EP3019463A1 - Procédé de production d'esters d'acide alpha-hydroxycarboxylique - Google Patents

Procédé de production d'esters d'acide alpha-hydroxycarboxylique

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Publication number
EP3019463A1
EP3019463A1 EP14739371.4A EP14739371A EP3019463A1 EP 3019463 A1 EP3019463 A1 EP 3019463A1 EP 14739371 A EP14739371 A EP 14739371A EP 3019463 A1 EP3019463 A1 EP 3019463A1
Authority
EP
European Patent Office
Prior art keywords
alpha
pressure
reactor
reaction
alcohol
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Withdrawn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
EP14739371.4A
Other languages
German (de)
English (en)
Inventor
Steffen Krill
Alexander May
Jörg BECKER
Martin Köstner
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.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm 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 Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP3019463A1 publication Critical patent/EP3019463A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
    • C07C67/20—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from amides or lactams
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of alpha-hydroxycarboxylic acid esters by means of alcoholysis of the corresponding alpha-Hydroxycarbonklareamids under heterogeneous catalysis.
  • Hydroxycarboxylic acid amides are known in the art. These are e.g. in the literature both homogeneous catalytic with lanthanum or
  • Titanium compounds (Canadian Journal of Chemistry, 1994.72 (1): p.142-145;
  • 06345692 are aimed exclusively at a heterogeneous catalysis with metal oxides, which are used both unsupported and applied to SiO 2 carriers. Particularly suitable here are called antimony, tellurium, bismuth or zirconium oxide.
  • the object of the present invention is therefore to provide a method that is optimized for high single-path conversions in terms of.
  • the educt aHCA has a high robustness and thus long service life - even in circulation operation - allowed. Furthermore, the process has a high tolerance to the presence of water and by-products, which are introduced into the reaction with the starting material from the precursor, coupled with the possibility of a
  • Circulation mode of operation which allows without a possible pre-cleaning the unreacted starting materials or by-products from the alcoholysis of the reaction to re-feed, and in particular the former without loss of efficiency in the desired recyclable material.
  • alpha-hydroxycarboxamide characterized in that a) feed streams comprising an alpha-hydroxycarboxamide and an alcohol in a pressure reactor containing a heterogeneous catalyst, fed, b) this reaction mixture in the pressure reactor at a pressure in the range of 1 -100 bar in liquid C) reacting the product mixture resulting from step b) comprising alpha-hydroxycarboxylic acid ester and unreacted alpha-hydroxycarboxamide from the pressure reactor, d) depleting the product mixture formed from c) of alcohol and ammonia and e) the product mixture from step d) contained unreacted starting materials and by-products
  • Step a) recycled.
  • Carboxylic acid amides which have at least one hydroxyl group in the alpha position to the carboxylic acid amide group.
  • Carboxylic acid amides are well known in the art. These are usually taken to mean compounds with groups of the formula - CONR'R "-, in which R 'and R" independently represent hydrogen or a group having 1-30 carbon atoms, especially 1-20, preferably 1-10 and
  • the carboxylic acid amide may comprise 1 to 4 or more groups of the formula - CONR'R "-
  • R represents a group having 1 to 30 carbon atoms, in particular 1 to 20, preferably 1 to 10, in particular 1 to 5 and particularly preferably 2 to 3
  • aromatic and heteroaromatic groups denotes residues of organic compounds having 1 to 30 carbon atoms.
  • aromatic and heteroaromatic groups also includes aliphatic and heteroaliphatic groups, such as, for example, alkyl, cycloalkyl, alkoxy, cycloalkoxy, cycloalkylthio and alkenyl groups.
  • the groups mentioned can be branched or unbranched.
  • aromatic groups radicals of mono- or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12 C-atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group is replaced by N and / or at least two adjacent CH groups are replaced by S, NH or O.
  • Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, Diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3, 4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1, 3,4-triazole, 1, 2,5-triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4-tetrazole, benzo [b] thiophene,
  • Dibenzothiophene carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-triazine, tetrazine, quinoline, isoquinoline, quinoxaline, Quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine or quinolizine, 4H-quinolizine, diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole,
  • Benzooxadiazole benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, indolizine, pyridopyridine, imidazopyrinnidine, pyrazinopyrimidine, carbazole, aciridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridizine,
  • Benzopteridin, phenanthroline and phenanthrene which may optionally be substituted.
  • Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1, 1 - dimethylpropyl, hexyl, heptyl, octyl, 1, 1, 3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl -Group.
  • Preferred cycloalkyl groups include the cyclopropyl
  • the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propylene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
  • heteroaliphatic groups include the aforementioned preferred alkyl and cycloalkyl radicals in which at least one
  • Carbon unit is replaced by O, S or a group NR 1 or NR 1 R 2 and R 1 and R 2 is independently an alkyl group having 1 to 6 carbon atoms, a 1 to 6 carbon atoms alkoxy or an aryl group.
  • the carboxylic acid amides have branched or unbranched alkyl or alkoxy groups having 1 to 20
  • Carbon atoms preferably 1 to 12, suitably 1 to 6,
  • substituents in particular 1 to 4 carbon atoms and cycloalkyl or cycloalkyloxy groups having 3 to 20 carbon atoms, preferably 5 to 6 carbon atoms. These may have substituents. Among the preferred substituents are i.a. Halogens, in particular fluorine, chlorine, bromine, and alkoxy or hydroxy radicals.
  • alpha-hydroxycarboxamides can be used in the process according to the invention individually or as a mixture of two or more different aHCA.
  • Particularly preferred aHCA include alpha-hydroxyisobutyric acid amide and / or alpha-hydroxyisopropionic acid amide.
  • the carbonyl compound for example a ketone, in particular acetone, or an aldehyde, for example acetaldehyde,
  • Propanal, Butanal, reacted with hydrogen cyanide to the respective cyanohydrin It is particularly preferred to react acetone and / or acetaldehyde in a typical manner using a small amount of alkali or an amine as the catalyst.
  • the resulting cyanohydrin is reacted with water to aHCA.
  • This reaction is typically carried out in the presence of a catalyst.
  • a catalyst particularly suitable for this purpose are manganese oxide catalysts, as described, for example, in EP 0945429, EP 0561614, EP 0545697 and EP 2268396.
  • the manganese oxide can be used in the form of manganese dioxide, which by treatment of manganese sulfate with
  • Alcohols which can be used in the process of the invention include all alcohols known to the person skilled in the art as well as precursor compounds of alcohols which, under the stated conditions of pressure and temperature, are capable of reacting with the aHCA in the sense of alcoholysis.
  • the aHCA in the sense of alcoholysis.
  • Preferred alcohols are i.a. Methanol, ethanol, propanol, butanol, in particular n-butanol and 2-methyl-1-propanol, pentanol, hexanol, heptanol, 2-ethylhexanol, octanol, nonanol and decanol.
  • Methanol and / or ethanol is particularly preferred as the alcohol, with methanol being particularly useful.
  • the use of precursors of an alcohol is possible in principle. So can
  • alkyl formates are used.
  • Methyl formate or a mixture of methanol and carbon monoxide is Methyl formate or a mixture of methanol and carbon monoxide.
  • reaction between aHCA and alcohol is carried out in the context of the invention in a pressure reactor in the liquid phase. This is basically a reaction space to understand, which allows it during the implementation of a
  • the pressure reactor is designed in the context of the invention as a tubular reactor.
  • Tubular reactors are known in the art and e.g. in Cresswell, D., Gough, A. and Milne, G. 2000. Tubular Reactors.
  • Overpressure in this context means a pressure greater than
  • Atmospheric pressure i. in particular greater than 1 bar.
  • the pressure can be in a range from greater than 1 bar to less than or equal to 100 bar, preferably 10-90 bar, particularly preferably 20-70 bar and very particularly preferably 30-65 bar.
  • Atmospheric pressure or greater than 1 bar Atmospheric pressure or greater than 1 bar.
  • auxiliaries such as strip gas for distillative removal of the ammonia is completely dispensed with.
  • the best separation results of ammonia and methanol without stripping agent are obtained when the pressure is less than the reactor pressure but greater than 1 bar.
  • the product mixture is depleted in the meaning of the invention not only of ammonia but also of unreacted alcohol.
  • methanol is used for the alcoholysis, a product mixture results, inter alia, with the components, which are in principle very difficult to separate from one another, ammonia and methanol.
  • the said two components are removed directly as a mixture of substances from the product mixture.
  • the two substances are then subjected to a subsequent separation operation, for example, a rectification.
  • a subsequent separation operation for example, a rectification.
  • the two components alcohol (methanol) and ammonia in one operation of the product mixture
  • pressure reactors For example, provide one or more pressure reactors and connect them to a pressure distillation column. This is one or more reactors, which are arranged outside the column in a separate area.
  • the reaction in the pressure reactor is repeated one or more times with the depleted in the direction of the bottom of the separation column (pressure distillation column) of ammonia and alcohol product mixture, wherein the reaction step is shifted to a plurality of pressure reactors connected in series are.
  • This process step can be repeated as desired, particularly favorable, for example, three to four repetitions.
  • preference is given to a process which is characterized by the fact that the reaction in the pressure reactor, the relaxation of the reacted mixture, the feed into the first
  • n can be a positive integer greater than zero.
  • n is in the range of 2 to 10.
  • the pressure distillation column generally has a temperature in the range of about 60 ° C to 220 ° C, preferably 80 ° C-190 ° C, most preferably 90 ° C-180 ° C.
  • the exact temperature is typically set by the boiling system as a function of the prevailing pressure conditions.
  • the temperature in the reactor is preferably in the range of about 120-240 ° C. It is particularly useful at the start of the reaction with fresh
  • Another measure to increase the selectivity may also be to reduce the amount of catalyst from reactor to reactor. With decreasing amount of catalyst with increasing total conversion also gives an improved selectivity.
  • the process according to the invention it is advantageous to remove the product mixture to be taken from the pressure distillation column at certain points of the column.
  • the distance of the removal point to the bottom (column bottom) of the column is used for orientation as a relative location.
  • Destillation column is fed, based on the feed of the
  • the reaction temperature may also vary over a wide range, with the rate of reaction generally increasing with increasing temperature.
  • the upper temperature limit generally results from the
  • the reaction temperature is in the range of 40-300 ° C, more preferably 120-240 ° C.
  • process variants in which the reaction of the educts takes place at a molar starting ratio of alcohol to aHCA in the range from 1: 3 to 20: 1. Most preferably, the ratio is 1: 2 to 15: 1 and more preferably 1: 1 to 10: 1. Furthermore, process variants are preferred, which are characterized in that is used as aHCA alpha-hydroxyisobutyramide and as alcohol methanol.
  • Preferred process variants are those in which the catalyst is an insoluble metal oxide, which is at least one of those from Sc, V, La, Ti, Zr, Y, Hf, V, Nb, Ta, Cr, Mo, W, Tc , Re, Fe, Co, Ni, Cu, Al, Si, Sn, and Pb group selected element.
  • catalysts based on ZrO 2 and Al 2 O 3 very particular preference being given to using lanthanum oxide, silicon oxide or yttrium oxide-doped ZrO 2 catalysts.
  • the latter are commercially available e.g. available as zirconium oxide catalyst SZ 61 157 from Saint-Gobain Nopro.
  • the yttrium incorporated in the zirconium oxide crystal lattice stabilizes the tetragonal phase of the zirconium oxide which is otherwise stable only above 1200 ° C.
  • composition with 8 mol% Y 2 O 3 is typical here.
  • Processes are lanthanum oxide, silicon oxide or yttrium oxide contents based on ZrO 2 of 0.05-20 mol%, preferably of 0.5-15 mol%, particularly preferably 1-10 mol% and very particularly preferably 2-5 mol% used. It is also possible to use mixtures of the stated catalysts.
  • heterogeneous catalysts of the invention are designed as a fixed bed within the above-mentioned pressure reactor.
  • Embodiments of catalytic fixed bed reactors are known to the person skilled in the art and are described, for example, in US Pat Eigenberger, G. and Ruppel, W. 2012. Catalytic Fixed-Bed Reactors. Ullmann's Encyclopedia of Industrial Chemistry.
  • the temperature is traced in the fixed catalyst bed in dependence on the conversion by the reaction temperature is increased depending on the loss of conversion.
  • the original value of the conversion can be set again.
  • HIBSM Hydroxyisobutyrate
  • Impurities such as alpha-hydroxyisobutyric acid (HIBS), alpha-aminoisobutyric acid amide (A-HIBA), formamide (FA) or tetra-methyl-oxazolidinone (TMO).
  • HIBS alpha-hydroxyisobutyric acid
  • A-HIBA alpha-aminoisobutyric acid amide
  • FA formamide
  • TMO tetra-methyl-oxazolidinone
  • MIBSM Methyl methoxyisobutyrate
  • MIBMA Methoxyisobutyric acid methylamide
  • the proportion of all by-products contained in the product mixture from step c) in the total feed in step a) should be at most 85% by weight, preferably at most 65% by weight and particularly preferably 50% by weight.
  • HIBA is metered into a feed tank (B1) and combined there with two recycle streams (from K2 and K5). From this receiver, the mixture obtained is metered onto the reactor R1 (loop 1). Depending on the water content of fed into the reactor
  • Methanol required for the reaction (MeOH) is made available on the one hand as recycle MeOH via the return of K4, on the other hand via a metered addition from a feed tank (B2) as fresh MeOH. All loops are operated at 200 ° C. The weight fractions of the catalyst distribution in the individual loops is 2.7: 2.0: 1, 3: 1, 0.
  • R1 the partial conversion of HIBA and MeOH to HIBSM and NH 3 takes place.
  • the effluent is passed into the column K1, wherein NH 3 partially evaporated.
  • the reaction is repeated in three further reactors (R2 to R4), with the content of HIBSM increasing towards the bottom.
  • the catalyst loading also increases due to decreasing catalyst amounts downwards. Space-time yield and selectivity are kept constant.
  • the effluent of the last reactor R4 is largely freed from MeOH and NH 3 in the stripping section of K1.
  • NH 3 accumulates pressure-dependently from all reaction steps to a concentration of 8-10% by weight in MeOH.
  • Trace components are separated.
  • the vapors of the W1 are passed into the column K5, at the head of which HIBMA is discharged in concentrated form from the process.
  • HIBA-rich stream In the bottom of a high-boiling by-products and partially purified by HIBMA, falls HIBA-rich stream, which is dosed into the HIBA template (B1).
  • Zirconia catalysts give the best yields of HIBSM (Y-HIBSM). The best performance is with Ytthumoxid-, lanthanum oxide or
  • Silicon oxide dopants achieved. This is followed by the aluminum oxides, which have advantages in the selective derivative (S-HIBSM) at low barium oxide doping.
  • Example 10 Water influence on kinetics
  • Table 4
  • Am-HIBS can also be used in the process according to the invention as feed for the methanolysis (step b)). It results in a standard driving style (Example 12) similar equilibrium position - Am-HIBS reacts with a large proportion to HIBA back - which is slightly displaced by the comparatively high water content.
  • the HIBSM yield is similar and is in the range 25-30%.
  • Ammonium HIBS ammonium HIBS
  • Example 1 was repeated with a feed consisting of 9.5 wt%
  • HIBMA in MeOH run at a feed rate of 2 ml / min at 220 ° C over a Y 2 O 3 + ZrO 2 catalyst from Saint Gobain Norpro. Analysis was by GC (see Appendix).
  • Example 1 was repeated at 210 ° C with a Y 2 O 3 + ZrO 2 catalyst from Saint Gobain Norpro.
  • the temperature program envisages heating at 40 - 230 ° C at 15 K / min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'esters d'acide alpha-hydroxycarboxylique par alcoolyse de l'amide d'acide alpha-hydroxycarboxylique correspondant lors d'une catalyse hétérogène.
EP14739371.4A 2013-07-12 2014-07-03 Procédé de production d'esters d'acide alpha-hydroxycarboxylique Withdrawn EP3019463A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013213699.4A DE102013213699A1 (de) 2013-07-12 2013-07-12 Verfahren zur Herstellung von alpha-Hydroxycarbonsäureestern
PCT/EP2014/064194 WO2015003998A1 (fr) 2013-07-12 2014-07-03 Procédé de production d'esters d'acide alpha-hydroxycarboxylique

Publications (1)

Publication Number Publication Date
EP3019463A1 true EP3019463A1 (fr) 2016-05-18

Family

ID=51205352

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14739371.4A Withdrawn EP3019463A1 (fr) 2013-07-12 2014-07-03 Procédé de production d'esters d'acide alpha-hydroxycarboxylique

Country Status (10)

Country Link
US (1) US20160137583A1 (fr)
EP (1) EP3019463A1 (fr)
JP (1) JP2016529225A (fr)
KR (1) KR20160031500A (fr)
CN (1) CN105431406A (fr)
DE (1) DE102013213699A1 (fr)
RU (1) RU2016103966A (fr)
SG (1) SG11201600056YA (fr)
TW (1) TW201518270A (fr)
WO (1) WO2015003998A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017526717A (ja) 2014-09-10 2017-09-14 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ アンモニアをリサイクルしてα−ヒドロキシカルボン酸エステルを製造する方法
EP3026039A1 (fr) 2014-11-25 2016-06-01 Evonik Röhm GmbH Régénération de catalyseurs hétérogènes lors de la fabrication d'esters d'acide carboxylique alpha- ou bêta-substitués
EP3689851A1 (fr) * 2019-02-04 2020-08-05 Evonik Operations GmbH Production sans sel de méthionine à partir de nitrile de méthionine

Family Cites Families (10)

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FR2315498A1 (fr) * 1975-06-26 1977-01-21 Roehm Gmbh Procede de preparation d'esters d'acides carboxyliques a partir d'amines d'acides carboxyliques
US5387715A (en) 1991-12-03 1995-02-07 Mitsui Toatsu Chemicals, Inc. Process for producing α-hydroxy-isobutyramide
US5268503A (en) 1992-03-16 1993-12-07 Mitsui Toatsu Chemicals, Incorporated Process for producing α,β-unsaturated carboxylic acid esters
JP3222639B2 (ja) 1993-06-15 2001-10-29 三菱レイヨン株式会社 α−ヒドロキシイソ酪酸エステルの製造法
JP3229496B2 (ja) 1994-09-06 2001-11-19 三菱レイヨン株式会社 ヒドロキシカルボン酸エステルの製造法
US6124501A (en) 1998-03-24 2000-09-26 Mitsubishi Gas Chemical Company, Inc. Process for preparing lactamide
ES2200429T3 (es) * 1998-03-25 2004-03-01 Mitsubishi Gas Chemical Company, Inc. Procedimiento de preparacion de alfa-hidroxicarboxilato.
DE102006034273A1 (de) * 2006-07-21 2008-01-24 Röhm Gmbh Verfahren zur Herstellung von Alpha-Hydroxycarbonsäuren
DE102008001319A1 (de) 2008-04-22 2009-10-29 Evonik Röhm Gmbh Katalysator zur Umsetzung von Carbonsäurenitrilen
DE102011081256A1 (de) 2011-08-19 2013-02-21 Evonik Röhm Gmbh Verfahren zur Herstellung von Alpha-Hydroxycarbonsäureestern

Non-Patent Citations (2)

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Also Published As

Publication number Publication date
RU2016103966A (ru) 2017-08-17
WO2015003998A1 (fr) 2015-01-15
TW201518270A (zh) 2015-05-16
KR20160031500A (ko) 2016-03-22
JP2016529225A (ja) 2016-09-23
DE102013213699A1 (de) 2015-01-15
CN105431406A (zh) 2016-03-23
US20160137583A1 (en) 2016-05-19
SG11201600056YA (en) 2016-02-26

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