EP0000532B1 - Procédé de préparation du vinyloxiranne - Google Patents

Procédé de préparation du vinyloxiranne Download PDF

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Publication number
EP0000532B1
EP0000532B1 EP78100418A EP78100418A EP0000532B1 EP 0000532 B1 EP0000532 B1 EP 0000532B1 EP 78100418 A EP78100418 A EP 78100418A EP 78100418 A EP78100418 A EP 78100418A EP 0000532 B1 EP0000532 B1 EP 0000532B1
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acid
hydrogen peroxide
stage
reaction
carboxylic acid
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EP0000532A1 (fr
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Hermann Dr. Seifert
Helmut Dr. Waldmann
Wulf Dr. Schwerdtel
Wolfgang Dr. Swodenk
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

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  • the present invention relates to an improved process for the continuous production of vinyl oxirane.
  • Vinyloxirane the monoepoxide of butadiene, is an important technical intermediate product which, due to its bifunctional character, is widely used in the field of polymers (FC Frostick, B. Phillips and PS Starcher, Journal of Am. Chem. Society, Vol 81, p 3351 (1959)).
  • Vinyloxirane belongs to the class of compounds of epoxy vinyl monomers, which are characterized in that they can be converted into polyethers by reaction of the epoxy ring. These polyethers then contain free vinyl groups suitable for crosslinking or copolymerization with other olefinic compounds. However, it is also possible to polymerize vinyloxirane first on the olefinic double bond of the molecule, so that polymers are then obtained which have epoxy groups in the hydrocarbon chain which can be used for the further reaction.
  • Peracetic acid obtained by oxidation of acetaldehyde is also described in Japanese Patent No. J 7-4046-284 as a suitable reagent for the production of vinyl oxirane. However, no yields are given.
  • British Patent 735,974 (Union Carbide Corp.) proposes using acetaldehyde or propionaldehyde monoperacylate for the epoxidation of butadiene to vinyloxirane, likewise obtained by oxidation of the corresponding aldehydes.
  • alkyl hydroperoxides such as cumene and tert-butyl hydroperoxide
  • tert-butyl hydroperoxide for the epoxidation of dienes under the catalytic influence of molybdenum or vanadium compounds
  • Sheng and Zajacek Journal of Organic Chemistry Vol 35, 6, 1839-1843 (1970)
  • Butadiene can be converted into vinyl oxirane using this process with 85% selectivity leads.
  • the alkyl hydroperoxide R-OOH in this reaction as can be seen from equation (1), in the corresponding alcohol R-OH converted.
  • the hydrocarbon peroxide R-OOH thus acts as an oxygen carrier, so that after the peroxide oxygen has been released, the corresponding alcohol is obtained as a by-product and often has to be removed as an undesirable by-product.
  • the technical application possibilities of such a process are accordingly limited, since the by-product alcohol cannot be used in every case.
  • the process according to the above patent provides a saline wastewater, even if the acetate-containing aqueous solution obtained after neutralization of the acetic acid would be worked up after the addition of a strong acid in order to recover the free acetic acid.
  • Percarboxylic acids suitable for the process according to the invention are those which are derived from aliphatic carboxylic acids having 2 to 5 carbon atoms, such as acetic acid, propionic acid, n-butyric acid, isobutyric acid and valeric acid or trimethylacetic acid and dimethylpropionic acid.
  • acetic acid, perpropionic acid and perisobutyric acid are particularly suitable.
  • Perpropionic acid is particularly suitable.
  • water-soluble acid catalyst e.g. Sulfuric acid or methanesulfonic acid
  • 20 to 50 wt .-% hydrogen peroxide-containing aqueous solution containing the carboxylic acid in pure, undiluted form it is also possible to use a carboxylic acid containing water, a hydrogen peroxide-containing or an acidic catalyst, in which case the concentration of the aqueous solution must be changed accordingly in order to maintain the ratio of hydrogen peroxide, acidic catalyst, carboxylic acid and water required for the reaction.
  • a mixture of carboxylic acid and hydrogen peroxide e.g.
  • the hydrogen peroxide content in the aqueous acidic catalyst and hydrogen peroxide feed solution must then be adjusted in accordance with the hydrogen peroxide content in the carboxylic acid, so that the hydrogen peroxide contained in the carboxylic acid and that in the aqueous solution result in a total use of hydrogen peroxide, which corresponds to a content of 20 to 50 wt .-% hydrogen peroxide in the aqueous solution.
  • the hydrogen peroxide content in the aqueous solution may be less than 20% by weight, e.g. 12 to 19 wt .-%. All conceivable mixing ratios can be used within the stated concentration ratios of catalyst and hydrogen peroxide.
  • An aqueous solution containing 20 to 43, particularly preferably 23 to 38% by weight of acid catalyst and 22 to 35% by weight of hydrogen peroxide is preferably reacted.
  • Sulfuric acid is advantageously used as the water-soluble acid catalyst.
  • Other water-soluble acids can also be used are used, for example sulfonic acids such as methane, ethane, propane, butane, isobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethane, 1-fluoroethane, perfluoroethane, perfluoropropane or perfluorobutanesulfonic acid; Phosphoric acid, phosphonic acids, such as methane or ethanephosphonic acid, phosphinic acids, or acidic salts, such as sodium bisulfate or potassium bisulfate. Mixtures of water-soluble acids can also be used.
  • hydrogen peroxide for example 30 to 90% by weight H 2 O 2
  • H 2 O 2 hydrogen peroxide
  • hydrogen peroxide which is obtained as a by-product of other chemical processes or as a recycle stream, is also suitable.
  • the reaction temperature is generally about 10 to 70 ° C. It is expedient to work at 20-60 ° C. Temperatures below 43 ° C, e.g. Temperatures of 25-43 ° C.
  • reaction is carried out until equilibrium is established between the carboxylic acid and the percarboxylic acid.
  • the pressure is not important for the reaction of the carboxylic acid with hydrogen peroxide, so that it is possible to work at normal pressure, elevated pressures or even at reduced pressure. In general, it is expedient to implement at pressures below 1.1 bar, e.g. at pressures from 0.8 to 1.1 bar.
  • the reaction can be carried out in a wide variety of reaction vessels. It is expedient to ensure a steady concentration profile and in particular to avoid so-called dead zones in which parts of the reaction mixture remain for an unreasonably long time.
  • Suitable are, for example, the usual reaction tubes of different diameters and lengths, which are also used as a closed circuit, e.g. can be arranged as loop reactors, and agitator kettle.
  • reaction mixture from reaction stage (a) is now fed to countercurrent extraction with the inert organic solvent according to (b).
  • This countercurrent extraction can be carried out in one or more extraction units.
  • Suitable solvents for the percarboxylic acids are all water-immiscible organic solvents which are inert to the reaction mixture of reaction (a).
  • aromatic hydrocarbons containing 6 to 10 carbon atoms, aliphatic or cycloaliphatic hydrocarbons each containing up to 12 carbon atoms, chlorinated hydrocarbons containing 1 to 10 carbon atoms and 1 to 4 chlorine atoms, and esters of 1 to 5 C atoms have been found to be suitable containing carboxylic acids with straight-chain or branched alcohols in which there are 1 to 8 carbon atoms in the molecule, and ethers which contain 2 to 10 carbon atoms.
  • Suitable solvents are: benzene, toluene, xylene, n-pentane, isooctane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, 1,2-dichloropropane, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , Isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate, as well as chlorobenzene and ether.
  • solvents for the percarboxylic acid it is also possible to use mixtures of the solvents mentioned as solvents for the percarboxylic acid, in which case the components of the mixture are then advantageously chosen so that they have a similar boiling point.
  • Chlorinated hydrocarbons such as methylene chloride, dichloroethane or dichloropropane, aromatic hydrocarbons such as benzene or ether such as diisopropyl ether or mixtures of these solvents are preferably used.
  • Benzene is very particularly preferably used as the solvent for the process according to the invention.
  • the quantitative ratio of organic solvent to the reaction mixture containing the percarboxylic acid to be extracted is generally 10 to 0.1: 1. However, larger amounts of inert, organic solvent can also be used.
  • the most favorable range in each case of the ratio of the reaction mixture obtained according to (a) to the organic solvent to be used for the extraction according to (b) depends on the particular percarboxylic acid chosen and the extraction properties of the organic solvent and can be easily determined by a person skilled in the art. For the perpropionic acid / benzene system, for example, it is favorable to choose a ratio of 4 to 0.3: 1 of the reaction mixture to be extracted, which was obtained in step (a), and benzene. If the extraction according to (b) is carried out in several extraction units, the amount of organic solvent can vary from unit to unit within the specified limits.
  • the content of percarboxylic acid in the extract can be varied within wide limits by the amount of extractant and by the number of extraction stages.
  • the procedure is such that an approximately 3 to 40% by weight percarboxylic acid is obtained in the organic solvent.
  • An organic extract containing 5-30% by weight of percarboxylic acid is preferably obtained.
  • the number of extraction stages should be as high as possible.
  • an extraction unit with 3 to 10 theoretical extraction stages is sufficient to prepare the solutions with the desired concentration of percarboxylic acids.
  • a percarboxylic acid is used, the corresponding carboxylic acid of which has a higher boiling point than the vinyloxirane and an organic solvent which has a boiling point which is either higher than the boiling point of the carboxylic acid corresponding to the percarboxylic acid, or between the boiling point of vinyloxirane and that of Carboxylic acid is.
  • an inert organic solvent for the percarboxylic acid is preferably a solvent which boils at normal pressure at least 5 ° C. above the boiling point of vinyloxirane and at least 20 ° C. below the boiling point of the percarboxylic acid.
  • the selection of the percarboxylic acid or the corresponding carboxylic acid and the solvent for the process according to the invention is advantageously carried out in such a way that no pronounced azeotropes of binary or external type occur within the combination of carboxylic acid / solvent / vinyloxirane.
  • the temperature during the extraction can be varied within wide limits. In general, temperatures from 10 to 70 ° C. It is expedient to choose the same temperature as in the production of the percarboxylic acid according to (a), so that the other temperatures mentioned for the reaction step (a) are also suitable for the extraction (b). As far as pressure is concerned, work can be carried out at normal pressure, reduced pressure or even at elevated pressures.
  • Suitable are e.g. Mixer-separators, sieve tray extractors, pulsed sieve tray columns or spray columns. However, one-stage or multi-stage centrifugal extractors can also be used.
  • the organic extract also contains small amounts of free hydrogen peroxide, water and traces of the acid used as catalyst, e.g. Sulfuric acid.
  • the raffinate essentially contains the unreacted hydrogen peroxide and the acid catalyst.
  • This is essentially water, hydrogen peroxide and e.g.
  • sulfuric acid-containing raffinate from the extraction is then reprocessed for the reaction of the carboxylic acid and hydrogen peroxide by concentrating all or part of it in a distillation by removing water.
  • the amount of water to be distilled off from the raffinate stream supplied to this concentration essentially corresponds to both the amount of water which is formed when hydrogen peroxide is reacted with the carboxylic acid according to (a) and the amount of water which is used with the fresh hydrogen peroxide to supplement the amounts used is required, is introduced into the process.
  • the top product of the distillation is water, which can contain small amounts of hydrogen peroxide, percarboxylic acid and carboxylic acid.
  • the distillation is carried out under reduced pressure, e.g. at pressures from 10 to 250 torr, preferably 40 to 150 torr, and at temperatures in the swamp from 40 to 120 ° C, preferably from 60 to 85 ° C.
  • the entire raffinate stream leaving the extraction is also suitable for the concentration if the extraction is carried out in a single extraction unit.
  • the reaction mixture obtained in (a) is extracted in, for example, two extraction units, both the raffinate from the first and the raffinate from the second extraction stage can be fed to the concentration. If the raffinate of the first unit is divided into a larger and a smaller partial stream in an extraction that takes place in two extraction units, each of these portions is in principle suitable for the concentration.
  • the raffinate leaving the first unit is divided into a small and a larger partial stream and the smaller portion is fed into the second unit
  • the raffinate from the second extraction unit is advantageously subjected to the distillation for concentration.
  • the fresh hydrogen peroxide to supplement the consumed amounts can be added in any concentration.
  • Commercially available e.g. 30 to 90 wt .-% aqueous hydrogen peroxide, which can be mixed with the usual stabilizers.
  • stabilizers come into consideration, such as those listed in Gmelins “Handbuch der inorganic chemie”, 8th edition, oxygen volume, delivery 7, 1966, on page 2274 and page 2275.
  • the fresh hydrogen peroxide can be mixed with the raffinate to be concentrated from the extraction according to process step (b) before entering the distillation unit; the two streams can also be fed separately into the distillation unit. It is also possible to add the fresh hydrogen peroxide to the raffinate after concentration. It is also possible to add a portion of the fresh hydrogen peroxide to the raffinate before concentration and to add the remaining amount of the fresh hydrogen peroxide to the raffinate after concentration.
  • the known tray columns or packed columns are suitable for distillation.
  • the number of distillation stages is chosen so that the top product contains as little hydrogen peroxide as possible. It is desirable to obtain less than 0.1% by weight of hydrogen peroxide in the condensate.
  • the known evaporators are basically suitable as the evaporator unit. Suitable evaporator units are, for example, in which the residence time of the product is less than 20 minutes, preferably less than 10 minutes. Downflow or thin film evaporators are particularly suitable.
  • Suitable materials for the distillation unit are high-alloy, rustproof stainless steels which essentially contain chromium and nickel in addition to iron, such as a material with the DIN designation 1.4571, which in addition to iron contains 17.5% by weight chromium, 11.5% by weight .-% nickel, 2.25 wt .-% molybdenum, and up to 2 wt .-% manganese, up to 1 wt .-% silicon, up to 0.1 wt .-% carbon and small amounts of titanium, or a material which, in addition to iron, contains 25% by weight chromium, 25% by weight nickel, 2.25% by weight molybdenum and up to 2% by weight manganese, up to 1% by weight silicon, up to 0 , 06 wt .-% carbon and small amounts of titanium and is designated according to DIN with the number 1.4577.
  • Particularly suitable as a material for the destination unit in particular for the evaporator, zircon, zircon-containing materials and
  • This side stream is advantageously removed at a point in the process where the circulating stream has the lowest possible concentration of hydrogen peroxide and acid catalyst and, if appropriate, of percarboxylic acid and carboxylic acid.
  • the raffinate of the extraction before addition of fresh hydrogen peroxide and before concentration according to (c) is particularly suitable for this side stream withdrawal.
  • This side stream which is part of the recycle stream, is an aqueous solution essentially containing hydrogen peroxide and acid catalyst, can either be discarded or be worked up in a regeneration stage. A regeneration of this portion of the circulating stream can be carried out, for example, by distilling off the hydrogen peroxide contained therein in vacuo with water vapor, an aqueous solution of the acid catalyst being obtained as the distillation residue.
  • the aqueous solution containing hydrogen peroxide obtained as a distillate can, if appropriate after concentration, be returned to the process.
  • the aqueous solution of the acidic catalyst can also be returned to the process.
  • a corresponding part of the catalyst e.g. the sulfuric acid, which must be supplemented in the process.
  • the organic extract which essentially contains the percarboxylic acid and the carboxylic acid and is obtained in process step (b) is treated in process step (e) with water or an aqueous solution.
  • the procedure is such that the organic percarboxylic acid extract is washed with water in one of the customary devices.
  • this laundry is convenient to use this laundry as an extraction, e.g. as a multi-stage countercurrent extraction, with water, for example in a three-stage extraction unit.
  • extraction in cocurrent or crosscurrent can of course also be used.
  • the extraction can also be carried out partly in cocurrent and partly in countercurrent.
  • 0.1 to 10% by volume of water or aqueous solution based on the organic extract. Preferably 0.5 to 7% by volume of water is used.
  • an aqueous solution which is essentially free of hydrogen peroxide and mineral acid.
  • an aqueous phase which is obtained in the process.
  • the distillate obtained in carrying out process step (d) is suitable.
  • the aqueous phase of the water treatment can be returned to the extraction according to (b) in order to obtain the proportions of percarboxylic acid, carboxylic acid and hydrogen peroxide contained therein for the process.
  • the known extraction systems are suitable as devices for water treatment according to process stage (e), e.g. Mixer-separators, sieve plate extractors, pulsed sieve plate columns or extraction centrifuges.
  • process stage e.g. Mixer-separators, sieve plate extractors, pulsed sieve plate columns or extraction centrifuges.
  • an essentially hydrogen peroxide and sulfuric acid-free organic solution of the percarboxylic acid is obtained, which is now subjected to the azeotropic distillation according to process step (f), in which contain organic solution water is removed.
  • the water content of the organic solution to be separated is generally 0.5 to 7% by weight. This water content is essentially dependent both on the nature of the organic solvent used in each case and on the selected concentration of percarboxylic acid in the extract obtained in (b).
  • the entrainer used to remove water from the percarboxylic acid organic solution by azeotropic distillation is generally the inert organic solvent. However, it is also possible to add another suitable entrainer to the organic solution of the percarboxylic acid before entering process step (f) or directly into the distillation unit according to (f) and to use it to carry out the azeotropic distillation.
  • the amount of distillate is generally chosen such that the residual water content in the bottom product of the azeotrope column is less than 0.5% by weight, preferably less than 0.2% by weight, e.g. 0.05-0.2% by weight. However, it is also possible to reduce the water content to a negligible value.
  • the entrainer which separates out as the organic phase after condensation of the top vapors of the azeotropic column is fed to the column as reflux.
  • the aqueous phase obtained after condensation of the top vapors which generally contains small amounts of percarboxylic acid, carboxylic acid and hydrogen peroxide, is fed back to the process at a suitable point, for example the extraction according to (e) or (b); however, it can also be removed from the process.
  • the azeotropic distillation (f) can be carried out under normal or reduced pressure, for example at 200 to 400 torr.
  • the bottom temperature is, for example, 30 to 80 ° C. In general, a bottom temperature of below 70 ° C is sufficient.
  • the usual columns for example the known tray or packed columns, are suitable for azeotropic distillation.
  • the usual devices can be used as evaporators. Downflow or thin-film evaporators are particularly suitable.
  • the reaction temperature is preferably kept at 10 to 70 ° C.
  • the reaction of butadiene with the organic solution of percarboxylic acid is very particularly preferably carried out at from 20 to 60.degree.
  • the reaction can also be carried out with the formation of a so-called temperature gradient, which generally increases with the progress of the reaction.
  • the reaction can also be carried out in such a way that a gradient of falling temperature is formed as the reaction proceeds.
  • the pressure when carrying out process step (g) is expediently chosen such that the reaction mixture is essentially in the liquid phase.
  • a molar ratio of butadiene to percarboxylic acid of, for example, 2.5: 1 and at a reaction temperature of 40 to 50 ° C., the pressure is, for example, 2 to 3.5 bar.
  • the molar ratio of butadiene to percarboxylic acid is preferably 1.5 to 4: 1. It is very particularly advantageous to use a molar ratio of 2.0 to 3.0 moles of butadiene per mole of percarboxylic acid.
  • the devices which are customary for reactions of this type can be used to carry out the reaction.
  • a device is used that behaves like a cascade of at least two ideally mixed kettles. It is particularly advantageous to use a reaction system which behaves like a cascade of 4 to 50, preferably 10 to 30, ideally mixed vessels.
  • a sequence of several agitator tanks for example a cascade of 3 to 6 tank reactors.
  • the butadiene can be introduced into the reaction unit in various ways.
  • Butadiene can be used in liquid or gaseous form.
  • the butadiene can also be passed into the reactor unit together with the percarboxylic acid solution. Both feed materials can also be introduced into the reactor separately from one another. It is also possible to pass the butadiene and the percarboxylic acid solution into the reactor unit at various points. When using several reactors connected in cascade, it may be expedient to introduce all of the butadiene into the first reactor. Butadiene can also be divided between the various reactors.
  • the considerable heat of reaction is dissipated by internal and external coolers.
  • the reaction can also be carried out under reflux, ie in boiling reactors.
  • the reaction is conveniently carried out with the most complete possible conversion of the percarboxylic acid men. In general, more than 98% of the percarboxylic acid is converted. It is advisable to convert more than 99% percarboxylic acid.
  • the reaction can be carried out with a particularly high selectivity if it is partially carried out in a reaction tube through which turbulent flow flows and which is connected, for example, to the sequence of agitator vessels. It is particularly favorable to use a reaction tube which is equipped with internals which largely prevent backmixing, for example perforated transverse bottoms.
  • the reaction is first carried out in a few, for example 1 to 3, stirred reaction units connected in series, and the reaction mixture is then passed into a reaction tube to complete the reaction.
  • the reaction tube can be operated under adiabatic conditions; but you can also cool, for example by external cooling, or you can install coolers between individual pipe sections.
  • the dimensioning of a suitable reaction tube depends on the intended throughput. It is essential that the flow rate in the reaction tube is so high that backmixing of the reaction components is essentially excluded.
  • the diameter of the reaction tube can be 0.01 to 10 meters with a length of 1 to 200 meters. You can also operate several pipes in parallel. For example, you can also use tube bundles. If a reaction tube with perforated transverse plates is used, the transverse plates are generally at a distance of 0.1 to 5 m from one another.
  • step g) When carrying out the reaction between butadiene and the percarboxylic acid (step g) according to the invention, it is possible to achieve vinyloxirane yields of over 95%, based on the percarboxylic acid used.
  • the amount of by-products, e.g. the butene (1) diol (3,4) and its mono- and diester with the carboxylic acid corresponding to the percarboxylic acid is less than 2%, based on vinyl oxirane formed.
  • the amount of polymerized butadiene, based on the total amount of butadiene used in the reaction stage according to (g), is less than 1% by weight.
  • the reaction mixture is worked up by distillation, pure vinyloxirane being obtained and excess butadiene, the carboxylic acid and the organic solvent being isolated to such a degree of purity that it can be recycled into the process, which may also be only partial. It is useful to separate vinyl oxirane and the carboxylic acid very quickly.
  • a distillation column is used for this purpose, for example, in which vinyloxirane and butadiene, if appropriate together with lower-boiling constituents and part of the solvent, are initially removed overhead and the remaining solvent and the carboxylic acid are obtained as bottom product.
  • the overhead product is worked up in a further distillation column in order to obtain pure vinyl oxirane.
  • the organic solvent and the carboxylic acid are recovered from the bottoms of these two distillation columns.
  • the distillation residue of carboxylic acid distillation is the small amount of higher-boiling by-products already mentioned.
  • the organic solvent can basically be recovered quantitatively.
  • the reaction mixture can also be worked up by distillation without using a stabilizer. All compounds which are capable of binding oxygen or traces of peroxidic compounds are suitable as stabilizers. These compounds can also contain nitrogen and / or sulfur.
  • Examples include hydroquinone, 4-tert-butyl pyrocatechol, 2,6-di-tert-butyl-4-methylphenol, phenothiazine, N, N-dimethylaniline, tetramethylhydroquinone, N-nitrosodiphenylamine, pyrogallol , 2-methyl-benzothiazole, 6-methoxy-2-amino-benzothiazole, 2,3-dihydroxyquinoxaline and the addition compound of diisobutylene and nitrogen oxide.
  • an aqueous solution containing 30 to 40% by weight of sulfuric acid and 25 to 35% by weight of hydrogen peroxide and (3) propionic acid in a molar ratio of hydrogen peroxide to propionic acid such as 0.9 are simultaneously added via (2) to 1.2: 1 at a temperature of 25 to 45 ° C.
  • the residence time in the reaction system (1) is 10 to 30 minutes.
  • the reaction mixture, which leaves the reaction system (1) via (4), contains about 26 to 32% by weight of perpropionic acid, 12 to 17% by weight of propionic acid, 17 to 21% by weight of sulfuric acid, 5 to 8% by weight. -% hydrogen peroxide and 2 to 5% by weight Caro's acid.
  • an extraction system (5) which consists of a pulsed sieve plate column with 60 to 90 sieve plates and which is charged with benzene with a propionic acid content of less than 0.5% via (6).
  • the raffinate of this extraction which is removed from the extraction system (5) via (7), contains the unreacted hydrogen peroxide and the sulfuric acid in the reaction system (1). It is passed together with about 50% commercially available aqueous hydrogen peroxide, which is fed in via (9), into the distillation unit (8) consisting of evaporator and column, in which at 40-120 torr and a bottom temperature of 60 to 80 ° C.
  • the benzene perpropionic acid extract from the extraction system (5) is passed via (11) into the extraction system (12) consisting of 3 mixer separators, where the extract is extracted in countercurrent with water which is fed in via (13).
  • the amount of water is 3 to 6 percent by volume of the benzene solution.
  • the aqueous phase of this extraction unit (12) is returned to the extraction unit (5) via (14).
  • the water-treated benzene perpropionic acid solution passes through (15) into the distillation unit (16), where an azeotropic dewatering is carried out.
  • the pressure within the distillation system (16) is 100 to 300 torr.
  • the bottom temperature is 50 to 75 ° C.
  • the water content of the benzene perpropionic acid flowing out of the bottom of this column is less than 0.3% by weight.
  • the essentially water and hydrogen peroxide-free benzene perpropionic acid obtained as the bottom of the azeotropic distillation is passed via (17) into the reaction system (18), where the reaction with butadiene in a molar ratio of butadiene to perpropionic acid such as 2 to 4: 1 takes place.
  • the butadiene reaches the reaction system (18) via (19), (20) and (22).
  • the pressure in (18) is 3-5 bar.
  • the reaction system (18) consists of 2 loop reactors connected in series with a downstream retention tube of 10 to 80 m in length.
  • the temperature in the two loop reactors, in which the reactants are mixed by means of a circulation pump, is 20 to 50 ° C.
  • Perpropionic acid is converted to 80 to 95%.
  • the further reaction of the perpropionic acid up to a conversion of 99.8% takes place in the downstream retention tube, which is operated without cooling.
  • the reaction mixture obtained is passed via (23) into an expansion vessel (21) and expanded there.
  • the gas phase obtainable essentially contains butadiene, which is returned to the reaction with perpropionic acid via (22).
  • Vinyloxirane is first separated off from the liquid phase, which passes into the distillation unit (25) via (24), together with butadiene and with part of the benzene by distillation.
  • the stream containing butadiene, vinyloxirane and benzene is fed via (26) to the distillation unit (27), where the further separation of the components takes place and pure vinyloxirane is obtained, which leaves the process via (28).
  • Butadiene is returned to the reaction system (18) via (20).
  • the bottoms from columns (25) and (27) are fed via (29) and (30) to a further distillation unit (31), where benzene is recovered as the top product and returned to the extraction system (5) via (6).
  • the products boiling higher than propionic acid are obtained as the bottom product of distillation (33) and discharged via (34).
  • vinyloxirane can be produced in yields of at least 90%, based on the hydrogen peroxide used, and at least 95%, based on the butadiene used.
  • the mixture now consisting of propionic acid, sulfuric acid, hydrogen peroxide, water and Carosic acid is heated to 40 ° C. for about 18 minutes, 59% of the propionic acid being converted to perpropionic acid.
  • the degassed mixture after having been combined with the mixture of the two aqueous phases running out of the extraction unit (12), is fed to the extraction system (5).
  • the extraction process is carried out at a temperature of 32 ° C.
  • a pulsed sieve plate column is used, which is provided with 80 sieve plates, has a length of 4 m and a diameter of 25 mm, and is equipped at the top and bottom with a separating vessel, in which the phases are separated.
  • the raffinate from the extraction collects as a heavy phase in the lower separating vessel and is continuously removed from there via line (7).
  • This raffinate which is obtained in an amount of about 587 g per hour, contains on average 34.58% by weight of sulfuric acid, 11.16% by weight of hydrogen peroxide, 6.12% by weight of Caro's acid, and 0.1 % By weight propionic acid and 0.06% by weight perpropionic acid.
  • the mixture consisting of the raffinate of the extraction (5) and the aqueous solution of hydrogen peroxide is introduced into the lower part of the column (8).
  • a bottom temperature of 68-70 ° C a temperature at the top of the column of 32 ° C, and a reflux ratio of 0.7 (reflux / withdrawal), 202 ml of water distill over per hour.
  • This distillate contains traces of hydrogen peroxide and 0.2% by weight of perpropionic acid and 0.3% by weight of propionic acid.
  • 619 g of an aqueous solution which in turn contains 32.8% by weight of sulfuric acid, 29.1% by weight of hydrogen peroxide and 5.8% by weight of Caro's acid, are drawn off from the bottom of the column via line (2) per hour . After cooling to room temperature, this mixture is returned to the reaction system (1).
  • the loss of hydrogen peroxide resulting from this cycle exchange is 0.5%, based on the fresh hydrogen peroxide used before the distillation unit (8).
  • the benzene solution of perpropionic acid removed from the extraction system (5) as a light phase is formed via line (11) to the extraction system (12), which is a three-stage mixer-separator battery, each consisting of a mixing pump with a subsequent separating vessel of about 2 liters is fed in and goes through the system from bottom to top.
  • the extraction system (12) which is a three-stage mixer-separator battery, each consisting of a mixing pump with a subsequent separating vessel of about 2 liters is fed in and goes through the system from bottom to top.
  • the mixing pump of the lower stage is fed 67 ml of an aqueous solution per hour, which is obtained if the water phase of the top product of the subsequent azeotropic distillation (distillation unit (16)) is added in an amount of 60 ml per hour is obtained and contains 1.48% by weight H 2 0 2 , 2.43% by weight perpropionic acid and 0.27% propionic acid, mixed with 7 ml deionized water.
  • the benzene solution which is taken from the lower separating vessel as a light phase, is fed together with 17 ml / h fresh water to the mixing pump belonging to the upper mixer-separator unit.
  • the aqueous phase obtained here after phase separation is passed into the middle extraction stage.
  • the aqueous solutions collecting as a heavy phase in the middle and lower separating vessels are combined and re-introduced into the extraction unit (5) via (14) in such a way that this stream, consisting of an aqueous solution, contains 25.23% by weight.
  • the distillation unit (16) is operated at 210 Torr and consists of a thin-film evaporator, a 50 cm long column with 5 bubble-cap trays and a diameter of 50 mm, a condenser and a separator for phase separation of the distillate at the top of the column.
  • the temperature in the bottom of the column is 65 ° C. 60 ml of water and about 915 ml of benzene are obtained as the distillate per hour.
  • the benzene is added to the column as reflux, while the water obtained in the separator, as already described, is introduced as washing water via (35) into the lower stage of the extraction unit (12).
  • the yield of perpropionic acid in the benzene extract thus dried is 96.15% based on the hydrogen peroxide used in the process.
  • the dried benzene solution of perpropionic acid thus obtained is reacted with excess butadiene in a four-stage cascade (reaction system (18)).
  • the reaction is carried out at a pressure of 2 bar.
  • the butadiene is introduced into the first reactor in gaseous form via lines (22), (20) and (19).
  • the first reactor of this four-stage cascade which, like the three subsequent reaction vessels, is equipped with a stirring device and has a content of 1600 ml, is at a temperature of 35 ° C., the second, third and fourth reactor at a temperature of 40 ° each C operated.
  • the perpropionic acid used is converted to 99.8% under these reaction conditions.
  • the reaction mixture which is produced at a rate of 1920 g per hour and on average the composition of 15.62% by weight of butadiene, 11.67% by weight of vinyloxirane, 21.46% by weight of propionic acid and Has 50.08 wt .-% benzene and 0.13 wt .-% water, after cooling to 30 ° C in the separator (21) to normal pressure, a small part of the butadiene (37 g / h) outgassing the (22) is fed back to the reaction system (18).
  • This distillate which contains an average of 32.6% by weight of butadiene, 27.25% by weight of vinyloxirane, 39.9% by weight of benzene and small amounts of water and is obtained at a rate of 822 g per hour, is carried out to the distillation column (27) via (26), where 224 g of a 99.9% vinyl oxirane (product stream 28) and 268 g of butadiene are obtained per hour, which is fed via line (20) into the reaction system (18) .
  • the bottom products of columns (25) and (27) are fed via line (29) and (30) to column (31), where the benzene is recovered as top product at a rate of 961 g / h and then via line (6) is conveyed back into the extraction system (5).
  • the bottom of the column (31) reaches the distillation column (33) via line (32).
  • the top product obtained here is 415 g / h of propionic acid per hour, which are returned to the reaction system (1) via line (3).
  • 15 g per hour of a mixture of higher-boiling compounds are discharged via (34), which essentially contains butane (1) diol (3,4) mono- and dipropionate .
  • the yield of vinyloxirane is thus, based on the perpropionic acid used in the reaction system (18), 96.7% or, based on hydrogen peroxide used in the process at (8) via (9), 93%.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Claims (10)

1. Procédé de préparation du vinyloxirane à partir du peroxyde d'hydrogène et du butadiène, caractérisé en ce que
a) on fait réagir une solution aqueuse contenant de 10 à 45% en poids d'un catalyseur acide hydrosoluble et de 20 à 50% en poids de peroxyde d'hydrogène avec un acide carboxylique contenant de 2 à 5 atomes de carbone dans un rapport molaire peroxyde d'hydrogène/acide carboxylique de 0,5 à 30:1, à des températures de 10 à 70°C,
b) on extrait le mélange de réaction obtenu à contre-courant par un solvant organique inerte,
c) on concentre en totalité ou en partie, par élimination de l'eau par distillation, le raffinat aqueux de l'extraction contenant essentiellement du peroxyde d'hydrogène et le catalyseur acide,
d) on recycle le raffinat concentré et la partie éventuellement non concentrée du raffinat en rétablissant les concentrations en peroxyde d'hydrogène et catalyseur acide hydrosoluble nécessaires pour la réaction avec l'acide carboxylique au stade de réaction (a), le peroxyde d'hydrogène nécessaire pour le rétablissement de la concentration en peroxyde d'hydrogène exigée pour la réaction avec l'acide carboxylique étant ajouté à la partie à concentrer du raffinat avant ou après l'élimination de l'eau par distillation selon (c) ou à la partie du raffinat éventuellement non concentrée,
e) on traite l'extrait organique contenant essentiellement l'acide percarboxylique et l'acide carboxylique par l'eau ou une solution aqueuse et,
f) on soumet l'extrait organique aqueux maintenant pratiquement exempt de peroxyde d'hydrogène à une distillation azéotropique dans des conditions telles que la teneur résiduelle en humidité dans le produit de pied de la colonne azéotropique soit inférieure à 0,5% en poids,
g) on fait réagir la solution organique alors obtenue, contenant de l'acide percarboxylique et l'acide carboxylique avec du butadiène en excès, à un rapport molaire butadiène/acide percarboxylique de 1,5 à 6:1, à des températures de 0 à 80°C et sous une pression de 0,8 bar à 20 bars et,
h) on traite le mélange de réaction contenant le vinyloxirane par distillation en isolant le vinyloxirane pur, en récupérant l'excès de butadiène, l'acide carboxylique et le solvant organique inerte et en les recyclant en totalité ou en partie dans l'opération.
2. Procédé selon la revendication 1, caractérisé en ce que, au stade (a), on utilise une solution aqueuse contenant de 20 à 43% en poids d'acide sulfurique et de 22 à 35% en poids de peroxyde hydrogène.
3. Procédé selon la revendication 1 et 2, caractérisé en ce que l'on utilise au stade (a) le peroxyde d'hydrogène et l'acide carboxylique dans un rapport molaire de 0,5 à 1,3 ou 3,5 à 25:1.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que, au stade (a), l'acide carboxylique utilisé pour la réaction est l'acide acétique, l'acide propionique, l'acide n-butyrique ou l'acide iso-butyrique.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que, au stade (b), on utilise en tant que solvant organique inerte le 1,2-dichloropropane, le chlorobenzène, le toluène, le benzène, l'acétate de n-butyle ou l'éther diisopropylique.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que, au stade (b), on opère avec des proportions relatives de 4 à 0,3:1 entre le solvant organique inerte et le mélange de réaction contenant l'acide percarboxylique obtenu au stade (a).
7. Procédé selon les revendications 1 à 6, caractérisé en ce que, au stade (c), l'élimination de l'eau par distillation est effectuée sous des pressions de 40 à 150 mmHg et à des températures de 60 à 85°C.
8. Procédé selon les revendications 1 à 7, caractérisé en ce que l'on envoie le courant dévié contenant du peroxyde d'hydrogène et de l'acide sulfurique à un stade de régénération et le cas échéant on retourne dans le procédé les fractions récupérées de peroxyde d'hydrogène et d'acide sulfurique.
9. Procédé selon les revendications 1 à 8, caractérisé en ce que, au stade (g), on effectue la réaction à un rapport molaire butadiène/acide percarboxylique de 1,5 à 4:1.
10. Procédé selon les revendications 1 à 9, caractérisé en ce que l'on recycle au stade (b) le solvant organique obtenu au stade (h), au stade (a) l'acide carboxylique obtenu au stade (h) et au stade (g) le butadiène obtenu au stade (h).
EP78100418A 1977-07-29 1978-07-18 Procédé de préparation du vinyloxiranne Expired EP0000532B1 (fr)

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DE2734240 1977-07-29
DE19772734240 DE2734240A1 (de) 1977-07-29 1977-07-29 Verfahren zur herstellung von vinyloxiran

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EP0000532B1 true EP0000532B1 (fr) 1981-10-07

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Publication number Priority date Publication date Assignee Title
FR2421168A1 (fr) * 1978-03-28 1979-10-26 Propylox Sa Procede pour la fabrication de peracides carboxyliques
JPH0375518A (ja) * 1989-08-18 1991-03-29 Tokimec Inc 撓み継手型支持装置およびその装置を有する２軸自由度ジャイロ
US5811601A (en) * 1996-08-09 1998-09-22 The Dow Chemical Company Isomerization of vinyl glycols to unsaturated diols

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GB846534A (en) * 1957-06-04 1960-08-31 Columbia Southern Chem Corp Improvements in and relating to butadiene monoxide
GB1535313A (en) * 1975-02-04 1978-12-13 Interox Chemicals Ltd Production of peracids and of epoxides
DE2519298B2 (de) * 1975-04-30 1981-06-04 Bayer Ag, 5090 Leverkusen Verfahren zur kontinuierlichen Herstellung von Propylenoxid
DE2519297B2 (de) * 1975-04-30 1981-05-14 Bayer Ag, 5090 Leverkusen Verfahren zur kontinuierlichen Herstellung von Propylenoxid
FR2369273A1 (fr) * 1976-10-26 1978-05-26 Propylox Sa Procede pour l'epoxydation d'olefines

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DE2734240A1 (de) 1979-02-08
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EP0000532A1 (fr) 1979-02-07

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