EP1848682A1 - Procede pour recuperer des composes organiques de melanges contenant de l'acide (meth)acrylique par extraction avec un solvant protogene - Google Patents

Procede pour recuperer des composes organiques de melanges contenant de l'acide (meth)acrylique par extraction avec un solvant protogene

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Publication number
EP1848682A1
EP1848682A1 EP06706721A EP06706721A EP1848682A1 EP 1848682 A1 EP1848682 A1 EP 1848682A1 EP 06706721 A EP06706721 A EP 06706721A EP 06706721 A EP06706721 A EP 06706721A EP 1848682 A1 EP1848682 A1 EP 1848682A1
Authority
EP
European Patent Office
Prior art keywords
acrylic acid
meth
composition
aldehyde
phase
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.)
Withdrawn
Application number
EP06706721A
Other languages
German (de)
English (en)
Inventor
Torsten Balduf
Andreas Sabbagh
Thomas Nehrkorn
Manfred Lucas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Stockhausen GmbH
Chemische Fabrik Stockhausen GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stockhausen GmbH, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH
Publication of EP1848682A1 publication Critical patent/EP1848682A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a process for producing (meth) acrylic acid, an apparatus for producing (meth) acrylic acid, foams, molded articles, fibers and the like based on (meth) acrylic acid obtained by the process of the present invention and the use of the process according to the invention obtained (meth) acrylic acid in such products.
  • (meth) acrylic acid is understood as meaning both methacrylic acid and acrylic acid, acrylic acid being preferred.
  • acrylic acid and especially acrylic acid is a monomer used today in many polymers.
  • acrylic acid is used in the preparation of polymers which are used for water treatment, for example as flocculants, or which are incorporated as superabsorbent polymers into hygiene articles, in particular diapers (cf Modern Supersorbent Polymer Technology, FL Buchholz, AT Graham, Wiley -VCH 1998).
  • acrylic acid and frequently also methacrylic acid can often be prepared by heterogeneously catalyzed gas phase oxidation of propylene or isobutene with oxygen at generally solid state at temperatures between 200 and 400 ° C.
  • WO 03/051809 A1 it is known from WO 03/051809 A1 to bring a product gas comprising (meth) acrylic acid obtained from the gas-phase oxidation of propylene into contact with an aqueous phase and obtaining an aqueous quench phase.
  • the (meth) acrylic acid is also accompanied by various other reaction products which are regarded as impurities and moreover by water as absorption medium.
  • This fact usually makes it necessary to supply the quenching phase obtained above to at least one further purification process.
  • this purification process is a distillation in which, in particular, the absorbent, if appropriate in the presence of an entraining agent, is separated off and a so-called crude (meth) acrylic acid is obtained.
  • This crude (meth) acrylic acid can then be further purified by distillation for the purpose of separating any remaining light or high-boiling by-products.
  • hi usually contains the crude (meth) acrylic acid or optionally distillatively further purified crude (meth) acrylic acid nor a non-negligible amount of aldehydes such as benzaldehyde or furfural.
  • aldehydes hinder the polymerization of acrylic acid and also lead to discolored polymers.
  • these aldehydes are questionable for health reasons, so that (meth) acrylic acid, which is used in particular for the production of hygiene articles, must have a particularly high purity with regard to aldehydes.
  • WO 03/014172 A1 proposes adding to the crude (meth) acrylic acid so-called aldehyde scavengers which react with the aldehydes to form high-boiling reaction products.
  • the (meth) acrylic acid can then be separated by distillation. The costs incurred in this distillation the, the high-boiling reaction products containing bottom product is usually disposed of by incineration.
  • the aldehyde scavengers are usually used in excess in view of the aldehydes present in the crude (meth) acrylic acid in order to ensure as complete a conversion of the aldehydes into the high-boiling reaction products.
  • This has the consequence that contained in the bottom product, unreacted aldehyde scavenger is lost in the above-mentioned disposal of the bottom product, which is particularly disadvantageous for cost reasons.
  • mercaptans are used as aldehyde captors, the high proportion of sulfur compounds in the bottom product when burned lead to a significant environmental impact.
  • the present invention has the object to overcome the disadvantages resulting from the prior art.
  • the object of the present invention was to provide a process by which (meth) acrylic acid can be prepared as inexpensively as possible with extremely low residual content of aldehydes and thus with the lowest possible toxicological load.
  • a process for the preparation of (meth) acrylic acid comprising the following process steps: i) contacting a composition Z 1 comprising (meth) acrylic acid and aldehydes with an aldehyde-scavenger at a temperature in a range of 10 to 100 ° C and at a pressure in a range of 0.1 to 10 bar to obtain a composition Z 2 , including
  • Z 2 b is a preferably high-boiling reaction product of the aldehyde and the aldehyde scavenger and Z 2 C unreacted aldehyde scavenger;
  • composition Z 3 comprising Z 3 a the preferably high-boiling reaction product of the reaction between the aldehyde and the aldehyde-scavenger and Z 3 b unreacted aldehyde scavenger;
  • Phase P 1 less protic, preferably organic phase P 2 is obtained;
  • composition Z 1 is used in method step i) as composition Z 1 , which was obtained by a method comprising the method steps:
  • the oxidation of the C 3 -C 4 -hydrocarbons in process step a), which in the case of the preparation of acrylic acid is preferably propane, propylene and / or acrolein and in the case of the preparation of methacrylic acid is preferably isobutylene, Meth) acrylic acid in the gas phase is carried out in a manner known per se.
  • the optionally mixed with an inert diluent gas feed is mixed with oxygen at elevated temperatures, usually 200 to 400 ° C, and optionally elevated pressure via at least one heterogeneous catalyst, usually transition metal, z. B.
  • molybdenum, vanadium, tungsten and / or iron-containing mixed oxide catalysts passed while oxidatively converted to (meth) acrylic acid passed while oxidatively converted to (meth) acrylic acid.
  • the implementation can be carried out in one or two stages.
  • the propylene or isobutylene preferably used as starting compound is oxidized in a first stage to (meth) acrolein in a two-stage reaction and the (meth) acrolein is oxidized in a second stage to (meth) acrylic acid.
  • Heterogeneous catalysts which are preferred in the first stage are multicomponent oxidic catalysts based on the oxides of molybdenum, bismuth and iron and, in the second stage, corresponding catalysts based on the oxides of molybdenum and vanadium.
  • the conversion of propane, propylene or isobutylene to (meth) acrylic acid is highly exothermic.
  • the feed stream is therefore advantageously mixed with an inert diluent gas, e.g. As air nitrogen, carbon dioxide, methane and / or water vapor diluted.
  • an inert diluent gas e.g. As air nitrogen, carbon dioxide, methane and / or water vapor diluted.
  • reaction gases obtained in the one or two-stage catalytic gas-phase oxidation contain, in addition to (meth) acrylic acid, usually unreacted starting compounds, water vapor, carbon monoxide, carbon dioxide, Nitrogen, oxygen, acetic acid, propionic acid, formaldehyde, other aldehydes and maleic acid or malic anhydride.
  • process stage b the workup of the product gas mixture obtained in process step a) begins. Two different procedures are conceivable.
  • (meth) acrylic acid is absorbed from the reaction gases in an absorption liquid.
  • the absorption liquid liquids are suitable in which (meth) acrylic acid has a pronounced solubility, for. B. higher than (meth) acrylic acid boiling liquids.
  • oligomeric acrylic acids such as mixtures containing di-, tri- and tetraacrylic acid, can be used as a high-boiling liquid.
  • Diphenyl, diphenyl ether, o-dimethyl phthalate or mixtures thereof are preferred, in particular a mixture of 25 to 30% by weight of diphenyl and 70 to 75% by weight of diphenyl ether, based on the mixture, from 0.1 to 25% by weight. Contains o-dimethyl phthalate.
  • water is used as the absorption liquid.
  • the absorption liquid is intimately contacted with the product gas mixture in an appropriate manner.
  • the product gas mixture is expediently carried in an absorption column in countercurrent to the descending absorption liquid.
  • absorption column can be z. B. use a packed, packing, valve bottom or bubble tray column.
  • the reaction gases which generally have a temperature of 200 to 400 ° C, before being introduced into the absorption column, preferably to a suitable absorption temperature of, for example, 100 to 18O 0 C cooled.
  • the cooling of the reaction gases to the absorption temperature can be achieved by indirect cooling, for. B. by means of a heat exchanger can be made. However, this cooling is preferably carried out by direct contact with a cooling liquid, preferably in a spray scrubber. Before the reaction gases enter the absorption column, the cooling liquid is expediently again largely separated, cooled and recycled in a separator.
  • the cooling liquid is preferably identical to the liquid used for the subsequent absorption of the acrylic acid from the reaction gases.
  • the absorption liquid laden with (meth) acrylic acid usually also contains volatile impurities, such as water, acrolein, formaldehyde and also formic acid and acetic acid. Secondary components such as water, acrolein, formaldehyde and acetic and formic acids can be at least partially removed by stripping with a stripping gas, in particular when using a high-boiling liquid as the absorption liquid.
  • a stripping gas such as nitrogen or air, out.
  • the required Strippgasmenge depends mainly on the desorption temperature, which is advantageously 20 to 5O 0 C higher than the absorption temperature; it is preferable to operate at the same pressure as in the absorption step.
  • the stripping gas is preferably, based on the amount of reaction gas, 5 to 25 vol .-%.
  • the desorption column may, for. B. be a packed, packing, valve bottom or bubble tray column.
  • the cooling liquid and / or the absorption liquid usually contain z.
  • at least one process polymerization inhibitor such as phenothiazine, phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, p-nitrosophenol, tert-butylphenols, 1-oxyl-2,2,6,6 tetramethylpiperidin-4-ol or mixtures thereof.
  • the composition Z 3 also referred to as crude (meth) acrylic acid, is then isolated.
  • a high-boiling liquid as the absorption liquid is usually a rectificative separation of the crude (meth) acrylic acid.
  • the rectifiable separation is advantageously carried out under reduced pressure, for. B. 0.04 to 0.1 bar, z. B. in a packed or tray column.
  • a polymerization inhibitor is advantageously added at the top or in the upper region of the rectification column.
  • the crude (meth) acrylic acid can be removed as an overhead product; however, it is preferably taken off via a side draw in the upper region of the rectification column, with small amounts being withdrawn more easily than (meth) acrylic acid boiling impurities, such as water and acetic acid, at the top of the column.
  • the high-boiling liquid obtained after separation of the crude (meth) acrylic acid is expediently recycled and reused for absorption.
  • ester-like oligomeric (meth) acrylic acids present as impurity split up and the resulting ( Meth) acrylic acid distilled off together with the high-boiling liquid.
  • the maleic acid or its anhydride which is still present in particular in the preparation of acrylic acid can be used in a conventional manner before the reuse of the high-boiling liquid, for. B. by extraction with water.
  • the crude (meth) acrylic acid is preferably isolated from the aqueous (meth) acrylic acid solution obtained by extraction with an extractant and subsequent distillation of the extract ,
  • the extractant should have a high distribution coefficient for (meth) acrylic acid and a low solubility in water and it must be an azeotrope with water form.
  • Lower-boiling (meth) acrylic acid-extracting agents such as ethyl acetate, butyl acetate, ethyl acrylate, 2-butanone or mixtures thereof, or higher than (meth) acrylic acid boiling extractants can be used.
  • toluene is a particularly preferred extractant.
  • the aqueous (meth) acrylic acid solution is suitably passed in an extraction column countercurrent to the selected extractant.
  • crude (meth) acrylic acid is then separated by distillation.
  • the performance of the distillation depends on whether a higher or lower than (meth) acrylic acid boiling extractant is used.
  • the extract is supplied, for example, to a solvent separation column in which the extractant and residual amounts of water are distilled off overhead.
  • the bottoms fraction of the solvent separation column is then advantageously fed to a low-boiling column in which impurities boiling more easily than (meth) acrylic acid are removed overhead and crude (meth) acrylic acid is obtained as bottoms fraction.
  • a further removal of high-boiling impurities from this crude (meth) acrylic acid by means of a further distillation step.
  • crude (meth) acrylic acid can also be obtained by fractional condensation of the reaction gases, optionally with subsequent crystallisative purification.
  • reaction gases whose temperature is preferably by direct cooling with a cooling liquid to z. B. 100 to 180 ° C has been reduced, conveniently in the lower part of a
  • a crude (meth) acrylic acid fraction as composition Z 1 can be removed as a medium boiling fraction by means of a suitably attached catch bottom.
  • Such a method is z. B. in DE 197 40 253 or DE 197 40 252 described.
  • In the column is usually added to a process polymerization inhibitor, such as those mentioned above.
  • the crude (meth) acrylic acid fraction of the composition Z 3 obtained in the fractional condensation can be subjected to crystallization for the purpose of further purification.
  • the crystallization process is subject to no restriction.
  • the crystallisative purification, if used, is carried out as suspension crystallization.
  • composition Z 1 a crude (meth) acrylic acid containing aldehydes is obtained as composition Z 1 .
  • the composition Z 1 used is a crude (meth) acrylic acid which is obtained by absorption of the product gas mixture with water in a quench tower and subsequent removal of the water by azeotropic distillation in the presence of toluene as entrainer as bottom product was obtained, wherein advantageously still existing low and high boiling impurities were separated by further distillation steps.
  • aldehydes which in the case of the production of acrylic acid are, for example, benzaldehyde, acrolein or furfural, 0.001 to 1 wt .-%, preferably 0.01 to 0.5 wt .-% and particularly preferably 0.05 to 0.2 wt .-% water,
  • composition Z 1 is brought in process step i) into contact with an aldehyde at a temperature in a range of 10 to 7O 0 C, preferably in a range of 15 to 50 ° C and particularly preferably in a range of 20 to 30 ° C wherein room temperature is most preferred, and at a pressure in a range of 0.1 to 10 bar, preferably in a range of 0.5 to 5 bar, and most preferably in a range of 0.9 to 2 bar, wherein Atmospheric pressure is most preferred, to obtain a composition Z 2 comprising (meth) acrylic acid, preferably high-boiling reaction product of the aldehyde and the aldehyde scavenger and unreacted aldehyde scavenger.
  • aldehyde scavengers it is possible according to the invention to use all compounds which, with aldehydes, preferably form high-boiling reaction products under the abovementioned pressure and temperature conditions.
  • Nitrogen compounds having at least one primary amino group such as aminoguanidine salts, hydrazine, alkyl- and arylhydrazines, carboxylic acid hydrazides or aminophenols, may be mentioned as possible aldehyde-scavengers.
  • mercaptans preferably C 6 - to C 2 o-mercaptans, more preferably C 8 - to C 16 -mercaptans.
  • dodecylmercaptan is dodecylmercaptan.
  • the aldehyde-capturing agent is preferably used in excess of the aldehyde present in the crude (meth) acrylic acid, preferably in an amount of from 1.1 to 5 mol, more preferably from 1.5 to 2.5 mol, per mole of aldehyde. Usually, a reaction time of 10 minutes to 72 hours, preferably 1 hour to 50 hours, more preferably maintained 1.1 to 10 hours.
  • the residual aldehyde content of the crude (meth) acrylic acid can be reduced to below 20 ppm, in particular below 5 ppm, particularly preferably below 3 ppm.
  • the contacting of the composition Z 1 with the aldehyde scavenger can be effected, for example, by introducing the aldehyde scavenger directly into a pipeline, by means of which the crude (meth) acrylic acid is passed on for further work-up. It is also conceivable to add the aldehyde catcher in a residence time in which the crude (meth) acrylic acid is stored before it is fed to further workup.
  • this fixed bed reactor is a reactor comprising a reaction space and a stationary packed bed (a porous fixed bed) located in the reaction space.
  • the porous fixed bed is preferably introduced in bulk on a carrier arranged in the reactor, such as a filter.
  • the porous fixed bed comprises packed bulk materials such as Raschig rings, Berl saddles, Walox saddles or Pall rings, or else spherical fillers, ball shaped fillers being the most preferred.
  • these fillers are based on an ion exchange material, preferably on an ion exchange material. zeolite material.
  • a fixed bed reactor is used, which contains on a sieve in bulk supported ion exchange balls.
  • the (meth) acrylic acid is at least partially separated from the composition Z 2 obtained in process step i), which contains the preferably high-boiling reaction products from the reaction between the aldehyde scavenger and the aldehyde and unreacted aldehyde scavenger in addition to (meth) acrylic acid , Accordingly, the composition Z 2 differs from the composition Z 1 essentially in that it contains less (meth) acrylic acid compared to the composition Z 1 . It is preferred that more than 50% by weight, preferably more than 75% by weight, more preferably more than 95% by weight and most preferably more than 99% by weight of the composition Z 1 contained (meth) acrylic acid is separated.
  • this separation is carried out by distillation.
  • distillative separation is intended both a simple distillation, d. H. a distillation in which there is essentially no mass transfer between condensate and vapors, as well as a rectification in which a portion of the condensate is passed in countercurrent to the ascending vapors comprise.
  • the distillation can be carried out in process step ii) by distillation apparatuses known to the person skilled in the art.
  • step ii) In the distillation in process step ii) is obtained as a top product or in a side stream (depending on the type of distillation process chosen) a pure (meth) acrylic acid as the target product, while the bottom product
  • Composition Z 3 comprising, in addition to still present (meth) acrylic acid, the preferably high-boiling reaction product of the aldehyde and the aldehyde-catcher and unreacted aldehyde-catcher.
  • this composition Z 3 is based on:
  • the unreacted aldehyde scavenger is extracted from the bottom product obtained in process step ii) with (composition Z 3 ) by means of a protic solvent, preferably by means of an aqueous phase, more preferably by means of water.
  • the composition Z 3 is from 1 to 75 wt .-%, more preferably 2.5 to 50 wt .-% and most preferably 5 to 25 wt .-% of Solvent, preferably the aqueous phase, especially water, in each case based on the weight of the composition Z 3 , brought into contact, the bringing into contact preferably at a temperature in a range of 15 to 50 ° C, particularly preferably 20 to 30 ° C. and at an absolute pressure in a range of 0.5 to 5 bar, more preferably 0.9 to 2 bar, takes place.
  • a first, more protic, preferably aqueous phase P 1 and a second, compared to the phase P 1 less protic, preferably organic phase P 2 are obtained.
  • the aldehyde scavenger accumulates in one of the two phases P 1 or P 2 .
  • Enrichment means that more than 50% by weight, preferably more than 60% by weight, more preferably more than 70% by weight, and most preferably more than 90% by weight of that in the composition Z 3 the extraction with the solvent contained amount of unreacted Aldehydfanger after extraction in the first phase P 1 or the second phase P 2 , preferably in the second phase P 2 , are.
  • water is used as the solvent and mercaptans as aldehyde scavengers, most of the unreacted mercaptan is in the second organic phase P 2 after extraction.
  • the first, preferably aqueous phase P 1 obtained during the extraction is preferably based on
  • the second, preferably organic phase P 2 obtained as part of the extraction is preferably based on
  • the first, preferably aqueous phase P 1 is separated from the second, preferably organic phase P 2 .
  • the extraction of the composition Z 3 obtained in process step ii) with water in process step iii) and the subsequent separation of the two phases thus obtained in process step iv) can be achieved by any apparatus which performs an extraction and a subsequent separation during the process Extraction obtained phases allows.
  • an “extraction” is understood to mean any process which comprises a compound of one starting phase (the composition Z 3 ) in which it is dissolved or suspended in another liquid phase (second organic phase P is enriched 2). in the batchwise procedure is also called from shaking in continuous of perforation.
  • the separation of the first, preferably aqueous phase P 1 from the second, preferably organic, phase P 2 takes place in a procedure known to the person skilled in the art in connection with conventional extraction methods.
  • the separation can be carried out with suitable separation devices, such as a separating funnel.
  • suitable separation devices such as a separating funnel.
  • the extraction in process step iii) on an industrial scale to achieve high extraction yields and simultaneous use of low water quantities are operated in a multi-stage extraction process, for example by means of a mixer-separator combination, preferably a mixer-separator cascade, or by the use of extraction columns.
  • the second, preferably organic, phase P 2 obtained in step iv) after separation is optionally followed by removal of impurities, such as high boilers, oligomers or polymers, for example by filtration or distillation, in the process step i) recycled.
  • impurities such as high boilers, oligomers or polymers, for example by filtration or distillation
  • the first, preferably aqueous phase P 1 obtained in step iv) after separation for example, in the process step b) of the process for the production of crude (meth) acrylic acid, in particular in the process step b), in which an absorption of the product gas mixture in Water is returned.
  • a further contribution to solving the above-mentioned objects provides an apparatus for preparing (meth) acrylic acid comprising as fluidly interconnected device components: (61) a (meth) Acrylsä 'urereaktor;
  • distillation devices connected to the quenching device ( ⁇ 2) for separating off light and / or
  • ( ⁇ 4_3) a feed line for a recycled aldehyde capture agent; ( ⁇ 4_3) a derivative for a composition comprising reaction products from the reaction between the aldehydes and the aldehyde-scavenger and unreacted aldehyde scavenger;
  • the second derivative (56_4) is connected to the reactor ( ⁇ _3) and optionally the first derivative (66_3) is connected to the quenching device ( ⁇ 2) or to the condensation device ( ⁇ 2).
  • fluid-conducting is understood to mean that the conduits, preferably conduits, are designed and configured in such a way that they can carry gases or liquids or hypercritical fluids or solids suspended in liquids or at least two of them.
  • the reactor ( ⁇ 5) is a fixed bed reactor, which is preferably characterized by the features already mentioned in connection with the description of the method according to the invention.
  • the extraction device (56) is a device comprising both a mixing unit and a separation unit.
  • These mixing and separating units can be individual, fluid-conducting device components, as is the case with the preferred mixer-separator cascade, for example. It is also conceivable that these two device units are combined into a single device component, as is the case for example in the extraction column.
  • the first derivative ( ⁇ 6_3) is connected to the quench device (52).
  • the present invention also relates to a process for the production of (meth) acrylic acid using the apparatus described above.
  • the present invention relates to foams, molded articles, fibers, films, cables, sealing materials, superabsorbents, liquid-absorbent hygiene articles, carriers for plant and fungi growth-regulating agents, packaging materials, bottom additives or building materials based on (meth) acrylic acid obtained by the above described inventive method.
  • "Based” means that they are at least 10 wt .-%, preferably at least 25 wt .-% and most preferably at least 50 wt .-% of this (meth) acrylic acid.
  • the present invention relates to the use of (meth) acrylic acid obtained by the process according to the invention in foams, shaped articles, fibers, films, films, cables, sealing materials, superabsorbents, liquid-absorbent hygiene articles, carriers for plant and fungi growth regulating agents, packaging materials, soil additives , for the controlled release of active substances or in building materials.
  • the figure shows the method according to the invention and an apparatus according to the invention for the production of (meth) acrylic acid in which the product gas mixture is absorbed in water in a quench tower and the water is subsequently separated off in a distillation column.
  • the gaseous starting compounds in the case of the preparation of acrylic acid, a gas mixture of propene, oxygen, water vapor and nitrogen
  • the reactor 1 the gaseous starting compounds
  • the product gas mixture obtained in the reactor 1 is then transferred to a quench tower 2, in which the acrylic acid and other by-products are absorbed in water to obtain an aqueous acrylic acid solution.
  • the aqueous acrylic acid solution obtained in the bottom of the quenching tower is introduced into a distillation column in which the water is removed by azeotropic distillation in the presence of toluene.
  • the bottom product obtained in the distillation column 3 (crude acrylic acid) is introduced into a reactor 4, which is preferably a fixed bed reactor. It is also conceivable to further purify still further the distillate product obtained in the distillation column 3 and only then to introduce it into the reactor 4 (not shown).
  • a reactor 4 Via the feed line 6, an aldehyde trap is introduced into the reactor 4 and brought into contact there with the bottom product, so that high-boiling reac tion products are formed from the reaction between the aldehyde scavenger and the aldehydes still contained in the bottom product.
  • the composition thus obtained is transferred via the discharge line 7 into a further distillation device 8 in which pure acrylic acid is distilled off at the top.
  • the bottom product obtained in the further distillation column 8 is transferred via the feed line 10 into an extraction device 9.
  • impurities such as high boilers, oligomers or polymers can be removed from the bottom product thus obtained by means of a separation device, which is, for example, a distillation or filtration device, prior to transfer to the extraction device 9 (not shown) ).
  • a separation device which is, for example, a distillation or filtration device, prior to transfer to the extraction device 9 (not shown) ).
  • the extraction device 9 is introduced via the supply line 11 water as extractant.
  • two phases P 1 and P 2 are formed in the extraction device 9, the lighter, organic phase P 2 , which contains, above all, unreacted aldehyde scavenger, via the outlet 13, which is connected to the reactor 4 again recycled into the reactor 4.
  • impurities such as high boilers, oligomers or polymers can be removed from the organic phase P 2 by means of a separation device 14, which is, for example, a distillation or filtration distribution, before being returned to the reactor 4.
  • a separation device 14 which is, for example, a distillation or filtration distribution
  • impurities special preference is given to removing solids-like impurities.
  • aqueous phase P 1 obtained in the extraction device 9 can be returned to the quench device 2 via the discharge line 12.
  • the analysis is carried out by gas chromatography with a heat conductivity detector (all data in% by weight).

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

Abstract

L'invention concerne un procédé pour produire de l'acide (méth)acrylique selon les opérations suivantes : i) mettre en contact une composition Z1 contenant de l'acide (méth)acrylique et de l'aldéhyde avec un capteur d'aldéhyde à une température allant de 10 à 100 °C et à une pression variant de 0,1 à 10 bars pour obtenir une composition Z2 contenant de l'acide (méth)acrylique, le produit réactionnel à point d'ébullition élevé de l'aldéhyde et du capteur d'aldéhyde, et le capteur d'aldéhyde non transformé; ii) séparer l'acide (méth)acrylique de la composition Z2 par distillation, le résidu de distillation étant une composition Z3 contenant le produit réactionnel à point d'ébullition élevé obtenu de la réaction entre l'aldéhyde et le capteur d'aldéhyde, et le capteur d'aldéhyde non transformé; iii) extraire le capteur d'aldéhyde non transformé de la composition Z2 avec de l'eau, pour obtenir une première phase aqueuse P1 et une deuxième phase organique P2; iv) séparer la première phase aqueuse de la deuxième phase organique. La présente invention porte également sur un dispositif pour produire de l'acide (méth)acrylique, des mousses, des éléments moulés, des fibres et d'autres articles similaires à base d'acide (méth)acrylique obtenu par ledit procédé, ainsi que sur l'utilisation de l'acide (méth)acrylique obtenu par ledit procédé dans des produits de ce type.
EP06706721A 2005-02-08 2006-02-07 Procede pour recuperer des composes organiques de melanges contenant de l'acide (meth)acrylique par extraction avec un solvant protogene Withdrawn EP1848682A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005005439A DE102005005439A1 (de) 2005-02-08 2005-02-08 Verfahren zur Rückgewinnung von organischer Verbindungen von (Meth)Acrylsäurehaltigen Gemischen durch Extraktion mit einem protischen Lösungsmittel
PCT/EP2006/001077 WO2006084667A1 (fr) 2005-02-08 2006-02-07 Procede pour recuperer des composes organiques de melanges contenant de l'acide (meth)acrylique par extraction avec un solvant protogene

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EP1848682A1 true EP1848682A1 (fr) 2007-10-31

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EP06706721A Withdrawn EP1848682A1 (fr) 2005-02-08 2006-02-07 Procede pour recuperer des composes organiques de melanges contenant de l'acide (meth)acrylique par extraction avec un solvant protogene

Country Status (8)

Country Link
US (1) US20080119669A1 (fr)
EP (1) EP1848682A1 (fr)
JP (1) JP2008529988A (fr)
CN (1) CN101119959A (fr)
BR (1) BRPI0607317A2 (fr)
DE (1) DE102005005439A1 (fr)
WO (1) WO2006084667A1 (fr)
ZA (1) ZA200706511B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004005863A1 (de) * 2004-02-05 2005-09-08 Stockhausen Gmbh Reaktor mit einem einen Einsatz aufweisenden Wärmetauscherbereich
DE102006039205A1 (de) * 2006-08-22 2008-03-20 Stockhausen Gmbh Auf nachwachsenden Rohstoffen basierende Acrylsäure und wasserabsorbierende Polymergebilde sowie Verfahren zu deren Herstellung mittels Dehydratisierung
EP2085376B1 (fr) * 2008-01-30 2012-09-05 Evonik Röhm GmbH Procédé pour la préparation d'acide méthacrylique de grande pureté
WO2020020697A1 (fr) * 2018-07-26 2020-01-30 Basf Se Procédé pour inhiber la polymérisation radicalaire non souhaitée d'acide acrylique se trouvant dans une phase liquide p

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Publication number Priority date Publication date Assignee Title
JP2001213839A (ja) * 2000-02-03 2001-08-07 Nippon Shokubai Co Ltd （メタ）アクリル酸の製造方法
DE10138101A1 (de) * 2001-08-03 2002-11-14 Basf Ag Verfahren zur Abtrennung von Acrylsäure aus den Reaktionsgasen der katalytischen Gasphasenoxidation
DE10138150A1 (de) * 2001-08-03 2003-02-13 Basf Ag Verfahren zur Herstellung wasserabsorbierender Harze
JP2003321419A (ja) * 2002-05-07 2003-11-11 Mitsubishi Chemicals Corp 高純度（メタ）アクリル酸の製造方法
DE10301040B4 (de) * 2003-01-13 2005-07-21 Stockhausen Gmbh Aufreinigung eines Monomers durch Extraktion mit einem Phasenbildner und Kristallisation

Non-Patent Citations (1)

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Title
See references of WO2006084667A1 *

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JP2008529988A (ja) 2008-08-07
US20080119669A1 (en) 2008-05-22
DE102005005439A1 (de) 2006-08-17
CN101119959A (zh) 2008-02-06
ZA200706511B (en) 2009-07-29
WO2006084667A1 (fr) 2006-08-17
BRPI0607317A2 (pt) 2009-09-01

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