppe) technology, propionic aldehyde oxidation style, ethanol oxo synthesis, vinyl cyanide method and vinylformic acid hydrogenation method again by the raw material sources difference later on.Wherein, propionic aldehyde oxidation style technological reaction condition relaxes, and the product selectivity height is that the our times various countries produce the operational path that propionic acid the most generally adopts, and is suitable for large-scale plant and adopts.
Prepare carboxylic acid from corresponding formoxy-ization, the synthetic method of having reported is more.Usually adopt air or oxygen to make oxygenant, make catalyzer with the metal carboxylate of variable valency metals such as cobalt, manganese, iron, copper, the reaction of aldehyde generation free-radical oxidn generates corresponding carboxylic acid.Synthesis technique can be a successive, also can be intermittently.
Typical previous preparation technology has done to elaborate in Japanese Patent JP 4-108758: under the katalysis at nickel compound, contain the aldehyde cpd and the oxygen-containing gas reaction of straight or branched alkyl, aromatic base, generate corresponding carboxylic acid.The catalyzer that is adopted is the polyoxy heterogeneous ring compound of a class complexity, the nickeliferous heterogeneous ring compound complex structure of this class, and synthetic difficulty, and cost an arm and a leg, use as commercial catalysts, will cause production cost to increase.
GB 2 059 419 has introduced a kind of preparation technology of saturated organic single acid, and the compound that it is characterized in that adopting copper, manganic compound is as catalyst for reaction, preferably manganese acetate and neutralized verdigris, and consumption accounts for 2～6% of reactant.This reaction preference reaches more than 90%, and relatively Shi Yi aldehyde is to contain the aldehyde of 6～9 carbon atoms such as hexanal etc.The shortcoming of this invented technology maximum is to contain copper compound in the product.In the purification process of product, copper can precipitate the heavy corrosion that causes equipment.
SU 1 020 423 has described a kind of in gas phase, produces the processing method of propionic acid by the propionic aldehyde oxidation.Use air oxidant, under flow condition, adopt Pyrex reactor (handled with Klorvess Liquid on the surface) to react.The glass weighting material is housed in the reactor, and when the propionic aldehyde transformation efficiency was 70%, selectivity of product reached 95%, 2 minutes reaction times.This speed of response is fast, does not use catalyzer.But react under gas phase state, need the temperature of reaction more than 160 ℃, the transformation efficiency of propionic aldehyde and selectivity of product are all lower.
SU 793 988 has introduced the method that the propionic aldehyde liquid-phase oxidation prepares propionic acid: in the presence of the oxygen-containing gas, make reaction medium with benzene, make catalyzer, 45～75 minutes reaction times with boron copper or titanium boride, molybdenum boride, the selectivity 88～93% of reaction process, the propionic aldehyde transformation efficiency can reach 96%.Though this technology reaction times is shorter, catalyzer costs an arm and a leg, and adds solvent recuperation, and processing step is long.
3. summary of the invention
According to described background information, the liquid phase oxidation reaction of propionic aldehyde all adopts catalyzer, though gas phase oxidation can not use catalyzer, the transformation efficiency of reaction is low, and the propionic acid synthetic method advanced person, that technology is succinct is still had big demand, particularly under the catalyst-free condition, adopt the technical process of simple possible, save the catalyzer postprocessing working procedures, can keep high yield and while optionally, obtain highly purified propionic acid product, improve competitiveness of product.
The present invention intends in the weak point that solves aforementioned patent, under the prerequisite of not using catalyzer, provides a kind of reaction preference and product yield height, processing step is few, reaction conditions is gentle, be easier to the new synthetic method of industrialized propionic acid.
The present invention adopts the synthesis technique of liquid-phase oxidation, and the preparation method is as follows:
In the plastics bubble tower or reactor of stainless steel, lass lining or organic solvent-resistant, add propionic aldehyde, in the presence of oxygen-containing gas and/or solvent, reaction generates propionic acid.Reaction can be carried out in the presence of solvent, also can directly carry out oxidizing reaction.The solvent that is adopted is generally acetic acid, propionic acid, butanic acid, isopropylformic acid, sad etc.These solvents both may be used alone, can also be used in combination.Reasonable solvent is a propionic acid, not only helps obtaining high product yield, does not have the separation problem of solvent simultaneously.The quality compositing range of propionic aldehyde is 10%～99.5% in the general reaction raw materials, and the quality compositing range of solvent is 90%～0.5%.
Particularly importantly, propionic acid synthesized according to processing method provided by the invention, can not adopt catalyzer, reaction process is safe and reliable, and the growing amount of main by product acetic acid is little, and the reaction mixture separating step is few, and product yield obviously improves in last handling process.
Introduce processing method of the present invention below in detail.The present invention both can adopt batch reactor, also can adopt flow reactor.In the present invention, oxygen or oxygen-containing gas are fed by bubble tower or reactor bottom, are divided into bubble in small, broken bits through gas distributor, can increase the gas-to-liquid contact area like this, improve gas effciency.Because oxidizing reaction is a strong exothermal reaction, reaction mass is extracted out by bubble tower or reactor bottom through pump in reaction process, through injecting by bubble tower or reactor top again after the external heat exchanger cooling, thereby form the outer circulation of reaction mass, liberated heat is just taken out of by heat-eliminating medium in the reactor jacket and outer circulation.Outer circulation rises stirs and condensation, the selectivity of control reaction temperature and product effectively.The ratio of outer circulation and inlet amount is by exothermic heat of reaction amount decision, and generally greater than 20, reaction mass can be at the reactor internal recycle once in 1～10 minute.
In bubble tower or tank reactor, temperature of reaction is controlled in 10～90 ℃ of scopes, temperature raises, main reaction speed is obviously accelerated, but the also corresponding quickening of side reaction speed, by products such as the acetate in the reaction, ethanol increase, and make when being reflected at the transformation efficiency raising, and the selectivity of product descends to some extent.Say that from another point of view after temperature of reaction raise, volatile propionic aldehyde more easily escaped into the gas-phase space at oxidizing tower or still top, has increased the explosion hazard of tail gas.Temperature of reaction is 40～80 ℃ preferably.
The system pressure of reaction is 0.1～1.0MPa (absolute pressure), and suitable raising reaction pressure plays three aspect effects: the oxidation of a propionic aldehyde is the reaction that reduces volume, and pressurization helps improving the transformation efficiency of reaction.The b pressure boost helps the diffusion and the dissolving of oxygen.The c pressurization can improve the propionic aldehyde boiling point, reduces the loss of propionic aldehyde to gas phase.The negative effect of bringing simultaneously is that process cost improves, and pressure is less to the selectivity influence of reaction.
Being used for oxygen-containing gas of the present invention can be oxygen, air or oxygen and the mixture that reaction is inert gasses.Oxygen aldehyde is than too small, and then the propionic aldehyde reaction is incomplete, and transformation efficiency is low, the unit consumption height; Oxygen aldehyde is than too high, and then the propionic acid selectivity obviously descends, and mainly is by-product acetic acid content showed increased, influences quality product, brings difficulty for the separation of product; In addition, make oxygen content raising in oxidizing tower or the still top gas phase, thereby increase the danger of vapor phase areas.Should accurately measure in the reaction process, relatively Shi Yi oxygen aldehyde ratio is 0.50～2.00: 1 (mol ratio), is preferably 0.55～0.90: 1 (mol ratio).
Propionic acid in the reaction solution can be separated by the mode of normal pressure or rectification under vacuum.Except that propionic acid, other product mainly contains acetate, acetaldehyde, ethanol, ethyl formate, ethyl propionate and unreacted propionic aldehyde in the reaction solution.In the sepn process, at first remove light constituents such as acetate, carry out the refining of product again.
Adopt the manufacture method of propionic acid disclosed in this invention, the transformation efficiency of propionic aldehyde can reach more than 99.5% greater than 99%, and the selectivity of propionic acid reaches more than 97%.Product purity after the separation, stratographic analysis are more than 99.8%.
The synthesis technique of the propionic acid that the present invention proposes can not adopt catalyzer to reach high reaction yield, does not introduce other impurity, thereby saved operations such as catalyst separating, recovery, production cost is low, the selectivity of product height, directly simplified separation circuit, and the product purity height.On the other hand, reaction heat can shift out by outer circulation and water coolant, needn't adopt low temperature control system, and facility investment is less, and energy consumption reduces.The condition that adopts the present invention to recommend is reacted, and does not use catalyzer, can reach the purpose of safety in production.Whole process flow is simple, and the product yield height is easy to industry and promotes.
The invention will be further described below by embodiment and comparative example, but the present invention is not limited only to these examples.Also can fully understand essence of the present invention and invention scope by these embodiment, further understand the relative merits of technology of the present invention.
4 embodiments
Embodiment 1
At internal diameter is to add 150 gram propionic aldehyde in the stainless steel bubbling tower of 25mm, high 1000mm.To 0.3MPa, in 5 hours, at the uniform velocity feed 99 gram oxygen with the nitrogen punching press.Reaction mass carries out outer circulation with the speed of 70ml/min in reaction process, and keeping temperature of reaction is 50～60 ℃, and reaction heat can shift out by outer circulation and water coolant, and afterreaction finished in 5 hours.Through gas chromatographic analysis, the propionic aldehyde transformation efficiency is 99.5%, and the propionic acid selectivity is 98.0%.
Embodiment 2
Employing is with the same bubbling column reactor of embodiment 1.Add 100 gram propionic aldehyde, 50 gram propionic acid.To 0.4MPa, in 4 hours, at the uniform velocity feed 25 gram oxygen and 120 gram air with the nitrogen punching press.Reaction mass carries out outer circulation with the speed of 80ml/min in reaction process, and the maintenance temperature of reaction is 45～55 ℃.Afterreaction finished in 4 hours.Analyze through vapor-phase chromatography, drawing the propionic aldehyde transformation efficiency is 99.3%, and the propionic acid selectivity is 97.2%.
Embodiment 3
Employing is with the same bubbling column reactor of embodiment 1.Add 150 gram propionic aldehyde.To 0.5MPa, in 5 hours, at the uniform velocity feed 215 gram air with the nitrogen punching press.Reaction mass carries out outer circulation with the speed of 80ml/min in reaction process.Temperature of reaction is 60～70 ℃, 5 hours reaction times.Through sampling analysis, drawing the propionic aldehyde transformation efficiency is 99.6%, and the propionic acid selectivity is 97.4%.
Embodiment 4
Oxidation reactor is of a size of: Φ 57mm * 3.5mm * 1000mm, a thermopair is equipped with in the axle center.Add 1740g propionic aldehyde raw material earlier in reactor, to 0.3MPa, oxygen feeds from reactor bottom after the mass-flow gas meter metering, carries out rhythmic reaction with the nitrogen roof pressure.Sampling detection reaction liquid is formed, and when the propionic aldehyde transformation efficiency reaches 99% left and right sides, begins the speed of raw material propionic aldehyde by 0.7L/h is fed in the reactor, and oxygen feeding amount is 2.15L/min.Tail gas emptying after condensation and gas-liquid separation.Reaction mass carries out outer circulation with the speed of 40L/h in reaction process, 50～55 ℃ of control reaction temperature.After successive reaction was stable, sampling analysis obtained propionic aldehyde transformation efficiency 99%, and the selectivity of propionic acid is 97.8%,
Reaction solution is fed acetate by volume pump remove in the tower from tower, under normal pressure, carry out rectifying and remove component more than the acetate; Tower kettle product enters weight-removing column, removes heavy component.After the rectifying, cat head is the propionic acid product, and through stratographic analysis, purity is 99.88%.
Embodiment 5
The device of experiment and step are with embodiment 4.To 0.5MPa, carry out successive reaction with the nitrogen punching press.The speed that the raw material propionic aldehyde is pressed 0.4L/h feeds in the reactor, and oxygen feeding amount is 1.2L/min.Reaction mass carries out outer circulation with the speed of 40L/h in reaction process, 65～75 ℃ of control reaction temperature.After the stable reaction, sampling analysis obtains propionic aldehyde transformation efficiency 99.4%, and the selectivity of propionic acid is 97.3%.Behind the separation and purification, the product purity stratographic analysis is 99.81%.
Comparative example 6
Experiment condition adds 150 gram propionic aldehyde, 0.2 gram manganese acetate with example 1 in reactor.To 0.3MPa, in 5 hours, at the uniform velocity feed 99 gram oxygen with the nitrogen punching press.Reaction mass carries out outer circulation with the speed of 70ml/min in reaction process, and keeping temperature of reaction is 50～60 ℃, and reaction heat shifts out by outer circulation and water coolant, and afterreaction finished in 5 hours.Through gas chromatographic analysis, the propionic aldehyde transformation efficiency is 99.8%, and the propionic acid selectivity is 95.7%.
Claims (8)
1, a kind ofly prepare the method for propionic acid, it is characterized in that it comprises by propionic aldehyde:
(1) in the plastics bubble tower or reactor of stainless steel, lass lining or organic solvent-resistant, add propionic aldehyde, under the catalyst-free condition, propionic aldehyde and oxygen-containing gas liquid phase contact reacts generate propionic acid, 10～90 ℃ of oxidizing reaction temperatures, described oxygen-containing gas are oxygen, air or oxygen and reaction are the inert gasses mixture;
(2) oxygen-containing gas is fed by bubble tower or reactor bottom, is divided into bubble in small, broken bits through gas distributor;
(3) reaction mass is extracted out by bubble tower or reactor bottom through pump, through injecting by bubble tower or reactor top again after the external heat exchanger cooling, form the outer circulation of reaction mass, the volume ratio of outer circulation amount and inlet amount is greater than 20, and 1～10 minute inner reaction device of reaction mass internal recycle once.
2, preparation method according to claim 1 is characterized in that oxidizing reaction temperature is 40～80 ℃.
3, preparation method according to claim 1 is characterized in that described reaction pressure is 0.1～1.0MPa.
4, preparation method according to claim 1 is characterized in that oxygen aldehyde mol ratio is 0.50～2.00: 1.
5, preparation method according to claim 1 is characterized in that oxygen aldehyde mol ratio is 0.55～0.90: 1.
6, preparation method according to claim 1 is characterized in that reaction raw materials is propionic aldehyde or propionic aldehyde and solvent composition, and the solvent quality composition accounts for 90%～0.5% of reaction raw materials total amount.
7, preparation method according to claim 6 is characterized in that described solvent is acetic acid, propionic acid, butanic acid, isopropylformic acid or sad.
8, preparation method according to claim 1 is characterized in that temperature of reaction passes through material outer circulation mode and control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 03138831 CN1277801C (en) | 2003-07-15 | 2003-07-15 | Method for preparation of propionic acid |
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| CN 03138831 CN1277801C (en) | 2003-07-15 | 2003-07-15 | Method for preparation of propionic acid |
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| CN1569798A CN1569798A (en) | 2005-01-26 |
| CN1277801C true CN1277801C (en) | 2006-10-04 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308281C (en) * | 2005-03-02 | 2007-04-04 | 新疆新峰股份有限公司 | Continuously producing method for proplonic acid by oxidizing propionic aldehyde |
| CN101835733B (en) | 2007-08-21 | 2014-06-25 | 巴斯夫欧洲公司 | Method and apparatus for oxidizing organic compounds |
| CN102108048A (en) * | 2009-12-24 | 2011-06-29 | 四川省申联生物科技有限责任公司 | Method for preparing acetic acid and carboxylic ester |
| CN105254484A (en) * | 2015-11-10 | 2016-01-20 | 天津大学 | Continuous production method and device for preparing propionic acid through air oxidation of propionaldehyde |
| CN110526814A (en) * | 2019-07-27 | 2019-12-03 | 宁夏沃凯珑新材料有限公司 | The method that serialization prepares butyric acid |
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