WO2010149527A1 - Procédé de fabrication de l'acétate de vinyle - Google Patents

Procédé de fabrication de l'acétate de vinyle Download PDF

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Publication number
WO2010149527A1
WO2010149527A1 PCT/EP2010/058351 EP2010058351W WO2010149527A1 WO 2010149527 A1 WO2010149527 A1 WO 2010149527A1 EP 2010058351 W EP2010058351 W EP 2010058351W WO 2010149527 A1 WO2010149527 A1 WO 2010149527A1
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WIPO (PCT)
Prior art keywords
oxyl
vinyl acetate
added
compound
compounds
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PCT/EP2010/058351
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German (de)
English (en)
Inventor
Willibald Dafinger
Peter Holl
Günther RUDOLF
Martin SCHÖNLEBEN
Original Assignee
Wacker Chemie Ag
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Publication date
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Publication of WO2010149527A1 publication Critical patent/WO2010149527A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds

Definitions

  • the invention relates to a process for the preparation of vinyl acetate in a heterogeneously catalyzed, continuous gas phase process by reacting ethylene with acetic acid and oxygen and working up the product gas stream, wherein the by-product formation, due to the polymerization of vinyl acetate, is inhibited in the workup of the product gas stream.
  • Vinyl acetate (VAM) is produced in a continuous process with recycling of the purified product stream (Kreiagas system) .
  • ethylene reacts with acetic acid and oxygen over catalysts which generally contain palladium and alkali metal salts on a support material and additionally can be doped with gold, rhodium or cadmium, preferably a Pd / Au catalyst mixture with potassium acetate promoter is used.
  • VAM exothermic reaction
  • the major secondary reaction is the total ethylene oxidation to CO 2 : C 2 H 4 + 3 O 2 -> 2 CO 2 + 2 H 2 O
  • the ethylene conversion is about 10%, the Essigklatnsatz at 20 to 30% and the oxygen conversion at up to 90%.
  • a gas mixture consisting predominantly of ethylene, carbon dioxide, ethane, nitrogen and oxygen is circulated.
  • the gas stream is mixed with the reactants acetic acid, ethylene and oxygen in front of the fixed-bed tubular reactor and heated with heating steam. exchangers brought to reaction temperature.
  • the enrichment of the recycle gas with acetic acid is usually carried out by means of a hot steam heated Essigklares decisivtiger.
  • reaction products and unreacted acetic acid are condensed out of the recycle gas and fed to the workup. Uncondensed product is washed out in a scrubber operated with acetic acid.
  • the condensed products vinyl acetate and water and unreacted acetic acid are separated in a multi-stage, usually operated with heating steam, distillation process from each other. The usual distillation steps are dehydration (if appropriate also pre-dewatering), azeotropic distillation, pure VAM column, residue workup, and low boiler and high boiler removal.
  • the invention relates to a process for the preparation of vinyl acetate in a heterogeneously catalyzed, continuous gas phase process by reacting ethylene with acetic acid and oxygen and subsequent workup of the product gas stream, characterized in that for inhibiting the polymerization of vinyl acetate, during the workup of the
  • Product gas mixture one or more compounds are added as inhibitors containing at least one N-oxyl radical group -N-O-.
  • N-oxyl compounds are those based on secondary amines in which the N-oxyl group is part of a saturated or unsaturated five-membered ring, for example pyrrolidine-1-oxyl compounds or Azacyclopentyl-3-oxyl compounds, or a saturated or unsaturated six-membered ring, for example, piperidine-1-oxyl compounds or pyridine-1-oxyl compounds or 1, 4-diazacyclohexyl-l, 4-dioxyl compounds or 1,4 - Diazacyclohexenyl-l, 4-dioxyl compounds, and wherein the C-atoms adjacent to the N-oxyl group each carry two C 1 - to C 4 alkyl groups, preferably methyl groups.
  • the 5-ring N-oxyl compounds or 6-ring N-oxyl compounds may also be substituted, for example with halogen, amino, cyano, hydroxy, C 1 - to C 4 -alkyl or C 1 - to C 4 - alkoxy, carboxyl or carboalkoxy radicals with C 1 - to C 4 - alkoxy.
  • 5-ring N-oxyl compounds are 2, 2, 5, 5-tetramethylpyrrolidinyloxyl; 3-amino-2,2,5,5-tetramethylpyrrolidinyloxy; 2,2,4,4-tetramethyl-1-oxa-3-azacyclopentyl-3-oxyl; 2,2,4,4-tetramethyl-1-oxa-3-pyrrolinyl-1-oxy-3-carboxylic acid.
  • Particularly preferred 5-ring N-oxyl compounds are 2,2,6,6-tetramethylpiperidinyloxy / 4-amino-2, 2,6, 6-tetramethylpiperidinyloxyl; 4-hydroxy-2, 2, 6, S-tetramethylpiperidinedyloxyl; 4-oxo-2,2,6,6-tetramethylpiperidinyloxy, - 4-dimethyl-amino-2, 2, 6, 6-tetramethylpiperidinyloxy; 4-ethanoyloxy-2, 2, 6, 6-tetramethylpiperidinyloxyl; 4-bromo-2,2,6,6-tetramethylpiperidinyloxy; 4-chloro-2, 2,6, 6-tetramethylpiperidino yloxyl; 4-iodo-2, 2, 6, 6-tetramethylpiperidinyloxyl; 4-fluoro-2,2,6,6-tetramethylpiperidinyloxy, -4-cyano-2, 2,6, 6-tetramethylpiperidinyloxy; 4-carboxy-2
  • the amount of N-oxyl compound required for the process depends, on the one hand, on the design and capacity of the particular plant. The required amount can be determined by monitoring and analyzing the material flows in the plant, that is by means of quantitative determination of the total polymer formation or polymer formation in individual plant parts. The amount used also depends on whether with the use of N-oxyl compound a prophylactic treatment for lifetime extension of the entire system is sought, or the polymer accumulation is to be inhibited in individual parts of the system, there to reduce the treatment costs for cleaning. In general, amounts of from 50 to 500 ppm, preferably from 50 to 200 ppm of H-oxyl compound, in each case per ton of vinyl acetate in the product gas stream, are sufficient for the entire plant. This amount can be added to one or distributed over several points of the plant for processing the product gas stream, that is, in one or more columns, lines or reservoir. Preferred points A to L for the addition of the inhibitor are shown in FIG.
  • the N-oxyl compound is generally dosed as 0.5 to 20% by weight solution.
  • Suitable solvents are to be selected depending on the location of the dosage, and preferably vinyl acetate, vinyl acetate-water mixtures or crude vinyl acetate.
  • vinyl acetate is used as the solvent.
  • Oxyl compound is preferably used alone and not in combination with other additives in solution.
  • An additional advantage of the radical inhibitor is its oxygen-independent effect. It is known that the use of hydroquinone as an inhibitor requires oxygen in order to activate the hydroquinone. On the other hand, the addition of oxygen creates the potential for oxygen / peroxide radicals and thus also the initiators for polymerization. In contrast, N-oxyl compounds do not require this activation by oxygen. On the contrary, they even counteract the oxygen / peroxide induced polymerization.
  • FIG. 1 shows a simplified scheme for the production of vinyl acetate in a gas phase process and subsequent workup of the product gas stream.
  • the recycle gas compressed with the cycle gas compressor v-101 (1) is enriched with prochlorethylene replacing the ethylene fraction consumed in the reaction and supplied to the acetic acid saturate K-IOl (2).
  • the acetic acid reacted in the reaction is replaced in the acetic acid saturator (2) by the addition of fresh acetic acid.
  • the high boilers and other by-products, such as all recycled polymers and unused inhibitors are stripped off at the bottom of the acetic acid saturator (2), freed from residual acetic acid in the acetic acid workup, and the remaining residues discarded.
  • the gas stream leaving the fixed bed tubular reactor C-101 (3) is fed to the lower part of the pre-dewatering column K-103 (4). supplied.
  • a first condensate from this column is passed into the crude VAM tank B-103 (5).
  • the dosage in the crude VAM container B-103 (5) is point A at which inhibitor addition can take place.
  • the crude VAM from the crude VAM container B-103 (5) is then pumped into the azeotrope column K-304 (6).
  • the main gas stream from the pre-dewatering column K-103 (4) can be inhibited before the subsequent condensation in the recycle gas scrubber K-102 (8) (point B).
  • the N-oxyl compound can be added on the way to the pre-dewatering column K-103 (4) (location O.
  • the non-condensed constituent of the head vapors of the pre-dewatering column (4) essentially ethylene, CO 2 and vinyl acetate, is discharged to the recycle gas scrubber K-102 (8).
  • the uncondensed VAM fractions are absorbed in acetic acid-operated recycle gas scrubber K-102 (8).
  • the absorbency AcOH required for cycle gas scrubbing may be supplied from the azeotrope column K-304 (6).
  • the now VAJVJ-free circulating gas is returned to the reaction in the reactor C-101 (3) via the cycle gas compressor V-101 (1) and the acetic ester K-101 (2).
  • the bottom product from the cycle gas scrubber K-102 (8) is passed into the crude VAM container B-102 (9) and from there into the dewatering column K-301 (10).
  • the crude VAM container B-102 (9) and / or in the ROH-VAM container B-103 (5) also inhibitor can be added (site D).
  • a second raw VAM stream is generally passed:
  • This is first distilled in the azeotrope column K-304 (6).
  • the top product of this distillation in the azeotropic column K-304 (6) essentially vinyl acetate and water, is distilled off into the phase separator A-. 325 (11), and inhibitor can be added between azeotrope column (6) and phase separator (11) (position H).
  • phase separator A-325 (11) is fed to wastewater column K-401 (12), in which all the aqueous phases are separated from phase separators A-125 (7), phase separator A-302
  • phase separator A-325 (11) of the entire distillation.
  • the aqueous bottom product of the wastewater column (12) is disposed of, the overhead product in the dewatering column K-301 (10) recycled.
  • the inhibitor can be fed to the effluent column K-401 (12) at the aqueous phase inlet (location L).
  • a side draw of the azeotrope column K-304 (6) can be passed to the ethyl acetate column K-303 (14) to remove the ethyl acetate. In the reflux of this ethyl acetate column K-303
  • dewatering column K-301 (10) is essentially the bottom product from the cycle gas scrubber ⁇ -102 (8), which contains essentially water, vinyl acetate, acetic acid and low boilers (especially acetaldehyde) separated:
  • the low boilers and water are of vinyl acetate and acetic acid separated.
  • the acetaldehyde formed here by vinyl acetate hydrolysis is separated off via the top of the dewatering column K-301 (10), subsequently condensed and pumped for further work-up. Inhibitor can be added at this point (site E).
  • Inhibitor can be added to this line (site F).
  • the organic phase is optionally inhibited (site G) and then, optionally at several sites, as reflux of the dewatering column K-301 (10) fed back.
  • the bottom product of the dehydration column K-301 (10), vinyl acetate and acetic acid is passed to the pure VAM column K-302 (15). About the top pure VAM is separated and partially recycled as reflux. Inhibitor may also be added to this reflux (site K).
  • the bottoms product, essentially acetic acid, is added to the acetic acid workup.
  • a total of 1300 to 2100 ppm of hydroquinone per ton of VAM was initially added over a period of one month at sites A to L.
  • Example 1 In the course of Example 1, a total of 50 to 200 ppm of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) per ton of VAM was added at points A to L over a period of one month.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl

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

Abstract

L'invention porte sur un procédé de fabrication de l'acétate de vinyle dans un procédé en phase gazeuse, continu, à catalyse hétérogène, par réaction de l'éthylène avec de l'acide acétique et de l'oxygène, puis traitement du courant gazeux produit. Ce procédé est caractérisé en ce que, pour inhiber la polymérisation de l'acétate de vinyle, on ajoute pendant le traitement du mélange gazeux produit un ou plusieurs composants en tant qu'inhibiteurs, qui contiennent au moins un groupe radical N-Oxyde -N-O.
PCT/EP2010/058351 2009-06-23 2010-06-15 Procédé de fabrication de l'acétate de vinyle WO2010149527A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009027115.5 2009-06-23
DE200910027115 DE102009027115A1 (de) 2009-06-23 2009-06-23 Verfahren zur Herstellung von Vinylacetat

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WO2010149527A1 true WO2010149527A1 (fr) 2010-12-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012058196A1 (fr) * 2010-10-28 2012-05-03 Celanese International Corporation Procédés d'obtention de composition d'acétate de vinyle avec faible teneur en impuretés
WO2015082450A1 (fr) 2013-12-06 2015-06-11 Wacker Chemie Ag Procédé de production d'acétate de vinyle mettant en œuvre une formation de produits secondaires inhibée
WO2019101296A1 (fr) 2017-11-21 2019-05-31 Wacker Chemie Ag Procédé de préparation d'acétate de vinyle

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0576010A1 (fr) * 1992-06-26 1993-12-29 Nalco Chemical Company Inhibition d'obstruction de compresseur dans les unités de production d'acétate de vinyle
EP0791573A1 (fr) * 1996-02-21 1997-08-27 Nalco/Exxon Chemicals Company L.P. Nitroxydes comme antipolymérisants pour des unités d'acétate de vinyle
WO2007045886A1 (fr) * 2005-10-20 2007-04-26 A H Marks And Company Limited Inhibition de la polymerisation
KR20080097529A (ko) * 2007-05-02 2008-11-06 전병준 비닐아세테이트 단량체 제조공정중의 중합방지방법

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US3467696A (en) 1964-08-07 1969-09-16 Kuraray Co Stabilized vinyl acetate and process
US6143205A (en) 1996-06-05 2000-11-07 Basf Aktiengesellschaft Mixtures containing monomers and stabilizers
DE19651307A1 (de) 1996-12-10 1998-06-18 Basf Ag Stoffmischungen, enthaltend vinylgruppenhaltige Verbindungen und Stabilisatoren
MXPA02005423A (es) 1999-12-02 2002-11-29 Crompton Corp Inhibicion de polimerizacion de monomeros no saturados.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576010A1 (fr) * 1992-06-26 1993-12-29 Nalco Chemical Company Inhibition d'obstruction de compresseur dans les unités de production d'acétate de vinyle
EP0791573A1 (fr) * 1996-02-21 1997-08-27 Nalco/Exxon Chemicals Company L.P. Nitroxydes comme antipolymérisants pour des unités d'acétate de vinyle
WO2007045886A1 (fr) * 2005-10-20 2007-04-26 A H Marks And Company Limited Inhibition de la polymerisation
KR20080097529A (ko) * 2007-05-02 2008-11-06 전병준 비닐아세테이트 단량체 제조공정중의 중합방지방법

Non-Patent Citations (1)

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Title
POHL M M ET AL: "Bimetallic PdAu-KOac/SiO2 catalysts for vinyl acetate monomer (VAM) synthesis: Insights into deactivation under industrial conditions", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US LNKD- DOI:10.1016/J.JCAT.2009.01.008, vol. 262, no. 2, 10 March 2009 (2009-03-10), pages 314 - 323, XP025988845, ISSN: 0021-9517, [retrieved on 20090131] *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012058196A1 (fr) * 2010-10-28 2012-05-03 Celanese International Corporation Procédés d'obtention de composition d'acétate de vinyle avec faible teneur en impuretés
US9193663B2 (en) 2010-10-28 2015-11-24 Celanese International Corporation Methods for producing a vinyl acetate composition having a low impurity content
WO2015082450A1 (fr) 2013-12-06 2015-06-11 Wacker Chemie Ag Procédé de production d'acétate de vinyle mettant en œuvre une formation de produits secondaires inhibée
DE102013225114A1 (de) 2013-12-06 2015-06-11 Wacker Chemie Ag Verfahren zur Herstellung von Vinylacetat mit inhibierter Nebenproduktbildung
CN105793230A (zh) * 2013-12-06 2016-07-20 瓦克化学股份公司 通过抑制副产物形成用于生产乙酸乙烯酯的方法
US9561997B2 (en) 2013-12-06 2017-02-07 Wacker Chemie Ag Process for preparing vinyl acetate with inhibited by-product formation
CN105793230B (zh) * 2013-12-06 2017-08-25 瓦克化学股份公司 通过抑制副产物形成用于生产乙酸乙烯酯的方法
WO2019101296A1 (fr) 2017-11-21 2019-05-31 Wacker Chemie Ag Procédé de préparation d'acétate de vinyle
CN111372909A (zh) * 2017-11-21 2020-07-03 瓦克化学股份公司 用于生产乙酸乙烯酯的方法
US10947178B2 (en) 2017-11-21 2021-03-16 Wacker Chemie Ag Method for producing vinyl acetate
CN111372909B (zh) * 2017-11-21 2023-03-24 瓦克化学股份公司 用于生产乙酸乙烯酯的方法

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