EP0000536B1 - Procédé de séparation de solutions contenant du vinyloxiranne - Google Patents

Procédé de séparation de solutions contenant du vinyloxiranne Download PDF

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Publication number
EP0000536B1
EP0000536B1 EP78100423A EP78100423A EP0000536B1 EP 0000536 B1 EP0000536 B1 EP 0000536B1 EP 78100423 A EP78100423 A EP 78100423A EP 78100423 A EP78100423 A EP 78100423A EP 0000536 B1 EP0000536 B1 EP 0000536B1
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EP
European Patent Office
Prior art keywords
vinyloxirane
column
distillation column
distillation
benzene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100423A
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German (de)
English (en)
Other versions
EP0000536A1 (fr
Inventor
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
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • 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

Definitions

  • the present invention relates to a process for the separation of mixtures which consist essentially of vinyloxirane (the monoepoxide of butadiene), a carboxylic acid, butadiene and benzene.
  • a mixture is generally obtained as the reaction product, which essentially contains vinyloxirane, a low molecular weight carboxylic acid and butadiene (cf.Pudovik and Ivanov, Journal of Gen.Chem. Of USSR, Vol 26, 3087 ( 1956) in English translation, and FC Frostick et al., Journal of Am. Chem. Soc., 81, 3354 (1959), as well as those in Japanese Patent J 7-4046-284 and in German Patent 1 216 306 described method).
  • Such a mixture is very often present as a solution in an organic solvent which has a boiling point which is between that of vinyloxirane and the carboxylic acid.
  • French patent specification 1,468,814 proposes that the reaction mixture obtained after the epoxidation of the butadiene with percarboxylic acids contains free carboxylic acid - in this case acetic acid - which also contains an acetic acid ester as solvent, vinyloxirane and butadiene, with strong bases, such as Alkali or alkaline earth hydroxides, to neutralize the free carboxylic acid, which is thus removed from the reaction with vinyl oxirane. After the neutralization step, the aqueous acetate-containing phase is separated off. In any case, this process provides saline wastewater, which poses particular ecological problems.
  • carboxylic acid containing 1 to 5 carbon atoms formic acid, acetic acid, propionic acid, isobutyric acid, n-butyric acid, n-valeric acid, trimethyl acetic and dimethyl propionic acid may be mentioned.
  • carboxylic acids and questions that are substituted, for example by fluorine or chlorine such as trifluoroacetic acid, monofluoroacetic acid, monochloroacetic acid, 1-chloropropionic acid, 2-chloropropionic acid, 2-fluoropropionic acid, 1-fluoropropionic acid.
  • Mixtures containing vinyloxirane and containing acetic acid, propionic acid, n-butyric acid or isobutyric acid are preferably used for the process according to the invention.
  • the process according to the invention is very particularly suitable for the separation of mixtures containing acetic acid or propionic acid.
  • the concentration of vinyloxirane and carboxylic acid in the starting benzene solution can vary within wide limits. In general, the concentration of vinyloxirane is 1 to 50, preferably 3 to 30% by weight. Solutions with a vinyloxirane content of 5 to 20% by weight are very particularly suitable.
  • the carboxylic acid content is generally 3 to 50, preferably 5 to 40,% by weight.
  • the butadiene content can be up to the solubility limit of butadiene in the mixture to be separated. Small amounts of other compounds may also be present. It is particularly advantageous to apply the process according to the invention to mixtures which are obtained in the production of vinyloxirane by reacting butadiene with a percarboxylic acid in a benzene solution.
  • Such mixtures generally contain small amounts of acetaldehyde, methyl formate, propionaldehyde, methacrolein, crotonaldehyde, butene- (1) -diol- (3,4) -mono- and diester and butene- (1) -diol- (3,4 ) itself.
  • Such mixtures can also contain small amounts of free hydrogen peroxide.
  • the proportion of benzene in the mixture to be separated by the process according to the invention is generally 20 to 80% by weight. In special cases, this concentration range can also be exceeded or fallen below. Mixtures containing 30 to 70% by weight of benzene are particularly suitable for the separation according to the invention.
  • the mixtures obtained by the process according to the invention can contain small amounts of water. Water contents of up to 5% by weight are generally of no importance for the process. However, mixtures which contain less than 3% by weight of water are advantageously used.
  • the process according to the invention is very particularly suitable for the separation of solutions whose water content is below 1.0% by weight, for example solutions with a water content of 0.05-1.0% by weight.
  • a mixture of the composition described is metered into the first distillation column and a butadiene, vinyloxirane and part of the benzene at a pressure of 0.5 to 2.5, preferably 1.0 to 2.0 bar containing overhead product distilled off.
  • the amount of benzene which is also distilled off at the top is generally 20 to 70, preferably 25 to 70,% by weight of the top product.
  • the distillate particularly preferably contains 30 to 50% by weight of benzene.
  • the head is temperature of the distillation column generally 35 to 80 ° C.
  • a particular advantage of the process according to the invention is that water can be used for cooling at the top of the column, a cooling water temperature of 20 to 35 ° C. being sufficient. This means that cooling water can be used that is available in large quantities as backflow from the cooling towers of technical systems.
  • the top product of the first distillation column is passed into the second distillation column.
  • butadiene optionally together with compounds which have a lower boiling point than vinyloxirane, e.g. the butenes, distilled off and vinyl oxirane obtained as the bottom product and the part of the benzene distilled over in the first column.
  • Part of the bottom product of the second distillation unit is returned in the required amount as reflux to the first distillation unit. The remaining portion of the bottom product of the second distillation column is removed.
  • the reflux ratio in the first distillation column in the process according to the invention is generally 3 to 0.1, frequently 2.4 to 0.3. It is preferably 2.0 to 0.4. A reflux ratio of 1.5 to 0.5 is particularly advantageous.
  • the pressure in the second distillation column can be varied within wide limits and it can be distilled at normal pressure, elevated pressures or at reduced pressure.
  • the second distillation column is preferably operated at elevated pressure. It is particularly advantageous to operate the column at such a high pressure that a substantial part of the vaporous overhead product can be condensed with water at the top of the column. However, it is also possible to condense the entire top product with water or brine.
  • the second distillation column is operated at pressures from 1.1 to 40 bar. A preferred pressure range is pressures from 1.5 to 15 bar.
  • the pressure in the second distillation column is very particularly advantageously chosen so that after complete condensation of the butadiene-containing top product of this column, it can be obtained as a liquid phase at a temperature above 0 ° C.
  • the condensation in the second distillation unit is carried out in the usual way.
  • the butadiene obtained at the top can optionally be condensed in a mixture with butenes and the liquid top product returned to the column as reflux and discharged from the column in liquid form.
  • a dephlegmator can also be used as the condensation unit, butadiene leaving the distillation column in gaseous form.
  • the gaseous butadiene can, for example, be freed from vinyloxirane which may be present in the outgassing butadiene by washing with a suitable solvent.
  • the gaseous butadiene washed in this way can, however, also be liquefied, for example by compression, and returned in whole or in part as reflux to the second column.
  • An appropriate reflux ratio in this second distillation column can easily be determined. Basically, it can be varied within wide limits. It can be values from 0.1 to 10, for example.
  • a reflux ratio which may be used in this order of magnitude does not imply any particular technical outlay for the process, since essentially only butadiene, optionally in a mixture with butenes, is present at the top of this second distillation column. The total amount of this butadiene / butene mixture is so small that even a high reflux ratio means no special effort.
  • All conventional devices for example packed columns or tray columns, are suitable as distillation columns for the first and second distillation stages. All common shapes are suitable as fillers and bottoms.
  • the known devices such as circulation evaporators, thin-film evaporators or falling-film evaporators can also be used as evaporators.
  • the mixture containing vinyloxirane and carboxylic acid can be passed into the first distillation unit in liquid or gaseous form. But you can also use special implementation methods of product feed.
  • the liquid mixture can be passed through an evaporator unit, for example a thin-film evaporator, and the gas and liquid from this evaporation stage can be introduced separately into the column. This can be advantageous in that a particularly rapid separation of vinyloxirane and carboxylic acid can be achieved.
  • stabilizers or inhibitors are to be understood as compounds which are capable of moderatingly influencing the polymerization tendency of vinyloxirane and butadiene.
  • stabilizers or inhibitors are to be understood as compounds which are capable of moderatingly influencing the polymerization tendency of vinyloxirane and butadiene.
  • all those compounds are possible which, due to their chemical structure, can bind or destroy oxygen or traces of peroxidic compounds. These compounds can also ent nitrogen and / or sulfur hold.
  • Examples include hydroquinone, 4-tert-butyibrate catechol, 2,6-di-tert-butyl-4-methylphenol, alkylanthrahydroquinones, phenothiazine and its derivatives, N, N-dimethylaniline, tetramethylhydroquinone, N-nitroso diphenylamine, pyrogallol, 2-methyl-benzothiazole, 6-methoxy-2-amino-benzothiazole, 2,3-dihydroxyquinoxaline and the addition compound of diisobutylene and nitrogen oxide. Mixtures of these compounds can of course also be used. If the stabilizer is used in solution, it is advantageous to use carboxylic acid or benzene as the solvent.
  • the amounts of stabilizer can vary within wide limits. In general, it is sufficient to use 0.05 to 0.5% by weight of stabilizer, based on the amount which reaches the first distillation unit.
  • the stabilizer or its solution can be added to the mixture to be separated, which essentially contains vinyloxirane, butadiene, the carboxylic acid and benzene, before entering the first distillation unit. This measure generally gives satisfactory results. It is more advantageous to add the stabilizer to the reflux on the first distillation column.
  • the stabilizer it is particularly advantageous to add the stabilizer to the inlet into the second distillation column, which enables it to run through the process according to the invention as follows: After passing through the stripping section of the second distillation column, the stabilizer comes in because it has a higher boiling point than the butadiene the bottom of this column and from there is partially fed with the reflux for the first distillation unit of the process to this first column, which it passes through from top to bottom. Ultimately, the stabilizer or its reaction products with the bottom product of the first column, which contains the carboxylic acid and benzene, are discharged from the process.
  • a distillation line consisting of 2 columns (1) and (2) is used.
  • % 4-tert-butylbrenzka-techin has been added.
  • the second distillation column (2) is operated at a pressure of 2 to 3 bar.
  • the bottom of this second column heated with the evaporator (9) is a butadiene-free mixture of about 45 to 55% by weight of benzene and about 45 to 55% by weight of vinyloxirane, which is released via (10) and the cooler (11) Part is passed as reflux to the column (1).
  • the reflux ratio in column (1) is 0.5 to 1.5.
  • the other part of the butadiene-free bottom from column (2) is removed via (12) and represents the desired carboxylic acid-free solution of vinyloxirane in benzene.
  • the butadiene is obtained in liquid form at the top of the column (2), which is partly given via (14) as reflux to column (2).
  • the remaining butadiene is removed via (15).
  • the particular advantage of the process according to the invention is that the formation of reaction products of vinyloxirane with the carboxylic acid is reduced so much that this by-product formation can no longer be detected using the customary analytical methods.
  • Another advantage of the process according to the invention is that the condensation in the first column can be carried out using water as the coolant, a water temperature of 20 to 30 ° C. being sufficient.
  • a particular economic advantage of the process according to the invention is the lossless separation of the vinyloxirane from a low molecular weight aliphatic carboxylic acid by distillation with a surprisingly low reflux ratio.
  • the distillation column (1) is fed 2 720 g per hour of a reaction mixture from the reaction of excess butadiene with a benzene solution of perpropionic acid to produce vinyloxirane via (3).
  • the mixture fed into column (1) contains 12.0% by weight of vinyl oxirane, 21.7% by weight of propionic acid, 52.25% by weight of benzene and 13.8% by weight of butadiene and small amounts of water, butene- 1) diol (3,4) monopropionate and low-boiling by-products.
  • this mixture is 0.5 g / h of N-nitrosodiphenylamine, dissolved in 10 ml of benzene, added.
  • the column (1) has a length of 3.6 m, 1.2 m being accounted for by the amplifier section.
  • the column is filled with 4 x 4 mm glass Raschig rings.
  • the diameter of the column is 5 cm.
  • the column is provided with a condensation device (5) for the top product and an evaporator unit (8).
  • the pressure in the column is 1 bar.
  • 2,120 of a mixture are obtained as distillate in the hour after condensation, which in addition to 39.1% by weight vinyloxirane and 17.8% by weight.
  • % Butadiene still contains 42.2% by weight of benzene.
  • the water content in this distillate is less than 1% by weight.
  • distillate from column (1) (2120 g / h) is introduced into the second column.
  • the column (2) has a length of 2.6 m, a diameter of 2.5 cm and is filled with 4 x 4 mm glass rings.
  • the inflow into the column is in the middle.
  • the column is operated at a pressure of 1.7 bar.
  • the bottom temperature is 78 to 80 ° C; the temperature at the head 3 to 5 ° C.
  • the reflux ratio is 0.7. After condensation and separation of small amounts of water, butadiene (373 g / h) is obtained as the top product, which has a purity of more than 98.5% by weight.
  • the bottom product which is drawn off in an amount of 1,742 g / h, contains 47.6% by weight of vinyloxirane and 51.3% by weight of benzene. From this product stream, which is free of butadiene, 1,060 g per hour are added as reflux to the first column, while the rest is simply separated into pure vinyloxirane and benzene in a subsequent distillation stage. The ratio of reflux to top draw in the first column is therefore 0.5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Claims (8)

1. Procédé pour séparer les composants d'une solution contenant principalement du vinyloxirane, du butadiène, un acide carboxylique présentant 1 à 5 atomes de carbone et du benzène par distillation, caractérisé en ce qu'on fait arriver la solution à une première colonne de distillation et on sépare par distillation en courant aérien à une pression de 0,5 à 2,5 bars le butadiène, le vinyloxirane et autant du benzène contenu dans la solution qu'il en faut pour que le produit de tête de cette première distillation contienne 20 à 70 % en poids de benzène, l'acide carboxylique et le benzène résiduel étant obtenus comme produit de queue, et en ce qu'on introduit le produit de tête de la première distillation dans une seconde colonne de distillation dans laquelle le butadiène et, le cas échéant, de faibles proportions de composants de plus bas point d'ébullition que le vinyloxirane sont séparés par distillation en tête et on obtient un produit de queue principalement formé de vinyloxirane et de benzène qui est en partie recyclé comme reflux dans la première colonne de distillation.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on prélève dans la première colonne de distillation un produit de tête qui contient 25 à 70 % en poids de vinyloxirane.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'on fait fonctionner la première colonne de distillation à des pressions de 1,0 à 2,0 bars et la seconde colonne de distillation à des pressions de 1,5 à 15 bars.
4. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'on fait fonctionner la première colonne de distillation avec un rapport de reflux de 2,0 à 0,4.
5. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on choisit la pression dans la seconde colonne de distillation de manière qu'après la condensation totale du produit de tête de cette colonne, ce produit soit obtenu à des températures de plus de 0°C comme phase liquide.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce qu'on utilise dans la séparation une solution contenant du vinyloxirane qui renferme moins de 3% en poids d'eau.
7. Procédé suivant les revendications 1 à 6, caractérisé en ce que la solution contenant du vinyloxirane, devant être séparée en ses composants, est additionnée, avant son introduction dans la première colonne de distillation, d'un agent stabilisant ou de la solution d'un agent stabilisant.
8. Procédé suivant les revendications 1 à 7, caractérisé en ce que l'agent stabilisant est ajouté au produit de tête de la première colonne de distillation avant l'introduction dans la seconde unité de distillation.
EP78100423A 1977-07-29 1978-07-18 Procédé de séparation de solutions contenant du vinyloxiranne Expired EP0000536B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734241 1977-07-29
DE19772734241 DE2734241A1 (de) 1977-07-29 1977-07-29 Verfahren zur auftrennung vinyloxiranhaltiger loesungen

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EP0000536A1 EP0000536A1 (fr) 1979-02-07
EP0000536B1 true EP0000536B1 (fr) 1981-12-02

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EP78100423A Expired EP0000536B1 (fr) 1977-07-29 1978-07-18 Procédé de séparation de solutions contenant du vinyloxiranne

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JP (1) JPS5427512A (fr)
DE (2) DE2734241A1 (fr)

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JPS60252804A (ja) * 1984-05-28 1985-12-13 Nissan Motor Co Ltd シリンダ装置
JPS6367411A (ja) * 1986-09-10 1988-03-26 Kubota Ltd ストロ−クセンサ内蔵型シリンダ装置
KR20060052774A (ko) * 2003-07-01 2006-05-19 티악스 엘엘씨 용량성 위치 센서 및 감지 방법
CA2807143C (fr) 2010-08-04 2020-04-28 Silgan Plastics Corporation Procede et appareil de moulage par soufflage pour la formation d'un recipient en plastique compressible

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Publication number Priority date Publication date Assignee Title
GB846534A (en) * 1957-06-04 1960-08-31 Columbia Southern Chem Corp Improvements in and relating to butadiene monoxide
DE2519292C3 (de) * 1975-04-30 1979-03-29 Bayer Ag, 5090 Leverkusen Verfahren zur Auftrennung einer im wesentlichen Propylenoxid, Propylen, eine 1-4 Kohlenstoff atome aufweisende Carbonsäure und Benzol enthaltenden Losung

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JPS5427512A (en) 1979-03-01
DE2734241A1 (de) 1979-02-08
DE2861398D1 (en) 1982-01-28
EP0000536A1 (fr) 1979-02-07

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