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WO2006082224A1 - Procede pour eliminer des constituants secondaires resultant de la production d'ester d'acide acrylique ou (meth)acrylique - Google Patents

Procede pour eliminer des constituants secondaires resultant de la production d'ester d'acide acrylique ou (meth)acrylique Download PDF

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Publication number
WO2006082224A1
WO2006082224A1 PCT/EP2006/050631 EP2006050631W WO2006082224A1 WO 2006082224 A1 WO2006082224 A1 WO 2006082224A1 EP 2006050631 W EP2006050631 W EP 2006050631W WO 2006082224 A1 WO2006082224 A1 WO 2006082224A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylic acid
meth
acid ester
production
secondary components
Prior art date
Application number
PCT/EP2006/050631
Other languages
German (de)
English (en)
Inventor
Volker Schliephake
Rolf-Dieter Becher
Michael Blechschmitt
Steffen Rissel
Original Assignee
Basf Aktiengesellschaft
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
Priority claimed from DE200510053982 external-priority patent/DE102005053982A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006082224A1 publication Critical patent/WO2006082224A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/38—Polymers

Definitions

  • the present invention relates to a process for the disposal of secondary components arising in the (meth) acrylic acid ester preparation.
  • (meth) acrylic acid in this document is abbreviated to acrylic acid and / or methacrylic acid, (meth) acrylic esters for acrylic acid esters and / or methacrylic acid esters.
  • the polymers or copolymers prepared on the basis of (meth) acrylic esters are of great economic importance in the form of polymer dispersions. They are used, for example, as adhesives, paints or in the textile, leather and paper industries.
  • EP 0 925 272 B1 describes a process for the disposal of secondary components resulting from the preparation of acrylic acid or methacrylic acid, in which the light and medium-boiling secondary components dissolved in water are passed into the combustion stage of the gaseous low-boiling secondary components.
  • US 2003/0143143 A1 discloses a process for the treatment of common waste from the production of acrylic acid and the subsequent production of polyacrylic acid.
  • (Meth) acrylic esters in the context of the present invention are esters of acrylic acid or methacrylic acid of alcohols having 1 to 12 carbon atoms.
  • butyl acrylate In general, these low-boiling components contain, for example, dialkyl ethers and acetic acid alkyl esters.
  • the term "low-boiling secondary components" in the PRESENT invention understood that at standard conditions (25 0 C and 1 bar) are liquid and at atmospheric pressure (1 bar) having a lower boiling point have as the Wunschpodukt, ie in this Trap have a lower boiling point at 1 bar than n-butyl acrylate.
  • the inventive method is particularly suitable for (meth) acrylic acid esters of alcohols having 1 to 12 carbon atoms.
  • the alcohol used is usually any alcohol containing 1 to 12 carbon atoms, for example monohydric or polyhydric alcohols, preferably mono- to tetravalent, particularly preferably mono- to tri-valent, very particularly preferably mono- or divalent and in particular monohydric.
  • Examples are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, 1,3-propanediol monomethyl ether, 1, 2 Propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, dimethylaminoethanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol, 2-ethylhexanol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,
  • Preferred alcohols are methanol, ethanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-ethylhexyl alcohol, n-octanol and dimethylaminoethanol.
  • Very particular preference is given to methanol, ethanol, n-butanol, 2-ethylhexyl alcohol and dimethylamino alcohol and, in particular, n-butanol.
  • Mixtures of several alcohols can be used, for example 2 or 3, but preferably only one alcohol is used.
  • (Meth) acrylic acid with an alcohol for.
  • (Meth) acrylic acid esters are generally obtained via a homogeneous or heterogeneously catalyzed esterification, as described, for example, in Kirk Othmer, Encyclopedia of Chemical Technology, 4th Ed., 1994, pages 301-302 and Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol A1, pages 167-169.
  • the usable acid catalysts are preferably sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid (Lutensit ® from BASF Aktiengesellschaft), methanesulfonic acid or mixtures thereof, are also conceivable acid ion exchangers or zeolites.
  • Sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and methanesulfonic acid are particularly preferably used, very particular preference is given to sulfuric acid and p-toluenesulfonic acid.
  • the catalyst concentration based on the reaction mixture is for example 0.1 to 20, preferably 1 to 20 and particularly preferably 5 to 15 wt .-%.
  • a crude acrylic acid is used, in addition to acrylic acid and small amounts of minor components such.
  • B. contains acetic acid.
  • acetic acid As further impurities water, low molecular weight aldehydes, such as. As benzaldehyde or furfural, low molecular weight carboxylic acids and their anhydrides, such as.
  • propionic acid maleic acid, maleic anhydride, phthalic acid, phthalic anhydride or benzoic acid, and stabilizer may be included.
  • the water of reaction formed is removed in various ways, the crude product is purified by combining several separation steps and freed from the secondary components. Essentially, the following process variants are important:
  • reaction product of the esterification is prepared with sulfuric acid as an acidic esterification catalyst.
  • the liquid reaction product is separated off and washed several times with water of different pH.
  • reaction product of the esterification is reacted with the aid of alkylsulfonic acids, e.g. For example, methanesulfonic acid, or alkyl-arylsulfonic acids, e.g. As dodecylbenzenesulfonic acid prepared, removed overhead and purified by distillation.
  • alkylsulfonic acids e.g. For example, methanesulfonic acid, or alkyl-arylsulfonic acids, e.g. As dodecylbenzenesulfonic acid prepared, removed overhead and purified by distillation.
  • alkylsulfonic acids e.g.
  • methanesulfonic acid or alkyl-arylsulfonic acids, e.g. As dodecylbenzenesulfonic acid prepared, removed overhead and purified by distillation.
  • acrylic acid esters may also be prepared by reacting an alkene with acrylic acid such as isobutene to tert-
  • (meth) acrylic esters can also be effected by transesterification.
  • higher (meth) acrylic esters are obtained in this way by transesterification of lower (meth) acrylic esters with higher alcohols.
  • the preparation of (meth) acrylic esters by transesterification in the presence of acidic or basic catalysts is generally known (Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, page 171).
  • transesterifications for the preparation of (meth) acrylic acid esters from (meth) acrylic acid esters with alcohols, such as, for example, the preparation of dimethylaminoethyl acrylate by transesterification of methyl acrylate with dimethylaminoethanol in EP 0 906 902 A2, are found in the literature.
  • a discontinuous transesterification is z. As described in EP 1 078 913 A2.
  • Titanium alcoholates whose alkyl groups are C 1 -C 4 -alkyl radicals, for example, are proposed as catalysts.
  • Further titanium compounds are also described in DE 101 27 939 A1.
  • catalysts u. a. Titanphenolate (DE-OS 200 86 18), dibutyltin oxide (EP 0 906 902 A2), metal chelate compounds of z.
  • hafnium, titanium, zirconium or calcium, alkali metal and magnesium, organic tin compounds or calcium and lithium compounds for example -oxides, - proposed hydroxides, carbonates or halides.
  • the (meth) acrylic esters obtained via the transesterification contain less readily boiling secondary components since, depending on the composition of the starting materials, the content of acetic acid or acetates is reduced.
  • the process of the invention is particularly directed to the obtained by direct esterification (meth) acrylic acid ester.
  • acrylic monomers are stabilized by suitable polymerization inhibitors in order to avoid undesired polymerization.
  • suitable stabilizers are in principle all polymerization inhibitors which are used for the stabilization of (meth) acrylic acid and (meth) acrylic acid esters in z. B. be recommended DE 102 58 329 A1.
  • Suitable stabilizers may be, for example, N-oxides (nitroxyl or N-oxyl)
  • Radicals ie compounds which have at least one> N-0 group), such as. 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl or 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl, phenols and naphthols, such as p-aminophenol, p-nitrosophenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert. Butylphenol, 2,6-tert-butyl-4-methylphenol or 4-tert-butyl-2,6-dimethylphenol, quinones such.
  • aromatic amines such as. B. N 1 N-diphenylamine
  • phenylenediamines such as. B. N, N'-dialkyl-p-phenylenediamine, wherein the alkyl radicals may be the same or different and each independently consist of 1 to 4 carbon atoms and may be straight or branched, such as. B. N, N'-dimethyl-p-phenylenediamine or N, N'-diethyl-p-phenylenediamine, hydroxy xylamine, such as N, N-diethylhydroxylamine, imines such.
  • methylethylimine or methylene violet sulfonamides such.
  • oximes such as Aldoxime, Ketoxime or amidoximes, such as.
  • metal salts such as. Cerium (III) acetate or cerium (III) ethyl hexanoate, or mixtures thereof.
  • the stabilization is preferably carried out with phenothiazine, hydroquinone, hydroquinone monomethyl ether, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-0x0-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,6 tert-butyl 4-methylphenol or mixtures thereof.
  • variants (a) and (b) of the process according to the invention can be carried out both separately from one another and in parallel according to the extent or volume of the secondary components formed in the (meth) acrylic acid ester preparation.
  • Both variants have in common that the low-boiling secondary components of the (meth) acrylic acid ester preparation are mixed with a waste product of (meth) acrylic acid production.
  • Variant b) is characterized by the fact that the mixture forms a stable emulsion which can be easily applied, i. without phase separation of the components, is fed via a burner nozzle of the combustion.
  • the ratio of low-boiling secondary component from the (meth) acrylic acid ester is usually
  • variant a) is carried out alone. This is particularly advantageous since the high-boiling residue from the (meth) acrylic acid
  • Production preferably from the production of acrylic acid, is highly viscous.
  • This high-boiling residue is the fission residue that arises in the production of acrylic acid, in the high-boiling waste containing the oligomeric acrylic acid is cleaved.
  • the high-viscosity high-boiling residue as described in the example of DE 102 17 121 A1, diluted with methanol. Dilution with methanol causes the residue to become pumpable and can then be disposed of.
  • the inventive method can surprisingly be dispensed with the dilution with methanol, the highly viscous residue is mixed with the low-boiling secondary components from the (meth) acrylic acid ester preparation.
  • the process is thereby economically and ecologically more efficient than the previous disposal methods.
  • acrylic acid also involves large amounts of waste products. Due to the oxidation of propene with atmospheric oxygen, the nitrogen flow introduced with the air must be discharged. This usually also contains gaseous by-products such as carbon monoxide and acrolein, which must be highly oxidized to carbon dioxide. This gas flow is advantageously disposed of in an incinerator, which is in close proximity to the acrylic acid plant to keep the pressure losses through short distances as low as possible and thereby save costs.
  • the incinerator is described in EP 0 925 272 B1, to which reference is expressly made at this point.
  • the combustion itself takes place in a combustion chamber at adiabatic combustion temperatures of 750 to 1200 0 C, preferably from 800 to 1000 0 C instead.
  • the released during combustion energy can be in a separate from the combustion chamber arranged waste heat favorable, z. B. in the form of high-tensioned steam, to be recovered.
  • the heat generated during combustion waste heat is advantageously used to generate steam, eg. As water vapor, used.
  • the process according to the invention is suitable in industrial applications, in particular for those plant complexes in which the plants for preparing the (meth) acrylic esters are in the immediate vicinity of the plant for the preparation of (meth) acrylic acid.
  • the cooled and diluted cleavage residue remained liquid and could be sent to combustion.
  • the low-boiler waste was burned from a plant for the production of n-butyl acrylate.
  • This incinerator is connected to a plant for the production of acrylic acid by means of piping.
  • the low-boiling secondary components from the n-butyl acrylate preparation were mixed with the high-boiling residue from the acrylic acid preparation and fed to the combustion.

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

Abstract

L'invention concerne un procédé pour éliminer des constituants secondaires résultant de la production d'ester d'acide (méth)acrylique, selon lequel les constituants secondaires à point d'ébullition bas de la production d'ester d'acide (méth)acrylique sont mélangés aux résidus à point d'ébullition élevé de la production d'ester d'acide (méth)acrylique, puis ce mélange est mis en combustion, et/ou les constituants secondaires à point d'ébullition bas de la production d'ester d'acide (méth)acrylique sont mélangés à l'eau de réaction de la production d'ester d'acide (méth)acrylique, puis ce mélange est introduit dans la combustion par une buse de brûleur.
PCT/EP2006/050631 2005-02-03 2006-02-02 Procede pour eliminer des constituants secondaires resultant de la production d'ester d'acide acrylique ou (meth)acrylique WO2006082224A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102005005206 2005-02-03
DE102005005206.1 2005-02-03
DE102005053982.3 2005-11-10
DE200510053982 DE102005053982A1 (de) 2005-11-10 2005-11-10 Verfahren zur Entsorgung von bei der Acrylsäureester- oder Methacrylsäureester-Herstellung anfallenden Nebenkomponenten

Publications (1)

Publication Number Publication Date
WO2006082224A1 true WO2006082224A1 (fr) 2006-08-10

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Application Number Title Priority Date Filing Date
PCT/EP2006/050631 WO2006082224A1 (fr) 2005-02-03 2006-02-02 Procede pour eliminer des constituants secondaires resultant de la production d'ester d'acide acrylique ou (meth)acrylique

Country Status (2)

Country Link
RU (1) RU2006103127A (fr)
WO (1) WO2006082224A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468383A1 (fr) * 2010-12-22 2012-06-27 Evonik Degussa GmbH Procédé de combustion thermique ultérieure de gaz d'échappement à partir de la fabrication d'acroléine et d'acide cyanhydrique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0925272B1 (fr) * 1996-06-20 2001-09-12 Basf Aktiengesellschaft Procede pour l'elimination de sous-produits se presentant lors de la fabrication d'acide acrylique ou d'acide methacrylique
DE10154714A1 (de) * 2001-11-09 2002-11-07 Basf Ag Verfahren zur Herstellung von (Meth)acrylsäureestern
EP1319648A1 (fr) * 2001-12-14 2003-06-18 STOCKHAUSEN GmbH & CO. KG Procédé de préparation de l'acide acrylique
US20040055970A1 (en) * 2002-09-19 2004-03-25 Yukihiro Matsumoto Method for disposal of waste from acrylic acid process and acrylic ester process
EP1452518A1 (fr) * 2001-12-04 2004-09-01 Mitsubishi Chemical Corporation Procede de production d'un compose d'acide (meth)acrylique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0925272B1 (fr) * 1996-06-20 2001-09-12 Basf Aktiengesellschaft Procede pour l'elimination de sous-produits se presentant lors de la fabrication d'acide acrylique ou d'acide methacrylique
DE10154714A1 (de) * 2001-11-09 2002-11-07 Basf Ag Verfahren zur Herstellung von (Meth)acrylsäureestern
EP1452518A1 (fr) * 2001-12-04 2004-09-01 Mitsubishi Chemical Corporation Procede de production d'un compose d'acide (meth)acrylique
EP1319648A1 (fr) * 2001-12-14 2003-06-18 STOCKHAUSEN GmbH & CO. KG Procédé de préparation de l'acide acrylique
US20040055970A1 (en) * 2002-09-19 2004-03-25 Yukihiro Matsumoto Method for disposal of waste from acrylic acid process and acrylic ester process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468383A1 (fr) * 2010-12-22 2012-06-27 Evonik Degussa GmbH Procédé de combustion thermique ultérieure de gaz d'échappement à partir de la fabrication d'acroléine et d'acide cyanhydrique
WO2012084767A1 (fr) * 2010-12-22 2012-06-28 Evonik Degussa Gmbh Procédé de post-combustion thermique des effluents gazeux provenant de la fabrication d'acroléine et d'acide cyanhydrique
CN103260723A (zh) * 2010-12-22 2013-08-21 赢创德固赛有限公司 用于热后燃烧来自丙烯醛和氢氰酸生产的废气的方法
US9927120B2 (en) 2010-12-22 2018-03-27 Evonik Degussa Gmbh Method for thermally after-burning waste gases from acrolein and hydrocyanic acid production

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Publication number Publication date
RU2006103127A (ru) 2007-08-20

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